CN1942538A - Aqueous printing ink compositions - Google Patents

Abstract

This invention relates to an aqueous printing ink composition comprising at least one binder, a modified ketone/aldehyde resin, a colorant, and desired auxiliaries and additives.

Description

Water-based printing ink composition

technical field

The invention relates to a water-based printing ink composition composed of at least one binder, a modified ketone-aldehyde resin, a colorant and, if desired, auxiliaries and additives.

The printing ink composition is used for printing various substrates, such as plastic films and/or laminates such as aluminized films, textiles, fibers, woven materials, leather, metal, cardboard, paper, veneer, glass, paper layers Pressed bodies and/or synthetic materials such as synthetic leather etc., the coating is largely free of formaldehyde. The printing ink compositions are suitable for all customary printing methods, such as offset printing, flexographic printing, screen printing, gravure printing, pad printing, inkjet printing or xerographic printing and the like.

The printing ink compositions are notable for particularly high initial drying rates, good water resistance, high gloss, high abrasion resistance and hardness, and very good elasticity.

Background technique

Printing inks assume decorative properties and are used to inform, decorate and attract attention in sales promotion through visualization, embellishment, and graphic representation of text (see "Rmpp Lexikon, Lacke und Druckfarben, Dr. Ulrich Zorll, ed., GeorgThieme Verlag, Stuttgart, 1998").

For example, the printing of paper and film serves information (brochures, packaging materials) on the one hand; on the other hand, with the help of layout design, this information is transformed into the most eye-catching form. Apart from properties such as maximum initial dry rate, properties such as not only good adhesion and elastic properties but also good abrasion resistance are also important.

After printing inks have been applied, rapid dry-out is desirable in order to ensure rapid further processing and to prevent defects such as contamination caused by, for example, dust and dirt.

Hard resins based on ketones and aldehydes are known to increase the hardness of coatings at the expense of elastic properties.

Water-dispersible condensation products of ketones and aldehydes or derivatives thereof and reaction products which may contain such products are described in EP 0 617 103 A1, EP 0838485, EP 0838486 (DE19643704), DE 25 42 090, DE-A 31 44 673 and DE-A 3406474 (EP0154835).

DE-A 25 42 090 describes water-soluble compounds which carry sulfonic acid groups and - deviating from the process according to the invention - are obtainable in a joint condensation reaction from cycloalkanones, formaldehyde and alkali metal bisulfites.

DE-A 31 44 673 describes water-soluble condensation products also obtained from the joint reaction of ketones, aldehydes, and compounds capable of introducing acid groups. Examples of the latter are sulfites and amidosulfonates, glycines, and phosphites.

According to DE-A 25 42 090 and DE-A 31 44 673, products containing electrolytes (for example Na ions) are obtained. However, one of the effects of such resins is to impair the water resistance of the coating system.

EP 0 617 103 A1 describes polyisocyanates (a) and dihydroxy compounds ( b) response (see lines 17-21 of p.3). The polyurethane thus obtained is further reacted with a compound (c) which, in addition to the NCO-reactive groups, also contains groups which can be converted into ionic groups, and if desired with a diol with a molecular weight of 60-500 which does not carry further functional groups or Polyol (d) reaction (see lines 5-15 of p.4). This reaction product is then 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 of protective colloids remaining in the subsequent coating and possibly detrimentally affecting some properties such as resistance to water and moisture prevents their use in high value coating compositions.

EP 0838485 describes esterification products. Ester groups are known to undergo hydrolysis, causing polymer degradation and detrimentally affecting storage stability. Furthermore, freely accessible acid groups may also cause reactions and/or incompatibility with pigments.

EP 0838486 describes aqueous resin dispersions obtainable by reaction or partial reaction of the following components:

I. Ketone resins, ketone/aldehyde resins and/or urea/aldehyde resins or hydrogenated derivatives thereof containing hydroxyl groups, and

II. At least one hydrophilically 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 containing hydrophilic groups In addition to the group or the potential hydrophilic group, there is at least one functional group capable of reacting with the isocyanate group, having an active hydrogen in the Zerewitinoff test, and also having at least one hydrophilic group and/or a potential hydrophilic group,

and the subsequent combination of the neutralized resin and water.

