WO2015152617A1 - Coating method for preventing bending phenomenon of substrate - Google Patents

Coating method for preventing bending phenomenon of substrate Download PDF

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Publication number
WO2015152617A1
WO2015152617A1 PCT/KR2015/003192 KR2015003192W WO2015152617A1 WO 2015152617 A1 WO2015152617 A1 WO 2015152617A1 KR 2015003192 W KR2015003192 W KR 2015003192W WO 2015152617 A1 WO2015152617 A1 WO 2015152617A1
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Prior art keywords
methyl
pomma
glyp
phenyl
eche
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PCT/KR2015/003192
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French (fr)
Korean (ko)
Inventor
신규순
정희정
최승석
Original Assignee
주식회사 동진쎄미켐
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Priority to US15/129,416 priority Critical patent/US10280336B2/en
Priority claimed from KR1020150044976A external-priority patent/KR102367173B1/en
Publication of WO2015152617A1 publication Critical patent/WO2015152617A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2252/00—Sheets
    • B05D2252/02—Sheets of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2252/00—Sheets
    • B05D2252/10—Applying the material on both sides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat

Definitions

  • the present invention relates to a method for preventing warpage coating of a substrate, and more particularly, to a method for preventing warpage coating of a substrate to form a coating layer having different densities on the surface of the substrate to form two or more coating layers, wherein the two or more coating layers At least one layer of the coating composition comprising a silsesquioxane composite polymer represented by a specific chemical formula and the coating can be cured not only to prevent warpage of the substrate, but also at the same time high surface hardness, excellent transparency, scratch resistance
  • the present invention relates to a coating method for preventing warpage of a substrate capable of imparting water repellency, antifouling properties, fingerprint resistance, thermal stability, and gloss property.
  • Substrates such as plastic, glass, wood or paper are used for various purposes.
  • the above substrates are warped as the area becomes larger.
  • the flatness was excellent as shown in FIG. 1, but as time goes by, the warpage may occur as shown in the thick line of FIG. 1, and even when the functional material is coated on the surface of the substrate to provide functionality. It may occur.
  • Such a warpage phenomenon of the substrate may act as a cause of a device defect, or there is a problem that degrades the utility of the overall product by aesthetics.
  • the present invention can not only prevent the warpage of the substrate through a simple coating process on the surface of the substrate, but also at the same time high surface hardness, excellent transparency, scratch resistance, water repellency,
  • An object of the present invention is to provide a coating method for preventing warpage of a substrate which can impart antifouling properties, anti-fingerprint properties, thermal stability, and gloss properties, and a substrate for preventing warpage.
  • the present invention provides a coating method for preventing warpage of the substrate
  • At least one of the two or more coating layers provides a coating method for preventing warpage of the substrate, characterized in that the coating composition comprising the silsesquioxane composite polymer represented by any one of the following formulas (1) to (9):
  • Each Y is independently O, NR 21 or [(SiO 3/2 R) 4 + 2n O], at least one is [(SiO 3/2 R) 4 + 2n O],
  • Each X is independently R 22 or [(SiO 3/2 R) 4 + 2n R], at least one is [(SiO 3/2 R) 4 + 2n R],
  • R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C 1 -C 40 alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; C 2 -C 40 alkenyl group; C 1 ⁇ C 40 Alkoxy group; C 3 -C 40
  • a and d are each independently an integer of 1 to 100,000, preferably a is 3 to 1000, d is 1 to 500, more preferably a is 5 to 300, d is 2 to 100,
  • b are each independently an integer of 1 to 500
  • e are each independently 1 or 2, preferably 1,
  • n is independently an integer of 1-20, Preferably it is 3-10.
  • the present invention is provided with a coating layer of two or more layers formed by coating a coating composition having a different density on the surface, at least one of the coating layer is a coating comprising a silsesquioxane composite polymer represented by any one of the formulas (1) to (9)
  • a warpage preventing substrate characterized in that formed in the composition.
  • the present invention also provides an article comprising the warpage preventing substrate.
  • the warpage prevention coating method of the substrate according to the present invention can not only prevent the warpage of the substrate through a simple coating process but at the same time high surface hardness, excellent transparency, scratch resistance, water repellency, antifouling properties, anti-fingerprint on the surface of the substrate By imparting heat stability and glossiness, the durability and utility value of the product can be greatly increased.
  • FIG. 1 is a schematic diagram showing a base material exhibiting the bending phenomenon according to the prior art.
  • 2 to 5 are schematic views showing the warpage phenomenon preventing substrate according to the present invention, respectively.
  • Figure 6 shows an imaginary reference point of the coating surface used in the warpage measurement method in the present invention.
  • the present invention is a coating method for preventing warpage of the substrate
  • At least one of the two or more coating layers provides a coating method for preventing warpage of the substrate, characterized in that the coating composition comprising the silsesquioxane composite polymer represented by any one of the following formulas (1) to (9):
  • Each Y is independently O, NR 21 or [(SiO 3/2 R) 4 + 2n O], at least one is [(SiO 3/2 R) 4 + 2n O],
  • Each X is independently R 22 or [(SiO 3/2 R) 4 + 2n R], at least one is [(SiO 3/2 R) 4 + 2n R],
  • R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C 1 -C 40 alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; C 2 -C 40 alkenyl group; C 1 ⁇ C 40 Alkoxy group; C 3 -C 40
  • a and d are each independently an integer of 1 to 100,000, preferably a is 3 to 1000, d is 1 to 500, more preferably a is 5 to 300, d is 2 to 100,
  • b are each independently an integer of 1 to 500
  • e are each independently 1 or 2, preferably 1,
  • n is independently an integer of 1-20, Preferably it is 3-10.
  • R 1 , R 2 , R 16 , D, a and d are the same as defined in Chemical Formulas 1 to 9.
  • a third step of condensation reaction by adding a basic catalyst to the reactor after step 2 to convert the reaction solution to basic.
  • the pH of the reaction solution of the first step of the present invention in the method for preparing the formula 1 to 6 is 9 to 11.5, the pH of the reaction solution of the second step is preferably 2 to 4, The pH of the reaction solution of the third step is preferably 8 to 11.5, and the pH of the reaction solution of the fourth step of introducing Ee is preferably 1.5 to 4.
  • the pH of the reaction solution of the first step of the present invention in the method for preparing the formula 1 to 6 is 9 to 11.5
  • the pH of the reaction solution of the second step is preferably 2 to 4
  • the pH of the reaction solution of the third step is preferably 8 to 11.5, and the pH of the reaction solution of the fourth step of introducing Ee is preferably 1.5 to 4.
  • the yield of the silsesquioxane composite polymer prepared is high, but also the mechanical properties of the manufactured silsesquioxane composite polymer can be improved.
  • step 1 Mixing a basic catalyst and an organic solvent in a reactor, and then adding an organic silane compound and preparing two types of Chemical Formula 10 in which the degree of condensation is controlled;
  • the reaction solution was adjusted to acid by adding an acidic catalyst to the reactor, and then an organic silane compound was added.
  • a second step of stirring A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after each two-step reaction; Condensing and connecting two or more substances obtained through the three steps under basic conditions; A fifth step of adding an acidic catalyst to the reactor for introducing [D] d (OR 13 ) 2 after the fourth step to adjust the reaction solution to acid, followed by adding and stirring an organic silane compound; And a sixth step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the five step reaction.
  • the pH of the reaction solution of the first step is 9 to 11.5, the pH of the reaction solution of the second step is preferably 2 to 4 in the method for preparing the polymer of Formula 7 to 9,
  • the pH of the reaction solution of the third stage is preferably 8 to 11.5, the pH of the reaction solution of the fourth stage is preferably 9 to 11.5, the pH of the reaction solution of the fifth stage is preferably 2 to 4, It is preferable that it is 8-11.5 of the reaction liquid of a 6th step, and it is preferable that pH of the reaction liquid of the 7th step which introduces Ee is 1.5-4.
  • the yield of the silsesquioxane composite polymer prepared is high, but also the mechanical properties of the manufactured silsesquioxane composite polymer can be improved.
  • the terminal may further include a repeating unit of [E] e.
  • a mixed catalyst of two or more basic catalysts is preferably used as a basic catalyst, and neutralized and acidified with an acidic catalyst to induce rehydrolysis, and again two or more basic catalysts. Acidity and basicity can be continuously controlled in one reactor by proceeding to basic condensation using a mixed catalyst of.
  • the basic catalyst may be prepared by appropriately combining two or more materials selected from a metal based catalyst and an amine based catalyst selected from the group consisting of Li, Na, K, Ca and Ba.
  • the amine based catalyst may be tetramethylammonium hydroxide (TMAH)
  • the metallic basic catalyst may be potassium hydroxide (KOH) or sodium bicarbonate (NaHCO 3 ).
  • the content of each component in the mixed catalyst is preferably in the ratio of 10 to 90: 10 to 90 parts by weight of the ratio of the amine basic catalyst and the metal basic catalyst can be arbitrarily adjusted.
  • the reactivity between the functional group and the catalyst may be minimized during hydrolysis, and thus, the defects of organic functional groups such as Si-OH or Si-alkoxy may be significantly reduced, thereby freely controlling the degree of condensation.
  • the acidic catalyst may be used without limitation so long as it is an acidic material commonly used in the art, for example, may be used a general acidic material such as HCl, H 2 SO 4 , HNO 3 , CH 3 COOH, Organic acids such as latic acid, tartaric acid, maleic acid and citric acid can also be applied.
  • the organic solvent may be used without limitation as long as it is an organic solvent commonly used in the art.
  • organic solvent commonly used in the art.
  • solvents such as nit
  • the silsesquioxane composite polymer of the present invention may be R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , Organosilanes comprising R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 can be used
  • the organic silane compound containing a phenyl group or an amino group having an effect of improving the chemical resistance of the silsesquioxane composite polymer to improve the non-swelling property, or the mechanical strength and hardness of the cured layer by increasing the curing density of the composite polymer
  • the organosilane compound containing the epoxy group or (meth) acryl group which has the effect of improving the can be used.
  • organosilane compound examples include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3 -Glycidoxy propyl) dimethyl ethoxy silane, 3- (methacryloxy) propyl trimethoxy silane, 3, 4- epoxy butyl trimethoxy silane, 3, 4- epoxy butyl triethoxy silane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltri-t-butoxy Silane, vinyltriisobutoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, phenyltriethoxysilane,
  • n of the [(SiO 3/2 R) 4 + 2n O] structure introduced into the repeating unit [D] d of the above formulas may be substituted with an integer of 1 to 20, preferably 3 to 10, and More preferably, the average n value is 4 to 5, for example, when n is 4, the substituted structure is represented by Formula 11 below:
  • R is as defined above.
  • n of the [(SiO 3/2 R) 4 + 2n R] structure introduced into the repeating units [B] b or [E] e of the above formulas may be substituted with an integer of 1 to 20, preferably Below 3 to 10, more preferably, the average n value is 4 to 5, for example, when n is 4 to represent a structure substituted by the formula (12):
  • R is as defined above.
  • the silsesquioxane polymer according to the present invention may be a polymer shown in Tables 1 to 18 below.
  • ECHE Epoxycyclohexyl
  • GlyP means Glycidoxypropyl
  • POMMA means (methacryloyloxy) propyl, and when two or more are described, it means mixed use.
  • n is 1-8 each independently.
  • the silsesquioxane composite polymer of Chemical Formula 1 may be a polymer described in Table 1 or 2 below.
  • the silsesquioxane composite polymer of Chemical Formula 2 may be a polymer described in Tables 3 and 4 below.
  • the silsesquioxane composite polymer of Chemical Formula 3 may be a polymer described in Table 5 or 6 below.
  • the silsesquioxane composite polymer of Chemical Formula 4 may be a polymer described in Tables 7 and 8 below.
  • the silsesquioxane composite polymer of Formula 5 may be a polymer described in Tables 9 and 10.
  • the silsesquioxane composite polymer of Chemical Formula 6 may be a polymer described in Tables 11 and 12 below.
  • the silsesquioxane composite polymer of Chemical Formula 7 may be a polymer described in Tables 13 and 14 below.
  • the silsesquioxane composite polymer of Chemical Formula 8 may be a polymer described in Tables 15 and 16 below.
  • the silsesquioxane composite polymer of Chemical Formula 9 may be a polymer described in Tables 17 and 18 below.
  • the silsesquioxane composite polymer of the present invention may be adjusted to 1 to 99.9% or more in order to secure excellent storage stability to obtain a wide range of applications. That is, the content of alkoxy groups bonded to Si at the terminal and center can be controlled from 50% to 0.01% with respect to the bonding groups of the entire polymer.
  • the weight average molecular weight of the silsesquioxane composite polymer according to the present invention may be 1,000 to 1,000,000, preferably 5,000 to 100,000, and more preferably 7,000 to 50,000. In this case, the processability and physical properties of the silsesquioxane can be improved simultaneously.
  • the coating composition including the silsesquioxane composite polymer represented by any one of Formulas 1 to 9 may use two or more composite polymers, and preferably, the yarn represented by any one of Formulas 3 to 9 It is preferable to use sesquioxane composite polymer.
  • the physical properties of the transparent substrate including the surface hardness can be further improved by including the repeating unit [B] b or [E] e.
  • the coating composition may be coated alone as a solventless type when the silsesquioxane composite polymer is in a liquid state, and may include an organic solvent in the case of a solid phase.
  • the coating composition may further include an initiator or a curing agent.
  • the coating composition is characterized in that it comprises a silsesquioxane composite polymer represented by any one of Formulas 1 to 9, an organic solvent commonly used in the art that is compatible with the composite polymer, the initiator It may optionally further include additives such as hardeners, plasticizers, sunscreens, and other functional additives to improve curability, heat resistance, UV protection, plasticizing effects and the like.
  • additives such as hardeners, plasticizers, sunscreens, and other functional additives to improve curability, heat resistance, UV protection, plasticizing effects and the like.
  • the silsesquioxane composite polymer may be included at least 5 parts by weight or more, based on 100 parts by weight of the coating composition, preferably 5 to 90 parts by weight, more preferably 10 to 50 parts by weight. It is preferably included in negative amounts. If within the above range can further improve the mechanical properties of the cured film of the coating composition.
  • organic solvent examples include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol and cellosolve, ketones such as lactate, acetone and methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol,
  • polar solvents such as furan-based compounds such as tetrahydrofuran, dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone, hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, Dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acronitrile, methylene chloride, octadecylamine, aniline, dimethylsulfoxide, benzyl alcohol can be used, but is not limited thereto.
  • the initiator or the curing agent may be appropriately selected and used according to the organic functional group contained in the silsesquioxane composite polymer.
  • an organic system capable of post-curing such as an unsaturated hydrocarbon, a siol system, an epoxy system, an amine system, or an isocyanate group
  • various curing using heat or light is possible.
  • the change due to heat or light can be achieved in the polymer itself, but preferably, the curing step can be achieved by diluting with an organic solvent as described above.
  • various initiators may be used, and the initiator may be included in an amount of 0.1-20 parts by weight based on 100 parts by weight of the total composition, and when included in an amount within the above range, After curing, the transmittance and coating stability can be satisfied at the same time.
  • a radical initiator may be used, and the radical initiator may include trichloro acetophenone, diethoxy acetophenone, and 1-phenyl-2-hydride.
  • sulfoniums such as triphenylsulfonium and diphenyl-4- (phenylthio) phenylsulfonium, diphenyliodonium and bis (dode) are used as photopolymerization initiators (cations).
  • Iodonium such as silphenyl) iodonium, diazonium, such as phenyldiazonium, ammonium, such as 1-benzyl-2-cyanopyridinium and 1- (naphthylmethyl) -2-cyanofridinium, (4- Methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate iodonium, bis (4-t-butylphenyl) hexafluorophosphate iodonium, diphenylhexafluorophosphate iodonium, diphenyltrifluoro Romethanesulfonate iodonium, triphenylsulfonium tetrafuluroborate, tri-p-toylsulfonium hexafulurophosphate, tri-p-toylsulfonium trifluoromethanesulfonate and (2,4- cyclopent
  • the cationic initiators acting by heat include cationic or protonic acid catalysts such as triflate, boron trifluoride ether complex, boron trifluoride, etc. Bromide, ethyltriphenylphosphonium bromide, phenyltriphenylphosphonium bromide and the like can be used without limitation, and these initiators can also be added in various mixed forms, and can be mixed with the various radical initiators specified above. Do.
  • phthalic anhydride trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, methylhydride anhydride, trialkyltetra Acid anhydride hardeners, such as hydrophthalic anhydride, dodecenyl succinic anhydride, and 2, 4- diethyl glutaric anhydride, can also be used widely.
  • the hardener is preferably included in 0.1-20 parts by weight based on 100 parts by weight of the composition.
  • triazine-based compounds such as acetoguanamine, benzoguanamine, 2,4-diamino-6-vinyl-s-triazine, imidazole, 2-methylimidazole Imidazole compounds such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, vinylimidazole, and 1-methylimidazole, 1, 5-diazabicyclo [4.3.0] nonene-5,1,8-diazabicyclo [5.4.0] undecene-7, triphenylphosphine, diphenyl (p-tril) phosphine, tris (alkylphenyl Phosphine, tris (alkoxyphenyl) phosphine, ethyltriphenylphosphonium phosphate, tetrabutylphosphonium hydroxide, tetrabutyl
  • the coating composition may further include a pigment.
  • the silsesquioxane composite polymer represented by any one of Chemical Formulas 1 to 9 of the present invention may improve dispersibility of the pigment and have excellent compatibility with the pigment, and thus may have an excellent coloring effect.
  • the pigment may be a well-known pigment can be used, the content of the pigment can be selected and used by those skilled in the art in the appropriate range.
  • the present invention may further include additives such as UV absorbers, antioxidants, antifoaming agents, leveling agents, water repellents, flame retardants, and adhesion improving agents for the purpose of improving hardness, strength, durability, formability, etc. through a curing process or a post reaction.
  • additives such as UV absorbers, antioxidants, antifoaming agents, leveling agents, water repellents, flame retardants, and adhesion improving agents for the purpose of improving hardness, strength, durability, formability, etc. through a curing process or a post reaction.
  • Such additives are not particularly limited in use, but may be appropriately added within a range that does not impair the properties of the substrate, that is, properties such as flexibility, light transmittance, heat resistance, hardness, and strength.
  • Each of the additives is preferably included in an amount of 0.01-10 parts by weight based on 100 parts by weight of the composition.
  • Additives usable in the present invention include polyether-modified polydimethylsiloxane (eg, BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK-306, BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310, etc.), polyether hydroxy polydimethylsiloxanes (e.g., manufactured by BYK BYK-308, BYK-373, etc.), polymethylalkylsiloxane (e.g., BYK-077, BYK-085, etc.), polyether polymethylalkylsiloxane (e.g., BYK- 320, BYK-325, etc.), polyester modified poly-methyl-alkyl-siloxane (e.g., BYK-315, etc.), allylalkyl polymethylalkylsiloxane (aral
  • polyester hydroxy polydimethylsiloxane Polydimethylsiloxane (Polyester modified hydroxy functional polydimethylsiloxane, such as BYK-370), polyester acrylic polydimethylsiloxane (Acrylic functional polyester modified polydimethylsiloxane, such as BYK-371, BYK-UV 3570, etc.), polyether-polyester hydroxy Polyeher-polyester modified hydroxy functional polydimethylsiloxane (e.g., BYK-375, etc.), polyether polydimethylsiloxane (e.g., BYK-345, BYK-348, BYK-346) , BYK-UV3510, BYK-332, BYK-337, etc.), nonionic polyacrylic (Non-ionic acrylic copolymer, such as BYK-380, etc.), Ionic acrylic copolymer (eg, BYK -381, etc
  • the base material includes all of the conventional base materials in which warpage occurs, and concrete examples thereof include plastic, glass, metal thin film, wood, or pulp, and in particular, plastic (polyethylene, PE) , Polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET, PET), polyamides (PA), polyester (PES), polyvinyl chloride , PVC), polyurethane (PU), polycarbonate (PC), high hardness polycarbonate (PC), polyvinylidene chloride (PVDC), polytetrafluoroethylene (PTFE) ), Polyetheretherketone (PEEK), epoxy, polyacrylonitrile (PAN), silicone polymer, polyethylene oxide (pol) two or more plastic materials as well as a single plastic material such as yethylen oxide (PEO), polymethylen oxide (PMO), polyimide (PI), bioplastics, and polyetherimide (PEI), acrylic May be mixed, and may be a composite plastic mixed with plastic and inorganic plastic (poly
  • the substrate can be applied to all types of products, including sheets, films, injection moldings, moldings and beads because the solution process is also used in the form.
  • specific articles include a window cover substrate, a protective film, a protective plate of the display; Wooden furniture; Wood building interior and exterior materials; Wood accessories; Wood public facilities; Walls, floors, tiles, roofs, windows of buildings or structures; Cups, plates, bowls; Semiconductor manufacturing apparatus; Corrugated or paper coated products; Glass of the car; glasses; Or optical products, electronic products, glass used in solar cells, and the like, but are not limited thereto.
  • the coating composition including the silsesquioxane composite polymer represented by any one of Formulas 1 to 9 may use two or more composite polymers, and preferably, the yarn represented by any one of Formulas 1 to 9 In the sesquioxane composite polymer, it is good to synthesize different materials with different densities by varying substituents, and coat the coating composition with the silsesquioxane composite polymer having different densities.
  • At least one coating composition used for forming two or more coating layers in the present invention is a coating composition containing a silsesquioxane composite polymer represented by any one of Formulas 1 to 9, and the other coating layer (single layer or a plurality of layers) Can be used as a coating composition having a different density from the coating composition containing the silsesquioxane composite polymer or a silsesquioxane represented by any one of Formulas 1 to 9 above. It may be a coating composition containing a composite polymer. The coating composition having different densities is coated on the substrate to correct the warpage of the substrate.
  • At least one of the coating compositions including the silsesquioxane composite polymer may be used to increase the surface stability, thereby allowing the substrate to have excellent flatness.
  • all of the coating layers may be formed using a coating composition containing the silsesquioxane composite polymer represented by any one of Formulas 1 to 9.
  • the number of layers of the coating layer may be appropriately selected and applied by those skilled in the art as two or more layers, preferably 2 to 10 layers, and more preferably 2 to 6 layers. In this case, the productivity and the warpage prevention effect can be satisfied at the same time.
  • two or more coating layers may be formed on one surface of the substrate as shown in FIG. 2, or may be formed on both sides of the substrate as illustrated in FIGS. 3 and 4.
  • the second coating layer and the fourth coating layer of Figure 5 may be formed, and preferably, the outermost layer of the coating layer may be a coating composition containing a silsesquioxane composite polymer.
  • the polymer density difference of coating compositions having different densities is preferably 0.001 g / cm 3 or more, and more preferably 0.01 to 2 g / cm 3 .
  • the method of coating the coating composition on the surface of the substrate is spin coating, bar coating, slit coating, dip coating, natural coating, reverse coating, roll coating, spin coating, curtain coating, spray coating, dipping method
  • a person skilled in the art can arbitrarily select and apply a well-known method, such as a method of impregnation, gravure coating, and of course, in the curing method, the photocuring or thermal curing can be appropriately selected and applied according to the functional group of the composite polymer. to be.
  • the curing temperature in the case of thermosetting is 80 to 120.
  • the other coating layer may be formed thereon while one coating layer is finished until the curing process, and after coating and drying the first coating composition, the second coating composition on the dried coating layer After coating and drying, two coating layers may be formed through one curing process.
  • the coating thickness of the coating composition may be arbitrarily adjusted, preferably 0.01 to 500 um, more preferably 0.1 to 300 um, still more preferably 1 to 100 um.
  • the coating thickness of the outermost layer is preferably 1 to 100um.
  • the surface hardness of 7H or more be stably secured to the outermost surface, but also excellent coating properties.
  • the surface hardness of the coating layer can stably exhibit 9H.
  • the present invention is provided with a coating layer of two or more layers formed by coating a coating composition having a different density on the surface, at least one of the coating layer is a coating comprising a silsesquioxane composite polymer represented by any one of the formulas (1) to (9)
  • the warpage preventing substrate can be prepared by the warpage preventing coating method of the substrate.
  • the warpage preventing substrate according to the present invention has a flatness within 0.1 mm based on a 100 mm ⁇ 300 mm substrate, and in the case of a substrate having a coating layer on both sides of the substrate (FIGS. 3 and 4), the warpage prevention effect is more excellent.
  • the coating layer When the coating layer is formed of a coating composition containing a silsesquioxane composite polymer in the outermost layer, the coating layer has a very high surface hardness, excellent transparency, scratch resistance, water repellency, antifouling properties, and It has the properties of moonshine, heat stability and gloss.
  • An article including the warpage preventing substrate according to the present invention is not particularly limited, and as a specific example, a window cover substrate, a protective film, a protective plate of a display; Wooden furniture; Wood building interior and exterior materials; Wood accessories; Wood public facilities; Walls, floors, tiles, roofs, windows of buildings or structures; Cups, plates, bowls; Semiconductor manufacturing apparatus; Corrugated or paper coated products; Glass of the car; glasses; Or glass used for optical products, electronic products, and solar cells.
  • ECHETMS is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
  • GPTMS is Glycidoxypropytrimethoxysilane
  • MAPTMS is (methacryloyloxy) propyltrimethoxysilane
  • PTMS is Phenyltrimethoxysilane
  • MTMS is Methyltrimethoxysilane
  • ECHETMDS is Di (epoxycyclohexyethyl) Di (glycidoxypropyl) tetramethoxy disiloxane
  • MAPTMDS stands for Di (methacryloyloxy) propy
  • PTMDS stands for Di (phenyl) tetramethoxy disiloxane
  • MTMDS stands for Di
  • a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
  • KOH Potassium hydroxide
  • TMAH tetramethylammonium hydroxide
  • Example 1-a To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, 1 part by weight of the catalyst prepared in Example 1-a was added dropwise, followed by stirring at room temperature for 1 hour, and then 2 20 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 15 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 5 hours.
  • the mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having the same linear structure as the chemical formula 4 had a molecular weight of 8,000 styrene.
  • Example 1-b To the mixed solution of Example 1-b 0.36% by weight of HCl aqueous solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 °C 30 minutes. Thereafter, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at one time to achieve stable hydrolysis. After stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 1-a was added again to adjust the pH of the mixed solution in a basic state. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy.
  • Example 1-c 30 g of the silsesquioxane composite polymer obtained in Example 1-c was dissolved in methyl isobutyl ketone at 30% by weight to prepare a coating composition of 100 g. Thereafter, 3 parts by weight of chloro acetophenone, 1 part by weight of BYK-347, and 1 part by weight of BYK-UV 3500 were added to 100 parts of the coating composition, and stirred for 10 minutes to prepare a photocurable coating composition.
  • Example 1-c 50 g of the silsesquioxane composite polymer obtained in Example 1-c was dissolved in methyl ethyl ketone at 50% by weight to prepare 100 g of a coating composition. Thereafter, 3 parts by weight of 1,3-diaminopropane and 1 part by weight of BYK-357 and BYK-348 were added to 100 parts by weight of the prepared coating composition, followed by stirring for 10 minutes to prepare a thermosetting coating composition.
  • Example 1-c alone constitute a coating composition without a separate composition.
  • Example 1 In order to prepare a composite polymer having a D-A-D structure, the following examples were used, and a coating composition was prepared by a method similar to that described in Example 1 above. Preparation of the catalyst and the linear structure was used in the same manner as in Example 1-a and 1-b, and then to produce a continuous D-A-D structure was carried out by the following method.
  • Example 1-b To the mixed solution of Example 1-b 0.36% by weight of HCl aqueous solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 °C 30 minutes. Thereafter, 25 parts by weight, which is 5 times the amount of Diphenyltetramethoxydisiloxane used in Example 1-b, was added dropwise at one time to achieve stable hydrolysis, and after stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer.
  • silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 20 below. At this time, the manufacturing method was equally applied to the method used in Example 2.
  • Example 1 In order to prepare an E-A-D composite polymer, the following examples were used, and a coating composition was prepared by a method similar to that described in Example 1 above. Preparation of the catalyst and the linear structure was used in the same manner as in Example 1, and then to produce the E-A-D structure was carried out by the following method.
  • Example 1-c To the AD mixture obtained in Example 1-c, 20 parts by weight of methylene chloride were added dropwise without further purification, 5 parts by weight of an aqueous 0.36% by weight HCl solution was added dropwise, and the pH was adjusted to have an acidity, and 30 ° C at a temperature of 4 ° C. Stirred for a minute. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.
  • Example 3-a After preparing the organic layer of the resultant obtained in Example 3-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 3-a in progress, to achieve stable hydrolysis, and after stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced to the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (3). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
  • Example 3-b After the reaction mixture was obtained in Example 3-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum pressure. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5, and stored at a temperature of -20 ° C for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 3 was obtained along with various byproducts by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was 17,000 in terms of styrene
  • n value was 4-6
  • the results of formula (3) are as follows.
  • silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 21 below. In this case, the method used in Example 3 was equally applied.
  • a continuous hydrolysis and condensation were carried out stepwise to prepare a composite polymer having an E-A-D structure, and a coating composition was prepared by a method equivalent to that described in Example 1.
  • a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
  • KOH Potassium hydroxide
  • TMAH tetramethylammonium hydroxide
  • Example 4-a To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, 0.5 parts by weight of the catalyst prepared in Example 4-a were added dropwise, followed by stirring at room temperature for 1 hour, and then 2 10 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 20 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 2 hours.
  • the mixed solution was stirred and washed twice to remove the catalyst and impurities, and then filtered, and then linear silsesquioxane containing 0.1 mmol / g or less of the alkoxy group remaining through 1 H-NMR analysis. This was then used to introduce the cage into the continuous reaction.
  • XRD analysis confirmed that the overall structure is a linear structure through the XRD analysis. As a result of measuring the molecular weight, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 6,000 styrene.
  • Example 4-b To the mixture of Example 4-b in progress, 0.36 wt% HCl aqueous solution was added dropwise very slowly to 5 parts by weight, the pH was adjusted to have acidity, and stirred at a temperature of 4 ° C. for 30 minutes. Thereafter, 5 parts by weight of DiPhenyltetramethoxydisiloxane was added dropwise, and after stirring for 1 hour, 5 parts by weight of the catalyst prepared in Example 4-a was added again to adjust the pH of the mixed solution in a basic state.
  • the cage-type structure was introduced into the polymer chain separately from the linear structure, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum, and the overall reactant was converted into the aqueous mixture. It was made. After 4 hours of mixing, some of the alkoxy groups in the B structure were changed to 0.025 mmol / g as a result of partial extraction and analysis by 29 Si-NMR and 1 H-NMR. It was confirmed that the ratio was introduced at 5: 5. In addition, the styrene reduced molecular weight was measured to 10,000. In addition, although the cage type structure was introduced, the molecular weight distribution of the single cage type material was not found in the GPC form of the polymer, and thus the cage structure was well introduced into the polymer chain through the continuous reaction.
  • the terminal was converted into a cage structure using a trifunctional monomer.
  • 100 parts by weight of the material obtained in Example 4-c was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 4-a was added again to adjust the pH of the mixed solution in a basic state.
  • the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (4). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Formula 4 was obtained without various by-products by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was obtained in the styrene conversion value of 12,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 4 results are as follows.
  • silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 22 below. In this case, the method used in Example 4 was equally applied.
  • Example 1 The following method was used to prepare a composite polymer having a D-A-B-D structure, and a coating composition was prepared by the same method as in Example 1.
  • Example 4-b To the mixture of Example 4-b in progress, 0.36 wt% HCl aqueous solution was added dropwise very slowly to 5 parts by weight, the pH was adjusted to have acidity, and stirred at a temperature of 4 ° C. for 30 minutes. Thereafter, the amount of diphenyltetramethoxydisiloxane was prepared by adding 5 parts by weight to 25 parts by weight, which is 5 times the amount of Example 4-b, and after stirring for 1 hour, 5 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic pH of the mixed solution. Was adjusted.
  • Example 5-a After the organic layer of the resultant obtained in Example 5-a was prepared without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 100 parts by weight of the material obtained in Example 5-a was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 4-a was added again to adjust the pH of the mixed solution in a basic state.
  • the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (5). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 5 was obtained without various by-products by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was obtained in the styrene conversion value of 16,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 5 results are as follows.
  • silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 23 below. At this time, the manufacturing method was equally applied to the method used in Example 5.
  • Example 1 To prepare a composite polymer having an E-A-B-D structure, the following method was used, and a coating composition was prepared by the same method as in Example 1.
  • Example 4-c To the mixture obtained in Example 4-c, 20 parts by weight of methylene chloride were added dropwise without further purification, 5 parts by weight of 0.36% by weight aqueous HCl solution was added dropwise, the pH was adjusted to have an acidity, and 30 minutes at a temperature of 4 ° C. Stirred. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.
  • Example 6-a After the organic layer of the resultant obtained in Example 6-a was prepared without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 6-a in progress at a time to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced at the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in formula (6). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
  • Example 6-b the reaction mixture was obtained, washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5, and stored at a temperature of -20 ° C for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 6 was obtained along with various by-products by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was obtained in the styrene conversion value of 21,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 6 results are as follows.
  • silsesquioxane composite polymer was prepared by applying the monomers described in Table 24 below. At this time, the manufacturing method was equally applied to the method used in Example 6.
  • Synthesis step was carried out step by step, hydrolysis and condensation step by step, to prepare a coating composition in the same manner as in Example 1.
  • a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
  • KOH Potassium hydroxide
  • TMAH tetramethylammonium hydroxide
  • Example 7-a To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, 1 part by weight of the catalyst prepared in Example 7-a was added dropwise, and stirred at room temperature for 1 hour, followed by 2 20 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 15 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 5 hours.
  • the mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 6,000 styrene.
  • Example 7-a To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, 0.5 parts by weight of the catalyst prepared in Example 7-a were added dropwise, followed by stirring at room temperature for 1 hour, and then 2 10 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 20 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 2 hours.
  • the mixed solution was stirred and washed twice to remove the catalyst and impurities, and then filtered, and then linear silsesquioxane containing 0.1 mmol / g or less of the alkoxy group remaining through 1 H-NMR analysis. This was then used to introduce the cage into the continuous reaction.
  • XRD analysis confirmed that the overall structure is a linear structure through the XRD analysis. As a result of measuring the molecular weight, it was confirmed that the silsesquioxane having a linear structure had a molecular weight in terms of 8,000 styrene.
  • Example 7-a catalyst To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 5 parts by weight of tetrahydrofuran, 10 parts by weight of the prepared Example 7-a catalyst were added dropwise and stirred at room temperature for 1 hour, followed by Example 20 parts by weight of the 7-b precursor and the 7-c precursor were added dropwise, and 10 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 24 hours.
  • the mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 15,000 styrene.
  • Example 7-d 0.36% by weight of HCl solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 °C 30 minutes. Thereafter, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at a time to achieve stable hydrolysis. After stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 7-a was added again to adjust the pH of the mixed solution in a basic state. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy.
  • the terminal was converted into a cage structure using a trifunctional monomer.
  • 100 parts by weight of the material obtained in Example 7-e was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was added again to adjust the pH of the mixed solution in a basic state.
  • the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (7). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 7 was obtained without various by-products by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was a styrene conversion value of 24,000
  • the n value of X was 4-6
  • the n value of Y was 4-6.
  • silsesquioxane composite polymer was prepared by applying the monomers described in Table 25 below. At this time, the manufacturing method was equally applied to the method used in Example 7.
  • Example 1 In order to manufacture a composite polymer having a D-A-B-D structure, the following examples were used, and a coating composition was prepared by the same method as in Example 1.
  • Example 7-d 15 parts by weight of a 0.36 wt% HCl aqueous solution was added very slowly to the mixed solution of Example 7-d, the pH was adjusted to have acidity, and the mixture was stirred at a temperature of 4 ° C. for 30 minutes. Thereafter, the amount of diphenyltetramethoxydisiloxane was prepared by adding 25 parts by weight, which is 5 times the amount of Example 7-e, and added dropwise at once, and after stirring for 1 hour, 20 parts by weight of the catalyst prepared in Example 7-a was added again to give a basic pH of the mixed solution. Was adjusted.
  • the terminal was converted into a cage structure using a trifunctional monomer.
  • 100 parts by weight of the material obtained in Example 8-a was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was added again to adjust the pH of the mixed solution in a basic state.
  • the cage-type polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (8). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 1 was obtained without various by-products by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was obtained in the styrene conversion value of 36,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 8 results are as follows.
  • Example 1 In order to prepare a composite polymer having an E-A-B-A-D structure, the following examples were used, and a coating composition was prepared by the same method as in Example 1.
  • Example 7-g To the mixture obtained in Example 7-g, 20 parts by weight of methylene chloride were added dropwise without further purification, 5 parts by weight of 0.36% by weight aqueous HCl solution was added dropwise, and the pH was adjusted to have an acidity, and 30 minutes at a temperature of 4 ° C. Stirred. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.
  • Example 9-a After preparing the organic layer of the resultant obtained in Example 9-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 9-a in progress at a time to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced at the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in formula (9). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
  • Example 9-b After the reaction mixture was obtained in Example 9-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5, and stored at a temperature of -20 ° C for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Formula 9 was obtained along with various by-products by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was obtained in the styrene conversion value of 28,000, the n value of X was 4-6, the n value of Y was 4-6.
  • silsesquioxane composite polymer was prepared by applying the monomers described in Table 27 below. In this case, the method used in Example 9 was equally applied.
  • silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 26 below. At this time, the manufacturing method was equally applied to the method used in Example 8.
  • the base material was evaluated for the anti-bending properties of plastic PC (i-components, Glastic 0.5T), glass (Asahi, soda lime 0.5T) and natural wood (wood and human non-conveyor), and the results are shown in Table 28 (Plastic 28). ), Table 29 (glass) and Table 30 (wood).
  • Tables 28 to 30 the structure shown in FIG. 2 in the case of two-layer lamination, the structure shown in FIG. 5 in the case of four-layer lamination, and the structure shown in FIG.
  • the coating thickness is 10 um for single layer, 5 um for each layer (2 um for total thickness 10 um for two layers, 20 um for four layers), and for each layer. Coated to a thickness of 10 um.
  • Evaluation method was stored in 85%, 85 °C reliability chamber for 240 hours and evaluated the bending characteristics.
  • the evaluation method measured the degree of warp using a three-dimensional warpage measuring instrument, and as shown in Figure 6, the front part is divided into nine, and after designating the points 1, 3, 7 and 9 as the virtual reference plane, all 1 to 9 The height of the point was measured. At this time, the maximum (+ height) and the minimum (-height) value of the distance away from the reference plane was obtained and expressed.
  • the negative value of warp means downward warp, and the positive value of warp means upward warp.
  • Examples 1 to 9 refer to thermosetting coating compositions prepared in Examples 1 to 9, respectively, where a single layer is a single layer and a two layer layer is stacked as shown in FIG. It becomes the 1st coating layer of FIG. 2, the layer described later becomes a 2nd coating layer, and a 4-layer lamination is laminated
  • the first coating layer, the 2nd coating layer, the 3rd coating layer, A fourth coating layer is formed, and both surfaces are stacked as shown in FIG. 3, and the coating layer described first constitutes the first coating layer, and the coating layer described later constitutes the second coating layer.
  • Example 1 (single) 0.401 2
  • Example 2 (single) 0.310 3
  • Example 3 (single) 0.300 4
  • Example 4 (single) 0.502 5
  • Example 5 (single) -0.525 6
  • Example 6 (single) -0.301 7
  • Example 7 (single) -0.505 8
  • Example 8 (single) -0.355 9
  • Example 9 (single) -0.404 10
  • Example 1 Example 9 (two-layer lamination) 0.150 11
  • Example 2 + Example 8 (two-layer lamination) 0.195 12
  • Example 3 Example 7 (Lamination Layer) 0.181 13
  • Example 5 Example 1 (two-layer lamination) 0.181 15
  • Example 6 (Lamination Layer) 0.138 16
  • Example 7 + Example 3 (two-layer lamination) 0.145 17
  • Example 9 + Example 5 (two-layer
  • Example 9 (Glass material) Coating Layer No Coating layer composition Warp Measurement (mm) One Example 1 (single) 0.201 2 Example 2 (single) 0.160 3 Example 3 (single) 0.180 4 Example 4 (single) 0.152 5 Example 5 (single) -0.255 6 Example 6 (single) -0.151 7 Example 7 (single) -0.205 8 Example 8 (single) -0.175 9 Example 9 (single) -0.104 10 Example 1 + Example 9 (two-layer lamination) 0.115 11 Example 2 + Example 8 (two-layer lamination) 0.114 12 Example 3 + Example 7 (Lamination Layer) 0.104 13 Example 4 + Example 6 (Layer Layers) 0.103 14 Example 5 + Example 1 (two-layer lamination) 0.113 15 Example 6 + Example 2 (Lamination Layer) 0.115 16 Example 7 + Example 3 (two-layer lamination) 0.108 17 Example 8 + Example 6 (two-layer lamination) 0.112 18 Example 9 + Example 5 (two-layer lamination) 0.114 19
  • Example 9 Coating Layer No Coating layer composition Warp Measurement (mm) One Example 1 (single) 0.311 2 Example 2 (single) 0.350 3 Example 3 (single) 0.300 4 Example 4 (single) 0.352 5 Example 5 (single) -0.355 6 Example 6 (single) -0.451 7 Example 7 (single) -0.325 8 Example 8 (single) -0.305 9 Example 9 (single) -0.354 10 Example 1 + Example 9 (two-layer lamination) 0.180 11 Example 2 + Example 8 (two-layer lamination) 0.175 12 Example 3 + Example 7 (Lamination Layer) 0.191 13 Example 4 + Example 6 (Layer Layers) 0.170 14 Example 5 + Example 1 (two-layer lamination) 0.191 15 Example 6 + Example 2 (Lamination Layer) 0.165 16 Example 7 + Example 3 (two-layer lamination) 0.175 17 Example 8 + Example 6 (two-layer lamination) 0.171 18 Example 9 + Example 5 (two-layer lamination)
  • the anti-bending substrate of the present invention exhibited significantly improved excellent anti-bending properties when the material of the laminate is properly adjusted.
  • the double-sided coating showed very good bending resistance.
  • thermosetting coating composition in Tables 28 to 30, the results of the photocurable resin composition also showed comparable results with the thermosetting resin composition.
  • the pencil hardness method (JIS 5600-5-4) is generally rated at 750 g load, which is 10 mm horizontal at a rate of 0.5 mm per second at a 45-degree angle to the coating surface at a more severe 1 kgf load.
  • the coating film was moved to evaluate the scratches. If more than 3 mm of scratches are not found more than 2 times in 5 experiments, the pencil of the higher hardness is selected and evaluated. To evaluate the results are shown in Table 31 below. The evaluation results confirmed the 9H hardness of the glass level regardless of the substrate type at a coating thickness of 10 um or more.
  • the anti-bending substrate of the present invention showed excellent physical properties of the coating layers, and even in the case of four-layer lamination, the phenomenon of lifting due to excellent adhesion between the coating layers did not occur.
  • the warpage prevention coating method of the substrate according to the present invention can not only prevent the warpage of the substrate through a simple coating process but at the same time high surface hardness, excellent transparency, scratch resistance, water repellency, antifouling properties, anti-fingerprint on the surface of the substrate By imparting heat stability and glossiness, the durability and utility value of the product can be greatly increased.

Abstract

The present invention relates to a coating method for preventing the bending phenomenon of a substrate and, more specifically, to a coating method for preventing the bending phenomenon of a substrate, which forms two or more coating layers by coating the surface of a substrate with coating compositions having different densities, and forming at least one layer among the two or more coating layers by coating a coating composition containing a silsesquioxane composite polymer represented by a specific chemical formula and curing the coated product, thereby preventing the bending phenomenon of a substrate and simultaneously providing, to the surface of the substrate, high surface hardness, excellent transparency, scratch resistance, water repellent characteristics, anti-fouling characteristics, anti-fingerprint property, thermal stability and gloss characteristics.

Description

기재의 휨현상 방지 코팅방법Warping prevention coating method of substrate
본 발명은 기재의 휨현상 방지 코팅방법에 관한 것으로, 보다 상세하게는 기재의 휨현상 방지 코팅방법으로서 기재의 표면에 밀도가 서로 다른 코팅 조성물을 코팅하여 2층 이상의 코팅층을 형성하며, 상기 2층 이상의 코팅층 중 적어도 한층은 특정 화학식으로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물을 코팅하고 경화시켜 기재의 휨현상을 방지할 수 있을 뿐만 아니라 동시에 기재의 표면에 높은 표면경도, 우수한 투명성, 내스크레치성, 발수특성, 방오특성, 내지문성, 열안정성 및 광택특성을 부여할 수 있는 기재의 휨현상 방지 코팅방법에 관한 것이다.The present invention relates to a method for preventing warpage coating of a substrate, and more particularly, to a method for preventing warpage coating of a substrate to form a coating layer having different densities on the surface of the substrate to form two or more coating layers, wherein the two or more coating layers At least one layer of the coating composition comprising a silsesquioxane composite polymer represented by a specific chemical formula and the coating can be cured not only to prevent warpage of the substrate, but also at the same time high surface hardness, excellent transparency, scratch resistance The present invention relates to a coating method for preventing warpage of a substrate capable of imparting water repellency, antifouling properties, fingerprint resistance, thermal stability, and gloss property.
플라스틱, 유리, 목재 또는 종이 등과 같은 기재는 다양한 용도로 사용되고 있다. 그러나 위의 기재들은 면적이 넓어짐에 따라 휨현상이 발생한다. 또한 최초에는 도 1의 실선과 같이 평탄도가 우수하였으나 시간이 지남에 따라 도 1의 굵은 선과 같이 휨현상이 발생하는 경우가 있으며, 기재의 표면에 기능성 부여를 위해 기능성 물질을 코팅하는 경우에도 휨현상이 발생하는 경우가 있다. 이와 같은 기재의 휨현상은 기기불량의 원인으로 작용할 수 있으며, 또는 미관을 해쳐 전체적인 제품의 효용을 떨어뜨리게 되는 문제점이 있다.Substrates such as plastic, glass, wood or paper are used for various purposes. However, the above substrates are warped as the area becomes larger. In addition, as shown in FIG. 1, the flatness was excellent as shown in FIG. 1, but as time goes by, the warpage may occur as shown in the thick line of FIG. 1, and even when the functional material is coated on the surface of the substrate to provide functionality. It may occur. Such a warpage phenomenon of the substrate may act as a cause of a device defect, or there is a problem that degrades the utility of the overall product by aesthetics.
