EP0584736A1 - Use of polyvinyl alcohols as detergent additive - Google Patents

Abstract

The present invention relates to the use of polyvinyl alcohols containing the repeating structural unit of the formula I <IMAGE> as detergent additive to prevent reuptake of dyes and dye breakdown products which have been dissolved off.

Description

The laundry washed nowadays in the household and industry consists of uniform or, especially in the household, mostly of different fiber types, in particular of natural fibers, mainly cotton or wool, of regenerated cellulose fibers, for example viscose, of synthetic fibers, for example polyester, polyamide and polyacrylonitrile, and 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 genuine dye is favored, for example, by higher temperatures, repeated washing operations, liquor ratio of wash liquor to laundry, composition of the detergents used and their concentration in the wash liquor, the type of washing machines and washing programs used also being one Influence on the detachment of dye or dye degradation products of a color that is not sufficiently "suitable for household laundry", for example due to the mechanical stress on the laundry during washing, etc. The reasons used for a decrease in authenticity can also be that used Water quality (e.g. due to chlorine content), the composition of certain additives for easy maintenance and the quality and structure of the textile material or the fibers are mentioned. 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 are the same as those described above Leads to problems.

• Ablösung der Farbstoffpartikel von der Textilfaser
• Redeposition 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
• Speech position on another part of the laundry.

Various proposals have been described in the literature to prevent this reaction.

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.

In addition to bleach activators, enzymes with peroxidase properties are also suitable for these applications (CA-A-2 067 748).

Another way to prevent color transfer is to incorporate polymeric color transfer inhibitors into the detergent formulation. In this case, the detached dye particles in the wash liquor are complexed and stabilized by the polymer and thus prevented from being re-absorbed on the fiber.

Homopolymers of vinylimidazole and vinylpyrrolidone are used as preferred inhibitors.
CA-A-0 094 635 describes detergent formulations with reduced color transfer during the washing process, which contain polyvinylpyrrolidone (PVP).
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.
DE-A-37 11 299 discloses polyvinylpyrrolidones grafted with vinyl esters as graying inhibitors for textiles containing synthetic fibers.

Disadvantages of these polymeric color transfer inhibitors are their often low solubility, in particular in the case of modified polyvinylpyrrolidones, which makes incorporation into liquid detergent formulations more difficult and the insufficient biodegradability.

It has now been found that using the compounds defined below in washing or as detergent additives, these problems are better solved, i.e. Color transfer inhibitors are provided, which can be easily incorporated into powdery and liquid cleaning agents and are also biodegradable.

und gegebenenfalls weitere wiederkehrende Struktureinheiten, die sich durch Hydrolyse/Alkoholyse von mit Vinylacetat copolymerisierbaren Monomeren ableiten, als Waschmittelzusatz zur Verhinderung des Wiederaufziehens von abgelösten Farbstoffen und Farbstoffprodukten.The invention relates to the use of polymers containing the recurring structural unit of the formula I.

and optionally further recurring structural units, which are derived from the hydrolysis / alcoholysis of monomers copolymerizable with vinyl acetate, as a detergent additive to prevent the detachment of detached dyes and dye products.

Polyvinylalkohole sind Polymere des in freier Form nicht existenzfähigen Vinylalkohols und werden durch Polymerisation des stabilen Vinylacetats und anschließender Alkoholyse des erhaltenen Polyvinylacetats hergestellt.
Die Polymerisation erfolgt nach dem Prinzip der Radikalkettenpolymerisation in einem organischen Lösungsmittel, zumeist Methanol. Die erforderlichen Radikale liefern Initiatoren mit Peroxy- oder Azo-Gruppen durch Zerfall im Reaktionsgemisch.Preferred uses are “partially” and / or “fully hydrolyzed” polyvinyl alcohols of the general formulas II and III

Polyvinyl alcohols are polymers of vinyl alcohol which is not viable in free form and are produced by polymerizing the stable vinyl acetate and subsequent alcoholysis of the polyvinyl acetate obtained.
The polymerization is carried out according to the principle of radical chain polymerization in an organic solvent, usually methanol. The radicals required provide initiators with peroxy or azo groups by decomposition in the reaction mixture.

