EP0582550A1 - Process for dyeing of wool-containing fibrous materials - Google Patents

Abstract

Described is a process for dyeing wool-containing fibrous materials with anionic dyes, characterised in that these materials are dyed in the presence of a wool preservative (protectant) containing at least one compound of the formula R-CH2-CH(OH)-CH2-Y (I> where the variables are each as defined in the claims. The process provides rub-fast level dyeings without loss of wool quality.

Description

The present invention relates to a new process for high-temperature dyeing wool or wool-containing fiber materials.

It is known to dye wool or wool-containing fiber materials in the presence of auxiliaries in order to counteract fiber damage which occurs in particular during high-temperature dyeing. Many of the known auxiliaries contain formaldehyde or release formaldehyde when heated, which is not toxicologically harmless.

Surprisingly, an improved process for high-temperature dyeing of wool-containing fiber materials has now been found, which is based on the use of a new class of wool protection agents.

• (Ia) der Rest einer ethylenisch ungesättigten Mono-, Di- oder Tricarbonsäure, worin im Fall einer Di- oder Tricarbonsäure die verbleibende Carboxylgruppe bzw. Carboxylgruppen gegebenenfalls teilweise oder vollständig mit einer Verbindung der Formel
  
          HO - CH₂ - CH(OH) - CH₂ - Y   (II)
  
  verestert sind und Y die oben angegebene Bedeutung hat,
• (Ib)) der Rest eines Homo- oder Copolymerisats aus ethylenisch ungesättigten Mono-, Di- oder Tricarbonsäurederivaten und gegebenenfalls einem oder mehreren Comonomeren, worin die Carboxylgruppen teilweise oder vollständig mit einer Verbindung der oben angegebenen Formel (II) verestert sind,
• (Ic) der Rest eines carboxylgruppenhaltigen, modifizierten Zuckerderivats, worin, sofern dieses mehr als eine Carboxylgruppe aufweist, die verbleibende Carboxylgruppe bzw. Carboxylgruppen gegebenenfalls mit einer Verbindung der oben angegebenen Formel (II) verestert sind, oder
• (Id) der Rest einer gesättigten Mono-, Di-, Tri-, Tetra- oder Pentacarbonsäure, worin im Fall einer Di-, Tri-, Tetra- oder Pentacarbonsäure die verbleibende Carboxylgruppe bzw. Carboxylgruppen gegebenenfalls teilweise oder vollständig mit einer Verbindung der oben angebenen Formel (II)
  verestert sind, ist,
  färbt.

The present invention thus relates to a process for dyeing wool-containing fiber materials with anionic dyes, which is characterized in that these materials in the presence of a wool protection agent containing at least one compound of the formula

R - CH₂ - CH (OH) - CH₂ - Y (I),


where Y is halogen, R is hydroxy or a radical R * -C (O) -O- and R *

• (Ia) the remainder of an ethylenically unsaturated mono-, di- or tricarboxylic acid, wherein in the case of a di- or tricarboxylic acid the remaining carboxyl group or carboxyl groups may be partially or completely with a compound of the formula
  
  HO - CH₂ - CH (OH) - CH₂ - Y (II)
  
  are esterified and Y has the meaning given above,
• (Ib)) the remainder of a homo- or copolymer of ethylenically unsaturated mono-, di- or tricarboxylic acid derivatives and optionally one or more comonomers, wherein the carboxyl groups are partially or completely linked to a compound of the above specified formula (II) are esterified,
• (Ic) the remainder of a modified sugar derivative containing carboxyl groups, in which, if this has more than one carboxyl group, the remaining carboxyl group or carboxyl groups are optionally esterified with a compound of the formula (II) given above, or
• (Id) the remainder of a saturated mono-, di-, tri-, tetra- or pentacarboxylic acid, wherein in the case of a di-, tri-, tetra- or pentacarboxylic acid the remaining carboxyl group or carboxyl groups may be partially or completely with a compound of the above specified formula (II)
  are esterified is
  colors.

Y stands e.g. for bromine and preferably for chlorine.

entsprechen, worin R₁ und R₂ unabhängig voneinander z.B. Wasserstoff, Hydroxy, Halogen, Alkyl, oder eine Gruppe -(CH₂)_p-COOB bedeuten, B z.B. für Wasserstoff, den Rest -CH₂-CH(OH)-CH₂Y, Alkyl, eine Gruppe -(CH₂-CH₂-O)_x-(CH₂-CH[CH₃]-O)_y-R₃ oder für ein Kation steht, p und q unabhängig voneinander je eine Zahl 0 bis 2 bedeuten, x und y unabhängig voneinander je für eine Zahl von 0 bis 250 stehen, wobei die Summe (x + y) ≧1 ist und R₃ unabhängig die Bedeutung von R₁ hat, mit der Massgabe, dass mindestens einer der im Molekül vorhandenen Substituenten B ein Rest -CH₂-CH(OH)-CH₂Y ist und Y die zuvor angegebene Bedeutung hat.If R is a radical R * -C (O) -O- and R * is a radical of an ethylenically unsaturated mono-, di- or tricarboxylic acid according to (Ia), the compound used according to the invention can be, for example, of the formula

correspond in which R₁ and R₂ independently of one another are, for example, hydrogen, hydroxyl, halogen, alkyl, or a group - (CH₂) _p -COOB, B, for example, for hydrogen, the radical -CH₂-CH (OH) -CH₂Y, alkyl, a group - (CH₂-CH₂-O) _x - (CH₂-CH [CH₃] -O) _y -R₃ or represents a cation, p and q each independently represent a number 0 to 2, x and y each independently of one another Are from 0 to 250, the sum (x + y) ≧ 1 and R₃ independently has the meaning of R₁, with the proviso that at least one of the substituents B present in the molecule is a radical -CH₂-CH (OH) - Is CH₂Y and Y has the meaning given above.

R₁ or any other substituent than halogen is, for example, bromine, fluorine or, in particular, chlorine.

R₁ or any substituents other than alkyl are e.g. to C₁-C₄ alkyl. Examples are n- or iso-propyl, n-, iso-, sec- or tert-butyl or, preferably, methyl or ethyl.

p is preferably the number 0 or 1.

q is preferably the number 0.

R₃ is preferably hydrogen or alkyl.

If B stands for a cation, this can e.g. an alkali or alkaline earth metal e.g. Na⁺, K⁺ or Li⁺, or a quaternary inorganic or organic ammonium cation, e.g. NH₄⁺ or NR₄⁺, where R is optionally e.g. is hydroxy substituted alkyl.

B is preferably hydrogen, the radical -CH₂-CH (OH) -CH₂Cl, methyl, ethyl, a group - (CH₂-CH₂-O) _x - (CH₂-CH [CH₃] -O) _y -R₃, wherein R₃ is hydrogen , Is methyl or ethyl, or a cation. B particularly preferably represents hydrogen, a cation or in particular the radical -CH₂-CH (OH) -CH₂Cl.

Preferred carboxylic acid derivatives according to (Ia) used according to the invention are α, β-ethylenically unsaturated compounds of the formula (1) in which q is 0, R₁ and R₂ independently of one another are hydrogen, hydroxyl, chlorine, methyl, ethyl, -COOB or -CH₂-COOB , B represents hydrogen, a cation or the radical -CH₂-CH (OH) -CH₂Cl and R₃ independently has the meaning of R₁, with the proviso that at least one of the substituents B present in the molecule is a radical -CH₂-CH (OH) -CH₂Y is.

