CA2175138A1 - Emulsifier- and solvent-free multimodal synthetic-resin systems - Google Patents

Abstract

Emulsifier and solvent-free multimodal synthetic-resin systems which are suitable as a constituent of binders for deinkable printing inks and which contain at least one amino-containing polymer A and at least one nonionic, water-dilutable polymer B and, optionally, a water-insoluble polymer C in the form of latex particles which can be prepared by emulsion polymerization of ethylenically unsaturated compounds in the presence of the polymers A and B.
Methods of making the synthetic-resin systems and pigment pastes and binders for printing inks and varnishes also are disclosed.

Description

217~138 -EMULSIFIER- AND SOLVENT-F~EE MULTIMODAL
SYNTHETIC-RESIN SYSTEMS

BACKGROUND OF THE INVENTION

l; Field of the Invention The invention relates to multimodal, cationic synthetic-resin systems which are water-dilutable in the presence of acids and are free from low molar mass emulsifiers and solvents. The invention relates further to processes for their preparation and to their use as ~rin~in~ resins, in pigment pastes or as binder components for print varnishes and printing inks.

lo 2. DescriptionofRelatedArt Ecologically advantageous, water-based printing inks which are currently employed in industry have the disadvantage that printed products produced therewith, unlike conventional solvent-cont~ining systems, are not deinkable given the current state of the art. For this reason, it is desirable to employ binders which offer not only printability under high-speed conditions but also offer an acceptable quality of the recovered pulp on deinking.
For this purpose, cationic or nonionic, water-dilutable polymers are preferably suitable. For instance, DE-A 41 15 731 and DE 42 31 566 describe aqueous ir~ compositions of preferred deinkability, which they achieve owing to the partial use of cornmercially available acrylic resins of this kind. Cationic binders also are described in U.S. Patent No. 4,554,212. The aqueous phase of these cathodically depositable coating compositions comprises cationic polymers which are produced by polymerization of ethylenically lln.c~lrated compounds in the presence of cationic polymers. These binders, however, are unsuitable for use in the printing sector, since it is imposible with polymers of such flexibility to achieve either adequate drying speeds or tack-free prints.
Furthermore, these systems are also disadvantageous from an ecological standpoint since they contain considerable quantities of organic solvents.

EP-A 0 622 385 and EP Application No. 94116608.4 also relate to binders which are dilutable in water following protonation with acid. As binder for printing inks, however, the cationic polymers described therein are in need of further improvement with respect to their wetting capacity for pigments and their absorption capacity for further nonpolar polymers.
Thus, there exists a need to develop synthetic-resin systems, based on cationic polymer mixtures, which are dilutable in water in the presence of an acid, and which have not only good deinkability but also an improved wetting capacity for pigments. There also exists a need to develop synthetic-resin systems that have a heightened absorption capacity for further nonpolar polymers.

SUMMAR Y OF THE INVENTION
It is therefore an object of the present invention to provide synthetic-resin systems which are based on cationic polymer mixtures and are dilutable in water in the presence of acid, and which have not only good deinkability but also an improved wetting capacity for pigments and a heightened absorption capacity for further nonpolar polymers. It is an additional object of the present invention to provide methods of m~king the aforementioned synthetic-resin systems, as well as provide methods of using these resin systems.
In accordance with these objectives, there is provided an at least bimodal synthetic-resin mixture and a method of producing such a resin mixture from an amino-cont~ining polymer A and from a nonionic, water-dilutable polymer B, which mixture can be introduced into water which has been provided with a neutralizing agent. Nonpolar monomers can be added to this synthetic-resin mixture to produce a polymer C in the form of latex particles.
The present invention therefore provides emulsifier- and solvent-free multimodal synthetic-resin systems which comprise at least one amino-co~ g polymer A and at least one nonionic water-dilutable polymer B and, if desired, a water-insoluble polymer C in the form of latex particles, which can be prepared by emulsion polymerization of ethylenically lln.~turated compounds in the presence of a mixture of the polymers A and B.
In accordance with an additional object of the present invention, there is provided a method of m~kin~ an emulsifier- and solvent-free multimodal synthetic-resin system compriC~in~ first preparing at least one amino-cont~iningpolymer A and at least one nonionic, water-dilutable polymer B, and then combining A and B. Polymers A and B can be neutralized or partially neutralized in water, if desired. After mixing polymers A and B together, the method also comprises preparing a water-insoluble polymer C in the form of latex particles by emulsion polymerization of ethylenically unsaturated com-pounds in the presence of the polymers A and B.
These and other objects of the invention will be readily apparent to those skilled in the art upon review of the detailed description which follows.

DETAILED DESCRIPTION OFPREFERRED EMBODIMENTS
Throughout this description, the expression "cationic polymers A"
denotes amino-co~ polymers whose amino groups can be converted, by the use of quaterni7.ing agents or by neutralization with acid, at least partially to cationic groups. Throughout this description, the term "nonionic, water-dilutable polymers B" refers to polymers which comprise a nonionic hydrophilic substructure. The expression "emulsifier-free," as it is used in thecontext of the present invention, denotes a resin system that contains subst~nti~lly no em~ ifiers or emulsifying agents, preferably less than 1% and most preferably no emulsifier. The expression "solvent-free," as it is used in the context of the present invention, also denotes a resin system that contains substantially no solvent, preferably less than 1% of solvent and most preferablyno solvent, whereby solvent is not meant to include water in this context.
The terms "bimodal" and "multimodal" are used in this application to denote multiphase systems consisting of an aqueous phase and two (or more) non-aqueous, disperse phases which are made up of polymers that are not miscible or not completely miscible, giving rise to two (or more) disperse phases of different chemical compositions.

The mean molar mass (weight-average) of the amino-cont~ining polymer A and nonionic, water-dilutable polymer B usually is any molar mass that enables their mixture and subsequent addition to water cont~ining a neutralizing agent. Preferably, the mean molar mass (weight-average) of the amino-containing polymer A is in the range between 3000 and 50,000, in particular from 4000 to 25,000, particularly preferably from 6000 to 10,000.
The mean molar mass (weight-average) of the polymer B preferably is in the range from 400 to 5000, and more preferably in the range of from 1000 to 4000.
. The synthetic-resin systems according to the invention contain the polymers A and B preferably in any weight ratio sufficient to enable their mixture and subsequent addition to water cont~ining a neutralizing agent.
Preferably, the weight ratio of polymers A to B is from 95: 5 to 5: 95, more preferably from 85: 15 to 15: 85, and most preferably in particular from 75: 25 to 25: 75. The glass transition temperature of the resin mixture preferably is at least 25 C, in particular at least 45 C, particularly preferably at least 65C.
The cationic polymers A according to the present invention preferably are reaction products of at least one compound from each of the groups (a) epoxides, carbonates or epoxide-carbonates, (b) amines, and (c) phenols.
Specifically, group (a) can include resins (al) cont~ining epoxide groups, preferably having terminal epoxide groups, andlor resins (a2) cont~ining carbonate groups, preferably having tennin~l carbonate groups, group (c) can include polyglycidyl ethers, polyglycidyl esters and polyglycidyl amines with mono- andlor polyhydric phenols (c) andlor alcohols, and group (b) can include saturated andlor unsaturated secondary andlor primary amines (b) or amino alcohols. The latter (group (b)) can be modified on the aL~yl radical by at least one primary andlor secondary hydroxyl group, by a diaL~ylamino group andlor by a primary amino group which is temporarily protected by ketimine formation.
The epoxide compounds (al) employed in accordance with the present invention can possess on average at least one, preferably two, 1,2-epoxide groups per molecule. They can be either saturated or lm~ rated and aliphatic, cycloaliphatic, aromatic or heterocyclic and may also contain hydroxyl groups.
In addition, they can comprise substituents which do not give rise to any disrupting secondary reactions under the conditions of mixin~ or reaction, examples of such substituents being aLkyl, aryl, alkyl/aryl, ether groups or thelike. Examples of useful epoxide compounds (al) include glycidyl ethers of polyhydric phenols, for example resorcinol, hydroquinone, 4,4'-dihydroxydiphenylmethane, isomer ~ es of dihydroxydiphenylmethane (bisphenol F), 4,4'-dihydroxy-3,3'-dimethyldiphenylmethane, 4,4'-dihydroxy-diphenyldimethylmethane (bisphenol A), 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylcyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenylpropane, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl sulfone, tris(4-hydroxy-phenyl)methane, 4,4'-dihydroxybenzophenone, 1,1-bis(4-hydroxy-phenyl)isobutane, 2,2-bis(4-hydroxy-tert-butylphenyl)propane, bis(2-hydroxynaphthyl)methane, 1,5-dihydroxynaphthalene, bis(4-hydroxyphenyl) ether or the hydrogenation, chlorination and bromination products of the abovementioned compounds, and also novolaks. The partial use of glycidyl ethers of polyhydric alcohols as compounds (al) is also suitable in accordance with the present invention. Examples of such polyhydric alcohols which may be used in the invention include ethylene glycol, diethylene glycol, triethyleneglycol, 1,2-propylene glycol, 1,4-propylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, glycerol, trimethylolpropane and 2,2-bis(4-hydroxycyclohexyl)propane .
The term "glycidyl ethers" as it is used in the context of this invention, preferably dentoes glycidyl ethers of the formula I

