CA2131097A1 - Polyesters based on hydroxyl-containing prepolymers of olefinically unsaturated monomers and their use as binders for electrophotographic toners - Google Patents
Polyesters based on hydroxyl-containing prepolymers of olefinically unsaturated monomers and their use as binders for electrophotographic tonersInfo
- Publication number
- CA2131097A1 CA2131097A1 CA002131097A CA2131097A CA2131097A1 CA 2131097 A1 CA2131097 A1 CA 2131097A1 CA 002131097 A CA002131097 A CA 002131097A CA 2131097 A CA2131097 A CA 2131097A CA 2131097 A1 CA2131097 A1 CA 2131097A1
- Authority
- CA
- Canada
- Prior art keywords
- mixture
- weight
- hydroxyl
- alkyl
- polyester resin
- 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.)
- Abandoned
Links
Classifications
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- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08786—Graft polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B41M5/5272—Polyesters; Polycarbonates
-
- 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
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08755—Polyesters
Abstract
Polyester resins on the basis of hydroxyl groups-containing prepolymers from olefinically unsaturated monomers are prepared by (1) polymerizing a mixture of (a) 60 to 90% by weight styrol or a styrol derivate having the general formula (I), in which R1, R2 and R3 stand for hydrogen, methyl or ethyl and n equals 1 or 2, or a C2-C10-olefin with one or two conjugated double bonds, or a mixture thereof; (b) 0 to 40% by weight C1-C12-alkylester of acrylic or methacrylic acid, acryl- or methacryl-nitril, acryl-or methacrylamide, which may be substituted at the amide-nitrogen by one or two C1-C4-alkyl groups, maleic anhydride or maleic acid imide, which may be substituted at the imide-nitrogen by a C1-C4-alkyl group, or a mixture thereof; (c) 0 to 20% by weight one or several hydroxyl group-containing acrylic or methacrylic acid derivates; and (d) 0 to 2% by weight one or several olefinically poly-unsaturated monomers; to obtain a prepolymer A, into which the hydroxyl groups are inserted by means of hydroxyl groups-containing regulators when the monomer component (c) is missing and by a mixture of (A) 5 to (95% by weight prepolymer A;
(B) 0 to 95% by weight another low molecular or high molecular polyol, a polyester or a polyamid, or a mixture thereof; and (C) 5 to 70% by weight one or several aliphatic or aromatic dicarboxylic acids C or their C1-C4-alkylesters. Carboxylic acids or their C1-C4-alkylesters having more than two carboxyl groups per molecule, monocarboxylic acids or their C1-C4 alkylesters, hydroxymonocarboxylic acids or their C1-C4-alkylesters or mixtures thereof, as well as waxes may also be present during polycondensation. These polyester resins are suitable as binders for electrophotographic toners and for the receiving layers in the thermodiffusion printing method.
(B) 0 to 95% by weight another low molecular or high molecular polyol, a polyester or a polyamid, or a mixture thereof; and (C) 5 to 70% by weight one or several aliphatic or aromatic dicarboxylic acids C or their C1-C4-alkylesters. Carboxylic acids or their C1-C4-alkylesters having more than two carboxyl groups per molecule, monocarboxylic acids or their C1-C4 alkylesters, hydroxymonocarboxylic acids or their C1-C4-alkylesters or mixtures thereof, as well as waxes may also be present during polycondensation. These polyester resins are suitable as binders for electrophotographic toners and for the receiving layers in the thermodiffusion printing method.
Description
~ 1 3 1 0 9 7 o. z . 0050/43136 PolYe~t-rs ba~ed on hydroxyl-containlna DroDolYmers of olefinicallY unoaturated mo~omers and their use a~ bl~der~ for electro~hotoaraDhic to~ers - The pre~-nt inv ntion r-lat-o to novol polyostor rosins ba~ed on hydroxyl-contai~ing prepolymers of ol~flnically u~aturat-d monQm ro and their U8e a8 blnd-ro for l-ctrophotographlc ton-ro Th- pr-~ nt inv nt~on furth-rmor- r-lat-o to l-ctrophotographic ton-ro conta~n~ng th-J- poly-Jt-r r-Jin~ ao binder~
El-ctrophotographlc tonor~ hav- to meet a largo numb-r of r-gulr~m-nt~ whlch arl~- from the copying proco~o, to~-r production or th- ha~dling of tho ton-r~
Many of th r-qulrom-nt~ whlch a ton-r ha~ to meot are d t-rmi~-d by th blnd r, i- by th tonor resin Thuo, a to~er r-oi~ mu~t b- capa~l-, for oxample, of r-ad~ly diop-rolng additiv-~ ouch ao carbon blac~, f-rr~t-J, magn-tlt-, A roJll, charg- stabiliz-r~ and w~x-~ ~omog neouo diop-rolng io n-c-~ary since other-wi~- ton-r particl-o having v-ry diff-ront electro~tatic proportl-s may b- pr-~ nt Anothor reguiromo~t 18 good millability of tho tonor rosin In tonor production, rov-r~o-~et mill~ are gon-rally usod Somo re~ giv- ton-rs which reguire very long time~ before they can be brought to the desired particlo ~ize, preferably from 5 to 15 ~m, in a reverse-~et mill Another frequent problem in milling in the ro~orso-~et mill i~ the production of f~ne dust, ie of parti~le~ which have a particle ~ize which is less than S ~
The shelf life of a toner i~ al~o influenced by the toner resin A re~in which become~ soft at room temperature or at the temperatures prevailing in the copier and can stic~ together give~ toner powder~ which c~ cake and are no longer free-flowing Caking of the to~-r powder may also occur if a moi~ture-sen~itive resin wh~ch ~ e~en only slightly hygroscopic iB u~ed In add$tion, resin~ which ab~orb isture from the ~13~0~17
El-ctrophotographlc tonor~ hav- to meet a largo numb-r of r-gulr~m-nt~ whlch arl~- from the copying proco~o, to~-r production or th- ha~dling of tho ton-r~
Many of th r-qulrom-nt~ whlch a ton-r ha~ to meot are d t-rmi~-d by th blnd r, i- by th tonor resin Thuo, a to~er r-oi~ mu~t b- capa~l-, for oxample, of r-ad~ly diop-rolng additiv-~ ouch ao carbon blac~, f-rr~t-J, magn-tlt-, A roJll, charg- stabiliz-r~ and w~x-~ ~omog neouo diop-rolng io n-c-~ary since other-wi~- ton-r particl-o having v-ry diff-ront electro~tatic proportl-s may b- pr-~ nt Anothor reguiromo~t 18 good millability of tho tonor rosin In tonor production, rov-r~o-~et mill~ are gon-rally usod Somo re~ giv- ton-rs which reguire very long time~ before they can be brought to the desired particlo ~ize, preferably from 5 to 15 ~m, in a reverse-~et mill Another frequent problem in milling in the ro~orso-~et mill i~ the production of f~ne dust, ie of parti~le~ which have a particle ~ize which is less than S ~
The shelf life of a toner i~ al~o influenced by the toner resin A re~in which become~ soft at room temperature or at the temperatures prevailing in the copier and can stic~ together give~ toner powder~ which c~ cake and are no longer free-flowing Caking of the to~-r powder may also occur if a moi~ture-sen~itive resin wh~ch ~ e~en only slightly hygroscopic iB u~ed In add$tion, resin~ which ab~orb isture from the ~13~0~17
- 2 - O Z 0050/43136 ~ur~ounding air lead to toners who~e eleetro~tatic proport~es aro groatly depsndent on the atmo~pherie h~m~dity Tho eonsequonee~ are the oeeurronce of back-~round and irregular blacken~ng in ~olid area~ on the S copy.
A furthor problem i~ the increa~e in the fixing rate of an imag0 tran~ferrod to the print medium (aeeeptor) by heat, ie the increaoe ln the cyele time of the eopier The proporties of a tonor during fixing aro greatly influoneed by the melting behavior of the toner rosin A higher f~xing rate is ~ehieved by u~ing a re~n hav ng a low ~oftening point However, thi~ may re~ult in tho problem of hot off~ot, ie some of the molten toner romains adhering to the hot fixing roller of the eop~er and is transforred to subseguont eopie~
In US-A 4 657 837 (1), the problem of hot offsot i~ ~olved by ~ing a braneh d polye~ter of terephthalie aeid, trimellitie aeid and ethoxylated or propoxylatod bi~phenol A Toner~ eon~isting of th$s re~in have very good ~nt$-off~et propertie~ but, ow~ng to their high softenlng point, are un~uitable for eopiers having eyele time~ of more than 50 eopies per minuto, sinee adeguate fixing on the print medium (aeeoptorl i~ not aehieved Polyester~ having a lower softening point but poorer anti-offset properties are deseribod in ~S-A 4 980 448 (2) The~e polyesters are obtainable by reacting a diearboxylie aeid eomponent, a d~ol eomponent and a eros~l-inking agent However, in the preparation of these resin~ there iR a danger that oxee~ive ero~linking may 39 oeeur in the polyeonden~ation EP-195 604 (3) disclo~es polye~ter~ for u~e in toner mlxtures, which are obtainable by copoly-eondensation of a diol eomponent of ethoxylated or propoxylated bi~phenol A with a eopolymer of styrene or a styrene derivative and a earboxyl-eontaining vinyl nomer These polyester~, too, do not ~olve the prior art problem~ de~eribed ~2131037 _ 3 _ o z 0050/43136 _ Tonor re~ins which h~ve a very high viscosity aftor melting or whic~ molt only vory 810wly oxhibit the phon onon of cold off~ot, io toner particles are not corroctly flxod on the papor and may thorefore remain adh-ring to the fixing rollor~ The litorature frogu-nt-ly doscribo~ th- u~e of r-~n~ hav~ng a bimod~l molecular we~ght di~tribut'on, which avo'd cold and hot off~ot Thi~ can al~o be achi-vod by us~ng ros~n mixturos or re~ins having a broad mol-cular weight distr'bution Thu~, tho low l-cular weight fraction en~uros good melting of the bind-r and good fix'ng on the pap-r, and th- high-r l-cular w ight fraction en~uro~ a ~uffi-c'~ntly high v~co~ity of th- binder and imparts to tho lton ton-r a c-rtain coho~ion which prevont~ hot off~t Th el-ctro~tatlc charg-ability of tonor resins ~ o important Th charg- bu'ld-up can b- controll~d by m an~ of chargo ~t~b~liz-rs Anothor important crit-r'on i~ th- ~tability of th- chargo Mb~y ton-rs h v a tend ncy of buildiDy up too much chargo during tho dev lopmont proc-~ Th chargo ~tabilizor koeps ths charge at a very particular lov-l, a~d very uniform blackne~ of tho copies i~ thus obtained In thi~
contoxt, tho r-action botwoon charge stabilizer and tonor resin i8 the critical paramoter It is an ob;ect of the present invention to romedy the prior art doficiencios described It was thorofiore intonded to provido a tonor ro~in which can be produced particularly oasily and without problems, has good dispersing propertios, is roadily millable and has a long shelf life as well as good cold and hot ofset properties in conju~ction with a high fixing rate We have found that this object i~ achieved by polyester resins based on hydroxyl-containing prepolymers of olofinically unsaturatod nomers, which are obtain-able by (1) polymerization of a mixturo of ~ 213IO97 - 4 - o.Z. 0050/43136 - (a) from 60 to 90% by weight of styrone or of a styrene dorivati~e of tho general formula I
Rl ~
~=CH R2 (R3) n ~
whore Rl, R2 and R3 aro eaeh hydrog~n, methyl or ethyl and n is 1 or 2, or of a C2-C10-olefin ha~ing one or two eonjugated double bo3ds, or of a mixture thoreof, (b) from 0 to 40% by weight of a Cl-Cl2-alkyl ester of aerylie or m~thaerylie aeid, aerylonitrile or mothaerylonitrile, aeryl~m~de or methaeryl-amid- whieh may be ~ubstituted by one or two :
Cl-C~-alkyl group~ on th~ ~mide nitrogen, maleie anhydrido or male~de whieh may be sub~titutod by Cl-C~-alkyl on the ~mide nitrog~n, or a mixture th~rsof, (e) from 0 to 20% by we~ght of o~e or re hydroxyl-eontaining aerylie or methaerylic aeid derivative~, and (d) from 0 to 2% by weight of one or re poly-olefi~ieally un~aturated monomer~, to gi~e th~ prepolymer A, the hydroxyl groups being ineorporated in A by u~ing hydroxyl-eontaining regulators whon the mono~or eo~ponent (e) i~ absent, and ~ubQequ~ntly S2) polyeond~n~ation of a mlxture o4 A) from S to 95% by weight of the prepolymer A, B) from 3 to 95% by weight of a further low moleeular weight or relatively high moleoular weight polyol, of a polyester or of a polyamide or a mixture thereof and C) from 5 to 70% by weig~t of one or more alipha-tie or aromatic dicarboxylic acids C or C~-C~-alkyl ester~ thereof, - 5 - O.Z. 0050/43136 _ where carboxylic acids or C1-C~-alkyl e~ters thereof having more than two carboxyl groupo in the molecule or monocarboxylic acid~ or Cl-C~-alkyl ester~ thereof or hydroxymonocarboxylic acid~ or C~-C~-alkyl esters thereof, or a mixture of these, and waxos may al80 be present in the polycondon~ation.
In the styrene and ~tyrono dor~vative~ I serv~ng as monomers (a) for the polymorization (1), Rl is prefer-ably hydrogon or mothyl, R~ and R3 are oach preferably hydrogen and ~ is pr~f~rably 1. If, when n 1, R3 iR
methyl or ethyl, the ph~nyl nucleus i~ ortho-, meta- or, pr~ferably, para-~ub~tituted. If, where n ia 2, R3 i~
methyl or ethyl, the substitution pattern on the phenyl nucleus i~ preferably 2, 4.
Furthor ~uitablo monomors (a) for the polymeriza-t~on (l) aro straight-chaln or branchod C2-C10-olefins, such a~ ethylone, propylo~e, l-butylene, 2-butylene, butadion~, isoprone, l-pontono, 2-p-ntene, 3-pentene, 1-h~xo~e, 2-hexene, 3-hoxono, 2,4-hoxadiene, heptenes, octenes, nonene~ and dec~nos.
Preferred monomer~ (a) for the polymerization (1) are styrene, a-met~ylstyrene, ethylene, propylene, butadiene or a mixture thereof.
