EP1781720A1

EP1781720A1 - Water-soluble, radiation-curable products and use thereof

Info

Publication number: EP1781720A1
Application number: EP05771263A
Authority: EP
Inventors: Christian Krüger; Bernd Bruchmann; Ulrike Hees; Michael Kluge; Cedric Dieleman; Jürgen WEISER
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2004-08-19
Filing date: 2005-08-05
Publication date: 2007-05-09
Also published as: CN101006113A; US20090227701A1; JP2008510046A; WO2006018152A1; DE102004040419A1

Abstract

The invention relates to the use of water-soluble, radiation-curable products (A), which are obtained by mixing and, optionally, reacting at least one hyper cross-linked polyurethane (a) with at least one photoinitiator (b) or by synthesising at least one hyper cross-linked polyurethane (a) in the presence of at least one photoinitiator (b), for producing aqueous tints for the Ink-Jet method.

Description

Water soluble radiation curable products and their use

description

The present invention relates to the use of water-soluble radiation-curable products (A) obtainable by mixing and optionally reacting at least one hyperbranched polyurethane (a) with at least one photoinitiator (b).

or by synthesis of at least one hyperbranched polyurethane (a) in the presence of at least one photoinitiator (b)

for the preparation of aqueous inks for the ink-jet process.

Furthermore, the present invention relates to aqueous ink for the ink-jet process with a dynamic viscosity in the range of 2 to 80 mPa-s, measured at 23 ⁰ C, containing

(A) at least one water-soluble radiation-curable product obtainable by

Mixing and optionally reacting at least one hyperbranched polyurethane (a) with at least one photoinitiator (b)

furthermore (B) at least one pigment.

Furthermore, the present invention relates to processes for the production of ink-jet inks, methods for printing flat substrates by the ink-jet process and printed flat substrates.

A number of requirements are imposed on recording fluids and in particular on inks used in the ink-jet process (ink-jet printing processes such as thermal inkjet, piezo inkjet, continuous ink jet, transfer printing): they must be suitable for printing They must be stable in storage, ie they should not coagulate or flocculate, and they must not lead to clogging of the printer nozzle, which can be problematic in particular with dispersed, ie undissolved colorant particles containing Tin¬ th. The storage stability requirements of this In addition, in particular, inks include that dispersed colorant particles do not settle. Furthermore, in the case of the continuous ink jet, the inks must be stable to the addition of conductive salts and should show no tendency to flocculate when the ion content is increased. In addition, the prints obtained must meet the coloristic requirements, ie show high brilliance and color depth, and have good fastness properties, for example rub fastness, light fastness, waterfastness and wet rub fastness, optionally after aftertreatment such as fixation, and good drying behavior.

To ensure particularly good fastness properties such as, for example, rub fastness, wet rub fastness and washfastness of printed substrates, the prints can be fixed by so-called radiation curing. For this purpose, it is possible to use what are known as radiation-curable inks. For example, US Pat. No. 5,623,001 and EP 0 993 495. Radiation curable ink jet inks usually contain a material that can be cured by irradiation of actinic radiation. In addition, radiation-curable ink-jet inks may be accompanied by a photoinitiator.

The problem, however, is that in some cases the radiation curing is not uniform over the printed substrate. A very good curing is observed in some places, while other areas show poor curing, so-called "soft spots." Uneven curing will worsen the rubbing fastness in some places, and the feel of printed substrates will deteriorate We are therefore looking for inks for the ink-jet process, which can be cured particularly uniformly.

The object was to provide inks for the ink-jet process, which can be cured particularly well by the action of actinic radiation. A further object was to provide radiation-curable products which are particularly suitable for the production of inks for the ink-jet process. Another object was to provide processes for the production of inks for the ink-jet process. Finally, the object was to provide printed substrates and in particular printed textile substrates which have a particularly good feel and good fastness properties.

Accordingly, the above-defined use of water-soluble radiation-curable products (A) and the inks defined at the outset for the ink-jet process were found.

In the context of the present invention, the terms "inks for the ink-jet process" and "ink-jet inks" are used equivalently. The use according to the invention is based on such water-soluble radiation-curable products (A) which are obtainable

by mixing and optionally reacting at least one hyperbranched polyurethane (a) with at least one photoinitiator (b)

or by synthesizing at least one hyperbranched polyurethane (a) in the presence of at least one photoinitiator (b).

In the following, mixing and optionally reaction of at least one hyperbranched polyurethane (a) with at least one photoinitiator (b) is also referred to as route 1.

Synthesis of at least one hyperbranched polyurethane (a) in the presence of at least one photoinitiator (b) is also referred to below as path 2.

In the context of the present invention, hyperbranched polyurethanes (a) are understood to mean not only those polymers which are exclusively linked by urethane groups, but in a more general sense polymers which can be obtained by reacting di- or polyisocyanates with compounds which contain active hydrogen atoms. Polyurethanes for the purposes of the present invention can therefore contain, in addition to urethane groups, urea, allophanate, biuret, carbodiimide, amide, ester, ether, uretonimine, uretdione, isocyanurate or oxazolidine groups. An overview may be mentioned by way of example: Kunststoffhandbuch / Saechtling, 26th edition, Carl-Hanser-Verlag, Munich 1995, page 491 ff. In particular, polyurethanes in the context of the present invention contain urea groups.

Hyperbranched polyurethanes (a) are molecularly and structurally nonuniform. They differ by their molecular nonuniformity of dendrimers and are produced with considerably less effort.

Hyperbranched polyurethanes (a) is preferably adjusted from AB monomers _X forth, which are monomers, for example, have both isocyanate groups and groups which can react with isocyanate groups to form a linkage, and further, of course, a spacer, by the isocyanate groups and groups that can react with isocyanate groups to form a linkage. X is a natural number from 2 to 8. Preferably, x is 2 or 3. Either A is isocyanate groups and B is isocyanate-reactive groups or may be the reverse case.

Isocyanate-reactive groups are preferably OH, NH ₂ , NH, SH or COOH groups.

The synthesis of the hyperbranched polyurethanes (a) used for carrying out the present invention can be carried out, for example, as described below.

AB _X monomers can be prepared in a known manner by various techniques.

For example, AB _X monomers can be synthesized according to the method disclosed in WO 97/02304 using protective group techniques. By way of example, this technique is illustrated by the preparation of an AB ₂ monomer from 2,4-tolylene diisocyanate (TDI) and trimethylolpropane. First, one of the isocyanate groups of the TDI is capped in a known manner, for example by reaction with an oxime. The remaining free NCO group is reacted with trimethylolpropane, wherein one of the three OH groups reacts with the isocyanate group. After cleavage of the protecting group, an AB ₂ monomer having an isocyanate group and two OH groups is obtained.

Particularly advantageously, the AB _X monomers can be synthesized by the method disclosed by DE-A 199 04 444, in which no protective groups are required. In this method, di- or polyisocyanates are used and reacted with compounds having at least two groups capable of reacting with isocyanate groups. At least one of the reactants has groups with different reactivity than the other reactant. Preferably, both reactants have groups with reactivity differing from the other reactant. The reaction conditions are chosen so that only certain groups capable of reacting with one another can react with one another.

Preferred di- and / or polyisocyanates with NCO groups of different reactivities are, in particular, readily and cheaply available isocyanates, for example aromatic isocyanates, such as 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate (2,4 ^' -MDI), triisocyanatotoluene, or aliphatic isocyanates, such as isophorone diisocyanate (IPDI), 2-butyl-2-ethylpentamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 2,4,4- or 2,2,4-trimethylhexa methylene diisocyanate, 2,4'-methylenebis (cyclohexyl) diisocyanate and 4-methylcyclohexane-1,3-diisocyanate (H-TDI). Further examples of isocyanates having groups of different reactivity are 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl diisocyanate, tolidine diisocyanate and 2,6-toluene diisocyanate. In this case, the reactivity of the second NCO group is reduced by electronic effects by addition of an NCO-reactive group to one of the two initially identically reactive NCO groups.

Of course, one can use mixtures of the above isocyanates.

Preferred compounds having at least two groups capable of reacting with isocyanate are di-, tri- or tetra-functional compounds whose functional groups have a different reactivity to NCO groups. Preference is given to compounds having at least one primary and at least one secondary hydroxyl group, at least one hydroxyl group and at least one mercapto group, particularly preferably having at least one hydroxyl group and at least one amino group in the molecule, in particular amino alcohols, aminodiols and aminotrioles, since the reactivity of the amino group relative to the Hydroxyl group is significantly higher in the reaction with isocyanate.

Examples of compounds having at least two isocyanate-reactive groups of different reactivity are propylene glycol, glycerol, mercaptoethanol, ethanolamine, N-methylethanolamine, diethanolamine, ethanolpropanolamine, dipropanolamine, diisopropanolamine, 2-amino-1,3-propanediol, 2 Amino-2-methyl-1,3-propanediol or tris (hydroxymethyl) aminomethane. Furthermore, mixtures of the genann¬ th compounds can be used. Furthermore, compounds such as trimethylolpropane or trimethylolethane can be used. In this case, the reactivity of the second and in particular of the third group capable of reacting with isocyanate is reduced by steric and electronic effects by adding an NCO group to one of the OH groups which is initially capable of reacting with isocyanate.

The preparation of an AB ₂ monomer is exemplified in the case of a diisocyanate with an amino diol. Here, first one mole of a diisocyanate with one mole of an aminodiol, for example N, N-diethanolamine, at low temperatures Tempe¬, preferably to +30 ⁰ C, is reacted in the range between -10. In this temperature range, a virtually complete suppression of the urethane formation reaction takes place, and the NCO groups of the isocyanate react exclusively with the amino group of the aminodiol. The formed AB ₂ monomer has a free NCO group and two free OH groups and can be used for the synthesis of a hyperbranched polyurethane (a).

By heating or catalyst addition, this AB ₂ monomer can intermolecularly react to form a hyperbranched polyurethane. Examples of catalysts for the preparation of the hyperbranched polyurethanes are organic tin compounds. such as tin diacetate, tin dioctoate, dibutyltin dilaurate or strongly basic amines such as diazabicyclooctane, diazabicyclononane, diazabicycloundecane, triethylamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether or preferably triethylenediamine or bis (A /, Λ / -dimethylaminoethyl) ether or weakly basic amines such as imidazoles used. It is also possible to use mixed catalysts composed of at least one organic tin compound and at least one strongly basic amine. The catalysts are preferably used in an amount of from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, based on isocyanate. The synthesis of hyperbranched polyurethane (a) is advantageously carried out without previous isolation of the AB ₂ monomer in a further reaction step at elevated temperature, preferably in the range between 30 and 8O ⁰ C. When using the described AB ₂ monomer with two OH Groups and an NCO group results in a hyperbranched polymer which has a free NCO group per molecule and a number dependent on the degree of polymerization of OH groups. The reaction can be carried out to high conversions, resulting in very high molecular structures. It is preferably stopped by addition of suitable mono-functional compounds or by addition of one of the starting compounds for the production of the AB ₂ monomer upon reaching the desired molecular weight. Depending on the starting compound used for termination, either completely NCO-terminated or completely OH-terminated molecules are formed.

In another embodiment, for example, it is also possible to prepare an AB ₂ monomer from one mole of glycerol and 2 moles of TDI. At low temperature, preferably primary alcohol groups and the isocyanate group react in the 4-position, and an adduct is formed which has one OH group and two isocyanate groups and which, as described above, becomes a hyperbranched polyurethane at higher temperatures (a) can be implemented. The result is first a hyperbranched polyurethane (a), which has a free OH group and a degree of polymerization dependent on the average number of NCO groups.

The number of NCO groups per molecule is from 2 to 100, preferably from 3 to 20 and particularly preferably to 10.

