CA1073593A - Composition containing a monoethylenically unsaturated adduct and one of a polyisocyanate, polycarboxylic polyanhydride or polyepoxide - Google Patents
Composition containing a monoethylenically unsaturated adduct and one of a polyisocyanate, polycarboxylic polyanhydride or polyepoxideInfo
- Publication number
- CA1073593A CA1073593A CA261,597A CA261597A CA1073593A CA 1073593 A CA1073593 A CA 1073593A CA 261597 A CA261597 A CA 261597A CA 1073593 A CA1073593 A CA 1073593A
- Authority
- CA
- Canada
- Prior art keywords
- adduct
- radiation curable
- coating composition
- curable coating
- monoethylenically unsaturated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 229920002732 Polyanhydride Polymers 0.000 title claims abstract description 6
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 6
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 5
- 229920000647 polyepoxide Polymers 0.000 title claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 19
- 150000002596 lactones Chemical class 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 16
- -1 hydroxyalkyl ester Chemical class 0.000 claims abstract description 13
- 230000005855 radiation Effects 0.000 claims abstract description 13
- 239000008199 coating composition Substances 0.000 claims abstract description 10
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 238000007259 addition reaction Methods 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 11
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 6
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 6
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 239000003504 photosensitizing agent Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 2
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 12
- 150000002148 esters Chemical class 0.000 abstract description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 20
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 16
- 238000000576 coating method Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229940024874 benzophenone Drugs 0.000 description 6
- 239000012965 benzophenone Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 125000004386 diacrylate group Chemical group 0.000 description 4
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 229940086542 triethylamine Drugs 0.000 description 2
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- YWCPWZFRYVVVRS-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate;2-methyloxirane Chemical compound CC1CO1.OCCOC(=O)C=C YWCPWZFRYVVVRS-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241000357437 Mola Species 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- VAMFXQBUQXONLZ-UHFFFAOYSA-N icos-1-ene Chemical compound CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention as disclosed provides a radiation curable coating composition comprising the addition reaction product of (i) a monoethylenically unsaturated adduct of a monoethylenically unsaturated carboxylic acid or a hydroxyalkyl ester thereof with an anhydride containing at least 3 carbon atoms and selected from monepoxides, lactones and mixtures thereof, said adduct containing an average of at least 1 mole of anhydride per mole of hydroxyester and an average of at least 2 moles of anhydride per mole of acid moiety, with (ii) an organic compound containing a plurality of groups capable of reacting with active hydrogen. The organic compound (ii) includes those (such as polyisocyanates) which form a urethane linkage, those (such as polycarboxylic polyanhydrides) which form an ester linkage, or those (such as polyexpoxides) which form an ether linkage.
The present invention as disclosed provides a radiation curable coating composition comprising the addition reaction product of (i) a monoethylenically unsaturated adduct of a monoethylenically unsaturated carboxylic acid or a hydroxyalkyl ester thereof with an anhydride containing at least 3 carbon atoms and selected from monepoxides, lactones and mixtures thereof, said adduct containing an average of at least 1 mole of anhydride per mole of hydroxyester and an average of at least 2 moles of anhydride per mole of acid moiety, with (ii) an organic compound containing a plurality of groups capable of reacting with active hydrogen. The organic compound (ii) includes those (such as polyisocyanates) which form a urethane linkage, those (such as polycarboxylic polyanhydrides) which form an ester linkage, or those (such as polyexpoxides) which form an ether linkage.
Description
~ 3~j9~
The present invention relat~s to coatlng composltlons and more particularly to radlation curable coating composltlons.
Coatlng compositions normally contain a vehicle in addition to the actual film-forming resins. This vehlcle, which ls present only to assist the application of the film-forming resins, has to be removed usually by the application o~ heat. Thls ls energy-consuming and may also lead to atmospheric pollutlon i~
the solvent vapor~ are not recovered. The solvent ltself may be lost and this can represent an economic disadvantage. Emulsion type composltions ln which the film-~orming resln is suspended as a flne di~perslon ln water have been used in an attempt to avoid the use of solvents but again, the water has to be removed, usually by the use of heat, and this is even more energy-consuming than the remo~al o~ volatile hydrocarbon solvent because of the relatively hlgh boiling point and latent heat o~ vaporization of the water.
We have now found that extremely satlsfactory radiatlon curable coating compositions can be made using the reactlon products of (1) certain carboxyllc acld adducts with (il) compounds contalnlng a plurality of groups capable of reacting wlth actlve hydrogens.
The present invention, therefore, resides in a radiation curable coating composition comprising the addition reaction product of (i) a monoethylenically unsaturated adduct of a monoethylenically unsaturated carboxylic acid or hydroxyalkyl ester thereof with an anhydride containing at least 3 carbon atoms and selected from monoepoxides, lactones, and mixtures thereof, said adduct containing an average of at least l mole of anhydride per mole of hydroxyester and an average of at least 2 moles of anhydride per mole of acid moiety, with (ii) an organic compound containing a plurality of groups capable -of reacting with active hydrogen, said organic compound being a polyisocyanate, polycarboxylic polyanhydride or polyepoxide.
B
~ 3~
~ he composltions can be cured by radiation (preferably ultra-vlolet or electron beam) and form good coatings. .i photo-sensitizer may be present when an ultra-violet cure is used although lt is not necessary when an electron beam cure is employed.
The adduct is an adduct of a monoethylenically un-saturated acid or its hydroxyalkyl ester and an anhydride (epoxide or lactone). In preparing the adduct, the monoethylenlcally unsaturated carboxylic acid or its hydroxyalkyl derivative is reacted wlth an appropriate proportion of an anhydride of a dihydrlc la-, 1~3~j.9;3 alcohol or an hydr xy acid ti.e. a monoepoxide or a lactone) containlng at leas' three carbon atoms. These are partlcularly illustrated by 1,2-propylene oxide, which ~s the anhydride of 1,2-propylene diol, or by epsilon-caprolactone, which is the anhydride of the corresponding hydroxy acid. The use of other similar anhydrides will be discussed below.
Preferably a hydroxyaIkyl est~r of the mcnoethylenically unsaturated carboxylic acld is reacted (adducted) wlth at least 1 mole of the monoepoxide or lactone. The reaction is preferably carried out in the presence o~ a Lewis acid catalyst, such as BF3 etherate or stannic chloride, and at a typical temperature of 30 to 70C.
Under these conditions, an ether or ester forms, the a~erage number of added groups corresponding to the number of moles of monoepoxide or lactone employed. In order to produce a product whlch wlll be reactlve in the coatlngs, the unsaturatlon must be malntained and thls llmits the temperature of the reaction which is exothermic.
By slow addition of the monoepoxide or lactone, and in the presence of inhibitors, higher temperatures up to 120C. may be used, but practical operation suggests an upper llmlt of 80C.
Very low temperatures are useful, but the reaction slows with decreasing temperature. In the same way, the adduction reaction can be carried out with the mon oe thylenically unsaturated acid itself, but in this case at least 2 moles of the monoepoxide or lactone must be used for each mole of acld. The monoe~oxide reactant or the lactone reactant can be constituted by a mi~ture of monoepo~ides, a mlxture of lactones, or a mixture of the two.