The Cl-Cl~-alkyl acrylate~ and methacrylates which are suitable as monomers (b) for the polymarization (1) carry a~ a stra~ght-chai~ or branched alcohol radical, for example methyl, ethyl, n-propyl, i opropyl, n-butyl, i~obutyl, sec-butyl, tert-butyl, n-amyl, isoamyl, ~ec-amyl, tert-amyl, neopentyl, n-hexyl, n-h~ptyl, n-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, n-undecyl or n-dodecyl. Cl-C~-Alkyl acrylate and methacrylate are preferred among these. Suitable C1-C~-alkyl groups which may occur as ~ub~titutents on the amide nitrogen of acrylam;de or methacrylam~de and on the imide nitrogen of maleim~de are the abovementioned groups.
C1-C~-alkyl esters of acrylic and methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide and 21~1037 mot~acrylamid-, or a m~xturo thoreof, aro proferred as mo~om-rs (b) for the polym rization (1) In particular, the methacryl~c acid derivativo~ giv- outstanding ro~-ults S Partlcularly ~u~tabl- hydroxyl-containing acrylic or methacrylic acid dorivatlvo~ (c) for tho polymoriza-tion (1) ar- hydroxy-C~-C,-alkyl acrylat~ or meth-acrylat-~, og 2-hydroxyothyl acrylato, 2-hydroxyothyl methacrylat-, 2- or 3-hydroxypropyl acrylat-, 2- or 3-hydroxypropyl m th~crylat-, 4-hydroxybutyl acrylate or 4-hydroxybutyl m th~crylat-, N-(hydroxy-C,-C~-al~yl)-acryl-amid ~ or -m thacrylamld ~, eg N-(2-hydroxyethyl)-acryl-a~ldo, N-(2-hydroxy thyl)-~thacryla~ldo, N-(4-hydroxy-butyl)-acrylamid- or N-(4-hydroxybutyl)-mothacrylA~d-, or mixturo~ th-r-of Howev-r, N-(hydroxy-C~-C~-al~yl)-m~l-i~ld ~, ~g N-(2-hydroxy-thyl)-~aloimid , hydroxyl-contalning ~tyr-n- d-rivativ-~, g ortho-, mota- or p~r~-hydroxy~tyr-~e or ortho-, mota- or para-(hydroxy-m thyl)-~tyr-~ or al~-nol~, og but-2-on-1-ol or prop-2-o~-l-ol (allyl alcohol), are al~o suitabl-Particularly ~uitabl- polyolofinically un-~aturat-d monomor~ (d) aro tho~e ha~ing from 2 to S vinyl or allyl groups in the molecul-, for exam~le glycol di(moth)acrylat-, butanediol di(meth)acrylate, glyceryl tri(meth)acrylat-, (meth)allyl (moth)acrylate, penta-eryth ityl triallyl ether, pentallylsucrose, di(meth)-acrylates of polyethylene glycols having a molecular weighS of up to 3,000, divinyldioxane and especially divinylbenzene If desired, the prop-rties of the propolymers A can be modified within certain limits by the~- mo~omer~ acting as crosslinking agents If nomer component (c) i8 ab~ent, a hydroxyl-containing regulator i8 used in the polymerization (1) in order to incorporate the nece~ary hydroxyl groups into the prepolymer A These regulators are used in the conventional amounts, eg from about 0 1 to 5, in par-ticular from 0 3 to 2, % by weight, based on the total amount of the monomer~ (a) and (b) Partlcularly suitable hydroxyl-containing regula-tor~ are hydroxyl-containing m rcaptans, eg 2-hydroxy-eth~l mercaptan (2-m rcapto-thanol), 1-m rcapto-2,3-propanediol, 3-mercaptopropanol, 4-mercaptobutanol, 2-hydroxy-thyl mercaptoacetat- or 2-hydroxyethyl 3-m rcaptopropionate Th- be~t r-~ults are obtained with 2-m rcapto-thanol In a pr-ferred ombodtm nt, a m~xture of from 65 10to 85% by weight of monom rs (-), from 0 to 35% by w iyht of monom r~ (b), from 0 to 15% by we~ght of nomerc (c) and from 0 to 0 5~ by welght of monomer~ (d) are used in th- polym rization (1) The prepolymer ~ can be pr-pared by su~pons~on, 15~olut~on or bloc~ polym rlzat~on according to th- conven-tio~al thod~ Iu th- ~ub~-gu-~t poly¢ond-n~at~on (2), ho~ v r, pr-poly~or- A pr-p-r-d by ~olutlo~ polymeriza-tlon are pr-f-rably u~ed lnce th- polymer~zat~on (1) a~d th- polycoud n~atlou (2) ca~ th-u b- carried out lu 20ucce~lon in o~e re~ct~ou ve~el becau-~ lsolatlon of a pr-polym r i~ di~p-n~-d wlth In a suspon~lon polym rization, a mixture of wat-r and a water-mi~cible orgaulc solv~t, eg a wat-r/etha~ol mixture or water/isopropa~ol mixture having 25a low alcohol contont, or in particular water alone, i~
advantageously used as the su~pending medium For oxample, polyvinylpyrrolidone iB used as a protective colloid In solution polym rization, advantag-ously used 30~olvents are inert organic solvents, in partlcular aliphatic or aromatic hydrocarbons, eg toluene, xylene, cyclohexane, methylcyclohexane, petroleum ether or naphtha However, halohydrocarbons, eg chloroform, are also suitable.
35Tho polym rization (1) iB advantagoously carried out a~ a froo radical polymerization, suitable froe radical i~itiatorc being, for oxample, benzoyl peroxide or _tort-butyl poroetanoate A ~uitablo polymerization temporaturo i- from 60 to 130C, in parti¢ular from 80 to 120C In ~olution polymorization, it i~ ad~antageoue to ue~revaporativ eooli~g Tho avorag- moloeular w~ight M~ of th- propolymer A ~hould b- from 800 to 40,000, in partieular from 800 to 15,000 Th- O~ numb-r of A ~hould be 1088 than 60, in partleular 1-~ than 50, mg of ~OH/g Solutlon polymore A having O~ ~u~b-r~ of from 1 to 16 mg of RO~/g a~d a ratlo of eompon~nt- A to B of more tha~ 40 60 ar-pr-f-rr-d in th polyeond~ation (2) If tho ratio of A to B in th- polyeond-~ation (2) ~ tha~ 40 60, polymer~ A having O~ numb-r~ ~r-~ter than 10 mg of RO~/g may al~o advantageou~ly b- u~-d Partleularly sultabl- eompo~nte B for th polyeond ~at~on (2) ar- C~-C~-al~an-diols, g ethyl-ne glyeol, 1,2- and 1,3-prop ~-dlol, 1,4-buta~-diol, 1,6-h-xan-diol, n-op~ntylglyeol, thoxylat-d or propoxylated bl~ph-~ol A, for ~xampl- bl~ph nol A r-aet-d with from 2 to 20 mol of thyl-~- oxld- or propyl~ oxide, or mixtur-s th r-of ~ow v r, high l-eular w~ght polyole havl~g a~ averag- moleeular w lght N~ of more than 500, for oxample poly ~t-rdlols, polyeth-rdiols or poly-e~rbo~atediols, polyoeters, ~ueh as polyeaprolaetone or polyamidee, sueh as polyeaprolaetam, may al~o be ueed Partleularly eultable diearboxylie aeide C- for the polyeondensation (2) ar- phthalie aeid, isophthalie ae~d, -terephthalie aeid or tho~r Cl-C~-monoal~yl esters and in part~eular Cl-C~-dial~yl est-r~ or a mixturo thoroof However, for example eyelohexanodiearboxylie aeids or aliphatie dicarboxylic aeids euch aR succinic acid or adipic aeid or the correeponding Cl-C~-monoalkyl e~tere and in particular Cl-C~-dial~yl eeter~ may also be used.
A mixture of from S to 95% by weight of the prepolymer A, from 0 to 95% by weight of the component B
~nd from 5 to 70% by weight of the dicarboxylic acid C or _ g - o z 0050/43136 an ~t-r ther-of aro usod in tho polyconden~ation (2), A
and B tog-ther accounting for frQm 30 to 95% by woight of thia mixturo In a preferr-d ~mbodim~nt, a mixturo of fr~ 30 to 70% by w ight of A, from 10 to 50% by weight S of B and from 10 to 50% by w lght of C is used, A and B
tog-th-r accountlng for from 50 to 90% by w ight of th~s mixtur-In th- polyconden~atlon (2), for x~mpl-, tr~-m llitlc acid, b-nzoic acid, o- or p-hydroxyb~nzoic ac~d, nicotinic acld or t-aric acid or th corr-~onding Cl-C~-~l~yl e~t-r~ may b- pre~ont a- addit~onal carboxyl~c acld~, a~ w ll a~ waxe~, for ~a~le polypropyl~n- wax Th ~- additlonal oarboxylic acid~ or th ir st-r~ are th~ pre~-nt i~ a unt~ of up to 15% by ~ ight, and the wax-~ ln amount~ of up to 15% by ~ lght, ba~ed in oach ca~- o~ th- total amDunt of th- mixture of A, B and C
8ultabl- Cl-C,-alkanol~ ln th- carboxylic acld ~t-r~ ~mploy d ar- n-propanol, i~opropanol, n-butanol, ~-¢-but nol, tert-butanol and in particular m thanol and ~thanol The water formed in the polycond n~ation (2) or th- Cl-C~-al~anol formed i- advantag-ou~ly di~tilled off dir-ctly from th- r-~n melt if no ontraining agent ~ 8 pr-~ent, or iB romoved by means of an entraining agent, such as toluone, xylene, mothylcyclohexane or chloroform Tho polycondensation i~ u~ually carriod out in the prosence of a catalyst, for oxample dibutyltin ox~de, a tit~nium alcoholato, p-toluono~ulfonic acid or sulfuric acid, in the conventional amounts Tho polycondensation (2) ~B carried out either BO
that the prepolymer A is added to the components B and C
which have been precondensed to an OH number of les~ than 90 mg of ROH/g, or all three c~ponents A, B and C are added togoth~r ~imultaneously The condensation is compl-t-d towards the end of the reaction at from 180 to The present invention furthermore relates to a - 10 - O.Z. 0050/43136 pro~e~ for the proparation of polyester resins base~ on hydroxyl-containing prepolymers of olefinically un~aturated monomer~, wherein (1)- a polymerization of a ~ixture of (a) from 60 to 90% by weight of ~tyrene or of a styrene d-rivative of the general formula I
~Rl C _ CH R2 ~R3) ~
where Rl, R' and R3 are each hydrogo~ methyl or ethyl and n i8 1 or 2, or of a C~-Cl0-olefin having ons or two con~ugated double bond~, or of a mlxtur~ thereof, (b) from 0 to 40% by we~ght of a Cl-Cl2-alkyl e~ter of acryl~c or methacrylic acid, acrylonitrile, methacrylon~trile, acrylamide or m~thacrylamide which may be sub~t~tuted by one or two Cl-C~-alkyl group~ on the ~mide nitrogen, maleic anhydride or male;mtde which may be ~ub~tituted by Cl-C~-al~yl on the ~de nitrogen, or a mixture thereof, . (c) from 0 to 20% by weight of one or more hydroxyl-containing acrylic ox methacrylic acid derivati~e~, and (d) from 0 to 2% by wsight of one or more poly-- olefinically unsaturatod monomers, to giv~ a prepolymer A, the hydroxyl groups being incorporated in A by u~ing hydroxyl-containing regulator~ if monomer component (c) i8 ab~ent, iand ~ubsequently (2) a polycondensation of a mixture of A) from 5 to 95% by weight of the prepolymer A, B) from 0 to 95% by weight of a further low lecular weight or higher molecular weight polyol, of a polyester or of a polyamide or a _ mixture thereof and C) from 5 to 70% by weight of one or more al~phatic or aromatic dicarboxylic ~cids C or - Cl-C~-alkyl estors thereof, where carboxylic ac~d~ or Cl-C,-alkyl e~ters thereof hav~ng moro than two carboxyl groups in the molecule or monocarboxylic acid~ or Cl-C~-alkyl e~ters thereof or hydroxymonocarboxylic acid~ or C~-C~-alkyl esters thereof, or a mixture of theso, and waxos may also be present ~n the polyconden~ation, are carried out The novol polyo~t~r resins are vory usoful as binders for electrophotographic toners Thus, the present invention also relates to electrophotographic toner~ which conta~n, as binders, one or mor~ novel polyester re~ins in tho conventional amoun~
gloctrophotogr3phic tonerfl are propared from the novel polye~ter reeins, for ~xample, by milling the resin to a particle ~z- of l~- than 1 mm, m~xing it with carbon blac~, a magn~tic pigm~nt or a colorant, wax, if necossary a cobinder, such a~ a copolymer of styrene and an acrylic acid derivati~e or of styrene and butadie~e or a polyester resin, ~eros~l and a charge ~tabilizer, ~5 kneading thi~ mixture to a uniform ~ass and then mllling the latter to a particlo ~ize of from 5 to 15 ~-and coat~ng it w~th Aerosil in a fluid mixer - If the ton~r composition al~o lacks certain a~ tants required for u~e in the copiers, or if they ars not y~t in their final phy~ical f~rm, the term p~eudotoner~ is also used The novel polyester resins are mixture~ of ~ariou~ species of macromolecule~ having different average molecular weights Since it i~ desirable to have toner re~ins with a very broad molecular weight di~tribution, the presence of such a mixture is partly respon~ible for the advantageous behavior of the novel 2131097 ``- 12 - o Z OOS0/43136 polyoster ro~ins Rhoolog~cal tests show thom to have a ~tructurally viscous behavlor The novol polyestor ro~ns can be propared rop~oduc~bly and w~thout probl~m~; in particular, tho S dangor of u~co~trollablo cro~ n~ng in th~ reaction v-~ol ~ ~ub~ta~tially rul-d out Thoy have good dl~p-r~i~g proportie- for carbon blac~, colorants, f-rrlt-- or oth-r finely divid-d mag~-t~c mat~r~al~, A~ro~l, charg- ~tab~l~z-r~ and waxe~ Th-y ar~ read~ly 0 millabl- in a rever~ ot mill a~d their throughput h-re ~- highor tha~ ln th- ca~- of comparablo prlor art rosins a~d th-ir co~t~nt of fln- du-t i~ very low The nov l poly-st-r ro~lns hav- a ~ub~tantially lowor ol-ctro-tatlc charg-ability comparod wlth tho prior art _ dia, for ~xampl- the r-~ln~ (1) Thls property co~ld-rably facllltato~ char~e ~tablllzatlon of tho tou-r~ which can b- proparod u-~g th- novol polyost~r r-c~
