JPH09123628A - Coating comprising more than one layer in printed matter and method for forming the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To modify a printing layer so as to certainly avoid the blocking of printing ink without obstructing processing treatment. SOLUTION: In the coating in printed matter having at least two layers having different compsns., the softening temp. of a top layer and, according to circumstances, that of a separate top layer are at least 60 deg.C and higher than that of a base layer by at least 10 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating having a plurality of layers on a printed material and a method for forming the coating.

[0002]

DE-A 42 05 713 is a printing ink in which the binder consists of an amorphous part of a polymeric and a low molecular weight crystalline part which melts on heating and dissolves this polymeric part. , Especially intaglio printing inks. On cooling, the low molecular weight parts recrystallize and the ink becomes solid. One advantage of this fusible printing ink is that it does not contain volatile solvents, so that no solvent recovery or incineration equipment is required.
Yet another advantage is that it is not necessary to protect the printing press and the electrical equipment in the printing plant from explosions, whereas such protection measures are usually required when using flammable organic solvents. is there.

However, in this printing ink, when the melt is cooled, at least a part of the low molecular weight crystalline part remains dissolved in the amorphous part of the polymer, which considerably lowers the softening temperature. There are drawbacks. When printed materials such as magazines printed with such inks are exposed to high temperatures, for example, when they are placed in an automobile or on a radiator under the sun that burns, this printed material is The so-called blocking of the printing inks makes it impossible to stick them to each other and separate them. This blocking is caused by the mutual diffusion of resin molecules at the interface.
This diffusion cannot be reduced or even avoided by adaptively selecting the components to give the printing ink a higher softening temperature. This is because when such a measure is taken, the temperature at which the viscosity of the printing ink becomes sufficiently low for processing naturally increases.

DE-A 25 34 845 discloses thermoplastic synthetic resins having a softening temperature of 90-140 ° C., optionally blended with other resins, for example rosin, in particular two resins. A melt-type printing ink is described which contains as a binder a polyamide resin based on quantified fatty acids. This printing ink also softens on the print and, if the appropriate temperature is exceeded, this likewise leads to blocking.

[0005]

The object of the present invention was therefore to modify the print layer in such a way that blocking of the printing ink was avoided without interfering with the processing.

[0006]

Means for Solving the Problems The present inventors have found that the above-mentioned problems are caused by an overprint varnish in which a printed matter printed with a melt-type printing ink is neither melted nor softened by a crystalline portion in the melt-type printing ink. We have found that coating can be a surprisingly simple solution.

Suitable overprint varnishes for this purpose are in principle all varnishes which fulfill the above-mentioned conditions, for example oil-printed varnishes and nitrocellulose lacquers. However, it is preferred to use organic solvent-free nonionic, anionic or cationic aqueous overprint varnishes like the melt-type printing inks. Anionic overprint varnish contains vinyl monomer, 0.
It is an aqueous solution of a polymer obtained by copolymerization with one or more α, β-olefinically unsaturated carboxylic acids in a mass proportion of 5 to 20%. By neutralizing with a base, preferably ammonia or amine, the polymer becomes soluble in water.

The cationic overprint varnish is
It contains a film-forming component consisting of a basic synthetic resin which becomes soluble in water by neutralizing with an acid, especially a non-oxidizing mineral acid such as phosphoric acid, or an organic acid such as formic acid, acetic acid or lactic acid. Suitable basic synthetic resins are aminopolyether polyols obtained by reacting epoxy resins with primary and / or secondary amines.

The invention therefore relates to a novel coating in printed matter, wherein the coating has at least two layers of different composition, and its topcoat layer and optionally further topcoat layers. Has a softening temperature of at least 60 ° C, preferably at least
It provides a coating at 80 ° C and at least 10K (10 ° C), preferably at least 20K (20 ° C) above the softening temperature of the base layer.

Generally, one topcoat layer is sufficient to reliably prevent blocking of printing inks that soften at low temperatures. However, a plurality of top layers may be provided in the present invention. This is because the top layer, by itself, has a softening temperature that is high enough to prevent blocking of the printing ink, but is plasticized by one or more components of the printing ink, which results in an insufficient softening temperature. It is especially advantageous when it is lowered to. In this case, a first topcoat is applied on the base layer, the softening temperature of which in all cases does not need to be high enough to prevent blocking by itself. The composition of this first topcoat is selected such that the mutual solubility of the first topcoat and base layer components is so low that the first topcoat is not softened at all or is negligible. To be done. Furthermore, it also functions as a barrier layer, which prevents diffusion of the softening component by this first topcoat layer, or at least the softening temperature of the further topcoat layer by the internal diffusion component of the base layer. The decrease is 20K (20 ° C) or less, preferably 10K (10 ° C) or less, and the degree of this diffusion is decreased to such an extent that the effect of the next topcoat layer is not impaired. Preferably, contact with the base layer should not reduce the softening temperature of the topcoat layer to below 70 ° C.

At the same time, the top layer exhibits some absorbance,
The average absorbance in the visible range is preferably 10% or less. Normally, only the base layer should contain the coloring pigments or dyes and the topcoat layer should be as transparent as possible. The average absorbance in the visible range in the top coat layer is preferably 10% or less, particularly preferably 5% or less. However, for example, in a structure having three layers, a so-called special effect pigment such as a dye or a pearl pigment or a semi-transparent color pigment can be added to, for example, the lower topcoat layer, and these pigments are added to the base layer. You can change the appearance of the printed image.

The novel multi-layer structure of the coating in the print according to the invention is chosen in particular when using a melt-type printing ink which on heating brings the binder into a liquid form with a viscosity compatible with the printing method. When using such printing inks, problems can arise if the printed matter is subjected to relatively high temperatures, even temporarily, after its production. The top coat layer prevents not only the so-called blocking of printed matter in which printed surfaces overlap but also surface running.
In addition, the top layer needs to be sufficiently tacky with respect to the underlying base layer area. This factor is taken into account in selecting the appropriate topcoat binder for a given base layer binder.

The novel multi-layer structure is disclosed in German Patent Application Publication (D
It is particularly advantageous in the case of solvent-free printing inks known from EA) 42 05 713. This printing ink comprises a color-forming pigment or dye and a film-forming material (a) and a low-melting material (b) having a softening temperature higher than 40 ° C. or, in a preferred embodiment of a crystalline substance, a melting point higher than 40 ° C. It is composed of a binder and the substance (a) and
(b) forms a fluid mixture with a viscosity compatible with the printing method when they are heated. In the meantime, the material
(b) functions as a solvent for the film-forming material (a). Cooling to ambient temperature results in complete separation of components (a) and (b),
Most of the material (b) forms one separated phase, and most of it dislocations to a crystalline state.

In the novel multilayer structure, the film-forming material (a) is
By adding an auxiliary agent (c) consisting of at least one volatile solvent and at least one non-volatile solvent (b), the viscosity of the solvent-containing printing ink adjusted to the printing method at the processing temperature can be improved. It is also advantageous in this case. After removal of the volatile solvent and optionally after cooling at ambient temperature as described above, this material (b) forms substantially, preferably for the most part, one separate phase,
And, preferably, it dislocations to a crystalline state.

To form the topcoat layer, film-forming components dissolved in a solvent or dispersed in an aqueous solution can be used. It is preferred to use an aqueous dispersion of the topcoat to reduce solvent emissions and to avoid the use of organic solvents. in this case,
The binder is modified by incorporating ionic or non-ionic hydrophilic groups so that they can form stable aqueous dispersions.

The present invention further relates to a method for forming a coating on a printed matter, wherein in a first step, a coating material containing a color-forming pigment or dye and a film-forming material (a) is provided on the surface of the substrate to be printed. Coating, and then coating the auxiliary agent (c), then in the second step, removing the auxiliary agent or forming a base layer film consisting of the paint of the first step by physical or chemical conversion, and In a step, at least the entire printed surface is coated with a further coating material containing a film-forming material (a ') and an auxiliary agent (C') and then in a fourth step the solvent is removed or physically or chemically. The top layer film formed from the third stage coating material is formed by a dynamic conversion, wherein the top layer film formed in the fourth stage is transparent and exhibits an average absorbance of 10% or less in the visible range. Method To provide.

In the case of solvent-containing printing inks, the auxiliary (c) corresponds to the solvent which is volatilized by heating.
In the case of the melt-type printing ink according to DE-A 42 05 713, the auxiliaries (c) correspond to crystalline substances (b). Upon heating, component (b) is able to dissolve component (a), and upon cooling the two components separate and component (b) is largely translocated to the crystalline state.

However, it is also possible to use a mixture of the non-volatile crystalline substance (b) and a volatile solvent under dry conditions. At this time, the crystalline substance does not have to be a solvent for the binder resin (a) by itself, and in this case, the solubility of the binder resin (a) depends only on the presence of the volatile solvent in the auxiliary agent (c). To be achieved. After removing the volatile solvent,
The components (a) and (b) of the printing ink separate, which results in a very rapid increase in viscosity. In the meantime, complete separation is usually not necessary and in all cases a mixture of at least two phases is present, one phase containing a high proportion of (a) and a small proportion of (b). , And the other phase contains a small amount of (a) and a large amount of (b). Ingredient (b)
This latter layer can likewise be crystalline or predominantly crystalline, if is a crystalline material. Ingredient (b)
Preferably has a softening point (melting point if (b) is crystalline) higher than 40 ° C., particularly preferably higher than 60 ° C., particularly preferably higher than 80 ° C.

Suitable binders for the top phase are resins which can be applied from organic solvents, for example oil-printed varnishes or nitrocellulose lacquers. However, resins that can be applied from aqueous solutions are preferred. The resin can be made water soluble or water dispersible by modification with hydrophilic components. Suitable nonionic hydrophilic units are, for example, mehrere consecutive oxyethylene or oxypropylene components or several consecutive both components. Also suitable are resins that have been made soluble or dispersible in water by the inclusion of anionic or cationic groups. The cationically or anionically modified resin may further contain non-ionic hydrophilic groups. Several cationic resins
Mixture of (A), cationic resin (A) and nonionic resin
Also suitable are mixtures of (B), mixtures of several anionic resins (D), and mixtures of anionic resins (D) and nonionic resins (B). Suitably the matrix is such that all resins which can be hydrophilically modified during the synthesis reaction by incorporating appropriate comonomers, ie the products of addition polymerization, polycondensation and polyaddition reactions, and sufficient hydrophilicity are obtained. In addition, after the synthesis reaction, chemically similar reaction (polymeranaloge U
resin that can be modified by molecular expansion or molecular reduction.

