EP1658341A2

EP1658341A2 - Formulations, and use thereof for coating substrates

Info

Publication number: EP1658341A2
Application number: EP04741051A
Authority: EP
Inventors: Nidia Bustos; Klaus Dieter HÖRNER; Günter Renz; Holger SCHÖPKE
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2003-08-22
Filing date: 2004-07-15
Publication date: 2006-05-24
Also published as: WO2005028570A3; WO2005028570A2; AR045282A1

Abstract

Disclosed is a formulation containing (a) at least one polymer or copolymer that is produced in the presence of at least one photoinitiator, (b) at least one plasticizer, and (c) at least one branched compound comprising at least two terminal double bonds.

Description

Formulation and its use in the coating of substrates

description

The present invention relates to at least one formulation containing

a) at least one polymer or copolymer which has been prepared in the presence of at least one photoinitiator, b) at least one plasticizer and c) at least one branched compound having at least two terminal double bonds.

Furthermore, the present invention relates to a method for producing the formulations according to the invention, the use of the formulations according to the invention for coating fibrous substrates and fibrous substrates coated with at least one formulation according to the invention.

Numerous substrates, especially fibrous substrates such as textiles and leather, only get the desired properties through a coating. In many cases, coatings are first applied and then hardened, for example thermally or by actinic, i.e. electromagnetic radiation. This places demanding requirements on the coatings. They should be inexpensive and should no longer tend to stick after hardening. In addition, no toxicologically questionable substances should be used in the application. That is why modern water-based formulations are usually used.

EP 0392352 discloses aqueous formulations of radiation-curable polyester urethanes and their use for coating leather, for example. However, the systems used are expensive.

From EP 0486278 aqueous radiation-curable coating compositions are known which contain a polymer latex with an acrylate content of over 47 mol% and a glass transition temperature below 28 ° C as well as a multifunctional (meth) acrylate and which can be cured in the presence of a photoinitiator. However, such coating compositions are only suitable for the treatment of hard substrates such as steel.

EP 0 624610 discloses the use of aqueous dispersions for the production of radiation-hardened coatings, which A) comprise 20 to 90% by weight of a contain dispersed polymers, which is characterized, among other things, by a glass transition temperature of above 30 °, and B) 10 to 80% by weight of a tri, tetra, penta- or hexa- (meth) acrylate of an alkoxylated, 3- to 6- valuable alcohol, the production can take place thermally or in the presence of photoinitiators. However, it is found that dark-colored and especially black substrates still tend to stick.

EP 0 877067 discloses aqueous radiation-curable coating compositions which, inter alia, comprise 5 to 90% by weight of a water-dispersible polymer which contains at least one αr, β-unsaturated carboxylic acid, furthermore at least one radiation-curable compound S, optionally at least one photoinitiator and water. The coating compositions disclosed are suitable as primers for coating absorbent and non-absorbent substrates and provide very good cross-cut values according to ISO 2409 or DIN 53151. However, it is found that dark-colored and in particular black substrates still tend to stick.

The object was therefore to provide formulations which are suitable for coating fibrous substrates and avoid the above-mentioned weaknesses from the prior art. A further object was to provide a method for producing formulations suitable for coating fibrous substrates. Another object was to provide a method for coating fibrous substrates. Finally, the task was to provide coated fibrous substrates.

Accordingly, the formulations defined at the outset were found which contain: at least one polymer or copolymer which was prepared in the presence of at least one photoinitiator, at least one plasticizer and at least one branched compound having at least two terminal double bonds.

At least one polymer or copolymer (a) is a polymer or copolymer, which is preferably obtainable by emulsion polymerization or emulsion copolymerization.

You can choose different procedures for emulsion polymerization for the production of at least one polymer or copolymer (a), for example a batch process (discontinuous) or semi-continuous or fully continuous processes such as feed processes, which can also be operated in a step-wise manner. So-called seed procedures, as described for example in EP 0 810 831, are also suitable. Using the seed procedure, it is particularly easy to produce polymers or copolymers (a) with a particularly reproducible particle size distribution.

Polymerization is usually carried out using at least one initiator. At least one initiator can be a peroxide. Examples of suitable peroxides are alkali metal peroxodisulfates such as e.g. Sodium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide, organic peroxides such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis- (o-toluyl) butyl peroxide, succinic peroxide, succinyl peroxide , tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl peroct.oate, tert-butyl pemeodecanoate, tert-butyl perbenzoate, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy-2 ethyl hexanoate and diisopropyl peroxidicarbamate. Azo compounds such as, for example, azobisisobutyronitrile, azobis (2-amidopropane) dihydrochloride and 2,2'-azobis (2-methylbutyronitrile) are also suitable.

Redox initiators are also suitable, for example from peroxides and oxidizable sulfur compounds. Systems of acetone bisulfite and organic peroxide such as tert-C ₄ H ₉ -OOH, Na ₂ S ₂ O ₅ (sodium disulfite) and organic peroxide such as tert-C ₄ H ₉ -OOH or NaO-CH ₂ SO ₂ are very particularly preferred H and organic peroxide such as tert-C ₄ H ₉ -OOH. Systems such as ascorbic acid / H ₂ O _{2 are also} particularly preferred.

Temperatures in the range from 20 to 105 ° C., preferably 50 to 85 ° C., can be selected as the polymerization temperature. The selected temperature depends on the decay characteristics of the initiator or initiators used.

The pressure conditions are generally not critical, for example pressures in the range from normal pressure to 10 bar are suitable.

You can use at least one emulsifier, which can be anionic, cationic or nonionic.

Common nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C ₄ -C ₁₂ ) and ethoxylated fatty alcohols (degree of ethoxylation: 3 to 80; alkyl radical: C ₈ -C ₃₆ ). Examples are the Lutensol ^® brands from BASF Aktiengesellschaft and the Triton ^® brands from Union Carbide. Typical anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C ₈ to C ₁₂ ), of sulfuric acid semiesters of ethoxylated alkanols (degree of ethoxylation: 4 to 30, alkyl radical: C ₁₂ -C ₁₈ ) and ethoxylated alkyl phenols (degree of ethoxylation: 3 to 50, Alkyl radical: C ₄ -C ₁₂ ), of alkyl sulfonic acids (alkyl radical: C ₁₂ -Cι ₈ ) and of alkylarylsulfonic acids (alkyl radical: C ₉ -C ₁₈ ).

Suitable cationic emulsifiers are usually a C ₆ -C ₁₈ alkyl, aralkyl or heterocyclyl-containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and also salts of amine oxides, quinolinium , Isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts. Examples include dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- (N, N, N-trimethylammonium) ethyl paraffinic acid esters, -C / -cetylpyridiniumchloride, Λ / -laurylpyridinium sulfate and Λ-cetyl-Λ /, Λ , Λ / -trimethylammonium bromide, Λ / -dodecyl-Λ /, Λ /, Λ / - trimethylammonium bromide, / V, Λ / -distearyl-V, / V-dimethylammonium chloride and the gemini surfactant V, Λ ^ (lauryldimethyl) ethyIendiamindibromid. Numerous other examples can be found in H. Stächen, Tensid-Taschenbuch, Carl-Hanser-Verlag, Munich, Vienna, 1981 and in McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989.

Of course, other additives that are common in emulsion polymerization, for example glycols, polyethylene glycols, protective colloids and buffer / pH regulators, can be added to the reaction mixture.

A time period in the range from 30 minutes to 12 hours can be selected as the time period for the emulsion polymerization or emulsion copolymerization, preferably 2 to 3 hours.