종래 기재의 휨현상을 방지하기 위하여 기재에 지지대를 설치하거나 기재의 표면에 휨현상이 적은 별도의 기재를 부착하는 방법이 적용되었으나 대부분 적용에 많은 노력이 필요로 하여 코팅과 같은 간단한 방법으로 기재의 휨현상을 방지하기 위한 연구가 절실한 실정이다. Conventionally, in order to prevent warpage of the base material, a method of installing a support on the base material or attaching a separate base material having a low warpage phenomenon to the surface of the base material has been applied. There is an urgent need for research.
상기와 같은 문제점을 해결하기 위해, 본 발명은 기재의 표면 위에 간단한 코팅공정을 통하여 기재의 휨현상을 방지할 수 있을 뿐만 아니라 동시에 기재의 표면에 높은 표면경도, 우수한 투명성, 내스크레치성, 발수특성, 방오특성, 내지문성, 열안정성 및 광택특성을 부여할 수 있는 기재의 휨현상 방지 코팅방법 및 휨현상이 방지된 기재를 제공하는 것을 목적으로 한다.In order to solve the above problems, the present invention can not only prevent the warpage of the substrate through a simple coating process on the surface of the substrate, but also at the same time high surface hardness, excellent transparency, scratch resistance, water repellency, An object of the present invention is to provide a coating method for preventing warpage of a substrate which can impart antifouling properties, anti-fingerprint properties, thermal stability, and gloss properties, and a substrate for preventing warpage.
또한 본 발명은 상기 휨현상이 방지된 기재를 포함하는 물품을 제공하는 것을 목적으로 한다.It is another object of the present invention to provide an article including the base material of which the warpage phenomenon is prevented.
상기 목적을 달성하기 위해 본 발명은 기재의 휨현상 방지 코팅방법으로서,In order to achieve the above object, the present invention provides a coating method for preventing warpage of the substrate,
기재의 표면에 밀도가 서로 다른 코팅 조성물을 코팅하여 2층 이상의 코팅층을 형성하며,Coating the coating composition of different densities on the surface of the substrate to form two or more coating layers,
상기 2층 이상의 코팅층 중 적어도 한층은 하기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물을 코팅하고 경화하는 것을 특징으로 하는 기재의 휨현상 방지 코팅방법을 제공한다:At least one of the two or more coating layers provides a coating method for preventing warpage of the substrate, characterized in that the coating composition comprising the silsesquioxane composite polymer represented by any one of the following formulas (1) to (9):
[화학식 1][Formula 1]
Figure PCTKR2015003192-appb-I000001
Figure PCTKR2015003192-appb-I000001
[화학식 2][Formula 2]
Figure PCTKR2015003192-appb-I000002
Figure PCTKR2015003192-appb-I000002
[화학식 3][Formula 3]
Figure PCTKR2015003192-appb-I000003
Figure PCTKR2015003192-appb-I000003
[화학식 4][Formula 4]
Figure PCTKR2015003192-appb-I000004
Figure PCTKR2015003192-appb-I000004
[화학식 5][Formula 5]
Figure PCTKR2015003192-appb-I000005
Figure PCTKR2015003192-appb-I000005
[화학식 6][Formula 6]
Figure PCTKR2015003192-appb-I000006
Figure PCTKR2015003192-appb-I000006
[화학식 7][Formula 7]
Figure PCTKR2015003192-appb-I000007
Figure PCTKR2015003192-appb-I000007
[화학식 8][Formula 8]
Figure PCTKR2015003192-appb-I000008
Figure PCTKR2015003192-appb-I000008
[화학식 9][Formula 9]
Figure PCTKR2015003192-appb-I000009
Figure PCTKR2015003192-appb-I000009
A는
Figure PCTKR2015003192-appb-I000010
이고,B는
Figure PCTKR2015003192-appb-I000011
이고,A is
Figure PCTKR2015003192-appb-I000010
And B is
Figure PCTKR2015003192-appb-I000011
ego,
D는D is
Figure PCTKR2015003192-appb-I000012
이고, E는
Figure PCTKR2015003192-appb-I000013
이며,
Figure PCTKR2015003192-appb-I000012
And E is
Figure PCTKR2015003192-appb-I000013
Is,
Y는 각각 독립적으로 O, NR21 또는 [(SiO3/2R)4+2nO]이며, 적어도 하나는 [(SiO3/2R)4+2nO]이며, Each Y is independently O, NR 21 or [(SiO 3/2 R) 4 + 2n O], at least one is [(SiO 3/2 R) 4 + 2n O],
X는 각각 독립적으로 R22 또는 [(SiO3/2R)4+2nR]이고, 적어도 하나는 [(SiO3/2R)4+2nR]이고,Each X is independently R 22 or [(SiO 3/2 R) 4 + 2n R], at least one is [(SiO 3/2 R) 4 + 2n R],
R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22는 각각 독립적으로 수소; 중수소; 할로겐; 아민기; 에폭시기; 사이클로헥실에폭시기; (메타)아크릴기; 사이올기; 이소시아네이트기; 니트릴기; 니트로기; 페닐기; 중수소, 할로겐, 아민기, 에폭시기, (메타)아크릴기, 사이올기, 이소시아네이트기, 니트릴기, 니트로기, 페닐기로 치환되거나 치환되지 않은 C1~C40의 알킬기; C2~C40의 알케닐기; C1~C40의 알콕시기; C3~C40의 시클로알킬기; C3~C40의 헤테로시클로알킬기; C6~C40의 아릴기; C3~C40의 헤테로아릴기; C3~C40의 아르알킬기; C3~C40의 아릴옥시기; 또는 C3~C40의 아릴사이올기이며, 바람직하기로는 중수소, 할로겐, 아민기, (메타)아크릴기, 사이올기, 이소시아네이트기, 니트릴기, 니트로기, 페닐기, 사이클로헥실 에폭시기로 치환되거나 치환되지 않은 C1~C40의 알킬기, C2~C40의 알케닐기, 아민기, 에폭시기, 사이클로헥실 에폭시기, (메타)아크릴기, 사이올기, 페닐기 또는 이소시아네이트기를 포함하며,R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C 1 -C 40 alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; C 2 -C 40 alkenyl group; C 1 ~ C 40 Alkoxy group; C 3 -C 40 cycloalkyl group; C 3 ~ C 40 Heterocycloalkyl group; C 6 -C 40 aryl group; C 3 ~ C 40 heteroaryl group; An aralkyl group of C 3 ~ C 40; C 3 -C 40 aryloxy group; Or a C 3 to C 40 arylcyol group, preferably substituted or unsubstituted with deuterium, halogen, amine group, (meth) acryl group, siol group, isocyanate group, nitrile group, nitro group, phenyl group, cyclohexyl epoxy group Unsubstituted C 1 to C 40 alkyl groups, C 2 to C 40 alkenyl groups, amine groups, epoxy groups, cyclohexyl epoxy groups, (meth) acrylic groups, siol groups, phenyl groups or isocyanate groups,
a 및 d는 각각 독립적으로 1 내지 100,000의 정수이고, 바람직하기로는 a는 3 내지 1000이고, d는 1 내지 500이며, 더욱 바람직하기로는 a는 5 내지 300이고, d는 2 내지 100이며,a and d are each independently an integer of 1 to 100,000, preferably a is 3 to 1000, d is 1 to 500, more preferably a is 5 to 300, d is 2 to 100,
b는 각각 독립적으로 1 내지 500의 정수이며,b are each independently an integer of 1 to 500,
e는 각각 독립적으로 1 또는 2이며, 바람직하기로 1이며,e are each independently 1 or 2, preferably 1,
n은 각각 독립적으로 1 내지 20의 정수이며, 바람직하기로는 3 내지 10이다.n is independently an integer of 1-20, Preferably it is 3-10.
또한 본 발명은 표면 위에 밀도가 서로 다른 코팅 조성물을 코팅하여 형성된 2층 이상의 코팅층을 구비하며, 상기 코팅층 중의 적어도 하나는 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물로 형성된 것을 특징으로 하는 휨현상 방지 기재를 제공한다.In another aspect, the present invention is provided with a coating layer of two or more layers formed by coating a coating composition having a different density on the surface, at least one of the coating layer is a coating comprising a silsesquioxane composite polymer represented by any one of the formulas (1) to (9) Provided is a warpage preventing substrate, characterized in that formed in the composition.
또한 본 발명은 상기 휨현상 방지 기재를 포함하는 물품을 제공한다.The present invention also provides an article comprising the warpage preventing substrate.
본 발명에 따른 기재의 휨현상 방지 코팅방법은 기재의 휨현상을 간단한 코팅공정을 통하여 방지할 수 있을 뿐만 아니라 동시에 기재의 표면에 높은 표면경도, 우수한 투명성, 내스크레치성, 발수특성, 방오특성, 내지문성, 열안정성 및 광택특성을 부여함으로써 제품의 내구성 및 효용가치를 크게 높일 수 있다.The warpage prevention coating method of the substrate according to the present invention can not only prevent the warpage of the substrate through a simple coating process but at the same time high surface hardness, excellent transparency, scratch resistance, water repellency, antifouling properties, anti-fingerprint on the surface of the substrate By imparting heat stability and glossiness, the durability and utility value of the product can be greatly increased.
도 1은 종래기술에 따라 휨현상이 나타난 기재를 나타낸 모식도이다.1 is a schematic diagram showing a base material exhibiting the bending phenomenon according to the prior art.
도 2 내지 5는 각각 본 발명에 따른 휨현상 방지 기재를 나타낸 모식도이다.2 to 5 are schematic views showing the warpage phenomenon preventing substrate according to the present invention, respectively.
도 6은 본 발명에서 휨 측정방법에 사용된 코팅면의 가상의 기준점을 나타낸 것이다.Figure 6 shows an imaginary reference point of the coating surface used in the warpage measurement method in the present invention.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 기재의 휨현상 방지 코팅방법으로서,The present invention is a coating method for preventing warpage of the substrate,
기재의 표면에 밀도가 서로 다른 코팅 조성물을 코팅하여 2층 이상의 코팅층을 형성하며,Coating the coating composition of different densities on the surface of the substrate to form two or more coating layers,
상기 2층 이상의 코팅층 중 적어도 한층은 하기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물을 코팅하고 경화하는 것을 특징으로 하는 기재의 휨현상 방지 코팅방법을 제공한다:At least one of the two or more coating layers provides a coating method for preventing warpage of the substrate, characterized in that the coating composition comprising the silsesquioxane composite polymer represented by any one of the following formulas (1) to (9):
[화학식 1][Formula 1]
Figure PCTKR2015003192-appb-I000014
Figure PCTKR2015003192-appb-I000014
[화학식 2][Formula 2]
Figure PCTKR2015003192-appb-I000015
Figure PCTKR2015003192-appb-I000015
[화학식 3][Formula 3]
Figure PCTKR2015003192-appb-I000016
Figure PCTKR2015003192-appb-I000016
[화학식 4][Formula 4]
Figure PCTKR2015003192-appb-I000017
Figure PCTKR2015003192-appb-I000017
[화학식 5][Formula 5]
Figure PCTKR2015003192-appb-I000018
Figure PCTKR2015003192-appb-I000018
[화학식 6][Formula 6]
Figure PCTKR2015003192-appb-I000019
Figure PCTKR2015003192-appb-I000019
[화학식 7][Formula 7]
Figure PCTKR2015003192-appb-I000020
Figure PCTKR2015003192-appb-I000020
[화학식 8][Formula 8]
Figure PCTKR2015003192-appb-I000021
Figure PCTKR2015003192-appb-I000021
[화학식 9][Formula 9]
Figure PCTKR2015003192-appb-I000022
Figure PCTKR2015003192-appb-I000022
A는
Figure PCTKR2015003192-appb-I000023
이고,B는
Figure PCTKR2015003192-appb-I000024
이고,A is
Figure PCTKR2015003192-appb-I000023
And B is
Figure PCTKR2015003192-appb-I000024
ego,
D는D is
Figure PCTKR2015003192-appb-I000025
이고, E는
Figure PCTKR2015003192-appb-I000026
이며,
Figure PCTKR2015003192-appb-I000025
And E is
Figure PCTKR2015003192-appb-I000026
Is,
Y는 각각 독립적으로 O, NR21 또는 [(SiO3/2R)4+2nO]이며, 적어도 하나는 [(SiO3/2R)4+2nO]이며, Each Y is independently O, NR 21 or [(SiO 3/2 R) 4 + 2n O], at least one is [(SiO 3/2 R) 4 + 2n O],
X는 각각 독립적으로 R22 또는 [(SiO3/2R)4+2nR]이고, 적어도 하나는 [(SiO3/2R)4+2nR]이고,Each X is independently R 22 or [(SiO 3/2 R) 4 + 2n R], at least one is [(SiO 3/2 R) 4 + 2n R],
R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22는 각각 독립적으로 수소; 중수소; 할로겐; 아민기; 에폭시기; 사이클로헥실에폭시기; (메타)아크릴기; 사이올기; 이소시아네이트기; 니트릴기; 니트로기; 페닐기; 중수소, 할로겐, 아민기, 에폭시기, (메타)아크릴기, 사이올기, 이소시아네이트기, 니트릴기, 니트로기, 페닐기로 치환되거나 치환되지 않은 C1~C40의 알킬기; C2~C40의 알케닐기; C1~C40의 알콕시기; C3~C40의 시클로알킬기; C3~C40의 헤테로시클로알킬기; C6~C40의 아릴기; C3~C40의 헤테로아릴기; C3~C40의 아르알킬기; C3~C40의 아릴옥시기; 또는 C3~C40의 아릴사이올기이며, 바람직하기로는 중수소, 할로겐, 아민기, (메타)아크릴기, 사이올기, 이소시아네이트기, 니트릴기, 니트로기, 페닐기, 사이클로헥실 에폭시기로 치환되거나 치환되지 않은 C1~C40의 알킬기, C2~C40의 알케닐기, 아민기, 에폭시기, 사이클로헥실 에폭시기, (메타)아크릴기, 사이올기, 페닐기 또는 이소시아네이트기를 포함하며,R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C 1 -C 40 alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; C 2 -C 40 alkenyl group; C 1 ~ C 40 Alkoxy group; C 3 -C 40 cycloalkyl group; C 3 ~ C 40 Heterocycloalkyl group; C 6 -C 40 aryl group; C 3 ~ C 40 heteroaryl group; An aralkyl group of C 3 ~ C 40; C 3 -C 40 aryloxy group; Or a C 3 to C 40 arylcyol group, preferably substituted or unsubstituted with deuterium, halogen, amine group, (meth) acryl group, siol group, isocyanate group, nitrile group, nitro group, phenyl group, cyclohexyl epoxy group Unsubstituted C 1 to C 40 alkyl groups, C 2 to C 40 alkenyl groups, amine groups, epoxy groups, cyclohexyl epoxy groups, (meth) acrylic groups, siol groups, phenyl groups or isocyanate groups,
a 및 d는 각각 독립적으로 1 내지 100,000의 정수이고, 바람직하기로는 a는 3 내지 1000이고, d는 1 내지 500이며, 더욱 바람직하기로는 a는 5 내지 300이고, d는 2 내지 100이며,a and d are each independently an integer of 1 to 100,000, preferably a is 3 to 1000, d is 1 to 500, more preferably a is 5 to 300, d is 2 to 100,
b는 각각 독립적으로 1 내지 500의 정수이며,b are each independently an integer of 1 to 500,
e는 각각 독립적으로 1 또는 2이며, 바람직하기로 1이며,e are each independently 1 or 2, preferably 1,
n은 각각 독립적으로 1 내지 20의 정수이며, 바람직하기로는 3 내지 10이다.n is independently an integer of 1-20, Preferably it is 3-10.
본 발명의 상기 화학식 1로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by Formula 1 of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합하여 하기 화학식 10을 제조하는 제1단계; 및 상기 제1단계 이후에 화학식 10에 [D]d(OR2)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 및 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계를 포함하여 제조될 수 있다.Mixing a basic catalyst and an organic solvent in a reactor and then adding an organic silane compound and condensing to prepare Chemical Formula 10; And a second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid after the first step, to introduce an [D] d (OR 2 ) 2 structure into the chemical formula 10, and then adding and stirring an organic silane compound. step; And a third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the two steps.
[화학식 10][Formula 10]
Figure PCTKR2015003192-appb-I000027
Figure PCTKR2015003192-appb-I000027
상기 식에서 R1, R2, R16, D, a 및 d는 화학식 1 내지 9에서 정의한 바와 같다.Wherein R 1 , R 2 , R 16 , D, a and d are the same as defined in Chemical Formulas 1 to 9.
본 발명의 상기 화학식 2로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by Formula 2 of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합하여 상기 화학식 10을 제조하는 제1단계; 및 상기 제1단계 이후에 화학식 10에 [D]d(OR3)2 및 [D]d(OR4)2 구조를 화학식 2와 같이 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 과량의 유기 실란 화합물을 첨가하고 교반하는 제2단계; 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 및 제3단계 반응을 거쳐, 단독으로 생성되는 부산물인 cage 구조를 재결정으로 제거하여주는 정제단계를 진행하여 제조될 수 있다.A first step of preparing Chemical Formula 10 by mixing a basic catalyst and an organic solvent in a reactor and then adding and condensing an organic silane compound; And adding an acidic catalyst to the reactor to introduce the [D] d (OR 3 ) 2 and [D] d (OR 4 ) 2 structures into the chemical formula 10 after the first step, as shown in the chemical formula 2. A second step of adding and stirring an excess of the organic silane compound after the adjustment; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; And through a third step of the reaction, it can be prepared by proceeding to the purification step to remove the cage structure as a by-product generated by recrystallization.
본 발명의 상기 화학식 3으로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by Formula 3 of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합하여 상기 화학식 10을 제조하는 제1단계; 및 상기 제1단계 이후에 화학식 10에 [D]d(OR5)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 및 상기 제3단계 이후에 복합고분자의 말단에 [E]eX2 구조를 도입하여 위하여 반응기에 산성 촉매를 투입하여 반응액을 산성 분위기로 변환하고 유기실란 화합물을 혼합하여 교반하는 제4단계를 포함하여 제조될 수 있다.A first step of preparing Chemical Formula 10 by mixing a basic catalyst and an organic solvent in a reactor and then adding and condensing an organic silane compound; And a second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid after the first step, to introduce an [D] d (OR 5 ) 2 structure into the chemical formula 10, and then adding and stirring an organic silane compound. step; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; And a fourth step of introducing an [E] eX 2 structure at the end of the composite polymer into the reactor after the third step, converting the reaction solution into an acidic atmosphere, and mixing and stirring the organosilane compound. Can be prepared.
본 발명의 상기 화학식 4로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by Formula 4 of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합도를 조절하여 상기 화학식 10을 제조하는 제1단계; 및 상기 제1단계 이후에 화학식 10에 [B]b 구조 및 [D]d(OR7)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 및 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계를 포함하여 제조될 수 있다.A first step of preparing Chemical Formula 10 by mixing a basic catalyst and an organic solvent in a reactor, adding an organic silane compound, and adjusting the degree of condensation; And after the first step, an acidic catalyst is added to the reactor to introduce the [B] b structure and the [D] d (OR 7 ) 2 structure into the chemical formula 10 to adjust the reaction solution to acidic acid, and then the organic silane compound A second step of adding and stirring; And a third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the two steps.
본 발명의 상기 화학식 5로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by the formula (5) of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합하여 상기 화학식 10을 제조하는 제1단계; 및 상기 제1단계 이후에 화학식 10에 [B]b 구조 및 [D]d(OR8)2, [D]d(OR9)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 과량의 유기 실란 화합물을 첨가하고 교반하는 제2단계; 및 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 제3단계; 및 제3단계 이후 재결정과 필터과정을 통하여, 단독 cage 생성 구조를 제거하는 제4단계를 포함하여 제조될 수 있다.A first step of preparing Chemical Formula 10 by mixing a basic catalyst and an organic solvent in a reactor and then adding and condensing an organic silane compound; And adding an acidic catalyst to the reactor to introduce the [B] b structure and the [D] d (OR 8 ) 2 , [D] d (OR 9 ) 2 structure into the chemical formula 10 after the first step. A second step of adding and stirring an excess of the organic silane compound after adjusting to acidity; And a third step of condensation reaction by adding a basic catalyst to the reactor after step 2 to convert the reaction solution to basic. And a fourth step of removing the single cage generation structure through recrystallization and filtering after the third step.
본 발명의 상기 화학식 6으로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by the formula (6) of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합하여 상기 화학식 10을 제조하는 제1단계; 및 상기 제1단계 이후에 화학식 10에 [B]b 구조 및 [D]d(OR10)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 상기 2단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 및 상기 제3단계 이후에 복합고분자의 말단에 [E]eX2 구조를 도입하여 위하여 반응기에 산성 촉매를 투입하여 반응액을 산성 분위기로 변환하고 유기실란 화합물을 혼합하여 교반하는 제4단계를 포함하여 제조될 수 있다.A first step of preparing Chemical Formula 10 by mixing a basic catalyst and an organic solvent in a reactor and then adding and condensing an organic silane compound; And after the first step, an acidic catalyst is added to the reactor to introduce the [B] b structure and the [D] d (OR 10 ) 2 structure into the chemical formula 10 to adjust the reaction solution to acidic, and then the organic silane compound A second step of adding and stirring; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; And a fourth step of introducing an [E] eX 2 structure at the end of the composite polymer into the reactor after the third step, converting the reaction solution into an acidic atmosphere, and mixing and stirring the organosilane compound. Can be prepared.
바람직하기로 상기 화학식 1 내지 6을 제조하는 방법에서 본 발명의 제1단계의 반응액의 pH는 9 내지 11.5인 것이 바람직하고, 제2단계의 반응액의 pH는 2 내지 4인 것이 바람직하고, 제3단계의 반응액의 pH는 8 내지 11.5인 것이 바람직하고, Ee을 도입하는 제4단계의 반응액의 pH는 1.5 내지 4인 것이 바람직하다. 상기 범위 내인 경우 제조되는 실세스퀴옥산 복합 고분자의 수율이 높을 뿐만 아니라 제조된 실세스퀴옥산 복합 고분자의 기계적 물성을 향상시킬 수 있다.Preferably the pH of the reaction solution of the first step of the present invention in the method for preparing the formula 1 to 6 is 9 to 11.5, the pH of the reaction solution of the second step is preferably 2 to 4, The pH of the reaction solution of the third step is preferably 8 to 11.5, and the pH of the reaction solution of the fourth step of introducing Ee is preferably 1.5 to 4. Within the above range, not only the yield of the silsesquioxane composite polymer prepared is high, but also the mechanical properties of the manufactured silsesquioxane composite polymer can be improved.
본 발명의 상기 화학식 7로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by the formula (7) of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합도가 조절된 두 가지 형태의 상기 화학식 10을 제조하는 1단계; 상기 1단계에서 얻어진 화학식 10에 [B]b 구조 및 [D]d(OR12)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 상기 각각의 2단계 반응 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 및 상기 3단계를 통해 얻어진 2가지 이상의 물질을 염기성 조건에서 축합하여 연결하는 4단계를 포함하여 제조될 수 있다.Mixing a basic catalyst and an organic solvent in a reactor, and then adding an organic silane compound and preparing two types of Chemical Formula 10 in which the degree of condensation is controlled; In order to introduce the structure [B] b and the structure [D] d (OR 12 ) 2 to the formula (10) obtained in step 1, the reaction solution was adjusted to acid by adding an acidic catalyst to the reactor, and then an organic silane compound was added. A second step of stirring; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after each two-step reaction; And four steps of condensing and connecting two or more materials obtained through the three steps under basic conditions.
본 발명의 상기 화학식 8로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by the formula (8) of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합도가 조절된 두 가지 형태의 상기 화학식 10을 제조하는 1단계; 상기 1단계에서 얻어진 화학식 10에 [B]b 구조, [D]d(OR14)2 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 상기 각각의 2단계 반응 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 상기 3단계를 통해 얻어진 2가지 이상의 물질을 염기성 조건에서 축합하여 연결하는 4단계; 상기 4단계 이후 [D]d(OR13)2를 도입하기 위한 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제5단계; 및 상기 5단계 반응 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제6단계를 포함하여 제조될 수 있다.Mixing a basic catalyst and an organic solvent in a reactor, and then adding an organic silane compound and preparing two types of Chemical Formula 10 in which the degree of condensation is controlled; In order to introduce the [B] b structure, the [D] d (OR 14 ) 2 structure into the formula (10) obtained in step 1, the reaction solution was adjusted to acid by adding an acidic catalyst to the reactor, and then an organic silane compound was added. A second step of stirring; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after each two-step reaction; Condensing and connecting two or more substances obtained through the three steps under basic conditions; A fifth step of adding an acidic catalyst to the reactor for introducing [D] d (OR 13 ) 2 after the fourth step to adjust the reaction solution to acid, followed by adding and stirring an organic silane compound; And a sixth step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the five step reaction.
본 발명의 상기 화학식 9로 표시되는 실세스퀴옥산 복합 고분자는 Silsesquioxane composite polymer represented by the formula (9) of the present invention
반응기에 염기성 촉매와 유기용매를 혼합한 후 유기 실란 화합물을 첨가하고 축합도가 조절된 두 가지 형태의 상기 화학식 10을 제조하는 1단계; 상기 1단계에서 얻어진 화학식 10에 [B]b 구조를 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제2단계; 상기 각각의 2단계반응 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제3단계; 상기 3단계를 통해 얻어진 2가지 이상의 화합물을 염기성 조건에서 축합하여 연결하는 4단계; 상기 제4단계 이후 [D]d(OR5)2를 도입하기 위한 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 제5단계; 상기 5단계 반응 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 제6단계; 상기 제6단계 이후에 복합고분자의 말단에 [E]eX2 구조를 도입하여 위하여 반응기에 산성 촉매를 투입하여 반응액을 산성 분위기로 변환하고 유기실란 화합물을 혼합하여 교반하는 제7단계를 포함하여 제조될 수 있다.Mixing a basic catalyst and an organic solvent in a reactor, and then adding an organic silane compound and preparing two types of Chemical Formula 10 in which the degree of condensation is controlled; A second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid in order to introduce the structure [B] b into the chemical formula 10 obtained in step 1, and then adding and stirring an organic silane compound; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after each two step reaction; Condensing and connecting two or more compounds obtained through the three steps in basic conditions; A fifth step of adding an acidic catalyst to a reactor for introducing [D] d (OR 5 ) 2 to adjust the reaction solution to acidic acid after the fourth step, and then adding and stirring an organic silane compound; A sixth step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the five step reaction; After the sixth step, to introduce the [E] eX 2 structure at the end of the composite polymer to the acidic catalyst in the reactor to convert the reaction solution into an acidic atmosphere and a mixture of the organosilane compound comprising a seventh step of stirring Can be prepared.
바람직하기로 상기 화학식 7 내지 9의 고분자를 제조하는 방법에서 제1단계의 반응액의 pH는 9 내지 11.5인 것이 바람직하고, 제2단계의 반응액의 pH는 2 내지 4인 것이 바람직하고, 제3단계의 반응액의 pH는 8 내지 11.5인 것이 바람직하고, 제4단계의 반응액의 pH는 9 내지 11.5인 것이 바람직하고, 제5단계의 반응액의 pH는 2 내지 4인 것이 바람직하고, 제6단계의 반응액의 8 내지 11.5인 것이 바람직하고, Ee를 도입하는 제7단계의 반응액의 pH는 1.5 내지 4인 것이 바람직하다. 상기 범위 내인 경우 제조되는 실세스퀴옥산 복합 고분자의 수율이 높을 뿐만 아니라 제조된 실세스퀴옥산 복합 고분자의 기계적 물성을 향상시킬 수 있다.Preferably, the pH of the reaction solution of the first step is 9 to 11.5, the pH of the reaction solution of the second step is preferably 2 to 4 in the method for preparing the polymer of Formula 7 to 9, The pH of the reaction solution of the third stage is preferably 8 to 11.5, the pH of the reaction solution of the fourth stage is preferably 9 to 11.5, the pH of the reaction solution of the fifth stage is preferably 2 to 4, It is preferable that it is 8-11.5 of the reaction liquid of a 6th step, and it is preferable that pH of the reaction liquid of the 7th step which introduces Ee is 1.5-4. Within the above range, not only the yield of the silsesquioxane composite polymer prepared is high, but also the mechanical properties of the manufactured silsesquioxane composite polymer can be improved.
또한 필요한 경우 각각의 복합 고분자에 [B]b 구조 및 [D]d(OR)2 구조를 더욱 도입하기 위하여 반응기에 산성 촉매를 첨가하여 반응액을 산성으로 조절한 후, 유기 실란 화합물을 첨가하고 교반하는 단계; 및 상기 단계 이후에 반응기에 염기성 촉매를 첨가하여 반응액을 염기성으로 변환하여 축합반응을 실시하는 단계를 통하여 복합 고분자 내에 [B]b 반복단위를 더욱 포함할 수 있다.If necessary, in order to further introduce the [B] b structure and the [D] d (OR) 2 structure to each of the composite polymers, an acidic catalyst was added to the reactor to adjust the reaction solution to acidic acid, and then an organic silane compound was added. Stirring; And [B] b repeating units in the composite polymer through the step of performing a condensation reaction by adding a basic catalyst to the reactor and converting the reaction solution to basic after the above step.
또한 필요한 경우 각각의 복합 고분자의 말단에 [E]eX2 구조를 도입하기 위하여 반응기에 산성 촉매를 투입하여 반응액을 산성 분위기로 변환하고 유기실란 화합물을 혼합하여 교반하는 단계를 포함하여 복합 고분자의 말단에 [E]e의 반복단위를 더욱 포함할 수 있다.In addition, if necessary, in order to introduce an [E] eX 2 structure at the end of each composite polymer, an acidic catalyst was added to the reactor to convert the reaction solution into an acidic atmosphere, and the mixture of the organosilane compounds was stirred. The terminal may further include a repeating unit of [E] e.
상기 실세스퀴옥산 복합 고분자의 제조방법에서는 염기성 촉매로서 바람직하기로는 2종 이상의 염기성 촉매의 혼합촉매를 사용하고, 이를 산성 촉매로 중화 및 산성화하여 재 가수분해를 유도하며, 다시 2종 이상의 염기성 촉매의 혼합촉매를 이용하여 염기성으로 축합을 진행함으로써 하나의 반응기내에서 산도와 염기도를 연속적으로 조절할 수 있다.In the production method of the silsesquioxane composite polymer, a mixed catalyst of two or more basic catalysts is preferably used as a basic catalyst, and neutralized and acidified with an acidic catalyst to induce rehydrolysis, and again two or more basic catalysts. Acidity and basicity can be continuously controlled in one reactor by proceeding to basic condensation using a mixed catalyst of.
이때, 상기 염기성 촉매는 Li, Na, K, Ca 및 Ba 으로 이루어진 군에서 선택된 금속계 염기성 촉매 및 아민계 염기성 촉매에서 선택되는 2종 이상의 물질을 적절히 조합하여 제조될 수 있다. 바람직하게는 상기 아민계 염기성 촉매가 테트라메틸암모늄 하이드록시드(TMAH)이고, 금속계 염기성 촉매가 포타슘 하이드록시드(KOH) 또는 중탄산나트륨 (NaHCO3)일 수 있다. 상기 혼합촉매에서 각 성분의 함량은 바람직하기로는 아민계 염기성 촉매와 금속계 염기성 촉매의 비율이 10 내지 90: 10 내지 90 중량부의 비율에서 임의로 조절할 수 있다. 상기 범위 내인 경우 가수분해시 관능기와 촉매와의 반응성을 최소화시킬 수 있으며, 이로 인해 Si-OH 또는 Si-알콕시 등의 유기 관능기의 결함이 현저히 감소하여 축합도를 자유로이 조절할 수 있는 장점이 있다. 또한, 상기 산성 촉매로는 당분야에서 통상적으로 사용하는 산성 물질이라면 제한 없이 사용될 수 있으며, 예를 들어, HCl, H2SO4, HNO3, CH3COOH 등의 일반 산성물질을 사용할 수 있고, 또한 latic acid, tartaric acid, maleic acid, citric acid 등의 유기계 산성물질도 적용할 수 있다.In this case, the basic catalyst may be prepared by appropriately combining two or more materials selected from a metal based catalyst and an amine based catalyst selected from the group consisting of Li, Na, K, Ca and Ba. Preferably, the amine based catalyst may be tetramethylammonium hydroxide (TMAH), and the metallic basic catalyst may be potassium hydroxide (KOH) or sodium bicarbonate (NaHCO 3 ). The content of each component in the mixed catalyst is preferably in the ratio of 10 to 90: 10 to 90 parts by weight of the ratio of the amine basic catalyst and the metal basic catalyst can be arbitrarily adjusted. Within the above range, the reactivity between the functional group and the catalyst may be minimized during hydrolysis, and thus, the defects of organic functional groups such as Si-OH or Si-alkoxy may be significantly reduced, thereby freely controlling the degree of condensation. In addition, the acidic catalyst may be used without limitation so long as it is an acidic material commonly used in the art, for example, may be used a general acidic material such as HCl, H 2 SO 4 , HNO 3 , CH 3 COOH, Organic acids such as latic acid, tartaric acid, maleic acid and citric acid can also be applied.
본 발명의 실세스퀴옥산 복합 고분자의 제조방법에서 상기 유기용매는 당분야에서 통상적으로 사용하는 유기용매라면 제한 없이 사용될 수 있으며, 예를 들어, 메틸알콜, 에틸알콜, 이소프로필알콜, 부틸알콜, 셀로솔브계 등의 알코올류, 락테이트계, 아세톤, 메틸(아이소부틸)에틸케톤 등의 케톤류, 에틸렌글리콜 등의 글리콜류, 테트라하이드로퓨란 등의 퓨란계, 디메틸포름아미드, 디메틸아세트아미드, N-메틸-2-피롤리돈 등의 극성용매 뿐 아니라, 헥산, 사이클로헥산, 사이클로헥사논, 톨루엔, 자일렌, 크레졸, 클로로포름, 디클로로벤젠, 디메틸벤젠, 트리메틸벤젠, 피리딘, 메틸나프탈렌, 니트로메탄, 아크로니트릴, 메틸렌클로라이드, 옥타데실아민, 아닐린, 디메틸설폭사이드, 벤질알콜 등 다양한 용매를 사용할 수 있다.In the method for preparing the silsesquioxane composite polymer of the present invention, the organic solvent may be used without limitation as long as it is an organic solvent commonly used in the art. For example, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, Alcohols such as cellosolves, ketones such as lactate, acetone, methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol, furan systems such as tetrahydrofuran, dimethylformamide, dimethylacetamide, N- Polar solvents such as methyl-2-pyrrolidone, as well as hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane and acro Various solvents, such as nitrile, methylene chloride, octadecylamine, aniline, dimethyl sulfoxide, benzyl alcohol, can be used.
또한, 상기 유기 실란계 화합물로는 본 발명의 실세스퀴옥산 복합 고분자인 화학식 1 내지 9의 R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22를 포함하는 유기 실란이 사용될 수 있으며, 바람직하기로 실세스퀴옥산 복합 고분자의 내화학성을 증가시켜 비팽윤성을 향상시키는 효과가 있는 페닐기 또는 아미노기를 포함하는 유기 실란 화합물, 또는 복합 고분자의 경화 밀도를 증가시켜 경화층의 기계적 강도 및 경도를 향상시키는 효과가 있는 에폭시기 또는 (메타)아크릴기를 포함하는 유기 실란 화합물을 사용할 수 있다.In addition, as the organosilane compound, the silsesquioxane composite polymer of the present invention may be R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , Organosilanes comprising R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 can be used Preferably, the organic silane compound containing a phenyl group or an amino group having an effect of improving the chemical resistance of the silsesquioxane composite polymer to improve the non-swelling property, or the mechanical strength and hardness of the cured layer by increasing the curing density of the composite polymer The organosilane compound containing the epoxy group or (meth) acryl group which has the effect of improving the can be used.
상기 유기 실란계 화합물의 구체적인 예로는 (3-글리시드옥시프로필)트리메톡시실란, (3-글리시드옥시프로필)트리에톡시실란, (3-글리시드옥시프로필)메틸디메톡시실란, (3-글리시드옥시프로필)디메틸에톡시실란, 3-(메타아크릴옥시)프로필트리메톡시실란, 3,4-에폭시부틸트리메톡시실란, 3,4-에폭시부틸트리에톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리에톡시실란, 아미노프로필트리에톡시실란, 비닐트리에톡시실란, 비닐트리-t-부톡시실란, 비닐트리이소부톡시실란, 비닐트리이소프로폭시실란, 비닐트리페녹시실란, 페닐트리에톡시실란, 페닐트리메톡시실란, 아미노프로필트리메톡시실란, N-페닐-3-아미노프로필트리메톡시실란, 디메틸테트라메톡시실록산, 디페닐테트라메톡시실록산 등을 들 수 있으며, 이들 중 1종 단독으로 또는 2종 이상을 병용하여 사용할 수도 있다. 최종 제조되는 조성물의 물성을 위하여 2종 이상을 혼합하여 사용하는 것이 보다 바람직하다.Specific examples of the organosilane compound include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3 -Glycidoxy propyl) dimethyl ethoxy silane, 3- (methacryloxy) propyl trimethoxy silane, 3, 4- epoxy butyl trimethoxy silane, 3, 4- epoxy butyl triethoxy silane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltri-t-butoxy Silane, vinyltriisobutoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimeth Methoxysilane, dimethyl tetramethoxysiloxane, diphenyltetramethoxysiloxane, etc. are mentioned, You may use individually by 1 type or in combination of 2 or more types. It is more preferable to mix and use 2 or more types for the physical property of the composition currently manufactured.
본 발명에서 상기 화학식들의 반복단위 [D]d에 도입된[(SiO3/2R)4+2nO] 구조의 n은 1 내지 20의 정수로 치환될 수 있으며, 바람직하기로는 3 내지 10이며, 더욱 바람직하기로는 평균 n 값이 4 내지 5이며, 예를 들어, 상기 n이 4일 때 치환된 구조를 표현하면 하기 화학식 11과 같다:In the present invention, n of the [(SiO 3/2 R) 4 + 2n O] structure introduced into the repeating unit [D] d of the above formulas may be substituted with an integer of 1 to 20, preferably 3 to 10, and More preferably, the average n value is 4 to 5, for example, when n is 4, the substituted structure is represented by Formula 11 below:
[화학식 11][Formula 11]
Figure PCTKR2015003192-appb-I000028
Figure PCTKR2015003192-appb-I000028
상기 식에서, R은 상기에서 정의한 바와 같다.Wherein R is as defined above.
본 발명에서, 상기 화학식들의 반복단위 [B]b 또는 [E]e에 도입된[(SiO3/2R)4+2nR] 구조의 n은 1 내지 20의 정수로 치환될 수 있으며, 바람직하기로는 3 내지 10이며, 더욱 바람직하기로는 평균 n 값이 4 내지 5이며, 예를 들어, 상기 n이 4일 때 치환된 구조를 표현하면 하기 화학식 12와 같다: In the present invention, n of the [(SiO 3/2 R) 4 + 2n R] structure introduced into the repeating units [B] b or [E] e of the above formulas may be substituted with an integer of 1 to 20, preferably Below 3 to 10, more preferably, the average n value is 4 to 5, for example, when n is 4 to represent a structure substituted by the formula (12):
[화학식 12][Formula 12]
Figure PCTKR2015003192-appb-I000029
Figure PCTKR2015003192-appb-I000029
상기 식에서, R은 상기에서 정의한 바와 같다.Wherein R is as defined above.
구체적인 예로 본 발명에 따른 실세스퀴옥산 고분자는 하기 표 1 내지 18에 고분자일 수 있다. 하기 표 1 내지 9에서 ECHE는 (Epoxycyclohexyl)ethyl, GlyP는 Glycidoxypropyl, POMMA는 (methacryloyloxy)propyl을 의미하며, 두 개 이상이 기재된 경우 혼합사용을 의미한다. n은 각각 독립적으로 1 내지 8이다.As a specific example, the silsesquioxane polymer according to the present invention may be a polymer shown in Tables 1 to 18 below. In Tables 1 to 9, ECHE means (Epoxycyclohexyl) ethyl, GlyP means Glycidoxypropyl, POMMA means (methacryloyloxy) propyl, and when two or more are described, it means mixed use. n is 1-8 each independently.
상기 화학식 1의 실세스퀴옥산 복합고분자는 하기 표 1 또는 2에 기재된 고분자일 수 있다.The silsesquioxane composite polymer of Chemical Formula 1 may be a polymer described in Table 1 or 2 below.
표 1
No R1 R2 R16 R19 Y의 R
1-1 OH,메톡시 H,메틸 ECHE ECHE ECHE
1-2 OH,메톡시 H,메틸 페닐 페닐 페닐
1-3 OH,메톡시 H,메틸 메틸 메틸 메틸
1-4 OH,메톡시 H,메틸 GlyP GlyP GlyP
1-5 OH,메톡시 H,메틸 POMMA POMMA POMMA
1-6 OH,메톡시 H,메틸 ECHE 페닐 페닐
1-7 OH,메톡시 H,메틸 ECHE 메틸 메틸
1-8 OH,메톡시 H,메틸 ECHE GlyP GlyP
1-9 OH,메톡시 H,메틸 ECHE POMMA POMMA
1-10 OH,메톡시 H,메틸 페닐 ECHE ECHE
1-11 OH,메톡시 H,메틸 페닐 메틸 메틸
1-12 OH,메톡시 H,메틸 페닐 GlyP GlyP
1-13 OH,메톡시 H,메틸 페닐 POMMA POMMA
1-14 OH,메톡시 H,메틸 메틸 ECHE ECHE
1-15 OH,메톡시 H,메틸 메틸 페닐 페닐
1-16 OH,메톡시 H,메틸 메틸 GlyP GlyP
1-17 OH,메톡시 H,메틸 메틸 POMMA POMMA
1-18 OH,메톡시 H,메틸 GlyP ECHE ECHE
1-19 OH,메톡시 H,메틸 GlyP 페닐 페닐
1-20 OH,메톡시 H,메틸 GlyP 메틸 메틸
1-21 OH,메톡시 H,메틸 GlyP POMMA POMMA
1-22 OH,메톡시 H,메틸 POMMA ECHE ECHE
1-23 OH,메톡시 H,메틸 POMMA 페닐 페닐
1-24 OH,메톡시 H,메틸 POMMA 메틸 메틸
1-25 OH,메톡시 H,메틸 POMMA GlyP GlyP
Table 1
No R1 R2 R16 R19 Y R
1-1 OH, methoxy H, methyl ECHE ECHE ECHE
1-2 OH, methoxy H, methyl Phenyl Phenyl Phenyl
1-3 OH, methoxy H, methyl methyl methyl methyl
1-4 OH, methoxy H, methyl GlyP GlyP GlyP
1-5 OH, methoxy H, methyl POMMA POMMA POMMA
1-6 OH, methoxy H, methyl ECHE Phenyl Phenyl
1-7 OH, methoxy H, methyl ECHE methyl methyl
1-8 OH, methoxy H, methyl ECHE GlyP GlyP
1-9 OH, methoxy H, methyl ECHE POMMA POMMA
1-10 OH, methoxy H, methyl Phenyl ECHE ECHE
1-11 OH, methoxy H, methyl Phenyl methyl methyl
1-12 OH, methoxy H, methyl Phenyl GlyP GlyP
1-13 OH, methoxy H, methyl Phenyl POMMA POMMA
1-14 OH, methoxy H, methyl methyl ECHE ECHE
1-15 OH, methoxy H, methyl methyl Phenyl Phenyl
1-16 OH, methoxy H, methyl methyl GlyP GlyP
1-17 OH, methoxy H, methyl methyl POMMA POMMA
1-18 OH, methoxy H, methyl GlyP ECHE ECHE
1-19 OH, methoxy H, methyl GlyP Phenyl Phenyl
1-20 OH, methoxy H, methyl GlyP methyl methyl
1-21 OH, methoxy H, methyl GlyP POMMA POMMA
1-22 OH, methoxy H, methyl POMMA ECHE ECHE
1-23 OH, methoxy H, methyl POMMA Phenyl Phenyl
1-24 OH, methoxy H, methyl POMMA methyl methyl
1-25 OH, methoxy H, methyl POMMA GlyP GlyP
표 2
No R1 R2 R16 R19 Y의R n
2-1 OH,메톡시 H,메틸 ECHE 알킬사이올 ECHE 1~8
2-2 OH, CF3 H,에틸 페닐 페닐 페닐 1~8
2-3 OH,메톡시 H,아세틸틸 알킬사이올 메틸 메틸 1~8
2-4 CF3,메톡시 비닐,메틸 GlyP 도데실 GlyP 1~8
2-5 OH,메톡시 H,메틸 POMMA 알킬사이올 POMMA 1~8
2-6 OH, C8F13 H, F ECHE 페닐 페닐 1~8
2-7 OH, CF3 CF3,메틸 ECHE 옥틸 메틸 1~8
2-8 OH, C8F13 H,메틸 F 알킬사이올 GlyP 1~8
2-9 OH,메톡시 H, CF3 ECHE POMMA POMMA 1~8
2-10 OH,메톡시 H,메틸 페닐 알킬사이올 ECHE 1~8
2-11 OH, C8F13 아릴,메틸 알킬사이올 메틸 헥실 1~8
2-12 OH,알킬사이올 H,메타크릴 페닐 GlyP GlyP 1~8
2-13 OH,메톡시 H,메틸 알킬사이올 POMMA POMMA 1~8
2-14 OH, 아크릴 H,옥틸 메틸 ECHE 아미노프로필 1~8
2-15 비닐 ,메톡시 H,메틸 메틸 알킬사이올 페닐 1~8
2-16 알킬아민 H,메틸 메틸 GlyP GlyP 1~8
2-17 OH,에틸,메틸 알킬사이올,메틸 메틸 POMMA POMMA 1~8
2-18 아세톡시,메톡시 H,메틸 GlyP ECHE 아미노프로필 1~8
2-19 프로폭시,메톡시 H, CF3 GlyP 페닐 페닐 1~8
2-20 OH, 메톡시 H,메틸 아미노프로필 메틸 옥틸 1~8
2-21 C8F13,메톡시 C8F13,메틸 GlyP POMMA POMMA 1~8
2-22 OH,아릴 H,프로필 POMMA 프로필 ECHE 1~8
2-23 OH,메톡시 F,메틸 POMMA 페닐 페닐 1~8
2-24 CF3,메타크릴 H,메틸 POMMA 메틸 메틸 1~8
2-25 OH,메톡시 H,에틸 아미노프로필 GlyP GlyP 1~8
TABLE 2
No R1 R2 R16 R19 Y, R n
2-1 OH, methoxy H, methyl ECHE Alkyl siol ECHE 1-8
2-2 OH, CF 3 H, ethyl Phenyl Phenyl Phenyl 1-8
2-3 OH, methoxy H, acetyltyl Alkyl siol methyl methyl 1-8
2-4 CF 3 , methoxy Vinyl, methyl GlyP Dodecyl GlyP 1-8
2-5 OH, methoxy H, methyl POMMA Alkyl siol POMMA 1-8
2-6 OH, C 8 F 13 H, F ECHE Phenyl Phenyl 1-8
2-7 OH, CF 3 CF 3 , methyl ECHE Octyl methyl 1-8
2-8 OH, C 8 F 13 H, methyl F Alkyl siol GlyP 1-8
2-9 OH, methoxy H, CF 3 ECHE POMMA POMMA 1-8
2-10 OH, methoxy H, methyl Phenyl Alkyl siol ECHE 1-8
2-11 OH, C 8 F 13 Aryl, methyl Alkyl siol methyl Hexyl 1-8
2-12 OH, alkyl siol H, methacryl Phenyl GlyP GlyP 1-8
2-13 OH, methoxy H, methyl Alkyl siol POMMA POMMA 1-8
2-14 OH, acrylic H, octyl methyl ECHE Aminopropyl 1-8
2-15 Vinyl, methoxy H, methyl methyl Alkyl siol Phenyl 1-8
2-16 Alkylamine H, methyl methyl GlyP GlyP 1-8
2-17 OH, ethyl, methyl Alkyl siol, methyl methyl POMMA POMMA 1-8
2-18 Acetoxy, methoxy H, methyl GlyP ECHE Aminopropyl 1-8
2-19 Propoxy, methoxy H, CF 3 GlyP Phenyl Phenyl 1-8
2-20 OH, methoxy H, methyl Aminopropyl methyl Octyl 1-8
2-21 C 8 F 13 , methoxy C 8 F 13 , methyl GlyP POMMA POMMA 1-8
2-22 OH, aryl H, profile POMMA profile ECHE 1-8
2-23 OH, methoxy F, methyl POMMA Phenyl Phenyl 1-8
2-24 CF 3 , methacryl H, methyl POMMA methyl methyl 1-8
2-25 OH, methoxy H, ethyl Aminopropyl GlyP GlyP 1-8
구체적인 예로 상기 화학식 2의 실세스퀴옥산 복합고분자는 하기 표 3 및 4에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Chemical Formula 2 may be a polymer described in Tables 3 and 4 below.