Examples of suitable carboxylic acid residues R * according to (Ia) are the residues of (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, vinyl acetic acid, vinyl propionic acid, crotonic acid, aconitic acid, allylacetic acid, vinyloxyacetic acid, allyloxyacetic acid, α, β-dimethyl (meth ) acrylic acid, methylene malonic acid, 2-hydroxy (meth) acrylic acid, 2-halogeno (meth) acrylic acid, α-carboxyethyl acrylate, acrylamidoglycolic acid, β-carboxyethyl acrylate, allyloxy-3-hydroxybutanoic acid, allyloxymalonic acid, allylsuccinic acid or allylmalonic acid, with other molecules present Carboxyl groups with each a compound of the formula (II) given above may be esterified. R * is particularly preferably an ethylenically unsaturated carboxylic acid residue for the rest of acrylic acid, methacrylic acid, maleic acid or fumaric acid, a second carboxyl group present in the molecule optionally with a compound of the ones mentioned above

Formula (II) is esterified.

If R is a radical R * -C (O) -O- and R * is the radical of a homo- or copolymer according to (Ib), then R * is e.g. for the remainder of a homopolymer or copolymer which is composed of one or more of the abovementioned α, β-unsaturated carboxylic acid derivatives and, if appropriate, one or more copolymerizable monoethylenically unsaturated monomers and is partially or completely esterified with a compound of the formula (II) given above.

Suitable copolymerizable monoethylenically unsaturated monomers are e.g. Esters, amides or nitriles of unsaturated carboxylic acids, e.g. Methyl or ethyl acrylate, methyl or ethyl methacrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, acrylamide, methacrylamide, N-alkyl- ( meth) acrylamides, acrylonitrile or methacrylonitrile. Another group of suitable comonomers includes sulfonic acid groups or monomers containing phosphonic acid group, e.g. (Meth) allylsulfonic acid, vinylsulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, styrene sulfonic acid, acrylamidomethanesulfonic acid, 3-sulfopropyl (meth) acrylates, 3-sulfopropyl itaconate, 2-acrylamido-2-methylpropanesulfonic acid, vinyl phosphonate, allyl phosphonate and acrylamidomethylpropane. Also suitable as monomers are N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinylimidazole, N-vinylmethylimidazole, N-vinyl-2 -methylimidazole, N-vinylimidazoline, methyl vinyl ketone, vinyl acetate, vinyl propionate, vinyl butyrate, styrene, olefins with, for example 2 to 10 carbon atoms such as ethylene, propylene, isobutylene, hexene, diisobutene and vinyl alkyl ethers such as methyl vinyl ether, ethyl vinyl ether, dimethoxyethylene, n-butyl vinyl ether, isobutyl vinyl ether, hexyl vinyl ether or octyl vinyl ether, and mixtures of the monomers mentioned.

The homopolymers and copolymers on which R * is based preferably have a molecular weight of 100 to 1,000,000, particularly preferably from 500 to 50,000 and particularly preferably from 500 to 5,000.

worin B und q unabhängig je die zuvor angegebene Bedeutung haben und R₄ und R₅ unabhängig voneinander je die Bedeutung von R₁ haben, und gegebenenfallsThe homopolymers or copolymers according to (Ib) used according to the invention are, for example, polymers containing structural elements of the formula

wherein B and q each independently have the meaning given above and R₄ and R₅ each independently have the meaning of R₁, and optionally

worin A der Rest eines der zuvor genannten copolymerisierbaren monoethylenisch ungesättigten Monomere ist.Structural elements of the formula

wherein A is the residue of one of the aforementioned copolymerizable monoethylenically unsaturated monomers.

Here, the meanings and preferences given above apply to B and for R₄ and R₅ independently the meanings and preferences given previously for R₁; q preferably represents the number 0.

Homopolymers and copolymers of mono-, di- or tricarboxylic acid derivatives and optionally one or more comonomers are preferred, in which 5-100%, preferably 10-85% and particularly preferably 10-40% of the carboxyl groups present in the form of 2-hydroxy-3 chloropropyl ester and the remaining carboxyl groups in the form of a C₁-C₄ alkyl ester or, preferably, in the form of the free acid or one of its salts. Homopolymers or copolymers based on acrylic acid or maleic acid are particularly preferred.

If R is a radical of the formula R * -C (O) -O- and R * is the radical of a modified sugar derivative according to (Ic), R * is, for example, the radical of a carboxyl group-containing one Mono-, di-, tri-, oligo- or polysaccharides. Examples of such saccharides are carboxymethyl cellulose, carboxymethyl starch, oxidized sugar derivatives, reaction products of a carbohydrate material with an α, β-unsaturated dicarboxylic acid, as are known, for example, from DE-A 2,439,155, or alkyl mono- and alkyl polyglucoside ether carboxylates, as described, for example, from EP-A 0 457 155 are known; the saccharides mentioned are in each case partially or completely esterified with a compound of the formula (II) given above.

If R is a radical R * -C (O) -O- and R * is a radical of a saturated carboxylic acid according to (Id), the underlying carboxylic acid has e.g. a molecular weight of 46 to 50,000, and preferably 60 to 5,000.

Examples of saturated carboxylic acids which can form the basis of the radical R * are e.g. saturated C₁-C₂₀ mono- or dicarboxylic acids such as e.g. Acetic acid, propionic acid or succinic acid, isoderinediacetic acid, nitrilotriacetic acid, ethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylenediaminotrieslacetic acid, hydroxycarboxylic acids, e.g. Malic acid, citric acid, hydroxycitric acid, lactic acid, tartronic acid, tartaric acid, amino acid derivatives, e.g. Aspartic acid, β-alanine, glutamic acid, polyaspartic acid, hydroxyiminodisuccinic acid or their derivatives, e.g. in US-A 4,983,315, oligo- or polyglycerol ether carboxylates, e.g. are known from DE-A 4 014 202, or glycerol derivatives such as those e.g. are known from US-A 4,639,325.

R * as the residue of a saturated carboxylic acid is preferably the residue of a C₂-C₁₀ mono- or dicarboxylic acid, C₂-C₁₀-hydroxycarboxylic acid or hydroxyiminodisuccinic acid and particularly preferably the residue of a saturated C₂-C₄-mono- or dicarboxylic acid or C₃-C₆- Hydroxy carboxylic acid.

The diols of the formula

HO CH₂ - CH (OH) - CH₂Y,


the ethylenically unsaturated mono-, di- or tricarboxylic acid derivatives according to (Ia) and the polymers according to (Ib) are known, for example, from DE-OS 2,424,892 or can be obtained by methods known per se.

The polymers according to (Ib) can be known per se, for example by (co) polymerizing the corresponding monomers, which correspond, for example, to the formula (1) given above Way will be obtained. If appropriate, the monomers of the formula (1) are copolymerized with further monomers, for example those on which the radical A is based.