To~-rs obtal~od from th ~ov l polyostor resin~
hav- a long ~h-lf ilf-, ar- ln~ ltiv~ to molsturo a~d xhiblt good cold a~d hot off~ot prop-rti-~ ln con~unc-tlou wlth a h~gh fixing rato Coplo~ produced U8~ ng a toner obtai~ed from thi~ re~in have unlform blackness in the solld area and no background in unprinted areas and aro fast to m~gration Migration in this context mean~
the dotachment of toner particles from the copy by film~, for example tran~parent foldors EXAMPL~S
Parts and porcentages are by weight, unlo~s ~tatod otherwise Preparation of prepolymer A
EXAMPLES l-TO 7 (Suspen~ion polymerization) 300 0 g of monomer mixture (cf Table 1), 0 6 g of polyvinylpyrrol~done, 12 0 g of benzoyl peroxide (75%
str~ngth in E~O) and 600 ml of wator were ~tirred at from 80 to 90C The su~ponsion polymers 1 to 7 were obtained (cf Table 1) _ TAB~ 1 O~-functionalizod styrono/acrylato copolymors by cu~p-n~ion polymorization (S etyr~no, BA ~ n-butyl acrylat-, BDA 1,4-butan diol noacrylate, HEA 2-hydroxyothyl acrylato) Ex~mple S BA BDA O~ numbor alaae tran~i-N~ [~l l~] 1~l lmg ~O~/g] tion to~p TG
A furthor problem i~ the increa~e in the fixing rate of an imag0 tran~ferrod to the print medium (aeeeptor) by heat, ie the increaoe ln the cyele time of the eopier The proporties of a tonor during fixing aro greatly influoneed by the melting behavior of the toner rosin A higher f~xing rate is ~ehieved by u~ing a re~n hav ng a low ~oftening point However, thi~ may re~ult in tho problem of hot off~ot, ie some of the molten toner romains adhering to the hot fixing roller of the eop~er and is transforred to subseguont eopie~
In US-A 4 657 837 (1), the problem of hot offsot i~ ~olved by ~ing a braneh d polye~ter of terephthalie aeid, trimellitie aeid and ethoxylated or propoxylatod bi~phenol A Toner~ eon~isting of th$s re~in have very good ~nt$-off~et propertie~ but, ow~ng to their high softenlng point, are un~uitable for eopiers having eyele time~ of more than 50 eopies per minuto, sinee adeguate fixing on the print medium (aeeoptorl i~ not aehieved Polyester~ having a lower softening point but poorer anti-offset properties are deseribod in ~S-A 4 980 448 (2) The~e polyesters are obtainable by reacting a diearboxylie aeid eomponent, a d~ol eomponent and a eros~l-inking agent However, in the preparation of these resin~ there iR a danger that oxee~ive ero~linking may 39 oeeur in the polyeonden~ation EP-195 604 (3) disclo~es polye~ter~ for u~e in toner mlxtures, which are obtainable by copoly-eondensation of a diol eomponent of ethoxylated or propoxylated bi~phenol A with a eopolymer of styrene or a styrene derivative and a earboxyl-eontaining vinyl nomer These polyester~, too, do not ~olve the prior art problem~ de~eribed ~2131037 _ 3 _ o z 0050/43136 _ Tonor re~ins which h~ve a very high viscosity aftor melting or whic~ molt only vory 810wly oxhibit the phon onon of cold off~ot, io toner particles are not corroctly flxod on the papor and may thorefore remain adh-ring to the fixing rollor~ The litorature frogu-nt-ly doscribo~ th- u~e of r-~n~ hav~ng a bimod~l molecular we~ght di~tribut'on, which avo'd cold and hot off~ot Thi~ can al~o be achi-vod by us~ng ros~n mixturos or re~ins having a broad mol-cular weight distr'bution Thu~, tho low l-cular weight fraction en~uros good melting of the bind-r and good fix'ng on the pap-r, and th- high-r l-cular w ight fraction en~uro~ a ~uffi-c'~ntly high v~co~ity of th- binder and imparts to tho lton ton-r a c-rtain coho~ion which prevont~ hot off~t Th el-ctro~tatlc charg-ability of tonor resins ~ o important Th charg- bu'ld-up can b- controll~d by m an~ of chargo ~t~b~liz-rs Anothor important crit-r'on i~ th- ~tability of th- chargo Mb~y ton-rs h v a tend ncy of buildiDy up too much chargo during tho dev lopmont proc-~ Th chargo ~tabilizor koeps ths charge at a very particular lov-l, a~d very uniform blackne~ of tho copies i~ thus obtained In thi~
contoxt, tho r-action botwoon charge stabilizer and tonor resin i8 the critical paramoter It is an ob;ect of the present invention to romedy the prior art doficiencios described It was thorofiore intonded to provido a tonor ro~in which can be produced particularly oasily and without problems, has good dispersing propertios, is roadily millable and has a long shelf life as well as good cold and hot ofset properties in conju~ction with a high fixing rate We have found that this object i~ achieved by polyester resins based on hydroxyl-containing prepolymers of olofinically unsaturatod nomers, which are obtain-able by (1) polymerization of a mixturo of ~ 213IO97 - 4 - o.Z. 0050/43136 - (a) from 60 to 90% by weight of styrone or of a styrene dorivati~e of tho general formula I
Rl ~
~=CH R2 (R3) n ~
whore Rl, R2 and R3 aro eaeh hydrog~n, methyl or ethyl and n is 1 or 2, or of a C2-C10-olefin ha~ing one or two eonjugated double bo3ds, or of a mixture thoreof, (b) from 0 to 40% by weight of a Cl-Cl2-alkyl ester of aerylie or m~thaerylie aeid, aerylonitrile or mothaerylonitrile, aeryl~m~de or methaeryl-amid- whieh may be ~ubstituted by one or two :
Cl-C~-alkyl group~ on th~ ~mide nitrogen, maleie anhydrido or male~de whieh may be sub~titutod by Cl-C~-alkyl on the ~mide nitrog~n, or a mixture th~rsof, (e) from 0 to 20% by we~ght of o~e or re hydroxyl-eontaining aerylie or methaerylic aeid derivative~, and (d) from 0 to 2% by weight of one or re poly-olefi~ieally un~aturated monomer~, to gi~e th~ prepolymer A, the hydroxyl groups being ineorporated in A by u~ing hydroxyl-eontaining regulators whon the mono~or eo~ponent (e) i~ absent, and ~ubQequ~ntly S2) polyeond~n~ation of a mlxture o4 A) from S to 95% by weight of the prepolymer A, B) from 3 to 95% by weight of a further low moleeular weight or relatively high moleoular weight polyol, of a polyester or of a polyamide or a mixture thereof and C) from 5 to 70% by weig~t of one or more alipha-tie or aromatic dicarboxylic acids C or C~-C~-alkyl ester~ thereof, - 5 - O.Z. 0050/43136 _ where carboxylic acids or C1-C~-alkyl e~ters thereof having more than two carboxyl groupo in the molecule or monocarboxylic acid~ or Cl-C~-alkyl ester~ thereof or hydroxymonocarboxylic acid~ or C~-C~-alkyl esters thereof, or a mixture of these, and waxos may al80 be present in the polycondon~ation.
In the styrene and ~tyrono dor~vative~ I serv~ng as monomers (a) for the polymorization (1), Rl is prefer-ably hydrogon or mothyl, R~ and R3 are oach preferably hydrogen and ~ is pr~f~rably 1. If, when n 1, R3 iR
methyl or ethyl, the ph~nyl nucleus i~ ortho-, meta- or, pr~ferably, para-~ub~tituted. If, where n ia 2, R3 i~
methyl or ethyl, the substitution pattern on the phenyl nucleus i~ preferably 2, 4.
Furthor ~uitablo monomors (a) for the polymeriza-t~on (l) aro straight-chaln or branchod C2-C10-olefins, such a~ ethylone, propylo~e, l-butylene, 2-butylene, butadion~, isoprone, l-pontono, 2-p-ntene, 3-pentene, 1-h~xo~e, 2-hexene, 3-hoxono, 2,4-hoxadiene, heptenes, octenes, nonene~ and dec~nos.
Preferred monomer~ (a) for the polymerization (1) are styrene, a-met~ylstyrene, ethylene, propylene, butadiene or a mixture thereof.
The Cl-Cl~-alkyl acrylate~ and methacrylates which are suitable as monomers (b) for the polymarization (1) carry a~ a stra~ght-chai~ or branched alcohol radical, for example methyl, ethyl, n-propyl, i opropyl, n-butyl, i~obutyl, sec-butyl, tert-butyl, n-amyl, isoamyl, ~ec-amyl, tert-amyl, neopentyl, n-hexyl, n-h~ptyl, n-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, n-undecyl or n-dodecyl. Cl-C~-Alkyl acrylate and methacrylate are preferred among these. Suitable C1-C~-alkyl groups which may occur as ~ub~titutents on the amide nitrogen of acrylam;de or methacrylam~de and on the imide nitrogen of maleim~de are the abovementioned groups.
C1-C~-alkyl esters of acrylic and methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide and 21~1037 mot~acrylamid-, or a m~xturo thoreof, aro proferred as mo~om-rs (b) for the polym rization (1) In particular, the methacryl~c acid derivativo~ giv- outstanding ro~-ults S Partlcularly ~u~tabl- hydroxyl-containing acrylic or methacrylic acid dorivatlvo~ (c) for tho polymoriza-tion (1) ar- hydroxy-C~-C,-alkyl acrylat~ or meth-acrylat-~, og 2-hydroxyothyl acrylato, 2-hydroxyothyl methacrylat-, 2- or 3-hydroxypropyl acrylat-, 2- or 3-hydroxypropyl m th~crylat-, 4-hydroxybutyl acrylate or 4-hydroxybutyl m th~crylat-, N-(hydroxy-C,-C~-al~yl)-acryl-amid ~ or -m thacrylamld ~, eg N-(2-hydroxyethyl)-acryl-a~ldo, N-(2-hydroxy thyl)-~thacryla~ldo, N-(4-hydroxy-butyl)-acrylamid- or N-(4-hydroxybutyl)-mothacrylA~d-, or mixturo~ th-r-of Howev-r, N-(hydroxy-C~-C~-al~yl)-m~l-i~ld ~, ~g N-(2-hydroxy-thyl)-~aloimid , hydroxyl-contalning ~tyr-n- d-rivativ-~, g ortho-, mota- or p~r~-hydroxy~tyr-~e or ortho-, mota- or para-(hydroxy-m thyl)-~tyr-~ or al~-nol~, og but-2-on-1-ol or prop-2-o~-l-ol (allyl alcohol), are al~o suitabl-Particularly ~uitabl- polyolofinically un-~aturat-d monomor~ (d) aro tho~e ha~ing from 2 to S vinyl or allyl groups in the molecul-, for exam~le glycol di(moth)acrylat-, butanediol di(meth)acrylate, glyceryl tri(meth)acrylat-, (meth)allyl (moth)acrylate, penta-eryth ityl triallyl ether, pentallylsucrose, di(meth)-acrylates of polyethylene glycols having a molecular weighS of up to 3,000, divinyldioxane and especially divinylbenzene If desired, the prop-rties of the propolymers A can be modified within certain limits by the~- mo~omer~ acting as crosslinking agents If nomer component (c) i8 ab~ent, a hydroxyl-containing regulator i8 used in the polymerization (1) in order to incorporate the nece~ary hydroxyl groups into the prepolymer A These regulators are used in the conventional amounts, eg from about 0 1 to 5, in par-ticular from 0 3 to 2, % by weight, based on the total amount of the monomer~ (a) and (b) Partlcularly suitable hydroxyl-containing regula-tor~ are hydroxyl-containing m rcaptans, eg 2-hydroxy-eth~l mercaptan (2-m rcapto-thanol), 1-m rcapto-2,3-propanediol, 3-mercaptopropanol, 4-mercaptobutanol, 2-hydroxy-thyl mercaptoacetat- or 2-hydroxyethyl 3-m rcaptopropionate Th- be~t r-~ults are obtained with 2-m rcapto-thanol In a pr-ferred ombodtm nt, a m~xture of from 65 10to 85% by weight of monom rs (-), from 0 to 35% by w iyht of monom r~ (b), from 0 to 15% by we~ght of nomerc (c) and from 0 to 0 5~ by welght of monomer~ (d) are used in th- polym rization (1) The prepolymer ~ can be pr-pared by su~pons~on, 15~olut~on or bloc~ polym rlzat~on according to th- conven-tio~al thod~ Iu th- ~ub~-gu-~t poly¢ond-n~at~on (2), ho~ v r, pr-poly~or- A pr-p-r-d by ~olutlo~ polymeriza-tlon are pr-f-rably u~ed lnce th- polymer~zat~on (1) a~d th- polycoud n~atlou (2) ca~ th-u b- carried out lu 20ucce~lon in o~e re~ct~ou ve~el becau-~ lsolatlon of a pr-polym r i~ di~p-n~-d wlth In a suspon~lon polym rization, a mixture of wat-r and a water-mi~cible orgaulc solv~t, eg a wat-r/etha~ol mixture or water/isopropa~ol mixture having 25a low alcohol contont, or in particular water alone, i~
advantageously used as the su~pending medium For oxample, polyvinylpyrrolidone iB used as a protective colloid In solution polym rization, advantag-ously used 30~olvents are inert organic solvents, in partlcular aliphatic or aromatic hydrocarbons, eg toluene, xylene, cyclohexane, methylcyclohexane, petroleum ether or naphtha However, halohydrocarbons, eg chloroform, are also suitable.
