MXPA01001821A - Aqueous compositions of uv-active agents, their production and use - Google Patents

Abstract

Aqueous dispersions (U) containing:(A) a UV-light-absorbing textile treatment agent, (B) a dispersant system and (C) a carboxyl-containing cross-linked copolymer and optionally (D) at least one formulation additive, are useful for the corresponding UV-active finishing of textile material, in particular textile material which can be dyed with disperse dyes or optically brightened with disperse brighteners, especially for treating cheeses with liquors comprising disperse dyes and UV absorbers or liquors comprising disperse brighteners, without fear of troublesome pressure build-up or dye or brightener deposits.

Description

AQUEOUS COMPOSITIONS OF ACTIVE UV AGENTS, THEIR PRODUCTION AND USE DESCRIPTION OF THE INVENTION Textile material used in an environment in which ultraviolet (UV) light acts on the textile material, especially UV light that filters through the glass, by interior accessories in cars (carpets, belts, ornaments and covers of seats), stained glass or galleries under glass cover (wall to wall carpets), are advantageously finished with a UV absorber so that the fibers, especially synthetic and cellulose fibers, and the dyes also to a certain extent, can be protected against the damage of the action of UV rays. A preferred method for textile material used in an environment of filtered UV light involves applying the UV absorbers to the substrate, in particular to the yarns, together with the respective dyes or dyes. Since the threads, according to a technically preferred process, are dyed on packages, in particular cross coils, it is also desirable to apply the UV absorbers at the same time. Nevertheless, Ref: 127186 When the packages are stained with the dispersed dyes, a problem is that, in the presence of UV absorbers that have been formulated with surfactants, the liquors can, under the action of the high cut forces that occur in the cross coil, be altered in such a way that the dyes of the cross-coil do not become level, in particular due to the dyeing that is extracted by filtration, in such a way that the yarn when it is further processed, for example in knitted or woven fabrics, provides a appearance not leveled, or / and, if the dispersion changes in its flow behavior under the action of high shear forces, the liquor flow through the cross coils can gradually lead to an untimely development of pressure, which - especially depends on the quality of the yarn and type of winding - it leads to more pronounced changes correspondingly in the cutting forces in the package and can even lead to a complete stop of the flow of liquor through the package. The situation may be analogous with the use of dispersed brighteners or optical brighteners. EP-A-468921, 474595 and 490819 describe certain dispersions of the aqueous UV absorber containing UV absorbers and anionic surfactants or non-ionogenic and anionic surfactant compounds and also such dispersions which additionally contain polysaccharides or other linear polymeric compounds as stabilizers and / or thickening agents. EP-A-328485 discloses aqueous dispersions of certain dyes, optical brighteners or UV absorbers containing, in addition dispersants, an alkylene-bisamide defoamer and in some examples also certain linear polymers (polyvinyl alcohol or a block polymer 3000 oxide). propylene / ethylene oxide) or a polysaccharide. It has now been found, surprisingly, that by employing formulations containing (C) defined herein below, the problems described in the above can be solved or avoided, so that it becomes possible as a result also to process coils crossed with disperse tinctures and UV absorbing liquors or with disperse polishing liquors without fear of untimely pressure development or dye or brightener filtration tanks. The invention relates to the defined compositions, their production and their use. The invention of this form provides mainly aqueous dispersions (U) containing: (A) a textile treatment agent absorbing UV light (B) a dispersing system and (C) a crosslinked carboxyl-containing copolymer. The textile treatment agents (A) that absorb UV light are active UV agents, that is, their fundamental property is the absorbance of UV light, while they become visible wavelengths, as in the case of optical brighteners, or to become other forms of energy or other wavelengths, as is the case with typical UV absorbers. Thus, the active agents of UV (A) are in particular (Ai) UV absorbers or (A2) optical brighteners. Suitable UV absorbers (Ai) generally include known substances as are usually used for finishes that absorb UV light from synthetic or semi-synthetic textile fibers from an aqueous dispersion, especially those from the benzophenone, triazine or benzotriazole series. , in particular phenols bearing a substituent of the triazine, benzoyl or benzotriazole series in the ortho position relative to the hydroxyl group and which may carry additional substituents, in particular nonchromophoric and non-water soluble solubilizing substituents. Suitable UV absorbers of the benzophenone series generally include 2-hydroxybenzo-phenones in which the two benzene rings can optionally be substituted with customary substituents in UV absorbers, in particular non-chromophoric and water-free solubilising substituents, for example with hydroxyl, alkyl, alkoxy, aryl, aryloxy, aralkoxy or halogen, aryl (in aryl, aryloxy and aralkoxy) which is naphthyl or preferably phenyl, alkyl and alkoxy radicals containing for example 1 to 4 carbon atoms, phenyl as aryl which is optionally further substituted by alkyl, halogen and / or alkoxy, and halogen which preferably means chlorine, and the alkoxy bridge in aralkoxy containing for example 1 or 2 carbon atoms. Examples of 2-hydroxybenzophenones of the following formulas can be mentioned (I) wherein Ri means hydrogen, hydroxyl, phenoxy, aralkoxy or C? _4 alkoxy, R2 signifies hydrogen, halogen or C? _4 alkyl, R3 signifies hydrogen or hydroxyl, R4 signifies hydrogen, hydroxyl, phenoxy, aralkoxy or C? -4, Rs means hydrogen or C? _4 alkyl, Re means hydrogen or C? _4 alkyl and X means a hydrocarbon bridge member having 2 to 12 carbon atoms or hydroxyalkylene. In the compounds of the formula (I), R2 R3 and R4 each preferably means hydrogen, Ri preferably means hydrogen, hydroxyl, phenoxy or C1-14 alkoxy. In the formula (II), the two substituents R5 and R are advantageously in the ortho and para positions in the carbonyl group. Preferably, R5 and also Re mean hydrogen. When X means hydroxyalkylene, it advantageously contains at least 3. carbon atoms and the hydroxyl group is not advantageously linked to the first or last carbon atom of the bridge. X may, for example, mean 1,4-phenylene, 1,4-naphthylene or C 2-4 alkylene or also 2-hydroxy-1,3-propylene. The following may be mentioned in particular: 2-hydroxy-4-methoxybenzophenone, 2, -dihydroxybenzophenone, 2-hydroxy-5-chlorobenz-ofenone, 1,3-bis- (3'-hydroxy-4'-benzoyl phenyl) -2 -hydroxypropane. Suitable UV absorbers of the triazine series generally include 2- (2'-hydroxyphenyl) -s-triazines wherein positions 4 and 6 are replaced by hydrocarbon radicals which in turn can be further substituted, in each case the Substituents are neither chromophoric nor water solubilizers. The hydrocarbon radicals in the 4-position and the 6-position are for example aryl, alkyl or aralkyl, aryl which means, for example naphthyl or preferably phenyl, aralkyl preferably means benzyl and alkyl containing for example from 1 to 18 atoms of carbon. Substituents which occur in the phenyl rings are for example hydroxyl, halogen, alkyl, alkoxy or alkylthio low molecular weight, and the substituents which occur in the alkyl radicals are for example hydroxyl, alkoxy, alkylthio or dialkylamino of low molecular weight. Mention may be made, for example, of 2- (2'-hydroxyphenyl) -striazines of the following formula wherein R7 signifies hydroxyl, halogen, C? _4 alkyl or C? _4 alkoxy, Rs signifies C? -18 alkyl, which is optionally substituted by hydroxyl, halogen, C? _ alkoxy, C? _ alkylthio. di- (C? -) -no-alkyl, or phenyl, which is optionally substituted with hydroxyl, halogen, C? _4 alkyl or C? -4 alkoxy, Rg means Ci-ig alkyl, which is optionally hydroxyl, halogen, C? _ alkoxy, C? -4 alkylthio or di- (C? -4) -amino alkyl, or phenyl, which is optionally substituted with hydroxyl, halogen, C? _4 alkyl or alkoxy C? -4, and m means 0, 1 or 2.

