HK1147770B - Preparations comprising disperse dye and/or uv absorber - Google Patents

Description

Preparations containing disperse dyes and/or UV absorbers

Technical Field

Disperse dyes and UV absorbers are used in the textile industry for dyeing and finishing hydrophobic fibre materials, in particular polyesters. These products are insoluble or sparingly soluble in water, but are applied to the textile material from the aqueous phase. The preparations, i.e. the storage-stable formulations, for example for trade purposes, and also the treatment liquids and baths obtained therefrom, must contain dispersants which keep these products in a finely divided state. Dispersants used for this purpose are subject to continuous further development and have to meet ever-increasing expectations.

Background

Polycarboxylate ethers (PCEs) are polymeric compounds based primarily on acrylic or methacrylic acid and esterified with polyether diols. These compounds are known and are used as concrete superplasticizers. For example, DE 102006005093 a1 describes concrete superplasticizer dispersions comprising silica and a polycarboxylate ether and DE 102006005094 a1 describes similar dispersions composed of titanium dioxide and a polycarboxylate ether. DE 102005052817B 3 describes self-compacting concrete mixtures which likewise contain polycarboxylate ethers. The function of these auxiliaries is described in chem.unserer Zeit, 2005, 39, 262-.

It has surprisingly been found that polycarboxylate ethers are very useful for dispersing disperse dyes and uv absorbers.

Disclosure of Invention

The present invention therefore provides the use of polycarboxylate ethers for dispersing organic pigments, in particular disperse dyes and UV absorbers. The present invention also provides a preparation comprising a disperse dye and/or an ultraviolet absorber and further comprising a polycarboxylate ether as a dispersant.

The preparation of the present invention may contain a disperse dye or an ultraviolet absorber, but may also contain a disperse dye and an ultraviolet absorber. The disperse dyes and the UV absorbers are present in particular in a particle size of between 0.2 and 5 μm, preferably between 0.4 and 1.2 μm, respectively.

Preferred preparations of the present invention comprise 1 to 50% by weight and more preferably 5 to 40% by weight of a disperse dye and/or an ultraviolet absorber and 1 to 25% by weight of a polycarboxylate ether.

The preparations according to the invention may further comprise further conventional auxiliaries, in particular anionic surfactants, nonionic surfactants, thickeners, antifoam or foam-inhibiting ingredients, so-called "acid donors", wetting agents, oxidizing agents, preservatives and also dirt-repellent agents and/or solvents.

Examples of anionic surfactants are lignosulphonates, condensates of naphthalenesulphonates with formaldehyde, alkyl or alkylaryl sulphonates or alkylaryl polyglycol ether sulphates. Nonionic surfactants are, for example, the reaction products of alkylene oxides, such as ethylene oxide or propylene oxide, with alkylatable compounds, such as fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols and carboxamides. "acid donors" are, for example, butyrolactone, monochloroacetamide, sodium chloroacetate, sodium dichloroacetate, the sodium salt of 3-chloropropionic acid, monoesters of sulfuric acid, such as lauryl sulfate, and also sulfuric acid esters of ethoxylated and propoxylated alcohols, such as butylglycol sulfate.

Oxidizing agents are, for example, sodium m-nitrobenzenesulfonate, fungicidal preservatives are, for example, sodium orthophenylphenolate, sodium pentachlorophenolate and also methyl and benzyl isothiazolones, and the latter may also be substituted.

Any disperse dye is in principle suitable. Disperse dyes are known to those skilled in the art and are widely described in the literature, for example in the Colour Index (Colour Index) published by the British Society of Dyers and Colourists and the American Association of Textile chemistry and dyeing workers (American Association of Textile Chemists and Colourists).

Preferred disperse dyes are, in particular, monoazo, anthraquinone, quinophthalone and methine dyes and also coumarins.

Particularly preferred disperse dyes are azo dyes of the formula (I)

Wherein

A represents a residue of a diazo component;

R¹represents hydrogen, C₁-C₄Alkyl radical, C₁-C₄Alkoxy, -NHCO-C₁-C₄Alkyl, -NHSO₂-C₁-C₄Alkyl or halogen;

R²represents hydrogen, C₁-C₄Alkyl or C₁-C₄An alkoxy group; and

R³and R⁴Independently represent hydrogen, C₂-C₄Alkenyl radical, C₁-C₄Alkyl, or substituted by cyano, hydroxy, phenoxy, C₁-C₄Alkoxy, -OCO-C₁-C₄Alkyl, -OCO phenyl, -COO-C₁-C₄Alkyl, -OCOO-C₁-C₄Alkyl or-OCOO phenyl substituted C₁-C₄An alkyl group.

