MXPA96001590A - Synthetic resin systems multimodals free of emulsifying and solve - Google Patents

Abstract

Synthetic multi-modal resin and solvent free resin systems are described which are suitable as a binder constituent for non -intaintable printing inks and which comprise at least one polymer A containing amino and at least one polymer B dilutable with water, and if Desires a polymer C insoluble in water in the form of latex particles, which can be prepared by emulsion polymerization of ethylenically unsaturated compounds in the presence of polymers A and

Description

SYNTHETIC RESIN SYSTEMS MULTIMODALS FREE EMULSIFYING AND SOLVENT DESCRIPTION OF THE INVENTION The invention relates to cationic synthetic resin systems, which are water-soluble in the presence of acids and are free of low molecular weight e? Ulsants and solvents, to process 1 ') prepax ation and its use as grinding resins, in pigment pastes or as binder components for printing varnishes and printing inks. Water-based printing inks, ecologically advantageous, which are curly used in the In the industry, they present the disadvantage that the printed products produced with them, as well as systems containing conventional solvents, are not disclosed in the cur state of the art. For this reason, it is desired to use binders that offer not only the capacity of P.O printing under high speed conditions but also an acceptable quality of the pulp recovered when desent intarse. For this purpose, water-dilutable, cationic or non-cationic polymers are preferably suitable. For example DE-A MI 15 731 DE H2 1 bb describe -7t. Water-based ink compositions of preferred intactness, which are achieved for the partial use of acrylic resins available to this type. Cationic binders are also subject of US-A - < z 5 - 21 2. The aqueous phase of these cathodically disposable coating compositions comprises cationic polymers which are produced by the polymerization of ethylene-unsaturated compounds in the presence of cationic polymers. However, these binders are unsuitable for use in the printing sector, since it is impossible with polymers of such flexibility to achieve at speeds adequate drying or oeqajasity free impressions. Moreover, these systems are also disadvantageous from an ecological point of view, since they comprise considerable quantities of organic solvents. EP-A 0 622 3? 5 and the application for EP No. 94116608.4 also refer to binders that are dilutable with water following protonation with acid. As the binder for the printing inks, however, the cationic polymers described therein need further improvement with respect to their wettability for pigments and their absorption capacity for other non-polar polymers. The object of the present invention, therefore, is to provide synthetic resin systems which are based on mixtures of cationic polymer and are dilutable with water in the presence of acid, and which not only have good , > 5 desent intabí 1 idad, but also a good wetting capacity for pigments and an increased absorption capacity for other non-polar polymers. This object is achieved according to the invention by producing a mixture of at least bimodal synthetic resin from a polymer containing ino (A) and a polymer dilutable with nonionic water (B), said mixture can be introduced into the iqua, which has been provided with a neutralizing agent to prepare a resin solution to which non-polar monomers can be added to produce a polymer (or in the form of latex particles.) The term cationic polymers A later it refers to polymers containing α, whose groups can not be converted, by means of quaternization agents or by neutralization with acid, at least partially to cationic groups The term water-dilutable, non-ionic polymers B is referred to below to polymers comprising a nonionic hydrophilic substructure, L3 invention provides synthetic resin systems free of emulsifier and solvent e comprising at least one polymer containing amine (A) and at least one polymer dilutable in nonionic water (B) and, if desired, a water insoluble polymer (C) in the form of latex particles, which can be prepared by the emulsion polymerization of ethically unsaturated compounds in the presence of polymers A v B. The average molecular weight (weight average) of the polymer containing amins A is preferably found in the e. eptr; 2000/50, OO, particular size of 40 < "» 0 to 25, (>, particularly preferable from 6 00 to 10,000.) The average molecular weight: weight average of the polymer is preferably on the scale of 400 to 500 O, in particular 1000 to 4000. The synthetic resin systems according to the invention contain the polymers A v B preferably in a weight ratio of 95: 5 to 5:95, preferably of S5: 15 to 15:85, in particular of 75:25 to 25. : 75. The glass transition temperature of the resin blends is preferably at least 25 ° C, in particular at least 45 ° C, particularly preferably at least 65 ° C. The polymers A according to the invention are preferably reaction products of at least one compound of each of the groups (a) epoxies, carbonates or epoxide carbonates, (b) amines and (c) phenols, especially resins (a) containing epoxide groups, pref. they have terminal epoxide groups, and / or resins (2) containing carbon groups Ato, preferably having terminal carbonate groups, of the groups consisting of polyglycidyl ethers, polyethylene glycol esters and polyglucides with mono- and / or polyhydric phenols (C) and / or alcohols. with secondary and / or primary amines, saturated and / or unsaturated (b) or amino alcohols. The latter can be modified in the alkyl radical by at least one primary and / or secondary hydroxyl group, by a dyalkylamine group and / or by a primary amine group which is temporarily protected by ketimine formation. The epoxide compounds to the employees possess, on average, at least one, preferably two, 1,2-epoxide groups per molecule. They may be either saturated or unsaturated and aliphatic, cyclic, phthalic, aromatic or heterocyclic and may also contain hydroxyl groups. In addition, they may comprise substances which do not give rise to any secondary reaction of disruption under the conditions of mixing or reaction, examples of such substituents being alkyl, aryl, alkyl, ether, ether, or the like. Examples of such epoxide compounds are glycidyl ethers of polyhydric phenols, for example, resorcinol, hydroquinone, 4,4'-dihydroxydiphenyl ethane, isomer mixtures of dihydro-1-yl-ethane (bisphenol F), 4,4'- dih idrox? -3, 3 '-dimet ild i feni l methane, 4,4'-dih? drox? differe Id i et i lmethane (bisphenol A), 4, 4' -d ih idrox idi fen i 1 methane, 4 , 4'-dihydro ifeni le iclohexano, 4,4'-dih? Droxi-3,3'-di et ildifenil-propane, 4, 4 '-d ih idro ib i fen i 1,, 4' -d ihidro id i phen 11 sulfone, tris (4-hydrox? phen 11) methane, 4, 4 '-d ih idrox ibenzophenone, ljl- bis (4-h idro i feni 1) isobutane, 2, 2-b is (4-h idrox i-ter-but i 1-pheny1) propane, b ís (2-h idrox inaft i 1) ethane, 1, 5-d ih idro i-naphthalene, ether b is (4-h idro if eni 1 ico ), or the products of hydrogenation, chlorination or bromination of the aforementioned compounds, and also novola s. The partial use of glycidyl ethers of polyhydric alcohols as alkoxy compounds is also suitable. Examples of such polyhydric alcohols that may be mentioned are et i lepgl icol, d iie i legl icol, triet i lengl icol, 1, 2-prop i lengl icol, 1, 4-pro? i lengl icol, 1,5-pentanediol, 1, 2, 6-hexanotrol, glycerol, trimethylalpropane and 2,2-bis (4-h idrox ichexyl) propane. The term "glycidyl ethers" in the context of this invention preferably refers to glycidyl ethers of the formula I CHa-CRi-Rse (-aR-0-CHa-CR-lR? Β) -0-R-0-Ra! CRi-CHS! \ / | 0 OH 0 Formula I where R- R1 '= independently of each other H or C "H2m + ?, Ra = is a linear or branched saturated hydrocarbon radical having up to & carbon atoms, preferably -CHa-, R3, R8 '= in each case independently of one another, halogen, aryl, alkyl, aralkyl, = 0 to A, preferably 1 to 6, = 1 to 8, preferably 1, , u = independently of each other, from to 4, preferably from 0 or 1. These polyester polymers have an average molecular weight of approximately 200 to 10,000 / approximately equivalent epoxide weight. to 5000. Such resins are products of reaction of epichloroidine or methylactophenol with dihydric acid and phenomethane (bisphenol F) or dihydroxifine inpropane (bisphenol A), and with hydroxy ibenzof enona od ihidi ox inaf taleno. Suitable molecular weight polyepoxides are prepared either by selecting the molar ratios of bisphenol and epichlorohydrin or by reacting the monomeric diglycidyl compounds with another bisphenol, with or without the addition of catalysts such as Lewis acids or salts. of phosphonium. The epoxy resins can be completely or partially hydrogenated or can be used in mixtures of different structure and molecular mass. In addition, part of the described polyethylene ether may be replaced by aliphatic polyetheric ethers of the formula T 0 0 / \ / \ CHa-CH-CHa [-u- (CHR *> v ] w-0-CHa-CH-CHa Formula TI where R * - »= H or an alkyl radical (Ct - (^) - substituted or not subst itunjo, v = 2 to 6 and w - a 100, preferably of 3 ^ 50. The examples are b isgl ic ethers of prop i lengl i col or pol ibut i legl icol of various molecular weights. Epoxy resins can also be modified by reaction with long-chain polyol alcohols such as 1,6-hexanediol, neopentyl glycol, neopentyl glycol glycol, hydropentyl vatium hydrochloride, and hydroxyethyl hydroxide. 