WO1994024249A1

WO1994024249A1 - Washing agents which inhibit dye transfer

Info

Publication number: WO1994024249A1
Application number: PCT/EP1994/001112
Authority: WO
Inventors: Eduard Smulders; Günther VOGT; Gertrud Nienhaus
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1993-04-19
Filing date: 1994-04-11
Publication date: 1994-10-27
Also published as: EP0695340A1; DE4312648A1

Abstract

Described are washing agents containing non-ionic surfactants, builders and polyvinyl pyrrolidone and which exhibit high primary and secondary washing power. The washing agents contain (a) more than 8 % by wt. and up to a maximum of 45 % by wt. of non-ionic and optionally inorganic, cationic, zwitterionic and/or amphoteric surfactants, the ratio by weight of the non-ionic surfactants to the sum of the other surfactants being greater than 1:1 and the content of alkoxylated fatty alcohols and/or alkoxylated fatty-acid alkyl esters being greater than 8 % by wt. relative to the agent, (b) 10 to 80 % by wt. of builders and (c) 0.1 to 5 % by wt. of polyvinyl pyrrolidone.

Description

"Detergents with color transfer inhibiting properties"

The invention relates to a detergent containing polyvinylpyrrolidone, which prevents the transfer of detached dyes during washing to other washed textiles.

When washing colored textiles or textile sections with undyed or light-colored textiles or textile parts at the same time, it is frequently observed that dye is transferred from the more colored textiles or textile parts to the uncolored or light-colored textiles or textile parts and the original color tone is thereby changed. In the same way, this also applies to the transmission of optical brighteners, with which textiles are often equipped by the manufacturer or by washing with detergents containing brighteners. Preventing or reducing this undesired transfer of dyes or optical brighteners is the subject of numerous patent applications. Polyvinylpyrrolidone (PVP) is a suitable agent for the desired prevention of discoloration. An example of patent applications in which PVP is described alone or in combination with other active ingredients in detergents is German patent application 2232353. It is important that the detergent with the addition of PVP is essentially free of anionic surfactants. According to the disclosure of German patent application 35 19 012, the presence of strong electrolytes also reduces the color transfer-inhibiting effect of PVP. The PVP-containing agents in European patent application 262897, on the other hand, have both relatively high amounts of anionic surfactants and electrolytes. It is essential that the nonionic surfactants used or their mixture have an HLB value of at most 10.5. The international patent application WO-A-92/18597 describes agents containing anionic surfactants and electrolytes which contain PVP with a low relative molecular weight between 5000 and 22000, while the international application WO-A-92/18598 supports the color transfer inhibiting effect of the PVP cellulase is additionally used. In the recent applications, more anionic surfactants than nonionic surfactants are used to increase the primary washing performance, the weight ratio of anionic surfactants to PVP usually being at least 3: 1, for example in the range from 4: 1 to 16: 1 or far above. According to the older publication mentioned, however, the relatively high amounts of anionic surfactants accept a reduced effect of the PVP.

The object of the invention was to provide an agent which meets the requirements of modern detergents with regard to the primary and secondary detergent properties and yet has outstanding color-transfer-inhibiting performance.

The invention accordingly relates to a detergent containing nonionic surfactants, builder substances and polyvinylpyrrolidone, the agent a) totaling more than 8% by weight and a maximum of 45% by weight of nonionic and optionally anionic, cationic, zwitterionic and / or amphoteric surfactants, wherein the weight ratio of nonionic surfactants to the sum of the other surfactants is above 1: 1 and the content of alkoxylated fatty alcohols and / or alkoxylated fatty acid alkyl esters is more than 8% by weight, based on the composition, b) 10 to 80 % By weight of builder substances and c) 0.1 to 5% by weight of polyvinylpyrrolidone.

The agents according to the invention can be in solid or liquid to pasty form. However, powdery to granular agents are particularly preferred. Due to the special formulation of the agents, which are made up of relatively high amounts of nonionic surfactant with relatively low amounts of anionic surfactant, and also formulations free of anionic surfactants, in combination with certain builder substances, the agents not only have a very high primary and secondary washing performance, but also in combination with PVP also has a color transfer inhibition which is superior to the color transfer inhibition performance of the agents of the prior art.

