WO2006094847A1

WO2006094847A1 - Aqueous printing ink compositions

Info

Publication number: WO2006094847A1
Application number: PCT/EP2006/050228
Authority: WO
Inventors: Patrick GLÖCKNER; Andreas Wenning; Lutz Mindach
Original assignee: Degussa Gmbh
Priority date: 2005-03-10
Filing date: 2006-01-16
Publication date: 2006-09-14
Also published as: CN1942538A; DE102005010966A1

Abstract

The invention relates to aqueous printing ink compositions comprising at least one binding agent, one modified ketone/aldehyde resin, one colorant and optionally, auxiliary agents and additional substances.

Description

Aqueous printing ink compositions

The invention relates to aqueous printing ink compositions comprising at least one binder, a modified ketone / aldehyde resin, a colorant and optionally auxiliaries and additives.

The printing ink compositions are used for printing differently

Substrates, such. As films of plastics and / or composites such. As aluminum-laminated films, textiles, fibers, fabric materials, leather, metals, cardboard, paper, cardboard, glass, paper laminates and / or synthetic materials, such as. B.

Artificial leather, etc., wherein the coating is largely free of formaldehyde. Suitable printing ink compositions for all conventional printing methods, such. B. offset,

Flexo, screen, gravure, tampon, ink-jet ink or toner.

The printing ink compositions are characterized by a particularly high rate of drying, good water resistance, high gloss and high abrasion resistance and hardness with very good elasticity.

Printing inks take on decorative functions and are used to inform, to decorate and to be effective in advertising through the visualization of text, ornaments and pictorial representations (see "Römpp Lexikon, Lacke und Druckfarben, publisher Dr. Ulrich Zorll, Georg Thieme Verlag, Stuttgart, 1998 ") .Printing eg paper, cardboard and foils serves on the one hand for information (brochures, packaging materials), on the other hand layout information converts this information into an appealing form as well as features such as the highest possible drying speed Both good adhesion and elasticity properties as well as good abrasion resistance are of importance.

After the application of the printing inks, rapid drying is desirable in order to ensure rapid further processing and to prevent defects caused by, for. As soiling such as dust and dirt, etc., to avoid.

Hard resins based on ketones and aldehydes have been known to reduce hardness Reduction of elasticity properties of coating materials increase.

Water-dispersible condensation products of ketones and aldehydes or their derivatives or reaction products which may contain such products are described in EP 0 617 103 A1, EP 0838485, EP 0838486 (DE 19643704), DE 25 42 090, DE-OS 31 44 673 and DE-OS 3406474 (EP 0154835).

In DE-OS 25 42 090 sulfo groups carrying water-soluble compounds are described, which are available deviating from the process of the invention in a common condensation reaction of cycloalkanone, formaldehyde and alkali metal bisulfite.

In DE-OS 31 44 673 water-soluble condensation products are listed, which are also obtained by joint reaction of ketones, aldehydes and acid groups introducing compounds. Examples of the latter are sulfites, amidosulfonic acid, aminoacetic acid and phosphorous acid salts.

According to DE-OS 25 42 090 and DE-OS 31 44 673, products containing electrolyte (eg Na ions) are obtained. However, such resins, among other things, deteriorate the water resistance of coating systems.

EP 0 617 103 A1 describes the reaction of polyisocyanates (a) and dihydroxyl compounds (b) with a molecular weight of 500 to 5,000 which do not convert groups into ionic groups (eg carboxylic acid groups), but rather other functional groups such as ester groups. or ether groups (see page 3, lines 17-21). The polyurethane thus obtained is still with a compound (c) which contains not only NCO-reactive groups nor a group convertible into an ionic group, and optionally with diols or polyols (d) having a molecular weight of 60 to 500, which are no further functional Wear groups (see page 4, lines 5 to 15), implemented. Subsequently, this reaction product is reacted with a condensation resin and transferred to the aqueous phase.

DE 3406474 (EP 0154835) describes aqueous dispersions of ketone resins or ketone / aldehyde resins using organic protective colloids. The disadvantage, The fact that protective colloids remain in the subsequent coating and can adversely affect properties such as resistance to water and moisture prevents their use in high-grade coating compositions.

EP 0838485 describes esterified products. It is known that ester groups hydrolyze resulting in polymer degradation and negatively affecting storage stability. In addition, a reaction or incompatibility with pigments can be caused by freely accessible acid groups.

