DE19536679A1 - Coating in printed products, consisting of several layers, and process for their preparation - Google Patents

Description

DE-A 42 05 713 printing inks, especially gravure inks be known whose binder from a polymeric, amorphous portion and a low molecular weight, crystalline portion which melts when heated and dissolves the polymeric portion. Upon cooling, the low molecular weight crystallizes Share again, and the color will solidify. An advantage of these hot melt inks is because they contain no volatile solvents and therefore no Plants for the recovery or combustion of the solvents are needed. Another advantage arises from the fact that z. B. the electrical installation to the Printing machines and in the printers not explosion-proof what must be when using the most flammable organic solvents is required.

However, it may be disadvantageous that the low molecular weight, crystalline Proportions in the cooling of the melt at least partly in the polymeric, remain dissolved amorphous portion and its softening temperature significantly decrease. If such printed products such. As magazines increased Temperatures exposed, such as in the blazing sun, inside of Vehicles or on a radiator, so they stick by the so-called Block the ink undetachably together. This blocking is done by Interdiffusion of the resin molecules at the interface causes. This diffusion can not be prevented or reduced by the fact that the softening Temperature of the ink by appropriate selection of the components is set higher because inevitably also increases the temperature at which the viscosity of the ink for processing is sufficient is low.  

DE-A 25 34 845 discloses melt printing inks whose binders thermoplastic resins with softening temperatures from 90 to 140 ° C, in particular polyamide resins based on dimerized fat acids, optionally in admixture with other resins such. B. Kolopho niumharzen.

These inks also soften on the printed product and can be used during printing Exceeding the corresponding temperature also lead to blockage.

It was therefore the object to modify the print layer so that the Blocking the printing inks is safely prevented without the processing is difficult.

It has now been found that the described problem is surprisingly simple can be solved by that be with a melt ink be Printed printed matter coated with an overprint varnish, the of the in neither dissolved nor contained in the crystalline ink contained crystalline portion is softened.

In principle, all overprint varnishes which are suitable for this purpose are suitable for this purpose comply, for example, oil-based paints and nitrocellulose paints. Prefers but one uses nonionic, anionic or cationic aqueous over Printing inks, like the melt inks, are not organic solvents contain.

Anionic overprint varnishes are aqueous solutions of polymers which by copolymerization of vinyl monomers and a mass fraction of 0.5 up to 20% of one or more α, β-olefinically unsaturated carboxylic acid (s) to be obtained. By neutralization with a base, preferably with Ammonia or amines, these polymers are water-soluble.  

Cationic overprint varnishes contain basic components as film-forming constituents Synthetic resins obtained by neutralization with an acid, in particular non-oxidised mineral acids such as phosphoric acid or organic acids such as Amei acid, acetic acid or lactic acid, become water-soluble. Preferred basi synthetic resins are aminopolyetherpolyols obtained by reaction of Epoxy resins are obtained with primary and / or secondary amines.

The invention therefore relates to coatings in printed products, characterized in that the coating comprises at least two layers having mutually different composition, wherein the Erwei temperature of the top layer and optionally the other deck layers at least 60 ° C, preferably at least 80 ° C and at least 10 K (10 ° C), preferably at least 20 K (20 ° C) is higher than that of the base layer.

Usually, a cover layer is sufficient to block the at lower To prevent temperature softening inks safely. However, it is Also provided in the invention, aufzubrin several layers This is particularly advantageous if the top layer, although a sufficiently high softening temperature to block the To prevent ink, however, by one or more components of Is plasticized, whereby their softening temperature on a insufficient height is lowered. In this case it will be on the base layer a first topcoat printed, the softening temperature alone is not yet in any case must be sufficient to prevent blocking. The Zu Composition of the first topcoat is chosen here so that the against lateral solubility of the first topcoat and the base components layer is so small that the first top coat is not or only slightly is softened. Next he also serves as a barrier layer by the diffusion the softening components through this first topcoat layer prevented or at least reduced so far that the lowering of the  Softening temperature of the subsequent topcoat layer by eindiffun dierende components of the base layer below 20 K (20 ° C), preferably below 10 K (10 ° C) and thus the effect of the upper top coat layer is not is impaired. Preferably is intended by the contact with the base layer no lowering of the softening temperature of the cover layer below 70 ° C respectively.

In this case, the cover layer has only a low absorption of light, preferably The average visible light absorption is less than 10%.

Usually, only the base layer contains color pigments or Dyes, the topcoat layers should have the highest possible transparency respectively. Preferably, the average light absorption in the visible region is in the topcoat layer at most 10%, more preferably at most 5%. It is However, also possible in a structure with, for example, three layers of lower topcoat layer, for example, dyes or so-called Effektpig pigments, such as pearlescent pigments or translucent color pigments can modify the appearance of the printed image of the base layer.

The inventive multilayer structure of the coating in pressure equipment is chosen especially when using melt inks, in which the binder by heating in a fluid form with a Printing method is brought appropriate viscosity. Using such inks can cause problems when the print products at least temporarily after its completion, higher temperature be exposed. The top coat layer is not only the Blocking means gluing on one another with the printed side Printed products prevented, but also the flat bleeding. Is to it is necessary that the cover layer to the underlying base layer zones have sufficiently high adhesion. This point of view goes along  the choice of the appropriate topcoat binder for a given base layer binder.

Particularly advantageous is the multilayer structure of the invention in the from DE-A 42 05 713 known solvent-free inks. These Printing inks consist of coloring pigments or dyes and a binder consisting of a film-forming material (a) and a low refractory material (b) with a softening temperature, or in preferred case of a crystalline substance, a melting temperature of about 40 ° C, wherein the substances (a) and (b) on heating a form fluid mixture with a viscosity adapted to the printing process. The material (b) acts as a solvent for the film-forming material (a). After cooling to ambient temperature, the components separate (a) and (b) largely, material (b) then forms predominantly one separate phase and is mainly in the crystalline state.

Advantageously, the multilayer structure of the invention is also in solution medium-pressure inks, the film-forming material (a) by adding a Auxiliary (c) consisting of at least one volatile solvent and a nonvolatile solvent (b) at one at the processing temperature brought the printing process adapted viscosity. This material (b) forms after removal of the volatile solvent and optionally after Cool at ambient temperature as described above by segregation to a substantial extent, preferably for the most part a separate Phase and is preferably in the crystalline state.

To prepare the topcoat can be dissolved in solvents film-forming components or even dispersed in aqueous solution filmbil insert the components. In the course of reducing the solvent Pollution and avoidance of organic solvents, it is preferable to use aqueous dispersions of topcoats. This will be the bandage  by incorporation of ionic groups or nonionic hydrophilic Groups modified so that the stable form aqueous dispersions.

The invention further relates to a method for producing a Be coating in printed products, characterized in that in the first Step on the parts to be printed on the surface of the substrate a Be coating agent is applied, the coloring pigments or color and a film-forming material (a) contains and auxiliaries (c), the in a second step by removing the same or by a physi or chemical conversion, the formation of a base-layer film the coating composition of the first step causes, and that in the third step at least on the entire printed surface further coating agent is applied, which consists of a film-forming Material (a ') and a tool (c') consists, in a fourth step by removing it or by a physical or chemical Conversion of the formation of a topcoat film from the coating middle composition of the third step causes, in the fourth Step formed topcoat film is transparent and an average Visible absorption of less than 10%.

In the case of a solvent-containing printing ink, the auxiliary corresponds to (c) the solvent which is volatilized by heating. In the case of one Melt ink according to DE-A 42 05 713 corresponds to the auxiliary (c) the crystalline substance (b). The component (b) is capable of heating the Component (a) to solve, on cooling demix the two components and (b) for the most part changes to the crystalline state.

However, it is also possible mixtures of one in the Trocknungsbedin nonvolatile crystalline substance (b) and a volatile solvent use, wherein the crystalline substance alone also a non-solvent for the binder resin (a) may be; the solubility of (a) then becomes alone  caused by the presence of the volatile solvent in the auxiliary (c). After removing the volatile solvent, separate the components (a) and (b) the ink, thereby causing the viscosity to skyrocket. It is usually no complete segregation required; in any case lies then an at least two-phase mixture in which a phase rich in (a) and arm to (b) and another phase poor in (a) and rich in (b). is (b) a crystalline substance, this latter phase may also be crystalline or predominantly crystalline. The component (b) preferably has one Softening point (melting point, if (b) is crystalline) above 40 ° C, more preferably above 60 ° C and most preferably above 80 ° C.

Suitable binders for the cover layer (s) are resins which are composed of organic Solvent can be applied, such as oil-based or nitrocel luloselacke.

However, preference is given to resins which can be applied from aqueous solution. The Resins can become water-soluble by modification with hydrophilic building blocks or water-dispersible. Suitable nonionic hydrophilic Blocks are, for example, several consecutive Oxyäthylen- or Oxypropylene building blocks or mixtures thereof. Also suitable are such Resins containing by content of anionic or cationic groups be rendered water-soluble or water-dispersible. The cationic or anionically modified resins can also be used in addition to nonionic hydrophilic resins Contain groups. There are also mixtures of several cationic Resins (A), mixtures of cationic (A) and nonionic (B) resins, Mi mixtures of anionic resins (D) and mixtures of anionic (D) and nonionic (B) resins. As the basic body are all resins, ie Polymers, polycondensates and polyadducts used in the synthesis reaction can be modified hydrophilic by incorporation of appropriate comonomers NEN, and such resins, which after the building reaction by polymer-analogous Implementation or under molecular enlargement or reduction so chemically can be modified so that a sufficient hydrophilicity is achieved.  

According to the invention it is also possible from solution or from aqueous Dispersion on top of each other to apply several topcoat layers.

The glass transition temperature of the resins (A), (B) and (D) is preferably at least 60 ° C, preferably at least 70 ° C, more preferably at least 80 ° C.

Suitable examples are ionic vinyl polymers (D), which are used as monomers Esters of α, β-olefinically unsaturated carboxylic acids and the α, β-olefinic unsaturated carboxylic acids themselves, in admixture with other vinyl mono mers such as vinyl halides and vinyl aromatics. These polymers, the individually or in mixture or in mixture with the below closer described polymers (B) can be used by at least partially neutralization with alkalis soluble in water or water-dispersed gierbar.

