EP0277580B1 - Modification de la solidité au mouillé de teintures effectuées avec des colorants au soufre - Google Patents

Modification de la solidité au mouillé de teintures effectuées avec des colorants au soufre Download PDF

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Publication number
EP0277580B1
EP0277580B1 EP88101068A EP88101068A EP0277580B1 EP 0277580 B1 EP0277580 B1 EP 0277580B1 EP 88101068 A EP88101068 A EP 88101068A EP 88101068 A EP88101068 A EP 88101068A EP 0277580 B1 EP0277580 B1 EP 0277580B1
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EP
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Prior art keywords
sulphur
formula
component
denote
dyeing
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EP88101068A
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German (de)
English (en)
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EP0277580A3 (fr
EP0277580A2 (fr
Inventor
Wolfgang Dr. Bauer
Karl-Heinz Dr. Keil
Gert Dr. Nagl
Manfred Kaiser
Joachim Steinbach
Klaus Sternberger
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Sanofi Aventis Deutschland GmbH
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Cassella AG
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/30—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using sulfur dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
    • D06P1/5242—Polymers of unsaturated N-containing compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/04—After-treatment with organic compounds
    • D06P5/08—After-treatment with organic compounds macromolecular
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916—Natural fiber dyeing
    • Y10S8/918—Cellulose textile

Definitions

  • the invention relates to a method for improving the wet fastness of dyeings with sulfur dyes on cellulose.
  • Cellulose can be dyed with sulfur dyes by pulling them out of a long or short liquor or by a variety of processes on dyeing machines and dyeing machines.
  • Semi-continuously e.g. can be dyed on pad-roll systems or by the pad-docking method or by the cold dwell process.
  • Sulfur dyes can also be colored continuously, e.g. according to the pad steam process or the thermosol continuous process, among others
  • water-insoluble sulfur dyes are first converted into the soluble, fiber-affine leuco form by reduction, usually with sodium sulfide or sodium sulf hydrate, and are applied to the fiber in this form and then oxidized.
  • Modified sulfur dyes e.g. in water-soluble form, commercially.
  • the water-soluble sulfur dyes can be dissolved in water without a reducing agent and only become fiber-affine after the addition of reducing agents and alkali.
  • reaction temperatures close to 100 ° C. are required for the use of the aftertreatment agents.
  • the alkylating aftertreatment agents react not only with the sulfur dye, but also with the cellulose and are thereby anchored to the fiber. In the event of a false color, the auxiliary can therefore no longer simply be removed, but it must be destroyed under such drastic oxidation conditions that fiber damage cannot be reliably avoided if the sulfur dye is to be applied evenly when it is dyed again.
  • the object of the present invention is therefore to provide a method by which the wet fastness properties, in particular the wash fastness properties, of dyeings with sulfur dyes can be improved without the disadvantages customary hitherto occurring.
  • the invention is achieved according to the claims.
  • the invention relates to a method for improving the wet fastness of dyeings of the sulfur dyes CI Sulfur Black 1, CI No. 53185; CI Sulfur Black 2, CI No. 53195; CI Sulfur Black 18; CI Sulfur Blue 1, CI No. 53235; CI Sulfur Blue 3, CI No. 53235; CI Sulfur Blue 4, CI No. 53235; CI Sulfur Blue 5, CI No. 53235; CI Sulfur Blue 11, CI No. 53235; CI Sulfur Green 2, CI No. 53571; CI Sulfur Green 36; CI Sulfur Brown 46, CI No. 53015; CI Sulfur Brown 31, CI No.
  • cellulose is treated before, during or after the dyeing process with a polymer containing 16 2/3 to 100 mol% of a compound of the formula I. contains in polymerized form, wherein R1, R2 are hydrogen, (C1-C22) alkyl, which may optionally be interrupted by -CO-NH- or -NH-CO-, or hydroxyalkyl, R3, R4 are hydrogen or methyl, Y is a monovalent anion or a part of a polyvalent anion equivalent to a monovalent anion.
  • the radicals R1 and R2 on the one hand and R3 and R4 on the other hand can be the same or different.
  • the radicals R1, R2, R3 and R4 can all be the same and denote hydrogen or methyl.
  • the alkyl radicals representing R1 and R2 and hydroxyalkyl radicals can be straight-chain or branched.
  • R 1 and R 2 are preferably uninterrupted alkyl radicals having 1 to 10 C atoms, very particularly preferably uninterrupted alkyl radicals having 1 to 4 C atoms.
  • alkyl radicals for R 1 and / or R 2 are: n-docosyl, n-pentadecyl, n-decyl, i-octyl, i-heptyl, n-hexyl, i-pentyl, preferably n-butyl, i-butyl, sec-butyl, i-propyl, n-propyl, ethyl and methyl.
  • the radicals R1 and R2 are preferably the same and are preferably both methyl.
  • R3 and R4 are the same and preferably both mean hydrogen.
  • a monovalent anion for Y can be, for example, nitrate, hydrogen sulfate, benzenesulfonate, fluoride, chloride, bromide, iodide, acetate, propionate or another radical of a carboxylic acid.
  • a part of a multivalent anion equivalent to a monovalent anion can be, for example, 1/2 equivalent of sulfate or 1/3 equivalent of phosphate.
  • Y is preferably for a halogen anion, such as bromide or iodide, in particular for chloride.
  • the compounds of the formula I like polymers derived therefrom, are known (cf. for example Ottenbrite and Ryan, Cyclopolymerization of N, N-Dialkyldiallylammonium Halides, Ind.Eng.Chem.Prod.Res.Dev. Vol.19, No.4 , (1980), 528,532). It can be assumed that in the homopolymerization and copolymerization of compounds of the formula I in the polymer there are mainly 5- or 6-membered ring-shaped repeating units of the formulas II and III form. In the case of copolymers, the repeating units formed from compound I can also have other structures, depending on the comonomers used. For example, repeat units of the formulas IV, V or VI can form if sulfur dioxide is used in addition to compounds of the formula I in a polymerization.
  • the polymer used contains 16 2/3 to 100 mol%, preferably 40 to 100 mol%, and very particularly preferably 80 to 100 mol%, of a compound of Formula I in polymerized form.
  • a polymer with 100 mol% of a compound of the formula I in copolymerized form is prepared by polymerizing one or more compounds of the formula I in a manner known per se.
  • Suitable comonomers for such a copolymerization are e.g.
  • All alkyl radicals in the formulas VII to XI above can be straight-chain or branched and preferably have 1 to 4 carbon atoms.
  • Z can one of the for Y have the meanings indicated and is preferably Y. identical.
  • X1 and X2 are preferably -NH-.
  • the diallylammonium component A can consist of one compound of the formula I or of several compounds of the formula I.
  • the other components B, B1, B2, B3, B4, C, D, E1 and E2 can each consist of one compound or of several compounds.