표 3
No R3 R4 R16 R19 Y의 R
3-1 H,메틸 H,메틸 ECHE ECHE ECHE
3-2 H,메틸 H,메틸 페닐 페닐 페닐
3-3 H,메틸 H,메틸 메틸 메틸 메틸
3-4 H,메틸 H,메틸 GlyP GlyP GlyP
3-5 H,메틸 H,메틸 POMMA POMMA POMMA
3-6 H,메틸 H,메틸 ECHE 페닐 페닐
3-7 H,메틸 H,메틸 ECHE 메틸 메틸
3-8 H,메틸 H,메틸 ECHE GlyP GlyP
3-9 H,메틸 H,메틸 ECHE POMMA POMMA
3-10 H,메틸 H,메틸 페닐 ECHE ECHE
3-11 H,메틸 H,메틸 페닐 메틸 메틸
3-12 H,메틸 H,메틸 페닐 GlyP GlyP
3-13 H,메틸 H,메틸 페닐 POMMA POMMA
3-14 H,메틸 H,메틸 메틸 ECHE ECHE
3-15 H,메틸 H,메틸 메틸 페닐 페닐
3-16 H,메틸 H,메틸 메틸 GlyP GlyP
3-17 H,메틸 H,메틸 메틸 POMMA POMMA
3-18 H,메틸 H,메틸 GlyP ECHE ECHE
3-19 H,메틸 H,메틸 GlyP 페닐 페닐
3-20 H,메틸 H,메틸 GlyP 메틸 메틸
3-21 H,메틸 H,메틸 GlyP POMMA POMMA
3-22 H,메틸 H,메틸 POMMA ECHE ECHE
3-23 H,메틸 H,메틸 POMMA 페닐 페닐
3-24 H,메틸 H,메틸 POMMA 메틸 메틸
3-25 H,메틸 H,메틸 POMMA GlyP GlyP
TABLE 3
No R3 R4 R16 R19 Y R
3-1 H, methyl H, methyl ECHE ECHE ECHE
3-2 H, methyl H, methyl Phenyl Phenyl Phenyl
3-3 H, methyl H, methyl methyl methyl methyl
3-4 H, methyl H, methyl GlyP GlyP GlyP
3-5 H, methyl H, methyl POMMA POMMA POMMA
3-6 H, methyl H, methyl ECHE Phenyl Phenyl
3-7 H, methyl H, methyl ECHE methyl methyl
3-8 H, methyl H, methyl ECHE GlyP GlyP
3-9 H, methyl H, methyl ECHE POMMA POMMA
3-10 H, methyl H, methyl Phenyl ECHE ECHE
3-11 H, methyl H, methyl Phenyl methyl methyl
3-12 H, methyl H, methyl Phenyl GlyP GlyP
3-13 H, methyl H, methyl Phenyl POMMA POMMA
3-14 H, methyl H, methyl methyl ECHE ECHE
3-15 H, methyl H, methyl methyl Phenyl Phenyl
3-16 H, methyl H, methyl methyl GlyP GlyP
3-17 H, methyl H, methyl methyl POMMA POMMA
3-18 H, methyl H, methyl GlyP ECHE ECHE
3-19 H, methyl H, methyl GlyP Phenyl Phenyl
3-20 H, methyl H, methyl GlyP methyl methyl
3-21 H, methyl H, methyl GlyP POMMA POMMA
3-22 H, methyl H, methyl POMMA ECHE ECHE
3-23 H, methyl H, methyl POMMA Phenyl Phenyl
3-24 H, methyl H, methyl POMMA methyl methyl
3-25 H, methyl H, methyl POMMA GlyP GlyP
표 4
No R3 R4 R16 R19 Y의 R
4-1 OH,메톡시 H,메틸 ECHE 알킬사이올 ECHE
4-2 OH, CF3 H,에틸 페닐 페닐 페닐
4-3 OH,메톡시 H,아세틸틸 알킬사이올 메틸 메틸
4-4 CF3,메톡시 비닐,메틸 POMMA 도데실 GlyP
4-5 OH, 아크릴 H,메틸 POMMA 알킬사이올 옥틸
4-6 비닐 ,메톡시 H, F ECHE 페닐 POMMA
4-7 알킬아민 CF3,메틸 ECHE 옥틸 메틸
4-8 OH,에틸,메틸 H,메틸 F 아미노프로필 GlyP
4-9 아세톡시,메톡시 H, CF3 아미노프로필 POMMA 헥실
4-10 프로폭시,메톡시 H,메틸 페닐 알킬사이올 ECHE
4-11 OH, C8F13 아릴,메틸 알킬사이올 메틸 헥실
4-12 OH,메톡시 H,메타크릴 페닐 GlyP GlyP
4-13 CF3,메톡시 H,메틸 옥틸 POMMA POMMA
4-14 OH, 아크릴 H,옥틸 메틸 ECHE 아미노프로필
4-15 비닐 ,메톡시 H,메틸 옥틸 알킬사이올 페닐
4-16 알킬아민 H,메틸 옥틸 GlyP GlyP
4-17 OH,메톡시 알킬사이올,메틸 메틸 POMMA POMMA
4-18 아세톡시,메톡시 H,메틸 GlyP ECHE 아미노프로필
4-19 프로폭시,메톡시 H, CF3 GlyP 아미노프로필 페닐
4-20 OH, 메톡시 H,메틸 아미노프로필 메틸 옥틸
4-21 프로폭시,메톡시 C8F13,메틸 GlyP POMMA POMMA
4-22 OH, 메톡시 H,프로필 POMMA 프로필 ECHE
4-23 C8F13,메톡시 F,메틸 POMMA 페닐 페닐
4-24 OH,아릴 H,메틸 GlyP 메틸 GlyP
4-25 OH,메톡시 H,에틸 아미노프로필 GlyP GlyP
Table 4
No R3 R4 R16 R19 Y R
4-1 OH, methoxy H, methyl ECHE Alkyl siol ECHE
4-2 OH, CF 3 H, ethyl Phenyl Phenyl Phenyl
4-3 OH, methoxy H, acetyltyl Alkyl siol methyl methyl
4-4 CF 3 , methoxy Vinyl, methyl POMMA Dodecyl GlyP
4-5 OH, acrylic H, methyl POMMA Alkyl siol Octyl
4-6 Vinyl, methoxy H, F ECHE Phenyl POMMA
4-7 Alkylamine CF 3 , methyl ECHE Octyl methyl
4-8 OH, ethyl, methyl H, methyl F Aminopropyl GlyP
4-9 Acetoxy, methoxy H, CF 3 Aminopropyl POMMA Hexyl
4-10 Propoxy, methoxy H, methyl Phenyl Alkyl siol ECHE
4-11 OH, C 8 F 13 Aryl, methyl Alkyl siol methyl Hexyl
4-12 OH, methoxy H, methacryl Phenyl GlyP GlyP
4-13 CF 3 , methoxy H, methyl Octyl POMMA POMMA
4-14 OH, acrylic H, octyl methyl ECHE Aminopropyl
4-15 Vinyl, methoxy H, methyl Octyl Alkyl siol Phenyl
4-16 Alkylamine H, methyl Octyl GlyP GlyP
4-17 OH, methoxy Alkyl siol, methyl methyl POMMA POMMA
4-18 Acetoxy, methoxy H, methyl GlyP ECHE Aminopropyl
4-19 Propoxy, methoxy H, CF 3 GlyP Aminopropyl Phenyl
4-20 OH, methoxy H, methyl Aminopropyl methyl Octyl
4-21 Propoxy, methoxy C 8 F 13 , methyl GlyP POMMA POMMA
4-22 OH, methoxy H, profile POMMA profile ECHE
4-23 C 8 F 13 , methoxy F, methyl POMMA Phenyl Phenyl
4-24 OH, aryl H, methyl GlyP methyl GlyP
4-25 OH, methoxy H, ethyl Aminopropyl GlyP GlyP
구체적인 예로 상기 화학식 3의 실세스퀴옥산 복합고분자는 하기 표 5 또는 6에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Chemical Formula 3 may be a polymer described in Table 5 or 6 below.
표 5
No R5 R16 R19 R20 Y의 R X의 R
5-1 H,메틸 ECHE ECHE ECHE ECHE ECHE
5-2 H,메틸 페닐 페닐 페닐 페닐 페닐
5-3 H,메틸 메틸 메틸 메틸 메틸 메틸
5-4 H,메틸 GlyP EGCDX GlyP EGCDX GlyP
5-5 H,메틸 POMMA POMMA POMMA POMMA POMMA
5-6 H,메틸 ECHE ECHE 페닐 ECHE 페닐
5-7 H,메틸 ECHE ECHE 메틸 ECHE 메틸
5-8 H,메틸 ECHE ECHE GlyP ECHE GlyP
5-9 H,메틸 ECHE ECHE POMMA ECHE POMMA
5-10 H,메틸 ECHE 페닐 ECHE 페닐 ECHE
5-11 H,메틸 ECHE 메틸 ECHE 메틸 ECHE
5-12 H,메틸 ECHE GlyP ECHE GlyP ECHE
5-13 H,메틸 ECHE POMMA ECHE POMMA ECHE
5-14 H,메틸 페닐 페닐 ECHE 페닐 ECHE
5-15 H,메틸 페닐 페닐 메틸 페닐 메틸
5-16 H,메틸 페닐 페닐 EGDCX 페닐 EGDCX
5-17 H,메틸 페닐 페닐 POMMA 페닐 POMMA
5-18 H,메틸 페닐 ECHE 페닐 ECHE 페닐
5-19 H,메틸 페닐 메틸 페닐 메틸 페닐
5-20 H,메틸 페닐 GlyP 페닐 GlyP 페닐
5-21 H,메틸 페닐 POMMA 페닐 POMMA 페닐
5-22 H,메틸 메틸 메틸 ECHE 메틸 ECHE
5-23 H,메틸 메틸 메틸 페닐 메틸 페닐
5-25 H,메틸 메틸 메틸 GlyP 메틸 GlyP
5-25 H,메틸 메틸 메틸 POMMA 메틸 POMMA
5-26 H,메틸 메틸 ECHE 메틸 ECHE 메틸
5-27 H,메틸 메틸 페닐 메틸 페닐 메틸
5-28 H,메틸 메틸 GlyP 메틸 GlyP 메틸
5-29 H,메틸 메틸 POMMA 메틸 POMMA 메틸
5-30 H,메틸 GlyP GlyP ECHE GlyP ECHE
5-31 H,메틸 GlyP GlyP 페닐 GlyP 페닐
5-32 H,메틸 GlyP GlyP 메틸 GlyP 메틸
5-33 H,메틸 GlyP GlyP POMMA GlyP POMMA
5-34 H,메틸 GlyP ECHE GlyP ECHE GlyP
5-35 H,메틸 GlyP 페닐 GlyP 페닐 GlyP
5-36 H,메틸 GlyP 메틸 GlyP 메틸 GlyP
5-37 H,메틸 GlyP POMMA GlyP POMMA GlyP
5-35 H,메틸 POMMA POMMA ECHE POMMA ECHE
5-39 H,메틸 POMMA POMMA 페닐 POMMA 페닐
5-40 H,메틸 POMMA POMMA 메틸 POMMA 메틸
5-41 H,메틸 POMMA POMMA GlyP POMMA GlyP
5-42 H,메틸 POMMA ECHE POMMA ECHE POMMA
5-43 H,메틸 POMMA 페닐 POMMA 페닐 POMMA
5-44 H,메틸 POMMA 메틸 POMMA 메틸 POMMA
5-45 H,메틸 POMMA GlyP POMMA GlyP POMMA
Table 5
No R5 R16 R19 R20 Y R X, R
5-1 H, methyl ECHE ECHE ECHE ECHE ECHE
5-2 H, methyl Phenyl Phenyl Phenyl Phenyl Phenyl
5-3 H, methyl methyl methyl methyl methyl methyl
5-4 H, methyl GlyP EGCDX GlyP EGCDX GlyP
5-5 H, methyl POMMA POMMA POMMA POMMA POMMA
5-6 H, methyl ECHE ECHE Phenyl ECHE Phenyl
5-7 H, methyl ECHE ECHE methyl ECHE methyl
5-8 H, methyl ECHE ECHE GlyP ECHE GlyP
5-9 H, methyl ECHE ECHE POMMA ECHE POMMA
5-10 H, methyl ECHE Phenyl ECHE Phenyl ECHE
5-11 H, methyl ECHE methyl ECHE methyl ECHE
5-12 H, methyl ECHE GlyP ECHE GlyP ECHE
5-13 H, methyl ECHE POMMA ECHE POMMA ECHE
5-14 H, methyl Phenyl Phenyl ECHE Phenyl ECHE
5-15 H, methyl Phenyl Phenyl methyl Phenyl methyl
5-16 H, methyl Phenyl Phenyl EGDCX Phenyl EGDCX
5-17 H, methyl Phenyl Phenyl POMMA Phenyl POMMA
5-18 H, methyl Phenyl ECHE Phenyl ECHE Phenyl
5-19 H, methyl Phenyl methyl Phenyl methyl Phenyl
5-20 H, methyl Phenyl GlyP Phenyl GlyP Phenyl
5-21 H, methyl Phenyl POMMA Phenyl POMMA Phenyl
5-22 H, methyl methyl methyl ECHE methyl ECHE
5-23 H, methyl methyl methyl Phenyl methyl Phenyl
5-25 H, methyl methyl methyl GlyP methyl GlyP
5-25 H, methyl methyl methyl POMMA methyl POMMA
5-26 H, methyl methyl ECHE methyl ECHE methyl
5-27 H, methyl methyl Phenyl methyl Phenyl methyl
5-28 H, methyl methyl GlyP methyl GlyP methyl
5-29 H, methyl methyl POMMA methyl POMMA methyl
5-30 H, methyl GlyP GlyP ECHE GlyP ECHE
5-31 H, methyl GlyP GlyP Phenyl GlyP Phenyl
5-32 H, methyl GlyP GlyP methyl GlyP methyl
5-33 H, methyl GlyP GlyP POMMA GlyP POMMA
5-34 H, methyl GlyP ECHE GlyP ECHE GlyP
5-35 H, methyl GlyP Phenyl GlyP Phenyl GlyP
5-36 H, methyl GlyP methyl GlyP methyl GlyP
5-37 H, methyl GlyP POMMA GlyP POMMA GlyP
5-35 H, methyl POMMA POMMA ECHE POMMA ECHE
5-39 H, methyl POMMA POMMA Phenyl POMMA Phenyl
5-40 H, methyl POMMA POMMA methyl POMMA methyl
5-41 H, methyl POMMA POMMA GlyP POMMA GlyP
5-42 H, methyl POMMA ECHE POMMA ECHE POMMA
5-43 H, methyl POMMA Phenyl POMMA Phenyl POMMA
5-44 H, methyl POMMA methyl POMMA methyl POMMA
5-45 H, methyl POMMA GlyP POMMA GlyP POMMA
표 6
No R5 R16 R19 R20 Y의 R X의 R
6-1 H,메틸 ECHE ECHE ECHE ECHE ECHE
6-2 H,에틸 페닐 페닐 페닐 페닐 페닐
6-3 H,아세틸틸 알킬사이올 메틸 메틸 메틸 메틸
6-4 비닐,메틸 POMMA 도데실 GlyP EGCDX GlyP
6-5 H,메틸 POMMA 알킬사이올 POMMA POMMA POMMA
6-6 H, F ECHE 페닐 페닐 ECHE 페닐
6-7 CF3,메틸 ECHE 옥틸 메틸 ECHE 메틸
6-8 H,메틸 F 아미노프로필 GlyP ECHE GlyP
6-9 H, CF3 아미노프로필 POMMA POMMA ECHE POMMA
6-10 H,메틸 페닐 알킬사이올 ECHE 페닐 ECHE
6-11 아릴,메틸 알킬사이올 메틸 ECHE 메틸 ECHE
6-12 H,메타크릴 페닐 GlyP ECHE GlyP ECHE
6-13 H,메틸 옥틸 POMMA ECHE POMMA ECHE
6-14 H,옥틸 메틸 ECHE ECHE 페닐 ECHE
6-15 H,메틸 옥틸 알킬사이올 메틸 페닐 메틸
6-16 H,메틸 옥틸 GlyP EGDCX 페닐 EGDCX
6-17 알킬사이올,메틸 메틸 POMMA POMMA 페닐 POMMA
6-18 H,메틸 GlyP GlyP 페닐 ECHE 페닐
6-19 H, CF3 POMMA POMMA 페닐 메틸 페닐
6-20 H,메틸 ECHE 아미노프로필 페닐 GlyP 페닐
6-21 C8F13,메틸 알킬사이올 페닐 페닐 POMMA 페닐
6-22 H,프로필 GlyP GlyP ECHE 메틸 ECHE
6-23 F,메틸 POMMA POMMA 페닐 메틸 페닐
6-24 H,메틸 ECHE 아미노프로필 GlyP 메틸 GlyP
6-25 H,에틸 아미노프로필 페닐 POMMA 메틸 POMMA
6-26 H,아세틸틸 메틸 옥틸 메틸 ECHE 메틸
6-27 비닐,메틸 POMMA POMMA 메틸 페닐 메틸
6-28 H,메틸 메틸 메틸 메틸 GlyP 메틸
6-29 H, F 도데실 GlyP 메틸 POMMA 메틸
6-30 CF3,메틸 알킬사이올 옥틸 ECHE GlyP ECHE
6-31 H,메틸 페닐 POMMA 페닐 GlyP 페닐
6-32 H,옥틸 옥틸 메틸 메틸 GlyP 메틸
6-33 H,메틸 아미노프로필 GlyP POMMA GlyP POMMA
6-34 H,메틸 POMMA 헥실 GlyP ECHE GlyP
6-35 H,아세틸틸 알킬사이올 ECHE GlyP 페닐 GlyP
6-36 비닐,메틸 메틸 헥실 GlyP 메틸 GlyP
6-37 H,메틸 GlyP GlyP GlyP POMMA GlyP
6-38 H, F POMMA POMMA ECHE POMMA ECHE
6-39 CF3,메틸 ECHE 아미노프로필 페닐 POMMA 페닐
6-40 H,메틸 알킬사이올 페닐 메틸 POMMA 메틸
6-41 비닐,메틸 GlyP GlyP GlyP POMMA GlyP
6-42 H,메틸 POMMA POMMA POMMA ECHE POMMA
6-43 H, F ECHE 아미노프로필 POMMA 페닐 POMMA
6-44 CF3,메틸 아미노프로필 페닐 POMMA 메틸 POMMA
6-45 H,메틸 POMMA GlyP POMMA GlyP POMMA
Table 6
No R5 R16 R19 R20 Y R X, R
6-1 H, methyl ECHE ECHE ECHE ECHE ECHE
6-2 H, ethyl Phenyl Phenyl Phenyl Phenyl Phenyl
6-3 H, acetyltyl Alkyl siol methyl methyl methyl methyl
6-4 Vinyl, methyl POMMA Dodecyl GlyP EGCDX GlyP
6-5 H, methyl POMMA Alkyl siol POMMA POMMA POMMA
6-6 H, F ECHE Phenyl Phenyl ECHE Phenyl
6-7 CF 3 , methyl ECHE Octyl methyl ECHE methyl
6-8 H, methyl F Aminopropyl GlyP ECHE GlyP
6-9 H, CF 3 Aminopropyl POMMA POMMA ECHE POMMA
6-10 H, methyl Phenyl Alkyl siol ECHE Phenyl ECHE
6-11 Aryl, methyl Alkyl siol methyl ECHE methyl ECHE
6-12 H, methacryl Phenyl GlyP ECHE GlyP ECHE
6-13 H, methyl Octyl POMMA ECHE POMMA ECHE
6-14 H, octyl methyl ECHE ECHE Phenyl ECHE
6-15 H, methyl Octyl Alkyl siol methyl Phenyl methyl
6-16 H, methyl Octyl GlyP EGDCX Phenyl EGDCX
6-17 Alkyl siol, methyl methyl POMMA POMMA Phenyl POMMA
6-18 H, methyl GlyP GlyP Phenyl ECHE Phenyl
6-19 H, CF 3 POMMA POMMA Phenyl methyl Phenyl
6-20 H, methyl ECHE Aminopropyl Phenyl GlyP Phenyl
6-21 C 8 F 13 , methyl Alkyl siol Phenyl Phenyl POMMA Phenyl
6-22 H, profile GlyP GlyP ECHE methyl ECHE
6-23 F, methyl POMMA POMMA Phenyl methyl Phenyl
6-24 H, methyl ECHE Aminopropyl GlyP methyl GlyP
6-25 H, ethyl Aminopropyl Phenyl POMMA methyl POMMA
6-26 H, acetyltyl methyl Octyl methyl ECHE methyl
6-27 Vinyl, methyl POMMA POMMA methyl Phenyl methyl
6-28 H, methyl methyl methyl methyl GlyP methyl
6-29 H, F Dodecyl GlyP methyl POMMA methyl
6-30 CF 3 , methyl Alkyl siol Octyl ECHE GlyP ECHE
6-31 H, methyl Phenyl POMMA Phenyl GlyP Phenyl
6-32 H, octyl Octyl methyl methyl GlyP methyl
6-33 H, methyl Aminopropyl GlyP POMMA GlyP POMMA
6-34 H, methyl POMMA Hexyl GlyP ECHE GlyP
6-35 H, acetyltyl Alkyl siol ECHE GlyP Phenyl GlyP
6-36 Vinyl, methyl methyl Hexyl GlyP methyl GlyP
6-37 H, methyl GlyP GlyP GlyP POMMA GlyP
6-38 H, F POMMA POMMA ECHE POMMA ECHE
6-39 CF 3 , methyl ECHE Aminopropyl Phenyl POMMA Phenyl
6-40 H, methyl Alkyl siol Phenyl methyl POMMA methyl
6-41 Vinyl, methyl GlyP GlyP GlyP POMMA GlyP
6-42 H, methyl POMMA POMMA POMMA ECHE POMMA
6-43 H, F ECHE Aminopropyl POMMA Phenyl POMMA
6-44 CF 3 , methyl Aminopropyl Phenyl POMMA methyl POMMA
6-45 H, methyl POMMA GlyP POMMA GlyP POMMA
구체적인 예로 상기 화학식 4의 실세스퀴옥산 복합고분자는 하기 표 7 및 8에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Chemical Formula 4 may be a polymer described in Tables 7 and 8 below.
표 7
No R6 R7 R16 R17 R18 R19 X의 R Y의 R
7-1 OH,메톡시 H,메틸 ECHE ECHE H,메틸 ECHE ECHE ECHE
7-2 OH,메톡시 H,메틸 페닐 페닐 H,메틸 페닐 페닐 페닐
7-3 OH,메톡시 H,메틸 메틸 메틸 H,메틸 메틸 메틸 메틸
7-4 OH,메톡시 H,메틸 GlyP GlyP H,메틸 GlyP GlyP GlyP
7-5 OH,메톡시 H,메틸 POMMA POMMA H,메틸 POMMA POMMA POMMA
7-6 OH,메톡시 H,메틸 ECHE ECHE H,메틸 페닐 ECHE 페닐
7-7 OH,메톡시 H,메틸 ECHE ECHE H,메틸 메틸 ECHE 메틸
7-8 OH,메톡시 H,메틸 ECHE ECHE H,메틸 GlyP ECHE GlyP
7-9 OH,메톡시 H,메틸 ECHE ECHE H,메틸 POMMA ECHE POMMA
7-10 OH,메톡시 H,메틸 페닐 페닐 H,메틸 ECHE 페닐 ECHE
7-11 OH,메톡시 H,메틸 페닐 페닐 H,메틸 메틸 페닐 메틸
7-12 OH,메톡시 H,메틸 페닐 페닐 H,메틸 GlyP 페닐 GlyP
7-13 OH,메톡시 H,메틸 페닐 페닐 H,메틸 POMMA 페닐 POMMA
7-14 OH,메톡시 H,메틸 메틸 메틸 H,메틸 ECHE 메틸 ECHE
7-15 OH,메톡시 H,메틸 메틸 메틸 H,메틸 페닐 메틸 페닐
7-16 OH,메톡시 H,메틸 메틸 메틸 H,메틸 GlyP 메틸 GlyP
7-17 OH,메톡시 H,메틸 메틸 메틸 H,메틸 POMMA 메틸 POMMA
7-18 OH,메톡시 H,메틸 GlyP GlyP H,메틸 ECHE GlyP ECHE
7-19 OH,메톡시 H,메틸 GlyP GlyP H,메틸 페닐 GlyP 페닐
7-20 OH,메톡시 H,메틸 GlyP GlyP H,메틸 메틸 GlyP 메틸
7-21 OH,메톡시 H,메틸 GlyP GlyP H,메틸 POMMA GlyP POMMA
7-22 OH,메톡시 H,메틸 POMMA POMMA H,메틸 ECHE POMMA ECHE
7-23 OH,메톡시 H,메틸 POMMA POMMA H,메틸 페닐 POMMA 페닐
7-24 OH,메톡시 H,메틸 POMMA POMMA H,메틸 메틸 POMMA 메틸
7-25 OH,메톡시 H,메틸 POMMA POMMA H,메틸 GlyP POMMA GlyP
TABLE 7
No R6 R7 R16 R17 R18 R19 X, R Y R
7-1 OH, methoxy H, methyl ECHE ECHE H, methyl ECHE ECHE ECHE
7-2 OH, methoxy H, methyl Phenyl Phenyl H, methyl Phenyl Phenyl Phenyl
7-3 OH, methoxy H, methyl methyl methyl H, methyl methyl methyl methyl
7-4 OH, methoxy H, methyl GlyP GlyP H, methyl GlyP GlyP GlyP
7-5 OH, methoxy H, methyl POMMA POMMA H, methyl POMMA POMMA POMMA
7-6 OH, methoxy H, methyl ECHE ECHE H, methyl Phenyl ECHE Phenyl
7-7 OH, methoxy H, methyl ECHE ECHE H, methyl methyl ECHE methyl
7-8 OH, methoxy H, methyl ECHE ECHE H, methyl GlyP ECHE GlyP
7-9 OH, methoxy H, methyl ECHE ECHE H, methyl POMMA ECHE POMMA
7-10 OH, methoxy H, methyl Phenyl Phenyl H, methyl ECHE Phenyl ECHE
7-11 OH, methoxy H, methyl Phenyl Phenyl H, methyl methyl Phenyl methyl
7-12 OH, methoxy H, methyl Phenyl Phenyl H, methyl GlyP Phenyl GlyP
7-13 OH, methoxy H, methyl Phenyl Phenyl H, methyl POMMA Phenyl POMMA
7-14 OH, methoxy H, methyl methyl methyl H, methyl ECHE methyl ECHE
7-15 OH, methoxy H, methyl methyl methyl H, methyl Phenyl methyl Phenyl
7-16 OH, methoxy H, methyl methyl methyl H, methyl GlyP methyl GlyP
7-17 OH, methoxy H, methyl methyl methyl H, methyl POMMA methyl POMMA
7-18 OH, methoxy H, methyl GlyP GlyP H, methyl ECHE GlyP ECHE
7-19 OH, methoxy H, methyl GlyP GlyP H, methyl Phenyl GlyP Phenyl
7-20 OH, methoxy H, methyl GlyP GlyP H, methyl methyl GlyP methyl
7-21 OH, methoxy H, methyl GlyP GlyP H, methyl POMMA GlyP POMMA
7-22 OH, methoxy H, methyl POMMA POMMA H, methyl ECHE POMMA ECHE
7-23 OH, methoxy H, methyl POMMA POMMA H, methyl Phenyl POMMA Phenyl
7-24 OH, methoxy H, methyl POMMA POMMA H, methyl methyl POMMA methyl
7-25 OH, methoxy H, methyl POMMA POMMA H, methyl GlyP POMMA GlyP
표 8
No R6 R7 R16 R17 R18 R19 X의 R Y의 R
8-1 OH,메톡시 H,메틸 ECHE 알킬사이올 H,메틸 ECHE 알킬사이올 ECHE
8-2 OH, CF3 H,에틸 ECHE 페닐 H,옥틸 페닐 페닐 페닐
8-3 OH,메톡시 H,아세틸틸 ECHE 메틸 H,메틸 메틸 메틸 메틸
8-4 CF3,메톡시 비닐,메틸 페닐 GlyP H,메틸 GlyP GlyP GlyP
8-5 OH,메톡시 H,메틸 페닐 POMMA 알킬사이올,메틸 POMMA POMMA POMMA
8-6 OH, C8F13 H, F 페닐 ECHE H,메틸 페닐 ECHE 페닐
8-7 OH, CF3 CF3,메틸 ECHE ECHE H, CF3 메틸 ECHE 메틸
8-8 OH, C8F13 H,메틸 헥실 ECHE H,에틸 GlyP ECHE GlyP
8-9 OH,메톡시 H, CF3 GlyP ECHE H,아세틸틸 POMMA ECHE POMMA
8-10 OH,메톡시 H,메틸 POMMA 페닐 비닐,메틸 ECHE 페닐 ECHE
8-11 OH, C8F13 아릴,메틸 아미노프로필 페닐 H,메틸 헥실 페닐 헥실
8-12 OH,알킬사이올 H,메타크릴 페닐 페닐 H, F GlyP 페닐 GlyP
8-13 OH,메톡시 H,메틸 GlyP ECHE 비닐,메틸 POMMA 페닐 POMMA
8-14 OH, 아크릴 H,옥틸 POMMA 헥실 H,메틸 아미노프로필 메틸 아미노프로필
8-15 비닐 ,메톡시 H,메틸 아미노프로필 GlyP H, F 페닐 메틸 페닐
8-16 알킬아민 H,메틸 페닐 POMMA CF3,메틸 GlyP 메틸 GlyP
8-17 OH,에틸,메틸 알킬사이올,메틸 옥틸 아미노프로필 H,메틸 POMMA 메틸 POMMA
8-18 아세톡시,메톡시 H,메틸 POMMA 페닐 H, CF3 아미노프로필 GlyP 아미노프로필
8-19 프로폭시,메톡시 H, CF3 ECHE GlyP H,메틸 페닐 GlyP 페닐
8-20 OH, 메톡시 H,메틸 페닐 POMMA H,메틸 옥틸 GlyP 옥틸
8-21 C8F13,메톡시 C8F13,메틸 메틸 아미노프로필 H,메틸 POMMA GlyP POMMA
8-22 OH,아릴 H,프로필 GlyP 페닐 알킬사이올,메틸 ECHE POMMA ECHE
8-23 OH,메톡시 F,메틸 POMMA 옥틸 H,메틸 페닐 POMMA 페닐
8-24 CF3,메타크릴 H,메틸 POMMA POMMA H, CF3 메틸 POMMA 메틸
8-25 OH,메톡시 H,에틸 POMMA ECHE H,메틸 GlyP POMMA GlyP
Table 8
No R6 R7 R16 R17 R18 R19 X, R Y R
8-1 OH, methoxy H, methyl ECHE Alkyl siol H, methyl ECHE Alkyl siol ECHE
8-2 OH, CF 3 H, ethyl ECHE Phenyl H, octyl Phenyl Phenyl Phenyl
8-3 OH, methoxy H, acetyltyl ECHE methyl H, methyl methyl methyl methyl
8-4 CF 3 , methoxy Vinyl, methyl Phenyl GlyP H, methyl GlyP GlyP GlyP
8-5 OH, methoxy H, methyl Phenyl POMMA Alkyl siol, methyl POMMA POMMA POMMA
8-6 OH, C 8 F 13 H, F Phenyl ECHE H, methyl Phenyl ECHE Phenyl
8-7 OH, CF 3 CF 3 , methyl ECHE ECHE H, CF 3 methyl ECHE methyl
8-8 OH, C 8 F 13 H, methyl Hexyl ECHE H, ethyl GlyP ECHE GlyP
8-9 OH, methoxy H, CF 3 GlyP ECHE H, acetyltyl POMMA ECHE POMMA
8-10 OH, methoxy H, methyl POMMA Phenyl Vinyl, methyl ECHE Phenyl ECHE
8-11 OH, C 8 F 13 Aryl, methyl Aminopropyl Phenyl H, methyl Hexyl Phenyl Hexyl
8-12 OH, alkyl siol H, methacryl Phenyl Phenyl H, F GlyP Phenyl GlyP
8-13 OH, methoxy H, methyl GlyP ECHE Vinyl, methyl POMMA Phenyl POMMA
8-14 OH, acrylic H, octyl POMMA Hexyl H, methyl Aminopropyl methyl Aminopropyl
8-15 Vinyl, methoxy H, methyl Aminopropyl GlyP H, F Phenyl methyl Phenyl
8-16 Alkylamine H, methyl Phenyl POMMA CF 3 , methyl GlyP methyl GlyP
8-17 OH, ethyl, methyl Alkyl siol, methyl Octyl Aminopropyl H, methyl POMMA methyl POMMA
8-18 Acetoxy, methoxy H, methyl POMMA Phenyl H, CF 3 Aminopropyl GlyP Aminopropyl
8-19 Propoxy, methoxy H, CF 3 ECHE GlyP H, methyl Phenyl GlyP Phenyl
8-20 OH, methoxy H, methyl Phenyl POMMA H, methyl Octyl GlyP Octyl
8-21 C 8 F 13 , methoxy C 8 F 13 , methyl methyl Aminopropyl H, methyl POMMA GlyP POMMA
8-22 OH, aryl H, profile GlyP Phenyl Alkyl siol, methyl ECHE POMMA ECHE
8-23 OH, methoxy F, methyl POMMA Octyl H, methyl Phenyl POMMA Phenyl
8-24 CF 3 , methacryl H, methyl POMMA POMMA H, CF 3 methyl POMMA methyl
8-25 OH, methoxy H, ethyl POMMA ECHE H, methyl GlyP POMMA GlyP
구체적인 예로 상기 화학식 5의 실세스퀴옥산 복합고분자는 하기 표 9 및 10에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Formula 5 may be a polymer described in Tables 9 and 10.
표 9
No R8 R9 R16 R17 R18 R19 X의 R Y의 R
9-1 H,메틸 H,메틸 ECHE ECHE H,메틸 ECHE ECHE ECHE
9-2 H,메틸 H,메틸 페닐 페닐 H,메틸 페닐 페닐 페닐
9-3 H,메틸 H,메틸 메틸 메틸 H,메틸 메틸 메틸 메틸
9-4 H,메틸 H,메틸 GlyP GlyP H,메틸 GlyP GlyP GlyP
9-5 H,메틸 H,메틸 POMMA POMMA H,메틸 POMMA POMMA POMMA
9-6 H,메틸 H,메틸 ECHE ECHE H,메틸 페닐 ECHE 페닐
9-7 H,메틸 H,메틸 ECHE ECHE H,메틸 메틸 ECHE 메틸
9-8 H,메틸 H,메틸 ECHE ECHE H,메틸 GlyP ECHE GlyP
9-9 H,메틸 H,메틸 ECHE ECHE H,메틸 POMMA ECHE POMMA
9-10 H,메틸 H,메틸 페닐 페닐 H,메틸 ECHE 페닐 ECHE
9-11 H,메틸 H,메틸 페닐 페닐 H,메틸 메틸 페닐 메틸
9-12 H,메틸 H,메틸 페닐 페닐 H,메틸 GlyP 페닐 GlyP
9-13 H,메틸 H,메틸 페닐 페닐 H,메틸 POMMA 페닐 POMMA
9-14 H,메틸 H,메틸 메틸 메틸 H,메틸 ECHE 메틸 ECHE
9-15 H,메틸 H,메틸 메틸 메틸 H,메틸 페닐 메틸 페닐
9-16 H,메틸 H,메틸 메틸 메틸 H,메틸 GlyP 메틸 GlyP
9-17 H,메틸 H,메틸 메틸 메틸 H,메틸 POMMA 메틸 POMMA
9-18 H,메틸 H,메틸 GlyP GlyP H,메틸 ECHE GlyP ECHE
9-19 H,메틸 H,메틸 GlyP GlyP H,메틸 페닐 GlyP 페닐
9-20 H,메틸 H,메틸 GlyP GlyP H,메틸 메틸 GlyP 메틸
9-21 H,메틸 H,메틸 GlyP GlyP H,메틸 POMMA GlyP POMMA
9-22 H,메틸 H,메틸 POMMA POMMA H,메틸 ECHE POMMA ECHE
9-23 H,메틸 H,메틸 POMMA POMMA H,메틸 페닐 POMMA 페닐
9-24 H,메틸 H,메틸 POMMA POMMA H,메틸 메틸 POMMA 메틸
9-25 H,메틸 H,메틸 POMMA POMMA H,메틸 GlyP POMMA GlyP
Table 9
No R8 R9 R16 R17 R18 R19 X, R Y R
9-1 H, methyl H, methyl ECHE ECHE H, methyl ECHE ECHE ECHE
9-2 H, methyl H, methyl Phenyl Phenyl H, methyl Phenyl Phenyl Phenyl
9-3 H, methyl H, methyl methyl methyl H, methyl methyl methyl methyl
9-4 H, methyl H, methyl GlyP GlyP H, methyl GlyP GlyP GlyP
9-5 H, methyl H, methyl POMMA POMMA H, methyl POMMA POMMA POMMA
9-6 H, methyl H, methyl ECHE ECHE H, methyl Phenyl ECHE Phenyl
9-7 H, methyl H, methyl ECHE ECHE H, methyl methyl ECHE methyl
9-8 H, methyl H, methyl ECHE ECHE H, methyl GlyP ECHE GlyP
9-9 H, methyl H, methyl ECHE ECHE H, methyl POMMA ECHE POMMA
9-10 H, methyl H, methyl Phenyl Phenyl H, methyl ECHE Phenyl ECHE
9-11 H, methyl H, methyl Phenyl Phenyl H, methyl methyl Phenyl methyl
9-12 H, methyl H, methyl Phenyl Phenyl H, methyl GlyP Phenyl GlyP
9-13 H, methyl H, methyl Phenyl Phenyl H, methyl POMMA Phenyl POMMA
9-14 H, methyl H, methyl methyl methyl H, methyl ECHE methyl ECHE
9-15 H, methyl H, methyl methyl methyl H, methyl Phenyl methyl Phenyl
9-16 H, methyl H, methyl methyl methyl H, methyl GlyP methyl GlyP
9-17 H, methyl H, methyl methyl methyl H, methyl POMMA methyl POMMA
9-18 H, methyl H, methyl GlyP GlyP H, methyl ECHE GlyP ECHE
9-19 H, methyl H, methyl GlyP GlyP H, methyl Phenyl GlyP Phenyl
9-20 H, methyl H, methyl GlyP GlyP H, methyl methyl GlyP methyl
9-21 H, methyl H, methyl GlyP GlyP H, methyl POMMA GlyP POMMA
9-22 H, methyl H, methyl POMMA POMMA H, methyl ECHE POMMA ECHE
9-23 H, methyl H, methyl POMMA POMMA H, methyl Phenyl POMMA Phenyl
9-24 H, methyl H, methyl POMMA POMMA H, methyl methyl POMMA methyl
9-25 H, methyl H, methyl POMMA POMMA H, methyl GlyP POMMA GlyP
표 10
No R8 R9 R16 R17 R18 R19 B의 R D의 R
10-1 H,메틸 CF3,메틸 ECHE 알킬사이올 H,메틸 ECHE 알킬사이올 ECHE
10-2 H,에틸 H,메틸 ECHE 페닐 알킬사이올,메틸 헥실 페닐 헥실
10-3 H,아세틸틸 H, CF3 ECHE 메틸 H,메틸 GlyP 메틸 GlyP
10-4 비닐,메틸 H,메틸 페닐 GlyP H, CF3 POMMA GlyP POMMA
10-5 H,메틸 H,메틸 페닐 POMMA H,에틸 아미노프로필 POMMA 아미노프로필
10-6 H, F H,옥틸 페닐 ECHE H, F 페닐 ECHE 페닐
10-7 CF3,메틸 H,메틸 ECHE ECHE 비닐,메틸 GlyP ECHE GlyP
10-8 H,메틸 H,메틸 헥실 ECHE H,메틸 POMMA ECHE POMMA
10-9 H, CF3 알킬사이올,메틸 GlyP ECHE H, F 아미노프로필 ECHE 아미노프로필
10-10 H,메틸 H,메틸 POMMA 페닐 CF3,메틸 페닐 페닐 페닐
10-11 아릴,메틸 H,메틸 아미노프로필 페닐 H,메틸 옥틸 페닐 옥틸
10-12 H,메타크릴 H,메틸 페닐 페닐 H, CF3 POMMA 페닐 POMMA
10-13 H,메틸 알킬사이올,메틸 GlyP ECHE H,메틸 ECHE ECHE ECHE
10-14 H,옥틸 H,메틸 POMMA 헥실 H,메틸 페닐 헥실 페닐
10-15 H,메틸 H, F 아미노프로필 GlyP H,옥틸 메틸 GlyP 메틸
10-16 H,메틸 CF3,메틸 페닐 POMMA H,메틸 GlyP POMMA GlyP
10-17 알킬사이올,메틸 H,메틸 옥틸 아미노프로필 H,메틸 POMMA 아미노프로필 POMMA
10-18 H,메틸 H, CF3 POMMA 페닐 알킬사이올,메틸 아미노프로필 페닐 아미노프로필
10-19 H, CF3 H,메틸 ECHE GlyP H,메틸 페닐 GlyP 페닐
10-20 H,메틸 H,메틸 페닐 POMMA H,메틸 옥틸 POMMA 옥틸
10-21 C8F13,메틸 H,메틸 메틸 아미노프로필 H,메틸 POMMA 아미노프로필 POMMA
10-22 H,프로필 알킬사이올,메틸 GlyP 페닐 알킬사이올,메틸 ECHE 페닐 ECHE
10-23 F,메틸 H,메틸 POMMA 옥틸 H,메틸 페닐 옥틸 페닐
10-24 H,메틸 H, CF3 POMMA POMMA H, CF3 메틸 POMMA 메틸
10-25 H,에틸 H,메틸 POMMA ECHE H,메틸 GlyP ECHE GlyP
Table 10
No R8 R9 R16 R17 R18 R19 B, R D, R
10-1 H, methyl CF 3 , methyl ECHE Alkyl siol H, methyl ECHE Alkyl siol ECHE
10-2 H, ethyl H, methyl ECHE Phenyl Alkyl siol, methyl Hexyl Phenyl Hexyl
10-3 H, acetyltyl H, CF 3 ECHE methyl H, methyl GlyP methyl GlyP
10-4 Vinyl, methyl H, methyl Phenyl GlyP H, CF 3 POMMA GlyP POMMA
10-5 H, methyl H, methyl Phenyl POMMA H, ethyl Aminopropyl POMMA Aminopropyl
10-6 H, F H, octyl Phenyl ECHE H, F Phenyl ECHE Phenyl
10-7 CF 3 , methyl H, methyl ECHE ECHE Vinyl, methyl GlyP ECHE GlyP
10-8 H, methyl H, methyl Hexyl ECHE H, methyl POMMA ECHE POMMA
10-9 H, CF 3 Alkyl siol, methyl GlyP ECHE H, F Aminopropyl ECHE Aminopropyl
10-10 H, methyl H, methyl POMMA Phenyl CF 3 , methyl Phenyl Phenyl Phenyl
10-11 Aryl, methyl H, methyl Aminopropyl Phenyl H, methyl Octyl Phenyl Octyl
10-12 H, methacryl H, methyl Phenyl Phenyl H, CF 3 POMMA Phenyl POMMA
10-13 H, methyl Alkyl siol, methyl GlyP ECHE H, methyl ECHE ECHE ECHE
10-14 H, octyl H, methyl POMMA Hexyl H, methyl Phenyl Hexyl Phenyl
10-15 H, methyl H, F Aminopropyl GlyP H, octyl methyl GlyP methyl
10-16 H, methyl CF 3 , methyl Phenyl POMMA H, methyl GlyP POMMA GlyP
10-17 Alkyl siol, methyl H, methyl Octyl Aminopropyl H, methyl POMMA Aminopropyl POMMA
10-18 H, methyl H, CF 3 POMMA Phenyl Alkyl siol, methyl Aminopropyl Phenyl Aminopropyl
10-19 H, CF 3 H, methyl ECHE GlyP H, methyl Phenyl GlyP Phenyl
10-20 H, methyl H, methyl Phenyl POMMA H, methyl Octyl POMMA Octyl
10-21 C 8 F 13 , methyl H, methyl methyl Aminopropyl H, methyl POMMA Aminopropyl POMMA
10-22 H, profile Alkyl siol, methyl GlyP Phenyl Alkyl siol, methyl ECHE Phenyl ECHE
10-23 F, methyl H, methyl POMMA Octyl H, methyl Phenyl Octyl Phenyl
10-24 H, methyl H, CF 3 POMMA POMMA H, CF 3 methyl POMMA methyl
10-25 H, ethyl H, methyl POMMA ECHE H, methyl GlyP ECHE GlyP
구체적인 예로 상기 화학식 6의 실세스퀴옥산 복합고분자는 하기 표 11 및 12에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Chemical Formula 6 may be a polymer described in Tables 11 and 12 below.