Contents of the invention

It was an object of the present invention to find aqueous printing ink compositions for printing on various substrates, with the intention that the coating should be very largely free of formaldehyde. The printing ink composition should have a high initial drying rate and should have a positive effect on hardness, abrasion resistance, water resistance, and elastic properties.

The object on which the invention is based is surprisingly achieved by the use of a specific coating composition described in more detail below.

The invention provides an aqueous printing ink composition for printing on various substrates, comprising essentially

A) 20wt%-90wt% of at least one aqueous vehicle, and

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

C) 0.5% to 50% by weight of at least one colorant, and

D) 0wt% to 70wt% of at least one additive,

The sum of the weights of components A) to D) is 100wt%.

It has been found that the combinations of printing ink compositions described below and comprising components A) to D) meet all the required criteria.

Detailed ways

Component A)

The substantial water-based vehicle A) of the present invention is used in an amount of 20wt%-90wt%, preferably 30wt%-75wt%.

Preference is given to the use of aqueous vehicles selected from the group consisting of polyurethanes, polyacrylates, polyethers, polyesters, alkyds, polyamides, casein, cellulose ethers, cellulose derivatives, polyethylene Alcohols and derivatives, polyvinyl acetate, polyvinyl chloride, polyvinylpyrrolidone, rubber, natural resins, carbohydrate resins such as coumarone resins, indene resins, cyclopentadiene resins, terpene resins, maleic acid esters resins, phenol resins, phenol/urea resins, amino resins (e.g. melamine resins, benzoguanamine resins), epoxy acrylates, epoxy resins, silicates, and alkali metal silicates (e.g. water glass) and/or or silicone resins and/or fluoropolymers. The aqueous vehicle can be externally and/or self-crosslinking, air-dried (physically dried) and/or oxidatively cured.

ingredient B)

The essential component B) of the present invention is used in an amount of 5wt%-75wt%, preferably 10wt%-60wt%.

Suitable components B) include aqueous resin dispersions obtainable by reaction or partial reaction of the following components:

I. Ketone/aldehyde resins or hydrogenated derivatives thereof containing hydroxyl groups, and

II. At least one plain water-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 containing hydrophilic groups In addition to the group or the potential hydrophilic group, there is at least one functional group that can react with the isocyanate group,

After the reaction the resin - neutralized if necessary - is combined with water.

Ketones suitable for the preparation of ketone/aldehyde resins (component I) include all ketones, especially acetone, acetophenone, methyl ethyl ketone, heptan-2-one, pentan-3-one, methyl isobutyl ketone, cyclopentanone, cyclodeca Dialkylones, 2,2,4- and 2,4,4-trimethylcyclopentanones, cycloheptanones and cyclooctanones, cyclohexanones and all of which have one or more of them containing a total of 1 to 8 carbon atoms Alkyl mixtures of alkyl-substituted cyclohexanones, alone or in mixtures. Possible examples of alkyl-substituted cyclohexanone include 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone, and 3,3,5-Trimethylcyclohexanone.

Ketones with further functional groups such as amino and/or acid groups are also possible in principle, although less preferred.

In general, however, all ketones reported in the literature as suitable for ketone resin and ketone/aldehyde resin synthesis can be used; in general, all C-H-acidic ketones. Preference is given to the bases of acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone, and heptanone, alone or in mixture.

As aldehyde components of ketone/aldehyde resins (component I), suitable in principle are unbranched or branched aldehydes, such as formaldehyde, acetaldehyde, n-butyraldehyde and/or isobutyraldehyde, valeraldehyde, and Two (alk) aldehydes. In general, all aldehydes reported in the literature to be suitable for ketone/aldehyde resin synthesis can be used. However, preference is given to using formaldehyde alone or in admixture.

The required formaldehyde is typically used as an aqueous or alcoholic (eg methanol or butanol) solution at a concentration of about 20% to 40% by weight. Other forms of use of formaldehyde, including uses such as paraformaldehyde or trioxane, are likewise possible. Aromatic aldehydes such as benzaldehyde can likewise be present in mixtures with formaldehyde.

Particularly good starting compounds for the ketone/aldehyde resin of component I are acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone, and heptanone, either alone or Mixed form, and formaldehyde.