The alkyl radicals that occur may be linear or, if they contain three or more carbon atoms, they may also be branched or, if they contain six or more carbon atoms, they may also be cyclic. R7 preferably represents chlorine or alkyl C1-4. When m means 2, the two substituents R may have the same or different meanings, where the latter case is preferable for the second R7 to signify methyl. When m means 1 or 2, one of R is preferably in the para position relative to the 2-position of the hydroxyl group. Mention may be made, by way of example, of 2- (2'-hydroxyphenyl) -striazine wherein R 8 and Rg have the same meaning and each means propyl or t-butyl, 4,6-dimethyl-2- (2'-hydroxy-5'-chloro-, -methyl- or -t-butyl-phenyl) -s-triazine , 4, 6-dimethyl-2- (2 '-hydroxy-4', 5 '- or -3', 5'-dimethyl phenyl) -s-triazine, 4,6-diethyl-2- (2'-hydroxy) -4 ', 5'-dimethyl-ilphenyl) -s-triazine, 4,6-diphenyl-2- (2'-hydroxy-4'-methoxy-, -ethoxy-o -isopropyl-phenyl) -s-triazine.

Suitable UV absorbers of the benzotriazole series generally include 2- (2'-hydroxy-phenyl) -benzot riazoles wherein two benzene rings can optionally be substituted in particular with customary substituents in UV absorbers, in particular solubilizing substituents non-chromophoric and water-free, for example, hydroxyl, alkyl, alkoxy, aryl, aralkyl, alkylaryl, alkoxycarbonyl or halogen, aryl meaning naphthyl or preferably phenyl, alkyl radicals containing, for example, from 1 to 12 carbon atoms, alkoxy radicals containing for example from 1 to 4 carbon atoms, phenyl as aryl which is optionally further substituted with halogen, C? - and / or C? _4 alkoxy and halogen which preferably means chlorine. Mention may be made, for example, of 2- (2'-hydroxyphenyl) -benzotriazoles of the following formula wherein Rio means C? _? ?alkyl, C? _5alkoxy, aryl, aralkyl, (C? _?) alkyl-aryl, (C? _5) alkoxycarbonyl or halogen, and rings A and B are each optionally substituted with one or more of their hydroxyl components, C ?5 alkyl, C ?5 alkoxy, C ?5 alkoxycarbonyl or halogen, and B may also carry an alkyl radical of C? -? 2 in the ortho position to the hydroxyl group. The alkyl radicals that occur may be linear or, if they contain three or more carbon atoms, they may also be branched, or, if they contain six or more carbon atoms, they may also be cyclic. Aralkyl preferably means benzyl. Halogen preferably means chlorine. In the ring B, the position 6 is preferably unsubstituted; in the benzotriazole ring, positions 4 and 7 are preferably unsubstituted. The preferred UV absorbers of the benzotriazole series make up for the formula wherein R 'is hydrogen, C1-5 alkyl, C1-5 alkoxy, (C5-5) alkoxycarbonyl or chloro, R "means hydrogen or chlorine, R "'means hydrogen, C? _2 alkyl, phenyl, (C 1-5 alkyl) -phenyl, benzyl or chloro, R "" signifies hydrogen, hydroxyl, C 1-5 alkyl, C 1 5 alkoxy or chloro, and Rio 'means C 1 _ 2 alkyl, alkoxy C? _5, phenyl, (C 1-5 alkyl) -phenyl, benzyl, (C 1-5 alkoxy) -carbonyl or chloro, especially for the formula wherein R 1 is C 1-5 alkyl, C 1-5 alkoxy or chloro, preferably C 1 _ 5 alkyl, R 1 'denotes hydrogen, chloro, C 1-5 alkyl or C 1-5 alkoxy, preferably hydrogen or alkyl of C _, and Ro "means hydrogen, chlorine, C 1-5 alkyl or C 1-5 alkoxy, preferably hydrogen, chlorine or methyl, there may be mentioned by way of the example: 2- (2'-hydroxy-5 '- methyl phenyl) -benzotriazole, 2- (2'-hydroxy-3 ', 5'-dimethylphenyl) -benzotriazole, 2- (2'-Hydroxy-5'-t-butylphenyl) -benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2 ') -hydroxy-3 ', 5'-di-t-butylphenyl) -benzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) -5-chlorotriazole, 2'- (2'- hydroxy-3 ', 5'-di-t-amylphenyl) -benzotriazole. Useful optical brighteners (A2) are generally known substances of the type usually used for the optical brightener of synthetic and cellulosic textile fibers from an aqueous dispersion, in particular those of the coumarin, naphthalimide, benzoxazole, stilbene, bis-type series. it is irilbenzene, thiophene or pyrene and can carry any usual substituents in optical brighteners, especially non-chromophoric and water-free solubilizing substituents. Suitable optical brighteners (A2) are for example those of the following formulas (V) to (XI) R. wherein R n means C? -4 -4 alkyl, Ri 2 means C 1 -4 alkyl and R 13 means hydrogen or C? -4 alkoxy, wherein Ri 4 means hydrogen, chloro or C 4 alkyl, R 15 means hydrogen or C 1-4 alkyl, Y means a radical of the formula (a) (b).