217513~

CH2 -/CR' R2 (-O-R-O-CH2-CR' -R2)n-O-R-O-R2-C\' - CH2 O OH O
- Formula I

where R=

k~ ~

Rl, Rl, Rl~ = independently of one another H or CmH2m+l, R2 = linear or branched saturated hydrocarbon radical having up to 8 carbon atoms, preferably -CH2-, R3, R3 = in each case independently of one another, halogen, aryl, alkyl, aralkyl, n = an integer from 0 to 8, preferably 1 to 6, m = an integer from 1 to 8, preferably 1, u, u' = independently of one another, an integer from 0 to 4, preferably 0 or 1.

- These particular pl~felled polyglycidyl ethers possess a mean molecularmass (Mn) of from about 200 to about 10,000 and an epoxide equivalent weight of from about 120 to about 5000. Such resins typically are prepared by reacting epichlorohydrin or methylepichlorohydrin with dihydroxy-diphenylmethane (bisphenol F) or dihydroxydiphenylpropane (bisphenol A), and with dihydroxybenzophenone or dihydroxynaphthalene. Polyepoxides of suitable molar mass can be prepared either by selecting the molar ratios of bisphenol and epichlorohydrin or by reacting the monomeric diglycidyl compounds with further bisphenol, with or without the addition of catalysts such as Lewis acids or phosphonium salts. The epoxy resins can be 217513~

completely or partially hydrogenated or can be employed in mixtures of different structure and molecular mass.
Furthermore, part ofthe polyglycidyl ether described can be replaced by aliphatic polyglycidyl ethers of the formula II
-/o\ /o\
CH2 - CH - CH2 [-o-(CHR4)V~w - O- CH2 - CH - CH2 Formula II

where R4 = H or a substituted or unsubstituted (C,-C4)-aL~yl radical, v = an integer of from 2 to 6 and w = an integer from 2 to 100, preferably 3 to 50.

Examples of useful compounds of Formula II include bisglycidyl ethers of polypropylene glycol or polybutylene glycol of various molar masses. The epoxy resins can also be modified by reaction with long-chain polyalcohols such as 1,6-hexanediol, neopentylglycol, bisethoxylated neopentylglycol, neopentylglycol hydroxypivalate and bis(hydroxymethyl)cyclohexane, monoanhydropentaerythritol and polytetrahydrofurandiol, polycapro-lactonediol, polycaprolactamdiol or polybutadienediol in the presence of suitable basic or acidic catalysts, such as boron fluoride-amine complexes.
Whereas polyalcohols with primary hydroxyl groups can be reacted directly with polyglycidyl ethers given appropriate catalysis, secondary hydroxyl groups can be reacted first of all with diisocyanate. The resulting isocyanate-termin~ted reaction product can then be incorporated without problems as a bridge between two polyglycidyl ether units with an increase in the molar mass and in the functionality.

Further suitable epoxide compounds include (poly)glycidyl esters of the formula III

Rs(-c-ocH2-c\H-lcH2)p O O
Formula III

where S R5 = linear or branched, saturated or unsaturated hydrocarbon radical having up to 40, preferably up to l0, carbon atoms or a substituted or unsubstituted phenyl radical and p = an integer of from 1 to 5, preferably 2 or 3, especially 2.

0 These polyglycidyl esters of polycarboxylic acids can be obtained by reacting epichlorohydrin or similar epoxy compounds with an aliphatic, cycloaliphatic or aromatic polycarboxylic acid, such as oxalic acid, adipic acid, glutaric acid, terephthalic acid, hexahydrophthalic acid, 2,6-naphthalenedicarboxylic and dimerized fatty acids. Examples thereof include diglycidyl terephth~l~te and diglycidyl hexahydrophth~l~te. Those skilled in the art are capable of synthesizing a polyglycidyl ether and/or a polyglycidyl ester for use in the present invention using the guidelines provided herein.
Other compounds suitable as resins (al) which contain epoxide groups include those in which some of the epoxide groups are reacted with amines.
Such amino-epoxy resins can also be modified further with saturated or unsaturated polycarboxylic acids and/or hydroxyalkylcarboxylic acids in order to reduce the amine number. Examples of aliphatic, cycloaliphatic and/or aromatic polycarboxylic acids of various chain lengths are adipic acid, sebacic acid, fumaric acid and maleic acid and their anhydrides, isophthalic acid and dimeric fatty acid. Lactic acid, dimethylolpropionic acid or else carboxyl- and hydroxyl-containing polyesters are understood as hydroxyaLkylcarboxylic acids. In the reaction of excess polyglycidyl ether of low molar mass with polycarboxylic acids and/or polyalcohols, the intermediates obtained can be 2175~8 g modified polyglycidyl ethers which are able then to react further with amines and/or amino alcohols.
It also is possible to use heterocyclic polyepoxide compounds, such as 1,3-diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate or diepoxides of bisimides in accordance with the invention described herein. Another suitable class of polyepoxides is that comprising polyglycidyl ethers of phenolic novolak resins, with which the functionality can be raised from 2 to about 6 glycidyl groups per molecule. By defunction~ tion with long-chain aLkylphenols such as dodecylphenol, it is possible to incorporate additional substructures.
Other suitable epoxide compounds are described in the handbook "Epoxidverbindungen und Epoxidharze" [Epoxide compounds and epoxy resins] by A.M. Paquin, Springer Verlag, Berlin 1958, Chapter IV; in Lee, Neville "Handbook of Epoxy Resins" 1967, Chapter 2; and in Wagner/Sarx "T ~ckklln~tharze" [Synthetic resins for coatings], Carl Hanser Verlag (1971) p 174 ff.
As carbonates (a2), it is possible to employ any desired materials provided they contain at least one, preferably two or three, 2-oxo-1,3-dioxolane groups (cyclic carbonate groups) per molecule and have no other functional groups which disrupt the reaction with component b. The molar mass Mn (number-average, determined by gel chromatography using polystyrenes as standard) should in general be between about 100 and 10,000, preferably between about 150 and 5000 and the 2-oxo- 1,3-dioxolane equivalent weight should be between about 100 and 1500. The cyclic carbonate groups are preferably terminal, but the compounds used as component (a2) can also contain these groups in random distribution along the molecular chain. The compounds useful as component (a2) can be prepared by copolymerization using olefinically unsaturated compounds which comprise these cyclic carbonate groups. For example, a preparation process of this kind is described in DE-A 3 644 373.