  • the amide component B can consist of an amide component B1 or an amide component B2 or an N-vinylacylamide component B3 or an ammonium component B4.
  • the amide component B can also e.g. from two individual components (e.g. B1 + B2, B1 + B3, B2 + B3 or B3 + B4) or e.g. consist of three individual components (e.g.
  • the amide component B can also contain all four individual components (B1 + B2 + B3 + B4). In all cases mentioned, the individual components B1, B2, B3, B4 can in turn consist of one or more individual compounds of the formulas given.
  • X is preferably -NH- and n is preferably the number 0 and m is preferably one of the numbers 2, 3 or 4.
  • R5 and R6 can be identical or different and are preferably (C1-C4) Alkyl.
  • R7 and R8 can also be the same or different. Examples of particularly preferred compounds of the formula VII are: where in the formulas VIIa to VIId R5, R6 and m in particular have the preferred meanings.
  • R9 and R10 on the one hand and R11 and R12 on the other hand can be the same or different.
  • R9 and R10 are preferably hydrogen or (C1-C4) alkyl.
  • R11 and R12 can also be the same or different. Examples of particularly preferred compounds of the formula VIII are: where in the formulas VIIIa to VIIId R9 and R10 in particular have the preferred meanings.
  • R14 is preferably (C1-C4) alkyl.
  • R13 preferably means Hydrogen or (C1-C4) alkyl.
  • R13 and R14 preferably together also mean - (CH2) 3-, - (CH2) 4- or - (CH2) 5-.
  • Examples of preferred compounds of the formula IX are N-vinyl-2-pyrrolidone, N-vinyl-2-piperidinone, N-vinyl- ⁇ -caprolactam.
  • X2 is preferably -NH-.
  • R15, R16 and R17 may be the same or different and are preferably (C1-C4) alkyl, very particularly preferably methyl, r is preferably the number 0 and q is preferably one of the numbers 2, 3 or 4.
  • R21 is usually (C1-C8) alkyl, preferably (C1-C4) alkyl.
  • R20 hydrogen
  • the polyfunctional alkylation component D has, for example, the formula XIV wherein x is the number 0, 1, 2 or 3, preferably 0, and A, A1 and A2 are identical or different radicals of the formula -CH2A3 or an epoxy radical (oxirane radical) of the formulas XVI or XVII mean.
  • A3 is a substituent which can be split off as an anion, in particular chloride, bromide or iodide, or a group which can be split off as an anion, such as, for example, hydroxyl, a sulfate residue, a phosphate residue and Z stands for a direct bond or for a (x + 2) -valent organic Z can be an aliphatic, aromatic or araliphatic radical, aliphatic and araliphatic radicals also keto groups -CO- or heteroatoms, such as -O- or -S-, or heteroatom groups, such as -SO-, -SO2-, -NH- , -N (CH3) - may contain.
  • bifunctional alkylating agents correspond to formula XVIII A ⁇ Z1 ⁇ A1 (XVIII) wherein Z1 is a direct bond, a phenylene radical, in particular a 1,4-phenylene radical, or a radical of the formula - (CH2) y - or - (CH2) k -G- (CH2) 1-, where y is a number 1 to 6, k and l numbers from 1 to 6 and G -O-, -S-, -SO-, SO2-, -NH-, -N (CH3) -, -CO-, -CHOH- or phenylene, in particular 1,4-phenylene.
  • K and l are preferably the same and are preferably 1 or 2, in particular 1.
  • the polyamine component E can consist of a component E1 or E2 or of the two components E1 and E2.
  • s is preferably the number 2.
  • preferred suitable representatives of the polyamine component E1 of the formula XII are commercially available polyethyleneimines having a molecular weight between 2000 and 27000, preferably between 2000 and 20,000, particularly preferably between 2000 and 5000.
  • polyethyleneimines are commercially available. They are made by polymerizing ethyleneimine and contain about 50 to 600 ethyleneimine units and usually primary, secondary and tertiary nitrogen atoms in a number ratio of about 1: 2: 1. The different nitrogen atoms are statistically distributed in the molecule. They are preferably used directly in the form of their commercially available aqueous solutions in the process for the preparation of the crosslinked copolymers.
  • the alkylene radical which represents R22 can be branched or preferably straight-chain.
  • a phenylene radical representing R22 is preferably a 1,4- or 1,2-phenylene radical.
  • the compounds of the formula XIII are reaction products of amines of the formula XIX with dicarboxylic acids of formula XX HOOC-R22-COOH (XX) in a molar ratio of 1: (0.5 to 1).
  • u is preferably 2 or 3 and w is preferably 1, 2 or 3.
  • Preferred amines of the formula XIX are, for example: H2N-CH2-CH2-NH-CH2-CH2-NH2, H2N-CH2-CH2-CH2-NH-CH2-CH2-CH2-NH2, H2N-CH2-CH2-NH-CH2-CH2-NH-CH2-CH2-NH-CH2-CH2-NH-CH2-CH2-NH2.
  • Suitable dicarboxylic acids of formula XX are e.g. Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid and isophthalic acid.
  • the molar ratio A: B: C 1: (0.02 to 2.5): 0.
  • the molar ratio B 1: E: D 1: (0.05 to 10) : (0.002 to 1), preferably 1: (0.1 to 5): (0.01 to 1).
  • the starting components required for the preparation of the polymers and copolymers are known or can be prepared by processes which are known for the respective substance class.
  • the preparation of the water-soluble polymers and copolymers used according to the invention by polymerization or copolymerization, in particular by homopolymerization of the diallyl component A or copolymerization of the diallyl component A, the amide component B and the (meth) acrylic ester component C, is carried out in a suitable solvent.
  • suitable solvents are water mixed with a water-miscible solvent.
  • Suitable water-miscible solvents are, for example, lower alcohols, such as methanol, ethanol, n-propanol, i-propanol, n-butanol, tert-butanol, glycols and diols such as, for example, ethylene glycol, propylene glycol, 1,3-propanediol, di- and polyglycols such as, for example, diethylene glycol, triethylene glycol, glycol ethers, such as, for example, diethylene glycol mono-methyl ether, diethylene glycol mono-ethyl ether, ethylene glycol mono-methyl ether, ethylene glycol mono-ethyl ether, ethylene glycol mono-n-propyl ethers, ethylene glycol mono-n-butyl ether, ethylene glycol di-methyl ether, ethylene glycol di-ethyl ether, ketones such as acetone or methyl ethyl ketone. Alcohols with 1
  • the homo- or copolymerization can also be carried out in a mixture of different solvents, preferably in a solvent mixture which contains small amounts of water. If e.g. the diallylammonium component A is used in the form of an aqueous solution, no further addition of water is normally necessary.
  • Homo- or copolymerization in pure water usually does not lead to good products.