und gegebenenfalls Strukturelemente der Formel

worin für R₄, R₅, A und q jeweils die zuvor angegebenen Bedeutungen und Bevorzugungen gelten und X für Wasserstoff oder ein Kation steht, mit einem Epihalogenohydrin, vorzugsweise Epibromhydrin oder insbesondere Epichlorhydrin, in Gegenwart eines Katalysators umsetzt. Als Katalysator verwendet man tertiäre Amine, quaternären Ammoniumsalze oder, bevorzugt, Metallsalze wie NaCl, KCl und LiCl. Man führt die Reaktion z.B. im wässrigen Medium oder in einem aus Wasser und einem organischen Lösungsmittel bestehenden Medium aus und verwendet Temperaturen von z.B. 50-100°C und vorzugsweise 70-90°C. Vorzugsweise verwendet man für die Reaktion ein (Co)Polymerisat aus einer oder mehreren der zuvor genannten ethylenisch ungesättigten Mono-, Di- oder Tricarbonsäuren und gegebenenfalls einem oder mehreren Comonomeren ohne freie Säurefunktion, und setzt dieses mit einem Epihalogenohydrin um; hierbei ist der Einsatz eines Ueberschusses an Epihalogenohydrin bevorzugt, jedoch kann durch Variierung der molaren Mengen der Veresterungsgrad beeinflusst werden. Das bei der Reaktion entstehende Dihalogenopropanol und 3-Halogeno-1,2-dihydroxypropan kann in üblicher Weise, z.B. durch azeotrope Destillation, abgetrennt werden; es ist jedoch bevorzugt, das nach der destillativen Entfernung des Dihalogenopropanols erhaltene Gemisch aus Polymer gemäss (Ib) und Diol der Formel (I), worin R Hydroxy ist, nach entsprechender Aufarbeitung und/oder Formulierung direkt als Wollschutzmittel zu verwenden.The polymers according to (Ib) can advantageously be obtained by using a homo- or copolymer containing, for example, structural elements of the formula

and optionally structural elements of the formula

wherein R₄, R₅, A and q each have the meanings and preferences given above and X represents hydrogen or a cation, with an epihalohydrin, preferably epibromohydrin or in particular epichlorohydrin, in the presence of a catalyst. Tertiary amines, quaternary ammonium salts or, preferably, metal salts such as NaCl, KCl and LiCl are used as catalysts. The reaction is carried out, for example, in an aqueous medium or in a medium consisting of water and an organic solvent, and temperatures of, for example, 50-100 ° C. and preferably 70-90 ° C. are used. A (co) polymer of one or more of the aforementioned ethylenically unsaturated mono-, di- or tricarboxylic acids and optionally one or more comonomers without a free acid function is preferably used for the reaction, and this is reacted with an epihalohydrin; the use of an excess of epihalohydohydrin is preferred, but the degree of esterification can be influenced by varying the molar amounts. The dihalopropanol and 3-halo-1,2-dihydroxypropane formed in the reaction can be separated off in a conventional manner, for example by azeotropic distillation; it is preferred, however, to obtain the mixture of polymer according to (Ib) and after the distillative removal of the dihalopropanol Diol of the formula (I), in which R is hydroxy, can be used directly as wool protection agent after appropriate work-up and / or formulation.

The modified sugar derivatives according to (Ic) can be obtained analogously to the polymers according to (Ib) by reacting the known carboxyl group-containing modified sugar derivatives with an epihalohydrin.

The carboxylic acid derivatives according to (Id) can be obtained analogously to the compounds according to (Ia).

• (aI) die Verwendung eines Wollschutzmittels enthaltend als alleinige Wirksubstanz das Diol der Formel HO-CH₂-CH(OH)-CH₂Cl;
• (aII) die Verwendung eines Wollschutzmittels enthaltend eine oder mehrere Verbindungen der zuvor angegebenen Formel (1), worin B für den Rest -CH₂-CH(OH)-CH₂Cl steht, als Wirksubstanz;
• (aIII) die Verwendung eines Wollschutzmittels enthaltend ein Homo- oder Copolymer, welches aus Strukturelementen der zuvor angegebenen Formel (2) und gegebenenfalls Strukturelementen der Formel (3) aufgebaut ist, und worin 5-100 %, vorzugsweise 10-85% und besonders bevorzugt 10-40 % der vorhandenen Carboxylgruppen in Form des 2-Hydroxy-3-chlorpropylesters und die verbleibenden Carboxylgruppen in Form eines C₁-C₄-Alkylesters oder in Form der freien Säure oder eines ihrer Salze vorliegen, als Wirksubstanz;
• (aIV) die Verwendung eines Wollschutzmittels enthaltend ein Gemisch aus dem Diol der Formel HO-CH₂-CH(OH)-CH₂Cl und einem Homo- oder Copolymerisat enthaltend Strukturelemente der Formel (2), worin B den Rest -CH₂-CH(OH)-CH₂Cl bedeutet;
• (aV) die Verwendung eines Wollschutzmittels enthaltend ein Gemisch aus dem Diol der Formel HO-CH₂-CH(OH)-CH₂Cl und einer Verbindung der zuvor angegebenen Formel (I), worin Y Chlor ist, R für einen Rest R*-C(O)-O- steht und R* den Rest einer gesättigten C₂-C₄-Mono- oder Dicarbonsäure bedeutet.

The wool protection agents used according to the invention can contain one or more of the compounds of the formula (I). Preferred embodiments of the present invention relate to

• (aI) the use of a wool protection agent containing, as the sole active substance, the diol of the formula HO-CH₂-CH (OH) -CH₂Cl;
• (aII) the use of a wool protection agent containing one or more compounds of the formula (1) given above, in which B represents the radical -CH₂-CH (OH) -CH₂Cl, as the active substance;
• (aIII) the use of a wool protection agent containing a homopolymer or copolymer which is composed of structural elements of the formula (2) given above and optionally structural elements of the formula (3), and in which 5-100%, preferably 10-85% and particularly preferably 10-40% of the carboxyl groups present are in the form of the 2-hydroxy-3-chloropropyl ester and the remaining carboxyl groups are in the form of a C₁-C₄ alkyl ester or in the form of the free acid or one of its salts, as the active substance;
• (aIV) the use of a wool protection agent containing a mixture of the diol of the formula HO-CH₂-CH (OH) -CH₂Cl and a homo- or copolymer containing structural elements of the formula (2), in which B represents the radical -CH₂-CH (OH) -CH₂Cl;
• (aV) the use of a wool protection agent containing a mixture of the diol of the formula HO-CH₂-CH (OH) -CH₂Cl and a compound of the formula (I) given above, in which Y is chlorine, R for a radical R * -C ( O) -O- stands and R * the rest of one saturated C₂-C₄ mono- or dicarboxylic acid.

• (a) ethylenisch ungesättigte Mono-, Di- oder Tricarbonsäurederivate,
• (b) Homo- oder Copolymerisate aus ethylenisch ungesättigten Mono-, Di- oder Tricarbonsäurederivaten und gegebenenfalls einem oder mehreren Comonomeren,
• (c) carboxylgruppenhaltige, modifizierte Zuckerderivate,
• (d) gesättigte Mono-, Di-, Tri-, Tetra- oder Pentacarbonsäurederivate oder
• (e) Salze von Mineralsäuren.

Another preferred embodiment of the present invention relates to the use of a wool protection agent containing a diol of the formula

HO-CH₂-CH (OH) -CH₂Y (II),


where Y has the meaning given above and in particular represents chlorine, and other compounds which have no radical of the formula -O-CH₂-CH (OH) -CH₂-Y. Examples of such compounds without a radical -O-CH₂-CH (OH) -CH₂-Y are mentioned

• (a) ethylenically unsaturated mono-, di- or tricarboxylic acid derivatives,
• (b) homopolymers or copolymers of ethylenically unsaturated mono-, di- or tricarboxylic acid derivatives and optionally one or more comonomers,
• (c) modified sugar derivatives containing carboxyl groups,
• (d) saturated mono-, di-, tri-, tetra- or pentacarboxylic acid derivatives or
• (e) salts of mineral acids.

Suitable ethylenically unsaturated carboxylic acid derivatives according to (a) correspond, for example, to the formula (1) given above, in which B is hydrogen, alkyl, a group - (CH₂-CH₂-O) _x - (CH₂-CH [CH₃] -O) _y -R₃ or is a cation and R₁, R₂, R₃, p, q, x and y each have the meaning given above.