217~138 The carbonate component (a2) preferably has the formula IV
(I H2 - CIH - CH2-)~R6 O\ /o Formula IV

where R6 = a z-valent radical of a phenol, polyether, polyetherpolyol, polyester, polyesterpolyol, which can if desired also comprise amino or aL~ylamino groups; or a z-valent hydrocarbon radical, preferably an aL~ylene radical having 2 to 18 carbon atoms, which can if desired carry inert groups; or a z-valent poly(secondary)amine radical; or a z-valent radical of a reaction product of an epoxy-carbonate com-pound with polyamines, polyols, polycaprolactonepolyols, hydroxyl-cont~ining polyesters, polyethers, polyglycols, hydroxy-, carboxy- and amino-functional polymer oils having mean molar masses of from 800 to 10,000, polycarboxylic acids, hydroxy- or amino-functional polytetrahydrofurans and reaction products of polyamines with glycidyl esters of oc,~-dialkylaL~anemono-carboxylic acids ofthe empirical formula Cl2H22O3 to C14H26O3, for example of Versatic acid (Shell Chemie, ~-branched mono-carboxylic acid having 9 to 12 carbon atoms); and z = an integer of from 1 to 5, preferably 2 or 3, especially 2.

Such compounds and their preparation are described, for example, in DE-A 37 26 497.

In some cases it may be expedient to use, as additional or, if desired, sole component (a), mixed epoxide-carbonates of the formula V
(Cl H2 - CIH-CH2-)" R~(- CH2 - CH - CH2)y O O
lC
Formula V

where R6'- = an (x+y)-valent radical of a phenol, polyether, polyetherpolyol, polyester, polyesterpolyol, which can if desired also contain amino or aL~ylamino groups; or an (x+y)-valent h~ydrocarbon radical, preferably an alkylene radical having 2 to 18 carbon atoms, which can if desired carry inert lo groups; or an (x+y)-valent poly(secondary)amine radical; or an (x+y)-valent radical of a reaction product of an epoxy-carbonate compound with polyamines, polyols, polycaprolactonepolyols, hydroxyl-cont~ining polyesters, polyethers, polyglycols, hydroxy-, carboxy- and amino-functional polymer oils having mean molar masses of from 800 to 10,000, polycarboxylic acids, hydroxy- or amino-functional polytetrahydrofurans and reaction products of polyamines with glycidyl esters of a,~-diaL~yl-alkanemonocarboxylic acids of the empirical formula Cl2H22O3 to Cl4H26O3, for example of Versatic acid; and x,y = independently of one another, an integer of from 1 to 5, preferably 2 or 3, especially 1.

Preferred stalting materials for preparing cyclic carbonates and the mixed epoxy-carbonate compounds which are employed in the present invention, if desired, include the polyglycidyl ethers of polyhydric phenols andalcohols, for example bisphenol A or bisphenol F. The glycidyl ethers, for 21751~8 example, can be obtained by reacting a polyphenol with epichlorohydrin.
Examples of polyphenols useful in accordance with the present invention include 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 4,4'-dihydroxybenzophenone, bis(4-hydroxyphenyl) ether, 1,1-bis(4-fiydroxyphenyl)isobutane, bis(2-hydroxynaphthyl)methane, and 1,5-dihydroxynaphthalene. Preferably, free hydroxyl groups are present in addition to the epoxide groups in the polyglycidyl ether of the polyphenol.
Diglycidyl adducts of cyclic ureas can also be employed.
As amines (b), it is possible to use primary monoamines, preferably c~ g alkyl and alkanol groups, examples being methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, 2-aminobutane, 4-amino-2-butanol, isoamylamine, pentylamine, 3-methylbutylamine, heptyl~mine, octylamine, 2-ethylhexylamine, isononylamine, isotridecylamine, 2-aminomethyl- 1 -propanol, monoethanolamine, mono(n- or iso)propanolamine, neopentanolamine, methoxypropylamine, 2-(2-aminoethoxy)ethanol, coconut fatty amine, oleylamine, stearylamine, tallow fatty amine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, cyclopentylamine, cyclohexylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-butoxypropylamine, 3-isononyloxypropylamine, 3-aminopropyltrimethoxy(ethoxytridecyloxy)silane, and 2-amino-2-hydroxy-methyl- 1 ,3-propanediol.
It also is possible to use secondary monoamines, preferably diaL~cyl-amines, monoalkylhydroxyalkylamines or dihydroxyalkylamines. Examples of such compounds include dimethylamine, diethylamine, dipropylamine, di(n- or iso)propylamine, dibutylamine, diisobutylamine, di-sec-butylamine, N-methylbutylamine, N-methylaminoethanol, diethanolamine, dipentylamine, dioctylamine, di(2-ethylhexyl)amine, diisononylamine, N-ethylbutylamine, N-ethylcyclohexylamine, dicyclohexylamine, distearylamine, dicocol~ llline, ditallow fatty amine or else cyclic amines, such as morpholine, pyrrolidine or oxazolidine or substituted or unsubstituted aniline. Reaction products of primary monoamines with monoepoxides can also be used as a substitute for the secondary amines.

217~138 Furthermore, it is possible to employ primary amines of the formula VI

H2N-CR7R8-R9-0-(CHRI0-CHRIlO-)qRl2 Formula VI

where R7 and R8 = hydrogen, an alkyl radical or a hydroxyl group, R9 = a linear or branched aL~yl radical, in particular an alkyl radical having 1 to 3 carbon atoms, Rl and Rll = hydrogen or an aL~yl radical having 1 to 4 carbon atoms, Rl2 = hydrogen, an alkyl, cycloalkyl or phenyl radical, preferably an alkyl radical having 1 to 6 carbon atoms, and q = an integer of from 0 to 5.

Examples of compounds of this type which can be employed in accordance with the present invention include ethanolamine, propanolamine, butanolamine, ethylene glycol 2-aminoethyl ether and diethylene glycol mono(3-aminopropyl) ether. When primaTy amines are used, the amine should be capable of reacting with the epoxide group, depending on the stoichiometric conditions available, with molecular enlargement. Examples of diamines which may be useful in the invention include (~Jeffamin M series, ~)Jeffamin D series, ~)Jeffamin ED series (Texaco). Also suitable are di- or triamines with primary and/or secondaIy amino groups, for example laurylpropyldiamine and tallow fatty propylenediamine.
In accordance with the present invention, polyamines (b) are understood to be compounds which contain at least two amino groups in the molecule.
These compounds in general possess from 2 to 50 carbon atoms, and preferably from 2 to 20 carbon atoms. Examples of suitable polyamines (b) are those which contain only primary amino groups and are preferably diprimary.
These polyamines are preferably employed as a blend with primary/tertiary dlammes.

217~138 Examples of other suitable polyamines (b) are those which contain only secondary amino groups and are preferably disecondary. Preference usually is given to long-chain diamines, for example N,N'-diaL~cyldiaminoaL~anes or reaction products of monoepoxides, for example saturated glycidyl ethers or glycidyl esters, or epoxyalkanes with primary diaminoalkanes, for example, the addition product of 1,6-hexanediamine with 2 mol of the glycidyl ester of Versatic acid. Other monoepoxides which can be employed for this purpose include sa~ d or unsaturated glycidyl ethers or a-epoxides of various chain lengths, such as 1,2-epoxydodecane or butylene oxide.
. Further suitable polyamines (b) useful in the present invention include polyamines which contain at least one free primary amino group and, in addition, secondary and/or tertiary amino groups. These polyamines (b) can be represented for example by the formula VII below.
R1~
H2N - (R'3N),- R"
Formula VII

1 5 where s = zero or an integer from 1 to 6, preferably 1 to 4, - Rl3= a divalent, preferably nonaromatic hydrocarbon radical having 2 to 18 carbon atoms, preferably a branched or unbranched aL~ylene radical having 2 to 10 carbon atoms, in particular 2 to 6 carbon atoms, or a cycloaL~ylene radical having 5 to 12 carbon atoms, preferably 6 to 10 carbon atoms, or an araL~ylene radical having 7 to 12 carbon atoms, preferably 8 to 10 carbon atoms, or a polyoxalkylene radical having 2 to 18 carbon atoms, 217513~

Rl4, Rl4 = independently of one another H or ~ s R~6 N

Rl5, Rl5 = H, (C,-C20)-aL~cyl, preferably (Cl-C6)-aL~yl, (Cl-CI6)-hydroxyaL~cyl, preferably . -CH2-CH-R"
OH

Rl6 = independently of R'3 the definition given for Rl3, R'7 = (C,-C,2)-alkyl,-CH2-O-(CI-C,2)-aL~yl,-CH2-O-aryl, CH2-O-C-(C,-C~J-alkyl or -CH2- ICH-CN, Rl8 = H or (C,-C6)-aL~yl, or Rl5 and Rl6 = part of a 5-, 6- or 7-membered aliphatic ring, with the proviso that if s is zero, Rl4 is not H.