  • Water in a mixture with alcohols, in particular those with 1 to 4 carbon atoms, and in a mixture with diols or glycols is preferred.
  • an acid preferably an organic acid, especially acetic acid, is generally used for this pH adjustment.
  • the homo- or copolymerization is carried out at temperatures from 40 to 100.degree. C., preferably 60 to 90.degree. C., very particularly preferably at temperatures from 65 to 85.degree. C., and started in the customary manner, for example by adding suitable initiators.
  • Suitable initiators are radical-forming substances, such as, for example, benzoyl peroxide, tert-butyl hydroperoxide, cumene peroxide, methyl ethyl ketone peroxide, lauryl peroxide, tert-butyl perbenzoate, di-tert-butyl perphthalate, azodiisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2-phenyl ailyl, 2-phenyl 2,4-dimethyl-4-methoxy-valeronitrile, 2-cyano-2-propyl-azoformamide, azodiisobutyramide, dimethyl-, diethyl- or di-n-butyl-azobis-methylvalerate, tert-butyl-perneodecanoate, di-isononanoyl- peroxide tert-amyl perpivalate, di-2-ethylhexyl per
  • the initiator is 2,2 2-azobis- (2-amidino-propane) dihydrochloride, 2,2 ⁇ -azobis (2-imidazol-2-yl-propane) dihydrochloride, 2,2 ⁇ -azobis (2-carbamoyl Propane) dihydrate or 2,2'-azobis- (2-methoxycarbonyl-propane) used det.
  • Based on the amount of monomers of components A + B + C 0.01 to 2% by weight, preferably 0.1 to 1% by weight, of initiator is used. It is expedient to carry out the copolymerization in the absence of oxygen. This can be done in a manner known per se by purging or passing through an inert gas, such as nitrogen.
  • the homo- or copolymerization is complete after about 30 minutes to about 4 hours, in many cases after 30 minutes to 2 1/2 hours
  • water-soluble copolymers those are preferred in the production of which an amide component B is used which consists of a basic component B1 of the formula IV or contains such a basic component B1, in particular if these copolymers are still subjected to a crosslinking reaction after the copolymerization have been.
  • the compounds of the formulas IIIa to IIId are preferred as the basic component B1.
  • the solution obtained in the copolymerization is reacted in the presence of water with a polyfunctional alkylation component D and preferably also with a polyamine component E.
  • the polyamine component E can consist of a polyamine component E1 or E2 or a mixture of these components. If a polyamine component E is used in the crosslinking, it is added to the aqueous solution of the copolymer to be crosslinked before the polyfunctional alkylation component D.
  • the molar ratio B 1: D: E in the crosslinking reaction is 1: (0.002 to 2): (0 to 5), preferably 1: (0.002 to 1): (0.05 to 5), particularly preferably 1: (0.01 to 1): (0.1 to 4.5).
  • the crosslinking is carried out at temperatures from 30 to 90.degree. C., preferably from 40 to 60.degree. C., and is carried out after only a few minutes, for example 5 to 20 minutes, preferably 5 to 10 minutes, by adding a mineral acid such as hydrochloric acid or sulfuric acid , Phosphoric acid or nitric acid terminated.
  • a pH of 4 to 7 is set by adding the mineral acid.
  • the solutions of the uncrosslinked or crosslinked homo- or copolymer obtained in the preparation have an active substance content of approximately 15 to 55% by weight and can be used directly in this form, but preferably after dilution to an active substance content of approximately 25 to 35% by weight.
  • the pH is adjusted to values of 3 to 8.5, preferably 7 to 8, before use as a textile auxiliary.
  • a strong acid e.g. Hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid are used.
  • solutions of the crosslinked or uncrosslinked homopolymers or copolymers obtained in the preparation can either be dissolved genuinely, or at least colloidally, in water.
  • the process according to the invention is suitable for improving the wet fastness, in particular for improving the fastness to washing of dyeings on cellulose of the following sulfur dyes: CI Sulfur Black 1, CI No. 53185; CI Sulfur Black 2, CI No. 53195; CI Sulfur Black 18; CI Sulfur Blue 1, CI No. 53235; CI Sulfur Blue 3, CI No.53235; CI Sulfur Blue 4, CI No.53235; CI Sulfur Blue 5, CI No.
  • the process according to the invention is also particularly suitable for the leuco and solubilised forms of the dyes mentioned above, which are listed in the Color Index under C.I. Leuco Sulfur Black 1 etc. or C.I. Solubilised Sulfur Black 1 etc. are listed.
  • the process according to the invention is very particularly suitable for the sulfur dyes C.I. Sulfur Black 1, C.I. No. 53185; C.I. Sulfur Black 2, C.I. No. 53195; C.I. Sulfur Blue 1, C.I. No. 53235; C.I. Sulfur Blue 3, C.I. No. 53235; C.I. Sulfur Blue 4, C.I. No. 53235; C.I. Sulfur Blue 5, C.I. No. 53235; C.I. Sulfur Blue 11, C.I. No. 53235 and for the corresponding forms C.I. Leuco and C.I. Solubilized.
  • the polymer to be used according to the invention is applied to the cellulose before, during or after the dyeing process.
  • the actual dyeing with the sulfur dyes is carried out in a manner known per se using the exhaust process or a semi-continuous or fully continuous process.
  • the sulfur dye is applied to the cellulose in a reduced form, ie in leuco form, and then oxidized in a suitable manner, which is usually done by using a special oxidation bath.
  • Insoluble sulfur dyes are brought to a boil with sodium sulfide in solution.
  • sodium sulfide instead of sodium sulfide, other or some other reducing agents can also be used, e.g. Hydrogen sulfides, alkali and dithionites, alkali and glucose, alkali and mercapto compounds, alkali and thiourea dioxide and alkali and hydroxyacetone.
  • Cellulose can be dyed with sulfur dyes in all processing states. Yarn, flake and sliver are e.g. dyed on apparatus in which the fleet circulates. Jersey goods are dyed on the reel runner, knitwear on the jigger, the reel runner or semi-continuously using the pad-docking process, on pad-roll systems or using the cold dwell process. Fully continuous dyeing is possible using the one-bath process (padding liquor contains reduced dye) or the two-bath process (1st padding liquor contains dispersed or dissolved dye, 2nd padding liquor contains the reducing agent). The dye is then fixed in a damper (pad-steam process), but can also be done in an air passage or in compartments of a washing machine.
  • a damper pad-steam process
  • the process according to the invention is also suitable for the cellulose component of mixtures of cellulose with other fibers, in particular polyesters.
  • the oxidation of the leuco dyes can be carried out with various oxidizing agents known per se, for example with bichromate / acetic acid, with alkaline hypochlorite solution, with bromate, optionally with the addition of metavanadate, or with hydrogen peroxide in the alkaline or acidic range.