35Tho polym rization (1) iB advantagoously carried out a~ a froo radical polymerization, suitable froe radical i~itiatorc being, for oxample, benzoyl peroxide or _tort-butyl poroetanoate A ~uitablo polymerization temporaturo i- from 60 to 130C, in parti¢ular from 80 to 120C In ~olution polymorization, it i~ ad~antageoue to ue~revaporativ eooli~g Tho avorag- moloeular w~ight M~ of th- propolymer A ~hould b- from 800 to 40,000, in partieular from 800 to 15,000 Th- O~ numb-r of A ~hould be 1088 than 60, in partleular 1-~ than 50, mg of ~OH/g Solutlon polymore A having O~ ~u~b-r~ of from 1 to 16 mg of RO~/g a~d a ratlo of eompon~nt- A to B of more tha~ 40 60 ar-pr-f-rr-d in th polyeond~ation (2) If tho ratio of A to B in th- polyeond-~ation (2) ~ tha~ 40 60, polymer~ A having O~ numb-r~ ~r-~ter than 10 mg of RO~/g may al~o advantageou~ly b- u~-d Partleularly sultabl- eompo~nte B for th polyeond ~at~on (2) ar- C~-C~-al~an-diols, g ethyl-ne glyeol, 1,2- and 1,3-prop ~-dlol, 1,4-buta~-diol, 1,6-h-xan-diol, n-op~ntylglyeol, thoxylat-d or propoxylated bl~ph-~ol A, for ~xampl- bl~ph nol A r-aet-d with from 2 to 20 mol of thyl-~- oxld- or propyl~ oxide, or mixtur-s th r-of ~ow v r, high l-eular w~ght polyole havl~g a~ averag- moleeular w lght N~ of more than 500, for oxample poly ~t-rdlols, polyeth-rdiols or poly-e~rbo~atediols, polyoeters, ~ueh as polyeaprolaetone or polyamidee, sueh as polyeaprolaetam, may al~o be ueed Partleularly eultable diearboxylie aeide C- for the polyeondensation (2) ar- phthalie aeid, isophthalie ae~d, -terephthalie aeid or tho~r Cl-C~-monoal~yl esters and in part~eular Cl-C~-dial~yl est-r~ or a mixturo thoroof However, for example eyelohexanodiearboxylie aeids or aliphatie dicarboxylic aeids euch aR succinic acid or adipic aeid or the correeponding Cl-C~-monoalkyl e~tere and in particular Cl-C~-dial~yl eeter~ may also be used.
A mixture of from S to 95% by weight of the prepolymer A, from 0 to 95% by weight of the component B
~nd from 5 to 70% by weight of the dicarboxylic acid C or _ g - o z 0050/43136 an ~t-r ther-of aro usod in tho polyconden~ation (2), A
and B tog-ther accounting for frQm 30 to 95% by woight of thia mixturo In a preferr-d ~mbodim~nt, a mixturo of fr~ 30 to 70% by w ight of A, from 10 to 50% by weight S of B and from 10 to 50% by w lght of C is used, A and B
tog-th-r accountlng for from 50 to 90% by w ight of th~s mixtur-In th- polyconden~atlon (2), for x~mpl-, tr~-m llitlc acid, b-nzoic acid, o- or p-hydroxyb~nzoic ac~d, nicotinic acld or t-aric acid or th corr-~onding Cl-C~-~l~yl e~t-r~ may b- pre~ont a- addit~onal carboxyl~c acld~, a~ w ll a~ waxe~, for ~a~le polypropyl~n- wax Th ~- additlonal oarboxylic acid~ or th ir st-r~ are th~ pre~-nt i~ a unt~ of up to 15% by ~ ight, and the wax-~ ln amount~ of up to 15% by ~ lght, ba~ed in oach ca~- o~ th- total amDunt of th- mixture of A, B and C
8ultabl- Cl-C,-alkanol~ ln th- carboxylic acld ~t-r~ ~mploy d ar- n-propanol, i~opropanol, n-butanol, ~-¢-but nol, tert-butanol and in particular m thanol and ~thanol The water formed in the polycond n~ation (2) or th- Cl-C~-al~anol formed i- advantag-ou~ly di~tilled off dir-ctly from th- r-~n melt if no ontraining agent ~ 8 pr-~ent, or iB romoved by means of an entraining agent, such as toluone, xylene, mothylcyclohexane or chloroform Tho polycondensation i~ u~ually carriod out in the prosence of a catalyst, for oxample dibutyltin ox~de, a tit~nium alcoholato, p-toluono~ulfonic acid or sulfuric acid, in the conventional amounts Tho polycondensation (2) ~B carried out either BO
that the prepolymer A is added to the components B and C
which have been precondensed to an OH number of les~ than 90 mg of ROH/g, or all three c~ponents A, B and C are added togoth~r ~imultaneously The condensation is compl-t-d towards the end of the reaction at from 180 to The present invention furthermore relates to a - 10 - O.Z. 0050/43136 pro~e~ for the proparation of polyester resins base~ on hydroxyl-containing prepolymers of olefinically un~aturated monomer~, wherein (1)- a polymerization of a ~ixture of (a) from 60 to 90% by weight of ~tyrene or of a styrene d-rivative of the general formula I
~Rl C _ CH R2 ~R3) ~
where Rl, R' and R3 are each hydrogo~ methyl or ethyl and n i8 1 or 2, or of a C~-Cl0-olefin having ons or two con~ugated double bond~, or of a mlxtur~ thereof, (b) from 0 to 40% by we~ght of a Cl-Cl2-alkyl e~ter of acryl~c or methacrylic acid, acrylonitrile, methacrylon~trile, acrylamide or m~thacrylamide which may be sub~t~tuted by one or two Cl-C~-alkyl group~ on the ~mide nitrogen, maleic anhydride or male;mtde which may be ~ub~tituted by Cl-C~-al~yl on the ~de nitrogen, or a mixture thereof, . (c) from 0 to 20% by weight of one or more hydroxyl-containing acrylic ox methacrylic acid derivati~e~, and (d) from 0 to 2% by wsight of one or more poly-- olefinically unsaturatod monomers, to giv~ a prepolymer A, the hydroxyl groups being incorporated in A by u~ing hydroxyl-containing regulator~ if monomer component (c) i8 ab~ent, iand ~ubsequently (2) a polycondensation of a mixture of A) from 5 to 95% by weight of the prepolymer A, B) from 0 to 95% by weight of a further low lecular weight or higher molecular weight polyol, of a polyester or of a polyamide or a _ mixture thereof and C) from 5 to 70% by weight of one or more al~phatic or aromatic dicarboxylic ~cids C or - Cl-C~-alkyl estors thereof, where carboxylic ac~d~ or Cl-C,-alkyl e~ters thereof hav~ng moro than two carboxyl groups in the molecule or monocarboxylic acid~ or Cl-C~-alkyl e~ters thereof or hydroxymonocarboxylic acid~ or C~-C~-alkyl esters thereof, or a mixture of theso, and waxos may also be present ~n the polyconden~ation, are carried out The novol polyo~t~r resins are vory usoful as binders for electrophotographic toners Thus, the present invention also relates to electrophotographic toner~ which conta~n, as binders, one or mor~ novel polyester re~ins in tho conventional amoun~
gloctrophotogr3phic tonerfl are propared from the novel polye~ter reeins, for ~xample, by milling the resin to a particle ~z- of l~- than 1 mm, m~xing it with carbon blac~, a magn~tic pigm~nt or a colorant, wax, if necossary a cobinder, such a~ a copolymer of styrene and an acrylic acid derivati~e or of styrene and butadie~e or a polyester resin, ~eros~l and a charge ~tabilizer, ~5 kneading thi~ mixture to a uniform ~ass and then mllling the latter to a particlo ~ize of from 5 to 15 ~-and coat~ng it w~th Aerosil in a fluid mixer - If the ton~r composition al~o lacks certain a~ tants required for u~e in the copiers, or if they ars not y~t in their final phy~ical f~rm, the term p~eudotoner~ is also used The novel polyester resins are mixture~ of ~ariou~ species of macromolecule~ having different average molecular weights Since it i~ desirable to have toner re~ins with a very broad molecular weight di~tribution, the presence of such a mixture is partly respon~ible for the advantageous behavior of the novel 2131097 ``- 12 - o Z OOS0/43136 polyoster ro~ins Rhoolog~cal tests show thom to have a ~tructurally viscous behavlor The novol polyestor ro~ns can be propared rop~oduc~bly and w~thout probl~m~; in particular, tho S dangor of u~co~trollablo cro~ n~ng in th~ reaction v-~ol ~ ~ub~ta~tially rul-d out Thoy have good dl~p-r~i~g proportie- for carbon blac~, colorants, f-rrlt-- or oth-r finely divid-d mag~-t~c mat~r~al~, A~ro~l, charg- ~tab~l~z-r~ and waxe~ Th-y ar~ read~ly 0 millabl- in a rever~ ot mill a~d their throughput h-re ~- highor tha~ ln th- ca~- of comparablo prlor art rosins a~d th-ir co~t~nt of fln- du-t i~ very low The nov l poly-st-r ro~lns hav- a ~ub~tantially lowor ol-ctro-tatlc charg-ability comparod wlth tho prior art _ dia, for ~xampl- the r-~ln~ (1) Thls property co~ld-rably facllltato~ char~e ~tablllzatlon of tho tou-r~ which can b- proparod u-~g th- novol polyost~r r-c~
To~-rs obtal~od from th ~ov l polyostor resin~
hav- a long ~h-lf ilf-, ar- ln~ ltiv~ to molsturo a~d xhiblt good cold a~d hot off~ot prop-rti-~ ln con~unc-tlou wlth a h~gh fixing rato Coplo~ produced U8~ ng a toner obtai~ed from thi~ re~in have unlform blackness in the solld area and no background in unprinted areas and aro fast to m~gration Migration in this context mean~
the dotachment of toner particles from the copy by film~, for example tran~parent foldors EXAMPL~S
Parts and porcentages are by weight, unlo~s ~tatod otherwise Preparation of prepolymer A
EXAMPLES l-TO 7 (Suspen~ion polymerization) 300 0 g of monomer mixture (cf Table 1), 0 6 g of polyvinylpyrrol~done, 12 0 g of benzoyl peroxide (75%
str~ngth in E~O) and 600 ml of wator were ~tirred at from 80 to 90C The su~ponsion polymers 1 to 7 were obtained (cf Table 1) _ TAB~ 1 O~-functionalizod styrono/acrylato copolymors by cu~p-n~ion polymorization (S etyr~no, BA ~ n-butyl acrylat-, BDA 1,4-butan diol noacrylate, HEA 2-hydroxyothyl acrylato) Ex~mple S BA BDA O~ numbor alaae tran~i-N~ [~l l~] 1~l lmg ~O~/g] tion to~p TG
3 78 819 7 1 5 5 84 62
4 78 ~19 6 2 0 7 80 64 69 029.0 2 0 7 80 49 7 78 719.7 1 6 7 80 65 The O~ numbor~ w ro calculatod EXA~P~88 8 TO 18 (8u p-n~on polymorization) 1,300 g of ~onomer m~-xturo (cf Tablo i), 0 75 g of polyvinylpyrrolldone, S O g of bonzoyl peroxido (75~
str~gth in E~O) a~d 1,000 ml of water wero stirrod at fr~m ~0 to 90C The ~u~pons~on polymer~ 8 to 18 wero obtainod (c$ Table 2) TAB~ 2 O~-$unctionalized ~tyrono/mothacrylato copolymors, ~omo of whlch aro cro~linked, by suspension polymor~zation (S ~tyreno, BMA = n-butyl methacrylate, HEA
2-hydroxyethyl acrylate, DVB = divinylbenzene) ~131097 ~xa~ple S - - DV8 OH number Glass transi-No t~ t~] t~] [~l lmg ROH/g] t~on temp TG
8 79 0 19 0 2 0 _ ~ 80 9 78 0 18 0 ~ 0 _ ~ 19 3 80 77 0 17 0 6 0 _ ~ 29 0 78 11 76 0 16 0 8 0 _ 38 7 75 12 ~ 75 0 15 0 10 0 _ 48 4 80 1~ 76 9 17 0 6 0 0 10 29 80 76 9~ 17 0 6 0 0 06 29 82 The 0~ numb-r~ w-r- calculat-d; mea~ured OH
number~ for ~xample~ 8/9/12/16 3/6/14/8 EXAMPL~S 19 TO 22 (8Olut~on polyo r~zation) A solution of 480 g of the monomer mixture, 19 2 g of benzoyl psroxide (75% str~ngth in H20) and 48 g of toluene was added dropwise to 120 g of monomor m~xture (cf Table 3), 4 8 g of benzoyl peroxide ~75% strength in ~2) ~nd 12 g of toluens while otirring at 90C in the cour~e of 2 hours, ~tirring wa~ continued for 1 hour at from 90 to 100C and a ~olution of 6 0 g of benzoyl perox~de (75% strength in H2O~ in 140 g of toluene was added dropwise while stirring in the course of 1 hour After 5 hours at 100C an about 65% strength solution of the polymer in toluene wa~ obtained ~,i5-,~; ~,; ; "_, ~
_ TAB~E 3 OH-functionalized styrone/acrylate copolymors by solution polym rization (S ~tyrono, BA n-butyl acrylato, ~A
, Z~hydroxyethyl acrylate) S Exampl- ~A O~ nuab-r Glas~ transi-o [~1 t~l I~] tmg ~O~/g] tion tomp TG
19 79 6 20 0 0 ~ 1 91 70 79 3 19 9 o.a 3 87 70 The 0~ nu~b~r~ w r- calculated E~AMP~ 23 (Solut~on polymorization u~ing a cro~-lln~$ng ag-nt) 400 g of tolu-n- w ro initially ta~on ~nd h-ated 15to th boil A m~tur- of 1,659 0 g (78 95%) of styr~no, 399 0 g (19 0%) of n-butyl methacrylato, 42 0 g (2 0 g) of butanediol monoacrylat- und 1.1 g (0 05%) of divinyl-b~z no in 200 g of toluon- and slmultaneou~ly a solution of 25 2 g of t-rt-butyl perbenzoato in 240 g of tolu-ne woro addea aropwis- in the cour~o of three hours at a rate such that the temperaturo did not exceed 120C
After tho re~ction had continuod for a further hour at the boiling point, 6 3 g of tert-butyl porbenzoate in 60 g of tolueno were added dropwis- in th- course of one hour Tho roactlon was allowod to continu- for a further threo hours, after which the mixture wa8 cooled to room temperature The solution polymer obtained had a calcu-lated OH number of 8 and a gla~s transition temperature TG of 81C