It is preferred to react at least 3 moles of the mon oepoxide and~or la~'one with the mon oe thylenically unsaturated carboxylic B-lOt~3~9..~
acid or its hydroxyalkyl ester because this maximizes water resistance and ultraviolet sensitivity. It also significantly reduces volatility and toxicity. The polyethers provide the best ultraviolet sensitivity, and are preferred.
There is normally little purpose served by using more than 10 moles of the monoepoxide and/or lactone on the basis noted above, but so long as the reaction is substantlally complete or if unreacted monoepoxide or lactone is removed, the product will be useful.
Various monoepoxides may be used herein, such as propylene oxide, butylene oxide, butyl glycidyl ether, phenyl glycldyl ether, cyclohexene oxide, and the llke. The oxirane group i8 preferably carried by an aliphatic group. While other functionallty whlch ls lnert under the conditions of reactlon may be present, such as the halogen group as in epichlorohydrin, lt is usually preferred that a single 1,2-epoxide group be the 801e functional group present. Propylene oxide is the preferred monoepoxide. Whlle the 1,2-epoxlde group is preferred, thls is not essential and tetrahydrofuran and 1,3-dioxolane are fully useful to illustrate this. In some instances, and to provide polyacrylates directly, glycidyl acrylate may be used, particularly to~ether with a conventlonal monoepoxlde such as propylene oxide.
While ethylene oxide produces undesired water solubility when used alone, it is possible to have some of it present herein where other agents overcome or minimize the problem o~ water sensitivity.
Various lactones may be used, such as butyrolactone or caprolactone. Epsilon caprolactone is the preferred lactone.
When the acid itself is used (as distinct from the hydroxyalkyl .
1073~9~3 ester), the lactone is not reacted with the unsaturated acld in the abse~ce of an epoxide since hydroxy functlonal derivatives are desired.
Ihe mDnoethylenically unsaturat~ carbcxylic add is preferably acrylic acid, but other slmilar acids, such as methacryllc acld, and crotonlc acid are also useful. The acld is preferably monocarboxylic~ but polycarboxylic aclds may be used, such as ltaconlc acld or fumarlc acld. Monobutyl maleate and monohydro~y-propyl,maleate will further lllustrate use~ul monoethylenically unsaturated carboxylic acids.
Ihese sr~noe ~ylenically ~sa~rat~d acids can ~e used as such, or they can be employed ln the form of hydroxy alkyl ester3 in which the alkyl group preferably contains ~rom 2 to 4 carbon atoms.
These esters are typlfled by hydroxyethyl acrylate. The mono-functional acids noted before and their hydro2y esters provide mono~unctional adducts.
The adduct ls reacted with a compound which contains a plurality of groups which are reacti~e wlth active hydrogens.
Such reactive groups lnclude isocyanate (~orms a urethane linkage), carboxylic acid anhydrlde (forms an ester llnkage), or epoxide (~or,ms an ether llnkage). Suitable compounds for reactlon with the adduct therefore lnclude polyisocyanates e.g.dllsocyanates such a~ tolylene diisocyanate, polyanhydrides e.g. dianhydrides such as benzophenone tetracarboxylic acld dianhydride, styrene~
maleic anhydride copolymers or ethylene/malelc anhydrlde copolymers especlally low molecular welght styrene/maleic anhydrlde copolymers, polyepoxldes e.g. Epon 828 (trade mark), dimethyl dichlorosllane, methyl trichlorosilane.
.
~' lO~S9;1 The reactive compound is reacted with the adduct in amounts up to the stoichiometric requirement. More of the compound may be used but since it will not take part in the reaction, this will not be economically favored.
The selection of benzophenone-tetracarboxylic acid dlanhydrlde is particularly preferred since this leads directly to ultraviolet curable reaction products, especially polyacrylates, whlch are lnternally sensitized to ultraviolet light. This permits omission of photo~ensitizers such as benzophenone. For an electron beam cure there is no need of a photosensitiser.
The reactlon of the adducts with the organic-poly-isocyanates or the polycarboxylic acid polyanhydrides or other compounds is a slmple addition reaction which proceeds at moderate temperature (20C. - 100C., preferably 50CC. - 80C.).
The unsaturatlon is not destroyed in this reaction so that a compound wlth polyethylenic unsaturation ls produced.
It should be observed that the reactlon product o~
The present invention relat~s to coatlng composltlons and more particularly to radlation curable coating composltlons.
Coatlng compositions normally contain a vehicle in addition to the actual film-forming resins. This vehlcle, which ls present only to assist the application of the film-forming resins, has to be removed usually by the application o~ heat. Thls ls energy-consuming and may also lead to atmospheric pollutlon i~
the solvent vapor~ are not recovered. The solvent ltself may be lost and this can represent an economic disadvantage. Emulsion type composltions ln which the film-~orming resln is suspended as a flne di~perslon ln water have been used in an attempt to avoid the use of solvents but again, the water has to be removed, usually by the use of heat, and this is even more energy-consuming than the remo~al o~ volatile hydrocarbon solvent because of the relatively hlgh boiling point and latent heat o~ vaporization of the water.
We have now found that extremely satlsfactory radiatlon curable coating compositions can be made using the reactlon products of (1) certain carboxyllc acld adducts with (il) compounds contalnlng a plurality of groups capable of reacting wlth actlve hydrogens.
The present invention, therefore, resides in a radiation curable coating composition comprising the addition reaction product of (i) a monoethylenically unsaturated adduct of a monoethylenically unsaturated carboxylic acid or hydroxyalkyl ester thereof with an anhydride containing at least 3 carbon atoms and selected from monoepoxides, lactones, and mixtures thereof, said adduct containing an average of at least l mole of anhydride per mole of hydroxyester and an average of at least 2 moles of anhydride per mole of acid moiety, with (ii) an organic compound containing a plurality of groups capable -of reacting with active hydrogen, said organic compound being a polyisocyanate, polycarboxylic polyanhydride or polyepoxide.
B
~ 3~
~ he composltions can be cured by radiation (preferably ultra-vlolet or electron beam) and form good coatings. .i photo-sensitizer may be present when an ultra-violet cure is used although lt is not necessary when an electron beam cure is employed.
The adduct is an adduct of a monoethylenically un-saturated acid or its hydroxyalkyl ester and an anhydride (epoxide or lactone). In preparing the adduct, the monoethylenlcally unsaturated carboxylic acid or its hydroxyalkyl derivative is reacted wlth an appropriate proportion of an anhydride of a dihydrlc la-, 1~3~j.9;3 alcohol or an hydr xy acid ti.e. a monoepoxide or a lactone) containlng at leas' three carbon atoms. These are partlcularly illustrated by 1,2-propylene oxide, which ~s the anhydride of 1,2-propylene diol, or by epsilon-caprolactone, which is the anhydride of the corresponding hydroxy acid. The use of other similar anhydrides will be discussed below.
Preferably a hydroxyaIkyl est~r of the mcnoethylenically unsaturated carboxylic acld is reacted (adducted) wlth at least 1 mole of the monoepoxide or lactone. The reaction is preferably carried out in the presence o~ a Lewis acid catalyst, such as BF3 etherate or stannic chloride, and at a typical temperature of 30 to 70C.