In one embodiment, formulations according to the invention contain at least one polymer or copolymer (a) which comprises at least 40% by weight, preferably at least 60% by weight and particularly preferably at least 80% by weight, based on the respective polymer or Copolymer, is built up from so-called main monomers, main monomers being selected from

Compounds of the general formula I

unsaturated esters of the general formula II,

Vinyl aromatics of the general formula III,

unsaturated compounds of the general formula IV

IV a IV b

and non-aromatic hydrocarbons with 2 to 8 carbon atoms and at least one C-C double bond, the variables being defined in the formulas as follows:

R \ R ⁴ , R ^{10 the} same or different and selected from unbranched or branched CrCio-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n -Pentyl, iso-pentyl, sec.-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-a yl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, n-octyl, 2- Ethylhexyl, n-nonyl, n-decyl; particularly preferably CC - alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl; or hydrogen, very particularly preferred are hydrogen and methyl;

R ² , R ⁵ , R ^{11 the} same or different and selected from unbranched or branched CτCι ₀ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, 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, 2-ethylhexyl, n-nonyl, n-decyl; particularly preferably -CC alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl; or very particularly preferably hydrogen,

X selected identically or differently from halogen, such as fluorine, bromine or in particular chlorine, CN and OR ¹² ,

R ³ , R ⁶ , R ^{12 are the} same or different and are selected from CC ₂ o-alkyl, for example n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n -Octadecyl, n-nonadecyl, n-eicosyl; preferably unbranched or branched CC ₁₀ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, 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, 2-ethylhexyl, n-nonyl, n-decyl; particularly preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl;

R ⁷ , R ⁸ , R ^{9 the} same or different and selected from hydrogen and -CC ₁₀ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, 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 , 2-ethylhexyl, n-nonyl, n-decyl; particularly preferably dC-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl; methyl, n-butyl, isobutyl, n-decyl and in particular hydrogen are preferred,

k is an integer in the range from 0 to 3, preferably 0 and 1 and very particularly preferably 0.

Main monomers of the general formula I to be mentioned by way of example are methyl (meth) acrylate, n-butyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or mixtures thereof.

Unsaturated esters of general formula II to be mentioned as examples are vinyl acetate, allyl acetate, vinyl laurate, vinyl stearate, vinyl versatic acid such as vinyl pivalate, vinyl 2,2-dimethylbutyrate, vinyl 2,2-dimethyloctanoate and 2,2-ethylmethylbutyrate.

Examples of vinylaromatic compounds of the formula III to be mentioned are, for example, ff-methylstyrene, para-methylstyrene, α-n-butylstyrene, para-n-butylstyrene, 4-n-decylstyrene and in particular styrene. Unsaturated compounds of formula IV to be mentioned as examples are vinyl chloride, vinylidene chloride, methyl vinyl ether, methyl allyl ether, ethyl vinyl ether, (meth) acrylonitrile, vinyl isobutyl ether.

Examples of non-aromatic hydrocarbons with 2 to 8 carbon atoms and at least one double carbon bond are ethylene, propylene, 1-octene, isoprene, 1, 3-butadiene and chloroprene.

Polymers or copolymers (a) can be composed of at least 40% by weight of at least one main monomer.

In one embodiment of the present invention, copolymers (a) are composed of mixtures of at least 40% by weight of two different main monomers.

In addition to the main monomer (s), copolymers (a) can contain other monomers in copolymerized form. Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid are suitable, for example; Unsaturated sulfonic acids or phosphonic acids, monomers containing hydroxyl groups such as CτC ₁₀ hydroxyalkylene (meth) acrylates and other di- and polyols esterified with (meth) acrylic acid, in which at least one hydroxyl group is unesterified, examples include 2-hydroxyethyl (meth ) acrylate), 3-hydroxypropyl (meth) acrylate, ω-hydroxy-n-butyl (meth) acrylate; (Meth) acrylamide phenyloxyethylene glycol (meth) acrylate, glycidyl (meth) acrylate, compounds of the general formula V

in which the variables are defined as follows:

Y selected from oxygen and nitrogen,

A ¹ selected from C ₂ -C ₆ alkylene, such as -CH ₂ -, -CH (CH ₃ ) -, - (CH ₂ ) ₂ -, -CH ₂ -CH (CH ₃ ) -, - (CH ₂ ) ₃ -, -CH ₂ -CH (C ₂ H ₅ ) -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ -, preferably C ₂ -C ₄ alkylene; in particular - (CH ₂ ) ₂ -, -CH ₂ -CH (CH ₃ ) -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ - and -CH ₂ -CH (C ₂ H ₅ ) -;

R ¹³ different or preferably the same and selected from C 1 -C ₁₀ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, 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, 2-ethylhexyl, n-nonyl, n-decyl; particularly preferably C _t -C -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl; very particularly preferably methyl, hydrogen and phenyl; Ureido (meth) acrylate.

In one embodiment of the present invention, the amount of further comonomers is chosen so that at most 10% by weight of each individual comonomer, based on copolymer (a), is polymerized.

The glass transition temperature, for example determinable according to ASTM 3418/82, of at least one polymer or copolymer (a) is a maximum of 80 ° C. The glass transition temperature of at least one polymer or copolymer (a) is preferably in the range from -50 ° C. to + 60 ° C., particularly preferably -20 ° C. to + 50 ° C.

In one embodiment of the present invention, all of the polymers and copolymers contained in formulations according to the invention have a glass transition temperature of at most 80 ° C., preferably in the range from -50 ° C. to + 60 ° C., particularly preferably -20 ° C. to + 50 ° C.

At least one polymer or copolymer contained in formulations according to the invention is prepared in the presence of at least one photoinitiator. Examples of suitable photoinitiators can be found, for example, in P.K.T. Old-Ring, Chemistry and Technology of UV and EB Formulations for Coatings, Inks and Paints, SITA Technology, London 1991, Volume 3, "Photoinitiators for Free Radical and Catalytic Polymerization".

The photoinitiator or photoinitiators, in the presence of which or polymers or copolymers (a) were prepared, preferably do not themselves serve for the production of polymers or copolymers (a). Polymers or copolymers (a) are preferably represented by peroxidic activators and / or redox initiators.

At least one photoinitiator (P) can be a photoinitiator which disintegrates on activation, so-called σ-decayers such as, for example, photoinitiators of the benzil dialkyl ketal type such as, for example, benzil dimethyl ketal. Further examples of suitable σ-decayers are derivatives of benzoin, isobutylbenzoin ether, phosphine oxides, in particular mono- and bisacylphosphine oxides, for example 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phosphine sulphide fide and ethyl 4-dimethylaminobenzoate as well

At least one photoinitiator (P) is preferably a hydrogen-abstracting photoinitiator, for example of the type of optionally substituted acetophenones, anthraquinones, thioxanthones, benzoic acid esters or optionally substituted benzophenones. Particularly preferred examples are isopropylthioxanthone, benzophenone, 4-methylbenzophenone, halogen-methylated benzophenones, anthrone, Michler's ketone (4,4'-bis-dimethylamino-benzophenone), 4-chlorobenzophenone, 4,4'-dichlorobenzophenone, anthraquinone.

In one embodiment of the present invention, at least two photoinitiators are added in the production of at least one polymer or copolymer (a), preferred photoinitiators being activatable at the same or preferably at different wavelengths of long-wave UV light or visible light.

In one embodiment of the present invention, a further or more further photoinitiators P are polymerized into at least one copolymer (a), for example by using comonomers which contain photoactivatable groups.