표 11
No R16 R17 R18 R19 R20 X의 R Y의 R E의 X의 R
11-1 ECHE ECHE H,메틸 ECHE ECHE ECHE ECHE ECHE
11-2 페닐 페닐 H,메틸 페닐 페닐 페닐 페닐 페닐
11-3 메틸 메틸 H,메틸 메틸 메틸 메틸 메틸 메틸
11-4 GlyP EGCDX H,메틸 EGCDX GlyP EGCDX EGCDX GlyP
11-5 POMMA POMMA H,메틸 POMMA POMMA POMMA POMMA POMMA
11-6 ECHE ECHE H,메틸 ECHE 페닐 ECHE ECHE 페닐
11-7 ECHE ECHE H,메틸 ECHE 메틸 ECHE ECHE 메틸
11-8 ECHE ECHE H,메틸 ECHE GlyP ECHE ECHE GlyP
11-9 ECHE ECHE H,메틸 ECHE POMMA ECHE ECHE POMMA
11-10 ECHE 페닐 H,메틸 페닐 ECHE 페닐 페닐 ECHE
11-11 ECHE 메틸 H,메틸 메틸 ECHE 메틸 메틸 ECHE
11-12 ECHE GlyP H,메틸 GlyP ECHE GlyP GlyP ECHE
11-13 ECHE POMMA H,메틸 POMMA ECHE POMMA POMMA ECHE
11-14 페닐 페닐 H,메틸 페닐 ECHE 페닐 페닐 ECHE
11-15 페닐 페닐 H,메틸 페닐 메틸 페닐 페닐 메틸
11-16 페닐 페닐 H,메틸 페닐 EGDCX 페닐 페닐 EGDCX
11-17 페닐 페닐 H,메틸 페닐 POMMA 페닐 페닐 POMMA
11-18 페닐 ECHE H,메틸 ECHE 페닐 ECHE ECHE 페닐
11-19 페닐 메틸 H,메틸 메틸 페닐 메틸 메틸 페닐
11-20 페닐 GlyP H,메틸 GlyP 페닐 GlyP GlyP 페닐
11-21 페닐 POMMA H,메틸 POMMA 페닐 POMMA POMMA 페닐
11-22 메틸 메틸 H,메틸 메틸 ECHE 메틸 메틸 ECHE
11-23 메틸 메틸 H,메틸 메틸 페닐 메틸 메틸 페닐
11-24 메틸 메틸 H,메틸 메틸 GlyP 메틸 메틸 GlyP
11-25 메틸 메틸 H,메틸 메틸 POMMA 메틸 메틸 POMMA
11-26 메틸 ECHE H,메틸 ECHE 메틸 ECHE ECHE 메틸
11-27 메틸 페닐 H,메틸 페닐 메틸 페닐 페닐 메틸
11-28 메틸 GlyP H,메틸 GlyP 메틸 GlyP GlyP 메틸
11-29 메틸 POMMA H,메틸 POMMA 메틸 POMMA POMMA 메틸
11-30 GlyP GlyP H,메틸 GlyP ECHE GlyP GlyP ECHE
11-31 GlyP GlyP H,메틸 GlyP 페닐 GlyP GlyP 페닐
11-32 GlyP GlyP H,메틸 GlyP 메틸 GlyP GlyP 메틸
11-33 GlyP GlyP H,메틸 GlyP POMMA GlyP GlyP POMMA
11-34 GlyP ECHE H,메틸 ECHE GlyP ECHE ECHE GlyP
11-35 GlyP 페닐 H,메틸 페닐 GlyP 페닐 페닐 GlyP
11-36 GlyP 메틸 H,메틸 메틸 GlyP 메틸 메틸 GlyP
11-37 GlyP POMMA H,메틸 POMMA GlyP POMMA POMMA GlyP
11-38 POMMA POMMA H,메틸 POMMA ECHE POMMA POMMA ECHE
11-39 POMMA POMMA H,메틸 POMMA 페닐 POMMA POMMA 페닐
11-40 POMMA POMMA H,메틸 POMMA 메틸 POMMA POMMA 메틸
11-41 POMMA POMMA H,메틸 POMMA GlyP POMMA POMMA GlyP
11-42 POMMA ECHE H,메틸 ECHE POMMA ECHE ECHE POMMA
11-43 POMMA 페닐 H,메틸 페닐 POMMA 페닐 페닐 POMMA
11-44 POMMA 메틸 H,메틸 메틸 POMMA 메틸 메틸 POMMA
11-45 POMMA GlyP H,메틸 GlyP POMMA GlyP GlyP POMMA
Table 11
No R16 R17 R18 R19 R20 X, R Y R E x r
11-1 ECHE ECHE H, methyl ECHE ECHE ECHE ECHE ECHE
11-2 Phenyl Phenyl H, methyl Phenyl Phenyl Phenyl Phenyl Phenyl
11-3 methyl methyl H, methyl methyl methyl methyl methyl methyl
11-4 GlyP EGCDX H, methyl EGCDX GlyP EGCDX EGCDX GlyP
11-5 POMMA POMMA H, methyl POMMA POMMA POMMA POMMA POMMA
11-6 ECHE ECHE H, methyl ECHE Phenyl ECHE ECHE Phenyl
11-7 ECHE ECHE H, methyl ECHE methyl ECHE ECHE methyl
11-8 ECHE ECHE H, methyl ECHE GlyP ECHE ECHE GlyP
11-9 ECHE ECHE H, methyl ECHE POMMA ECHE ECHE POMMA
11-10 ECHE Phenyl H, methyl Phenyl ECHE Phenyl Phenyl ECHE
11-11 ECHE methyl H, methyl methyl ECHE methyl methyl ECHE
11-12 ECHE GlyP H, methyl GlyP ECHE GlyP GlyP ECHE
11-13 ECHE POMMA H, methyl POMMA ECHE POMMA POMMA ECHE
11-14 Phenyl Phenyl H, methyl Phenyl ECHE Phenyl Phenyl ECHE
11-15 Phenyl Phenyl H, methyl Phenyl methyl Phenyl Phenyl methyl
11-16 Phenyl Phenyl H, methyl Phenyl EGDCX Phenyl Phenyl EGDCX
11-17 Phenyl Phenyl H, methyl Phenyl POMMA Phenyl Phenyl POMMA
11-18 Phenyl ECHE H, methyl ECHE Phenyl ECHE ECHE Phenyl
11-19 Phenyl methyl H, methyl methyl Phenyl methyl methyl Phenyl
11-20 Phenyl GlyP H, methyl GlyP Phenyl GlyP GlyP Phenyl
11-21 Phenyl POMMA H, methyl POMMA Phenyl POMMA POMMA Phenyl
11-22 methyl methyl H, methyl methyl ECHE methyl methyl ECHE
11-23 methyl methyl H, methyl methyl Phenyl methyl methyl Phenyl
11-24 methyl methyl H, methyl methyl GlyP methyl methyl GlyP
11-25 methyl methyl H, methyl methyl POMMA methyl methyl POMMA
11-26 methyl ECHE H, methyl ECHE methyl ECHE ECHE methyl
11-27 methyl Phenyl H, methyl Phenyl methyl Phenyl Phenyl methyl
11-28 methyl GlyP H, methyl GlyP methyl GlyP GlyP methyl
11-29 methyl POMMA H, methyl POMMA methyl POMMA POMMA methyl
11-30 GlyP GlyP H, methyl GlyP ECHE GlyP GlyP ECHE
11-31 GlyP GlyP H, methyl GlyP Phenyl GlyP GlyP Phenyl
11-32 GlyP GlyP H, methyl GlyP methyl GlyP GlyP methyl
11-33 GlyP GlyP H, methyl GlyP POMMA GlyP GlyP POMMA
11-34 GlyP ECHE H, methyl ECHE GlyP ECHE ECHE GlyP
11-35 GlyP Phenyl H, methyl Phenyl GlyP Phenyl Phenyl GlyP
11-36 GlyP methyl H, methyl methyl GlyP methyl methyl GlyP
11-37 GlyP POMMA H, methyl POMMA GlyP POMMA POMMA GlyP
11-38 POMMA POMMA H, methyl POMMA ECHE POMMA POMMA ECHE
11-39 POMMA POMMA H, methyl POMMA Phenyl POMMA POMMA Phenyl
11-40 POMMA POMMA H, methyl POMMA methyl POMMA POMMA methyl
11-41 POMMA POMMA H, methyl POMMA GlyP POMMA POMMA GlyP
11-42 POMMA ECHE H, methyl ECHE POMMA ECHE ECHE POMMA
11-43 POMMA Phenyl H, methyl Phenyl POMMA Phenyl Phenyl POMMA
11-44 POMMA methyl H, methyl methyl POMMA methyl methyl POMMA
11-45 POMMA GlyP H, methyl GlyP POMMA GlyP GlyP POMMA
표 12
No R16 R17 R18 R19 R20 X의 R Y의 R E의 X의 R
12-1 ECHE POMMA H,메틸 ECHE POMMA POMMA ECHE POMMA
12-2 페닐 POMMA H,에틸 페닐 POMMA POMMA 페닐 POMMA
12-3 POMMA ECHE H,아세틸틸 메틸 ECHE ECHE 메틸 ECHE
12-4 메틸 ECHE 비닐,메틸 EGCDX ECHE ECHE EGCDX ECHE
12-5 POMMA F H,메틸 POMMA F F POMMA F
12-6 프로필 아미노프로필 CF3,메틸 ECHE 아미노프로필 아미노프로필 ECHE 아미노프로필
12-7 페닐 페닐 H,메틸 ECHE 페닐 페닐 ECHE 페닐
12-8 메틸 알킬사이올 H,아세틸틸 ECHE 알킬사이올 알킬사이올 ECHE 알킬사이올
12-9 GlyP 페닐 비닐,메틸 ECHE 페닐 페닐 ECHE 페닐
12-10 ECHE 옥틸 H,메틸 페닐 옥틸 옥틸 페닐 옥틸
12-11 알킬사이올 메틸 H,메틸 메틸 메틸 메틸 메틸 메틸
12-12 페닐 옥틸 비닐,메틸 GlyP 옥틸 옥틸 GlyP 옥틸
12-13 옥틸 옥틸 H,메틸 POMMA 옥틸 옥틸 POMMA 옥틸
12-14 메틸 메틸 H, F 페닐 메틸 메틸 페닐 메틸
12-15 옥틸 GlyP CF3,메틸 페닐 ECHE GlyP 페닐 ECHE
12-16 옥틸 GlyP 비닐,메틸 페닐 페닐 GlyP 페닐 페닐
12-17 메틸 아미노프로필 H,메틸 페닐 POMMA 아미노프로필 페닐 POMMA
12-18 GlyP GlyP H, F ECHE 메틸 GlyP ECHE 메틸
12-19 GlyP POMMA CF3,메틸 메틸 POMMA POMMA 메틸 POMMA
12-20 아미노프로필 메틸 H,메틸 GlyP 프로필 메틸 GlyP 프로필
12-21 GlyP POMMA 알킬사이올,메틸 POMMA 페닐 POMMA POMMA 페닐
12-22 POMMA 프로필 H,아세틸틸 메틸 메틸 프로필 메틸 메틸
12-23 POMMA 메틸 비닐,메틸 메틸 GlyP 메틸 메틸 GlyP
12-24 GlyP GlyP 비닐,메틸 메틸 ECHE GlyP 메틸 ECHE
12-25 아미노프로필 GlyP H,메틸 메틸 GlyP GlyP 메틸 GlyP
12-26 메틸 아미노프로필 H, F ECHE 아미노프로필 아미노프로필 ECHE 아미노프로필
12-27 메틸 GlyP CF3,메틸 페닐 GlyP GlyP 페닐 GlyP
12-28 메틸 옥틸 H,메틸 GlyP 옥틸 옥틸 GlyP 옥틸
12-29 메틸 메틸 H,아세틸틸 POMMA 메틸 메틸 POMMA 메틸
12-30 아미노프로필 GlyP 비닐,메틸 GlyP GlyP GlyP GlyP GlyP
12-31 GlyP GlyP H,메틸 GlyP GlyP GlyP GlyP GlyP
12-32 POMMA 아미노프로필 H,메틸 GlyP 아미노프로필 아미노프로필 GlyP 아미노프로필
12-33 메틸 GlyP 비닐,메틸 GlyP GlyP GlyP GlyP GlyP
12-34 POMMA POMMA H,메틸 ECHE POMMA POMMA ECHE POMMA
12-35 프로필 POMMA H, F 페닐 POMMA POMMA 페닐 POMMA
12-36 메틸 GlyP CF3,메틸 메틸 GlyP GlyP 메틸 GlyP
12-37 GlyP 아미노프로필 비닐,메틸 POMMA 아미노프로필 아미노프로필 POMMA 아미노프로필
12-38 GlyP 메틸 H,메틸 POMMA 메틸 메틸 POMMA 메틸
12-39 아미노프로필 메틸 H, F POMMA 메틸 메틸 POMMA 메틸
12-40 아미노프로필 메틸 CF3,메틸 POMMA 메틸 메틸 POMMA 메틸
12-41 GlyP 메틸 H,메틸 POMMA 메틸 메틸 POMMA 메틸
12-42 POMMA GlyP 알킬사이올,메틸 ECHE GlyP GlyP ECHE GlyP
12-43 POMMA 아미노프로필 H,아세틸틸 페닐 아미노프로필 아미노프로필 페닐 아미노프로필
12-44 POMMA GlyP 비닐,메틸 메틸 GlyP GlyP 메틸 GlyP
12-45 POMMA POMMA H,메틸 GlyP POMMA POMMA GlyP POMMA
Table 12
No R16 R17 R18 R19 R20 X, R Y R E x r
12-1 ECHE POMMA H, methyl ECHE POMMA POMMA ECHE POMMA
12-2 Phenyl POMMA H, ethyl Phenyl POMMA POMMA Phenyl POMMA
12-3 POMMA ECHE H, acetyltyl methyl ECHE ECHE methyl ECHE
12-4 methyl ECHE Vinyl, methyl EGCDX ECHE ECHE EGCDX ECHE
12-5 POMMA F H, methyl POMMA F F POMMA F
12-6 profile Aminopropyl CF 3 , methyl ECHE Aminopropyl Aminopropyl ECHE Aminopropyl
12-7 Phenyl Phenyl H, methyl ECHE Phenyl Phenyl ECHE Phenyl
12-8 methyl Alkyl siol H, acetyltyl ECHE Alkyl siol Alkyl siol ECHE Alkyl siol
12-9 GlyP Phenyl Vinyl, methyl ECHE Phenyl Phenyl ECHE Phenyl
12-10 ECHE Octyl H, methyl Phenyl Octyl Octyl Phenyl Octyl
12-11 Alkyl siol methyl H, methyl methyl methyl methyl methyl methyl
12-12 Phenyl Octyl Vinyl, methyl GlyP Octyl Octyl GlyP Octyl
12-13 Octyl Octyl H, methyl POMMA Octyl Octyl POMMA Octyl
12-14 methyl methyl H, F Phenyl methyl methyl Phenyl methyl
12-15 Octyl GlyP CF 3 , methyl Phenyl ECHE GlyP Phenyl ECHE
12-16 Octyl GlyP Vinyl, methyl Phenyl Phenyl GlyP Phenyl Phenyl
12-17 methyl Aminopropyl H, methyl Phenyl POMMA Aminopropyl Phenyl POMMA
12-18 GlyP GlyP H, F ECHE methyl GlyP ECHE methyl
12-19 GlyP POMMA CF 3 , methyl methyl POMMA POMMA methyl POMMA
12-20 Aminopropyl methyl H, methyl GlyP profile methyl GlyP profile
12-21 GlyP POMMA Alkyl siol, methyl POMMA Phenyl POMMA POMMA Phenyl
12-22 POMMA profile H, acetyltyl methyl methyl profile methyl methyl
12-23 POMMA methyl Vinyl, methyl methyl GlyP methyl methyl GlyP
12-24 GlyP GlyP Vinyl, methyl methyl ECHE GlyP methyl ECHE
12-25 Aminopropyl GlyP H, methyl methyl GlyP GlyP methyl GlyP
12-26 methyl Aminopropyl H, F ECHE Aminopropyl Aminopropyl ECHE Aminopropyl
12-27 methyl GlyP CF 3 , methyl Phenyl GlyP GlyP Phenyl GlyP
12-28 methyl Octyl H, methyl GlyP Octyl Octyl GlyP Octyl
12-29 methyl methyl H, acetyltyl POMMA methyl methyl POMMA methyl
12-30 Aminopropyl GlyP Vinyl, methyl GlyP GlyP GlyP GlyP GlyP
12-31 GlyP GlyP H, methyl GlyP GlyP GlyP GlyP GlyP
12-32 POMMA Aminopropyl H, methyl GlyP Aminopropyl Aminopropyl GlyP Aminopropyl
12-33 methyl GlyP Vinyl, methyl GlyP GlyP GlyP GlyP GlyP
12-34 POMMA POMMA H, methyl ECHE POMMA POMMA ECHE POMMA
12-35 profile POMMA H, F Phenyl POMMA POMMA Phenyl POMMA
12-36 methyl GlyP CF 3 , methyl methyl GlyP GlyP methyl GlyP
12-37 GlyP Aminopropyl Vinyl, methyl POMMA Aminopropyl Aminopropyl POMMA Aminopropyl
12-38 GlyP methyl H, methyl POMMA methyl methyl POMMA methyl
12-39 Aminopropyl methyl H, F POMMA methyl methyl POMMA methyl
12-40 Aminopropyl methyl CF 3 , methyl POMMA methyl methyl POMMA methyl
12-41 GlyP methyl H, methyl POMMA methyl methyl POMMA methyl
12-42 POMMA GlyP Alkyl siol, methyl ECHE GlyP GlyP ECHE GlyP
12-43 POMMA Aminopropyl H, acetyltyl Phenyl Aminopropyl Aminopropyl Phenyl Aminopropyl
12-44 POMMA GlyP Vinyl, methyl methyl GlyP GlyP methyl GlyP
12-45 POMMA POMMA H, methyl GlyP POMMA POMMA GlyP POMMA
구체적인 예로 상기 화학식 7의 실세스퀴옥산 복합고분자는 하기 표 13 및 14에 기재된 고분자일 수 있다. As a specific example, the silsesquioxane composite polymer of Chemical Formula 7 may be a polymer described in Tables 13 and 14 below.
표 13
No R11 R12 R16 R17 R18 R19 X의 R Y의 R
13-1 OH,메톡시 H,메틸 ECHE ECHE H,메틸 ECHE ECHE ECHE
13-2 OH,메톡시 H,메틸 페닐 페닐 H,메틸 페닐 페닐 페닐
13-3 OH,메톡시 H,메틸 메틸 메틸 H,메틸 메틸 메틸 메틸
13-4 OH,메톡시 H,메틸 GlyP GlyP H,메틸 GlyP GlyP GlyP
13-5 OH,메톡시 H,메틸 POMMA POMMA H,메틸 POMMA POMMA POMMA
13-6 OH,메톡시 H,메틸 ECHE ECHE H,메틸 페닐 ECHE 페닐
13-7 OH,메톡시 H,메틸 ECHE ECHE H,메틸 메틸 ECHE 메틸
13-8 OH,메톡시 H,메틸 ECHE ECHE H,메틸 GlyP ECHE GlyP
13-9 OH,메톡시 H,메틸 ECHE ECHE H,메틸 POMMA ECHE POMMA
13-10 OH,메톡시 H,메틸 페닐 페닐 H,메틸 ECHE 페닐 ECHE
13-11 OH,메톡시 H,메틸 페닐 페닐 H,메틸 메틸 페닐 메틸
13-12 OH,메톡시 H,메틸 페닐 페닐 H,메틸 GlyP 페닐 GlyP
13-13 OH,메톡시 H,메틸 페닐 페닐 H,메틸 POMMA 페닐 POMMA
13-14 OH,메톡시 H,메틸 메틸 메틸 H,메틸 ECHE 메틸 ECHE
13-15 OH,메톡시 H,메틸 메틸 메틸 H,메틸 페닐 메틸 페닐
13-16 OH,메톡시 H,메틸 메틸 메틸 H,메틸 GlyP 메틸 GlyP
13-17 OH,메톡시 H,메틸 메틸 메틸 H,메틸 POMMA 메틸 POMMA
13-18 OH,메톡시 H,메틸 GlyP GlyP H,메틸 ECHE GlyP ECHE
13-19 OH,메톡시 H,메틸 GlyP GlyP H,메틸 페닐 GlyP 페닐
13-20 OH,메톡시 H,메틸 GlyP GlyP H,메틸 메틸 GlyP 메틸
13-21 OH,메톡시 H,메틸 GlyP GlyP H,메틸 POMMA GlyP POMMA
13-22 OH,메톡시 H,메틸 POMMA POMMA H,메틸 ECHE POMMA ECHE
13-23 OH,메톡시 H,메틸 POMMA POMMA H,메틸 페닐 POMMA 페닐
13-24 OH,메톡시 H,메틸 POMMA POMMA H,메틸 메틸 POMMA 메틸
13-25 OH,메톡시 H,메틸 POMMA POMMA H,메틸 GlyP POMMA GlyP
Table 13
No R11 R12 R16 R17 R18 R19 X, R Y R
13-1 OH, methoxy H, methyl ECHE ECHE H, methyl ECHE ECHE ECHE
13-2 OH, methoxy H, methyl Phenyl Phenyl H, methyl Phenyl Phenyl Phenyl
13-3 OH, methoxy H, methyl methyl methyl H, methyl methyl methyl methyl
13-4 OH, methoxy H, methyl GlyP GlyP H, methyl GlyP GlyP GlyP
13-5 OH, methoxy H, methyl POMMA POMMA H, methyl POMMA POMMA POMMA
13-6 OH, methoxy H, methyl ECHE ECHE H, methyl Phenyl ECHE Phenyl
13-7 OH, methoxy H, methyl ECHE ECHE H, methyl methyl ECHE methyl
13-8 OH, methoxy H, methyl ECHE ECHE H, methyl GlyP ECHE GlyP
13-9 OH, methoxy H, methyl ECHE ECHE H, methyl POMMA ECHE POMMA
13-10 OH, methoxy H, methyl Phenyl Phenyl H, methyl ECHE Phenyl ECHE
13-11 OH, methoxy H, methyl Phenyl Phenyl H, methyl methyl Phenyl methyl
13-12 OH, methoxy H, methyl Phenyl Phenyl H, methyl GlyP Phenyl GlyP
13-13 OH, methoxy H, methyl Phenyl Phenyl H, methyl POMMA Phenyl POMMA
13-14 OH, methoxy H, methyl methyl methyl H, methyl ECHE methyl ECHE
13-15 OH, methoxy H, methyl methyl methyl H, methyl Phenyl methyl Phenyl
13-16 OH, methoxy H, methyl methyl methyl H, methyl GlyP methyl GlyP
13-17 OH, methoxy H, methyl methyl methyl H, methyl POMMA methyl POMMA
13-18 OH, methoxy H, methyl GlyP GlyP H, methyl ECHE GlyP ECHE
13-19 OH, methoxy H, methyl GlyP GlyP H, methyl Phenyl GlyP Phenyl
13-20 OH, methoxy H, methyl GlyP GlyP H, methyl methyl GlyP methyl
13-21 OH, methoxy H, methyl GlyP GlyP H, methyl POMMA GlyP POMMA
13-22 OH, methoxy H, methyl POMMA POMMA H, methyl ECHE POMMA ECHE
13-23 OH, methoxy H, methyl POMMA POMMA H, methyl Phenyl POMMA Phenyl
13-24 OH, methoxy H, methyl POMMA POMMA H, methyl methyl POMMA methyl
13-25 OH, methoxy H, methyl POMMA POMMA H, methyl GlyP POMMA GlyP
표 14
No R11 R12 R16 R17 R18 R19 X의 R Y의 R
14-1 OH,메톡시 H,메틸 ECHE 알킬사이올 H,메틸 ECHE 알킬사이올 ECHE
14-2 OH, CF3 H,에틸 ECHE 페닐 H,에틸 페닐 페닐 페닐
14-3 OH,메톡시 H,아세틸틸 ECHE 메틸 H,아세틸틸 메틸 메틸 메틸
14-4 CF3,메톡시 비닐,메틸 페닐 GlyP 비닐,메틸 GlyP GlyP GlyP
14-5 OH,메톡시 H,메틸 페닐 POMMA H,메틸 POMMA POMMA POMMA
14-6 OH, C8F13 H, F 페닐 ECHE H, F 페닐 ECHE 페닐
14-7 OH, CF3 CF3,메틸 ECHE ECHE CF3,메틸 메틸 ECHE 메틸
14-8 OH, C8F13 H,메틸 헥실 ECHE H,메틸 GlyP ECHE GlyP
14-9 OH,메톡시 H, CF3 GlyP ECHE H, CF3 POMMA ECHE POMMA
14-10 OH,메톡시 H,메틸 POMMA 페닐 H,메틸 ECHE 페닐 ECHE
14-11 OH, C8F13 아릴,메틸 아미노프로필 페닐 아릴,메틸 헥실 페닐 헥실
14-12 OH,알킬사이올 H,메타크릴 페닐 페닐 H,메타크릴 GlyP 페닐 GlyP
14-13 OH,메톡시 H,메틸 GlyP ECHE H,메틸 POMMA ECHE POMMA
14-14 OH, 아크릴 H,옥틸 POMMA 헥실 H,옥틸 아미노프로필 헥실 아미노프로필
14-15 비닐 ,메톡시 H,메틸 아미노프로필 GlyP H,메틸 페닐 GlyP 페닐
14-16 알킬아민 H,메틸 페닐 POMMA H,메틸 GlyP POMMA GlyP
14-17 OH,에틸,메틸 알킬사이올,메틸 옥틸 아미노프로필 알킬사이올,메틸 POMMA 아미노프로필 POMMA
14-18 아세톡시,메톡시 H,메틸 POMMA 페닐 H,메틸 아미노프로필 페닐 아미노프로필
14-19 프로폭시,메톡시 H, CF3 ECHE GlyP H, CF3 페닐 GlyP 페닐
14-20 OH, 메톡시 H,메틸 페닐 POMMA H,메틸 옥틸 POMMA 옥틸
14-21 C8F13,메톡시 C8F13,메틸 메틸 아미노프로필 C8F13,메틸 POMMA 아미노프로필 POMMA
14-22 OH,아릴 H,프로필 GlyP 페닐 H,프로필 ECHE 페닐 ECHE
14-23 OH,메톡시 F,메틸 POMMA 옥틸 F,메틸 페닐 옥틸 페닐
14-24 CF3,메타크릴 H,메틸 POMMA POMMA H,메틸 메틸 POMMA 메틸
14-25 OH,메톡시 H,메틸 POMMA POMMA H,메틸 GlyP POMMA GlyP
Table 14
No R11 R12 R16 R17 R18 R19 X, R Y R
14-1 OH, methoxy H, methyl ECHE Alkyl siol H, methyl ECHE Alkyl siol ECHE
14-2 OH, CF 3 H, ethyl ECHE Phenyl H, ethyl Phenyl Phenyl Phenyl
14-3 OH, methoxy H, acetyltyl ECHE methyl H, acetyltyl methyl methyl methyl
14-4 CF 3 , methoxy Vinyl, methyl Phenyl GlyP Vinyl, methyl GlyP GlyP GlyP
14-5 OH, methoxy H, methyl Phenyl POMMA H, methyl POMMA POMMA POMMA
14-6 OH, C 8 F 13 H, F Phenyl ECHE H, F Phenyl ECHE Phenyl
14-7 OH, CF 3 CF 3 , methyl ECHE ECHE CF 3 , methyl methyl ECHE methyl
14-8 OH, C 8 F 13 H, methyl Hexyl ECHE H, methyl GlyP ECHE GlyP
14-9 OH, methoxy H, CF 3 GlyP ECHE H, CF 3 POMMA ECHE POMMA
14-10 OH, methoxy H, methyl POMMA Phenyl H, methyl ECHE Phenyl ECHE
14-11 OH, C 8 F 13 Aryl, methyl Aminopropyl Phenyl Aryl, methyl Hexyl Phenyl Hexyl
14-12 OH, alkyl siol H, methacryl Phenyl Phenyl H, methacryl GlyP Phenyl GlyP
14-13 OH, methoxy H, methyl GlyP ECHE H, methyl POMMA ECHE POMMA
14-14 OH, acrylic H, octyl POMMA Hexyl H, octyl Aminopropyl Hexyl Aminopropyl
14-15 Vinyl, methoxy H, methyl Aminopropyl GlyP H, methyl Phenyl GlyP Phenyl
14-16 Alkylamine H, methyl Phenyl POMMA H, methyl GlyP POMMA GlyP
14-17 OH, ethyl, methyl Alkyl siol, methyl Octyl Aminopropyl Alkyl siol, methyl POMMA Aminopropyl POMMA
14-18 Acetoxy, methoxy H, methyl POMMA Phenyl H, methyl Aminopropyl Phenyl Aminopropyl
14-19 Propoxy, methoxy H, CF 3 ECHE GlyP H, CF 3 Phenyl GlyP Phenyl
14-20 OH, methoxy H, methyl Phenyl POMMA H, methyl Octyl POMMA Octyl
14-21 C 8 F 13 , methoxy C 8 F 13 , methyl methyl Aminopropyl C 8 F 13 , methyl POMMA Aminopropyl POMMA
14-22 OH, aryl H, profile GlyP Phenyl H, profile ECHE Phenyl ECHE
14-23 OH, methoxy F, methyl POMMA Octyl F, methyl Phenyl Octyl Phenyl
14-24 CF 3 , methacryl H, methyl POMMA POMMA H, methyl methyl POMMA methyl
14-25 OH, methoxy H, methyl POMMA POMMA H, methyl GlyP POMMA GlyP
구체적인 예로 상기 화학식 8의 실세스퀴옥산 복합고분자는 하기 표 15 및 16에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Chemical Formula 8 may be a polymer described in Tables 15 and 16 below.
표 15
No R13 R14 R16 R17 R18 R19 X의 R Y의 R
15-1 H,메틸 H,메틸 ECHE ECHE H,메틸 ECHE ECHE ECHE
15-2 H,메틸 H,메틸 페닐 페닐 H,메틸 페닐 페닐 페닐
15-3 H,메틸 H,메틸 메틸 메틸 H,메틸 메틸 메틸 메틸
15-4 H,메틸 H,메틸 GlyP GlyP H,메틸 GlyP GlyP GlyP
15-5 H,메틸 H,메틸 POMMA POMMA H,메틸 POMMA POMMA POMMA
15-6 H,메틸 H,메틸 ECHE ECHE H,메틸 페닐 ECHE 페닐
15-7 H,메틸 H,메틸 ECHE ECHE H,메틸 메틸 ECHE 메틸
15-8 H,메틸 H,메틸 ECHE ECHE H,메틸 GlyP ECHE GlyP
15-9 H,메틸 H,메틸 ECHE ECHE H,메틸 POMMA ECHE POMMA
15-10 H,메틸 H,메틸 페닐 페닐 H,메틸 ECHE 페닐 ECHE
15-11 H,메틸 H,메틸 페닐 페닐 H,메틸 메틸 페닐 메틸
15-12 H,메틸 H,메틸 페닐 페닐 H,메틸 GlyP 페닐 GlyP
15-13 H,메틸 H,메틸 페닐 페닐 H,메틸 POMMA 페닐 POMMA
15-14 H,메틸 H,메틸 메틸 메틸 H,메틸 ECHE 메틸 ECHE
15-15 H,메틸 H,메틸 메틸 메틸 H,메틸 페닐 메틸 페닐
15-16 H,메틸 H,메틸 메틸 메틸 H,메틸 GlyP 메틸 GlyP
15-17 H,메틸 H,메틸 메틸 메틸 H,메틸 POMMA 메틸 POMMA
15-18 H,메틸 H,메틸 GlyP GlyP H,메틸 ECHE GlyP ECHE
15-19 H,메틸 H,메틸 GlyP GlyP H,메틸 페닐 GlyP 페닐
15-20 H,메틸 H,메틸 GlyP GlyP H,메틸 메틸 GlyP 메틸
15-21 H,메틸 H,메틸 GlyP GlyP H,메틸 POMMA GlyP POMMA
15-22 H,메틸 H,메틸 POMMA POMMA H,메틸 ECHE POMMA ECHE
15-23 H,메틸 H,메틸 POMMA POMMA H,메틸 페닐 POMMA 페닐
15-24 H,메틸 H,메틸 POMMA POMMA H,메틸 메틸 POMMA 메틸
15-25 H,메틸 H,메틸 POMMA POMMA H,메틸 GlyP POMMA GlyP
Table 15
No R13 R14 R16 R17 R18 R19 X, R Y R
15-1 H, methyl H, methyl ECHE ECHE H, methyl ECHE ECHE ECHE
15-2 H, methyl H, methyl Phenyl Phenyl H, methyl Phenyl Phenyl Phenyl
15-3 H, methyl H, methyl methyl methyl H, methyl methyl methyl methyl
15-4 H, methyl H, methyl GlyP GlyP H, methyl GlyP GlyP GlyP
15-5 H, methyl H, methyl POMMA POMMA H, methyl POMMA POMMA POMMA
15-6 H, methyl H, methyl ECHE ECHE H, methyl Phenyl ECHE Phenyl
15-7 H, methyl H, methyl ECHE ECHE H, methyl methyl ECHE methyl
15-8 H, methyl H, methyl ECHE ECHE H, methyl GlyP ECHE GlyP
15-9 H, methyl H, methyl ECHE ECHE H, methyl POMMA ECHE POMMA
15-10 H, methyl H, methyl Phenyl Phenyl H, methyl ECHE Phenyl ECHE
15-11 H, methyl H, methyl Phenyl Phenyl H, methyl methyl Phenyl methyl
15-12 H, methyl H, methyl Phenyl Phenyl H, methyl GlyP Phenyl GlyP
15-13 H, methyl H, methyl Phenyl Phenyl H, methyl POMMA Phenyl POMMA
15-14 H, methyl H, methyl methyl methyl H, methyl ECHE methyl ECHE
15-15 H, methyl H, methyl methyl methyl H, methyl Phenyl methyl Phenyl
15-16 H, methyl H, methyl methyl methyl H, methyl GlyP methyl GlyP
15-17 H, methyl H, methyl methyl methyl H, methyl POMMA methyl POMMA
15-18 H, methyl H, methyl GlyP GlyP H, methyl ECHE GlyP ECHE
15-19 H, methyl H, methyl GlyP GlyP H, methyl Phenyl GlyP Phenyl
15-20 H, methyl H, methyl GlyP GlyP H, methyl methyl GlyP methyl
15-21 H, methyl H, methyl GlyP GlyP H, methyl POMMA GlyP POMMA
15-22 H, methyl H, methyl POMMA POMMA H, methyl ECHE POMMA ECHE
15-23 H, methyl H, methyl POMMA POMMA H, methyl Phenyl POMMA Phenyl
15-24 H, methyl H, methyl POMMA POMMA H, methyl methyl POMMA methyl
15-25 H, methyl H, methyl POMMA POMMA H, methyl GlyP POMMA GlyP
표 16
No R13 R14 R16 R17 R18 R19 X의 R Y의 R
16-1 H,메틸 CF3,메틸 ECHE 알킬사이올 H,메틸 ECHE 알킬사이올 ECHE
16-2 H,에틸 H,메틸 ECHE 페닐 알킬사이올,메틸 헥실 페닐 헥실
16-3 H,아세틸틸 H, CF3 ECHE 메틸 H,메틸 GlyP 메틸 GlyP
16-4 비닐,메틸 H,메틸 페닐 GlyP H, CF3 POMMA GlyP POMMA
16-5 H,메틸 H,메틸 페닐 POMMA H,에틸 아미노프로필 POMMA 아미노프로필
16-6 H, F H,옥틸 페닐 ECHE H, F 페닐 ECHE 페닐
16-7 CF3,메틸 H,메틸 ECHE ECHE 비닐,메틸 GlyP ECHE GlyP
16-8 H,메틸 H,메틸 헥실 ECHE H,메틸 POMMA ECHE POMMA
16-9 H, CF3 알킬사이올,메틸 GlyP ECHE H, F 아미노프로필 ECHE 아미노프로필
16-10 H,메틸 H,메틸 POMMA 페닐 CF3,메틸 페닐 페닐 페닐
16-11 아릴,메틸 H,메틸 아미노프로필 페닐 H,메틸 옥틸 페닐 옥틸
16-12 H,메타크릴 H,메틸 페닐 페닐 H, CF3 POMMA 페닐 POMMA
16-13 H,메틸 알킬사이올,메틸 GlyP ECHE H,메틸 ECHE ECHE ECHE
16-14 H,옥틸 H,메틸 POMMA 헥실 H,메틸 페닐 헥실 페닐
16-15 H,메틸 H, F 아미노프로필 GlyP H,옥틸 메틸 GlyP 메틸
16-16 H,메틸 CF3,메틸 페닐 POMMA H,메틸 GlyP POMMA GlyP
16-17 알킬사이올,메틸 H,메틸 옥틸 아미노프로필 H,메틸 POMMA 아미노프로필 POMMA
16-18 H,메틸 H, CF3 POMMA 페닐 알킬사이올,메틸 아미노프로필 페닐 아미노프로필
16-19 H, CF3 H,메틸 ECHE GlyP H,메틸 페닐 GlyP 페닐
16-20 H,메틸 H,메틸 페닐 POMMA H,메틸 옥틸 POMMA 옥틸
16-21 C8F13,메틸 H,메틸 메틸 아미노프로필 H,메틸 POMMA 아미노프로필 POMMA
16-22 H,프로필 알킬사이올,메틸 GlyP 페닐 알킬사이올,메틸 ECHE 페닐 ECHE
16-23 F,메틸 H,메틸 POMMA 옥틸 H,메틸 페닐 옥틸 페닐
16-24 H,메틸 H, CF3 POMMA POMMA H, CF3 메틸 POMMA 메틸
16-25 H,에틸 H,메틸 POMMA ECHE H,메틸 GlyP ECHE GlyP
Table 16
No R13 R14 R16 R17 R18 R19 X, R Y R
16-1 H, methyl CF 3 , methyl ECHE Alkyl siol H, methyl ECHE Alkyl siol ECHE
16-2 H, ethyl H, methyl ECHE Phenyl Alkyl siol, methyl Hexyl Phenyl Hexyl
16-3 H, acetyltyl H, CF 3 ECHE methyl H, methyl GlyP methyl GlyP
16-4 Vinyl, methyl H, methyl Phenyl GlyP H, CF 3 POMMA GlyP POMMA
16-5 H, methyl H, methyl Phenyl POMMA H, ethyl Aminopropyl POMMA Aminopropyl
16-6 H, F H, octyl Phenyl ECHE H, F Phenyl ECHE Phenyl
16-7 CF 3 , methyl H, methyl ECHE ECHE Vinyl, methyl GlyP ECHE GlyP
16-8 H, methyl H, methyl Hexyl ECHE H, methyl POMMA ECHE POMMA
16-9 H, CF 3 Alkyl siol, methyl GlyP ECHE H, F Aminopropyl ECHE Aminopropyl
16-10 H, methyl H, methyl POMMA Phenyl CF 3 , methyl Phenyl Phenyl Phenyl
16-11 Aryl, methyl H, methyl Aminopropyl Phenyl H, methyl Octyl Phenyl Octyl
16-12 H, methacryl H, methyl Phenyl Phenyl H, CF 3 POMMA Phenyl POMMA
16-13 H, methyl Alkyl siol, methyl GlyP ECHE H, methyl ECHE ECHE ECHE
16-14 H, octyl H, methyl POMMA Hexyl H, methyl Phenyl Hexyl Phenyl
16-15 H, methyl H, F Aminopropyl GlyP H, octyl methyl GlyP methyl
16-16 H, methyl CF 3 , methyl Phenyl POMMA H, methyl GlyP POMMA GlyP
16-17 Alkyl siol, methyl H, methyl Octyl Aminopropyl H, methyl POMMA Aminopropyl POMMA
16-18 H, methyl H, CF 3 POMMA Phenyl Alkyl siol, methyl Aminopropyl Phenyl Aminopropyl
16-19 H, CF 3 H, methyl ECHE GlyP H, methyl Phenyl GlyP Phenyl
16-20 H, methyl H, methyl Phenyl POMMA H, methyl Octyl POMMA Octyl
16-21 C 8 F 13 , methyl H, methyl methyl Aminopropyl H, methyl POMMA Aminopropyl POMMA
16-22 H, profile Alkyl siol, methyl GlyP Phenyl Alkyl siol, methyl ECHE Phenyl ECHE
16-23 F, methyl H, methyl POMMA Octyl H, methyl Phenyl Octyl Phenyl
16-24 H, methyl H, CF 3 POMMA POMMA H, CF 3 methyl POMMA methyl
16-25 H, ethyl H, methyl POMMA ECHE H, methyl GlyP ECHE GlyP
구체적인 예로 상기 화학식 9의 실세스퀴옥산 복합고분자는 하기 표 17 및 18에 기재된 고분자일 수 있다.As a specific example, the silsesquioxane composite polymer of Chemical Formula 9 may be a polymer described in Tables 17 and 18 below.