Ri6 means hydrogen or C1-4 alkyl, R? means hydrogen, chloro or C alquilo _4 alkyl, Ríe signifies -CN, (C? -4) alkoxycarbonyl, phenyl or a radical of the formula Rig means C 1-4 alkyl and Z means -CH = CH-, 3,4-thiophenylene or 1,4'-naphthylene, j5 ~ CH = CH- CH = CH- -CH = CH-R-0 (VII), wherein R20 means -CN or (C? -4) alkoxycarbonyl, where R2? means hydrogen, chlorine, -CN or alkyl Cl-4, wherein R22 means 1-pyrazolyl which is substituted with chloro or C alquilo _ alkyl at the 3 or 4 position, or means phenyl and R23 means 2-triazolyl or 1-pyrazolyl which are substituted with C? _ alkyl and / or phenyl, or means 2-naphthotriazolyl, wherein R24 means C alquilo _ alkyl and R 25 means C alquilo _ alkyl. The dispersing system (B) is used to disperse the active UV textile treatment agents (A) in water and therefore contain suitable, appropriate surfactants and optionally suitable auxiliaries. (B) in this manner conveniently consists of (Bi) at least one surfactant and optionally (B2) at least one dispersing aid.

The surfactants (Bi) are suitable surfactants to disperse (A) in water and therefore have dispersing characteristics; they also include inerts such surfactants as are known in the art also as emulsifiers. Advantageously, anionic and / or (B12) non-ionogenic dispersants are used as (Bi) (Bu) dispersants. Any anion-active surfactants having dispersing or emulsifying properties, in particular compounds of distinctly anionic character, containing at least one lipophilic radical, in particular at least one lipophilic hydrocarbon radical, and at least one group can be used as (Bu) distinctly anionic (sulfo group, phosphoric acid group or carboxyl group), the lipophilic hydrocarbon radical advantageously contains at least 9 carbon atoms, for example 9 to 30 carbon atoms. The following may be mentioned by way of example: condensation products of formaldehyde with sulfonated aromatic compounds (for example sulfonated naphthalene, mono- or di- (C1-) alkyl-naphthalene, biphenyl, diphenylether, ditolylether, phenol, C1-alkylphenol -4 and / or corresponding sulfones) and / or with ligninsulfonate, optionally in a mixture with dihydroxydiphenylsulfone; ligninsulfonates; Ci2-24 alkyl sulfonates; paraffin sulphonation products (prepared for example by sulfoxidation or sulfoxidation), of α-olefins, of alkylbenzenes and of unsaturated fatty acids; fatty acid salts of C? 2-24; esterification products of non-ionogenic surfactants as described below, in particular of oligoetyl glycol ethers of fatty alcohols, alkylphenols or di-otr-isophenylphenols, with sulfuric acid, phosphoric acid or aminosulfonic acid, or alkylation products of the non-ionogenic surfactants mentioned with chloroacetic acid or chloropropionic acid, to form the corresponding esters or carboxymethylated or carboxylated products. The anionic surfactants are advantageously present, at least partially, in the form of salts, mainly in the form of alkali metal salts (preferably sodium or potassium salts) or ammonium salts. It is possible to use simple compounds or also mixtures of compounds, which especially include mixtures of technical grade.

They can be used as non-ionogenic surfactants (Bi2) those that act directly as emulsifiers or dispersants or that are also used as cosuritants for (Bu). Generally known substances are suitable, especially those containing from 9 to 30, preferably from 12 to 24, carbon atoms in the lipophilic portion, or also those having an oligomeric or polymeric basic structure, and whose hydrophilic moieties contain ethylene glycol radicals, glycerol radicals and / or sorbitan radicals. Examples may be mentioned: Adducts of ethylene oxide for fatty alcohols, alkylphenols, di- or tri-es-t-ylphenols, novolans or N, N-diethanolamide of fatty acid or diisopropanolamide.; fatty acid monoesters of polyethylene glycols. The polypropylene glycol chains can occasionally also be present in the molecule as lipophilic radicals, and therefore the non-ionogenic surfactants used can also comprise block copolymers containing propyleneoxy and ethyleneoxy units, and also optionally styrenoxy and / or butyleneoxy units (eg example those known under the designation "Pluronic"). Non-ionogenic surfactants are advantageously selected in such a way that they can present an adequate dispersing action in (A). The HLB value of the non-ionogenic surfactants is advantageously > 10, preferably in the range of 12 to 18, while those having an HLV value of > 15, preferably > ^ 16, can also be used as protective colloids. Dispersants can, for example, be used (Bu) alone [ie without (B? 2)] or (B? 2) alone [ie without (Bu)] or mixtures of (Bu) and (Bi2). Preferably, at least one non-ionogenic surfactant (B? 2) is used either as a dispersant or, when (Bu) is used as a dispersant, also as a cosurfactant for (Bu). The weight ratio of (Bu) to (B? 2) in this is for example in the range of 30/70 to 95/5, preferably 40/60 to 90/10. To disperse (A) in water, an appropriate amount of (Bi) is advantageously selected, which may vary according to the class of the components and their concentration. The weight ratio of the total dispersants (Bi) to (A), ie from [(Bu) + (B? 2)] to (A), is advantageously in the range of /100 to 150/100, preferably 6/100 to 80/100, particularly preferably 10/100 to 70/100. When (B? 2) is used as a cosurfactant for (Bu), the weight ratio of (B? 2) / (Bn) is advantageously 1/100 to 40/100, preferably 5/100 to 20/100.