  • oxidizing agents known per se, for example with bichromate / acetic acid, with alkaline hypochlorite solution, with bromate, optionally with the addition of metavanadate, or with hydrogen peroxide in the alkaline or acidic range.
  • All known oxidizing agents can be used.
  • the oxidation is preferably carried out with hydrogen peroxide in the alkaline range, which offers various advantages over oxidation with hydrogen peroxide in the acidic range, for example that it is carried out at a lower temperature (for example 40 ° C. instead of 70 ° C.) , can be carried out without odor nuisance and without pH-controlled addition of acid.
  • the polymer used is calculated in amounts of 0.001 to 5%, preferably from 0.01 to 2.5%, very particularly preferably in amounts of 0.01 to 1.0%, based on the cellulose weight and on 100% polymer applied to the cellulose.
  • This application can be done in various ways, e.g. by dipping, spraying, padding, splashing, etc.
  • the polymer is used during the dyeing process, it is added to the oxidation bath, for example.
  • the polymer When applied after the dyeing process, the polymer can be applied after the oxidation bath before rinsing, after rinsing or even after drying. Application before the dyeing process is also suitable.
  • the use of the polymer which contains 16 2/3 to 100 mol% of a compound of the formula I in copolymerized form, results in a considerable improvement in the authenticity of the laundry. For example, the staining of cotton and acetate in the 60 ° C wash is reduced by 1 to 3 notes improved.
  • the polymer is used before the actual dyeing process, not only does the fastness to washing improve, but also a deepening of the color. Regardless of whether the polymer is applied to the cellulose before, during or after the dyeing process, the fiber damage occurring with CI Sulfur Black 1 and 2 is also reduced.
  • the advantages mentioned are basically achieved when the polymer is in the form of e.g. to 20% by weight solution is applied in an amount of 0.005 to 25%, preferably 0.05 to 12.5%, in particular 0.05 to 5%, of the weight of the goods.
  • the treatment is expediently carried out at temperatures from room temperature to 100 ° C., preferably to 70 ° C., particularly preferably at room temperature to 40 ° C. There is no need to rinse during post-treatment. A significant improvement in wet fastness properties is achieved.
  • the process according to the invention can also be used in the context of simultaneous quasi single-bath sizing and dyeing of cellulose materials with sulfur dyes.
  • the polymer in the form of the approx. 25 to 55% strength by weight solution obtained in the preparation is generally added to the size dye liquors in amounts of 20 to 80 g / l, preferably 30 to 60 g / l. A higher addition is possible, but is usually not necessary. Smaller than the specified additional amounts may also be sufficient in individual cases, e.g. if very light shades are dyed or if the requirements for improving the authenticity are not quite as high.
  • This quasi single-bath sizing process using the polymer is carried out according to the sizing or staining processes known per se and carried out in the units used for this purpose.
  • a fourth water trough is additionally switched on.
  • the impregnating troughs are loaded with the sizing dye liquor in a conventional manner, the concentration of the sizing agent in the liquor being based on the amount of the size application required for the further processing process and on the fiber quality.
  • the dye concentration depends on the desired depth of color.
  • the liquors contain 30 to 80 g per liter of sizing agent and 10 to 50 g per liter of the dye.
  • the dye concentration in the first impregnation trough somewhat higher than in the following ones and to set the concentration of the sizing agent in the last troughs higher than in the previous ones.
  • concentration of the polymer is expediently kept somewhat lower in the baths which have higher dye concentrations and in baths that have lower dye concentrations, a slightly higher auxiliary concentration is used.
  • the auxiliary concentrations in the first bath are preferably set between 0 and 20 g / l, those in the last bath in the range from 20 to 60 g / l.
  • sizing agents e.g. Starch and starch derivatives, sizing agents based on carboxymethyl cellulose, vinyl homo- or copolymers, acrylate copolymers or water-soluble polyesters.
  • the agents which are particularly suitable for cellulose materials are preferably used, in particular those based on starch and starch derivatives, carboxymethyl cellulose. Starch and starch derivatives are particularly preferred as sizing agents.
  • the sulfur dyes are added to the size dyeing liquors in their reduced and thus water-soluble form.
  • the sizing dye liquors can also contain other auxiliaries and additives as are known from customary dyeing processes.
  • the use of the polymer not only results in a very considerable improvement in the wet fastness of the size dyeings, but also results also improved sizing of the yarn through better film formation of the sizing agent. Finally, an increased weaving efficiency can also be determined.
  • textile materials dyed with reactive dyes include treated with a diallyl-dimethyl-ammonium chloride homopolymer.
  • Examples 1 to 5 relate to the preparation of suitable homopolymers and copolymers. Unless stated otherwise, the percentages given in the examples are percentages by weight.
  • K value (measured as a 1% aqueous solution) before polymerization: 16.8.103 at 25 ° C after polymerization: 25.5.103 at 25 ° C
  • the authenticity test is carried out after the wash fastness test 1, with the difference that the laundry is carried out five times with a renewed wash liquor before the evaluation.
  • the authenticity test is carried out according to International Standard ISO 105-C 03-1982 (E), Color fastness to washing: Test 3, with the following changes: Instead of two undyed single-fiber accompanying fabrics, a 100 mm x 40 mm multi-fiber accompanying fabric with the sections acetate, cotton, polyamide, polyester, polyacrylic and wool is used. Instead of 5 g of soap, 4 g of ECE color fastness test detergent without optical brightener are used per liter of distilled water. Instead of 2 g of sodium carbonate, 1 g of sodium perborate (NaBO2.H2O2.3H2O) is used per liter of distilled water.
  • the dye C.I. Solubilized Sulfur Black 1. Take so many grams of a commercial product that a deep black color results. The dye is dissolved in deionized water and then 0.4 g of sodium carbonate are added, which is 1.5 times the amount of a 30% aqueous solution of sodium hydrogen sulfide, 0.3 ml of a 43% aqueous solution of sodium tetrasulfide and 2 g of sodium sulfate. The volume of the dye liquor is adjusted to 100 ml by adding further demineralized water.
  • the tissue is immediately placed in 500 ml of a 70 ° C warm aqueous solution containing 0.5 g of sodium bromate, 0.025 g of sodium metavanadate, 0.96 g of acetic acid, 0.5 g of sodium acetate and 0.24 g of the product from Preparation Example 1 contains.
  • the tissue is agitated for 15 minutes at 70 ° C in the oxidation bath, then removed from the bath, rinsed thoroughly with deionized water and dried at 100 ° C.
  • the wash fastness of the dyeing is improved, for example, in wash fastness tests 1, 2 and 4 with regard to the staining of cotton and acetate compared to a dyeing which was carried out in the same manner but without the product from preparation example 1.