Other suitable polyamines in this context are those of the formula VIII.

X-(RI9NH)t-R20-Y Formula VIII

in which X and Y are NH2 or OH, but are not both the same, and Rl9 and R20, independently of one another, are as defined for Rl3 in formula VII above, and t is as defined for s in forrnula VII above.

In addition, examples of other suitable polyamines and polyaminopolyols useful in the present invention include those described in the Patent Applications DE-A 36 44 371, DE-A 37 26 497 and DE-A 38 09 695.

217~1~8 Reference is hereby made to these publications, including the preferred embodiments described therein. Also suitable are polyaminoamides or condensation products of diprimary amines with dicarboxylic acids, for example adipic acid or dimeric fatty acids, and also polyglycol polyamines or amine adducts, for example amine-epoxy resin adducts.
Examples of suitable polyamines (b) are ethylene~ mine, propyleneAi~mine, 2-methylpentamethylenediamine, pentamethylenediamine, hexamethylene~ mine, trimethylhexamethylene~ mine, neopentyldiamine, octamethylenediamine, triacetonediamine, dioxadecanediamine, dioxado-dec~nediamine and higher homologs, cycloaliphatic diamines such as 1,2-, 1,3-Qr 1,4-cyclohexanediamine, and also laurylpropylenediamine and tallowfattypropylenediamine, 4,4'-methylenebiscyclohexylamine, 4,4'-isopropylenebiscyclohexylamine, isophoronediamine, tricyclododecenyl-diamine, menthanediamine, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 3 -aminomethyl- 1-(3 -aminopropyl- 1 -methyl)-4-methylcyclohexane, N-methyl-ethylenediamine, N-aminoethylpiperazine, 2-aminoethylpiperazine, N,N-dimethylethylenediamine, N,N-dimethylpropylene~ mine, N,N-dimethylaminopropylamine, N,N-bisaminopropyl-N,N'-dimethylaminopropyl-amine, N,N-dihydroxyethylenediamine, aromatic amines such as m-xylylene(li~mine, aliphatic poly(tri-, tetra-)amines such as diethylenetriamine,dipropylenetriamine, bishexamethylenetriamine, triethylenetramine, tetraethylenepe~ "lil~e, pentaethylenehexamine, methyliminobispropylamine, N-aLkylaminodipropylenetriamines (alkyl = CH3-, C4Hg-, (CH3)2N(CH2)3-), tetrapropylenepent:~mine, and also alkanolamines such as aminoethylethanol-amine, N-(2-hydroxypropyl)ethylenediamine, ethylene glycol bispropylamine, hydroxyethylaminoethylamine, hydroxyethyldiethylenetriamine, and polyoxypropylenediamine, preferably with a mean molar mass of from about 200 to 400. Prefered polyarnines are N,N-bisaminopropyl-N-methylamine, N-aminopropyl~nethylamine, N-aminopropylpropylamine, tallowfattypropy-lenediamine and, in particular, dimethylarninopropylarnine, and also die~yl aminopropylamine and N-cyclohexyl- 1,3-propylenediamine, 3-dimethyl-aminopropylamine,2-diethylaminoethyl~mine~nddimethylaminoneopentylamine.

Useful phenols (c) in the present invention include, either individually or as a mixture, phenol, m-cresol, 3,5-dimethylphenol, m-ethoxyphenol, p-hydroxybenzylphenol, and o-hydroxybenzylphenol. It is preferred to employ phenols (c) which contain at least two phenolic hydroxy functions, examples being resorcinol, hydroquinone, 4,4'-dihydroxydiphenylmethane, isomer mixtures of dihydroxydiphenylmethane (bisphenol F), 4,4'-dihydroxy-3,3'-dimethyldiphenylmethane, 4,4'-dihydroxydiphenyldimethylmethane (bisphenol A), 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylcyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenylpropane, 1,2-, 1,3-, 1,5-, 1,6-, 2,2'- and 4,4'-dihydroxybiphenyl, 4,4'-, 2,5'- and 3,3'-dihydroxy-2,2'-bipyridyl, 4,4'-dihydroxydiphenyl sulfone, 4,4'-bis(4-hydroxyphenyl)valeric acid and its amide, bis(4-hydroxyphenyl)~sulfide, 2,2-bis(4-hydroxyphenyl)acetic acid and its amide, tris(4-hydroxyphenyl)methane, 4,4'-dihydroxybenzophenone, 1,1-bis(4-hydroxyphenyl)isobutane, 2,2-bis(4-hydroxy-tert-butylphenyl)propane, bis(2-hydroxynaphthyl)methane, 1,5-dihydroxynaphthalene and bis(4-hydroxyphenyl) ether or the hydrogenation, chlorination and bromination products of the abovementioned compounds, and also novolaks. Resorcinol, bisphenol A and bisphenol F are particularly prefered for use as phenol (c) in the present invention.
The phenols used as phenols (c) are, in particular, alkylated, arylated or alkarylated, mono- and!or polyhydric phenols which if desired are isomerized.
In this context, alkylation, arylation or aralkylation refers to the electrophilic substitution on aromatic nuclei of phenol parent structures with unsaturated compounds. The phenols (c) can be characterized in particular by the for-mulae IX below:

-~/(~H)d, HO~

~1~,e Formula IX

where R2l= (C2-CI8)-aLkyl, preferably (C2-C4)-aL~cyl, (C5-C6)-cycloaLkyl, phenyl, phenyl substituted with at least one (Cl-CI8)-aLkyl radical, (C2-CIg)-aLkyl substituted with at least one phenyl radical, d = an integer from O to 4, preferably 1 or 2, and e = an integer from 1 to 5, the value of e being less than or equal to the difference of 5 minus d, or formula X

(HO), ~JJ K ~J (OH)f. FormulaX
-- -- h where f = 1 or2, g = an integer of from 1 to 4, g' = an integer of from O to 4, h = an integer of from 1 or 2, - 217~i138 M = =CH- or a heteroatom, preferably a nitrogen atom, R22 = the same definition as R2' in Formula IX above, R22 = H or the same definition as R2l in Formula IX above, K = a single bond, CH2, C(CH3)2, S(O), S, S-S, C(O) or a group of - the formula XI

- ICI(- - IH
O = C - L or CH2CH2 - C - L Formula XI

L = a hydroxyl group, -NH-(CH2)l-N\

or a group of the formula XII

R2~ R24~
C . ' D25 N (G~J2)i--N=¢
(C~2)j R2s Formula XII

where lS R23, R24, R25 R23~ R24 R25~= independently of one another, are hydrogen or (Cl-C4)-alkyl;
i, j = independently of one another, are inte-gers from 1 to 4, preferably 2 or 3.

217~ t38 For the preparation of the aL~ylated, arylated or alkarylated phenols (c) which can be employed with preference in accordance with the invention, phenolic parent structures which can be employed are mono- or polynuclear phenols, for example phenol itself. Preferably, phenolic parent structures which carry two or more hydroxyl groups on the same aromatic ring can be used, examples including phloroglucinol, pyrogallol, hydroquinone, pyrocatechol, and especially resorcinol.
Suitable phenolic parent structures are also phenols based on condensed aromatic ring systems. The latter are described, for example, by the formu-0 la ~III:
~ '' .
(HO)k ~ (OH)I
Formula XIII

or formula XIV

)k = (OHJI
Formula XIV

where k = an integer of from 0 to 2, 1 = an integer of from 1 to 3, preferably 1 or 2, whereby the sum of k and 1 is at least 2, and Z = =CH-, >C=O, an oxygen atom or a nitrogen atom.