Examples of preferred carboxylic acid derivatives according to (a) are itaconic acid, mesaconic acid, citraconic acid, vinyl acetic acid, vinyl propionic acid, crotonic acid, aconitic acid, allylacetic acid, vinyloxyacetic acid, allyloxyacetic acid, α, β-dimethyl (meth) acrylic acid, methylene malonic acid, 2-hydroxy (meth) acrylic acid, 2 -Halogeno (meth) acrylic acid, α-carboxyethyl acrylate, acrylamidoglycolic acid, β-carboxyethyl acrylate, allyloxy-3-hydroxy-butanoic acid, allyloxymalonic acid, allylsuccinic acid, allylmalonic acid or especially acrylic acid, methacrylic acid, maleic acid or fumaric acid.

Examples of suitable homopolymers or copolymers according to (b) are homopolymers or copolymers which are composed of one or more of the abovementioned α, β-unsaturated carboxylic acid derivatives and, if appropriate, one or more of the abovementioned copolymerizable monoethylenically unsaturated monomers. Homo- or copolymers based on (meth) acrylic acid or maleic acid with a molecular weight of, for example, 500 to 5000 are preferred.

Examples of modified sugar derivatives according to (c) are carboxymethyl cellulose, carboxymethyl starch, oxidized sugar derivatives, reaction products from a carbohydrate material, an α, β-unsaturated dicarboxylic acid and an alkaline earth metal hydroxide, as described e.g. are known from DE-A 2,439,155, or alkyl mono- and alkyl polyglucoside ether carboxylates, such as those e.g. are known from EP-A 0 457 155.

Examples of suitable saturated carboxylic acid derivatives according to (d) are saturated C₁-C₂₀ mono- or dicarboxylic acids such as e.g. Acetic acid, propionic acid or succinic acid, isoderinediacetic acid, nitrilotriacetic acid, ethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylenediaminotrieslacetic acid, hydroxycarboxylic acids, e.g. Malic acid, citric acid, hydroxycitric acid, lactic acid, tartronic acid, tartaric acid, amino acid derivatives, e.g. Aspartic acid, β-alanine, glutamic acid, polyaspartic acid, hydroxyiminodisuccinic acid or their derivatives, e.g. in US-A 4,983,315, oligo- or polyglycerol ether carboxylates, e.g. are known from DE-A 4 014 202, or glycerol derivatives such as those e.g. are known from US-A 4 639 325, and their salts.

The saturated carboxylic acid derivatives (d) used are preferably saturated C₂-C₁₀ mono- or dicarboxylic acids, C₂-C₁₀-hydroxycarboxylic acids or hydroxyiminodisuccinic acid, and their alkaline earth metal, alkali metal or ammonium salts and particularly preferably a C₂-C₄ mono- or dicarboxylic acid or one C₃-C₅-hydroxycarboxylic acid. Examples of particularly preferred carboxylic acid derivatives (d) are malic acid, citric acid, lactic acid, tartaric acid, acetic acid, propionic acid or succinic acid.

Examples of suitable salts of mineral acids (e) are alkaline earth, alkali or ammonium salts of mineral acids such as e.g. Hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid. Alkali metal salts of hydrochloric acid, sulfuric acid or phosphoric acid, e.g. Sodium, potassium or lithium chloride, sulfate or phosphate.

• (bI) die Verwendung eines Wollschutzmittels enthaltend das Diol der Formel
  
          HO-CH₂-CH(OH)-CH₂Cl
  
  und eine C₂-C₁₀-Hydroxycarbonsäure;
• (bII) die Verwendung eines Wollschutzmittels enthaltend das Diol der Formel
  
          HO-CH₂-CH(OH)-CH₂Cl
  
  und eine gesättigte C₂-C₁₀-Mono- oder Dicarbonsäure;
• (bIII) die Verwendung eines Wollschutzmittels enthaltend das Diol der Formel
  
          HO-CH₂-CH(OH)-CH₂Cl
  
  und Acrylsäure, Methacrylsäure, Maleinsäure oder Fumarsäure;
• (bIV) die Verwendung eines Wollschutzmittels enthaltend das Diol der Formel
  
          HO-CH₂-CH(OH)-CH₂Cl
  
  und ein Homo- oder Copolymerisat enthaltend Strukturelemente der zuvor angegebenen Formel (2), worin B Wasserstoff oder ein Kation bedeutet;
• (bV) die Verwendung eines Wollschutzmittels enthaltend das Diol der Formel
  
          HO-CH₂-CH(OH)-CH₂Cl
  
  und ein Homo- oder Copolymer auf der Basis von (Meth)acrylsäure oder Maleinsäure mit einem Molekulargewicht von 500 bis 5000;
• (bVI) die Verwendung eines Wollschutzmittels enthaltend das Diol der Formel
  
          HO-CH₂-CH(OH)-CH₂Cl
  
  und ein Erdalkali-, Alkali- oder Ammoniumsalz der Salzsäure, Schwefelsäure oder Phosphorsäure.

In particular, preferred embodiments of the present invention relate to

• (bI) the use of a wool protection agent containing the diol of the formula
  
  HO-CH₂-CH (OH) -CH₂Cl
  
  and a C₂-C₁₀ hydroxycarboxylic acid;
• (bII) the use of a wool protection agent containing the diol of the formula
  
  HO-CH₂-CH (OH) -CH₂Cl
  
  and a saturated C₂-C₁₀ mono- or dicarboxylic acid;
• (bIII) the use of a wool protection agent containing the diol of the formula
  
  HO-CH₂-CH (OH) -CH₂Cl
  
  and acrylic acid, methacrylic acid, maleic acid or fumaric acid;
• (bIV) the use of a wool protection agent containing the diol of the formula
  
  HO-CH₂-CH (OH) -CH₂Cl
  
  and a homo- or copolymer containing structural elements of the above formula (2), in which B is hydrogen or a cation;
• (bV) the use of a wool protection agent containing the diol of the formula
  
  HO-CH₂-CH (OH) -CH₂Cl
  
  and a homo- or copolymer based on (meth) acrylic acid or maleic acid with a molecular weight of 500 to 5000;
• (bVI) the use of a wool protection agent containing the diol of the formula
  
  HO-CH₂-CH (OH) -CH₂Cl
  
  and an alkaline earth, alkali or ammonium salt of hydrochloric acid, sulfuric acid or phosphoric acid.

If a wool protection agent is used, a mixture of a diol of formula (II) and other compounds e.g. a mixture according to (aIV), (aV) or (bI) - (bVI), the components are advantageously in a weight ratio diol: other compounds from 5:95 to 80:20, preferably 5:95 to 50:50, in particular preferably 5:95 to 30:70 and particularly preferably from 10:90 to 30:70.

An aqueous solution containing ≦ 10% by weight, in particular 5-10% by weight, of a diol of the formula (II) and optionally 30 to 50% by weight, in each case based on the overall formulation, are preferably used as wool protection agents another connection eg according to (aIV), (aV) or (bI) - (bVI).

The general procedure is to have the wool-containing fiber material in the presence from, for example, 0.5 to 10% by weight, preferably 1 to 6% by weight, based on the weight of the material to be dyed, dyes one or more compounds of the formula (I) according to the invention.

A preferred embodiment of the present invention relates to a process for dyeing wool-containing fiber materials with anionic dyes, which is characterized in that these materials contain a wool preservative in the presence of 0.5 to 10% by weight, based on the weight of the material to be dyed the diol of the formula

HO -CH₂ CH (OH) - CH₂Cl


colors.

A further preferred embodiment of the present invention relates to a method for dyeing wool-containing fiber materials with anionic dyes, which is characterized in that these materials in the presence of 0.5 to 10% by weight, based on the weight of the material to be dyed, of a wool protection agent containing the diol of the formula

HO -CH₂ CH (OH) - CH₂Cl


and a homo- or copolymer containing structural elements of the formula (2) given above, in which B is hydrogen or a cation and R₄ and R₅ independently of one another are hydrogen, hydroxyl, cyano, halogen or C₁-C₄alkyl and q is the number 0, in the weight ratio of diol: polymer colors 5:95 to 30:70 and preferably 10:90 to 30:70.