Under these conditions, an ether or ester forms, the a~erage number of added groups corresponding to the number of moles of monoepoxide or lactone employed. In order to produce a product whlch wlll be reactlve in the coatlngs, the unsaturatlon must be malntained and thls llmits the temperature of the reaction which is exothermic.
By slow addition of the monoepoxide or lactone, and in the presence of inhibitors, higher temperatures up to 120C. may be used, but practical operation suggests an upper llmlt of 80C.
Very low temperatures are useful, but the reaction slows with decreasing temperature. In the same way, the adduction reaction can be carried out with the mon oe thylenically unsaturated acid itself, but in this case at least 2 moles of the monoepoxide or lactone must be used for each mole of acld. The monoe~oxide reactant or the lactone reactant can be constituted by a mi~ture of monoepo~ides, a mlxture of lactones, or a mixture of the two.
It is preferred to react at least 3 moles of the mon oepoxide and~or la~'one with the mon oe thylenically unsaturated carboxylic B-lOt~3~9..~
acid or its hydroxyalkyl ester because this maximizes water resistance and ultraviolet sensitivity. It also significantly reduces volatility and toxicity. The polyethers provide the best ultraviolet sensitivity, and are preferred.
There is normally little purpose served by using more than 10 moles of the monoepoxide and/or lactone on the basis noted above, but so long as the reaction is substantlally complete or if unreacted monoepoxide or lactone is removed, the product will be useful.
Various monoepoxides may be used herein, such as propylene oxide, butylene oxide, butyl glycidyl ether, phenyl glycldyl ether, cyclohexene oxide, and the llke. The oxirane group i8 preferably carried by an aliphatic group. While other functionallty whlch ls lnert under the conditions of reactlon may be present, such as the halogen group as in epichlorohydrin, lt is usually preferred that a single 1,2-epoxide group be the 801e functional group present. Propylene oxide is the preferred monoepoxide. Whlle the 1,2-epoxlde group is preferred, thls is not essential and tetrahydrofuran and 1,3-dioxolane are fully useful to illustrate this. In some instances, and to provide polyacrylates directly, glycidyl acrylate may be used, particularly to~ether with a conventlonal monoepoxlde such as propylene oxide.
While ethylene oxide produces undesired water solubility when used alone, it is possible to have some of it present herein where other agents overcome or minimize the problem o~ water sensitivity.
Various lactones may be used, such as butyrolactone or caprolactone. Epsilon caprolactone is the preferred lactone.
When the acid itself is used (as distinct from the hydroxyalkyl .
1073~9~3 ester), the lactone is not reacted with the unsaturated acld in the abse~ce of an epoxide since hydroxy functlonal derivatives are desired.
Ihe mDnoethylenically unsaturat~ carbcxylic add is preferably acrylic acid, but other slmilar acids, such as methacryllc acld, and crotonlc acid are also useful. The acld is preferably monocarboxylic~ but polycarboxylic aclds may be used, such as ltaconlc acld or fumarlc acld. Monobutyl maleate and monohydro~y-propyl,maleate will further lllustrate use~ul monoethylenically unsaturated carboxylic acids.
Ihese sr~noe ~ylenically ~sa~rat~d acids can ~e used as such, or they can be employed ln the form of hydroxy alkyl ester3 in which the alkyl group preferably contains ~rom 2 to 4 carbon atoms.
These esters are typlfled by hydroxyethyl acrylate. The mono-functional acids noted before and their hydro2y esters provide mono~unctional adducts.
The adduct ls reacted with a compound which contains a plurality of groups which are reacti~e wlth active hydrogens.
Such reactive groups lnclude isocyanate (~orms a urethane linkage), carboxylic acid anhydrlde (forms an ester llnkage), or epoxide (~or,ms an ether llnkage). Suitable compounds for reactlon with the adduct therefore lnclude polyisocyanates e.g.dllsocyanates such a~ tolylene diisocyanate, polyanhydrides e.g. dianhydrides such as benzophenone tetracarboxylic acld dianhydride, styrene~
maleic anhydride copolymers or ethylene/malelc anhydrlde copolymers especlally low molecular welght styrene/maleic anhydrlde copolymers, polyepoxldes e.g. Epon 828 (trade mark), dimethyl dichlorosllane, methyl trichlorosilane.
.
~' lO~S9;1 The reactive compound is reacted with the adduct in amounts up to the stoichiometric requirement. More of the compound may be used but since it will not take part in the reaction, this will not be economically favored.
The selection of benzophenone-tetracarboxylic acid dlanhydrlde is particularly preferred since this leads directly to ultraviolet curable reaction products, especially polyacrylates, whlch are lnternally sensitized to ultraviolet light. This permits omission of photo~ensitizers such as benzophenone. For an electron beam cure there is no need of a photosensitiser.
The reactlon of the adducts with the organic-poly-isocyanates or the polycarboxylic acid polyanhydrides or other compounds is a slmple addition reaction which proceeds at moderate temperature (20C. - 100C., preferably 50CC. - 80C.).
The unsaturatlon is not destroyed in this reaction so that a compound wlth polyethylenic unsaturation ls produced.
It should be observed that the reactlon product o~
2 moles of hydroxyethyl acrylate and 1 mole of toluene diisocy-anate is a solid. Replacing the hydroxyethyl acrylate with the 5 mole propylene oxide adduct thereof produces a liquid diacrylate, and the liquid form is much more attractive, since it can be used wlthout solvents. Also, the final cured products are less brittle.
By virtue of the polyether or polyester structure of the adduct, the compo~itions have lowered volatlllty, reduced toxicity, are easily handled and cure excellently. Particularly where the polyether structure is present, amine cosensitizers are not needed, and while they wlll still benefit the cure some-what, the amines create yellowing or extraction problems, and 10'~3.~
their omission can be important in certain instances.
The polyethylenically unsaturated derivatives of the adduct can be used alone, or they can be combined with other ethyleni-cally unsaturated monomers and polymers to provide radiation curable systems which are particularly useful for coating.
Other ethylenically unsaturated materials which may be used are illustrated by styrene, acrylonitrile, the polyacrylates such as butylene glycol diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, epoxy polyacrylates (both di- and tetraacrylates) and maleic polyesters.
Radiation curable coatings are also described and claimed in related copending Canadian Patent Application No. 261,598 of Kaufman, filed September 20, 1976. m e coatings therein described comprise a monoethylenically unsaturated adduct of a monoethylenically unsaturated carboxylic acid or hydroxyalkyl ester thereof with an anhydride containing at least 3 carbon atoms and selected from the group consisting of monoepoxides, lactones, and mixtures thereof, said adduct containing an average of at least 1 mole of said anhydricle per mole of said hydroxy ester or an average of at least 2 moles of said anhydride per mole of ~aid acid, said monoethylenically unsaturated adduct being in admixture with a polyacrylate providing a plurality of ethylenically unsaturated acrylic acid ester groups.
The present invention is illustrated in the Examples which follow. Examples 1 to 7 and 16 illustrate the preparation of the adducts. Examples 8 to 12 illustrate the preparation and use of the reaction products and Examples 13 to 15 illustrate coatings containing the products. ; -- . . ~ . .. . -. ..
10~3~
Example l Charge a dry reaction vessel fitted with a stirrer, thermometer, condenser, drying tube and two additional funnels with 928g hydroxyethyl acrylate (8.o moles). Add enough boron-trifluoride etherate to initiate the-reaction, approximately 1 ml.