The molecular weight M _{n of} the hyperbranched polyurethanes (a) to be used for the present invention may be, for example, 500 to at most 50,000 g / mol, preferably at most 15,000 g / mol and more preferably at most 10,000 g / mol and most preferably up to 5,000 g / mol.

The preparation of hyperbranched polyurethanes (a) can be carried out in principle without solvents, but preferably in solution. Suitable solvents in principle are all compounds which are liquid at the reaction temperature and inert to the monomers and polymers. Other examples of hyperbranched polyurethanes (a) are accessible by further Syntheseva¬ variants. By way of example, AB ₃ monomers may be mentioned at this point. AB ₃ monomers can be obtained, for example, by reacting diisocyanates with compounds having 4 groups which are capable of reacting with isocyanate. By way of example, the reaction of tolylene diisocyanate with tris (hydroxymethyl) aminomethane may be mentioned.

To terminate the preparation of hyperbranched polyurethanes (a) it is possible to use polyfunctional compounds which can react with the respective A groups. In this way, several small hyperbranched molecules can be linked to form a large hyperbranched molecule.

Hyperbranched polyurethanes (a) with chain-extended branches can be obtained beispiels- example, by addition to the polymerization reaction in addition to _X AB monomers in the molar ratio 1: 1, a diisocyanate and a compound containing two isocyanate with natgruppen-reactive groups which are used , These additional AA or BB compounds may also have further functional groups which may not be reactive to the A or B groups under the reaction conditions. In this way, further functionalities can be introduced into hyperbranched polyurethane (a).

Further synthesis variants for hyperbranched polyurethanes can be found in WO 02/36695, DE-A 100 13 187 and DE-A 100 30 869.

For the preparation of hyperbranched polyurethane (a) one or more catalysts can be used. Suitable catalysts are in principle all catalysts customarily used in polyurethane chemistry.

Catalysts customarily used in polyurethane chemistry are, for example, organic amines, in particular tertiary aliphatic, cycloaliphatic or aromatic amines, and Lewis-acidic organic metal compounds.

Examples of suitable Lewis acidic organic metal compounds are tin compounds, for example tin (II) salts of organic carboxylic acids, for example tin (II) acetate, tin (II) octoate, tin (II) ethyl hexoate and tin (II ) -Iaurate and the dialkyltin (IV) derivatives of organic carboxylic acids, eg dimethyltin diacetate, dibutyltin diacetate, dibutyltin dibutyrate, dibutyltin bis (2-ethylhexanoate), dibutyltin dilaurate, dibutyltin maleate, dioctyltin dilaurate and dioctyltin diacetate. Metal complexes such as acetylacetonates of iron, titanium, aluminum, zirconium, manganese, nickel and cobalt are also possible. Other metal catalysts are described by Blank et al. in Progress in Organic Coatings, 1999, 35, 19 et seq. Preferred Lewis-acidic organic metal compounds are dimethyltin diacetate, dibutyltin dibutyrate, dibutyltin bis (2-ethylhexanoate), dibutyltin dilaurate, diocytotin dilaurate, zirconium acetylacetonate and zirconium 2,2,6,6-tetramethyl-3, 5-heptanedionate.

Also bismuth and cobalt catalysts and cesium salts can be used as hydrophobic catalysts. Suitable cesium salts are those compounds in which the following anions are used: F ^" , Cl ^" , CIO ^" , CIO ₃ ^" , CIO ₄ ^" , Br, J-, JO ₃ -, CN-, OCN ^" , NO ₂ -, NO ₃ ^" , HCO ₃ ^" , CO ₃ ² -, S ^{2 "} , SH ^" , HSO ₃ ^" , SO ₃ ^2" , HSO ₄ -, SO ₄ ² -, S ₂ O ₂ ^{2 "} , p ₂ O ₄ ^{2 "} , S ₂ O ₅ ^2" , S ₂ O ₆ ^{2 "} , S ₂ O ₇ ^2" , S ₂ O ₈ ^{2 "} , H ₂ PO ₂ -, H ₂ PO ₄ -, HPO ₄ ^2" , PO ₄ ^{3 "} , P ₂ O ₇ ^4" , (OC _n H _{2n + 1} ) -, (C _n H _2n- !! O ₂ ) -, (C _n H _2n _ ₃ O ₂ ) - and (C _{n + 1} H _2n _ ₂ O ₄ ) ² -, where n stands for integers from 1 to 20.

Preference is given to cesium carboxylates in which the anion conforms to formulas (C _n H _2n _i0 ₂₎ -. (C _{n + 1} H _2n _ ₂ O ₄₎ and ^{2 ',} obeys n is 1 to 20 A particularly bevorzug¬ have te cesium salts as anions monocarboxylates of the general formula (C _n H _2n ^ O ₂ ) -, where n stands for integers from 1 to 20. In this case mention should be made in particular of formate, acetate, propionate, hexanoate and 2-ethylhexanoate.

Examples of customary organic amines are: triethylamine, 1,4-diazabicyclo [2,2,2] octane, tributylamine, dimethylbenzylamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N ', N'-tetramethylbutane-1,4-diamine, N, N, N', N'-tetramethylhexane-1,6-diamine, dimethylcyclohexylamine, dimethyldodecylamine, pentamethyldipropylenetriamine, pentamethyldiethylenetriamine, 3-methyl-6-dimethylamino 3-azapentol, dimethylaminopropylamine, 1,3-bisdimethylaminobutane, bis (2-dimethylaminoethyl) ether, N-ethylmorpholine, N-methylmorpholine, N-cyclohexylmorpholine, 2-dimethylaminoethoxyethanol, dimethylethanolamine, tetramethylhexamethylenediamine, dimethylamino-N-methylethanolamine , N-methylimidazole, N-formyl-N, N'-dimethylbutylenediamine, N-dimethylaminoethylmorpholine, 3,3'-bis-dimethylamino-di-n-propylamine and / or 2,2'-di-piparazinediisopropyl ether, dimethylpiparazine, Tris- (N, N-dimethylaminopropyl) -s-hexahydrotriazine, imidazoles such as 1,2-dimethylimidazole, 4-chloro-2,5-dimethyl-1- (N-methylaminoethyl) imi dazole, 2-aminopropyl-4,5-dimethoxy-1-methylimidazole, 1-aminopropyl-2,4,5-tributylimidazole, 1-aminoethyl-4-hexylimidazole, 1-aminobutyl-2,5-dimethylimidazole, 1 - (3 -Aminopropyl) -2-ethyl-4-methylimidazole, 1- (3-aminopropyl) imidazole and / or 1- (3-aminopropyl) -2-methylimidazole.

Preferred organic amines are trialkylamines having, independently of one another, two C ₁ - to C ₄ -alkyl radicals and one alkyl or cycloalkyl radical having 4 to 20 carbon atoms, for example dimethyl-C ₄ -C ₁₅ -alkylamine, such as dimethyldodecylamine or dimethyl-C ₃ - C 6 -cycloalkylamine , Also preferred organic amines are bicyclic amines, which may optionally contain a further heteroatom such as oxygen or nitrogen nen, such as 1, 4-diazabicyclo [2,2,2] octane. Of course, mixtures of two or more of the abovementioned compounds can also be used as catalysts.

Particular preference is given to using hydrophobic catalysts selected from the compounds mentioned above.

Catalyst is preferably used in an amount of 0.0001 to 10 wt .-%, particularly preferably in an amount of 0.001 to 5 wt .-%, based on the total amount of isocyanate and compound having isocyanate-reactive groups ,

Depending on the nature of the catalyst or of the catalysts, it is possible to add the catalyst (s) in solid or liquid form or dissolved. Suitable solvents are water-immiscible solvents such as aromatic or aliphatic hydrocarbons such as toluene, ethyl acetate, hexane and cyclohexane and carboxylic acid esters such as ethyl acetate. It is preferable to add the catalyst (s) in solid or liquid form.

Hyperbranched polyurethanes (a) for the purposes of the present invention advantageously have on average per molecule at least one group which is ionizable in aqueous solution, or they are characterized by the incorporation of nonionic hydrophilic end groups or molecular building blocks. Examples of ionizable groups which may be mentioned are COOH groups and SO ₃ H groups and their alkali metal and ammonium salts, and also quaternized amino groups. Examples of nonionic hydrophilic end groups or molecular building blocks are:

- (OCH ₂ CH ₂ ) _Z OR ⁶ , where z is an integer in the range from 2 to 100, preferably 5 to 50,

R ⁶ is C 1 -C ₄ -alkyl, for example tert-butyl, sec-butyl, isobutyl, n-butyl, isopropyl, n-propyl, ethyl and especially methyl; oligomeric and polymeric ethylene glycol of the formula HO- (CH ₂ CH ₂ O) _Z H, where z is as defined above.

Particularly advantageous is the use of such hyperbranched polyurethanes (a) whose functional groups have been hydrophilized or repunctionalized. In this way, the application according to the invention of the hyperbranched polyurethanes (a) for the preparation of water-soluble radiation-curable products (A) is made particularly well-suited for hyperbranched polyurethanes (a) by introducing pigment-affine groups. Due to their reactivity, the hyperfunctional polyurethanes (a) which have terminal NCO groups are particularly suitable for re-functionalization. Of course, OH- or NH ₂ -terminated polyurethanes can also be functionalized by means of suitable reaction partners. Examples of pigment affine groups which are introduced by means of suitable reactants are -COOH, -COOR ⁴ , -CONHR ⁴ , -CONH ₂ , -OH ₁ -SH, -NH ₂ , -NHR ⁴ , -N (R ⁴ ) ₂ , -SO ₃ H, -SO ₃ R ⁴ , - / V (phthalimide), -NHCOOR ⁴ , -NHCONH ₂ , -NHCONHR ⁴ or -CN. The radicals R ^{4 of} the abovementioned groups are unbranched or branched alkyl radicals, aralkyl radicals or aryl radicals which may be further substituted, for example C ₁ -C ₄₀ -alkyl radicals or C ₆ -C ₁₄ -aryl radicals , The following radicals may be mentioned by way of example:

C ₁ -C ₄₀ -Alkyl, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, seα-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl , neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, n- Dodecyl, n-hexadecyl or n-eicosyl, particularly preferred is methyl; C ₆ -C ₁₄ -aryl, for example phenyl, α-naphthyl, β-naphthyl, 1-anthracenyl, 2-anthracenyl or 9-anthracenyl, C ₇ -C ₁₃ -aralkyl, preferably C ₇ - to C ₁₂ -phenylalkyl, such as benzyl , 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1-methyl-1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl.

Groups which have sufficiently acidic H atoms can be converted into the corresponding salts by treatment with bases. Suitable bases are, for example, hydroxides and bicarbonates of alkali metals or alkaline earth metals or the carbonates of alkali metals. Further suitable bases are volatile amines, ie amines having a boiling point at atmospheric pressure of up to 180 ^° C., for example ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine or N-methyldiethanolamine. Analogously, basic groups with acids such as, for example, α-hydroxycarboxylic acids or α-amino acids or else α-hydroxysulfonic acids can be converted into the corresponding salts. This makes it possible to obtain particularly suitable hyperbranched polyurethanes (a).

Acid groups can be introduced, for example, by reaction with hydroxycarboxylic acids, mercaptocarboxylic acids, hydroxysulfonic acids or amino acids into hyperbranched polyurethanes (a). Examples of suitable reactants are hydroxyacetic acid, hydroxypivalic acid, 4-hydroxybenzoic acid, 12-

Hydroxydodecanoic acid, 2-hydroxyethanesulfonic acid, mercaptoacetic acid, dimethylolpropionic acid, dimethylolbutyric acid, glycine, β-alanine or taurine.