Examples of radicals A correspond in particular to the formula (II)

Wherein

T¹And T²Independently represent hydrogen, halogen, C₁-C₄Alkyl radical, C₁-C₄Alkoxy, cyano, -SO₂-C₁-C₄Alkyl) or nitro; and

T³and T⁴Independently represent hydrogen, halogen, trifluoromethyl, cyano, -SO₂CH₃-SCN or nitro;

or examples of the radical A conform to the formula (III)

Wherein

T⁵And T⁵' independently represents hydrogen or halogen; and

T⁶represents hydrogen, -SO₂CH₃、-SCN、C₁-C₄Alkoxy, halogen or nitro;

or examples of the radical A conform to the formula (IV)

Wherein

T¹²Represents hydrogen or halogen;

or examples of the radical A conform to the formula (IVa)

Wherein

T⁷Represents nitro, -CHO, cyano, -COCH₃Or a group of the formula

Wherein T is¹⁰Represents hydrogen, halogen, nitro or cyano;

T⁸represents hydrogen, C₁-C₆Alkyl or halogen; and

T⁹represents nitro, cyano or-COCH₃or-COOT¹¹(ii) a Wherein T is¹¹Is represented by C₁-C₄An alkyl group.

Further particularly preferred disperse dyes are anthraquinone dyes of the formula (V)

Wherein

D¹And D²Independently represent hydrogen, hydroxy, amino or nitro;

D³and D⁴Independently represents hydroxy, amino or-NHR⁵；

D⁵And D⁶Independently represent hydrogen, halogen, cyano, C₁-C₆Alkoxy, hydroxy-C₁-C₆Alkoxy, phenoxy-C₁-C₆Alkoxy, phenoxy, by C₁-C₄Alkyl, cyano-C₁-C₆Alkyl, hydroxy, halogen, C₁-C₄Alkoxy or C₁-C₄alkyl-COO-C₁-C₄An alkyl-substituted phenoxy group, a phenyl group,by hydroxy, C₁-C₄Alkyl or C₁-C₄Alkoxy-substituted phenyl, -SO₂O phenyl, -CO-C₁-C₄Alkyl or-COO-C₁-C₄An alkyl group; and

R⁵is represented by C₁-C₄Alkyl, hydroxy-C₁-C₄Alkyl, phenyl, by C₁-C₄Alkyl radical, C₁-C₄Alkoxy, hydroxy-C₁-C₄Alkyl, -OSO₂-C₁-C₄Alkyl or halogen substituted phenyl, -SO₂-phenyl or by C in the phenyl radical₁-C₄Alkyl substituted-SO₂-a phenyl group; or

Wherein

D⁵And D⁶Taken together to represent-CONR⁵' CO-and forms a five-membered ring in combination with the attached carbon atom, wherein

R⁵' represents C₁-C₄Alkyl radical, C₁-C₄alkoxy-C₂-C₄Alkyl or C₁-C₄alkoxy-C₂-C₄alkoxy-C₂-C₄An alkyl group.

A further particularly preferred disperse dye is a quinophthalone dye of the formula (VI)

Wherein

R⁶Represents hydrogen or halogen, in particular bromine;

R⁷represents hydrogen or-COOR⁸And an

R⁸Represents hydrogen, C₁-C₄Alkyl or C₁-C₄alkoxy-C₁-C₄Alkoxy radical。

Further particularly preferred disperse dyes are methine dyes of the formulae (VII), (VIIb), (VIIc) and (VIId)

Wherein

L¹Denotes a 5-or 6-membered carbocyclic or heterocyclic group, preferably phenyl, substituted phenyl, thiazolyl, substituted thiazolyl, thienyl or substituted thienyl, in which case useful substituents include in particular C₁-C₄Alkyl radical, C₁-C₄Alkoxy, hydroxy, cyano, nitro and halogen; and

R³⁰is represented by C₁-C₂₀Alkyl, which may be linear or branched;

wherein

L²Represents an aryl group; and

R³¹represents hydrogen, C₁-C₂₀Alkyl or C₂-C₂₀An alkenyl group;

wherein

R³²Represents hydrogen or C₁-C₄An alkyl group, a carboxyl group,

R³³and R³⁴Independently represent C₁-C₂₀Alkyl, which may be straightChain and branched.

Particularly preferred dyes for the purposes of the present invention are the following color index dyes:

c.i. disperse yellows 3, 4, 5, 7, 9, 13, 24, 30, 33, 34, 42, 49, 50, 51, 54, 56, 58, 60, 63, 64, 65, 66, 68, 71, 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 108, 114, 116, 118, 119, 122, 124, 126, 135, 140, 141, 148, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 184:1, 186, 192, 198, 199, 202, 204, 210, 211, 215, 216, 218, 224, 227, 230, 235, 241, and 246;

c.i. disperse oranges 1, 3, 5, 7, 11, 13, 17, 20, 21, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 47, 48, 49, 50, 53, 54, 56, 57, 58, 59, 60, 61, 62, 66, 71, 73, 76, 78, 80, 89, 90, 91, 96, 97, 119, 127, 128, 130, 139, 142, 146, 148, 151 and 157;