The polyvinyl acetate dissolved in methanol is converted into polyvinyl alcohol by transesterification with methanol (alcoholysis). Bases, in particular sodium hydroxide, are preferably used as catalysts.

The content of residual acetyl groups can be adjusted by varying the catalyst concentration, reaction temperature and reaction time. A distinction is therefore made between "fully" and "partially hydrolyzed" polyvinyl alcohols. The partially hydrolyzed polyvinyl alcohols of the formula II are theoretically to be regarded as a copolymer of vinyl alcohol with vinyl acetate, the vinyl alcohol content predominating to such an extent that the entire molecule is water-soluble. In general, the acetyl content is approximately 11% by weight, corresponding to a degree of hydrolysis of the underlying polyvinyl acetate of 88 mol% and an ester number of approximately 140 mg KOH / g. The acetyl content can also be significantly higher: in practice, degrees of hydrolysis of up to approx. 45 to 50 mol% are used.

The remaining acetyl groups can be distributed irregularly, regularly or heaped / block-like over a polyvinyl alcohol chain. The type of distribution is determined by the choice of catalyst and, if solvents are used, by their type. In the case of alkaline alcoholysis, the residual acetyl groups are largely block-like, and in the case of acidic alcoholysis they are predominantly statistically distributed.

_w liegt im Bereich von 5000 bis 300000, bevorzugt 20000 bis 200000, besonders bevorzugt 60000 bis 160000. Die Bestimmungsmethoden ergeben jeweils verschiedene Zahlen, hier sind Werte nach Reacetylierung des Polyvinylalkohols in Pyridin angeführt. Der Polymerisationsgrad $\overline{\text{P}}$

_w liegt zwischen 200 und 5000, bevorzugt 400 bis 3000.
Die Viskosität (4 gew.-%ige wäßrige Lösung bei 20°C (DIN 530 15) liegt im Bereich zwischen 2 und 50 mPa·s, bevorzugt 10 bis 30 mPa·s.In the partially hydrolyzed polyvinyl alcohols of the formula II, preference is given to using compounds having a residual acetyl content of less than 50% by weight, particularly preferably less than 30% by weight.
The weight-based molar mass $\overline{\text{M}}$

_w is in the range from 5,000 to 300,000, preferably 20,000 to 200,000, particularly preferably 60,000 to 160,000. The determination methods give different numbers in each case, here values are given after the reactylation of the polyvinyl alcohol in pyridine. The degree of polymerization $\overline{\text{P}}$

_w is between 200 and 5000, preferably 400 to 3000.
The viscosity (4% by weight aqueous solution at 20 ° C. (DIN 530 15) is in the range between 2 and 50 mPa · s, preferably 10 to 30 mPa · s.

The degree of hydrolysis (degree of saponification) is preferably in the range between 70 and 95 mol%.

_w liegt im Bereich zwischen 5000 und 300000, bevorzugt 30000 bis 200000, besonders bevorzugt 60000 bis 120000.
Der Polymerisationsgrad $\overline{\text{P}}$