Comonomers of the formulas P1 to P6 are particularly preferred

and

in which the variables are defined as follows:

Z is selected from hydrogen and hydroxyl

R ¹⁴ is selected from CC ₄ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl; and C ₆ -C ₁₄ aryl, optionally substituted, such as phenyl, p-hydroxyphenyl, p-dimethylaminophenyl, p-methylphenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 1-anthryl, 2-anthryl, in particular phenyl,

A ² C ₂ -C ₃₀ alkylene, preferably C ₂ -C ₆ alkylene, such as - (CH ₂ ) ₂ -, -CH ₂ -CH (CH ₃ ) -, - (CH ₂ ) ₃ -, -CH ₂ -CH (C ₂ H ₅ ) -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ -,

preferably C ₂ -C alkylene; in particular - (CH ₂ ) ₂ -, -CH (C ₂ H ₅ ) -, -CH ₂ -CH (CH ₃ ) -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ - and -CH ₂ - CH (C ₂ H ₅ ) -;

and the remaining variables are defined as above.

Comonomers of the general formulas P1 to P4 can be prepared by methods known per se. A esterification step or transesterification step of precursors of the formulas is customary in the production

Preliminary stage P1

Preliminary stage P2 and

Preliminary stage P3 or P4

with acids or esters of the formula

preferably in the presence of a catalyst, the variables in the formulas being defined as above and Me being methyl.

If desired, the effectiveness of photoinitiators can be increased by adding at least one synergist, for example at least one amine, in particular tertiary amine. Suitable amines are, for example, triethylamine, N, N-dimethylethanolamine, N-methylethanolamine, triethanolamine, amino acrylates such as, for example, amine-modified polyether acrylates. Usually can up to 5% by weight, based on the total weight of the formulation according to the invention, of synergist is added.

Formulations according to the invention further contain at least one plasticizer (b).

Plasticizer (b) is preferably in liquid form under normal conditions (1 atm, 20 ° C.).

Examples of plasticizers (b) are ester compounds selected from the groups of aliphatic or aromatic di- or polycarboxylic acids fully esterified with alkanols and phosphoric acid esterified at least once with alkanol.

In one embodiment of the present invention, alkanols are CC ₁₀ alkanols.

Preferred examples of aromatic di- or polycarboxylic acids fully esterified with alkanol are phthalic acid, isophthalic acid and mellitic acid fully esterified with alkanol; examples of his: di-n-octyl phthalate, di-n-nonyiphthalate, di-n-decyl phthalate, di-n-octyl isophthalate, di-n-nonyl isophthalate, di-n-decyl isophthalate.

Preferred examples of aliphatic di- or polycarboxylic acids fully esterified with alkanol are, for example, dimethyl adipate, diethyl adipate, di-n-butyl adipate, diisobutyl adipate, dimethyl glutarate, dimethyl glutarate, glutarate, glutarate Butyl ester of diisobutyl succinate and mixtures of the above-mentioned compounds.

Preferred examples of phosphoric acid esterified at least once with alkanol are CrCio-alkyl-di-C- _6- Cu-aryl-phosphates such as isodecyldiphenylphosphate.

Further suitable examples of plasticizers are aliphatic or aromatic diols or polyols which are esterified at least once with C 1 -C ₁₀ -alkyl carboxylic acid.

A preferred example of aliphatic or aromatic di- or polyols esterified at least once with CC ^ -alkylcarboxylic acid is 2,2,4-trimethylpentane-1,3-diol-monoisobutyrate. Other suitable plasticizers are polyesters obtainable by polycondensation of aliphatic dicarboxylic acid and aliphatic diol, for example adipic acid or succinic acid and 1,2-propanediol, preferably with an M _w of 200 g / mol, and polypropylene glycol alkylphenyl ether, preferably with an M _w of 450 g / mol.

Further suitable plasticizers are polypropylene glycols etherified with two different alcohols and having a molecular weight M _w in the range from 400 to 800 g / mol, it being possible for one of the alcohols to be an alkanol, in particular a CC ₁₀ alkanol, and the other alcohol preferably to be an aromatic alcohol, for example o-cresol, m-cresol, p-cresol and in particular phenol.

Formulations according to the invention further comprise at least one branched compound having at least two terminal double bonds (c).

In one embodiment of the present invention, at least one branched compound having at least two terminal double bonds (c) can be added in solution to a reaction mixture comprising (a) and (b).

In another embodiment of the present invention, at least one branched compound having at least two terminal double bonds (c) can be added in solution together with at least one photoinitiator to a reaction mixture comprising (a) and (b), with (b) as solvent can serve if (b) is in liquid form under normal conditions.

In another embodiment of the present invention, at least one branched compound having at least two terminal double bonds can be added as a comonomer for the pre-crosslinking during the preparation of (a). However, the proportion of branched compound with at least two double bonds should not exceed 1% by weight, based on (a).

Examples of branched compounds having at least two terminal double bonds (c) are triols, tetraols and pentaols esterified several times with (meth) acrylic acid.

Preferred examples of branched compounds having at least two terminal double bonds (c) are compounds of the general formula VI

in which the variables are defined as follows:

R ^{15 are the} same or different and are selected from methyl and hydrogen;

m is an integer from 0 to 2, preferably 1;

A ³ CH ₂ or -CH ₂ -CH ₂ - or R ¹⁶ -CH or para-C ₆ H ₄ if m = 0, CH, R ^1δ -C or 1, 3,5-C ₆ H ₃ in the event that m = 1, and carbon in the event that m = 2;

R ^{16 is} selected from CrC-alkyl, such as, for example, nC ₄ H ₉ , nC ₃ H ₇ , iso-C ₃ H ₇ and preferably C ₂ H ₅ and CH ₃ , or phenyl,

A ⁴ , A ⁵ , A ^{6 the} same or different and selected from CC ₂₀ alkylene, such as -CH ₂ -, -CH (CH ₃ ) -, -CH (C ₂ H ₅ ) -, -CH (C ₆ H ₅ ) -, - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ -, - (CH ₂ ) ₇ -, - (CH ₂ ) ₈ -, - (CH ₂ ) ₉ -, - (CH ₂ ) ₁ o- _> -CH (CH ₃ ) - (CH ₂ ) ₂ -CH (CH ₃ ) -; ice or French C ₁₀ -C ₁₀ -cycloalkylene, such as c / s-1, 3-cyclopentylidene, trans-1, 3-cyclopentylidene c / s-1, 4-cyclohexylidene, trans-, 4-cyclohexylidene; CrC ₂₀ alkylene in which one to seven non-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 -;

CC ^ alkylene, substituted with up to 4 hydroxyl groups, wherein in _{CrC 2cr} alkylene of one to seven non-adjacent C atoms are replaced by oxygen, such as -CH ₂ -O-CH ₂ -CH (OH) -CH ₂ -, -CH ₂ -O- [CH ₂ -CH (OH) -CH2] ₂ -, -CH ₂ -O- [CH ₂ -CH (OH) -CH2] ₃ -;

C ₆ -C ₁₄ aryls, such as, for example, para-C ₆ H ₄ .

Other preferred examples of branched compounds with at least two terminal double bonds are polyester (meth) acrylates, obtainable by, for example, reacting hydroxyl-terminated polyesters having a molecular weight M _n. preferably in the range from 250 to 4000 g / mol or polyethers with a molecular weight M _π in the range from 400 to 4000 g / mol, with (meth) acrylic acid, as described, for example, in EP-B 0 126 341.

Other preferred examples of branched compounds having at least two terminal double bonds are (meth) acrylate urethanes, preferably available as aqueous dispersions, which can be prepared by reacting polyeter (meth) acrylates with preferably aromatic di- or triisocyanates, as described, for example, in WO 98/47975.