표 17
No R16 R17 R18 R19 R20 X의 R Y의 R E의 말단 R
17-1 ECHE ECHE H,메틸 ECHE ECHE ECHE ECHE ECHE
17-2 페닐 페닐 H,메틸 페닐 페닐 페닐 페닐 페닐
17-3 메틸 메틸 H,메틸 메틸 메틸 메틸 메틸 메틸
17-4 GlyP EGCDX H,메틸 EGCDX GlyP EGCDX EGCDX GlyP
17-5 POMMA POMMA H,메틸 POMMA POMMA POMMA POMMA POMMA
17-6 ECHE ECHE H,메틸 ECHE 페닐 ECHE ECHE 페닐
17-7 ECHE ECHE H,메틸 ECHE 메틸 ECHE ECHE 메틸
17-8 ECHE ECHE H,메틸 ECHE GlyP ECHE ECHE GlyP
17-9 ECHE ECHE H,메틸 ECHE POMMA ECHE ECHE POMMA
17-10 ECHE 페닐 H,메틸 페닐 ECHE 페닐 페닐 ECHE
17-11 ECHE 메틸 H,메틸 메틸 ECHE 메틸 메틸 ECHE
17-12 ECHE GlyP H,메틸 GlyP ECHE GlyP GlyP ECHE
17-13 ECHE POMMA H,메틸 POMMA ECHE POMMA POMMA ECHE
17-14 페닐 페닐 H,메틸 페닐 ECHE 페닐 페닐 ECHE
17-15 페닐 페닐 H,메틸 페닐 메틸 페닐 페닐 메틸
17-16 페닐 페닐 H,메틸 페닐 EGDCX 페닐 페닐 EGDCX
17-17 페닐 페닐 H,메틸 페닐 POMMA 페닐 페닐 POMMA
17-18 페닐 ECHE H,메틸 ECHE 페닐 ECHE ECHE 페닐
17-19 페닐 메틸 H,메틸 메틸 페닐 메틸 메틸 페닐
17-20 페닐 GlyP H,메틸 GlyP 페닐 GlyP GlyP 페닐
17-21 페닐 POMMA H,메틸 POMMA 페닐 POMMA POMMA 페닐
17-22 메틸 메틸 H,메틸 메틸 ECHE 메틸 메틸 ECHE
17-23 메틸 메틸 H,메틸 메틸 페닐 메틸 메틸 페닐
17-24 메틸 메틸 H,메틸 메틸 GlyP 메틸 메틸 GlyP
17-25 메틸 메틸 H,메틸 메틸 POMMA 메틸 메틸 POMMA
17-26 메틸 ECHE H,메틸 ECHE 메틸 ECHE ECHE 메틸
17-27 메틸 페닐 H,메틸 페닐 메틸 페닐 페닐 메틸
17-28 메틸 GlyP H,메틸 GlyP 메틸 GlyP GlyP 메틸
17-29 메틸 POMMA H,메틸 POMMA 메틸 POMMA POMMA 메틸
17-30 GlyP GlyP H,메틸 GlyP ECHE GlyP GlyP ECHE
17-31 GlyP GlyP H,메틸 GlyP 페닐 GlyP GlyP 페닐
17-32 GlyP GlyP H,메틸 GlyP 메틸 GlyP GlyP 메틸
17-33 GlyP GlyP H,메틸 GlyP POMMA GlyP GlyP POMMA
17-34 GlyP ECHE H,메틸 ECHE GlyP ECHE ECHE GlyP
17-35 GlyP 페닐 H,메틸 페닐 GlyP 페닐 페닐 GlyP
17-36 GlyP 메틸 H,메틸 메틸 GlyP 메틸 메틸 GlyP
17-37 GlyP POMMA H,메틸 POMMA GlyP POMMA POMMA GlyP
17-38 POMMA POMMA H,메틸 POMMA ECHE POMMA POMMA ECHE
17-39 POMMA POMMA H,메틸 POMMA 페닐 POMMA POMMA 페닐
17-40 POMMA POMMA H,메틸 POMMA 메틸 POMMA POMMA 메틸
17-41 POMMA POMMA H,메틸 POMMA GlyP POMMA POMMA GlyP
17-42 POMMA ECHE H,메틸 ECHE POMMA ECHE ECHE POMMA
17-43 POMMA 페닐 H,메틸 페닐 POMMA 페닐 페닐 POMMA
17-44 POMMA 메틸 H,메틸 메틸 POMMA 메틸 메틸 POMMA
17-45 POMMA GlyP H,메틸 GlyP POMMA GlyP GlyP POMMA
Table 17
No R16 R17 R18 R19 R20 X, R Y R Terminal R of E
17-1 ECHE ECHE H, methyl ECHE ECHE ECHE ECHE ECHE
17-2 Phenyl Phenyl H, methyl Phenyl Phenyl Phenyl Phenyl Phenyl
17-3 methyl methyl H, methyl methyl methyl methyl methyl methyl
17-4 GlyP EGCDX H, methyl EGCDX GlyP EGCDX EGCDX GlyP
17-5 POMMA POMMA H, methyl POMMA POMMA POMMA POMMA POMMA
17-6 ECHE ECHE H, methyl ECHE Phenyl ECHE ECHE Phenyl
17-7 ECHE ECHE H, methyl ECHE methyl ECHE ECHE methyl
17-8 ECHE ECHE H, methyl ECHE GlyP ECHE ECHE GlyP
17-9 ECHE ECHE H, methyl ECHE POMMA ECHE ECHE POMMA
17-10 ECHE Phenyl H, methyl Phenyl ECHE Phenyl Phenyl ECHE
17-11 ECHE methyl H, methyl methyl ECHE methyl methyl ECHE
17-12 ECHE GlyP H, methyl GlyP ECHE GlyP GlyP ECHE
17-13 ECHE POMMA H, methyl POMMA ECHE POMMA POMMA ECHE
17-14 Phenyl Phenyl H, methyl Phenyl ECHE Phenyl Phenyl ECHE
17-15 Phenyl Phenyl H, methyl Phenyl methyl Phenyl Phenyl methyl
17-16 Phenyl Phenyl H, methyl Phenyl EGDCX Phenyl Phenyl EGDCX
17-17 Phenyl Phenyl H, methyl Phenyl POMMA Phenyl Phenyl POMMA
17-18 Phenyl ECHE H, methyl ECHE Phenyl ECHE ECHE Phenyl
17-19 Phenyl methyl H, methyl methyl Phenyl methyl methyl Phenyl
17-20 Phenyl GlyP H, methyl GlyP Phenyl GlyP GlyP Phenyl
17-21 Phenyl POMMA H, methyl POMMA Phenyl POMMA POMMA Phenyl
17-22 methyl methyl H, methyl methyl ECHE methyl methyl ECHE
17-23 methyl methyl H, methyl methyl Phenyl methyl methyl Phenyl
17-24 methyl methyl H, methyl methyl GlyP methyl methyl GlyP
17-25 methyl methyl H, methyl methyl POMMA methyl methyl POMMA
17-26 methyl ECHE H, methyl ECHE methyl ECHE ECHE methyl
17-27 methyl Phenyl H, methyl Phenyl methyl Phenyl Phenyl methyl
17-28 methyl GlyP H, methyl GlyP methyl GlyP GlyP methyl
17-29 methyl POMMA H, methyl POMMA methyl POMMA POMMA methyl
17-30 GlyP GlyP H, methyl GlyP ECHE GlyP GlyP ECHE
17-31 GlyP GlyP H, methyl GlyP Phenyl GlyP GlyP Phenyl
17-32 GlyP GlyP H, methyl GlyP methyl GlyP GlyP methyl
17-33 GlyP GlyP H, methyl GlyP POMMA GlyP GlyP POMMA
17-34 GlyP ECHE H, methyl ECHE GlyP ECHE ECHE GlyP
17-35 GlyP Phenyl H, methyl Phenyl GlyP Phenyl Phenyl GlyP
17-36 GlyP methyl H, methyl methyl GlyP methyl methyl GlyP
17-37 GlyP POMMA H, methyl POMMA GlyP POMMA POMMA GlyP
17-38 POMMA POMMA H, methyl POMMA ECHE POMMA POMMA ECHE
17-39 POMMA POMMA H, methyl POMMA Phenyl POMMA POMMA Phenyl
17-40 POMMA POMMA H, methyl POMMA methyl POMMA POMMA methyl
17-41 POMMA POMMA H, methyl POMMA GlyP POMMA POMMA GlyP
17-42 POMMA ECHE H, methyl ECHE POMMA ECHE ECHE POMMA
17-43 POMMA Phenyl H, methyl Phenyl POMMA Phenyl Phenyl POMMA
17-44 POMMA methyl H, methyl methyl POMMA methyl methyl POMMA
17-45 POMMA GlyP H, methyl GlyP POMMA GlyP GlyP POMMA
표 18
No R16 R17 R18 R19 R20 X의 R Y의 R E의 말단 R
18-1 ECHE POMMA H,메틸 ECHE POMMA POMMA ECHE POMMA
18-2 페닐 POMMA H,에틸 페닐 POMMA POMMA 페닐 POMMA
18-3 POMMA ECHE H,아세틸틸 메틸 ECHE ECHE 메틸 ECHE
18-4 메틸 ECHE 비닐,메틸 EGCDX ECHE ECHE EGCDX ECHE
18-5 POMMA F H,메틸 POMMA F F POMMA F
18-6 프로필 아미노프로필 CF3,메틸 ECHE 아미노프로필 아미노프로필 ECHE 아미노프로필
18-7 페닐 페닐 H,메틸 ECHE 페닐 페닐 ECHE 페닐
18-8 메틸 알킬사이올 H,아세틸틸 ECHE 알킬사이올 알킬사이올 ECHE 알킬사이올
18-9 GlyP 페닐 비닐,메틸 ECHE 페닐 페닐 ECHE 페닐
18-10 ECHE 옥틸 H,메틸 페닐 옥틸 옥틸 페닐 옥틸
18-11 알킬사이올 메틸 H,메틸 메틸 메틸 메틸 메틸 메틸
18-12 페닐 옥틸 비닐,메틸 GlyP 옥틸 옥틸 GlyP 옥틸
18-13 옥틸 옥틸 H,메틸 POMMA 옥틸 옥틸 POMMA 옥틸
18-14 메틸 메틸 H, F 페닐 메틸 메틸 페닐 메틸
18-15 옥틸 GlyP CF3,메틸 페닐 ECHE GlyP 페닐 ECHE
18-16 옥틸 GlyP 비닐,메틸 페닐 페닐 GlyP 페닐 페닐
18-17 메틸 아미노프로필 H,메틸 페닐 POMMA 아미노프로필 페닐 POMMA
18-18 GlyP GlyP H, F ECHE 메틸 GlyP ECHE 메틸
18-19 GlyP POMMA CF3,메틸 메틸 POMMA POMMA 메틸 POMMA
18-20 아미노프로필 메틸 H,메틸 GlyP 프로필 메틸 GlyP 프로필
18-21 GlyP POMMA 알킬사이올,메틸 POMMA 페닐 POMMA POMMA 페닐
18-22 POMMA 프로필 H,아세틸틸 메틸 메틸 프로필 메틸 메틸
18-23 POMMA 메틸 비닐,메틸 메틸 GlyP 메틸 메틸 GlyP
18-24 GlyP GlyP 비닐,메틸 메틸 ECHE GlyP 메틸 ECHE
18-25 아미노프로필 GlyP H,메틸 메틸 GlyP GlyP 메틸 GlyP
18-26 메틸 아미노프로필 H, F ECHE 아미노프로필 아미노프로필 ECHE 아미노프로필
18-27 메틸 GlyP CF3,메틸 페닐 GlyP GlyP 페닐 GlyP
18-28 메틸 옥틸 H,메틸 GlyP 옥틸 옥틸 GlyP 옥틸
18-29 메틸 메틸 H,아세틸틸 POMMA 메틸 메틸 POMMA 메틸
18-30 아미노프로필 GlyP 비닐,메틸 GlyP GlyP GlyP GlyP GlyP
18-31 GlyP GlyP H,메틸 GlyP GlyP GlyP GlyP GlyP
18-32 POMMA 아미노프로필 H,메틸 GlyP 아미노프로필 아미노프로필 GlyP 아미노프로필
18-33 메틸 GlyP 비닐,메틸 GlyP GlyP GlyP GlyP GlyP
18-34 POMMA POMMA H,메틸 ECHE POMMA POMMA ECHE POMMA
18-35 프로필 POMMA H, F 페닐 POMMA POMMA 페닐 POMMA
18-36 메틸 GlyP CF3,메틸 메틸 GlyP GlyP 메틸 GlyP
18-37 GlyP 아미노프로필 비닐,메틸 POMMA 아미노프로필 아미노프로필 POMMA 아미노프로필
18-38 GlyP 메틸 H,메틸 POMMA 메틸 메틸 POMMA 메틸
18-39 아미노프로필 메틸 H, F POMMA 메틸 메틸 POMMA 메틸
18-40 아미노프로필 메틸 CF3,메틸 POMMA 메틸 메틸 POMMA 메틸
18-41 GlyP 메틸 H,메틸 POMMA 메틸 메틸 POMMA 메틸
18-42 POMMA GlyP 알킬사이올,메틸 ECHE GlyP GlyP ECHE GlyP
18-43 POMMA 아미노프로필 H,아세틸틸 페닐 아미노프로필 아미노프로필 페닐 아미노프로필
18-44 POMMA GlyP 비닐,메틸 메틸 GlyP GlyP 메틸 GlyP
18-45 POMMA POMMA H,메틸 GlyP POMMA POMMA GlyP POMMA
Table 18
No R16 R17 R18 R19 R20 X, R Y R Terminal R of E
18-1 ECHE POMMA H, methyl ECHE POMMA POMMA ECHE POMMA
18-2 Phenyl POMMA H, ethyl Phenyl POMMA POMMA Phenyl POMMA
18-3 POMMA ECHE H, acetyltyl methyl ECHE ECHE methyl ECHE
18-4 methyl ECHE Vinyl, methyl EGCDX ECHE ECHE EGCDX ECHE
18-5 POMMA F H, methyl POMMA F F POMMA F
18-6 profile Aminopropyl CF 3 , methyl ECHE Aminopropyl Aminopropyl ECHE Aminopropyl
18-7 Phenyl Phenyl H, methyl ECHE Phenyl Phenyl ECHE Phenyl
18-8 methyl Alkyl siol H, acetyltyl ECHE Alkyl siol Alkyl siol ECHE Alkyl siol
18-9 GlyP Phenyl Vinyl, methyl ECHE Phenyl Phenyl ECHE Phenyl
18-10 ECHE Octyl H, methyl Phenyl Octyl Octyl Phenyl Octyl
18-11 Alkyl siol methyl H, methyl methyl methyl methyl methyl methyl
18-12 Phenyl Octyl Vinyl, methyl GlyP Octyl Octyl GlyP Octyl
18-13 Octyl Octyl H, methyl POMMA Octyl Octyl POMMA Octyl
18-14 methyl methyl H, F Phenyl methyl methyl Phenyl methyl
18-15 Octyl GlyP CF 3 , methyl Phenyl ECHE GlyP Phenyl ECHE
18-16 Octyl GlyP Vinyl, methyl Phenyl Phenyl GlyP Phenyl Phenyl
18-17 methyl Aminopropyl H, methyl Phenyl POMMA Aminopropyl Phenyl POMMA
18-18 GlyP GlyP H, F ECHE methyl GlyP ECHE methyl
18-19 GlyP POMMA CF 3 , methyl methyl POMMA POMMA methyl POMMA
18-20 Aminopropyl methyl H, methyl GlyP profile methyl GlyP profile
18-21 GlyP POMMA Alkyl siol, methyl POMMA Phenyl POMMA POMMA Phenyl
18-22 POMMA profile H, acetyltyl methyl methyl profile methyl methyl
18-23 POMMA methyl Vinyl, methyl methyl GlyP methyl methyl GlyP
18-24 GlyP GlyP Vinyl, methyl methyl ECHE GlyP methyl ECHE
18-25 Aminopropyl GlyP H, methyl methyl GlyP GlyP methyl GlyP
18-26 methyl Aminopropyl H, F ECHE Aminopropyl Aminopropyl ECHE Aminopropyl
18-27 methyl GlyP CF 3 , methyl Phenyl GlyP GlyP Phenyl GlyP
18-28 methyl Octyl H, methyl GlyP Octyl Octyl GlyP Octyl
18-29 methyl methyl H, acetyltyl POMMA methyl methyl POMMA methyl
18-30 Aminopropyl GlyP Vinyl, methyl GlyP GlyP GlyP GlyP GlyP
18-31 GlyP GlyP H, methyl GlyP GlyP GlyP GlyP GlyP
18-32 POMMA Aminopropyl H, methyl GlyP Aminopropyl Aminopropyl GlyP Aminopropyl
18-33 methyl GlyP Vinyl, methyl GlyP GlyP GlyP GlyP GlyP
18-34 POMMA POMMA H, methyl ECHE POMMA POMMA ECHE POMMA
18-35 profile POMMA H, F Phenyl POMMA POMMA Phenyl POMMA
18-36 methyl GlyP CF 3 , methyl methyl GlyP GlyP methyl GlyP
18-37 GlyP Aminopropyl Vinyl, methyl POMMA Aminopropyl Aminopropyl POMMA Aminopropyl
18-38 GlyP methyl H, methyl POMMA methyl methyl POMMA methyl
18-39 Aminopropyl methyl H, F POMMA methyl methyl POMMA methyl
18-40 Aminopropyl methyl CF 3 , methyl POMMA methyl methyl POMMA methyl
18-41 GlyP methyl H, methyl POMMA methyl methyl POMMA methyl
18-42 POMMA GlyP Alkyl siol, methyl ECHE GlyP GlyP ECHE GlyP
18-43 POMMA Aminopropyl H, acetyltyl Phenyl Aminopropyl Aminopropyl Phenyl Aminopropyl
18-44 POMMA GlyP Vinyl, methyl methyl GlyP GlyP methyl GlyP
18-45 POMMA POMMA H, methyl GlyP POMMA POMMA GlyP POMMA
본 발명의 상기 실세스퀴옥산 복합 고분자는 우수한 보관 안정성을 확보하여 폭넓은 응용성을 얻기 위해, 축합도가 1 내지 99.9% 이상으로 조절될 수 있다. 즉, 말단 및 중앙의 Si에 결합된 알콕시 그룹의 함량이 전체 고분자의 결합기에 대해 50%에서 0.01%까지 조절될 수 있다.The silsesquioxane composite polymer of the present invention may be adjusted to 1 to 99.9% or more in order to secure excellent storage stability to obtain a wide range of applications. That is, the content of alkoxy groups bonded to Si at the terminal and center can be controlled from 50% to 0.01% with respect to the bonding groups of the entire polymer.
또한 본 발명에 실세스퀴옥산 복합 고분자의 중량평균분자량은 1,000 내지 1,000,000, 바람직하게는 5,000 내지 100,000이며, 더욱 바람직하게는 7,000 내지 50,000일 수 있다. 이 경우 실세스퀴옥산의 가공성 및 물리적 특성을 동시에 향상시킬 수 있다.In addition, the weight average molecular weight of the silsesquioxane composite polymer according to the present invention may be 1,000 to 1,000,000, preferably 5,000 to 100,000, and more preferably 7,000 to 50,000. In this case, the processability and physical properties of the silsesquioxane can be improved simultaneously.
본 발명에서 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물은 2종 이상의 복합 고분자를 사용하는 것도 가능하며, 바람직하기로는 화학식 3 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 사용하는 것이 좋다. 이 경우 반복단위 [B]b 또는 [E]e를 포함함으로써 표면경도를 포함한 투명기판의 물성을 더욱 향상시킬 수 있다.In the present invention, the coating composition including the silsesquioxane composite polymer represented by any one of Formulas 1 to 9 may use two or more composite polymers, and preferably, the yarn represented by any one of Formulas 3 to 9 It is preferable to use sesquioxane composite polymer. In this case, the physical properties of the transparent substrate including the surface hardness can be further improved by including the repeating unit [B] b or [E] e.
본 발명에서 상기 코팅조성물은 실세스퀴옥산 복합 고분자가 액상인 경우 무용제 타입으로 단독으로 코팅이 가능하며, 고상인 경우 유기용매를 포함하여 구성될 수 있다. 또한 코팅 조성물은 개시제 또는 경화제를 더욱 포함할 수 있다.In the present invention, the coating composition may be coated alone as a solventless type when the silsesquioxane composite polymer is in a liquid state, and may include an organic solvent in the case of a solid phase. In addition, the coating composition may further include an initiator or a curing agent.
바람직하기로 상기 코팅조성물은 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자, 상기 복합 고분자와 상용성이 있는 당분야에서 통상적으로 사용하는 유기용매, 개시제를 포함하는 것을 특징으로 하며, 선택적으로 경화제, 가소제, 자외선 차단제, 기타 기능성 첨가제 등의 첨가제를 추가로 포함하여 경화성, 내열특성, 자외선차단, 가소 효과 등을 향상시킬 수 있다.Preferably, the coating composition is characterized in that it comprises a silsesquioxane composite polymer represented by any one of Formulas 1 to 9, an organic solvent commonly used in the art that is compatible with the composite polymer, the initiator It may optionally further include additives such as hardeners, plasticizers, sunscreens, and other functional additives to improve curability, heat resistance, UV protection, plasticizing effects and the like.
본 발명의 코팅 조성물에 있어서 상기 실세스퀴옥산 복합 고분자는 코팅 조성물 100 중량부에 대하여 적어도 5 중량부 이상으로 포함되는 것이 좋으며, 바람직하게는 5 내지 90 중량부, 더욱 바람직하게는 10 내지 50 중량부의 양으로 포함되는 것이 바람직하다. 상기 범위 내인 경우 코팅 조성물의 경화막의 기계적 물성을 더욱 향상시킬 수 있다.In the coating composition of the present invention, the silsesquioxane composite polymer may be included at least 5 parts by weight or more, based on 100 parts by weight of the coating composition, preferably 5 to 90 parts by weight, more preferably 10 to 50 parts by weight. It is preferably included in negative amounts. If within the above range can further improve the mechanical properties of the cured film of the coating composition.
상기 유기용매로는 메틸알콜, 에틸알콜, 이소프로필알콜, 부틸알콜, 셀로솔브계 등의 알코올류, 락테이트계, 아세톤, 메틸(아이소부틸)에틸케톤 등의 케톤류, 에틸렌글리콜 등의 글리콜 류, 테트라하이드로퓨란 등의 퓨란계, 디메틸포름아미드, 디메틸아세트아미드, N-메틸-2-피롤리돈 등의 극성용매 뿐 아니라, 헥산, 사이클로헥산, 사이클로헥사논, 톨루엔, 자일렌, 크레졸, 클로로포름, 디클로로벤젠, 디메틸벤젠, 트리메틸벤젠, 피리딘, 메틸나프탈렌, 니트로메탄, 아크로니트릴, 메틸렌클로라이드, 옥타데실아민, 아닐린, 디메틸설폭사이드, 벤질알콜 등 다양한 용매를 이용할 수 있으나, 이에 제한되지는 않는다. 상기 유기용매의 양은 복합고분자, 개시제, 및 선택적으로 추가되는 첨가제를 제외한 잔량으로 포함된다.Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol and cellosolve, ketones such as lactate, acetone and methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol, In addition to polar solvents such as furan-based compounds such as tetrahydrofuran, dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone, hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, Dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acronitrile, methylene chloride, octadecylamine, aniline, dimethylsulfoxide, benzyl alcohol can be used, but is not limited thereto. The amount of the organic solvent is included in the remaining amount excluding the composite polymer, the initiator, and optionally added additives.
또한 본 발명의 코팅 조성물에 있어서 상기 개시제 또는 경화제는 실세스퀴옥산 복합 고분자에 포함된 유기관능기에 따라 적절히 선택하여 사용할 수 있다.In the coating composition of the present invention, the initiator or the curing agent may be appropriately selected and used according to the organic functional group contained in the silsesquioxane composite polymer.
구체적인 예로서 상기 유기관능기에 불포화 탄화수소, 사이올계, 에폭시계, 아민계, 이소시아네이트계 등의 후경화가 가능한 유기계가 도입될 경우, 열 또는 광을 이용한 다양한 경화가 가능하다. 이때 열 또는 광에 의한 변화를 고분자 자체 내에서 도모할 수 있지만, 바람직하게는 상기와 같은 유기용매에 희석함으로써 경화공정을 도모할 수 있다. As a specific example, when an organic system capable of post-curing such as an unsaturated hydrocarbon, a siol system, an epoxy system, an amine system, or an isocyanate group is introduced into the organic functional group, various curing using heat or light is possible. At this time, the change due to heat or light can be achieved in the polymer itself, but preferably, the curing step can be achieved by diluting with an organic solvent as described above.
또한 본 발명에서는 복합 고분자의 경화 및 후 반응을 위하여, 다양한 개시제를 사용할 수 있으며, 상기 개시제는 조성물 총중량 100 중량부에 대하여 0.1-20 중량부로 포함되는 것이 바람직하며, 상기 범위 내의 함량으로 포함될 때, 경화 후 투과도 및 코팅안정성을 동시에 만족시킬 수 있다.In addition, in the present invention, for curing and post-reaction of the composite polymer, various initiators may be used, and the initiator may be included in an amount of 0.1-20 parts by weight based on 100 parts by weight of the total composition, and when included in an amount within the above range, After curing, the transmittance and coating stability can be satisfied at the same time.
또한 상기 유기관능기에 불포화 탄화수소 등이 도입될 경우에는 라디칼 개시제를 사용할 수 있으며, 상기 라디칼 개시제로는 트리클로로 아세토페논(trichloro acetophenone), 디에톡시 아세토페논(diethoxy acetophenone), 1-페닐-2-히드록시-2-메틸프로판-1-온(1-phenyl-2-hydroxyl-2-methylpropane-1-one), 1-히드록시사이클로헥실페닐케톤, 2-메틸-1-(4-메틸 티오페닐)-2-모르폴리노프로판-1-온(2-methyl-1-(4-methyl thiophenyl)-2-morpholinopropane-1-one), 2,4,6-트리메틸 벤조일 디페닐포스핀 옥사이드(trimethyl benzoyl diphenylphosphine oxide), 캠퍼 퀴논(camphor quinine), 2,2'-아조비스(2-메틸부티로니트릴), 디메틸-2,2'-아조비스(2-메틸 부틸레이트), 3,3-디메틸-4-메톡시-벤조페논, p-메톡시벤조페논, 2,2-디에톡시 아세토페논, 2,2-디메톡시-1,2-디페닐 에탄-1-온 등의 광 래디컬 개시제, t-부틸파옥시 말레인산, t-부틸하이드로퍼옥사이드, 2,4-디클로로벤조일퍼옥사이드, 1,1-디(t-부틸퍼옥시)-3,3,5-트리메틸시클로헥산, N-부틸-4,4'-디(t-부틸퍼옥시)발레레이트 등의 열 라디칼 개시제 및 이들의 다양한 혼합물 등이 사용될 수 있다. In addition, when an unsaturated hydrocarbon or the like is introduced into the organic functional group, a radical initiator may be used, and the radical initiator may include trichloro acetophenone, diethoxy acetophenone, and 1-phenyl-2-hydride. Hydroxy-2-methylpropane-1-one (1-phenyl-2-hydroxyl-2-methylpropane-1-one), 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methyl thiophenyl) 2-morpholinopropane-1-one (2-methyl-1- (4-methyl thiophenyl) -2-morpholinopropane-1-one), 2,4,6-trimethyl benzoyl diphenylphosphine oxide (trimethyl benzoyl diphenylphosphine oxide, camphor quinine, 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobis (2-methyl butyrate), 3,3-dimethyl- Optical radical initiators such as 4-methoxy-benzophenone, p-methoxybenzophenone, 2,2-diethoxy acetophenone, 2,2-dimethoxy-1,2-diphenyl ethan-1-one, t- Butylpaoxy maleic acid, t-butyl Iroperoxide, 2,4-dichlorobenzoylperoxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, N-butyl-4,4'-di (t-butyl Thermal radical initiators such as peroxy) valerate and various mixtures thereof and the like can be used.
또한, 상기 유기관능기에 에폭시 등이 포함되는 경우에는, 광중합 개시제(양이온)로서 트리페닐술포늄, 디페닐-4-(페닐티오)페닐술포늄 등의 술포늄계, 디페닐요오드늄이나 비스(도데실페닐)요오드늄 등의 요오드늄, 페닐디아조늄 등의 디아조늄, 1-벤질-2-시아노피리니늄이나 1-(나프틸메틸)-2-시아노프리디늄 등의 암모늄, (4-메틸페닐)[4-(2-메틸프로필)페닐]-헥사플루오로포스페이트 요오드늄, 비스(4-t-부틸페닐)헥사플루오로포스페이트 요오드늄, 디페닐헥사플루오로포스페이트 요오드늄, 디페닐트리플루오로메탄술포네이트 요오드늄, 트리페닐술포늄 테트라풀루오로보레이트, 트리-p-토일술포늄 헥사풀루오로포스페이트, 트리-p-토일술포늄 트리풀루오로메탄술포네이트 및 (2,4-시클로펜타디엔-1-일)[(1-메틸에틸)벤젠]-Fe 등의 Fe 양이온들과 BF4 -, PF6 -, SbF6 - 등의 [BQ4]- 오늄염 조합을 이용할 수 있다(여기서, Q는 적어도 2개 이상의 불소 또는 트리플루오로메틸기로 치환된 페닐기이다.). When the organic functional group contains an epoxy or the like, sulfoniums such as triphenylsulfonium and diphenyl-4- (phenylthio) phenylsulfonium, diphenyliodonium and bis (dode) are used as photopolymerization initiators (cations). Iodonium, such as silphenyl) iodonium, diazonium, such as phenyldiazonium, ammonium, such as 1-benzyl-2-cyanopyridinium and 1- (naphthylmethyl) -2-cyanofridinium, (4- Methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate iodonium, bis (4-t-butylphenyl) hexafluorophosphate iodonium, diphenylhexafluorophosphate iodonium, diphenyltrifluoro Romethanesulfonate iodonium, triphenylsulfonium tetrafuluroborate, tri-p-toylsulfonium hexafulurophosphate, tri-p-toylsulfonium trifluoromethanesulfonate and (2,4- cyclopentadiene-1-yl) s Fe cations such as [(1-methylethyl) benzene] -Fe and BF 4 -, PF 6 -, SbF 6 - [BQ 4 ] , such as-may be used in combination with onium salts (here, Q is a phenyl group substituted with at least a group of two or more fluorine or a trifluoromethyl group.).
또한, 열에 의해 작용하는 양이온 개시제로는 트리플산염, 3불화 붕소 에테르착화합물, 3불화 붕소 등과 같은 양이온계 또는 프로톤산 촉매, 암모늄염, 포스포늄염 및 술포늄염 등의 각종 오늄염 및 메틸트리페닐포스포늄 브롬화물, 에틸트리페닐포스포늄 브롬화물, 페닐트리페닐포스포늄 브롬화물 등을 제한 없이 사용할 수 있으며, 이들 개시제 또한 다양한 혼합형태로 첨가할 수 있으며, 상기에 명시한 다양한 라디칼 개시제들과의 혼용도 가능하다. In addition, the cationic initiators acting by heat include cationic or protonic acid catalysts such as triflate, boron trifluoride ether complex, boron trifluoride, etc. Bromide, ethyltriphenylphosphonium bromide, phenyltriphenylphosphonium bromide and the like can be used without limitation, and these initiators can also be added in various mixed forms, and can be mixed with the various radical initiators specified above. Do.
또한, 상기 유기관능기의 종류에 따라, 아민 경화제류인 에틸렌디아민, 트리에틸렌 테트라민, 테트라에틸렌 펜타민, 1,3-디아미노프로판, 디프로필렌트리아민, 3-(2-아미노에틸)아미노-프로필아민,N,N'-비스(3-아미노프로필)-에틸렌디아민, 4,9-디옥사도테칸-1,12-디아민, 4,7,10-트리옥사트리데칸-1,13-디아민, 헥사메틸렌디아민, 2-메틸펜타메틸렌디아민, 1,3-비스아미노메틸시클로헥산, 비스(4-아니모시클로헥실)메탄, 노르보르넨디아민, 1,2-디아미노시클로헥산 등을 이용할 수 있다. Moreover, according to the kind of said organic functional group, amine diamine, ethylenediamine, triethylene tetramine, tetraethylene pentamine, 1, 3- diamino propane, dipropylene triamine, 3- (2-amino ethyl) amino-propyl Amines, N, N'-bis (3-aminopropyl) -ethylenediamine, 4,9-dioxadotecan-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine, Hexamethylenediamine, 2-methylpentamethylenediamine, 1,3-bisaminomethylcyclohexane, bis (4-animocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane and the like can be used. .
아울러, 무수프탈산, 무수트리멜리트산, 무수피로멜리트산, 무수말레산, 테트라히드로 무수프탈산, 메틸헥사히드로 무수프탈산, 메틸테트라히드로 무수프탈산, 메틸나드산 무수물, 수소화메틸나드산 무수물, 트리알킬테트라히드로 무수프탈산, 도데세닐 무수숙신산, 무수2,4-디에틸글루타르산 등의 산무수경화제류도 폭넓게 사용될 수 있다.In addition, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, methylhydride anhydride, trialkyltetra Acid anhydride hardeners, such as hydrophthalic anhydride, dodecenyl succinic anhydride, and 2, 4- diethyl glutaric anhydride, can also be used widely.
상기 경화제는 조성물 100 중량부에 대하여 0.1-20 중량부로 포함되는 것이 좋다.The hardener is preferably included in 0.1-20 parts by weight based on 100 parts by weight of the composition.
또한 상기 경화작용을 촉진하기 위한 경화 촉진제로, 아세토구아나민, 벤조구아나민, 2,4-디아미노-6-비닐-s-트리아진 등의 트리아진계 화합물, 이미다졸, 2-메틸이미다졸, 2-에틸-4-메틸이미다졸, 2-페닐이미다졸, 2-페닐-4-메틸이미다졸, 비닐이미다졸, 1-메틸이미다졸 등의 이미다졸계 화합물, 1,5-디아자비시클로[4.3.0]논엔-5,1,8-디아자비시클로[5.4.0]운데센-7, 트리페닐포스핀, 디페닐(p-트릴)포스핀, 트리스(알킬페닐)포스핀, 트리스(알콕시페닐)포스핀, 에틸트리페닐포스포늄포스페이트, 테트라부틸포스포늄히드록시드, 테트라부틸포스포늄아세테이트, 테트라부틸포스포늄하이드로젠디플루오라이드, 테트라부틸포스포늄디하이드로젠트리플루오르 등도 사용될 수 있다.In addition, as a curing accelerator for promoting the curing action, triazine-based compounds such as acetoguanamine, benzoguanamine, 2,4-diamino-6-vinyl-s-triazine, imidazole, 2-methylimidazole Imidazole compounds such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, vinylimidazole, and 1-methylimidazole, 1, 5-diazabicyclo [4.3.0] nonene-5,1,8-diazabicyclo [5.4.0] undecene-7, triphenylphosphine, diphenyl (p-tril) phosphine, tris (alkylphenyl Phosphine, tris (alkoxyphenyl) phosphine, ethyltriphenylphosphonium phosphate, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate, tetrabutylphosphonium hydrogendifluoride, tetrabutylphosphonium dihydrogen tree Fluorine and the like can also be used.
또한 상기 코팅조성물은 안료를 더욱 포함할 수 있다. 본 발명의 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자는 안료의 분산성을 향상시키고, 안료와의 상용성이 우수하여 안료를 포함할 경우 우수한 착색효과를 가지게 할 수 있다. 상기 안료는 공지의 안료가 사용될 수 있음을 물론이며, 안료의 함량은 당업자가 적절한 범위에서 선택하여 사용할 수 있다.In addition, the coating composition may further include a pigment. The silsesquioxane composite polymer represented by any one of Chemical Formulas 1 to 9 of the present invention may improve dispersibility of the pigment and have excellent compatibility with the pigment, and thus may have an excellent coloring effect. Of course, the pigment may be a well-known pigment can be used, the content of the pigment can be selected and used by those skilled in the art in the appropriate range.
본 발명에서는 또한 경화공정 또는 후반응을 통한 경도, 강도, 내구성, 성형성 등을 개선하는 목적으로 자외선 흡수제, 산화 방지제, 소포제, 레벨링제, 발수제, 난연제, 접착개선제 등의 첨가제를 추가로 포함할 수 있다. 이러한 첨가제는 그 사용에 있어 특별하게 제한은 없으나 기판의 특성 즉, 유연성, 투광성, 내열성, 경도, 강도 등의 물성을 해치지 않는 범위 내에서 적절히 첨가할 수 있다. 상기 첨가제는 각각 독립적으로 조성물 100 중량부에 대하여 0.01-10 중량부로 포함되는 것이 좋다.The present invention may further include additives such as UV absorbers, antioxidants, antifoaming agents, leveling agents, water repellents, flame retardants, and adhesion improving agents for the purpose of improving hardness, strength, durability, formability, etc. through a curing process or a post reaction. Can be. Such additives are not particularly limited in use, but may be appropriately added within a range that does not impair the properties of the substrate, that is, properties such as flexibility, light transmittance, heat resistance, hardness, and strength. Each of the additives is preferably included in an amount of 0.01-10 parts by weight based on 100 parts by weight of the composition.
본 발명에서 사용가능한 첨가제로는 폴리에테르 디메틸폴리실록산계 (Polyether-modified polydimethylsiloxane, 예를 들어, BYK 사 제품인 BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK-306, BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310 등), 폴리에테르 하이드록시 폴리디메틸실록산계 (Polyether modified hydroxyfunctional poly-dimethyl-siloxane, 예를 들어, BYK 사의 BYK-308, BYK-373 등), 폴리메틸알킬실록산계 (Methylalkylpolysiloxane, 예를 들어, BYK-077, BYK-085 등), 폴리에테르 폴리메틸알킬실록산계 (Polyether modified methylalkylpolysiloxane, 예를 들어, BYK-320, BYK-325 등), 폴리에스테르 폴리메틸알킬실록산계 (Polyester modified poly-methyl-alkyl-siloxane, 예를 들어, BYK-315 등), 알랄킬 폴리메틸알킬실록산계 (Aralkyl modified methylalkyl polysiloxane, 예를 들어, BYK-322, BYK-323 등), 폴리에스테르 하이드록시 폴리디메틸실록산계 (Polyester modified hydroxy functional polydimethylsiloxane, 예를 들어, BYK-370 등), 폴리에스테르 아크릴 폴리디메틸실록산계 (Acrylic functional polyester modified polydimethylsiloxane, 예를 들어, BYK-371, BYK-UV 3570 등), 폴리에테르-폴리에스테르 하이드록시 폴리디메틸실록산계 (Polyeher-polyester modified hydroxy functional polydimethylsiloxane, 예를 들어, BYK-375 등), 폴리에테르 폴리디메틸실록산계 (Polyether modified dimethylpolysiloxane, 예를 들어, BYK-345, BYK-348, BYK-346, BYK-UV3510, BYK-332, BYK-337 등), 비이온 폴리아크릴계 (Non-ionic acrylic copolymer, 예를 들어, BYK-380 등), 이온성 폴리아크릴계 (Ionic acrylic copolymer, 예를 들어, BYK-381 등), 폴리아크릴레이트계 (Polyacrylate, 예를 들어, BYK-353, BYK-356, BYK-354, BYK-355, BYK-359, BYK-361 N, BYK-357, BYK-358 N, BYK-352 등), 폴리메타아크릴레이트계 (Polymethacrylate, 예를 들어, BYK-390 등), 폴리에테르 아크릴 폴리디메틸실록산계 (Polyether modified acryl functional polydimethylsiloxane, 예를 들어, BYK-UV 3500, BYK-UV3530 등), 폴리에테르 실록산계 (Polyether modified siloxane, 예를 들어, BYK-347 등), 알코올 알콕시레이트계 (Alcohol alkoxylates, 예를 들어, BYK-DYNWET 800 등), 아크릴레이트계 (Acrylate, 예를 들어, BYK-392 등), 하이드록시 실리콘 폴리아크릴레이트계 (Silicone modified polyacrylate (OH-functional), 예를 들어, BYK-Silclean 3700 등) 등을 들 수 있다.Additives usable in the present invention include polyether-modified polydimethylsiloxane (eg, BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK-306, BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310, etc.), polyether hydroxy polydimethylsiloxanes (e.g., manufactured by BYK BYK-308, BYK-373, etc.), polymethylalkylsiloxane (e.g., BYK-077, BYK-085, etc.), polyether polymethylalkylsiloxane (e.g., BYK- 320, BYK-325, etc.), polyester modified poly-methyl-alkyl-siloxane (e.g., BYK-315, etc.), allylalkyl polymethylalkylsiloxane (aralkyl modified methylalkyl polysiloxane, e.g. For example, BYK-322, BYK-323, etc.), polyester hydroxy polydimethylsiloxane (Polyester modified hydroxy functional polydimethylsiloxane, such as BYK-370), polyester acrylic polydimethylsiloxane (Acrylic functional polyester modified polydimethylsiloxane, such as BYK-371, BYK-UV 3570, etc.), polyether-polyester hydroxy Polyeher-polyester modified hydroxy functional polydimethylsiloxane (e.g., BYK-375, etc.), polyether polydimethylsiloxane (e.g., BYK-345, BYK-348, BYK-346) , BYK-UV3510, BYK-332, BYK-337, etc.), nonionic polyacrylic (Non-ionic acrylic copolymer, such as BYK-380, etc.), Ionic acrylic copolymer (eg, BYK -381, etc.), polyacrylates (e.g., BYK-353, BYK-356, BYK-354, BYK-355, BYK-359, BYK-361 N, BYK-357, BYK-358 N, BYK-352 etc.), polymethacrylate type (Polymethacrylate, for example, BYK-390 etc.), polyether Polyether modified acryl functional polydimethylsiloxane (eg, BYK-UV 3500, BYK-UV3530, etc.), polyether siloxane (polyether modified siloxane, eg, BYK-347, etc.), alcohol alkoxylates (Alcohol alkoxylates, eg BYK-DYNWET 800, etc.), acrylates (Acrylate, eg, BYK-392, etc.), hydroxy silicone polyacrylates (Silicone modified polyacrylate (OH-functional), eg BYK-Silclean 3700, etc. are mentioned, for example.
본 발명에서 상기 기재로는 휨현상이 발생하는 통상의 기재를 모두 포함하며, 구체적인 일예로 재질로는 플라스틱, 유리, 금속박막, 목재 또는 펄프를 들 수 있으며, 특히 플라스틱의 경우 폴리에틸렌(polyethylene, PE), 폴리프로필렌(polypropylene, PP), 폴리스타이렌(polystyrene, PS), 폴리에틸렌 테레프탈레이트(polyethylene terephthalate, PET, 페트), 폴리아미드(polyamides, PA), 폴리에스터(polyester, PES), 폴리염화비닐(polyvinyl chloride, PVC), 폴리우레탄(polyurethanes, PU), 폴리카보네이트(polycarbonate, PC), 고경도 폴리카보네이트(고경도 PC), 폴리염화비닐리덴(polyvinylidene chloride, PVDC), 폴리테트라플루오로에틸렌(polytetrafluoroethylene,PTFE),폴리에테르에테르케톤(polyetheretherketone, PEEK), 에폭시(epoxy), 폴리아크릴로니트릴(polyacrylonitrile, PAN), 실리콘 폴리머(silicon polymer), 폴리에틸렌옥사이드(polyethylen oxide, PEO), 폴리메틸렌옥사이드(polymethylen oxide, PMO), 폴리이미드(polyimide, PI), 바이오 플라스틱, 및 폴리에테르이미드(polyetherimide, PEI), 아크릴 등과 같이 단일 플라스틱 재질뿐만 아니라 2종 이상의 플라스틱 재료가 혼합된 것일 수 있으며, 플라스틱과 유리섬유 또는 탄소섬유와 같은 무기섬유가 혼합된 복합플라스틱일 수도 있으며, 상기 목재는 목재로 구성된 것이면 특별히 한정되지 않으며, 천연목재 뿐만 아니라 합판 및 섬유판(MDF 포함) 등을 모두 포함하며, 상기 펄프(pulp)는 목재나 그 밖의 섬유 식물에서 기계적화학적 또는 그 중간 방법에 의하여 얻는 셀룰로오스 섬유의 집합체로, 원래는 많은 수분을 포함하고 있어서 죽 모양으로 되어 있거나, 압착 등의 방법에 의하여 탈수한 습윤물(濕潤物)을 의미하며, 일반적으로 펄프의 원료로는 솜 같은 종모섬유(種毛纖維)와 대나무짚에스파르토버개스 등과 같은 벼과식물의 줄기, 마닐라삼의 줄기, 대마아마닥삼아안피 등의 나무껍질[靭皮部]을 들 수 있으나 이에 한정되는 것은 아니며, 한지(수록지, 기계지 포함)와 양지(종이, 판지 포함) 등의 종이를 포함한다.In the present invention, the base material includes all of the conventional base materials in which warpage occurs, and concrete examples thereof include plastic, glass, metal thin film, wood, or pulp, and in particular, plastic (polyethylene, PE) , Polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET, PET), polyamides (PA), polyester (PES), polyvinyl chloride , PVC), polyurethane (PU), polycarbonate (PC), high hardness polycarbonate (PC), polyvinylidene chloride (PVDC), polytetrafluoroethylene (PTFE) ), Polyetheretherketone (PEEK), epoxy, polyacrylonitrile (PAN), silicone polymer, polyethylene oxide (pol) two or more plastic materials as well as a single plastic material such as yethylen oxide (PEO), polymethylen oxide (PMO), polyimide (PI), bioplastics, and polyetherimide (PEI), acrylic May be mixed, and may be a composite plastic mixed with plastic and inorganic fibers such as glass fiber or carbon fiber, and the wood is not particularly limited as long as it is composed of wood, as well as natural wood, plywood and fiberboard (including MDF) The pulp (pulp) is a collection of cellulose fibers obtained by mechanical and chemical or intermediate methods in wood or other fiber plants, originally containing a lot of water, and is in the form of porridge, or pressed Dehydrated by the method of means (濕潤 物), generally pulp as a raw material Bark of stems of rice plants such as fibroblasts and bamboo straw Spartogas, stems of manila ginseng, and hemp bark, etc., but are not limited thereto. It includes paper such as Korean paper (including paper and paper) and sunny paper (including paper and cardboard).
또한 상기 기재는 형태에 있어서도 용액공정을 사용하기 때문에 시트, 필름, 사출물, 조형물 및 비드를 포함하여 모든 형태의 제품에 적용될 수 있다.In addition, the substrate can be applied to all types of products, including sheets, films, injection moldings, moldings and beads because the solution process is also used in the form.
또한 구체적인 물품으로는 디스플레이의 윈도우 커버 기판, 보호필름, 보호판; 목재가구; 목재 건축 내외장제; 목재 악세서리; 목재공공시설물; 건축물 또는 구조물의 벽재, 바닥재, 타일, 지붕재, 창문; 컵, 접시, 그릇; 반도체 제조장치; 골판지 또는 종이 코팅제품; 자동차의 유리; 안경; 또는 광학제품, 전자제품, 태양전지에 사용되는 유리 등을 들 수 있으나 이에 한정되는 것은 아니다.In addition, specific articles include a window cover substrate, a protective film, a protective plate of the display; Wooden furniture; Wood building interior and exterior materials; Wood accessories; Wood public facilities; Walls, floors, tiles, roofs, windows of buildings or structures; Cups, plates, bowls; Semiconductor manufacturing apparatus; Corrugated or paper coated products; Glass of the car; glasses; Or optical products, electronic products, glass used in solar cells, and the like, but are not limited thereto.
본 발명에서 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물은 2종 이상의 복합 고분자를 사용하는 것도 가능하며, 바람직하기로는 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자에서 치환기를 달리하여 밀도가 다른 물질 합성하여 밀도가 다른 실세스퀴옥산 복합 고분자를 코팅조성물을 교차로 코팅하는 것이 좋다.In the present invention, the coating composition including the silsesquioxane composite polymer represented by any one of Formulas 1 to 9 may use two or more composite polymers, and preferably, the yarn represented by any one of Formulas 1 to 9 In the sesquioxane composite polymer, it is good to synthesize different materials with different densities by varying substituents, and coat the coating composition with the silsesquioxane composite polymer having different densities.
본 발명에서 2층 이상의 코팅층 형성을 위하여 사용되는 코팅조성물은 적어도 하나는 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물이며, 나머지 다른 코팅층(단층 또는 복수의 층일 수 있음)은 상기 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물과는 밀도가 서로 다른 코팅조성물로서 기재에 사용될 수 있는 공지의 코팅조성물이거나 또는 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물일 수 있다. 밀도가 서로 다른 코팅조성물이 기재에 코팅됨으로써 기재의 휨현상을 보정하며, 특히 적어도 한층은 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물을 사용하여 표면안정성을 높여 기재가 우수한 평탄도를 가지게 할 수 있다. 바람직하기로는 모든 코팅층이 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물을 이용하여 코팅층을 형성하는 것이 좋다.At least one coating composition used for forming two or more coating layers in the present invention is a coating composition containing a silsesquioxane composite polymer represented by any one of Formulas 1 to 9, and the other coating layer (single layer or a plurality of layers) Can be used as a coating composition having a different density from the coating composition containing the silsesquioxane composite polymer or a silsesquioxane represented by any one of Formulas 1 to 9 above. It may be a coating composition containing a composite polymer. The coating composition having different densities is coated on the substrate to correct the warpage of the substrate. In particular, at least one of the coating compositions including the silsesquioxane composite polymer may be used to increase the surface stability, thereby allowing the substrate to have excellent flatness. . Preferably, all of the coating layers may be formed using a coating composition containing the silsesquioxane composite polymer represented by any one of Formulas 1 to 9.
상기 코팅층의 층의 개수는 2층 이상으로 당업자가 적절하게 선택하여 적용될 수 있으며, 바람직하기로는 2 내지 10층이며, 더욱 바람직하기로는 2 내지 6층이다. 이 경우 생산성 및 휨현상 방지 효과를 동시에 만족시킬 수 있다. 또한 2층 이상의 코팅층은 도 2와 같이 기재의 일면에 형성될 수도 있으며, 도 3 및 4와 같이 기재의 양면에 형성될 수도 있다. 또한 도 4 및 5와 같이 3층 이상의 코팅층을 형성하는 경우 동일한 코팅 조성물로 분리된 2개층(일예로 도 4의 제1코팅층과 제3코팅층), 도 5의 제2코팅층과 제4코팅층)의 코팅층을 형성할 수 있으며, 바람직하기로 상기 코팅층의 최외각층은 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물인 것이 좋다. 이 경우 기재의 표면에 높은 표면경도, 우수한 투명성, 내스크레치성, 발수특성, 방오특성, 내지문성, 열안정성 및 광택 특성을 부여할 수 있다. 바람직하기로는 서로 다른 밀도를 가지는 코팅조성물의 고분자 밀도 차이는 0.001 g/cm3 이상인 것이 좋으며, 더욱 바람직하기로는 0.01 내지 2 g/cm3인 것이 좋다.The number of layers of the coating layer may be appropriately selected and applied by those skilled in the art as two or more layers, preferably 2 to 10 layers, and more preferably 2 to 6 layers. In this case, the productivity and the warpage prevention effect can be satisfied at the same time. In addition, two or more coating layers may be formed on one surface of the substrate as shown in FIG. 2, or may be formed on both sides of the substrate as illustrated in FIGS. 3 and 4. In addition, when forming three or more coating layers as shown in Figures 4 and 5 of the two layers separated by the same coating composition (for example, the first coating layer and the third coating layer of Figure 4), the second coating layer and the fourth coating layer of Figure 5 The coating layer may be formed, and preferably, the outermost layer of the coating layer may be a coating composition containing a silsesquioxane composite polymer. In this case, high surface hardness, excellent transparency, scratch resistance, water repellent properties, antifouling properties, anti-fingerprint properties, thermal stability, and glossiness can be imparted to the surface of the substrate. Preferably, the polymer density difference of coating compositions having different densities is preferably 0.001 g / cm 3 or more, and more preferably 0.01 to 2 g / cm 3 .