c.i. disperse red 1, 4, 5, 77, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 56, 58, 59, 60, 65, 72, 73, 74, 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 151, 369152, 153, 154, 157, 158, 159, 164, 167, 169, 177, 178, 179, 181, 182, 183, 184, 185, 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 208, 210, 221, 224, 225, 227, 257, 229, 240, 257, 258, 263, 281, 278, 281, 296, 376, 279, 288, 277, 364, 312, 364, 303, 312, 356, 311, 356, 310, 343, 356, 311, 343, 356, 310, 356, 311, 356, 310, 356, 343, 356, 310, 356, 382. 383 and 385;

c.i. violet 1, 4, 8, 17, 23, 26, 27, 28, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 52, 56, 57, 59, 61, 63, 69, 77, 90, 93, 94, 95, 98 and 107;

c.i. blue 3, 7, 9, 14, 16, 19, 20, 26, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 70, 72, 73, 74, 75, 77, 79, 81, 82, 83, 84, 85, 87, 91, 93, 94, 95, 06, 102, 104, 106, 108, 112, 113, 115, 118, 119, 120, 122, 125, 128, 130, 131, 139, 141, 142, 143, 145, 146, 148, 149, 152, 153, 154, 158, 165, 171, 173, 174, 178, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207, 211, 214, 224, 225, 257, 259, 267, 268, 270, 280, 284, 285, 286, 287, 288, 291, 293, 295, 297, 301, 315, 321, 330, 341, 358, 367, 354, 356, and 371;

c.i. disperse green 9;

c.i. disperse brown 1, 2, 4, 9, 13, 16 and 19;

c.i. disperse blacks 1, 3, 10 and 24;

c.i. solvent yellow 163; and

c.i. solvent orange 60.

Ultraviolet absorbers considered are in particular those from the list: substituted benzophenones, benzoxazinones, benzotriazoles and triazines.

Particularly preferred UV absorbers are benzotriazoles of the formula (VIII)

Wherein

R⁹Represents hydrogen, halogen, C₁-C₁₂Alkyl radical, C₂-C₁₂Alkenyl radical, C₁-C₁₂Alkoxy or C₂-C₁₂An alkenyloxy group;

R¹⁰represents hydrogen, halogen, C₁-C₁₂Alkyl radical, C₂-C₁₂Alkenyl radical, C₁-C₁₂Alkoxy radical, C₂-C₁₂Alkenyloxy, aryl-C₁-C₄Alkyl, aryl-C wherein the aryl group is substituted₁-C₄Alkyl or a radical of the formula (IX)

R¹¹Represents hydrogen, hydroxy, C₇-C₁₀Aralkyloxy, benzoyloxy or substituted benzoyloxy; and

R¹²represents hydrogen, halogen, benzoyl, substituted benzoyl, C₁-C₁₂Alkyl radical, C₂-C₁₂Alkenyl radical, C₁-C₁₂Alkoxy radical, C₇-C₁₀Aralkyl radical, C₂-C₁₂Alkenyloxy or a group of formula (IX);

R¹³represents hydrogen, C₁-C₁₀Alkyl radical, C₂-C₁₂Alkenyl, -CO-C₁-C₁₀Alkyl, -CO-C₂-C₁₂Alkenyl radical, C₅-C₈Cycloalkyl radical, C₇-C₁₀Aralkyl or C₆-C₁₀An aryl group;

R¹⁴is represented by C₁-C₂₀Alkyl radical, C₂-C₁₇Alkenyl radical, C₅-C₈Cycloalkyl radical, C₇-C₁₀Aralkyl radical, C₆-C₁₀Aralkenyl or C₆-C₁₀An aryl group; and

n represents 1 or 2;

and when n is 1, R¹³And R¹⁴Can be combined with the support atoms to form a 5-8 membered heterocyclic ring with a single or multiple core.

In the particularly preferred benzotriazoles of formula (VIII),

R⁹represents hydrogen, methyl or chlorine;

R¹⁰represents hydrogen or C₁-C₅Alkyl, especially tert-butyl; and

R¹²is represented by C₁-C₅Alkyl, in particular methyl.

Further particularly preferred UV absorbers are triazines of the formula (X)

Wherein

R¹⁵Is represented by C₁-C₄Alkyl radical, C₁-C₄Alkoxy, halogen or hydroxy;

R¹⁶and R¹⁷Independently represent C₁-C₄Alkylthio radical, C₁-C₄Alkoxy radical, C₁-C₁₈Alkyl, hydroxy-, halogen-, C₁-C₄alkoxy-C₁-C₄Alkylthio-, amino-or mono-or di-C₁-C₄Alkylamino-substituted C₁-C₁₈Alkyl, phenyl, or chloro-, hydroxy-, C₁-C₄Alkyl-or C₁-C₈Alkoxy-mono-or poly-substituted phenyl; and

m represents 0, 1 or 2.