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

50 to 95% by weight, preferably 75 to 90% by weight, based on the solids content of the formulation according to the invention, of polymer (a) or sum of copolymers (a),

0.2 to 12% by weight, preferably 0.5 to 5% by weight, based on the polymer or sum of copolymers (a), of at least one photoinitiator, amounts of photoinitiator in the upper range being preferred if you want to add one or more pigments,

1 to 20% by weight, preferably 4 to 12% by weight, based on the solids content of the formulation according to the invention, of plasticizer,

0.5 to 30% by weight, preferably 1 to 15% by weight, based on the solids content of the formulation according to the invention, of at least one branched compound having at least two terminal double bonds.

Formulations according to the invention can have a solids content of 20 to 70% by weight, preferably 35 to 50% by weight; the rest is water.

Another object of the present invention is a method for producing formulations according to the invention, hereinafter also referred to as the production method according to the invention.

In one embodiment, the production process according to the invention is characterized in that at least one plasticizer (b) is mixed with a dispersion which contains:

(a) at least one polymer or copolymer which has been prepared in the presence of at least one photoinitiator,

(c) optionally at least one branched compound with at least two terminal double bonds and

(d) water. In another embodiment, the production process according to the invention is characterized in that at least one branched compound with at least two terminal double bonds (c) and at least one plasticizer (b) is mixed with one another and then the mixture thus obtainable with a preferably aqueous dispersion of at least one polymer or Copolymer (a), which was prepared in the presence of at least one photoinitiator, mixed.

In another embodiment, the production process according to the invention is characterized in that at least one branched compound having at least two terminal double bonds (c) with a preferably aqueous dispersion of at least one polymer or copolymer (a) which has been prepared in the presence of at least one photoinitiator, and mixed at least one plasticizer (b).

Another object of the present invention is the use of the formulations according to the invention for coating fibrous substrates. Another object of the present invention is a method for coating fibrous substrates using the formulations according to the invention, hereinafter also referred to as coating method according to the invention, and a further subject of the present invention are coated fibrous substrates obtainable by a coating method according to the invention.

Fibrous substrates in the sense of the present invention are in particular leather and textile or textile substrates.

To carry out the coating process according to the invention, the procedure is advantageously such that fibrous substrates are treated with at least one formulation according to the invention and then exposed to actinic radiation. For example, electromagnetic rays with a wavelength range from 200 nm to 450 nm are suitable as actinic radiation. With the formulation according to the invention, substrates contacted with actinic radiation can be exposed to an energy in the range from 70 mJ / cm ² to 1500 mJ / cm ² . Actinic radiation can be introduced continuously or in the form of lightning, for example. If one has polymerized in benzophenone derivatives, for example of the formula P1 or P3 to P7, a proportion of UV-C radiation of 250-260 nm wavelength is important so that crosslinking can occur via the benzophenone group. In the context of the present invention, leather is understood to mean pre-tanned, tanned and, if appropriate, retanned leather or suitably processed synthetic exchange material, which may have already been treated with at least one dye during at least one tanning step. Leather in the context of the present invention is preferably hydrophobic and / or greased.

Formulations according to the invention are compatible with the commercially available auxiliaries for finishing leather, which can be used to regulate the feel, color, flow and viscosity. These are generally solutions (e.g. leveling agents, products based on glycol ethers, ethers such as butyl glycol, methoxypropanol, tributoxyethyl phosphate) or emulsions / dispersions with casein, waxes, silicones in the usual application amounts or application concentrations (see F. Stather, tanning chemistry and tanning technology, Akademie Verlag Berlin, 1967, pp.507-632).

In the context of the present invention, textile or textile substrates are to be understood as meaning textile fibers, textile semi-finished and finished products and finished products made therefrom which, in addition to textiles for the clothing industry, also include carpets and other home textiles and textile structures serving technical purposes. This also includes unshaped structures such as flakes, line-shaped structures such as twine, threads, yarns, linen, cords, ropes, threads and body structures such as felts, fabrics, nonwovens and wadding. The textiles can be of natural origin, for example cotton, wool or flax, or synthetic, for example polyamide, polyester, modified polyester, polyester blend fabric, polyamide blend fabric, polyacrylonitrile, triacetate, acetate, polycarbonate, polypropylene, polyvinyl chloride, polyester microfibers and glass fiber fabric.

In a special embodiment of the present invention, the coating of textile substrates according to the invention is an inventive method for textile printing.

In a special embodiment of the present invention, the coating method according to the invention is a method for finishing leather. The aim of finishing leather, also called coating leather, is to give leather the desired look, special haptic properties and fastness to use, e.g. Kink elasticity, wet and dry rub fastness, sweat resistance and water fastness.

A primer dispersion can be applied, which consists of conventional components. In one embodiment, the coating method according to the invention is based on pre-tanned, tanned and, if appropriate, retanned leather, which can be hydrophobicized and dyed in a manner known per se.

First, at least one primer dispersion, containing one or more formulation according to the invention, is applied to the leather to be colored in an amount such that about 10 to 100 g of solid are applied per m ^{2 of} leather surface. The application can be carried out by methods known per se, for example by plushing, ie application with a sponge or a brush-like device, which can be covered with plush or velvet fabric, by brushing, roll coating, pouring, spraying or spraying. The leather treated in this way can then be dried, for example at a temperature in the range from 30 to 120 ° C., preferably 60 to 80 ° C. At least one primer dispersion can be applied in one or more steps, which can be carried out identically or differently and can each be interrupted by intermediate drying at the above-mentioned temperatures.

In a preferred embodiment of the present invention, a primer dispersion used according to the invention contains at least one formulation according to the invention.

Priming dispersions used according to the invention, which are also referred to below as priming dispersions according to the invention, are usually aqueous. They can contain other, non-aqueous solvents such as ethylene glycol, N-methylpyrrolidone, 3-methoxypropanol and propylene carbonate. In a preferred embodiment, primer dispersions according to the invention contain the following constituents:

σ1) at least one formulation according to the invention, preferably 20 to 70% by weight, based on the total weight of the primer dispersion according to the invention; jffl) optionally at least one wax, such as oxidized polyethylene wax or montan wax, preferably 1 to 15% by weight, based on the total weight of the primer dispersion according to the invention; y \) optionally at least one biocide, for example 1, 2-benzisothiazolin-3-one (“BIT”) commercially available as Proxel brands (commercially available as Proxel® brands from Avecia Lim.) and its alkali metal salts; others suitable biozides are 2-methyl-2H-isothiazol-3 ("MIT") and 5-chloro-2-methyl-2H-isothiazol-3-one ("CIT"). In general, 10 to 50 ppm biocide, based on primer dispersion, sufficient. δ \) optionally at least one pigment in particulate form, e1) optionally at least one further binder.

Primer dispersions can also contain at least one filler and anti-adhesive. For example, aqueous formulations of fatty acid esters, protein and inorganic fillers, which can be selected from silicates and clay minerals, are suitable.

Primer dispersions according to the invention can have a solids content of 10 to 80% by weight, 20 to 50% by weight being preferred.

A top layer can then be applied by methods known per se. The cover layer can consist of conventional components.

In one embodiment of the present invention, the top layer σ2) contains at least one formulation according to the invention, preferably 20 to 70% by weight, based on the total weight of the top layer according to the invention, ß2) at least one wax, such as oxidized polyethylene wax or montan wax or silicone wax, preferably 1 up to 15% by weight, based on the total weight of the top layer according to the invention; γ2) optionally at least one biocide, for example selected from MIT, BIT and CIT, for example in the amounts mentioned for primer dispersions, 62) optionally at least one pigment in particulate form, e2) optionally at least one thickener.

Cover layers can also contain at least one filler and anti-adhesive. For example, aqueous formulations of fatty acid esters, protein and inorganic fillers, which can be selected from silicates and clay minerals, are suitable.