Then, with suitable cooling, add 2320g propylene oxide (40.0 moles) and additional BF3 etherate (15-20 ml.) at such a rate 80 as to maintain react~on temperature at 50~C. Total ~ddition time i8 2-2.5 hours. Maintain the temperature as high as pos-sible by decreasing cooling. When the temperature drops to about 40C., sample the reaction for gas chromatography. When gas chromatography shows no propylene oxide, add 0.32g hydro-qu~none (lO0 parts per million) and 2 ml. triethylamine to stabilize the product. The product is a clear, light yellow ~5 liquid of 35-40 centipoise viscosity. A complete gas chroma-tography analysis indicates the product is a mixture of hydroxy-ethyl acrylate (~u2%) and adducts thereof having the formula shown below in which x ranges from 1 to about lO, and has an ~ average value of 5. NMR analysis of the products shows the j 20 correct ratlo oi vinyl protons to the remaining types of pro-¦ tons and lnfrared analysis shows the presence ce hydroxyl, acrylate unsaturation and ether bands, all consistent with the I following structure:
.
CH2= C-C OCH2CH2-O ~CH-CH2-~0~ XH AV1--05 .
;
.
.
l~q~59~
Ex~ple 2 Following the procedure of Example 1, except using 10 moles of propyl~ne oxide to 1 mole of hydrox~ethyl acrylate, the product is a li~ht colored liquid of 70-75 centipoise vi~cosity ~ith the st~ucture noted in Exa~ple 1, but with x .
averaging 10.
Example 3 Following the procedure of Fxample L, except using 6 moles of propylene oxide to 1 mole of acrylic acid, the product ha~ the structure noted below:
x=6 (average) Example 4 .
Following the procedure of Example l, except using
By virtue of the polyether or polyester structure of the adduct, the compo~itions have lowered volatlllty, reduced toxicity, are easily handled and cure excellently. Particularly where the polyether structure is present, amine cosensitizers are not needed, and while they wlll still benefit the cure some-what, the amines create yellowing or extraction problems, and 10'~3.~
their omission can be important in certain instances.
The polyethylenically unsaturated derivatives of the adduct can be used alone, or they can be combined with other ethyleni-cally unsaturated monomers and polymers to provide radiation curable systems which are particularly useful for coating.
Other ethylenically unsaturated materials which may be used are illustrated by styrene, acrylonitrile, the polyacrylates such as butylene glycol diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, epoxy polyacrylates (both di- and tetraacrylates) and maleic polyesters.
Radiation curable coatings are also described and claimed in related copending Canadian Patent Application No. 261,598 of Kaufman, filed September 20, 1976. m e coatings therein described comprise a monoethylenically unsaturated adduct of a monoethylenically unsaturated carboxylic acid or hydroxyalkyl ester thereof with an anhydride containing at least 3 carbon atoms and selected from the group consisting of monoepoxides, lactones, and mixtures thereof, said adduct containing an average of at least 1 mole of said anhydricle per mole of said hydroxy ester or an average of at least 2 moles of said anhydride per mole of ~aid acid, said monoethylenically unsaturated adduct being in admixture with a polyacrylate providing a plurality of ethylenically unsaturated acrylic acid ester groups.
The present invention is illustrated in the Examples which follow. Examples 1 to 7 and 16 illustrate the preparation of the adducts. Examples 8 to 12 illustrate the preparation and use of the reaction products and Examples 13 to 15 illustrate coatings containing the products. ; -- . . ~ . .. . -. ..
10~3~
Example l Charge a dry reaction vessel fitted with a stirrer, thermometer, condenser, drying tube and two additional funnels with 928g hydroxyethyl acrylate (8.o moles). Add enough boron-trifluoride etherate to initiate the-reaction, approximately 1 ml.
Then, with suitable cooling, add 2320g propylene oxide (40.0 moles) and additional BF3 etherate (15-20 ml.) at such a rate 80 as to maintain react~on temperature at 50~C. Total ~ddition time i8 2-2.5 hours. Maintain the temperature as high as pos-sible by decreasing cooling. When the temperature drops to about 40C., sample the reaction for gas chromatography. When gas chromatography shows no propylene oxide, add 0.32g hydro-qu~none (lO0 parts per million) and 2 ml. triethylamine to stabilize the product. The product is a clear, light yellow ~5 liquid of 35-40 centipoise viscosity. A complete gas chroma-tography analysis indicates the product is a mixture of hydroxy-ethyl acrylate (~u2%) and adducts thereof having the formula shown below in which x ranges from 1 to about lO, and has an ~ average value of 5. NMR analysis of the products shows the j 20 correct ratlo oi vinyl protons to the remaining types of pro-¦ tons and lnfrared analysis shows the presence ce hydroxyl, acrylate unsaturation and ether bands, all consistent with the I following structure:
.
CH2= C-C OCH2CH2-O ~CH-CH2-~0~ XH AV1--05 .
;
.
.
l~q~59~
Ex~ple 2 Following the procedure of Example 1, except using 10 moles of propyl~ne oxide to 1 mole of hydrox~ethyl acrylate, the product is a li~ht colored liquid of 70-75 centipoise vi~cosity ~ith the st~ucture noted in Exa~ple 1, but with x .
averaging 10.
Example 3 Following the procedure of Fxample L, except using 6 moles of propylene oxide to 1 mole of acrylic acid, the product ha~ the structure noted below:
x=6 (average) Example 4 .
Following the procedure of Example l, except using
3 moles of butylglycidyl ether to l mole of hydroxyethyl acrylate yields an adduct having an average of three butylglycidyl ether groups per molecule of hydroxyethyl acrylate.
. .
Example 5 Following the procedure o~ Example 1, eXcept using ~our moles o~ propylene oxide and 1 mole of phenyl glycidyl ether to 1 le of hydroxyethyl acrylate yields an adduct having an average of 4 propylene oxide group~ and 1 phenyl glycidyl ether group per molecule of hydroxyethyl acrylate.
. i .
;
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., i . . .
- .. . . . . ..... . . . ... .
: . . . - . . - . . -~1073S~:~
Example 6 Following the procedure of Example 1, except using'
. .
Example 5 Following the procedure o~ Example 1, eXcept using ~our moles o~ propylene oxide and 1 mole of phenyl glycidyl ether to 1 le of hydroxyethyl acrylate yields an adduct having an average of 4 propylene oxide group~ and 1 phenyl glycidyl ether group per molecule of hydroxyethyl acrylate.
. i .
;
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,.,,1, . . .
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., i . . .
- .. . . . . ..... . . . ... .
: . . . - . . - . . -~1073S~:~
Example 6 Following the procedure of Example 1, except using'
4 ~oles of propylene oxide and 1 mole of tetrahydrofuran to 1 mole of hydroxyethyl acrylate yields an adduct having an average of 4 propylene oxide groups and l tetrahydrofur~n group per mo~ecule of hydroxyethyl acrylate.
.
Example 7 ':
Followi~g the procedure of Example 1, except using 4 moles of propylene oxide and t mole o epsilon-capro~actone to ~0 1 mole of hydroxyethyl acrylate yields an adduct having an a~erage of 4 propylene oxide groups a~d 1 caprolactone group per molecule of hydroxyethyl acrylate.