In the triazine of the formula (X), m is preferably 1, in which case R¹⁵Preferably meta-linked relative to the hydroxyl group.

Very particularly preferred UV absorbers conform to the formula (XXII)

The ultraviolet absorbers mentioned are known and are obtainable by known methods and are commercially available.

For example, UV absorbers of the formula X can be obtained by heating amidines and esters of o-hydroxyphenylcarboxylic acids in a ratio of approximately 2: 1, preferably in boiling organic solvents, see U.S. Pat. No. 4, 3,896,125 and Helv. Chim. acta 1972, 55, 1566-1595.

The polycarboxylate ethers used according to the invention or more precisely the polycarboxylate ethers present in the preparations according to the invention are in particular copolymers of acrylic acid and/or methacrylic acid esterified with polyether diols. They may preferably comprise further ingredients. More preferably, they comprise structural repeat units A, B and C defined below.

The structural repeating unit A is a mono-or dicarboxylic acid derivative and corresponds to the formula (XIa), (XIb) or (XIc)

Wherein

R¹⁸Represents hydrogen or C₁-C₂₀An alkyl group;

x represents-OM_a、-O-(C_pH_2pO)_q-R¹⁹and/or-NH- (C)_pH_2pO)_q-R¹⁹；

Y represents O or NR¹⁹；

M represents hydrogen, a monovalent or divalent metal cation, ammonium, or an organic amine group;

R¹⁹is represented by C₁-C₂₀Alkyl radical, C₂-C₂₀Alkenyl radical, C₅-C₈Cycloalkyl radical, C₆-C₁₄Aryl, hydroxy-, carboxy-or sulfo-substituted C₆-C₁₄An aryl group;

p represents an integer of 2 to 4;

q represents a number of 0 to 200;

and is

When M represents a monovalent cation, a represents 1, and when M represents a divalent cation, a represents 1/2.

The organic amine groups M are preferably substituted ammonium groups which are derived from primary, secondary or tertiary C₁-C₂₀Alkylamine, C₁-C₂₀Alkanolamines or C₅-C₈A cycloalkylamine. Examples of corresponding amines are methylamine, dimethylamine, trimethylamine, ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, cyclohexylamine, dicyclohexylamine, aniline and diphenylamine in protonated (ammonium) form.

R¹⁸Preferably represents a methyl group.

p preferably represents 2 or 3.

The structural repeating unit B conforms to the formula (XII)

Wherein

p, q and R¹⁹Each as defined above; and

R²⁰represents hydrogen or C₁-C₄Alkyl or C₂-C₅An alkenyl group.

The structural repeating unit C corresponds to the formula (XIIIa) or (XIIIb)

Wherein

R²¹Represents hydrogen or methyl;

u represents hydrogen, -COOM_aor-COOR²²；

Q represents-COOR²²；

R²²Is represented by C₃-C₂₀Alkyl radical, C₃-C₂₀Alkenyl radical, C₅-C₈Cycloalkyl, preferably cyclopentyl or cyclohexyl, or C₆-C₁₄Aryl, preferably phenyl or naphthyl;

R¹⁹as defined above, in the above-mentioned manner,

v represents a polydimethylsiloxane radical of formula (XVI) or-O-CO-C₆H₄-CO-O-; and

z represents a value of 0 to 4.

The structural repeat unit C may optionally further comprise a group of formula (XIV) and/or (XV).

In the group of formula (XIV)

U and R²¹Each as defined above;

and Q¹According to the formula

——E¹——(CH(CH₃)-CH₂-O)_x-(CH₂-CH₂-O)_y-R²³

Wherein

E¹represents-CO-NH-, -O-or-CH₂-O-；

x represents a number of 1 to 150; and

y represents a number of 0 to 15; and

R²³having R¹⁹One of the meanings of (A) or represents a group of the formula

Wherein R is²¹And U are each as defined above; and

E²represents-NH-CO-, -O-or-O-CH₂-。

In the radical of formula (XV)

U and R²¹Each as defined above;

w represents a group of formula (XVI), (XVII) or (XVIII)

Wherein

b represents 1 or 2;

r represents a number of 2 to 100;

z represents a number of 0 to 4; and

R²⁴having R¹⁹Or a group of the formula (XIX) or (XX)

Wherein R is²¹U and z are each as defined above and s represents 1 or 2.

The polycarboxylate ethers to be used according to the invention or more precisely the polycarboxylate ethers present in the preparations according to the invention may also comprise structural repeating unit D as well as structural repeating units A, B and C. The structural repeating unit D corresponds to the formula (XXIa) or (XXIb)

Wherein X, Y and M_aEach as defined above.