In the present invention, it is also possible to coat several top coat layers from a solution or an aqueous dispersion. The glass transition temperature of resins (A), (B) and (D) is preferably at least 60 ° C, more preferably at least 70 ° C.
C., particularly preferably at least 80.degree. Examples of suitable compounds include, as monomers, esters of α, β-olefinically unsaturated carboxylic acids and α, β-olefinically unsaturated carboxylic acids themselves, as well as other vinyl monomers such as vinyl halides and aromatics. It is an anionic vinyl polymer (D) containing together with a vinyl compound. The polymers can each be used alone or as a mixture or as a mixture with the polymers (B) described in detail below and are soluble or soluble in water by at least partial neutralization with alkali. Become dispersible.

Among the anionic polymers, particularly preferred are i) volatile basic compounds of an ethylenically unsaturated compound containing an acid group, preferably a carboxyl group, with another ethylenically unsaturated compound. Polymerization in the presence of a neutralizing agent and optionally "in situ" condensation with a monohydroxy compound ("i
n-situ "-Kondensation), optionally neutralized or partially neutralized acid group-containing polymer (D), and, optionally, ii) in the presence of the above polymer (D) Polymers with reduced foamability in water, including water-insoluble polymers (C) in the form of latex particles, which can be produced by emulsion polymerization of ethylenically unsaturated compounds in.

The acid value of the polymer (D) (mg mass of potassium hydroxide required to neutralize 1 g of solid resin) is preferably in the range of 90 to 400 mg / g, especially 170 to 275 mg / g. Within range. The weight proportion of hydroxy compounds attached in the ester group is preferably between 0 and 25%, in particular 0 and 18%.
%. Preferably 300 to 100,000 g / mol, especially 800 to 40,000 g / mol, particularly preferably 1 to 25 kg / mol.
Polymer (D) having a weight average molecular weight of is used. The glass transition temperature of this polymer is preferably 0 and 180 ° C.
Between, especially between 30 and 160 ° C, particularly preferably between 50 and 150 ° C
It is.

In the present invention, the above novel polymer (D)
During the polymerization to obtain a volatile base compound,
It is necessary to at least partially neutralize the acid group-containing monomer. For example, the carboxyl-containing monomer is a stronger acid than the carboxyl-containing polymer produced from it, which drives it out of the salt of the polymer. Therefore, during polymerization, there is always a sufficient amount of neutralized carboxylato-containing monomer available for polymerization. In this way,
Localized aggregation of polar monomers caused by polar interactions is suppressed during the production of the polymeric material so that most of the monomers can be randomly incorporated into the polymeric material.

To introduce the carboxylic acid groups into the polymer of type (D), it is possible to use olefinically unsaturated mono- or dicarboxylic acids or mixtures thereof. Examples of unsaturated monocarboxylic acids used are acrylic acid, methacrylic acid, crotonic acid, angelic acid and tiglic acid, which can be used individually or as a mixture. Monoesters of maleic acid and fumaric acid with saturated alcohols having 1 to 10 carbon atoms can also be used. Unsaturated dicarboxylic acids which may be mentioned are such dicarboxylic acids having 4 to 6 carbon atoms, such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, methylenemalonic acid, citraconic acid, salts thereof, or optionally Are these anhydrides. The mass proportion of carboxyl-containing monomers, based on the total mass of monomers in polymer (D), is preferably 5 to 70%, in particular 15 to 55%.

Suitable comonomers for the above carboxyl-containing monomers are in principle all radically polymerizable olefinically unsaturated compounds, preferably hydrophobic monomers such as aromatic vinyl compounds or open-chain conjugated dienes. To use. Examples which may be mentioned are styrene, vinyltoluene, α-methylstyrene, ethylstyrene, isopropylstyrene, tert.-butylstyrene, 2,4-dimethylstyrene, diethylstyrene, o-methyl-p-isopropylstyrene, halostyrenes (for example chlorostyrene). styrene,
Fluorostyrene and iodostyrene), 2,4-cyanostyrene, hydroxystyrene, nitrostyrene, aminostyrene and / or phenylstyrene. Particularly preferred are styrene, vinyltoluene and α-methylstyrene. Open-chain dienes are: 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene,
Pentadiene, 2-neopentyl-1,3-butadiene and substituted 1,3-butadiene (eg 2-chloro-1,3-butadiene, 2-cyano-1,3-butadiene), substituted linear conjugation Pentadienes, linear and branched conjugated hexadienes, other linear or branched conjugated dienes having from 4 to 12 carbon atoms, and mixtures thereof. polymer
The comonomer mass proportion based on the total mass of the monomers in (D) is preferably 30 to 95%, especially 45 to 85%.

Other starting monomers can also be used to obtain specific properties, for example acrylic acid, methacrylic acid and crotonic acid and saturated alcohols containing 1 to 12 carbon atoms in the alcohol moiety. The esters of can be used alone or as a mixture. Examples which may be mentioned are methyl methacrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate. The weight proportion of this comonomer, based on the total weight of the monomers in polymer (D), is preferably 0-10%, in particular 0-5%.

Further comonomers include acrylamide, methacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, acrylamidosulfonic acid, vinyl acetate, vinylsulfonic acid, allylsulfonic acid, vinylphosphonic acid, allylphosphonic acid, acrylonitrile, Methacrylonitrile, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, N-vinylpyrrolidone, N-
One or more can be selected from the group consisting of vinylformamide, N-vinylimidazole, N-vinylimidazoline, and 1-vinyl-2-methyl-2-imidazoline. The acid group-containing monomer selected from the above group can be used in the copolymerization in the form of a free acid or partially or completely neutralized by an alkali metal base or an ammonium base. These basic acrylates, such as diethylaminoethyl acrylate, are neutralized with acid or quaternized,
Then, it is used for the copolymerization reaction. Vinyl esters of α, α-dialkylalkanemonocarboxylic acids, eg Versatic
It is also possible to use the vinyl ester of acid®, as well as vinyl acetate and vinyl propionate. This modifying monomer serves only to achieve specific properties, and in the composition of the copolymer (D) 0 to
It is present in a mass proportion of 10%, preferably 0-4%.

In the present invention, a monohydroxy compound and
The term refers to monoalcohol and monoetherified
Refers to a polyalkylene oxide compound. Suitable mono
Cole has an alkane or cycloalkane moiety
And preferably C₈-C ₃₂-Alcohol and this
Isomers such as 2-ethylhexanol, octanol,
Nonanol, decanol, dodecanol, and steer
Ril-, cetyl-, ceryl- and myricyl alcohol,
TDC-Alkohol M (registered trademark of Hoechst AG, molecular weight = 166g
/ mol, OH value = 327 mg / g), wool wax alcohol,
Cholesterols, borneols, isoborneol
And tall oil fatty alcohols.

As an option, to modify the properties, C ₁ -C ₆ -alcohols containing alkane and cycloalkane chains are used in a proportion by weight of 0 to 35%, based on the proportion of monohydroxy compound. It can also be, for example, butanol, hexanol, cyclohexanol and / or mixtures thereof.
The polyalkylene oxide compounds monoetherified formula ^{I R 41 - (O-CHR} 42 -CHR 43) n - polyalkylene oxide compound represented by OH Formula I is used. In this formula, R ⁴¹ is an alkyl, cycloalkyl or phenyl group, preferably an alkyl group having 1 to 12, especially 1 to 4 carbon atoms, and R ⁴² and R ⁴³ are hydrogen or 1 to 4 Is an alkyl group having a carbon atom of
And n is 1 to 10, preferably 1 to 4. Examples of such compounds that may be mentioned are methyl glycol (2-methoxyethanol), ethyl glycol (2-ethoxyethanol), butyl glycol, methyldiglycol (2- (2
-Methoxyethoxy) ethanol), ethyl diglycol, butyl diglycol, methyl triglycol (triethylene glycol monomethyl ether), ethyl triglycol, butyl triglycol, methyl tetraglycol (tetraethylene glycol monomethyl ether), ethyl tetraglycol, butyl Tetraglycol, Polyglykol M-250 (registered trademark of Hoechst of polyethylene glycol monomethyl ether, molecular weight = 260 to 27)
5 g / mol, OH value = 204-215 mg / g), Polyglykol M-350
(Molecular weight = 335-365 g / mol, OH number = 154-167 mg /
g), propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether and propylene glycol phenyl ether.

Other compounds which are considered in the present invention as monohydroxy compounds are cyclic esters, preferably cyclic esters having 4 or more carbon atoms in the ring, the carbon atoms of the ring being hydrogen. Instead of the atom, it may have other substituents such as alkyl, cycloalkyl, aryl, aralkyl and alkoxy.
This includes monoalkyl-substituted ε-caprolactones such as monomethyl-, monoethyl- and monopropyl-, monoisopropyl-, monoethylhexyl-, monodecyl.
-And monododecyl-ε-caprolactone, and dialkyl-ε-caprolactones in which the two alkyl groups are on the same carbon atom or on two different carbon atoms, but not both on the ε carbon atom , And trialkyl-ε-caprolactones in which two or three carbon atoms in the ring are substituted, but two substituents are not located on the ε carbon atom, and alkoxy-
ε-caprolactones such as methoxy- and ethoxy
-ε-caprolactone and cycloalkyl-, aryl- and aralkyl-ε-caprolactones such as cyclohexyl-, phenyl- and benzyl-ε-caprolactone may be mentioned by way of example. Unsubstituted ε
-Caprolactone is preferred.

Other cyclic esters which can be used in the present invention and which contain at least one internal ester capable of ring opening are γ-butyrolactone, γ-valerolactone, ethylene carbonate, tetramethylene carbonate, 2,2-dimethyl- 4-phenyl-1,3-dioxolane-5-
On, α-n-propyl-δ-valerolactone, δ, δ-
Dimethyl-δ-valerolactone, 3-ethyl-1,4-dioxan-2-one, 3,3,6-trimethyl-1,4-dioxan-2-
On, tetramethylglycolide, tetraphenylglycolide, 3-oxa-ε-caprolactone, β-propiolactone, α, α-bis (chloromethyl) propiolactone, β-butyrolactone, pivalolactone (PVL), thiobutyrolactone (TBL) ), Δ-valerolactone (DVL),
α, β, γ-trimethoxy-δ-valerolactone, 1,4-
Dithian-2,5-dione, trimethylene carbonate, neopentyl carbonate, ethylene oxolane, β-methyl-ε-isopropyl-ε-caprolactone, propylene oxolane, 4-hydroxycyclohexanecarboxylic acid lactone, cis-disalicylide and trisalicylide, And mixtures thereof. Preferred compounds are γ
-Butyrolactone, δ-valerolactone, pivalolactone, thiobutyrolactone, β-butyrolactone, ε-caprolactone and mixtures thereof.