A particularly preferred embodiment of the present invention relates to a method for dyeing wool-containing fiber materials with anionic dyes, which is characterized in that these materials in the presence of 0.5 to 10 wt .-%, based on the weight of the material to be dyed, a wool protection agent containing the diol of the formula

HO -CH₂ CH (OH) - CH₂Cl


and a homo- or copolymer containing structural elements of the formula (2) given above, in which B is a radical -CH₂-CH (OH) -CH₂Cl, R₄ and R₅ independently of one another hydrogen, hydroxy, cyano, halogen, C₁-C₄-alkyl or - C (O) O-CH₂-CH (OH) -CH₂Cl mean and q represents the number 0, in the weight ratio diol: polymer colors from 5:95 to 30:70 and preferably 10:90 to 30:70.

A particularly preferred embodiment of the present invention relates to a A process for dyeing wool-containing fiber materials with anionic dyes, which is characterized in that these materials in the presence of 0.5 to 10 wt .-%, based on the weight of the material to be dyed, of a wool protection agent containing the diol of the formula

HO -CH₂ CH (OH) - CH₂Cl


and a C₂-C₁₀ hydroxycarboxylic acid, a saturated C₂-C₁₀ mono- or dicarboxylic acid or an alkaline earth metal, alkali metal or ammonium salt of hydrochloric acid, sulfuric acid or phosphoric acid in a weight ratio of diol: hydroxycarboxylic acid, carboxylic acid or mineral salt from 5:95 to 30:70 and preferably colors 10:90 to 30:70.

The wool-containing fiber material can be wool alone or a mixture of e.g. Trade wool / polyamide or wool / polyester. Mixtures of wool and synthetic polyamide are preferably dyed with anionic dyes and mixtures of wool and polyester fibers are preferably dyed with disperse and anionic dyes. Suitable anionic dyes and disperse dyes are known to the person skilled in the art.

The fiber material can be in various stages of processing, e.g. in the form of yarns, flakes, sliver, knitwear such as knitwear or knitted fabrics, as a nonwoven fabric or preferably as a woven fabric.

The mixed fiber materials are preferably fiber blends of wool and polyester, which are generally present in a proportion of 20 to 50 parts by weight of wool to 80-50 parts by weight of polyester. The fiber mixtures preferred for the process contain 45 parts of wool and 55 parts of polyester fibers.

The liquor ratio can be selected within a wide range in the process according to the invention; it is e.g. 1: 1 to 1: 100 and preferably 1:10 to 1:50.

In addition to the dye, water and the wool auxiliary, the dyebath can contain other customary additives. Worth mentioning are e.g. Mineral acids, organic acids and / or their salts, which serve to adjust the pH value of the dye bath, further electrolytes, leveling agents, wetting agents and defoamers and, if dyeing wool / polyester mixtures, carriers and / or dispersant.

The dyebath has a pH of, for example, 4 to 6.5 and preferably 5.2 to 5.8 on. The process according to the invention is generally carried out at a temperature of, for example, 60 to 130.degree.

If the material to be dyed is wool alone, the dyeing is expediently carried out using the exhaust process, e.g. at a temperature in the range 60 to 106 ° C, preferably 95 to 98 ° C. The dyeing time can vary depending on the requirements, but is preferably 60-120 minutes.

The dyeing of the polyester / wool mixed fiber materials is advantageously carried out in a single bath from an aqueous liquor using the exhaust process. Dyeing is preferably carried out by the so-called high-temperature process in closed, pressure-resistant apparatus at temperatures above 100 ° C., expediently between 110 and 125 ° C. and preferably at 118-120 ° C. and optionally under pressure.

The mixed fiber materials can also be processed by the usual carrier dyeing process at temperatures below 106 ° C, e.g. in the temperature range from 75 to 98 ° C in the presence of one or more carriers.

The dyeing of the polyester / wool mixed fiber materials can be carried out by first treating the material to be dyed with the wool protection agent and, if appropriate, the carrier, and then dyeing. One can also proceed in such a way that the material to be dyed is treated simultaneously with the wool preservative, the dyes and, if appropriate, auxiliaries. The textile mixed fiber material is preferably added to a liquor which contains the wool protection agent and, if appropriate, other customary auxiliaries and has a temperature of 40-50 ° C., and the material is treated at this temperature for 5 to 15 minutes. The temperature is then increased to about 60 to 70 ° C., the dye is added, the mixture is slowly heated to the dyeing temperature and then dyeing is carried out at this temperature for about 20 to 60, preferably 30 to 45 minutes. Finally, the liquor is cooled to about 60 ° C and the colored material is worked up as usual.

By means of the method according to the invention, it is possible to dye wool or in particular wool / polyester fiber mixtures at high temperature with perfect protection of the wool content, ie while maintaining the important fiber-technological properties of the wool, such as tear resistance, bursting resistance and elongation. It should also be emphasized that the proportion of polyester in mixed fabrics shows no yellowing.

The following examples illustrate the invention. Parts mean parts by weight, percentages by weight.

Production of homopolymers and copolymers

Example 1: 87.5 parts of hydrolyzed polymaleic anhydride (0.5 COOH equivalents, molecular weight 500-2000, for example Belclene® 200), 80 parts of water and 3 parts of NaCl are placed in a sulfonation flask. After 31 parts of epichlorohydrin have been added, the mixture is heated to 80-85 ° C. for about 1 hour, allowed to cool to room temperature and the reaction mixture is neutralized by adding sodium hydroxide solution (pH ca.6.8). Excess epichlorohydrin and dichloropropanol formed during the reaction are then distilled off azeotropically. It is adjusted to a dry content concentration of 50% and the product is a mixture of 35% polymer, 15% 3-chloro-1,2-propanediol and 50% water.

Example 2: 107 parts of a terpolymer of acrylic ester, vinyl acetate and maleic anhydride (0.6 COOH equivalents, for example Belclene® 283), 90 parts of water and 4 parts of NaCl are placed in a suitable reaction vessel. After adding 90 parts of epichlorohydrin, the mixture is heated to 80-85 ° C. for about 1 hour, allowed to cool to room temperature and the reaction mixture is neutralized by adding sodium hydroxide solution (pH about 6.8). Excess epichlorohydrin and dichloropropanol formed during the reaction are then distilled off azeotropically. The product is adjusted to contain 25% polymer, 25% 3-chloro-1,2-propanediol and 50% water.

Example 3: 41.6 parts of a copolymer of acrylic acid and maleic acid (0.3 acid equivalents, for example Sokalan® 12 S), 10 parts of water and 1.8 parts of NaCl are placed in a suitable reaction vessel. After adding 39.3 parts of epichlorohydrin, the mixture is heated to 80-85 ° C. for about 90 minutes, allowed to cool to room temperature and the reaction mixture is neutralized by adding sodium hydroxide solution (pH about 6.8). Excess epichlorohydrin and dichloropropanol formed during the reaction are then distilled off azeotropically. The product is adjusted to contain 35% polymer, 15% 3-chloro-1,2-propanediol and 50% water.

EXAMPLE 4 The procedure is as described in Example 1, but the copolymer used is a copolymer of acrylic acid and maleic acid (molecular weight approx. 50,000, for example Sokalan® CP 7), and the polymeric product obtained after the reaction with epichlorohydrin is precipitated in ethanol and isolate it. It is a polycarboxylic acid derivative in which 30% of the carboxyl groups present are in the form of the 2-hydroxy-3-chloropropyl ester and the remaining 70% are in the form of the free acid or its sodium salt.