In one embodiment of the present invention, in the preparation of hyperbranched polyurethane (a), up to 10 mol%, based on (a), can be added to compounds which have only one isocyanate-reactive group, for example monoalcohols, primary or secondary monoamines or mercaptans. In a preferred embodiment of the present invention, at least one hyperbranched polyurethane (a) is one having at least one NCO group per molecule (number average), preferably at least 2 NCO groups per molecule (number average).

In a preferred embodiment of the present invention, water-soluble radiation-curable products (A) are water-soluble radiation-curable products (A) having at least one COOH group per molecule (number average). At least water-soluble radiation-curable products (A) are preferably those in which the COOH group is introduced by adding (a) hydroxyacetic acid and particularly preferably β-alanine toward the end or after the synthesis of hyperbranched polyurethane, and although especially after a certain time has elapsed. By reacting the hydroxyl group of the hydroxyacetic acid or, in particular, the amino group of the β-alanine with an NCO group, COOH groups can be introduced into particularly suitable water-soluble radiation-curable products (A).

Preference is given to those water-soluble radiation-curable products (A) having COOH groups which are located at the end of a branch of the hyperbranched polyurethanes (a) in question.

In the context of the present invention, "per molecule" means in the case of only incompletely or not at all proceeding reaction of (a) with (b): hyperbranched polyurethane (a) used per molecule.

For the use according to the invention, according to route 1, at least one hyperbranched polyurethane (a) can be mixed with at least one photoinitiator (b) and, if appropriate, effect its conversion.

It may be used for the reaction and thus conversion of hyperbranched polyurethane

(A) come with photoinitiator (b), which can proceed quantitatively (based on photoinitiator) or incomplete.

The mixing of (a) and (b) can be carried out in any vessel. One or more organic solvents and / or water may be added for the purpose of mixing. Suitable methods are stirring, shaking, but also dispersing in dispersing apparatus such as, for example, ball mills and in particular stirred ball mills or shaking apparatuses, for example Skandex. In one embodiment of the present invention, (a) and (b) are mixed in a weight ratio of from 3: 1 to 10,000: 1, preferably from 5: 1 to 5,000: 1, very particularly preferably in a weight ratio of from 10: 1 to 1,000: 1.

In radiation-curable product (A) according to the invention, photoinitiator (b) may be mixed in with hyperbranched polyurethane (a). Photoinitiator (b) may also be a photoinitiator covalently bound to hyperbranched polyurethane (a). If one wishes to covalently link photoinitiator to hyperbranched polyurethane (a), the proportions of hyperbranched polyurethane (a) and of photoinitiator (b) are in each case based on starting material, ie. hyperbranched polyurethane (a) and photoinitiator (b) prior to covalent linking.

In a preferred embodiment of the present invention, Photoini¬ tiator (b) at the beginning or during the synthesis of hyperbranched polyurethane (a) to (route 2) and thus synthesized hyperbranched polyurethane (a) in the presence of at least one photoinitiator (b).

For this purpose, at least one photoinitiator (b) can be added at the beginning or during the synthesis of hyperbranched polyurethane (a) described above.

This can lead to a reaction and thus conversion of forming hyperver¬ branched polyurethane (a) with photoinitiator (b), which can proceed quantitatively (based on photoinitiator) or incomplete.

In one embodiment of the present invention, during the synthesis of (a), so much (b) is added that the weight ratio of (a) to (b) behaves as 3: 1 to 10,000: 1, preferably 5: 1 to 5,000: 1, very particularly preferably from 10: 1 to 1,000: 1, it being assumed that the formation of hyperbranched polyurethane (a) proceeds quantitatively.

You can add (b) in one or more portions.

In one embodiment of the present invention, path 1 and path 2 may be combined, i. For example, first hyperbranched polyurethane (a) in the presence of a photoinitiator (b) synthesize and then with a further photoinitiator (b), which is identical or different from the in the synthesis of (a) send anwe¬ send photoinitiator, mix.

Suitable photoinitiators (b) may be, for example, photoinitiators known to the person skilled in the art, for example those in "Advances in Polymer Science", Volume 14, Springer Berlin 1974 or in KK Dietliker, Chemistry and Technology of UV and EB- Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Radical and Cationic Polymerization, PKT Oldring (Eds), SITA Technology Ltd, London.

Consider, for example, Mono or bisacyl phosphine oxides, as described e.g. EP-A 0 007 508, EP-A 0 057 474, DE-A 196 18 720, EP-A 0 495 751 and EP-A 0 615 980, for example 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphinate, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, benzophenone, hydroxyacetophenone, phenylglyoxylic acid and its derivatives or mixtures of the above-mentioned photoinitiators. Examples which may be mentioned are benzophenone, acetophenone, acetonaphthoquinone, methyl ethyl ketone, vaIerophenone, hexanophenone, α-phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone, 4-morpholinodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4 ' -Methoxyacetophenone, β-methylanthraquinone, tert-butylanthraquinone, anthraquinone-carboxylic acid ester, benzaldehyde, α-tetralone, 9-

Acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1 -andanone, 1, 3,4-triacetylbenzene, thioxanthen-9-one, xanthen-9-one, 2,4- Dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-di- / propylthioxanthone, 2,4-dichlorothioxanthone, benzoin, benzoin / so-butyl ether, chloroxanthenone, benzoin tetrahydropyranyl ether, benzoin methyl ether, benzoin ethyl ether, Benzoin butyl ether, benzoin / so-propyl ether, 7-H-benzoin methyl ether, benz [de] anthracen-7-one, 1-naphthaldehyde, 4,4'-bis (dimethylamino) benzophenone, 4-phenylbenzophenone, 4- Chlorobenzophenone, Michler's ketone, 1-acetonaphthone, 2-acetonaphthone, 1-benzoylcyclohexan-1-ol, 2-hydroxy-2,2-dimethylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone , 1,1-dichloroacetophenone, 1-hydroxyacetophenone, acetophenone dimethyl ketal, o-methoxybenzophenone, triphenylphosphine, tri-o-tolylphosphine, benz [a] anthracene-7,12-dione, 2,2-diethoxyacetophenone, benzil ketals, as described in US Pat Benzildimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2 -Amyl-anthraquinone and 2,3-butanedione.

Also suitable are non-yellowing or slightly yellowing photoinitiators of the phenylglyoxalic acid ester type, as described in DE-A 198 26 712, DE-A 199 13 353 or WO 98/33761.

Examples of preferred photoinitiators (b) are those photoinitiators which decompose upon activation, so-called α-decayers, such as, for example, benzildialkylketal-type photoinitiators, such as, for example, benzil dimethyl ketal. Further examples of suitable α-disintegrators are derivatives of benzoin, isobutylbenzoin ethers, phosphine oxides, in particular mono- and bisacylphosphine oxides, for example benzoyldiphenylphosphine oxide, 2,4,6- Trimethylbenzoyldiphenylphosphine oxide, α-hydroxyalkylacetophenones such as, for example, 2-hydroxy-2-methylphenylpropanone (b.1),

2-Hydroxy-1 - [- 4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propanone (b.2)

Phosphine sulfides and ethyl 4-dimethylaminobenzoate and

Further examples of preferred photoinitiators (b) are hydrogen-abstracting photoinitiators, for example of the type of the optionally substituted acetophenones, anthraquinones, thioxanthones, benzoic esters or the optionally substituted benzophenones. Particularly preferred examples are isopropylthioxanthone, benzophenone, phenylbenzyl ketone, 4-methylbenzophenone, halogenated benzophenones, anthrone, Michler's ketone (4,4'-bis-N, N-dimethylaminobenzophenone), 4-chlorobenzophenone, 4,4'-dichlorobenzophenone, anthraquinone ,

If photoinitiator (b) and hyperbranched polyurethane (a) are desired to be covalently linked to one another, then those photoinitiators which have at least one group with acidic H atom, for example compounds which contain at least one free OH group, are preferably selected or at least one free NH ₂ group. For example, 2-hydroxy-2-methylphenylpropanone (b.1) and 2-hydroxy-1 - [- 4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propanone (b.2) are particularly suitable. The effectiveness of photoinitiators (b) in radiation-curable products (A) according to the invention or inks for the ink-jet process according to the invention can be, if desired, by the addition of at least one synergist, for example at least one amine, in particular of at least one tertiary amine. Suitable amines are, for example, triethylamine, N, N-dimethylethanolamine, N-methylethanolamine, triethanolamine, amino acrylates such as, for example, amine-modified polyether acrylates. If one has used amines such as tertiary amines as a catalyst in the synthesis of hyperbranched polyurethane (a) and not separated after the synthesis, as a catalyst used tertiary amine can act as a synergist. Furthermore, for the neutralization of acidic groups such as COOH groups or SO ₃ H groups used tertiary amine act as a synergist. It is possible to add up to twice the molar amount of synergist, based on the photoinitiator (b) used.

Water-soluble radiation-curable products (A) according to the invention can be added to at least one radical scavenger, for example sterically hindered amines, for example so-called HALS or stabilized nitroxyl radicals such as 4-hydroxy-TEMPO (formula III)

Preferably, up to 1% by weight, based on (a), of radical scavenger can be added, more preferably up to 0.5% by weight.

Water-soluble radiation-curable products (A) according to the invention can be hardened by actinic radiation, for example actinic radiation having a wavelength range from 200 nm to 450 nm is suitable. For example, actinic radiation having an energy in the range from 70 mJ / cm ² to 2000 mJ / cm ² is suitable. Actinic radiation can expediently be introduced, for example, continuously or in the form of blots.

Radiation-curable products (A) according to the invention are particularly suitable for the production of inks for the ink-jet process, in particular of aqueous inks for the ink-jet process. Radiation-curable products (A) according to the invention can be used particularly well for the preparation of pigment-containing aqueous inks for the ink-jet process. In the context of the present invention, inks for the ink-jet process are also referred to as ink-jet inks or in short as inks.

Another object of the present invention are inks for the ink-jet process, in particular aqueous inks for the ink-jet process, containing

(A) at least one water-soluble radiation-curable product obtainable by mixing and if appropriate reacting at least one hyperbranched polyurethane (a) with at least one photoinitiator (b)

or by synthesis of at least one hyperbranched polyurethane (a) in the presence of at least one photoinitiator (b),

(B) at least one pigment.

Hyperbranched polyurethanes (a) and photoinitiators (b) are described above.

Inventive aqueous inks for the ink-jet process further contain at least one pigment (B). For the purposes of the present invention, pigments (B) are to be understood as meaning virtually insoluble, dispersed finely divided, organic or inorganic colorants as defined in DIN 55944. The process according to the invention preferably starts from organic pigments, with carbon black being included. The following are examples of particularly suitable pigments.