또한 본 발명에 있어서, 상기 코팅조성물을 기재의 표면 위에 코팅하는 방법은 스핀코팅, 바코팅, 슬릿코팅, 딥 코팅, 내츄럴 코팅, 리버스 코팅, 롤 코팅, 스핀코팅, 커텐코팅, 스프레이 코팅, 침지법, 함침법, 그라비어 코팅 등 공지된 방법 중에서 당업자가 임의로 선택하여 적용할 수 있음은 물론이며, 경화방법에 있어도 광경화 또는 열경화를 복합고분자의 관능기에 따라 적절하게 선택하여 적용할 수 있음은 물론이다. 바람직하기로 열경화의 경우 경화온도는 80 내지 120 이다.In addition, in the present invention, the method of coating the coating composition on the surface of the substrate is spin coating, bar coating, slit coating, dip coating, natural coating, reverse coating, roll coating, spin coating, curtain coating, spray coating, dipping method Of course, a person skilled in the art can arbitrarily select and apply a well-known method, such as a method of impregnation, gravure coating, and of course, in the curing method, the photocuring or thermal curing can be appropriately selected and applied according to the functional group of the composite polymer. to be. Preferably the curing temperature in the case of thermosetting is 80 to 120.
기재의 일면에 2층 이상의 코팅층을 형성하는 경우 하나의 코팅층을 경화공정까지 마친 상태에서 그 위에 다른 코팅층을 형성할 수 있으며, 1차 코팅조성물을 코팅하고 건조한 후, 건조된 코팅층 위에 제2 코팅조성물을 코팅하고 건조한 후 한번의 경화공정을 거쳐 2개의 코팅층을 형성할 수도 있다. In the case of forming two or more coating layers on one surface of the substrate, the other coating layer may be formed thereon while one coating layer is finished until the curing process, and after coating and drying the first coating composition, the second coating composition on the dried coating layer After coating and drying, two coating layers may be formed through one curing process.
본 발명에서 상기 코팅조성물의 코팅 두께는 임의로 조절 가능하며, 바람직하게는 0.01 내지 500 um이며, 더욱 바람직하게는 0.1 내지 300 um, 더더욱 바람직하기로는 1 내지 100 um 범위가 좋다. 특히 최외곽층의 코팅두께는 1 내지 100 um인 것이 좋다. 상기 범위 내인 경우 최외곽 표면에 7H 이상의 표면경도를 안정적으로 확보할 수 있을 뿐만 아니라 코팅 표면 특성에 있어서도 우수한 물성을 나타낸다. 특히 5 um 이상의 두께로 코팅층이 적층된 경우 코팅층의 표면경도가 9H를 안정적으로 나타낼 수 있다.In the present invention, the coating thickness of the coating composition may be arbitrarily adjusted, preferably 0.01 to 500 um, more preferably 0.1 to 300 um, still more preferably 1 to 100 um. In particular, the coating thickness of the outermost layer is preferably 1 to 100um. Within the above range, not only can the surface hardness of 7H or more be stably secured to the outermost surface, but also excellent coating properties. In particular, when the coating layer is laminated to a thickness of 5um or more, the surface hardness of the coating layer can stably exhibit 9H.
또한 본 발명은 표면 위에 밀도가 서로 다른 코팅 조성물을 코팅하여 형성된 2층 이상의 코팅층을 구비하며, 상기 코팅층 중의 적어도 하나는 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물로 형성된 것을 특징으로 하는 휨현상 방지 기재 및 이를 포함하는 물품을 제공하는 바, 상기 휨현상 방지 기재는 상기 기재의 휨현상 방지 코팅방법에 의하여 제조될 수 있다. 본 발명에 따른 휨현상 방지 기재는 100 mm × 300 mm의 기재를 기준으로 0.1 mm 이내의 평탄도를 가지며, 기재의 양면에 코팅층을 구비한 기재의 경우(도 3 및 도4) 더욱 우수한 휨현상 방지 효과를 나타낼 수 있으며, 또한 최외곽층에 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물로 코팅층을 형성한 경우 코팅층은 매우 높은 표면경도를 가지며, 우수한 투명성, 내스크레치성, 발수특성, 방오특성, 내지문성, 열안정성 및 광택특성을 가진다. In another aspect, the present invention is provided with a coating layer of two or more layers formed by coating a coating composition having a different density on the surface, at least one of the coating layer is a coating comprising a silsesquioxane composite polymer represented by any one of the formulas (1) to (9) It provides a warpage preventing substrate and an article comprising the same, characterized in that formed in the composition, the warpage preventing substrate can be prepared by the warpage preventing coating method of the substrate. The warpage preventing substrate according to the present invention has a flatness within 0.1 mm based on a 100 mm × 300 mm substrate, and in the case of a substrate having a coating layer on both sides of the substrate (FIGS. 3 and 4), the warpage prevention effect is more excellent. When the coating layer is formed of a coating composition containing a silsesquioxane composite polymer in the outermost layer, the coating layer has a very high surface hardness, excellent transparency, scratch resistance, water repellency, antifouling properties, and It has the properties of moonshine, heat stability and gloss.
본 발명에 따른 휨현상 방지 기재를 포함하는 물품은 특별히 한정되지 않으며, 구체적인 일예로 디스플레이의 윈도우 커버 기판, 보호필름, 보호판; 목재가구; 목재 건축 내외장제; 목재 악세서리; 목재공공시설물; 건축물 또는 구조물의 벽재, 바닥재, 타일, 지붕재, 창문; 컵, 접시, 그릇; 반도체 제조장치; 골판지 또는 종이 코팅제품; 자동차의 유리; 안경; 또는 광학제품, 전자제품, 태양전지에 사용되는 유리를 들 수 있다.An article including the warpage preventing substrate according to the present invention is not particularly limited, and as a specific example, a window cover substrate, a protective film, a protective plate of a display; Wooden furniture; Wood building interior and exterior materials; Wood accessories; Wood public facilities; Walls, floors, tiles, roofs, windows of buildings or structures; Cups, plates, bowls; Semiconductor manufacturing apparatus; Corrugated or paper coated products; Glass of the car; glasses; Or glass used for optical products, electronic products, and solar cells.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다. 하기 본 발명의 실시예에서 ECHETMS는 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,GPTMS는 Glycidoxypropytrimethoxysilane, MAPTMS는(methacryloyloxy)propyltrimethoxysilane,PTMS는 Phenyltrimethoxysilane, MTMS는 Methyltrimethoxysilane, ECHETMDS는 Di(epoxycyclohexyethyl) tetramethoxy disiloxane, GPTMDS는 Di(glycidoxypropyl) tetramethoxy disiloxane, MAPTMDS는 Di(methacryloyloxy)propy, PTMDS는 Di(phenyl) tetramethoxy disiloxane, MTMDS는 Di(Methyl) tetramethoxy disiloxane을 의미한다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples. In the embodiment of the present invention, ECHETMS is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, GPTMS is Glycidoxypropytrimethoxysilane, MAPTMS is (methacryloyloxy) propyltrimethoxysilane, PTMS is Phenyltrimethoxysilane, MTMS is Methyltrimethoxysilane, and ECHETMDS is Di (epoxycyclohexyethyl) Di (glycidoxypropyl) tetramethoxy disiloxane, MAPTMDS stands for Di (methacryloyloxy) propy, PTMDS stands for Di (phenyl) tetramethoxy disiloxane, and MTMDS stands for Di (Methyl) tetramethoxy disiloxane.
[실시예 1] 공중합체 1 및 9을 포함하는 코팅조성물의 제조Example 1 Preparation of a Coating Composition Comprising Copolymers 1 and 9
합성단계는 아래와 같이, 연속가수분해 및 축합을 단계적으로 진행하였다. In the synthesis step, continuous hydrolysis and condensation were carried out step by step as follows.
[실시예 1-a] 촉매의 제조Example 1-a Preparation of Catalyst
염기도 조절을 위하여, Tetramethylammonium hydroxide (TMAH) 25 중량% 수용액에 10 중량% Potassium hydroxide (KOH) 수용액을 혼합하여 촉매 1a를 준비하였다.In order to adjust the basicity, a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
[실시예 1-b] 선형 실세스퀴옥산 구조의 합성Example 1-b Synthesis of Linear Silsesquioxane Structure
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 5 중량부, 테트라하이드로퓨란 15 중량부, 상기 실시예 1-a에서 제조된 촉매 1 중량부를 적가하고, 1시간 동안 상온에서 교반 한 후, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 20중량부를 적가하고, 다시 테트라하이드로류란을 15 중량부 적가하여 5시간 추가 교반 하였다. 교반 중의 혼합용액을 적취하여, 두 차례 세정하는 것으로 촉매와 불순물을 제거하고 필터 한 후, IR 분석을 통하여 말단기에 생성된 SI-OH 관능기를 확인할 수 있었으며(3200 cm-1), 분자량을 측정한 결과, 화학식 4구조와 같은 선형구조의 실세스퀴옥산이 8,000 스티렌 환산 분자량을 가짐을 확인할 수 있었다.To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, 1 part by weight of the catalyst prepared in Example 1-a was added dropwise, followed by stirring at room temperature for 1 hour, and then 2 20 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 15 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 5 hours. The mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having the same linear structure as the chemical formula 4 had a molecular weight of 8,000 styrene.
[실시예 1-c] 연속적 cage 구조의 생성Example 1-c Generation of a continuous cage structure
상기 실시예 1-b 혼합용액에 0.36 중량% HCl 수용액을 매우 천천히 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 ℃의 온도에서 30분간 교반하였다. 이후 Diphenyltetramethoxydisiloxane 5 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하고, 1시간 교반 후 실시예 1-a에서 제조된 촉매를 7 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, 선형고분자와는 별도로 alkoxy가 열려있는 D구조의 전구체가 형성된다. 소량의 샘플을 적취하여, H-NMR과 IR로 분석하여 methoxy의 잔존율을 확인한 후, 잔존율이 20% 일 때, 0.36 중량% HCl 수용액을 10 중량부 천천히 적가하여, pH를 산성으로 조절해 주었다. 이후 Phenyltrimethoxysilane 1 중량부를 한번에 적가하여 15분간 교반 후, 1-a에서 제조된 촉매 20 중량부를 첨가하였다. 4시간의 혼합교반 이후, 확인결과 고분자내에 cage 형태의 고분자가 생성됨을 확인 할 수 있었다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여, 전체적인 반응물이 수용액 혼합물로 변환되도록 하였다. 4시간의 혼합 교반 이후, 일부를 적취하여 29Si-NMR을 통해 분석한 결과 phenyl기를 이용해 도입된 구조의 분석피크가 날카로운 형태의 2개로 나타나고 별도로 잔존하는 부산물 없이 화학식 1과 같은 A-D 고분자가 50% 이상 제조되었음을 확인할 수 있었다. 또한 스티렌 환산 분자량은 11,000으로 측정되었으며, n 값은 4-6이었다. 29Si-NMR (CDCl3)δ To the mixed solution of Example 1-b 0.36% by weight of HCl aqueous solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 ℃ 30 minutes. Thereafter, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at one time to achieve stable hydrolysis. After stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 1-a was added again to adjust the pH of the mixed solution in a basic state. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy. When the residual ratio was 20%, 10 parts by weight of 0.36 wt% HCl aqueous solution was slowly added dropwise to adjust the pH to acidic. gave. Thereafter, 1 part by weight of Phenyltrimethoxysilane was added dropwise at a time, stirred for 15 minutes, and then 20 parts by weight of the catalyst prepared in 1-a was added. After 4 hours of mixing and stirring, it was confirmed that cage type polymer was formed in the polymer. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing and agitation, a portion was collected and analyzed by 29 Si-NMR. As a result, analytical peaks of the structure introduced by using a phenyl group appeared as two sharp forms, and 50% of the AD polymer of Formula 1 without remaining by-products remained. It was confirmed that the above was manufactured. In addition, the styrene reduced molecular weight was measured to 11,000, n value was 4-6. 29 Si-NMR (CDCl 3 ) δ
[실시예 1-d] 광경화형 수지 조성물 제조Example 1-d Photocurable Resin Composition
상기 실시예 1-c에서 수득한 실세스퀴옥산 복합 고분자 30 g을 메틸아이소부틸케톤에 30 중량%로 녹여 100 g의 코팅조성물을 제조하였다. 이후, 코팅 조성물 100 중량부에 클로로 아세토페논(chloro acetophenone) 3 중량부와 BYK-347 1 중량부, BYK-UV 3500 1 중량부를 각각 첨가하고 10분간 교반하여 광경화형 코팅 조성물을 제조하였다.30 g of the silsesquioxane composite polymer obtained in Example 1-c was dissolved in methyl isobutyl ketone at 30% by weight to prepare a coating composition of 100 g. Thereafter, 3 parts by weight of chloro acetophenone, 1 part by weight of BYK-347, and 1 part by weight of BYK-UV 3500 were added to 100 parts of the coating composition, and stirred for 10 minutes to prepare a photocurable coating composition.
[실시예 1-e] 열경화형 수지 조성물의 제조Example 1-e Preparation of Thermosetting Resin Composition
상기 실시예 1-c에서 수득한 실세스퀴옥산 복합 고분자 50 g을 메틸에틸케톤에 50 중량%로 녹여 100 g의 코팅조성물을 제조하였다. 이후, 준비된 코팅 조성물 100 중량부에 1,3-디아미노프로판 3 중량부와 BYK-357 및 BYK-348을 각 1 중량부씩 첨가하고 10분간 교반하여 열경화형 코팅 조성물을 제조하였다.50 g of the silsesquioxane composite polymer obtained in Example 1-c was dissolved in methyl ethyl ketone at 50% by weight to prepare 100 g of a coating composition. Thereafter, 3 parts by weight of 1,3-diaminopropane and 1 part by weight of BYK-357 and BYK-348 were added to 100 parts by weight of the prepared coating composition, followed by stirring for 10 minutes to prepare a thermosetting coating composition.
[실시예 1-f] 고분자 자체로 구성된 코팅 조성물Example 1-f Coating composition composed of polymer itself
실시예 1-c 만으로 별도의 조성 없이 코팅 조성물을 구성하였다.Example 1-c alone constitute a coating composition without a separate composition.
또한, 하기 표 19에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자를 제조 및 코팅 조성물을 제조하였다. 이때 제조 방법은 상기 실시예 1-b, 1-c, 1-d, 1-e 및 1-f에서 사용한 방법을 대등하게 적용하였다.In addition, by applying the monomers described in Table 19 to prepare a silsesquioxane composite polymer and to prepare a coating composition. In this case, the method used in Examples 1-b, 1-c, 1-d, 1-e, and 1-f was equally applied.
표 19
실시방법 1-b 방법적용 단량체 1-c 방법적용 단량체 분자량(Mw)
전구체 cage도입
1 ECHETMS PTMDS PTMS 11,000
1-1 PTMS PTMDS PTMS 8,000
1-2 MTMS MTMDS MTMS 48,000
1-3 GPTMS GPTMDS GPTMS 25,000
1-4 MAPTMS MAPTMDS MAPTMS 21,000
1-5 ECHETMS ECHETMDS ECHETMS 3,000
1-6 ECHETMS MTMDS MTMS 9,000
1-7 ECHETMS GPTMDS GPTMS 11,000
1-8 ECHETMS MAPTMDS MAPTMS 18,000
1-9 PTMS ECHETMDS ECHETMS 36,000
1-10 PTMS MTMDS MTMS 120,000
1-11 PTMS GPTMDS GPTMS 11,000
1-12 PTMS MAPTMDS MAPTMS 110,000
1-13 MTMS ECHETMDS ECHETMS 18,000
1-14 MTMS PTMDS PTMS 5,000
1-15 MTMS GPTMDS GPTMS 80,000
1-16 MTMS MAPTMDS MAPTMS 35,000
1-17 GPTMS ECHETMDS ECHETMS 7,000
1-18 GPTMS PTMDS PTMS 120,000
1-19 GPTMS MTMDS MTMS 100,000
1-20 GPTMS MAPTMDS MAPTMS 4,000
1-21 MAPTMS ECHETMDS ECHETMS 35,000
1-22 MAPTMS PTMDS PTMS 2,800
1-23 MAPTMS MTMDS MTMS 8,000
1-24 MAPTMS GPTMDS GPTMS 180,000
Table 19
Method of implementation 1-b Method Applicable Monomer 1-c method applied monomer Molecular Weight (Mw)
Precursor Introduction of cage
One ECHETMS PTMDS PTMS 11,000
1-1 PTMS PTMDS PTMS 8,000
1-2 MTMS MTMDS MTMS 48,000
1-3 GPTMS GPTMDS GPTMS 25,000
1-4 MAPTMS MAPTMDS MAPTMS 21,000
1-5 ECHETMS ECHETMDS ECHETMS 3,000
1-6 ECHETMS MTMDS MTMS 9,000
1-7 ECHETMS GPTMDS GPTMS 11,000
1-8 ECHETMS MAPTMDS MAPTMS 18,000
1-9 PTMS ECHETMDS ECHETMS 36,000
1-10 PTMS MTMDS MTMS 120,000
1-11 PTMS GPTMDS GPTMS 11,000
1-12 PTMS MAPTMDS MAPTMS 110,000
1-13 MTMS ECHETMDS ECHETMS 18,000
1-14 MTMS PTMDS PTMS 5,000
1-15 MTMS GPTMDS GPTMS 80,000
1-16 MTMS MAPTMDS MAPTMS 35,000
1-17 GPTMS ECHETMDS ECHETMS 7,000
1-18 GPTMS PTMDS PTMS 120,000
1-19 GPTMS MTMDS MTMS 100,000
1-20 GPTMS MAPTMDS MAPTMS 4,000
1-21 MAPTMS ECHETMDS ECHETMS 35,000
1-22 MAPTMS PTMDS PTMS 2,800
1-23 MAPTMS MTMDS MTMS 8,000
1-24 MAPTMS GPTMDS GPTMS 180,000
실시예 2Example 2 : 실세스퀴옥산 D-A-D 구조 복합 고분자의 합성Synthesis of Silsesquioxane D-A-D Structured Polymer
D-A-D구조의 복합 고분자를 제조하기 위하여 아래의 실시예를 이용하였으며, 상기 실시예 1에 기재된 방법과 대등한 방법으로 코팅 조성물을 제조하였다. 촉매 및 선형구조의 제조는 실시예 1-a 및 1-b의 방법을 동일하게 사용하였으며, 이후 연속적 D-A-D 구조를 생성하기 위하여 아래의 방법으로 제조를 실시하였다.In order to prepare a composite polymer having a D-A-D structure, the following examples were used, and a coating composition was prepared by a method similar to that described in Example 1 above. Preparation of the catalyst and the linear structure was used in the same manner as in Example 1-a and 1-b, and then to produce a continuous D-A-D structure was carried out by the following method.
[실시예 2-a] 과량의 연속적 cage 구조의 생성Example 2-a Generation of Excess Continuous Cage Structure
상기 실시예 1-b 혼합용액에 0.36 중량% HCl 수용액을 매우 천천히 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 ℃의 온도에서 30분간 교반하였다. 이후 실시예 1-b에서 사용된 Diphenyltetramethoxydisiloxane의 5배인 25 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하고, 1시간 교반 후 실시예 1-a에서 제조된 촉매를 7 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, 선형고분자와는 별도로 alkoxy가 열려있는 D구조의 전구체가 형성된다. 소량의 샘플을 적취하여, H-NMR과 IR로 분석하여 methoxy의 잔존율을 확인한 후, 잔존율이 20% 일 때, 0.36 중량% HCl 수용액을 10 중량부 천천히 적가하여, pH를 산성으로 조절해 주었다. 이후 Phenyltrimethoxysilane 1 중량부를 한번에 적가하여 15분간 교반 후, 1-a에서 제조된 촉매 20 중량부를 첨가하였다. 4시간의 혼합교반 이후, 확인결과 고분자내에 cage 형태의 고분자가 생성됨을 확인 할 수 있었다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여, 전체적인 반응물이 수용액 혼합물로 변환되도록 하였다. 4시간의 혼합 교반 이후, 일부를 적취하여 29Si-NMR을 통해 분석한 결과 phenyl기를 이용해 도입된 구조의 분석피크가 날카로운 형태의 2개로 나타나고 별도로 잔존하는 부산물 없이 화학식 1과 같은 A-D 고분자가 제조되었음을 확인할 수 있었다. 또한 스티렌 환산 분자량은 14,000으로 측정되었으며, n 값은 4-6이었다. 또한, Si-NMR 분석에서 A-D구조와는 달리 A구조의 말단에서 보이던 -68ppm 근방의 피크가 사라져, A구조의 말단이 D구조로 모두 변환되어 D-A-D구조로 생성됨을 확인 하였다. 29Si-NMR (CDCl3) δ -72.3(broad), -81.1(sharp), -80.8(sharp), -82.5(broad)To the mixed solution of Example 1-b 0.36% by weight of HCl aqueous solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 ℃ 30 minutes. Thereafter, 25 parts by weight, which is 5 times the amount of Diphenyltetramethoxydisiloxane used in Example 1-b, was added dropwise at one time to achieve stable hydrolysis, and after stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy. When the residual ratio was 20%, 10 parts by weight of 0.36 wt% HCl aqueous solution was slowly added dropwise to adjust the pH to acidic. gave. Thereafter, 1 part by weight of Phenyltrimethoxysilane was added dropwise at a time, stirred for 15 minutes, and then 20 parts by weight of the catalyst prepared in 1-a was added. After 4 hours of mixing and stirring, it was confirmed that cage type polymer was formed in the polymer. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing and agitation, part of the sample was analyzed and analyzed by 29 Si-NMR. As a result, analytical peaks of the structure introduced using the phenyl group appeared as two sharp forms, and the AD polymer of Formula 1 was prepared without any remaining by-products. I could confirm it. In addition, the styrene reduced molecular weight was measured as 14,000, n value was 4-6. In addition, unlike the AD structure in the Si-NMR analysis, the peak around -68ppm, which was seen at the end of the A structure, disappeared, and the end of the A structure was converted into the D structure, thereby confirming that the DAD structure was generated. 29 Si-NMR (CDCl 3 ) δ -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)
또한, 하기 표 20에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자 및 코팅 조성물을 제조하였다. 이때 제조 방법은 상기 실시예 2에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 20 below. At this time, the manufacturing method was equally applied to the method used in Example 2.
표 20
실시방법 1-b 방법적용 단량체 2-a 방법적용 단량체 분자량(Mw)
전구체 cage도입
2 ECHETMS PTMDS PTMS 14,000
2-1 PTMS PTMDS PTMS 9,000
2-2 MTMS MTMDS MTMS 52,000
2-3 GPTMS GPTMDS GPTMS 30,000
2-4 MAPTMS MAPTMDS MAPTMS 24,000
2-5 ECHETMS ECHETMDS ECHETMS 6,000
2-6 ECHETMS MTMDS MTMS 12,000
2-7 ECHETMS GPTMDS GPTMS 13,000
2-8 ECHETMS MAPTMDS MAPTMS 21,000
2-9 PTMS ECHETMDS ECHETMS 38,000
2-10 PTMS MTMDS MTMS 150,000
2-11 PTMS GPTMDS GPTMS 18,000
2-12 PTMS MAPTMDS MAPTMS 123,000
2-13 MTMS ECHETMDS ECHETMS 23,000
2-14 MTMS PTMDS PTMS 9,000
2-15 MTMS GPTMDS GPTMS 91,000
2-16 MTMS MAPTMDS MAPTMS 41,000
2-17 GPTMS ECHETMDS ECHETMS 12,000
2-18 GPTMS PTMDS PTMS 131,000
2-19 GPTMS MTMDS MTMS 110,000
2-20 GPTMS MAPTMDS MAPTMS 6,000
2-21 MAPTMS ECHETMDS ECHETMS 38,000
2-22 MAPTMS PTMDS PTMS 5,000
2-23 MAPTMS MTMDS MTMS 12,000
2-24 MAPTMS GPTMDS GPTMS 192,000
Table 20
Method of implementation 1-b Method Applicable Monomer 2-a method applied monomer Molecular Weight (Mw)
Precursor Introduction of cage
2 ECHETMS PTMDS PTMS 14,000
2-1 PTMS PTMDS PTMS 9,000
2-2 MTMS MTMDS MTMS 52,000
2-3 GPTMS GPTMDS GPTMS 30,000
2-4 MAPTMS MAPTMDS MAPTMS 24,000
2-5 ECHETMS ECHETMDS ECHETMS 6,000
2-6 ECHETMS MTMDS MTMS 12,000
2-7 ECHETMS GPTMDS GPTMS 13,000
2-8 ECHETMS MAPTMDS MAPTMS 21,000
2-9 PTMS ECHETMDS ECHETMS 38,000
2-10 PTMS MTMDS MTMS 150,000
2-11 PTMS GPTMDS GPTMS 18,000
2-12 PTMS MAPTMDS MAPTMS 123,000
2-13 MTMS ECHETMDS ECHETMS 23,000
2-14 MTMS PTMDS PTMS 9,000
2-15 MTMS GPTMDS GPTMS 91,000
2-16 MTMS MAPTMDS MAPTMS 41,000
2-17 GPTMS ECHETMDS ECHETMS 12,000
2-18 GPTMS PTMDS PTMS 131,000
2-19 GPTMS MTMDS MTMS 110,000
2-20 GPTMS MAPTMDS MAPTMS 6,000
2-21 MAPTMS ECHETMDS ECHETMS 38,000
2-22 MAPTMS PTMDS PTMS 5,000
2-23 MAPTMS MTMDS MTMS 12,000
2-24 MAPTMS GPTMDS GPTMS 192,000
실시예 3Example 3 : 실세스퀴옥산 E-A-D 구조 복합 고분자의 합성: Synthesis of Silsesquioxane E-A-D Structured Composite Polymer
E-A-D구조의 복합 고분자를 제조하기 위하여 아래의 실시예를 이용하였으며, 상기 실시예 1에 기재된 방법과 대등한 방법으로 코팅 조성물을 제조하였다. 촉매 및 선형구조의 제조는 실시예 1의 방법을 동일하게 사용하였으며, 이후 E-A-D 구조를 생성하기 위하여 아래의 방법으로 제조를 실시하였다.In order to prepare an E-A-D composite polymer, the following examples were used, and a coating composition was prepared by a method similar to that described in Example 1 above. Preparation of the catalyst and the linear structure was used in the same manner as in Example 1, and then to produce the E-A-D structure was carried out by the following method.
[실시예 3-a] 사슬 말단 E구조의 생성Example 3-a Generation of Chain Terminal E Structure
실시예 1-c 에서 얻어진 A-D 혼합물에 별도의 정제 없이 메틸렌크로라이드 20 중량부를 적가하고, 0.36 중량% HCl 수용액을 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4℃의 온도에서 30분간 교반하였다. 이후 dimethyltetramethoxysilane 1 중량부를 한번에 적가하였다. 이때, 아직 분자구조 내에서 가수분해되지 않고 존재하던 부분들이 용매와 분리된 산성 수용액 층에서 가수분해물로 쉽게 변환되며, 생성된 별도의 반응물과 유기용매 층에서 축합되어 말단단위에 E가 도입되었다. 5시간의 교반 후, 반응의 교반을 정지하고 상온으로 반응기의 온도를 조절 하였다. To the AD mixture obtained in Example 1-c, 20 parts by weight of methylene chloride were added dropwise without further purification, 5 parts by weight of an aqueous 0.36% by weight HCl solution was added dropwise, and the pH was adjusted to have an acidity, and 30 ° C at a temperature of 4 ° C. Stirred for a minute. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.
[실시예 3-b] 말단 E 구조에 cage 도입Example 3-b Introduction of a Cage to the Terminal E Structure
상기 실시예 3-a에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 반응이 진행 중인 실시예 3-a 혼합용액에 Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하고, 24시간 교반 후 실시예 1-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, E 구조 말단에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 3과 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After preparing the organic layer of the resultant obtained in Example 3-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 3-a in progress, to achieve stable hydrolysis, and after stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced to the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (3). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 3-c] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 3-c] Removal of By-products by Precipitation and Recrystallization, Obtaining the Result
상기 실시예 3-b에서 반응이 완료된 혼합물을 얻어낸 후, 증류수를 이용하여 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 ℃의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. After the reaction mixture was obtained in Example 3-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum pressure. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5, and stored at a temperature of -20 ° C for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 3의 고분자를 여러 부산물과 함께 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 17,000이었으며, n 값은 4-6이었으며, 특히 화학식 3의 결과는 다음과 같다.     After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 3 was obtained along with various byproducts by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was 17,000 in terms of styrene, n value was 4-6, in particular, the results of formula (3) are as follows.
29Si-NMR (CDCl3) δ -68.2, -71.8(sharp). -72.3(broad), -81.1(sharp), -80.8(sharp), -82.5(broad) 29 Si-NMR (CDCl 3 ) δ −68.2, −71.8 (sharp). -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)
또한, 하기 표 21에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자 및 코팅 조성물을 제조하였다. 이때 제조 방법은 상기 실시예 3에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 21 below. In this case, the method used in Example 3 was equally applied.
표 21
실시방법 1-b 방법적용 단량체 1-c 방법적용 단량체 3-a방법적용 단량체 3-b방법적용단량체 Mw
전구체 cage도입
3 ECHETMS PTMDS PTMS MTMDS MAPTMS 17,000
3-1 ECHETMS ECHETMDS ECHETMS ECHETMDS ECHETMS 12,000
3-2 PTMS PTMDS PTMS PTMDS PTMS 18,000
3-3 MTMS MTMDS MTMS MTMDS MTMS 59,000
3-4 GPTMS ECHETMDS ECHETMS GPTMDS GPTMS 41,000
3-5 MAPTMS MAPTMDS MAPTMS MAPTMDS MAPTMS 31,000
3-6 ECHETMS ECHETMDS ECHETMS PTMDS PTMS 16,000
3-7 ECHETMS ECHETMDS ECHETMS MTMDS MTMS 12,000
3-8 ECHETMS ECHETMDS ECHETMS GPTMDS GPTMS 16,000
3-9 ECHETMS ECHETMDS ECHETMS MAPTMDS MAPTMS 92,000
3-10 ECHETMS PTMDS PTMS ECHETMDS ECHETMS 25,000
3-11 ECHETMS MTMDS MTMS ECHETMDS ECHETMS 38,000
3-12 ECHETMS GPTMDS GPTMS ECHETMDS ECHETMS 56,000
3-13 ECHETMS MAPTMDS MAPTMS ECHETMDS ECHETMS 97,000
3-14 PTMS PTMDS PTMS ECHETMDS ECHETMS 24,000
3-15 PTMS PTMDS PTMS MTMDS MTMS 31,000
3-16 PTMS PTMDS PTMS ECHETMDS ECHETMS 21,000
3-17 PTMS PTMDS PTMS MAPTMDS MAPTMS 64,000
3-18 PTMS ECHETMDS ECHETMS PTMDS PTMS 120,000
3-19 PTMS MTMDS MTMS PTMDS PTMS 210,000
3-20 PTMS GPTMDS GPTMS PTMDS PTMS 23,000
3-21 PTMS MAPTMDS MAPTMS PTMDS PTMS 160,000
3-22 MTMS MTMDS MTMS ECHETMDS ECHETMS 63,000
3-23 MTMS MTMDS MTMS PTMDS PTMS 52,000
3-24 MTMS MTMDS MTMS GPTMDS GPTMS 73,000
3-25 MTMS MTMDS MTMS MAPTMDS MAPTMS 98,000
3-26 MTMS ECHETMDS ECHETMS MTMDS MTMS 41,000
3-27 MTMS PTMDS PTMS MTMDS MTMS 15,000
3-28 MTMS GPTMDS GPTMS MTMDS MTMS 110,000
3-29 MTMS MAPTMDS MAPTMS MTMDS MTMS 45,000
3-30 GPTMS GPTMDS GPTMS ECHETMDS ECHETMS 35,000
3-31 GPTMS GPTMDS GPTMS PTMDS PTMS 33,000
3-32 GPTMS GPTMDS GPTMS MTMDS MTMS 48,000
3-33 GPTMS GPTMDS GPTMS MAPTMDS MAPTMS 29,000
3-34 GPTMS ECHETMDS ECHETMS GPTMDS GPTMS 19,000
3-35 GPTMS PTMDS PTMS GPTMDS GPTMS 156,000
3-36 GPTMS MTMDS MTMS GPTMDS GPTMS 116,000
3-37 GPTMS MAPTMDS MAPTMS GPTMDS GPTMS 12,000
3-38 MAPTMS MAPTMDS MAPTMS ECHETMDS ECHETMS 31,000
3-39 MAPTMS MAPTMDS MAPTMS PTMDS PTMS 28,000
3-40 MAPTMS MAPTMDS MAPTMS MTMDS MTMS 35,000
3-41 MAPTMS MAPTMDS MAPTMS GPTMDS GPTMS 31,000
3-42 MAPTMS ECHETMDS ECHETMS MAPTMDS MAPTMS 57,000
3-43 MAPTMS PTMDS PTMS MAPTMDS MAPTMS 9,000
3-44 MAPTMS MTMDS MTMS MAPTMDS MAPTMS 19,000
3-45 MAPTMS GPTMDS GPTMS MAPTMDS MAPTMS 213,000
Table 21
Method of implementation 1-b Method Applicable Monomer 1-c method applied monomer 3-a method applied monomer 3-b method applied monomer Mw
Precursor Introduction of cage
3 ECHETMS PTMDS PTMS MTMDS MAPTMS 17,000
3-1 ECHETMS ECHETMDS ECHETMS ECHETMDS ECHETMS 12,000
3-2 PTMS PTMDS PTMS PTMDS PTMS 18,000
3-3 MTMS MTMDS MTMS MTMDS MTMS 59,000
3-4 GPTMS ECHETMDS ECHETMS GPTMDS GPTMS 41,000
3-5 MAPTMS MAPTMDS MAPTMS MAPTMDS MAPTMS 31,000
3-6 ECHETMS ECHETMDS ECHETMS PTMDS PTMS 16,000
3-7 ECHETMS ECHETMDS ECHETMS MTMDS MTMS 12,000
3-8 ECHETMS ECHETMDS ECHETMS GPTMDS GPTMS 16,000
3-9 ECHETMS ECHETMDS ECHETMS MAPTMDS MAPTMS 92,000
3-10 ECHETMS PTMDS PTMS ECHETMDS ECHETMS 25,000
3-11 ECHETMS MTMDS MTMS ECHETMDS ECHETMS 38,000
3-12 ECHETMS GPTMDS GPTMS ECHETMDS ECHETMS 56,000
3-13 ECHETMS MAPTMDS MAPTMS ECHETMDS ECHETMS 97,000
3-14 PTMS PTMDS PTMS ECHETMDS ECHETMS 24,000
3-15 PTMS PTMDS PTMS MTMDS MTMS 31,000
3-16 PTMS PTMDS PTMS ECHETMDS ECHETMS 21,000
3-17 PTMS PTMDS PTMS MAPTMDS MAPTMS 64,000
3-18 PTMS ECHETMDS ECHETMS PTMDS PTMS 120,000
3-19 PTMS MTMDS MTMS PTMDS PTMS 210,000
3-20 PTMS GPTMDS GPTMS PTMDS PTMS 23,000
3-21 PTMS MAPTMDS MAPTMS PTMDS PTMS 160,000
3-22 MTMS MTMDS MTMS ECHETMDS ECHETMS 63,000
3-23 MTMS MTMDS MTMS PTMDS PTMS 52,000
3-24 MTMS MTMDS MTMS GPTMDS GPTMS 73,000
3-25 MTMS MTMDS MTMS MAPTMDS MAPTMS 98,000
3-26 MTMS ECHETMDS ECHETMS MTMDS MTMS 41,000
3-27 MTMS PTMDS PTMS MTMDS MTMS 15,000
3-28 MTMS GPTMDS GPTMS MTMDS MTMS 110,000
3-29 MTMS MAPTMDS MAPTMS MTMDS MTMS 45,000
3-30 GPTMS GPTMDS GPTMS ECHETMDS ECHETMS 35,000
3-31 GPTMS GPTMDS GPTMS PTMDS PTMS 33,000
3-32 GPTMS GPTMDS GPTMS MTMDS MTMS 48,000
3-33 GPTMS GPTMDS GPTMS MAPTMDS MAPTMS 29,000
3-34 GPTMS ECHETMDS ECHETMS GPTMDS GPTMS 19,000
3-35 GPTMS PTMDS PTMS GPTMDS GPTMS 156,000
3-36 GPTMS MTMDS MTMS GPTMDS GPTMS 116,000
3-37 GPTMS MAPTMDS MAPTMS GPTMDS GPTMS 12,000
3-38 MAPTMS MAPTMDS MAPTMS ECHETMDS ECHETMS 31,000
3-39 MAPTMS MAPTMDS MAPTMS PTMDS PTMS 28,000
3-40 MAPTMS MAPTMDS MAPTMS MTMDS MTMS 35,000
3-41 MAPTMS MAPTMDS MAPTMS GPTMDS GPTMS 31,000
3-42 MAPTMS ECHETMDS ECHETMS MAPTMDS MAPTMS 57,000
3-43 MAPTMS PTMDS PTMS MAPTMDS MAPTMS 9,000
3-44 MAPTMS MTMDS MTMS MAPTMDS MAPTMS 19,000
3-45 MAPTMS GPTMDS GPTMS MAPTMDS MAPTMS 213,000
실시예 4Example 4 : A-B-D 구조 복합 실세스퀴옥산 고분자의 합성: Synthesis of A-B-D Structured Composite Silsesquioxane Polymer
합성단계는 아래와 같이, 연속가수분해 및 축합을 단계적으로 진행하여 E-A-D구조의 복합 고분자를 제조하였으며, 상기 실시예 1에 기재된 방법과 대등한 방법으로 코팅 조성물을 제조하였다. In the synthesis step, a continuous hydrolysis and condensation were carried out stepwise to prepare a composite polymer having an E-A-D structure, and a coating composition was prepared by a method equivalent to that described in Example 1.
[실시예 4-a] 가수분해 및 축합 반응을 위한 촉매의 제조Example 4-a Preparation of Catalysts for Hydrolysis and Condensation Reactions
염기도 조절을 위하여, Tetramethylammonium hydroxide (TMAH) 25 wt% 수용액에 10 wt% Potassium hydroxide (KOH) 수용액을 혼합하여 촉매 1a를 준비하였다.To adjust the basicity, a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
[실시예 4-b] 선형 실세스퀴옥산 구조의 합성 (A-B전구체의 합성)Example 4-b Synthesis of Linear Silsesquioxane Structure (Synthesis of A-B Precursor)
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 5 중량부, 테트라하이드로퓨란 40 중량부, 상기 실시예 4-a에서 제조된 촉매 0.5 중량부를 적가하고, 1시간 동안 상온에서 교반 한 후, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 10 중량부를 적가하고, 다시 테트라하이드로류란을 20 중량부 적가하여 2시간 추가 교반 하였다. 교반 중의 혼합용액을 적취하여, 두 차례 세정하는 것으로 촉매와 불순물을 제거하고 필터 한 후, 1H-NMR 분석을 통하여 잔존하는 alkoxy group이 0.1 mmol/g 이하로 잔존하고 있는 선형 실세스퀴옥산을 얻어 내었고, 이는 이후 cage를 연속반응으로 도입하는데 이용되는 부분이다. 선형 구조의 형태 분석은 XRD 분석을 통해 전체적인 구조가 선형구조체임을 확인하였다. 분자량을 측정한 결과, 선형구조의 실세스퀴옥산이 6,000 스티렌 환산 분자량을 가짐을 확인할 수 있었다. To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, 0.5 parts by weight of the catalyst prepared in Example 4-a were added dropwise, followed by stirring at room temperature for 1 hour, and then 2 10 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 20 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 2 hours. The mixed solution was stirred and washed twice to remove the catalyst and impurities, and then filtered, and then linear silsesquioxane containing 0.1 mmol / g or less of the alkoxy group remaining through 1 H-NMR analysis. This was then used to introduce the cage into the continuous reaction. XRD analysis confirmed that the overall structure is a linear structure through the XRD analysis. As a result of measuring the molecular weight, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 6,000 styrene.
1H-NMR (CDCl3)δ 3.7, 3.4, 3.3(broad), 3.1, 2.8, 2.6, 1.5(broad), 0.6. 1 H-NMR (CDCl 3 ) δ 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6.
[실시예 4-c] 사슬 내 cage 구조의 생성을 위한 pH 변환 반응 (B,D 구조의 도입)[Example 4-c] pH conversion reaction for generation of cage structure in chain (introduction of B, D structure)
반응이 진행 중인 실시예 4-b 혼합용액에 0.36 wt% HCl 수용액을 매우 천천히 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 ℃의 온도에서 30분간 교반하였다. 이후 DiPhenyltetramethoxydisiloxane 5 중량부를 한번에 적가하여, 1시간 교반 후 실시예 4-a에서 제조된 촉매를 5 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, 선형구조체와는 별도로 cage 형태의 구조체가 생성되어 고분자 사슬에 도입됨을 확인 할 수 있었으며, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여, 전체적인 반응물이 수용액 혼합물로 변환되도록 하였다. 4시간의 혼합교반 이후, 일부를 적취하여 29Si-NMR 및 1H-NMR 을 통해 분석한 결과 B 구조내에 존재하는 alkoxy group의 양이 0.025 mmol/g으로 변화되어 B 와 D의 반복단위가 약 5:5 비율로 도입되었음을 확인할 수 있었다. 또한 스티렌 환산 분자량은 10,000으로 측정되었다. 또한, cage형 구조가 도입되었음에도, 고분자의 GPC 형태에서 단독 cage형 물질의 분자량 분포를 찾아볼 수 없으므로, cage구조가 연속반응을 통해 고분자 사슬에 잘 도입되었음을 확인할 수 있었다.To the mixture of Example 4-b in progress, 0.36 wt% HCl aqueous solution was added dropwise very slowly to 5 parts by weight, the pH was adjusted to have acidity, and stirred at a temperature of 4 ° C. for 30 minutes. Thereafter, 5 parts by weight of DiPhenyltetramethoxydisiloxane was added dropwise, and after stirring for 1 hour, 5 parts by weight of the catalyst prepared in Example 4-a was added again to adjust the pH of the mixed solution in a basic state. At this time, it could be confirmed that the cage-type structure was introduced into the polymer chain separately from the linear structure, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum, and the overall reactant was converted into the aqueous mixture. It was made. After 4 hours of mixing, some of the alkoxy groups in the B structure were changed to 0.025 mmol / g as a result of partial extraction and analysis by 29 Si-NMR and 1 H-NMR. It was confirmed that the ratio was introduced at 5: 5. In addition, the styrene reduced molecular weight was measured to 10,000. In addition, although the cage type structure was introduced, the molecular weight distribution of the single cage type material was not found in the GPC form of the polymer, and thus the cage structure was well introduced into the polymer chain through the continuous reaction.
1H-NMR (CDCl3) δ 7.5, 7.2, 3.7, 3.4, 3.3(broad), 3.1, 2.8, 2.6, 1.5(broad), 0.6. 29Si-NMR (CDCl3) δ -72.5(broad), -81.1(sharp), -80.8(sharp), -79.9(sharp), -82.5(broad) 1 H-NMR (CDCl 3 ) δ 7.5, 7.2, 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6. 29 Si-NMR (CDCl 3 ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -82.5 (broad)
[실시예 4-d] B 구조내 X도입 (B,D 구조의 도입)[Example 4-d] X introduction into B structure (introduction of B and D structure)
상기 실시예 4-c에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 실시예 4-c에서 얻어진 물질 100 중량부를 50 중량부의 테트라하이드로퓨란에 녹인 후, 5 중량부의 증류수를 넣어 혼합용액을 제조하였다. 이후 제조된 혼합용액에 0.36 wt% HCl 10 중량부를 첨가하고 10분간 교반 후, Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하였다. 24시간 교반 후 실시예 4-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, B 구조의 X 부분에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 4와 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After preparing the organic layer of the resultant obtained in Example 4-c without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 100 parts by weight of the material obtained in Example 4-c was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 4-a was added again to adjust the pH of the mixed solution in a basic state. At this time, the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (4). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 4-e] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 4-e] Removal of By-products by Precipitation and Recrystallization, Obtained Result
상기 실시예 4-d에서 반응이 완료된 혼합물에 메틸렌크로라이드 200 중량부를 넣어, 증류수와 함께 분별 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 ℃의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. 200 parts by weight of methylene chloride was added to the mixture in which the reaction was completed in Example 4-d, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum reduction. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5, and stored at a temperature of -20 ° C for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 4의 고분자가 여러 부산물 없이 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 12,000의 값을 얻을 수 있었으며, X의 n 값은 4-6이었으며, Y의 n 값은 4-6이었으며, 특히 화학식 4의 결과는 다음과 같다.     After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Formula 4 was obtained without various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in the styrene conversion value of 12,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 4 results are as follows.
29Si-NMR (CDCl3) δ -72.5(broad), -81.1(sharp), -80.8(sharp), -79.9(sharp), -81.5(sharp), -82.5(broad) 29 Si-NMR (CDCl 3 ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -81.5 (sharp), -82.5 (broad)
또한, 하기 표 22에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자 및 코팅 조성물을 제조하였다. 이때 제조 방법은 상기 실시예 4에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 22 below. In this case, the method used in Example 4 was equally applied.