Example 5 : A 40% solution of a terpolymer of acrylic ester, vinyl acetate and maleic anhydride (0.6 COOH equivalents, eg Belclene® 283) is prepared and this is approximately neutralized with sodium hydroxide solution (pH approx. 6.8). 85 parts of this polymer solution are mixed with 15 parts of an aqueous solution containing 40% by weight of 3-chloro-1,2-propanediol and stirred homogeneously.

Example 6: 890.4 g of an oxidized oligosaccharide (0.8 COOH equivalents, molecular weight 500-3000) are brought to pH 1.1 in a sulfonation flask by adding 800 ml of 1N hydrochloric acid. After adding 162.8 g of epichlorohydrin, the mixture is heated to 80-85 ° C. until approximately 90% of the carboxyl groups have reacted (approximately 2 hours), then allowed to cool to room temperature and the reaction mixture is neutralized. Excess epichlorohydrin and dichloropropanol formed during the reaction are then distilled off azeotropically and the remaining solution is adjusted so that it contains 34% by weight of sugar derivative, 16% by weight of 3-chloro-1,2-propanediol and 50% by weight of water .

Example 7 : 80 parts of a 15% strength aqueous carboxymethyl starch solution (Brookfield viscosity of a 10% strength solution at 85 ° C. about 60 cps with spindle 1, for example Emsize® 60 from Emsland-Starch) are mixed with 20 parts of a 15 % aqueous 3-chloro-1,2-propanediol solution mixed.

Example 8 : 80 parts of a 50% aqueous solution of the compound of the formula CH₂ (COOH) -CH (COOH) -O-CH₂-CH [O-CH (COOH) -CH₂-COOH] -CH₂-O-CH (COOH ) -CH₂-COOH with pH 8 (preparation according to US-A 4,639,325) are mixed homogeneously with 20 parts of a 50% aqueous 3-chloro-1,2-propanediol solution.

Example 9 : 85 parts of a 50% aqueous solution of the compound of the formula CH₂ (COOH) -CH (COOH) -NH-CO-CH₂-NH-CH (COOH) -CH₂ (COOH) with pH 7 (preparation according to US A 4 983 315) are mixed homogeneously with 15 parts of an aqueous 50% 3-chloro-1,2-propanediol solution.

Example 10 : 85 parts of a 50% acetic acid solution with pH 3 are mixed with 15 parts a 50% aqueous 3-chloro-1,2-propanediol solution mixed homogeneously.

Example 11 : 75 parts of a 30% succinic acid solution with pH 5.5 are mixed homogeneously with 25 parts of a 30% aqueous 3-chloro-1,2-propanediol solution.

Example 12 : 85 parts of a 50% malic acid solution with pH 6 are homogeneously mixed with 15 parts of a 50% aqueous 3-chloro-1,2-propanediol solution.

Example 13 : 82 parts of a 50% lactic acid solution with pH 4 are mixed homogeneously with 18 parts of a 50% aqueous 3-chloro-1,2-propanediol solution.

Example 14 : 85 parts of a 50% N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid solution with pH 6.5 are mixed homogeneously with 15 parts of a 50% aqueous 3-chloro-1,2-propanediol solution .

Example 15 : 80 parts of a 50% polyaspartic acid solution (molecular weight approx. 3000) with pH 6.5 are mixed homogeneously with 20 parts of a 50% aqueous 3-chloro-1,2-propanediol solution.

Example 16 : 57.6 g of citric acid, 55.5 g of epichlorohydrin and 0.5 g of benzyltributylammonium bromide are placed in a sulfonation flask, heated to 80 ° C. for about 4.5 hours and then dried in vacuo. The solution is then adjusted to a dry matter content of 50%.

Example 17 : 69.7 g of maleic acid, 2.6 g of ferric chloride and 100 ml of chloroform are placed in a sulfonation flask. The suspension is heated to 60 ° C. with stirring and then 111 g of epichlorohydrin are added dropwise at 60 to 70 ° C. in the course of about 2 hours. The mixture is left to stir at about 60 to 65 ° C. for about 20 hours, then the reaction solution is diluted by adding water and the pH is adjusted to about 6. The product is extracted with chloroform and then dried in vacuo.

Example 18 : 75 parts of a 35% sulfuric acid solution, which had previously been adjusted to pH 3.3 with sodium hydroxide solution, are mixed homogeneously with 25 parts of a 35% aqueous 3-chloro-1,2-propanediol solution.

Coloring examples

60 Gew.-% Farbstoff der Formel

(R = 50% -CH₂-CH₃ + 50% -C₆H₅)
5,0 Gew.-% Farbstoff der Formel

4,0 Teile Farbstoff der Formel

3,3 Teile Farbstoff der Formel

15,0 Teile Farbstoff der Formel

und 10 Teile Natriumsulfat
der Flotte zugefügt werden. Darauf färbt man 40 min. bei 120°C und kühlt anschliessend die Färbeflotte auf 60°C ab. Darauf wird die übliche Nachwäsche durchgeführt. Man erhält eine reibechte, egale, rote Ton-in-Ton Färbung ohne Einbusse der Wollqualität. Example 19 : 100 parts of a mixed fabric, consisting of 55% polyester and 45% wool, are in a circulation apparatus with a liquor which
2.0 parts of an aqueous preparation according to Example 1,
0.5 parts of a sulfated fatty amine polyglycol ether,
1.0 parts of a commercially available auxiliary mixture (based on carboxylic and phosphoric acid aromatic compounds) and
2.0 parts sodium acetate
contains in 1200 parts of water and is adjusted to pH 5.5 with acetic acid, 5 min. pretreated at 40 ° C. The liquor is then heated to 120 ° C. in the course of 30 minutes, 2.0 parts of the dye mixture consisting of at 70 ° C.
1.6% by weight of dye of the formula

60% by weight of dye of the formula

(R = 50% -CH₂-CH₃ + 50% -C₆H₅)
5.0% by weight of dye of the formula

4.0 parts of dye of the formula

3.3 parts of dye of the formula

15.0 parts of dye of the formula

and 10 parts of sodium sulfate
be added to the fleet. It is stained for 40 min. at 120 ° C and then cools the dye liquor to 60 ° C. The usual post-wash is then carried out. You get a rub-fast, level, red tone-on-tone coloring without loss of wool quality.

• (a) 2 Teile der Zubereitung gemäss Beispiel 2,
• (b) 2 Teile der Zubereitung gemäss Beispiel 3,
• (c) 1,5 Teile der Zubereitung gemäss Beispiel 4,
• (d) 2,5 Teile der Zubereitung gemäss Beispiel 5,
• (e) 0,4 Teile 2-Hydroxy-3-chlor-propylacrylat,
• (f) 1 Teil 3-Chlor-1,2-propandiol,
• (g) 3,3 Teile der Zubereitung gemäss Beispiel 6,
• (h) 9 Teile der Zubereitung gemäss Beispiel 7,
• (i) 3 Teile der Zubereitung gemäss Beispiel 9,
• (j) 3,6 Teile der Zubereitung gemäss Beispiel 8,
• (k) 2,4 Teile der Zubereitung gemäss Beispiel 10,
• (l) 4,7 Teile der Zubereitung gemäss Beispiel 11,
• (m) 2,4 Teile der Zubereitung gemäss Beispiel 12,
• (n) 3 Teile der Zubereitung gemäss Beispiel 13,
• (o) 2,6 Teile der Zubereitung gemäss Beispiel 14,
• (p) 3,5 Teile der Zubereitung gemäss Beispiel 15,
• (q) 2 Teile der Zubereitung gemäss Beispiel 16,
• (r) 1,5 Teile der Zubereitung gemäss Beispiel 17 oder
• (s) 3,9 Teile der Zubereitung gemäss Beispiel 18,

so erhält man ebenfalls Färbungen mit guten Eigenschaften und ohne negative Beeinflussung der Wollqualität.Is used instead of the aqueous preparation according to Example 1