EP 0838486 describes aqueous resin dispersions obtainable by reaction or proportionate reaction of

I. hydroxyl-containing ketone, ketone / aldehyde, urea / aldehyde resins or their hydrogenated derivatives and

II. At least one hydrophilic modified isocyanate and / or polyisocyanate having at least one free NCO group, obtainable by reacting at least one isocyanate and / or polyisocyanate with compounds which have at least one isocyanate-reactive function in addition to the hydrophilic or potentially hydrophilic group and the one according to the Zerewitinoff test have active hydrogen, and at least one hydrophilic group and / or have a potentially hydrophilic group, and then mixing the neutralized resin with water.

The object of the present invention was to find aqueous printing ink compositions for printing on different substrates, wherein the coating should be largely free from formaldehyde. The ink compositions should have a high drying rate and positively affect hardness, abrasion resistance, water resistance and elasticity properties.

The object underlying the invention has surprisingly been achieved by the use of special coating compositions, which are described in more detail below. The invention relates to aqueous printing ink compositions for printing on different substrates, substantially containing

A) 20 to 90 wt .-% of at least one aqueous binder, and B) 5 to 75 wt .-% of a hydrophilized ketone / aldehyde resin and / or a hydrophilized, hydrogenated ketone / aldehyde resin, and C) 5 to 50 wt .-% of at least one colorant, and D) 0 to 70 wt .-% of at least one additive, wherein the sum of the weights of component A) to D) is 100 wt .-%.

It has been found that the combination of the printing ink compositions described below from components A) to D) fulfill all the required criteria.

Component A)

The aqueous binders A) essential to the invention are used in amounts of from 20 to 90% by weight, preferably from 30 to 75% by weight. Preference is given to aqueous binders, from the group of polyurethanes, polyacrylates, polyethers, polyesters, alkyd resins, polyamides, casein, cellulose ethers, derivatives of cellulose, polyvinyl alcohols and derivatives, polyvinyl acetates, polyvinyl chlorides, polyvinyl pyrrolidones, rubbers, natural resins, hydrocarbon resins such. Coumarone, indene, cyclopentadiene resins, terpene resins, maleate resins, phenolic resins, phenol / urea-aldehyde resins, aminoplasts (e.g., melamine, benzoguanamine resins), epoxy acrylates, epoxy resins, silicic acid esters and alkali silicates (e.g., waterglass) and / or silicone resins and / or fluorine-containing polymers used. The aqueous binders may be foreign and / or self-crosslinking, air-drying (physically drying) and / or oxidatively curing.

Component B)

Essential to the invention component B) is used in amounts of 5 to 75 wt .-%, preferably from 10 to 60 wt .-%. Suitable as component B) are aqueous resin dispersions obtainable by reaction or proportionate reaction of I. hydroxyl-containing ketone / aldehyde resins or their hydrogenated derivatives and II. At least one hydrophilic modified isocyanate and / or polyisocyanate having at least one free NCO group, obtainable by reacting at least one Isocyanate and / or polyisocyanate with compounds which in addition to the hydrophilic or potentially hydrophilic group have at least one isocyanate-reactive function, and subsequent mixing of the optionally neutralized resin with water.

Suitable ketones for the preparation of the ketone / aldehyde resins (component I) are all ketones, in particular acetone, acetophenone, methyl ethyl ketone, heptanone-2, pentanone-3, methyl isobutyl ketone, cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2, 4,4-trimethylcyclopentanone, cycloheptanone and cyclooctanone, cyclohexanone and all alkyl-substituted cyclohexanones having one or more alkyl radicals having a total of 1 to 8 carbon atoms, individually or in admixture. As examples of alkyl-substituted cyclohexanones, mention may be made of 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.

It is in principle also possible, although less preferred, to use ketones which have other functional groups, such as. B. amino and / or acid groups grout.

In general, however, all in the literature for ketone and ketone / aldehyde resin syntheses called suitable ketones, usually all C-H-acidic ketones, can be used. Preferred are ketone / aldehyde resins based on acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone alone or in a mixture.

As aldehyde component of the ketone / aldehyde resins (component I.) are in principle unsubstituted or branched aldehydes, such as. As formaldehyde, acetaldehyde, n-butyraldehyde and / or iso-butyraldehyde, valeric aldehyde and dodecanal. In general, all the aldehydes mentioned in the literature as suitable for ketone / aldehyde resin syntheses can be used become. Preferably, however, formaldehyde is used alone or in mixtures.