. .
Example 8 ,;'' ' To 406 grams of the hydroxy~ethyl acrylate-propylene oxide adduct produced in Example l,are added 28.7 grams o the commercial 80l20 i~omeric mixture o~ toluene diisocyanates, 0.17 gra~
hydroquinone and 3 drops dibutyl tin dilau~at,e catalyst. The ' reaction mixture is heated at 60-65C. for about 2 hours after which the infrared spectrum show~ complete reaction of the ' ~socyanate. The product is a l~w viscosity li~uit ~(Gardner-Holdt ~G! (165 centipoise)] containing a mixture of a diacrylate resin li and unreacted monoacrylate monomer. The ~tructure of ~he i diacrylate resin i8 shown below:
: CH3 H 0 . ~ ~-C-HEA.5P0 , ~ N-C-HEA.5P0 HEA identifies hydroxyethyl acrylate P0 identifies propylene oxide.
i .
_ 9 _ .' , ' :, . .
~ 10~3~3 Example 9 To 406 grams of the hydroxyethyl acrylate-propylene oxide additian product o~ Example 1 are added 40.3 grams benzophenone-tetracarboxylic dianhydride, 2.2 grams triethyl amine, and 0.178 grams hydroquinone. The reaction mixture is heated ~t 70C. for 3-4 hours after which the in~rared spectrum shGws no anhydride re-maining. At thls point the reae~ion mixture consists o~ a diiu~c-t~onal acrylate resin and a mono~unctional acrylate moncmer of low ~is~osity ~(Gardner-Holdt = J (250 centipoise)~. The structure o~ ~he diacrylate 18 shown below:
.
Example 7 ':
Followi~g the procedure of Example 1, except using 4 moles of propylene oxide and t mole o epsilon-capro~actone to ~0 1 mole of hydroxyethyl acrylate yields an adduct having an a~erage of 4 propylene oxide groups a~d 1 caprolactone group per molecule of hydroxyethyl acrylate.
. .
Example 8 ,;'' ' To 406 grams of the hydroxy~ethyl acrylate-propylene oxide adduct produced in Example l,are added 28.7 grams o the commercial 80l20 i~omeric mixture o~ toluene diisocyanates, 0.17 gra~
hydroquinone and 3 drops dibutyl tin dilau~at,e catalyst. The ' reaction mixture is heated at 60-65C. for about 2 hours after which the infrared spectrum show~ complete reaction of the ' ~socyanate. The product is a l~w viscosity li~uit ~(Gardner-Holdt ~G! (165 centipoise)] containing a mixture of a diacrylate resin li and unreacted monoacrylate monomer. The ~tructure of ~he i diacrylate resin i8 shown below:
: CH3 H 0 . ~ ~-C-HEA.5P0 , ~ N-C-HEA.5P0 HEA identifies hydroxyethyl acrylate P0 identifies propylene oxide.
i .
_ 9 _ .' , ' :, . .
~ 10~3~3 Example 9 To 406 grams of the hydroxyethyl acrylate-propylene oxide additian product o~ Example 1 are added 40.3 grams benzophenone-tetracarboxylic dianhydride, 2.2 grams triethyl amine, and 0.178 grams hydroquinone. The reaction mixture is heated ~t 70C. for 3-4 hours after which the in~rared spectrum shGws no anhydride re-maining. At thls point the reae~ion mixture consists o~ a diiu~c-t~onal acrylate resin and a mono~unctional acrylate moncmer of low ~is~osity ~(Gardner-Holdt = J (250 centipoise)~. The structure o~ ~he diacrylate 18 shown below:
5 ~ ,0 ~ - EA. 5'0 _ EEA identiiies hydroxyèthyl acrylate P0 ident~ies pro~ylene oxide.
The benzophenonetetracarboxylic dia~hydride, as will be ~hown.hereina~ter, pro~ides photosensit~e characteristics, rendering the product intrinsically sensiti~e to ul~ra~lolet light in the ab-sence cr any addition~ photosensitizer.
Example 10 Slmple coating ~ormulations based on the products described in the prev~ous examples, pentaerythritol triacrylate and a photosensitizer, were drawn down on metal panels using a ~3 wire wound rod. Ihe coatlngs were cured by ~ osure to 2 x 200 watt/l~ch medium pressure mercury lamps at aspeed of 2~ fe~ per minute ln air. The compositions and surface characteristics of the coatings are shown in Table I which also shows how much of the film remains arter baking 5 minutes at 350 F. ~ :
~ . ..
.
' . .
': . ~ ' ' - : . .
~ 9;3 Table I
Pentaerythritol Hydroxypolyoxyalkylene Film Triacrylate Acrylate: ,Sensitizer Surface Yield % % (note 1) Tack %
HEA.5P0 63% - 7% Tack Free 85 28 HEA.4PO.lC1 65% 7% Tack Free 77 27 HEA.4PO.lPGE 66% . 7% Tack Free 88 26 HEA.3BGE 67%, 7% Slight Tack 82 , HEA.4PO.lT,HF 63% . 77O Tack Free 85 ~ote 1 The sensitizer i~ a weight ratio mixture of S parts benzophenone to 2 parts methyldiethanol amine HEA identified hydroxyethyl acrylate P0 identified propylene oxide L5 PGE identifies phenyl glycidyl ether . . ' , Cl identifies caprolactone(epsilon) .
~, BGE identifies butyl glycidyl ether THF identifies.tetrahydrofuran ' Example 11 '' 20:. ,.' ,' , T~i9 ,example describes a unique advantage,when using the.
products of thi~ invent~on. For example, in Table I above, t~ë
I sensitizer is shown to be a combination of benzophenone (5 parts) ' ¦ and methyldiethanol amine (2 parts). It is also possible to use benzophenone alone without the methyldiethanol amine cosen~itizer.
2a A formulation identical to that in Table I with HEA.4PO.lPGE without . methyldiethanol amine cured to a yield of 87% vs. 88% with methyl-. diethanol amine present. Thu5, the products o~ this invention surprisingly cure well in the absence of amine sensitizers which are usuall~ needed for a good ultraviolet cure in an air atmosphere.
1 .
10~3~
Example 12 In the previous example, the products of this inven-tion were used without resins, but it is also possible to use these in admixture with other resinous materials, including other radiation curable materials. The formulating latitudes available are illustrated in Table II be~ow. These materials were appl~ed and cured under the conditions set forth in Example 10.
Table II
Trimethylol Sensitizer Polymer Propane HEA.5P0 Note 1 o~ Sur~ace Yield Type % Trlacrylate ~ % Table I Tack _ %
A-Urethane 21~ 21% 51% 7% Slight 89 B-Urethane 21~ 21% 51% 7% Tacky 87 C-Urethane 21% 21% 51~ 7% Slight 88 D-Urethane 21~ 21% 51% 7~ Slight 90 E-Epoxyacrylate 23% 21% 49% 7~ Tac~ Free 88 A = Polycapr~lactone Diol-Toluene Diisocyanate-Diacrylate B = Dimer Acid Diisocyanate-Diacrylate C 5 Polyether Diol-Toluene Di~socyanate-Diacrylate D - Isophoronedii~ocyanate-Diac~Ylate E = Epon 828-Diacrylate Example 13 To the composition of Example 8 (30 grams) was added 5 3 grams tr~methylolpropane triacrylate, 1.8 gram benzo-`~ phenone and 0.74 gram methyldiethanol amine. The coatlng was j drawn down on aluminum panels with #3 wire wound r~d and cured 1 by paaslng the coated panel at 25 feet per m~nute under 2 x 200 watt/inch medium pressure mercury lamps. The coating cured to a hard, tack free, mar resistant surface with a yield o~ 90+%
after baking 5 minutes at 350F.