A finish, also called a finish dispersion, can then be applied, with a finish of about 5 to 30 g / m ^{2 of} leather surface being applied. The finish or top coat serves to protect the leather and, in addition to high flexibility, should also ensure good scratch resistance, oil and water resistance. Depending on the desired article, it should have gloss or mattness, ie you can also add matting agents. Finishes can include, for example: formulations of at least one binder based on acrylate or polyurethane, a crosslinking agent, protein, nitrocellulose emulsion, fillers based on organic or inorganic matting agents, silicone wax, fatty acid esters.

Finishing dispersions according to the invention can contain polyurethane dispersions known per se, produced according to EP-A2 0392352. Top layers and finishing dispersions can contain one or more thickeners. Crosslinkable copolymers based on acrylic acid and acrylamide and thickeners based on polyurethane or polyvinylpyrrolidone or acrylate (co) polymers may be mentioned as examples.

After the finish has been applied, it can be dried under customary conditions, for example at temperatures in the range from 60 to 80 ° C., and then ironed, for example at temperatures in the range from 140 to 180 ° C. You can also iron hydraulically, for example at reduced pressure and temperatures in the range of 70 to 100 ° C. Conventional ironing devices are possible, such as ironing presses or continuous ironing machines.

After applying the finish, you can emboss an artificial scar image, e.g. under otherwise usual conditions with standard embossing machines.

In the process for finishing leather according to the invention, at least one formulation according to the invention is used in at least one step - priming, application of the top layer and finishing.

Another embodiment of the present invention is a method for producing printed textile using at least one formulation according to the invention, hereinafter also referred to as the textile printing method according to the invention.

To carry out the textile printing process according to the invention, one can proceed, for example, by incorporating at least one formulation according to the invention into a printing paste, hereinafter also referred to as printing paste according to the invention, and then printing textile substrates according to methods known per se.

The printing paste according to the invention for textile printing is advantageously produced by mixing at least one formulation according to the invention with auxiliaries and pigment common in the printing process. The color depth is usually adjusted by adjusting the pigment to binder ratio.

Common aids are known from Ulimann, Handbook of Technical Chemistry and Process Engineering, compare for example Ullmann's Enyclopedia of Industrial Chemistry, 5th edition, keyword: Textile Auxiliaries, Vol. A26, pp. 286 ff. And 296 ff., Verlag Chemie, Weinheim, Deerfield / Florida, Basel; 1996. Thickeners, fixers, grip improvers and emulsifiers are examples of common auxiliaries: Natural or synthetic thickeners can be used as thickeners. It is preferred to use synthetic thickeners, for example generally liquid solutions of synthetic (co) polymers in, for example, white oil or as aqueous solutions or as water-in-oil emulsions, preferably with about 40% by weight (co-) Polymer.

Preferred examples of thickeners are copolymers with 85 to 95% by weight of acrylic acid, 4 to 14% by weight of acrylamide and 0.01 to 1% by weight of the (meth) acrylamide derivative of the formula VII

with molecular weights M _w in the range from 100,000 to 200,000 g / mol, in which the radicals R ^{17 can be the} same or different and can be methyl or hydrogen.

The finished printing paste according to the invention can contain 30 to 70% by weight of white oil. Aqueous thickeners usually contain up to 25% by weight of (co) polymer, in some cases up to 50% by weight (so-called thickener dispersions). If it is desired to use aqueous formulations of a thickener, aqueous ammonia is generally added. The use of granular, solid formulations of a thickener is also conceivable in order to be able to produce emission-free pigment prints.

Printing pastes according to the invention can furthermore contain grip improvers which are usually selected from silicones, in particular polydimethylsiloxanes, and fatty acid esters. Examples of commercially available grip improvers which can be added to the printing pastes according to the invention are Acramin® plasticizer Sl (Bayer AG), Luprimol SIG® and Luprimol CW® (BASF Aktiengesellschaft).

Printing pastes according to the invention can be added as further additives, one or more emulsifiers, especially when the pastes contain thickeners containing white oil and are obtained as an oil-in-water emulsion. Examples of suitable emulsifiers are aryl- or alkyl-substituted polyglycol ethers. Commercially available examples of suitable emulsifiers are Emulsifier W® (Bayer), Luprintol PE New® and Luprintol MP® (BASF Aktiengesellschaft), and Solegal W® (Hoechst AG). Bπzmsted acids such as ammonium hydrogenphosphate can be added as further additives; preference is given to not adding Bransted acid.

Pigment printing using at least one printing paste according to the invention can be carried out by various methods which are known per se. As a rule, a stencil is used through which the printing paste according to the invention is pressed with a squeegee. This process is part of the screen printing process. Pigment printing processes according to the invention using at least one printing paste according to the invention deliver printed substrates with particularly high brilliance and depth of color of the prints with an excellent grip of the printed substrates at the same time. The present invention therefore relates to substrates printed by the printing process according to the invention using the printing pastes according to the invention.

Another object of the present invention are coated fibrous substrates obtainable by the coating process according to the invention. Fibrous substrates coated according to the invention are distinguished, for example, by good wet rub fastnesses and can also be produced with very good crosslinking yield (quantum yield) of photoinitiators even in deep color shades.

The invention is illustrated by working examples.

example 1

I. Preparation of Formulations According to the Invention 1.1. Preparation of formulation F.1

The following mixtures were made up: Mixture 1.1

430 g of n-butyl acrylate, 450 g of methyl methacrylate, 18.6 g of methacrylamide, 10 g of freshly distilled acrylic acid, 20 g of ureidomethacrylate, dissolved in a further 45 methyl methacrylate, 24 g of photoinitiator NP1.1

15 g photo initiator P2.1 dissolved in 45 g xylene (mixture of isomers)

11 g of sodium lauryl sulfate, dissolved in 62.3 ml of water, together dispersed in a further 770 ml of completely deionized water.

Mix 1.2:

3 g Na ₂ S ₂ O ₈ (sodium peroxodisulfate), dissolved in 200 ml deionized water

460 g of fully demineralized water and 15 g of polystyrene seed with an average particle diameter of 25 ^' nm were placed in a 5 l kettle with stirrer, nitrogen connection and two metering devices.

Nitrogen was bubbled through the receiver with stirring for 15 minutes and then heated to 85.degree. During the subsequent copolymerization, the temperature was kept at 85 ° C.

First 90 g of mixture 1.1 and 10 g of mixture 1.2 were added for presentation.

Subsequently, the dosing of the rest of mixture 1.1 and the rest of mixture 1.2 was started at the same time, the addition of the rest of mixture 1.1 taking about 90 minutes and the addition of mixture 1.2 about 135 minutes.

After the addition of mixture 1.2 had ended, the mixture was left to polymerize for a further 30 minutes and then, for deodorization, a solution of 4.3 g of tert-butyl hydroperoxide (70% by weight in water) in 45 ml of distilled water and a solution of Add 2.0 g HO-CH ₂ -O-SO ₂ Na in 50 g distilled water over a period of 90 minutes.

The mixture was then cooled to 40 ° C. and the pH was adjusted to 6.4 with 25% by weight aqueous ammonia.

Then 2,2,4-trimethylpentane-1,3-diolmonoisobutyrate (b1) and 160 g of VI.1 metered in within 30 minutes. The mixture was then cooled to room temperature and filtered through a 250 μm network.

The properties of the formulation F.1 obtainable in this way are shown in Table 1.