The volatile neutralizing agent suitable in the present invention is a basic compound which does not form a covalent bond with a carboxyl group under the reaction conditions. Preferred and preferred are amines, especially tertiary amines, amides, and heterocyclic compounds, especially electron-deficient heteroaromatic compounds such as pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline. Particularly preferred volatile basic neutralizing agents are those of formula II

[0033]

Embedded image

[Wherein R ⁴ is alkyl or cycloalkyl, preferably alkyl or cycloalkyl having 1 to 18 carbon atoms, particularly preferably 1 to 8 carbon atoms, wherein the alkyl group is It may be branched, R ⁵ is (CH ₂ ) _l , z is (CH ₂ ) _m or O, l is 0-5, and m is 1-5. It is represented by.

Examples which may be mentioned are N-methyl-2-piperidine, N-ethyl-2-piperidine, N-methylpyrrolidone,
N-ethylpyrrolidone, N-methylcaprolactam, 2,5-piperazinedione and N-methyl-2-oxazolidone. N-methylpyrrolidone (N-methyl-2-pyrrolidinone)
Is particularly preferred. The volatile basic neutralizing agent is added at a rate such that the carboxyl-containing monomer is sufficiently neutralized before it is incorporated into the growing polymer. For polymerizations under standard conditions, this is preferably at least 10%, especially 20-70%, based on the molar amount of carboxyl-containing monomers.
It means that the molar ratio of the volatile basic neutralizing agent is sufficient.

The polymer (D) is usually synthesized at 20 to 400 ° C.
It is preferably carried out at a temperature of 80 to 300 ° C, especially 100 to 230 ° C. The synthesis is preferably carried out under atmospheric pressure at a constant temperature and optionally with simultaneous removal of low-boiling components, but under pressure, preferably up to 15 bar.
It can also be carried out especially under pressure up to 5 bar. polymer
Polymerization to produce (D) is initiated by thermal decomposition of a radical initiator known to those skilled in the art and selected from the group consisting of azo compounds, peroxides, peresters and hydroperoxides. it can. Preferably organic peroxides, especially dialkyl peroxides, particularly preferably di-tert.-butyl peroxide, di-tert.-.
Amyl peroxide or cumene hydroperoxide is used.

In order to control the copolymerization, it is possible, if appropriate, to operate by adding a solvent, which is removed after completion of the reaction, preferably by distillation under reduced pressure. The weight proportion of this solvent is up to 50%, preferably up to 20%, based on the polymer (D), but in particular no solvent is added. The solvent preferably used is β-ethoxyethyl propionate, which under the reaction conditions reacts as masked ethyl acrylate. If desired, regulators known to the person skilled in the art can be added to limit the degree of polymerization, for example regulators based on organic thio compounds are used.

When the synthesis is complete, the volatile basic neutralizing agent can be separated from the polymer (D), preferably by distillation under reduced pressure, and the separated neutralizing agent is generally , Can be reused without going through complicated purification steps. The copolymer (D) is a base such as ammonia or amines, preferably tri-, di- or monoalkylamines such as triethanolamine, morpholine, or alkanolamines such as 2-amino-1-.
It can be dissolved in water after being at least partially neutralized with methyl-1-propanol or an alkali metal hydroxide or alkaline earth metal hydroxide, or a mixture thereof, so that an aqueous overprint dispersion It is very advantageous as a binder for the body or as a stabilizer for emulsion polymerization. In this case, generally 50 to 95
% Partial neutralization is sufficient, but is preferably over-neutralized to provide a pH of 7.5-11, preferably 8-9.

A technique which has been found to be useful for producing a solution of at least partially neutralized resin on a production scale is a reverse dilution technique, that is to say a resin melt of a type (D) copolymer at least 100 to 250 at atmospheric pressure
It is a direct introduction technique of introducing into water / neutralizing agent at a resin temperature of ℃, preferably 150-220 ℃. Advantageously, this aqueous mixture is then subjected to at least 80-95 at atmospheric pressure.
C., preferably about 90.degree. C., for 30 minutes to 3 hours. Optionally and especially in the case of high-viscosity resin melts with high glass transition temperatures, low molecular weight saturated aliphatic carboxylic acids and / or glycol ethers can be added in order to significantly reduce the melt viscosity. In the meantime, it is expedient to add up to 20% by weight of additive, based on the resin component. The carboxylic acids that can be used are
Formic acid, lactic acid, malonic acid, succinic acid, tartaric acid and citric acid, preferably acetic acid. Glycol ethers that may be mentioned are ethers of ethylene glycol, propylene glycol, butylene glycol, such as 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 glycol monomethyl ether, 2,5,8,11-tetraoxadodecane, 1-methoxy- 2-propanol, 1-ethoxy-2-propanol,
Tripropylene glycol monomethyl ether.
Preferably 2- (2-ethoxyethoxy) ethanol and /
Or use 1-methoxy-2-propanol. However, the reverse dilution technique is usually performed without the addition of any solvent.

In the present invention, the synthetic resin mixture contains, in addition to the anionic polymer (D), optionally a nonionic hydrophilic polymer (B). This polymer (B) is
Prepared as described below by emulsion polymerization in the presence of at least partially neutralized polymer (D). This polymer (D) should be present in an amount sufficient to produce the desired emulsifying effect. On the other hand, the proportion of polymer (D) should not be too high, both for reasons of economy and likely to affect the performance properties of the emulsion polymer to be produced. Therefore, it is preferred to use polymer (D) in a mass proportion of 4 to 56%, especially 10 to 50%, based on the total mass of polymers (D) and (B). (D) and (B)
Very good results are obtained when preferably 12 to 42% by weight of polymer (D), based on the total weight of

Particularly preferably, cationic (A) and nonionic (B) water-soluble or water-dispersible resins are used. This is because they can be separated well from the cellulose part when the paper is recycled by the so-called deinking method in an alkaline bath. The resins of polymers (A) and (B) can in each case be used individually or as a mixture.

Particularly suitable cationic polymers (A) are amino-containing polymers which can be converted into cationic groups at least in part by neutralization with quaternizing agents or acids. The nonionic water-dilutable polymer (B) is a polymer containing a nonionic hydrophilic structure. The weight average molecular weight of this amino-containing polymer (A) is preferably 3 and 50 kg.
/ mol, especially 4 to 25 kg / mol, particularly preferably 6
It is ~ 10 kg / mol.

The weight average molecular weight of the polymer (B) is preferably in the range of 0.4 to 5 kg / mol, especially in the range of 1 to 4 kg / mol. The novel polymer (A) is preferably an epoxide,
Group of carbonates and epoxy-carbonates (A
1), a reaction product of a compound selected from at least one of the group of amines (A2) and the group of phenols (A3), particularly selected from the group consisting of polyglycidyl ether, polyglycidyl ester and polyglycidyl amine. , Preferably an epoxide group-containing resin having a terminal epoxide group (A11) and / or preferably a carbonate group-containing resin having a terminal carbonate group (A12), and a monohydric or polyhydric phenol (A3) and / or alcohol ,
And saturated and / or unsaturated secondary and / or primary amines (A2) or amino alcohols. This latter is, in its alkyl group, at least one primary and / or secondary hydroxyl group,
It can be modified with dialkylamino groups and / or primary amino groups which are temporarily protected by ketimine formation.

The epoxide compound (A11) used has at least one, and preferably two, on average per molecule.
It has a 1,2-epoxide group. It may be saturated or unsaturated and may be aliphatic, cycloaliphatic, aromatic and heterocyclic and may also carry hydroxyl groups. In addition, it may contain substituents which, under mixing or reaction conditions, do not lead to disturbing side reactions, such substituents being, for example, alkyl substituents, aryl substituents, alkyl / aryl substituents. Group, ether group and the like. Such an epoxide compound (A11)
Are polyphenols such as resorcinol, hydroquinone, 4,4'-dihydroxydiphenylmethane, an isomer mixture of dihydroxydiphenylmethane (bisphenol F), 4,4'-dihydroxy-3,3'-dimethyldiphenylmethane, 2,2 -Bis (4-hydroxyphenyl) propane (bisphenol A), 4,4'-dihydroxydiphenylcyclohexane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4'-dihydroxybiphenyl, 4,
4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, tris (4-hydroxyphenyl)
Methane, 1,1-bis (4-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxy-3-tert.-butylphenyl) propane, bis (2-hydroxynaphthyl) methane,
1,5-dihydroxynaphthalene, bis (4-hydroxyphenyl) ether or hydrogenated, chlorinated and brominated products of the above compounds, and glycidyl ethers of novolaks. As the compound (A11), a glycidyl ether of a polyhydric alcohol can be appropriately used. Examples of this polyhydric alcohol that may be mentioned are ethylene glycol,
Diethylene glycol, triethylene glycol, 1,2-
Propylene glycol, 1,3-Propylene glycol, 1,
5-pentanediol, 1,2,6-hexanetriol, glycerol, trimethylolpropane and 2,2-bis (4-hydroxycyclohexyl) propane.

In the present invention, the term glycidyl ether preferably has the formula III

[0046]

Embedded image

[Wherein R is

[0048]

Embedded image

R ¹ , R ¹⁰ , R ¹ ″ are, independently of one another, H or C _m H _{2m + 1} and R ² is straight-chain or having up to 8 carbon atoms or A branched saturated hydrocarbon group, preferably -CH _2- , R ³ and R ³ 'independently of each other
Halogen, aryl, alkyl, aralkyl, n
Is 0-8, preferably 1-6, m is 1-8,
It is preferably 1 and u and u ′ independently of each other are 0 to
4, preferably 0 or 1].

These polyglycidyl ethers have a concentration of about 0.
2 to 10 kg / number-average molecular weight M _n and about 200 ~8400 mmo of mol
Epoxide group content of l / kg ("epoxide equivalent", which is the molecular weight divided by the number of epoxide groups per molecule, is about 12
0 to 5000 g / mol). Resins of this type include epichlorohydrin or methylepichlorohydrin and dihydroxydiphenylmethane (bisphenol F) or 2,
2-bis (4-hydroxyphenyl) propane (bisphenol A), and reaction products with, for example, dihydroxybenzophenone or dihydroxynaphthalene. A polyepoxide of suitable molecular weight can be obtained in the presence or absence of a catalyst such as a Lewis acid or phosphonium salt by selecting the molar ratio of bisphenol and epichlorohydrin or by reacting the monomeric diglycidyl compound with additional bisphenol. Manufactured below. The epoxy resin may be fully or partially hydrogenated and may be used as a mixture of various structures and molecular weights.

Further, some of the above polyglycidyl ethers have the formula IV

[0052]

Embedded image

[Wherein R ⁴ is H or a substituted or unsubstituted C ₁ -C ₄ -alkyl group, and v is 2
~ 6 and w is 2-100, preferably 3-50
Can be replaced by a purely aliphatic polyglycidyl ether.