Resins derived from ketones and aldehydes can also be hydrogenated with hydrogen at pressures up to 300 bar in the presence of suitable catalysts. During this hydrogenation, some of the carbonyl groups of the ketone/aldehyde resin are converted to secondary hydroxyl groups. In the case of resins derived from aldehydes and ketones which, in addition to carbonyl moieties, have further hydrogenatable functions, such as aromatic structures, these further structures can also be converted by appropriate hydrogenation. In the case of such aromatic structures, cycloaliphatic structures are obtained.

A possibly necessary hydrophilic modification is achieved, for example, by reacting resin I with component II, the latter consisting of at least one hydrophilically modified isocyanate and/or polyisocyanate having at least one free NCO group, by making at least An isocyanate and/or polyisocyanate obtained by reacting a compound which, in addition to a hydrophilic or potentially hydrophilic group—that is, a group which becomes hydrophilic only after neutralization—has at least one pair Isocyanate groups are reactive groups such as hydroxyl or amino groups.

Examples of such compounds for water modification of (poly)isocyanates are amino acids, hydroxysulfonic acids, sulfamic acids, and hydroxycarboxylic acids. Preference is given to the use of di(hydroxymethyl)propionic acid or derivatives thereof. The hydrophilic modification can also be carried out with nonionic groups (for example with polyethers) or with already neutralized compounds.

Hydroxycarboxylic acids, such as especially di(hydroxymethyl)propionic acid, are particularly preferred due to the fact that they show a strong hydrophilic effect when neutralized with volatile bases such as amines etc., however, such The effect disappears rapidly after evaporation of the volatile base. Thus, the coating does not lose its protective function due to, for example, exposure to moisture, since any initial swelling does not occur.

Di(hydroxymethyl)propionic acid is also particularly preferred due to its ability to carry out the (potential) hydrophilic modification of two hydrophobic polyisocyanates via its two hydroxyl groups.

Polyisocyanates suitable for preparing component II are preferably difunctional to tetrafunctional polyisocyanates. Examples thereof are cyclohexane diisocyanate, methyl cyclohexane diisocyanate, ethyl cyclohexane diisocyanate, propyl cyclohexane diisocyanate, methyl diethylcyclohexane diisocyanate, benzene diisocyanate, toluene diisocyanate, Isocyanates, bis(isocyanatophenyl)methane, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate such as hexamethylene diisocyanate (HDI) or 1,5-diisocyanate Heptane-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-isocyanatomethyloctane-1,8-diisocyanate (TIN), Decane diisocyanate and triisocyanate, undecane diisocyanate and triisocyanate, dodecane diisocyanate and triisocyanate, 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 mixtures thereof.

Another preferred class of polyisocyanates are compounds having more than 2 isocyanate groups per molecule, prepared by dimerization or trimerization, allophanation, biuretization and/or polyurethaneization of simple diisocyanates, Examples are the reaction products of these simple diisocyanates such as IPDI, HDI and/or H ₁₂ MDI etc. Examples include trimerized triisocyanates such as IPDI, HDI, and H ₁₂ MDI .

Particular preference is given to _{hydrophilically} modified polyisocyanates ( II).

Component B) is prepared in the melt or as a solution in a suitable organic solvent which, if desired, can be separated off by distillation after preparation.

In the case of reacting in solution, the preferred solid content is 30wt% to 95wt%, more preferably 60wt% to 80wt%.

Suitable auxiliary solvents used are low-boiling inert solvents, which do not form a miscibility gap with water at least in a wide range, have a boiling point below 100 °C at atmospheric pressure, and can be easily separated by distillation. Based on the final dispersion or aqueous solution, the residual level is lower than 2 wt%, especially lower than 0.5 wt%, and reused. Examples of suitable such solvents include acetone, methyl ethyl ketone, and tetrahydrofuran. Also suitable in principle are higher-boiling solvents such as n-butylene glycol, di-n-butylene glycol, and N-methylpyrrolidone etc., which then remain in the dispersion.

In particular, however, the advantage of component B) is the fact that it is possible to completely eliminate organic solvents in the final aqueous resin dispersion and still obtain a stable high solids dispersion.