30EXAMP~S 24 TO 28 (Solution polymerization using a regulator) A solution of 240 g of the nomer mixture, 9 6 g of ~onzoyl poroxido (75% strongth ~n H,O) and 48 g of tolu~no was addod dropw~o to 60 g of monomor mixture (cf Tablo 4), 2 4 g of benzoyl poroxide (75~ strongth in H,O~ and 12 g of toluon- while ~tirring at 90C in tho cour~o of 2 hours, ot~rr~ng wa~ continu-d for 1 hour at from 90 to 100C and a colut~on of 3 0 g of benzoyl p-roxide ~75% ~tr-ngth i~ E~O) ~n 70 ml of toluono was add-d dropwi~- wh~ t~rrlug ln th- cour~o of 1 hour Aft-r S hour~ at 100C, ~ bout 65% ~trongth ~olution of th- polym r in tolu~n- ~ae obta~n-d TABL~ 4 O~-functlo~al~z-d tyr~o/acrylato copolymors by ~olution ~olymorizat~on u-lng a r~gulator (S - ~tyrono, BA -n-butyl acrylat-, M~ 2-m~rcaptoethanol) ~xampl~ 8 ~ O~ numbor No [~1 t~l [~I tmg ~O~/g]
The OH numbors wore calculated EXAMP~S 29 TO 32 (Block polymorizat~on) Examples 29 to 32 woro carriod out similarly to ~xamplo~ 19 to 22 by omitt~ng the solvent 480 g of the particular monomer mixture and 24 0 g of tert-butyl peroctanoate were simultaneously added dropwise to 120 g of nomer mixture (cf Table 3) while ~tirring at 120C in the course of 5 hours, ~tirr~ng wa~ contiuuod for 1 hour at fr 90 to 100C and 6 0 g of tort-butyl peroctanoato wore added dropw~se whilo ~tirring in the course of 1 hour After 5 hours at 100C, a slightly turbid melt of the polymer was - 17 _ 1 3 1 0 ~ 7 o~ Z . oOSO/43136 obtainod Pr-paration of the polyestor rosins ~XANP~S 33 TO 39 207 0 g of 1,6-h~xanodiol, 290 7 g of ter-ph-S thalic acid und 2 24 g of dlbutylti~ oxld- wero hoatod to 250C whilo ~tirri~g; wator wa~ dl~till-d off untll an acid numb-r of about 90 q of ~O~/g had b--n roached Th r-after, 1050 9 g of a ~u~p-n~lon polym r from Ex-a~pl~o 1 to 7 w r~ added, u~d ~t-r wa~ distillod off whil- ~tlrri~g at 260C u~tll ~ co~lty of the reaction ~ixtur- incroa~-d ~harply und a~ far a~ po~iblo an acid nu~b-r of lo~ than 25 mg of ~O~/g h~d beon roach~d ~abl- S ~how~ th ro~ult~ of th xp-rim~nts TWB~E S
~x~pl- ~r poly- Acld al-~- Soft~n- Cro~llnklng No r A nu~b-r tr-~d - l~g t~ - ) fro~ ~x- AN tlon ~olnt lh]
a~pl- No ~ ~ ~O~/~l t--p ~a t Cl 33 1 103 _ _ No cro llnk-3~ 2 25 65 130 No cro~llnk-lnq ft-r 3 h 3 25 51 133No cro~sl~nk-~ng aft-r 3 h 36 4 2~ 65 1~0 No cro~link-_ lng aft-r 3 h 37 5 35 50 _ 1 0 38 6 _ _ - 0 5 39 7 24 61 137 No cro~link-ing after 3 h Tho acid numbers were determined by titration5 a) T~me between addition of A and cro~slinking or dramatic increa~e in vi~co~ity ~1310~7 b) _ At AN . 103 mg of RO~/g, 18 2 g of octadocanol were addod Blaphonol A thoxylat-d doubly and ~ymmetrically, dim thyl torophthalat-, dibutyltin oxido (0 15~, ba~-d on tho total amount) and a styr-n- mothacrylato containing hydroxyl functlonal group~, accordlng to ~xamplo~ 8 to 18, w r- hoat-d ln th pr-- nc- of 100 g of tolu-no and, aft-r th mlxturo had b-gun to m lt, th- ~tlrror wa~
~wltch d on at 40 rpm Th mixturo wa~ th n h-atod to 200 C (lnt-rn l t-mp-ratur-) and m thanol wa~ di~till-d off untll th ~l~co~ty of th r-actlon ~ixturo increa~-d oharply Tho chango ln tho vl~coslty wlth time was mo~ltorod by tho torguo of th- ~tlrror Tho curvo lov l-d off lncr-a~ingly a~ th- r-action procood~d and flnally no long r had any ~lop-, ma~lng it pos~lblo to d-t-rmin- th- ond polnt of tho roactlon Aftor tho tolu-~- had b- n dl~tlll-d off, tho product was di~-ch~r~ d into a tln can and th n mochanlcally communitod Th flst-~lz~d frag~nt~ w r- mill-d ln a cuttlng mill to particlo ~1ZOB of from ono to two millim-tros Tablo 6 shows tho ro~ults of tho t-~ts 2`1310~7 - 19 - O.Z. 00S0/43136 _ TABLE 6 ~x~- Bl~-A TD~ Pr-poly~r R ~c- Gl~-- ~oft-n~g pl- a fro~ tlon tr~tlon polnt SP
No ~xpl No tl~ t-~p 1~ ~gl tgl thl t Cl t Cl ~0 3~7.6 17~.8 8 10~2.1 lS.S 61116 ~1 293.C 18~.5 9 10~ 13.0 66120 ~2 237.3 203.9 10 10~ ~.2s 56126 ~3 206.~ 19~.2 11 10~ 8.25 59127 ~ 127.7 17~.8 12 10~ 9.0 55119 ~S 297.0 271.8 13 10~ l.S 50128 ~6 233.8 19~.2 1~ 10~ 2.0 53129 ~7 233.8 19~.2 lS 6~2 s 1.7S 5~126 ~8 290.9 19~.2 16 318.0 ~.75 63120 ~9 285.2 19~.2 16 390.3 6.5 58109 27C .3 19~ .2 16 S03.0 5.5 6313~
Sl 233.8 19~.2 17 10~ 3.25 55127 s2 288.6 19~.2 18 10~ s.75 57127 (Bi~-A ~ Bisphonol A othoxylatod doubly and symmotrical-ly, TDM s Dimothyl terephthalate~
EXAMP~ES 53 TO 56 207.0 g of 1,6-hexanodiol, 290.7 g of teroph-thalic acidJ 2.24 g of dibutyltin oxide and 972.1 g of a solution polymer from Examplos 19 to 22 ~in the form of ~n about 65% strength solution in toluene) were heated while stirring, toluene was distilled off, the mixture was then heated to 260C and water was distilled off until the ~iscosity of the reaction mixture increased ~harply and as far as possible an acid number of less than 45 mg of ~OHJg had been reachod. Table 7 shows the r-~ults of the oxporiments.
BX~- Pr-poly- Acld Gla~ Soft-nlng Cro~lln~lng pl- ~r A nu~b-r AN tr n-ltlon point g~ ti~ ) No fro~ ~x- ~g ~OH/gl t-mp Ta I Cl lh}
ampl- No [ Cl 53 19 32 S3 123 No cro~lln~-~n~ ~ft-r 3 h
str~gth in E~O) a~d 1,000 ml of water wero stirrod at fr~m ~0 to 90C The ~u~pons~on polymer~ 8 to 18 wero obtainod (c$ Table 2) TAB~ 2 O~-$unctionalized ~tyrono/mothacrylato copolymors, ~omo of whlch aro cro~linked, by suspension polymor~zation (S ~tyreno, BMA = n-butyl methacrylate, HEA
2-hydroxyethyl acrylate, DVB = divinylbenzene) ~131097 ~xa~ple S - - DV8 OH number Glass transi-No t~ t~] t~] [~l lmg ROH/g] t~on temp TG
8 79 0 19 0 2 0 _ ~ 80 9 78 0 18 0 ~ 0 _ ~ 19 3 80 77 0 17 0 6 0 _ ~ 29 0 78 11 76 0 16 0 8 0 _ 38 7 75 12 ~ 75 0 15 0 10 0 _ 48 4 80 1~ 76 9 17 0 6 0 0 10 29 80 76 9~ 17 0 6 0 0 06 29 82 The 0~ numb-r~ w-r- calculat-d; mea~ured OH
number~ for ~xample~ 8/9/12/16 3/6/14/8 EXAMPL~S 19 TO 22 (8Olut~on polyo r~zation) A solution of 480 g of the monomer mixture, 19 2 g of benzoyl psroxide (75% str~ngth in H20) and 48 g of toluene was added dropwise to 120 g of monomor m~xture (cf Table 3), 4 8 g of benzoyl peroxide ~75% strength in ~2) ~nd 12 g of toluens while otirring at 90C in the cour~e of 2 hours, ~tirring wa~ continued for 1 hour at from 90 to 100C and a ~olution of 6 0 g of benzoyl perox~de (75% strength in H2O~ in 140 g of toluene was added dropwise while stirring in the course of 1 hour After 5 hours at 100C an about 65% strength solution of the polymer in toluene wa~ obtained ~,i5-,~; ~,; ; "_, ~
_ TAB~E 3 OH-functionalized styrone/acrylate copolymors by solution polym rization (S ~tyrono, BA n-butyl acrylato, ~A
, Z~hydroxyethyl acrylate) S Exampl- ~A O~ nuab-r Glas~ transi-o [~1 t~l I~] tmg ~O~/g] tion tomp TG
19 79 6 20 0 0 ~ 1 91 70 79 3 19 9 o.a 3 87 70 The 0~ nu~b~r~ w r- calculated E~AMP~ 23 (Solut~on polymorization u~ing a cro~-lln~$ng ag-nt) 400 g of tolu-n- w ro initially ta~on ~nd h-ated 15to th boil A m~tur- of 1,659 0 g (78 95%) of styr~no, 399 0 g (19 0%) of n-butyl methacrylato, 42 0 g (2 0 g) of butanediol monoacrylat- und 1.1 g (0 05%) of divinyl-b~z no in 200 g of toluon- and slmultaneou~ly a solution of 25 2 g of t-rt-butyl perbenzoato in 240 g of tolu-ne woro addea aropwis- in the cour~o of three hours at a rate such that the temperaturo did not exceed 120C
After tho re~ction had continuod for a further hour at the boiling point, 6 3 g of tert-butyl porbenzoate in 60 g of tolueno were added dropwis- in th- course of one hour Tho roactlon was allowod to continu- for a further threo hours, after which the mixture wa8 cooled to room temperature The solution polymer obtained had a calcu-lated OH number of 8 and a gla~s transition temperature TG of 81C
30EXAMP~S 24 TO 28 (Solution polymerization using a regulator) A solution of 240 g of the nomer mixture, 9 6 g of ~onzoyl poroxido (75% strongth ~n H,O) and 48 g of tolu~no was addod dropw~o to 60 g of monomor mixture (cf Tablo 4), 2 4 g of benzoyl poroxide (75~ strongth in H,O~ and 12 g of toluon- while ~tirring at 90C in tho cour~o of 2 hours, ot~rr~ng wa~ continu-d for 1 hour at from 90 to 100C and a colut~on of 3 0 g of benzoyl p-roxide ~75% ~tr-ngth i~ E~O) ~n 70 ml of toluono was add-d dropwi~- wh~ t~rrlug ln th- cour~o of 1 hour Aft-r S hour~ at 100C, ~ bout 65% ~trongth ~olution of th- polym r in tolu~n- ~ae obta~n-d TABL~ 4 O~-functlo~al~z-d tyr~o/acrylato copolymors by ~olution ~olymorizat~on u-lng a r~gulator (S - ~tyrono, BA -n-butyl acrylat-, M~ 2-m~rcaptoethanol) ~xampl~ 8 ~ O~ numbor No [~1 t~l [~I tmg ~O~/g]
The OH numbors wore calculated EXAMP~S 29 TO 32 (Block polymorizat~on) Examples 29 to 32 woro carriod out similarly to ~xamplo~ 19 to 22 by omitt~ng the solvent 480 g of the particular monomer mixture and 24 0 g of tert-butyl peroctanoate were simultaneously added dropwise to 120 g of nomer mixture (cf Table 3) while ~tirring at 120C in the course of 5 hours, ~tirr~ng wa~ contiuuod for 1 hour at fr 90 to 100C and 6 0 g of tort-butyl peroctanoato wore added dropw~se whilo ~tirring in the course of 1 hour After 5 hours at 100C, a slightly turbid melt of the polymer was - 17 _ 1 3 1 0 ~ 7 o~ Z . oOSO/43136 obtainod Pr-paration of the polyestor rosins ~XANP~S 33 TO 39 207 0 g of 1,6-h~xanodiol, 290 7 g of ter-ph-S thalic acid und 2 24 g of dlbutylti~ oxld- wero hoatod to 250C whilo ~tirri~g; wator wa~ dl~till-d off untll an acid numb-r of about 90 q of ~O~/g had b--n roached Th r-after, 1050 9 g of a ~u~p-n~lon polym r from Ex-a~pl~o 1 to 7 w r~ added, u~d ~t-r wa~ distillod off whil- ~tlrri~g at 260C u~tll ~ co~lty of the reaction ~ixtur- incroa~-d ~harply und a~ far a~ po~iblo an acid nu~b-r of lo~ than 25 mg of ~O~/g h~d beon roach~d ~abl- S ~how~ th ro~ult~ of th xp-rim~nts TWB~E S
~x~pl- ~r poly- Acld al-~- Soft~n- Cro~llnklng No r A nu~b-r tr-~d - l~g t~ - ) fro~ ~x- AN tlon ~olnt lh]
a~pl- No ~ ~ ~O~/~l t--p ~a t Cl 33 1 103 _ _ No cro llnk-3~ 2 25 65 130 No cro~llnk-lnq ft-r 3 h 3 25 51 133No cro~sl~nk-~ng aft-r 3 h 36 4 2~ 65 1~0 No cro~link-_ lng aft-r 3 h 37 5 35 50 _ 1 0 38 6 _ _ - 0 5 39 7 24 61 137 No cro~link-ing after 3 h Tho acid numbers were determined by titration5 a) T~me between addition of A and cro~slinking or dramatic increa~e in vi~co~ity ~1310~7 b) _ At AN . 103 mg of RO~/g, 18 2 g of octadocanol were addod Blaphonol A thoxylat-d doubly and ~ymmetrically, dim thyl torophthalat-, dibutyltin oxido (0 15~, ba~-d on tho total amount) and a styr-n- mothacrylato containing hydroxyl functlonal group~, accordlng to ~xamplo~ 8 to 18, w r- hoat-d ln th pr-- nc- of 100 g of tolu-no and, aft-r th mlxturo had b-gun to m lt, th- ~tlrror wa~
~wltch d on at 40 rpm Th mixturo wa~ th n h-atod to 200 C (lnt-rn l t-mp-ratur-) and m thanol wa~ di~till-d off untll th ~l~co~ty of th r-actlon ~ixturo increa~-d oharply Tho chango ln tho vl~coslty wlth time was mo~ltorod by tho torguo of th- ~tlrror Tho curvo lov l-d off lncr-a~ingly a~ th- r-action procood~d and flnally no long r had any ~lop-, ma~lng it pos~lblo to d-t-rmin- th- ond polnt of tho roactlon Aftor tho tolu-~- had b- n dl~tlll-d off, tho product was di~-ch~r~ d into a tln can and th n mochanlcally communitod Th flst-~lz~d frag~nt~ w r- mill-d ln a cuttlng mill to particlo ~1ZOB of from ono to two millim-tros Tablo 6 shows tho ro~ults of tho t-~ts 2`1310~7 - 19 - O.Z. 00S0/43136 _ TABLE 6 ~x~- Bl~-A TD~ Pr-poly~r R ~c- Gl~-- ~oft-n~g pl- a fro~ tlon tr~tlon polnt SP
No ~xpl No tl~ t-~p 1~ ~gl tgl thl t Cl t Cl ~0 3~7.6 17~.8 8 10~2.1 lS.S 61116 ~1 293.C 18~.5 9 10~ 13.0 66120 ~2 237.3 203.9 10 10~ ~.2s 56126 ~3 206.~ 19~.2 11 10~ 8.25 59127 ~ 127.7 17~.8 12 10~ 9.0 55119 ~S 297.0 271.8 13 10~ l.S 50128 ~6 233.8 19~.2 1~ 10~ 2.0 53129 ~7 233.8 19~.2 lS 6~2 s 1.7S 5~126 ~8 290.9 19~.2 16 318.0 ~.75 63120 ~9 285.2 19~.2 16 390.3 6.5 58109 27C .3 19~ .2 16 S03.0 5.5 6313~
Sl 233.8 19~.2 17 10~ 3.25 55127 s2 288.6 19~.2 18 10~ s.75 57127 (Bi~-A ~ Bisphonol A othoxylatod doubly and symmotrical-ly, TDM s Dimothyl terephthalate~
EXAMP~ES 53 TO 56 207.0 g of 1,6-hexanodiol, 290.7 g of teroph-thalic acidJ 2.24 g of dibutyltin oxide and 972.1 g of a solution polymer from Examplos 19 to 22 ~in the form of ~n about 65% strength solution in toluene) were heated while stirring, toluene was distilled off, the mixture was then heated to 260C and water was distilled off until the ~iscosity of the reaction mixture increased ~harply and as far as possible an acid number of less than 45 mg of ~OHJg had been reachod. Table 7 shows the r-~ults of the oxporiments.