Particularly preferred among the anionic polymers are the polymers with reduced foaming in water containing

• i) an optionally neutralized or partially neutralized acid groups containing polymer (D) prepared by polymerization of acid group penicylic, preferably carboxyl group-containing ethylenically unsaturated Compounds with other ethylenically unsaturated compounds in Presence of volatile basic neutralizing reagents and optionally "in situ" condensation with monohydroxy compounds, and optionally
• ii) a water-insoluble polymer (C) in the form of latex particles, manufactured bar by emulsion polymerization of ethylenically unsaturated Ver bonds in the presence of the polymer (D).

The acid numbers (the mass of potassium hydroxide in mg, used for neutralization of 1 g of solid resin is required) of the polymers (D) are preferably in  Range of 90 to 400 mg / g, in particular in the range of 170 to 275 mg / g. The mass fraction of hydroxy compounds bound in ester groups is preferably between 0 and 25%, in particular between 0 and 18%. Preferably, polymers (D) having a weight average molar mass of 300 to 100,000 g / mol, in particular 800 to 40,000 g / mol, more preferably 1 to 25 kg / mol used. The glass transition temperatures of the polymers are preferably between 0 and 180 ° C, in particular 30 and 160 ° C, particularly preferably 50 and 150 ° C.

According to the present invention, at least a partial neutralization the acid group-bearing monomers with volatile basic compounds during the polymerization to the polymers (D) according to the invention required. The carboxyl group-containing monomers z. B. are stronger Acids as the carboxyl group-containing polymers produced therefrom, so that the monomers displace the polymers from their salts. Therefore, it stands always a sufficient proportion throughout the polymerization neutralized carboxylate group-containing monomers for the polymerization to disposal. This is probably a polar change Effect of local accumulation of polar monomers during the Prevented macromolecule formation, so that the monomers largely stati can be incorporated into the macromolecule.

For introduction of carboxylic acid groups into the polymer of type (D) olefinically unsaturated mono- or dicarboxylic acids or mixtures thereof settable. Examples of unsaturated monocarboxylic acids are acrylic acid, methacrylic acid, crotonic acid, angelic acid and tiglic acid, individually or in a mixture. These include half-esters of male and female Fumaric acid with saturated alcohols containing 1 to 10 carbon atoms contain. As unsaturated dicarboxylic acids are dicarboxylic acids, the 4 to 6 Contain carbon atoms, called, for example, maleic acid, itacon acid, mesaconic acid, fumaric acid, methylenemalonic acid, citraconic acid, their  Salts or optionally anhydrides. The mass fraction of the carboxyl groups containing monomers is preferably 5 to 70%, especially 15 to 55%, based on the total mass of the monomers in the polymer (D).

Suitable comonomers for the carboxylic acid group-containing monomers in principle, all radically polymerizable olefinically unsaturated Verbindun are preferred, hydrophobic monomers, such as vinyl aromatics or open-chain conjugated dienes used. For example, be mentioned Styrene, vinyltoluene, α-methylstyrene, ethylstyrene, iso-propylstyrene, tert. Butylstyrene, 2,4-dimethylstyrene, diethylstyrene, o-methyl-p-isopropylstyrene, Halogen styrenes such as chlorostyrene, fluorostyrene and iodostyrene, 2,4-cyanostyrene, Hydroxystyrene, nitrostyrene, aminostyrene and / or phenylstyrene. Preferred are in particular styrene, vinyltoluene and α-methylstyrene. As open-chain dienes 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 such as 2-chloro-1,3-butadiene, 2-cyano-1,3-butadiene, substituted straight-chain conjugated pentadienes, straight and branched conjugated hexadienes, other straight or branched conjugated dienes of 4 to 12 carbon atoms atoms and their mixtures. The mass fraction of these comonomers is preferably 30 to 95%, in particular 45 to 85%, based on the total mass of the monomers in the polymer (D).

To achieve special properties can also other output mono such as esters of acrylic, methacrylic and crotonic acid with saturated alcohols containing 1 to 12 carbon atoms in the alcohol residue th, individually or in mixture. For example, be ge named methyl methacrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate. The mass fraction of these comonomers is preferably 0 to 10%, in particular 0 to 5%, based on the total mass of the monomers in Polymer (D).  

As further comonomers one or more can be selected from Acrylamide, methacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, acrylic amidosulfonic acid, vinyl acetate, vinylsulfonic acid, allylsulfonic acid, vinyl phosphonic acid, allylphosphonic acid, acrylonitrile, methacrylonitrile, dimethyl aminoethyl acrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, N-vinylpyrrolidone, N-vinylformamide, N-vinylimidazole, N-vinylimidazoline, 1- Vinyl-2-methyl-2-imidazoline. Those monomers of this group, the acid groups contained in the copolymerization in the form of the free acid or partially or completely with alkali metal bases or ammonium bases of neutralized form. The basic acrylates, at For example Diäthylaminoäthylacrylat be neutralized with acid or quaternized and then fed to the copolymerization. In addition, you can Vinyl esters of α, α-dialkylalkane monocarboxylic acids, for example vinyl esters the ®Versaticsäure, but also vinyl acetate and vinyl propionate used become. These modifying monomers are merely for the purpose of achieving special properties and are in mass proportions of 0 to 10%, preferential example 0 to 4%, involved in the structure of the copolymers (D).

Monohydroxy compounds according to the invention monoalcohols and understood mono-etherified polyalkylene oxide compounds. As monoalcohols are those with alkane or cycloalkane radicals, preferably (C₈-C₃₂) alcohols and their isomers, for example 2-ethylhexanol, octanol, nonanol, decanol, Dodecanol, also stearyl, cetyl, ceryl, myricyl alcohol, ®TCD-alcohol M (Registered trademark of the company Hoechst AG, molar mass 166 g / mol, OH number 327 mg / g), wool wax alcohols, cholesterols, borneols, isoborneols and tall oil fatty alcohols.

Optionally, to modify the properties also (C₁-C₆) alcohols with alkane and cycloalkane chains in mass fractions of 0 to 35% be used on the proportion of monohydroxy compounds, for example Example, butanol, hexanol, cyclohexanol and / or mixtures thereof.  

As mono-etherified polyalkylene oxide polyalkylene oxide Ver compounds of general formula I.

R⁴¹- (O-CHR⁴²-CHR⁴³) _n -OH formula I

used. In this formula, R⁴¹ is an alkyl, cycloalkyl, or phenyl radical, preferably an alkyl radical having 1 to 12, in particular 1 to 4 Carbon atoms, R⁴² and R⁴³ are hydrogen or alkyl radicals with 1 to 4 carbon atoms and n is 1 to 10, preferably 1 to 4. Als Examples of such compounds are methyl glycol (2-methoxyethanol), Ethyl glycol (2-ethoxyethanol), butyl glycol, methyl diglycol (2- (2-methoxy ethoxy) ethanol), ethyldiglycol, butyldiglycol, methyltriglycol (triethylene glycol monomethyl ether), ethyl triglycol, butyl triglycol, methyl tetraglycol (Tetraäthy glycol monomethyl ether), ethyl tetraglycol, butyl tetraglycol, ® polyglycol M- 250 (registered trademark of the company Hoechst for polyethylene glycol monomethyl ether, molar mass 260 to 275 g / mol, OH number 204 to 215 mg / g), ®glycol M-350 (molar mass 335 to 265 g / mol, OH number 154 to 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 called.

As monohydroxy compounds in the context of this invention are also cycli ester, preferably having four or more carbon atoms in the ring, wherein the carbon atoms of the ring instead of hydrogen also other sub substituents such as alkyl, cycloalkyl, aryl, aralkyl, alkoxy. Mention may be monoalkyl-substituted ε-caprolactones such as monomethyl, Monoethyl, monopropyl, monoisopropyl, monoethylhexyl, monodecyl, Monododecyl-ε-caprolactone; furthermore dialkyl-ε-caprolactone, in which themselves the two alkyl groups on the same or on two different not but both are located at the ε-C atom; furthermore trialkyl-ε-caprolactones in which  two or three carbon atoms in the ring are substituted, as long as at ε-C Atom does not have two substituents; furthermore alkoxy-ε-caprolactones such as Methoxy and ethoxy-ε-caprolactone; furthermore cycloalkyl, aryl and aralkyl ε- caprolactones such as cyclohexyl, phenyl and benzyl-ε-caprolactone. Prefers is the unsubstituted ε-caprolactone.

Other cyclic esters used in the invention can and at least one capable of ring opening inner ester enthal Th are γ-butyrolactone, γ-valerolactone, ethylene carbonate, tetramethylenecar carbonate, 2,2-dimethyl-4-phenyl-1,3-dioxolan-5-one, α-n-propyl-δ-valerolactone, δ, δ-dimethyl-δ-valerolactone, 3-ethyl-1,4-dioxan-2-one, 3,3,6-trimethyl-1,4-di oxan-2-one, tetramethyl glycolide, tetraphenyl glycolide, 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-dithiane-2,5-dione, trimethylene carbonate, neopentyl carbonate, Ethyleneoxolane, β-methyl-ε-isopropyl-ε-caprolactone, propyleneoxolane, 4-hydroxycyclohexanecarboxylic acid lactone, cis-disalicylidene and trisalicyclid, as well as their mixtures. Preferred compounds are γ-butyrolactone, δ-valero lactone, pivalolactone, thiobutyrolactone, β-butyrolactone, ε-caprolactone and their mixtures.

In the context of the invention come as volatile neutralizing reagents basic compounds which under the reaction conditions with the Carboxyl groups do not form a covalent bond. Preferably suitable are amines, in particular tertiary amines, amides, furthermore heterocycles, ins particular electron-poor heteroaromatics, for example pyridine, pyridazine, Pyrimidine, pyrazine, quinoline or isoquinoline. Particularly preferred volatile basic neutralizing reagents are represented by formula II,

in the
R⁴⁴ is alkyl or cycloalkyl, preferably having 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms, wherein the alkyl radical may also be branched
R⁴⁵: (CH₂) _l ,
Z: (CH₂) _m or O,
l: 0 to 5 and
m: 1 to 5 mean.