_w liegt zwischen 100 und 5000, bevorzugt zwischen 600 bis 3000.
Die Viskosität (4 gew.-%ige wäßrige Lösung bei 20°C, DIN 530 15) liegt üblicherweise zwischen 0,1 und 100 mPa·s, bevorzugt 6 bis 50 mPa·s, besonders bevorzugt 10 bis 30 mPa·s.
Der Hydrolysegrad (Verseifungsgrad) liegt bevorzugt im Bereich oberhalb 98 Mol.-%.
Die erfindungsgemäß verwendeten Polyvinylalkohole sind wasserlöslich und biologisch gut abbaubar.
Die Lösecharakteristik eines Polyvinylalkohols kann durch die in Lösung gegangene Produktmenge bei bestimmter Temperatur (z.B. bei 90, 60, 40 und 20°C) in vorgegebenem Zeitraum unter vergleichbaren apparativen Bedingungen beschrieben werden (Lösekurve). Die Ermittlung der relativen Lösegeschwindigkeit erfolgt nach den üblichen Labormethoden. Je nach Viskosität (K-Wert) und Hydrolysegrad dauert der Lösevorgang unterschiedlich lang. Ganz allgemein ist jedoch zu sagen, daß Polyvinylalkohole Verwendung finden, die bei Temperaturen im Bereich von 30 bis 90°C eine Löslichkeit von mindestens 10 Gew.-%, bevorzugt mindestens 50 Gew.-%, besonders bevorzugt mindestens 90 Gew.-% besitzen, wobei die Lösezeit nicht mehr als 45 min betragen soll.
Es hat sich gezeigt, daß bei niedrigviskosen teilhydrolysierten Polyvinylalkoholen mit einer Viskosität im Bereich von 2 bis 10 mPa·s nach einer Zeit von 30 min. ungefähr 96 % des Polymeren in Lösung gegangen sind. Die noch nicht gelösten Bestandteile lösen sich aber bei ungefähr 90°C rückstandslos auf.
Beim Auflösen der vollhydratisierten Polyvinylalkohole hat sich gezeigt, daß nur verhältnismäßig geringe Mengen an Polyvinylalkohol in Lösung geht. Erst beim Überschreiten dieser Temperatur erfolgt ein deutliches Lösen, wobei schließlich bei 90°C quantitative, klare und stippenfreie Lösungen erhalten werden.Fully hydrolyzed polyvinyl alcohols of the formula III are understood to mean polyvinyl alcohols with a degree of hydrolysis of approximately 97 to 100 mol%.
In the case of the fully hydrolyzed polyvinyl alcohols, preference is given to using compounds with a residual acetyl content of less than 5% by weight, particularly preferably less than 2% by weight.
The weight-based molar mass $\overline{\text{M}}$

_w is in the range between 5,000 and 300,000, preferably 30,000 to 200,000, particularly preferably 60,000 to 120,000.
The degree of polymerization $\overline{\text{P}}$

_w is between 100 and 5000, preferably between 600 and 3000.
The viscosity (4% by weight aqueous solution at 20 ° C., DIN 530 15) is usually between 0.1 and 100 mPas, preferably 6 to 50 mPas, particularly preferably 10 to 30 mPas.
The degree of hydrolysis (degree of saponification) is preferably in the range above 98 mol%.
The polyvinyl alcohols used according to the invention are water-soluble and readily biodegradable.
The dissolving characteristics of a polyvinyl alcohol can be described by the amount of product dissolved in a certain temperature (e.g. at 90, 60, 40 and 20 ° C) in a given period under comparable apparatus conditions (dissolving curve). The determination of the relative dissolution rate is carried out according to the usual laboratory methods. Depending on the viscosity (K value) and degree of hydrolysis, the dissolving process takes different lengths. In general, however, it should be said that polyvinyl alcohols are used which have a solubility of at least 10% by weight, preferably at least 50% by weight, particularly preferably at least 90% by weight, at temperatures in the range from 30 to 90 ° C. , the dissolving time should not be more than 45 min.
It has been shown that with low-viscosity partially hydrolyzed polyvinyl alcohols with a viscosity in the range from 2 to 10 mPa · s after a time of 30 min. approximately 96% of the polymer has gone into solution. The not solved yet Components dissolve without residue at around 90 ° C.
When the fully hydrated polyvinyl alcohols were dissolved, it was found that only relatively small amounts of polyvinyl alcohol went into solution. Only when this temperature is exceeded does a clear dissolution occur, quantitative, clear and speck-free solutions finally being obtained at 90 ° C.

The rate of dissolution of polyvinyl alcohols is also very strongly influenced by the type and amount of other detergent products present. Particularly in the presence of perborate / borate or ionic compounds of a higher concentration, the polyvinyl alcohols preferred by us with a degree of hydrolysis of <approx. 80 mol% have proven to be particularly suitable for the intended use. Furthermore, copolymeric types of polyvinyl alcohol (e.g. internally plasticized products such as ®Mowiol GE 4-86) also behave as less problematic / suitable in this regard.

The polyvinyl alcohols used in accordance with the invention can be used in various ways.
When used in detergent powders, the polyvinyl alcohols are usually used in the form of granules, the grain size being 200 to 1500 μm and the smallest grain size being 200 μm.
When used in liquid detergents, the polyvinyl alcohols are used in dissolved form. The polyvinyl alcohols can be added to the liquid detergent as a solution, preferably an aqueous solution, or they can be incorporated as a powder with dissolution.