The required formaldehyde is usually used as about 20 to 40 wt .-% aqueous or alcoholic (eg, methanol or butanol) solution. Other uses of formaldehyde such. As well as the use of para-formaldehyde or trioxane are also possible. Aromatic aldehydes, such as. B. benzaldehyde may also be included in admixture with formaldehyde.

As starting compounds for the ketone / aldehyde resins of component I, particular preference is given to using acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and also heptanone alone or in a mixture and formaldehyde.

The resins of ketone and aldehyde can also be hydrogenated in the presence of a suitable catalyst with hydrogen at pressures of up to 300 bar. In this case, part of the carbonyl groups of the ketone / aldehyde resin is converted into secondary hydroxyl groups. For resins of aldehydes and ketones, in addition to the Carbonylgruppierung on other hydrogenatable functions such. B. have aromatic structures, these other structures can be converted by suitable hydrogenation. In the case of z. B. aromatic structures are obtained cycloaliphatic structures.

The possibly necessary hydrophilic modification takes place for. Example by reacting the resin I with a component IL, consisting of at least one hydrophilic modified isocyanate and / or polyisocyanate having at least one free NCO group, obtainable by reacting at least one isocyanate and / or polyisocyanate with compounds in addition to the hydrophilic or potentially hydrophilic group - ie those groups which become hydrophilic only after neutralization - have at least one isocyanate-reactive function such as. B. hydroxy or amino groups.

Examples of such compounds for the hydrophilic modification of (poly) isocyanates are amino acids, hydroxysulfonic acids, aminosulfonic acids and hydroxycarboxylic acids. Preference is given to using dimethylolpropionic acid or derivatives thereof. The hydrophilic modification can also be carried out with non-ionic groups (eg with polyethers) or already neutralized compounds. Hydroxycarboxylic acids, in particular dimethylolpropionic acid, are therefore particularly preferred because they are neutralized with volatile bases, such as. As amines, show strong hydrophilic effect, after evaporation of the volatile base, however, this effect decreases greatly. Coatings therefore do not lose by z. B. Moisture their protective function, as a swelling does not take place.

The dimethylolpropionic acid is also particularly preferred since it is capable of hydrophilically modifying (potentially) two hydrophobic polyisocyanates via its two hydroxyl groups.

Suitable polyisocyanates for the preparation of II. Are preferably di- to tetrafunctional

Polyisocyanates. Examples of these are cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, phenylene diisocyanate, toluene diisocyanate, bis (isocyanatophenyl) methane, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, such as hexamethylene diisocyanate (HDI) or 1,5-diisocyanato-2-methylpentane (MPDI). Heptane diisocyanate, octane diisocyanate, nonane diisocyanate such as 1,6-diisocyanato-2,4,4-trimethylhexane or 1,6-diisocyanato-2,2,4-trimethylhexane (TMDI), nonane triisocyanate such as 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), decane and triisocyanate, undecanediisocyanate and triisocyanate, dodecandi- and triisocyanates, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (H ₁₂ MDI),

Isocyanatomethylmethylcyclohexyl isocyanate, 2,5 (2,6) -bis (isocyanatomethyl) bicyclo [2.2.1] heptane (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane (1,3-H ₆ -XDI) or 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ -XDI) alone or in admixture. Another preferred class of polyisocyanates are the compounds prepared by di- or trimerization, allophanatization, biuretization and / or urethanization of simple diisocyanates with more than two isocyanate groups per molecule, for example the reaction products of these simple diisocyanates, such as IPDI, HDI and / or H. ₁₂ MDI with polyhydric alcohols (for example glycerol, trimethylolpropane, pentaerythritol) or polyvalent polyamines or the triisocyanurates obtainable by trimerization of the simple diisocyanates, for example IPDI, HDI and H ₁₂ MDI.

Particularly preferred is a hydrophilically modified polyisocyanate (II) of dimethylolpropionic acid or derivatives thereof and IPDI and / or TMDI and / or H ₁₂ MDI and / or HDI in the molar ratio 1: 2.

The preparation of component B) is carried out in the melt or in solution of a suitable organic solvent, which - if desired - can be separated by distillation after preparation.