11) -cyclohexane, onion and polypropylene tetrahydrofuran diol, polycarboxylate, polypropane or polybutadiene diol in the presence of suitable basic catalysts, such as boron-amine fluoride complexes. Since polyol alcohols with primary hydroxyl groups can be reacted directly with the polyetheric ethers giving appropriate catalysts, the secondary hydroxyl groups can be reacted first with all the diisoate. The finished isocyanate reaction product can then be incorporated without problems as a bridge between two poly ether units with an increase in molecular weight and functionality. Other suitable epoxide compounds are polyglycidyl esters of the formula III R "(-C-OCHa-CH-CHa) p J 0l x07 Formula III wherein R" 3 = linear or branched, saturated or unsaturated hydrocarbon radical it has up to 40, preferably up to 10 c-irbono atoms or a substituted or unsubstituted phenyl radical and p = 1 to 5, preferably 2 or 3, esDec tally 2. Such polycarboxylic acid esters of polycarboxylic acids 1 icos are obtained by reacting epichlorohyd or similar epoxy compounds with an aliphatic, aromatic or aromatic polycarboxylic acid, such as oxalic acid, adipic acid, glutaric acid, terephthalic acid, hexahydrofluoric acid. , 2,6-naphthalenedicarboxylic acid and dimethylated fatty acids, examples of which are diglycidyl terephthalate and hexahydrophthalate of dig 11 cid 11. Other suitable compounds as resins to which they comprise epoxide groups are those wherein Some of the epoxide groups are reacted with amines. Such amino-epoxy resins can also be modified with polycarboxylic acids and / or hydroxyalkylcarboxylic acids saturated or more saturated to reduce the number of amine. Examples of aliphatic polycarboxylic acids, cyclic acids and / or aromatics of vains Chain lengths are adipic acid, sebasic acid, fumápco acid and aleic acid and its anhydrides, isophthalic acid and dimeric fatty acid. Lactic acid, dimethyl or l-propionic acid or any polyester containing carboxyl and hydroxyl are understood as hydrocarboxylic acids. In the reaction of an excess of polyethylene glycol ether or molecular weight with polycarboxylic acids and / or polyhydric alcohols, the intermediates obtained are modified polyester ethers which are capable then to react with amines v / or aminoalcohole. It is also possible to use etherocyclic polyepoxide compounds, such as 1, 3-d igl ic id 1-5, 5-d i and ih idantoin, r; isocyanurate of triglycidyl or diepoxides of bisimides. Another suitable class of polyepoxides is that comprising phenolic novolak phenolic resin ethers, with which the functionality can be increased from 2 to about 6 glycidyl groups per molecule. By means of the unique deflection i zac ion With long chain alkyl phenols such as dodecyl, it is possible to incorporate additional substrates. Other suitable epoxide compounds are described in the book "Epo ídverb indungen und Epox ídhar ze" TEpoxide compounds and epoxy resinsD by A.M. Paquin, Sppnger Verlag, Berlin 1956, chapter IV, in Lee, Neville "Handbook of Epoxy Resins" 1967, chapter 2 and in Wagner / Sarx "Lacl 'V unstharze" CSynthetic resins for coatmgs, Cari Hanser Verlag (1971) p. 174 ff. As carbonates a2 it is possible to use any desired materials as long as they contain at least 1, Preferably 2 or 3 2-oxo-l, 3-d-oxolane groups (cyclic carbonate groups), per molecule and having no other groups > functional that break the reaction with component b. The molecular weight Mn '. Average in number, determined by means of chromatography using polyesters irenos as a rule 'J) 5 to be generally between 100 and 10,000, preferably between 15 and 5,000, and the equivalent weight of 2-oxo-l -3-d-oxolane should be He's between 100 - '5üO. The cyclic carbonate groups are preferably terminal, but the compounds used as a component will also contain these groups in an alkatope distribution along the molecular chain and are prepared by copolymer using olefinically unsaturated compounds comprising these cyclic carbonate groups. For example, a preparation process of this type is described in DE-A 3 644 373. The carbonate component a.2 preferably has the formula IV Formula IV Where? = z-valent radical of a phenol, polyether, polyetherpolyol, polyester, polyesterpolyol, which may, if desired, also comprise amino or alkylamino groups, or a z-valent hydrocarbon radical, preferably an alkylene radical having 2 to 18 carbon atoms, which, if desired, can carry inert groups, or a secondary polyamine radical of valency z, a z-valent radical of a reaction product of an epocarbonate compound with polyanes, paloli, polyaprol actona palyols, hydroxyl-containing polyesters, polyethers, polyphenols, hydroxy polymer, cabaxi and amino functional oils having average molecular weights of 800 to 10,000, polycarboxylic acids, hydroxy or amino functional polyhydro-urea or polyamines and reaction products of polyamines with qcididyl esters of acids > x, xd ialqui lalcan onocarbox í ics of the empirical formula CisHaaOa to CmUa? Og, for example of Versatic acid (Shell Che ie, α-branched monocarboxylic acid having 9 to 12 carbon atoms), z = 1 to 5, preferably 2 to 3, especially 2. Such compounds and their preparation are described, for example, in DE-A 37 26 497., In some cases, it may be possible to use, as an additional component or if desired as only component, epoxide-mixed carbonates of the formula V (CH2 - CH - CH2 -) X R6 '(- CH2 - CH - CHJ, II O Formula V wherein R * 4"'= valence radical (x + y) of a phenol, polyether, polyetherolol, polyester, polyester polyol, which if desired may also contain amino or alkylamino groups, or a radical ti i clrocaí bureau of aleñe ia 'x + y), preferably an alkylene radical having 2 to 18 carbon atoms, which if desired can carry inert groups, or a secondary polyamine radical of valence (x + y) or a valence radical (x + y) of a reaction product of an epocarbonate compound with polyamipads, palols, polycaprolactane polyols, hydroxyl-containing polyesters, pol esters, polyglotics, hydroxy polymer, carboxy and amine oils functional polymers having average molecular weights of 800 to 10,000, polycarboxylic acids, hydroxy or non-functional polyhydroxy urans, and reaction products of polyesters with glycidyl esters of acids and, or, alkanocarboxycarboxylic acids of the empirical formula CjLaHaaOa a C ^ Ha ^ Oa, for example Versatic acid, and x, y = independently of each other, 1 to 5, preferably 2 to 3, especially 1. The preferred starting materials for preparing cyclic carbonates and the mixed epo-carbonate compounds which are used, if desired, are the polyglycide ethers of phenols and polyhydric alcohols, for example. bisphenol A or Bisphenol F. The glycol ethers, for example, are obtained by reacting a polyphenol with epichlorohydrin. Examples of polyphenols are 2,2-b? S (4-h? Drox? Phenl) -propane, b? S (4- hydrox if in 11) methane, 4, 4 '-d? H? Dro ibenzofone, ether b? s (4-hydroxy-1-yl), 1, 1-b-LS (4-hydroxyphenyl) isobutane, (2-hydroxynaphthylmethane, and 1-d-hydroxylphthalene.