The described partially and fully hydrolyzed polyvinyl alcohols used according to the invention are available under the trademark ®Mowiol (Hoechst AG, DE).

In addition to the polyvinyl alcohols described above, polyvinyl alcohol-stabilized synthetic resin dispersions based on homo- or copolymeric dispersions and, in particular, surprisingly can also Spray drying, redispersible dispersion powders are used as a color transfer inhibitor.
Such dispersions or dispersion powders produced therefrom preferably consist of homo- or copolymers, preferably based on vinyl acetate or vinyl acetate / ethylene, vinyl acetate / ethylene / acrylic acid derivatives and vinyl acetate / versatic acid vinyl esters.
In addition to polyvinyl acetate or copolymers based on vinyl acetate, etc., the liquid and solid products mentioned usually contain 3 to 20% by weight of PVAL. The above-mentioned dispersions or dispersion powders produced from them by the known emulsion polymerization method contain polyvinyl alcohol, which is partly present as a protective colloid in aqueous solution and partly grafted into the water-insoluble polymer particle by the radical polymerization method in the water-insoluble particle.

The processes for producing such dispersion powders from the aqueous synthetic resin dispersions are known and need not be explained in more detail. The additives described above therefore offer the advantage of being able to be added to a detergent as a liquid dispersion or as a dry, redispersible dispersion powder.
Examples of such homopolymeric polyvinyl acetate dispersion powders are ®Mowilith powder D and ®Mowilith powder DS (Hoechst AG, DE).
As copolymeric polyvinyl acetate dispersion powders, ®Mowilith powder DM 117 P and ®Mowilith powder DM 200 P may be mentioned.

In addition to the "normal polyvinyl alcohols" described above, copolymer types and hydrolyzed graft products can also be used with advantage. Such copolymers contain the recurring structural unit of the formula I and other recurring structural units which are derived from monomers which can be copolymerized with vinyl acetate and which have no adverse effect on the water solubility and biodegradability in the copolymer.
Suitable comonomers are, for example, α-olefins, such as ethylene, vinyl laurate, vinyl acetate, Versatic acid vinyl ester and / or (meth) acrylic acid derivatives, such as (meth) acrylic acid ester.
The comonomers can be used as individual substances, so that copolymers are obtained which contain two different recurring structural units, preferably the recurring structural unit of the formula I and the structural unit derived from the monomer ethylene.

The comonomers can also be used as a mixture, so that copolymers are obtained which contain at least three different repeating structural units, one of which is that of the formula I.
A suitable group of compounds to be used according to the invention are terpolymers based on polyvinyl alcohol.
Such terpolymers contain, in addition to the recurring structural unit of the formula I, in particular structural units which are derived from the monomers ethylene and (meth) acrylic acid derivatives.

Another advantageous property of the polymers of the formula I used according to the invention, in particular of the formulas II and III, is, besides the water solubility mentioned, their biodegradability (tooth-wave test, see Melliand textile reports 59 , 487, 582, 659 (1978 ) and 65 , 269, 340 (1984)).

The polymers of the formula I described above, in particular of the formulas II and III, are used as detergent additives to prevent the detachment of detached dyes and dye products.

• (a) anionische, nicht-ionogene und/oder zwitterionische waschaktive Tenside sind.
  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 α-Sulfofettsäuren oder noch Seiten 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.
  Als nicht-ionogene waschaktive Tenside kommen vornehmlich Polyethylenglykolether höherer Alkohole oder Alkylphenole, Polyethylenglykolester von Fettsäuren und Polyoryethylierungsprodukte 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.
  Bevorzugt als (a) unter den anionischen Tensiden sind die Alkylbenzolsulfonate, die Alkansulfonate, die Alkylsulfonate und die Seiten und unter den nicht-ionogenen Tensiden die Alkylpolyglykolether.
  Beispiele 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.
  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 weiter 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 (d₁) Aktivatoren und/oder (d₂) Stabilisatoren
• (e) Waschalkalien
• (f) Schmutzträger.