Organic pigments:

- monoazo pigments: Cl. Pigment Brown 25; Cl. Pigment Orange 5, 13, 36 and 67; Cl. Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 52: 1, 52: 2, 53, 53: 1, 53: 3, 57: 1, 63, 112, 146, 170, 184, 210, 245 and 251; Cl. Pigment Yellow 1, 3, 73, 74, 65, 97, 151 and 183;

- Disazo pigments: Cl. Pigment Orange 16, 34 and 44; Cl. Pigment Red

144, 166, 214 and 242; Cl. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188; - Anthanthrone pigments: Cl. Pigment Red 168 (Cl. Vat Orange 3);

Anthraquinone pigments: Cl. Pigment Yellow 147 and 177; Cl. Pigment Violet 31; Anthraquinone pigments: Cl. Pigment Yellow 147 and 177; Cl. Pigment Violet 31;

Anthrapyrimidine pigments: Cl. Pigment Yellow 108 (CI Vat Yellow 20);

- Quinacridone pigments: Cl. Pigment Red 122, 202 and 206; Cl. Pigment Violet 19; - Quinophthalone pigments: Cl. Pigment Yellow 138;

Dioxazine pigments: Cl. Pigment Violet 23 and 37;

Flavanthrone pigments: Cl. Pigment Yellow 24 (CI Vat Yellow 1);

- Indanthrone pigments: Cl. Pigment Blue 60 (Clat Vat Blue 4) and 64 (Clat Vat Blue 6); Isoindoline pigments: Cl. Pigment Orange 69; Cl. Pigment Red 260; Cl. Pigments Yellow 139 and 185;

- isoindolinone pigments: Cl. Pigment Orange 61; Cl. Pigment Red 257 and 260; Cl. Pigment Yellow 109, 110, 173 and 185;

Isoviolanthrone pigments: Cl. Pigment Violet 31 (Cl. Vat Violet 1); - metal complex pigments: Cl. Pigment Yellow 117, 150 and 153; Cl. Pigment Green 8;

- Perinone pigments: Cl. Pigment Orange 43 (Cl. Vat Orange 7); Cl. Pigment Red 194 (Cl. Vat Red 15);

- Perylene pigments: Cl. Pigment Black 31 and 32; Cl. Pigment Red 123, 149, 178, 179 (Cl.Vat Red 23), 190 (Cl. Vat Red 29) and 224; Cl. Pigment Violet 29;

Phthalocyanine pigments: Cl. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and 16; Cl. Pigment Green 7 and 36;

- Pyranthrone pigments: Cl. Pigment Orange 51; Cl. Pigment Red 216 (CI Vat Orange 4);

- thioindigo pigments: Cl. Pigment Red 88 and 181 (CI Vat Red 1); Cl. Pigment Violet 38 (Cl. Vat Violet 3);

Triaryl carbonium pigments Cl. Pigment Blue 1, 61 and 62; Cl. Pigment Green 1; Cl. Pigment Red 81, 81: 1 and 169; Cl. Pigment Violet 1, 2, 3 and 27; Cl. Pigment Black 1 (aniline black); Cl. Pigment Yellow 101 (Aldazingelb); Cl. Pigment Brown 22.

Inorganic pigments:

- white pigments: titanium dioxide (CI Pigment White 6), zinc white, colored zinc oxide; Zinc sulfide, lithopone; White lead;

Black pigments: iron oxide black (CI Pigment Black 11), iron manganese black, spinel black (CI Pigment Black 27); Carbon black (CI Pigment Black 7); - colored pigments: chromium oxide, chromium oxide hydrate green; Chrome green (Cl. Pigment

Green 48); Cobalt green (CI Pigment Green 50); Ultramarine green; Cobalt blue (CI Pigment Blue 28 and 36); Ultramarine blue; Iron blue (CI Pigment Blue 27); Manganese blue; Ultramarine violet; Cobalt and manganese violet; Iron oxide red (CI Pigment Red 101); Cadmium sulphoselenide (CI Pigment Red 108); Molybdate red (CI Pigment Red 104); ultramarine;

Iron oxide brown, mixed brown, spinel and corundum phases (CI Pigment Brown 24, 29 and 31), chrome orange;

Iron oxide yellow (CI Pigment Yellow 42); Nickel titanium yellow (CI Pigment Yellow 53, CI Pigment Yellow 157 and 164); Chromium titanium yellow; Cadmium sulfide and cadmium zinc sulfide (CI Pigment Yellow 37 and 35); Chrome yellow (CI Pigment Yellow 34), zinc yellow, alkaline earth dichromates; Naples yellow; Bismuth vanadate (CI Pigment Yellow 184);

Interference pigments: metallic effect pigments based on coated metal flakes; Pearlescent pigments based on metal oxide-coated mica platelets; Liquid crystal pigments.

Preferred pigments (B) are monoazo pigments (in particular laked BONS pigments, naphthol AS pigments), disazo pigments (in particular diaryl yellow pigments, bisacetacetic acid acetanilide pigments, disazopyrazolone pigments), quinacridone pigments, quinophthalone pigments, perinone pigments, phthalocyanine pigments, triarylcarbonium pigments (alkali lake pigments, laked rhodamines, dye salts with complex anions), isoindoline pigments and carbon blacks.

Specific examples of particularly preferred pigments (B) are: carbon black, Cl. Pigment Yellow 138, Cl. Pigment Red 122 and 146, Cl. Pigment Violet 19, Cl. Pigment Blue 15: 3 and 15: 4, Cl. Pigment Black 7, Cl. Pigment Orange 5, 38 and 43 and Cl. Pigment Green 7.

For the preparation of inks according to the invention for the ink-jet process, pigment (B) is mixed to form a radiation-curable product according to the invention.

Preferably, radiation-curable product (A) according to the invention has less than 0.1% by weight of terminal NCO groups at the time at which pigment (B) is added, more preferably no NCO groups which are blocked by, for example, se titration are detectable. In a preferred embodiment of the present invention, inks according to the invention contain for the ink-jet process

(C) at least one photopolymerizable compound selected from compounds having at least two preferably terminal ethylenic double bonds per molecule and compounds of general formula I.

in which the variables are defined as follows: R ¹ , R ^{2 are the} same or different and are selected independently of one another

Hydrogen and

C ₁ -C ₁₀ -alkyl, branched or unbranched, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isobutyl, Pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C 1 -C ₄ -alkyl, such as

Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl and very particularly preferably methyl,

X ¹ selected from NR ³ and preferably oxygen,

A ¹ selected from C _r C ₂ o-alkylene, unsubstituted or mono- or polysubstituted with C ₁ -C ₄ -Alk ^, phenyl or OC _r C ₄ alkyl, wherein in C _r C ₂ o-alkylene one or more non-adjacent CH ₂ groups may be replaced by oxygen;

For example, A ¹ can stand for the following groups:

-CH ₂ -, -CH ₂ -CH ₂ -, - (CHz) ₃ -. - (CHa) ₄ -. - (CH ₂ ) ₅ -, - (CH ₂ ) _β -, - (CH ₂ ) ₇ -, - (CH ₂ ) _β -, - (CH ₂ ) ₉ -, - (CH ₂ ) _IO -. - (CH ₂ ) I ₂ -, - (CH ₂ ) ₁₄ -, - (CH ₂ ) W, - (CH ₂ ) _1β -, - (CH ₂ J ₂₀ -, preferably - (CH ₂ ) _a -; - CH ₂ -CH (CH ₃ ) -, -CH ₂ -CH (C ₂ H ₅ ) -, -CH ₂ -CH (CH [CH ₃ ] ₂ ) -, -CH ₂ -CH (nC ₃ H ₇ ) - , - [CH (CH ₃ ) Jr. -CH (CHa) -CH ₂ -CH ₂ -CH (CH ₃ ) -, -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -, -CH ₂ - C (CHa) ₂ -CH ₂ -, -CH ₂ -CH (nC ₄ H ₉ ) -, -CH ₂ -CH (tC ₄ H ₉ ) -,

-CH ₂ -O-, -CH ₂ -O-CH ₂ -, - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -, - [(CH ₂ ) ₂ -O] ₂ - (CH ₂ ) ₂ -, - [(CH ₂ ) ₂ -O] ₃ - (CH ₂ ) ₂ -,

-COO-, -O-CO-, -CH ₂ -COO-, -CH ₂ -O-CO-, - (CH ₂ ) _a -COO-, - (CH ₂ ) _B -O-CO-, -COO (CH ₂ ) _a -, -O-CO (CH ₂ ) _y -,

- (CH ₂ ) _y -COO- (CH ₂ ) _y -, -CH ₂ -O-CO-CH ₂ -, -CH (CH ₃ ) -COO-CH ₂ -, - (CH ₂ ) _a -O- CO-CH ₂ -, -CH ₂ -O-CO- (CH ₂ ) _a -, -CH ₂ -COO- (CH ₂ ) _a -, -COO-CH ₂ -COO-, -CH ₂ -COO-CH ₂ -COO-, -COO- (CH ₂ ) _a -O-CO-, O-CO- (CH ₂ ) _a -COO-, -COO-CH (CH ₃ ) -, -O-C (O) -O-, -CH ₂ -OC (O) -O-, - (CHa) ₈ -OC (O) -O-, -OC (O) -O- (CH ₂ ) _a -, - CH ₂ -OC (O) -O-CH ₂ -, - (CH ₂ J _a -OC (O) -O-CH ₂ -, -CH ₂ -OC (O) -O- (CH ₂ ) _a ,

-CO-, -CH ₂ -CO-, -CO-CH ₂ -, -CH ₂ -CO-CH ₂ -, -CH (CH ₃ ) -CO-CH ₂ -,

-CO-N (R ³ ) -, -N (R ³ ) -CO-, - (CH ₂ ) _y -CO-N (R ³ ) -, - (CH ₂ ) _y -N (R ³ ) -CO -, - (CH ₂ ) _y -N (R ³ ) -CO- (CH ₂ V,

-N (R ³ ) -CO-N (R ³ ) -, - (CH ₂ ) _y -N (R ³ ) -CO-N (R ³ ) -, - (CH ₂ ) _y -N (R ³ ) -CO-N (R ³ HCH ₂ ) _y -, - (CH ₂ ) _y -N (R ³ ) -CO-N (R ³ ) - (CH ₂ ) _y -N (R ³ ) -CO-N ( R ³ ) -,

y is the same or different and is in each case an integer in the range from 1 to 10, preferably from 2 to 8 and particularly preferably up to 6; a is an integer in the range from 2 to 10, preferably 2 to 6 and particularly preferably up to 4.

If a group A ¹ carries a plurality of radicals R ³ , then the radicals R ³ may be the same or different.

Particularly preferred groups A ¹ are

-CH ₂ -CH ₂ -O-, - (CH ₂ VO-CO-O-, - (CH ₂ ) ₃ -O-CO-O-, - (CH ₂ ) ₄ -O-CO-O-, - (CH ₂ ) ₆ -O-CO-O-, -NH-CH ₂ -NH-CO-, -NH-CH ₂ -NH-CO- (CH ₂ V, -NH-CH ₂ -NH-CO- ( CH ₂ V, -NH-CH ₂ -NH-CO- (CH ₂ VO-, -NH-CH ₂ -NH-CO- (CH ₂ VO-, -NH-CH ₂ -NH-CO- (CH ₂ VO -.

and

-CH ₂ -CH ₂ -, - (CH ₂ V, - (CH ₂ V, - (CH ₂ V, - (CHz) ₆ -.

X ² selected from hydroxyl and NH-R ³ ,

R ^{3 is} identical or different and selected from hydrogen, phenyl and C 1 -C 10 -alkyl, branched or unbranched, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert Butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl , n-nonyl, n-decyl; particularly preferably C ₁ -C ₄ -AIRyI as

Methyl, ethyl, n -propyl, iso -propyl, n -butyl, iso -butyl, sec -butyl and tert -butyl

and most preferably methyl.