Preferred solids contents in the case of a reaction in solution are 30 to 95 wt .-%, particularly preferably 60 to 80 wt .-%.

Suitable auxiliary solvents are low-boiling inert solvents which do not form a miscibility gap with water over wide ranges, have a boiling point at atmospheric pressure below 100 ° C. and, if desired, can be easily distilled to a residual content of less than 2% by weight and in particular of less than 0.5% by weight, based on the final dispersion or aqueous solution, and that it can be reused. Suitable solvents of this type are for. As acetone, methyl ethyl ketone or tetrahydro-uranium. Basically suitable are also higher-boiling solvents such. As n-butyl glycol, di-n-butyl glycol and N-methylpyrrolidone, which then remain in the dispersion.

However, one advantage of component B) lies precisely in the fact that it is possible completely to dispense with organic solvents in the finished aqueous resin dispersion and still obtain solids-rich, stable dispersions.

The reaction of I and II is preferably allowed to proceed to the extent that a residual NCO content of 1% NCO (determined according to DIN 53185) is exceeded, and particularly preferably progresses so far that the residual NCO content of the product of I and II is in the range of 0.1 to 0.5% NCO. In the reaction of I and II unreacted remaining NCO functions can be, according to the prior art, either chain extension reactions, eg. For example, by adding polyamines or water use, or if necessary, a chain termination by addition to NCO groups monofunctional compounds (eg., Monoalcohols, monoamines) initiate.

In the case of potentially hydrophilic groups, the products according to the invention can be mixed with a suitable neutralizing agent, whereby water-dilutable, water-dispersible or water-soluble products.

The neutralization of the potentially hydrophilic groups of the resins according to the invention can be carried out with inorganic and / or organic bases, such as. As ammonia or organic amines. Preferably used are primary, secondary and / or tertiary amines, such as. For example, ethylamine, propylamine, dimethylamine, dibutylamine, cyclohexalamine, benzylamine, morpholine, piperidine and triethanolamine. Particular preference is given to volatile, tertiary amines, in particular dimethylethanolamine, diethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, triethylamine, tripropylamine and tributylamine in the case of anionic potential groups. So-called cationic potential ionic groups can be neutralized with inorganic and / or organic acids, such as. As acetic acid, formic acid, phosphoric acid, hydrochloric acid, etc.

The degree of neutralization is preferably 50 to 130% of the neutralization amount necessary for stoichiometric neutralization.

The neutralized hydrophilic resin or the resin solution is either passed into water or it is preferably mixed with water while stirring. Before addition of water, the reaction product of I and II may optionally be combined with other non-hydrophilic resins or other components and then dispersed together. By this measure, a technically advantageous high solids content of the dispersions of over 45 wt .-% can be achieved. Basically, the solids content ranges between 20 and 70 wt .-%, preferably between 25 and 60 wt .-%.

After dispersing, the organic auxiliary solvent can preferably be removed in vacuo and, if appropriate, worked up again.

Component C)

The invention essential component C) is used in amounts of 5 to 50 wt .-%, preferably from 10 to 40 wt .-%. Basically, all colorants are suitable in the

Used in the printing ink industry. They are selected according to coloristic aspects and requirements such. Hue, brightness, saturation, transparency, hiding power, Light fastness, bleed fastness etc.

There are inorganic pigments such. As milori blue, titanium dioxide, iron oxides, metal pigments and carbon blacks and organic pigments such. As isoindoline, azo, phthalocyanine pigments used. In addition, dyes are used. A list of pigments used is in "Rompp Encyclopedia, paints and inks, publisher dr. Ulrich Zorll, Georg Thieme Verlag, Stuttgart, 1998 "given.

Component D)

Component D) is used in amounts of from 0 to 70% by weight, preferably from 0 to 50% by weight.

As component D) are suitable auxiliaries and additives such as inhibitors, organic solvents, surface-active substances, oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers and initiators, additives for influencing theological properties such. As thixotropic and / or thickening agents, leveling agents, anti-skinning agents, defoamers, antistatic agents, lubricants, wetting and dispersing agents, preservatives such. As well as fungicides and / or biocides, thermoplastic additives, plasticizers, matting agents,

Fire protection equipment, internal release agents, fillers and / or blowing agents.