The reaction of I and II can preferably be carried out to such a point: the residual NCO content (measured according to DIN 53185) is lower than 1% NCO; it is particularly preferred to reach such a point: the residual NCO content of the product generated from I and II is between 0.1% ~ 0.5% NCO range. According to the current state of the art, NCO functions which remain unreacted in the reactions of I and II can be used for chain extension reactions by adding polyamines or water etc., or, when desired, can be used for NCO groups by adding Functional compounds (eg monoalcohols, monoamines) to initiate chain termination.

In the case of latent hydrophilic groups, suitable neutralizing agents may be added to the products of the invention to give water dilutable, water dispersible or water soluble products.

The latent hydrophilic groups of the resins prepared according to the present invention can be neutralized using organic and/or inorganic bases such as organic amines or ammonia. Preference is given to the use of primary, secondary and/or tertiary amines, such as ethylamine, propylamine, dimethylamine, dibutylamine, cyclohexylamine, benzylamine, morpholine, piperidine, and triethanolamine. In the case of anionic latent groups, particular preference is given to volatile tertiary amines, especially dimethylethanolamine, diethylethanolamine, 2-dimethylamino-2-methyl-4-propanol, triethyl amine, tripropylamine, and tributylamine. Cationic potentially ionic groups can be neutralized using organic and/or inorganic acids such as acetic acid, formic acid, phosphoric acid, hydrochloric acid, and the like.

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

Either the neutralized hydrophilic resin or resin solution is introduced into the water, or the water is added thereto, preferably with agitation. Before the addition of water, the reaction product of I and II can if desired be combined with further resins which have not been hydrophilically modified or with other constituents, which are then dispersed together. As a result of this measure, a technically advantageous high solids content of above 45% by weight in the dispersion can be achieved. In principle, the solid fraction is in the range of 20 wt% to 70 wt%, preferably 25 wt% to 60 wt%.

After dispersion, the organic auxiliary solvent can be removed, preferably under reduced pressure, and, if desired, reworked.

ingredient C)

Ingredient C), which is essential in the present invention, is used in an amount of 5 wt % to 50 wt %, preferably 10 wt % to 40 wt %. In principle, all colorants used in the printing ink industry are suitable. They are selected according to the color scheme and needs such as hue, brightness, saturation, transparency, opacity, light fastness, bleed fastness, etc. Used are inorganic pigments such as Milori blue, titanium dioxide, iron oxide, metallic pigments, and pigment black, and organic pigments such as isoindoline, azo, and phthalocyanine pigments, and the like. Dyes are also used. A list of the pigments used. See "Rmpp Lexikon, Lacke und Druckfarben, ed. Dr. Ulrich Zorll, Georg Thieme Verlag, Stuttgart, 1998".

ingredient D)

Component D) is used in an amount of 0-70 wt%, preferably 0-50 wt%.

Suitable constituents D) are auxiliaries and additives such as inhibitors, organic solvents, surface-active substances, oxygen scavengers and/or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers and photoinitiators additives, additives affecting rheological properties such as thixotropic and/or thickeners, flow control agents, anti-skinning agents, defoamers, antistatic agents, lubricants, wetting agents, dispersants, preservatives including Fungicides and/or biocides, etc., thermoplastic additives, plasticizers, matting agents, flame retardants, internal release agents, fillers, and/or foaming agents.

Preparation of printing ink composition from components A) to D)

The printing ink composition is prepared by intensive mixing of the components at a temperature of 20-80°C ("Lehrbuch der Lacktechnologie", edited by Th. Brock, M. Groteklaes, P. Mischke, V. Zorll, Vincentz Verlag, Hannover, 1998, p. 229ff).

Ingredients not in liquid form, when desired, are brought into solution in a suitable solvent or in water prior to mixing and the remaining ingredients are then added with stirring. In the case of pigments and/or fillers, etc., dispersion is performed.

The formaldehyde content of the printing ink composition is lower than 100 ppm, preferably lower than 50 ppm, more preferably lower than 10 ppm.

The claimed aqueous printing ink compositions are suitable for printing, for example, plastic films and/or laminates such as aluminized films, textiles, fibers, woven materials, leather, metal, cardboard, paper, glued board, glass, paper laminates and/or synthetic materials, such as synthetic leather, etc., the coating is very largely free of formaldehyde. The printing ink compositions are suitable for all customary printing methods.