표 22
실시방법 4-b 방법적용 단량체 4-c 방법적용 단량체 4-d 방법적용 단량체 분자량(Mw)
4 ECHETMS PTMDS MTMS 12,000
4-1 PTMS PTMDS PTMS 15,000
4-2 MTMS MTMDS MTMS 16,000
4-3 GPTMS GPTMDS GPTMS 56,000
4-4 MAPTMS MAPTMDS MAPTMS 9,500
4-5 ECHETMS ECHETMDS ECHETMS 7,500
4-6 ECHETMS MTMDS MTMS 16,000
4-7 ECHETMS GPTMDS GPTMS 23,000
4-8 ECHETMS MAPTMDS MAPTMS 9,500
4-9 PTMS ECHETMDS ECHETMS 72,000
4-10 PTMS MTMDS MTMS 68,000
4-11 PTMS GPTMDS GPTMS 11,000
4-12 PTMS MAPTMDS MAPTMS 110,000
4-13 MTMS ECHETMDS ECHETMS 23,000
4-14 MTMS PTMDS PTMS 9,500
4-15 MTMS GPTMDS GPTMS 64,000
4-16 MTMS MAPTMDS MAPTMS 12,000
4-17 GPTMS ECHETMDS ECHETMS 8,000
4-18 GPTMS PTMDS PTMS 451,000
4-19 GPTMS MTMDS MTMS 320,000
4-20 GPTMS MAPTMDS MAPTMS 15,000
4-21 MAPTMS ECHETMDS ECHETMS 45,000
4-22 MAPTMS PTMDS PTMS 351,000
4-23 MAPTMS MTMDS MTMS 14,000
4-24 MAPTMS GPTMDS GPTMS 160,000
Table 22
Method of implementation 4-b method applied monomer 4-c method applied monomer 4-d method applied monomer Molecular Weight (Mw)
4 ECHETMS PTMDS MTMS 12,000
4-1 PTMS PTMDS PTMS 15,000
4-2 MTMS MTMDS MTMS 16,000
4-3 GPTMS GPTMDS GPTMS 56,000
4-4 MAPTMS MAPTMDS MAPTMS 9,500
4-5 ECHETMS ECHETMDS ECHETMS 7,500
4-6 ECHETMS MTMDS MTMS 16,000
4-7 ECHETMS GPTMDS GPTMS 23,000
4-8 ECHETMS MAPTMDS MAPTMS 9,500
4-9 PTMS ECHETMDS ECHETMS 72,000
4-10 PTMS MTMDS MTMS 68,000
4-11 PTMS GPTMDS GPTMS 11,000
4-12 PTMS MAPTMDS MAPTMS 110,000
4-13 MTMS ECHETMDS ECHETMS 23,000
4-14 MTMS PTMDS PTMS 9,500
4-15 MTMS GPTMDS GPTMS 64,000
4-16 MTMS MAPTMDS MAPTMS 12,000
4-17 GPTMS ECHETMDS ECHETMS 8,000
4-18 GPTMS PTMDS PTMS 451,000
4-19 GPTMS MTMDS MTMS 320,000
4-20 GPTMS MAPTMDS MAPTMS 15,000
4-21 MAPTMS ECHETMDS ECHETMS 45,000
4-22 MAPTMS PTMDS PTMS 351,000
4-23 MAPTMS MTMDS MTMS 14,000
4-24 MAPTMS GPTMDS GPTMS 160,000
실시예 5Example 5 : D-A-B-D 구조 복합 실세스퀴옥산 고분자의 합성: Synthesis of D-A-B-D Structured Composite Silsesquioxane Polymer
D-A-B-D구조의 복합 고분자를 제조하기 위하여 아래의 방법을 이용하였으며, 상기 실시예 1과 대등한 방법으로 코팅 조성물을 제조하였다.The following method was used to prepare a composite polymer having a D-A-B-D structure, and a coating composition was prepared by the same method as in Example 1.
[실시예 5-a] D구조의 과량 생성을 위한 pH 변환 반응 (B,D 구조의 도입)Example 5-a pH Conversion Reaction for Excess Production of D Structure (Introduction of B, D Structure)
반응이 진행 중인 실시예 4-b 혼합용액에 0.36 wt% HCl 수용액을 매우 천천히 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 ℃의 온도에서 30분간 교반하였다. 이후 Diphenyltetramethoxydisiloxane의 양을 실시예 4-b의 5배인 25 중량부로 준비하여 한번에 적가하고, 1시간 교반 후 실시예 1-a에서 제조된 촉매를 5 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 반응 완료 후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여, 전체적인 반응물이 수용액 혼합물로 변환되도록 하였다. 4시간의 혼합교반 이후, 일부를 적취하여 29Si-NMR 및 1H-NMR 을 통해 분석한 결과 B 구조내에 존재하는 alkoxy group의 양이 0.012 mmol/g으로 변화되고 B 와 D의 반복단위가 약 1:9 비율로 도입되었음을 확인할 수 있었다. 또한 스티렌 환산 분자량은 24,000으로 측정되었다. 또한, cage형 구조가 도입되었음에도, 고분자의 GPC 형태에서 단독 cage형 물질의 분자량 분포를 찾아볼 수 없으므로, cage구조가 연속반응을 통해 고분자 사슬에 잘 도입되었음을 확인할 수 있었다.To the mixture of Example 4-b in progress, 0.36 wt% HCl aqueous solution was added dropwise very slowly to 5 parts by weight, the pH was adjusted to have acidity, and stirred at a temperature of 4 ° C. for 30 minutes. Thereafter, the amount of diphenyltetramethoxydisiloxane was prepared by adding 5 parts by weight to 25 parts by weight, which is 5 times the amount of Example 4-b, and after stirring for 1 hour, 5 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic pH of the mixed solution. Was adjusted. After the reaction was completed, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing, some of them were collected and analyzed by 29 Si-NMR and 1 H-NMR. The amount of alkoxy groups in the B structure was changed to 0.012 mmol / g and the repeating units of B and D were about It was confirmed that the 1: 9 ratio was introduced. In addition, styrene conversion molecular weight was measured as 24,000. In addition, although the cage type structure was introduced, the molecular weight distribution of the single cage type material was not found in the GPC form of the polymer, and thus the cage structure was well introduced into the polymer chain through the continuous reaction.
1H-NMR (CDCl3) 7.5, 7.2, 3.7, 3.4, 3.3(broad), 3.1, 2.8, 2.6, 1.5(broad), 0.6. 29Si-NMR (CDCl3) δ -72.5(broad), -81.1(sharp), -80.8(sharp), -79.9(sharp), -82.5(broad) 1 H-NMR (CDCl 3 ) 7.5, 7.2, 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6. 29 Si-NMR (CDCl 3 ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -82.5 (broad)
[실시예 5-b] B 구조내 X도입 (B,D 구조의 도입)[Example 5-b] X Introduction in B Structure (Introduction of B, D Structure)
상기 실시예 5-a에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 실시예 5-a에서 얻어진 물질 100 중량부를 50 중량부의 테트라하이드로퓨란에 녹인 후, 5 중량부의 증류수를 넣어 혼합용액을 제조하였다. 이후 제조된 혼합용액에 0.36 wt% HCl 10 중량부를 첨가하고 10분간 교반 후, Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하였다. 24시간 교반 후 실시예 4-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, B 구조의 X 부분에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 5와 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After the organic layer of the resultant obtained in Example 5-a was prepared without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 100 parts by weight of the material obtained in Example 5-a was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 4-a was added again to adjust the pH of the mixed solution in a basic state. At this time, the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (5). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 5-c] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 5-c] Removal of By-products by Precipitation and Recrystallization
상기 실시예 5-b에서 반응이 완료된 혼합물에 메틸렌크로라이드 200 중량부를 넣어, 증류수와 함께 분별 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 ℃의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. 200 parts by weight of methylene chloride was added to the mixture in which the reaction was completed in Example 5-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum pressure. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5, and stored at a temperature of -20 ° C for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 5의 고분자가 여러 부산물 없이 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 16,000의 값을 얻을 수 있었으며, X의 n 값은 4-6이었으며, Y의 n 값은 4-6이었으며, 특히 화학식 5의 결과는 다음과 같다.     After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 5 was obtained without various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in the styrene conversion value of 16,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 5 results are as follows.
29Si-NMR (CDCl3) δ -72.5(broad), -81.1(sharp), -80.8(sharp), -79.9(sharp), -81.5(sharp), -82.5(broad) 29 Si-NMR (CDCl 3 ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -81.5 (sharp), -82.5 (broad)
또한, 하기 표 23에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자 및 코팅 조성물을 제조하였다. 이때 제조 방법은 상기 실시예 5에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 23 below. At this time, the manufacturing method was equally applied to the method used in Example 5.
표 23
실시방법 4-b 방법적용 단량체 4-a 방법적용 단량체 5-b 방법적용 단량체 분자량(Mw)
2 ECHETMS PTMDS MTMS 16,000
5-1 PTMS PTMDS PTMS 19,000
5-2 MTMS MTMDS MTMS 20,000
5-3 GPTMS GPTMDS GPTMS 63,000
5-4 MAPTMS MAPTMDS MAPTMS 12,000
5-5 ECHETMS ECHETMDS ECHETMS 14,500
5-6 ECHETMS MTMDS MTMS 19,000
5-7 ECHETMS GPTMDS GPTMS 25,000
5-8 ECHETMS MAPTMDS MAPTMS 11,500
5-9 PTMS ECHETMDS ECHETMS 78,000
5-10 PTMS MTMDS MTMS 79,000
5-11 PTMS GPTMDS GPTMS 15,000
5-12 PTMS MAPTMDS MAPTMS 124,000
5-13 MTMS ECHETMDS ECHETMS 30,000
5-14 MTMS PTMDS PTMS 12,000
5-15 MTMS GPTMDS GPTMS 64,000
5-16 MTMS MAPTMDS MAPTMS 13,000
5-17 GPTMS ECHETMDS ECHETMS 12,000
5-18 GPTMS PTMDS PTMS 631,000
5-19 GPTMS MTMDS MTMS 421,000
5-20 GPTMS MAPTMDS MAPTMS 18,000
5-21 MAPTMS ECHETMDS ECHETMS 65,000
2-22 MAPTMS PTMDS PTMS 425,000
5-23 MAPTMS MTMDS MTMS 25,000
5-24 MAPTMS GPTMDS GPTMS 213,000
Table 23
Method of implementation 4-b method applied monomer 4-a method applied monomer 5-b method applied monomer Molecular Weight (Mw)
2 ECHETMS PTMDS MTMS 16,000
5-1 PTMS PTMDS PTMS 19,000
5-2 MTMS MTMDS MTMS 20,000
5-3 GPTMS GPTMDS GPTMS 63,000
5-4 MAPTMS MAPTMDS MAPTMS 12,000
5-5 ECHETMS ECHETMDS ECHETMS 14,500
5-6 ECHETMS MTMDS MTMS 19,000
5-7 ECHETMS GPTMDS GPTMS 25,000
5-8 ECHETMS MAPTMDS MAPTMS 11,500
5-9 PTMS ECHETMDS ECHETMS 78,000
5-10 PTMS MTMDS MTMS 79,000
5-11 PTMS GPTMDS GPTMS 15,000
5-12 PTMS MAPTMDS MAPTMS 124,000
5-13 MTMS ECHETMDS ECHETMS 30,000
5-14 MTMS PTMDS PTMS 12,000
5-15 MTMS GPTMDS GPTMS 64,000
5-16 MTMS MAPTMDS MAPTMS 13,000
5-17 GPTMS ECHETMDS ECHETMS 12,000
5-18 GPTMS PTMDS PTMS 631,000
5-19 GPTMS MTMDS MTMS 421,000
5-20 GPTMS MAPTMDS MAPTMS 18,000
5-21 MAPTMS ECHETMDS ECHETMS 65,000
2-22 MAPTMS PTMDS PTMS 425,000
5-23 MAPTMS MTMDS MTMS 25,000
5-24 MAPTMS GPTMDS GPTMS 213,000
실시예 6Example 6 : 실세스퀴옥산 E-A-B-D 구조 복합 고분자의 합성: Synthesis of Silsesquioxane E-A-B-D Structured Composite Polymer
E-A-B-D구조의 복합 고분자를 제조하기 위하여 아래의 방법을 이용하였으며, 상기 실시예 1과 대등한 방법으로 코팅 조성물을 제조하였다.To prepare a composite polymer having an E-A-B-D structure, the following method was used, and a coating composition was prepared by the same method as in Example 1.
[실시예 6-a] 사슬 말단 E구조의 생성Example 6-a Generation of Chain Terminal E Structure
실시예 4-c 에서 얻어진 혼합물에 별도의 정제 없이 메틸렌크로라이드 20 중량부를 적가하고, 0.36 중량% HCl 수용액을 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4℃의 온도에서 30분간 교반하였다. 이후 dimethyltetramethoxysilane 1 중량부를 한번에 적가하였다. 이때, 아직 분자구조 내에서 가수분해되지 않고 존재하던 부분들이 용매와 분리된 산성 수용액 층에서 가수분해물로 쉽게 변환되며, 생성된 별도의 반응물과 유기용매 층에서 축합되어 말단단위에 E가 도입되었다. 5시간의 교반 후, 반응의 교반을 정지하고 상온으로 반응기의 온도를 조절 하였다. To the mixture obtained in Example 4-c, 20 parts by weight of methylene chloride were added dropwise without further purification, 5 parts by weight of 0.36% by weight aqueous HCl solution was added dropwise, the pH was adjusted to have an acidity, and 30 minutes at a temperature of 4 ° C. Stirred. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.
[실시예 6-b] B구조 및 말단 E 구조의 X에 cage 도입[Example 6-b] Cage introduction into X of B structure and terminal E structure
상기 실시예 6-a에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 반응이 진행 중인 실시예 6-a 혼합용액에 Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하고, 24시간 교반 후 실시예 1-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, E 구조 말단에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 6과 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After the organic layer of the resultant obtained in Example 6-a was prepared without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 6-a in progress at a time to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced at the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in formula (6). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 6-c] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 6-c] Removal of By-products by Precipitation and Recrystallization
상기 실시예 6-b에서 반응이 완료된 혼합물을 얻어낸 후, 증류수를 이용하여 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 ℃의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. In Example 6-b, the reaction mixture was obtained, washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5, and stored at a temperature of -20 ° C for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 6의 고분자를 여러 부산물과 함께 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 21,000의 값을 얻을 수 있었으며, X의 n 값은 4-6이었으며, Y의 n 값은 4-6이었으며, 특히 화학식 6의 결과는 다음과 같다.     After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 6 was obtained along with various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in the styrene conversion value of 21,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 6 results are as follows.
29Si-NMR (CDCl3) δ -68.2, -71.8(sharp). -72.3(broad), -81.1(sharp), -80.8(sharp), -82.5(broad) 29 Si-NMR (CDCl 3 ) δ −68.2, −71.8 (sharp). -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)
또한, 하기 표 24에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자를 제조하였다. 이때 제조 방법은 상기 실시예 6에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer was prepared by applying the monomers described in Table 24 below. At this time, the manufacturing method was equally applied to the method used in Example 6.
표 24
실시방법 4-b 방법적용 단량체 4-c 방법적용 단량체 6-a방법적용 단량체 6-b방법적용단량체 Mw
6 ECHETMS PTMDS MTMDS MAPTMS 21,000
6-1 ECHETMS ECHETMDS ECHETMDS ECHETMS 18,000
6-2 PTMS PTMDS PTMDS PTMS 19,000
6-3 MTMS MTMDS MTMDS MTMS 31,000
6-4 GPTMS ECHETMDS GPTMDS GPTMS 63,000
6-5 MAPTMS MAPTMDS MAPTMDS MAPTMS 125,000
6-6 ECHETMS ECHETMDS PTMDS PTMS 18,000
6-7 ECHETMS ECHETMDS MTMDS MTMS 14,000
6-8 ECHETMS ECHETMDS GPTMDS GPTMS 20,000
6-9 ECHETMS ECHETMDS MAPTMDS MAPTMS 91,000
6-10 ECHETMS PTMDS ECHETMDS ECHETMS 18,000
6-11 ECHETMS MTMDS ECHETMDS ECHETMS 121,000
6-12 ECHETMS GPTMDS ECHETMDS ECHETMS 80,000
6-13 ECHETMS MAPTMDS ECHETMDS ECHETMS 112,000
6-14 PTMS PTMDS ECHETMDS ECHETMS 35,000
6-15 PTMS PTMDS MTMDS MTMS 91,000
6-16 PTMS PTMDS ECHETMDS ECHETMS 45,000
6-17 PTMS PTMDS MAPTMDS MAPTMS 75,000
6-18 PTMS ECHETMDS PTMDS PTMS 140,000
6-19 PTMS MTMDS PTMDS PTMS 220,000
6-20 PTMS GPTMDS PTMDS PTMS 51,000
6-21 PTMS MAPTMDS PTMDS PTMS 73,000
6-22 MTMS MTMDS ECHETMDS ECHETMS 69,000
6-23 MTMS MTMDS PTMDS PTMS 51,000
6-24 MTMS MTMDS GPTMDS GPTMS 91,000
6-25 MTMS MTMDS MAPTMDS MAPTMS 128,000
6-26 MTMS ECHETMDS MTMDS MTMS 68,000
6-27 MTMS PTMDS MTMDS MTMS 45,000
6-28 MTMS GPTMDS MTMDS MTMS 265,000
6-29 MTMS MAPTMDS MTMDS MTMS 105,000
6-30 GPTMS GPTMDS ECHETMDS ECHETMS 101,000
6-31 GPTMS GPTMDS PTMDS PTMS 95,000
6-32 GPTMS GPTMDS MTMDS MTMS 73,000
6-33 GPTMS GPTMDS MAPTMDS MAPTMS 51,000
6-34 GPTMS ECHETMDS GPTMDS GPTMS 31,000
6-35 GPTMS PTMDS GPTMDS GPTMS 315,000
6-36 GPTMS MTMDS GPTMDS GPTMS 125,000
6-37 GPTMS MAPTMDS GPTMDS GPTMS 45,000
6-38 MAPTMS MAPTMDS ECHETMDS ECHETMS 94,000
6-39 MAPTMS MAPTMDS PTMDS PTMS 35,000
6-40 MAPTMS MAPTMDS MTMDS MTMS 80,000
6-41 MAPTMS MAPTMDS GPTMDS GPTMS 83,000
6-42 MAPTMS ECHETMDS MAPTMDS MAPTMS 74,000
6-43 MAPTMS PTMDS MAPTMDS MAPTMS 10,000
6-44 MAPTMS MTMDS MAPTMDS MAPTMS 65,000
6-45 MAPTMS GPTMDS MAPTMDS MAPTMS 418,000
Table 24
Method of implementation 4-b method applied monomer 4-c method applied monomer 6-a method applied monomer 6-b method applied monomer Mw
6 ECHETMS PTMDS MTMDS MAPTMS 21,000
6-1 ECHETMS ECHETMDS ECHETMDS ECHETMS 18,000
6-2 PTMS PTMDS PTMDS PTMS 19,000
6-3 MTMS MTMDS MTMDS MTMS 31,000
6-4 GPTMS ECHETMDS GPTMDS GPTMS 63,000
6-5 MAPTMS MAPTMDS MAPTMDS MAPTMS 125,000
6-6 ECHETMS ECHETMDS PTMDS PTMS 18,000
6-7 ECHETMS ECHETMDS MTMDS MTMS 14,000
6-8 ECHETMS ECHETMDS GPTMDS GPTMS 20,000
6-9 ECHETMS ECHETMDS MAPTMDS MAPTMS 91,000
6-10 ECHETMS PTMDS ECHETMDS ECHETMS 18,000
6-11 ECHETMS MTMDS ECHETMDS ECHETMS 121,000
6-12 ECHETMS GPTMDS ECHETMDS ECHETMS 80,000
6-13 ECHETMS MAPTMDS ECHETMDS ECHETMS 112,000
6-14 PTMS PTMDS ECHETMDS ECHETMS 35,000
6-15 PTMS PTMDS MTMDS MTMS 91,000
6-16 PTMS PTMDS ECHETMDS ECHETMS 45,000
6-17 PTMS PTMDS MAPTMDS MAPTMS 75,000
6-18 PTMS ECHETMDS PTMDS PTMS 140,000
6-19 PTMS MTMDS PTMDS PTMS 220,000
6-20 PTMS GPTMDS PTMDS PTMS 51,000
6-21 PTMS MAPTMDS PTMDS PTMS 73,000
6-22 MTMS MTMDS ECHETMDS ECHETMS 69,000
6-23 MTMS MTMDS PTMDS PTMS 51,000
6-24 MTMS MTMDS GPTMDS GPTMS 91,000
6-25 MTMS MTMDS MAPTMDS MAPTMS 128,000
6-26 MTMS ECHETMDS MTMDS MTMS 68,000
6-27 MTMS PTMDS MTMDS MTMS 45,000
6-28 MTMS GPTMDS MTMDS MTMS 265,000
6-29 MTMS MAPTMDS MTMDS MTMS 105,000
6-30 GPTMS GPTMDS ECHETMDS ECHETMS 101,000
6-31 GPTMS GPTMDS PTMDS PTMS 95,000
6-32 GPTMS GPTMDS MTMDS MTMS 73,000
6-33 GPTMS GPTMDS MAPTMDS MAPTMS 51,000
6-34 GPTMS ECHETMDS GPTMDS GPTMS 31,000
6-35 GPTMS PTMDS GPTMDS GPTMS 315,000
6-36 GPTMS MTMDS GPTMDS GPTMS 125,000
6-37 GPTMS MAPTMDS GPTMDS GPTMS 45,000
6-38 MAPTMS MAPTMDS ECHETMDS ECHETMS 94,000
6-39 MAPTMS MAPTMDS PTMDS PTMS 35,000
6-40 MAPTMS MAPTMDS MTMDS MTMS 80,000
6-41 MAPTMS MAPTMDS GPTMDS GPTMS 83,000
6-42 MAPTMS ECHETMDS MAPTMDS MAPTMS 74,000
6-43 MAPTMS PTMDS MAPTMDS MAPTMS 10,000
6-44 MAPTMS MTMDS MAPTMDS MAPTMS 65,000
6-45 MAPTMS GPTMDS MAPTMDS MAPTMS 418,000
실시예 7Example 7 : 실세스퀴옥산 A-B-A-D 구조 복합 고분자의 합성Synthesis of Silsesquioxane A-B-A-D Structured Polymer
합성단계는 아래와 같이, 연속가수분해 및 축합을 단계적으로 진행하였으며, 상기 실시예 1과 대등한 방법으로 코팅 조성물을 제조하였다.Synthesis step was carried out step by step, hydrolysis and condensation step by step, to prepare a coating composition in the same manner as in Example 1.
[실시예 7-a] 촉매의 제조Example 7-a Preparation of Catalyst
염기도 조절을 위하여, Tetramethylammonium hydroxide (TMAH) 25 중량% 수용액에 10 중량% Potassium hydroxide (KOH) 수용액을 혼합하여 촉매 1a를 준비하였다.In order to adjust the basicity, a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
[실시예 7-b] 선형 실세스퀴옥산 합성 (A 전구체)Example 7-b Linear Silsesquioxane Synthesis (A Precursor)
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 5 중량부, 테트라하이드로퓨란 15 중량부, 상기 실시예 7-a에서 제조된 촉매 1 중량부를 적가하고, 1시간 동안 상온에서 교반 한 후, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 20 중량부를 적가하고, 다시 테트라하이드로류란을 15 중량부 적가하여 5시간 추가 교반 하였다. 교반 중의 혼합용액을 적취하여, 두 차례 세정하는 것으로 촉매와 불순물을 제거하고 필터 한 후, IR 분석을 통하여 말단기에 생성된 SI-OH 관능기를 확인할 수 있었으며(3200 cm-1), 분자량을 측정한 결과, 선형구조의 실세스퀴옥산이 6,000 스티렌 환산 분자량을 가짐을 확인할 수 있었다.To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, 1 part by weight of the catalyst prepared in Example 7-a was added dropwise, and stirred at room temperature for 1 hour, followed by 2 20 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 15 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 5 hours. The mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 6,000 styrene.
[실시예 7-c] 선형 실세스퀴옥산 구조의 합성 (A-B전구체의 합성)Example 7-c Synthesis of Linear Silsesquioxane Structures (Synthesis of A-B Precursors)
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 5 중량부, 테트라하이드로퓨란 40 중량부, 상기 실시예 7-a에서 제조된 촉매 0.5 중량부를 적가하고, 1시간 동안 상온에서 교반 한 후, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 10 중량부를 적가하고, 다시 테트라하이드로류란을 20 중량부 적가하여 2시간 추가 교반 하였다. 교반 중의 혼합용액을 적취하여, 두 차례 세정하는 것으로 촉매와 불순물을 제거하고 필터 한 후, 1H-NMR 분석을 통하여 잔존하는 alkoxy group이 0.1 mmol/g 이하로 잔존하고 있는 선형 실세스퀴옥산을 얻어 내었고, 이는 이후 cage를 연속반응으로 도입하는데 이용되는 부분이다. 선형 구조의 형태 분석은 XRD 분석을 통해 전체적인 구조가 선형구조체임을 확인하였다. 분자량을 측정한 결과, 선형구조의 실세스퀴옥산이 8,000 스티렌 환산 분자량을 가짐을 확인할 수 있었다. To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, 0.5 parts by weight of the catalyst prepared in Example 7-a were added dropwise, followed by stirring at room temperature for 1 hour, and then 2 10 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 20 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 2 hours. The mixed solution was stirred and washed twice to remove the catalyst and impurities, and then filtered, and then linear silsesquioxane containing 0.1 mmol / g or less of the alkoxy group remaining through 1 H-NMR analysis. This was then used to introduce the cage into the continuous reaction. XRD analysis confirmed that the overall structure is a linear structure through the XRD analysis. As a result of measuring the molecular weight, it was confirmed that the silsesquioxane having a linear structure had a molecular weight in terms of 8,000 styrene.
[실시예 7-d] 선형 실세스퀴옥산 구조의 합성 (A-B-A전구체의 합성)Example 7-d Synthesis of Linear Silsesquioxane Structure (Synthesis of A-B-A Precursor)
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 5 중량부, 테트라하이드로퓨란 5 중량부, 제조된 실시예 7-a 촉매를 10 중량부를 적가하고, 1시간 동안 상온에서 교반 한 후, 실시예 7-b 전구체와 7-c 전구체를 20 중량부씩 각각 적가하고, 다시 테트라하이드로류란을 10 중량부 적가하여 24시간 추가 교반 하였다. 교반 중의 혼합용액을 적취하여, 두 차례 세정하는 것으로 촉매와 불순물을 제거하고 필터 한 후, IR 분석을 통하여 말단기에 생성된 SI-OH 관능기를 확인할 수 있었으며(3200 cm-1), 분자량을 측정한 결과, 선형구조의 실세스퀴옥산이 15,000 스티렌 환산 분자량을 가짐을 확인할 수 있었다.To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 5 parts by weight of tetrahydrofuran, 10 parts by weight of the prepared Example 7-a catalyst were added dropwise and stirred at room temperature for 1 hour, followed by Example 20 parts by weight of the 7-b precursor and the 7-c precursor were added dropwise, and 10 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 24 hours. The mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 15,000 styrene.
1H-NMR (CDCl3) δ 3.7, 3.4, 3.3(broad), 3.1, 2.8, 2.6, 1.5(broad), 0.6. 1 H-NMR (CDCl 3 ) δ 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6.
[실시예 7-e] 연속적 cage 구조의 생성 (D 구조의 도입)Example 7-e Generation of Continuous Cage Structure (Introduction of D Structure)
상기 실시예 7-d 혼합용액에 0.36 중량% HCl 수용액을 매우 천천히 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 ℃의 온도에서 30분간 교반하였다. 이후 Diphenyltetramethoxydisiloxane 5 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하고, 1시간 교반 후 실시예 7-a에서 제조된 촉매를 7 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, 선형고분자와는 별도로 alkoxy가 열려있는 D구조의 전구체가 형성된다. 소량의 샘플을 적취하여, H-NMR과 IR로 분석하여 methoxy의 잔존율을 확인한 후, 잔존율이 10% 일 때, 0.36 중량% HCl 수용액을 10 중량부 천천히 적가하여, pH를 산성으로 조절해 주었다. 이후 Phenyltrimethoxysilane 1 중량부를 한번에 적가하여 15분간 교반 후, 1-a에서 제조된 촉매 20 중량부를 첨가하였다. 4시간의 혼합교반 이후, 확인결과 고분자내에 cage 형태의 고분자가 생성됨을 확인 할 수 있었다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여, 전체적인 반응물이 수용액 혼합물로 변환되도록 하였다. 4시간의 혼합 교반 이후, 일부를 적취하여 29Si-NMR을 통해 분석한 결과 phenyl기를 이용해 도입된 구조의 분석피크가 날카로운 형태의 2개로 나타나고 별도로 잔존하는 부산물 없이 화학식 7과 같은 고분자가 제조되었음을 확인할 수 있었다. 또한 스티렌 환산 분자량은 18,000으로 측정되었다.To the mixed solution of Example 7-d 0.36% by weight of HCl solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 ℃ 30 minutes. Thereafter, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at a time to achieve stable hydrolysis. After stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 7-a was added again to adjust the pH of the mixed solution in a basic state. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy. When the residual ratio was 10%, 10 parts by weight of 0.36 wt% aqueous HCl solution was slowly added dropwise to adjust the pH to acidic. gave. Thereafter, 1 part by weight of Phenyltrimethoxysilane was added dropwise at a time, stirred for 15 minutes, and then 20 parts by weight of the catalyst prepared in 1-a was added. After 4 hours of mixing and stirring, it was confirmed that cage type polymer was formed in the polymer. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing and agitation, part of the sample was collected and analyzed by 29 Si-NMR. As a result, analytical peaks of the structure introduced using the phenyl group appeared as two sharp forms, and the polymer of formula 7 was prepared without any remaining by-products. Could. In addition, styrene conversion molecular weight was measured as 18,000.
29Si-NMR (CDCl3) δ -68.2, -72.3(broad), -81.1(sharp), -80.8(sharp), -82.5(broad) 29 Si-NMR (CDCl 3 ) δ -68.2, -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)
[실시예 7-f] B 구조내 X도입 (A-B-A-D구조의 완성)[Example 7-f] X introduction in B structure (completion of A-B-A-D structure)
상기 실시예 7-e에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 실시예 7-e에서 얻어진 물질 100 중량부를 50 중량부의 테트라하이드로퓨란에 녹인후, 5 중량부의 증류수를 넣어 혼합용액을 제조하였다. 이후 제조된 혼합용액에 0.36 wt% HCl 10 중량부를 첨가하고 10분간 교반 후, Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하였다. 24시간 교반 후 실시예 7-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, B 구조의 X 부분에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 7과 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After preparing the organic layer of the resultant obtained in Example 7-e without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 100 parts by weight of the material obtained in Example 7-e was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was added again to adjust the pH of the mixed solution in a basic state. At this time, the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (7). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 7-g] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 7-g] Removal of by-products by precipitation and recrystallization, yield of the result
상기 실시예 7-f에서 반응이 완료된 혼합물에 메틸렌크로라이드 200 중량부를 넣어, 증류수와 함께 분별 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 ℃의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. 200 parts by weight of methylene chloride was added to the mixture in which the reaction was completed in Example 7-f, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum reduction. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5, and stored at a temperature of -20 ° C for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 7의 고분자가 여러 부산물 없이 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 24,000의 값이었으며, X의 n 값은 4-6이었으며, Y의 n 값은 4-6이었다.     After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 7 was obtained without various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was a styrene conversion value of 24,000, the n value of X was 4-6, the n value of Y was 4-6.
또한, 하기 표 25에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자를 제조하였다. 이때 제조 방법은 상기 실시예 7에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer was prepared by applying the monomers described in Table 25 below. At this time, the manufacturing method was equally applied to the method used in Example 7.
표 25
실시방법 7-b,c 방법적용 단량체 7-e 방법적용 단량체 7-f 방법적용 단량체 분자량(Mw)
7 ECHETMS PTMDS MTMS 24,000
7-1 PTMS PTMDS PTMS 11,000
7-2 MTMS MTMDS MTMS 13,000
7-3 GPTMS GPTMDS GPTMS 23,000
7-4 MAPTMS MAPTMDS MAPTMS 14,500
7-5 ECHETMS ECHETMDS ECHETMS 12,500
7-6 ECHETMS MTMDS MTMS 53,000
7-7 ECHETMS GPTMDS GPTMS 11,000
7-8 ECHETMS MAPTMDS MAPTMS 9,000
7-9 PTMS ECHETMDS ECHETMS 48,000
7-10 PTMS MTMDS MTMS 90,000
7-11 PTMS GPTMDS GPTMS 32,000
7-12 PTMS MAPTMDS MAPTMS 150,000
7-13 MTMS ECHETMDS ECHETMS 17,000
7-14 MTMS PTMDS PTMS 38,500
7-15 MTMS GPTMDS GPTMS 15,000
7-16 MTMS MAPTMDS MAPTMS 17,000
7-17 GPTMS ECHETMDS ECHETMS 6,000
7-18 GPTMS PTMDS PTMS 18,000
7-19 GPTMS MTMDS MTMS 457,000
7-20 GPTMS MAPTMDS MAPTMS 16,000
7-21 MAPTMS ECHETMDS ECHETMS 97,000
7-22 MAPTMS PTMDS PTMS 951,000
7-23 MAPTMS MTMDS MTMS 15,000
7-24 MAPTMS GPTMDS GPTMS 12,000
Table 25
Method of implementation 7-b, c method applied monomer 7-e method applied monomer 7-f method applied monomer Molecular Weight (Mw)
7 ECHETMS PTMDS MTMS 24,000
7-1 PTMS PTMDS PTMS 11,000
7-2 MTMS MTMDS MTMS 13,000
7-3 GPTMS GPTMDS GPTMS 23,000
7-4 MAPTMS MAPTMDS MAPTMS 14,500
7-5 ECHETMS ECHETMDS ECHETMS 12,500
7-6 ECHETMS MTMDS MTMS 53,000
7-7 ECHETMS GPTMDS GPTMS 11,000
7-8 ECHETMS MAPTMDS MAPTMS 9,000
7-9 PTMS ECHETMDS ECHETMS 48,000
7-10 PTMS MTMDS MTMS 90,000
7-11 PTMS GPTMDS GPTMS 32,000
7-12 PTMS MAPTMDS MAPTMS 150,000
7-13 MTMS ECHETMDS ECHETMS 17,000
7-14 MTMS PTMDS PTMS 38,500
7-15 MTMS GPTMDS GPTMS 15,000
7-16 MTMS MAPTMDS MAPTMS 17,000
7-17 GPTMS ECHETMDS ECHETMS 6,000
7-18 GPTMS PTMDS PTMS 18,000
7-19 GPTMS MTMDS MTMS 457,000
7-20 GPTMS MAPTMDS MAPTMS 16,000
7-21 MAPTMS ECHETMDS ECHETMS 97,000
7-22 MAPTMS PTMDS PTMS 951,000
7-23 MAPTMS MTMDS MTMS 15,000
7-24 MAPTMS GPTMDS GPTMS 12,000
실시예 8Example 8 : D-A-B-A-D 구조 복합 실세스퀴옥산 고분자의 합성: Synthesis of D-A-B-A-D Structured Composite Silsesquioxane Polymers
D-A-B-D구조의 복합 고분자를 제조하기 위하여 아래의 실시예를 이용하였으며, 상기 실시예 1과 대등한 방법으로 코팅 조성물을 제조하였다.In order to manufacture a composite polymer having a D-A-B-D structure, the following examples were used, and a coating composition was prepared by the same method as in Example 1.
[실시예 8-a] D구조의 과량 생성을 위한 pH 변환 반응 Example 8-a pH Conversion Reaction for Excess Production of D Structure
반응이 진행 중인 실시예 7-d 혼합용액에 0.36 wt% HCl 수용액을 매우 천천히 15 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4 ℃의 온도에서 30분간 교반하였다. 이후 Diphenyltetramethoxydisiloxane의 양을 실시예 7-e의 5배인 25 중량부로 준비하여 한번에 적가하고, 1시간 교반 후 실시예 7-a에서 제조된 촉매를 20 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 반응 완료 후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여, 전체적인 반응물이 수용액 혼합물로 변환되도록 하였다. 4시간의 혼합교반 이후, 일부를 적취하여 29Si-NMR 및 1H-NMR 을 통해 분석한 결과 B 구조내에 존재하는 alkoxy group의 양이 0.006 mmol/g으로 변화되고 B 와 D의 반복단위가 약 5:5 비율로 도입되었음을 확인할 수 있었다. 또한 스티렌 환산 분자량은 32,000으로 측정되었다. 또한, cage형 구조가 도입되었음에도, 고분자의 GPC 형태에서 단독 cage형 물질의 분자량 분포를 찾아볼 수 없으므로, cage구조가 연속반응을 통해 고분자 사슬에 잘 도입되었음을 확인할 수 있었다.15 parts by weight of a 0.36 wt% HCl aqueous solution was added very slowly to the mixed solution of Example 7-d, the pH was adjusted to have acidity, and the mixture was stirred at a temperature of 4 ° C. for 30 minutes. Thereafter, the amount of diphenyltetramethoxydisiloxane was prepared by adding 25 parts by weight, which is 5 times the amount of Example 7-e, and added dropwise at once, and after stirring for 1 hour, 20 parts by weight of the catalyst prepared in Example 7-a was added again to give a basic pH of the mixed solution. Was adjusted. After the reaction was completed, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing, some of them were collected and analyzed by 29 Si-NMR and 1 H-NMR. The amount of alkoxy groups in the B structure was changed to 0.006 mmol / g and the repeating units of B and D were about It was confirmed that the ratio was introduced at 5: 5. In addition, styrene conversion molecular weight was measured as 32,000. In addition, although the cage type structure was introduced, the molecular weight distribution of the single cage type material was not found in the GPC form of the polymer, and thus the cage structure was well introduced into the polymer chain through the continuous reaction.
1H-NMR (CDCl3) 7.5, 7.2, 3.7, 3.4, 3.3(broad), 3.1, 2.8, 2.6, 1.5(broad), 0.6. 29Si-NMR (CDCl3) δ -72.5(broad), -81.1(sharp), -80.8(sharp), -79.9(sharp), -82.5(broad) 1 H-NMR (CDCl 3 ) 7.5, 7.2, 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6. 29 Si-NMR (CDCl 3 ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -82.5 (broad)
[실시예 8-b] B 구조내 X도입Example 8-b Introducing X in B Structure
상기 실시예 8-a에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 실시예 8-a에서 얻어진 물질 100 중량부를 50 중량부의 테트라하이드로퓨란에 녹인 후, 5 중량부의 증류수를 넣어 혼합용액을 제조하였다. 이후 제조된 혼합용액에 0.36 wt% HCl 10 중량부를 첨가하고 10분간 교반 후, Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하였다. 24시간 교반 후 실시예 7-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, B 구조의 X 부분에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 8와 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After preparing the organic layer of the resultant obtained in Example 8-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 100 parts by weight of the material obtained in Example 8-a was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was added again to adjust the pH of the mixed solution in a basic state. At this time, the cage-type polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (8). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 8-c] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 8-c] Removal of By-products by Precipitation and Recrystallization
상기 실시예 8-b에서 반응이 완료된 혼합물에 메틸렌크로라이드 200 중량부를 넣어, 증류수와 함께 분별 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 ℃의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. 200 parts by weight of methylene chloride was added to the mixture in which the reaction was completed in Example 8-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum reduction. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5, and stored at a temperature of -20 ° C for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 1의 고분자가 여러 부산물 없이 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 36,000의 값을 얻을 수 있었으며, X의 n 값은 4-6이었으며, Y의 n 값은 4-6이었으며, 특히 화학식 8의 결과는 다음과 같다.     After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 1 was obtained without various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in the styrene conversion value of 36,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 8 results are as follows.
29Si-NMR (CDCl3) δ -72.5(broad), -81.1(sharp), -80.8(sharp), -79.9(sharp), -81.5(sharp), -82.5(broad) 29 Si-NMR (CDCl 3 ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -81.5 (sharp), -82.5 (broad)
표 26
실시방법 7-b,c 방법적용 단량체 8-a 방법적용 단량체 8-b 방법적용 단량체 분자량(Mw)
8 ECHETMS PTMDS MTMS 36,000
8-1 PTMS PTMDS PTMS 14,000
8-2 MTMS MTMDS MTMS 18,000
8-3 GPTMS GPTMDS GPTMS 27,000
8-4 MAPTMS MAPTMDS MAPTMS 19,500
8-5 ECHETMS ECHETMDS ECHETMS 19,500
8-6 ECHETMS MTMDS MTMS 58,000
8-7 ECHETMS GPTMDS GPTMS 19,000
8-8 ECHETMS MAPTMDS MAPTMS 12,000
8-9 PTMS ECHETMDS ECHETMS 53,000
8-10 PTMS MTMDS MTMS 113,000
8-11 PTMS GPTMDS GPTMS 42,000
8-12 PTMS MAPTMDS MAPTMS 173,000
8-13 MTMS ECHETMDS ECHETMS 19,000
8-14 MTMS PTMDS PTMS 45,000
8-15 MTMS GPTMDS GPTMS 32,000
8-16 MTMS MAPTMDS MAPTMS 34,000
8-17 GPTMS ECHETMDS ECHETMS 12,000
8-18 GPTMS PTMDS PTMS 24,000
8-19 GPTMS MTMDS MTMS 486,000
8-20 GPTMS MAPTMDS MAPTMS 32,000
8-21 MAPTMS ECHETMDS ECHETMS 181,000
8-22 MAPTMS PTMDS PTMS 981,000
8-23 MAPTMS MTMDS MTMS 21,000
8-24 MAPTMS GPTMDS GPTMS 20,000
Table 26
Method of implementation 7-b, c method applied monomer 8-a Method Applicable Monomer 8-b Method Applicable Monomer Molecular Weight (Mw)
8 ECHETMS PTMDS MTMS 36,000
8-1 PTMS PTMDS PTMS 14,000
8-2 MTMS MTMDS MTMS 18,000
8-3 GPTMS GPTMDS GPTMS 27,000
8-4 MAPTMS MAPTMDS MAPTMS 19,500
8-5 ECHETMS ECHETMDS ECHETMS 19,500
8-6 ECHETMS MTMDS MTMS 58,000
8-7 ECHETMS GPTMDS GPTMS 19,000
8-8 ECHETMS MAPTMDS MAPTMS 12,000
8-9 PTMS ECHETMDS ECHETMS 53,000
8-10 PTMS MTMDS MTMS 113,000
8-11 PTMS GPTMDS GPTMS 42,000
8-12 PTMS MAPTMDS MAPTMS 173,000
8-13 MTMS ECHETMDS ECHETMS 19,000
8-14 MTMS PTMDS PTMS 45,000
8-15 MTMS GPTMDS GPTMS 32,000
8-16 MTMS MAPTMDS MAPTMS 34,000
8-17 GPTMS ECHETMDS ECHETMS 12,000
8-18 GPTMS PTMDS PTMS 24,000
8-19 GPTMS MTMDS MTMS 486,000
8-20 GPTMS MAPTMDS MAPTMS 32,000
8-21 MAPTMS ECHETMDS ECHETMS 181,000
8-22 MAPTMS PTMDS PTMS 981,000
8-23 MAPTMS MTMDS MTMS 21,000
8-24 MAPTMS GPTMDS GPTMS 20,000
실시예 9Example 9 : 실세스퀴옥산 E-A-B-A-D 구조 복합 고분자의 합성: Synthesis of Silsesquioxane E-A-B-A-D Structured Polymer
E-A-B-A-D구조의 복합 고분자를 제조하기 위하여 아래의 실시예를 이용하였으며, 상기 실시예 1과 대등한 방법으로 코팅 조성물을 제조하였다.In order to prepare a composite polymer having an E-A-B-A-D structure, the following examples were used, and a coating composition was prepared by the same method as in Example 1.
[실시예 9-a] 사슬 말단 E구조의 생성Example 9-a Generation of Chain Terminal E Structure
실시예 7-g 에서 얻어진 혼합물에 별도의 정제 없이 메틸렌크로라이드 20 중량부를 적가하고, 0.36 중량% HCl 수용액을 5 중량부 적가하고, pH가 산성을 가지도록 조절하였으며, 4℃의 온도에서 30분간 교반하였다. 이후 dimethyltetramethoxysilane 1 중량부를 한번에 적가하였다. 이때, 아직 분자구조 내에서 가수분해되지 않고 존재하던 부분들이 용매와 분리된 산성 수용액 층에서 가수분해물로 쉽게 변환되며, 생성된 별도의 반응물과 유기용매 층에서 축합되어 말단단위에 E가 도입되었다. 5시간의 교반 후, 반응의 교반을 정지하고 상온으로 반응기의 온도를 조절 하였다. To the mixture obtained in Example 7-g, 20 parts by weight of methylene chloride were added dropwise without further purification, 5 parts by weight of 0.36% by weight aqueous HCl solution was added dropwise, and the pH was adjusted to have an acidity, and 30 minutes at a temperature of 4 ° C. Stirred. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.
[실시예 9-b] B구조 및 말단 E 구조의 X에 cage 도입Example 9-b Introducing cage to X of B structure and terminal E structure
상기 실시예 9-a에서 얻어진 결과물의 유기층을 별도의 정제 없이 준비한 후, 3관능 단량체를 이용해서 말단을 cage구조로 변환하였다. 반응이 진행 중인 실시예 9-a 혼합용액에 Methyltrimethoxysilane 3 중량부를 한번에 적가하여, 안정적인 가수분해를 도모하고, 24시간 교반 후 실시예 7-a에서 제조된 촉매를 3 중량부 다시 첨가해 주어 염기성 상태로 혼합용액의 pH를 조절해 주었다. 이때, E 구조 말단에 cage 형태의 고분자가 도입되며, 반응기 내에서 연속적으로 반응이 진행되어 화학식 9과 같은 고분자가 형성된다. 그러나, 다른 부산물들과 함께 얻어지므로, 별도의 정제가 필요하였다. 이후, 상온으로 온도를 변화시키고, 혼합용액 내 테트라하이드로퓨란을 진공으로 제거하여 정제를 준비하였다. After preparing the organic layer of the resultant obtained in Example 9-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 9-a in progress at a time to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced at the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in formula (9). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
[실시예 9-c] 침전 및 재결정을 통한 부산물 제거, 결과물의 수득[Example 9-c] Removal of By-products by Precipitation and Recrystallization
상기 실시예 9-b에서 반응이 완료된 혼합물을 얻어낸 후, 증류수를 이용하여 세척하고, 증류수 층의 pH가 중성을 나타낼 때, 진공감압으로 용매를 완전히 제거하였다. 이후, 메탄올에 2회 침전하여, 미반응 단량체를 제거하고 테트라하이드로퓨란과 수용액이 9.5:0.5 중량비율로 혼합된 용매에 30 중량부로 녹여 -20 ℃의 온도에서 2일간 보관하였다. 이는 고분자에 도입되지 못하고, cage구조로 닫혀 버린 물질의 재결정을 도모하여, 정제가 쉽게 이루어지도록 하기 위함이다. After the reaction mixture was obtained in Example 9-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5, and stored at a temperature of -20 ° C for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.
재결정 과정을 마치고 얻어진 고체물질들을 필터 후, 진공감압을 통해 화학식 9의 고분자를 여러 부산물과 함께 얻어짐을 확인하였다. 또한, GPC 결과를 NMR 결과와 비교할 때, 각 단계의 고분자 성장에서 단독으로 얻어지는 저분자가 없이 Sharp한 형태의 Cage 형태가 결과로 도출되는 것으로 미루어 보아, 복합 고분자가 문제없이 얻어질 수 있음을 확인할 수 있었다. 이때, 분자량은 스티렌환산 값으로 28,000의 값을 얻을 수 있었으며, X의 n 값은 4-6이었으며, Y의 n 값은 4-6이었다.     After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Formula 9 was obtained along with various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in the styrene conversion value of 28,000, the n value of X was 4-6, the n value of Y was 4-6.
또한, 하기 표 27에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자를 제조하였다. 이때 제조 방법은 상기 실시예 9에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer was prepared by applying the monomers described in Table 27 below. In this case, the method used in Example 9 was equally applied.