Preparation of the printing ink compositions from components A) to D): The printing ink compositions are prepared by intensive mixing of the components at temperatures of 20 to 80 ° C ("Lehrbuch der Lacktechnologie", Th. Brock, M. Groteklaes, P. Mischke, ed V. Zorll, Vincentz Verlag, Hannover, 1998, page 229 et seq.) Non-liquid components may first be dissolved in suitable solvents or water prior to mixing, then the remaining components are added with stirring The formaldehyde content of the printing ink compositions is less than 100 ppm, preferably less than 50 ppm and more preferably less than 10 ppm The claimed aqueous printing ink compositions are suitable for printing on eg films Plastics and / or composites such as aluminum-clad foils, textiles, fibers, fabric materials, leather, Metals, cardboard, paper, cardboard, glass, Paper laminates and / or synthetic materials, such as. B., imitation leather, etc., wherein the coating is largely free of formaldehyde. The printing ink compositions are suitable for all customary printing processes.

The printing ink compositions are characterized by a particularly high rate of drying, good water resistance and high hardness and abrasion resistance with very good elasticity.

The dried, cured or crosslinked films have good adhesion properties on underlying coatings; Also, the intercoat adhesion to overlying layers is positively affected.

The claimed aqueous ink compositions have a satisfactory flow on the substrates used and are free of surface defects, such as craters and wetting disorders.

The claimed aqueous ink compositions have a solids content of from 10% to 80%, preferably from 20% to 60%.

The following examples are intended to further illustrate the invention but not to limit its scope:

Examples Preparation of component B) 1. Preparation of the adduct

444 g of isophorone diisocyanate are added with stirring to a mixture of 134 g of dimethylolpropionic acid, 380 g of acetone and 6 g of a 10% strength by weight solution of dibutyltin dilaurate in acetone so that the exothermic reaction remains readily controllable. It is heated to 60 ° C and held this temperature up to an NCO number of 9.2%.

To the cooled to room temperature solution is added with stirring, 2300 g of a 55% strength by weight acetone solution of a hydrogenated acetophenone / formaldehyde resin (resin SK Degussa AG) and 12 g of a 10 wt .-% acetone DBTL solution and heated to the reflux temperature of about 60 ° C. The mixture is allowed to stir at this temperature until the NCO number of the solution has fallen below 0.1% NCO.

2. Transfer to the aqueous phase

Alternative A:

The solution of the hydrophilically modified resin prepared under 1) is neutralized at room temperature with stirring by adding 89 g of dimethylaminoethanol and the solution is dispersed by adding 4200 g of demineralized water with stirring. The auxiliary solvent acetone and water proportionally are removed in vacuo to give a storage-stable, finely divided, slightly opalescent resin dispersion having a solids content of about 33% by weight.

Alternative B:

The solution prepared under 1) is added with stirring 3300 g of a 55 wt .-% strength acetone solution of a hydrogenated acetophenone / formaldehyde resin (synthetic resin SK Degussa AG), neutralized at room temperature with stirring with 89 g of dimethylaminoethanol and dispersed by adding the solution of 4400 g of demineralized water with stirring. The auxiliary solvent acetone and water as a proportion are removed in vacuo and obtain a storage-stable whitish dispersion having a solids content of about 50 wt .-%.

Properties of the dispersions Storage stability The dispersions A and B according to point 2) were examined for storage stability with regard to changes in the pH, the viscosity and the optical appearance.

* Rotational viscometer; D: 100 to 900 s ^"

Example of a coating material composition:

It was a commercial red, aqueous gravure ink used. To this ink was added various proportions of component B (Production Alternate A).

The paints were applied to a polyester film with a 10 μm doctor blade and dried at room temperature.

The films were mounted on glass plates with a 100 μm draw frame.

ΔL * brightness difference

ΔY * coloring ability

ΔC * difference in chroma:

If positive deviation, hue appears more brilliant and clear

Component B improves the hardness and water resistance of the films. The color becomes more brilliant. In addition, there is a re-solubility in alkaline water, which are important for cleaning the machines that are used for processing the printing inks.

Claims

claims:

1. Essentially containing aqueous printing ink compositions

A) 20 to 90 wt .-% of at least one aqueous binder, and

B) 5 to 75% by weight of a hydrophilized ketone / aldehyde resin and / or a hydrophilized, hydrogenated ketone / aldehyde resin, and

C) 5 to 50 wt .-% of at least one colorant, and

D) O to 70 wt .-% of at least one additive, wherein the sum of the weights of component A) to D) is 100 wt .-%.