The printing ink compositions are notable for particularly high initial drying rates, good water resistance, and high hardness and abrasion resistance combined with very good elasticity.

The dried, cured and crosslinked film has good adhesion properties to the basecoat; moreover, the intercoat adhesion to the overlying coating is positively affected.

The claimed aqueous printing ink compositions flow defect-free on the substrates used and are free from surface defects such as smearing and wetting defects.

The claimed water-based printing ink composition has a solid content of 10% to 80%, preferably 20% to 60%.

The following examples are intended to further illustrate the invention without limiting its scope of application.

Example

Preparation of component B)

1. Preparation of Adducts

A mixture of 134 g of bis(hydroxymethyl)propionic acid, 380 g of acetone and 6 g of a 10% by weight solution of dibutyltin dilaurate in acetone was mixed with 444 g of isophorone diisocyanate under stirring at such a rate that the exothermic reaction remained Can be managed with ease. The mixture was heated to 60° C. and maintained at this temperature until the NCO value was 9.2%.

After cooling to room temperature, the solution was mixed with 2300 g of 55 wt % strength hydrogenated acetophenone/formaldehyde resin (Kunstharz SK, purchased from Degussa AG) acetone solution and 12 g of 10 wt % concentration DBTL acetone solution under stirring, and the mixture was heated to about reflux temperature of 60°C. It was stirred further at this temperature until the NCO value of the solution fell below 0.1% NCO.

2. Transfer to the aqueous phase

Alternative A:

The solution of the plain water-modified resin prepared in 1) was neutralized by adding 89 g of dimethylaminoethanol under stirring at room temperature, and then the solution was dispersed by adding 4200 g of demineralized water and stirred. The co-solvent, acetone, together with a proportion of water, were removed under reduced pressure to give a storage stable, fine, light milky resin dispersion with a solids content of about 33% by weight.

Alternative B:

1) The solution prepared in 1) was mixed with 3300g 55wt% concentration hydrogenated acetophenone/formaldehyde resin (Kunstharz SK, purchased from Degussa AG) acetone solution under stirring, and the product was neutralized with 89g dimethylaminoethanol under stirring at room temperature, The solution was dispersed by introducing 4400 g of fully demineralized water with stirring. The auxiliary solvent, acetone, together with a proportion of water, is removed under reduced pressure to give a storage-stable, whitish dispersion with a solids content of about 50% by weight.

Dispersion Properties

storage stability

A storage stability investigation regarding changes in pH, viscosity, and visual appearance was performed on dispersions A and B of section 2).

performance A B pH initial 8.9 8.8 6 months later 8.9 8.8 Viscosity at 23°C ^* initial 375-714mPa·s 69-138mPa·s 6 months later 335-563mPa·s 67-135mPa·s Exterior After precipitation light cream White 6 months later light cream White

^* Rotational viscometer; D: 100 to 900s ^-1

Coating Composition Examples:

A commercially customary red water-based gravure ink was used. Added to this printing ink was a different fraction of component B (formulation instead of A). Compare Ink I Ink II Element Mass/g Mass/g Mass/g Item 1 printing ink 100.0 95.0 90.0 ingredient B - 5.0 10.0 The ingredients were combined in the order described under agitation (600rpm)

The ink was applied to a polyester film using a 10 μm doctor blade and dried at room temperature. performance Compare Ink I Ink II Knig pendulum hardness (s) ¹⁾ 83 91 94 ΔL ^* - 0.6 0.8 ΔY ^* - 0.4 0.6 ΔC ^* - 1.12 2.15 Gloss 60° 51 52 54 Water resistance after 1 minute good better very good Ability to partially redissolve in alkaline water slight good very good

1) Use a 100 μm draw frame to pull the film down onto a glass plate. ΔL ^* brightness difference ΔY ^* coloring power ΔC ^* Chromatic Aberration Degree: If it is a positive difference, the color tone will appear brighter and clearer

Component B improves the hardness and water resistance of the film. Colors become brighter. Furthermore, there is also the ability to partially redissolve in alkaline water, which is important for the cleaning of the machines used to process the printing ink.