• (a) 2 parts of the preparation according to Example 2,
• (b) 2 parts of the preparation according to Example 3,
• (c) 1.5 parts of the preparation according to Example 4,
• (d) 2.5 parts of the preparation according to Example 5,
• (e) 0.4 parts of 2-hydroxy-3-chloropropyl acrylate,
• (f) 1 part of 3-chloro-1,2-propanediol,
• (g) 3.3 parts of the preparation according to Example 6,
• (h) 9 parts of the preparation according to Example 7,
• (i) 3 parts of the preparation according to Example 9,
• (j) 3.6 parts of the preparation according to Example 8,
• (k) 2.4 parts of the preparation according to Example 10,
• (l) 4.7 parts of the preparation according to Example 11,
• (m) 2.4 parts of the preparation according to Example 12,
• (n) 3 parts of the preparation according to Example 13,
• (o) 2.6 parts of the preparation according to Example 14,
• (p) 3.5 parts of the preparation according to Example 15,
• (q) 2 parts of the preparation according to Example 16,
• (r) 1.5 parts of the preparation according to Example 17 or
• (s) 3.9 parts of the preparation according to Example 18,

this also gives dyeings with good properties and without adversely affecting the quality of the wool.

zugesetzt und weitere 5 min. behandelt. Anschliessend wird die Färbeflotte innerhalb von ca. 45 min. auf ca. 98°C erhitzt und das Gewebe 60 min. bei dieser Temperatur gefärbt. Danach lässt man auf ca. 60°C abkühlen, spült wie üblich und trocknet das gefärbte Gewebe. Man erhält eine reibechte, egale Blaufärbung ohne negative Beeinflussung der Wollqualität. Example 20 : 100 parts of a wool fabric with a m² weight of 180 g are in 1000 parts of an aqueous liquor containing 4 parts of ammonium sulfate, 2 parts of an aqueous preparation according to Example 1 and 0.5 parts of a naphthalenesulfonic acid condensate product at 50 ° C. for 10 minutes treated; the pH of the liquor is previously adjusted to about 6 with acetic acid. Then 3 parts of the dye of the formula

added and a further 5 min. treated. The dyeing liquor is then removed within approx. 45 min. heated to approx. 98 ° C and the tissue for 60 min. colored at this temperature. Then allow to cool to approx. 60 ° C, rinse as usual and dry the dyed fabric. You get a rub-fast, level blue color without negatively influencing the wool quality.

• (a) 2 Teile der Zubereitung gemäss Beispiel 2,
• (b) 2 Teile der Zubereitung gemäss Beispiel 3,
• (c) 1,5 Teile der Zubereitung gemäss Beispiel 4,
• (d) 2,5 Teile der Zubereitung gemäss Beispiel 5,
• (e) 0,4 Teile 2-Hydroxy-3-chlor-propylacrylat,
• (f) 1 Teil 3-Chlor-1,2-propandiol,
• (g) 3,3 Teile der Zubereitung gemäss Beispiel 6,
• (h) 9 Teile der Zubereitung gemäss Beispiel 7,
• (i) 3 Teile der Zubereitung gemäss Beispiel 9,
• (j) 3,6 Teile der Zubereitung gemäss Beispiel 8,
• (k) 2,4 Teile der Zubereitung gemäss Beispiel 10,
• (l) 4,7 Teile der Zubereitung gemäss Beispiel 11,
• (m) 2,4 Teile der Zubereitung gemäss Beispiel 12,
• (n) 3 Teile der Zubereitung gemäss Beispiel 13,
• (o) 2,6 Teile der Zubereitung gemäss Beispiel 14,
• (p) 3,5 Teile der Zubereitung gemäss Beispiel 15,
• (q) 2 Teile der Zubereitung gemäss Beispiel 16,
• (r) 1,5 Teile der Zubereitung gemäss Beispiel 17 oder
• (s) 3,9 Teile der Zubereitung gemäss Beispiel 18,

so erhält man ebenfalls Färbungen mit guten Eigenschaften und ohne negative Beeinflussung der Wollqualität.Is used instead of the aqueous preparation according to Example 1

• (a) 2 parts of the preparation according to Example 2,
• (b) 2 parts of the preparation according to Example 3,
• (c) 1.5 parts of the preparation according to Example 4,
• (d) 2.5 parts of the preparation according to Example 5,
• (e) 0.4 parts of 2-hydroxy-3-chloropropyl acrylate,
• (f) 1 part of 3-chloro-1,2-propanediol,
• (g) 3.3 parts of the preparation according to Example 6,
• (h) 9 parts of the preparation according to Example 7,
• (i) 3 parts of the preparation according to Example 9,
• (j) 3.6 parts of the preparation according to Example 8,
• (k) 2.4 parts of the preparation according to Example 10,
• (l) 4.7 parts of the preparation according to Example 11,
• (m) 2.4 parts of the preparation according to Example 12,
• (n) 3 parts of the preparation according to Example 13,
• (o) 2.6 parts of the preparation according to Example 14,
• (p) 3.5 parts of the preparation according to Example 15,
• (q) 2 parts of the preparation according to Example 16,
• (r) 1.5 parts of the preparation according to Example 17 or
• (s) 3.9 parts of the preparation according to Example 18,

this also gives dyeings with good properties and without negative ones Influencing wool quality.

Example 21 : 10 parts each of a wool fabric and 10 parts of a bleached polyester fabric are combined in 200 parts of a liquor adjusted to pH 5.5 with acetic acid, containing 0.8 parts of the aqueous preparation according to Example 1 and 0.4 parts of sodium acetate for 5 minutes. pretreated at 40 ° C. The liquor is then heated within 30 minutes. to 120 ° C, the fabric is treated for 40 min. at this temperature and then cools down to 60 ° C. After the blind bath treatment (without dye) carried out in this way, the wool fabric shows no loss in quality, for example with regard to bursting resistance; the polyester accompanying fabric also shows no yellowing due to the hydrolytic degradation of the wool.

• (a) 0,8 Teile der Zubereitung gemäss Beispiel 2,
• (b) 0,8 Teile der Zubereitung gemäss Beispiel 3,
• (c) 0,6 Teile der Zubereitung gemäss Beispiel 4,
• (d) 1 Teil der Zubereitung gemäss Beispiel 5,
• (e) 0,2 Teile 2-Hydroxy-3-chlor-propylacrylat,
• (f) 0,4 Teile 3-Chlor-1,2-propandiol,
• (g) 1,3 Teile der Zubereitung gemäss Beispiel 6,
• (h) 3,6 Teile der Zubereitung gemäss Beispiel 7,
• (i) 1,2 Teile der Zubereitung gemäss Beispiel 9,
• (j) 1,5 Teile der Zubereitung gemäss Beispiel 8,
• (k) 1 Teil der Zubereitung gemäss Beispiel 10,
• (l) 1,9 Teile der Zubereitung gemäss Beispiel 11,
• (m) 1 Teil der Zubereitung gemäss Beispiel 12,
• (n) 1,1 Teile der Zubereitung gemäss Beispiel 13,
• (o) 1,1 Teile der Zubereitung gemäss Beispiel 14,
• (p) 1,4 Teile der Zubereitung gemäss Beispiel 15,
• (q) 0,8 Teile der Zubereitung gemäss Beispiel 16,
• (r) 0,6 Teile der Zubereitung gemäss Beispiel 17 oder
• (s) 1,6 Teile der Zubereitung gemäss Beispiel 18,

verwendet.Similar good effects with regard to the bursting resistance of the wool and the non-yellowing of the polyester fabric are achieved if instead of the aqueous preparation according to Example 1