2. Aqueous printing ink compositions according to claim 1, characterized in that the solids content of the ink compositions is between 10 wt .-% to 80 wt .-%, preferably between 20 wt .-% and 60 wt .-%, the formaldehyde content of the ink compositions below 100 ppm, preferably below 50 ppm and more preferably below 10 ppm and the content of organic solvents is below 20% by weight, preferably below 10% by weight, particularly preferably below 2% by weight.

3. Aqueous printing ink compositions according to claims 1 and 2, characterized in that as component A) aqueous binders from the group polyurethanes, polyacrylates, polyethers, polyesters, alkyd resins, polyamides, casein, cellulose ethers, derivatives of

Cellulose, polyvinyl alcohols and derivatives, polyvinyl acetates, polyvinyl chlorides,

Polyvinylpyrolidone, rubbers, natural resins, hydrocarbon resins such. Cumaron,

Indene, cyclopentadiene resins, terpene resins, maleate resins, phenolic resins, phenol / urea

Aldehyde resins, aminoplasts (e.g., melamine, benzoguanamine resins), epoxyacrylates, epoxy resins, silicic acid esters and alkali silicates (e.g., water glass) and / or silicone resins, and / or fluorine-containing polymers may be used alone or in admixture.

4. Aqueous printing ink compositions according to claim 3, characterized in that as component A) preferred aqueous binder foreign and / or self-crosslinking, air-drying (physically drying) and / or oxidatively curing.

5. Aqueous ink compositions according to any one of the preceding claims, characterized in that as component B) aqueous resin dispersions are used, obtainable by reaction or proportionate reaction of I. hydroxy-containing ketone / aldehyde or their hydrogenated derivatives and II. At least one hydrophilic modified isocyanate and / or polyisocyanate having at least one free NCO group obtainable by reacting at least one

Isocyanate and / or polyisocyanate with compounds which in addition to the hydrophilic or potentially hydrophilic group have at least one isocyanate-reactive function, and subsequent mixing of the optionally neutralized resin with water.

6. Aqueous printing ink compositions according to claim 5, characterized in that as component I for the preparation of component B) resins are used which contain C-H-acidic ketones.

7. Aqueous printing ink compositions according to claim 6, characterized in that CH-acidic ketones selected from acetone, acetophenone, methyl ethyl ketone, heptanone-2, pentanone-3, methyl isobutyl ketone, cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2,4 , 4-trimethylcyclopentanone, cycloheptanone and cyclooctanone, cyclohexanone and all alkyl-substituted cyclohexanones having one or more alkyl radicals having a total of 1 to 8 carbon atoms, individually or in each case

Mixture be used.

8. Aqueous printing ink compositions according to claim 7, characterized in that as alkyl-substituted cyclohexanones 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3.3 , 5-trimethylcyclohexanone alone or in mixture.

9. Aqueous printing ink compositions according to claim 5, characterized in that as component I for the preparation of component B) resins are used which

Containing aldehydes.

10. Aqueous printing ink compositions according to one of the preceding claims, characterized in that as the aldehyde component for the preparation of component I of component B)

Formaldehyde, acetaldehyde, n-butyraldehyde and / or isobutyraldehyde, valeric aldehyde, dodecanal are used alone or in mixtures.

11. Aqueous printing ink compositions according to any one of the preceding claims, characterized in that hydrogenation products of the resins of acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone, heptanone alone or in mixture and formaldehyde are used as component I. ,

12. Aqueous printing ink compositions according to any one of the preceding claims, characterized in that the component II. Of component B) is prepared using tert.

Amino alcohols, aminocarboxylic acids, hydroxysulfonic acids, aminosulfonic acids or / and hydroxycarboxylic acids.

13. Aqueous ink compositions according to any one of the preceding claims, characterized Component II. of component B) is prepared using dimethylolpropionic acid.

14. Aqueous printing ink compositions according to one of the preceding claims, characterized in that component II. Of component B) is already neutralized before reaction with component I.

15. Aqueous printing ink compositions according to one of the preceding claims, characterized in that for the preparation of II. Of component B) di- to tetrafunctional polyisocyanates are used.

16. Aqueous printing ink compositions according to one of the preceding claims, characterized in that for the preparation of II. The component B) polyisocyanates with aromatic, aliphatic and / or cycloaliphatic bound isocyanate groups or mixtures thereof are used.