I.2. Preparation of formulation F.2

The following mixtures were made up: Mixture 2.1

500 g n-butyl acrylate, 300 g methyl methacrylate, 22 g methacrylamide, 10 g freshly distilled acrylic acid, 20 g ureidomethacrylate, dissolved in another 36 methyl methacrylate, 2 g 1,4-butanediol diacrylate, 18 g photo initiator NP1.2

14 g photo initiator P1.1

Mix 2.2:

In a 5-liter kettle with a stirrer, nitrogen connection and two metering devices, 360 g of demineralized water and 15 g of sodium lauryl sulfate, dissolved in a further 85 ml of water, and 10 g of iso-C ₁₃ H ₂₇ - (OCH ₂ CH ₂ ) ₈ OH, dissolved in another 40 ml of water. Nitrogen was bubbled through the receiver with stirring for 15 minutes and then heated to 85.degree. During the subsequent copolymerization, the temperature was kept at 85 ° C.

First, 90 g of mixture 2.1 and 10 g of mixture 2.2 were added to the initial charge and polymerized for about 15 minutes.

Subsequently, the dosing of the rest of mixture 2.1 and the rest of mixture 2.2 was started at the same time, the addition of the rest of mixture 2.1 taking about 90 minutes and the addition of mixture 2.2 about 135 minutes.

After the addition of mixture 2.2 had ended, the mixture was left to polymerize for a further 30 minutes and a solution of 4.3 g of tert-butyl hydroperoxide (70% by weight in water) in 45 ml of distilled water and a solution of Add 2.0 g HO-CH ₂ -O-SO ₂ Na in 50 g distilled water over a period of 90 minutes.

Subsequently, 70 g of dimethyl ester mixture (each 23.3 g of dimethyl adipate, dimethyl glutarate and dimethyl succinate) (b2) and 160 g VI.1

metered in within 30 minutes. The mixture was then cooled to room temperature and filtered through a 250 μm network.

The properties of the formulation F.2 obtainable in this way are shown in Table 1.

I.3. Preparation of formulation F.3

The following mixtures were used: Mix 3.1

400 g of n-butyl acrylate, 210 g of methyl methacrylate, 22 g of methacrylamide, 5 g of freshly distilled acrylic acid, 2 g of 1,4-butanediol diacrylate, 11 g of sodium lauryl sulfate, dissolved in 62.3 ml of water, together dispersed in a further 770 ml of completely deionized water ,

Mix 3.2

10 g ureido methacrylate, dissolved in 36 g methyl methacrylate, another 100 g methyl methacrylate, 100 g n-butyl acrylate, 5 g freshly distilled acrylic acid, 18 g photo initiator NP1.2

14 g photoinitiator P 1.1

Mix 3.3

In a 5-liter kettle with a stirrer, nitrogen connection and two metering devices, 360 g of demineralized water and 15 g of sodium lauryl sulfate, dissolved in a further 85 ml of water, and 10 g of iso-Cι ₃ H27- (OCH ₂ CH ₂ ) sOH, dissolved in another 40 ml of water.

First 90 g of mixture 3.1 and 10 g of mixture 3.3 were added to the initial charge and polymerized for about 15 minutes.

The dosing of the rest of mixture 3.1 and the rest of mixture 3.3 was then started simultaneously, the addition of the rest of mixture 3.1 taking about 60 minutes and the addition of mixture 3.3 about 135 Minutes. As well as the addition was completed by mixing 3.1, one began with the Zuga _¬ be of mixture 3.2; the addition took 30 minutes.

After the addition of mixture 3.3 had ended, the mixture was left to polymerize for a further 30 minutes and then, for deodorization, a solution of 4.3 g of tert-butyl hydroperoxide (70% by weight in water) in 45 ml of distilled water and a solution of Add 2.0 g HO-CH ₂ -O-SO ₂ Na in 50 g distilled water over a period of 90 minutes.

The properties of the formulation F.3 obtainable in this way are shown in Table 1.

I.4. Preparation of formulation F.4

The following mixtures were used:

Mix 4.1

400 g n-butyl acrylate, 300 g styrene, 80 g acrylonitrile, 5 g acrylamide, 10 g freshly distilled

Acrylic acid, 10 g ureidomethacrylate, dissolved in 48 methyl methacrylate, 18 g photoinitiator

NP1.4a

with Me = CH ₃ ,

14 g photo initiator P3.1

Mix 4.2:

The following were placed in a 5 liter kettle with a stirrer, nitrogen connection and two metering devices: 360 g of fully demineralized water and 15 g of sodium lauryl sulfate, dissolved in a further 85 ml of water, and 10 g of iso-C ₁₃ H27- (OCH ₂ CH ₂ ) ₈ OH, dissolved in another 40 ml of water.

First, 90 g of mixture 4.1 and 10 g of mixture 4.2 were added to the initial charge and polymerized for about 15 minutes.

Subsequently, the dosing of the rest of mixture 4.1 and the rest of mixture 4.2 was started at the same time, the addition of the rest of mixture 4.1 taking about 90 minutes and the addition of mixture 4.2 about 135 minutes.

After the addition of mixture 4.2 had ended, the mixture was left to polymerize for a further 30 minutes and then, for deodorization, a solution of 4.3 g of tert-butyl hydroperoxide (70% by weight in water) in 45 ml of distilled water and a solution of Add 2.0 g HO-CH ₂ -O-SO ₂ Na in 50 g distilled water over a period of 90 minutes.

Then 70 g of dimethyl ester mixture (each 23.3 g of dimethyl adipate, dimethyl glutarate and dimethyl succinate) (b2), in which 5 g of ethyl 4-dimethylaminobenzoate (NP1.4b) were dissolved, were separated and 400 g of polyurethane acrylate dispersion (solids content 40% by weight), produced according to WO 98/47975, example “Dispersion 7”, page 9, a polyester according to EP 0686 621 A1, example 1a being used instead of Laromer LR 8945, was added within 30 minutes, then cooled to room temperature and filtered through a 250 μm mesh.

The properties of the formulation F.4 obtainable in this way are shown in Table 1.

I.5. Preparation of formulation F.5

The following mixtures were used:

Mix 5.1

300 g n-butyl acrylate, 400 g styrene, 5 g acrylamide, 10 g freshly distilled acrylic acid, 10 g ureidomethacrylate, dissolved in 48 g methyl methacrylate, 24 g photo initiator NP1.5

12 g photo initiator P2.1

dissolved in 24 g xylene (mixture of isomers)

Mix 5.2:

3 g Na ₂ S ₂ O ₈ (sodium peroxodisulfate), dissolved in 200 ml deionized water.

The copolymerization according to Example I.4 was repeated, but in each case mixture 5.1 was added instead of mixture 4.1 and mixture 5.2 instead of mixture 4.2.

After the copolymerization and deodorization had ended, the mixture was cooled to 40 ° C. and the pH was adjusted to 6.4 with 25% by weight aqueous ammonia.

Subsequently, 120 g of diisononyl-1, 4- Dicyclohexanedicarboxylic acid ester (cis / trans isomer mixture) (b3), and 96 g VI.2

The properties of the formulation F.5 obtainable in this way are shown in Table 1.

I.6. Preparation of formulation F.6

The following mixtures were used:

Mix 6.1

300 g n-butyia acrylate, 400 g styrene, 80 g acrylonitrile, 5 g acrylamide, 10 g freshly distilled acrylic acid, 10 g ureidomethacrylate, dissolved in 48 g methyl methacrylate, 24 g photo initiator NP1.5

12 g photo initiator P5.1

dissolved in 24 g xylene (mixture of isomers) 11 g sodium lauryl sulfate, dissolved in 62.3 ml water, dispersed together in a further 770 ml deionized water.

Mix 6.2:

3 g Na ₂ S ₂ O ₈ (sodium peroxodisulfate), dissolved in 200 ml deionized water The copolymerization according to Example I.4 was repeated, but in each case mixture 6.1 instead of mixture 4.1 and mixture 6.2 instead of mixture 4.2 were metered in.

