EP0876466B1 - Washing and cleaning composition comprising coloured particle - Google Patents

Description

The present invention relates to a washing and cleaning agent containing a colored particle contains, and a method for washing textiles using such an agent.

Universal detergents sometimes contain colorants in the form of speckles. Often used Shades are green and blue. The colorants serve e.g. to the yellowing of to compensate for washed fabrics or to dye the particles and the detergent make it more appealing to the consumer. The colorants used should be sufficiently alkaline and heat-resistant and wash even after multiple washes do not stain. A formerly used colorant is ultramarine blue.

DE-A-17 94 180 e.g. described a granular blue toner mixture that is used as a colorant Ultramarine blue in combination with a water-soluble inorganic hydratable alkaline salt and special cationic quaternary ammonium compounds contains.

European patent application 0 138 410 describes a process for producing colored Detergent powder described in which a particulate colorant, for example is intensively mixed with a detergent powder in a screw conveyor and so a colored detergent powder can be obtained. Ultramarine blue, Duasyn Acid Blue and Polar Brilliant Blue are used.

US-A-3,519,054 describes a process for making multi-colored particulate Products described in which two liquid flows in the form of droplets in countercurrent are dried and one or both liquid streams each have a colorant is added, the droplets being converted into dried, multicolored particles. Ultramarine blue, for example, is used as the colorant. As further examples u. a. Phthalocyanine blue, indigo, rhodamine pigment, azo ruby, chrome orange, alizarin, Indanthrene called yellow, phthalocyanine green, wool violet or anthraquinone violet.

Japanese patent applications JP-A-1113499 and JP-A-1113500 describe colored ones Particles containing builder, surfactant and water-soluble dyes, which during the Washing can be destroyed oxidatively. Japanese patent application JP-A-5025493 describes colored particles containing builders and water-soluble dyes, which during the Washing can be destroyed oxidatively. U.S. Patent No. 3,355,392 describes colored particles containing builder, surfactant, bleach and water-soluble dyes, which are oxidatively destroyed during washing.

Powdery detergents are known from the prior art which contain colored mostly green or blue, speckles included. The colored particles are often around colored detergent additives, e.g. Bleach activator.

In recent years, manufacturers of food, household items, etc. proceeded to their products according to the aesthetic requirements of consumers to color. These products also include medical aids that used to be were mainly offered in skin tones. It is assumed that colored Products are more appealing to consumers.

However, using colored detergent powder is difficult. The colorants mentioned in the prior art are known to be textiles in particular stain at least to a certain extent at higher temperatures. Usually In practice, only the blue colorants are used, which cause yellowing of the laundry compensate. They are usually in such concentrations in detergents contain that even with multiple washes no undesirably strong blue tint or Discoloration occurs, in these concentrations are the detergents or those in the Particles to be incorporated into detergent powder, hardly or only very weakly colored, or the concentration of the colorants in the colored particles is so low that they only are weakly seen in the powder. A strong color of the detergent powder or Larger particles to be incorporated into the detergent can be used with those from the prior art Known colorants cannot be achieved without the disadvantages mentioned.

The present invention is accordingly based on the object, by incorporation a suitable colored particle colored washing and cleaning agent for To make available that has a strong color, but in the Concentrations do not stain the laundry even after multiple washes.

The present invention relates to a surfactant, builder and bleaching agent Detergent and cleaning agent, which is a colored particle containing a colorant, which partially or completely destroyed in the washing process, contains, and thereby is characterized in that the colored particle surfactant and optionally builder, bleach and / or bleach activator contains.

For the purposes of this invention are for incorporation into a detergent and cleaning agent suitable colored particles are those which, in addition to the colorant, contain at least one surfactant and optional Comply with component as described in claim 1. The particles can contain all ingredients of the detergent or cleaning agent contain or exist as a so-called compound, i.e. single or multiple components contained in pre-assembled form. It can be spray dried over a drying tower or particles obtained by agglomeration or extrusion. It Color mixtures can also be used which, in addition to those that can be oxidatively destroyed Colorants suitable for detergents and cleaning agents are blue dyes, which act as blue tones serve to compensate for the yellowing of washed fabrics.

Surprisingly, it was found that the colored particles as components of Universal detergent or as a universal detergent can be used and Despite their intense color as a solid, they quickly discolor in the wash liquor and do not give color to the laundry even at high washing temperatures.

All colorants which are oxidatively destroyed in the washing process are suitable as colorants and mixtures of these with suitable blue dyes, so-called blue toners. It has proved to be advantageous to use colorants in water or at room temperature liquid organic substances are soluble. As organic substances liquid nonionic surfactants are preferably used, since these also have a Contribute to washing performance. For example, anionic colorants are suitable, e.g. anionic nitroso dyes. A possible colorant is, for example, naphthol green (Color Index Part 1: Acid Green 1; Part 2: 10020), which as a commercial product for example as Basacid® Green 970 is available from BASF, Ludwigshafen, and mixtures of these with suitable blue dyes.