Claims (35)

1. A water-based printing ink composition comprising essentially A) 20wt%-90wt% of at least one aqueous vehicle, 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% by weight of at least one colorant, and D) 0wt% to 70wt% of at least one additive, The sum of the weights of components A) to D) is 100wt%. 2. The water-based printing ink composition claimed in claim 1, wherein the solid content of the printing ink composition is 10wt% to 80wt%, preferably 20wt% to 60wt%, and the formaldehyde content of the printing ink composition is lower than 100ppm, preferably less than 50ppm, more preferably less than 10ppm, and the organic solvent content is less than 20wt%, preferably less than 10wt%, more preferably less than 2wt%. 3. The water-based printing ink composition claimed in claim 1 or 2, wherein, use the water-based binder selected from the following group as component A): polyurethane, polyacrylate, polyether, polyester, alkyd resin, Polyamides, casein, cellulose ethers, cellulose derivatives, polyvinyl alcohol and derivatives, polyvinyl acetate, polyvinyl chloride, polyvinylpyrrolidone, rubber, natural resins, carbohydrate resins such as coumarone resins, indene resin, cyclopentadiene resin, terpene resin, maleate resin, phenol resin, phenol/urea resin, amino resin (such as melamine resin, benzoguanamine resin), epoxy acrylate, epoxy resin, Silicates, and alkali metal silicates (eg water glass) and/or silicone resins and/or fluoropolymers, alone or in mixtures thereof. 4. The water-based printing ink composition as claimed in claim 3, wherein the preferred water-based binder as component A) is externally linked and/or self-crosslinked, air-dried (physically dried) and/or oxidatively cured. 5. The water-based printing ink composition claimed by any one of the above claims, wherein, the water-based resin dispersion obtainable by the reaction or partial reaction of the following components is used as component B): I. Ketone/aldehyde resins or hydrogenated derivatives thereof containing hydroxyl groups, and II. At least one hydrophilically 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 containing hydrophilic groups In addition to the group or the potential hydrophilic group, there is at least one functional group capable of reacting with the isocyanate group, After the reaction the resin - neutralized if necessary - is combined with water. 6. The aqueous printing ink composition as claimed in claim 5, wherein a resin comprising a C—H acidic ketone is used as component I for the preparation of component B). 7. The water-based printing ink composition claimed in claim 6, wherein, use the following C-H acidic ketones: acetone, acetophenone, methyl ethyl ketone, heptan-2-one, pentan-3-one, methyl isobutyl Ketones, cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanone, mixtures of cycloheptanone and cyclooctanone, cyclohexanone and all A mixture of one or more alkyl-substituted cyclohexanones containing a total of 1 to 8 carbon atoms, either alone or as a mixture. 8. The water-based printing ink composition claimed in claim 7, wherein, use following as alkyl-substituted cyclohexanone: 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone Ketones, 4-tert-butylcyclohexanone, 2-methylcyclohexanone, and 3,3,5-trimethylcyclohexanone, alone or in mixtures thereof. 9. The aqueous printing ink composition as claimed in claim 5, wherein an aldehyde-containing resin is used as component I for the preparation of component B). 10. The water-based printing ink composition claimed by any one of the above claims, wherein, use the following as the aldehyde component of the composition I of the preparation component B): formaldehyde, acetaldehyde, n-butyraldehyde and/or isobutyraldehyde, Valeraldehyde, and dodecanal, alone or in mixtures thereof. 11. The water-based printing ink composition claimed by any one of the above claims, wherein, use from acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone, and heptanone, the hydrogenation product of resins made with heptanone, alone or in mixtures thereof, and formaldehyde as component I. 12. The water-based printing ink composition claimed by any one of the above claims, wherein, component B) component II is to use tertiary amino alcohol, aminocarboxylic acid, hydroxysulfonic acid, sulfamic acid and/or hydroxycarboxylic acid acid preparation. 13. An aqueous printing ink composition as claimed in any one of the preceding claims, wherein component II of component B) is prepared using di(hydroxymethyl)propionic acid. 14. An aqueous printing ink composition as claimed in any one of the preceding claims, wherein component II of component B) has been neutralized prior to reaction with component I. 15. An aqueous printing ink composition as claimed in any one of the preceding claims, wherein II of component B) is prepared using a difunctional to tetrafunctional polyisocyanate. 