Examples which may be mentioned are N-methyl-2-piperidine, N-ethyl-2-piperidine, N-methyl pyrrolidone, N-ethylpyrrolidone, N-methylcaprolactam, 2,5-piperazinedione and Called N-methyl-2-oxazolidone. Particularly preferred is N-methylpyrrolidone (N-methyl-2-pyrrolidinone).

The volatile basic neutralization reagents are in one part added sufficient neutralization of the carboxyl groups-containing Monomers allowed before their incorporation into the growing macromolecule. For a polymerization under standard conditions, this means that a Mole fraction of volatile basic neutralizing reagents of preferably at least 10%, in particular 20 to 70%, based on the molar amount of the carboxyl-containing monomers sufficient.

The synthesis of the polymers (D) is usually carried out at temperatures of 20 to 400 ° C, preferably at 80 to 300 ° C, especially at 100 to 230 ° C, performed. Advantageously, at constant temperature under Nor maldruck and if necessary with simultaneous separation of Low  boil, but also with overpressure, preferably up to 15 bar, in particular to 5 bar, worked.

The initiation of the polymerization for the preparation of the polymers (D) can by the thermally decomposing radical generator known to those skilled in the art the series of azo compounds, peroxides, peracid esters or hydroperoxides respectively. Preference is given to using organic peroxides, preferably Dialkyl peroxides, in particular di-tert-butyl peroxide, di-tert-amyl peroxide or Cumene hydroperoxide.

To control the copolymerization can optionally with the addition of a solution be worked through, after completion of the reaction by Distilling off, preferably under reduced pressure, is removed. The Mass fraction of the solvent is up to 50%, preferably up to 20%, especially without further solvent, based on the Polymer (D). The solvent used is preferably 3-ethoxyethyl propionate zen, which reacts under the reaction conditions as capped Äthylacrylat. If necessary, to limit the degree of polymerization of the Experts well-known regulator can be added, for example those based on organic thio compounds.

After completion of the synthesis, the volatile basic Neutralisa tion reagents of the polymers (D) by distillation, preferably under reduced pressure, are separated and are then usually without elaborate cleaning available for reuse.

The copolymers (D) can be at least partially neutralized with Bases such as ammonia or amines, preferably tri-, di- or monoalkyl amines, for example triethanolamine, morpholine, or alkanolamines such as Amino-1-methyl-1-propanol or alkali or alkaline earth metal hydroxides or their Dissolve mixtures in water and are very beneficial as a binder for  aqueous overpressure dispersions or as stabilizers for the emulsion poly to use. In general, it is sufficient, a part to carry out neutralization of 50 to 95%, but is preferably an over shot neutralization to a pH of 7.5 to 11, preferably 8 to 9th

For the preparation of the solution of at least partially neutralized resin in Fabri kationsmaßstab has the inverse dilution, so the direct entry of Resin melt of the copolymer of type (D) in water / neutralizing agent at a resin temperature of 100 to 250 ° C, preferably 150 to 220 ° C and proved to be advantageous at least normal pressure. Conveniently, is the aqueous mixture then at least normal pressure for 30 min to Held at 80 to 95 ° C, preferably at about 90 ° C for 3 hours. optional especially in high-viscosity melts of resins with high glass over transition temperature with low molecular weight saturated aliphatic carbon acids and / or added with glycol ethers to a significant Ab To achieve lowering of the melt viscosity. Here are mass shares up to 20% of aggregates based on the resin content appropriate. When Carboxylic acids are formic acid, lactic acid, malonic acid, succinic acid, Tartaric acid or citric acid, preferably acetic acid used. When Glycol ethers may be mentioned ethers of ethylene glycol, propylene glycol, butylene glycol, for example 2-n-propoxyethanol, 2- (1-methylethoxyethanol), 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- Äthoxyäthoxy) ethanol and / or 1-methoxy-2-propanol used. Übli However, the inverse dilution is completely without addition of Solvents performed.  

According to the invention contain the resin mixtures in addition to the ionic Polymers (D) optionally also nonionic hydrophilic polymers (B). The Preparation of the polymers (B) is carried out as described below via Emul polymerization in the presence of at least partially neutralized polymer (D). The polymers (D) should be present in an amount that is sufficient is to bring about the desired emulsifying effects. On the other hand should both for economic reasons and for reasons of influence the performance properties of the emulsion to be prepared polymerisate the proportion of polymers (D) should not be too high. It will therefore a mass fraction of polymers (D) of 4 to 56%, in particular 10 to 50% preferably used, based on the sum of the masses of the polymers (D) and (B). Very good results are achieved when mass fractions of preferably 12 to 42% polymers (D) are used, based on the Sum of the masses of (D) and (B).

Particularly preferred are cationic (A) and nonionic (B) water-soluble or water-dispersible resins, since these are used in the reprocessing of the Paper according to the so-called "de-inking process" in an alkaline bath better separated from the cellulosic shares. The resins or Polymers (A) and (B) can each be used individually or as a mixture use.

Suitable cationic polymers (A) are in particular amino-containing Polymers whose amino groups are replaced by quaternizing or by Neu at least partially converted into cationic groups with acid can be. Nonionic, water-dilutable polymers (B) are those Polymers containing a nonionic hydrophilic substructure.

The weight-average molar mass of the amino group-containing polymer (A) is preferably in the range between 3 and 50 kg / mol, in particular of 4 to 25 kg / mol, more preferably from 6 to 10 kg / mol.  

The weight average molar mass of the polymer (B) is preferably in the Range of 0.4 to 5 kg / mol, in particular from 1 to 4 kg / mol.

The polymers (A) according to the invention are preferably reaction products from at least one compound in each case from the groups (A1) epoxides, Carbonates or epoxide carbonates, (A2) amines and (A3) phenols, esp re epoxy-containing resins (A11) with preferably terminal Epoxy groups and / or carbonate group-containing resins (A12) with preference example, terminal carbonate groups from the groups polyglycidyl ether, Polyglycidyl esters and polyglycidylamines with optionally polyvalent ones Phenols (A3) and / or alcohols and with saturated and / or unsaturated secondary and / or primary amines (A2) or aminoalcohols. Latter can be attached to the alkyl radical by at least one primary and / or secondary Hydroxyl group, by a dialkylamino group and / or by a primary Amino group which is temporarily protected by ketimine formation, be modified.

The epoxide compounds used (A11) have on average at least one, preferably two 1,2-epoxide groups per molecule. You can both saturated and unsaturated and aliphatic, cycloaliphatic, aromatic and heterocyclic and also have hydroxyl groups. You can continue to contain such substituents, among the mixing or Reaction conditions cause no disruptive side reactions, at for example alkyl, aryl substituents, alkyl / aryl substituents, Ether groupings or similar. Such epoxy compounds (A11) are For example, glycidyl ethers of polyhydric phenols, for example Resorcinol, hydroquinone, 4,4'-dihydroxydiphenylmethane, mixtures of isomers of dihydroxydiphenylmethane (bisphenol F), 4,4'-dihydroxy-3,3'-dimethyl diphenylmethane, 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol A), 4,4'-dihy droxydiphenylcyclohexane, 2,2-bis- (4-hydroxy-3-methylphenyl) -propane, 4,4'-di hydroxydiphenyl, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxybenzophenone,  Tris (4-hydroxyphenyl) methane, 1,1-bis- (4-hydroxyphenyl) -isobutane, 2,2-bis (4-hydroxyphenyl) -methane hydroxy-3-tert-butylphenyl) -propane, bis (2-hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene, bis (4-hydroxyphenyl) ether or the hydrogenation, Chlorinating and brominating products of the above-mentioned Ver bonds, as well as novolacs. Also proportionate use of glycidyl ethers Polyhydric alcohols as compounds (A11) is possible. As examples such polyhydric alcohols are ethylene glycol, diethylene glycol, tri ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,5-pentanediol, 1,2,6- Hexanetriol, glycerin, trimethylolpropane and 2,2-bis (4-hydroxycyclo hexyl) -2,2-propane called.

Among glycidyl ethers in the context of this invention are preferably those Glycidyl ether of the general formula III

R 1, R ^{1 '} , R ^1'' = independently of one another H or C _m H _{2m + 1} ,
R² linear or branched saturated hydrocarbon radical having up to 8 carbon atoms, preferably -CH₂-,
R³, R ^{3 '} = each independently halogen, aryl, alkyl, aralkyl,
n = 0 to 8, preferably 1 to 6,
m = 1 to 8, preferably 1,
u, u '= independently understood 0 to 4, preferably 0 or 1 understood.

These polyglycidyl ethers have a number average molar mass M _n of about 0.2 to 10 kg / mol and an epoxide group content of about 200 to 8400 mmol / kg ("epoxide equivalent weight", molar mass divided by the number of epoxide groups per molecule, of about 120 to 5,000 g / mol). Such resins are reaction products of epichlorohydrin or Methylepi chlorohydrin with dihydroxydiphenylmethane (bisphenol F) or 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), and for example with dihydroxy benzophenone or dihydroxynaphthalene. Polyepoxides having a suitable molar mass are prepared either by selecting the molar ratios of bisphenol and epichlorohydrin or by reacting the monomeric Diglycidylverbin applications with further bisphenol optionally with the addition of cata- factors such as Lewis acids or phosphonium salts. The epoxy resins may be fully or partially hydrogenated or used in mixtures with different structure and molar mass.

Furthermore, a part of the polyglycidyl ether described by pure aliphatic polyglycidyl ethers of the formula IV

With
R⁴ = H or an optionally substituted (C₁-C₄) -alkyl radical,
v = 2 to 6 and
w = 2 to 100, preferably 3 to 50,

be replaced. Examples are bisglycidyl ethers of polypropylene glycol or Polybutylene glycol with different degree of polymerization. The epoxy resins can also by reaction with long-chain polyalcohols such as hexane diol-1,6, neopentyl glycol, ethoxylated neopentyl glycol, hydroxypivaline acid neopentyl glycol ester and bis (hydroxymethyl) cyclohexane, monoanhydro pentaerythritol and polytetrahydrofurandiol, polycaprolactone diol, polyca prolactamdiol or polybutadiene diol in the presence of suitable basic  or acidic catalysts such as boron fluoride-amine complexes. While polyhydric alcohols with primary hydroxyl groups are suitable Catalysts can be reacted directly with polyglycidyl ethers, polyols with secondary hydroxyl groups are first reacted with diisocyanate. The resulting isocyanate-terminated reaction product can then without Difficulties as a bridge between two polyglycidyl ether units below Magnification of the molecule and functionality are incorporated.