Very particularly preferred compounds of the general formula I are 2-hydroxyethyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate. Particularly suitable compounds having at least two terminal ethylenic double bonds per molecule are compounds of the general formula II

where the variables are defined as follows:

R, R are different or preferably the same and as defined above

m is an integer from 0 to 2, preferably 1; A ² CH ₂ or -CH ₂ -CH ₂ - or R ⁵ -CH or para-C ₆ H ₄ for the case that m = 0,

CH, C-OH, COC (O) -CH = CH ₂ , CO-CO-C (CH ₃ ) = CH ₂ , R ⁵ -C or 1, 3,5-

C ₆ H ₃ for the case that m = 1, and carbon for the case that m = 2; R ^{5 is} selected from C ₁ -C ₄ alkyl, for example nC ₄ H ₉ , nC ₃ H ₇ , isoC ₃ H ₇ and preferably C ₂ H ₅ and CH ₃ , or phenyl,

A ³ , A ⁴ , A ^{5 are the} same or different and selected from

C _r C ₂ o-alkylene, such as -CH ₂ -, -CH (CH ₃₎ -, -CH (C ₂ H ₅₎ -, - CH (C ₆ H ₅₎ -,

- (CHa) ₂ -, - (CH ₂ J ₃ -, - (CHz) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) _β -, - (CHa) ₇ -, - (CH ₂ J ₈ -, - (CHa) ₉ -,

- (CH ₂ W ₁ -CH (CH ₃ MCHa) ₂ -CH (CH ₃₎ -; cis or frans-C ₄ -C ₀ cycloalkylene, such as c / s-1, 3-

Cyclopentylidene, frans 1, 3-cyclopentylidene c / s-1, 4-cyclohexylidene, trans-1, 4-cyclohexylidene;

Ci-C ₂₀ -alkylene, in which from one to seven are not adjacent

C atoms are replaced by oxygen, such as -CH ₂ -O-CH ₂ -,

- (CH ₂ ) ₂ -O-CH ₂ -, - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -. - [(CH ₂ ) ₂ -O] ₂ - (CH ₂ ) ₂ -,

- [(CH ₂ ) ₂ -O] ₃ - (CH ₂ ) ₂ -; -C ₂₀ alkylene, substituted with up to 4 hydroxyl groups, wherein in C ₁ -C ₂₀ -

Alkylene of one to seven each non-adjacent carbon atoms by Oxygen are replaced, such as -CH ₂ -O-CH ₂ -CH (OH) -CH ₂ -, -CH ₂ -O- [CH ₂ -CH (OH) -CH ₂ ] ₂ -, -CH ₂ -O- [CH ₂ -CH (OH) -CH ₂ I ₃ -;

C ₆ -C ₁₄ -arylene, such as para-C ₆ H ₄ .

Particularly preferred examples of compounds of general formula II are trimethylolpropane triacrylate, triacrylate of tri-ethoxylated trimethylolpropane, pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate.

Another very suitable representative for molecules having at least two terminal ethylenically unsaturated double bonds per molecule is ethylene glycol diacrylate.

Other very suitable representatives of molecules having at least two terminal ethylenically unsaturated double bonds per molecule are partially or exhaustively (meth) acrylated polyols such as partially or exhaustively (meth) acrylated dimeric trimethylolpropane, partially or exhaustively (meth) acrylated dimeric trimethylolethane , partially or exhaustively (meth) acrylated dimeric pentaerythritol.

Photopolymerizable compound (C) can be freely present in the ink of the invention for the ink-jet process and then acts as a reactive diluent. However, it is particularly preferred if photopolymerizable compound (C) is reacted completely or incompletely with hyperbranched polyurethane (a). The reaction can be accelerated, for example, by heating or adding at least one catalyst, the catalysts described being the catalysts described above which are known from polyurethane chemistry.

In one embodiment of the present invention, inks according to the invention contain

1 to 20 wt .-%, preferably 1, 5 to 15 wt .-% (A), 0.01 to 20 wt .-%, preferably 1 to 10 wt .-% (B) 0 to 10 wt .-% , preferably 0.01 to 9 wt .-% (C), wherein in wt .-% are in each case based on the total weight of the relevant ink according to the invention.

Inventive inks for the ink-jet process may further contain at least one additive (D).

As additive (D), inks according to the invention for the ink-jet process may contain one or more organic solvents. Low molecular weight polytetrahydrofuran (polyTHF) is a preferred additive (D), it can be used alone or preferably be used in admixture with one or more poorly water-soluble, water-soluble or water-miscible organic solvents.

Preferably used low molecular weight polytetrahydrofuran usually has an average molecular weight M _n of 150 to 500 g / mol, preferably from 200 to 300 g / mol and more preferably from about 250 g / mol (corresponding to a Molekulargewichts¬ distribution).

Polytetrahydrofuran can be prepared in a known manner via cationic polymerization of tetrahydrofuran. This produces linear polytetramethylene glycols.

If polytetrahydrofuran is used in admixture with other organic solvents as an additive (D) for this purpose are generally high boiling (ie, usually at normal pressure a boiling point of> 100 ⁰ C) and hence a water-retaining effect owning organic solvent used in water soluble or miscible with water.

Suitable solvents are polyhydric alcohols, preferably unbranched and branched polyhydric alcohols having 2 to 8, in particular 3 to 6, carbon atoms, such as ethylene glycol, 1, 2 and 1, 3-propylene glycol, glycerol, erythritol, pentaerythritol, pentitols such as arabitol , Adonite and xylitol and hexitols such as sorbitol, mannitol and dulcitol.

Further suitable solvents are polyethylene and polypropylene glycols, which are to be understood as including the lower polymers (di-, tri- and tetramers), and their mono- (especially C ₁ -C ₆ -, in particular C ₁ -C ₄ ) alkyl ethers ethylene and polypropylene glycols having average molecular weights of from 100 to 1500 g / mol, in particular from 200 to 800 g / mol, especially from 300 to 500 g / mol, as examples of which di-, tri- and tetraethylene glycol, diethylene glycol monomethyl, ethyl, propyl and butyl ethers, triethylene glycol monomethyl, ethyl, propyl and butyl ethers, di-, tri- and tetra-1, 2- and -1, 3-propylene glycol and di-, tri- and tetra-1,2-and -1, 3-propylene glycol monomethyl, ethyl, propyl and butyl ether.

Also suitable as solvents are pyrrolidone and N-alkylpyrrolidones whose alkyl chain preferably contains 1 to 4, especially 1 to 2, carbon atoms. Examples of suitable alkylpyrrolidones are N-methylpyrrolidone, N-ethylpyrrolidone and N- (2-hydroxyethyl) pyrrolidone.

Examples of particularly preferred solvents are 1, 2 and 1, 3-propylene glycol, glycerol, sorbitol, diethylene glycol, polyethylene glycol (M _n 300 to 500 g / mol), diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, pyrrolidone, N-methylpyrrolidone and N- ( 2-hydroxyethyl) pyrrolidone. Polytetrahydrofuran can also be mixed with one or more (eg two, three or four) of the solvents listed above.

In one embodiment of the present invention, inks according to the invention for the ink-jet process may contain from 0.1 to 80% by weight, preferably from 5 to 60% by weight, more preferably from 10 to 50% by weight, and most preferably 10 to 30 wt .-%, non-aqueous solvent.

Non-aqueous solvents as adjuvants (D), in particular also the abovementioned particularly preferred solvent combinations, can advantageously be supplemented by urea (as a rule from 0.5 to 3% by weight, based on the weight of the colorant preparation), which enhances the water-retaining action of the solvent mixture.

Inventive inks for the ink-jet process may contain further additives (D), as are customary in particular for aqueous ink-jet inks and in the printing and coating industry. Mention may be made, for example, of preservatives such as, for example, 1,2-benzisothiazolin-3-one (commercially available as Proxel brands from Avecia Lim.) And its alkali metal salts, glutaric dialdehyde and / or tetramethylolacetylenediurea, Protectole®, antioxidants, degashers / defoamers such as For example, acetylenediols and ethoxylated acetylenediols, which usually contain 20 to 40 moles of ethylene oxide per mole of acetylenediol and at the same time can also have a dispersing effect, means for regulating the viscosity, leveling agents, wetting agents (for example wetting surfactants based on ethoxylated or wetting surfactants) propoxylated fatty or oxo alcohols, propylene oxide / ethylene oxide block copolymers, ethoxylates of oleic acid or alkylphenols, alkylphenol ether sulfates, alkylpolyglycosides, alkylphosphonates, alkylphenyl phosphonates, alkyl phosphates, alkylphenyl phosphates or preferably polyether siloxane copolymers, especially alkoxylated 2- (3-hydroxypropyl) heptam meth yltrisiloxanes, which generally have a block of 7 to 20, preferably 7 to 12, ethylene oxide units and a block of 2 to 20, preferably 2 to 10 propylene oxide units and in amounts of 0.05 to 1 wt .-% in the Farbmittelzube preparations may be included), anti-settling agents, gloss improvers, lubricants, Haft¬ improvers, skin preventatives, matting agents, emulsifiers, stabilizers, water repellents, light stabilizers, handle improvers, antistatic agents, bases such as triethanolamine or acids, especially carboxylic acids such as lactic acid or citric acid for regulation of the pH. If these agents are constituents of inks according to the invention for the ink-jet process, their total amount is generally 2% by weight, in particular 1% by weight, based on the weight of the colorant preparations according to the invention and in particular of the invention. Suitable inks for the ink-jet process. Further suitable additives (D) are optionally alkoxylated acetylenediols, for example of the general formula IV

where the variables are defined as follows:

AO represents identical or different alkylene oxide units, for example propylene oxide units, butylene oxide units and in particular ethylene oxide units,

R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are each the same or different and selected from

C ₁ -C ₁₀ -AlkVl, unbranched or branched, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl , seα-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl , especially preferred

C ₁ -C ₄ -A ^ yl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl; and hydrogen;

b is the same or different and selected from integers in the range of 0 to 50, preferably 0 or 1 to 30 and particularly preferably 3 to 20;

AO is defined as above.

In a preferred embodiment of the present invention R ⁹ or R ⁷ are methyl.

In a preferred embodiment of the present invention, R ⁹ and R ⁷ are methyl, and R ⁸ and R ¹⁰ are isobutyl.

Other preferred additives are optionally alkoxylated silicon compounds of the formula V

[(CH ₃ ) ₃ Si-O] ₂ -Si (CH ₃ ) -O (CH ₂ CH ₂ O) _b -HV

in which the variable b is as defined above. Inventive inks for the ink-jet process may furthermore comprise a further photoinitiator which is not equal to the photoinitiator (b) used in the preparation of radiation-curable product (A) according to the invention, but selected from the abovementioned photoinitiators becomes.

Inventive inks for the ink-jet process have a dynamic viscosity in the range from 2 to 80 mPa.s, preferably from 3 to 40 mPa.s, more preferably to 25 mPa.s, measured at 23 ° C. according to DIN 53018.

The surface tension of inks according to the invention for the ink-jet process is generally 24 to 70 mN / m, in particular 25 to 60 mN / m, measured at 25 ° C. according to DIN 53993.

The pH of inks according to the invention for the ink-jet process is generally from 5 to 10, preferably from 7 to 9.

Inks for the ink-jet process according to the invention exhibit overall advantageous application properties, above all good write-on behavior and good continuous writing behavior (kogation), and, in particular when using the particularly preferred solvent combination, good drying behavior, and result in high quality printed images, i. high brilliance and color depth and high friction, light, water and wet rub fastness. They are particularly suitable for printing on coated and uncoated paper and textile.

Another aspect of the present invention is a process for the preparation of inks for the ink-jet process according to the invention. The process according to the invention for the production of inks for the ink-jet process is characterized in that (A), (B), water and optionally (C) are mixed with one another, for example in one or more steps.

Mixturing and intensive shaking, for example, and dispersing, for example in ball mills or stirred ball mills, may be mentioned as suitable mixing techniques.

In one embodiment of the present invention one starts from one or more pigments (B) which are in particulate form, i. in the form of particles.

Preference is given to carrying out the present invention of predispersed pigment (B), that is to say dispersing one or more pigments in an apparatus with at least one additive before mixing with, inter alia, (A) and optionally (C), For example, at least one solvent, for example water, C ₁ -C ₄ -AlkBnOl, polyetherol, diethylene glycol, triethylene glycol, tetraethylene glycol, n- Butyl acetate before. Furthermore, it is possible to add dispersing additives during the dispersing or predispersing process. Examples of suitable dispersing additives are compounds which are described in greater detail below. Other suitable additives are biocides, for example 1, 2-benzisothiazolin-3-one ("BIT") (commercially available as Proxel® brands from Avecia Lim.) Or its alkali metal salts, other suitable biocides are 2-methyl-2H- isothiazol-3 ("MIT") and 5-chloro-2-methyl-2H-isothiazol-3-one ("CIT").