Examples are bisglycidyl ethers of polypropylene glycols or polybutylene glycols with varying degrees of polymerization. The epoxy resin is a long chain polyalcohol such as 1,6-hexanediol, neopentyl glycol, bisethoxylated neopentyl glycol, neopentyl glycol hydroxypivalate and bis (hydroxymethyl) cyclohexane, pentaerythritol and polytetrahydrofuran diol. It can also be modified by reaction with hydrates, polycaprolactone diols, polycaprolactam diols or polybutadiene diols in the presence of a suitable basic or acidic catalyst such as a boron fluoride-amine complex.
Polyalcohols with primary hydroxyl groups can be reacted directly with polyglycidyl ethers under suitable catalysis, while polyols with secondary hydroxyl groups can first be reacted with diisocyanates. The resulting isocyanate-terminated reaction product can then be easily incorporated as a bridge between two polyglycidyl ether units, thereby expanding the molecule and functionality.

Other suitable epoxide compounds are of formula V

[0056]

Embedded image

[Wherein R ⁵ is up to 40, preferably 10
A straight-chain or branched, saturated or unsaturated hydrocarbon radical having up to 4 carbon atoms, or unsubstituted or substituted by halogen or lower (C ₁ -C ₆ ) -alkyl or alkoxy radicals Is a phenyl group, and p is 1-5, preferably 2 or 3, and especially 2.] is a (poly) glycidyl ester.

Such polyglycidyl esters of polycarboxylic acids include epichlorohydrin or similar epoxy compounds and aliphatic, cycloaliphatic or aromatic polycarboxylic acids such as oxalic acid, adipic acid, glutaric acid. ,
It is obtained by reacting terephthalic acid, hexahydrophthalic acid, 2,6-naphthalenedicarboxylic acid and dimerized fatty acid. Examples of suitable compounds are diglycidyl terephthalate and diglycidyl hexahydrophthalate.

Other suitable epoxide group-containing resin (A11)
Is a compound in which the epoxide groups contained therein are partially reacted with amines. The amine value of such amino-epoxy resins can also be reduced by further modification with saturated or unsaturated polycarboxylic acids and / or hydroxyalkylcarboxylic acids. Examples of aliphatic, cycloaliphatic and / or aromatic polycarboxylic acids with different chain lengths are adipic acid, sebacic acid, fumaric acid and maleic acid and their anhydrides, isophthalic acid and dimerised fatty acids. is there. Hydroxyalkylcarboxylic acids are understood to include lactic acid, dimethylolpropionic acid, or carboxyl- and hydroxyl-containing polyesters. In the reaction of excess low molecular weight polyglycidyl ether with polycarboxylic acids and / or polyalcohols, the resulting intermediate product consists of modified polyglycidyl ether, which can then be further reacted with amines and / or aminoalcohols. it can.

Heterocyclic polyepoxide compounds, eg 1,
A diepoxide of 3-diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate, or a bisimide can also be used. Another suitable class of polyepoxides consists of polyglycidyl ethers of phenolic novolac resins, which can be used to increase the diglycidyl group functionality per molecule from 2 to about 6. Additional substructures can be incorporated by defunctionalizing with long chain alkylphenols such as dodecylphenol.

Other suitable epoxide compounds are AM Paq
uin's handbook “Epoxidverbindungen und Epoxi
dharze ”, Springer Verlag, Berlin 1958, Chapter IV, and Lee, Neville,“ Handbook of Epoxy Resins ”, 19
67, Chapter 2, and "Lackkunstharz" by Wagner / Sarx.
e ”, Carl Hanser Varlag (1971), pp. 174 et seq.

The carboats (A12) include at least one, preferably two or three 2-oxo groups in one molecule.
Any desired substance can be used provided that it has a 1,3-dioxolane group (cyclic carbonate group) and no other functional group that interferes with the reaction with the component (A2). The number average molecular weight M _n measured by gel chromatography using polystyrene as a standard substance is
Generally between 100 and 10,000 g / mol, preferably 150 and 500
It should be between 0 g / mol, and the content of cyclic carbonate groups is between 650 and 10,000 mmol / kg (molecular weight divided by the number of cyclic carbonate groups per molecule "2-
The oxo-1,3-dioxolane equivalent "should be between 100 and 1500 g / mol). This cyclic carbonate group is preferably in the terminal position, but this group is distributed randomly on the molecular chain. It is also possible to use as a component (A12) a compound containing and capable of being produced by copolymerizing with an olefinically unsaturated compound containing this cyclic carbonate group. It is described in DE-A 36 44 373.

The carbonate component (A12) is preferably of formula VI

[0064]

[Chemical 6]

[In the formula, R ⁶ may optionally contain an amino or alkylamino group, and includes phenol, polyether, polyether polyol, polyester,
A z-valent group of the polyester polyol, or a z-valent hydrocarbon group optionally having an inactive group, preferably an alkylene group having 2 to 18 carbon atoms, or a poly ( Secondary) amine z-valent groups, or epoxies
-Carbonate compounds with polyamines, polyols, polycaprolactone polyols, hydroxyl-containing polyesters, polyethers, polyglycols, 800-10,0
Hydroxy-, carboxy- and amino-functional polymer oils having an average molecular weight of 00 g / mol, polycarboxylic acids, hydroxy- or amino-functional polytetrahydrofurans, and polyamines with the empirical formulas C ₁₂ H ₂₂ O ₃ to C ₁₄ H ₂₆ O Α of ₃ ,
α-Dialkylalkane monocarboxylic acids, eg Versat
is a z-valent group of the reaction product of ic acid (Shell Chemie, α-branched monocarboxylic acid having 9 to 12 carbon atoms) with a glycidyl ester, and z is 1 to
5, preferably 2 or 3, especially 2.

Compounds of this kind and the process for their preparation are described, for example, in DE-A 37 26 497. In some cases, additionally or in some cases exclusively, the formula VII

[0067]

Embedded image

[Wherein R ⁶ 'is a (x + y) -valent group of phenol, polyether, polyether polyol, polyester, polyester polyol, which may additionally contain an amino or alkylamino group. , Or may have an inert group (x + y) -valent hydrocarbon group, preferably an alkylene group having 2 to 18 carbon atoms, or (x +
y) -valent poly (secondary) amine groups or epoxy-carbonate compounds with polyamines, polyols, polycaprolactone polyols, hydroxyl-containing polyesters, polyethers, polyglycols, 800-10,000 g
hydroxy-, carboxy- having an average molecular weight of / mol
And amino-functional polymer oils, polycarboxylic acids, hydroxy- or amino-functional polytetrahydrofurans, and polyamines with the empirical formulas C ₁₂ H ₂₂ O ₃ to C ₁₄ H ₂₆ O ₃ α, α-
Dialkylalkane monocarboxylic acids such as Versatic a
a (x + y) -valent group of the reaction product of cid (registered trademark) with a glycidyl ester, wherein x and y are each independently 1 to 5, preferably 2 or 3 , Especially 1] may be expediently used as component (A1).

Suitable starting compounds for preparing the cyclic carbonates (A12) and optionally the mixed epoxy-carbonate compounds (A13) are polyhydric phenols and alcohols, for example polyglycidyl bisphenol A or bisphenol F. It is ether. This glycidyl ether is obtained, for example, by reacting polyphenol with epichlorohydrin. Examples of suitable polyphenols are 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 4,4'-dihydroxybenzophenone, bis (4-hydroxyphenyl) ether, 1,1 -Bis (4-hydroxyphenyl) isobutane, bis (2-hydroxynaphthyl) methane and 1,5-dihydroxynaphthalene. Preferably, free hydroxyl groups are present in addition to epoxide groups in the polyglycidyl ether of polyphenols. Diglycidyl adducts of cyclic urea can also be used.

As the amine (A2), a primary monoamine,
Primary monoamines preferably having alkyl and alkanol groups, such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, 2-aminobutane, ethanolamine, 4-
Amino-2-butanol, isoamylamine, pentylamine, 3-methylbutylamine, heptylamine, octylamine, 2-ethylhexylamine, isononylamine, isotridecylamine, 2-aminomethyl-1-propanol, n- or isopropanol Amine, neopentanolamine, methoxypropylamine, 2- (2-aminoethoxy) ethanol, palm fatty amine, oleylamine, stearylamine, tallow amine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, Cyclopentylamine, cyclohexylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-butoxypropylamine, 3-isononyloxypropylamine, 3-aminopropyltrimethoxy (ethoxy-tridecyl ) Silane, 2-amino-2-hydroxymethyl-1,3-propanediol can be used. It is also possible to use secondary monoamines, preferably dialkylamines, monoalkylhydroxyalkylamines or dihydroxyalkylamines. Examples of such compounds are 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, dicoconut fat-amine, ditallow amine, Or a cyclic amine such as morpholine, pyrrolidine or oxazolidine, or a substituted or unsubstituted aniline. Similarly, the reaction product of a primary monoamine and a monoepoxide can be used in place of the secondary amine.

Formula VIII H ₂ N-CR ⁷ R ⁸ -R ⁹ -O- (CHR ¹⁰ -CHR ¹¹ O-) _q R ¹² Primary amines of the formula VIII can also be used, in which case In the above formula, R ⁷ and R ⁸ are hydrogen, an alkyl group or a hydroxyl group, R ⁹ is a linear or branched alkyl group, particularly an alkyl group having 1 to 3 carbon atoms, R ¹⁰ and R ¹¹ are hydrogen or an alkyl group having 1 to 4 carbon atoms, R ¹² is hydrogen, an alkyl, a cycloalkyl or a phenyl group, preferably an alkyl group having 1 to 6 carbon atoms And q is 0-5
It is.

Examples of such compounds which may be used which may be mentioned are ethanolamine, propanolamine, butanolamine, ethylene glycol 2-aminoethyl ether and diethylene glycol mono (3-aminopropyl).
It is ether. Using this primary amine, this amine can react with epoxide groups depending on the stoichiometric ratio provided, leading to molecular expansion. Examples of diamines that may be mentioned are Jeffamine M series, Jeffamine D
Series, Jeffamine ED series (Texaco Chemical C
o. is a registered trademark). Other suitable amines are di- or triamines having primary and / or secondary amino groups, such as lauryl propylene diamine and tallow propylene diamine.

The term polyamine according to (A2) refers to compounds containing at least two amino groups in the molecule. Generally, the compound has 2 to 50 carbon atoms, preferably 2 to 20 carbon atoms. Examples of suitable polyamines (A2) are those having only primary amino groups, which groups are preferably di-diprimary. This polyamine is preferably used by blending it with a diamine having one primary amino group and one tertiary amino group, respectively.