Next come as epoxy compounds (poly) glycidyl esters of the formula V.

in question with
R⁵ = linear or branched, saturated or unsaturated hydrocarbon radical having up to 40, preferably up to 10 carbon atoms or an optionally substituted by halogen or lower (C₁ to C₆) alkyl or alkoxy substituted phenyl radical and
p = 1 to 5, preferably 2 or 3, in particular 2.

Such polyglycidyl esters of polycarboxylic acids are obtained by the reaction tion of epichlorohydrin or similar epoxy compounds with an aliphati rule, cycloaliphatic or aromatic polycarboxylic acid, such as oxalic acid, Adipic acid, glutaric acid, terephthalic acid, hexahydrophthalic acid, 2,6-naphthalenedicarboxylic acid and dimerized fatty acid. examples for suitable compounds are terephthalic acid diglycidyl esters and Hexahydrophthalic.

As epoxy group-containing resins (A11) are also compounds in Question whose epoxide groups are partially reacted with amines. Such Amino-epoxy resins can also be used to lower the amine number with saturated or unsaturated polycarboxylic acids and / or hydroxyalkylcarboxylic acids  be further modified. Aliphatic, cycloaliphatic and / or aromatic Polycarboxylic acids of various chain lengths are, for example, adipic acid, Sebacic acid, fumaric acid and maleic acid and their anhydrides, iso phthalic acid and dimeric fatty acids. As hydroxyalkylcarboxylic acids Lactic acid, dimethylolpropionic acid or carboxyl and Hydroxylgrup understood pen-containing polyester. In the implementation of excess Low molecular weight polyglycidyl ethers with polycarboxylic acids and / or Polyalcohols are obtained as an intermediate modified polyglycidyl ether th, which can then react further with amines and / or amino alcohols.

Heterocyclic polyepoxide compounds may also be used such as 1,3-diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate or diep oxides from bisimides. Another suitable class of polyepoxides are Polyglycidyl ether of phenolic novolak resins with which the Funktionali can be increased from 2 to about 6 glycidyl groups per molecule. By defunctionalization with long-chain alkylphenols such as dodecylphenol additional partial structures can be installed.

Other suitable epoxy compounds are described in the manual "Epoxidverbin Applications and Epoxy Resins "by A. M. Paquin, Springer Verlag, Berlin 1958, Chapter IV, Lee, Neville's "Handbook of Epoxy Resins", 1967, Chapter 2 and in Wagner / Sarx, "Lackkunstharze", Carl Hanser Verlag (1971), p. 174 ff. described.

As carbonates (A12), any substances can be used, as long as they contain at least one, preferably two or three, 2-oxo-1,3-dioxolane groups (cyclic carbonate groups) per molecule and have no other functio nal groups, the reaction with the component (A2) disturb. The number-average molar mass M _n , determined by gel chromatography with polystyrenes as standard, should generally be between 100 and 10,000 g / mol, preferably between 150 and 5000 g / mol, and the content of cyclic carbonate groups between 650 and 10,000 mmol / kg ("2-oxo-1,3-dioxolane equivalent weight", molar mass divided by number of cyclic carbonate groups per molecule, between 100 and 1500 g / mol). The cyclic carbonate groups are preferably terminal, but compounds (A12) which contain these groups in random distribution throughout the molecular chain and which can be prepared by copolymerization using olefinically unsaturated compounds containing these cyclic carbonate groups can also be used. Such a manufacturing method is described for example in DE-A 36 44 373.

Preferably, the carbonate component (A12) has the general formula VI

with R⁶ = z-valent radical of a phenol, polyether, polyether polyol, polyester, polyester polyol, which may optionally also contain amino or alkylamino groups, or z-valent hydrocarbon radical, preferably alkylene radical having 2 to 18 carbon atoms, which may optionally carry inert groups , or
z-valent radical of a poly (sec.) amine or
Z-valent radical of a reaction product of an epoxy-carbonate compound with polyamines, polyols, Polycaprolactonpoly ols, hydroxyl-containing polyesters, polyethers, poly glycols, hydroxy, carboxy and amino-functional polymer oils having an average molar mass of 800 to 10 000 g / mol, polycarboxylic acids, hydroxy- or amino-functional polytetra hydrofurans and reaction products of polyamines with Glyci dylestern of α, α-Dialkylalkanmonocarbonsäuren the sum formula C₁₂H₂₂O₃ to C₁₄H₂₆O₃, such as Versatic acid (Shell chemistry, α-branched monocarboxylic acid with 9 to 12 carbon atoms),
z = 1 to 5, preferably 2 or 3, in particular 2.

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

In some cases, it may be appropriate as component (A1) in addition or optionally only mixed epoxide carbonates (A13) of general formula VII

with R⁶ '= (x + y) -value radical of a phenol, polyether, polyether polyol, polyester, polyester polyol, which may optionally also contain amino or alkylamino groups, or
(x + y) -valent hydrocarbon radical, preferably alkylene radical having 2 to 18 carbon atoms, which may optionally carry inert groups, or
(x + y) -valent poly (sec.) amine residue or
(x + y) -value radical of a reaction product of an epoxy-carbonate compound with polyamines, polyols, Polycapro lactonpolyolen, hydroxyl-containing polyesters, polyethers, polyglycols, hydroxy, carboxy and amino-functional polymer oils having average molar masses of 800 bis 10 000 g / mol, polycarboxylic acids, hydroxy- or amino-functional polytetrahydrofurans and reaction products of polyamines with glycidyl esters of α, α-dialkylalkane monocarboxylic acids of the empirical formula C₁₂H₂₂O₃ to C₁₄H₂₆O₃, for example the ®Versaticsäure,
x, y = independently of one another 1 to 5, preferably 2 or 3, in particular 1
to use.

Preferred starting materials for the preparation of the cyclic carbonates (A12) and optionally used mixed epoxy-carbonate compound (A13) are the polyglycidyl ethers of polyhydric phenols and Alkoho len, for example bisphenol A or bisphenol F. The glycidyl ether is obtained for example, by reacting a polyphenol with epichlorohydrin. Ge suitable polyphenols are, for example, 2,2-bis- (4-hydroxyphenyl) -propane, Bis (4-hydroxyphenyl) methane, 4,4'-dihydroxybenzophenone, bis (4-hydroxy phenyl) ether, 1,1-bis (4-hydroxyphenyl) isobutane, bis (2-hydroxynaphthyl) methane and 1,5-dihydroxynaphthalene. Preferably, additional free Hydroxyl groups to the epoxide groups in the polyglycidyl ether of polyphenol contain. Diglycidyl adducts of cyclic ureas can also be used.

As amines (A2), primary monoamines can be used, preferably with alkyl and alkanol groups, for example methylamine, ethylamine, propyl amine, isopropylamine, butylamine, isobutylamine, 2-aminobutane, ethanolamine, 4-aminobutanol-2, isoamylamine, pentylamine, 3-methylbutylamine, heptylamine, Octylamine, 2-ethylhexylamine, isononylamine, isotridecylamine, 2-amino methyl-1-propanol, n- or iso-propanolamine, neopentanolamine, methoxy propylamine, 2- (2-aminoethoxy) ethanol, coconut fatty amine, oleylamine, stearyl amine, tallow fatty amine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, Octadecylamine, cyclopentylamine, cyclohexylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-butoxypropylamine, 3-isononyloxypropylamine, 3 Aminopropyltrimethoxy (ethoxy-tridecyloxy) silane, 2-amino-2-hydroxymethyl  1,3-propanediol. It is also possible to use secondary monoamines, preferably dialkylamines, monoalkylhydroxyalkylamines or dihydroxyalkyl amines. 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, Dicokosamin, Ditalgfettamin or cyclic amines, such as morpholine, Pyrrolidine or oxazolidine or optionally substituted aniline. As well can reaction products of primary monoamines with monoepoxides be used as a substitute for the secondary amines.

Furthermore, primary amines of the general formula VIII

H₂N-CR⁷R⁸-R⁹-O- (CHR¹⁰-CHR¹¹O-) _q R¹² Formula VIII

be used with
R⁷ and R⁸ = hydrogen, an alkyl radical or a hydroxyl group,
R⁹ = linear or branched alkyl radical, in particular an alkyl radical having 1 to 3 carbon atoms,
R¹⁰ and R¹¹ = hydrogen or an alkyl radical having 1 to 4 Kohlenstoffato men,
R¹² = hydrogen, an alkyl, cycloalkyl or phenyl radical, preferably an alkyl radical having 1 to 6 carbon atoms
and
q = 0 to 5.

As examples of usable compounds of this type may be mentioned ethanol amine, propanolamine, butanolamine, ethylene glycol (2-aminoethyl) ether and di ethylene glycol mono (3-aminopropyl) ether. When using the primary amines the amine can be linked to the epoxide group depending on the offered  Stoichiometric ratios react under molecular enlargement. When Examples of diamines include ®Jeffamine M series, ®Jeffamine D series, ®Jeffamine ED series (registered trademark of Texaco Chemical Co.). Furthermore come di- or triamines with primary and / or secondary Amino groups in question, for example laurylpropylenediamine, tallow fat propyl diamine.

Polyamines according to (A2) are understood to mean compounds which are minde at least two amino groups in the molecule. Generally they have this Compounds 2 to 50, preferably 2 to 20 carbon atoms.

Examples of suitable polyamines (A2) are those which are only primary Contain amino groups and are preferably diprimär. These polyamines are preferably in admixture with diamines each having a primary and a tertiary amino group used.

As polyamines (A2), for example, those are suitable only seconds contain amino groups, preferably secondary diamines. Prefers become long-chain diamines, for example N, N'-Dialkyldiaminoalkane or Reaction products of monoepoxides, for example saturated glycidyl ethers or esters, or epoxyalkanes with primary diaminoalkanes For example, the addition product of 1,6-hexanediamine with 2 moles of glycidyls ester of Versatic acid. As monoepoxides can for this purpose too saturated or unsaturated glycidyl ethers or α-epoxides of various types Chain length such as 1,2-epoxydodecane or butylene oxide can be used.