Preferably, (Bx) includes at least one polymeric surfactant, especially at least one of the aforesaid condensation products of formaldehyde with sulfonated aromatics or at least one of the above-mentioned block copolymers containing propyleneoxy and ethyleneoxy units and optionally also units of styrenoxy and / or butyleneoxy. Dispersing auxiliaries (B2) can be used so that the dispersing effect of (Bi) can be sustained and / or the appearance of the dispersion improved. As (B2) there are particularly values mentioned: (B2?) Protective colloids, (B22) wetting agents (B23) solubilizers and / or (B2) dispersion stabilizers Polymeric protective colloids (B21) can be used if desired. , preferably (B2i) is at least one non-ionogenic and / or anionic protective colloid. Known substances are suitable as polymeric protective colloids (B21), which - in contrast to the high hydrophilicity surfactant protective colloids mentioned above under (Bi2) - they have the character of polymers capable of forming a protective cut around the dispersed colloidal particles. Mainly there are polyvinylpyrrolidones, polyvinyl alcohols, copolymers of N-vinylpyrrolidone and vinyl acetate or propionate, polyethylene glycols having for example an average molecular weight in the range of 300 to 10,000 or carboxymethylcellulose. Among the protective colloids (B2?), Preference is given for the only non-ionogenic ones. Advantageously, a protective colloid (B2?) Is used. The weight ratio of (B2?) / (A) is, for example, in the range of 1/100 to 200/100, preferably 2/100 to 150/100. (B22) can be any wetting agent known per se, preferably at least one non-ionogenic or anionic wetting agent. As non-ionogenic wetting agents, surfactants of the above-mentioned categories are generally considered, which, however, have a correspondingly lower HLB value or contain a correspondingly lower number in order to add ethyleneoxy units. Suitable anionic wetting agents are, for example, mono- and dialkyl esters of sulfosuccinic acid. The anionic groups, analogously as described in the above for (Bu), it can advantageously be present as alkali metal salts or ammonium salts. The use of wetting agents (B22) is possible, however, very effective dispersions can be prepared even without wetting agents. If a wetting agent is used, the weight ratio of (B22) / (A) is, for example, £ 10/100, for example in the range from 0/100 to 5/100. Solubilizers (B23) may be used if desired or required, in particular non-ionogenic solubilizers, for example mono-, di- or oligoethylene glycols or their mono- or di- (C? -4 alkyl) ethers or glycerol. A solubilizer (B23) can optionally be used, if desired. However, very good dispersions can be prepared even without a solubilizer. If a solubilizer is used, the weight ratio of (B23) / (A) is advantageously £ 10/100, for example in the range of 1/100 to 8/100. A dispersion stabilizer (B24) can be added, if desired. By the addition of a dispersion stabilizer (B24) the storage and transport stability of (U) can optionally also be influenced. Suitable dispersion stabilizers (B24) are, for example, polysaccharides, polysaccharide derivatives, acids (co) poly- (meth) acrylics and also such thickening substances when they are also useful as protective colloids, for example xanthan gum, cellulose gum, guar gum, dextrins, gum arabic, carboxy-methylcellulose, modified acrylic polysaccharides, and also the polyvinyl pyrrolidones and / or polyvinyl alcohols or polyethylene glycols mentioned in the foregoing, for example with an average molecular weight in the range of 200 to 6000. Advantageously, the acid groups, particularly the carboxylic acid groups, are at least partially present in the the salt form (so that the respective products are soluble in water), for example as alkali metal salts (mainly sodium salts). When thickeners are used, they are advantageously used in such quantities that the viscosity of the aqueous concentrated dispersion is < 1000 mPa's, in particular in values £ 300 mPa's, preferably in the range of 50 to 200 mPa's. The weight ratio of the dispersant system (B) to (A) total is for example in the range of 5/100 to 250/100, advantageously in the range of 10/100 to 150/100, preferably in the range of 50/100 to 150/100.

The dispersing system (B) serves to disperse (A) and consists essentially of the components (Bi) mentioned and optionally (B2), ie at least one surfactant (Bu) or (B? 2) having dispersing properties, wherein (B? 2) can optionally also serve as co-surfactant a (Bu), and optionally additional, dispersing auxiliary substances (B2i), (B22), (B23) and / or (B24). The copolymer (C) is a carboxyl-containing monomer and a cross-linked comonomer. It may be prepared in a conventional manner per se, by copolymerization of corresponding monomers containing an ethylenic double bond, of which at least a portion are carboxyl-containing monomers and at least one portion is a cross-linking comonomer. The non-ionogenic comonomers may also have been incorporated into the polymer, if desired. The carboxyl-containing monomers are advantageously monomers containing at least two carboxyl groups and 4 to 6 carbon atoms and are preferably used as anhydride, especially as cyclic dicarboxylic anhydride, for example itaconic acid or especially maleic acid or its anhydride respectively. The preferred monomers or comonomers for preparing (C) are in particular (Ci) maleic acid or maleic anhydride, (C2) at least one non-ionogenic monoethylenically unsaturated comonomer and (C3) a cross-linking comonomer. Comonomers (C2) which are particularly suitable are low molecular weight comonomers, in particular alkyl methacrylates, wherein alkyl advantageously contains 1 to 4 carbon atoms and preferably is methyl or ethyl, alkylvinylethers wherein alkyl advantageously contains 1 to 4 atoms. of carbon and preferably is methyl, vinyl esters of aliphatic carboxylic acids of low molecular weight, in particular those having 2 to 4 carbon atoms, mainly vinyl acetate, and / or vinylpyrrolidone. Suitable crosslinking comonomers (C) are especially non-ionogenic compounds containing at least two mutually unconjugated ethylenic double bonds, advantageously at least two terminal double bonds, for example N, N'-methylen-diacrylamide, a,? alkanedienes having 5 to 12 carbon atoms or divinyl ethers of α, β-alkanediols having, for example, from 2 to 12 carbon atoms in the alkane or polyethylene glycol portion, or also divinylbenzene. Of the aforementioned crosslinking comonomers, α, α-alkanedienes are preferred.