The nonionic surfactants, which can be used in combination with anionic, cationic, zwitterionic and / or amphoteric surfactants if desired, are preferably present in the compositions at least in amounts of 9% by weight. In particular, agents are preferred which contain 9 to 30% by weight of nonionic surfactants. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical has a methyl or linear branching in the 2-position may be, or may contain linear and ethyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 C atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Cn alcohol with 7 EO, Ci3-Ci5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-Ci8- Al ohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2 ~ i4 alcohol with 3 EO and C ^ -Ciss alcohol with 5 EO. The degrees of ethoxylation given represent statistical mean values which can be an integer or a fraction for a special product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese Patent Application JP-A-58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533 ¬ be put. The agents contain alkoxylated fatty acid alkyl esters preferably in amounts of 2 to 25% by weight, in particular in amounts of 5 to 20% by weight. Mixtures of ethoxylated fatty alcohols and alkoxylated fatty acid alkyl esters in a weight ratio of 3: 1 to 1: 3 are particularly preferred.

In addition, alkyl glycosides of the general formula R0 (G) _x in which R is a primary non-ionic surfactant can also be used. wheel-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G being the symbol which represents a glycose unit having 5 or 6 carbon atoms, preferably glucose . The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4. The content of alkylglycosides in the compositions is generally about 0 to 15% by weight and preferably 2 to 10% by weight.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols and the alkoxylated fatty acid alkyl esters, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

R3

I _R 2_co-N- [Z] (I)

in R2C0 for an aliphatic acyl radical with 6 to 22 carbon atoms, R3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 Hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkyl in or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. With regard to the processes for their preparation, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798, as well as international patent application WO 92/06984. The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose. The preferred polyhydroxy fatty acid amides are therefore fatty acid-N-alkylglucamides as represented by the formula (II):

R3 OH OH OH

IIII R2CO-N-CH ₂ -CH-CH-CH-CH-CH ₂ OH (II)

I.

OH

The polyhydroxy fatty acid amides used are preferably fatty acid N-alkylglucamides of the formula (II) in which R3 is hydrogen or an alkyl group and R ^ CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palitic acid, Palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures. Fatty acid N-alkylglucamides of the formula (II) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C12 / 14 ~ coconut fatty acid or a corresponding derivative are particularly preferred.

In a preferred embodiment, the agents contain, in addition to the nonionic surfactants, 1 to 10% by weight, in particular 1.5 to 8% by weight, of anionic surfactants, those of the sulfonate and / or sulfate type being preferred, for example.

Preferred surfactants of the sulfonate type are Cg-C ^ -alkybenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from Ci2-C: 8 * M ° ^no ° l ^e - finen with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates, which are obtained with subsequent hydrolysis or neutralization from Cχ2- i8 alkanes, for example by Su ^'fochlorie- tion or sulfoxidation. The sulfonate group is statistically distributed over the entire carbon chain, with the secondary alkanesulfonates to weigh. The esters of sulfo fatty acids (ester sulfonates) are also suitable, for example the α-sulfonated methyl esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids. Further suitable anionic surfactants are the .alpha.-sulfofatty acids obtainable by ester cleavage of the .alpha.-sulfofatty acid alkyl esters or their di-salts. The mono-salts of the α-sulfofatty acid alkyl esters are obtained in their large-scale production as an aqueous mixture with limited amounts of di-salts. The disalt content of such surfactants is usually below 50% by weight of the anionic surfactant mixture, for example up to about 30% by weight. In the context of this invention, the amounts given with respect to the α-sulfofatty acid alkyl esters are always understood to be the sum of the amounts of the α-sulfofatty acid alkyl ester mono salt and the corresponding α-sulfofatty acid disalt. Mixtures of mono-salts and di-salts with further surfactants, for example with alkylbenzenesulfonate or alkyl sulfates, are also preferred.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example capric acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. If one starts from fats and oils, that is to say natural mixtures of different fatty acid glycerol esters, it is necessary to largely saturate the starting products with hydrogen in a manner known per se, ie to harden them to iodine numbers less than 5, advantageously less than 2. Typical examples of suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, rapeseed oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or lard. Due to their high natural content of saturated fatty acids, it has proven to be particularly advantageous to start from coconut oil, palm kernel oil or beef tallow. The sulfonation of the saturated fatty acids with 6 to 22 carbon atoms or the mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, is preferably carried out by Reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as specified in international patent application WO-A-91/9009.

The sulfonation products are a complex mixture containing mono-, di- and triglyceride sulfonates with an α-position and / or internal sulfonic acid grouping. Sulfonated fatty acid salts, glyceride sulfates, glycerol sulfates, glycerol and soaps are formed as by-products. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of the α-sulfonated fatty acid disalts can be up to about 60% by weight, depending on the procedure.

