EP0610846A2 - Use of copolymers comprising vinyl/monomers and carbonamide as detergent additive - Google Patents

Use of copolymers comprising vinyl/monomers and carbonamide as detergent additive Download PDF

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Publication number
EP0610846A2
EP0610846A2 EP94101799A EP94101799A EP0610846A2 EP 0610846 A2 EP0610846 A2 EP 0610846A2 EP 94101799 A EP94101799 A EP 94101799A EP 94101799 A EP94101799 A EP 94101799A EP 0610846 A2 EP0610846 A2 EP 0610846A2
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EP
European Patent Office
Prior art keywords
copolymers
vinyl
weight
use according
detergent
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EP94101799A
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German (de)
French (fr)
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EP0610846A3 (en
EP0610846B1 (en
Inventor
Werner Antwerpen
Hermann Dr. Schindler
Gerd Dr. Reinhardt
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Clariant Produkte Deutschland GmbH
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Hoechst AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions

Definitions

  • the laundry to be cleaned nowadays in the household and industry consists of uniform or, especially in the household, mostly of different types of fibers, in particular of natural fibers, primarily cotton or wool, of regenerated cellulose fibers, e.g. Viscose, made of synthetic fibers, e.g. Polyester, polyamide and polyacrylonitrile, and from mixtures of such fibers.
  • the so-called "white laundry" which consists of undyed textiles
  • the so-called "colored laundry” is usually composed of colored textiles in different shades and depths, from light or pastel to dark. It goes without saying that textiles with a wide variety of color fastnesses can be present in one wash cycle.
  • Another way to prevent color transfer is to incorporate polymeric color transfer inhibitors into the detergent formulation.
  • DE-A-22 32 353 describes detergent formulations with reduced color transfer during the washing process, which contain polyvinylpyrrolidone (PVP).
  • PVP polyvinylpyrrolidone
  • DE-A-38 03 630 detergent additives to avoid color transfer during washing which contain polymers based on N-vinylpyrrolidone, N-vinylimidazole or N-vinyloxazolidone.
  • DE-A-37 11 299 discloses polyvinylpyrrolidones grafted with vinyl esters as graying inhibitors for textiles containing synthetic fibers.
  • European patent application No. 93113207.0 discloses the use of water-soluble copolymers based on acrylamidoalkylene sulfonic acid, vinyl acetamide and, if appropriate, further monomers as detergent additives to prevent the detachment of detached dyes and dye degradation products.
  • no polymer dispersions or redispersible dispersion powders, such as those obtained by drying aqueous polymers, can be made from the copolymers described dispersions are obtained, produce.
  • polymer dispersions are finely divided and form a more or less clear polymer film after drying. They are suitable e.g. for the consolidation of nonwovens, as a binder in emulsion paints and paper coating slips, for the production of adhesives and glues, for use in the building materials sector, as pigment binders for pigment printing and for textile finishing.
  • powders can be produced from emulsifier-free polymer dispersions based on vinyl ester / ethylene / acetamide copolymers, which give stable dispersions by redispersion in water.
  • the dispersion powders are suitable for the production of rewettable adhesive coatings and can also be used in wallpaper paste compositions and for wallpaper backing coatings, as well as binders in emulsion paints and plastic-bound plasters and for textile finishing.
  • DE-C-29 05 121 describes a process for the preparation of an aqueous stable polymer dispersion by polymerizing at least one vinyl monomer which is free from carboxyl and amide groups and at least one carboxamide of the formula (I)
  • R is a hydrogen atom or a methylol radical
  • R 1 is a hydrogen atom or a C 1 -C 3 alkyl radical
  • R 2 is a hydrogen atom or a methyl radical.
  • the polymer dispersions are suitable as binder dispersions in emulsion paints and preferably as starting materials for the production of redispersible films and powders for adhesive purposes. Such redispersible adhesive coatings are used in particular in the case of face rubbers, adhesive rolls, glues, finishes, carpet adhesives and carriers for washable stains.
  • R is a hydrogen atom or a methylol radical
  • R 1 is a hydrogen atom or a C1-C3-alkyl radical
  • R 2 is a hydrogen atom or a methyl radical and optionally together with a maximum of 5% by weight of a copolymerizable, unsaturated carboxylic acid as detergent additive to prevent re-
  • the invention relates to the use of copolymers according to claim 1 as a detergent additive for preventing the re-absorption of detached dyes and dye degradation products.
  • Compounds of the formula (11) are particularly suitable in which R 3 (a) represents a hydrogen atom or an alkyl radical having 1, 2 or 3 carbon atoms, (b) a homo- or heterocyclic radical having 5 or 6 ring members, (c) an alkoxy radical having 1, 2, 3 or 4 carbon atoms, (d) an alkylcarboxy radical having 2 to 18, preferably 2 to 10 carbon atoms, (ei a nitrile group, (f) a halogen atom or (g) an alkoxycarbonyl radical having 2 to 12, preferably 2 to 9 carbon atoms and R 4 is a hydrogen atom or a Is methyl residue.
  • Suitable vinyl monomers are in particular (a) olefins, e.g. Ethylene, propylene and isobutylene, (b) styrene, N-vinyl pyrrolidone and vinyl pyridine, (c) vinyl ether, e.g. Vinyl methyl ether, vinyl ethyl ether and vinyl n-butyl ether, (d) vinyl esters of aliphatic carboxylic acids, e.g. Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl laurate and vinyl decanates, (e) acrylonitrile and methacrylonitrile, (f) vinyl halides, e.g.
  • Vinyl chloride and propenyl chloride and (g) acrylic or methacrylic esters of monohydric alkanols e.g. Methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate and 2-ethylhexyl methacrylate.
  • suitable vinyl monomers are maleic acid diesters and fumaric acid diesters, in particular monohydric alkanols having 2 to 10, preferably 3 to 8, carbon atoms, e.g. Dibutyl maleate, dihexyl maleate, dioctyl maleate, dibutyl fumarate, dihexyl fumarate and dioctyl fumarate.
  • a vinyl ester as the vinyl monomer, optionally together with another of the vinyl monomers mentioned, preferably an olefin or a (meth) acrylic acid ester.
  • the amount of the vinyl monomer or vinyl monomer mixture used for the copolymerization with a carboxamide is 95 to 75% by weight, preferably 90 to 85% by weight, of the total amount of monomers. If a vinyl ester with another vinyl monomer is used, the proportion of the vinyl ester is usually at least 50% by weight, preferably 75 to 95% by weight, of the total amount of the vinyl monomers.
  • carboxylic acid amides of the formula (I) used are acrylamide, methacrylamide and crotonic acid amide, and N-methylolacrylamide, N-methylolmethacrylamide and N-methylolcrotonic acid amide.
  • the amount of the carboxylic acid amide is 5 to 20% by weight, preferably 7 to 14% by weight, of the total amount of the monomer.
  • a copolymerizable unsaturated carboxylic acid is optionally used as a further monomer, in particular an aliphatic monocarboxylic acid with 3 or 4 carbon atoms or an aliphatic dicarboxylic acid with 4 or 5 carbon atoms.
  • Suitable unsaturated carboxylic acids are, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid.
  • the amount of the carboxylic acid is at most 5% by weight, preferably 0.1 to 3.0% by weight, of the total amount of monomers.
  • copolymers used according to the invention can be prepared analogously to the process of EP-A-0 014 450.
  • poly (vinyl alcohol) e.g. as a protective colloid, which is why the copolymers used according to the invention are free of poly (vinyl alcohol).
  • the polymer dispersions produced generally have a solids content of 40 to 70% by weight, preferably 45 to 60% by weight.
  • the viscosity of the dispersions is usually in the range from 1 to 20 Pa. s, preferably from 1.5 to 7.0 Pa. (measured according to Epprecht).
