EP0584736B1 - 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 in the household and industry nowadays consists of uniform or, especially in the household, mostly from different Fiber types, in particular from natural fibers, primarily cotton or Wool, from regenerated cellulose fibers, e.g. Viscose, made of synthetic fibers, e.g. Polyester, polyamide and polyacrylonitrile, and from mixtures of such fibers. in the Contrary to the so-called "white wash", which is made from undyed textiles exists, the so-called "colored laundry" made of colored textiles is mostly in different shades and depths, from light or pastel to dark composed. It goes without saying that in one wash Colored household laundry Textiles with a wide variety of color fastnesses available could be. If the dyeings are not sufficiently washfast, it comes during the washing process to remove dyes or from Dye degradation products and for bleeding from them into the wash liquor. By the Reinsert these detached (bled) components onto the washed with other textiles results in "soiling", a Shift in nuances and / or staining due to bleeding, possibly unevenly distributed, newly drawn dye or dye degradation products. The detachment and / or decomposition of dye is not a real enough one Coloring is e.g. due to higher temperatures, repeated washing operations, Fleet ratio of wash liquor to laundry, composition of the favored detergents and their concentration in the washing liquor, also the type of washing machine and washing programs used an influence on the detachment of dye or dye degradation products may not have enough "household laundry" coloring, e.g. conditionally due to the mechanical stress on the laundry during washing etc. The reasons used for a loss of authenticity can also be 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 called. As an example of the above, wash items are out Cellulose fibers, especially called cotton; this is mostly with Direct dyes, reactive dyes, sulfur dyes, vat dyes or Colored 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 more during repeated washing less pronounced "bleeding" in the wash liquors - in the wash liquors consequently there are, for example, unfixed dye, hydrolyzed dye and / or cleaved dye - which leads to the problems described above leads.

• 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 made in the literature to prevent this reaction described.

For one, it is possible to remove the dye while it is being dissolved in the wash liquor is present to destroy oxidatively. When using conventional heavy duty detergents this is not a problem since this is usually a bleaching system consisting of perborate and a persalt activator such as tetraacetylethylene diamine, TAED. Which peracetic acid from it completely destroys the dissolved dyes before it can be pulled onto the fiber. The disadvantage, however, is that at reactive perborate activators also cause color damage by fading the Textile colors can come.

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

Another way to prevent color transfer is to incorporate it polymeric color transfer inhibitors in the detergent formulation. In this The detached dye particles in the wash liquor are trapped by the polymer complexed and stabilized and thus prevented from being pulled back onto 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.

A disadvantage of these polymeric color transfer inhibitors is that they are often low Solubility, especially with modified polyvinylpyrrolidones, the one Incorporation into liquid detergent formulations complicates as well insufficient biodegradability.

From DE-A-3 536 530 is the use of graft copolymers, by Grafting of polyalkylene oxides with vinyl acetate can be obtained as Graying inhibitors known when washing textile material.

EP-A-572 724 describes a bleaching agent which is in addition to a per compound Contains polyvinyl alcohol.

In WO-A-93/22417 capsules are made from a polymer composition described, this polymer composition from a hydrophobic Polymer core and another hydrophilic, non-ionic polymer.

WO-A-93/23444 describes copolymers of itaconic acid and vinyl alcohol and their use as builders in detergents.

WO-A-93/15174 describes color transfer inhibitors consisting of a Metal catalyst, a polymer and an enzyme system. Here comes as Polymer including polyvinyl alcohol in question.

It has now been found that using those defined below Compounds when washing or as detergent additives solve these problems better be solved, i.e. Color transfer inhibitors are provided that can be easily incorporated into powdered and liquid cleaning agents can and are also biodegradable.

und gegebenenfalls weitere wiederkehrende Struktureinheiten, die sich z.B. durch Hydrolyse/Alkoholyse von mit Vinylacetat copolymerisierbaren Monomeren ableiten, als Waschmittelzusatz zur Verhinderung des Wiederaufziehens von abgelösten Farbstoffen und Farbstoffprodukten, wobei die gleichzeitige Verwendung von metallhaltigen Katalysatoren aus der Gruppe der Metallporphine, Metallporphyrine, Metallphthalocyanine, sowie deren wasserlöslichen oder in Wasser dispergierbaren Derivate, ausgeschlossen ist.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, for example, from hydrolysis / alcoholysis of monomers copolymerizable with vinyl acetate, as a detergent additive to prevent the detachment of detached dyes and dye products, the simultaneous use of metal-containing catalysts from the group of metal porphins, metal porphyrins, metal phthalocyanines, and their water-soluble or water-dispersible derivatives is excluded.

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 obtained by transesterification with methanol (Alcoholysis) converted into polyvinyl alcohol. Preferably serve as catalysts Bases, especially sodium hydroxide.