Examples of these phenolic parent structures include 1,4-dihydroxy-naphthalene and its positional isomers, dihydroxyanthraquinone, quinizarine and anthraflavic acid. In addition, phenols (c) can also be used in turn as phenolic parent structures for preparing further compounds (c).

217~138 The mono(alkylaryl)phenols which are preferably used in the present invention as phenols (c~ are compounds known per se which are also frequently referred to in the lilela~ e as styrenized phenols. According to the statements in Austrian Patent AT-C 284 444, the reactions of styrenes with phenols are known and are essentially aLkylation reactions in which the vinyl group of the styrene adds onto the phenol in the position ortho or para to the hydroxyl group. This reaction is generally carried out using Fliedel-Crafts catalysts, for example acids and Lewis acids. Depending on the reaction conditions, catalysts and proportions of the reactants, the reaction produces mono-, di- or tri-styrenized phenols. German Laid-Open Specification DE-A
19 40 220 also discloses arylaLkylphenol products and processes for their preparation which can be used in the present invention.
Particularly prefered arylalkylphenols (c) can be prepared by subjecting phenols to an addition reaction with a vinyl compound, at a molar ratio of the phenolic hydroxyl groups in the phenol to the aromatic vinyl compound of from 1:1 to 1:2, in a known m~nner, in the presence of mineral acid or Friedel-Crafts catalysts. Vinyl compounds which can be used include natural or syn-thetic compounds containing one or more carbon-carbon double bonds. If more than one carbon-carbon double bond is present, conjugated double bonds may be present.
Natural unsaturated compounds which can be used include unsaturated fatty acids, the fatty oils derived therefrom, fatty acid amides or fatty alcohols.
Further suitable starting compounds are unsaturated natural substances based on terpene, for example, telpentine oil and rosin. Synthetic un~atllrated hydrocarbon compounds which can be used are aLkenes, dienes or higher unsaturated hydrocarbons, for example butene, isobutene, isooctene, isononene, isododecene, or diun~ahlrated compounds, for example butadiene, isoprene, chloroprene, dichlorobutadiene and dicyclopentadiene. It also is possible to use mixtures of aL~enes and, if desired, of aL~enes with aLIcanes, as are produced for example in the cracking or dehydrogenation of hydrocarbons, for example petroleum, or oligomerization of olefins, especially isobutylene, propylene or n-butene or from the oxidation of coal. Also suitable are 2 1 7 ~ 1 3 8 acetylenically unsaturated compounds, for example acetylene or (Cl-C1O)-alkyl-or di-(C,-C10)-alkylacetylenes.
Examples of unsaturated compounds which can be used as starting m~t~ for the preparation of compounds (c) are the following: n-pent-l-ene, n-hex-l-ene, n-oct-l-ene, n-non-l-ene, n-dec-l-ene, n-undec-l-ene, n-dodec-l-ene, l-propylene, n-but- l-ene, the abovementioned aL~enes which are substituted in position 2 or 3 or, if desired, 4 by the methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl group, 2,3-dimethyl-n-butene, 3,3-dimethyl-n-butene, 2,5-dimethylheptene, 3,3-dimethylheptene, 2,3,4-trimethylheptene, 2,4-dimethylheptene, 2,3-dimethylheptene, 4,4-dimethylheptene, 2,3-diethylhexene, 4,4-dimethylhexene, 2,3-dimethylhexene, 2,4-dimethylhexene, 2,5-dimethylhexene, 3,3-dimethylhexene, 3,4-dimethylhexene, 2-methyl-3-ethylpentene, 3-methyl-3-ethylpentene, 2,3,3-trimethylheptene, 2,4,4-trimethylpentene, 2,3,3-trimethylpentene, 2,3,4-trimethylpentene, 2,3,3,4-tetramethylpentene; analogous alkenes whose double bond is in position 2 or 3 in the molecule; branched alkenes as are obtained in the form of mixtures in the dimerization of isobutylene or n-butene (octenes) or trimerization of isobutylene or n-butene (dodecenes) or propylene (nonenes) or the tetramerization of propylene (dodecenes).
Suitable aromatic vinyl compounds include, in particular, styrene derivatives. Examples of useful styrene derivatives include oc-methylstyrene, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, commercial vinyltoluene (isomer mixture), 3,4-dimethylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, 3,4-diethylstyrene, 2,4-diethylstyrene, 2,5-diethylstyrene, 2,6-diethylstyrene, o-propylstyrene, m-propylstyrene, p-propylstyrene, o-isopropylstyrene, m-isopropylstyrene, p-isopropylstyrene, o-butylstyrene, m-butylstyrene, p-butylstyrene, o-isobutylstyrene, m-isobutylstyrene, p-isobutylstyrene, sec-butylstyrene, m-sec-butylstyrene, p-sec-butylstyrene, o-tert-butylstyrene, m-tert-butylstyrene, p-tert-butylstyrene, p-bromostyrene, p-chlorostyrene, 2,4-dibromostyrene, 2,4-dichlorostyrene and 2,4,6-trichlorostyrene .

217~138 Particular prere,ellce is given to the use as vinyl compounds of aromatic vinyl compounds of the formula XV