16. The aqueous printing ink composition as claimed in any one of the preceding claims, wherein polyisocyanates with aromatic, aliphatic and/or cycloaliphatic linked isocyanate groups or mixtures of these are used to prepare component B) II. 17. The water-based printing ink composition claimed in any one of the above claims, wherein 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane is used (isophorone diisocyanate; IPDI), trimethylhexamethylene diisocyanate (TMDI), 1,6-diisocyanatohexane (HDI) and bis(4-isocyanatohexyl)methane (H ₁₂ MDI), alone or in mixtures thereof. 18. The water-based printing ink composition claimed in any one of the above claims, wherein, use has biuret, isocyanate dimer (uretdione) or polyisocyanate of isocyanurate structure to prepare component B) II . 19. An aqueous printing ink composition as claimed in any one of the preceding claims, wherein II of component B) is prepared using polyisocyanates obtained from the reaction of polyols and/or amines with monomeric isocyanates. 20. The water-based printing ink composition claimed by any one of the above claims, wherein two (methylol) propionic acid and isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1, 6-Diisocyanatohexane and/or bis(4-isocyanatohexyl)methane in a molar ratio of 1:2 was used to prepare II of component B). 21. An aqueous printing ink composition as claimed in any one of the preceding claims, wherein the reaction of I and II of component B) and subsequent dispersion is carried out in bulk (without solvent) or in the presence of an auxiliary solvent. 22. Aqueous printing ink composition as claimed in the preceding claims, wherein the auxiliary solvent used has a boiling point below 100°C at 1013 hPa. 23. The aqueous printing ink composition as claimed in the preceding claims, wherein the auxiliary solvent used is acetone and/or methyl ethyl ketone and/or tetrahydrofuran. 24. An aqueous printing ink composition as claimed in any one of the preceding claims, wherein component B) is neutralized with an organic or inorganic base. 25. The water-based printing ink composition claimed in the above claims, wherein neutralization is to use dimethylethanolamine and/or diethylethanolamine and/or 2-dimethylamino-2-methyl-1- propanol. 26. An aqueous printing ink composition as claimed in any one of the preceding claims, wherein the neutralization is carried out using 50% to 130% of the neutralization amount required for stoichiometric neutralization. 27. An aqueous printing ink composition as claimed in any one of the preceding claims, wherein one or more water-insoluble or water-dilutable ingredients are added prior to the addition of water. 28. An aqueous printing ink composition as claimed in any one of the preceding claims, wherein a colorant is used as component C). 29. An aqueous printing ink composition as claimed in any one of the preceding claims, wherein inorganic pigments and/or organic pigments and/or dyes are used as component C). 30. An aqueous printing ink composition as claimed in any one of the preceding claims, wherein auxiliaries and additives are used as component D). 31. The water-based printing ink composition claimed in any one of the preceding claims, wherein, as component D), adjuvants and additives selected from the following group, alone or in admixture, are used: inhibitors, organic solvents, surface active Substances, oxygen scavengers and/or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers and photoinitiators, additives influencing rheological properties such as thixotropes and/or thickeners, flow Control agents, anti-skinning agents, defoamers, antistatic agents, lubricants, wetting agents, dispersants, preservatives including fungicides and/or biocides, etc., thermoplastic additives, plasticizers, matting agents, retardants Combustion agents, internal release agents, fillers, and/or blowing agents. 32. A method for preparing a water-based printing ink composition, the composition essentially comprising A) 20wt%-90wt% of at least one aqueous vehicle, 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% by weight of at least one colorant, and D) 0-70 wt% of at least one additive, The sum of the weight quantities of components A)～D) is 100wt%, The method involves stirring and/or dispersing the ingredients at a temperature of +20 to +80°C for thorough mixing. 33. Use of an aqueous printing ink composition as claimed in at least one of the preceding claims for printing articles. 34. Use of an aqueous printing ink composition as claimed in at least one of the preceding claims for printing articles such as plastic films and/or laminates such as aluminized films, textiles, fibers, woven materials, leather, metal, Cardboard, paper, veneer, glass, paper laminates and/or synthetic materials such as synthetic leather. 35. A coated article produced and/or reinforced with a printing ink composition as claimed in at least one of the preceding claims.