Suitable dispersing additives are, for example, sulfated and alkylated polyalkylene glycols. Other well-suited dispersing additives are naphthalenesulfonic acid

Formaldehyde condensation products which may be mixed with aliphatic long-chain carboxylic acids such as stearic acid or palmitic acid or their anhydrides. Particularly suitable are the dispersing additives disclosed in US Pat. No. 4,218,218 and in US Pat. No. 5,186,846.

Suitable dispersing additives are alcohols in particular continue to multiply alkoxylated Fettal¬, for example 3 to 50 times ethoxylated unbranched C ₁₀ -C ₂ o-alkanols.

Suitable apparatus for predispersing or dispersing are, for example, ball mills, stirred ball mills, ultrasound apparatuses, high-pressure homogenizers, ultra-Thurax and shaking apparatus, such as, for example, to name the company Skandex.

For example, ^Λ Λ hours to 48 hours have proven to be suitable for the predispersing or dispersing, although a longer period of time is also conceivable. Preference is given to a period of time for predispersing or dispersing from 1 to 24 hours.

Pressure and temperature conditions during predispersing are generally uncritical, for example, normal pressure has proven to be suitable. As temperatures, for example, temperatures in the range of 10 ⁰ C to 100 ⁰ C have proven to be suitable.

The order of addition in the mixing of (A), (B), optionally (C) and optionally (D) is not critical per se. Thus, in one variant of the present invention, it is possible first to synthesize a hyperbranched polyurethane (a) in the presence of photoinitiator (b) and thus to prepare (A), then pigment (B) with (A) and ( D) and then diluted with solvent such as water. In another variant of the present invention, (a) is synthesized in the presence of (b) and thus produces (A), (C) is added, then it is dispersed with (B), diluted with water and optionally mixed with further (b), (C) and (D).

The weight ratio of pigment (B) to water can be chosen within wide ranges and can be, for example, in the range of 1: 100 to 1: 2.

While the predispersion or dispersion is carried out, it is possible to add conventional grinding aids.

The average diameter of pigment (B) after predispersing is usually in the range from 20 nm to 1.5 μm, preferably in the range from 60 to 200 nm, particularly preferably in the range from 60 to 150 nm and referred to in the context with the present invention generally the volume average.

If it is desired to use carbon black as pigment (B) according to the invention, the particle diameter refers to the mean diameter of the primary particles.

A further aspect of the present invention is a process for printing flat or three-dimensional substrates by the ink-jet process using at least one ink according to the invention for the ink-jet process, hereinafter also referred to as printing process according to the invention. To carry out the printing process according to the invention, at least one ink-jet ink according to the invention is printed onto a substrate. In a preferred variant of the printing method according to the invention, at least one inkjet ink according to the invention is printed on a substrate and subsequently treated with actinic radiation.

In the ink-jet process, the usually aqueous inks are sprayed in small droplets directly onto the substrate. A distinction is made between a continuous process in which the ink is pressed uniformly through a nozzle and directed onto the substrate by an electric field, depending on the pattern to be printed, and an interrupted ink jet or "drop-on-demand". Method in which ink ejection occurs only where a colored dot is to be set. In the latter method, pressure is applied to the ink system either via a piezoelectric crystal or a heated cannula (bubble or thermo-jet method), thus ejecting an ink drop. Such procedures are in text. Chem. Color, Vol. 19 (8), pp. 23-29, 1987, and Vol. 21 (6) pp. 27-32, 1989.

Particularly suitable are the inks according to the invention for the bubble jet process and for the process by means of a piezoelectric crystal. Suitable substrate materials are:

cellulose-containing materials such as paper, cardboard, cardboard, wood and wood-based materials, which may also be painted or otherwise coated,

metallic materials such as films, sheets or workpieces made of aluminum, iron, copper, silver, gold, zinc or alloys of these metals, which may be painted or otherwise coated,

silicate materials such as glass, porcelain and ceramics that may be coated

polymeric materials of all types such as polystyrene, polyamides, polyesters, polyethylene, polypropylene, melamine resins, polyacrylates, polyacrylonitrile, polyurethanes, polycarbonates, polyvinyl chloride, polyvinyl alcohols, polyvinyl acetates, polyvinylpyrrolidones and corresponding copolymers and block copolymers, biodegradable polymers and natural polymers like gelatin,

Leather, both natural leather and synthetic leather, as smooth, nappa or suede leather,

Food and cosmetics,

and particularly

textile substrates such as fibers, yarns, threads, knits, woven fabrics, non-wovens and made-up articles of polyester, modified polyester, polyester blend fabrics, cellulosic materials such as cotton, cotton blended fabric, jute, flax, hemp and ramie, viscose, wool, silk, Polyamide, polyamide blend, polyacrylonitrile, triacetate, acetate, polycarbonate, polypropylene, polyvinyl chloride, polyester fibers and glass fiber fabrics.

As actinic radiation, electromagnetic radiation with a wavelength range of 200 nm to 450 nm is suitable. For example, actinic radiation with an energy in the range from 70 mJ / cm ² to 2000 mJ / cm ² is suitable. Actinic radiation can expediently be introduced, for example, continuously or in the form of flashes.

In one embodiment of the present invention, after printing and prior to treatment with actinic radiation, one may inter-dry, for example thermally or with IR radiation. Suitable are for example temperatures in Be¬ ranging from 30 to 120 ⁰ C for a period ranging from 1 minute to 24 hours, preferably up to 30 minutes, more preferably up to 5 minutes. For example, IR radiation in a wavelength range above 800 nm is suitable as IR radiation. Suitable devices for intermediate drying are, for example, drying ovens or vacuum drying ovens for intermediate thermal drying, furthermore IR lamps.

The heat developed by the action of actinic radiation can also act as a drying agent.

A further embodiment of the present invention are substrates, in particular textile substrates, which have been printed by one of the abovementioned printing methods according to the invention and are distinguished by particularly sharply printed images or drawings and by an excellent grip. In addition, printed substrates according to the invention have few "soft spots".

According to a further embodiment of the present invention, it is possible to combine at least two, preferably at least three, different inks according to the invention for the ink-jet process into sets, different inks according to the invention each containing different pigments each having a different color.

A further subject of the present invention are water-soluble radiation-curable products (A) obtainable by

Mixing and, where appropriate, implementation of

at least one hyperbranched polyurethane (a) having from 0.001 to 10% by weight of at least one photoinitiator (b),

or by synthesizing at least one hyperbranched polyurethane (a) in the presence of from 0.001 to 10% by weight, preferably from 0.01 to 5% by weight, of at least one photoinitiator (b).

In this case, details in% by weight are based on (a).

Hyperbranched polyurethane (a) and photoinitiators (b) are described above.

In a preferred embodiment of the present invention, at least one hyperbranched polyurethane (a) is a hyperbranched polymer. urethane (a) having at least one NCO group, preferably having at least two NCO groups per molecule (number average).

In another preferred embodiment of the present invention, water-soluble radiation-curable product (A) is a water-soluble radiation-curable product (A) having at least one COOH group per molecule (number average).

In one embodiment of the present invention, at least one photoinitiator is an α-decamer or a hydrogen-abstracting photoinitiator.

In one embodiment of the present invention, water-soluble radiation-curable products (A) comprise as further component (C) at least one photopolymerizable compound selected from compounds having at least two preferably terminal ethylenic double bonds per molecule and compounds of general formula I.

where the variables are defined as follows:

R ^1, R ^{2 are} identical or different and are independently selected from serstoff Was¬ and C ₁ -C _O -alkyl, X ¹ is selected from oxygen and NR ^3, A ¹ is selected from d ^ o-alkylene, unsubstituted or mono- or polysubstituted substi¬ tuiert with C ₁ -C ₄ -alkyl, phenyl or OC _r C, wherein -C ₂₀ alkylene one or more non-adjacent CH sets ₄ alkyl in C ₁ ₂ groups may be replaced by oxygen er¬;

X ² selected from hydroxyl and NH-R ³ , R ^{3 are} identical or different and selected from hydrogen, C ₁ -C ₁₀ alkyl and

Phenyl.

In one embodiment of the present invention, compounds having at least two preferably terminal ethylenic double bonds per molecule are selected from compounds of the general formula II

where the variables are defined as follows:

R ¹ , R ^{2 are} different or the same and independently selected from hydrogen and C 1 -C 10 -alkyl

m is an integer from 0 to 2,

A ² CH ₂ or -CH ₂ -CH ₂ - or R ⁵ -CH or para-C ₆ H ₄ for the case that m = 0,

CH, C-OH, COC (O) -CH = CH ₂ , CO-CO-C (CH ₃ ) = CH ₂ , R ⁵ -C or 1,3,5-

C ₆ H ₃ for the case that m = 1, and carbon for the case that m = 2; R ^{5 is} selected from C ₁ -C ₄ alkyl and phenyl,

A ³ , A ⁴ , A ^{5 are the} same or different and selected from

C ₁ -C ₂ o-alkylene, cis- or frans-C ₄ -C ₁₀ -cycloalkylene, C ₁ -C ₂₀ -alkylene in which NEN may be replaced by one to up to seven non-adjacent C atoms in each case by oxygen,

C _r C ₂₀ alkylene substituted with up to 4 hydroxyl groups, wherein in C ₁ -C ₂₀ - alkylene of one to seven non-adjacent C atoms may be replaced by oxygen, C ₆ -C ₁₄ arylene.

Radiation-curable products (A) according to the invention are particularly suitable for the production of inks for the ink-jet process.

The invention will be explained by working examples.

General preliminary remarks:

The NCO content was monitored in each case according to DIN 53185 by titration.

Β-Alanine solution AI-1 was prepared as follows: 57.0 g of β-alanine in 300 g of distilled water were dissolved in an Erlenmeyer flask, 65.0 g of triethylamine and 120.0 g of acetone were added, and the mixture was boiled under reflux for one hour. The mixture was allowed to cool to room temperature and received ß-alanine solution AI-1.

The mean particle diameter of pigments was determined using a Coulter Counter "Coulter LS230" from Coulter Dynamic viscosities were always measured at 23 ° C. in accordance with DIN 53018.

I. Preparation of radiation-curable products according to the invention

1.1. Preparation of Radiation-curable Product A.1 According to the Invention

200 g (0.9 mol) of isophorone diisocyanate (IPDI) were placed under nitrogen in a 2 l three-necked flask equipped with stirrer, reflux condenser, gas inlet tube and dropping funnel. A solution of 60 g (0.45 mol) of trimethylolpropane (TMP) and 16 g of 2-hydroxy-2-methylphenylpropanone (b.1) was added with stirring within 1 min.

in 276 g of 2-butanone.

Thereafter, dose 0.1 g of di-n-butyltin dilaurate, and heated the resulting re- action mixture with stirring to 60 ⁰ C. It is followed the decrease in the NCO content was monitored titrimetrically. Upon reaching an NCO content of 5.5 wt .-%, 129 g (0.17 mol) of a polyisocyanurate based on hexamethylene diisocyanate having an NCO content of 22.5 wt .-% and an average functionality of 3.7 NCO groups per molecule dissolved in 129 g of 2-butanone was added and the resulting Reaktionsmi¬ research for one hour at 6O ⁰ C stirred. The NCO content of the resulting hyperbranched polyurethane (a.1) was then 6.6% by weight. Thereafter, 31.0 g of 2-hydroxyethyl acrylate (C.1), stabilized with 100 ppm of 4-hydroxy-TEMPO (formula III), dissolved in 73 g of acetone, and then 0.1 g of di-n-butyltin dilaurate was added and stirred the reaction mixture resultie¬ yield for three hours at 6O ⁰ C. Thereafter, the continued resultieren¬ the reaction mixture 742 g at 60 ⁰ C temperature-ß-alanine AI-1.