Suitable sulfate-type surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin. Are fate as Alkoholsul¬ the Schwefelsäurehalbester the C _j _2-CI8 fatty alcohols beispiels¬ example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or 1koholen the Cιo-C2θ-O ^χoa, and those sekun¬ därer alcohols this chain length preferred. Also preferred are alcohol sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. Ci-Ci8-alcohol sulfates are particularly preferred from the point of view of washing technology. It can also be of particular advantage, and particularly advantageous for machine washing agents, that Ci5-Ci8 alcohol sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and at a relatively low washing temperature structures from, for example, room temperature to 40 ° C. show a low tendency to crystallize. In a preferred embodiment of the invention, the means therefore contain mixtures of short-chain and long-chain fatty alcohol sulfates, preferably mixtures of Ci2 '^ 18' fatty alcohol sulfates with C15-C18 fatty alcohol sulfates and in particular Mi¬ mixtures of Ci2-Ci4-fatty alcohol sulfates ^oc ^'he Ci2-Cι -Fettalkoholsulfaten With Ciss-Cj ^ fatty alcohol sulfates In a further preferred embodiment of the invention, however, not only saturated alcohol sulfates but also unsaturated alcohol sulfates with an alkenyl chain length of preferably C15 to C22 used. Mixtures of saturated sulfonated fatty alcohols predominantly consisting of C15 and unsaturated sulfonated fatty alcohols predominantly consisting of CIQ are particularly preferred, for example those derived from solid or liquid fatty alcohol mixtures of the HD-Ocenol ( ^R ) type (commercial product of the applicant) . Weight ratios of saturated alcohol sulfates to unsaturated alcohol sulfates of 10: 1 to 1: 2 and in particular of about 5: 1 to 1: 1 are preferred.

The sulfuric acid monoesters of the straight-chain or branched C7-C2i alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-Cu alcohols with an average of 3.5 mol of ethylene oxide (EO) or Ci2-Ci8 ~ Fatty alcohols with 2 to 4 EO are suitable. Because of their high foaming behavior, they are only used in relatively small amounts in detergents.

The content of the agents in saturated and / or unsaturated fatty alcohol sulfates, which are optionally ethoxylated, is preferably 1 to 5% by weight.

Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain CQ to C ß fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants when viewed in isolation. Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Preferred anionic surfactant mixtures contain combinations of alcohol sulfates, in particular mixtures of saturated and unsaturated fatty alcohols. alcohol sulfates, and alkylbenzenesulfonates, sulfated fatty acid glycerin esters and / or α-sulfofatty acid esters. Mixtures which contain alcohol sulfates and alkylbenzenesulfonates or alcohol sulfates and sulfated fatty acid glycerol esters as anionic surfactants are particularly preferred.

Soaps, in particular in quantities of 1 to 6% by weight, are particularly suitable as further constituents. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. In particular, those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated Ci2-C24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.

The anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The compositions advantageously contain at least 10% by weight of surfactants, where compositions containing 10 to 25% by weight of nonionic surfactants and optionally further surfactants, in particular anionic surfactants, with preference for the optionally ethoxylated saturated and / or or unsaturated alcohol sulfates are preferred.

In addition, so-called detergency boosters, which are known from the literature, for example 1,2-alkanediols, ethoxylated alkylamines such as coconut oil with 2E0 and / or quaternary ammonium halides such as trialkylmethylammonium chloride can also be used. c

Another essential feature is the content of builder substances which are inorganic and / or organic in nature. In this case, inorganic builder substances such as phosphates, zeolites and layer silicates, but in particular zeolites and layer silicates are preferred. In a preferred embodiment of the invention, however, both inorganic and organic builder substances are present in the compositions.

The fine crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. However, zeolite NaX and mixtures of NaA and NaX are also suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production. In the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 1 -C 6 fatty alcohols with 2 up to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22,% by weight of bound water.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula (III) aMSi _x θ2χ ₊ ι * yH2θ, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from Is 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline sheet silicates of the formula (III) are those in which M represents sodium and x assumes the values 2 or 3. In particular, ^'sodium disilicates Na2Si2θ5 * H2Ü are both .beta.- and δ preferred, with beta-sodium disilicate being obtainable for example by the method / described in the international patent application WO-A-91 08,171th

The content of water-containing zeolite and / or crystalline layered silicates is preferably 20 to 60% by weight, the use of zeolite or of zeolite and crystalline layered silicates in a weight ratio of 4: 1 to 1: 2, advantageously 3: 1 to 1: 1, is particularly preferred. Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons. and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. Their content in the compositions is preferably 2 to 20% by weight. In addition to zeolite-containing agents, zeolite-free agents are preferred which contain crystalline layered silicates and polycarboxylates, in particular citrate, and optionally alkali metal carbonates as builders.