As polyamines (A2) are also further such polyamines in question, the contain at least one free primary amino group and next to it additionally have secondary and / or tertiary amino groups.  

The polyamines (A2) can be obtained, for example, by the following formula IX be reproduced.

With
s = zero or an integer from 1 to 6, preferably 1 to 4,
R¹³ = a divalent, preferably non-aromatic hydrocarbon radical having 2 to 18 C-atoms, preferably a branched or unbranched alkylene radical having 2 to 10 C-atoms, in particular with 2 to 6 carbon atoms, or
a cycloalkylene radical having 5 to 12 carbon atoms, preferably 6 to 10 carbon atoms, or an aralkylene radical having 7 to 12 carbon atoms, preferably 8 to 10 carbon atoms,
or a polyoxyalkylene radical having 2 to 18 carbon atoms,
R¹⁴, R ^{14 '} = independently of one another H or

R¹⁵, R ^{15 '} = independently of one another H,
(C₁-C₂₀) -alkyl, preferably (C₁-C₆) -alkyl,
(C₁-C₁₆) -hydroxyalkyl, preferably

R¹⁶ = independently of R¹³ the meaning given for R¹³,
R¹⁷ = (C₁-C₁₂) -alkyl, -CH₂-O- (C₁-C₁₂) -alkyl,

R¹⁸ = H or (C₁-C₆) alkyl or
R¹⁵ and R¹⁶ = part of a 5-, 6- or 7-membered aliphatic ring with the proviso that for s equal to zero R ^{14 'is} not equal to H.

Furthermore, polyamines are also those of the formula X here

X- (R¹⁹NH) _t -R²⁰-Y formula X.

suitable, wherein X, Y = NH₂ or OH, but not the same meaning have and R¹⁹, R²⁰ independently of one another the meaning of R¹³ in the above formula IX and t have the meaning of s in the previous has the formula IX.

In addition, for example, the polyamines and polyaminopolyols ge in the patent applications DE-A 36 44 371, DE-A 37 26 497 and DE-A 38 09 695 are described. To these references including the The preferred embodiments described herein are hereby incorporated by reference taken. Furthermore, there are also polyaminoamides or condensations products of diprimary amines with dicarboxylic acids, for example Adipic acid or dimeric fatty acids, as well as polyglycol polyamines or amine adducts, for example amine-epoxy resin adducts into consideration.

Examples of suitable polyamines (A2) are ethylenediamine, propylenediamine, 2-methylpentamethylenediamine, pentamethylenediamine, hexamethylenediamine, Tri-methylhexamethylenediamine, neopentyldiamine, octamethylenediamine, Triacetonediamine, dioxadecanediamine, dioxadodecanediamine and higher homo loge, cycloaliphatic diamines such as 1,2-, 1,3- or 1,4-cyclohexanediamine and laurylpropylenediamine and tallow fatty propylenediamine, 4,4'-methylenebis cyclohexylamine, 4,4'-isopropylenebiscyclohexylamine, isophoronediamine, tri cyclododecenyldiamine, menthanediamine, 4,4'-diamino-3,3'-dimethyldicyclo hexylmethane, 3-aminomethyl-1- (3-aminopropyl-1-methyl) -4-methylcyclo hexane, N-methylethylenediamine, N-aminoethylpiperazine, 2-aminoethylpiperazine,  N, N-dimethylethylenediamine, N, N-dimethylpropylenediamine, N, N-dimethylamino propylamine, N, N-bisaminopropyl-N, N'-dimethylaminopropylamine, N, N-di hydroxyethylenediamine, aromatic amines such as m-xylylenediamine, aliphatic Poly (tri-, tetra-) amines such as diethylenetriamine, dipropylenetriamine, bishexa methylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylene hexamine, methyliminobispropylamine, N-alkylaminodipropylenetriamine (alkyl = CH₃-, C₄H₉-, (CH₃) ₂N (CH₂) ₃-), Tetrapropylenpentamin, further alkanolamines such as Aminoethylethanolamine, N- (2-hydroxypropyl) ethylenediamine, ethylene glycol bis propylamine, hydroxyethyl aminoethylamine, hydroxyethyl diethylenetriamine, poly oxypropylenediamine, preferably with a mean molar mass of about 200 to 400 g / mol. Preferred polyamines are N, N-bisaminopropyl-N-methylamine, N- Aminopropylmethylamine, N-aminopropylpropylamine, tallow fatty propylenediamine and in particular dimethylaminopropylamine and diethylaminopropylamine and N-cyclohexyl-1,3-propylenediamine, 3-dimethylaminopropylamine, 2-diethyl aminoethylamine, dimethylaminoneopentylamine.

As phenols (A3), which can be used individually or in a mixture, may be phenol, m-cresol, 3,5-dimethylphenol, m-ethoxyphenol, p-oxybenzylphenol and o-oxybenzylphenol. Preferably, phenols (A3) used which contain at least two phenolic hydroxyl groups, for example, resorcinol, hydroquinone, 4,4'-dihydroxydiphenylmethane, isomes ren mixtures 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'-dihydroxydiphenyl, 4,4'-, 3,4'- and 3,3'-dihydroxy-2,2'-bipyridyl, 4,4'-dihydroxydiphenylsulfone, 4,4'-bis (4-hydroxyphenyl) valeric acid and their amide, bis (4-hydroxyphenyl) sulfide, 2,2-bis (4-hydroxyphenyl) acetic acid and their 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 the hydrogenation, chlorination and bromination products of the aforementioned compounds, as well as novolacs. Beson Preferred are resorcinol, bisphenol A and bisphenol F.

As phenols (A3) find in particular alkylated, arylated or alkarylated, optionally isomerized, mono- and / or polyhydric phenols use. As alkylation, arylation or aralkylation here is the electrophilic Substitution on aromatic nuclei of phenolic parent with unsaturated Connections understood. The phenols (A3) are in particular characterized by the formulas XI

With
R²¹ = (C₂-C₁₈) -, preferably (C₂-C₄) alkyl, (C₅-C₆) -cycloalkyl, phenyl, with at least one (C₁-C₁₈) alkyl substituted phenyl, substituted with at least one phenyl radical (C₂-C₁₈ ) alkyl,
d = a number from 0 to 4, preferably 1 or 2, and
e = a number from 1 to 5, where the value for e is less than or equal to the difference 5 of minus d,
or formula XII

With
f = 1 or 2,
g = 1 to 4,
g '= 0 to 4,
h = 1 or 2,
M = -CH- or a heteroatom, preferably a nitrogen atom,
R ²² = the same meaning as R 21,
R ^{22 '} = H or the same meaning as R 21,
K = a single bond, CH₂, C (CH₃) ₂, S (O), S, SS, C (O) or a group of formula XIII

L = a hydroxyl group,

or a group of formula XIV

With
R²³, R²⁴, R²⁵, R ^{23 '} , R ^24' , R ^{25 '} = independently of one another hydrogen or (C₁-C₄) -alkyl,
i, j = independently 1 to 4.

For the preparation of the alkylated, preferably used according to the invention, arylated or alkarylated phenols (A3) can be used as phenolic bases mono- or polynuclear phenols, for example phenol, preferably those which carry a plurality of hydroxyl groups on the same aromatic ring, for example Phloroglucin, pyrogallol, hydroquinone, pyrocatechol, in particular Resorcinol, used.

Suitable phenolic bases are also phenols based on condensed aromatic ring systems. The latter are described for example by the formula XV

or formula XVI

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

Examples include 1,4-dihydroxynaphthalene and its position isomers, dihydroxyanthraquinone, quinizarin, anthraflavinic acid.  

It is also phenols (A3) in turn as phenol for the production serve further compounds (A3).

The preferred as phenols (A3) mono (alkylaryl) phenols are compounds known per se, which are also frequently styrenated in the literature te phenols are called. According to the statements in the Österreichi patent AT-C 284 444 are the reactions of styrenes with Known phenols; they are essentially alkylation reactions in which the vinyl group of the styrenes is ortho or para to the hydroxyl group of phenol added. In this reaction are generally Friedel-Crafts catalysts, for example acids and Lewis acids, used. Depending on the reaction conditions, catalysts and proportions of the reactants are obtained mono-, di- or tri-styrenated phenols. Also from the German Offenlegungsschrift DE- A 19 40 220 are arylalkylphenol products and methods of preparation the same known.

The preferred arylalkylphenols (A3) can be prepared by addition of a Vinyl compound to phenols at a ratio of the molar amount of phenoli hydroxyl groups in the phenol to the amount of aromatic vinyl ver from 1: 1 to 1: 2 in the presence of mineral acid or Friedel-Crafts Catalysts are prepared in a known manner.

As vinyl compounds may be natural or synthetic compounds with one or more carbon-carbon double bonds, in the latter Case also conjugated double bonds, can be used. As natural Unsaturated compounds may contain unsaturated fatty acids derived fatty oils, fatty acid amides or fatty alcohols. Suitable starting compounds are also unsaturated natural substances Terpene base, for example turpentine oil and rosin. As synthetic  Unsaturated hydrocarbon compounds can be alkenes, dienes or even higher unsaturated hydrocarbons are used, for example Butene, isobutene, isooctene, isonons, isododecene, or diunsaturated Compounds, for example butadiene, isoprene, chloroprene, dichlorobutadiene, Dicyclopentadiene. It is also possible to use mixtures of alkenes and optionally used by alkenes with alkanes, such as those used in the Cracking or dehydrogenation of hydrocarbons, such as petroleum, or oligomerization of olefins, especially isobutylene, propylene or n-butene or carbon oxidation arise. Also suitable are acety lenically unsaturated compounds, for example acetylene or (C₁-C₁₀) - Alkyl or di (C₁-C₁₀) alkyl acetylenes.

For example, the following unsaturated compounds may be used as starting material Substances for the preparation of modified phenolic compounds (A3) ver 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), the aforementioned Alkenes in the 2-position or 3-position or optionally 4-position the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, -tert.- Butyl group are substituted; 2,3-dimethyl-n-butene, 3,3-dimethyl-n-butene, 2,5-dimethylheptene, 3,3-dimethylheptene, 2,3,4-trimethylheptene, 2,4-di methylheptene, 2,3-dimethylheptene, 4,4-dimethylheptene, 2,3-diethylhexene, 4,4-dimethylhexene, 2,3-dimethylhexene, 2,4-dimethylhexene, 2,5-dimethyl hexene, 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; analog Alkenes whose double bond is in the 2-position or in the 3-position in the molecule lie; branched alkenes, as in the form of mixtures at the Di merization of isobutylene or n-butene (octene) or trimerization of Isobutylene or n-butene (dodecenes) or propylene (nonenes) or tetra merization of propylene (dodecenes) incurred.  