The detergents 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) are anionic, non-ionic and / or zwitterionic detergent surfactants.
  The anionic detersive surfactants are primarily sulfonates, such as alkylarylsulfonates, for example dodecylbenzenesulfonate, alkylsulfonates and alkenylsulfonates, and sulfates, for example alkylsulfates, sulfates of ethoxylated amides, esters of α-sulfo fatty acids or still natural, optionally modified or synthetic fatty acids, the anionic surfactants being advantageous, the anionic surfactants being advantageous are in salt form, for example 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.
  Suitable non-ionic detergent surfactants are primarily polyethylene glycol ethers of higher alcohols or alkylphenols, polyethylene glycol esters of fatty acids and polyoryethylation 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 sides and among the nonionic surfactants the alkylpolyglycol ethers.
  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.
  Depending on the area of use 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 conventional bleaching additives, in particular (d₁) activators and / or (d₂) stabilizers
• (e) Washing alkalis
• (f) dirt carrier.

Suitable 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), for example, hydroxyl acrylates (e.g. (e.g. sodium citrate, sodium tartrate and sodium gluconate).

The usual proteases, tipases and amylases can be mentioned as enzymes (c).

Conventional peroxy compounds can be mentioned as bleaching agents (d), 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.

Common bases can be used as washing alkalis (e), for example ammonium or alkali metal silicates, phosphates, carbonates or hydroxides; the above respective alkaline per compounds can optionally also act as washing alkalis.

Possible dirt carriers (f) which may be present are customary substances, in particular benzotriazoles, ethylene thiourea, cellulose ethers (e.g. carboxymethyl cellulose) or polyvinyl pyrrolidones.

If necessary, the detergents can also contain other additives, for example defoamers (or foam stabilizers), fragrances, disinfectants, test salts, active chlorine-releasing compounds, corrosion inhibitors, solvents, solubilizers, finishing agents or carriers, preservatives and other electrolytes (for example sodium sulfate).

The quantitative compositions of the detergents can vary widely depending on the manufacturer and intended use.

The polyvinyl alcohols used according to the invention can be added individually to the washing liquors or, if desired, can be 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 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 of aqueous washing liquor are used. 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. In the strongly alkaline range, when polyvinyl alcohols are added as color transfer inhibitors, products with a relatively high acetyl content are suitable because of their better dissolution behavior ("degree of saponification"<88 mol%).

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. Of particular note are the cellulose-containing substrates and, above all, colored laundry that contains colored cellulose substrates.

The detergent additives according to the invention are sufficiently compatible with the customary detergent, for example as listed above, and practically do not impair their washing action, 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. Due to the solubility in water, especially in the case of partially hydrolyzed polyvinyl alcohols, one is given easy incorporation into liquid washing and cleaning formulations.

Examples

Investigated color transfer inhibitors connection Viscosity ¹⁾ (mPas) Degree of hydrolysis (mol%)

_w g/Mol $\overline{\text{M}}$

_w g / mol Residual acetyl content (% by weight) Mowiol 10-74 10 ± 1.5 73.4 ± 1.8 20,000 20.8 Mowiol 15-79 15 ± 2.0 81.5 ± 2.2 100,000 15.4 Mowiol 18-95 Mowiol 40-88 40 ± 2.0 87.7 ± 1.1 31,000 10.8 ¹⁾ a 4% by weight aqueous solution at 20 ° C. (DIN 53 015) ²⁾ DIN 53 401

Trials in a beaker:

While stirring, 1,000 ml of water (15.6 ° dH) were placed in a beaker at 40 ° C. and 2.5 g of WMP detergent (laundry research Krefeld), followed by the addition of a color transfer inhibitor. After about 5 minutes, 2.5 g of cotton fabric, dyed with ®Diamine Brown BR (Direct brown 235), 2.5 g of white cotton fabric and 2.5 g of white terry fabric were added. After a reaction time of 30 minutes, the originally white cotton fabric was removed from the wash liquor, rinsed with water and dried. The whiteness was then determined using an Elrepho whiteness measuring device at 460 nm. The whiteness of the cotton fabric before the washing process was 85%. connection Operational concentration Remission after washing ®Mowiol 10-74 0.060 g / l 53% ®Mowiol 18-95 0.060 g / l 52% ®Mowiol 40-88 0.050 g / l 52% ®Mowiol 15-79 0.060 g / l 51% Comparison (PVP) 0.060 g / l 50% without addition --- 46%

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 4 g / l WMP test detergent (laundry research Krefeld). The water hardness was 16 ° dH.