Then 100 g of polyester based on adipic acid and the polyhydric alcohols 2,2-dimethyl-1,3-propanediol and 1,2-propanediol, isononyl ester, dynamic viscosity: 2,300 mPa-s at 20 ° C (CAS -Number; 208945-13-5, b4), and 120 g VI.1

The properties of the formulation F.6 obtainable in this way are shown in Table 1.

Example I.7. Preparation of formulation F.7

The following mixtures were used:

Mix 7.1

300 g n-butyl acrylate, 400 g styrene, 80 g acrylonitrile, 5 g acrylamide, 10 g freshly distilled acrylic acid, 10 g ureidomethacrylate, dissolved in 48 g methyl methacrylate, 24 g photo initiator NP1.5

with Me = methyl,

12 g photo initiator P6.1 dissolved in 24 g xylene (mixture of isomers) 11 g sodium lauryl sulfate, dissolved in 62.3 ml water, all dispersed together in a further 770 ml deionized water

Mix 7.2:

The copolymerization according to Example I.4 was repeated, but in each case mixture 7.1 instead of mixture 4.1 and mixture 7.2 instead of mixture 4.2 were metered in.

Then 100 g of polyester (b4) and 120 g of VI.1

The properties of the formulation F.7 obtainable in this way are shown in Table 1.

Example I.8 Preparation of Formulation F.8

The following mixtures were used:

Mix 8.1

300 g n-butyl acrylate, 400 g styrene, 80 g acrylonitrile, 5 g acrylamide, 10 g freshly distilled acrylic acid, 10 g ureidomethacrylate, dissolved in 48 g methyl methacrylate, 24 g photo initiator NP1.5 with Me = methyl, 12 g photoinitiator P7.1

dissolved in 24 g xylene (mixture of isomers)

11 g of sodium lauryl sulfate, dissolved in 62.3 ml of water, together dispersed in a further 770 ml of completely deionized water

Mix 8.2:

The copolymerization according to Example I.4 was repeated, but in each case mixture 8.1 instead of mixture 4.1 and mixture 8.2 instead of mixture 4.2 were metered in.

Then 100 g of polyester (b4) and 120 g of VI.1

The properties of the formulation F.8 obtainable in this way are shown in Table 1.

Example I.9 Preparation of Formulation F.9 The following mixtures were used:

Mix 9.1

250 g n-butyl acrylate, 450 g styrene, 80 g acrylonitrile, 5 g acrylamide, 10 g freshly distilled acrylic acid, 10 g ureidomethacrylate, dissolved in 48 g methyl methacrylate, 24 g photoinitiator NP9

12 g photo initiator P2.1

dissolved in 24 g xylene (mixture of isomers)

Mix 9.2:

The copolymerization according to Example I.4 was repeated, but in each case mixture 9.1 instead of mixture 4.1 and mixture 9.2 instead of mixture 4.2 were metered in.

Subsequently, 70 g of isodecyl diphenyl phosphate (b5) and 120 g of a polyester acrylate, prepared according to EP 0 126 341 B1, example 1, were metered in over the course of 30 minutes via the separate metering devices. The mixture was then cooled to room temperature and filtered through a 250 μm network.

The properties of the formulation F.9 obtainable in this way are shown in Table 1.

Example 1.10 Preparation of formulation 1.10

The following mixtures were used:

Mix 10.1

250 g n-butyl acrylate, 450 g styrene, 80 g acrylonitrile, 5 g acrylamide, 10 g freshly distilled acrylic acid, 10 g ureidomethacrylate, dissolved in 48 g methyl methacrylate, 24 g photo initiator NP10 NP10

12 g photo initiator P2.1

dissolved in 24 g xylene (mixture of isomers)

Mix 10.2:

The copolymerization according to Example I.4 was repeated, but in each case mixture 10.1 instead of mixture 4.1 and mixture 10.2 instead of mixture 4.2 were metered in.

Subsequently, 70 g of isodecyl diphenyl phosphate (b5) and 120 g of a polyester acrylate, prepared according to EP 0 126 341 B1, example 1, were metered in over the course of 30 minutes via the separate metering devices. 6 g of N-methyldiethanolamine were then added, the mixture was cooled to room temperature and filtered through a 250 μm mesh.

The properties of the formulation F.10 obtainable in this way are shown in Table 1.

Example 1.11 Preparation of formulation 1.11

Mix 11.1

300 g of n-butyl acrylate, 400 g of styrene, 80 g of acrylonitrile, 5 g of acrylamide, 10 g of freshly distilled acrylic acid, 10 g of ureidomethacrylate, dissolved in 48 g of methyl methacrylate, 60 g of photoinitiator mixture, each in equal proportions by weight

12 g photo initiator P2.1

dissolved in 24 g xylene (mixture of isomers)

Mix 10.2:

The copolymerization according to Example I.4 was repeated, but in each case mixture 11.1 instead of mixture 4.1 and mixture 11.2 instead of mixture 4.2 were metered in.

Then 80 g of polypropylene glycol alkylphenyl ether, produced from polypropylene glycol and dimethylphenol isomer mixture, with a molecular weight M _{w of} around 450 g / mol (b6), and 400 g of polyurethane acrylate dispersion (solids content 40% by weight) were produced by the separate metering devices WO 98/47975, example “Dispersion 7”, page 9, wherein a polyester according to EP 0686621 A1, example 1a) had been used instead of Laromer LR 8945, was metered in over 30 minutes. The mixture was then cooled to room temperature and filtered through 250 μm network.

The properties of the formulation F.11 obtainable in this way are shown in Table 1. Table 1 Analytical data of the formulations according to the invention

II. Production of pigment printing pastes according to the invention (general rule)

2.1. Production of pigment preparations 2.1.1. Preparation of a blue pigment preparation In a stirred ball mill Drais Superflow DCP SF 12 were ground together: 1800 g Pigment Blue 15: 3 450 g nC ₁₈ H ₃ 7θ (CH ₂ CH ₂ O) ₂ 5H 3700 g distilled water

The milling was continued until the pigment particles had an average diameter of 120 nm. A blue pigment preparation was obtained.

2.1.2. Preparation of a Red Pigment Preparation In a Drais Superflow DCP SF 12 stirred ball mill, the following were ground: 1800 g Pigment Red 122 450 g nC ₁₈ H ₃₇ θ (CH ₂ CH ₂ O) ₂₅ H 3700 g distilled water

The milling was continued until the pigment particles had an average diameter of 120 nm. A red pigment preparation was obtained. 2.2. Processing of pigment preparation and formulation according to the invention into printing pastes

700 ml of fully demineralized water were placed in a beaker, a defoamer (0.5 g of 2,4,7,9-tetramethyl-5-decyne-4,7-diol) was added and 120 g of the respective formulation according to the invention were added with stirring 25 g of a conventional thickener were then stirred in (crosslinked copolymer of acrylic acid and acrylamide as water in an oil emulsion, 40% by weight solids content), followed by stirring with a high-speed stirrer for 8-10 minutes until the thickener had swelled 40 g of one of the pigment preparations described above were added, the pH was adjusted to a final value of 8.5 with ammonia, and finally the mixture was homogenized by stirring for a further 12-15 minutes and made up to 1 liter with deionized water in each case at about 70 d Pa-s (= 70 poise), measured with the Viscotester VT 02 from Haake Mess-Technik GmbH & Co., Karlsruhe, which resulted in smooth-looking, rapid, agglomerate-free Pigment printing paste DP.