  • Example 6 The procedure is the same as in Example 6 with the exception of Oxidation. Instead of the oxidation with bromate, it is oxidized with hydrogen peroxide as follows: Then the tissue is immediately placed in 500 ml of a 70 ° C aqueous solution, the 1 ml of a 35% aqueous solution of hydrogen peroxide, 0.8 g acetic acid, 1.25 contains sodium acetate and 0.24 g of the product from preparation example 1. The tissue is agitated for 15 minutes at 70 ° C in the oxidation bath, then removed from the bath, rinsed thoroughly with deionized water and dried at 100 ° C.
  • wash fastness of the dyeing is improved, for example, in wash fastness tests 1, 2 and 4 with regard to the staining of cotton and acetate compared to a dyeing which was carried out in the same manner but without the product from preparation example 1.
  • oxidation is carried out with hydrogen peroxide as follows: Then the tissue is immediately put into 500 ml of a 70th Brought ° C warm aqueous solution containing 1 ml of a 35% aqueous solution of hydrogen peroxide, 0.8 g of acetic acid, 1.25 g of sodium acetate and 0.36 g of the product from Preparation Example 3. The tissue is agitated for 15 minutes at 70 ° C in the oxidation bath, then removed from the bath, rinsed thoroughly with deionized water and dried at 100 ° C.
  • wash fastness of the dyeing is, for example, in wash fastness tests 1, 2 and 4 with regard to the staining of cotton and acetate in comparison with a dye, which was carried out in the same way but without the product from Preparation Example 3.
  • Example 6 If, in Example 6, 0.36 g of the product from Preparation Example 4 is used instead of the product from Preparation Example 1, a dyeing is obtained, the washfastness of which, for example, in Washfastness Tests 1, 2 and 4 with regard to the staining of cotton and acetate in Compared to a staining that is improved in the same way but without the product.
  • Example 6 instead of C.I. Solubilized Sulfur Black 1 the dye C.I. Leuco Sulfur Black 2, a dyeing is obtained whose washfastness with regard to the staining of cotton and acetate is improved compared to a dyeing which was carried out in the same manner but without the product from Preparation Example 1.
  • the colorant CI Solubilized Sulfur Blue 11 is placed in a sealable cylindrical stainless steel container with a volume of 150 ml. Sufficient grams of a commercial product are used to give a color with 1/1 standard depth.
  • the dye is dissolved in deionized water and then 0.4 g of sodium carbonate, 0.5 ml of a 30% aqueous solution of sodium hydrogen sulfide, 0.3 ml of a 43% aqueous solution of sodium tetrasulfide and 2 g of sodium sulfate are added.
  • the volume of the dye liquor is adjusted to 100 ml by adding further demineralized water.
  • tissue is immediately placed in 500 ml of a 70 ° C warm aqueous solution containing 0.5 g of sodium bromate, 0.025 g of sodium metavanadate, 0.96 g of acetic acid, 0.5 g of sodium acetate and 0.24 g of the product from Preparation Example 1 contains.
  • the tissue is agitated for 15 minutes at 70 ° C in the oxidation bath, then removed from the bath, rinsed thoroughly with deionized water and dried at 100 ° C.
  • wash fastness of the dyeing is improved, for example, in wash fastness tests 1, 2 and 4 with regard to the staining of cotton and acetate compared to a dyeing which was carried out in the same manner but without the product from preparation example 1.
  • Example 11 The procedure is the same as in Example 11, except for the oxidation. Instead of oxidation with bromate, it is oxidized with hydrogen peroxide as follows: Then the tissue is immediately placed in 500 ml of a 70 ° C warm aqueous solution, the 1 ml of a 35% aqueous solution of hydrogen peroxide, 0.8 g acetic acid, 1.25 g sodium acetate and 0.24 g of the product from the preparation example 1 contains. The tissue turns 15 Minutes at 70 ° C in the oxidation bath, then removed from the bath, rinsed thoroughly with deionized water and dried at 100 ° C.
  • wash fastness of the dyeing is improved, for example, in wash fastness tests 1, 2 and 4 with regard to the staining of cotton and acetate compared to a dyeing which was carried out in the same manner but without the product from preparation example 1.
  • Example 11 Using Example 11 in place of dye C.I. Solubilized Sulfur Blue 11 the dye C.I. Sulfur Blue 11 and instead of sodium carbonate and sodium hydrogen sulfide 0.75 g 60% sodium sulfide, the same result is obtained as in Example 11.
  • Example 11 Using Example 11 in place of dye C.I. Solubilized Sulfur Blue 11 the dye C.I. Sulfur Blue 1 and instead of sodium carbonate and sodium hydrogen sulfide 0.75 g of 60% sodium sulfide, a dyeing is obtained whose wash fastness with respect to the staining of cotton and acetate compared to a dyeing which is carried out in the same way but without the product from the Production Example 1 was carried out is improved.
  • Example 11 the dye CI Sulfur Blue 3 is used instead of the CI Solubilized Sulfur Blue 11 dye and 0.75 g of 60% sodium sulfide instead of sodium carbonate and sodium hydrogen sulfide, a dyeing is obtained whose washfastness is related the staining of cotton and acetate compared to a dyeing which was carried out in the same manner but without the product from preparation example 1.
  • Example 11 in place of dye C.I. Solubilized Sulfur Blue 11 the dye C.I. Solubilized Sulfur Blue 4, sc gives a dyeing whose wash fastness with regard to the staining of cotton and acetate is improved compared to a dyeing which was carried out in the same manner but without the product from Preparation Example 1.
  • Example 11 Using Example 11 in place of dye C.I. Solubilized Sulfur Blue 11 the dye C.I. Leuco Sulfur Blue 5, a dyeing is obtained whose wash fastness with regard to the staining of cotton and acetate is improved compared to a dyeing which was carried out in the same manner but without the product from Preparation Example 1.
  • the dye CI Leuco Sulfur Black 1 is mixed with deionized water, 5 ml of a 30% aqueous solution of sodium hydrogen sulfide, 5 ml of a 43% aqueous solution of sodium tetrasulfide and 5 ml Leonil®KS of an anionic wetting agent from Hoechst AG , and make up to 1000 ml with deionized water. Sufficient grams of a liquid commercial dye are used to give a black color. With the padding liquor prepared in this way, a cotton fabric is padded on the foulard with a liquor absorption of 80%. The padded fabric is immediately inserted into an air-free damper and steamed at 105 ° C for 60 seconds.
  • the cotton fabric is then rinsed thoroughly with deionized water and squeezed to a weight of 178% of the original dry weight.
  • the squeezed tissue is immediately padded on the padding with an aqueous solution containing 35 g of the product from preparation example 1 per liter and squeezed to a weight of 183% of the original dry weight.
  • the tissue treated in this way is immediately placed in a 40 ° C. oxidation bath which contains 3 ml of a 35% strength aqueous hydrogen peroxide solution and 1.5 g of sodium carbonate per liter. After 60 seconds, the tissue is removed from the bath, rinsed thoroughly with deionized water and dried at 100 ° C.