When the structural repeating unit D is additionally present, the proportion of these structural repeating units present is preferably as follows: 55-75 mol% of a structural repeating unit A, 19.5-39.5 mol% of a structural repeating unit B, 0.5-2 mol% of a structural repeating unit C and 5-20 mol% of a structural repeating unit D.

The polycarboxylate ethers which are particularly preferably used according to the invention or which are present in the preparations according to the invention comprise, in addition to the structural repeating units A to D, from 1 to 50 mol%, in particular from 1 to 20 mol%, based on the total number of structural repeating units A to D, of monomers based on vinyl or (meth) acrylic acid derivatives, such as styrene, methylstyrene, vinyl acetate, vinyl propionate, ethylene, propylene, isobutene, hydroxyalkyl (meth) acrylates, acrylamide, methacrylamide, N-vinylpyrrolidone, allylsulfonic acid, methallylsulfonic acid, vinylsulfonic acid, vinylphosphonic acid, AMPS, methyl methacrylate, methyl acrylate, butyl acrylate, allylhexyl acrylate and the like, depending on the structure of the monomers.

In the above definitions of the compounds of the formulae (I) to (XXI), the alkyl radical may be linear or branched. Examples are in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, isooctyl, n-nonyl, isononyl, n-dodecyl, heptadecyl and octadecyl. The same logic applies to alkoxy, alkenyloxy and alkylene groups, the first group representing in particular methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy or tert-butoxy. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio and tert-butylthio. Cycloalkyl radicals are in particular cyclopentyl, cyclohexyl and cycloheptyl, more preferably cyclohexyl. Aralkyl radicals are in particular benzyl and phenethyl, and aryl radicals are in particular phenyl and naphthyl. Halogen is in particular chlorine and bromine, of which chlorine is preferred.

The polycarboxylate ethers to be used according to the invention or more precisely present in the preparation of the invention have a molecular weight preferably in the range of from 5000 to 50000, more preferably in the range of from 20000 to 40000.

Has been identified from BASF construction polymers GmbH9360 and9560 the polycarboxylate ethers available under the commercial name are particularly preferred.

The polycarboxylate ethers to be used according to the invention or more precisely present in the preparations according to the invention are obtainable by known methods, for example by the method described in DE 102006005094 a 1.

The preparation of the invention is obtainable by known methods. They are obtained in particular by: disperse dyes and/or uv absorbers are slurried with dispersants in a liquid medium, preferably in water, and the mixture is subjected to shear forces to mechanically comminute the originally present dye and uv absorber particles to such an extent that an optimum specific surface area is achieved and sedimentation is minimized. This is done in a suitable mill, such as a ball mill or a sand mill. The particle size of these dyes and/or UV absorbers is generally between 0.5 and 5 μm and preferably between 0.8 and 1.2. mu.m.

The preparations thus obtained should be pourable for most applications. Therefore, the contents of the dye, the ultraviolet absorber, and the dispersant are limited in these cases. In general, the preparation is adjusted to a dye and/or UV absorber content of 15 to 50 wt.% and a dispersant content of 5 to 25 wt.%. When the preparation of the invention comprises further auxiliaries, these are added in the desired amounts during the preparation process described above.

The dye dispersions thus obtained are very advantageous for formulating dye liquors and also for printing pastes.

The aqueous, i.e. liquid, preparations of the invention described are preferred, but for certain fields of application powder formulations are preferred. These powders contain dyes or UV absorbers, dispersants and, where appropriate, further auxiliaries.

A preferred method of preparing powdered preparations is to strip the above-mentioned liquid preparations from their liquid, for example by vacuum drying, freeze drying, by drying on a drum dryer, but preferably by spray drying.

When the preparations of the present invention contain disperse dyes, they are used to prepare dyeing liquors by diluting them with a dyeing medium, preferably water, in the required amount to obtain a bath ratio of from 5: 1 to 50: 1. In addition, it is common practice to add further dyeing auxiliaries such as dispersing, wetting and fixing auxiliaries to the liquor. Organic and inorganic acids such as acetic acid, succinic acid, boric acid or phosphoric acid are added to set the pH in the range of 4 to 5, preferably 4.5. It is advantageous to buffer the pH setting and to add a sufficient amount of the buffer system. The acetic acid/sodium acetate system is an example of an advantageous buffer system.

To use the disperse dye preparations of the invention in textile printing, the required amounts of the preparations are mixed together with thickeners, such as alkali metal alginates and the like, and suitable further additives, such as fixing accelerators, wetting agents and oxidizing agents, in a conventional manner to form a printing paste.

Example 1

Mixing in a glass bead mill

23 parts of 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole,

14 parts of a 60% by weight polycarboxylate ether solution (from Pasteur building Polymer Co., Ltd.)9560)，

4 parts of a condensation product of naphthalenesulfonic acid and formaldehyde, and

48.8 parts of softened water.