Styrenic derivatives are used in particular as aromatic vinyl compounds puts. As styrene derivatives are, for example, α-methyl styrene, styrene, o-methyl styrene, m-methylstyrene, p-methylstyrene, commercial vinyltoluene (isomers mixture), 3,4-dimethylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,6- Dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, 3,4-diethylstyrene, 2,4-diethylstyrene, 2,5-diethylstyrene, 2,6-diethylstyrene, o-propylstyrene, m- Propylstyrene, p-propylstyrene, o-isopropylstyrene, m-isopropylstyrene, p-isopropyl styrene, o-butylstyrene, m-butylstyrene, p-butylstyrene, o-isobutylstyrene, m-isobutyl styrene, p-isobutylstyrene, sec-butylstyrene, m-sec-butylstyrene, p-sec-butylstyrene, o-tert-butylstyrene, m-tert-butylstyrene, p-tert-butylstyrene, p-bromostyrene, p- Chlorostyrene, 2,4-dibromostyrene, 2,4-dichlorostyrene, 2,4,6-trichlorostyrene.

Particularly preferred vinyl compounds are vinyl aromatics Formula XVII

in the R²⁶ is a hydrogen atom or a methyl radical and R²⁷ is a hydrogen atom or an alkyl radical having 1-3 carbon atoms or the rest

in which R²⁸ independently may have the same meaning as R²⁶, for example, styrene and α-methylstyrene.

For the preparation of the polymers or polymer mixtures (A) from the components (A1), (A2) and (A3) are the molar ratios between epoxide, cyclic carbonate, amino and phenol group-containing compounds so to choose that complete incorporation of the phenol, carbonate and epoxide groups is guaranteed. This reaction sequence can be incremental  take place on compounds (A1) or be carried out so that at For example, compounds (A2) in admixture with compounds (A3) with the Compounds (AI) are reacted. The implementation will be in the so long made until a constant or the theoretical Amine number is reached. Reactions of compounds (A1), (A2) and (A3) are thereby in the required stoichiometric proportions at elevated temperatures, for example 40 to 300 ° C, preferably 50 to 250 ° C, more preferably between 80 and 200 ° C carried out, wherein optionally worked with the aid of solvents and / or catalysts can be. It is important to ensure that no gelation occurs. It can all amines simultaneously with the epoxide groups and / or carbonate groups implemented or it can be done gradually. It can do that too Mixtures of various epoxide-amine adducts and / or carbonate-amine Adducts are obtained. The reaction with the amines begins at Room temperature and is generally exothermic. To a complete To achieve implementation, it is usually necessary to change the temperature temporarily increase to values between 40 and 250 ° C. While for the Reaction of primary amino groups with the 2-oxo-1,3-dioxolane (carbonate) - Groups generally no catalyst is required is a catalysis for the reaction of the reactive secondary amino groups appropriate. Suitable catalysts for this are strongly basic compounds, such as Quaternary ammonium compounds, for example alkyl, aryl and / or Benzylammonium hydroxides and carbonates. Special representatives for Quaternary Ammonium compounds are here (C₁₆-C₂₂) alkylbenzyldimethylammonium hydroxide, benzyltrimethylammonium hydroxide and tetrabutylammonium hydroxide. Preferred catalysts are strongly basic amines, for example example diazabicyclooctane (DABCO) and guanidine. Furthermore, here are also so-called supranucleophilic catalysts, for example 4-pyrrolidinyl pyridine, poly (N, N-dialkylaminopyridine) are suitable (see R. A. Vaidya et al. in Polymer Preprints, Vol. 2 (1986), pp. 101-102).  

Optionally, for the preparation of the resin systems of the invention with additive be worked by solvents, which after completion of the Harzsyn theses can be removed in vacuo, for example with glycol ethers such as ethylene glycols, propylene glycols, butylene glycols, for example Methyl glycol, ethyl glycol, butyl glycol, methyl diglycol, ethyl diglycol, Butyl diglycol, methyl triglycol, ethyl triglycol, butyl triglycol, methyl tetraglycol, Ethyltetraglycol, butyltetraglycol, ®Polyglycol M-250 (registered Trademark of the company Hoechst AG for Polyäthylenglykolmonomethyläther, molar mass 260 to 275 g / mol, OH number 204 to 215 mg / g), ®Polyglykol M- 350 (molar mass 335 to 265 g / mol, OH number 154 to 167 mg / g), 2-n-Pro epoxyethanol, 2- (1-methylethoxy) -ethanol, 2-n-butoxyethanol, 2,5,8,11- Tetraoxadodecane, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, tripropylene glycol monomethyl 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 polymers (B) contain at least one hydrophilic substructure, which in the present pH range is nonionic. Examples of such polymers (B) are adducts of hydroxy compounds to epoxy-containing resins with preferably terminal epoxide groups from the groups polyglycidyl ether and polyglycidyl esters.

As epoxy-containing resins are preferably polymers with end permanent epoxide groups from the groups polyglycidyl ether and polyglycidyl ester used.

As hydroxy compounds are organic compounds which at least contain a hydroxyl group, used individually or as mixtures. before are added to mono-, bis- or tris-hydroxy compounds used, especially It prefers monohydroxy compounds.  

Monohydroxy compounds according to the invention monoalcohols and understood mono-etherified polyoxyalkylene glycols. As monoalcohols are preferably alkane or cycloalkane monoalcohols, in particular (C₈ to C₃₂) - Alcohols and their isomers, for example 2-ethylhexanol, octanol, nonanol, Decanol, dodecanol, also stearyl, cetyl, ceryl, myricyl alcohol, ®TCD- Alcohol M (registered trademark of the company Hoechst AG, molar mass 166 g / mol, OH number 327 mg / g), wool wax alcohols, cholesterols, borne-n-olane, Isoborneole and Tallölfettalkohole used. Optionally, to modify tion of properties also (C₁-C₆) alcohols with alkane and cycloalkane chains be used in mass fractions of 0 to 95%, based on the sum the masses of monohydroxy compounds, for example butanol, hexanol, Cyclohexanol and / or mixtures thereof.

As monoperätherte polyoxyalkylene glycols are preferably Ver compounds of general formula XVIII

R²⁹- (O-CHR³⁰-CHR³¹) _r -OH formula XVIII

used. In this formula, R²⁹ is an alkyl, cycloalkyl, or phenyl radical, preferably an alkyl radical having 1 to 12, in particular 1 to 4 Carbon atoms, R³⁰ and R³¹ are hydrogen or alkyl radicals with 1 to 4 carbon atoms and r is 1 to 10, preferably 1 to 4. Als Examples of such compounds are: methyl glycol, ethyl glycol, Butylglycol, methyldiglycol, ethyldiglycol, butyldiglycol, methyltriglycol, Ethyl triglycol, butyl triglycol, methyl tetraglycol, ethyl tetraglycol, butyl tetra glycol, ®Polyglycol M-250 (molar mass 260 to 275 g / mol, OH number 204 to 215 mg / g), ®glycol M-350 (molar mass 335 to 265 g / mol, OH number 154 to 167 mg / g), propylene glycol methyl ether, dipropylene glycol methyl ether, Tripropylenglykolmethyläther, propylene glycol n-butyl ether, Dipropyleng-lykol-n- butyl ether, tripropylene glycol n-butyl ether and propylene glycol phenyl ether.  

The preparation of the polymers (B) is carried out in a conventional manner Reaction of epoxy-containing resins with hydroxyl compound in the presence of catalysts, for example Lewis acids (according to EP A 0 272 595) 1 imidazoles (Macromolecules, 1989, 22, 99), cyclic quaternary ammonium compounds (US Pat. No. 5,019,639), tin compounds (EP A 0498 504) or alkaline earth perchlorates (Polymer Bulletin 1989, 22, p. 221-226).

The mixtures of polymers (A) and (B) can be prepared from the separately formed Be prepared polymers, optionally before in water neutra lisiert or teilneutralisiert, (A) and (B) are united and given if a water-insoluble polymer (C) is prepared in the form of latex particles is prepared by emulsion polymerization of ethylenically unsaturated Verbindun in the presence of the optionally neutralized or partially neutralized Polymers (A) and (B).

In a preferred process variant, the amino-containing poly Mer (A) in the presence of at least one nonionic wasserverdünn Baren polymer (B).

As neutralizing agent for the polymer mixture of (A) according to the invention and (B) both organic acids, for example formic acid, Dimethylolpropionic acid, acetic acid, glycolic acid, gluconic acid, hydroxyacetic acid acid, propionic acid, butyric acid, lactic acid, valeric acid, caproic acid, Enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristin acid, palmitic acid, and stearic acid, preferably formic acid, acetic acid and lactic acid, as well as inorganic acids, for example phosphoric acid, Sulfuric acid, boric acid and hydrochloric acid in question. The neutralisa tion level is generally between 5 and 120%, preferably 10 and 90%, based on the amino groups present.  

According to the invention, the synthetic resin mixtures contain, in addition to the polymer resin zen (A) and (B) optionally also polymer resins (C). The preparation of the polymer Resins (C) via emulsion polymerization in the presence of at least partially neutralized polymer resins (A) and polymer resins (B). The resins (A) and (B) should be present in an amount which is suitable for the To bring about desired emulsifying and stabilizing effects. It should both for economic reasons and for reasons of influence the performance properties, such as water resistance, Re-solubility and drying rate to be produced Emulsion polymers, the proportion of resins (A) and (B) neither too high nor be too low. It is therefore a mass fraction of solids in polymers (A) and (B) together from 4 to 40%, especially 8 to 20% preferred. Very good rheology-controlled dispersions (RC dispersions) become so also obtained when the sum of the mass fractions of resins A and B less than 20%, preferably less than 15% of the sum of the masses of (A), (B) and (C).