Thereafter, it was stirred again at 60 ^° C. for 30 minutes. Subsequently, acetone and 2-butanone were removed on a rotary evaporator under reduced pressure (2 mbar) at 60 ° C. until the residue is taken up in distilled water. A 30% by weight aqueous solution of radiation-curable product (A.1) according to the invention was obtained.

1.2. Preparation of a hyperbranched polyurethane (a.2)

200 g (0.9 mol) of isophorone diisocyanate (IPDI) were placed under nitrogen in a 2 l three-necked flask equipped with stirrer, reflux condenser, gas inlet tube and dropping funnel. A solution of 60 g (0.45 mol) of trimethylolpropane (TMP) in 260 g of 2-butanone was added with stirring within 1 min.

Thereafter dosed to 0.02 g of di-n-butyltin dilaurate, and heated the resulting reaction mixture under stirring at 60 ⁰ C. It is followed the decrease in the NCO content. Upon reaching an NCO content of 5.5 wt .-%, 129 g (0.17 mol) of a polyisocyanurate based on hexamethylene diisocyanate having an NCO content of 22.5 wt .-% and an average functionality of 3.7 NCO Groups per molecule, dissolved in 129 g of 2-butanone, added and the resulting reaction mixture stirred at 60 ⁰ C for one hour. The NCO content of the resulting hyperbranched polyurethane (a.2) was then 6.3% by weight. Hyperbranched polyurethane (a.2) was obtained, dissolved in 2-butanone.

1.3. Preparation of water-soluble radiation-curable product (A.2) according to the invention

192 g of solution of hyperbranched polyurethane (a.2) from 1.2 were placed in a 2 l three-necked flask equipped with stirrer, reflux condenser, gas inlet tube and drip funnel under nitrogen. With stirring, a mixture of 4 g of 2-hydroxy-2-methylphenylpropanone (b.1), 16 g of 2-hydroxyethyl acrylate (C.1), stabilized with 100 ppm of 4-hydroxy-TEMPO (formula III), 0.02 g of di-n-butyltin dilaurate and 20 g of 2-butanone. It was then heated to 60 ⁰ C and stirred at 60 ° C for three hours. Then 156.2 g tempered to 60 ⁰ C ß-alanine solution AI-1 was added to the reaction mixture.

Thereafter, the reaction mixture was stirred for 30 min at 60 ⁰ C then acetone and 2-butanone were distilled off on a rotary evaporator under reduced pressure (2 mbar) at 60 ⁰ C and the residue taken up with distilled water. A 20% by weight aqueous solution of the water-soluble radiation-curable product (A.2) according to the invention was obtained.

1.4. Preparation of water-soluble radiation-curable product according to the invention (A.3) 192 g of hyperbranched polyurethane (a.2) from I.2 were initially charged in a 2 l three-necked flask equipped with stirrer, reflux condenser, gas inlet tube and drip funnel under nitrogen. With stirring, a mixture of 8 g of 2-hydroxy-2-methylphenylpropanone (b.1), 16 g of 2-hydroxyethyl acrylate (C.1), stabilized with 100 ppm of 4-hydroxy-TEMPO (formula III), 0.02 g of di-n-butyltin dilaurate and 24 g of 2-butanone. It was then heated to 60 ⁰ C and stirred at 60 ⁰ C for three hours. Then 156.2 g tempered to 60 ⁰ C ß-alanine solution AI-1 was added to the reaction mixture.

Thereafter, the reaction mixture was stirred at 60 ° C for 30 minutes. Subsequently, acetone and 2-butanone were distilled off on a rotary evaporator under reduced pressure (2 mbar) at 60 ^° C. and the residue was taken up with distilled water. A 30% by weight aqueous solution of the water-soluble radiation-curable product (A.3) according to the invention was obtained.

1.5. Preparation of radiation-curable product according to the invention (A.4)

192 g of hyperbranched polyurethane (a.2) from 1.2 were initially charged in a 2 l three-necked flask equipped with stirrer, reflux condenser, gas inlet tube and dropping funnel under nitrogen. While stirring, a mixture of 4 g of 2-hydroxy-2-methylphenylpropanone (b.1), 4 g of ethyl 4- (N, N-dimethylamino) benzoate (b.3), 16 g of 2-hydroxyethyl acrylate (C.1 ) stabilized with 100 ppm 4-hydroxy-TEMPO (formula III), 0.02 g of di-n-butyltin dilaurate and 24 g of 2-butanone. On closing was heated to 60 ° C and stirred at 60 ° C for three hours. Subsequently, the reaction mixture 156.2 g to 6O ⁰ C tempered ß-alanine solution AI-1 zuge¬ sets.

Thereafter, the reaction mixture was stirred for 30 min at 6O ⁰ C. Subsequently, acetone and 2-butanone were distilled off on a rotary evaporator under reduced pressure (2 mbar) at 6O ⁰ C and the residue taken up in distilled water. A 30% by weight aqueous solution of the water-soluble radiation-curable product (A.4) according to the invention was obtained.

1.6. Preparation of radiation-curable product according to the invention (A.5)

192 g of hyperbranched polyurethane (a.2) from 1.2 were initially charged in a 2 l three-necked flask equipped with stirrer, reflux condenser, gas inlet tube and drip funnel under nitrogen. With stirring, a mixture of 4 g of 2-hydroxy-2-methylphenylpropanone (b.1), 4 g of benzoylphosphine oxide (b.4), 16 g of 2-hydroxyethyl acrylate (C.1), stabilized with 100 ppm of 4-hydroxypropane TEMPO (formula III), 0.02 g of di-n-butyltin dilaurate and 24 g of 2-butanone. It was then heated to 60 ⁰ C. and stirred at 60 ⁰ C for three hours. Then 156.2 g tempered to 60 ⁰ C β-alanine solution AI-1 was added to the reaction mixture.

Thereafter, the reaction mixture was stirred for 30 min at 6O ⁰ C. Then acetone and 2-butanone were distilled off on a rotary evaporator under reduced pressure (2 mbar) at 60 ⁰ C and the residue taken up with distilled water. A 30% by weight aqueous solution of the radiation-curable product (A.5) according to the invention was obtained.

I.7. Preparation of radiation-curable product according to the invention (A.6)

192 g of hyperbranched polyurethane (a.2) from 1.2 were initially charged in a 2 l three-necked flask equipped with stirrer, reflux condenser, gas inlet tube and drip funnel under nitrogen. While stirring, a mixture of 2 g of 2-hydroxy-2-methylphenylpropanone (b.1), 2 g of benzoylphosphine oxide (b.4), 16 g of 2-

Hydroxyethyl acrylate (C.1) stabilized with 100 ppm 4-hydroxy-TEMPO (formula III), 0.02 g of di-n-butyltin dilaurate and 20 g of 2-butanone. It was then heated to 60 ⁰ C and stirred at 60 ° C for three hours. Subsequently, the reaction mixture 156.2 g to 6O ⁰ C tempered ß-alanine solution AI-1 was added.

Followed by stirring the reaction mixture for 30 min at 60 ⁰ C. Thereafter, the solvent, acetone and 2-butanone (2 mbar), and distilled off on a rotary evaporator under reduced pressure at 60 ° C men aufgenom¬ with distilled water, the residue. A 30% by weight aqueous solution of the water-soluble radiation-curable product according to the invention (A.6) was obtained.

1.8 Preparation of water-soluble radiation-curable product (A.7) according to the invention

192 g of hyperbranched polyurethane (a.2) from 1.2 were mixed in a 2-l

Three-necked flask equipped with stirrer, reflux condenser, gas inlet tube and drip funnel, placed under nitrogen. While stirring, a mixture of 10.3 g of 2-hydroxy-2-methylphenylpropanone (b.1), 5.3 g of 2-hydroxyethyl acrylate (C.1), stabilized with 100 ppm of 4-hydroxy-TEMPO (formula III), 0.02 g of di-n-butyltin dilaurate and 15.6 g of acetone. The mixture was then heated to 60 ⁰ C and stirred for three hours at 60 ⁰ C ge. Then 156.2 g tempered to 60 ⁰ C ß-alanine solution AI-1 was added to the reaction mixture.

Thereafter, the reaction mixture was stirred for 30 min at 60 ⁰ C, then the solvents acetone and 2-butanone were removed on a rotary evaporator under reduced pressure (2 mbar) at 60 ⁰ C and the residue taken up in distilled water. A 30% by weight aqueous solution of the water-soluble radiation-curable product according to the invention (A.7) was obtained.

1.9 Preparation of water-soluble radiation-curable product according to the invention (A.8)

192 g of hyperbranched polyurethane (a.2) from 1.2 were initially charged in a 2 l three-necked flask equipped with stirrer, reflux condenser, gas inlet tube and drip funnel under nitrogen. While stirring, a mixture of 4 g of phenylbenzyl ketone (b.5), 16 g of 2-hydroxyethyl acrylate (C.1), stabilized with 100 ppm of 4-hydroxy-TEMPO (formula III), 0.02 g of di-n-butyltin dilaurate and 20 g of 2-butanone. On closing was heated to 60 ⁰ C and stirred at 60 ⁰ C for three hours. Subsequently, the reaction mixture 156.2 g tempered to 60 ° C β-alanine solution AI-1 zuge¬ sets.

Followed by stirring the reaction mixture for 30 min at 60 ⁰ C. Thereafter, the solvent 2-butanone on a rotary evaporator under reduced pressure (2 mbar) at 6O ⁰ C was added to the residue and distilled water. A 30% by weight aqueous solution of the water-soluble radiation-curable product according to the invention (A.8) was obtained.

II. Application examples

11.1. Preparation of pigmented rubies, general instructions

Pigment rubs for organic pigments were on a 60 g Skandex

Glass balls (diameter 0.25 - 0.5 mm) made. The formulations are summarized in Table 1. After weighing the ingredients and the glass beads in Skandex, the resulting mixture was shaken for a time according to Table 1. Thereafter, a sample was taken and the average diameter of dispersed pigment was determined (Coulter Counter). The pH was measured and, if necessary, adjusted to 7.5 with triethanolamine. The pigment preparations PA.1.1 to PA.1.3 were obtained.

Table 1: Ingredients and recipe parameters for pigment dries PA.1.1 to PA.1.3

Quantities of ingredients are always given in g unless otherwise stated. It means: biocide 1: 20 wt .-% solution of 1, 2-benzisothiazolin-3-one in propylene glycol

Further pigmentary triturations were obtained by proceeding as described above, but substituting (A.1) for (A.2), (A.3), etc., respectively. The following pigment drifts were obtained:

PA.2.1 (magenta, using (A.2)), PA.2.2 (black, using (A.2)), PA.2.3 (yellow, using (A.2)),

PA.3.1 (magenta, using (A.3)), PA.3.2 (black, using (A.3)), PA.3.3 (yellow, using (A.3)),

PA.4.1 (magenta, using (A.4)), PA.4.2 (black, using (A.4)), PA.4.3 (yellow, using (A.4)),

PA.5.1 (magenta, using (A.5)), PA.5.2 (black, using (A.5)), PA.5.3 (yellow, using (A.5)),

PA.6.1 (magenta, using (A.6)), PA.6.2 (black, using (A.6)), PA.6.3 (yellow, using (A.6)),

PA.7.1 (magenta, using (A.7)), PA.7.2 (black, using (A.7)), PA.7.3 (yellow, using (A.7)),

PA.8.1 (magenta, using (A.8)), PA.8.2 (black, using (A.8)), PA.8.3 (yellow, using (A.8)).