To prevent decomposition of the colorant during storage, it is advantageous to when the colorant is stable at temperatures up to 40 ° C. The stability of the Colored particles can be contained by the lowest possible water content increase. It is particularly preferred if the Colorants in the presence of water to a certain extent with atmospheric oxygen or react with oxygen present in the water. In this case, the presence bleaching agents can be dispensed with, which is particularly advantageous for mild detergents is. The colorants should preferably have no substantivity towards textile fibers, so they don't stain. Should the colorants react with the textile fibers, then so the color applied to the textiles should also react with the oxidizing agent be destroyed, so that a dyeing of the textiles, especially over several Washing cycles, is avoided.

The oxidative reaction of the coloring agents with an oxidizing agent should be as fast as possible so that the coloring agent decomposes as soon as it comes into contact with the oxidizing agent. If the colored particles come into contact with water, a colored wash liquor is usually formed first, which is bleached within a short time by the bleach, which also dissolves on contact with water. The colored wash liquor is decolorized at 60 ° C., preferably within 5 to 10 minutes after dissolving in water to a degree of at least 50%, particularly preferably at least 80%, in particular at least 90%. The degree of oxidative decomposition of the colorant can be determined, for example, by means of extinction measurements by measuring the extinction E _{0 of} the wash liquor with a known concentration c ₀ of colorant and the extinction E _{1 of} the wash liquor after a defined time. From the determined extinction values, the amount of colorant still present can be calculated from Lambert-Beer law. The rate of oxidation of the colorant should be greater, the higher the substantivity towards the laundry.

The washing and cleaning agents according to the invention which contain these particles show preferably such a low substantivity towards textiles that after 25 washing cycles in the case of cotton textiles that have a whiteness of over 200, the Color deviation number according to Ganz / Griesser is between -1.5 to ≤ 2.5.

Suitable oxidizing agents are, for example, the substances usually present in the washing and cleaning agents as bleaching agents. These include in particular the compounds which supply H ₂ O ₂ in water. Among them, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. In order to decolorize the colorant as completely as possible and in the period mentioned above, the oxidizing agent should be present in a sufficient amount. The colorant and the oxidizing agent can be present in a weight ratio of up to about 1 to 10 ⁴ , preferably 1: 100 to 8 x 10 ³ , the amount of oxidizing agent should be kept as low as possible in order to protect the colors of the textiles.

The detergent and cleaning agent can be a universal, a color or a mild detergent his. If the detergent is a mild detergent, it should, unless the colorant is in Presence of water is already oxidized by oxygen, in addition to that for the oxidation of the Coloring agent required bleach contain no further bleach.

In detergents and cleaning agents, in which the bleaching agents also contribute to the washing power should, like to remove bleachable stains, the content is Total bleaching agents preferably 5 to 30% by weight and in particular 10 to 25% by weight.

The effect of the oxidizing or bleaching agents can be increased by adding so-called bleach activators. These are usually incorporated into detergents and cleaning agents containing bleach in order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below. Examples of bleach activators are N-acyl or O-acyl compounds which form organic peracids with H ₂ O ₂ , preferably N, N'tetraacylated diamines, alkanoyloxybenzenesulfonates such as iso- and n-nonanoyloxybenzenesulfonates, furthermore carboxylic anhydrides and esters of polyols such as glucose pentaacetate , Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239. The bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 2 and 8% by weight. Particularly preferred bleach activators are N, N, N, N'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures ( SORMAN®).

The colored particles contain those usually contained in washing and cleaning agents anionic, nonionic and / or amphoteric surfactants and optional Builder As already described, the liquid nonionic surfactants can also be used as a solvent for the colorants.

The colored particles can all be used as surfactants, usually in detergents and cleaning agents contain surfactants used.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C ₉ -C ₁₃ -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C ₁₂ -C ₁₈ monoolefins with an end or internal double bond by sulfonation contains gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin. As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C ₁₂ -C ₁₈ fatty alcohols are used, for example, on coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which has an analog