Preferably, the free hydroxyl groups are present-in addition to the epoxide groups in the polyphenol ether of polyphenol. Cyclic ureas can also be used as adducts for cyclic ureas. As amines (b) it is possible to use primary monoamines, preferably containing alkyl and alkanol groups, the examples being methylamine, ethylamine, propylamine, isopropyl sheet, butylane, isobutylamine, isobutyl, 2-a -butane, 4- Am? no-2-butanol, i soami lamina, pentilamma, 3-met i Ibut i lamina, heptylamine, octylamine, 2-ei Ihex i lamina, isononi lamina, isotr idee Ilamine, 2-am? nomet i 1-1- propanol, monoethanolamine, ono (n- or iso) propanalamin, neopentanole in, methoxypropylamine, 2- (-am? noetox i) -ethanol, amine coconut fat, oleylamine, stear and lime, tallow fatty amine, decylamine, dodec i lamina, tetradeci lamina, hexadec i lamina, octadec il axna, ciclapenti lamina, ciclohe i lamina, 3- ethoxyprop i lamina, 3-ethoxpropylamina, 3-butoxidropylamin, 3- ionone ipropy lamina, 3-a ?no pro?? Itr ímeto i- (eto itrideciloxi) s? laño, and 2-am? no-2-h? drox? met? l-l, 3-propanediol. It is also possible to use secondary monoamines, preferably lamellar, monoalkyl, alkylamines or d-hydroxyalkines. Examples of such compounds are dimethylamine, diethylamine, dipropylamine, d? (N-o? S) prop? Lamina, dibu 1 J ain, dibutobu 11 amine, di-sec-butylamine, N-met i lbut i lamina, N-met i lammoethanol, dietanolamine, d ipent i lamina, dioct i lamin, d (2 ~ et? l-hex? l) am? na, di isonon 11 amine, N-eti Ibu i lamina, Ne i le iohe * 1 a in, d iccid, tin and lamina, dicocoamine, fatty amine any cyclic amines, such as raorfol ina =, irrolidine or azolidine or substituted or unsubstituted aniline. Reaction products of primary onoamines with monoepoxides can also be used as substi tutents for the secondary amines. In addition, it is possible to use primary amines of the formula VT. HaN-CR Rβ-R ^ -O- (CHR »" '- HR1 * 0-) "Ri: to Formula VI i-sn where R' and R? = Hydrogen, an alkyl radical or a hydroxyl group, R ** = linear or branched alkyl radical, in particular an alkyl radical having from 1 to 3 carbon atoms, RAO and RA1- = hydrogen or an alkyl radical having from 1 to 4 carbon atoms, R112 = hydrogen, an alkyl radical, cycloalkyl or phenyl, preferably an alkyl radical having 1 to or carbon atoms, and q = 0 to 5. Examples of compounds of this type that may be employed are ethanolamine, propane, min, butane amine, ether, ethyl ether, and the like. Ethyl amine and di-ethylene glycol mono-3-aminopropyl ion When primary amines are used, the amine is capable of reacting with the epoxide group, depending on available stoichiometric conditions, with molecular enlargement The number of sheets that can be mentioned are 1 ^ p ^ eff ^ ^ rnin M, the series R3ef farnin D, the sene "ütíf famín FD (Texac o) Also suitable are di- or tpamines with primary and / or secondary groups, for example, laxylprobates, laminates, and propolent sheets of tallow. Polylamines (b) are understood to be compounds that contain at least two ino groups in the molecule. These compounds generally have 2 to 50 carbon atoms, preferably from 2 to 20 carbon atoms. Examples of suitable polyamines (b) are those which contain only primary amine groups and preferably are diprimaps. These polyesters are preferably used as a mixture with primary / tertiary days. Examples of suitable polyesters (b) are those which contain only secondary groups and are preferably free. Preference is given to long-chain sheets, for example, monoalkoxides or reaction products of monoepoxides, for example saturated diglyc ides or glycid esters, or epoxyalkanes with diammoniums. or primary alkanes, for example the addition product of 1,6-hexanediol with 2 moles of glycidyl ester of Versatic acid. Other msnoepoxides that can be used for this purpose are saturated or unsaturated glycol ethers or "-oxides of various chain lengths, such as 1,2-epoxide dodecane or butylene oxide. Other suitable sheets (b) are pallets containing at least one free primary ammo group 7, in addition, secondary and / or tertiary groups. The μolyamines' b) can be represented, for example, by the following formula VII ? HaN - (Ri »N) B - Ril * 'Formula Vil wherein s = zero to an integer from 1 to 6, preferably from 1 to 4, R? a = divalent hydrocarbon radical. preferably no aromatic group having 2 to 18 carbon atoms, preferably an alkylene radical branched or unbranched alkyl having from 2 to 10 carbon atoms, in particular 2 to 6 carbon atoms, or a radical c ici oalqu i firelog having 5 to 12 carbon atoms, preferably 6 to 10 carbon atoms, or an aralkylene radical having from 7 to 12 carbon atoms preferably 8 to 10 carbon atoms, or pol radical ío xalqu i him or has from 2 to 18 carbon atoms, R? t *, R? + '= independently of each other H or Ras -RA * -N lß ' R 1 -s, R 19 '= H, alkyl of CL - [' 2) preferably alkyl-C ?, preferably hydroxy, preferably LH 2, -CH-Ri 3 ' pa? Ri = independently: s the definition given for R13, alkyl CL - C ± a, _ ~ CHa 0- () -a i iqu it, -CHA-a- plo,: Ha- 0-C-? (Ct- la) - 4-alkyl-CHa-CH-CN, R1- * 3 = H or C? -C alkyl? or R15 and RaA = part of an aliphatic ring of 5, 6 or 7 members, provided that if s is zero, R11 * 'is not H. Other suitable polylamines in this context are those of the formula VIII X- (R1 '»NH) t-Ra? O-Y Formula HIV wherein X and Y ion MHa or OH but both are not the same, and R1 '* and R * °, independently of each other, are as defined for RJS in formula VII above, and t is as defined for s in In addition, examples of other suitable polyamines and polymers are those described in patent applications DE-A 36 44 371, DE-A 37 26 497 and DE-A 38 09 695. Reference is made to the present applications, including the preferred embodiments described therein.