Examples of other suitable polyamines (A2) are polyamines containing only secondary amino groups, preferably secondary diamines. Preferably long chain diamines such as N, N'-
Reaction products of dialkyldiaminoalkanes, or epoxyalkanes or monoepoxides, eg saturated glycidyl ethers or glycidyl esters, with addition products of primary diaminoalkanes, eg 1,6-hexanediamine and 2 mol of glycidyl ester of Versatic acid. To use. Monoepoxides that can be used for this purpose include saturated or unsaturated glycidyl ethers or α-epoxides of various chain lengths, such as
Included are 1,2-epoxydodecane or butylene oxide.

Other suitable polyamines (A2) are polyamines which also contain at least one free primary amino group and, in addition thereto, secondary and / or tertiary amino groups. This polyamine (A2) has, for example, the following formula IX

[0076]

Embedded image

Wherein s is 0 or an integer from 1 to 6, preferably 1 to 4 and R ¹³ is a divalent, preferably non-aromatic, system having 2 to 18 carbon atoms. A hydrocarbon group, preferably a branched or unbranched alkylene group having 2 to 10 carbon atoms, especially 2 to 6 carbon atoms, or 5 to 12 carbon atoms, preferably 6 to 10 Cycloalkylene groups having 4 carbon atoms, or aralkylene groups having 7 to 12 carbon atoms, preferably 8 to 10 carbon atoms, or polyoxalkylene radicals having 2 to 18 carbon atoms. ) And R ¹⁴ ,
R ¹⁴ 'is, independently of each other, H or

[0078]

Embedded image

And R ¹⁵ and R ¹⁵ 'are independent of each other,
H, (C ₁ -C ₂₀ ) -alkyl, preferably (C ₁ -C ₆ ) -alkyl, (C ₁ -C ₁₆ ) -hydroxyalkyl, preferably

[0080]

Embedded image

[0081] a and, R ¹¹ has the same meaning as R ^13, provided that have the meanings independently of R ^13, R ¹⁷ is, (C ₁ -C
₁₂ ) -alkyl, -CH ₂ -O- (C ₁ -C ₁₂ ) -alkyl, -CH ₂ -O-
_{Aryl, -CH 2 -O-CO- (C} 1 -C 12) - alkyl or

[0082]

Embedded image

And R ¹⁸ is H or (C ₁ -C ₆ ) -alkyl, or R ¹⁵ and R ¹⁶ are R ¹⁴ 'when s is 0.
Is a part of a 5-, 6-, or 7-membered aliphatic ring, provided that it is not H].

Other suitable polyamines are of the formula X X- (R ¹⁹ NH) _t -R ²⁰ -Y Formula X where X, Y are NH ₂ or OH, provided they have the same meaning. And R ¹⁹ and R ²⁰ independently of each other have the meaning of R ¹³ in formula IX above, and t has the meaning of s in formula IX above].

Further examples of other suitable compounds are, for example, DE-A 36 44 371, published German patent application DE-A 36 44 371.
(DE-A) 37 26 467 and German patent application publication (DE-A)
These are the polyamines and polyaminopolyols described in 38 09 695. Reference is made to these documents, including the preferred embodiments described. Still other preferred compounds are polyaminoamides, or condensation products of diprimary amines with dicarboxylic acids such as adipic acid or dimerized fatty acids, and polyglycol polyamines or amine adducts such as amine-epoxy resin adducts. Is.

Examples of suitable polyamines (A2) are ethylenediamine, propylenediamine, 2-methylpentamethylenediamine, pentamethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, neopentyldiamine, octamethylenediamine, triacetonediamine, Dioxadecanediamine, dioxadodecanediamine and higher homologues thereof, cycloaliphatic diamines such as 1,2-, 1,3- or 1,4-cyclohexanediamine, and laurylpropylenediamine and tallowpropylenediamine, 4,4'-methylenebiscyclohexylamine, 4,4'-isopropylenebiscyclohexylamine,
Isophoronediamine, tricyclododecenyldiamine,
Menthanediamine, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 3-aminomethyl-1- (3-aminopropyl-1-methyl) -4-methylcyclohexane, N-methylethylenediamine, N-amino Ethylpiperazine, 2-aminoethylpiperazine, N, N-dimethylethylenediamine,
N, N-dimethylpropylenediamine, N, N-dimethylaminopropylamine, N, N-bisaminopropyl-N, N'-dimethylaminopropylamine, N, N-dihydroxyethylenediamine, aromatic amines such as m-xylene Diamines, aliphatic poly (tri-, tetra-) amines such as diethylenetriamine, dipropylenetriamine, bishexamethylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine,
Methylamino-bis propylamine, N- alkylamino dipropylenetriamine amines (alkyl _{= CH 3 -, C 4 H} 9 -,
(CH ₃ ) ₂ N (CH ₂ ) _3- ), tetrapropylenepentamine, and alkanolamines such as aminoethylethanolamine, N- (2-hydroxypropyl) ethylenediamine, ethylene glycol bispropylamine, hydroxyethylaminoethylamine, Hydroxyethyldiethylenetriamine, polyoxypropylenediamine (preferably having an average molecular weight of about 200 to 400 g / mol). A preferred polyamine is N, N-bisaminopropyl
-N-methylamine, N-aminopropylmethylamine, N-
Aminopropylpropylamine, tallow propylenediamine, and especially dimethylaminopropylamine, and diethylaminopropylamine and N-cyclohexyl-1,3
-Propylenediamine, 3-dimethylaminopropylamine, 2-diethylaminoethylamine and dimethylaminoneopentylamine.

Phenol (A3), which can be used alone or as a mixture, is phenol,
Mention may be made of m-cresol, 3,5-dimethylphenol, m-ethoxyphenol, p-hydroxybenzylphenol and o-hydroxybenzylphenol. Preferably, a phenol (A3) containing at least two phenolic hydroxyl groups, such as resorcinol, hydroquinone, 4,4'-di-hydroxydiphenylmethane, an isomer mixture of dihydroxydiphenylmethane (bisphenol F), bis (4-hydroxy-3). -Methylphenyl) methane, 2,2-bis (4-hydroxyphenyl)
Propane (bisphenol A), 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy)
-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,2-, 1,3-, 1,
5-, 1,6-, 2,2'- and 4,4'-dihydroxybiphenyl,
4,4'-, 3,4'- and 3,3'-dihydroxy-2,2'-bipyridyl, 4,4'-dihydroxydiphenyl sulfone, 4,4'-bis (4-hydroxyphenyl) valeric acid and It's 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-3-tert.-
(Butylphenyl) propane, bis (2-hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene, bis (4-hydroxyphenyl) ether, or hydrogenated, chlorinated and brominated products of the above compounds, and novolaks . Particularly preferably, resorcinol, bisphenol A and bisphenol F are used.

The phenols used in particular as phenol (A3) are alkylated, arylated or alkalized, optionally isomerized, mono- and / or polyhydric phenols. In the meantime, alkylation, arylation or aralkylation refers to electrophilic substitution with an unsaturated compound on the aromatic ring of the phenolic matrix structure. Phenol (A3) has especially the formula XI

[0089]

Embedded image

[Wherein R ¹² is (C ₂ -C ₁₈ ) -alkyl, preferably (C ₂ -C ₄ ) -alkyl, (C ₅ -C ₆ ) -cycloalkyl,
Phenyl, phenyl substituted by at least one (C ₁ -C ₁₈ ) -alkyl group, (C ₂ -C ₁₈ ) -alkyl substituted by at least one phenyl group, and d is
A number from 0 to 4, preferably 1 or 2, and e
Is a number from 1 to 5, where the value of e is less than or equal to the difference of 5-d] or formula XII

[0091]

Embedded image

[Wherein f is 1 or 2 and g is 1 to 2]
4, g'is 0 to 4, h is 1 or 2,
M is = CH- or heteroatom, preferably a nitrogen atom, R ²² is R ^21, R ^{22 'is} H or R ^21,
K is a single bond, CH ₂ , C (CH ₃ ) ₂ , S (O), S, SS, C (O)
Or formula XIII

[0093]

Embedded image

Is a group represented by:

[0095]

Embedded image

A group of the formula: or the formula XIV

[0097]

Embedded image

A group represented by the following formula:
R ²³ , R ²⁴ , R ²⁵ , R ²³ ′, R ²⁴ ′, R ²⁵ ′ are, independently of each other, hydrogen or (C ₁ -C ₄ ) -alkyl, and i and j are independently of each other. 1 to 4].
Alkylation, which is preferably used in the present invention,
In order to produce arylated or alkalized phenols (A3), the phenolic parent structure is a monocyclic or polycyclic phenol, such as phenol, preferably two or more hydroxyls on the same aromatic ring. Phenols having groups such as phloroglucinol, pyrogallol, hydroquinone, pyrocatechol, especially resorcinol can be used.

Other suitable phenolic matrix structures are phenols based on fused aromatic systems. This is, for example,
Formula XV

[0100]

Embedded image

Or formula XVI

[0102]

Embedded image

[In the above formulas, k is 0 to 2 and l
Is 1 to 3, preferably 1 or 2, where k
And l are at least 2, and z is = CH-,
> C = O 2, oxygen atom or nitrogen atom].

These include, for example, 1,4-dihydroxynaphthalene and its positional isomers, dihydroxyanthraquinone, quinizarine, anthraflavic acid. Furthermore, phenol (A3) can also be used as a phenolic matrix structure to produce further compounds (A3).

Mono (alkylaryl) phenols, which are preferably used as phenol (A3), are compounds known per se and are frequently cited in the literature as styrenated phenols. Austrian Patent (AT-C) No. 28
According to JP 4444, the reaction of styrenes with phenols is known, which is essentially an alkylation reaction, in which the vinyl group of the styrene is attached to the hydroxyl group of the phenyl in the ortho or para position. . In this reaction,
Friedel-Crafts catalysts such as acids and Lewis acids are commonly used. Depending on the reaction conditions, the catalyst and the proportion of each reactant, the product is mono-, di- or tri-styrenated phenol. German patent application publication (DE-A) No. 19 4
No. 0 220 also describes arylalkylphenol products and processes for their preparation.

Preferred arylalkylphenols (A3)
Add vinyl compounds to phenolic compounds in the presence of mineral acids or Friedel-Crafts catalysts in a known manner, wherein the molar amount of phenolic hydroxyl groups in the phenol and the molar amount of aromatic vinyl compounds are It can be produced by setting the ratio to the amount of 1: 1 to 1: 2. Vinyl compounds that can be used are natural or synthetic compounds with one or more carbon-carbon double bonds, which in the latter case can also include conjugated double bonds. Unsaturated fatty acids, fatty oils derived therefrom, fatty acid amides or fatty alcohols can be used as natural unsaturated compounds. Other suitable starting compounds are unsaturated natural substances based on terpenes, such as turpentine oil and rosins. Synthetic unsaturated hydrocarbon compounds include alkenes, dienes or hydrocarbons having a higher degree of unsaturation, such as butene, isobutene, isooctene, isononene and isododecene, or diunsaturated compounds such as butadiene, isoprene, chloroprene, dichloro. Butadiene and dicyclopentadiene can be used. Also, a mixture of alkenes, such as occurs in the cracking or dehydrogenation of hydrocarbons such as petroleum, or in the oligomerization of olefins, especially isobutylene, propylene or n-butene, or in the coal oxidation of coal. , And optionally a mixture of alkenes and alkanes can be used. Furthermore, acetylenically unsaturated compounds such as acetylene, or (C ₁ -C ₁₀ ) -alkyl- and / or di-
(C ₁ -C ₁₀ ) -Alkylacetylene is also suitable.