.... - . . ~ - - : . -. . . ~ .. . . .. . . . . . : .. . .
10~3S
. ~ Exam~le 14 ~ o the composition of Example g (30 grams) was added 5.3 grams trimethylolpropane triacrylate, 1.8 gram benzo-phenone, and 0.74 gram methyldiethanol amine. The coating was cured as in Example 13 above. The coating cured to a hard, : tack free, mar resistant surface, with an a~ter-bake yield of . ` 77Z.
Example 15 . To the composition of Example 4 (20 grams) was added 6.7 grams.pentaerythritol triacrylate. The coating wa~
. .- . ,,~, , , , .- , .
cused a~ ~n Example ~3 above. The coating cured to a tack free, . mar re8istant surface with an after-bake yield of 76%. This . example il~ustrates a unique property, namely, that a photo-sénsitizer can bé incorporated into the resin component, . . . .
. 15 thereby rendering it completely reactive. That is, it cannot be extracted from the cured composition because it is an integral part of this coating~
. .. ..
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. .- . . .
~S9~
Example 16 ~ . . Follow~ng the procedure of Example.l, except i . using 4 moles of propylene oxide and 1 mole of glycidyl ac~yl~t~ to 1 mola of acryl-c.~.id, ~h~ produc~ uas a' . . .
liquid containing an average of 4 propylene ether g~oups . . . . . . . . . ........... . . . . . . ................ .. . . ..
. ~ -and l ,, . ' . group per molecule,' CH2=CH-C-O-C~2-C~I-O- - . .
f pro~iding a liquid polyacrylate'in a quick and convenient mannerO Thi8 product cures in the same manner as the . . . .... . . . .
, , pr'oduc't of Example'l, but'ultraviolet cure superiority , ' 10, can be expected to flow out of the presence of the second : acrylate moiety.
, , The invent~on is de~ined in the claim~ which follow.
. ., ' . .
, ..
., ,~, .
, . ''.
ll .. .
.~ .,' .. .... ......... . ...... ...
. , . . .. ,. ; , . . , . ' -.. .. ' . ' . ' ', ' :' :
~ .
' ' .
.
.. .
`.. j .
.. ~ ., . , - . - - ~ , ,.: . - . - , . .-- .: , ........... . . . . .
- . . . ..
. .
The benzophenonetetracarboxylic dia~hydride, as will be ~hown.hereina~ter, pro~ides photosensit~e characteristics, rendering the product intrinsically sensiti~e to ul~ra~lolet light in the ab-sence cr any addition~ photosensitizer.
Example 10 Slmple coating ~ormulations based on the products described in the prev~ous examples, pentaerythritol triacrylate and a photosensitizer, were drawn down on metal panels using a ~3 wire wound rod. Ihe coatlngs were cured by ~ osure to 2 x 200 watt/l~ch medium pressure mercury lamps at aspeed of 2~ fe~ per minute ln air. The compositions and surface characteristics of the coatings are shown in Table I which also shows how much of the film remains arter baking 5 minutes at 350 F. ~ :
~ . ..
.
' . .
': . ~ ' ' - : . .
~ 9;3 Table I
Pentaerythritol Hydroxypolyoxyalkylene Film Triacrylate Acrylate: ,Sensitizer Surface Yield % % (note 1) Tack %
HEA.5P0 63% - 7% Tack Free 85 28 HEA.4PO.lC1 65% 7% Tack Free 77 27 HEA.4PO.lPGE 66% . 7% Tack Free 88 26 HEA.3BGE 67%, 7% Slight Tack 82 , HEA.4PO.lT,HF 63% . 77O Tack Free 85 ~ote 1 The sensitizer i~ a weight ratio mixture of S parts benzophenone to 2 parts methyldiethanol amine HEA identified hydroxyethyl acrylate P0 identified propylene oxide L5 PGE identifies phenyl glycidyl ether . . ' , Cl identifies caprolactone(epsilon) .
~, BGE identifies butyl glycidyl ether THF identifies.tetrahydrofuran ' Example 11 '' 20:. ,.' ,' , T~i9 ,example describes a unique advantage,when using the.
products of thi~ invent~on. For example, in Table I above, t~ë
I sensitizer is shown to be a combination of benzophenone (5 parts) ' ¦ and methyldiethanol amine (2 parts). It is also possible to use benzophenone alone without the methyldiethanol amine cosen~itizer.
2a A formulation identical to that in Table I with HEA.4PO.lPGE without . methyldiethanol amine cured to a yield of 87% vs. 88% with methyl-. diethanol amine present. Thu5, the products o~ this invention surprisingly cure well in the absence of amine sensitizers which are usuall~ needed for a good ultraviolet cure in an air atmosphere.
1 .
10~3~
Example 12 In the previous example, the products of this inven-tion were used without resins, but it is also possible to use these in admixture with other resinous materials, including other radiation curable materials. The formulating latitudes available are illustrated in Table II be~ow. These materials were appl~ed and cured under the conditions set forth in Example 10.
Table II
Trimethylol Sensitizer Polymer Propane HEA.5P0 Note 1 o~ Sur~ace Yield Type % Trlacrylate ~ % Table I Tack _ %
A-Urethane 21~ 21% 51% 7% Slight 89 B-Urethane 21~ 21% 51% 7% Tacky 87 C-Urethane 21% 21% 51~ 7% Slight 88 D-Urethane 21~ 21% 51% 7~ Slight 90 E-Epoxyacrylate 23% 21% 49% 7~ Tac~ Free 88 A = Polycapr~lactone Diol-Toluene Diisocyanate-Diacrylate B = Dimer Acid Diisocyanate-Diacrylate C 5 Polyether Diol-Toluene Di~socyanate-Diacrylate D - Isophoronedii~ocyanate-Diac~Ylate E = Epon 828-Diacrylate Example 13 To the composition of Example 8 (30 grams) was added 5 3 grams tr~methylolpropane triacrylate, 1.8 gram benzo-`~ phenone and 0.74 gram methyldiethanol amine. The coatlng was j drawn down on aluminum panels with #3 wire wound r~d and cured 1 by paaslng the coated panel at 25 feet per m~nute under 2 x 200 watt/inch medium pressure mercury lamps. The coating cured to a hard, tack free, mar resistant surface with a yield o~ 90+%
after baking 5 minutes at 350F.
.... - . . ~ - - : . -. . . ~ .. . . .. . . . . . : .. . .
10~3S
. ~ Exam~le 14 ~ o the composition of Example g (30 grams) was added 5.3 grams trimethylolpropane triacrylate, 1.8 gram benzo-phenone, and 0.74 gram methyldiethanol amine. The coating was cured as in Example 13 above. The coating cured to a hard, : tack free, mar resistant surface, with an a~ter-bake yield of . ` 77Z.