또한, 하기 표 26에 기술한 단량체들을 적용하여 실세스퀴옥산 복합 고분자 및 코팅 조성물을 제조하였다. 이때 제조 방법은 상기 실시예 8에서 사용한 방법을 대등하게 적용하였다.In addition, the silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 26 below. At this time, the manufacturing method was equally applied to the method used in Example 8.
표 27
실시방법 7-b,c 방법적용 단량체 7-e 방법적용 단량체 9-a방법적용 단량체 9-b방법적용단량체 Mw
9 ECHETMS PTMDS MTMDS MAPTMS 28,000
9-1 ECHETMS ECHETMDS ECHETMDS ECHETMS 24,000
9-2 PTMS PTMDS PTMDS PTMS 21,000
9-3 MTMS MTMDS MTMDS MTMS 36,000
9-4 GPTMS ECHETMDS GPTMDS GPTMS 62,000
9-5 MAPTMS MAPTMDS MAPTMDS MAPTMS 153,000
9-6 ECHETMS ECHETMDS PTMDS PTMS 24,000
9-7 ECHETMS ECHETMDS MTMDS MTMS 19,000
9-8 ECHETMS ECHETMDS GPTMDS GPTMS 26,000
9-9 ECHETMS ECHETMDS MAPTMDS MAPTMS 99,000
9-10 ECHETMS PTMDS ECHETMDS ECHETMS 21,000
9-11 ECHETMS MTMDS ECHETMDS ECHETMS 142,000
9-12 ECHETMS GPTMDS ECHETMDS ECHETMS 70,000
9-13 ECHETMS MAPTMDS ECHETMDS ECHETMS 72,000
9-14 PTMS PTMDS ECHETMDS ECHETMS 15,000
9-15 PTMS PTMDS MTMDS MTMS 51,000
9-16 PTMS PTMDS ECHETMDS ECHETMS 85,000
9-17 PTMS PTMDS MAPTMDS MAPTMS 95,000
9-18 PTMS ECHETMDS PTMDS PTMS 160,000
9-19 PTMS MTMDS PTMDS PTMS 240,000
9-20 PTMS GPTMDS PTMDS PTMS 56,000
9-21 PTMS MAPTMDS PTMDS PTMS 71,000
9-22 MTMS MTMDS ECHETMDS ECHETMS 81,000
9-23 MTMS MTMDS PTMDS PTMS 63,000
9-24 MTMS MTMDS GPTMDS GPTMS 121,000
9-25 MTMS MTMDS MAPTMDS MAPTMS 153,000
9-26 MTMS ECHETMDS MTMDS MTMS 82,000
9-27 MTMS PTMDS MTMDS MTMS 63,000
9-28 MTMS GPTMDS MTMDS MTMS 310,000
9-29 MTMS MAPTMDS MTMDS MTMS 125,000
9-30 GPTMS GPTMDS ECHETMDS ECHETMS 97,000
9-31 GPTMS GPTMDS PTMDS PTMS 45,000
9-32 GPTMS GPTMDS MTMDS MTMS 61,000
9-33 GPTMS GPTMDS MAPTMDS MAPTMS 52,000
9-34 GPTMS ECHETMDS GPTMDS GPTMS 37,000
9-35 GPTMS PTMDS GPTMDS GPTMS 365,000
9-36 GPTMS MTMDS GPTMDS GPTMS 85,000
9-37 GPTMS MAPTMDS GPTMDS GPTMS 75,000
9-38 MAPTMS MAPTMDS ECHETMDS ECHETMS 144,000
9-39 MAPTMS MAPTMDS PTMDS PTMS 85,000
9-40 MAPTMS MAPTMDS MTMDS MTMS 60,000
9-41 MAPTMS MAPTMDS GPTMDS GPTMS 53,000
9-42 MAPTMS ECHETMDS MAPTMDS MAPTMS 12,000
9-43 MAPTMS PTMDS MAPTMDS MAPTMS 10,000
9-44 MAPTMS MTMDS MAPTMDS MAPTMS 32,000
9-45 MAPTMS GPTMDS MAPTMDS MAPTMS 231,000
Table 27
Method of implementation 7-b, c method applied monomer 7-e method applied monomer 9-a method applied monomer 9-b method applied monomer Mw
9 ECHETMS PTMDS MTMDS MAPTMS 28,000
9-1 ECHETMS ECHETMDS ECHETMDS ECHETMS 24,000
9-2 PTMS PTMDS PTMDS PTMS 21,000
9-3 MTMS MTMDS MTMDS MTMS 36,000
9-4 GPTMS ECHETMDS GPTMDS GPTMS 62,000
9-5 MAPTMS MAPTMDS MAPTMDS MAPTMS 153,000
9-6 ECHETMS ECHETMDS PTMDS PTMS 24,000
9-7 ECHETMS ECHETMDS MTMDS MTMS 19,000
9-8 ECHETMS ECHETMDS GPTMDS GPTMS 26,000
9-9 ECHETMS ECHETMDS MAPTMDS MAPTMS 99,000
9-10 ECHETMS PTMDS ECHETMDS ECHETMS 21,000
9-11 ECHETMS MTMDS ECHETMDS ECHETMS 142,000
9-12 ECHETMS GPTMDS ECHETMDS ECHETMS 70,000
9-13 ECHETMS MAPTMDS ECHETMDS ECHETMS 72,000
9-14 PTMS PTMDS ECHETMDS ECHETMS 15,000
9-15 PTMS PTMDS MTMDS MTMS 51,000
9-16 PTMS PTMDS ECHETMDS ECHETMS 85,000
9-17 PTMS PTMDS MAPTMDS MAPTMS 95,000
9-18 PTMS ECHETMDS PTMDS PTMS 160,000
9-19 PTMS MTMDS PTMDS PTMS 240,000
9-20 PTMS GPTMDS PTMDS PTMS 56,000
9-21 PTMS MAPTMDS PTMDS PTMS 71,000
9-22 MTMS MTMDS ECHETMDS ECHETMS 81,000
9-23 MTMS MTMDS PTMDS PTMS 63,000
9-24 MTMS MTMDS GPTMDS GPTMS 121,000
9-25 MTMS MTMDS MAPTMDS MAPTMS 153,000
9-26 MTMS ECHETMDS MTMDS MTMS 82,000
9-27 MTMS PTMDS MTMDS MTMS 63,000
9-28 MTMS GPTMDS MTMDS MTMS 310,000
9-29 MTMS MAPTMDS MTMDS MTMS 125,000
9-30 GPTMS GPTMDS ECHETMDS ECHETMS 97,000
9-31 GPTMS GPTMDS PTMDS PTMS 45,000
9-32 GPTMS GPTMDS MTMDS MTMS 61,000
9-33 GPTMS GPTMDS MAPTMDS MAPTMS 52,000
9-34 GPTMS ECHETMDS GPTMDS GPTMS 37,000
9-35 GPTMS PTMDS GPTMDS GPTMS 365,000
9-36 GPTMS MTMDS GPTMDS GPTMS 85,000
9-37 GPTMS MAPTMDS GPTMDS GPTMS 75,000
9-38 MAPTMS MAPTMDS ECHETMDS ECHETMS 144,000
9-39 MAPTMS MAPTMDS PTMDS PTMS 85,000
9-40 MAPTMS MAPTMDS MTMDS MTMS 60,000
9-41 MAPTMS MAPTMDS GPTMDS GPTMS 53,000
9-42 MAPTMS ECHETMDS MAPTMDS MAPTMS 12,000
9-43 MAPTMS PTMDS MAPTMDS MAPTMS 10,000
9-44 MAPTMS MTMDS MAPTMDS MAPTMS 32,000
9-45 MAPTMS GPTMDS MAPTMDS MAPTMS 231,000
[실험예] 휨 측정Experimental Example Warp Measurement
기재를 플라스틱 PC(i-components사, Glastic 0.5T), 유리(아사히, 소다라임 0.5T) 및 천연목재(우드앤휴먼 미송)에 대하여 휨방지 특성을 평가하였으며, 그 결과를 각각 표 28(플라스틱), 표 29(유리) 및 표 30(목재)에 나타내었다. 표 28 내지 30에서 2층 적층의 경우 도 2와 같은 구조를, 4층 적층의 경우 도 5와 같은 구조를, 양면 적층의 경우 3층 적층의 경우 도 3과 같은 구조를 가지도록 하였다. 코팅두께는 단층의 경우 10 um의 두께로 코팅하고, 2층 이상의 경우 각 층을 5 um씩 코팅(2층의 경우 전제 두께 10 um, 4층의 경우 20 um)하였으며, 양면의 경우 각 층을 10 um의 두께로 코팅하였다. 평가방법은 85%, 85℃ 신뢰성 챔버에 240시간 보관하고 휨 특성을 평가하였다. 평가방법은 3차원 휨 측정기를 이용하여 휨 정도를 측정하였으며, 도 6에 나타낸 바와 같이 전면을 9등분하고, 1,3,7 및 9번 포인트를 가상의 기준평면으로 지정한 후, 1 내지 9 모든 포인트의 높이를 측정하였다. 이때, 기준평면과 떨어진 거리의 최대(+높이).최소(-높이)값을 구하여 표기하였다. 휨의 -값은 아래로 휨을 의미하며, 휨의 +값은 위로 휨을 의미한다.The base material was evaluated for the anti-bending properties of plastic PC (i-components, Glastic 0.5T), glass (Asahi, soda lime 0.5T) and natural wood (wood and human non-conveyor), and the results are shown in Table 28 (Plastic 28). ), Table 29 (glass) and Table 30 (wood). In Tables 28 to 30, the structure shown in FIG. 2 in the case of two-layer lamination, the structure shown in FIG. 5 in the case of four-layer lamination, and the structure shown in FIG. The coating thickness is 10 um for single layer, 5 um for each layer (2 um for total thickness 10 um for two layers, 20 um for four layers), and for each layer. Coated to a thickness of 10 um. Evaluation method was stored in 85%, 85 ℃ reliability chamber for 240 hours and evaluated the bending characteristics. The evaluation method measured the degree of warp using a three-dimensional warpage measuring instrument, and as shown in Figure 6, the front part is divided into nine, and after designating the points 1, 3, 7 and 9 as the virtual reference plane, all 1 to 9 The height of the point was measured. At this time, the maximum (+ height) and the minimum (-height) value of the distance away from the reference plane was obtained and expressed. The negative value of warp means downward warp, and the positive value of warp means upward warp.
하기 표 28 내지 30에서 실시예 1 내지 실시예 9는 각각 실시예 1 내지 9에서 제조한 열경화성 코팅 조성물을 의미하며, 단일은 단일층, 2층 적층은 도 2와 같이 적층되며 먼저 기재한 층이 도 2 기재의 제1코팅층이 되고, 뒤에 기재된 층이 제2코팅층이 되며, 4층 적층은 도 5에 기재된 것과 같이 적층되며, 먼저 기재한 층부터 제1코팅층, 제2코팅층, 제3코팅층, 제4코팅층을 구성하며, 양면의 경우 도 3과 같이 적층되며, 먼저 기재한 코팅층이 제1코팅층, 뒤에 기재된 코팅층이 제2코팅층을 구성한다.In Tables 28 to 30, Examples 1 to 9 refer to thermosetting coating compositions prepared in Examples 1 to 9, respectively, where a single layer is a single layer and a two layer layer is stacked as shown in FIG. It becomes the 1st coating layer of FIG. 2, the layer described later becomes a 2nd coating layer, and a 4-layer lamination is laminated | stacked as described in FIG. 5, The first coating layer, the 2nd coating layer, the 3rd coating layer, A fourth coating layer is formed, and both surfaces are stacked as shown in FIG. 3, and the coating layer described first constitutes the first coating layer, and the coating layer described later constitutes the second coating layer.
표 28 (플라스틱 기재)
코팅층 No 코팅층 구성 휨 측정값(mm)
1 실시예 1 (단일) 0.401
2 실시예 2 (단일) 0.310
3 실시예 3 (단일) 0.300
4 실시예 4 (단일) 0.502
5 실시예 5 (단일) -0.525
6 실시예 6 (단일) -0.301
7 실시예 7 (단일) -0.505
8 실시예 8 (단일) -0.355
9 실시예 9 (단일) -0.404
10 실시예 1 + 실시예 9 (2층 적층) 0.150
11 실시예 2 + 실시예 8 (2층 적층) 0.195
12 실시예 3 + 실시예 7 (2층 적층) 0.181
13 실시예 4 + 실시예 6 (2층 적층) 0.160
14 실시예 5 + 실시예 1 (2층 적층) 0.181
15 실시예 6 + 실시예 2 (2층 적층) 0.138
16 실시예 7 + 실시예 3 (2층 적층) 0.145
17 실시예 8 + 실시예 6 (2층 적층) 0.161
18 실시예 9 + 실시예 5 (2층 적층) 0.181
19 실시예 1 + 실시예 5 + 실시예 4 + 실시예 6 (4층 적층) 0.088
20 실시예 2 + 실시예 6 + 실시예 8 + 실시예 4 (4층 적층) 0.080
21 실시예 3 + 실시예 7 + 실시예 5 + 실시예 2 (4층 적층) 0.093
22 실시예 4 + 실시예 8 + 실시예 6 + 실시예 9 (4층 적층) 0.070
23 실시예 5 + 실시예 9 + 실시예 2 + 실시예 7 (4층 적층) 0.065
24 실시예 6 + 실시예 1 + 실시예 3 + 실시예 5 (4층 적층) 0.085
25 실시예 7 + 실시예 2 + 실시예 5 + 실시예 3 (4층 적층) 0.081
26 실시예 8 + 실시예 3 + 실시예 7 + 실시예 1 (4층 적층) 0.051
27 실시예 9 + 실시예 4 + 실시예 1 + 실시예 8 (4층 적층) 0.055
28 실시예 1 + 실시예 9 (양면) 0.008
29 실시예 2 + 실시예 8 (양면) 0.010
30 실시예 3 + 실시예 7 (양면) 0.011
31 실시예 4 + 실시예 6 (양면) 0.008
32 실시예 5 + 실시예 1 (양면) 0.001
33 실시예 6 + 실시예 2 (양면) 0.005
34 실시예 7 + 실시예 3 (양면) 0.003
35 실시예 8 + 실시예 6 (양면) 0.007
36 실시예 9 + 실시예 5 (양면) 0.012
Table 28 (Plastic base material)
Coating Layer No Coating layer composition Warp Measurement (mm)
One Example 1 (single) 0.401
2 Example 2 (single) 0.310
3 Example 3 (single) 0.300
4 Example 4 (single) 0.502
5 Example 5 (single) -0.525
6 Example 6 (single) -0.301
7 Example 7 (single) -0.505
8 Example 8 (single) -0.355
9 Example 9 (single) -0.404
10 Example 1 + Example 9 (two-layer lamination) 0.150
11 Example 2 + Example 8 (two-layer lamination) 0.195
12 Example 3 + Example 7 (Lamination Layer) 0.181
13 Example 4 + Example 6 (Layer Layers) 0.160
14 Example 5 + Example 1 (two-layer lamination) 0.181
15 Example 6 + Example 2 (Lamination Layer) 0.138
16 Example 7 + Example 3 (two-layer lamination) 0.145
17 Example 8 + Example 6 (two-layer lamination) 0.161
18 Example 9 + Example 5 (two-layer lamination) 0.181
19 Example 1 + Example 5 + Example 4 + Example 6 (4-layer lamination) 0.088
20 Example 2 + Example 6 + Example 8 + Example 4 (4-layer Lamination) 0.080
21 Example 3 + Example 7 + Example 5 + Example 2 (4-layer Lamination) 0.093
22 Example 4 + Example 8 + Example 6 + Example 9 (4-layer Lamination) 0.070
23 Example 5 + Example 9 + Example 2 + Example 7 (4-layer Lamination) 0.065
24 Example 6 + Example 1 + Example 3 + Example 5 (4-layer lamination) 0.085
25 Example 7 + Example 2 + Example 5 + Example 3 (4-layer lamination) 0.081
26 Example 8 + Example 3 + Example 7 + Example 1 (4-layer lamination) 0.051
27 Example 9 + Example 4 + Example 1 + Example 8 (4-layer lamination) 0.055
28 Example 1 + Example 9 (both sides) 0.008
29 Example 2 + Example 8 (both sides) 0.010
30 Example 3 + Example 7 (both sides) 0.011
31 Example 4 + Example 6 (both sides) 0.008
32 Example 5 + Example 1 (both sides) 0.001
33 Example 6 + Example 2 (both sides) 0.005
34 Example 7 + Example 3 (both sides) 0.003
35 Example 8 + Example 6 (both sides) 0.007
36 Example 9 + Example 5 (both sides) 0.012
표 29 (유리 기재)
코팅층 No 코팅층 구성 휨 측정값(mm)
1 실시예 1 (단일) 0.201
2 실시예 2 (단일) 0.160
3 실시예 3 (단일) 0.180
4 실시예 4 (단일) 0.152
5 실시예 5 (단일) -0.255
6 실시예 6 (단일) -0.151
7 실시예 7 (단일) -0.205
8 실시예 8 (단일) -0.175
9 실시예 9 (단일) -0.104
10 실시예 1 + 실시예 9 (2층 적층) 0.115
11 실시예 2 + 실시예 8 (2층 적층) 0.114
12 실시예 3 + 실시예 7 (2층 적층) 0.104
13 실시예 4 + 실시예 6 (2층 적층) 0.103
14 실시예 5 + 실시예 1 (2층 적층) 0.113
15 실시예 6 + 실시예 2 (2층 적층) 0.115
16 실시예 7 + 실시예 3 (2층 적층) 0.108
17 실시예 8 + 실시예 6 (2층 적층) 0.112
18 실시예 9 + 실시예 5 (2층 적층) 0.114
19 실시예 1 + 실시예 5 + 실시예 4 + 실시예 6 (4층 적층) 0.008
20 실시예 2 + 실시예 6 + 실시예 8 + 실시예 4 (4층 적층) 0.007
21 실시예 3 + 실시예 7 + 실시예 5 + 실시예 2 (4층 적층) 0.006
22 실시예 4 + 실시예 8 + 실시예 6 + 실시예 9 (4층 적층) 0.006
23 실시예 5 + 실시예 9 + 실시예 2 + 실시예 7 (4층 적층) 0.005
24 실시예 6 + 실시예 1 + 실시예 3 + 실시예 5 (4층 적층) 0.008
25 실시예 7 + 실시예 2 + 실시예 5 + 실시예 3 (4층 적층) 0.007
26 실시예 8 + 실시예 3 + 실시예 7 + 실시예 1 (4층 적층) 0.007
27 실시예 9 + 실시예 4 + 실시예 1 + 실시예 8 (4층 적층) 0.006
28 실시예 1 + 실시예 9 (양면) 0.001
29 실시예 2 + 실시예 8 (양면) 0.002
30 실시예 3 + 실시예 7 (양면) 0.002
31 실시예 4 + 실시예 6 (양면) 0.002
32 실시예 5 + 실시예 1 (양면) 0.001
33 실시예 6 + 실시예 2 (양면) 0.002
34 실시예 7 + 실시예 3 (양면) 0.001
35 실시예 8 + 실시예 6 (양면) 0.002
36 실시예 9 + 실시예 5 (양면) 0.002
Table 29 (Glass material)
Coating Layer No Coating layer composition Warp Measurement (mm)
One Example 1 (single) 0.201
2 Example 2 (single) 0.160
3 Example 3 (single) 0.180
4 Example 4 (single) 0.152
5 Example 5 (single) -0.255
6 Example 6 (single) -0.151
7 Example 7 (single) -0.205
8 Example 8 (single) -0.175
9 Example 9 (single) -0.104
10 Example 1 + Example 9 (two-layer lamination) 0.115
11 Example 2 + Example 8 (two-layer lamination) 0.114
12 Example 3 + Example 7 (Lamination Layer) 0.104
13 Example 4 + Example 6 (Layer Layers) 0.103
14 Example 5 + Example 1 (two-layer lamination) 0.113
15 Example 6 + Example 2 (Lamination Layer) 0.115
16 Example 7 + Example 3 (two-layer lamination) 0.108
17 Example 8 + Example 6 (two-layer lamination) 0.112
18 Example 9 + Example 5 (two-layer lamination) 0.114
19 Example 1 + Example 5 + Example 4 + Example 6 (4-layer lamination) 0.008
20 Example 2 + Example 6 + Example 8 + Example 4 (4-layer Lamination) 0.007
21 Example 3 + Example 7 + Example 5 + Example 2 (4-layer Lamination) 0.006
22 Example 4 + Example 8 + Example 6 + Example 9 (4-layer Lamination) 0.006
23 Example 5 + Example 9 + Example 2 + Example 7 (4-layer Lamination) 0.005
24 Example 6 + Example 1 + Example 3 + Example 5 (4-layer lamination) 0.008
25 Example 7 + Example 2 + Example 5 + Example 3 (4-layer lamination) 0.007
26 Example 8 + Example 3 + Example 7 + Example 1 (4-layer lamination) 0.007
27 Example 9 + Example 4 + Example 1 + Example 8 (4-layer lamination) 0.006
28 Example 1 + Example 9 (both sides) 0.001
29 Example 2 + Example 8 (both sides) 0.002
30 Example 3 + Example 7 (both sides) 0.002
31 Example 4 + Example 6 (both sides) 0.002
32 Example 5 + Example 1 (both sides) 0.001
33 Example 6 + Example 2 (both sides) 0.002
34 Example 7 + Example 3 (both sides) 0.001
35 Example 8 + Example 6 (both sides) 0.002
36 Example 9 + Example 5 (both sides) 0.002
표 30
코팅층 No 코팅층 구성 휨 측정값(mm)
1 실시예 1 (단일) 0.311
2 실시예 2 (단일) 0.350
3 실시예 3 (단일) 0.300
4 실시예 4 (단일) 0.352
5 실시예 5 (단일) -0.355
6 실시예 6 (단일) -0.451
7 실시예 7 (단일) -0.325
8 실시예 8 (단일) -0.305
9 실시예 9 (단일) -0.354
10 실시예 1 + 실시예 9 (2층 적층) 0.180
11 실시예 2 + 실시예 8 (2층 적층) 0.175
12 실시예 3 + 실시예 7 (2층 적층) 0.191
13 실시예 4 + 실시예 6 (2층 적층) 0.170
14 실시예 5 + 실시예 1 (2층 적층) 0.191
15 실시예 6 + 실시예 2 (2층 적층) 0.165
16 실시예 7 + 실시예 3 (2층 적층) 0.175
17 실시예 8 + 실시예 6 (2층 적층) 0.171
18 실시예 9 + 실시예 5 (2층 적층) 0.175
19 실시예 1 + 실시예 5 + 실시예 4 + 실시예 6 (4층 적층) 0.012
20 실시예 2 + 실시예 6 + 실시예 8 + 실시예 4 (4층 적층) 0.011
21 실시예 3 + 실시예 7 + 실시예 5 + 실시예 2 (4층 적층) 0.010
22 실시예 4 + 실시예 8 + 실시예 6 + 실시예 9 (4층 적층) 0.011
23 실시예 5 + 실시예 9 + 실시예 2 + 실시예 7 (4층 적층) 0.012
24 실시예 6 + 실시예 1 + 실시예 3 + 실시예 5 (4층 적층) 0.013
25 실시예 7 + 실시예 2 + 실시예 5 + 실시예 3 (4층 적층) 0.013
26 실시예 8 + 실시예 3 + 실시예 7 + 실시예 1 (4층 적층) 0.012
27 실시예 9 + 실시예 4 + 실시예 1 + 실시예 8 (4층 적층) 0.011
28 실시예 1 + 실시예 9 (양면) 0.006
29 실시예 2 + 실시예 8 (양면) 0.007
30 실시예 3 + 실시예 7 (양면) 0.006
31 실시예 4 + 실시예 6 (양면) 0.005
32 실시예 5 + 실시예 1 (양면) 0.002
33 실시예 6 + 실시예 2 (양면) 0.004
34 실시예 7 + 실시예 3 (양면) 0.006
35 실시예 8 + 실시예 6 (양면) 0.002
36 실시예 9 + 실시예 5 (양면) 0.005
Table 30
Coating Layer No Coating layer composition Warp Measurement (mm)
One Example 1 (single) 0.311
2 Example 2 (single) 0.350
3 Example 3 (single) 0.300
4 Example 4 (single) 0.352
5 Example 5 (single) -0.355
6 Example 6 (single) -0.451
7 Example 7 (single) -0.325
8 Example 8 (single) -0.305
9 Example 9 (single) -0.354
10 Example 1 + Example 9 (two-layer lamination) 0.180
11 Example 2 + Example 8 (two-layer lamination) 0.175
12 Example 3 + Example 7 (Lamination Layer) 0.191
13 Example 4 + Example 6 (Layer Layers) 0.170
14 Example 5 + Example 1 (two-layer lamination) 0.191
15 Example 6 + Example 2 (Lamination Layer) 0.165
16 Example 7 + Example 3 (two-layer lamination) 0.175
17 Example 8 + Example 6 (two-layer lamination) 0.171
18 Example 9 + Example 5 (two-layer lamination) 0.175
19 Example 1 + Example 5 + Example 4 + Example 6 (4-layer lamination) 0.012
20 Example 2 + Example 6 + Example 8 + Example 4 (4-layer Lamination) 0.011
21 Example 3 + Example 7 + Example 5 + Example 2 (4-layer Lamination) 0.010
22 Example 4 + Example 8 + Example 6 + Example 9 (4-layer Lamination) 0.011
23 Example 5 + Example 9 + Example 2 + Example 7 (4-layer Lamination) 0.012
24 Example 6 + Example 1 + Example 3 + Example 5 (4-layer lamination) 0.013
25 Example 7 + Example 2 + Example 5 + Example 3 (4-layer lamination) 0.013
26 Example 8 + Example 3 + Example 7 + Example 1 (4-layer lamination) 0.012
27 Example 9 + Example 4 + Example 1 + Example 8 (4-layer lamination) 0.011
28 Example 1 + Example 9 (both sides) 0.006
29 Example 2 + Example 8 (both sides) 0.007
30 Example 3 + Example 7 (both sides) 0.006
31 Example 4 + Example 6 (both sides) 0.005
32 Example 5 + Example 1 (both sides) 0.002
33 Example 6 + Example 2 (both sides) 0.004
34 Example 7 + Example 3 (both sides) 0.006
35 Example 8 + Example 6 (both sides) 0.002
36 Example 9 + Example 5 (both sides) 0.005
상기 표 28 내지 30에 나타난 바와 같이 본 발명의 휨방지 기재는 적층의 소재를 적절히 조절할 경우, 현저히 향상된 우수한 휨현상 방지 특성을 나타내었다. 특히 양면 코팅의 경우 매우 우수한 휨방지 특성을 나타내었다.As shown in Tables 28 to 30, the anti-bending substrate of the present invention exhibited significantly improved excellent anti-bending properties when the material of the laminate is properly adjusted. In particular, the double-sided coating showed very good bending resistance.
또한 상기 표 28 내지 30에는 열경화성 코팅 조성물에 대해서만 측정결과를 기재하였지만 광경화성 수지 조성물에 대하여도 열경화성 수지 조성물과 대등한 결과를 나타내었다.In addition, although the measurement results are described only for the thermosetting coating composition in Tables 28 to 30, the results of the photocurable resin composition also showed comparable results with the thermosetting resin composition.
- 표면경도측정 : 일반적으로 연필경도법(JIS 5600-5-4)은 일반적으로 750 g 하중으로 평가하는데 이보다 가혹조건인 1 kgf 하중으로 코팅면에 45도 각도로 연필을 매초 0.5 mm의 속도로 수평으로 10 mm 이동해서 코팅막을 긁어서 긁힌 흔적으로 평가하였다. 5회 실험 중 3 mm 이상의 긁힌 흔적이 2회 이상 확인되지 않으면 상위 경도의 연필을 선택하여 평가하고, 긁힌 흔적이 2회 이상 확인되면 그 연필경도보다 한단 하위의 연필을 선택하여 해당 코팅막의 연필경도를 평가하여 하기 표 31에 나타내었다. 평가 결과는 10 um 이상의 코팅 두께에서 기판 종류에 상관없이 유리수준의 9H 경도를 확인하였다.-Surface hardness measurement In general, the pencil hardness method (JIS 5600-5-4) is generally rated at 750 g load, which is 10 mm horizontal at a rate of 0.5 mm per second at a 45-degree angle to the coating surface at a more severe 1 kgf load. The coating film was moved to evaluate the scratches. If more than 3 mm of scratches are not found more than 2 times in 5 experiments, the pencil of the higher hardness is selected and evaluated. To evaluate the results are shown in Table 31 below. The evaluation results confirmed the 9H hardness of the glass level regardless of the substrate type at a coating thickness of 10 um or more.
- Scratch test 측정(JIS K5600-5-9): Steel wool에 의한 마모 평가법은 1kg 정도 무게의 쇠망치의 선단에 #0000의 Steel wool을 감아서 15회 왕복 시험편을 문지르고 그 헤이즈를 값을 측정하는데, 이번 평가에서는 이보다 가혹한 조건인 400회 시험편을 문지르고 헤이즈 측정 및 현미경으로 육안 평가 진행하였다. 결과는 헤이즈 증가가 0.05% 이상 증가할 경우 실패로 판단하였다. 코팅두께가 5 um 이상의 코팅에서는 표면에 발생되는 스크레치에 대한 내성이 우수한 것을 확인하였다.-Scratch test measurement (JIS K5600-5-9): The wear evaluation method by steel wool is to rub the # 0000 steel wool on the tip of iron hammer weighing about 1kg, rub the 15 round trip specimens and measure the haze value. In this evaluation, the test piece was rubbed 400 times under severer conditions and visually evaluated by haze measurement and microscope. The result was judged to be failure when the increase in haze increased by more than 0.05%. In the coating thickness of more than 5 um it was confirmed that the resistance to scratches generated on the surface is excellent.
- 접착력 평가(JIS K5600-5-6) : 코팅막을 1-5 mm간격으로 컷터날로 긁어서 그 위에 셀로판테이프를 붙이고 붙인 테입을 잡아당겼을 때 이탈된 갯수로 접착성 판단하는데 이때 컷터날로 100개의 칸을 만들어 100개 중 떨어지는 개수로 접착성 판단 시행하였으며, 하기 표 31에 나타내었다. 표기는 100개중 떨어지지 않은 개수로 "(떨어지지 않은 개수/100)"로 표기 예제로 100개가 떨어지지 않으면 "(100/100)"로 표기 하였다. 접착성은 매우 우수한 것을 확인하였다.-Evaluation of adhesive force (JIS K5600-5-6): When the coating film is scratched with a cutter blade at intervals of 1-5 mm, the cellophane tape is attached on it, and the adhesive tape is judged for its adhesiveness when the tape is pulled out. Adhesive determination was made by the number of falling made of 100, shown in Table 31 below. The notation is "(100/100) not falling out of the number of 100" In the example of not falling 100 ("100/100)". It was confirmed that the adhesiveness was very excellent.
- 투과도(ASTM D1746): 입사하는 빛의 전광선 투과율을 UV/vis spectroscopy를 이용하여 측정하였다.Transmission (ASTM D1746): The total light transmittance of incident light was measured using UV / vis spectroscopy.
- 접촉각 : 접촉각 측정기(KRUSS社의 DSA100)를 이용하여 시료 표면에 물방울을 적하한 후, 1분 후에 물방울에 대한 접촉각을 측정하였다. 접촉각은 시료 당 5회 측정하여 그 평균치를 사용하였다.Contact angle : After dropping water droplets on the surface of a sample using a contact angle measuring instrument (DSA100 manufactured by KRUSS Co., Ltd.), the contact angle with respect to the water droplets was measured after 1 minute. The contact angle was measured 5 times per sample and the average value was used.
표 31
평가항목 PC 유리 목재
코팅전 코팅후 코팅전 코팅후 코팅전 코팅후
단층 2층 적층 4층 적층 양면적층 단층 2층 적층 4층 적층 양면적층 단층 2층 적층 4층 적층 양면적층
표명경도(1Kgf)(성공횟수/시도횟수) 6B이하 9H (5/5) 9H(5/5) 9H(5/5) 9H(5/5) 9H 9H(5/5) 9H(5/5) 9H(5/5) 9H(5/5) 9H(5/5) 9H(5/5) 9H(5/5) 9H(5/5)
접착력(PASS-100/100) - pass pass pass pass - pass pass pass pass - pass pass pass pass
투과율(%)UV-Vis 89.2 88.5 88.5 88.5 88.4 92.3 91.8 91.7 91.8 91.9 - - - - -
Scrath test(Steel wool, 1kgf하중,400회) fail pass pass pass pass - pass pass pass pass - pass pass pass pass
Haze(%) 0.15 0.12 0.11 0.09 0.03 0.01 0.05 0.08 0.01 0.01 - - - - -
접촉각(°)(D20 31 111 110 113 113 25 113 110 112 111 침습 110 111 113 112
Table 31
Evaluation item PC Glass wood
Before coating After coating Before coating After coating Before coating After coating
fault 2-layer lamination 4-layer lamination Double sided fault 2-layer lamination 4-layer lamination Double sided fault 2-layer lamination 4-layer lamination Double sided
Manifestation hardness (1Kgf) (number of success / attempts) Less than 6B 9H (5/5) 9H (5/5) 9H (5/5) 9H (5/5) 9H 9H (5/5) 9H (5/5) 9H (5/5) 9H (5/5) 9H (5/5) 9H (5/5) 9H (5/5) 9H (5/5)
Adhesive force (PASS-100 / 100) - pass pass pass pass - pass pass pass pass - pass pass pass pass
Transmittance (%) UV-Vis 89.2 88.5 88.5 88.5 88.4 92.3 91.8 91.7 91.8 91.9 - - - - -
Scrath test (Steel wool, 1kgf load, 400 times) fail pass pass pass pass - pass pass pass pass - pass pass pass pass
Haze (%) 0.15 0.12 0.11 0.09 0.03 0.01 0.05 0.08 0.01 0.01 - - - - -
Contact angle (°) (D 2 0 31 111 110 113 113 25 113 110 112 111 Invasion 110 111 113 112
상기 표 31에 나타난 바와 같이 본 발명의 휨방지 기재는 코팅층들이 우수한 물성을 나타내었으며, 4층 적층의 경우에도 코팅층 사이에 접착성이 우수하여 들뜨는 현상은 발생되지 않았다.As shown in Table 31, the anti-bending substrate of the present invention showed excellent physical properties of the coating layers, and even in the case of four-layer lamination, the phenomenon of lifting due to excellent adhesion between the coating layers did not occur.
본 발명에 따른 기재의 휨현상 방지 코팅방법은 기재의 휨현상을 간단한 코팅공정을 통하여 방지할 수 있을 뿐만 아니라 동시에 기재의 표면에 높은 표면경도, 우수한 투명성, 내스크레치성, 발수특성, 방오특성, 내지문성, 열안정성 및 광택특성을 부여함으로써 제품의 내구성 및 효용가치를 크게 높일 수 있다.The warpage prevention coating method of the substrate according to the present invention can not only prevent the warpage of the substrate through a simple coating process but at the same time high surface hardness, excellent transparency, scratch resistance, water repellency, antifouling properties, anti-fingerprint on the surface of the substrate By imparting heat stability and glossiness, the durability and utility value of the product can be greatly increased.

Claims (16)

  1. 기재의 휨현상 방지 코팅방법으로서,As a warping prevention coating method of the substrate,
    기재의 표면에 밀도가 서로 다른 코팅 조성물을 코팅하여 2층 이상의 코팅층을 형성하며,Coating the coating composition of different densities on the surface of the substrate to form two or more coating layers,
    상기 2층 이상의 코팅층 중 적어도 한층은 하기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물을 코팅하고 경화하는 것을 특징으로 하는 기재의 휨현상 방지 코팅방법:At least one of the two or more coating layers is a coating method for preventing warpage of the substrate, characterized in that for coating and curing a coating composition comprising a silsesquioxane composite polymer represented by any one of the following formulas (1) to (9):
    [화학식 1][Formula 1]
    Figure PCTKR2015003192-appb-I000030
    Figure PCTKR2015003192-appb-I000030
    [화학식 2][Formula 2]
    Figure PCTKR2015003192-appb-I000031
    Figure PCTKR2015003192-appb-I000031
    [화학식 3][Formula 3]
    Figure PCTKR2015003192-appb-I000032
    Figure PCTKR2015003192-appb-I000032
    [화학식 4][Formula 4]
    Figure PCTKR2015003192-appb-I000033
    Figure PCTKR2015003192-appb-I000033
    [화학식 5][Formula 5]
    Figure PCTKR2015003192-appb-I000034
    Figure PCTKR2015003192-appb-I000034
    [화학식 6][Formula 6]
    Figure PCTKR2015003192-appb-I000035
    Figure PCTKR2015003192-appb-I000035
    [화학식 7][Formula 7]
    Figure PCTKR2015003192-appb-I000036
    Figure PCTKR2015003192-appb-I000036
    [화학식 8][Formula 8]
    Figure PCTKR2015003192-appb-I000037
    Figure PCTKR2015003192-appb-I000037
    [화학식 9][Formula 9]
    Figure PCTKR2015003192-appb-I000038
    Figure PCTKR2015003192-appb-I000038
    A는 A is
    Figure PCTKR2015003192-appb-I000039
    이고,B는
    Figure PCTKR2015003192-appb-I000040
    이고,
    Figure PCTKR2015003192-appb-I000039
    And B is
    Figure PCTKR2015003192-appb-I000040
    ego,
    D는
    Figure PCTKR2015003192-appb-I000041
    이고, E는
    Figure PCTKR2015003192-appb-I000042
    이며,    D is
    Figure PCTKR2015003192-appb-I000041
    And E is
    Figure PCTKR2015003192-appb-I000042
    Is,
    Y는 각각 독립적으로 O, NR21 또는 [(SiO3/2R)4+2nO]이며, 적어도 하나는 [(SiO3/2R)4+2nO]이며, Each Y is independently O, NR 21 or [(SiO 3/2 R) 4 + 2n O], at least one is [(SiO 3/2 R) 4 + 2n O],
    X는 각각 독립적으로 R22 또는 [(SiO3/2R)4+2nR]이고, 적어도 하나는 [(SiO3/2R)4+2nR]이고,Each X is independently R 22 or [(SiO 3/2 R) 4 + 2n R], at least one is [(SiO 3/2 R) 4 + 2n R],
    R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22는 각각 독립적으로 수소; 중수소; 할로겐; 아민기; 에폭시기; 사이클로헥실에폭시기; (메타)아크릴기; 사이올기; 이소시아네이트기; 니트릴기; 니트로기; 페닐기; 중수소, 할로겐, 아민기, 에폭시기, (메타)아크릴기, 사이올기, 이소시아네이트기, 니트릴기, 니트로기, 페닐기로 치환되거나 치환되지 않은 C1~C40의 알킬기; C2~C40의 알케닐기; C1~C40의 알콕시기; C3~C40의 시클로알킬기; C3~C40의 헤테로시클로알킬기; C6~C40의 아릴기; C3~C40의 헤테로아릴기; C3~C40의 아르알킬기; C3~C40의 아릴옥시기; 또는 C3~C40의 아릴사이올기이며, R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C 1 -C 40 alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; C 2 -C 40 alkenyl group; C 1 ~ C 40 Alkoxy group; C 3 -C 40 cycloalkyl group; C 3 ~ C 40 Heterocycloalkyl group; C 6 -C 40 aryl group; C 3 ~ C 40 heteroaryl group; An aralkyl group of C 3 ~ C 40; C 3 -C 40 aryloxy group; Or an C 3 ~ C 40 aryl siol group,
    a 및 d는 각각 독립적으로 1 내지 100,000의 정수이고,a and d are each independently an integer of 1 to 100,000,
    b는 각각 독립적으로 1 내지 500의 정수이며,b are each independently an integer of 1 to 500,
    e는 각각 독립적으로 1 또는 2이며,e are each independently 1 or 2,
    n은 각각 독립적으로 1 내지 20의 정수이다.n is independently an integer of 1-20.
  2. 제1항에 있어서,The method of claim 1,
    상기 기재는 플라스틱, 유리, 금속박막, 목재 또는 펄프인 것을 특징으로 하는 기재의 휨현상 방지 코팅방법.Said substrate is plastic, glass, metal thin film, wood or pulp anti-bending coating method of the substrate, characterized in that.
  3. 제2항에 있어서,The method of claim 2,
    상기 플라스틱은 폴리에틸렌(polyethylene, PE), 폴리프로필렌(polypropylene, PP), 폴리스타이렌(polystyrene, PS), 폴리에틸렌 테레프탈레이트(polyethylene terephthalate, PET, 페트), 폴리아미드(polyamides, PA, 나일론), 폴리에스터(polyester, PES), 폴리염화비닐(polyvinyl chloride, PVC), 폴리우레탄(polyurethanes, PU), 폴리카보네이트(polycarbonate, PC), 폴리염화비닐리덴(polyvinylidene chloride, PVDC), 폴리테트라플루오로에틸렌(polytetrafluoroethylene, PTFE), 폴리에테르에테르케톤(polyetheretherketone, PEEK), 및 폴리에테르이미드(polyetherimide, PEI)로 이루어진 군으로부터 1종 이상 선택되는 것을 특징으로 하는 기재의 휨현상 방지 코팅방법.The plastic is polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (polyethylene terephthalate, PET, PET), polyamides (PA, nylon), polyester ( polyester, PES), polyvinyl chloride (PVC), polyurethane (PU), polycarbonate (PC), polyvinylidene chloride (PVDC), polytetrafluoroethylene (polytetrafluoroethylene, PTFE), polyetheretherketone (PEEK), and polyetherimide (polyetherimide, PEI) is selected from the group consisting of at least one of the anti-warp coating method of the substrate.
  4. 제1항에 있어서,The method of claim 1,
    상기 각각의 코팅층의 코팅 두께는 0.01 내지 500 um인 것을 특징으로 하는 기재의 휨현상 방지 코팅방법.Coating thickness of each coating layer is 0.01 to 500um coating method of preventing warpage of the substrate, characterized in that.
  5. 제1항에 있어서,The method of claim 1,
    a는 3 내지 1000이고, b는 1 내지 500, d는 1 내지 500인 것을 특징으로 하는 기재의 휨현상 방지 코팅방법.a is 3 to 1000, b is 1 to 500, d is 1 to 500, the anti-bending coating method of the substrate.
  6. 제1항에 있어서,The method of claim 1,
    상기 실세스퀴옥산 복합 고분자의 중량평균분자량이 1,000 내지 1,000,000인 것을 특징으로 하는 기재의 휨현상 방지 코팅방법.The coating method of the warpage phenomenon prevention substrate, characterized in that the weight average molecular weight of the silsesquioxane composite polymer is 1,000 to 1,000,000.
  7. 제1항에 있어서,The method of claim 1,
    서로 다른 상기 코팅조성물들의 밀도차이는 적어도 0.001 g/cm3 이상인 것을 특징으로 하는 휨현상 방지 코팅방법.Density difference of the different coating composition is at least 0.001 g / cm 3 or more coating method characterized in that the.
  8. 제1항에 있어서,The method of claim 1,
    상기 코팅층을 기재의 양면에 형성하는 것을 특징으로 하는 휨현상 방지 코팅방법.Bending phenomenon preventing coating method characterized in that the coating layer is formed on both sides of the substrate.
  9. 제1항에 있어서,The method of claim 1,
    코팅층의 최외각층은 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물을 코팅하고 경화하는 것을 특징으로 하는 기재의 휨현상 방지 코팅방법.The outermost layer of the coating layer is a coating method for preventing warpage of the substrate, characterized in that for coating and curing the coating composition comprising the silsesquioxane composite polymer represented by any one of the formulas (1) to (9).
  10. 제1항에 있어서,The method of claim 1,
    모든 코팅층이 밀도가 서로 다른 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물을 코팅하고 경화하는 것을 특징으로 하는 기재의 휨현상 방지 코팅방법.A coating method for preventing warpage of a substrate, wherein all coating layers coat and cure a coating composition including a silsesquioxane composite polymer represented by any one of Formulas 1 to 9 having different densities.
  11. 제1항에 있어서,The method of claim 1,
    상기 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물은 The coating composition comprising the silsesquioxane composite polymer
    상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자;Silsesquioxane composite polymer represented by any one of Formulas 1 to 9;
    개시제; 및Initiator; And
    유기용매;Organic solvents;
    를 포함하는 것을 특징으로 기재의 휨현상 방지 코팅방법.Bending phenomenon prevention coating method of the substrate, characterized in that it comprises a.
  12. 표면 위에 밀도가 서로 다른 코팅 조성물을 코팅하여 형성된 2층 이상의 코팅층을 구비하며, 상기 코팅층 중의 적어도 하나는 상기 화학식 1 내지 9 중 어느 하나로 표시되는 실세스퀴옥산 복합 고분자를 포함하는 코팅조성물로 형성된 것을 특징으로 하는 휨현상 방지 기재.At least one coating layer formed by coating a coating composition having a different density on the surface, wherein at least one of the coating layer is formed of a coating composition containing a silsesquioxane composite polymer represented by any one of the formulas (1) to (9) Warping phenomenon prevention substrate characterized in that.
  13. 제12항에 있어서,The method of claim 12,
    상기 휨현상 방지 기재 기재는 제1항 기재의 방법에 의하여 형성된 것을 특징으로 하는 휨현상 방지 기재. The warpage preventing substrate base material is formed by the method of claim 1 wherein the warpage preventing substrate.
  14. 제12항에 있어서,The method of claim 12,
    상기 기재는 플라스틱, 유리, 목재 또는 펄프인 것을 특징으로 하는 휨현상 방지 기재.The substrate is a warpage preventing substrate, characterized in that the plastic, glass, wood or pulp.
  15. 제12항 기재의 휨현상 방지 기재를 포함하는 물품.An article comprising the warpage preventing substrate of claim 12.
  16. 제15항에 있어서,The method of claim 15,
    상기 물품은 디스플레이의 윈도우 커버 기판, 보호필름, 보호판; 목재가구; 목재 건축 내외장제; 목재 악세서리; 목재공공시설물; 건축물 또는 구조물의 벽재, 바닥재, 타일, 지붕재, 창문; 컵, 접시, 그릇; 반도체 제조장치; 자동차의 유리; 안경; 또는 광학제품, 전자제품, 태양전지에 사용되는 유리;인 것을 특징으로 물품.The article includes a window cover substrate, a protective film, a protective plate of the display; Wooden furniture; Wood building interior and exterior materials; Wood accessories; Wood public facilities; Walls, floors, tiles, roofs, windows of buildings or structures; Cups, plates, bowls; Semiconductor manufacturing apparatus; Glass of the car; glasses; Or glass used in optical products, electronic products, solar cells.
PCT/KR2015/003192 2014-03-31 2015-03-31 Coating method for preventing bending phenomenon of substrate WO2015152617A1 (en)

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