It is also possible to use, for example, the following unsaturated compounds as starting materials for the production of the modified phenolic compounds (A3): n-pentene- (1), n-hexene-
(1), n-octene- (1), n-nonene- (1), n-decene- (1), n
-Undecene- (1), n-dodecene- (1), propylene- (1), n
-Butene- (1), methyl at the 2 or 3 or optionally 4 position, ethyl, n-propyl, isopropyl,
Alkenes above substituted with n-butyl, isobutyl, sec.-butyl or tert.-butyl groups; 2,3-dimethyl-n-butene, 3,3-dimethyl-n-butene, 2,5-dimethyl Heptene, 3,3-dimethylheptene, 2,3,4-trimethylheptene, 2,4-dimethylheptene, 2,3-dimethylheptene, 4,4-dimethylheptene, 2,3-diethyl Hexen, 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; Similar alkenes with a double bond at the 2 or 3 position in the molecule; Isobutylene or n-butene dimerization (octenes), or isobutylene or n-butene trimerization (dodecenes) ) Or the branched alkenes obtained in the form of a mixture in the trimerization of propylene (nonenes) and / or the tetramerization of propylene (dodecenes).

The aromatic vinyl compounds used are especially styrene derivatives. Examples of styrene derivatives are α-methylstyrene, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, commercially available vinyltoluene (mixture of isomers), 3,4-dimethylstyrene, 2,4-dimethyl. Styrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, 3,4-diethylstyrene, 2,4-diethylstyrene, 2,5-diethylstyrene Styrene, 2,6-diethylstyrene, o-
Propylstyrene, m-propylstyrene, p-propylstyrene, o-isopropylstyrene, m-isopropylstyrene, p-isopropylstyrene, o-butylstyrene, m-
Butyl styrene, p-butyl styrene, o-isobutyl styrene, m-isobutyl styrene, p-isobutyl styrene,
sec.- butylstyrene, m-sec.-butylstyrene, p-se
c.- butylstyrene, o-tert.-butylstyrene, m-ter
t.-Butylstyrene, p-tert.-butylstyrene, p-bromostyrene, p-chlorostyrene, 2,4-dibromostyrene, 2,4-dichlorostyrene and 2,4,6-trichlorostyrene.

Particularly preferred vinyl compounds have the formula XVII

[0110]

Embedded image

[Wherein R ²⁶ is a hydrogen atom or a methyl group, and R ²⁷ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms or a formula

[0112]

Embedded image

(Wherein R ²⁸ independently has the same meaning as R ²⁶ )], and an aromatic vinyl compound such as styrene and α-methylstyrene. In order to produce the polymer (A) or the polymer mixture (A) from the components (A1), (A2) and (A3), an epoxide,
The molar ratio between the compounds containing cyclic carbonate, amino and phenol groups should be chosen such that the phenol, carbonate and epoxide groups are fully incorporated. As a reaction sequence of this, the compound (A1) is reacted with other components in a stepwise manner, or, for example, the compound (A2) blended with the compound (A3) is reacted with the compound (A1). You can also The reaction is usually run until a constant or theoretical amine number is obtained. In line with this,
The reaction of compounds (A1), (A2) and (A3) is carried out at elevated temperature,
For example, it is carried out at a stoichiometric ratio required at a temperature of 40 to 300 ° C., preferably 50 to 250 ° C., particularly preferably 80 to 200 ° C., and a solvent and / or a catalyst as required. Can be used. Care must be taken to prevent gelation. All amines can be reacted all at once with epoxide and / or carbonate groups, or a stepwise procedure can be applied to this. In this way, it is also possible to obtain mixtures of various epoxy-amine adducts and / or carbonate-amine adducts. The reaction with amines already begins at room temperature and is generally exothermic. In order to achieve complete reaction, it is generally necessary to raise the temperature temporarily to values between 40 and 250 ° C. A catalyst is generally not required for the reaction between a primary amino group and a 2-oxo-1,3-dioxolane (carbonate) group, but a catalyst for the reaction of a relatively low-reactivity secondary amino group. It is convenient to use Suitable catalysts for this purpose are strongly basic compounds such as quaternary ammonium compounds, for example alkyl-, aryl- and / or benzylammonium hydroxides and the corresponding carbonates. At this time, a particularly representative example of the quaternary ammonium compound is (C ₁₆ -C
₂₂ ) -Alkylbenzyldimethylammonium hydroxide, benzyltrimethylammonium hydroxide and tetrabutylammonium hydroxide. Preferred as catalysts are strongly basic amines such as diazabicyclooctane (DABCO) and guanidine. Other compounds suitable for this are so-called supernucleophilic catalysts.
(supranucleophilic catalyst), such as 4-pyrrolidinyl pyridine and poly (N, N-dialkylaminopyridine)
(For this, RA Vaidya et al.
lymer Preprints ”, Volume 2 (1986), pages 101-102).

In some cases, the production of the new resin system comprises
It can be carried out by adding a solvent, provided that the solvent can be removed under reduced pressure after the completion of the resin synthesis, for example, glycol ethers such as ethylene glycols, propylene glycols, butylene glycols, for example, methyl ether. Glycol, ethyl glycol, butyl glycol, methyldiglycol, ethyldiglycol, butyldiglycol, methyltriglycol, ethyltriglycol, butyltriglycol, methyltetraglycol, ethyltetraglycol, butyltetraglycol, Polyglykol M-250 (polyethylene Hoechst AG registered trademark of glycol monomethyl ether, molecular weight = 260 ~
275 g / mol, OH number = 204-215 mg / g), Polyglykol M-3
50 (registered trademark, molecular weight = 335 to 365 g / mol, OH value = 154
~ 167 mg / g), 2-n-propoxyethanol, 2- (1-methylethoxy) ethanol, 2-n-butoxyethanol, 2,
5,8,11-tetraoxadodecane, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, tripropylene glycol monoethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, Propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol
n-butyl ether and propylene glycol phenyl ether.

The polymer (B) contains at least one hydrophilic substructure which is nonionic under the pH conditions to which it is applied. An example of such a polymer (B) is an adduct of a hydroxy compound with a resin containing an epoxide group, preferably a terminal epoxide, belonging to the class of polyglycidyl ethers or polyglycidyl esters. As the epoxide-containing resin, it is preferable to use a polymer having a terminal epoxide group, which belongs to the class of polyglycidyl ether or polyglycidyl ester.

As the hydroxy compound, organic compounds containing at least one hydroxyl group are used alone or as a mixture. Preferably mono-, bis
-Or a tris-hydroxy compound, particularly preferably a monohydroxy compound is used. In the present invention, the term monohydroxy compound refers to monoalcohols and monoetherified polyoxyalkylene glycols. Monoalcohols which can be used are preferably alkane- or cycloalkane-monoalcohols, especially C ₈ to C ₃₂ alcohols and their isomers,
For example, 2-ethylhexanol, octanol, nonanol, decanol, dodecanol, and stearyl-,
Cetyl-, ceryl- and myricyl alcohol, TDC-Alko
hol M (registered trademark of Hoechst AG, molecular weight = 166 g / mol, OH
Value = 327 mg / g), wool wax alcohol, cholesterols, borneols, isoborneols and tallow oil fatty alcohols. The properties can optionally be modified by using C ₁ -C ₆ alcohols containing alkane and cycloalkane chains in a weight proportion of 0 to 95%, based on the total weight of the monohydroxy compound.
Examples of this alcohol are butanol, hexanol, cyclohexanol and / or mixtures thereof.

The monoetherified polyoxyalkylene glycols used are preferably compounds of the formula XVIII R ²⁹ — (O—CHR ³⁰ —CHR ³¹ ) _r —OH of the formula XVIII. In this formula, R ²⁹ is an alkyl, cycloalkyl or phenyl group, preferably 1 to
Is an alkyl group having 12 and especially 1 to 4 carbon atoms, R ³⁰ and R ³¹ are hydrogen or an alkyl group having 1 to 4 carbon atoms, and r is 1 to 10, preferably Is 1 to 4. Examples of such compounds that may be mentioned are:
Methyl glycol, ethyl glycol, butyl glycol, methyl diglycol, ethyl diglycol, butyl diglycol, methyl triglycol, ethyl triglycol, butyl triglycol, methyl tetraglycol, ethyl tetraglycol, butyl tetraglycol, Polyglykol M-250 ( Registered trademark, molecular weight = 260-275
g / mol, OH number = 204-215 mg / g), Polyglykol M-350
(Registered trademark, molecular weight = 335 ~ 365 g / mol, OH value = 154 ~
167 mg / g), propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-
Butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether and propylene glycol phenyl ether.

The polymer (B) can be obtained by a method known per se,
The epoxide group-containing resin is combined with a hydroxy compound and a catalyst such as Lewis acid (European Patent Application Publication No. 0 272 595).
No.), imidazoles (Macromolecules, 1989, 22 , 9)
9), cyclic quaternary ammonium compounds (US Pat.
639), tin compounds (European Patent Application Publication No. 0 4
98 504) or alkaline earth metal perchlorates (Polym
er Bulletin 1989, 22, pp. 221-226).

The mixture of polymers (A) and (B) can be made from polymers which have been prepared separately, in which case, if necessary, prior to complete or partial neutralization in water, Thereafter, the polymers (A) and (B) are combined and, if necessary, the water-insoluble polymer (C) in the form of latex particles, already completely or partially neutralized, if necessary, ) And (B) in the presence of an ethylenically unsaturated compound by emulsion polymerization.

In a preferred embodiment of this method, the amino-containing polymer (A) is prepared in the presence of at least one nonionic water-dilutable polymer (B). (A) and (B)
Suitable neutralizing agents for the novel polymer mixtures of organic acids such as formic acid, dimethylolpropionic acid, acetic acid,
Glycolic acid, gluconic acid, hydroxyacetic acid, propionic acid, butyric acid, lactic acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid and stearic acid,
Preferably both formic acid, acetic acid and lactic acid and inorganic acids such as phosphoric acid, sulfuric acid, boric acid and hydrochloric acid are included. The degree of neutralization is generally 5 and 12 based on the amino groups present.
It is between 0%, preferably between 10 and 90%.