  • Redispersible powders based on the aqueous dispersions are used according to the invention as color transfer inhibitors in solid detergents, the aggregate particle size generally being initially between 800 and 1000 ⁇ m.
  • copolymer dispersions according to the invention are dispersions based on vinyl acetate, ethylene and an acrylic acid derivative, such as acrylic acid amide.
  • the detergents which contain the color transfer inhibitors according to the invention can be both industrial detergents and household detergents. These include, in particular, powdery and liquid heavy-duty detergents, powdery and liquid mild detergents, machine dishwashing detergent boosters, such as stain salts and pastes, and laundry detergents (fabric conditioner and fabric softener).
  • powdery and liquid heavy-duty detergents powdery and liquid mild detergents
  • machine dishwashing detergent boosters such as stain salts and pastes
  • laundry detergents fabric conditioner and fabric softener.
  • the most important component of detergents are the detersive surfactants, which are primarily
  • (a) are anionic, non-ionic and / or zwitterionic detergent surfactants.
  • the anionic detersive surfactants are primarily sulfonates such as alkylarylsulfonates e.g. Dodecylbenzenesulfonate, alkyl sulfonates and alkenyl sulfonates, and sulfates, e.g. Alkyl sulfates, sulfates of ethoxylated amides, esters of a-sulfo fatty acids or soaps of natural, optionally modified or synthetic fatty acids, the anionic surfactants advantageously being in salt form, e.g.
  • the anionic surfactants also include sulfosuccinates, alkyl ether sulfates, alkyl ether carboxylates and fatty acid condensation products, as are customarily used in washing and cleaning formulations.
  • Suitable non-ionic detergent surfactants are primarily polyethylene glycol ethers of higher alcohols or alkylphenols, polyethylene glycol esters of fatty acids and polyoxyethylation products of fatty acid amides.
  • the fat residues or alkyl and alkylene residues in the above-mentioned surfactants or alcohols or fatty acids contain, for example, 8-20 carbon atoms;
  • Aryl primarily stands for phenyl;
  • the polyethylene glycol chains can contain, for example, 3-80 ethyleneoxy groups and optionally consist of propyleneoxy units.
  • Typical non-ionic surfactants are alkyl polyethoxylates, alkyl polyglycosides, glucamides, alkylamine N-oxides, alkylphosphine oxides and condensation products from fatty alcohols with ethylene oxide and propylene oxide.
  • Preferred as (a) among the anionic surfactants are the alkylbenzenesulfonates, the alkanesulfonates, the alkylsulfonates and the soaps and among the nonionic surfactants the alkylpolyglycol ethers.
  • zwitterionic surfactants are derivatives of aliphatic quaternary ammonium, phosphonium and sulphonium compounds, as are known from US Pat. Nos. 3,925,262 and 3,929,678.
  • the sequestering agents (b) which can be mentioned are customary complex-forming substances, for example aminopolyacetates (in particular nitrilotriacetate or ethylenediaminetetraacetate), aminopolymethylene phosphates, sodium triphosphate, sodium tripolyphosphates, sodium aluminum silicates, sodium silicate, magnesium silicate, zeolite A, polyacrylates (eg ammonium acrylates) and polyacrylates (e.g. (e.g. sodium citrate, sodium tartrate and sodium gluconate).
  • aminopolyacetates in particular nitrilotriacetate or ethylenediaminetetraacetate
  • aminopolymethylene phosphates aminopolymethylene phosphates
  • sodium triphosphate sodium triphosphate
  • sodium tripolyphosphates sodium aluminum silicates
  • sodium silicate sodium silicate
  • magnesium silicate zeolite A
  • polyacrylates eg ammonium acrylates
  • polyacrylates e.g. (
  • proteases for example.
  • lipases for example.
  • cellulases cellulases
  • amylases for example.
  • Suitable bleaching agents (d) are customary peroxy compounds, for example perborates, percarbonates, perphosphates or peroxides, in particular as alkali metal salts or, particularly in liquid formulations, also hydrogen peroxide.
  • the above-mentioned sequestering agents can be used as stabilizers for the per-compounds, for example, and customary carboxylic acids or amido derivatives can be mentioned as optional activators.
  • washing alkalis for example ammonium or alkali metal silicates, phosphates, carbonates, borates or hydroxides; the above respective alkaline per compounds can optionally also act as washing alkalis.
  • dirt carriers (f) which may be present.
  • the detergents can also contain further additives, for example defoamers (or foam stabilizers), fragrances, disinfectants, buffer salts, compounds which release active chlorine, corrosion inhibitors, solvents, solubilizers, finishing agents or carriers, preservatives and other electrolytes (for example sodium sulfate).
  • defoamers or foam stabilizers
  • fragrances for example, fragrance, disinfectants, buffer salts, compounds which release active chlorine, corrosion inhibitors, solvents, solubilizers, finishing agents or carriers, preservatives and other electrolytes (for example sodium sulfate).
  • copolymers used according to the invention can be added individually to the washing liquors or, if desired, incorporated into the detergents.
  • Washing is carried out primarily under weakly acidic to clearly basic conditions, advantageously at pH values in the range from 6 to 12, preferably from 7 to 10.
  • the additives according to the invention are advantageously used in concentrations of 0.05 to 10 g / l, preferably 0.5 to 4 g / l aqueous washing liquor.
  • the content of these compounds in the detergent formulation is advantageously in the range from 0.2 to 10% by weight, preferably 1-6% by weight.
  • the washing can be carried out under customary conditions and, as provided in the respective washing programs of commercially available washing machines, expediently in an overall washing process in which all the components are present in the liquor and are preferably added.
  • the washing temperature can also fluctuate in usual ranges, e.g. in the range of 15-95 ° C, with the temperatures in the range of 30-60 ° C which are common for colored laundry and nowadays preferred.
  • any materials can be washed, as they are intended for the respective washing processes in industry and household, e.g. loose fibers, filaments, threads, bobbins, fabrics, knitted fabrics, nonwovens, open webs, tubular goods, velvet, felt, tufted goods, carpets, structured, porous plastic-like plastic materials (as used for household and clothing) and especially semi-finished and finished goods.
  • the substrates can be made of any conventional material, e.g. natural or regenerated cellulose (e.g. cotton, linen, hemp, viscose), natural polyamides (e.g. wool, silk) or synthetic materials (e.g. polyamides, polyesters, polyacrylonitriles, polypropylene or polyurethanes) and their mixtures.
  • natural or regenerated cellulose e.g. cotton, linen, hemp, viscose
  • natural polyamides e.g. wool, silk
  • synthetic materials e.g. polyamides, polyesters, polyacrylonitriles, polypropy
  • the detergent additives according to the invention are mixed with the usual detergent, e.g. as listed above, well tolerated and practically do not impair their washing effect, but can even support them. They surprisingly well prevent bleeding-away dyestuffs and dyestuff degradation products from being re-absorbed onto the washed, in particular the washed, material and can be rinsed out of the washed material in a manner analogous to the other wash liquor components. You do not attack the laundry. Compared to the known polymeric color transfer inhibitors, they are usually superior in performance and moreover have good biodegradability. Depending on the consistency of the detergent formulation, whether liquid or powder, the color inhibiting additives according to the invention can be added during assembly either as an aqueous dispersion or as a redispersible dispersion powder.
  • Redispersible dispersion powder prepared by spray drying the aqueous polymer dispersion according to Example 1.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
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Abstract