  • wash fastness of the dyeing is improved, for example, in wash fastness tests 1, 2 and 3 with regard to the staining of cotton and acetate compared to a dyeing which was carried out in the same manner but without the product from preparation example 1.
  • the dye CI Leuco Sulfur Black 1 is mixed with deionized water, 5 ml of a 30% aqueous solution of sodium hydrogen sulfide, 5 ml of a 43% aqueous solution of sodium tetrasulfide and 5 ml Leonil®KS of an anionic wetting agent from Hoechst AG , and make up to 1000 ml with deionized water. Sufficient grams of a liquid commercial dye are used to give a black color. With the padding liquor prepared in this way, a cotton fabric is padded on the foulard with a liquor absorption of 80%. The padded fabric is immediately inserted into an air-free damper and Steamed at 105 ° C for 60 seconds.
  • the cotton fabric is then rinsed thoroughly with deionized water and squeezed to a weight of approx. 185% of the original dry weight.
  • the squeezed tissue is immediately placed in a 40 ° C oxidation bath which contains 3 ml of a 35% aqueous hydrogen peroxide solution and 1.5 g sodium carbonate per liter. After 60 seconds, the tissue is removed from the bath and squeezed to a weight of 178% of the original dry weight.
  • the squeezed tissue is immediately padded on the padding with an aqueous solution containing 35 g of the product from preparation example 1 per liter and squeezed to a weight of 183% of the original dry weight.
  • the fabric is then rinsed thoroughly with deionized water and dried at 100 ° C.
  • the wash fastness of the dyeing is, for example, in the wash fastness tests 1 and 2 with regard to the staining of cotton and acetate and in the wash fastness test 4 with respect to the staining with cotton in comparison to a dyeing which was carried out in the same manner but without the product from the production example 1 was improved.
  • Example 19 If, in Example 19, 50 g of the product from Preparation Example 4 is used instead of the product from Preparation Example 1 per liter of padding solution, a coloration is obtained whose washfastness, for example in Washfastness Tests 1 and 2, with regard to the staining of cotton and acetate and in the washing fastness test 4 with respect to the staining of cotton compared to a dyeing which was carried out in the same way but without the product.
  • the dye CI Solubilized Sulfur Green 2 is placed in a closable cylindrical stainless steel container with a volume of 150 ml. Sufficient grams of a commercial product are used to give a color with a depth of 1/1 standard.
  • the dye is dissolved in deionized water and then 0.4 g of sodium carbonate, 0.6 ml of a 30% aqueous solution of sodium hydrogen sulfide, 0.3 ml of a 43% aqueous solution of sodium tetrasulfide and 2 g of sodium sulfate are added.
  • the volume of the dye liquor is adjusted to 100 ml by adding further demineralized water.
  • the tissue is then immediately placed in 500 ml of a 40 ° C. warm aqueous solution which contains 0.5 ml of a 35% strength aqueous solution of hydrogen peroxide, 0.5 g of sodium carbonate and 0.24 g of the product from preparation example 1.
  • the tissue is agitated for 15 minutes at 40 ° C in the oxidation bath, then removed from the bath, rinsed thoroughly with deionized water and dried at 100 ° C.
  • the wash fastness of the dyeing is improved, for example, in the wash fastness test 1 with respect to the staining of cotton and acetate compared to a dyeing which was carried out in the same manner but without the product from preparation example 1.
  • the colorant CI Solubilized Sulfur Brown 46 is placed in a sealable cylindrical stainless steel container with a volume of 150 ml. Sufficient grams of a commercial product are used to give a color with a depth of 1/1 standard.
  • the dye is dissolved in deionized water and then 0.4 g of sodium carbonate, 0.5 ml of a 30% aqueous solution of sodium hydrogen sulfide, 0.3 ml of a 43% aqueous solution of sodium tetrasulfide and 2 g of sodium sulfate are added. The volume of the dye liquor is adjusted to 100 ml by adding further demineralized water.
  • tissue is immediately placed in 500 ml of a 70 ° C aqueous solution containing 0.5 g of sodium bromate, 0.025 g of sodium metavanadate, 0.96 g of acetic acid, 0.5 g of sodium acetate and 0.36 g of the product from Preparation Example 4 contains.
  • the tissue is agitated for 15 minutes at 70 ° C in the oxidation bath, then removed from the bath, rinsed thoroughly with deionized water and dried at 100 ° C.
  • the wash fastness of the dyeing is, for example, in the wash fastness tests 1 and 2 with regard to the staining of cotton and acetate and in the wash fastness test 4 with respect to the staining of cotton in comparison to a dyeing which is carried out in the same manner but without the product from the production example 1, has been improved.
  • Cotton fabric is dyed using the pad-steam method with so much CI Leuco Sulfur Green 36 in a liter of padding liquor that a dyeing with 1/1 standard depth results. After steaming and rinsing, the mixture is oxidized for 60 seconds in a 70 ° C. oxidation bath which contains 3 ml of a 35% strength aqueous hydrogen peroxide solution, 1.6 g of acetic acid and 2.5 g of sodium acetate per liter. Subsequently is rinsed as usual and dried at 100 ° C. The dyed and dried fabric is padded on the padder with a solution consisting of 9 g of the product from preparation example 4 and 991 g of deionized water per kg. The fleet intake is 80%. The padded fabric is dried at 100 ° C.
  • the wash fastness of the aftertreated dyeing is improved, for example, in the washfastness tests 1, 2 and 4 with regard to the staining of cotton and acetate in comparison with a dyeing which was produced in the same way but without the aftertreatment with the product from preparation example 4.
  • Cotton cord is dyed using the pad steam process with as much C.I. Leuco Sulfur Blue 5 in a liter of padding liquor that results in a dark color. After steaming and rinsing, the mixture is oxidized for 60 seconds in a 70 ° C. oxidation bath which contains 1 g of sodium bromate, 0.05 g of sodium metavanadate, 1.9 g of acetic acid and 1 g of sodium acetate per liter. It is then rinsed as usual and dried at 100 ° C. The dyed and dried cord fabric is padded on the padder with a solution consisting of 3 g of the product from preparation example 1 and 997 g of completely deionized water per kg. The fleet intake is 80%. The padded fabric is dried at 100 ° C.
  • the wash fastness of the aftertreated dyeing is improved, for example, in the washfastness test 1 and 4 with regard to the staining of cotton and acetate in comparison with a dyeing which was produced in the same way but without the aftertreatment with the product from preparation example 1.