- -2~--R25 Formula XV

in which R26 is a hydrogen atom or a methyl radical and R27 is a hydrogen atom or an aLkyl radical having 1-3 carbon atoms or the radical - C = CH2 in which R28 independently can be the same as R26, for example styrene and a-methylstyrene.
The molar ratios between the compounds cont~ining epoxide, cyclic carbonate, amino and phenol groups, for the preparation of the polymers or polymer mixtures A from the components (a), (b) and (c), can be chosen so as to ensure the complete incorporation of the phenol, carbonate and epoxide groups. This reaction can be carried out in steps based on compounds (a) or else can be carned out in such a manner that, for example, compounds (b) - mixed with compounds (c) are reacted with the compounds (a). The reaction generally is continued until a constant, or the theoretical, amine number has been reached. Reactions of compounds (a), (b) and (c) in the required stoichiometric proportions usually are carried out at elevated temperatures, forexample, from about 40 to 300C, preferably from about 50 to 250C and, with particular preference, between about 80 and 200C, it being possible if desired to use solvents and/or catalysts. Care must be taken, however, to avoid gelling.
All of the amines can be reacted simlllt~neously with the epoxide groups and/or carbonate groups, or a stepwise procedure can be adopted. Thus, it is also possible to obtain mixtures of different epoxide-amine adducts and/or carbonate-amine adducts. Reaction with the amines typically begins at room 21751~8 temperature and is generally exothermic. In order to achieve complete reaction, it generally is necessary to increase the temperature temporarily to values of between about 40 and 250C. Whereas no catalyst is generally necessary for the reaction of primary amino groups with the 2-oxo-1,3-dioxolane groups, catalysis is expedient for the reaction of the relatively unreactive secondary amino groups. Suitable catalysts for this purpose include, for example, strongly basic compounds, such as qll~qt~ ry ammonium compounds, for example alkyl-, aryl- and/or benzylammonium hydroxides and carbonates. Specific representatives of qll~tçrn~ry ammonium compounds in this context are (Cl6-C22)-aL~ylbenzyldimethylammonium hydroxide, benzyltrimethylammonium hydroxide and tetrabutylammonium hydroxide. Preferred catalysts are strongly basic amines, for example diazabicyclooctane (DABCO) and guanidine. Also suitable in this context are so-called supranucleophilic catalysts, for example 4-pyrrolidinylpyridine and poly(N,N-dialkylaminopyridine) (cf. in this context the article by R.A. Vaidya et al. in Polymer Pleplillls, Vol. 2 (1986), pp. 101-102).
As an option, solvents can be added in order to prepare the resin systems according to the invention, these solvents being removed in vacuo after the end of the resin syntheses and being, for example, glycol ethers such as ethylene glycols, propylene glycols, butylene glycols, for example methylglycol, ethylglycol, butylglycol, methyldiglycol, ethyldiglycol, butyldiglycol, methyltriglycol, ethyltriglycol, butyltriglycol, methyltetraglycol, ethyltetraglycol, butyltetraglycol, (~3Polyglycol M 250 (Hoechst, MW: 260-275, OH number: 204-215), t~)Polyglycol M 350 (Hoechst, MW:335-265, OH
number: 154-167), 2-n-propoxyethanol, 2-(1-methylethoxy)ethanol, 2-n-butoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol, triethylene glycol monomethyl ether, tetraethylene glycolmonomethylether,2,5,8,11-tetraoxadodecane, 1-methoxy-2-propanol, l-ethoxy-2-propanol, tripropylene glycol monomethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, lliprol)ylene glycol methyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether and propylene glycol phenyl ether. Those skilled in the aTt are capable of synthesizing polymers A in accordance with theguidelines presented herein.
The polymers B comprise at least one hydrophilic substructure which is nonionic at the prevailing pH. Examples of such polymers B include adducts of hydroxy compounds with resins co~ g epoxide groups, preferably termin~l epoxide groups, from the classes of the polyglycidyl ethers and polyglycidyl esters. Resins co~ i"g epoxide groups which can be employed preferably include polymers cont~ining t~rmin~l epoxide groups, from the classes of the polyglycidyl ethers and polyglycidyl esters.
Useful hydroxy compounds include individual organic compounds or mixtures thereof, which contain at least one hydroxyl group. Preference typically is given to the use of mono-, bis- or tris-hydroxy compounds, especially monohydroxy compounds. Throughout this description, the term "monohydroxy compounds," is understood in accordance with the invention to include monoalcohols and mono-etherified polyaL~ylene oxide compounds.
Monoalcohols which can be employed are preferably those cont~ining alkane or cycloalkane radicals, especially (C8-C32) alcohols and isomers thereof, for example 2-ethylhexanol, octanol, nonanol, decanol, dodecanol, and also stearyl, cetyl, ceryl and myristyl alcohol, (~)TCD Alcohol M (Hoechst, MW:
166, OH number: 327), wool wax alcohols, cholesterols, borneols, isoborneols and tall oil fatty alcohols. The properties can also be modified, optionally, using (C,-C6) alcohols cont~ining alkane and cycloalkane chains in proportions of from 0 to 95 % by weight, based on the amount of monohydroxy compounds, examples of these alcohols being butanol, hexanol, cyclohexanol and/or mixtures thereof.
Mono-etherified polyalkylene oxide compounds which can be employed in the present invention preferably include compounds of the formula XVI
,.
R294O-CHR3-CHR3l) OH Formula XVI
In this formula, R29 is an aL~cyl, cycloaL~yl or phenyl radical, preferably an aLkyl radical having 1 to 12, especially 1 to 4, carbon atoms, R30 and R3' are 217Sl~S

hydrogen or alkyl radicals having 1 to 4 carbon atoms, and r is an integer from 1 to 10, preferably 1 to 4. Examples of such compounds which may be used in accordance with the present invention are methylglycol, ethylglycol, butylglycol, methyldiglycol, ethyldiglycol, butyldiglycol, methyltriglycol, ethyltriglycol, butyltriglycol, methyltetraglycol, ethyltetraglycol, butyl-tetraglycol, polyglycol M 250 (MW: 260-275, OH number: 204-215), polyglycol M 350 (MW: 335-265, OH number: 154-167), propylene glycol methyl ether, dipropylene glycol methyl ether, llipropylene glycol methyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, lli~opylene glycol n-butyl ether and propylene glycol phenyl ether.
The polymers B can be prepared in a manner known per se by reacting resins co"~i"i"g epoxide groups with hydroxyl compounds in the presence of catalysts such as, for example, Lewis acids (EP-A 0 272 595), imidazoles (Macromolecules, 1989, 22, 99), cyclic quaternary ammonium compounds (U.S. PatentNo. 5,019,639), tin compounds (EP-A 0 498 504) or aLkaline earth metal perchlorates (Polymer Bulletin 1989, ~, pp. 221-226).
The present invention additionally provides a process for the preparation of em~ ifier- and solvent-free multimodal synthetic-resin systems comprising polymers A and B, which comprises preparing at least one amino-Cont~ining polymer A and at least one nonionic water-dilutable polymer B
which are then, if desired, neutralized or partially neutralized in water.
Polymers A and B then can be combined and, if desired, a water-insoluble polymer C in the form of latex particles can be prepared by emulsion polymerization of ethylenically unsaturated compounds in the presence of the polymers A and B which have, if desired, been neutralized or partially neutral-ized. In a pl~relled variant of the aforementioned process, the amino-contain-ing polymer A can be prepared in the presence of at least one nonionic water-dilutable polymer B.
Suitable neutralizing agents for use in the present invention include organic acids, for example formic acid, dimethylolpropionic acid, acetic acid, glycolic acid, gluconic acid, hydroxyacetic acid, propionic acid, butyric acid, lactic acid, valelic acid, caproic acid, oenanthoic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid and stearic acid, preferably folmic acid, acetic acid and lactic acid. In addition, inorganic acids, for example, phosphoric acid, sulfuric acid, boric acid and hydrochloric acid can be used as neutralizing agents. The degree of neutralization should typically be between about 5 and 120 %, preferably between about 10 and 90 %, based on the amino groups present.
In accordance with the invention, the synthetic-resin ~ uleS contain not only polymer resins A and B but also, optionally, polymer resins C.
Polymer resins C can be prepared by emulsion polymerization in the presence of polymer resins A and at least partially neutralized polymer resins B. The resins A and B should be present in a quantity which is suitable for bringing about the desired emulsifying and stabilizing effects. In this context, both foreconomic reasons and for reasons of influencing the performance properties of the emulsion polymers to be prepared, for example water resistance, re-dissolvability and drying speed, the proportion of resins A and B should be neither too high nor too low. The content of the polymers A and B employed together preferably is, therefore, from about 4 to 40 % by weight, in particularfrom about 8 to 20 % by weight, based on the solids content of the dispersion comprising polymers A, B and C. Very good rheology-controlled (RC) dispersions are also obtained in this way if less than about 20 % by weight, preferably less than about 15 % by weight, of the sum of the resins A and B is employed, based on the sum of A, B and C. Those skilled in the art are capable of monitoring and modifying the content of polymers A, B and C in accordance with the guidelines provided herein.
Processes of emulsion polymerization are f~mili~r to the person skilled in the art. Customary features thereof usually incluce a free-radical polymerization of ethylenically unsaturated monomers in the aqueous phase in the presence of free-radical initiators and emulsifiers, protective colloids or other stabilizers. The components mentioned can be introduced into the emulsion polymerization in various ways. When polymer resins A according to the invention are used as stabilizers in emulsion polymerizations, the excellent emulsifying performance of these polymers makes it unnecessary to 217513~

use low molar mass surfactants and protective colloids. The major part of the aqueous phase usually is present as the initial charge, with the addition of part of the water during the reaction, in the form of a solution of free-radical initiator or of a monomer preemulsion, being a possibility. All or some of the S stabilizers can be included in the initial charge, and the rest metered in during the polymerization.
The monomers can all be present in the initial charge or can be metered in in pure form or as a pre-emulsion in water. Usually, some of the free-radical initiator is included in the initial charge and some is metered in as an0 aq ~eous solution. Those skilled in the art will recognize that the initial charge is that ~ e which is introduced into the reactor before the reaction temperature of, usually, from about 20 to 99C is established. The polymeri7~ion is in most cases initiated by thermal decomposition of the free-radical initiators or by means of redox systems and can be regarded as ended when the majority of the monomers which can be reacted by free-radical chain reaction have reacted (at between 20 and 99C). This procedure usually leaves about 0.001 to 0.1 % by weight of residual monomers. Further processes and process variants are set out in detail in, for example, Ullm~nn Enzyklopadie der technischen Chemie [Encyclopedia of industrial chemistry], 4th edition, Verlag Chemie, Weinheim (1980), Volume 19, pages 132 ff. and in Encyclopedia of Polymer Science and Engineering, Volume 6, Wiley & Sons, New York 1986, pages 1-51. Using the guidelines presented herein, those skilled in the art are capable of modifying various parameters of the aforementioned processes.
The polymer C of the dispersion can be produced by monomers 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 asolubility of less than 10 % by weight, in particular less than 5 % by weight, at 25 C. The proportion of monomers of low solubility typically should be at least sufficient to render the emulsion polymer formed insoluble in the aqueous phase under the polymerization conditions, and sufficient to make the emulsion polymer exist in the form of dispersed particles. Within the meaning of the 217513~