• (a) 0.8 parts of the preparation according to Example 2,
• (b) 0.8 parts of the preparation according to Example 3,
• (c) 0.6 parts of the preparation according to Example 4,
• (d) 1 part of the preparation according to Example 5,
• (e) 0.2 parts of 2-hydroxy-3-chloropropyl acrylate,
• (f) 0.4 parts of 3-chloro-1,2-propanediol,
• (g) 1.3 parts of the preparation according to Example 6,
• (h) 3.6 parts of the preparation according to Example 7,
• (i) 1.2 parts of the preparation according to Example 9,
• (j) 1.5 parts of the preparation according to Example 8,
• (k) 1 part of the preparation according to Example 10,
• (l) 1.9 parts of the preparation according to Example 11,
• (m) 1 part of the preparation according to Example 12,
• (n) 1.1 parts of the preparation according to Example 13,
• (o) 1.1 parts of the preparation according to Example 14,
• (p) 1.4 parts of the preparation according to Example 15,
• (q) 0.8 parts of the preparation according to Example 16,
• (r) 0.6 parts of the preparation according to Example 17 or
• (s) 1.6 parts of the preparation according to Example 18,

used.

Claims (19)

Process for dyeing wool-containing fiber materials with anionic dyes, characterized in that these materials in the presence of a wool protection agent containing at least one compound of the formula

R - CH₂ - CH (OH) - CH₂ - Y (I),

where Y is halogen, R is hydroxy or a radical R * -C (O) -O- and R * (Ia) the remainder of an ethylenically unsaturated mono-, di- or tricarboxylic acid, wherein in the case of a di- or tricarboxylic acid the remaining carboxyl group or carboxyl groups may be partially or completely with a compound of the formula

HO-CH₂-CH (OH) -CH₂-Y (II)

are esterified and Y has the meaning given above, (Ib)) the remainder of a homo- or copolymer of ethylenically unsaturated mono-, di- or tricarboxylic acid derivatives and optionally one or more comonomers, in which the carboxyl groups are partially or completely esterified with a compound of the formula (II) given above, (Ic) the remainder of a modified sugar derivative containing carboxyl groups, in which, if this has more than one carboxyl group, the remaining carboxyl group or carboxyl groups are optionally esterified with a compound of the formula (II) given above, or (Id) the remainder of a saturated mono-, di-, tri-, tetra- or pentacarboxylic acid, wherein in the case of a di-, tri-, tetra- or pentacarboxylic acid the remaining carboxyl group or carboxyl groups may be partially or completely with a compound of the above specified formula (II)
are esterified is
colors. A method according to claim 1, characterized in that Y is chlorine. A method according to claim 1 or 2, characterized in that a wool protection agent containing a compound according to (Ia) of the formula

wherein R₁ and R₂ independently of one another are hydrogen, hydroxy, halogen, alkyl, or a group - (CH₂) _p -COOB, B is hydrogen, the radical -CH₂-CH (OH) -CH₂Y, alkyl, a group - (CH₂- CH₂-O) _x - (CH₂-CH [CH₃] -O) _y -R₃ or represents a cation, p and q each independently represent a number 0 to 2, x and y each independently represent a number from 0 to 250 stand, the sum (x + y) ≧ 1 and R₃ independently has the meaning of R1, with the proviso that at least one of the substituents B present in the molecule is a radical -CH₂-CH (OH) -CH₂Y and Y has the meaning given in claim 1. Process according to one of claims 1 to 3, characterized in that R * in formula (I) denotes the residue of acrylic acid, methacrylic acid, maleic acid or fumaric acid, a second carboxyl group present in the molecule optionally having a compound of the formula given in claim 1 ( II) is esterified. A method according to claim 1 or 2, characterized in that R * as the residue of a homo- or copolymer according to (Ib) structural elements of the formula

wherein R₄ and R₅ each independently represent hydrogen, hydroxy, chlorine, methyl, ethyl or a group -CH₂-COOB, B represents hydrogen, the radical -CH₂-CH (OH) -CH₂Cl or a cation and q is the number 0 means, with the proviso that at least one of the substituents B present in the molecule is a radical -CH₂-CH (OH) -CH₂Y and Y has the meaning given in claim 1, and optionally structural elements of the formula

wherein A is the residue of a copolymerizable monoethylenically unsaturated monomer. A method according to claim 5, characterized in that the homo- and copolymer has a molecular weight of 500-50000 and preferably from 500 to 5000. A method according to claim 5 or 6, characterized in that 5-100%, preferably 10-85% and particularly preferably 10-40% of the carboxyl groups present in the homo- and copolymer in the form of the 2-hydroxy-3-chloropropyl ester and the remaining carboxyl groups are in the form of a C₁-C₄ alkyl ester or in the form of the free acid or one of its salts. A method according to claim 1 or 2, characterized in that R * stands for the rest of a C₂-C₁₀ mono- or dicarboxylic acid or C₂-C₁₀-hydroxycarboxylic acid or for the rest of the hydroxyiminodisuccinic acid. A method according to claim 1 or 2, characterized in that the wool-containing fiber materials in the presence of a wool protection agent containing as the sole active substance, the diol of the formula

HO-CH₂-CH (OH) -CH₂-Cl

colors. A method according to claim 1 or 2, characterized in that the wool-containing fiber materials in the presence of a wool protection agent containing the diol of the formula

HO-CH₂-CH (OH) -CH₂-Cl

and a homo- or copolymer containing structural elements of the formula (2) given in Claim 5, in which B denotes the radical -CH₂-CH (OH) -CH₂-Cl, colors. A method according to claim 1 or 2, characterized in that the wool-containing fiber materials in the presence of a wool protection agent containing the diol of the formula

HO-CH₂-CH (OH) -CH₂-Cl

and a C₂-C₁₀ hydroxycarboxylic acid colors. A method according to claim 1 or 2, characterized in that the wool-containing fiber materials in the presence of a wool protection agent containing the diol of the formula

HO-CH₂-CH (OH) -CH₂-Cl

and colors a saturated C₂-C₁₀ mono- or dicarboxylic acid. A method according to claim 1 or 2, characterized in that the wool-containing fiber materials in the presence of a wool protection agent containing the diol of the formula

HO-CH₂-CH (OH) -CH₂-Cl

and a homo- or copolymer containing structural elements of the formula (2) given in Claim 5, in which B denotes hydrogen or a cation, colors. A method according to claim 1, 2 or 13, characterized in that the wool-containing fiber materials in the presence of a wool protection agent containing the diol of the formula

HO-CH₂-CH (OH) -CH₂-Cl

and dyes a homo- or copolymer based on (meth) acrylic acid or maleic acid with a molecular weight of 500 to 5000. A method according to claim 1 or 2, characterized in that the wool-containing fiber materials in the presence of a wool protection agent containing the diol of the formula

HO-CH₂-CH (OH) -CH₂-Cl

and colors an alkaline earth metal, alkali metal or ammonium salt of hydrochloric acid, sulfuric acid or phosphoric acid. Method according to one of claims 9 to 15, characterized in that the wool protection agent ≦ 10 wt .-%, based on the entire formulation, of the diol of the formula

HO-CH₂-CH (OH) -CH₂-Cl

contains. Process according to one of claims 1 to 16, characterized in that the wool-containing fiber material is dyed in the presence of 0.5 to 10% by weight, based on the material to be dyed, of one or more compounds of the formula (I). Method according to one of claims 1 to 17 for dyeing wool / polyester mixed fiber materials by the exhaust process. The material dyed by the method according to claim 1.