The present invention relates to the use of copolymers containing 75 - 95% by weight of the total monomer quantity of at least one vinyl monomer which is free of carboxyl and amide groups, 5 - 20% by weight of at least one carboxyamide of the formula (I) <IMAGE> in which R is a hydrogen atom or a methylol radical, R<1> is a hydrogen atom or a C1-C3-alkyl radical and R<2> is a hydrogen atom or a methyl radical and, where appropriate, together with a maximum of 5% by weight of a copolymerisable unsaturated carboxylic acid as detergent additive to prevent reuptake of dyes which have been dissolved off and of dye breakdown products.

Description

Das heutzutage in Haushalt und Industrie zu reinigende Waschgut besteht aus einheitlichen oder, besonders im Haushalt, größtenteils aus verschiedenen Fasertypen, insbesondere aus natürlichen Fasern, vornehmlich Baumwolle oder Wolle, aus regenierten Cellulosefasern, z.B. Viskose, aus synthetischen Fasern, z.B. Polyester, Polyamid und Polyacrylnitril, und aus Mischungen solcher Fasern. Im Gegensatz zur sogenannten "Weißwäsche", welche aus ungefärbten Textilien besteht, ist die sogenannte "Buntwäsche" aus gefärbten Textilien meist in verschiedenen Farbtönen und Farbtiefen, von hell bzw. pastell bis dunkel zusammengesetzt. Es ist selbstverständlich, daß in einem Waschgang Haushaltbuntwäsche Textilien mit den verschiedensten Farbechtheiten vorhanden sein können. Falls dabei die Färbungen nicht genügend waschecht sind, kommt es während des Waschprozesses zum Ablösen von Farbstoffen oder von Farbstoffabbauprodukten und zum Abbluten davon in die Waschflotte. Durch das Neuaufziehen dieser abgelösten (abgebluteten) Bestandteile auf die mitgewaschenen anderen Textilien resultiert ein "Anschmutzen", eine Nuancenverschiebung und/oder eine Fleckenbildung durch abgebluteten, eventuell ungleichmäßig verteilten, neu-aufgezogenen Farbstoff oder Farbstoffabbauprodukte. Das Ablösen und/oder Zersetzen von Farbstoff einer nicht genügend echten Färbung wird z.B. durch höhere Temperaturen, wiederholte Waschoperationen, Flottenverhältnis von Waschflotte zu Waschgut, Zusammensetzung der eingesetzten Waschmittel und deren Konzentration in der Waschflotte begünstigt, wobei auch der Typ der verwendeten Waschmaschinen und Waschprogramme einen Einfluß auf das Ablösen von Farbstoff bzw. Farbstoffabbauprodukten einer nicht genügend "haushaltwäschegerechten" Färbung haben können, z.B. bedingt durch die mechanische Beanspruchung des Waschgutes während des Waschens etc. Als weitere Gründe für einen Echtheitsabfall können auch die verwendete Wasserqualität (z.B. durch Chlorgehalt), die Zusammensetzung bestimmter Zusätze für die pflegeleichte Handhabung und die Qualität und Struktur des Textilmaterials bzw. der Fasern genannt werden. Als Beispiel für das genannte sei Waschgut aus Cellulosefasern, vor allem die Baumwolle genannt; dieses wird meistens mit Direktfarbstoffen, Reaktivfarbstoffen, Schwefelfarbstoffen, Küpenfarbstoffen oder Naphtholfarbstoffen gefärbt, hauptsächlich mit Direktfarbstoffen oder Reaktivfarbstoffen. Sowohl Färbungen mit Direktfarbstoffen als auch Färbungen mit Reaktivfarbstoffen auf Cellulose neigen beim wiederholten Washen zu mehr oder weniger ausgeprägtem "Abbluten" in die Waschflotten - in den Waschflotten befinden sich folglich beispielsweise unfixierter Farbstoff, hydrolysierter Farbstoff und/oder abgespaltener Farbstoff - was zu den oben geschilderten Problemen führt.The laundry to be cleaned nowadays in the household and industry consists of uniform or, especially in the household, mostly of different types of fibers, in particular of natural fibers, primarily cotton or wool, of regenerated cellulose fibers, e.g. Viscose, made of synthetic fibers, e.g. Polyester, polyamide and polyacrylonitrile, and from mixtures of such fibers. In contrast to the so-called "white laundry", which consists of undyed textiles, the so-called "colored laundry" is usually composed of colored textiles in different shades and depths, from light or pastel to dark. It goes without saying that textiles with a wide variety of color fastnesses can be present in one wash cycle. If the dyeings are not sufficiently wash-fast, dyes or dye degradation products are detached during the washing process and bleed off into the wash liquor. The new application of these detached (bled) components on the washed-off other textiles results in “soiling”, a shift in nuances and / or staining due to bled, possibly unevenly distributed, newly applied dye or dye degradation products. The detachment and / or decomposition of dye of an insufficiently true color is e.g. favored by higher temperatures, repeated washing operations, liquor ratio of washing liquor to laundry, composition of the detergents used and their concentration in the washing liquor, the type of washing machines and washing programs used also having an influence on the detachment of dye or dye degradation products of an insufficiently "household laundry" Can have color, for example due to the mechanical stress on the laundry during washing etc. The water quality used (e.g. due to chlorine content), the composition of certain additives for easy-care handling and the quality and structure of the textile material or fibers can also be mentioned as further reasons for a drop in authenticity . An example of the above is laundry made from cellulose fibers, especially cotton; this is mostly dyed with direct dyes, reactive dyes, sulfur dyes, vat dyes or naphthol dyes, mainly with direct dyes or reactive dyes. Both dyeings with direct dyes and dyeings with reactive dyes on cellulose tend to more or less pronounced "bleeding" in the wash liquors during repeated washing - consequently there are unfixed dye, hydrolyzed dye and / or cleaved dye in the wash liquors - which is the same as that described above Leads to problems.

Die Farbübertragungsreaktion wird häufig in zwei Teilschritte untergliedert:

  • - Ablösung der Farbstoffpartikel von der Textilfaser
  • - Redisposition auf einer anderen Stelle des Waschgutes.
The color transfer reaction is often divided into two steps:
  • - Detachment of the dye particles from the textile fiber
  • - Redisposition to another part of the laundry.

Zur Verhinderung dieser Reaktion sind in der Literatur verschiedene Vorschläge beschrieben.Various proposals have been described in the literature to prevent this reaction.

Zum einen ist es möglich, den Farbstoff, während er in der Waschflotte gelöst vorliegt, oxidativ zu zerstören. Bei Verwendung herkömmlicher Vollwaschmittel stellt dies kein Problem dar, da diese meist ein Bleichsystem bestehend aus Perborat und einem Persalzaktivator, wie Tetraacetylethylendiamin, TAED, enthalten. Die sich daraus bildende Peressigsäure zerstört die gelösten Farbstoffe vollständig, bevor ein Aufziehen auf die Faser möglich ist. Nachteilig ist jedoch dabei, daß bei reaktiven Perborataktivatoren auch zu Farbschäden durch Ausbleichen der Textilfarben kommen kann.On the one hand, it is possible to oxidatively destroy the dye while it is dissolved in the wash liquor. This is not a problem when using conventional heavy-duty detergents, since these usually contain a bleaching system consisting of perborate and a persalt activator, such as tetraacetylethylene diamine, TAED. The peracetic acid that forms completely destroys the dissolved dyes before it can be drawn onto the fiber. However, it is disadvantageous that reactive perborate activators can also cause color damage due to bleaching of the textile colors.

Neben Bleichaktivatoren sind auch Enzyme mit peroxidasischen Eigenschaften für diese Anwendungen geeignet (WO-A-91/05839).In addition to bleach activators, enzymes with peroxidase properties are also suitable for these applications (WO-A-91/05839).

Eine andere Möglichkeit zur Verhinderung der Farbübertragung ist das Einarbeiten polymerer Farbübertragungsinhibitoren in die Waschmittelformulierung.Another way to prevent color transfer is to incorporate polymeric color transfer inhibitors into the detergent formulation.

Als bevorzugte Inhibitoren werden Homopolymere des Vinylimidazols und Vinylpyrrolidons eingesetzt. DE-A-22 32 353 beschreibt Waschmittelformulierungen mit verminderter Farbübertragung während des Waschvorganges, die Polyvinylpyrrolidon (PVP) enthalten.Homopolymers of vinylimidazole and vinylpyrrolidone are used as preferred inhibitors. DE-A-22 32 353 describes detergent formulations with reduced color transfer during the washing process, which contain polyvinylpyrrolidone (PVP).

Aus DE-A-38 03 630 sind Waschmittelzusätze zur Vermeidung der Farbübertragung während des Waschens bekannt, die Polymere auf der Basis von N-Vinylpyrrolidon, N-Vinylimidazol oder N-Vinyloxazolidon enthalten.DE-A-38 03 630 detergent additives to avoid color transfer during washing are known which contain polymers based on N-vinylpyrrolidone, N-vinylimidazole or N-vinyloxazolidone.

Die DE-A-37 11 299 offenbart mit Vinylestern gepfropfte Polyvinylpyrrolidone als Vergrauungsinhibitoren für Synthesefasern enthaltende Textilien.DE-A-37 11 299 discloses polyvinylpyrrolidones grafted with vinyl esters as graying inhibitors for textiles containing synthetic fibers.

Nachteilig an diesen polymeren Farbübertragungsinhibitoren ist ihre oftmals geringe Löslichkeit, insbesondere bei modifizierten Polyvinylpyrrolidonen, die eine Einarbeitung in flüssige Waschmittelformulierungen erschwert, sowie die ungenügende biologische Abbaubarkeit.Disadvantages of these polymeric dye transfer inhibitors are their often low solubility, in particular in the case of modified polyvinylpyrrolidones, which complicates incorporation into liquid detergent formulations, and the inadequate biodegradability.

Die noch nicht veröffentlichte europäische Patentanmeldung Nr. 93113207.0 offenbart die Verwendung wasserlöslicher Copolymerer auf Basis von Acrylamidoalkylensulfonsäure, Vinylacetamid und gegebenenfalls weiterer Monomere als Waschmittelzusatz zur Verhinderung des Wiederaufziehens von abgelösten Farbstoffen und Farbstoffabbauprodukten. Aus den beschriebenen Copolymeren lassen sich jedoch keine Polymerdispersionen bzw. redispergierbaren Dispersionspulver, wie sie durch Trocknung wäßriger Polymerdispersionen erhalten werden, herstellen.European patent application No. 93113207.0, which has not yet been published, discloses the use of water-soluble copolymers based on acrylamidoalkylene sulfonic acid, vinyl acetamide and, if appropriate, further monomers as detergent additives to prevent the detachment of detached dyes and dye degradation products. However, no polymer dispersions or redispersible dispersion powders, such as those obtained by drying aqueous polymers, can be made from the copolymers described dispersions are obtained, produce.