They are also adequate? pol amines or amino condensation products of dmaps with dicarboxylic acids, for example, dipyric acid or dimethyl acids, and also polyethylene glycol or amine adducts, eg, epoxy-amine adducts . Examples of suitable examples (b) are et i lendiamine, prop i lend sheet, 2 ~ i ~ i ipenta et i lend sheet, pentam il nd i amina, hexa et i lend i mina, tpmeti lh amet ilen - diana, neopent and id iami na, octamet 11 end lamina, tpacetona-i dia dia, ioxadecand lamina, d loxadsdecand lamina, and superior homologs, cycloaliphatic diamines such as 1,2-, 1,3- or 1 , 4-c? C lohexandiamin, and also lup lprop i lend lamina and propyl lendiamine tallow grease, 4, -met i lenbisc iciohe i lamina, 4, -isopropilenbisc icohex i la in, i oforondi a ina, trioedeledodeceni idioin, mentandiamine, 4, 4 '-d? Am? No-3,3'- dimet i Id íc icohex i lmetano, 3-am? Nomet 11-1- (3-a? Noprop 11 -1- et 11) -4-meth i leohexane, IM-met 11-et i lend lamina, N-aminoet i piperazine, 2-amidoet i 1-p ipera ina, N, N-dimet i 1- etilend lamin, N, Nd imet i 1-prop i lend lamin, N, Nd? met? l- 0 aminoprop i lamina, N, Nb? sam? noprop? lN, N '-d imet ylamino-propyl ina, IM, Nd? H? Droxet and lendiamine, aromatic amines such as Mx 111 lend sheet, aliphatic poly (tp-, tetra-) amines such as dite and lentpamine, di prop i lentr lamina, b íshexament L lent lamina, tr íet i lentr sheet, tetraethylene-5-pentamine, pentathylbenzene, methylaminopropyl-lamin, N-alkylamine and propylamine (alkyl = CH;.) "i C * HV-, ', H-, i aN U "?? a-, tetraprop and lenpentamine / also alkanola ina such as aminoet 11 ethanolamine, N- (2-hdroxprop 11) et i len ~ -d la in, et i lengl icolb isprap i lamin, h Idro IET i ina OTS i, h idroxiet ldieti lentp amine and pol íoxi end prop 11 i amin, prefe iblemente with an average molecular weight of about 200-4 < > 0. The most preferred polias are H, Nb isaminaprop i 1-N-melamine, N-amopro-l et i la ina, N-aminopropylpropyl, propyl 1 tallow grease, and particular, dimet i laminopropí lamina, and also d let i laminoprop i lamina and N ~ c iciohe i 1-1, 3-prop i lend lamina, 3-d í et i laminorprop i lamina, 2-diet 11 aminoet i lamína and dimet i iammoneopent i lamina. As phenols (c), which can be used individually or as a mixture, phenol, m-cresol, 3, 5, -d -methylene, -ethoxy, and phenol, p-hydroxybenzyl, and o-hydroxybenz are mentioned. ílfenol. It is preferred to employ phenols (c) which contain at least two hydroxyl and phenolic functions, examples are resorcinol, hydroquinone, 4,4'-d -hydro-1-phenylmethane, mixtures of isomer of dihydroxydi-phenyl-methane (bisphenol F), , 4'-d? H? Drax? -3, 3 '-dimet ildiphenyl and no, 4,4'-d? H? Drox? D? Fen? Ld? Et i lmethane (bisphenol A), 4, 4' - Hydroxid ifne, 4,4'-dihydroxydifylcyclohexane, 4,4'-d? h? drox? -3,3 '-dimet and 1-diphenylpropane, 1,2-, 1,3-, 1 , 5-, 1,6-, 2,2'- 4,4'-dihydroxybifem, 4,4'-, 2,5'- and 3,3'-d? H? Drox? -2,2'- bipipdil, 4, 4 '-d íh ídrox id if eni lsulf ona, acid 4,4'-b? s (4-h ídrox if en i 1) vaiépco, and its amides, bis (4- h f eni lo), acid 2.2-b is (4-h? dr ox if in 11 acetic and its amide, tps (4-h? drox? phen? l) methane, 4, 4 '-d ih idrox iben ofenone, 1, 1-bis (4-h? Drax if eni 1) isobutane, 2, 2-bi yes 4 - h? Dro? -ter -but L lf eni 1) propane, b í (2 ~ h idrox inaf 11 it) methane, 1,5-dihydroxinaf taleno, and b b? s (4-h? i f drox ENI 1 ico) hydrogenation products, and bro cloraeióp ation of the aforementioned compounds, and also novalaks. Particularly preferred are resorcinol, bisphenil A and bisphenol F. Phenols used as phenols (c) san, in particular, alkylated phenols, flat or alkalized, ono-and / or pol íh 1 dpcos, which if desired are i somer i In this context, alkylation, apposition or substitution refers to the electrophysiological substitution on aromatic nuclei of phenol mother structures with unsaturated compounds. The phenols (c) are characterized in particular by the following formulas IX Formula IX wherein: 2: t = alkyl of (Ca "Cta), preferably (C5 i) alkyl, cycloalkyl of CS-I AJ, phenyl, phenyl substituted with at least one alkyl radical (C? -? '? a), alkylCa-C14) substituted with at least one phenyl radical, d = a number from 0 to 4, preferably 1 or 2, and e = a number from 1 to 5, the value of e being less than or equal to the difference of 5 minus d, or formula X Formula X where i - i or 2, 9 = 1 to 4, g '= 0 to 4 h = 1 or 2 M = = CH- or a heterogeneous atom, preferably a nitrogen atom, [! 2 ?: the same definition of R? A.? H or the same definition of Rs > ?., a single bond, CH2, C (CHa) z, S (0), S, SS, C (0), or a group of the formula XI CH3 -CH- CH-IO-CL or CH2CH2 -CL Formula XI L = hydroxyl group Q23 -NH- (CHJrN \ RCT or a group of formula XII Formula XII in which R523, Rz ", R5255, R * 39 ', R * 1 *', R '= independently of one another are hydrogen or alkyl i, j = independently of each other from 1 to 4, preferably 2 or 3. For the preparation of the phenols (c) alkylated, cyclised or alkylated, which are to be used preferably according to the invention, phenolic mother structures, which may be employed, In mono- or polynuclear phenols, for example the same phenol, preferably those carrying two or more hydroxyl groups on the same aromatic ring, the examples are f luorogluc inol, pyrogallol, hydroquinone, piracatecol, and especially resorcinol. , also suitable are phenols based on condensed aromatic ring systems.