By varying the catalyst concentration, reaction temperature and Reaction time, the content of residual acetyl groups can be adjusted. Man therefore differentiates between "fully" and "partially hydrolyzed" polyvinyl alcohols. The partially hydrolyzed polyvinyl alcohols of the formula II are theoretically as one Mixed polymer of vinyl alcohol with vinyl acetate, the Vinyl alcohol content predominates so far that the entire molecule is water-soluble. in the in general, the acetyl content is approximately 11% by weight, corresponding to one Degree of hydrolysis of the underlying polyvinyl acetate of 88 mol% and one Ester number of approx. 140 mg KOH / g. The acetyl content can also be significantly higher In practice, hydrolysis levels of up to approx. 45 to 50 mol% are Commitment.

The remaining acetyl groups can be irregular, regular or clustered be distributed over a polyvinyl alcohol chain. The type of distribution will by the choice of the catalyst and, when using solvents, by determines their type. So are the residual acetyl groups in alkaline alcoholysis largely block-like, predominantly statistically distributed in the case of acidic alcoholysis.

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 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 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%.

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 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 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 components that have not yet been dissolved dissolve without residue at about 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 dissolution rate of polyvinyl alcohols is also very strong due to the present other products of a detergent influenced in type and amount. Especially in the presence of perborate / borate or ionic compounds The polyvinyl alcohols that we prefer also prove to be of higher concentration a degree of hydrolysis <approx. 80 mol% as being particularly suitable for the intended use suitable. Furthermore, copolymeric types of polyvinyl alcohol behave (e.g. internally softened products, such as ®Mowiol GE 4-86) also in this regard as less problematic / suitable.

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

In addition to the polyvinyl alcohols described above, surprisingly, polyvinyl alcohol-stabilized synthetic resin dispersions based on homo- or copolymeric dispersions and, in particular, redispersible dispersion powders produced by spray drying can also be 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, vinyl versatic acid and / or (meth) acrylic acid derivatives, such as (meth) acrylic acid esters.
The comonomers can be used as individual substances, so that copolymers are obtained which contain two different repeating structural units, preferably the repeating 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 find use as a detergent additive to prevent Removal of detached dyes and dye products.

The invention also relates to detergent-containing detergents which use these polymers in the form of a powder, granules or in dissolved form contain, the detergents are free of metal-containing catalysts from the Group of metal porphins, metal porphyrins, metal phthalocyanines, and their water-soluble or water-dispersible derivatives of hydrophobic Polymer particles and copolymers of itaconic acid or methyl or ethyl substituted itaconic acid and Ethanol or vinyl ester.

(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 other sites of 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 nonionic 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 among the non-ionic surfactants, the alkyl polyglycol 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 application and intended use of the detergents, these may 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 (d ₁ ) activators and / or (d ₂ ) stabilizers

(e) Washing alkalis

(f) dirt carrier.

Conventional complexing substances can be mentioned as sequestering agents (b) are, for example aminopolyacetates (in particular nitrilotriacetate or Ethylenediaminetetraacetate, aminopolymethylene phosphates, sodium triphosphate, Sodium tripolyphosphates, sodium aluminum silicates, sodium silicate, magnesium silicate, Zeolite A, polyacrylates (e.g. ammonium polyacrylates), poly-α-hydroryacrylates and Salts of hydroxycarboxylic acids (e.g. sodium citrate, sodium tartrate and Sodium gluconate).

The usual proteases, tipases and Amylases can be mentioned.

Customary peroxy compounds can be mentioned as bleaching agents (d), for example perborates, percarbonates, perphosphates or peroxides, especially as alkali metal salts or, especially in liquid formulations, too Hydrogen peroxide. Can be used as stabilizers for the per compounds For example, the above sequestering agents come into question, and as optionally present activators can be conventional carboxylic acids or Amido derivatives may be mentioned.

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

Common substances come in as optional dirt carriers (f) Consider, especially benzotriazoles, ethylene thiourea, cellulose ethers (e.g. Carboxymethyl cellulose) or polyvinyl pyrrolidones.

If necessary, the detergents can contain further additives, for example defoamers (or foam stabilizers), fragrances, Disinfectants, buffer salts, active chlorine-releasing compounds, Corrosion protection agents, solvents, solubilizers, equipment or Carriers, preservatives and other electrolytes (e.g. Sodium sulfate).

The quantitative compositions of the detergents can vary Manufacturer and purpose vary widely.

The polyvinyl alcohols used according to the invention can individually in the Wash liquors are added or, if desired, can be added to the detergent be incorporated.

Washing takes place primarily under slightly 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 aqueous washing liquor used. The salary of these compounds in the detergent formulation is advantageously in the range of 0.2 to 10% by weight, preferably 1-6% by weight. Suitable in a strongly alkaline range products with the addition of polyvinyl alcohols as color transfer inhibitors with a relatively high acetyl content because of their better dissolving behavior ("Degree of saponification" <88 mol%).