Example 15 . To the composition of Example 4 (20 grams) was added 6.7 grams.pentaerythritol triacrylate. The coating wa~
. .- . ,,~, , , , .- , .
cused a~ ~n Example ~3 above. The coating cured to a tack free, . mar re8istant surface with an after-bake yield of 76%. This . example il~ustrates a unique property, namely, that a photo-sénsitizer can bé incorporated into the resin component, . . . .
. 15 thereby rendering it completely reactive. That is, it cannot be extracted from the cured composition because it is an integral part of this coating~
. .. ..
, ... . . .. . . .. ...
. .... . ,. ' ''. ., ' I
~' I
, .
.. : ~ - . .. . . - . . ' - ~, - . .
. .- . . .
~S9~
Example 16 ~ . . Follow~ng the procedure of Example.l, except i . using 4 moles of propylene oxide and 1 mole of glycidyl ac~yl~t~ to 1 mola of acryl-c.~.id, ~h~ produc~ uas a' . . .
liquid containing an average of 4 propylene ether g~oups . . . . . . . . . ........... . . . . . . ................ .. . . ..
. ~ -and l ,, . ' . group per molecule,' CH2=CH-C-O-C~2-C~I-O- - . .
f pro~iding a liquid polyacrylate'in a quick and convenient mannerO Thi8 product cures in the same manner as the . . . .... . . . .
, , pr'oduc't of Example'l, but'ultraviolet cure superiority , ' 10, can be expected to flow out of the presence of the second : acrylate moiety.
, , The invent~on is de~ined in the claim~ which follow.
. ., ' . .
, ..
., ,~, .
, . ''.
ll .. .
.~ .,' .. .... ......... . ...... ...
. , . . .. ,. ; , . . , . ' -.. .. ' . ' . ' ', ' :' :
~ .
' ' .
.
.. .
`.. j .
.. ~ ., . , - . - - ~ , ,.: . - . - , . .-- .: , ........... . . . . .
- . . . ..
. .
Claims (7)
1. A radiation curable coating composition comprising the addition reaction product of (i) a monoethylenically unsaturated adduct of a monoethylenically unsaturated carboxylic acid or hydroxyalkyl ester thereof with an anhydride containing at least 3 carbon atoms and selected from monoepoxides, lactones, and mixtures thereof, said adduct containing an average of at least 1 mole of anhydride per mole of hydroxy-ester and an average of at least 2 moles of anhydride per mole of acid moiety, with (ii) an organic compound containing a plurality of groups capable of reacting with active hydrogen, said organic compound being a polyisocyanate, polycarboxylic polyanhydride or polyepoxide.
2. A radiation curable coating composition as recited in claim 1 in which the monoethylenically unsaturated adduct is a polyether.
3. A radiation curable coating composition as recited in claim 1 in which the organic compound is benzophenone-tetracarboxylic add dianhydride, said composition including a photosensitiz--r.
4. A radiation curable coating composition as recited in claim 1 in which the adduct is derived from a hydroxyalkyl ester of acrylic acid containing from 2 to 4 carbon atoms in the alkyl group.
5. A radiation curable coating composition as recited in claim 1 in which the anhydride of the adduct is propylene oxide, butylene oxide, butyl glycidyl ether, cyclohexene oxide, phenyl glycidyl ether, tetrahydrofuran, ar epsilon caprolactone, and the monoethylenically unsaturated carboxylic acid is acrylic acid.
6. A radiation curable coating composition as recited in claim 3 in which the benzophenone-tetracarboxylic acid dianhydride moiety is the only photosensitizer present.
7. A radiation curable coating composition as recited in any of claims 1, 4 or 5 in which the adduct contains an average of from 3 to 10 moles of anhydride per mole of acid or hydroxyalkyl ester.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US61810175A | 1975-09-30 | 1975-09-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1073593A true CA1073593A (en) | 1980-03-11 |
Family
ID=24476328
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA261,597A Expired CA1073593A (en) | 1975-09-30 | 1976-09-20 | Composition containing a monoethylenically unsaturated adduct and one of a polyisocyanate, polycarboxylic polyanhydride or polyepoxide |
CA261,598A Expired CA1074046A (en) | 1975-09-30 | 1976-09-20 | Composition containing a monoethylenically unsaturated adduct and a polyacrylate |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA261,598A Expired CA1074046A (en) | 1975-09-30 | 1976-09-20 | Composition containing a monoethylenically unsaturated adduct and a polyacrylate |
Country Status (18)
Country | Link |
---|---|
US (1) | US4126527A (en) |
JP (2) | JPS5242531A (en) |
AU (2) | AU510840B2 (en) |
BE (2) | BE846643A (en) |
BR (2) | BR7606527A (en) |
CA (2) | CA1073593A (en) |
CH (1) | CH603772A5 (en) |
DE (2) | DE2643701A1 (en) |
DK (2) | DK437376A (en) |
ES (2) | ES451959A1 (en) |
FR (2) | FR2326458A1 (en) |
GB (2) | GB1566114A (en) |
IT (2) | IT1192128B (en) |
NL (2) | NL7610754A (en) |
NZ (2) | NZ182002A (en) |
PT (2) | PT65615B (en) |
SE (2) | SE7610672L (en) |
ZA (1) | ZA765647B (en) |
Families Citing this family (29)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS6052184B2 (en) * | 1978-01-18 | 1985-11-18 | 三菱レイヨン株式会社 | paint composition |
US4175177A (en) * | 1978-02-24 | 1979-11-20 | Union Carbide Corporation | Crosslinkable copolymer of a lactone and a polyfunctional acrylate |
US4188472A (en) * | 1978-10-06 | 1980-02-12 | Ppg Industries, Inc. | Curable lactone derived resins |
EP0041871B1 (en) * | 1980-06-11 | 1984-03-21 | BP Chemicals Limited | Unsaturated ester polyether polyols and the use thereof as non-ionic surfactants |
US4504635A (en) * | 1982-11-02 | 1985-03-12 | Union Carbide Corporation | Process for the preparation of polymeric compositions |
JPS59136466A (en) * | 1983-01-25 | 1984-08-06 | Sumitomo Electric Ind Ltd | Continuous hot dipping method |
EP0115160A3 (en) * | 1983-01-03 | 1984-08-22 | Mobil Oil Corporation | Abrasives with binder comprising adduct of polyisocyanate and polyalkoxyacrylate |
US4725653A (en) * | 1983-10-27 | 1988-02-16 | Union Carbide Corporation | Low viscosity adducts of a polycaprolactone polyol and a polyepoxide |
JPS6130557A (en) * | 1984-07-23 | 1986-02-12 | Nippon Kayaku Co Ltd | Novel (meth)acrylic acid ester, and ultraviolet-curable resin composition prepared from said ester |
JPS6268862A (en) * | 1985-09-19 | 1987-03-28 | Toyo Ink Mfg Co Ltd | Coating composition curable with actinic radiation |