invention, it is preferred to use those mixtures of which at least 70 % by weight, and in particular at least 90 % by weight, are composed of monomers of low solubility.
Appropriate monomers useful in the present invention usually comprise at least one ethylenically unsaturated group. The terms ethylenically m~atllrated, vinylically lm~ rated and a,~-lln~lrated are used synonymously in the context of the present invention. Those skilled in the art are aware that such monomers can be combined to form polymers under the aforedescribed conditions of emulsion polymerization in an aqueous medium.
These monomers include, for example, vinyl compounds, styrenes and acrylates, and derivatives thereof. Examples of suitable vinyl compounds include vinyl chloride and vinyl esters, such as vinyl acetate, vinyl propionate, vinyl esters of Versatic acid, and also vinyl fatty acid esters, such as vinyl laurate. Suitable styrene compounds include styrene, vinyltoluene, a-methyl-styrene, ethylstyrene, isopropylstyrene, tert-butylstyrene, 2,4-dimethylstyrene,diethylstyrene, o-methyl-p-isopropylstyrene, halostyrene such as chlorostyrene, fluorostyrene and iodostyrene, 2,4-cyanostyrene, hydroxystyrene, nitrostyrene, aminostyrene and/or phenylstyrene. Particular preference is given to styrene, vinyltoluene and a-methylstyrene.
Examples of suitable acrylates include acrylic esters, methacrylic esters and crotonic esters, and esters cont~ining hydroxyl functions, such as hydroxyethyl acrylate and hydroxyethyl methacrylate. In the emulsion polymerization, it is possible to polymerize mixtures of these ethylenically unsaturated monomers, provided they are suitable for copolymerization. In 2s order to obtain dispersions having glass transition temperatures of above about 75C, polymerization preferably begins or is initiated from styrene or styrene derivatives and/or methacrylates.
Suitable initiators useful in the present invention include the customarily water-soluble radical-forming compounds, for example, hydrogen peroxide, peracetic acid, perbenzoic acid and perdisulfates, for example potassium or ammonium peroxodisulfate, perphosphates, peroxycarbonates and hydroperoxides, such as telt-butyl hydroperoxide. Examples of suitable redox catalyst systems include sodium persulfate/sodium formaldehyde-sulfoxylate, cumene hydroperoxide/sodium metabisulfite, hydrogen peroxide/ascorbic acid and sulfur dioxide/ammonium persulfate. Also suitable are azo compounds, such as 4,4-azobis(cyanopentanoic acid). The initiators usually are used in customary, catalytically active concentrations. These concentrations are in general between 0.01 and 4.0 % by weight, based on the dispersion.
In particular embodiments, further components can be used which are customary for emulsion polymerization. These include, for example, accelerators, buffers and any other constituents which can be used together lo with the polyrners according to the invention in the emulsion polymerization reaction mixture and are known from the prior art as it relates to emulsion polymerization processes.
The multimodal structure of the synthetic-resin systems according to the invention makes it possible in particular to obtain binders having the drying rate, water resistance and high pigment wetting capacity which are required for use in the printing sector. Using the resins according to the present invention (polymers A and B and optionally C), it is possible to prepare pigment pastes and gloss resin solutions. These resins together with the dispersions according to the invention (polymers A, B and C) exhibit outstanding technical printing properties, good stability on storage, good gloss and color strength, and outstanding deinkability. The invention also provides for the use of the novel synthetic-resin systems as grinding resins (polymers A and B) and dispersions (polymers A, B and C) for pigment pastes and as resins (polyrners A and B) and dispersions (polyrners A, B and C), as principal binders for water-based printing inks and print varnishes.
When the synthetic-resin systems according to the invention are used as resins in aqueous varnishes, the polymer mixtures serve preferably as components for the precision formulation of the aqueous print varnish systems, for example in gloss resins (polymers A and B) for overprint varnishes for pnnting paper, board, cardboard packaging and the like, for example with the inking unit of a sheet-fed or roller offset machine, from damping units, separate coating units of sheet-fed or roller offset printing machines, sheet coating machines, intaglio printing and flexographic printing machines. When the resin solutions according to the invention (polymers A and B) and dispersions according to the invention (polymers A, B and C) are used as binder vehicles for print varnishes and printing inks, their solids content typically is in general from about 20 to 75 % by weight, preferably from about 30 to 60 % by weight.
These varnishes and inks can contain from about 1 to 70 % by weight of dispersions according to the invention and/or from about 1 to 40 % by weight of solid resins according to the invention and from about 0 to 60 % by weight of glycols or glycol ethers, from about 0 to 30 % by weight of wetting agents, fiom about 0 to 35 % by weight of neutralizing agents (acids), from about 0 to 30 % by weight of natural andlor synthetic waxes, from about 0 to 2.5 % by weight of antifoams, from about 0 to 80 % by weight of water and from about 0 to 60 % by weight of pigments. In grinding operations, the pigmentlbinder ratio typically is between 5: 9S and 95: S, preferably from 30 : 70 to 70: 30. For use as pigment grinding components, solids contents of more than 30 % by weight are also expedient. For the composition of these stock inks, pigments and printing inks, it is also expedient to use mixtures of different types of dispersions or resin solutions.
Equipment which can be used to incorporate pigments (for example l~iulll dioxide, color pigmçnt~, synthetic carbon blacks), fillers (for example talc, China clay, waxes), dyes and flow-control agents in the solutions and/or dispersions and/or mixtures thereof and/or diluted formulations of the present invention, include the customary milling, mixing, kneading and dispersing equipment, optionally in the presence of customary dispersion auxiliaries.
The pigment pastes can in principle contain all pigments which are suitable for printing processes; polyether-coated pigments are preferred. In addition to the pigments, the pigment pastes can also comprise other customary additives, for example plasticizers, fillers and wetting agents.
The preparation of suitable resins which can be used in accordance with the present invention and the preparation of stable polymer dispersions by 21751~8 emulsion polymerization, and the use thereof in printing inks and print varnishes, is illustrated by the following examples.

EXAMPLES
s l~n the examples, parts and percentages are by weight unless stated otherwise.
All reactions are carried out under inert gas (N2).

Example 1: Epoxide/epoxide-amine system Commercial polyglycidyl ether based on bisphenol A having an epoxide equivalent weight of about 180-192 ((~)Beckopox EP 140, Hoechst AG, 59 g) was held at 150C with methyltetraglycol (Mw 208, boiling range 280-350C, 67 g) and commercial amine-boron trifluoride adducts (~Anchor 1040, Anchor, 250 mg). As soon as an epoxide number of < 4 was reached, commercial stearylamine (~)Gen~min SH 100, Hoechst AG, 27 g), dimethylaminopropylamine (21 g) and commercial bisphenol A (95 g) were added in succession to the resin composition, and then commercial polyglycidyl ether based on bisphenol A having an epoxide equivalent weight of about 180- 192 ((~)Beckopox EP 140, 231 g) was metered in slowly so that no gelling occured. A synthetic-resin system was obtained which had an amine number of 50, a Mw of 8500 and a glass transition temperature (Tg) of 46C.