The latter are described, for example, by the formula XIII: Formula XIII or formula XIV Formula XIV ? where P.S = - ü to 2, 1 = 1 to 3, preferably? 1 or 2, i? sum of V / 1 = endo DOG l or less?, and 7. = = CH-, C = 0, an oxygen atom or a nitrogen atom. The examples that can be mentioned are the inactivated, its pos- itional isomers, 5 dihydro-anthraquinone, quinirazins, anthraflavic acid. The phenols (c) can also be used as phenolic mother structures to prepare other compounds (c). The mono (alkyl) phenols which are to be used, preferably as phenols (c), are compounds known per se, which are often referred to in the literature as styrenized phenols. Australian Patent AT-C 284 444, the reactions of styrenes with phenols are known and are essentially alkylation reactions where the vinyl group of the styrene is added on the phenol in the ortho position or for the hydroxyl group. It is generally carried out using Fr edel-Craft catalysts, for example acids and Lewis acids, depending on the reaction conditions, the catalysts, proportions of the reactants, the reaction produces mono-, di- or tri-ester phenols. The German specification open to the public DE-A 19 40 220 also describes the best products for their preparation 5 Preferred alternatives (c) can pre stop submitting phenols? an addition reaction with a vinyl compound at a molar ratio of the phenolic hydroxyl groups in the phenol to the vinyl aromatic compound from 1: 1 to 1: 2, in a known manner, in the presence of mineral acid or Friedel-Craf catalysts t. The vinyl compounds that may be used are natural or synthetic compounds containing one or more carbon-carbon double bonds; if it is more than one, conjugated double bonds may be present. The natural unsaturated compounds which can be used are unsaturated fatty acids, fatty oils derived therefrom, fatty acid amides or fatty alcohols. Other suitable starting compounds are unsaturated natural substances based on terpene, for example, terpeptin oil and calophony. The synthetic unsaturated hydrocarbon compounds that can be used are alkenes, dienes or higher unsaturated hydrocarbons, for example butepo, isobutene, isooctene, ionosonone, isododecene, or unsaturated compounds, for example butadiene, isoprene, chloroprene, dichlorobutadiene, and diethylpentadiene. It is also possible to use mixtures of alkenes, and, if desired, of alkenes with ranges, such as those produced, for example, in the cracking or dehydration of hydrocarbons, for example, petroleum or oleophilic oligomerization, especially isobutylene, propylene. or n-butene or carbon oxidation. Acetylenically unsaturated compounds are also suitable, for example acetylene or alkyl (Ct-C? A) or dialkyl ethers of (C? -C? Üj.

Examples of unsaturated compounds which can be used as starting materials for the preparation of compounds < c) are the following: n-pent-1-ene, n-hex-1-ene, n-oct-1-ene, n-non-1-ene, n-dec-i-ene, n-undec 1-ene, n-dodec-1-ene, 1-propylene, n-but-1-ene, the aforementioned alkenes which are substituted in the second or third position or, if desired, fourth by the methyl group , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secbutyl or tertbutyl; 2,3-di eti 1-n-bu ene, 3,3-diei 1-n-butene, 2, 5-d imet ílheptene, 3,3-d ímet i lhepteno, 2, 3, 4, -tpmet i lheptene, 2,4-d-Imetheptene, 2,3-d? -methyl heptene, 4,4-d? metheptene, 2,3-d? et Ihexene, 4,4-d-methexhexene, 2,3-d? Met i hehexene, 2,4-d? Methexhexene, 2,5-diethylhexene, 3,3-d? Met? lhexene, 3, 4-d? met i 1 hexene, 2-met? l-3-ethylpenteno, 3-met i 1-3-etlpenteno, 2, 3, 3-tr ímet i lpenteno, 2,4, 4 -tpmetlpentene, 2, 3,3-methylmethopene, 2,3,4-methylmethane, 2,3,3,4-tetramethylpentene; analogous alkenes whose double bond is in position two or three in the molecule; branched alkenes as obtained in the form of isobutylene or n-butene dimepzation mixtures (octenes) or isobutylene or n-butene (dodecenes) or propylene (nonenos) or tetramethylene propylene (dodecene) copolymers. As aromatic vinyl compounds, styrene derivatives can be used in particular. Examples of styrene derivatives are < x-met i lest ireno, styrene, o-et i lest i reno, -met i iest j reno, p-me i lest ireno,, n? l toluene 2 & commercial 'mixture of isomer), 3, 4-d, imet i, irene, 2,4-d, i, irene, 2, 5-demet i, iirene, 2,6-d imet i lest, i-et i Les ireno, -et i lest ireno, p-et i lest ireno, 3,4-d let i lest ireno, 2,4-diet i lest ireno, 2, 5-d.?et i lest iero, 2,6 -d iet i lest ireno, o-propilest ireno, m-propi lest .ireno, p-propí lest ireno, o-isoprop i lest ireno, -isoprop i lest. irene, p-isoprop ilest irene, o-but i lest irene, -but i lest irene, p-butyl irene, o-isobut i lest irene, m-isobut i lest irene, p-isobut i lest irene, sec- bit i lest ireno, m-sec-but i le = t ireno, p ~ sec-but i lest ireno, o-tert-but lest ireno, m-tert-but i.lest ireno, p-tert-but ilest ireno , p-bromoest irene, p-chlorosesthene, 2,4-dibromoest-irene, 2,4-diclaroest-irene and 2,4,6-trichloroest-irene. Particular preference is given to the use of vinyl compounds of aromatic vinyl compounds of the formula XV Formula XV wherein RZA is a hydrogen atom or a methyl radical and Rx t is a hydrogen atom to an alkyl radical having from 1 to 3 carbon atoms or the radical -C = CHa R ** < ? where RZ? independently it can be defined as R2 *, for example, 2st ireno / - et i J est i reno. For the preparation of the polymers or