The mixture is milled with the same amount of glass beads having a diameter of about 0.4 to 0.6mm until the particle size is at least less than 5 μm, and the dispersion is subsequently separated from the glass beads.

While stirring the mixture

Adding and stirring

1.4 parts of a pesticide combination, and

8.8 parts of softened water, namely,

until homogeneous.

This gives a storable dispersion.

Example 2

Mixing in a glass bead mill

23 parts of 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole,

14 parts of a 60% by weight polycarboxylate ether solution (Melpers 9360 from Pasteur building materials Polymer Co., Ltd.),

4 parts of a condensation product of naphthalenesulfonic acid and formaldehyde, and

48.8 parts of softened water.

The mixture is milled with the same amount of glass beads having a diameter of about 0.4 to 0.6mm until the particle size is at least less than 5 μm, and the dispersion is subsequently separated from the glass beads.

While the mixture is being stirred, the mixture is,

adding and stirring

1.4 parts of a pesticide combination, and

8.8 parts of softened water, namely,

until homogeneous.

This gives a storable dispersion.

Example 3

Mixing in a glass bead mill

12.5 parts of a commercially available UV absorber of the triazine type of the formula XXII

14 parts of a 60% by weight polycarboxylate ether solution (from Pasteur building Polymer Co., Ltd.)9560)，

4 parts of a condensation product of naphthalenesulfonic acid and formaldehyde, and

69.5 parts of softened water.

The mixture is milled with the same amount of glass beads having a diameter of about 0.4 to 0.6mm until the particle size is at least less than 5 μm, and the dispersion is subsequently separated from the glass beads.

This gives a storable dispersion.

Example 4

Mixing in a glass bead mill

12.5 parts of a triazine-type UV absorber of the formula XXII,

14 parts of a 60% by weight polycarboxylate ether solution (from Pasteur building Polymer Co., Ltd.)9560)，

16.6 parts of a 30% by weight solution of modified polyvinylpyrrolidone, and

46.7 parts of softened water.

The mixture is milled with the same amount of glass beads having a diameter of about 0.4 to 0.6mm until the particle size is at least less than 5 μm, and the dispersion is subsequently separated from the glass beads.

While the mixture is being stirred, the mixture is,

adding and stirring

1.4 parts of a pesticide combination, and

8.8 parts of softened water, namely,

until homogeneous.

This gives a storable dispersion.

Example 5

Mixing in a glass bead mill

10 parts of C.I. disperse blue 284,

10 parts of a 60% by weight polycarboxylate ether solution (from Pasteur building Polymer Co., Ltd.)9560)，

6 parts of a condensation product of naphthalenesulfonic acid and formaldehyde, and

63.8 parts of softened water.

The mixture is milled with the same amount of glass beads having a diameter of about 0.4 to 0.6mm until the particle size is at least less than 5 μm, and the dispersion is subsequently separated from the glass beads.

While the mixture is being stirred, the mixture is,

adding and stirring

1.4 parts of a pesticide combination, and

8.8 parts of softened water, namely,

until homogeneous.

This gives a storable dispersion.

Example 6

Mixing in a glass bead mill

21 parts of C.I. disperse blue 60M,

14 parts of a 60% by weight polycarboxylate ether solution (from Pasteur building Polymer Co., Ltd.)9560) And an

54.8 parts of softened water.

The mixture is milled with the same amount of glass beads having a diameter of about 0.4 to 0.6mm until the particle size is at least less than 5 μm, and the dispersion is subsequently separated from the glass beads.

While the mixture is being stirred, the mixture is,

adding and stirring

1.4 parts of a pesticide combination, and

8.8 parts of softened water, namely,

until homogeneous.

This gives a storable dispersion.

Claims (10)

1. Use of polycarboxylate ethers for dispersing mixtures of disperse dyes and UV absorbers, where

The polycarboxylate ether has a molecular weight in the range of 5000-50000, and

wherein the ultraviolet absorber is an ultraviolet absorber selected from benzotriazoles and triazines.

2. A preparation comprising:

a mixture of an ultraviolet absorber and a disperse dye, and

further comprising a polycarboxylate ether as a dispersant, wherein

The polycarboxylate ether has a molecular weight in the range of 5000-50000, and

wherein the ultraviolet absorber is an ultraviolet absorber selected from benzotriazoles and triazines.

3. The preparation of claim 2, comprising:

1 to 50% by weight of a mixture of a disperse dye and an ultraviolet absorber, and

1 to 25% by weight of a polycarboxylate ether.

4. The preparation according to claim 2 or 3, comprising a monoazo disperse dye, an anthraquinone disperse dye, a quinophthalone disperse dye, a methine disperse dye or a coumarin disperse dye.