In der noch nicht veröffentlichten europäischen Patentanmeldung Nr. 93113341.7wird die Verwendung von teil- und/oder vollhydrolysierten Polyvinylalkoholen als Waschmittelzusatz zur Verhinderung des Wiederaufziehens von Farbstoffen und Farbstoffprodukten genannt. Es hat sich gezeigt, daß diese Polymere in Gegenwart von Borsäure oder Borsäurederivaten, insbesondere auch Perboraten unerwünschte Nebenreaktionen eingehen können und damit zum Einsatz in borhaltigen Waschmitteln wenig geeignet sind.European Patent Application No. 93113341.7, which has not yet been published, mentions the use of partially and / or fully hydrolyzed polyvinyl alcohols as detergent additives to prevent the reabsorption of dyes and dye products. It has been shown that these polymers can undergo undesirable side reactions in the presence of boric acid or boric acid derivatives, in particular also perborates, and are therefore not very suitable for use in detergents containing boron.

Aus US-A-3 870 673 ist bekannt, emulgatorfreie Polymerdispersionen durch Polymerisieren von Vinylestern, Ethylen und einem Acrylamid in wäßrigem Medium mittels eines Redox-Initiator-Systems herzustellen.From US-A-3 870 673 it is known to prepare emulsifier-free polymer dispersions by polymerizing vinyl esters, ethylene and an acrylamide in an aqueous medium using a redox initiator system.

Diese Polymerdispersionen sind feinteilig und bilden nach dem Auftrocknen einen mehr oder weniger klaren Polymerfilm. Sie eignen sich z.B. für die Verfestigung von Faservliesen, als Bindemittel in Dispersionsfarben und Papierstreichmassen, zur Herstellung von Klebstoffen und Leimen, für den Einsatz im Baustoffsektor, als Pigmentbinder für den Pigmentdruck und zur Textilausrüstung.These polymer dispersions are finely divided and form a more or less clear polymer film after drying. They are suitable e.g. for the consolidation of nonwovens, as a binder in emulsion paints and paper coating slips, for the production of adhesives and glues, for use in the building materials sector, as pigment binders for pigment printing and for textile finishing.

Ferner ist aus US-A-3 950 302 bekannt, daß sich aus emulgatorfreien Polymerdispersionen auf der Grundlage von Vinylester/Ethylen/Acetamid-Copolymeren durch Trocknung Pulver herstellen lassen, die durch Redispergieren in Wasser stabile Dispersionen ergeben. Die Dispersionspulver eignen sich zur Herstellung wiederanfeuchtbarer Klebstoffbeschichtungen und lassen sich auch in Tapetenkleister-Kompositionen und für Tapetenrückseitenbeschichtungen, ferner als Bindemittel in Dispersionsfarben und Kunststoffgebundenen Putzen und zur Textilausrüstung verwenden.Furthermore, it is known from US Pat. No. 3,950,302 that powders can be produced from emulsifier-free polymer dispersions based on vinyl ester / ethylene / acetamide copolymers, which give stable dispersions by redispersion in water. The dispersion powders are suitable for the production of rewettable adhesive coatings and can also be used in wallpaper paste compositions and for wallpaper backing coatings, as well as binders in emulsion paints and plastic-bound plasters and for textile finishing.

Weiterhin ist aus DE-C-29 05 121 ein Verfahren zur Herstellung einer wäßrigen stabilen Polymerdispersion durch Polymerisieren mindestens eines Vinylmonomeren, das frei von Carboxyl- und Amidgruppen ist und mindestens eines Carbonsäureamids der Formel (I)Furthermore, DE-C-29 05 121 describes a process for the preparation of an aqueous stable polymer dispersion by polymerizing at least one vinyl monomer which is free from carboxyl and amide groups and at least one carboxamide of the formula (I)

Figure imgb0001
bekannt, in der R ein Wasserstoffatom oder ein Methylolrest, R1 ein Wasserstoffatom oder ein C1-C3-Alkylrest und R2 ein Wasserstoffatom oder einen Methylrest bedeuten. Die Polymerdisperionen eignen sich als Bindemitteldispersionen in Dispersionsfarben und vorzugsweise als Ausgangsmaterialien für die Herstellung von redispergierbaren Filmen und Pulvern für Klebezwecke. Derartige redispergierbare Klebebeschichtungen finden insbesondere Anwendung bei Plangummierungen, Kleberollen, Leimen, Appreturen, Teppichklebern und Trägern für abwaschbare Malfarben.
Figure imgb0001
 are known in which R is a hydrogen atom or a methylol radical, R 1 is a hydrogen atom or a C 1 -C 3 alkyl radical and R 2 is a hydrogen atom or a methyl radical. The polymer dispersions are suitable as binder dispersions in emulsion paints and preferably as starting materials for the production of redispersible films and powders for adhesive purposes. Such redispersible adhesive coatings are used in particular in the case of face rubbers, adhesive rolls, glues, finishes, carpet adhesives and carriers for washable stains.

Es wurde nun gefunden, daß sich Copolymere, enthaltend 75 - 95 Gew.-% der Gesamtmonomermenge mindestens eines Vinylmonomeres, das frei von Carboxyl- und Amidgruppen ist, 5 - 20 Gew.-% mindestens eines Carbonsäureamids der Formel (I)

Figure imgb0002

in der R ein Wasserstoffatom oder ein Methylolrest, R1 ein Wasserstoffatom oder ein C1-C3-Alkylrest und R2 ein Wasserstoffatom oder einen Methylrest bedeuten und gegebenenfalls zusammen mit maximal 5 Gew.-% einer copolymerisierbaren, ungesättigten Carbonsäure als Waschmittelzusatz zur Verhinderung des Wiederaufziehens von abgelösten Farbstoffen und Farbstoffabbauprodukten (Farbübertragungsinhibitoren) eignen.It has now been found that copolymers containing 75-95% by weight of the total amount of at least one vinyl monomer which is free from carboxyl and amide groups, 5-20% by weight of at least one carboxamide of the formula (I)
Figure imgb0002
in which R is a hydrogen atom or a methylol radical, R 1 is a hydrogen atom or a C1-C3-alkyl radical and R 2 is a hydrogen atom or a methyl radical and optionally together with a maximum of 5% by weight of a copolymerizable, unsaturated carboxylic acid as detergent additive to prevent re-absorption of detached dyes and dye degradation products (color transfer inhibitors).

Gegenstand der Erfindung ist die Verwendung von Copolymeren nach Anspruch 1 als Waschmittelzusatz zur Verhinderung des Wiederaufziehens von abgelösten Farbstoffen und Farbstoffabbauprodukten.The invention relates to the use of copolymers according to claim 1 as a detergent additive for preventing the re-absorption of detached dyes and dye degradation products.

Die erfindungsgemäß verwendeten Copolymeren enthalten als Vinylmonomere eine polymerisierbare Verbindung mit einer H2C = CH-Gruppe, die von Carboxyl- und Amidgruppen frei ist. Besonders geeignet sind Verbindungen der Formel (11)

Figure imgb0003

in der R3 (a) ein Wasserstoffatom oder einen Alkylrest mit 1, 2 oder 3 Kohlenstoffatomen, (b) einen homo-oder heterocyclischen Rest mit 5 oder 6 Ringgliedern, (c) einen Alkoxyrest mit 1, 2, 3 oder 4 Kohlenstoffatomen, (d) einen Alkylcarboxyrest mit 2 bis 18, vorzugsweise 2 bis 10 Kohlenstoffatomen, (ei eine Nitrilgruppe, (f) ein Halogenatom oder (g) einen Alkoxycarbonylrest mit 2 bis 12, vorzugsweise 2 bis 9 Kohlenstoffatomen bedeutet und R4 ein Wasserstoffatom oder ein Methylrest ist.The copolymers used according to the invention contain, as vinyl monomers, a polymerizable compound with an H 2 C = CH group which is free of carboxyl and amide groups. Compounds of the formula (11) are particularly suitable
Figure imgb0003
in which R 3 (a) represents a hydrogen atom or an alkyl radical having 1, 2 or 3 carbon atoms, (b) a homo- or heterocyclic radical having 5 or 6 ring members, (c) an alkoxy radical having 1, 2, 3 or 4 carbon atoms, (d) an alkylcarboxy radical having 2 to 18, preferably 2 to 10 carbon atoms, (ei a nitrile group, (f) a halogen atom or (g) an alkoxycarbonyl radical having 2 to 12, preferably 2 to 9 carbon atoms and R 4 is a hydrogen atom or a Is methyl residue.