mixtures of polymer A of components a, b and c, the molar reactions between the compounds containing epoxide groups, cyclic carbonate, amino and phenol are to be chosen to ensure the complete incorporation of the phenol, carbonate and epoxide groups. This reaction can be carried out in steps based on the compounds (a) or it can be carried out such as, for example, that the compounds (b) mixed with the compounds (c) are reacted with the compounds' a). The reaction is generally continued until a constant, or theoretical number of amine is reached. The reactions of the compounds a, b and c in the required stoichiometric proportions are carried out at elevated temperatures, for example from 40 to 300 ° C, preferably from 50 to 250 ° C and, with particular preference, from 80 to 200 ° C. C, it being possible, if desired, to use solvents and / or catalysts. Great care must be taken to avoid gel ication. All the amines can react simultaneously with the epoxide groups and / or carbonate groups, or a stepwise process can be adopted. In this way, it is also possible to obtain mixtures of different epoxide adducts-to ina and / or carbonate-amine adducts. The reaction with the amines starts at room temperature and is generally exothermic. To achieve a complete reaction, it is generally necessary to increase the temperature temporarily to values between 40 and 250 ° C. Since no catalyst is generally necessary for the reaction of the primary anim al groups with the 2-axa-l, 3-d-oxolane groups, the catalysis is convenient for the inactivation of the non-reactive secondary amino groups. Catalysts suitable for this purpose are strongly basic compounds, such as quaternary ammonium compounds, for example hydroxides and carbonates of alkyl, aryl and / or benzyl ammonium. The specific representatives of quaternary ammonium compounds in this context are alky1 (Ci? -C-aa) -benzyl hydroxide, hydroxide of benzyltrimonium ammonium and hydroxide of tetrabutyl ammonium hydroxide. Preferred catalysts are strongly basic amines, for example diazoic acid (DAE) and guanidine. Also suitable in this context are the so-called supranucleof 11 catalysts, for example 4-p irol id ín i lp id id and pol i (N, Nd? Al? Inopyridine), (cf. in this context, the article by RA Vaidya et al in Polymer Preppnts, Vol. 2 (1986), pp. 101-102). As an option, solvents may be added for the purpose of preparing the resin systems according to the invention, these solvents are removed in vacuo after the termination of the resin synthesis and are, for example, glycol ethers such as ethylene glycols, For example, ethylene glycol, ethylene glycol, butyl glycol, methyl glycol, and glycolic acid, but the organic, metallic, and glycolic, butyl and glycolic , Itetraglotolol, et i ltetragl icol, butiltetraglicol, (R >; Polyglycol M 250 (Hoechst, MW: 260-275, OH number: 2 - "'4-215), < H > PolvgLvcal M 35 (Hoechst, IW: 335-265, OH number: 154- 107), 2-n-pr opox ethanol, - (1-met i leto i) ethanol, 2-n-butox ethanol, 2'-methoxyethoi / ethanol, 2- (2-ethoxyethoxy) ethanol, 2 - (2-butoxyethoxyethanol, trotelemal glycol ether, methyl tetraethyl ether, 2,5,8,11-tetraoxadodecane, 1-me oi -2-prop nol, 1 -ethoxy? -2-pro? anol, tripepropyl ether monomethoxide, methyl propyl ether, methyl dipropyl ether, methyl tppropylene glycol ether, n-butyl propylene glycol ether, dipropyl ether n-butyl, n-butyl trpropyl ether, and phenyl propylene glycol ether Polymers B comprise at least one hydrophilic substructure which is non-ionic at the prevailing pH Examples of such B polymers are adducts of hydroxy compounds with resins which contain epoxide groups preferable Epoxy terminal groups, of the classes of polymers and polymers, and polymeric esters. The resins containing epoxide groups which are employed are preferably polymers containing terminal epoxide groups, of the classes of the polyglycide ethers and polyglycic esters. As hydro? I compounds, use is made of individual organic compounds or mixtures thereof, which contain at least one hydro group < ?the. Preference is given to the use of mono-, bis- or t ies-h ídrox i compounds, especially manoh i ro i compounds. 3? The < or can you monah? d? 0 1 is understood, according to the invention, to be mannoalcohols and polyalkyl or monoether oxide compounds. The monoalcohols which can be used are preferably those containing alkane or cycloalkane radicals, especially (C? -C.sub.32) isomers thereof, for example 2-ethexane, octanol, nonanoi, decanol, dodecanol, and also stearyl alcohol, cetyl , Crylic and Mipstyl < R > TCD Alcohol M (Hoechst, MW: 166, OH number: 327), wool wax alcohols, cholesterols, borneols, isoborneoles and tallow oil fatty alcohols. The properties can also be modified, optionally, using alcohols containing alkane chains and cycloalkane in proportions of 0 to 95% by weight, based on the amount of onohydroxy compounds, examples of these alcohols are butanol, hexanol, cyclohexanol and / or their mixtures. The monoether-containing polyalkylene oxide compounds that are used are preferably compounds of formula XVI R ^ -IO-CHR30- ™ 31), ^ Formula XVI In this formula, R35 ** is an alkyl, cycloalkyl or phenyl radical, preferably an alkyl radical having from 1 to 12 carbon atoms, especially from 1 to 4, R3 ° and P31 are hydrogen or alkyl radicals having from 1 to 4 carbon atoms, and r is from 1 to 10, preferably from 1 to 4.