Suitable poly ere polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. In particular, polymeric polycarboxylates which are biodegradable are preferred. These include, for example, terpolymers which are described in the older German patent applications P 4221 381.9 and P 4300 722.4. The content of the polymeric polycarboxylates and in particular of the biodegradable terpolymers is preferably 2 to 7% by weight.

Further suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 (atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223. Preferred Polyacetals are obtained from dialdehydes such as glyoxal, glu araldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid. The polyvinylpyrrolidones used generally have a relative molecular weight between 5,000 and 100,000, with the low molecular weight polyvinylpyrrolidones with relative molecular weights between 15,000 and 50,000 being preferred.

In particular, it is preferred that PVP is used in amounts of 0.1 to 4% by weight, advantageously 0.2 to 2% by weight. The agents advantageously contain saturated fatty alcohol sulfates and polyvinyl pyrrolidone, preferably in a weight ratio of 15: 1 to 3: 1. However, ratios less than 3: 1, for example from 2: 1 to 1: 1, are also possible.

Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these; In particular, alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na2θ: Siθ2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used. The content of sodium carbonate in the middle is preferably up to 20% by weight, advantageously between 5 and 15% by weight. The amorphous sodium silicate content of the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.

In addition to the ingredients mentioned, the detergents can contain known additives commonly used in detergents, for example graying inhibitors, foam inhibitors, salts of polyphosphonic acids, enzymes, enzyme stabilizers, small amounts of neutral filler salts and fragrances, opacifiers or pearlescent agents. The agents may also optionally contain bleaching agents, peroxy bleaching agents and / or conventional photobleaching agents. It was found that compositions, in particular with bleach contents of up to, for example, about 10% by weight, have advantages in terms of primary washing power, without the performance of the dye transfer inhibitor being adversely affected. In particular, the use of peroxy bleaching agents such as perborate tetrahydrate, perborate monohydrate and percarbonate, if appropriate in combination with customary bleach activators such as N, N, N ', N'-tetraacetylethylene diamine, is preferred. When used in machine washing processes, it can be an advantage

Add usual foam inhibitors. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci8 ~ C24 fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, e.g. those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediaids are particularly preferred.

In addition, the agents can also contain components which have a positive influence on the oil and fat washability from textiles. This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based on the nonionic cellulose ethers, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Furthermore, soluble ones Use starch preparations and starch products other than the abovementioned starch, for example degraded starch, aldehyde starches, etc. However, preference is given to using cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethyl cellulose, methylhydroxypropyl cellulose, methylcarboxymethyl cellulose and mixtures thereof.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of protease, amylase and lipase or proteases, lipase and amylase, are of particular interest. (Per) oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably up to about 2% by weight. The salts of polyphosphonic acids, in particular l-hydroxyethane-1,1-diphosphonic acid (HEDP) are suitable as stabilizers. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B4O7), is particularly advantageous.

The bulk density of the preferred granular agents is generally 300 to 1100 g / 1, in particular 500 to 1000 g / 1. They can be prepared by any of the known processes, such as mixing, spray drying, granulation and extrusion, although spray drying processes are less preferred owing to the known pluming behavior of the nonionic ethoxylated alcohols. Processes in which several partial components, for example spray-dry nete components and granulated and / or extruded components are mixed together. It is also possible for spray-dried or granulated components to be subsequently treated in the preparation, for example with nonionic surfactants, in particular ethoxylated fatty alcohols, by the customary processes. It is also possible and, depending on the recipe, to be advantageous if individual constituents of the agent, for example carbonates, citrate or citric acid or other polycarboxylates or polycarboxylic acids, polymeric polycarboxylates, zeolite and / or layered silicates can optionally be crystalline, are subsequently mixed into spray-dried, granulated and / or extruded components which may have nonionic surfactants and / or other ingredients which are liquid to wax-like at the processing temperature. A method is preferred in which the surface of partial components of the agent or of the entire agent is subsequently treated to reduce the stickiness of the granules rich in nonionic surfactants and / or to improve their solubility. Suitable surface modifiers are known from the prior art. In addition to other suitable, finely divided zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts, for example calcium stearate, are particularly preferred.