Washing can take place under normal conditions and as in the respective Washing programs provided by commercial washing machines, expedient in a total washing process in which all components in the Fleet are present and are preferably added. The washing temperature can also fluctuate in common areas, e.g. in the range of 15 - 95 ° C, where the temperatures for colored laundry and today's common temperatures in the range from 30 - 60 ° C are preferred here.

Any materials can be washed, as they are in industry and Household are provided for the respective washing processes, e.g. loose fibers, Filaments, threads, bobbins, woven fabrics, knitted fabrics, nonwovens, open webs, Tubular goods, velvet, felt, tufted goods, carpets, structured, porous fabric-like Plastic materials (such as those used for household and clothing) and especially semi-finished and finished goods. The substrates can be made from any usual materials, 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 polyurethane) and mixtures thereof. Especially Of particular note are the cellulose-containing substrates and, above all, colorful ones Laundry containing colored cellulose substrates.

The detergent additives according to the invention are mixed with the usual detergent, e.g. as listed above, sufficiently tolerable and practically impair not their washing effect, but can even support them. You prevent surprisingly good recovery of bled dyes and Dye degradation products on the washed, especially on the washed material and can be analogous to the others Wash out wash liquor components from the washed material. she do not attack the laundry. They stand out from the known ones polymeric color transfer inhibitors through mostly superior performance and also have good biodegradability. Due to the Solubility in water, especially in the case of partially hydrolyzed polyvinyl alcohols, is one easy incorporation into liquid washing and cleaning formulations given.

Examples

Investigated color transfer inhibitors connection viscosity
(mPas) Degree of hydrolysis
(Mol%) 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

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

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

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. connection White tissue remission after washing ®Mowiol 40-88 58.0% ®Mowiol 10-74 57.6% ®Mowiol 18-95 57.4% ®Mowiol LP-GE 5-97 57.1% comparison PVP 56.1% without addition 55.2% connection White tissue remission after washing ®Mowilith powder DS 59.9% ®Mowilith powder DM 117 P 59.4% ®Mowilith powder DM 200 P 57.8% ®Mowilith powder D 56.8% Compare PVP 56.3% without addition 55.0%

The result makes it clear that those claimed according to the invention Connections the color transfer of the brown dye from the colored to significantly suppress the white tissue. With comparable The concentrations according to the invention are the use concentrations previous standard polyvinylpyrrolidone (PVP) comparable in effectiveness, in even superior in many cases.

Claims (13)

1. The use of a polymer comprising the structural repeating unit of the formula I

   

   and if appropriate other structural repeating units which are derived from monomers which can be copolymerized with vinyl acetate as a detergent additive for preventing the redeposition of detached dyes and dye products, the simultaneous use of metal-containing catalysts from the group consisting of metal porphins, metal porphyrins, metal phthalocyanines, and water-soluble or water-dispersible derivatives thereof, being excluded.
2. The use of a copolymer of vinyl alcohol and vinyl acetate, the vinyl alcohol content predominating to such an extent that the overall molecule is water-soluble, as a detergent additive for preventing the redeposition of detached dyes and dye products.
3. The use of a copolymer as claimed in claim 2, wherein the residual acetyl content is less than 50% by weight, preferably less than 30% by weight.
4. The use of a copolymer as claimed in claim 3, wherein the residual acetyl content is less than 5% by weight, preferably less than 2% by weight.
5. The use of a compound as claimed in claim 1, wherein the compound contains the structural repeating unit of the formula I and other structural repeating units which are derived from an α-olefin, preferably ethylene, vinyl laurate, vinyl acetate, Versatic acid vinyl ester and/or a (meth)acrylic acid derivative.
6. The use of a compound as claimed in claim 1, wherein the compound is employed as an aqueous solution.
7. The use of a compound as claimed in claim 1, wherein the compound is employed as a dispersible powder, the polyvinyl alcohol acting as a protective colloid.
8. The use as claimed in claim 1 as an additive for a textile detergent, detergent booster and/or laundry after-treatment composition.
9. The use as claimed in claim 8 as an additive to an industrial detergent or household detergent.
10. A surfactant-containing detergent comprising a polymer as claimed in claim I in the form of a powder, of granules or in dissolved form, the detergent being free from metal-containing catalysts from the group consisting of metal porphins, metal porphyrins, metal phthalocyanines, and water-soluble or water-dispersible derivatives thereof, from hydrophobic polymer particles and from copolymers of itaconic acid or methyl- or ethyl-substituted itaconic acid and vinyl alcohol or vinyl esters.
11. A surfactant-containing detergent as claimed in claim 10 which is a textile detergent, detergent booster or laundry after-treatment composition.
12. A surfactant-containing detergent as claimed in claim 10 comprising anionic, nonionic and/or zwitterionic surfactants.
13. A surfactant-containing detergent as claimed in claim 10 comprising sequesterants, optical brighteners, enzymes, bleaches and, if desired, stabilizers and activators and/or washing alkalis.