5. The preparation as claimed in claim 2 or 3, comprising as disperse dye an azo dye of the formula (I)

Wherein

A represents a residue of a diazo component;

R¹represents hydrogen, C₁-C₄Alkyl radical, C₁-C₄Alkoxy, -NHCO-C₁-C₄Alkyl, -NHSO₂-C₁-C₄Alkyl or halogen;

R²represents hydrogen, C₁-C₄Alkyl or C₁-C₄An alkoxy group; and

R³and R⁴Independently represent hydrogen, C₂-C₄Alkenyl radical, C₁-C₄Alkyl, or substituted by cyano, hydroxy, phenoxy, C₁-C₄Alkoxy, -OCO-C₁-C₄Alkyl, aryl, heteroaryl, and heteroaryl,-OCOphenyl, -COO-C₁-C₄Alkyl, -OCOO-C₁-C₄Alkyl or-OCOO phenyl substituted C₁-C₄An alkyl group;

or anthraquinone dyes of the formula (V)

Wherein

D¹And D²Independently represent hydrogen, hydroxy, amino or nitro;

D³and D⁴Independently represents hydroxy, amino or-NHR⁵；

D⁵And D⁶Independently represent hydrogen, halogen, cyano, C₁-C₆Alkoxy, hydroxy-C₁-C₆Alkoxy, phenoxy-C₁-C₆Alkoxy, phenoxy, by C₁-C₄Alkyl, cyano-C₁-C₆Alkyl, hydroxy, halogen, C₁-C₄Alkoxy or C₁-C₄alkyl-COO-C₁-C₄Alkyl-substituted phenoxy, phenyl, by hydroxy, C₁-C₄Alkyl or C₁-C₄Alkoxy-substituted phenyl, -SO₂O phenyl, -CO-C₁-C₄Alkyl or-COO-C₁-C₄An alkyl group; and

R⁵is represented by C₁-C₄Alkyl, hydroxy-C₁-C₄Alkyl, phenyl, by C₁-C₄Alkyl radical, C₁-C₄Alkoxy, hydroxy-C₁-C₄Alkyl, -OSO₂-C₁-C₄Alkyl or halogen substituted phenyl, -SO₂-phenyl, or in the phenyl radical by C₁-C₄Alkyl substituted-SO₂-a phenyl group; or therein

D⁵And D⁶Taken together to represent-CONR^5'CO-and combined with a linking carbon atom to form a five-membered ring, wherein

R^5'Is represented by C₁-C₄Alkyl radical, C₁-C₄alkoxy-C₂-C₄Alkyl or C₁-C₄alkoxy-C₂-C₄alkoxy-C₂-C₄An alkyl group;

or a quinophthalone dye of the formula (VI)

Wherein

R⁶Represents hydrogen or halogen;

R⁷represents hydrogen or-COOR⁸And an

R⁸Represents hydrogen, C₁-C₄Alkyl or C₁-C₄alkoxy-C₁-C₄An alkoxy group;

or a methine dye of the formula (VIIa), (VIIb), (VIIc) or (VIId)

Wherein

L¹Represents a 5 or 6 membered carbocyclic or heterocyclic group; and

R³⁰is represented by C₁-C₂₀Alkyl, which may be linear or branched;

wherein

L²Represents an aryl group; and

R³¹represents hydrogen, C₁-C₂₀Alkyl or C₂-C₂₀An alkenyl group;

wherein

R³²Represents hydrogen or C₁-C₄An alkyl group, a carboxyl group,

R³³and R³⁴Independently represent C₁-C₂₀Alkyl, which may be linear or branched.

6. The preparation of claim 5, wherein A corresponds to formula (II)

Wherein

T¹And T²Independently represent hydrogen, halogen, C₁-C₄Alkyl radical, C₁-C₄Alkoxy, cyano, -SO₂-C₁-C₄Alkyl or nitro; and

T³and T⁴Independently represent hydrogen, halogen, trifluoromethyl, cyano, -SO₂CH₃-SCN or nitro;

or A is in accordance with (III)

Wherein

T⁵And T^5'Independently represents hydrogen or halogen; and

T⁶represents hydrogen, -SO₂CH₃、-SCN、C₁-C₄Alkoxy, halogen or nitro;

or A fitting type (IV)

Wherein

T¹²Represents hydrogen or halogen;

or A (IVa)

Wherein

T⁷Represents nitro, -CHO, cyano, -COCH₃Or a group of the formula

Wherein T is¹⁰Represents hydrogen, halogen, nitro or cyano;

T⁸represents hydrogen, C₁-C₆Alkyl or halogen; and

T⁹represents nitro, cyano or-COCH₃or-COOT¹¹(ii) a Wherein T is¹¹Is represented by C₁-C₄An alkyl group.