Examples of such compounds that may be mentioned are methylglycol, ethyl glycol, butyl glycol, methyl glycol, and diglycol, but i ldigl i col, met i 1 tr igl i col, et i. ltr ígl icol, but i ltr igl icol, I ltetragl icol, et i ltetragl icol, 5 but Itetraglycol, polyglycol M 250 (MW: 260-275, OH number: 204-215), polyglycol M 350 (MW: 335- 265, OH number: 154-167), methyl propylene glycol ether, methyl dipropylene glycol ether, methyl tripropylenyl ether, n-butyl propylene glycol ether, n-butyl ether and polypropylether, ether tr iprop i lengl icol n- The polymers B are prepared in a manner known per se by reacting resins containing epoxide groups with hydroxyl compounds in the presence of catalysts such as, for example, hydrocarbon acids. is (EP-A 0 272 595), i idazoles 5 (macro oleules, 1989, 22, 99), cyclic quaternary ammonium compounds (US-A 5 019 639), tin compounds (EP-A 0 498 504) or alkaline earth metal perchlorates (Polymer Bulletin 1989, 22, pp. 221-226) The invention also provides a process for the preparation n of multimodal synthetic resin systems free of emulsifier and solvent comprising polymers A and B, which comprises preparing at least one polymer A containing amino and at least one polymer B dilutable with nonionic water, which, if desired, neutralized or partially neutralized later in water, combining A and B and, if desired, preparing a water-soluble C polymer > 3n the form of latex particles by emulsion polymerization of ethylenically unsaturated compounds in the presence of polymers A and B which, if desired, have been neutralized or partially neutralized. In a preferred embodiment of the process, the A-containing polymer A is prepared in the presence of at least one polymer B dilutable with nonionic water. Suitable neutralizing agents for the polymer mixture according to the invention, comprising A and B, are organic acids, for example formic acid, dimethylol lolypropionic acid, d-methyl-1-ylpropic acid, acetic acid, glycolic acid, gluconic acid, hydroxyacetic acid, propionic acid, butyric acid, lactic acid, valeric acid, capric acid, oenogenic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, iric acid, palmitic acid and stearic acid, preferably acid formic acid, acetic acid and lactic acid, and also inorganic acids, for example, phosphoric acid, sulfuric acid, boric acid and hydrochloric acid. The degree of neutralization is generally between 5 and 120% ', preferably between 10 and 90% based on the amino groups present. According to the invention, the synthetic resin blends not only contain the polymer resins A and B but also, optionally, polymer resins C. The polymer resins C are prepared by the emulsion polymerization in the presence of resins of polymer A and at least partially polymerized B-polymer resins. L-ss A and b must be present in an amount that is adequate to present the desired mulsi f i cant / stabilization effects. In this context, both economically and for reasons of influence on the performance properties of the emulsion polymers to be • prepared, for example water resistance, re-dissolving ability and drying rate, the proportion of The resins A and B must be neither sufficiently high nor low enough. The content of the polymers A and B used as a whole is therefore, preferably, from 4 to 40% by weight, in particular from 8 to 2 by weight, based on the solids content of the dispersion comprising the polymers A, B and C. Very good rheology controlled dispersions (RC) are also obtained in this form, if less than 20% by weight, preferably less than 15% by weight of the sum of resins A and B, based on the sums are used. of A, B, and C. The emulsion polymerization procedures are familiar to those skilled in the art. The customary aspects thereof are a polymerization of the free radical of ethylenically unsaturated manomers in the aqueous phase, in the presence of free radical initiators and emulsifiers, protective colloids or other stabilizers. The mentioned components can be introduced to the emulsion polymerization in various forms. When the polymer resins A according to the invention are used as stabilizers: n polymerizations by emulsion, the good performance of these oliomer = makes it unnecessary to use low molecular weight protective colloids. Most of the aqueous phase is usually present as the initial charge, with the addition of part of the <During the reaction, in the form of a free radical initiator solution, or a monomer pre-emulsion, it is a possibility. All or some of the stabilizers can be included in the initial charge, and the rest is dosed during the polymerization. The monomers can all be present in the initial charge or can be dosed in a pure form or as a pre-emulsion in water. It is usual that some of the initiator of the free radical is included in the initial charge and some is dosed as an aqueous solution. The initial charge is that the mixture, which is introduced into the reactor before the reaction temperature of, usually, 20 99%, is established. The polymerization in most cases initiated by thermal decomposition of the free radical initiators or by means of redox systems and which can be considered as completed when the majority of the monomers that are reacted by the chain reaction of the free radical, have reacted (of between 20/99%). This procedure usually leaves approximately 0.001 to 0.1% by weight of residual monomers. Other methods and variants of procedures = e set out in detail in, for example, Ullmann, Fnz /? 1 opadie der technischen Cheie tEnc / clopedia of industrial chemistryl, 4th edition, Verlag Chemie, Weinheim (1980), Volume 19, p. 2 ff J in ¡¡ncycl cpedía de Polymer Science and Engineer mg, Volume 6, Wiley & Sons, New Vori- 1966, p. 1-51. The polymer C of the dispersion is produced by onomers, of which a considerable part are of low solubility in water and remain of low solubility even if the pH is changed. Low solubility in this context refers to a solubility of less than 10% by weight, in particular less than 5% by weight, at 25 ° C. The proportion of monomers of low solubility should be at least sufficient to render the emulsion polymer formed insoluble in the aqueous phase under the polymerization conditions and make it exist in the form of dispersed particles. Within the meaning of the invention, it is preferred to use those mixtures of which at least 70% in step, and in particular at least 90% by weight, are composed of monomers of low solubility. Suitable monomers comprise at least one etiically unsaturated group. The terms et i licamente msaturados, came only unsaturated and < x, ß-msaturada are used synonymously. Those skilled in the art are aware that such monomers can be combined to form polymers under the conditions of emulsion poly erization in an aqueous medium. These monomers include, for example, vinyl, styrene and acrylic compounds and their derivatives. Examples of suitable components / monomers are vinyl chloride and vinyl steres, such as vinyl acetate, vinyl propionate, vinyl esters of acid / esatic, and also vinyl fatty acid esters, such as vinyl laurate. Suitable styrene compounds are styrene, viol toluene, methyl-ethyl, ethyl-urethane, opium-11-styrene, tert-butyl-urethane, 2,4-methylene-irene, die-i-lest. ireno, o ~ me i 1 -? -? soprop i them ireno, hlógenoestire ireno such co chlorostearne, f luorosestine / iodinestyrene 2,4-cyanoesterrene, hdroxester irene, n i roest go ene, aminoesthetene and / or feni lest ireno. Particular preference is given to styrene, vinyltoluene and methylmethylene. Examples of suitable acrylics are acrylic esters, methacrylic esters and protonic esters, and for example esters containing hydroxyl functions, such as hydroxyethyl acrylate and hydroxyethyl metacrylate. In emulsion polymerization, it is also possible to polymerize mixtures of such ethically unsaturated monomers, as long as they are suitable for polymerization. In order to obtain dispersions having glass transition temperatures above 75 ° C, polymerization preferably starts from styrene or styrene derivatives and / or meta-plates. Suitable initiators are customary water-soluble radical-forming compounds, for example hydrogen peroxide, paracetic acid, perbenzoic acid and sulfuric acid, for example potassium or pmonium peroxodisulfate, perfosphates, but hydrocarbons and hydrocarbons. , such as hiper iper or i do of ter-butila. Examples of redox catalyst systems are sodium persulfate 10 / sulfoxide sodium sodium maldehyde, hydroperoxide exorbitant of sodium cumene / etabliss, hydrogen peroxide / ascorbic acid and carbon dioxide. persu lf to ammonium. Also suitable are azo compounds, such as acid, 4- zob ies (cyanopentapoi ca). The initiators are used in customary, catalytically active concentrations. These concentrations are generally between 0.01 and 4.0% by weight, based on dispersion. In particular embodiments, other components that are customary for emulsion polymerization can be used. These are, for example, accelerators, pH regulators and any other constituents which can be used together with the polymers according to the invention in the emulsion polymerization reaction mixture and are known from the prior art since they relate to to emulsion polymerization processes. The ultimodal structure of the synthetic resin systems according to the invention makes it possible in particular to obtain binders having the drying speed, water resistance and a high wetting capacity of pigment which are required for use in the printing sector. By using the resins according to the invention (polymers A and B) it is possible to prepare pigment pastes and gloss resin solutions. These and the dispersions which are likewise according to the invention, (polymers A, B and C) OR They exhibit excellent technical printing properties, good storage stability, good gloss and color fastness, / excellent printability. The invention also provides for the use of novel synthetic resin systems such as grinding resins (polymers A and B) and dispersions (polymers A)., B and C) for pigment pastes and as resins (A and EO polymers and dispersions (polymers A, B and C), as the main binders for water-based printing and printing varnishes. According to the invention co-resins are used in aqueous varnishes, the polymer blends preferably serve as components for the precision formulation of aqueous printing lacquer systems, for example in gloss resins (polymers A and B) for lacquers of over paint to print paper, boards, cardboard packaging, and the like, for example with the ink unit of a sheet feeding machine or roller deviator, of damping units, joined from separate coating of printing machines fed by ho ao deviated by roller, hoover coating machines, engraving printing machines and photographic printing machines. resin according to the invention (polymers A and B) and the dispersions according to the invention (polymers A, B and C) are used as binders for printing lacquers and printing inks, their solids content is generally less than 20%. to "5% by weight, pr ether and between 20 to 70% by weight. These varnishes / inks contain from 1 to 70% by weight of dispersions according to the invention and / or from 1 to 40% by weight of solid reams according to the invention and from 0 to 60% by weight of glycols or glycol ethers , from 0 to 30% by weight of wetting agents from 0 to 35% by weight of neutralizing agents (acids) from 0 to 30% by weight of natural and / or synthetic waxes, from 0 to 2.5% by weight of antifoams, from 0 to 80% by weight of water and from 0 to 60% by weight of pigments. In grinding operations, the pigment / binder ratio is between 5:95 and 95: 5 preferably from 30: 70 to 70:30. For use as pigment grinding components, solids content greater than 30% by weight may be convenient. For the composition of these supply inks, pigments and expression inks, it is also convenient to use mixtures of different types of dispersions or ream solutions. The equipment that can be used to incorporate pigments (for example titanium dioxide, color pigments, synthetic carbon black), fillers, (for example talc, china clay, wax), dyes and flow control agents in the solutions and / or dispersions and / or mixtures thereof and / or their diluted formulations are the usual equipment for milling, mixing, kneading and dispersing, optionally in the presence of customary dispersion aids. The pigment pastes can, in principle, contain all the pigments thatThey are suitable for printing process; polyester-coated pigments are preferred. In addition to the pigments, the pigment pastes may also comprise other customary additives, for example plasticizers, fillers and wetting agents. The preparation of suitable resins which can be used according to the invention and the preparation of stable polymer dispersions by emulsion polymerization, and their use in printing inks and printing varnishes, are illustrated by the following examples.