Methods for emulsion polymerization are known in the art. usual wise, they are characterized by the fact that in the aqueous phase in the presence of Radical starters and emulsifiers, protective colloids or other stabilizers a radical polymerization of ethylenically unsaturated monomers is carried out. The components mentioned can be different Way in the emulsion polymerization are introduced. Using the polymer resins (A) according to the invention in emulsion polymerizations as Stabilizers can due to the good emulsifying performance of these polymers the presence of low molecular weight surfactants and on protective colloids ver be canceled. The aqueous phase is usually present for the most part with a proportionate addition of water during the reaction in the form a radical starter solution or monomer preemulsion is possible. Stabili may be completely or partially submitted and the remainder during the  Polymerization are metered. The monomers can be completely charged be added in water or in pure form or as a pre-emulsion in water. The radical starter is usually partially submitted and partly as an aqueous Added solution. As a template, the mixture is called, before Ein Position of the reaction temperature of usually 20 to 99 ° C in the Reactor is introduced. The polymerization is mostly by thermal Decomposition of the radical initiator or initiated by redox systems and can considered to be finished when most of the radical by Chain reaction convertible monomers is reacted (between 20 and 99 ° C). Usually, this process remains a mass fraction of approximately 0.001 to 0.1% of residual monomers. Further procedures or procedural variants are described in detail, for example in Ullmann, Encyclopedia of Industrial Chemistry, 4th edition, Verlag Chemie, Weinheim (1980), Vol. 19, pp. 132 et seq. As well as in Encyclopedia of Polymer Science and Engineering, Volume 6, Wiley & Sons, New York 1986, pp. 1-51.

The polymer (C) of the dispersion is produced by monomers which are at least to a considerable extent are sparingly soluble in water and also when changing remain sparingly soluble in pH. As sparingly soluble substances referred to, the dissolved mass fraction less than 10%, in particular less than 5% at 25 ° C. The proportion of sparingly soluble mono meren must at least be so large that the resulting emulsion is insoluble under the polymerization conditions in the water phase and in the form of dispersed particles. Within the meaning of the invention preferably uses those mixtures which have a mass fraction of at least 70% and in particular at least 90% of sparingly soluble Have monomers.

Suitable monomers contain at least one ethylenically unsaturated Group. The terms ethylenically unsaturated, vinylically unsaturated and α, β- unsaturated are used synonymously. The expert is known that the  like monomers under the conditions of emulsion polymerization in an aqueous medium to polymerize. These include For example, vinyl compounds, styrenes and acrylates and their derivatives. To The suitable vinyl compounds include, for example, vinyl chloride as well Vinyl esters such as vinyl acetate, vinyl propionate, but vinyl ester of versatic acid also vinyl fatty acid esters such as vinyl laurate. Suitable styrene compounds are Styrene, vinyltoluene, α-methylstyrene, ethylstyrene, iso-propylstyrene, tert. Butylstyrene, 2,4-dimethylstyrene, diethylstyrene, o-methyl-p-isopropylstyrene, Halogen styrenes such as chlorostyrene, fluorostyrene and iodostyrene, 2,4-dicyanostyrene, Hydroxystyrene, nitrostyrene, aminostyrene and phenylstyrene. Preferred are in particular styrene, vinyltoluene and α-methylstyrene. As suitable acrylates be exemplary acrylic acid, methacrylic acid and crotonic acid ester ge called, for example, esters containing hydroxy functions, such as Hy hydroxyethyl acrylate and hydroxyethyl methacrylate. In the emulsion polymerisa Of course, mixtures of such ethylenically unge saturated monomers are polymerized, as far as the Copolymerisa tion suitable. Dispersions with glass transition temperatures above 75 ° C is preferably obtained from styrene, styrene derivatives and / or meth Acrylates went out.

Suitable initiators are usually water-soluble radical-forming Ver compounds, for example hydrogen peroxide, peracetic acid, perbenzoic acid and peroxodisulfates, for example potassium or ammonium peroxodisulfate, Perphosphates, peroxycarbonates and hydroperoxides, such as tert-butyl hydroper oxide. Suitable redox catalyst systems are, for example, sodium per sulphate / sodium formaldehyde sulphoxylate, cumene hydroperoxide / sodium metabisulphite, Hydrogen peroxide / ascorbic acid and sulfur dioxide / ammonium persulfate. Also suitable are azo compounds, such as 4,4-azobis (cyanopentanoic acid). The initiators are in the usual catalytically effective concentrations used. These are generally at mass fractions between 0.01 to 4.0%, based on the mass of the dispersion.  

In particular embodiments, others may be used for the emulsion polymer sation usual components are used. These are, for example Be accelerator, buffer and any other ingredients in addition to the inventions polymers according to the invention in the emulsion polymerization reaction mixture can be used and from the prior art to Emulsionpoly are known merisationsverfahren.

These novel dispersions of the polymers (A), (B) and (C) in the combinations described have an excellent drucktechni nice behavior, good storage stability, good gloss and excellent outstanding deinkability.

The synthetic resin systems according to the invention are outstandingly suitable for Overprint varnishes for printing on paper, cardboard, cardboard and the like, for example, with the inking of a sheet or web offset press, off Dampening units, separate coating units of sheet or web offset Printing machines, sheet-painting machines, gravure and flexo printing machines. at the use of the resin solutions of the invention (polymers (A) and optionally (B) and also polymers (D) and optionally (B)) and Dispersions (polymers (A), optionally (B) and (C) and polymers (D) and (C) and optionally (B)) as binder carrier for overprint varnishes their mass fraction of solids is generally from 20 to 75%, preferably Wise 30 to 60%. These paints contain mass fractions of 1 to 70% of the dispersions of the invention and / or 1 to 40% inventive Solid resins and 0 to 60% glycols or glycol ethers, 0 to 30% wetting agents, 0 to 35% neutralizing agent (acids), 0 to 30% natural and / or synthetic waxes, 0 to 2.5% defoamer and 0 to 80% water and optionally up to 20% pigments, wherein translucent pigments and Effect pigments are preferred. For incorporation of additives such as color substances and leveling agents in the solutions and / or dispersions and / or  their mixtures and / or their dilutions are the usual ones Grinding, mixing, kneading and Anreibegeräte optional in the presence of conventional Dispersing aids used.

The preparation of suitable, usable according to the invention resins and the Preparation of stable polymer dispersions by emulsion polymerization and their use in printing inks is illustrated by the following examples.

Examples

Information of parts and contents in the unit "%" (percent) in the case of play mean mass fractions, unless stated otherwise. All reactio NEN be carried out under inert gas (N₂).

Example 1: Epoxide / epoxy-amine system

Commercially available polyglycidyl ether based on bisphenol A having an epoxide group content of 5200 to 5600 mmol / kg (epoxy equivalent weight of about 180 to 192 g / mol, ®Beckopox EP 140, registered trademark of the company Hoechst AG, 59 g) with methyltetraethylene glycol (molar Mass 208 g / mol, boiling range 280 to 350 ° C., 67 g) and commercially available ®Anchor 1040 (amine-boron trifluoride adduct, registered trademark of Anchor, 250 mg) at 150 ° C. As soon as a mass content of epoxide oxygen atoms ("epoxide number") of less than 4 g / 100 g is reached, successively commercially available ®Genamin SH 100 (stearylamine, registered trademark of the company Hoechst AG, 27 g), N, N-dimethylaminopropylamine (21 g) and commercially available bisphenol A (95 g) added to the resin composition and then commercially available polyglycidyl ether based on bisphenol A with a Epoxidgruppengehalt from 5200 to 5600 mmol / kg (®Beckopox EP 140, 231 g) dosed so slowly that no gelation occurs , An artificial resin system having an amine number of 50 mg / g, a weight-average molar mass M _w of 8500 g / mol and a glass transition temperature T _g of 46 ° C. is obtained.

Example 2

Commercially available polyglycidyl ether based on bisphenol A having an epoxide group content of 5200 to 5600 mmol / kg (epoxide equivalent weight of about 180 to 192 g / mol, Beckopox EP 140, 66 g) is mixed with methyltetraethylene glycol (28 g), butyldiglycol (29 g) and Catalyst ® Anchor 1040 (500 mg) maintained at 150 ° C. As soon as an epoxide number of less than 4 g / 100 g is reached, bisphenol A (95 g), ®Genamin SH 100 (27 g) and N, N-dimethylaminopropylamine (21 g) are added in succession to the resin composition and then commercial polyglycidyl ether based Bisphenol A dosed with a Epoxidgrup pengehalt from 5200 to 5600 mmol / kg (epoxy equivalent weight of about 180 to 192 g / mol, Beckopox EP 140, 231 g). An artificial resin system having an amine number of 64 mg / g, a weight-average molar mass M _w of 8700 g / mol and a glass transition temperature T _g of 48 ° C. is obtained.

Example 3

Commercially available polyglycidyl ether based on bisphenol A having an epoxide group content of 5200 to 5600 mmol / kg (Beckopox EP 140, 67 g) is treated with methyltetraethylene glycol (25 g), butyldiglycol (31 g) and Anchor 1040 catalyst (380 mg) at 150.degree held. As soon as an epoxide number of less than 4 g / 100 g is reached, bisphenol A (96 g), cyclohexylamine (10 g) and N, N-dimethylaminopropylamine (22 g) are added in succession to the resin composition and then commercially available polyglycidyl ether based on bisphenol A with an epoxide group content of 5200 to 5600 mmol / kg (Beckopox EP 140, 231 g). This gives a synthetic resin system having an amine value of 74 mg / g, a weight-average molar mass M _w of 8800 g / mol and a glass transition temperature T _g of 67 ° C.

Example 4

The synthetic resin system of Example 1 (100 g) is heated with lactic acid (90%, 10 g) and water (60 g) mixed directly or inversely and with wide diluted water (117 g). This gives a glossy paste with a viscous 520 mPa.s (Ubbelohde), a pH of 3.8 and a solid content of 34% (3 hours / 100 ° C).

Example 5

A solution of the synthetic resin system of example 3 (48 g) with lactic acid (90%, 3.3 g) in water (95 g) is heated to 90 ° C. Now about one Period of 3 to 4 hours styrene (391 g) and parallel to ascorbic acid (6 g) in water (616 g) and tert-butyl hydroperoxide (4 g). You get so, after filtration through 30 micron filter, a finely divided dispersion with a Solid mass fraction of 35% (determined by drying, 3 hours, 100 ° C), a pH of 3.7 and a viscosity (Ubbelohde) of 480 mPas.