In the present invention, the synthetic resin mixture contains not only the polymer resins (A) and (B) but, in some cases, the polymer resin (C). The polymer resin (C) is produced by emulsion polymerization in the presence of the at least partially neutralized polymer resin (A) and polymer resin (B). resin
(A) and (B) should be present in an amount suitable to obtain the desired emulsifying and stabilizing effect. In the meantime, for both economic reasons and for the purpose of affecting the performance properties of the emulsion polymer to be produced, such as water resistance, redissolvability and drying rate, the resins (A) and (B ) Must not be too high or too low. Therefore, the preferred solids mass content of polymers (A) and (B) together is 4-40%, in particular 8-20%. According to this,
The total mass ratio of the resins (A) and (B) is such that the resins (A), (B) and
Very good flow control (rheology-contro) when less than 20%, preferably less than 15% of the total mass of (C).
lled) dispersion (RC dispersion) is also obtained.

Emulsion polymerization methods are well known to those skilled in the art.
A common feature of this is that the radical polymerization of ethylenically unsaturated monomers takes place in the aqueous phase in the presence of radical initiators and emulsifiers, protective colloids or other stability. Each of the above components can be incorporated into the emulsion polymerization process in various ways. The new polymer resin
If (A) is used as a stabilizer in emulsion polymerization, the good emulsification performance of this polymer makes the use of low molecular weight surfactants and protective colloids unnecessary. The majority of the aqueous phase is usually present as the initial charge, and a portion of the water can be added during the reaction in the form of a solution of the radical initiator or a monomer pre-emulsion. All or part of the stabilizer can be included in the initial charge, the rest being metered in during the polymerization. The monomers can be all present in the initial charge or can be metered in in pure form or as a pre-emulsion in water.
Some radical initiators are usually included in the initial charge and others are usually metered in as an aqueous solution. Initial filling is usually 20-99
The mixture introduced into the reactor before the reaction temperature of ° C was established. Polymerization is often initiated by thermal decomposition of radical initiators or by redox systems,
It can be considered as complete (between 20 and 99 ° C.) when most of the monomers that can react by radical chain reaction have reacted. This method typically leaves about 0.001-0.1% by weight residual monomer. Further methods and method embodiments are described, for example, in Ullmann, Enzyklopaedie der technischen C
hemie, 4th edition, Verlag Chemie, Weinheim (1980), 19th
Volume 132 pages and beyond, and Encyclopedia of Polymer Scienc
eand Engineering, 6th edition, Wiley & Sons, New York, 1
986, pages 1-51.

The polymer (C) of the dispersion is prepared, at least in large part, from monomers which have a low solubility in water and which remain soluble even when the pH is changed. The term low solubility here applies to substances having a solubility at 25 ° C. of less than 10% by weight, in particular less than 5% by weight. This low solubility monomer proportion must be at least not sufficient to render the resulting emulsion polymer insoluble in the aqueous phase under the polymerization conditions and to make it present in the form of dispersed particles. I won't. According to the invention, at least 70% by weight, in particular at least 90% by weight
Preference is given to using mixtures which consist of monomers of low solubility.

Suitable monomers include at least one ethylenically unsaturated group. "Ethylenically unsaturated",
The terms “vinyl unsaturated” and “α, β-unsaturated” are used interchangeably. Those skilled in the art will recognize that such monomers can be combined to form a polymer under emulsion polymerization conditions in an aqueous medium. Such monomers include, for example, vinyl compounds, styrenes and acrylates and their derivatives. Examples of suitable compounds include vinyl chloride and vinyl esters such as vinyl acetate, vinyl propionate, Versat.
Included are vinyl esters of ic acid as well as vinyl fatty acid esters such as vinyl laurate. Suitable styrene compounds include, for example, styrene, vinyltoluene, α-methylstyrene, ethylstyrene, isopropylstyrene, tert.-butylstyrene, 2,4-dimethylstyrene, diethylstyrene, o-methyl-p-isopropylstyrene,
Halostyrenes such as chlorostyrene, fluorostyrene and iodostyrene, 2,4-dicyanostyrene, hydroxystyrene, nitrostyrene, aminostyrene and phenylstyrene. Particularly preferred are styrene, vinyltoluene and α-methylstyrene. Examples of suitable acrylates include acrylic acid esters, methacrylic acid esters and crotonic acid esters, such as esters having a hydroxyl function such as hydroxyethyl acrylate and hydroxyethyl methacrylate. In emulsion polymerization, of course, it is also possible to polymerize mixtures of such ethylenically unsaturated monomers, provided that these monomers are suitable for copolymerization. To obtain a dispersion having a glass transition temperature higher than 75 ° C., preferably styrene,
Polymerization is initiated from styrene derivatives and / or methacrylates.

Suitable initiators are the customary water-soluble radical-forming compounds, such as hydrogen peroxide, peracetic acid, perbenzoic acid and peroxodisulfates, such as potassium or ammonium peroxodisulfate, perphosphates, peroxycarbonates and hydroperoxides. , For example tert.-butyl hydroperoxide. Examples of suitable redox catalyst systems are sodium persulfate / formaldehyde-sodium sulfoxylate, cumene hydroperoxide / sodium metabisulfite, hydrogen peroxide / ascorbic acid and sulfur dioxide / ammonium persulfate. Furthermore, 4,4-
Azo compounds such as azobis (cyanopentanoic acid) are also suitable. The initiator is used in customary, catalytically effective concentrations. This concentration is generally a weight percentage between 0.01 and 4.0%, based on the weight of the dispersion.

In one particular embodiment, further components customary for emulsion polymerization can be used. this is,
For example, accelerators, buffers, and any other ingredients conventionally known as relating to emulsion polymerization processes that can be used with the novel polymer in the emulsion polymerization reaction mixture. The novel dispersions of polymers (A), (B) and (C) in the above combination show excellent printing properties, good storage stability, good gloss and outstanding deinking properties.

The novel synthetic resin system is, for example, an inking device equipped with a dampening device for a sheet or roller offset machine, a sheet or roller offset printing machine, a sheet coating machine, a separate type coating machine for an intaglio printing and flexographic printing machine. Used paper, plywood (Pappe),
Very suitable for overprint varnish for printing thick paper (Kartonagen). The novel resin solution (polymer (A) and optionally polymer (B), and polymer (D) and optionally polymer (B)) and dispersion (polymer (A))
, Polymer (B) and (C) as required, and polymer (D) and (C), and optionally polymer (B)), when used as the binder vehicle of the overprint varnish, their solid mass Content is generally 20-75
%, Preferably 30 to 60%. This varnish is 1-70
% The novel dispersion and / or 1-40% new solid resin by weight, 0-60% by weight glycols or glycol ethers, 0-30% by weight wetting agent. , A neutralizing agent (acid) in a mass ratio of 0 to 35%,
Natural and / or synthetic waxes in a mass proportion of 0 to 30%,
It contains a defoamer in a weight proportion of 0 to 2.5%, water in a weight proportion of 0 to 80% and optionally a pigment in a weight proportion of up to 20%, preferably a translucent pigment and a special effect pigment. In order to incorporate additives such as colorants and leveling agents into the solution and / or dispersion and / or their mixtures and / or their dilutions, a common conventional roll machine (Mahlg
eraete), mixers, kneaders and kneaders (Anreibegeraete)
Can optionally be used in the presence of conventional dispersing aids.

Production of suitable resins which can be used in the present invention, and production of stable polymer dispersions by emulsion polymerization,
And its use in printing varnishes is further described in the examples below.

[0129]