EXAMPLES In the examples, the parts and percentages are by weight unless otherwise specified. All reactions are carried out under inert gas (Na).

EXAMPLE 1: EPQXIDO / EPOXIDP-AMINA SYSTEM A commercial polyglycidic ether based on bisphenol Having an epoxide equivalent weight of approximately 180-192 (RBeclOpa? EP 14", Hoechst AG, 59 g) is maintained at 150 ° C with met i ltetragl icol (Mw 208, boiling scale 280-350 ° C, 67 q) and "commercial Anchor 1040 (trifluoride adducts of m? na-bora, 250 mg). As soon as an epoxide number of 4 was reached, the "Genarnin SH 100 commercial (stear i lamin, Hoechst AG, 27 g), d imet i laminoprop i sheet (21 g) and commercial bisphenol A (95 g) were added. , in succession to the resin composition, and then the commercial polyethylene ether was dosed slowly over bisphenol A having an epoxide equivalent weight of about 180-192 (Beckopox EP 140, 231 g) so that it did not occur no gelation A synthetic resin system was obtained which has an amine number of 50, Mw of 8500 and a Ta of L6 ° C.

EXAMPLE 2 A commercial polyethylene ether based on bisphenol A having an epoxide equivalent weight of approximately? 180-192 (Beckopox EP 140, 66 g) is maintained at 150 ° C with methyltetraglycol (Mw 208), boiling scale 280 ~ 350 ° C, 28 g), butildiglycol (29 g) and Anchor 1040 (500 m) ) commercial. As soon as an epoxy number of < 4, commercially available Genamin SH 100 (27 g), dimethyl laminopropy (2.1 g) and commercial bisphenol A (95 g) were added in succession to the resin composition, and then commercially available polyethylene glycol ether was added. bisphenol A having an epoxide equivalent weight of about 180-192 (Beckopox EP 140, 231 g). A synthetic resin system was obtained, which has an amine number of 64, an Mw of 8700 and a Ta of 48 ° C. ?4 EXAMPLE 3 A commercial polyphenol ester based on bisphenol A having an epoxide equivalent weight of approximately 180-192 (Beckopax EP 140, 67 g), is maintained at 150 ° C by methylene glycol M? 208, boiling scale 280-350 ° C, 25 g), but íldigl icol! '31 g) and commercial Anchor 1040 (380 mg). As soon as an epoxide number of 4 was reached, cyclohexyl (10 g), dimeti laminoprapi (22 g) and commercial bisphenol A (96 g) were added in succession to the ream composition, and then dosed in succession. commercial polydigl icidyl ether based on bisphenol A having an epoxide equivalent weight of approximately 180-192 (Beckopox EP 140, 231 g). A synthetic resin system was obtained which has an amine number of 74, an M? of 880 and a Ta of 67 ° C.

EXAMPLE 4 The synthetic resin system of Example 1 (41 g) was combined, directly or inversely, under latent conditions with lactic acid (90%, 3 g) and water (81 g) and diluted with water ad libitum (12 g). ). A grinding paste having a viscosity of 540 Pa.s (Ubbelohde), a pH of 4.4 and a solids content of 30% (3 h / 10 ° C) was obtained.

EXAMPLE 5 The synthetic resin system of Example 2 (100 g) was combined, directly or inverted, under hot conditions with lactic acid (90%, 10 g) and water (60 g) and further diluted with water (117 g). A gloss paste having a viscosity of 520 mPa.s (Ubbelohde) was obtained, at a pH of 3.8 and a solids content of 34% (3 h / 100 ° C).

EXAMPLE 6 A solution of the synthetic resin system of Example 1 (48 g) with lactic acid (90%, 3.3 g) in water (95 g) was heated to 90 ° C. Then, styrene (391 g) was dosed and, in parallel to the same ascorbic acid (6 g) in water (616 g) and terbutyl hydroperoxide (4 g) over a period of 3-4 hours. Filtration through a 30 μm filter gave a fine dispersion with a solids content of 35% (3 h, 100 ° C), at a pH of 3.7 and a viscosity (Ubbelohde) of 480 mP. .

EXAMPLE 7 The ground paste of Example 4 (40 g) was intensively combined in a custom dispersion apparatus (Dispermat SL-C25, Getzmann) with Heliogen Blau D7099AQ (blue pigment, Hoechst AG, 12 g) and water (60 g). A pigment paste was obtained, which had a solids content of 36% and a flow time of 60 s from the 4 mm DIN cup at 23 ° C.

EXAMPLE ß The gloss paste of Example 5 (30 g) was mixed homogeneously with the dispersion of Example 6 (56 g). The addition of water (6 g) gave a varnish of over paint having a solids content of 33% and a flow time of 60 s of a cup of 4 m DIN at 23 ° C.

EXAMPLE 9 The pigment paste of Example 7 (7 g) was mixed homogeneously with the dispersion of Example 6 (12 g). A printing ink was thus obtained, which had a pigment content of about 7% and a solids content of about 35%.

Claims (9)

7 NOVELTY OF THE INVENTION CLAIMS

1. - A system of ultimodal synthetic resin free of emulsifier and solvent, characterized in that it comprises at least one polymer A containing amino, and at least one polymer B dilutable with water, nonionic, and if desired a polymer C insoluble in water in the form of latex particles which can be prepared by emulsion polymerization of ethically-synthesized compounds in the presence of polymers A and B.

claim 1, further characterized in that it has a glass transition temperature of at least 25 ° C.

3. The synthetic resin system according to claim 1, further characterized in that the polymer A has an average molecular weight (weight average) of from 3 to 50, OO.

4. The synthetic resin system according to claim 1, further characterized in that the polymer B has an average molecular weight (weight average) of 400 to 5000.

5. - The synthetic resin system according to claim 1, further characterized in that the weight ratio of polymers A to polymers te is 951

6. - A process for the preparation of a synthetic resin system, characterized in that it comprises? prepare at least one polymer A containing ammo and at least one polymer B dilutable with nonionic water, which, if desired, are then neutralized or partially neutralized in water, combining A and B and preparing, If desired, a C polymer insoluble in water in the form of latex particles by emulsion polymerization of ethically unsaturated compounds in the presence of polymers A and B, which have been neutralized or partially neutralized, if desired.

7. - The method according to claim 6, further characterized in that the polymer A is prepared in the presence of at least one polymer B.

8. - The use of a synthetic resin system according to claim 1, such as a grinding resin or grinding dispersion for igneous pastes.

9. - The use of a synthetic resin system according to claim 1, as a resin or dispersion in water-based printing inks and printing varnishes.

SYNTHETIC RESIN SYSTEMS MULTIMODALS FREE OF EMULSIFYING AND SOLVENT

SUMMARY OF THE INVENTION

Synthetic multimodal resin systems free of emulsifier and solvent are described which are suitable as a binder constituent for desentnable printing inks and comprising at least one polymer A containing amino and at least one polymer B dilutable with water, not ion, and if desired, a C polymer insoluble in water in the form of latex particles, which can be prepared by emulsion polymerization of ethylenically unsaturated compounds in the presence of polymers A and B.

GD / crm * mvs * ieoh *