BX~- Pr-poly- Acld Gla~ Soft-nlng Cro~lln~lng pl- ~r A nu~b-r AN tr n-ltlon point g~ ti~ ) No fro~ ~x- ~g ~OH/gl t-mp Ta I Cl lh}
ampl- No [ Cl 53 19 32 S3 123 No cro~lln~-~n~ ~ft-r 3 h
5~ 20 38 51 126 No cro~lln~-lng ~t-r 3 h 21 ~1 50 lS7 No cro~lin~-lng ~ft-r 3 h 56 22 ~S 52 ~200 No cro~lln~-ing ft-r 3 h Th- ac~d numb-r~ wero determin-d by titrat~on0 a) Time betw -n addltion of A and cros~l$n~ing or dramatic $ncr-a~- ~n v$~co~ity 207 0 g of 1,6-h~xa~-diol, 290 7 g of ter-ph-thal$c ac$d, 2 24 g of dibutyltin oxido ~nd 248 9 g of a solution polymer from ~xample~ 19 to 22 ($n the form of an about 65% strength solut$03 in toluene) were heated wh$1- ~t$rring, toluene was distilled off, the mixture waB then heated to 260C and water was distilled off until the v~ BCOB~I ty of the reaction mixture increased sharply and ae far as po~sible an ac~d ~umber of les~
th~n 100 mg of RO~/g had been roached ~able 8 ~hows the results of the experimont~
213.1~37 _ TAB~ 8 ~x - Pr-poly- ~cld al-~- 8Oft-n- Cro~lln~lng pl- ~ r A nu~b-r tr-n~l- lng t$m- ~) No fro~ ~x- AN tlon polnt Ihl ~pl-- No I~g ~OH/g] t I ClSG t Cl 57 l9 102 57 138 l 0 58 20 98 S9 lC3 1 5 59 21 ~1 50 l57 l 0 2~ 90 58 l~ No oro~ ~k-lng ~t-r 3 h The acid numb-r~ were d termined by titration0 a) Time betwe~n add~tion of A and cros~linking or dra~atic incr~a~- ~n vi~co-ity EXAMæ~S 61 T0 64 554 3 g of bi~phenol A ethoxylated doubly and oymm-trically to a degree of 90%, 290 7 g of terophthalic acid, 3 91 g of dibutyltin ox~de and 1745 1 g of a 801u-t~on polymer fr~m ~xample~ 19 to 22 l~n tho form of an about 65% strength solution in tolu-ne) wer~ hoated while ~t~rr~ng, toluono wa~ distillod off, the mixturo was then h-at-d to 260C and water was di~tilled off until the vi~cosity of the reaction mixture incroased sharply and an acid number of le~s than 25 mg of R0~/g had been reached Table 9 shows the results of tho exporiments ~XAMP~E 65 182 5 g of a bisphenol A doubly and symmetrically ethoxylated to a degree of 90%, 397 3 g of bisphenol A
doubly and symmetrically propoxylated to a degree of 95%, 290 7 g of torophthalic acid, 3 91 g of dibutyltin oxide and 1745 1 g of the solution polymer from Example 19 (in the form of an about 65% strength solution in toluene) were heated while stirring, toluene was distilled off, th- mixture was then heated to 260C and water was dl~tilled off until the ~iscosity of the reaction mixture increa~ed ~harply and an acid number of less than 25 mg 2131 ~97 of ~OH/g had been reachod Tablo 9 ~how~ tho re~ult of th~ 8 exper~ment ~x~- ~r-poly- Acld al~ ~oft-n- Cro~lln~lng S pl- m~r A nu~b-r tr~n~l- ldg tlm~ ~) No fro~ ~x- AN tlo~ pol~t thl u~pl- ~o [~q ~OH/~l t--p Ta 8~l Cl 61 _ ~ 65 1~ ln~ ft r 3 ;
Ci 20 S 63 200 1 75 0 C~ 22 13 69 131 1 0 C5 19 7_ 6~ 13~ ln~ ft r 3 h Th acld numb-r~ wer- det-rmin-d by titratio~
a) T~me betw ~ additlon of A and cro~linking or dramat$c increa~- in vi~co~ity EXA~PLES 66 TO 69 554 3 g of bi~ph~ol A ethoxylat-d doubly and ~ymmetrically to a degree of 90%, 290 7 g of terephthalic acid, 3 91 g of dibutyltin oxide and 422 5 g of a solu-tion polymer from Example~ 10 to 22 (in the form of an about 65% ~trongth solution in toluone) were heated while ~tirring, toluone wa~ di~tillod off, the mlxture was then heated ,to 260C and water was distilled off until the ~i~co~ity of tho roaction mixturo increa~ed ~harply and an acid nu ~ er of 1O~8 than 25 mg of RO~I/g had beon reached Table lO ~how~ the result~ of the experiment~
_ Bxum- Pr-poly- Acld Glas~ Soft-n- Crossl~nking pl~ m-r A numb-s tr~n~l- ~ng tlm~ a) No from ~x- AN tlon polnt thl umpl- No t~g ~OH/g~ t~mp TO 8P~Cl _ _ 66 19 10 78 _ No cro~lin~-lng ~ft-r 3 h 67 20 13 69 11~ No cro~lln~-ing aft-r 3 h 68 21 1~ 69 131 No cro~llnk-_ lng ~ft-r 3 h 69 22 18 68 136 No cro--lln~-lng aft-r 3 h The acid number~ were determin~d by titration.
a) Time betwo~n addltion of A and crosslin~ing or dramatic increa~e tn visco~tty EXAMPL~ 70 A polye~tsr having a glac~ tr~nsition temperature TG of 62C and a softening point SP of 135C wa~ prepared ~ larly to Examples 40 to 52 from 30S.l g of a bi phen-ol ~ ethoxylated doubly and symmetrically, 194.2 g of dimethyhl terephthalate, 1.5 g of titanium butoxylate and 714 g of the prepolymer A from ~xample 23 (70% strength ~olution in toluene).
EXAMP~ES 71 TO 75 - 554.3 g of bisphenol A ethoxylated doubly and symmetrically to a degree of 90%, 290.7 g of terephthalic acld, 3.91 g of dibutyltin oxide and 1745.1 g of a ~olu-tion poly~er from Examples 24 to 28 (in the form of an about 65% strength ~olu~ion in toluene) were heated while stirring, toluene wa~ dintilled off, the mixture was then heated to 260C and water wa~ diatilled off until the v~co~ity of the reaction mixture increased sharply and an acid number o le~ than 25 mg of KOH/g had been reached. The resin~ obtained had es~entially the same - 24 - o Z 0050/43136 ch~ractor~stics a8 tho product~ of Examplo~ 61 to 65 CO~lPARATIVE EXA~LE A
A polyost~r r~sin was proparod according to (1) from a doubly and ~ymmotrically thoxylat-d bisphonol A, S a doubly and symmotrically propoxylat~d bi~phonol A, tor-phthalic acid and trim llitlc anhydrid~ as the maln compon-~t~ Tho ro~in thus proparod had an acid numbor of 19 mg of ~0~/g, a glas- tranJition t~mp~raturo TG of 68C and a soft-~ng point of 14aC
Proparat~on of p~-udoton-r~
~XA~PL~S 76 TO 7 8 AND COMPARATIVI~ UWPL~: B
100 g of ach polyo~tor ros~n, pr-parod according to ~xa~pl-s 61, 65 a~d 66, wor~ knoad~d in a Jahnko &
~un~ boratory k~oad r, inlt~ally at 150C 5 g of ~5 carbon black (Mogul ~ from Cabot) woro addod and knoad~ng wa~ th n carri-d out for 3 hour~, tho tomporatur~
gradually b-i~g r-duc-d to 90C Ev ry 0 5 hour, gm~ll ~ ~pl-~ ~oro takon fro~ th- knoad-r and tho~r flne dl~tribution was vi~ually a~o~-d undor an optical micro~copo at about 700 tim ~ magnification. Aftor 3 hours, particlo sizo diJtrlbution in th- rosin was vory good (~ 1 ~m) to acceptablo.
Tho p~oudoton r~ woro each brought to a particle slze of from 5 to 15 ~m by milling in a revorse-~et mill from Alpine, Type AFG (6 bar nitrogen, speed of classi-fier wheel 8000 rpm).
For comparison, a pseudotoner having tho resin from Comparative ~xample A was prepared similarly by knoading and m~lling. This pseudotoner served as Com-parative kxample B.
The data for all 4 pseudotoners are summarized in Table 11.
To test the incorporation characteristics of color pigments, 40 g of Pigment Red 81 : 1 (Fanal Pink S
4830), as a pigment powd-r, were kneaded with 60 g of t~e ~tated polyestor resins and comparativo resin A, and the fine di~tribution wa~ invostigated. These data too are shown ~n Table ll No te~ts were carried out on the loctrostatic chargeabil~ty of the~e p~eudotoner~
P-rformanco charact~ristlcs of the ps~udoton~r from Exampl~s 76 to 78 and of Comparat~v~ ~xampl~ B
S A strip of copy pap-r about 40 cm long was dust~d with each of th~ ton~r powd~rs of Exp~r~monts 76 to 78 along the longth, cov~r~d with an untroat-d papor strip and uniformly load~d w~th 1 5 ~g for about 5 ~oconds on a ~oflor bonch (from 50 to 270C) For comparison, the p~oudoton-r B d-~cr~bod abov- wa~ tost-d ~ilarly The torp-ratur- for f~xlng on pap-r wa~ d-tormln~d by rubbing w~th tho f~nger, To~afllm and an ra~-r Th~ tomp-ra-tur- at th- boginning of fixlng and th- tomperature for complot- f~xl~g w~r- d t-rmln-d Th~ p~udotonor of R - ~pl-~ 76 to 78 ~ho~ d good f~xing b~hav~or wh~ch was ~imilar to th t of tho p~-udoto~or of Comparat~v~ Exp~r~-~ont B Th porfor~anc- char~ct-r~tic~ of th~ ps~udo-ton r~ ar- cummari~d ~ Tabl~ 11 Tho l-ctrostatic charg ability of th- p~-udoton r~ of ~xampl-~ 50 to 52 is ~ub~tantially lo~or than that of comparatlv~ tonsr B
pl- R-d ~ ~ro rl~- dl-trlbutlon ~lth ~111- ~l-ctro~t-tlc ~l~ln~
~o ~ pl- No blllty ch~rg blllty r~ngo ~lth c-rbon l Cl C~rbon ~lg -~t bl-c~) g/s bl--clc R d al 1 llc/g]
Accordl~g to th- l~-ntlon 76 61 good _ ~ood 1~. 3120-160 77 65 ~-ry good v ry good good 11 8 110-150 78 66 mod-r-t- sod-r-t- 10 5125-160 ~or co p-rl~on B ¦ A ¦good ¦~od r-t- lgood ¦ 17 5¦ 130-190 133 g of a polye~ter re~in pr-pared according to Ex~mple 70 wore kneaded in a Jahnke & ~unkel laboratory kn~ader at 100C 7 g of carbon black (Mogul L from Ca~t) wore add~d and knoading was thon cont~nued for 3 hours, tho tomporaturo gr~dually boing roducod to 70C
Sm~ll ~amplo~ woro ta~on from tho kn-ador ovory 0 5 h and tholr fino dlstribution was ass-~od visually undor tho optical microscopo at a magnificat~on of about 700 timo~
Th- particlo ~iz- distribution in tho rosin was very good aft-r 3 hour~
Th p~-udoton-r wa~ pr-par-d by milling in a Jahnko ~ ~uDk-l laboratory m~ll and ~ub~-guont sioving through a 36 ~m ~-vo to a particlo ~iz- of c 36 - For comparl~on, a p~-udoton-r wa~ pr-pared in a lar mann-r by kn-ading and m~lling, using th- resin fram Comparativ R-~mrlo A Thi~ sorvod as Comparativo ~pl- C.