The molar ratio of (Cx) / (C2) / (C3) is advantageously in the range of 1 / (0.2 -3) / (0.001-0.1), preferably 1 / (0.5-1.8) / (0.004- 0.04) . The copolymers (C) are known or can be prepared analogously for known methods, conveniently in the presence of a suitable free radical polymerization initiator [e.g. azobisisobut ironi taryl, benzoyl peroxide, acetylbenzoyl peroxide, di-t peroxide -butyl, t-butyl peroxy-pivalate, azobis- (2,4-dimethyl-valeronitrile), for example in concentrations of 0.001 to 1%] and advantageously in the presence of a suitable aprotic solvent, for example benzene, toluene, xylene , acetone, methyl ethyl ketone, methylene chloride, cyclohexane and / or ethyl acetate; it is particularly advantageous to use a mixture of cyclohexane and ethyl acetate. The polymerization is advantageously carried out at temperatures in the range of 50 to 100 ° C, preferably of 60 to 80 ° C. The production of the polymer is advantageously carried out in such a way that the crosslinking is carried out at least intramolecularly in part, especially in such a way that the linear sequence of the monomers forms loops in the course of the polymerization due to the monomer (C3) of copolymerized crosslinking. Since the monomer that contains carboxyl, especially (Ci), is advantageously used in the form of the anhydride, especially maleic anhydride, the polymer (C) prepared therefrom still contains the anhydride groups. This polymer (C) may if desired, after completion of the polymerization and removal of the solvent, be hydrolyzed to the carboxyl-containing polymer (C) in salt form. In a preferred process, this hydrolysis is carried out in the presence of at least a portion of the surfactants (Bi). The polymers (C) and (C) can be produced, for example, by the process described in United States Patent 5024779; the contents of this United States patent is incorporated herein by reference. The dispersions (U) of the invention can be produced by mixing (C) with the other components in an aqueous medium, and preferably by grinding. It is advantageous to preload water and at least a portion of the components (Bi) and add the other components thereto; the component (C) can be added before or also after grinding and optionally even after an optional dilution with water and / or optional addition of other components. Preferably, the component (C) is added before component (A). In a preferred process, (C) is added before (A) and hydrolyzed in the presence of a base (for example alkali metal hydroxide) so that (C) is formed therefrom in the corresponding salt form, and then they are mixed in the additional components (A) and optionally (B) and optionally additives (D) of the remaining formulation. The weight ratio of (C) / (A) is for example in the range of 0.1 / 100 to 15/100, advantageously in the range of 0.1 / 100 to 5/100, preferably in the range of 0.2 / 100 to 2/100. The amount of water used is in principle freely eligible; Advantageously, sufficient water is added for the dispersion which is agitable or pourable or pumpable respectively. During grinding, the amount of water present in the dispersion is advantageously such that the concentration of (A) in (U) is, for example, from 2 to 50% by weight, preferably from 5 to 45% by weight. Further dilute dispersions are for example application liquors and existing dispersions which may optionally also contain other application-prescribed additives. The concentrate to dilute dispersions can thus be produced, for example those having a content (A) in the range of 0.01 to 50% by weight. In application liquors, the concentrations (A) are, for example, from 0.01 to 20% by weight, preferably from 0.05 to 1% by weight, in existing dispersions, for example from 0.1 to 20% by weight, preferably from 0.5 to 10%. by weight, in concentrated dispersions for example from 2 to 50% by weight, preferably from 5 to 40% by weight. Concentrated dispersions (U) are a particular aspect of the invention. The relative amount of the respective components and the amount of water used are advantageously chosen so that even the concentrated dispersion (U), in particular, are those in which the content of (A) + (B) + (C) is advantageously in the range of 10 to 70, preferably 20 to 60% by weight. By the addition of suitable bases (for example of alkali metal hydroxide or carbonate and / or of an amine as described above for the formation of salt) or / and acids (for example of a mineral acid, such as hydrochloric acid) , sulfuric acid and phosphoric acid, or a low molecular weight aliphatic carboxylic acid, for example having from 1 to 4 carbon atoms) and optionally with salts buffers, in particular salt of mono- and / or di-sodium phosphoric acid and / or potassium salt, the pH of the dispersion can be adjusted, for example to values in the range 3.5 to 8.5, advantageously 3.5 to 7, of 4 to 6 preference. Other formulation additives (D) can be used if desired, to further adapt the properties of the dispersions (U) to particular requirements or desired in relation to transport, storage and / or use. Such additives are in particular at least one of the following: (Di) a defoamer (D2) an agent to protect against the damage of microorganisms and / or (D3) a dye. Any defoamers are suitable as (Di), for example paraffins or mineral oils in dispersed form, silicone defoamers, silica, eti lenbi sest aramid and / or mixtures of two or more thereof. In particular, commercially available products can be used. The amounts of defoamers that can be used in the compositions of the invention are in the conventional ranges per se and are generally dependent on the nature and amount of the surfactants. In In general, very small amounts of defoamer are sufficient, for example, 1% by weight based on the total aqueous composition (U). As components (D2), known substances are generally suitable, essentially fungi-or bacterial substances and / or microbicides, as are commercially available, and the concentrations used can conform to those recommended by each, for example, 1% by weight based on the total aqueous dispersion (U). If (A2) is used as (A), that is to say an optical brightener, a component (D3) can also be used. (D3) is advantageously a dispersed dye of the type generally usable for shading dispersed brighteners. Disperse dyes are a generally known category of dyes and are known in the art and described extensively in the technical literature, for example in the Color Index. Suitable components (D3) include any disperse dyes having a suitable color for shading optical brighteners, for example blue, violet and red scattered dyes. They are advantageously added in low concentrations, for example £ 0.1% by weight based on (A2), when it is generally sufficient for, for example, a yellowish form, The brownish or brown color of the substrate can be partially compensated or / and a, for example, semi-greenish color of the optical brightener, which can become evident at a certain concentration of application, can be balanced and thus the visual impression created by the optical brightener can be improved. The content (A) of the concentrated aqueous dispersions (U) is, for example, in the range from 2 to 50% by weight, advantageously from 5 to 45% by weight, preferably from 10 to 40% by weight. The water content of the concentrated aqueous dispersions (U) of the invention is advantageously in the range of 90 to 30%, preferably 70 to 33%, by weight. The dispersions (U) of the invention can be produced as described above, in particular with grinding, in which case the aid of suitable mills, for example ball mills or mills of beads or beads (glass or porcelain beads) , the dispersed particles can be milled to a particle size of desirable fineness, and, if desired, a portion of the components, particularly water-soluble or water-dilutable components, particularly for example a protective colloid (Bi) , a solubilizer (B23), a component (D2) and / or (D3), may also not be mixed until after grinding. The average particle size of the particles dispersed in the dispersions (U) of the invention is advantageously in the range of 0.05 to 10 μm, preferably 0.2 to 6 μm, particularly preferably 0.4 to 4 μm. Preferably, the dispersions are filtered through a suitable screen or a suitable filter such that the dispersed particles are not larger than 20 μm, preferably not larger than 10 μm, particularly preferably not larger than 6 μm . The aqueous (U) dispersions prepared in this form, even the concentrated dispersions, are surprisingly stable and flowing. The concentrated dispersions have in particular a viscosity which is < 1000 mPa's; preferably, they have a viscosity in the range of 20 to 300, preferably 50 to 200, mPa's. They can be handled, stored and / or processed and can also be used directly by measured addition, in this way they have been prepared. They are remarkable for the surprisingly good stability in storage and transport. The dispersions (U) of the invention serve for the corresponding UV active finishing of textile material, in particular textile material which can be dyed with dispersed dyes or optically brightened with dispersed brighteners. The suitable textile material includes, in particular, textile material composed of synthetic and semi-synthetic materials, mainly polyester., polyamides, polyurethanes and cellulose acetates, and also fiber mixtures comprising such synthetic or semi-synthetic materials (for example polyester / cotton, polyester / viscose, polyester / cotton / pitch). The textile material may be in any desirable processed state, suitable for the particular application, for example in the form of loose fibers, filaments, yarns, skeins, fabrics, embroidery, carpets, ready made and semi-made goods. Particular preference is given to use the dispersions (U) of the invention in the dyeing of HT (high temperature) of yarns, which are wrapped in packages, especially in the form of cross coils, or in optical brightening by the processes of HT or thermo-colloids. The dispersions (U) of the invention are highly compatible with disperse dyes (F) and, when (A) is a UV absorber (Ai), they are advantageously formulated together with a dye (F) dispersed suitable to form an aqueous liquor which includes both the disperse dye (F) and the UV absorber (Ai). The dispersed tincture (F) can be any dispersed tincture or desired dispersed tincture mixture as used in another way by the dyeing of synthetic or semi-synthetic textile material. Disperse dyes are generally known and extensively described in the technical literature, for example in the Color Index under the heading "Disperse Dyes". Disperse dyes are generally formulated with suitable dispersants so that they can be dispersed in the dye liquor; the dispersants used for this purpose are usually anionic and optionally non-ionogenic dispersants, for example as described under (Bi). Disperse dyes formulated in this manner usually include from 30 to 60% of the dye and from about 70 to 40% by weight of the dispersant in addition, optionally, traces of by-products. When (A) is an optical brightener (A2), dyeing will generally not be used at all or dyeing will be employed as described under (D3) for mat i zar.