17. Aqueous ink compositions according to any one of the preceding claims, characterized in that 1-isocyanato-3.3.S-trimethyl-S-isocyanatomethylcyclohexane (isophorone diisocyanate;

IPDI), trimethylhexamethylene diisocyanate (TMDI), 1,6-diisocyanatohexane (HDI), bis (4-isocyanatohexyl) methane (H ₁₂ MDI) can be used alone or in a mixture.

18. Aqueous printing ink compositions according to one of the preceding claims, characterized in that for the preparation of II. The component B) polyisocyanates with biuret, uretdione or isocyanurate structure are used.

19. Aqueous printing ink compositions according to one of the preceding claims, characterized in that that for the preparation of II. Component B) polyisocyanates from the reaction of polyhydric alcohols and / or amines are used with monomeric isocyanates.

20. Aqueous printing ink compositions according to one of the preceding claims, characterized in that for the preparation of II. The component B) dimethylolpropionic acid and isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1,6-diisocyanatohexane and / or bis (4-isocyanatohexyl) methane in a molar ratio 1: 2 become.

21. Aqueous printing ink compositions according to any one of the preceding claims, characterized in that the reaction of I. and II. The component B) and the subsequent dispersion carried out in bulk or in the presence of an auxiliary solvent.

22. Aqueous printing ink compositions according to the preceding claim, characterized in that the auxiliary solvent used has a boiling point below 100 ° C at 1013 hPa.

23. Aqueous printing ink compositions according to the preceding claim, characterized in that the auxiliary solvent used is acetone or / and methyl ethyl ketone or / and tetrahydro-uranium.

24. Aqueous printing ink compositions according to one of the preceding claims, characterized in that the neutralization of component B) takes place with inorganic or organic bases.

25. Aqueous printing ink compositions according to the preceding claim, characterized in that for the neutralization dimethylethanolamine or / and diethylethanolamine or / and 2-dimethylamino-2-methyl-1-propanol are used.

26. Aqueous ink compositions according to any preceding claim, characterized in that for neutralization 50 to 130% of the neutralization amount, which is necessary for a stoichiometric neutralization, is used.

27. Aqueous printing ink compositions according to any preceding claim, characterized in that one or more non-water-soluble or water-dilutable components are added before the addition of water.

28. Aqueous printing ink compositions according to any preceding claim, characterized in that as component C) colorants are used.

29. Aqueous printing ink compositions according to any preceding claim, characterized in that as component C) inorganic and / or organic pigments and / or dyes are used.

30. Aqueous printing ink compositions according to any preceding claim, characterized in that are used as component D) auxiliaries and additives.

31. Aqueous printing ink compositions according to any preceding claim, characterized in that as component D) auxiliaries and additives are used alone or in mixture, selected from the group of inhibitors, organic solvents, surface-active

Substances, oxygen and / or radical scavengers, catalysts, light stabilizers,

Color lighteners, photosensitizers and initiators, additives for influencing Theological properties such. As thixotropic and / or thickening agents, flow agents, anti-skinning agents, defoamers, antistatic agents, lubricants, wetting and dispersing agents, preservatives such. As well as fungicides and / or biocides, thermoplastic additives, plasticizers, matting agents, fire protection equipment, internal release agents, fillers and / or blowing agents.

32. A process for the preparation of aqueous ink compositions comprising substantially

A) from 20 to 90% by weight of at least one aqueous binder, and

B) 5 to 75 wt .-% of a hydrophilized ketone / aldehyde resin and / or a hydrophilized, hydrogenated ketone / aldehyde resin, and

C) from 5 to 50% by weight of at least one colorant, and

D) O to 70 wt .-% at least one additive, wherein the sum of the weights of component A) to D) is 100 wt .-%, by intensive mixing by stirring and / or dispersing the components at temperatures of +20 to + 80 ° C.

33. Use of the aqueous printing ink compositions according to at least one of the preceding claims for the printing of articles.

34. Use of the aqueous printing ink compositions according to at least one of the preceding claims for the printing of objects such as films of plastics and / or composite materials such. As aluminum-laminated films, textiles, fibers, fabric materials, leather, metals, cardboard, paper, cardboard, glass, paper laminates and / or synthetic materials such as artificial leathers.

35. Coated articles made and / or finished with an ink composition according to at least one of the preceding claims.