Geeignete Vinylmonomere sind insbesondere (a) Olefine, z.B. Ethylen, Propylen und Isobutylen, (b) Styrol, N-Vinylpyrrolidon und Vinylpyridin, (c) Vinylether, z.B. Vinylmethylether, Vinylethylether und Vinyl-n-butylether, (d) Vinylester von aliphatischen Carbonsäuren, z.B. Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinylpivalat, Vinyllaurat und Vinyldecanate, (e) Acrylnitril und Methacrylnitril, (f) Vinylhalogenide, z.B. Vinylchlorid und Propenylchlorid und (g) Acrylsäureester oder Methacrylsäureester von einwertigen Alkanolen, z.B. Methylacrylat, Ethylacrylat, Butylacrylat, 2-Ethylhexylacrylat, Methylmethacrylat, Ethylmethacrylat, Butylmethacrylat, Hexylmethacrylat, Octylmethacrylat und 2-Ethylhexylmethacrylat. Ebenfalls geeignete Vinylmonomere sind Maleinsäurediester und Fumarsäurediester, insbesondere von einwertigen Alkanolen mit 2 bis 10, vorzugsweise 3 bis 8 Kohlenstoffatomen, z.B. Dibutylmaleinat, Dihexylmaleinat, Dioctylmaleinat, Dibutylfumarat, Dihexylfumarat und Dioctylfumarat.Suitable vinyl monomers are in particular (a) olefins, e.g. Ethylene, propylene and isobutylene, (b) styrene, N-vinyl pyrrolidone and vinyl pyridine, (c) vinyl ether, e.g. Vinyl methyl ether, vinyl ethyl ether and vinyl n-butyl ether, (d) vinyl esters of aliphatic carboxylic acids, e.g. Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl laurate and vinyl decanates, (e) acrylonitrile and methacrylonitrile, (f) vinyl halides, e.g. Vinyl chloride and propenyl chloride and (g) acrylic or methacrylic esters of monohydric alkanols, e.g. Methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate and 2-ethylhexyl methacrylate. Also suitable vinyl monomers are maleic acid diesters and fumaric acid diesters, in particular monohydric alkanols having 2 to 10, preferably 3 to 8, carbon atoms, e.g. Dibutyl maleate, dihexyl maleate, dioctyl maleate, dibutyl fumarate, dihexyl fumarate and dioctyl fumarate.

Besonders vorteilhaft ist die Verwendung eines Vinylesters als Vinylmonomeres, gegebenenfalls zusammen mit einem anderen der genannten Vinylmonomeren, vorzugsweise einem Olefin oder einem (Meth- )Acrylsäureester. Die Menge des zur Copolymerisation mit einem Carbonsäureamid eingesetzten Vinylmonomeren oder Vinylmonomer-Gemisches beträgt 95 bis 75 Gew.-%, vorzugweise 90 bis 85 Gew.-%, der Gesamtmonomermenge. Wenn ein Vinylester mit einem weiteren Vinylmonomeren eingesetzt wird, beträgt der Anteil des Vinylesters üblicherweise mindestens 50 Gew.-%, vorzugsweise 75 bis 95 Gew.-%, der Gesamtmenge der Vinylmonomeren.It is particularly advantageous to use a vinyl ester as the vinyl monomer, optionally together with another of the vinyl monomers mentioned, preferably an olefin or a (meth) acrylic acid ester. The amount of the vinyl monomer or vinyl monomer mixture used for the copolymerization with a carboxamide is 95 to 75% by weight, preferably 90 to 85% by weight, of the total amount of monomers. If a vinyl ester with another vinyl monomer is used, the proportion of the vinyl ester is usually at least 50% by weight, preferably 75 to 95% by weight, of the total amount of the vinyl monomers.

Als Carbonsäureamide der Formel (I) werden beispielsweise Acrylamid, Methacrylamid und Crotonsäureamid verwendet sowie N-Methylolacrylamid, N-Methylolmethacrylamid und N-Methylolcrotonsäureamid. Die Menge des Carbonsäureamids beträgt 5 bis 20 Gew.-%, vorzugsweise 7 bis 14 Gew.-%, der Gesamtmonomermenge.Examples of carboxylic acid amides of the formula (I) used are acrylamide, methacrylamide and crotonic acid amide, and N-methylolacrylamide, N-methylolmethacrylamide and N-methylolcrotonic acid amide. The amount of the carboxylic acid amide is 5 to 20% by weight, preferably 7 to 14% by weight, of the total amount of the monomer.

Als weiteres Monomeres wird gegebenenfalls noch eine copolymerisierbare ungesättigte Carbonsäure eingesetzt, insbesondere eine aliphatische Monocarbonsäure mit 3 oder 4 Kohlenstoffatomen oder eine aliphatische Dicarbonsäure mit 4 oder 5 Kohlenstoffatomen.A copolymerizable unsaturated carboxylic acid is optionally used as a further monomer, in particular an aliphatic monocarboxylic acid with 3 or 4 carbon atoms or an aliphatic dicarboxylic acid with 4 or 5 carbon atoms.

Geeignete ungesättigte Carbonsäuren sind beispielsweise Acrylsäure, Methacrylsäure, Crotonsäure, Itaconsäure, Maleinsäure und Fumarsäure. Die Menge der Carbonsäure beträgt maximal 5 Gew.-%, vorzugsweise 0,1 bis 3,0 Gew.-%, der Gesamtmonomermenge.Suitable unsaturated carboxylic acids are, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid. The amount of the carboxylic acid is at most 5% by weight, preferably 0.1 to 3.0% by weight, of the total amount of monomers.

Die erfindungsgemäß verwendeten Copolymeren können analog dem Verfahren der EP-A-0 014 450 hergestellt werden. Aus den einleitend genannten Gründen ist jedoch der Einsatz von Poly(vinylalkohol), z.B. als Schutzkolloid, nicht geeignet, weshalb die erfindungsgemäß verwendeten Copolymeren frei von Poly(vinylalkohol) sind.The copolymers used according to the invention can be prepared analogously to the process of EP-A-0 014 450. For the reasons mentioned in the introduction, however, the use of poly (vinyl alcohol), e.g. as a protective colloid, which is why the copolymers used according to the invention are free of poly (vinyl alcohol).

Die hergestellten Polymerdispersionen weisen im allgemeinen einen Feststoffgehalt von 40 bis 70 Gew.-%, vorzugsweise von 45 bis 60 Gew.-% auf. Die Viskosität der Dispersionen liegt üblicherweise im Bereich von 1 bis 20 Pa. s, vorzugsweise von 1,5 bis 7,0 Pa. (gemessen nach Epprecht).The polymer dispersions produced generally have a solids content of 40 to 70% by weight, preferably 45 to 60% by weight. The viscosity of the dispersions is usually in the range from 1 to 20 Pa. s, preferably from 1.5 to 7.0 Pa. (measured according to Epprecht).

Sie eignen sich als Farbübertragungsinhibitoren in Flüssigwaschmitteln und dienen weiterhin als Ausgangsmaterial für die Herstellung von redispergierbaren Pulvern. Die Pulver werden durch Trocknung, z.B. Walzentrocknung, Gefriertrocknung und vorzugsweise Sprühtrocknung, der Polymerdispersion gewonnen. Redispergierbare Pulver auf der Grundlage der wäßrigen Dispersionen werden erfindungsgemäß als Farbübertragungsinhibitoren in festen Waschmitteln eingesetzt, wobei die Aggregatteilchengröße im allgemeinen zunächst zwischen 800 und 1000 um liegen kann.They are suitable as color transfer inhibitors in liquid detergents and also serve as the starting material for the production of redispersible powders. The powders are dried, e.g. Roller drying, freeze drying and preferably spray drying, the polymer dispersion obtained. Redispersible powders based on the aqueous dispersions are used according to the invention as color transfer inhibitors in solid detergents, the aggregate particle size generally being initially between 800 and 1000 μm.

Beispielhaft für erfindungsgemäße Copolymerisat-Dispersionen seien Dispersionen auf Basis von Vinylacetat, Ethylen und einem Acrylsäurederivat, wie Acrylsäureamid genannt.Examples of copolymer dispersions according to the invention are dispersions based on vinyl acetate, ethylene and an acrylic acid derivative, such as acrylic acid amide.

Die Waschmittel, welche die erfindungsgemäßen Farbübertragungsinhibitoren enthalten, können sowohl industrielle Waschmittel als auch Haushaltswaschmittel sein. Hierzu zählen insbesondere pulverförmige und flüssige Vollwaschmittel, pulverförmige und flüssige Feinwaschmittel, Maschinengeschirrspülmittelbooster, wie Fleckensalze und -pasten sowie Wäschenachbehandlungsmittel (Formspüler und Weichspüler). Die wesentlichste Komponente der Waschmittel sind die waschaktiven Tenside, welche vornehmlichThe detergents which contain the color transfer inhibitors according to the invention can be both industrial detergents and household detergents. These include, in particular, powdery and liquid heavy-duty detergents, powdery and liquid mild detergents, machine dishwashing detergent boosters, such as stain salts and pastes, and laundry detergents (fabric conditioner and fabric softener). The most important component of detergents are the detersive surfactants, which are primarily

(a) anionische, nicht-ionogene und/oder zwitterionische waschaktive Tenside sind.(a) are anionic, non-ionic and / or zwitterionic detergent surfactants.