Examples

Comparative example V, which represents an agent of the prior art, was produced by spray drying, the enzymes and the defoamer granules being subsequently admixed. The agents M1 to M7 according to the invention were largely produced by spray drying, the spray-dried granules being subsequently sprayed with ethoxylated non-surfactants. It is also possible to mix at least 2 spray-dried granules, one of which contains anionic surfactants in particular and another is based on, for example, zeolite, which has a high absorption capacity for liquid components and is impregnated with ethoxylated fatty alcohols. Bleaching agents, enzymes and defoamer granules (paraffin or silicone defoamers) and SKS δ ( ^R ) (crystalline disilicate, a commercial product from Hoechst AG, Federal Republic of Germany) were subsequently mixed in. The composition of the agents is given in Table 1.

The mean MI (0.4% by weight of PVP) was comparable to the agent of the prior art V (1.5% by weight of PVP) with regard to the inhibition of color transfer. Medium M2 was significantly superior to medium V. This result is based on a comparative study of 76 colorful textiles on the market.

Table 1: Compositions of compositions V and Ml to M7 in% by weight

Continuation of table 1: V Ml M2 M3 M4 M5 M6 M7

Protease 0.5 0.2 0.5 0.2 0.3 0.1 0.2 0.2 Lipase 0.2 0.2 0.2 0.1 0.3 0.2 0.2 Cellulase 0, 2 0.2 0.3 0.1 0.2 1.0 amylase 0.1 0.1 0.1 0.2

Polyvinylpyrro¬ 1.5 0.4 1.5 0.5 1 0.8 1.0 2.0 lidone (PVP) relative molecular mass 40,000

Sodium sulfate 1 1 2 6 - 2 8 4

Water and salt - rest from solutions

Claims

1. Detergent, containing nonionic surfactants, builder substances and polyvinylpyrrolidone, characterized in that the agent overall a) more than 8 wt .-% and a maximum of 45 wt .-% nonionic and optionally anionic, cationic, zwitterionic and / or ampho¬ tere surfactants, the weight ratio of nonionic surfactants to the sum of the other surfactants being above 1: 1 and the content of alkoxylated fatty alcohols and / or alkoxylated fatty acid alkyl esters being more than 8% by weight, based on the composition, b) 10 to 80 wt .-% builder substances and c) 0.1 to 5 wt .-% polyvinylpyrrolidone.

2. Composition according to claim 1, characterized in that there are 9 to 30 wt .-% nonionic surfactants, preferably ethoxylated Cs-Cis fatty alcohols and / or alkoxylated fatty acid alkyl esters, and 1 to 10 wt .-%, preferably 1.5 contains up to 8% by weight of anionic surfactants.

3. Composition according to claim 2, characterized in that it contains 1 to 5 wt .-% saturated and / or unsaturated fatty alcohol sulfates, which are optionally ethoxylated.

4. Agent according to one of claims 1 to 3, characterized in that it contains alkoxylated fatty acid alkyl esters in amounts of 2 to 25 wt .-%, preferably in amounts of 5 to 20 wt .-%, with particular preference being given to mixtures which from ethoxylated fatty alcohols and alkoxylated fatty acid alkyl esters in a weight ratio of 3: 1 to 1: 3.

5. Composition according to one of claims 1 to 4, characterized in that it contains 20 to 60 wt .-% water-containing zeolite and / or crystalline phyllosilicates as builder substances, the use of zeolite or of zeolite and crystalline phyllosilicates in weight ratio 4: 1 to 1: 2, advantageously from 3: 1 to 1: 1, is particularly preferred.

6. Composition according to claim 5, characterized in that it is 2 to 20 wt .-%

Contains salts of polycarboxylic acids, in particular salts of citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, of sugar acids and mixtures thereof.

7. Composition according to one of claims 1 to 6, characterized in that it contains 0.1 to 4 wt .-%, preferably 0.2 to 2 wt .-% polyvinylpyrrolidone.

8. Composition according to one of claims 1 to 7, characterized in that it contains 0.1 to 5 wt .-% cellulase or an enzyme mixture of cellulases and one or more enzymes from the group of proteases, lipases, amylases and (per -) contains oxidases.

9. Composition according to one of claims 1 to 8, characterized in that it contains up to 10 wt .-% peroxy bleach, preferably perborate or percarbonate.

10. Composition according to one of claims 1 to 9, characterized in that it has a bulk density of 300 to 1100 g / 1 and preferably from 500 to 1000 g / 1.