  • Cotton cord is dyed using the pad steam process with as much C.I. Leuco Sulfur Black 1 in a liter of padding liquor that results in a deep black color. After steaming and rinsing, the mixture is oxidized for 60 seconds in a 70 ° C. oxidation bath which contains 3 ml of a 35% strength aqueous hydrogen peroxide solution, 1.6 g of acetic acid and 2.5 g of sodium acetate per liter. It is then rinsed as usual and dried at 100 ° C. The dyed and dried fabric is padded on the padder with a solution consisting of 6 g of the product from preparation example 1 and 994 g of deionized water per kg. The fleet intake is 80%. The padded fabric is dried at 100 ° C.
  • the wash fastness of the aftertreated dyeing is improved, for example, in the washfastness tests 1 to 4 with regard to the staining of cotton and acetate in comparison with a dyeing which was produced in the same way but without the aftertreatment with the product from preparation example 1.
  • Dry undyed cotton fabric is padded on the padder with a solution consisting of 6 g of the product from preparation example 1 and 994 g of completely deionized water per kg.
  • the fleet intake is 80%.
  • the padded fabric is dried at 100 ° C.
  • the fabric is then dyed using the pad-steam method with so much CI Leuco Sulfur Blue 5 in a liter of padding liquor that dyeing with 1/1 standard depth results.
  • the pro Liter contains 1 g of sodium bromate, 0.05 g of sodium metavanadate, 1.9 g of acetic acid and 1 g of sodium acetate. It is then rinsed as usual and dried at 100 ° C.
  • the dyeing is much deeper than a dyeing which is carried out under the same dyeing conditions with the same amount of dye on non-pretreated cotton fabric. In order to achieve the same color depth on the non-pretreated fabric under the same dyeing conditions, around 50% more dye is required.
  • the wash fastness of the dyeing on the pretreated fabric is, for example, in the wash fastness tests 1 to 4 with regard to the staining of cotton and acetate in comparison with an equally strong dyeing which was produced in the same way but without the pretreatment with the product from preparation example 1 , improved.
  • Dry undyed cotton fabric is padded on the padder with a solution consisting of 6 g of the product from preparation example 1 and 994 g of deionized water per kg.
  • the fleet intake is 80%.
  • the padded fabric is dried at 100 ° C.
  • the fabric is then dyed using the pad-steam method with so much CI Leuco Sulfur Black 1 in a liter of padding liquor that a medium black color results.
  • the mixture is oxidized for 60 seconds in a 70 ° C. oxidation bath which contains 3 ml of a 35% strength aqueous hydrogen peroxide solution, 1.6 g of acetic acid and 2.5 g of sodium acetate per liter. It is then rinsed as usual and dried at 100 ° C.
  • the dyeing is significantly deeper than a dyeing which is carried out under the same dyeing conditions with the same amount of dye on non-pretreated cotton fabric. In order to achieve the same color depth on the non-pretreated fabric under the same dyeing conditions, an approx. 15% larger amount of dye is required.
  • the wash fastness of the dyeing on the pretreated fabric is, for example, in the wash fastness tests 1 to 4 with regard to the staining of cotton and acetate in comparison with an equally strong dyeing which was produced in the same way but without the pretreatment with the product from preparation example 1 , improved.
  • Cotton is dyed using the pad-steam process with so much CI Leuco Sulfur Black 1 in a liter of padding liquor that a deep black color results.
  • the mixture is oxidized for 60 seconds in a 40 ° C. oxidation bath which contains 3 ml of a 35% strength aqueous hydrogen peroxide solution and 1.5 g of sodium carbonate per liter. It is then rinsed as usual and squeezed to a weight of 178% of the original dry weight.
  • the fabric is then dried at 100 ° C.
  • the wash fastness of the dyeing is improved, for example, in the wash fastness test 1 with respect to the staining of cotton and acetate and in the wash fastness test 4 with respect to the staining with cotton compared to a dyeing which was carried out in the same manner but without the product from the production example 2 .
  • the washfastness of the dyeing is, for example, in the washfastness test 1 for the staining of cotton and acetate and in the washfastness test 4 for the staining of cotton in comparison with a dyeing, which was carried out in the same manner without the product from Preparation Example 5.
  • Example 31 If, instead of the product from production example 5, 6 g of the product from production example 1 or 7 g of the product from production example 2 or 9 g of the product from production example 3 or 9 g of the product from production example 4 are used per liter block solution in example 31, so the same results are obtained as in Example 31.

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Claims (10)

  1. Procédé pour améliorer les solidités au mouillé de teintures sur cellulose utilisant les colorants au soufre C.I. Sulphur Black 1, C.I. No 53185 ; C.I. Sulphur Black 2, C.I. N° 53195 ; C.I. Sulphur Black 18 ; C.I. Sulphur Blue 1, C.I. No 53235 ; C.I. Sulphur Blue 3, C.I. No 53235 ; C.I. Sulphur Blue 4, C.I. No 53235 ; C.I. Sulphur Blue 5, C.I. No 53235 ; C.I. Sulphur Blue 11, C.I. No 53235 ; C.I. Sulphur Green 2, C.I. No 53571 ; C.I. Sulphur Green 36 ; C.I. Sulphur Brown 46, C.I. No 53015 ; C.I. Sulphur Brown 31, C.I. No 53280 ; et leurs formes leucodérivées ou solubilisées, caractérisé en ce que la cellulose, avant, pendant ou après l'opération de teinture, est traitée par un polymère contenant de 16 2/3 à 100 % en moles d'un composé de formule I :
    Figure imgb0050
     sous forme polymérisée, où
    R¹ et R² représentent chacun un hydrogène ou un radical alkyle en C₁-C₂₂ pouvant éventuellement être interrompu par -CO-NH- ou par -NH-CO-, ou hydroxyalkyle,
    R³ et R⁴ sont chacun un hydrogène ou le radical méthyle,
    Y
    Figure imgb0051
    est un anion monovalent ou une partie, équivalente d'un anion monovalent, d'un anion polyvalent.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise un polymère contenant 40 à 100 % en moles et de préférence 80 à 100 % en moles d'un composé de formule I sous une forme introduite par polymérisation.
  3. Procédé selon les revendications 1 et/ou 2, caractérisé en ce qu'on utilise un polymère qui contient un composé de formule I, dans laquelle R¹ et R² sont des radicaux alkyle en C₁-C₁₀ et de préférence en C₁-C₄, sous une forme introduite par polymérisation.
  4. Procédé selon l'une ou plusieurs des revendications 1 à 3, caractérisé en ce qu'on utilise un polymère qui contient sous forme introduite par polymérisation un composé de formule I dans laquelle R¹ et R² sont chacun le radical méthyle, et/ou R³ et R⁴ sont chacun un hydrogène, et/ou Y⁻ est un anion halogénure, en particulier chlorure.