Die anionischen waschaktiven Tenside sind vornehmlich Sulfonate, wie Alkylarylsulfonate, z.B. Dodecylbenzolsulfonat, Alkylsulfonate und Alkenylsulfonate, und Sulfate, z.B. Alkylsulfate, Sulfate ethoxylierter Amide, Ester von a-Sulfofettsäuren oder auch Seifen von natürlichen, gegebenenfalls modifizierten oder synthetischen Fettsäuren, wobei die anionaktiven Tenside vorteilhaft in Salzform vorliegen, z.B. als Alkalimetallsalz (Natrium, Kalium), als Ammoniumsalz oder als Salz organischer Basen, insbesondere Monoethanolamin-, Diethanolamin- oder Triethanolaminsalze. Weiterhin zählen zu den anionischen Tensiden Sulfosuccinate, Alkylethersulfate, Alkylethercarboxylate und Fettsäurekondensationsprodukte, wie sie üblicherweise in Wasch- und Reinigungsformulierungen Verwendung finden.The anionic detersive surfactants are primarily sulfonates such as alkylarylsulfonates e.g. Dodecylbenzenesulfonate, alkyl sulfonates and alkenyl sulfonates, and sulfates, e.g. Alkyl sulfates, sulfates of ethoxylated amides, esters of a-sulfo fatty acids or soaps of natural, optionally modified or synthetic fatty acids, the anionic surfactants advantageously being in salt form, e.g. as an alkali metal salt (sodium, potassium), as an ammonium salt or as a salt of organic bases, in particular monoethanolamine, diethanolamine or triethanolamine salts. The anionic surfactants also include sulfosuccinates, alkyl ether sulfates, alkyl ether carboxylates and fatty acid condensation products, as are customarily used in washing and cleaning formulations.

Als nicht-ionogene waschaktive Tenside kommen vornehmlich Polyethylenglykolether höherer Alkohole oder Alkylphenole, Polyethylenglykolester von Fettsäuren und Polyoxyethylierungsprodukte von Fettsäureamiden in Betracht. Die Fettreste bzw. Alkyl- und Alkylenreste in den obengenannten Tensiden bzw. Alkoholen oder Fettsäuren enthalten beispielsweise 8 - 20 Kohlenstoffatome; Aryl steht vornehmlich für Phenyl; die Polyethylenglykolketten können beispielsweise 3 - 80 Ethylenoxygruppen enthalten und gegebenenfalls aus Propylenoxyeinheiten bestehen. Typische nicht-ionogene Tenside sind Alkylpolyethoxilate, Alkylpolyglycoside, Glucamide, Alkylamin-N-oxide, Alkylphosphinoxide und Kondensationsprodukte aus Fettalkoholen mit Ethylenoxid und Propylenoxid.Suitable non-ionic detergent surfactants are primarily polyethylene glycol ethers of higher alcohols or alkylphenols, polyethylene glycol esters of fatty acids and polyoxyethylation products of fatty acid amides. The fat residues or alkyl and alkylene residues in the above-mentioned surfactants or alcohols or fatty acids contain, for example, 8-20 carbon atoms; Aryl primarily stands for phenyl; the polyethylene glycol chains can contain, for example, 3-80 ethyleneoxy groups and optionally consist of propyleneoxy units. Typical non-ionic surfactants are alkyl polyethoxylates, alkyl polyglycosides, glucamides, alkylamine N-oxides, alkylphosphine oxides and condensation products from fatty alcohols with ethylene oxide and propylene oxide.

Bevorzugt als (a) unter den anionischen Tensiden sind die Alkylbenzolsulfonate, die Alkansulfonate, die Alkylsulfonate und die Seifen und unter den nichtionogenen Tensiden die Alkylpolyglykolether.Preferred as (a) among the anionic surfactants are the alkylbenzenesulfonates, the alkanesulfonates, the alkylsulfonates and the soaps and among the nonionic surfactants the alkylpolyglycol ethers.

Beispiel zwitterionischer Tenside sind Derivate aliphatischer quaternärer Ammonium-, Phosphonium-und Sulphoniumverbindungen, wie sie aus US-A-3 925 262 und US-A-3 929 678 bekannt sind.Examples of zwitterionic surfactants are derivatives of aliphatic quaternary ammonium, phosphonium and sulphonium compounds, as are known from US Pat. Nos. 3,925,262 and 3,929,678.

Je nach Einsatzgebiet und Verwendungszweck der Waschmittel können diese beispielsweise allein aus den Komponenten (a), wie oben beschrieben, bestehen (z.B. für industrielle Zwecke) oder noch einen oder mehrere weitere Zusätze enthalten (z.B. auch für industrielle Zwecke oder insbesondere für Haushaltswaschmittel), wobei im wesentlichen die folgenden Zusätze genannt werden können:

  • (b) Sequestriermittel
  • (c) Enzyme
  • (d) Bleichmittel - gegebenenfalls zusammen mit üblichen Bleichzusätzen, insbesondere (di) Altivatoren und/oder (d2) Stabilisatoren
  • (e) Waschalkalien
  • (f) Schmutzträger.
Depending on the area of application and intended use of the detergents, these can consist, for example, of components (a) as described above (for example for industrial purposes) or contain one or more further additives (for example also for industrial purposes or in particular for household detergents), where essentially the following additions can be mentioned:
  • (b) sequestrant
  • (c) enzymes
  • (d) bleaching agents - optionally together with customary bleaching additives, in particular (di) altivators and / or (d 2 ) stabilizers
  • (e) Washing alkalis
  • (f) dirt carrier.

Als Sequestriermittel (b) können übliche komplexbildende Substanzen genannt werden, beispielsweise Aminopolyacetate (insbesondere Nitrilotriacetat oder Ethylendiamintetraacetat) Aminopolymethylenphosphate, Natriumtriphosphat, Natriumtripolyphosphate, Natriumaluminiumsilikate, Natriumsilikat, Magnesiumsilikat, Zeolith A, Polyacrylate (z.B. Ammoniumpolyacrylate), Poly-a-hydroxyacrylate und Salze von Hydroxycarbonsäuren (z.B. Natriumcitrat, Natriumtartrat und Natriumgluconat).The sequestering agents (b) which can be mentioned are customary complex-forming substances, for example aminopolyacetates (in particular nitrilotriacetate or ethylenediaminetetraacetate), aminopolymethylene phosphates, sodium triphosphate, sodium tripolyphosphates, sodium aluminum silicates, sodium silicate, magnesium silicate, zeolite A, polyacrylates (eg ammonium acrylates) and polyacrylates (e.g. (e.g. sodium citrate, sodium tartrate and sodium gluconate).

Als Enzyme (c) können beispielsweise die üblichen Proteasen, Lipasen, Cellulasen und Amylasen erwähnt werden.The usual proteases, lipases, cellulases and amylases can be mentioned as enzymes (c), for example.

Als Bleichmittel (d) kommen übliche Peroxyverbindungen in Frage, beispielsweise Perborate, Percarbonate, Perphosphate oder Peroxide, insbesondere als Alkalimetallsalze oder, besonders in Flüssigformulierungen, auch Wasserstoffperoxid. Als Stabilisatoren für die Perverbindungen können beispielsweise die obengenannten Sequestriermittel in Frage kommen, und als gegebenenfalls vorhandene Aktivatoren können übliche Carbonsäuren oder Amidoderivate erwähnt werden.Suitable bleaching agents (d) are customary peroxy compounds, for example perborates, percarbonates, perphosphates or peroxides, in particular as alkali metal salts or, particularly in liquid formulations, also hydrogen peroxide. The above-mentioned sequestering agents can be used as stabilizers for the per-compounds, for example, and customary carboxylic acids or amido derivatives can be mentioned as optional activators.

Als Waschalkalien (e) können übliche Basen verwendet werden, beispielsweise Ammonium- oder Alkalimetallsilikate, -phosphate, -carbonate, -borate oder - hydroxide; die obigen jeweiligen alkalischen Perverbindungen können gegebenenfalls auch als Waschalkalien wirken.Common bases can be used as washing alkalis (e), for example ammonium or alkali metal silicates, phosphates, carbonates, borates or hydroxides; the above respective alkaline per compounds can optionally also act as washing alkalis.

Als gegebenenfalls vorhandene Schmutzträger (f) kommen die üblichen Substanzen in Betracht, insbesondere Benzotriazole, Ethylenthioharnstoff oder Celluloseether (z.B. Carboxymethylcellulose).The usual substances, in particular benzotriazoles, ethylene thiourea or cellulose ether (e.g. carboxymethyl cellulose) are suitable as dirt carriers (f) which may be present.