The concentrations of tinctures (F) in the respective liquor can vary without wide limits, depending on the substrate, the choice of the dyeing method and the choice of the depth of the hue. The concentration of (U) in the liquor is generally dependent on the nature and content of (A) and the desired UV active effect. The concentrations are used, for example, in such a way that the concentration of (Ai) based on the substrate is in the range of 0.1 to 4% by weight, preferably 0.2 to 2% by weight. The concentration of (A2) based on the substrate is advantageously chosen to obtain a good white effect and can also vary according to the substrate, method of application and constitution of (A2); this is for example within the range of 0.01 to 4%, advantageously 0.05 to 3%, preferably 0.1 to 2% by weight. The liquor pH is advantageously in the range of clearly acid to almost neutral, for example in the pH range of 4 to 6.5, preferably 5 to 6. The liquors can be applied to the textile material by conventional methods, for example by extraction processes or impregnation processes, and in appropriate, appropriate liquor lengths and temperature conditions. For impregnation processes, the Liquors can be applied to the substrate by customary methods, for example, by filling, wetting or spraying, and the impregnated substrate, optionally after intermediate dyeing, can then be heat set at elevated temperature, for example in the range of 150 to 220 ° C. , in which case a suitable fixing temperature can be chosen according to the material (for polyester for example from 160 to 220 ° C, for other synthetic fibers and for semi-synthetic fibers for example from 150 to 180 ° C). For short extraction processes or large liquors may also be employed, for example liquor ratios to genera in the range of 2: 1 to 100: 1, usually from 3: 1 to 60: 1. For HT processes and especially for the preferred treatment of cross coils, liquor ratios are preferred to genders of 4: 1 to 40: 1, in particular 5: 1 to 20: 1; the temperatures can also vary as desired in the respective suitable ranges, for example from 95 to 180 ° C, the HT conditions are preferred, for example in the range from 105 to 180 ° C, preferably > 125 ° C, for example in the range of 125 to 135 ° C. For dyeing or optically brightening the cross coils, according to a preferred method the packages are immersed within the liquor or they have the liquor poured on them and then the liquor is pumped through the cross coil (from inside to outside or vice versa or alternatively) during the total dyeing time. As the liquor is pumped through the package, the temperature increases slowly, for example at a rate of 0.5 to 5 ° C per minute, preferably from 1 to 4 ° C per minute, until the desired dyeing temperature is reached (HT conditions), where the dyeing can be carried out for example from 20 to 60 minutes, and then it is slowly lowered again , for example at a speed of 1 to 10 ° C per minute, preferably 2 to 6 ° C per minute. The upstream of the overpressure of the package can be, for example, in the range of 0.02 to 0.5 bar, preferably 0.5 to 0.2 bar, while the dispersions (U) of the invention are used, especially the only ones preferred - practically no Pressure development is carried out during the dyeing or full polishing operation. In the following Examples, the parts are parts by weight and the percentages are percentages by weight; temperatures are reported in degrees Celsius; the dispersed dyes and optical brighteners employed in the Examples are commercially available products containing about 50% pure tincture or pure brightener and approximately 50% dispersant; the other additives, apart from the products of Examples 1 to 5, are commercial products. The product (C3i) used in the Examples is a copolymer of maleic anhydride, methylene vinyl ether and 1, 9-decadiene in a molar ratio of 1: 1: 0.0125, prepared analogously for example 1 of United States patent 5024779, which as a 0.5% aqueous suspension at pH 7.0 has an average particle size < 75 μm and a viscosity of rotation of 45000 to 70000 mPa's (spindle No. 7, 20 rpm).