1.25 g of cotton fabric, dyed with ®Diamin Braun BR (Hoechst AG, DE) together with 5 g of white cotton fabric, were washed in 400 ml of wash liquor.

In each case 1.3% by weight, based on the test detergent, of the compound used according to the invention was added to the wash liquor and the whiteness of the white fabric after the washing process was determined by remission measurement. Polyvinylpyrrolidone (PVP) was used as the reference substance.

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 to the white fabric. At comparable application concentrations, the compounds according to the invention are comparable in effectiveness to the previous standard polyvinylpyrrolidone (PVP), in many cases even superior.

Claims (21)

Use of polymers containing the recurring structural unit of the formula I.

and optionally further recurring structural units, which are derived from monomers copolymerizable with vinyl acetate, as a detergent additive to prevent the re-absorption of detached dyes and dye products. Use according to claim 1 of partially hydrolyzed polyvinyl alcohols of the formula II

Use of compounds according to claim 2, characterized in that the compounds have a residual acetyl content of less than 50% by weight, preferably less than 30% by weight. Use of compounds according to claim 2, characterized in that the compounds have a weight-based molecular weight $\overline{\text{M}}$

_w in the range from 5,000 to 300,000, preferably 20,000 to 200,000, particularly preferably 6,000 to 160,000. Use of compounds according to claim 2, characterized characterized in that the compounds have a degree of polymerization $\overline{\text{P}}$

_{w have} between 200 to 5,000, preferably 400 to 3,000. Use of compounds according to claim 2, characterized in that the compounds have a viscosity in the range between 2 and 40 mPa · s, preferably 10 to 30 mPa · s. Use according to claim 1 of fully hydrolyzed polyvinyl alcohols of the formula III

Use of compounds according to claim 7, characterized in that the compounds have a residual acetyl content, measured after the reactylation of the polyvinyl alcohol in pyridine, of less than 5% by weight, preferably less than 2% by weight. Use of compounds according to claim 7, characterized in that the compounds have a weight-based molecular weight $\overline{\text{M}}$

_w in the range between 5,000 and 300,000, preferably 30,000 to 200,000, particularly preferably 60,000 to 120,000. Use of compounds according to claim 7, characterized in that the compounds have a degree of polymerization $\overline{\text{P}}$

_{w have} between 100 and 5,000, preferably between 600 and 3,000. Use of compounds according to claim 7, characterized in that the compounds have a viscosity in the range between 0.1 and 100 mPas, preferably 6 to 50 mPas, particularly preferably 10 to 30 mPas. Use of compounds according to claim 7, characterized in that the degree of hydrolysis is above 98 mol%. Use of compounds according to claim 1, characterized in that the compounds contain the recurring structural unit of the formula I and further recurring structural units which are derived from α-olefins, preferably ethylene, vinyl laurate, vinyl acetate, vinyl versatic acid and / or (meth) acrylic acid derivatives . Use of compounds according to claim 1, characterized in that the compounds are used as an aqueous solution. Use of compounds according to claim 1, characterized in that the compounds are used as a dispersion powder, the polyvinyl alcohol acting as a protective colloid. Use according to claim 1 as an additive for textile detergents, detergent boosters and / or laundry aftertreatment agents. Use according to claim 16 as an additive to industrial detergents or household detergents. Detergent characterized by a content of compounds according to claim 1. Textile detergent, detergent booster and / or laundry aftertreatment agent according to claim 18. Detergent according to claim 19, containing anionic, non-ionic and / or zwitterionic surfactants, - Compounds according to claim 1. Detergent according to claim 20, additionally comprising one or more of the following components - sequestering agents, - optical brighteners, - enzymes, Bleaches and, if appropriate, stabilizers and activators, - Washing alkalis.