  5. Procédé selon l'une ou plusieurs des revendications 1 à 4, caractérisé en ce qu'on utilise un polymère pouvant être préparé par copolymérisation
    a) d'un composant diallylammonium A de formule I et
    b) d'un composant amide B, qui est constitué d'un composant basique B¹ de formule VII :
    Figure imgb0052
     et/ou d'un composant amide B² de formule VIII :
    Figure imgb0053
     et/ou d'un composant N-vinylacylamide B³ de formule IX :
    Figure imgb0054
     et/ou d'un composant ammonium B⁴ de formule X :
    Figure imgb0055
     et
    c) d'un composant ester méth(acrylique) C de formule XI :
    Figure imgb0056
     selon une proportion molaire A:B:C de 1:(0 à 4,5):(0 à 0,5), de préférence de 1:(0,002 à 4,5):(0 à 0,5),
    puis, du moment qu'est présent un composant B¹, une éventuelle réticulation avec
    d) un composant d'alkylation polyfonctionnel D et
    e) un composant polyamine E, qui est constitué d'un composant polyamine E¹ de formule XII :
    Figure imgb0057
     et/ou d'un composant polyamine E² de formule XIII :
    Figure imgb0058
     selon une proportion pondérale B¹:E:D = 1:(0 à 5):(0,002 à 2), avec
    R⁵, R⁶ et R²¹ sont des radicaux alkyle en C₁-C₁₀,
    R⁷, R⁸, R¹¹, R¹², R¹⁸, R¹⁹ et R²⁰ sont des hydrogènes ou des radicaux méthyle,
    R⁹, R¹⁰ et R¹³ sont des hydrogènes ou des radicaux alkyle en C₁-C₈,
    R¹⁴, R¹⁵, R¹⁶ et R¹⁷ sont des radicaux alkyle en C₁-C₈,
    ou bien
    R¹³ et R¹⁴ forment ensemble les radicaux -(CH₂)₃-, -(CH₂)₄- ou -(CH₂)₅-,
    R²² est un radical alkylène ayant de 1 à 8 atomes de carbone ou phénylène,
    R²³ est un hydrogène ou le radical -CO-R²²-COOH,
    X¹ et X² sont des radicaux -NH- ou -O-,
    Z
    Figure imgb0059
    est un anion monovalent ou une partie équivalant à un anion monovalent d'un anion polyvalent,
    Figure imgb0060
     m et q sont chacun l'un des nombres 2, 3, 4, 5, 6, 7, 8, 9, 10,
    n, p, r et w sont chacun l'un des nombres 0, 1, 2 ou 3,
    s et u sont chacun l'un des nombres 2, 3, 4 ou 5,
    v est le nombre 0 ou est un nombre suffisamment grand pour que le composant polyamine E¹ ait, compte tenu de t, une masse moléculaire de 1000 à 30000,
    t est un nombre suffisamment grand pour que, compte tenu de v, la masse moléculaire du composant polyamine E¹ de formule XII soit comprise entre 1000 et 30000.
  6. Procédé selon l'une ou plusieurs des revendications 1 à 5, caractérisé en ce qu'on utilise un polymère dans lequel R⁵, R⁶, R¹⁴, R¹⁵, R¹⁶ et/ou R¹⁷ sont des radicaux alkyle en C₁-C₄, et/ou R⁹, R¹⁰, et/ou R¹³ sont des hydrogènes ou des radicaux alkyle en C₁-C₄, et/ou n, p et/ou v = 0.
  7. Procédé selon l'une ou plusieurs des revendications 1 à 6, caractérisé en ce qu'on l'utilise pour améliorer la solidité au mouillé de teintures obtenues par les colorants au soufre C.I. Sulphur Black 1, C.I. No 53185 ; C.I. Sulphur Black 2, C.I. No 53195 ; C.I. Sulphur Blue 1, C.I. No 53235 ; C.I. Sulphur Blue 3, C.I. No 53235 ; C.I. Sulphur Blue 4, C.I. No 53235 ; C.I. Sulphur Blue 5, C.I. No 53235 ; C.I. Sulphur Blue 11, C.I. No 53235 ; et les formes leucodérivées ou solubilisées de ces colorants au soufre.
  8. Procédé selon l'une ou plusieurs des revendications 1 à 7, caractérisé en ce qu'on utilise un polymère contenant de 40 à 100 % en moles et de préférence de 80 à 100 % en moles d'un composé de formule 1 sous forme introduite par polymérisation.
  9. Procédé selon l'une ou plusieurs des revendications 1 à 8, caractérisé en ce que le polymère est appliqué sur la cellulose, par rapport au poids de la cellulose, en une quantité de 0,001 à 5 %, de préférence de 0,01 à 2,5 % et tout particulièrement en des quantités de 0,01 à 1 %.
  10. Procédé selon l'une ou plusieurs des revendications 1 à 9, caractérisé en ce qu'on l'utilise-dans le cadre d'un procédé d'encollage-teinture pour encoller et teindre, presque en un seul bain, des matériaux cellulosiques avec des colorants au soufre.
EP88101068A 1987-02-04 1988-01-26 Modification de la solidité au mouillé de teintures effectuées avec des colorants au soufre Expired - Lifetime EP0277580B1 (fr)

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US5013328A (en) * 1988-11-14 1991-05-07 Sandoz Ltd. Aftertreatment of dyed substrates
DE3844194A1 (de) * 1988-12-29 1990-07-05 Hoechst Ag Verfahren zum faerben von textilmaterial mit pigmentfarbstoffen
PT94345A (pt) * 1989-06-16 1991-02-08 Hoechst Ag Processo para obtencao de efeitos de padrao no tingimento ou estampagem de material textil na ausencia de alcalis ou agentes de reducao
DE4325783A1 (de) * 1993-07-31 1995-02-02 Hoechst Ag Verfahren zum Modifizieren und Färben von modifizierten Fasermaterialien
US5853542A (en) * 1995-09-11 1998-12-29 Hercules Incorporated Method of sizing paper using a sizing agent and a polymeric enhancer and paper produced thereof
GB9703813D0 (en) * 1997-02-24 1997-04-16 Ici Plc Dyeing of textiles
US9797088B2 (en) * 2010-08-02 2017-10-24 Syntor Fine Chemicals Limited Methods of treating textile fibres
GB201604563D0 (en) 2016-03-17 2016-05-04 Syntor Specialty Chemicals Ltd Method of coating
CN108179642B (zh) * 2016-05-20 2020-11-13 南通市武鑫化工有限公司 一种用于活性染料染色的固色剂的制备方法
PL3535370T3 (pl) * 2016-11-01 2020-12-28 The Procter & Gamble Company Sposoby wykorzystania leuko barwników jako środków nadających niebieski odcień w kompozycjach środków piorących

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ATE93910T1 (de) 1993-09-15
US4810254A (en) 1989-03-07
DE3703293A1 (de) 1988-08-18
EP0277580A3 (fr) 1991-07-17
EP0277580A2 (fr) 1988-08-10
DE3883550D1 (de) 1993-10-07

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