Example 1 In 219.4 parts of demineralized water, 478.8 parts of 29.9% aqueous solution of a condensation product of ditolyl ether sulfonate and formaldehyde, consisting of 143.2 parts of dry substance and 335.6 parts of water, 13.1 parts of the addition product are added. of 8 moles of ethylene oxide with 1 mole of tridecyl alcohol, 2.2 parts of the product (C3i) and 3.3 parts of a 30% sodium hydroxide solution, and it is agitated. After 60 minutes, they are stirred in portions of sodium diacid phosphate, part of an 85% aqueous phosphoric acid solution, adduct parts of 40 moles of ethylene oxide to 1 mole of C? 4-? 8 fatty alcohol, parts of an ethylene oxide / propylene oxide block polymer (adduct of ethylene oxide and propylene oxide to polypropylene glycol, having 50% ethyleneoxy units, and wherein the propyleneoxy fraction has a base at the molecular weight of 1700-2400) parts of 2- (2'-hydroxy-3'-t-butyl-5'-me tyl) -5-chlorobenzothiazole. In this suspension, they are milled in a pearl or bead mill with glass beads, while maintaining the pH at 5.5-6.0 by the portionwise addition of an 85% aqueous phosphoric acid solution. The pearl grind is terminated when the particle size is < 2.2 μm. After the glass beads have been extracted by separation, they are added and mixed in 2. 4 parts of a commercially available fungicide (GivGard DXN). The resulting dispersion has a viscosity of 90 mPa's (Brookfield DV-1) and is storage stable.

Example 2 A UV absorbent composition is produced analogously as described in Example 1 using, instead of the 250 parts of 2- (2'-hydroxy-3'-t-butyl-5'-methyl) -5-chlorobenzotriazole , 250 parts of the UV absorber of the formula A stable dispersion is obtained Example 3 A brightening composition is produced analogously as described in Example 1 using, instead of the 250 parts of 2- (2'-hydroxy-3'-t-butyl-5'-methyl) -5-chlorobenzotriazole, 100 CI optical brightener parts Fluorescent Brightener 330. A stable dispersion is obtained.

Example 4 The polishing preparation of the following composition is produced analogously to the procedure described in Example 1: 20 parts of C.I. Fluorescent Brightener 135. 3 parts of polyethylene glycol ether de novolak having HLB = 14 3 parts of C13-16 alkanesulfonate 0.2 parts of product (C31) 0.4 parts of a commercially available defoamer 0.2 parts of fungicide (GivGard DXN) and 63.1 parts of water are pearls or ground beads until a uniform fine suspension has formed, and then mixed with 0.1 part of CI Disperse Blue 73 and 10 parts of molecular weight polyethylene glycol = 600 stirring until a uniform dispersion has formed.

Example 5 The polishing preparation of the following composition is produced analogously to the procedure described in Example 4: 24 parts of C.I. Fluorescent Brightener 199, 6 parts of nonylphenol decaethylene glycol ether 6 parts of polyethylene glycol of molecular weight = 600 4 parts of polyvinylpyrrolidone 0.2 parts of product (C3?) 0.4 parts of a commercially available defoamer 0.2 parts of fungicide (GivGard DXN) and 59.2 parts of water, which are milled in a pearl mill until a uniform suspension has been formed. The table below lists the percentage of the composition of additional aqueous dispersions of the invention which are preparable in a similar manner to the Example 4. The numbers reported for each component are percentages in the respective aqueous dispersion.

The products used in Examples 6-33 below are as follows: AIA UV absorber of the formula AIB absorber: 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole A2A C.I. Fluorescent Brightener 135 A2B C.I. Fluorescent Brightener 179 A2C C.I. Fluorescent Brightener 330 A2D C.I. Fluorescent Brightener 199 B? 2B phenolic novolak-polyethylene glycol methylated ether, with HLB 14 C3? as defined in the above B24A copolyvinyl pyrrolidone / vinyl propionate (average molecular weight Mw = 750000) B24B polyvinylpyrrolidone (average molecular weight Mw = 30000) B24c polyvinyl alcohol having residual acetyl content of 10.7% (viscosity of 4% aqueous solution at 20 ° C = 4 cP - according to DIN 53015) B 4D polyvinyl alcohol having residual acetyl content of 10.7% (viscosity of 4% aqueous solution at 20 ° C = 8 cP - according to DIN 53015) BIIA alcansul fonato de C? 3-? S (sodium salt) B? 2A addition product of 8 moles of ethylene oxide with 1 mole of isoundecanol BuB condensation product of dialkylnaphthalene sulfonate formaldehyde (sodium salt) B2IA polyethylene glycol 600 B2iB polyethylene glycol 400 B23A diet glycol B23B glycerol DAY defoaming emulsion ("Antifoam Emulsion B") D2A Biocide ("GivGard DXN") EA 30% hydrochloric acid EB phosphoric acid (85%) • In example 18, the optical brightener has been tinted with 0.5% CI Disperse Blue 73 Application Example A 1000 parts of a dyeing liquor containing (based on the substrate) 0.75% of the red scattered dye C.I. Disperse Red 74 and 3% of the dispersion according to Example 1 and whose pH has been adjusted to 5.0 by addition of ammonium sulfate and formic acid in a ratio of 10: 1, are heated to 60 ° C in a machine of dyeing of HT (high temperature) and 100 parts of a polyester fabric are introduced into this liquor. The dyeing autoclave is sealed and the circulating liquor is heated to 135 ° C. The dyeing is continued at 135 ° C for 20 minutes, where after the liquor it is cooled below 80 ° C and the dyeing material is removed. Then it is washed, the reduction is cleaned, washed again and finally dried. A satisfactory level and dyeing resistant to light is obtained.

Application Example B A small 40 g cross bobbin and a density of 0.41 g / cm3 (= package density when the dyeing machine is inserted) is entangled using a polyester yarn (dtex 167f) and a precision coiler or winder. This crossed coil is dyed with the dye mentioned in the above in a liquor circulation machine (for example Colorstar from Zeltex AG, Switzerland). The proportion of liquor: yarn is 10: 1, the hardness of the water is llcdH (German degrees of hardness). The tinctures are used: 0.19% of C.I. Disperse Yellow 86 0.185% of C.I. Disperse Yellow 42 0.122% of C.I. Disperse Red 91 0.05% of C.I. Disperse Blue 56 0.44% of C.I. Disperse Blue 77 3.5% of the dispersion is added according to Example 1. The pH is 5.5 (fixed with formic acid / ammonium sulfate). The liquor is poured at 40% on the package, the liquor circulation pump is started, and the liquor, which is circulated at a pressure of 2 bar, is heated from 40 ° C to 70 ° C at a speed of 3 ° C / minute and then 70 ° C to 130 ° C at a rate of 1 ° C / minute. The dyeing is continued at 130 ° C for 30 minutes, and then the batch is cooled below 130 to 70 ° C at a rate of 5 ° C / minute. This is followed by washing, reduction cleaning, additional washing and finally dyeing. During the total dyeing time, there is no pressure development. The dyeing obtained is leveled and there is no discernible dyeing deposit in the dyed package or in an embroidery produced therefrom.