US4879318A (en) * | 1986-01-28 | 1989-11-07 | Ophthalmic Research Group International, Inc. | Plastic lens composition and method for the production thereof |
US6201037B1 (en) | 1986-01-28 | 2001-03-13 | Ophthalmic Research Group International, Inc. | Plastic lens composition and method for the production thereof |
US5364256A (en) * | 1986-01-28 | 1994-11-15 | Ophthalmic Research Group International, Inc. | Apparatus for the production of plastic lenses |
US6730244B1 (en) | 1986-01-28 | 2004-05-04 | Q2100, Inc. | Plastic lens and method for the production thereof |
US5529728A (en) * | 1986-01-28 | 1996-06-25 | Q2100, Inc. | Process for lens curing and coating |
US5415816A (en) * | 1986-01-28 | 1995-05-16 | Q2100, Inc. | Method for the production of plastic lenses |
US4680361A (en) * | 1986-02-20 | 1987-07-14 | Union Carbide Corporation | Novel polymers and crosslinked compositions made therefrom |
JP2507481B2 (en) * | 1987-05-21 | 1996-06-12 | 株式会社東芝 | Polysilane and photosensitive composition |
US4847329A (en) * | 1987-06-30 | 1989-07-11 | Union Carbide Corporation | (N-substituted carbamoyloxy)alkanoyloxyalkyl acrylate polymers and compositions made therefrom |
AU618839B2 (en) * | 1988-09-13 | 1992-01-09 | Australian Wire Industries Pty Ltd | Jet wiping apparatus |
US5514214A (en) * | 1993-09-20 | 1996-05-07 | Q2100, Inc. | Eyeglass lens and mold spin coater |
US6022498A (en) | 1996-04-19 | 2000-02-08 | Q2100, Inc. | Methods for eyeglass lens curing using ultraviolet light |
US6280171B1 (en) | 1996-06-14 | 2001-08-28 | Q2100, Inc. | El apparatus for eyeglass lens curing using ultraviolet light |
US5728878A (en) * | 1996-07-02 | 1998-03-17 | Air Products And Chemicals, Inc. | Functional N-vinylformamides |
US7321013B2 (en) * | 2000-12-19 | 2008-01-22 | Basf Corporation | Method for obtaining coating compositions having reduced VOC |
US7696285B2 (en) | 2000-12-19 | 2010-04-13 | Basf Coatings Ag | Carbamate functional reactive polymer composition |
US7001930B2 (en) * | 2003-01-14 | 2006-02-21 | Dymax Corporation | Acrylic resin formulations curable to clear, heat-resistant bodies |
BRPI0506160A (en) * | 2004-06-11 | 2006-10-24 | Basf Corp | method for obtaining low VOC coating compositions |
DE102005008032A1 (en) * | 2005-02-22 | 2006-08-31 | Bayer Materialscience Ag | Process for the preparation of hydroxyalkyl (meth) acrylates and their use |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2945012A (en) * | 1958-01-08 | 1960-07-12 | Goodrich Co B F | Polymerizable polyesters and polymers thereof |
FR1489458A (en) * | 1965-08-13 | 1967-07-21 | Ford France | Radiation curable paint binder |
US3485732A (en) * | 1966-03-02 | 1969-12-23 | Ppg Industries Inc | Highly radiation-sensitive telomerized polyesters |
US3485733A (en) * | 1966-03-02 | 1969-12-23 | Ppg Industries Inc | Highly radiation-sensitive telomerized polyesters |
US3515656A (en) * | 1966-07-15 | 1970-06-02 | Mitsubishi Gas Chemical Co | Photopolymerization process for hydroxy alkyl acrylates |
US3453345A (en) * | 1967-03-06 | 1969-07-01 | Scm Corp | Heat hardenable resin compositions containing hydroxypolyoxyalkylene ester polymers and metal articles coated therewith |
US3615454A (en) * | 1968-06-26 | 1971-10-26 | Du Pont | Process for imaging and fixing radiation-sensitive compositions by sequential irradiation |
US3725116A (en) * | 1969-07-09 | 1973-04-03 | Ppg Industries Inc | Method of coating with acryloxy esters of anhydrides |
US3586528A (en) * | 1969-08-04 | 1971-06-22 | Ford Motor Co | Divinyl-resin paints and painting process |
US3817845A (en) * | 1971-05-18 | 1974-06-18 | American Can Co | Photopolymerizable epoxy systems containing sulfoxide gelation inhibitors |
US3804735A (en) * | 1972-04-10 | 1974-04-16 | Continental Can Co | Photopolymerizable compositions prepared from beta-hydroxy esters and polyitaconates |
-
1976
- 1976-09-07 GB GB37061/76A patent/GB1566114A/en not_active Expired
- 1976-09-07 GB GB37060/76A patent/GB1564296A/en not_active Expired
- 1976-09-10 NZ NZ182002A patent/NZ182002A/en unknown
- 1976-09-10 NZ NZ182003A patent/NZ182003A/en unknown
- 1976-09-15 AU AU17766/76A patent/AU510840B2/en not_active Expired
- 1976-09-15 AU AU17767/76A patent/AU511264B2/en not_active Expired
- 1976-09-20 JP JP51111917A patent/JPS5242531A/en active Pending
- 1976-09-20 JP JP51111916A patent/JPS6031228B2/en not_active Expired
- 1976-09-20 PT PT65615A patent/PT65615B/en unknown
- 1976-09-20 CA CA261,597A patent/CA1073593A/en not_active Expired
- 1976-09-20 CA CA261,598A patent/CA1074046A/en not_active Expired
- 1976-09-20 PT PT65614A patent/PT65614B/en unknown
- 1976-09-21 ZA ZA00765647A patent/ZA765647B/en unknown
- 1976-09-27 BE BE170991A patent/BE846643A/en not_active IP Right Cessation
- 1976-09-27 SE SE7610672A patent/SE7610672L/en unknown
- 1976-09-27 SE SE7610671A patent/SE7610671L/en unknown
- 1976-09-27 BE BE170990A patent/BE846642A/en not_active IP Right Cessation
- 1976-09-28 DE DE19762643701 patent/DE2643701A1/en not_active Withdrawn
- 1976-09-28 NL NL7610754A patent/NL7610754A/en not_active Application Discontinuation
- 1976-09-28 NL NL7610755A patent/NL7610755A/en not_active Application Discontinuation
- 1976-09-28 DE DE19762643702 patent/DE2643702A1/en not_active Ceased
- 1976-09-29 DK DK437376A patent/DK437376A/en not_active Application Discontinuation
- 1976-09-29 ES ES451959A patent/ES451959A1/en not_active Expired
- 1976-09-29 DK DK437476A patent/DK437476A/en not_active Application Discontinuation
- 1976-09-29 ES ES451960A patent/ES451960A1/en not_active Expired
- 1976-09-29 CH CH1233076A patent/CH603772A5/xx not_active IP Right Cessation
- 1976-09-29 IT IT27786/76A patent/IT1192128B/en active
- 1976-09-29 IT IT7787/76A patent/IT1091555B/en active
- 1976-09-30 BR BR7606527A patent/BR7606527A/en unknown
- 1976-09-30 BR BR7606528A patent/BR7606528A/en unknown
- 1976-09-30 FR FR7629449A patent/FR2326458A1/en active Granted
- 1976-09-30 FR FR7629448A patent/FR2326456A1/en active Granted
-
1977
- 1977-12-02 US US05/856,692 patent/US4126527A/en not_active Expired - Lifetime
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