11.2 formulation of inks according to the invention for the ink-jet process

11.2.1 Formulation of the Inventive Magenta Ink T1.1 for the Inkjet Process

In a beaker were mixed by stirring:

25 g PA.1.1,

1 g of urea,

3 g of triethylene glycol mono-n-butyl ether, 6 g of poly-THF having an average molecular weight M _n of 250 g / mol

5 g of polyethylene glycol with M _n = 400 g / mol,

6 g glycerol,

0.5 g of a 20 wt .-% solution of benzisothiazolin-3-one in propylene glycol, 0.5 g of ethoxylated trisiloxane of the formula [(CH ₃₎ ₃ Si-O] ₂ -Si (CH 3) -O (CH ₂ CH ₂ O) ₈ -H 53 g of distilled water.

It was filtered through a glass fiber filter (exclusion size 1 micron) and received the ink according to the invention T1.1. Ink T1.1 according to the invention had a pH of 7.0 and a dynamic viscosity of 2.8 mPa.s.

11.2.2 Formulation of the black ink T1.2 according to the invention for the ink-jet process

In a beaker were mixed by stirring: 35 g PA.1.2,

1 g of urea,

3 g of triethylene glycol mono-n-butyl ether,

6 g of poly THF having an average molecular weight M _n of 250 g / mol

5 g of polyethylene glycol with M _n = 400 g / mol, 6 g of glycerol,

0.5 g of a 20% by weight solution of benzisothiazolin-3-one in propylene glycol, 0.5 g of ethoxylated trisiloxane of the formula [(CH ₃ ) ₃ Si-O] 2-Si (CH ₃ ) -O (CH ₂ CH ₂ O) ₈ -H 43 g of distilled water.

The ink T1.2 according to the invention was obtained. Ink T1.2 according to the invention had a pH of 7.86 and a dynamic viscosity of 3.6 mPa.s.

11.2.3 Formulation of the yellow ink T1.3 according to the invention for the ink-jet process

In a beaker were mixed by stirring:

40 g PA.1.3,

1 g of urea,

3 g of triethylene glycol mono-n-butyl ether,

6 g of polyTHF with an average molecular weight M _n of 250 g / mol 5 g of polyethylene glycol with M _n = 400 g / mol,

6 g glycerol,

0.5 g of a 20% by weight solution of benzisothiazolin-3-one in propylene glycol,

0.5 g ethoxylated trisiloxane of the formula [(CH ₃ ) ₃ Si-O] ₂ -Si (CH ₃ ) -O (CH ₂ CH ₂ O) ₈ -H

38 g of distilled water.

The ink T1.3 according to the invention was obtained. Ink T1.3 according to the invention had a pH of 6.53 and a dynamic viscosity of 3.2 mPa.s.

11.2.4 Preparation of further inks according to the invention

The procedure was as described above, but replaced PA.1.1, PA.1.2 or PA1.3 by one of the descriptions PA.2.1 to PA.8.3. 25 g of magenta-colored pigment preparation were always used to prepare magenta inks, 35 g of black pigment dries to produce black inks and 40 g of yellow pigment slurry to prepare yellow inks, and the respective amount of distilled water. This gave the inks according to the invention T2.1 to T8.3. The dynamic viscosities of the inks T2.1 to T8.3 according to the invention are in the range from 2.5 to 4.0 mPa s.

III. Printing tests with inks according to the invention for the ink-jet process

The inks according to the invention were filled into cartridges and printed on paper with an Epson 3000 720 dpi printer. Each received 5 DIN A4 pages failure of a maximum of 5 nozzles. The rubbing fastness tests gave good values.

Furthermore, the inks according to the invention T1.1 to T1.3 were printed on cotton with a printer Ep¬ son 3000 720 dpi. After printing, you dried 5 minutes in a drying oven at 100 ⁰ C and treated with actinischer Strah¬ treatment. For this purpose, a UV irradiation device from the company IST was used with two different UV lamps: Eta Plus M-400-U2H, Eta Plus M-400-U2HC. The exposure was for 10 seconds and an energy of 1500 mJ / cm ^{2 was applied} .

The printed substrates S1.1 to S1.3 according to the invention according to Table 3 and certain the rubfastness according to ISO-105-D02: 1993 and the wash fastness according to ISO 105-C06: 1994 were obtained.

Table 3: fastnesses of printed cotton according to the invention

Claims

claims

1. Use of water-soluble radiation-curable products (A), obtainable by

for the preparation of aqueous inks for the ink-jet process.

2. Use according to claim 1, characterized in that at least one hyperbranched polyurethane (a) is a hyperbranched polyurethane (a) having at least one NCO group per molecule.

3. Use according to claim 1 or 2, characterized in that water-soluble radiation-curable products (A) are water-soluble radiation curable products (A) having at least one COOH group per molecule.

4. Use according to claims 1 to 3, characterized in that at least one photoinitiator (b) is an α-decamer or a hydrogen-abstracting photoinitiator.

5. Aqueous inks for the ink-jet process with a dynamic viscosity in the range of 2 to 80 mPa-s, measured at 23 ° C, containing

(A) at least one water-soluble radiation-curable product obtainable by

Mixing and optionally reacting at least one hyperbranched polyurethane (a) with at least one photoinitiator (b) or by synthesis of at least one hyperbranched polyurethane (a) in the presence of at least one photoinitiator (b),

(B) at least one pigment.

6. Inks according to claim 5, characterized in that at least one hyperbranched polyurethane (a) is a hyperbranched polyurethane (a) having at least one NCO group per molecule.

7. Inks according to claim 5 or 6, characterized in that water-soluble radiation-curable products (A) are water-soluble radiation-curable products (A) having at least one COOH group per molecule.

8. Inks according to claim 7, characterized in that one prepares water-soluble radiation-curable products (A) having at least one COOH group per molecule by adding β-alanine during the preparation of water-soluble radiation-curable products (A).

9. Inks according to one of claims 5 to 8, characterized in that at least one photoinitiator is an α-decamer or a hydrogen-abstracting photoinitiator.

10. Inks according to one of claims 5 to 9, comprising

(C) at least one photopolymerizable compound selected from compounds having at least two ethylenic double bonds per molecule and compounds of general formula I.

where the variables are defined as follows:

R ¹ , R ^{2 are the} same or different and are selected independently of one another

Hydrogen and C ₁ -C ₁₀ -alkyl, X ¹ selected from oxygen and NR ³ , A ¹ selected from C ₁ -C ₂₀ -alkylene, unsubstituted or mono- or polysubstituted with Ci-C ₄ alkyl, phenyl or 0-C ₁ -C ₄ -alkyl wherein C _{_1-2} groups may be replaced by oxygen C ₂ -alkylene one or more non-adjacent CH; X ² selected from hydroxyl and NH-R ³ , R ^{3 are} identical or different and selected from hydrogen, Ci-Ci _O alkyl and phenyl.

11. Inks according to claim 10, characterized in that (C) at least one photopolymerizable compound selected from compounds of the general formula M.

where the variables are defined as follows:

R ¹ , R ^{2 are} different or the same and independently selected from hydrogen and C ^ C ^ alkyl

m is an integer from 0 to 2, A ² CH ₂ or -CH ₂ -CH ₂ - or R ⁵ -CH or para-C ₆ H ₄ for the case that m

= 0,

CH, C-OH, COC (O) -CH = CH ₂ , CO-CO-C (CH ₃ ) = CH ₂ , R ⁵ -C or

1, 3,5-C ₆ H ₃ for the case that m = 1, and carbon for the case that m = 2;

R ^{5 is} selected from C 1 -C ₄ -alkyl and phenyl,

A ³ , A ⁴ , A ^{5 are the} same or different and selected from

C _r C ₂₀ alkylene cis- or frans-C ₄ -C ₁₀ cycloalkylene, C ^ C ^ alkylene, which can be substituted by one to seven nonadjacent carbon atoms are replaced by oxygen, dC ₂₀ alkylene substituted with up to 4 hydroxyl groups, where in C ₁ -

C ₂₀ -alkylene from one to seven non-adjacent C-

Atoms may be replaced by oxygen, C ₆ -C ₁₄ -arylene.

12. Inks according to one of claims 5 to 11, containing 1 to 20 wt .-% (A), 0.01 to 20% by weight (B)

0 to 10 wt .-% (C), each based on the total weight of the ink.

13. Inks according to one of claims 5 to 12, containing 1, 5 to 15 wt .-% (A),

1 to 10 wt .-% (B), 0, 1 to 9 wt .-% (C), each based on the total weight of the ink.

14. A process for the preparation of inks according to any one of claims 5 to 13, da¬ characterized in that one mixes (A), (B), water and optionally (C) mit¬ each other.

15. A method for printing flat substrates using Tin¬ th according to any one of claims 5 to 13.

16. A method for printing sheet-like substrates using Tin¬ th according to any one of claims 5 to 13 and subsequent treatment with acti- nischer radiation.

17. Water-soluble radiation-curable products (A), obtainable by

Mixing and optionally reaction of at least one hyperbranched polyurethane (a) with

0.001 to 10% by weight, based on (a), of at least one photoinitiator (b),

or by synthesizing at least one hyperbranched polyurethane (a) in the presence of from 0.001 to 10% by weight, based on (a), of at least one photoinitiator

18. Water-soluble radiation-curable products according to claim 17, characterized in that at least one hyperbranched polyurethane (a) is a hyperbranched polyurethane (a) having at least one NCO group per molecule.

19. Water-soluble radiation-curable products according to claim 17 or 18, characterized in that they have at least one COOH group per molecule.

20. Water-soluble radiation-curable products according to one of claims 17 to

19, characterized in that at least one photoinitiator is an α-decamer or a hydrogen-abstracting photoinitiator.

21. Water-soluble radiation-curable products according to any one of claims 18 to

20, characterized in that they additionally (C) at least one photopolymerizable compound selected from compounds having at least two ethylenic double bonds per molecule and compounds of the general For¬ mel I

in which the variables are defined as follows:

Hydrogen and C ₁ -C ₁₀ -alkyl, X ¹ selected from oxygen and NR ³ , A ¹ selected from dC _Σ o-alkylene, unsubstituted or mono- or polysubstituted with C ₁ -C ₄ -AlkYl ₁ phenyl or 0-C ₁ -C ₄ -alkyl wherein C _{_1-2} groups may be replaced by oxygen C ₂ -alkylene one or more non-adjacent CH; X ² selected from hydroxyl and NH-R ³ , R ^{3 are} identical or different and selected from hydrogen, _C 1 _-C 10 -alkyl and phenyl.

22. Water-soluble radiation-curable products according to claim 21, characterized ge indicates that (C) at least one photopolymerizable compound selected from compounds of general formula II

where the variables are defined as follows:

R, R are the same or different and are independently selected from hydrogen and C 1 -C 10 -alkyl

m is an integer from 0 to 2, A ² CH ₂ or -CH ₂ -CH ₂ - or R ⁵ -CH or para-C ₆ H ₄ for the case where m = 0,

CH, C-OH, COC (O) -CH = CH ₂ , CO-CO-C (CH ₃ ) = CH ₂ , R ⁵ -C or

1, 3,5-C ₆ H ₃ for the case that m = 1, and carbon for the case that m = 2; selected from C ₁ -C ₄ -alkyl and phenyl,

A ³ , A ⁴ , A ^{5 are the} same or different and selected from

C ^ C ^ alkylene, c / s or trans-C ₄ -C ₁₀ cycloalkylene, C _r C ₂₀ alkylene, which can be substituted by one to seven nonadjacent carbon atoms are replaced by oxygen,

C ₁ -C ₂₀ -alkylene substituted with up to 4 hydroxyl groups, where in C ₁ -

C ₂₀ -alkylene from one to seven non-adjacent C-

Atoms may be replaced by oxygen, C ₆ -C ₁₄ -arylene.