Printing substrate: polyester / cotton blend

Printing: squeegee 8 mm, magnetic rebound 6, stencil gauze E 55

Drying: at 80 ° C in the drying cabinet

Fixation: UV-exposed prints (radiator: 2x120W / cm) at 250-450 nm with high UV-C content, 20m / min - one pass

To evaluate the prints, the brush wash was used according to DIN EN ISO 105-C07 (textiles - color fastness tests part C07: color fastness of wet, pigment-printed textiles against brushing (ISO 105-C07: 1999); German version EN ISO 105-C07-.2001 ,

The brushed pieces were measured colorimetrically before and after UV exposure (crosslinking). The faded uncrosslinked pigment printing strips were compared with the strong-color UV crosslinked pigment printing strips and the color strength was assigned relative to one another.

So-called photograms were also generated. This is an experimentally simple method to obtain meaningful values both about the quality of the uncrosslinked textile print binder and about the increase in quality and authenticity through radiation crosslinking. For this purpose, large-area printing was carried out using the method described above. The getrock _¬ designated pressure was then covered with green plant leaves decorative, flashed with a UV flash attachment (250-450 nm) 4x, then the tissues boiled 45 minutes by a detergent and then subjected to a Bürstwäsche. The exposed areas had a virtually unchanged color strength, judged visually after the washing process and the brush wash. However, the areas previously covered by the green leaves were paler to varying degrees after treatment. The photograms showed tone-on-tone patterns up to the approximate whitening of the areas covered.

Table 2: Textile printing examples with formulations F.1, F.2, F.4, F.8, F.11 according to the invention

Brush wash according to DIN EN ISO 105-C07: Assessment scale carried out with grades: very good, good, satisfactory, sufficient, deficient, insufficient

The relative color strength was determined as the ratio of brush wash without UV crosslinking: brush wash after UV crosslinking

Assessment scale: strong contrast, medium, low. The experiments were carried out with pigment red (Pigment Red 122) and pigment blue (Pigment Blue 15: 3). In both cases, the assessment was identical.

The textiles printed according to the invention did not tend to stick. III. Use in the coating of leather 3.1. Example of leather finishing:

3.1.1. Cow box dressing (upper leather)

A primer, UV-crosslinkable, was prepared as follows:

Pigment preparation according to Example 1, EP-A1 0 548 619 100 g

Formulation F.2 according to the invention 440 g

Filler and anti-adhesive according to Example 1, Z1 from EP-A2 0441 196 200 g

Water 260 g

BIT was used as the biocide in the pigment preparation and 2,4,7,9-tetramethyl-5-decyne-4,7-diol as the anti-foaming agent.

The primer (approx. 6 g wet application per area DIN A4) was sprayed onto a commercially available cattle wet blue, dried at 80 ° C. with circulating air, ironed (80 ° C., 100 bar); sprayed the primer again (approx. 4g wet application per area DIN A4), dried again with circulating air and ironed.

A finish according to the invention was prepared by mixing 300 g of formulation F.6 according to the invention, 110 ml of water and 100 g of an aqueous dispersion of a commercially available silicone wax (5% by weight).

The finish (2 times approx. 2 g wet application per area DIN A4) was sprayed onto the leather primed as described above, and then dried as described above. The subsequent two UV irradiations were carried out at 120W / cm, 10m / min, 250-450 nm. Leather 1 prepared according to the invention was obtained.

Application properties of leather 1 prepared according to the invention:

50,000 dry flexes without damage (based on DIN 53351)

20,000 wet flexes without damage (based on DIN 53 351)

1,000 wet rubs without damage (based on DIN.EN ISO 11640)

3.1.2. Example of a UV-crosslinkable finish for upper leather (cattle box) A primer was prepared from the following constituents: pigment preparation according to Example 1, EP-A1 0548619 150 g formulation F.2 according to the invention 150 g aqueous polyurethane preparation Z2 according to DE-A 40 17 525 300 g filler and anti-adhesive according to Example 1, Z1 from EP-A20441 196 100 g water 280 g The Grundieruπg (about 6 g of wet adhesive per area A4) was injected onto a commercially _¬ conventional bovine wet blue, dried at 80 ° C with air circulation, ironed (80 ° C, 100 bar); sprayed the primer again (approx. 4g wet application per area DIN A4), dried again with circulating air and ironed.

A finish according to the invention was prepared by mixing 300 g of formulation F.9 according to the invention, 110 ml of water and 100 g of an aqueous dispersion of a commercially available silicone wax (5% by weight).

The finish (2 times approx. 2 g wet application per area DIN A4) was sprayed onto the leather primed as described above, and then dried as described above. The subsequent two-fold UV irradiation was carried out at 120W / cm, 10m / min, 250-450 nm. Leather 2 prepared according to the invention was obtained.

Application properties of leather 2 prepared according to the invention:

45,000 dry flexes without damage (based on DIN 53351)

18,000 wet flexes without damage (based on DIN 53 351)

1000 wet rubs without damage (based on DIN.EN ISO 11640, without

Damage)

Leather 1 and 2 according to the invention did not tend to be sticky.

Claims

claims

1. A formulation comprising (a) at least one polymer or copolymer which has been prepared in the presence of at least one photoinitiator, (b) at least one plasticizer and (c) at least one branched compound having at least two terminal double bonds.

2. Formulation according to claim 1, characterized in that it is at least one polymer or copolymer (a) is a polymer or copolymer obtainable by emulsion polymerization or emulsion copolymerization.

3. Formulation according to claim 1 or 2, characterized in that a polymer or copolymer (a) is a polymer or copolymer which comprises at least 40% by weight, based on the respective polymer or copolymer, of so-called Main monomers is built up, main monomers being selected from compounds of general formula I.

unsaturated esters of the general formula II,

Vinyl aromatics of the general formula III,

unsaturated compounds of the general formula IV a and IV b

IV a IV b and non-aromatic hydrocarbons with 2 to 8 carbon atoms and at least one CC double bond, the variables being defined in the formulas as follows: R ⁴ , R ¹⁰ identical or different and selected from hydrogen and CC ₁₀ - alkyl, R ² , R ⁵ , R ¹¹ identical or different and selected from hydrogen and C ₁ -C ₁₀ alkyl, X identical or different and selected from halogen, CN and OR ¹² , R ³ , R ^e , R ² identical or different and selected from CC ^ alkyl, R ⁷ , R ⁸ , R ⁹ identical or different and selected from hydrogen and CC ₁₀ alkyl, k is an integer in the range from 0 to 3.

4. Formulation according to one of claims 1 to 3, characterized in that it contains water as a further component (d).

5. Formulation according to one of claims 1 to 4, characterized in that at least one photoinitiator is a hydrogen-emitting photoinitiator.

6. Formulation according to one of claims 1 to 5, characterized in that at least one photoinitiator is a photoinitiator copolymerized in at least one copolymer (a).

7. Formulation according to one of claims 1 to 6, characterized in that at least one plasticizer (b) is phthalic acid fully esterified with C 1 -C alkanol or adipic acid fully esterified with CC ₁₀ alkanol.

8. Formulation according to one of claims 1 to 7, characterized in that it is at least one branched compound (c) is a triol, tetraol or pentaol esterified several times with (meth) acrylic acid.

9. A process for the preparation of formulations according to any one of claims 1 to 8, characterized in that at least one plasticizer (b) is mixed with a dispersion which comprises: (a) at least one polymer or copolymer which is present in the presence of at least one photoinitiator was produced, (c) optionally at least one branched compound with at least two terminal double bonds and (d) optionally water.

10. Use of formulations according to one of claims 1 to 9 for coating fibrous substrates.

11. A method for coating fibrous substrates, characterized in that they are first treated with a formulation according to one of claims 1 to 9 and then exposed to actinic radiation.

12. The method according to claim 11, characterized in that the fibrous substrates are textile or leather.

13. The method according to claim 11, characterized in that it is a textile printing process.

14. Fibrous substrates obtainable by a process according to one of claims 11 or 12.