Gegebenenfalls können die Waschmittel noch weitere Zusätze enthalten, beispielsweise Entschäumer (oder Schaumstabilisatoren), Duftstoffe, Desinfektionsmittel, Puffersalze, Aktivchlor freisetzende Verbindungen, Korrosionsschutzmittel, Lösungsmittel, Lösungsvermittler, Ausrüstungs- oder Trägerstoffe, Konservierungsmittel und sonstige Elektrolyten (beispielsweise Natriumsulfat).If necessary, the detergents can also contain further additives, for example defoamers (or foam stabilizers), fragrances, disinfectants, buffer salts, compounds which release active chlorine, corrosion inhibitors, solvents, solubilizers, finishing agents or carriers, preservatives and other electrolytes (for example sodium sulfate).

Die mengenmäßigen Zusammensetzungen der Waschmittel können je nach Hersteller und Zweckbestimmung weit schwanken.The quantitative compositions of the detergents can vary widely depending on the manufacturer and intended use.

Die erfindungsgemäß verwendeten Copolymerisate können einzeln in die Waschflotten gegeben oder gewünschtenfalls in die Waschmittel eingearbeitet werden.The copolymers used according to the invention can be added individually to the washing liquors or, if desired, incorporated into the detergents.

Das Waschen erfolgt vornehmlich unter schwach-sauren bis deutlich basischen Bedingungen, vorteilhaft bei pH-Werten im Bereich von 6 - 12, vorzugsweise 7 - 10. Die erfindungsgemäßen Zusätze werden vorteilhaft in Konzentrationen von 0,05 bis 10 g/I, vorzugsweise 0,5 bis 4 g/I wäßrige Waschflotte eingesetzt. Der Gehalt dieser Verbindungen in der Waschmittelformulierung liegt vorteilhaft im Bereich von 0,2 bis 10 Gew.-%, bevorzugt 1 - 6 Gew.-%.Washing is carried out primarily under weakly acidic to clearly basic conditions, advantageously at pH values in the range from 6 to 12, preferably from 7 to 10. The additives according to the invention are advantageously used in concentrations of 0.05 to 10 g / l, preferably 0.5 to 4 g / l aqueous washing liquor. The content of these compounds in the detergent formulation is advantageously in the range from 0.2 to 10% by weight, preferably 1-6% by weight.

Das Waschen kann unter üblichen Bedingungen erfolgen und wie in den jeweiligen Waschprogrammen von handelsüblichen Waschmaschinen vorgesehen, zweckmäßig in einem Gesamtwaschverfahren, in welchem alle Bestandteile in der Flotte vorhanden sind und vorzugsweise zugegeben werden. Die Waschtemperatur kann ebenfalls in üblichen Bereichen schwanken, z.B. im Bereich von 15 - 95 °C, wobei die für Buntwäsche und heute allgemein üblichen Temperaturen im Bereich von 30 - 60 °C hier bevorzugt sind.The washing can be carried out under customary conditions and, as provided in the respective washing programs of commercially available washing machines, expediently in an overall washing process in which all the components are present in the liquor and are preferably added. The washing temperature can also fluctuate in usual ranges, e.g. in the range of 15-95 ° C, with the temperatures in the range of 30-60 ° C which are common for colored laundry and nowadays preferred.

Es können beliebige Materialien gewaschen werden, so wie sie in Industrie und Haushalt für die jeweiligen Waschvorgänge vorgesehen sind, z.B. lose Fasern, Filamente, Fäden, Spulen, Gewebe, Gewirke, Vliesstoffe, offene Bahnen, Schlauchware, Samt, Filz, Tuftingware, Teppiche, strukturierte, poröse stoffähnliche Kunststoffmaterialien (wie sie für Haushalt und Bekleidung Verwendung finden) und insbesondere Halbfertig- und Fertigware. Die Substrate können aus beliebigen, üblichen Materialien bestehen, z.B. natürlicher oder regenerierter Cellulose (z.B. Baumwolle, Leinen, Hanf, Viskose), natürlichen Polyamiden (z.B. Wolle, Seide) oder synthetischen Materialien (z.B. Polyamiden, Polyester, Polyacrylnitrilen, Polypropylen oder Polyurethanen) und deren Gemischen. Besonders hervorzuheben sind daraus die cellulosehaltigen Substrate und vor allem buntes Waschgut, das gefärbte Cellulosesubstrate enthält.Any materials can be washed, as they are intended for the respective washing processes in industry and household, e.g. loose fibers, filaments, threads, bobbins, fabrics, knitted fabrics, nonwovens, open webs, tubular goods, velvet, felt, tufted goods, carpets, structured, porous plastic-like plastic materials (as used for household and clothing) and especially semi-finished and finished goods. The substrates can be made of any conventional material, e.g. natural or regenerated cellulose (e.g. cotton, linen, hemp, viscose), natural polyamides (e.g. wool, silk) or synthetic materials (e.g. polyamides, polyesters, polyacrylonitriles, polypropylene or polyurethanes) and their mixtures. Of particular note are the cellulose-containing substrates and, above all, colored laundry that contains colored cellulose substrates.

Die erfindungsgemäßen Waschmittelzusätze sind mit dem üblichen Waschmittel, z.B. wie oben aufgezählt, gut verträglich und beeinträchtigen praktisch nicht deren Waschwirkung, sondern können sie sogar unterstützen. Sie verhindern überraschend gut ein Wiederaufziehen von abgebluteten Farbstoffen und Farbstoffabbauprodukten auf das gewaschene, insbesondere auf das mitgewaschene Material und lassen sich analog wie die sonstigen Waschflottenkomponenten aus dem gewaschenen Material herausspülen. Sie greifen das Waschgut nicht an. Sie zeichnen sich gegenüber den bekannten polymeren Farbübertragungsinhibitoren durch eine zumeist überlegene Leistung aus und besitzen darüber hinaus eine gute biologische Abbaubarkeit. Je nach Konsistenz der Waschmittelformulierung -ob flüssig oder pulverförmig- kann eine Zudosierung der erfindungsgemäßen Farbinhibierungszusätze bei der Konfektionierung entweder als wäßrige Dispersion oder auch als redispergierbares Dispersionspulver erfolgen.The detergent additives according to the invention are mixed with the usual detergent, e.g. as listed above, well tolerated and practically do not impair their washing effect, but can even support them. They surprisingly well prevent bleeding-away dyestuffs and dyestuff degradation products from being re-absorbed onto the washed, in particular the washed, material and can be rinsed out of the washed material in a manner analogous to the other wash liquor components. You do not attack the laundry. Compared to the known polymeric color transfer inhibitors, they are usually superior in performance and moreover have good biodegradability. Depending on the consistency of the detergent formulation, whether liquid or powder, the color inhibiting additives according to the invention can be added during assembly either as an aqueous dispersion or as a redispersible dispersion powder.

Beispiele:Examples: Eingesetzte Farbübertragungsinhibitoren:Color transfer inhibitors used: Beispiel 1:Example 1:

55 gew.-%ige wäßrige Polymerdispersion eines Copolymerisats aus 80 Gew.-% Vinylacetat, 10 Gew.-% Ethylen und 10 Gew.-% Acrylsäureamid55% by weight aqueous polymer dispersion of a copolymer of 80% by weight vinyl acetate, 10% by weight ethylene and 10% by weight acrylic acid amide

Beispiel 2:Example 2:

Redispergierbares Dispersionspulver hergestellt durch Sprühtrocknung der wäßrigen Polymerdispersion nach Beispiel 1.Redispersible dispersion powder prepared by spray drying the aqueous polymer dispersion according to Example 1.

Waschversuche im Launder-O-meter:

  • Die Waschversuche wurden in einem Launder-O-meter bei 40°C durchgeführt. Die Waschzeit betrug 40 Minuten. Die Waschmittelkonzentration 4 g/I WMP-Testwaschmittel (Wäschereiforschung Krefeld). Die Wasserhärte betrug 160 dH. In 400 ml Waschlauge wurden 1,25 g Baumwollgewebe, eingefärbt mit einem braunen Textilfarbstoff (®Diamin Braun-BK; Hoechst AG, DE) zusammen mit weißem Baumwollgewebe gewaschen.
Washing attempts in the Launder-O-meter:
  • The washing tests were carried out in a Launder-O-meter at 40 ° C. The washing time was 40 minutes. The detergent concentration is 4 g / I WMP test detergent (laundry research Krefeld). The water hardness was 160 dH. 1.25 g of cotton fabric, dyed with a brown textile dye (®Diamin Braun-BK; Hoechst AG, DE) were washed together with white cotton fabric in 400 ml of wash liquor.