7. The preparation as claimed in claim 2 or 3, comprising as UV absorber a benzotriazole of the formula (VIII)

Wherein

R⁹Represents hydrogen, halogen, C₁-C₁₂Alkyl radical, C₂-C₁₂Alkenyl radical, C₁-C₁₂Alkoxy or C₂-C₁₂An alkenyloxy group;

R¹⁰represents hydrogen, halogen, C₁-C₁₂Alkyl radical, C₂-C₁₂Alkenyl radical, C₁-C₁₂Alkoxy radical, C₂-C₁₂Alkenyloxy, aryl-C₁-C₄Alkyl, aryl radicals in which the aryl radical is substituted-C₁-C₄Alkyl, or a radical of the formula (IX)

R¹¹Represents hydrogen, hydroxy, C₇-C₁₀Aralkyloxy, benzoyloxy or substituted benzoyloxy; and

R¹²represents hydrogen, halogen, benzoyl, substituted benzoyl, C₁-C₁₂Alkyl radical, C₂-C₁₂Alkenyl radical, C₁-C₁₂Alkoxy radical, C₇-C₁₀Aralkyl radical, C₂-C₁₂Alkenyloxy or a group of formula (IX);

R¹³represents hydrogen, C₁-C₁₀Alkyl radical, C₂-C₁₂Alkenyl, -CO-C₁-C₁₀Alkyl, -CO-C_2-C₁₂Alkenyl radical, C₅-C₈Cycloalkyl radical, C₇-C₁₀Aralkyl or C₆-C₁₀An aryl group;

R¹⁴is represented by C₁-C₂₀Alkyl radical, C₂-C₁₇Alkenyl radical, C₅-C₈Cycloalkyl radical, C₇-C₁₀Aralkyl radical, C₆-C₁₀Aralkenyl or C₆-C₁₀An aryl group; and

n represents 1 or 2;

and when n is 1, R¹³And R¹⁴Can be combined with the support atoms to form a mono-or polynuclear 5-to 8-membered heterocyclic ring;

or triazines of the formula (X)

Wherein

R¹⁵Is represented by C₁-C₄Alkyl radical, C₁-C₄Alkoxy, halogen or hydroxy;

R¹⁶and R¹⁷Independently represent C₁-C₄Alkylthio radical, C₁-C₄Alkoxy radical, C₁-C₁₈Alkyl, hydroxy-, halogen-, C₁-C₄alkoxy-C₁-C₄Alkylthio-, amino-or mono-or di-C₁-C₄Alkylamino-substituted C₁-C₁₈Alkyl, phenyl, or chloro-, hydroxy-, C₁-C₄Alkyl-or C₁-C₈Alkoxy-mono-or poly-substituted phenyl; and

m represents 0, 1 or 2.

8. The preparation of claim 2 or 3, comprising a copolymer derived from acrylic acid and/or methacrylic acid and esterified with a polyether diol as polycarboxylate ether.

9. The preparation of claim 2 or 3, wherein the polycarboxylate ether comprises structural repeating units A, B and C,

wherein

The structural repeat unit A corresponds to the formula (XIa), (XIb) or (XIc)

Wherein

R¹⁸Represents hydrogen or C₁-C₂₀An alkyl group;

x represents-OM_a、-O-(C_pH_2pO)_q-R¹⁹and/or-NH- (C)_pH_2pO)_q-R¹⁹；

Y represents O or NR¹⁹；

M represents hydrogen, a monovalent or divalent metal cation, ammonium or an organic amine group;

R¹⁹represents hydrogen, C₁-C₂₀Alkyl radical, C₂-C₂₀Alkenyl radical, C₅-C₈Cycloalkyl radical, C₆-C₁₄Aryl, hydroxy-, carboxy-or sulfo-substituted C₆-C₁₄An aryl group;

p represents an integer of 2 to 4;

q represents a number of 0 to 200;

and is

When M represents a monovalent cation, a represents 1, and when M represents a divalent cation, a represents 1/2;

the structural repeating unit B conforms to the formula (XII)

Wherein

p, q and R¹⁹Each as defined above; and

R²⁰represents hydrogen or C₁-C₅Alkyl or C₂-C₅An alkenyl group;

and

the structural repeating unit C corresponds to the formula (XIIIa) or (XIIIb)

Wherein

R²¹Represents hydrogen or methyl;

u represents hydrogen, -COOM_aor-COOR²²；

Q represents-COOR²²；

R²²Is represented by C₃-C₂₀Alkyl radical, C₃-C₂₀Alkenyl radical, C₅-C₈Cycloalkyl radicals, or C₆-C₁₄An aryl group;

R¹⁹as defined above, in the above-mentioned manner,

v represents a polydimethylsiloxane radical of formula (XVI) or-O-CO-C₆H₄-CO-O-; and

z represents a value of 0 to 4.

10. The preparation of claim 9, wherein R²²Represents cyclopentyl, cyclohexyl, phenyl or naphthyl.