In ~xampl- 79, Pig~t R-d 81 1 was al~o incorporat-d ~ llarly to ~xa~pl-~ 76 to 78 For this p~-udoton-r, too, no to~t~ w r- carriod out on tho l-ctro~t-t~c charg-abllity Th data for th-~- p~-udoto~ r~ ar- ~ummarizod ~n Tabl- 12 P-rformanc- charact-ri~tics of tho p~oudotoners from ~xamplo 79 a~d Comparativo ~xampl- C
Tho p~oudotonors of ~xample 79 and Comparative Bxample C w r- al-o tostod ~milarl~ to the fixing tost on the psoudotonor~, described in ~x~mple~ 76 to 78 The p~oudoto~er of Ex ~ple 79 exhibited sub~tantially lower electro~tatic charging than Comparative Example C
?l3I o97 - 27 - o Z 0050/43136 _ TABLE 12 ~x pl- ~ ln ~ln- dl trlb~tlon ~111- ~l-ctro- ~l~lng No ~ro~ ~lth ¢-rbos bl-c~ ~blllty ~t-tlc r ng-_ ~-~pl- Plg~ st ch~rg-- l C]
No R-d 81sl blllty (~lth c-r-qtl~c/~tt) accordlsg to th- 18~ stloss 79 ¦ 70 ¦v~ry good ¦~ ry good ¦~r-ry good ¦ 0 2 ~ ) ¦105-135 ~or co p-rl~oss C ¦ A ¦good ¦- ¦ ¦ 8 7 ~b) ¦
(a) Moa~uromont with a sph-rical uncoated steel carrier (b) Moa~ur~m nt with an irrogular coat-d stoel carrier 10The ro~ult~ of the el-ctro~tatic chargoability ~how that th- novol rosin~ ar- nogatively charged to a ~ub~tantially small~r oxt~nt Tho bottor fine dtstribu-tion~ with carbon black und in particular Pigment Red 81 1 in the ca~- of tho nov~l ro~ins in contrast to the 15coq~parison resln aro al 8 0 strilcing Furthermore, the lower fixing temperature of the novel psoudotoner~ in contrast to the comparative p~eudotoner indicate~ the ~uperiority of the novel agents
th~n 100 mg of RO~/g had been roached ~able 8 ~hows the results of the experimont~
213.1~37 _ TAB~ 8 ~x - Pr-poly- ~cld al-~- 8Oft-n- Cro~lln~lng pl- ~ r A nu~b-r tr-n~l- lng t$m- ~) No fro~ ~x- AN tlon polnt Ihl ~pl-- No I~g ~OH/g] t I ClSG t Cl 57 l9 102 57 138 l 0 58 20 98 S9 lC3 1 5 59 21 ~1 50 l57 l 0 2~ 90 58 l~ No oro~ ~k-lng ~t-r 3 h The acid numb-r~ were d termined by titration0 a) Time betwe~n add~tion of A and cros~linking or dra~atic incr~a~- ~n vi~co-ity EXAMæ~S 61 T0 64 554 3 g of bi~phenol A ethoxylated doubly and oymm-trically to a degree of 90%, 290 7 g of terophthalic acid, 3 91 g of dibutyltin ox~de and 1745 1 g of a 801u-t~on polymer fr~m ~xample~ 19 to 22 l~n tho form of an about 65% strength solution in tolu-ne) wer~ hoated while ~t~rr~ng, toluono wa~ distillod off, the mixturo was then h-at-d to 260C and water was di~tilled off until the vi~cosity of the reaction mixture incroased sharply and an acid number of le~s than 25 mg of R0~/g had been reached Table 9 shows the results of tho exporiments ~XAMP~E 65 182 5 g of a bisphenol A doubly and symmetrically ethoxylated to a degree of 90%, 397 3 g of bisphenol A
doubly and symmetrically propoxylated to a degree of 95%, 290 7 g of torophthalic acid, 3 91 g of dibutyltin oxide and 1745 1 g of the solution polymer from Example 19 (in the form of an about 65% strength solution in toluene) were heated while stirring, toluene was distilled off, th- mixture was then heated to 260C and water was dl~tilled off until the ~iscosity of the reaction mixture increa~ed ~harply and an acid number of less than 25 mg 2131 ~97 of ~OH/g had been reachod Tablo 9 ~how~ tho re~ult of th~ 8 exper~ment ~x~- ~r-poly- Acld al~ ~oft-n- Cro~lln~lng S pl- m~r A nu~b-r tr~n~l- ldg tlm~ ~) No fro~ ~x- AN tlo~ pol~t thl u~pl- ~o [~q ~OH/~l t--p Ta 8~l Cl 61 _ ~ 65 1~ ln~ ft r 3 ;
Ci 20 S 63 200 1 75 0 C~ 22 13 69 131 1 0 C5 19 7_ 6~ 13~ ln~ ft r 3 h Th acld numb-r~ wer- det-rmin-d by titratio~
a) T~me betw ~ additlon of A and cro~linking or dramat$c increa~- in vi~co~ity EXA~PLES 66 TO 69 554 3 g of bi~ph~ol A ethoxylat-d doubly and ~ymmetrically to a degree of 90%, 290 7 g of terephthalic acid, 3 91 g of dibutyltin oxide and 422 5 g of a solu-tion polymer from Example~ 10 to 22 (in the form of an about 65% ~trongth solution in toluone) were heated while ~tirring, toluone wa~ di~tillod off, the mlxture was then heated ,to 260C and water was distilled off until the ~i~co~ity of tho roaction mixturo increa~ed ~harply and an acid nu ~ er of 1O~8 than 25 mg of RO~I/g had beon reached Table lO ~how~ the result~ of the experiment~
_ Bxum- Pr-poly- Acld Glas~ Soft-n- Crossl~nking pl~ m-r A numb-s tr~n~l- ~ng tlm~ a) No from ~x- AN tlon polnt thl umpl- No t~g ~OH/g~ t~mp TO 8P~Cl _ _ 66 19 10 78 _ No cro~lin~-lng ~ft-r 3 h 67 20 13 69 11~ No cro~lln~-ing aft-r 3 h 68 21 1~ 69 131 No cro~llnk-_ lng ~ft-r 3 h 69 22 18 68 136 No cro--lln~-lng aft-r 3 h The acid number~ were determin~d by titration.
a) Time betwo~n addltion of A and crosslin~ing or dramatic increa~e tn visco~tty EXAMPL~ 70 A polye~tsr having a glac~ tr~nsition temperature TG of 62C and a softening point SP of 135C wa~ prepared ~ larly to Examples 40 to 52 from 30S.l g of a bi phen-ol ~ ethoxylated doubly and symmetrically, 194.2 g of dimethyhl terephthalate, 1.5 g of titanium butoxylate and 714 g of the prepolymer A from ~xample 23 (70% strength ~olution in toluene).
EXAMP~ES 71 TO 75 - 554.3 g of bisphenol A ethoxylated doubly and symmetrically to a degree of 90%, 290.7 g of terephthalic acld, 3.91 g of dibutyltin oxide and 1745.1 g of a ~olu-tion poly~er from Examples 24 to 28 (in the form of an about 65% strength ~olu~ion in toluene) were heated while stirring, toluene wa~ dintilled off, the mixture was then heated to 260C and water wa~ diatilled off until the v~co~ity of the reaction mixture increased sharply and an acid number o le~ than 25 mg of KOH/g had been reached. The resin~ obtained had es~entially the same - 24 - o Z 0050/43136 ch~ractor~stics a8 tho product~ of Examplo~ 61 to 65 CO~lPARATIVE EXA~LE A
A polyost~r r~sin was proparod according to (1) from a doubly and ~ymmotrically thoxylat-d bisphonol A, S a doubly and symmotrically propoxylat~d bi~phonol A, tor-phthalic acid and trim llitlc anhydrid~ as the maln compon-~t~ Tho ro~in thus proparod had an acid numbor of 19 mg of ~0~/g, a glas- tranJition t~mp~raturo TG of 68C and a soft-~ng point of 14aC
Proparat~on of p~-udoton-r~
~XA~PL~S 76 TO 7 8 AND COMPARATIVI~ UWPL~: B
100 g of ach polyo~tor ros~n, pr-parod according to ~xa~pl-s 61, 65 a~d 66, wor~ knoad~d in a Jahnko &
~un~ boratory k~oad r, inlt~ally at 150C 5 g of ~5 carbon black (Mogul ~ from Cabot) woro addod and knoad~ng wa~ th n carri-d out for 3 hour~, tho tomporatur~
gradually b-i~g r-duc-d to 90C Ev ry 0 5 hour, gm~ll ~ ~pl-~ ~oro takon fro~ th- knoad-r and tho~r flne dl~tribution was vi~ually a~o~-d undor an optical micro~copo at about 700 tim ~ magnification. Aftor 3 hours, particlo sizo diJtrlbution in th- rosin was vory good (~ 1 ~m) to acceptablo.
Tho p~oudoton r~ woro each brought to a particle slze of from 5 to 15 ~m by milling in a revorse-~et mill from Alpine, Type AFG (6 bar nitrogen, speed of classi-fier wheel 8000 rpm).
For comparison, a pseudotoner having tho resin from Comparative ~xample A was prepared similarly by knoading and m~lling. This pseudotoner served as Com-parative kxample B.
The data for all 4 pseudotoners are summarized in Table 11.
To test the incorporation characteristics of color pigments, 40 g of Pigment Red 81 : 1 (Fanal Pink S
4830), as a pigment powd-r, were kneaded with 60 g of t~e ~tated polyestor resins and comparativo resin A, and the fine di~tribution wa~ invostigated. These data too are shown ~n Table ll No te~ts were carried out on the loctrostatic chargeabil~ty of the~e p~eudotoner~
P-rformanco charact~ristlcs of the ps~udoton~r from Exampl~s 76 to 78 and of Comparat~v~ ~xampl~ B
S A strip of copy pap-r about 40 cm long was dust~d with each of th~ ton~r powd~rs of Exp~r~monts 76 to 78 along the longth, cov~r~d with an untroat-d papor strip and uniformly load~d w~th 1 5 ~g for about 5 ~oconds on a ~oflor bonch (from 50 to 270C) For comparison, the p~oudoton-r B d-~cr~bod abov- wa~ tost-d ~ilarly The torp-ratur- for f~xlng on pap-r wa~ d-tormln~d by rubbing w~th tho f~nger, To~afllm and an ra~-r Th~ tomp-ra-tur- at th- boginning of fixlng and th- tomperature for complot- f~xl~g w~r- d t-rmln-d Th~ p~udotonor of R - ~pl-~ 76 to 78 ~ho~ d good f~xing b~hav~or wh~ch was ~imilar to th t of tho p~-udoto~or of Comparat~v~ Exp~r~-~ont B Th porfor~anc- char~ct-r~tic~ of th~ ps~udo-ton r~ ar- cummari~d ~ Tabl~ 11 Tho l-ctrostatic charg ability of th- p~-udoton r~ of ~xampl-~ 50 to 52 is ~ub~tantially lo~or than that of comparatlv~ tonsr B
pl- R-d ~ ~ro rl~- dl-trlbutlon ~lth ~111- ~l-ctro~t-tlc ~l~ln~
~o ~ pl- No blllty ch~rg blllty r~ngo ~lth c-rbon l Cl C~rbon ~lg -~t bl-c~) g/s bl--clc R d al 1 llc/g]
Accordl~g to th- l~-ntlon 76 61 good _ ~ood 1~. 3120-160 77 65 ~-ry good v ry good good 11 8 110-150 78 66 mod-r-t- sod-r-t- 10 5125-160 ~or co p-rl~on B ¦ A ¦good ¦~od r-t- lgood ¦ 17 5¦ 130-190 133 g of a polye~ter re~in pr-pared according to Ex~mple 70 wore kneaded in a Jahnke & ~unkel laboratory kn~ader at 100C 7 g of carbon black (Mogul L from Ca~t) wore add~d and knoading was thon cont~nued for 3 hours, tho tomporaturo gr~dually boing roducod to 70C
Sm~ll ~amplo~ woro ta~on from tho kn-ador ovory 0 5 h and tholr fino dlstribution was ass-~od visually undor tho optical microscopo at a magnificat~on of about 700 timo~
Th- particlo ~iz- distribution in tho rosin was very good aft-r 3 hour~
Th p~-udoton-r wa~ pr-par-d by milling in a Jahnko ~ ~uDk-l laboratory m~ll and ~ub~-guont sioving through a 36 ~m ~-vo to a particlo ~iz- of c 36 - For comparl~on, a p~-udoton-r wa~ pr-pared in a lar mann-r by kn-ading and m~lling, using th- resin fram Comparativ R-~mrlo A Thi~ sorvod as Comparativo ~pl- C.