EXAMPLES In the following examples, parts and contents represented by "%" (percentage) are mass ratios unless otherwise specified. All reactions are performed under inert gas (N ₂ ). Example 1: Epoxy / epoxy-amine system Commercial polyglycidyl ether based on bisphenol A with an epoxide group content of 5200-5600 mmol / kg (epoxide equivalent of about 180-192 g / mol, Beckopox EP.
140 (registered trademark of Hoechst AG), 59 g) with methyl tetraethylene glycol (molecular weight 208 g / mol, boiling range 280
˜350 ° C., 67 g) and 150 ° C. with commercial Anchor 1040 (amine-boron trifluoride adduct, Achor®, 250 mg). As soon as the mass content of epoxide oxygen atoms (“epoxide value”) reaches a value lower than 4 g / 100 g, commercially available Genamin SH 100 (stearylamine, a registered trademark of Hoechst AG, 27 g), N, N-dimethyl Aminopropylamine (21g) and commercial bisphenol A
(95 g) were added sequentially to the above resin composition, then 5200-5
Commercially available polyglycidyl ether based on bisphenol A (Beck, with an epoxide group content of 600 mmol / kg)
opox EP 140®, 231 g) is slowly metered in so that no gelation occurs. 50 mg / g amine number, 85
A synthetic resin system with a weight average molecular weight M _{w of} 00 g / mol and a glass transition temperature T _g of 46 ° C. is obtained. Example 2 Commercially available polyglycidyl ether based on bisphenol A with an epoxide group content of 5200-5600 mmol / kg (epoxide equivalent weight of about 180-192 g / mol, Beckopox EP.
140, 66g) to methyltetraethylene glycol (28
g), butyldiglycol (29g) and catalyst Anchor 1040
Keep at 150 ° C with (registered trademark, 500 mg). As soon as the epoxide value reaches below 4 g / 100 g, bisphenol A (95 g), Genamin SH 100 (registered trademark, 27
g) and N, N-dimethylaminopropylamine (21 g),
Sequentially added to the above resin composition, then 5200-5600 mmol /
Commercially available polyglycidyl ethers based on bisphenol A with an epoxide group content of kg (about 180-192 g /
Epoxy equivalent of mol, Beckopox EP 140, 231g) are metered in. A synthetic resin system is obtained with an amine number of 64 mg / g, a weight average molecular weight M _{w of} 8700 g / mol and a glass transition temperature T _g of 48 ° C. Example 3 Commercially available polyglycidyl ether based on bisphenol A (Beckopox EP 140, 67 g) having an epoxide group content of 5200-5600 mmol / kg, methyl tetraethylene glycol (25 g), butyl diglycol (31 g) and Catalyst A
Keep at 150 ° C with nchor 1040 (380 mg). As soon as the epoxide value reached a value below 4 g / 100 g, bisphenol A (96 g), cyclohexylamine (10 g) and N, N-dimethylaminopropylamine (22 g) were sequentially added to the above resin composition, Then commercially available polyglycidyl ethers based on bisphenol A (Beckopox EP 140, 231 g, having an epoxide group content of 5200-5600 mmol / kg)
). 74 mg / g amine number, 8800 g / mol
A synthetic resin system is obtained having a weight average molecular weight M _{w of} and a glass transition temperature T _g of 67 ° C. Example 4 The synthetic resin system (100 g) of Example 1 was mixed with lactic acid (90% concentration, 10%).
g) and water (60 g) directly or vice versa under hot conditions, and the mixture is further diluted with water (117 g). 520
A glossy paste with a viscosity of mPa · s (Ubbelohde), a pH of 3.8 and a solids content of 34% (3 h / 100 ° C.) is obtained. Example 5 A solution of the synthetic resin system of Example 3 (48 g) is heated to 90 ° C. with lactic acid (90% strength, 3.3 g) in water (95 g). Styrene (391g) and, in parallel, ascorbic acid (6g) and tert.-butyl hydroperoxide in water (616g)
(4 g) are metered in over a period of 3-4 hours. 30
35% by filtering through a μm filter
A fine dispersion having a solids content by mass (measured by drying; 3 h, 100 ° C.), a pH of 3.7 and a viscosity of 480 mPa · s (Ubbelohde) is obtained. Example 6 The gloss paste of Example 4 (30 g) was mixed with the dispersion of Example 5 (59
Mix homogeneously with g). By adding water (8g),
33% solids mass content and 4mm DIN at 23 ° C
An overprint varnish with an outflow time of about 60 s in the cup is obtained. Example 7 A print is made with the melt-type printing ink described in DE-A 25 34 845 and is then coated with the overprint varnish of Example 6. Place two printed pages (DIN A4) with their printed sides on top of each other, and place a brass weight so that an area of about 5 cm in diameter exerts a mass force of 1 kg, and 90 ° C. Leave for 5 hours. After cooling, the two sheets could be separated from each other without any problems. Example 8 The procedure of Example 7 is repeated, except that the printed matter is printed with the melt-type printing ink described in DE-A 42 05 713. In this case, the binder is stearyl alcohol (50 parts) and hydroxyl-containing acrylate resin (50 parts, Macrynal SM 51
0 (registered trademark of Hoechst AG) was used as a binder. The two DIN A4 sheets, laid with their printed sides on top of each other, likewise showed no blocking in the above test method. Example 9 A monomer mixture consisting of acrylic acid (36g), styrene (27g) and α-methylstyrene (31g), and in parallel thereto cumene hydroperoxide (1.4g) was stabilized at a temperature of 170 ° C. N-Methylpyrrolidone (23 g) is metered in with stirring over a period of about 5 hours and the mixture is kept at this temperature for a further hour. After separation and removal of N-methylpyrrolidone under reduced pressure at 230 ° C, 243
Acid value of mg / g, glass transition temperature T _{g of} 141 ° C and 13 kg / mol
A solid resin having a molecular weight M _w of is obtained. 1-Methoxy-2-propanol was added to the liquid polymer before solidification.
(11.5g) and acetic acid (100%, 9.4g) were added and this material was placed in water (143g) / ammonia (25% concentration, 36g), solids mass content of 33.5%, pH of 9.1 and 1521 mPa
A resin solution having a viscosity of s (Ubbelohde) is obtained. Example 10 The resin solution of Example 9 diluted with water to a solids content of 25% is heated to 90 ° C. under a nitrogen atmosphere (600 g). temperature
Once at 90 ° C, styrene (10g) and in parallel water
Ammonium peroxodisulfate (0.
4 g) is added and the mixture is stirred at 90 ° C. for 20 minutes. Then styrene (440 g) and, in parallel thereto, ammonium peroxodisulfate (2 g) in water (200 g) are metered in over a period of about 3 hours. A redox system was added to the mixture as needed, and the mixture was reacted for about 1 hour and then cooled to give a solid content of about 47.8%, a pH of 8.7 and a viscosity of about 1230 mPa · s (Ubbelohde).
A homogeneous dispersion is obtained with Example 11 A print is made with the melt-type printing ink described in DE-A 25 34 845 and then coated with the overprint dispersion of Example 10. Place two printed pages (DIN A4) with their printed sides on top of each other, place a brass weight on it to add a mass of 1 kg to an area of about 5 cm in diameter, and at 90 ° C. Leave for 5 hours. After cooling, the two sheets could be separated from each other without any problems. Example 12 The procedure of Example 11 is repeated, except that prints printed with the melt-type printing ink described in DE-A 42 05 713 are used. In this case, as the binder, stearyl alcohol (50 parts) and hydroxyl-containing acrylate resin (50 parts, Macrynal SM
A binder consisting of a mixture of 510 (registered trademark of Hoechst AG) was used. The two DIN A4 sheets, laid with their printed sides on top of each other, likewise showed no blocking in the above test method. Example 13 Commercially available maleic acid-modified rosin (Alresat KM 379, registered trademark of Hoechst AG) and commercial soybean oil-modified alkyd resin (63% oil content, 25% phthalic anhydride, Alftalat AS,
A gloss overprint varnish containing Hoechst AG's) was produced: Boil the above material at 240 ° C for 30 minutes. After cooling,
This mixture was mixed with 33.0% by weight of Somentor 33 (Esso AG
(Hamburg) registered trademark, mineral oil, boiling range 205-250
Dilute using ℃, aniline point 65 ℃. Measurement data: Viscosity at 20 ° C 110 dPa ・ s (Rotary viscometer, disk / cone) Adhesion value (Tackscope) 30 ° C 140 Maximum adhesive value 220 Time until maximum value is obtained 1 minute Example 14 Commercially available phenol Resin-modified rosin (Albertol KP 351,
A gloss overprint varnish containing Hoechst AG® and a commercial ricinene oil-modified alkyd resin (68% oil content, Alftalat AR 680, Hoechst AG®) was prepared: These ingredients are dissolved within 45 minutes at 18 ° C and then cobalt octoate 0.2 and zirconium octoate 1.0 are added. Viscosity at 20 ℃ 125 dPa ・ s (Rotary viscometer, disk / cone) Adhesiveness / 30 ℃ * PKWF 4/7: Mineral oil, boiling range 240-270 ℃, aniline point
72 ° C., Johann Haltermann (Hamburg) Example 15 A printed matter was prepared using the melt-type printing ink described in German Patent Application Publication (DE-A) 25 34 845, and then the overprint dispersion of Example 13 was prepared. Use to coat. Place two printed pages (DIN A4) so that their printed surfaces overlap each other, and place a brass weight so that an area of about 5 cm in diameter adds a mass of 1 kg,
Then leave at 90 ° C for 5 hours. After cooling, the two sheets could be separated from each other without any problems. Example 16 The procedure of Example 15 is repeated, except that the German patent application is published.
(DE-A) The printed matter printed using the fusion type printing ink described in Japanese Patent No. 42 05 713 was used. At this time, as a binder, stearyl alcohol (50 parts) and a hydroxyl-containing acrylate resin (50 parts, Macrynal SM 510,
A binder consisting of a mixture of Hoechst AG®) was used. Example of overprint varnish used
14 things. The two DIN A4 sheets, placed with their printed sides on top of each other, also showed no blocking in the above test method.

Claims (23)

[Claims] 1. A coating in a print having at least two layers with different compositions, wherein the softening temperature of the top layer and optionally further top layers is at least 60 ° C. and the base layer The above coating at least 10 ° C higher than that. 2. The coating according to claim 1, wherein the softening temperature of the top layer and optionally of the further top layer is at least 80 ° C. 3. The softening temperature of the top layer and optionally of the further top layer is at least lower than that of the base layer.
The coating of claim 1 or 2 which is 20 ° C higher. 4. The coating according to claim 1, wherein the top layer has an average absorbance of less than 10% in the visible range. 5. The coating according to claim 1, wherein the softening temperature of the top layer is reduced by not more than 10 ° C. by contact with the substances present in the layer below it. 6. The coating according to claim 1, wherein the softening temperature of the top layer is reduced by 20 ° C. or less by contact with the substances present in the layer below it. 7. The coating according to claim 1, wherein the softening temperature of the top layer is reduced to a temperature not lower than 70 ° C. by contact with the substances present in the layer below it. 8. The base layer contains a color-forming pigment.
Any one coating. 9. The coating according to claim 1, wherein the base layer contains a dye. 10. The coating according to claim 1, wherein the top layer comprises a coloring pigment in an amount such that its absorbance in the visible range does not rise above 10%. 11. The coating according to claim 1, wherein the top layer comprises the dye in an amount such that its absorbance in the visible range does not rise above 10%. 12. The base layer is a film-forming material (a), capable of dissolving this material (a) in a fluidized state, 40
The coating according to any one of claims 1 to 11, which comprises a material (b) having a softening point higher than ° C and a coloring pigment or dye. 13. The coating of claim 12, wherein material (b) is crystalline in the solid state. 14. The coating according to claim 1, wherein the top layer is formed by film formation from an organic solvent solution of a binder. 15. The coating according to claim 1, wherein the top layer is formed by film-forming from a dispersion of an ionically or non-ionically stabilized binder in an aqueous medium. 16. In a first step, a coating containing a color-forming pigment or dye and a film-forming material (a) is applied to a portion of the surface of the substrate to be printed, and an auxiliary agent (c) is applied,
Then, in the second step, a film of the base layer consisting of the paint of the first step is formed by removing the auxiliaries or by physical or chemical conversion, and in the third step, the film is formed on at least the entire printed surface. Consisting of a third stage paint by applying a further paint containing the forming material (a ') and an auxiliary (c') and then removing the auxiliary in the fourth step or by physical or chemical conversion A coating according to any one of claims 1 to 15, which comprises forming a top layer film, wherein the top layer film formed in the fourth step is transparent and exhibits an average absorbance of less than 10% in the visible range. Forming method. 17. The auxiliary (c) is a material in a fluidized state.
a material (b) capable of dissolving (a) having a softening point higher than 40 ° C., and the film formation of the base layer in the second stage is carried out by cooling the paint in the first stage, 17. The method according to claim 16, wherein the material (b) and the film-forming material (a) are separated from each other, and at least most of the material (b) is transformed into a crystalline state. 18. Auxiliary agent (c) in the paint in the first step
Is composed of a volatile component and a non-volatile material (b), and the formation of the base layer film in the second step is carried out by heating the paint in the first step, at the time of volatilization of the auxiliary agent (c). 17. The method of claim 16, wherein the sex component evaporates, then the remaining material (b) and the film-forming material (a) separate, and the material (b) is transformed, at least for the most part, into the crystalline state. 19. The method according to claim 16, wherein the third-stage coating material is a solution of a film-forming component in an organic solvent. 20. The method according to claim 16, wherein the third stage paint is a dispersion of an ionically or non-ionically stabilized film-forming component in water. 21. The third stage paint is a dispersion of a cationically stabilized film forming component in water.
18 any one way. 22. The method of any one of claims 16-21, wherein a further top layer membrane is applied from a solution or aqueous dispersion onto the fourth stage top layer membrane. 23. A printed matter produced using the method according to any one of claims 16 to 22.