Example 6

The gloss paste from example 4 (30 g) is mixed with dispersion from example 5 (59 g). homogeneously mixed. After addition of water (8 g), an excess is obtained  Print varnish with a solids content of 33% and a flow time of approx. 60 s in the 4 mm DIN cup at 23 ° C.

Example 7

A printed product is made using melt inks according to DE-A 25 34 845 prepared and then with an overprint varnish coated according to Example 6. Two printed pages (DIN A4) are with the Pressure side piled up and with a brass weight of 1 kg Mass loaded on a surface about 5 cm in diameter and 5 hours at 90 ° C left. After cooling, the two leaves were readily available solve each other.

Example 8

The procedure of Example 7 was repeated with a printed product which was printed with a melt ink according to DE-A 42 05 713. there was a binder of a mixture of stearyl alcohol (50 parts) and a hydroxylated acrylate resin (50 parts, ®Macrynal SM 510, registered trademark of Hoechst AG). Two with the Printing side of superimposed DIN A4 sheets showed upwards also described no blocking.

Example 9

In 170 ° C tempered N-methylpyrrolidone (23 g) is stirred with a monomer mixture consisting of acrylic acid (36 g), styrene (27 g) and α-methylstyrene (31 g) and parallel to cumene hydroperoxide (1.4 g) over approx 5 hours and held for another hour at this temperature. After separation of N-methylpyrrolidone in vacuo at 230 ° C to obtain a solid resin having an acid number of 243 mg / g, a glass transition temperature T _g of 141 ° C and a molar mass M _w of 13 kg / mol. Before solidifying, add the still liquid polymer with 1-methoxy-2-propanol (11.5 g) and acetic acid (100%, 9.4 g) and carry this mass in water (143 g) / ammonia (25%). ig, 36 g), a resin solution having a solids content of 33.5% by weight, a pH of 9.1 and a viscosity of 1521 mPa · s (Ubbelohde) is obtained.

Example 10

A diluted with water to a solids content of 25% resin solution from Example 9 is heated under nitrogen to 90 ° C (600 g). After reaching of 90 ° C is styrene (10 g) and parallel thereto ammonium peroxodisulfate (0.4 g) in water (5 g) and stirred at 90 ° C for 20 minutes. Now it will within about 3 hours a dosage of styrene (440 g) and paral In addition a dosage of ammonium peroxodisulphate (2 g) in water (200 g). It is allowed to react for about 1 hour, optionally under Adding a redox system, cools and thus receives a speckle-free Disper With a solids content of about 47.8%, a pH of 8.7 and a Viscosity of about 1,230 mPa · s (Ubbelohde).

Example 11

A printed product is made using melt inks according to DE-A 25 34 845 prepared and then with an overpressure disperse coated according to Example 10. Two printed pages (DIN A4) will be superimposed with the pressure side and with a brass weight piece  of 1 kg mass loaded on a surface of about 5 cm in diameter and 5 Leave at 90 ° C for hours. After cooling, the two leaves without solve each other.

Example 12

The procedure of Example 11 was repeated with a printed product, which was printed with a melt ink according to DE-A 42 05 713. A binder was made from a mixture of stearyl alcohol (50 parts). and a hydroxyl group-containing acrylate resin (50 parts, ®Macrynal SM 510, registered trademark of Hoechst AG). Two with the Printing side of superimposed DIN A4 sheets showed upwards also described no blocking.

Example 13

It became a gloss overprint varnish of a commercial maleic acid modified rosin (Alresat® KM 379 from Hoechst AG) and a commercially available soybean oil-modified alkyd resin (63% oil content, 25% Phthalic anhydride, Alftalat® AS 632 from Hoechst AG):

Mass fraction (%) Alresat KM 379 33.5 Alftalat AS 632 5.4 Wood oil, raw 18.1 safflower 10.0

The specified substances are boiled at 240 ° C for 30 minutes. After cooling, it is diluted with

® Somentor 33 33.0

®Somentor 33 is a registered trademark of Esso AG, Hamburg (Mineral oil, boiling range 205 to 250 ° C, aniline point 65 ° C).

Measured values:
Viscosity at 20 ° C (rotational viscometer, plate / cone): 110 dPa · s
Tack-o-scope 30 ° C: 140
Tack maximum: 220
Maximum reached after: 1 min

Example 14

It became a gloss overprint varnish of a commercial phenolic resin modified rosin (Albertol® KP 351 from Hoechst AG) and a commercially available castor oil-modified alkyd resin (68% oil content, Alftalat® AR 680 from Hoechst AG):

mass fractions Albertol KP 351 30.0 Alftalat AR 680 10.0 safflower 28.0 PKWF 4/7 *) 30.8

*) PKWF4 / 7: mineral oil, boiling range 240 to 270 ° C, aniline point 72 ° C, Fa. Johann Haltermann, Hamburg

The components are dissolved at 18 ° C within 45 minutes, then become

Cobalt octoate 0.2 Zirconium octoate 1.0

added.

Viscosity at 20 ° C (rotational viscometer, plate / cone): 125 dPa · s
Tack / 30 ° C
Tack-o-scope
V = 50 m / min 70
V = 200 m / min: 110
V = 350 m / min: 130

Example 15

A printed product is made using melt inks according to DE-A 25 34 845 prepared and then with an overprint varnish coated according to Example 13. Two printed pages (DIN A4) are with the Pressure side piled up and with a brass weight of 1 kg Mass loaded on a surface about 5 cm in diameter and 5 hours at  90 ° C left. After cooling, the two leaves were readily available solve each other.

Example 16

The procedure of Example 0064900070 552 001000280000000200012000285910053800040 0002019536679 00004 00530iel 15 was repeated with a printed product, which was printed with a melt ink according to DE-A 42 05 713. A binder was made from a mixture of stearyl alcohol (50 parts). and a hydroxyl group-containing acrylate resin (50 parts, ®Macrynal SM 510, registered trademark of Hoechst AG). As an overprint varnish serves the product of Example 14. Two on top of each other with the print side DIN A4 sheets also showed by the test method described above no blocking.

Claims (23)

1. coating in printed products, characterized in that the coating has at least two layers with mutually different composition to, wherein the softening temperature of the cover layer and optionally the other cover layers is at least 60 ° C and at least 10 ° C higher than that of the base layer. 2. Coating according to claim 1, characterized in that the Erwei temperature of the top layer and optionally the other deck layers is at least 80 ° C. 3. Coating according to claim 1, characterized in that the Erwei temperature of the top layer and optionally the other deck layers is at least 20 ° C higher than that of the base layer. 4. Coating according to claim 1, characterized in that the deck layer has an average visible light absorption of below 10%. 5. Coating according to claim 1, characterized in that the Erwei temperature of the top layer due to contact with substances in the underlying layers are lowered by a maximum of 10 ° C becomes. 6. Coating according to claim 1, characterized in that the Erwei temperature of the top layer due to contact with substances in the underlying layers are lowered by a maximum of 20 ° C becomes.   7. Coating according to claim 1, characterized in that the Erwei temperature of the top layer due to contact with substances in the underlying layers are included, to a temperature not un is lowered below 70 ° C. 8. Coating according to claim 1, characterized in that the base layer contains coloring pigments. 9. Coating according to claim 1, characterized in that the base layer contains dyes. 10. Coating according to claim 1, characterized in that the deck layer contains coloring pigments in such an amount that the light absorption of the topcoat does not rise above 10% in the visible range. 11. Coating according to claim 1, characterized in that the deck layer contains dyes in such an amount that the light absorption of the Cover layer does not rise above 10% in the visible range. 12. Coating according to claim 1, characterized in that the base layer a film-forming material (a), a material (b) with a Softening point above 40 ° C, which in the fluid state, the material (a) too dissolves, and contains coloring pigments or dyes. 13. Coating according to claim 12, characterized in that the Material (b) is crystalline in the solid state. 14. Coating according to claim 1, characterized in that the deck layer by film formation from a solution of a binder in an organi is formed solvent.   15. A coating according to claim 1, characterized in that the deck layer by film formation from a dispersion of an ionic or nonionic stabilized binder is formed in an aqueous medium. 16. A method for producing a coating in printed products according to Claim 1, characterized in that in the first step to the bedruc kenden parts of the surface of the substrate, a coating agent is applied, the coloring pigments or dyes and a filmbil dendes material (a) and an auxiliary (c), in a second Step by removing the same or by a physical or chemi the transformation involves the formation of a base-layer film from the coating causes the composition of the first step, and that in the third Step on at least the entire printed surface another be coating agent is applied, which consists of a film-forming material (a ') and a tool (c '), which in a fourth step by removing same or by a physical or chemical transformation the Forming a topcoat film of the coating agent together causes the third step, wherein the formed in the fourth step Topcoat film is transparent and has an average light absorption in the visible range of less than 10%. 17. The method according to claim 16, characterized in that the auxiliary medium (c) a material (b) with a softening point above 40 ° C, which is in fluid state the material (a) is able to solve, and that the formation of the Base layer film in the second step by cooling the coating is effected by means of the first step, wherein the material (b) and the film-forming material (a) segregate and the material (b) at least for predominantly changes into the crystalline state.   18. The method according to claim 16, characterized in that the auxiliary medium (c) in the coating composition of the first step from a volatile And a nonvolatile material (b), and that the formation of the Base layer film in the second step by heating the Beschich caused by the first step means, wherein the volatile portion of the Auxiliary agent (c) evaporated and then the remaining material (b) and separate the film-forming material (a) and the material (b) at least for predominantly changes into the crystalline state. 19. The method according to claim 16, characterized in that the Be The third stage coating agent is a solution of a film-forming composition component in an organic solvent. 20. The method according to claim 16, characterized in that the Be coating agent of the third step, a dispersion of an ionic or nonionically stabilized film-forming component in water. 21. The method according to claim 16, characterized in that the Be coating agent of the third step, a dispersion of a cationic stabili sated film-forming component in water. 22. The method according to claim 16, characterized in that on the Cover layer film of the fourth step even more cover layer films a solution or an aqueous dispersion are applied. 23. Printed matter using the method according to claim 16 have been produced.