Jeweils 1,3 Gew.-%, bezogen auf das Testwaschmittel, des erfindungsgemäß verwendeten Copolymeren, bezogen auf den Feststoffgehalt, wurden der Waschlauge zugesetzt und der Weißgrad des weißen Gewebes nach dem Waschprozeß durch Remissionsmessung bestimmt. Als Vergleichssubstanz wurde Polyvinylpyrrolidon (PVP) mit einem gewichtsgemittelten Molekulargewicht Mw von ca. 10 000 eingesetzt.

Figure imgb0004
In each case 1.3% by weight, based on the test detergent, of the copolymer used according to the invention, based on the solids content, was added to the wash liquor and the whiteness of the white fabric after the washing process was determined by remission measurement. Polyvinylpyrrolidone (PVP) with a weight-average molecular weight M w of approximately 10,000 was used as the reference substance.
Figure imgb0004

Das Ergebnis macht deutlich, daß die erfindungsgemäß beanspruchten Verbindungen die Färbeübertragung des braunen Farbstoffes vom eingefärbten Gewebe auf das weiße Gewebe signifikant unterbinden. Bei vergleichbaren Anwendungskonzentrationen sind die erfindungsgemäßen Verbindungen dem bisherigen Standard Polyvinylpyrrolidon (PVP) an Wirksamkeit überlegen.The result makes it clear that the compounds claimed according to the invention significantly prevent the color transfer of the brown dye from the dyed fabric to the white fabric. At comparable application concentrations, the compounds according to the invention are superior in effectiveness to the previous standard polyvinylpyrrolidone (PVP).

Claims (15)

1. Verwendung von Copolymeren, enthaltend 75 - 95 Gew.-% der Gesamtmonomermenge mindestens eines Vinylmonomers, das frei von Carboxyl-und Amidgruppen ist, 5 - 20 Gew.-% mindestens eines Carbonsäureamids der Formel (I)
Figure imgb0005
in der R ein Wasserstoffatom oder ein Methylolrest, R1 ein Wasserstoffatom oder ein C, -Ca-Alkylrest und R2 ein Wasserstoffatom oder ein Methylrest
bedeuten und gegebenenfalls zusammen mit maximal 5 Gew.-% einer copolymerisierbaren ungesättigten Carbonsäure als Waschmittelzusatz zur Verhinderung des Wiederaufziehens von abgelösten Farbstoffen und Farbstoffabbauprodukten.1. Use of copolymers containing 75-95% by weight of the total amount of at least one vinyl monomer which is free of carboxyl and amide groups, 5-20% by weight of at least one carboxamide of the formula (I)
Figure imgb0005
in the R is a hydrogen atom or a methylol radical, R 1 is a hydrogen atom or a C, -Ca alkyl radical and R 2 is a hydrogen atom or a methyl radical
mean and optionally together with a maximum of 5 wt .-% of a copolymerizable unsaturated carboxylic acid as a detergent additive to prevent the re-absorption of detached dyes and dye degradation products. 2. Verwendung nach Anspruch 1 von Copolymeren enthaltend 85 - 90 Gew.-% der Gesamtmonomerenmenge mindestens eines Vinylmonomers, das frei von Carboxyl- und Amidgruppen ist, 7 - 14 Gew.-% mindestens eines Carbonsäureamids der Formel (I) und 0,1 - 3,0 Gew.-% einer copolymerisierbaren, ungesättigten Carbonsäure. 2. Use according to claim 1 containing copolymers 85-90% by weight of the total amount of monomers of at least one vinyl monomer which is free from carboxyl and amide groups, 7-14% by weight of at least one carboxamide of the formula (I) and 0.1-3.0% by weight of a copolymerizable, unsaturated carboxylic acid. 3. Verwendung nach Anspruch 1 von Copolymeren, dadurch gekennzeichnet, daß die Copolymeren als Vinylmonomere Olefine, bevorzugt Ethylen, Propylen und/oder Isobutylen, Vinylether, bevorzugt Vinylmethylether, Vinylethylether und/oder Vinyl-n-butylether, Vinylester von aliphatischen Carbonsäuren mit 2 bis 18, bevorzugt 2 bis 10 Kohlenstoffatomen und/oder (Meth-)Acrylsäureester von C2-Cs-Alkanolen enthalten.3. Use according to claim 1 of copolymers, characterized in that the copolymers as vinyl monomers olefins, preferably ethylene, propylene and / or isobutylene, vinyl ethers, preferably vinyl methyl ether, vinyl ethyl ether and / or vinyl n-butyl ether, vinyl esters of aliphatic carboxylic acids with 2 to Contain 18, preferably 2 to 10 carbon atoms and / or (meth) acrylic acid esters of C 2 -Cs alkanols. 4. Verwendung nach Anspruch 1 von Copolymeren, dadurch gekennzeichnet, daß die Copolymere mindestens zwei Vinylmonomere enthalten, die frei von Carboxyl- und Amidgruppen sind, wobei der Anteil des Vinylesters mindestens 50 Gew.-% der Gesamtmenge der Vinylmonomeren beträgt.4. Use according to claim 1 of copolymers, characterized in that the copolymers contain at least two vinyl monomers which are free of carboxyl and amide groups, the proportion of the vinyl ester being at least 50% by weight of the total amount of the vinyl monomers. 5. Verwendung nach Anspruch 4 von Copolymeren, dadurch gekennzeichnet, daß der Anteil des Vinylesters 75 bis 95 Gew.-% der Vinylmonomeren beträgt.5. Use according to claim 4 of copolymers, characterized in that the proportion of the vinyl ester is 75 to 95 wt .-% of the vinyl monomers. 6. Verwendung nach Anspruch 1 von Copolymeren, dadurch gekennzeichnet, daß die Copolymeren als copolymerisierbare, ungesättigte Carbonsäure eine aliphatische Monocarbonsäure mit 3 oder 4 Kohlenstoffatomen oder eine aliphatische Dicarbonsäure mit 4 oder 5 Kohlenstoffatomen enthalten.6. Use according to claim 1 of copolymers, characterized in that the copolymers contain, as copolymerizable, unsaturated carboxylic acid, an aliphatic monocarboxylic acid with 3 or 4 carbon atoms or an aliphatic dicarboxylic acid with 4 or 5 carbon atoms. 7. Verwendung nach Anspruch 1 von Copolymeren, dadurch gekennzeichnet, daß die Copolymeren in Form einer wäßrigen Polymerdispersion eingesetzt werden.7. Use according to claim 1 of copolymers, characterized in that the copolymers are used in the form of an aqueous polymer dispersion. 8. Verwendung nach Anspruch 7, dadurch gekennzeichnet, daß die wäßrige Polymerdispersion einen Feststoffgehalt von 40 bis 70 Gew.-%, bevorzugt 45 bis 60 Gew.-%, aufweist.8. Use according to claim 7, characterized in that the aqueous polymer dispersion has a solids content of 40 to 70 wt .-%, preferably 45 to 60 wt .-%. 9. Verwendung nach Anspruch 8, dadurch gekennzeichnet, daß die wäßrige Polymerdispersion eine Viskosität im Bereich von 1 bis 20 Pa. (gemessen nach Epprecht) besitzt.9. Use according to claim 8, characterized in that the aqueous polymer dispersion has a viscosity in the range of 1 to 20 Pa. (measured according to Epprecht). 10. Verwendung nach Anspruch 1 von Copolymeren, dadurch gekennzeichnet, daß die Copolymeren als Dispersionspulver eingesetzt werden.10. Use according to claim 1 of copolymers, characterized in that the copolymers are used as a dispersion powder. 11. Verwendung gemäß Anspruch 1 als Zusatz zu industriellen Waschmitteln oder Haushaltswaschmitteln.11. Use according to claim 1 as an additive to industrial detergents or household detergents. 12. Waschmittel gekennzeichnet durch einen Gehalt an Verbindungen gemäß Anspruch 1.12. Detergent characterized by a content of compounds according to claim 1. 13. Textilwaschmittel, Waschmittelbooster und/oder Wäschenachbehandlungsmittel gemäß Anspruch 12.13. Textile detergent, detergent booster and / or laundry aftertreatment agent according to claim 12. 14. Waschmittel gemäß Anspruch 13, enthaltend - anionische, nicht-ionische und/oder zwitterionische Tenside, - Verbindungen gemäß Anspruch 1. 14. Detergent according to claim 13, containing anionic, non-ionic and / or zwitterionic surfactants, - Compounds according to claim 1. 15. Waschmittel gemäß Anspruch 14, enthaltend zusätzlich eine oder mehrere der folgenden Komponenten - Sequestriermittel, - optische Aufheller, - Enzyme, - Bleichmittel und gegebenenfalls Stabilisatoren und Aktivatoren, - Waschalkalien. 15. Detergent according to claim 14, additionally containing one or more of the following components - sequestering agents, - optical brighteners, - enzymes, Bleaches and, if appropriate, stabilizers and activators, - Washing alkalis.
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