Application Example C 1000 parts of a brightening liquor containing (based on the substrate) 0.2% of the polishing dispersion of Example 3 and of the adduct of 40 moles of ethylene oxide to 1 mole of fatty alcohol of C? _? ß and whose pH has been adjusted to 5.5 by the addition of acetic acid are heated in a HT (high temperature) dyeing machine at 60 ° C and 100 parts of a polyester cloth are introduced into this liquor. The autoclave is sealed and the circulating liquor is heated to 130 ° C in the course of 35 minutes. The polishing treatment is continued at 130 ° C for 30 minutes, after which the liquor is cooled to below 80 ° C, and the optically brightened material is removed. Then it is washed and dried. A satisfactory optical brightening is obtained.

Application Example D 1000 parts of a polishing liquor containing (based on the substrate) 0.08% to 0.6% of the polishing dispersion according to Example 3, 0.1% of the optical brightener C.I. Optical Brightener 230 and 0.2% of the adduct of 40 moles of ethylene oxide to 1 mole of C? 4-? 8 fatty alcohol and whose pH has been adjusted to 5.5 by addition of acetic acid is heat in a HT (high temperature) dyeing machine at 60 ° C and 100 parts of a polyester / viscose blend fabric are introduced into this liquor. The autoclave is sealed and the circulating liquor is heated to 120 ° C at a rate of 2 ° C / minute. The polishing treatment is continued at 120 ° C for 25 minutes, after which the liquor is cooled to below 60 ° C, and the optically brightened material is removed. Then it is washed and finally dried. A satisfactory optical brightening is obtained.

Application Example E A polyester / cotton blend fabric is filled with an aqueous polishing liquor containing 0.8 to 4 g / 1 of the dispersion according to Example 3 and 0.2 g / 1 of the adduct of 6 moles of oxide from ethylene to 1 mole of tridecyl alcohol at pH 5.5 (fixed with acetic acid) to a wet operation of 70% based on the weight of the dry substrate, then pre-dried for 2 minutes at 130 ° C and thermo-colloid for 30 minutes at 180 ° C. For this reason, the polyester portion of the mixed fabric is visually polished satisfactorily. The cotton portion can then, in a second process step, in a conventional manner per se, under alkaline conditions, be simultaneously optically brightened with an optical brightener of the series of bistriazinylaminostilbene-disulphonic acid and bleached with hydrogen peroxide in the presence of a peroxide bleach liquor stabilizer (70% wet, 90 minutes dilated in hot at 95 ° C, then rinsed hot and cold and finally dried). A satisfactory optical brightening is obtained. In an analogous manner, the composition according to each of Examples 2 or 22 to 33 are employed in each of Examples A and B of Application in place of the composition according to Example 3. Good dyeings are obtained. In an analogous manner, the compositions according to each of Examples 4 to 21 are employed in each of Application Examples C, D and E in place of the composition according to Example 1. Satisfactory optical brighteners are obtained . It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (15)

1. Having described the invention as above, the content of the following claims is claimed as property: 1. An aqueous dispersion (U), characterized in that it contains: (A) a textile treatment agent absorbing UV light (B) a dispersing system and (C) a crosslinked carboxyl-containing copolymer.
2. 2. An aqueous dispersion (U) according to claim 1, characterized in that it additionally contains (D) at least one formulation additive.
3. 3. An aqueous dispersion (U) according to claim 1 2, characterized in that (A) is (Ai) a UV absorber or (A2) an optical brightener.
4. 4. An aqueous dispersion (U) according to any of claims 1 to 3, characterized in that (B) consists of (Bi) at least one surfactant and / or (B2) at least one dispersing aid
5. 5. An aqueous dispersion (U) according to claim 4, characterized in that (Bi) consists of anionic and / or non-ionogenic dispersants and / or emulsifiers and (B2) consists of protective colloids, wetting agents, solubilizers and / or dispersion stabilizers .
6. 6. An aqueous dispersion (U) according to any of claims 1 to 5, characterized in that (C) is a copolymer of (Ci) maleic acid or maleic anhydride, (C2) at least one non-ionogenic comonomer monoethylenically unsaturated and (C3) a crosslinking comonomer.
7. 7. An aqueous dispersion (U) according to any of claims 2 to 6, characterized in that (D) is selected from (Di) a defoamer (D2) a biocide and / or (D3) a dye.
8. 8. A process for the production of a dispersion (U) according to any of claims 1 to 7, characterized in that (C) is mixed with the other components of the dispersion in an aqueous medium.
9. 9. A process according to claim 8, characterized in that a polymer (C) is used which is a polymer corresponding to the constitution of (C) but wherein the carboxyl-containing monomer is a dicarboxylic acid which is present in the form of cyclic anhydride, and in this way is hydrolyzed in the presence of at least a portion of the components (B) and in the presence of a base to form (C) in a salt and then (A) and optionally the remaining components of (C) are added. OR) .
10. 10. The use of the aqueous dispersions (U) according to any of claims 1 to 7 for treating textile material in an aqueous liquor.
11. 11. Use according to claim 10 of an aqueous dispersion (U), wherein (A) is a UV absorber (Ai), in the dyeing of yarn material in the form of cross coils.
12. 12. Use according to claim 10 of an aqueous dispersion (U), wherein (A) is an optical brightener (A2), for the optical brightening of yarn material in the form of cross coils.
13. 13. Use according to any of claims 10 to 12 for treating synthetic or semi-synthetic textile material.
14. 14. A process for textile material finished with a UV absorbent textile treatment agent (A), characterized in that the UV absorbent textile treatment agent (A) is used in the form of a dispersion (U) according to any of the claims 1 to 7.
15. 15. A process according to claim 14, characterized in that the finishing of the synthetic or semi-synthetic fiber material is in the form of yarn on crossed coils.