In ~xampl- 79, Pig~t R-d 81 1 was al~o incorporat-d ~ llarly to ~xa~pl-~ 76 to 78 For this p~-udoton-r, too, no to~t~ w r- carriod out on tho l-ctro~t-t~c charg-abllity Th data for th-~- p~-udoto~ r~ ar- ~ummarizod ~n Tabl- 12 P-rformanc- charact-ri~tics of tho p~oudotoners from ~xamplo 79 a~d Comparativo ~xampl- C
Tho p~oudotonors of ~xample 79 and Comparative Bxample C w r- al-o tostod ~milarl~ to the fixing tost on the psoudotonor~, described in ~x~mple~ 76 to 78 The p~oudoto~er of Ex ~ple 79 exhibited sub~tantially lower electro~tatic charging than Comparative Example C
?l3I o97 - 27 - o Z 0050/43136 _ TABLE 12 ~x pl- ~ ln ~ln- dl trlb~tlon ~111- ~l-ctro- ~l~lng No ~ro~ ~lth ¢-rbos bl-c~ ~blllty ~t-tlc r ng-_ ~-~pl- Plg~ st ch~rg-- l C]
No R-d 81sl blllty (~lth c-r-qtl~c/~tt) accordlsg to th- 18~ stloss 79 ¦ 70 ¦v~ry good ¦~ ry good ¦~r-ry good ¦ 0 2 ~ ) ¦105-135 ~or co p-rl~oss C ¦ A ¦good ¦- ¦ ¦ 8 7 ~b) ¦
(a) Moa~uromont with a sph-rical uncoated steel carrier (b) Moa~ur~m nt with an irrogular coat-d stoel carrier 10The ro~ult~ of the el-ctro~tatic chargoability ~how that th- novol rosin~ ar- nogatively charged to a ~ub~tantially small~r oxt~nt Tho bottor fine dtstribu-tion~ with carbon black und in particular Pigment Red 81 1 in the ca~- of tho nov~l ro~ins in contrast to the 15coq~parison resln aro al 8 0 strilcing Furthermore, the lower fixing temperature of the novel psoudotoner~ in contrast to the comparative p~eudotoner indicate~ the ~uperiority of the novel agents
Claims (10)
1. A polyester resin based on hydroxyl-containing prepolymers of olefinically unsaturated monomers, obtain-able by (1) polymerization of a mixture of (a) from 60 to 90% by weight of styrene or of a styrene derivative of the formula I
I
where R1, R2 and R3 are each hydrogen, methyl or ethyl and n is 1 or 2, or of a C2-C10-olefin having one or two conjugated double bonds, or of a mixture thereof, (b) from 0 to 40% by weight of a C1-C12-alkyl ester of acrylic or methacrylic acid, acrylonitrile or methacrylonitrile, acrylamide or methacryl-amide which may be substituted by one or two C1-C4-alkyl groups on the amide nitrogen, maleic anhydride or maleimide which may be substituted by C1-C4-alkyl on the imide nitrogen, or a mixture thereof, (c) from 0 to 20% by weight of one or more hydroxyl-containing acrylic or methacrylic acid derivatives, and (d) from 0 to 2% by weight of one or more poly-olefinically unsaturated monomers, to give the prepolymer A, the hydroxyl groups being incorporated in A by using hydroxyl-containing regulators if the monomer component (c) is absent, and subsequently (2) polycondensation of a mixture of A) from 5 to 95% by weight of the prepolymer A, B) from 0 to 95% by weight of a further low molecular weight or relatively high molecular weight polyol, of a polyester or of a polyamide or a mixture thereof and C) from 5 to 70% by weight of one or more alipha-- tic or aromatic dicarboxylic acids C or C1-C4-alkyl esters thereof, where A and B together account for from 30 to 95% by weight of this mixture, and where carboxylic acids or C1-C4-alkyl esters thereof having more than two carboxyl groups in the molecule or monocarboxylic acids or C1-C4-alkyl esters thereof or hydroxymono-carboxylic acids or C1-C4-alkyl esters thereof, or a mixture of these, and waxes may also be present in the polycondensation.
I
where R1, R2 and R3 are each hydrogen, methyl or ethyl and n is 1 or 2, or of a C2-C10-olefin having one or two conjugated double bonds, or of a mixture thereof, (b) from 0 to 40% by weight of a C1-C12-alkyl ester of acrylic or methacrylic acid, acrylonitrile or methacrylonitrile, acrylamide or methacryl-amide which may be substituted by one or two C1-C4-alkyl groups on the amide nitrogen, maleic anhydride or maleimide which may be substituted by C1-C4-alkyl on the imide nitrogen, or a mixture thereof, (c) from 0 to 20% by weight of one or more hydroxyl-containing acrylic or methacrylic acid derivatives, and (d) from 0 to 2% by weight of one or more poly-olefinically unsaturated monomers, to give the prepolymer A, the hydroxyl groups being incorporated in A by using hydroxyl-containing regulators if the monomer component (c) is absent, and subsequently (2) polycondensation of a mixture of A) from 5 to 95% by weight of the prepolymer A, B) from 0 to 95% by weight of a further low molecular weight or relatively high molecular weight polyol, of a polyester or of a polyamide or a mixture thereof and C) from 5 to 70% by weight of one or more alipha-- tic or aromatic dicarboxylic acids C or C1-C4-alkyl esters thereof, where A and B together account for from 30 to 95% by weight of this mixture, and where carboxylic acids or C1-C4-alkyl esters thereof having more than two carboxyl groups in the molecule or monocarboxylic acids or C1-C4-alkyl esters thereof or hydroxymono-carboxylic acids or C1-C4-alkyl esters thereof, or a mixture of these, and waxes may also be present in the polycondensation.
2. A polyester resin as claimed in claim 1, in whose preparation styrene, .alpha.-methylstyrene, ethylene, prop-ylene, butadiene or a mixture thereof has been used as monomer (a) for the polymerization (1).
3. A polyester resin as claimed in claim 1 or 2, in whose preparation a C1-C4-alkyl ester of acrylic or methacrylic acid, acrylonitrile or methacrylonitrile, acrylamide or methacrylamide or a mixture thereof has been used as monomer (b) for the polymerization (1).
4. A polyester resin as claimed in any of claims 1 to 3, in whose preparation a hydroxy-C2-C4-alkyl acrylate or methacrylate or an N-(hydroxy-C2-C4-alkyl)-acrylamide or -methacrylamide or a mixture thereof can be used as monomer (c) for the polymerization (1), or, when monomer component (c) is absent, a hydroxyl-containing mercaptan has been used as a regulator.
5. A polyester resin as claimed in any of claims 1 to 4, in whose preparation divinylbenzene has been used as monomer (d) for the polymerization (1).
6. A polyester resin as claimed in any of claims 1 to 5, in whose preparation a C2-C6-alkanediol, ethoxylated or propoxylated bisphenol A or a mixture thereof has been used as component B for the polycondensation (2).
7. A polyester resin as claimed in any of claims 1 to 6, in whose preparation phthalic acid,isophthalicc acid, terephthalic acid or its C1-C4-dialkyl ester or a mixture thereof has been used as component C for the polycondensation (2).
8. - A process for the preparation of polyester resin based on hydroxyl-containing prepolymers of olefinically unsaturated monomers, wherein (1) a polymerization of a mixture of (a) from 60 to 90% by weight of styrene or of a styrene derivative of the formula I
I
where R1, R2 and R3 are each hydrogen, methyl or ethyl and n is 1 or 2, or of a C2-C10-olefin having one or two conjugated double bonds, or of a mixture thereof, (b) from 0 to 40% by weight of a C1-C12-alkyl ester of acrylic or methacrylic acid, acrylonitrile or methacrylonitrile, acrylamide or methacryl-amide which may be substituted by one or two C1-C4-alkyl groups on the amide nitrogen, maleic anhydride or maleimide which may be substituted by C1-C4-alkyl on the imide nitrogen, or a mixture thereof, (c) from 0 to 20% by weight of one or more hydroxyl-containing acrylic or methacrylic acid derivatives, and (d) from 0 to 2% by weight of one or more poly-olefinically unsaturated monomers, to give the prepolymer A, the hydroxyl groups being incorporated in A by using hydroxyl-containing regulators when the monomer component (c) is absent, and subsequently (2) polycondensation of a mixture of A) from 5 to 95% by weight of the prepolymer A, B) from 0 to 95% by weight of a further low molecular weight or relatively high molecular weight polyol, of a polyester or of a polyamide or a mixture thereof and C) from 5 to 70% by weight of one or more alipha-tic or aromatic dicarboxylic acids C or C1-C4-alkyl esters thereof, where A and B together account for from 30 to 95% by weight of this mixture, and where carboxylic acids or C1-C4-alkyl esters thereof having more than two carboxyl groups in the molecule or monocarboxylic acids or C1-C4-alkyl esters thereof or hydroxymono-carboxylic acid or C1-C4-alkyl esters thereof, or a mixture of these, and waxes may also be present in the polycondensation, are carried out.
I
where R1, R2 and R3 are each hydrogen, methyl or ethyl and n is 1 or 2, or of a C2-C10-olefin having one or two conjugated double bonds, or of a mixture thereof, (b) from 0 to 40% by weight of a C1-C12-alkyl ester of acrylic or methacrylic acid, acrylonitrile or methacrylonitrile, acrylamide or methacryl-amide which may be substituted by one or two C1-C4-alkyl groups on the amide nitrogen, maleic anhydride or maleimide which may be substituted by C1-C4-alkyl on the imide nitrogen, or a mixture thereof, (c) from 0 to 20% by weight of one or more hydroxyl-containing acrylic or methacrylic acid derivatives, and (d) from 0 to 2% by weight of one or more poly-olefinically unsaturated monomers, to give the prepolymer A, the hydroxyl groups being incorporated in A by using hydroxyl-containing regulators when the monomer component (c) is absent, and subsequently (2) polycondensation of a mixture of A) from 5 to 95% by weight of the prepolymer A, B) from 0 to 95% by weight of a further low molecular weight or relatively high molecular weight polyol, of a polyester or of a polyamide or a mixture thereof and C) from 5 to 70% by weight of one or more alipha-tic or aromatic dicarboxylic acids C or C1-C4-alkyl esters thereof, where A and B together account for from 30 to 95% by weight of this mixture, and where carboxylic acids or C1-C4-alkyl esters thereof having more than two carboxyl groups in the molecule or monocarboxylic acids or C1-C4-alkyl esters thereof or hydroxymono-carboxylic acid or C1-C4-alkyl esters thereof, or a mixture of these, and waxes may also be present in the polycondensation, are carried out.
9. Use of a polyester resin as claimed in any of claims 1 to 7 as a binder for electrophotographic toners.
10. An electrophotographic toner containing, as a binder, one or more polyester resins as claimed in any of claims 1 to 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4211062A DE4211062A1 (en) | 1992-04-03 | 1992-04-03 | Polyester based on prepolymers containing hydroxyl groups from olefinically unsaturated monomers and their use as binders for electrophotographic toners |
| DEP4211062.9 | 1992-04-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2131097A1 true CA2131097A1 (en) | 1993-10-04 |
Family
ID=6455884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002131097A Abandoned CA2131097A1 (en) | 1992-04-03 | 1993-03-23 | Polyesters based on hydroxyl-containing prepolymers of olefinically unsaturated monomers and their use as binders for electrophotographic toners |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5494964A (en) |
| EP (1) | EP0633906B1 (en) |
| JP (1) | JPH07505419A (en) |
| KR (1) | KR950700955A (en) |
| CA (1) | CA2131097A1 (en) |
| DE (2) | DE4211062A1 (en) |
| ES (1) | ES2091599T3 (en) |
| WO (1) | WO1993020129A1 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19741720A1 (en) * | 1997-09-22 | 1999-03-25 | Basf Ag | Cross-linked polymer composition used as binder for electrophotographic toner |
| US6248827B1 (en) | 1997-12-22 | 2001-06-19 | Bridgestone Corporation | Centipede polymers and preparation and application in rubber compositions |
| US6248825B1 (en) | 1998-05-06 | 2001-06-19 | Bridgestone Corporation | Gels derived from extending grafted centipede polymers and polypropylene |
| US6204354B1 (en) | 1998-05-06 | 2001-03-20 | Bridgestone Corporation | Soft compounds derived from polypropylene grafted disubstituted ethylene- maleimide copolymers |
| US6207763B1 (en) | 1998-06-12 | 2001-03-27 | Bridgestone Corporation | Application of disubstituted ethylene-maleimide copolymers in rubber compounds |
| US6184292B1 (en) | 1998-10-05 | 2001-02-06 | Bridgestone Corporation | Soft gel polymers for high temperature use |
| US6133354A (en) * | 1998-11-17 | 2000-10-17 | Bridgestone Corporation | Copolymers as additives in thermoplastic elastomer gels |
| US6191217B1 (en) | 1998-11-17 | 2001-02-20 | Bridgestone Corporation | Gels derived from polypropylene grafted alkyl vinylether-maleimide copolymers |
| US6476117B1 (en) | 2000-06-05 | 2002-11-05 | Bridgestone Corporation | Grafted near-gelation polymers having high damping properties |
| US6350800B1 (en) | 2000-06-05 | 2002-02-26 | Bridgestone Corporation | Soft polymer gel |
| US6417259B1 (en) | 2000-06-05 | 2002-07-09 | Bridgestone Corporation | Polyalkylene grafted centipede polymers |
| US6384134B1 (en) | 2000-06-05 | 2002-05-07 | Bridgestone Corporation | Poly(alkenyl-co-maleimide) and maleated polyalkylene grafted with grafting agent, and epoxy polymer |
| US6353054B1 (en) | 2000-07-31 | 2002-03-05 | Bridgestone Corporation | Alkenyl-co-maleimide/diene rubber copolymers and applications |
| US6359064B1 (en) | 2000-09-08 | 2002-03-19 | Bridgestone Corporation | Compound of polyester and polyalkylene grafted comb polymer |
| CN101029122B (en) * | 2006-03-03 | 2010-05-12 | 同济大学 | Production and use for acrylic ester modified polyester resin |
| JP5496108B2 (en) * | 2007-12-28 | 2014-05-21 | 株式会社ブリヂストン | Interpolymers containing isobutylene and diene mer units |
| JPWO2022131220A1 (en) * | 2020-12-15 | 2022-06-23 | ||
| WO2023032920A1 (en) * | 2021-08-31 | 2023-03-09 | 東洋紡株式会社 | Polyester resin |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5911902B2 (en) * | 1980-08-15 | 1984-03-19 | コニカ株式会社 | Toner for developing electrostatic images |
| US4788122A (en) * | 1985-03-14 | 1988-11-29 | Kao Corporation | Production of polyester and elecrophotographic toner containing the same |
| CA1331070C (en) * | 1988-03-17 | 1994-07-26 | Noriyuki Tajiri | Crosslinked polyester for toner and process for preparation thereof |
-
1992
- 1992-04-03 DE DE4211062A patent/DE4211062A1/en not_active Withdrawn
-
1993
- 1993-03-23 CA CA002131097A patent/CA2131097A1/en not_active Abandoned
- 1993-03-23 WO PCT/EP1993/000696 patent/WO1993020129A1/en active IP Right Grant
- 1993-03-23 EP EP93906588A patent/EP0633906B1/en not_active Expired - Lifetime
- 1993-03-23 JP JP5517041A patent/JPH07505419A/en active Pending
- 1993-03-23 ES ES93906588T patent/ES2091599T3/en not_active Expired - Lifetime
- 1993-03-23 US US08/307,790 patent/US5494964A/en not_active Expired - Fee Related
- 1993-03-23 DE DE59303983T patent/DE59303983D1/en not_active Expired - Lifetime
-
1994
- 1994-02-20 KR KR1019940703500A patent/KR950700955A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| ES2091599T3 (en) | 1996-11-01 |
| DE59303983D1 (en) | 1996-10-31 |
| JPH07505419A (en) | 1995-06-15 |
| US5494964A (en) | 1996-02-27 |
| WO1993020129A1 (en) | 1993-10-14 |
| EP0633906A1 (en) | 1995-01-18 |
| DE4211062A1 (en) | 1993-10-07 |
| KR950700955A (en) | 1995-02-20 |
| EP0633906B1 (en) | 1996-09-25 |
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| Date | Code | Title | Description |
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| FZDE | Discontinued |