Example 2:
Commercial polyglycidyl ether based on bisphenol A having an epoxide equivalent weight of about 180-192 ((~)Beckopox EP 140, 66 g) was held at 150C with methyltetraglycol (Mw 208, boiling range 280-350C, 28 g), butyldiglycol (29 g) and commercial amine-boron trifluoride adducts (~Anchor 1040 (500 mg)). As soon as an epoxide number of < 4 was reached, commercial stearylamine ((~Gen~min SH 100, Hoechst AG, 27 g), dimethyl-aminopropylamine (21 g) and commercial bisphenol A (95 g) were added in succession to the resin composition, and then commercial polyglycidyl ether based on bisphenol A having an epoxide equivalent weight of about 180-192 217513~

((g Beckopox EP 140, 231 g) was metered in. A synthetic-resin system was obtained which had an amine number of 64, a Mw of 8700 and a Tg of 48C.

Example 3:
~ Commercial polyglycidyl ether based on bisphenol A having an epoxide equivalent weight of about 180-192 (~)Beckopox EP 140, 67 g) was held at 150C with methyltetraglycol (Mw 208, boiling range 280-350C, 25 g), butyldiglycol (31 g) and commercial amine-boron trifluoride adducts (~Anchor 1040, 380 mg). As soon as an epoxide number of < 4 was reached, cyclohexylamine (10 g), dimethylaminopropylamine (22 g) and commercial bisphenol A (96 g) were added in succession to the resin composition, and then commercial polyglycidyl ether based on bisphenol A having an epoxide equivalent weight of about 180-192 ((~)Beckopox EP 140, 231 g) was metered in. A synthetic-resin system was obtained which had an amine number of 74, a Mw of 8800 and a Tg of 67C.

Example 4:
The synthetic-resin system from Example 1 (41 g) was combined, directly or invertedly, under hot conditions with lactic acid (90 %, 3 g) and water (81 g) and was diluted with further water (12 g). A grinding paste was thus obtained which had a viscosity of 540 mPa s (Ubbelohde), a pH of 4.4 and a solids content of 30 % (3 h/100C).

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

2i7~138 Example 6:
A solution of the synthetic-resin system from Example 1 (48 g) with ractic acid (90 %, 3.3 g) in water (95 g) was heated to 90C. Then, styrene (391 g) and, in parallel thereto, ascorbic acid (6 g) in water (616 g) and tert-butyl hydroperoxide (4 g) were metered in over a period of 3-4 hours. The resulting solution was filtered through a 30 ~m filter to produce a fine dispersion having a solids content of 35 % (3 h, 100C), a pH of 3.7 and a viscosity (Ubbelohde) of 480 mPa-s.

..
Example 7:
The ~rin(ling paste from Example 4 (40 g) was combined intensively in a customary dispersion apparatus (Dispermat SL-C25, Get7m~nn) with blue pigment ((~)Heliogen Blau D7099AQ, 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 about 60 s from the 4mm cup at 23 C (DIN 53 211).

Example 8:
The gloss paste from Example 5 (30 g) was mixed homogeneously with the dispersion from Example 6 (59 g). Addition of water (8 g) provided an overprint varnish having a solids content of 33 % and a flow time of about 60 s from the 4mm cup at 23 C (DIN 53 211).

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

The foregoing examples reveal that the emulsifier- and solvent-free multimodal synthetic resin systems of the present invention are useful as pigment pastes or as binder components for print varnishes and printing inks.

Throughout this description, all of the aforementioned documents are incorporated by reference herein in their entirety. While the invention has been described with reference to particularly preferred embodiments and examples, those skilled in the art will appreciate that various modifications can be made hereto without significantly departing from the spirit and scope of the mventlon.

Claims (20)

1. An emulsifier- and solvent-free multimodal synthetic-resin system comprising at least one amino-containing polymer A and at least one nonionic, water-dilutable polymer B and, optionally, a water-insoluble polymer C in the form of latex particles prepared by emulsion polymerization of ethylenically unsaturated compounds in the presence of the polymers A and B.

2. The synthetic-resin system as claimed in claim 1, which has a glass transition temperature of at least 25°C.

3. The synthetic-resin system as claimed in claim 2, which has a glass transition temperature of at least 65°C.

4. The synthetic-resin system as claimed in claim 1, wherein the polymer A has a mean molar mass (weight-average) of from 3000 to 50,000.

5. The synthetic-resin system as claimed in claim 4, wherein the polymer A has a mean molar mass (weight-average) of from 6000 to 10,000.

6. The synthetic-resin system as claimed in claim 1, wherein the polymer B has a mean molar mass (weight-average) of from 400 to 5000.

7. The synthetic-resin system as claimed in claim 6, wherein the polymer B has a mean molar mass (weight-average) of from 1000 to 4000.

8. The synthetic-resin system as claimed in claim 1, wherein the weight ratio of said polymer A to said polymer B is from 95:5 to 5:95.

9. The synthetic-resin system as claimed in claim 1, wherein the weight ratio of said polymer A to said polymer B is from 75:25 to 25:75.

10. A process for preparing a synthetic-resin system, comprising:
preparing at least one amino-containing polymer A and at least one nonionic, water-dilutable polymer B;
combining A and B; and preparing a water-insoluble polymer C in the form of latex particles by emulsion polymerization of ethylenically unsaturated compounds in the presence of the polymers A and B.

11. The process as claimed in claim 10, wherein the polymer A is prepared in the presence of at least one polymer B.

12. The process as claimed in claim 10, further comprising neutralizing or partially neutralizing said polymer A and polymer B in water.

13. The process as claimed in claim 10, whereby said polymer A is prepared by reacting at least one of (a) epoxides, carbonates and epoxide-carbonates with (b) an amine and (c) a phenol.

14. The process as claimed in claim 13, wherein said epoxides of component (a) are glycidyl ethers of polyhydric phenols of formula I:

Formula I

where R is represented by the formula:

where R1, R1', R1" are, independently of one another H or CmH2m+1;
R2 is a linear or branched saturated hydrocarbon radical having up to 8 carbon atoms;
R3 and R3' are in each case independently of one another, selected from the group consisting of a halogen, an aryl, an alkyl and an aralkyl group;
n is an integer from 0 to 8;
m is an integer from 1 to 8; and u and u' are independently of one another, an integer from 0 to 4.

15. The process as claimed in claim 13, wherein said carbonate is a compound of formula IV:

Formula IV

where R6 is selected from the group consisting of:
a z-valent radical of a phenol, polyether, polyetherpolyol, polyester, and polyesterpolyol;
an alkylene radical having 2 to 18 carbon atoms;
a z-valent poly(secondary)amine radical;
a z-valent radical of a reaction product of an epoxy-carbonate com-pound with polyamines, polyols, polycaprolactonepolyols, hydroxyl-containing polyesters, polyethers, polyglycols, hydroxy-, carboxy- and amino-functional polymer oils having mean molar masses of from 800 to 10,000, polycarboxylic acids, hydroxy- or amino-functional polytetrahydrofurans; and a z-valent radical of a reaction product of polyamines with glycidyl esters of .alpha.,.alpha.-dialkylalkanemonocarboxylic acids of the empirical formula C,2H22O3 to C14H26O3; and z is an integer of from 1 to 5.

16. An emulsifier- and solvent-free multimodal synthetic-resin system comprising at least one amino-containing polymer A and at least one nonionic, water-dilutable polymer B and, optionally, a water-insoluble polymer C in the form of latex particles, said synthetic-resin system prepared by a process comprising:
preparing said at least one polymer A and at least one polymer B;
combining A and B; and preparing a water-insoluble polymer C by emulsion polymerization of ethylenically unsaturated compounds in the presence of the polymers A
and B.

17. The synthetic resin as claimed in claim 16, wherein said polymer A
is prepared by reacting at least one of (a) epoxides, carbonates and epoxide-carbonates with (b) an amine and (c) a phenol.

18. The synthetic-resin system as claimed in claim 16, which has a glass transition temperature of at least 25°C.

19. A grinding resin or grinding dispersion for pigment pastes comprising a synthetic-resin system as claimed in claim 1.

20. A water-based printing ink or print varnish comprising a synthetic-resin system as claimed in claim 1.