Like the adequate compounds, they have degradation behavior based on oleochemical raw materials. C ₁₆ -C ₁₈ alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It may be of particular advantage for machine-wash detergents to use C ₁₆ -C ₁₈ alk (en) ylsurfate in combination with lower melting anionic surfactants, and in particular with those anionic surfactants which have a lower force point and at relatively low washing temperatures of, for example, room temperature to 40 ° C show a low tendency to crystallize. In a preferred embodiment of the invention, the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably C ₁₂ -C ₁₈ fatty alkyl sulfates or mixtures of C ₁₂ -C ₁₄ fatty alkyl sulfates or C ₁₂ -C ₁₈ fatty alkyl sulfates with C ₁₆ -C ₁₈ -Fatty alkyl sulfates and especially C ₁₂ -C ₁₆ fatty alkyl sulfates with C ₁₆ -C ₁₈ fatty alkyl sulfates. In a further preferred embodiment of the invention, however, not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C ₁₆ to C ₂₂ are used. Mixtures of saturated sulfated fatty alcohols predominantly consisting of C ₁₆ and unsaturated sulfated fatty alcohols predominantly consisting of C ₁₈ are particularly preferred, for example those derived from solid or liquid fatty alcohol mixtures of the HD-Ocenol® type (commercial product of the applicant). Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from 5: 1 to 1: 1 are preferred.

The sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 mol ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol ethylene oxide (EO) or C ₁₂ - C ₁₈ fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under Fatty acid glycerol esters are the mono-, di- and triesters as well as their mixtures understand how they are produced by esterification of a monoglycerin with 1 up to 3 moles of fatty acid or in the transesterification of triglicerides with 0.3 to 2 moles of glycerin be preserved. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example the Caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, Stearic acid or behenic acid. If you start from fats and oils, that is natural Mixtures of different fatty acid glycerol esters, so it is necessary to Products used before the sulfonation in a manner known per se with hydrogen largely saturate, i.e. to harden to iodine numbers less than 5, more advantageously less than 2. Typical examples of suitable feedstocks are palm oil, palm kernel oil, palm stearin, Olive oil, rape oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or lard. Because of their high natural content of saturated However, fatty acids have proven particularly beneficial, from coconut oil, Going out of palm kem oil or beef tallow. The sulfonation of the saturated fatty acids with 6 up to 22 carbon atoms or mixtures of fatty acid glycerol esters with Iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms preferably by reaction with gaseous sulfur trioxide and subsequent Neutralization with aqueous bases, as described in the international patent application WO-A-91/09009 is indicated. The sulfonation products are a complex mixture the mono-, di- and triglyceride sulfonates with α-and / or internal sulfonic acid grouping contains. As by-products, sulfonated fatty acid salts, glyceride sulfates, Glycerin sulfates, glycerin and soaps. If you go in the sulfation of saturated Fatty acids or hardened fatty acid glycerol ester mixtures, so the Percentage of the α-sulfonated fatty acid disalts, depending on the procedure, up to about 60% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants which will be described later. 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.

Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. Soap mixtures are particularly preferred which are composed of 50 to 100% by weight of saturated C ₁₂ -C ₂₄ fatty acid soaps and 0 to 50% by weight of oleic acid soap.

The synthetic anionic surfactants and soaps can be 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 Form of their sodium or potassium salts, especially in the form of the sodium salts.

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 can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-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 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohol with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohol with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.

The degree of oligomerization x, the distribution of monoglycosides and oligoglycosides indicates any number between 1 and 10, preferably x is 1.2 to 1.4.

As further nonionic surfactants, either as the sole nonionic surfactant or are used in combination with other nonionic surfactants alkoxylated, preferably ethoxylated or ethoxylated and propoxylated To name fatty acid alkyl esters, preferably those having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese Patent application JP 58/217598 are described or preferably according to the method described in international patent application WO-A-90/13533 getting produced.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.

in der R²-CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R³ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mis 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhyroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

in which R ² -CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ³ for hydrogen, an alkyl or hydroxyalkyl radical having 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 polyhyroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

Other ingredients include the surfactants already described in detail in particular inorganic and organic builder substances, components, which prevent the textile from being soiled again (soil repellents), and Graying inhibitors, alkaline salts, bleaching agents and bleach activators, foam inhibitors, fabric softening agents, neutral salts as well as colors and fragrances.

In addition to the conventional phosphates, suitable inorganic builders are also suitable in particular zeolite-type aluminosilicates. The fine crystalline Zeolite containing synthetic and bound water is preferably NaA zeolite in detergent quality. However, zeolite X and zeolite P are also suitable Mixtures of A and X and / or P.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 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 layered silicates are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

Useful organic builders are, for example, those in the preferred form the polycarboxylic acids used in its 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 permitted for ecological reasons is objectionable, 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.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 800 to 150,000 (based on acid). Suitable copolymers Polycarboxylates are in particular those of acrylic acid with methacrylic acid and Acrylic acid or methacrylic acid with maleic acid. Have proven to be particularly suitable Copolymers of acrylic acid with maleic acid have proven to be 50 to 90% by weight of acrylic acid and contain 50 to 10% by weight of maleic acid. Their relative molecular mass, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 12,000 and in particular 50,000 to 100,000. Organic are also particularly preferred degradable terpolymers, for example those which are salts of acrylic acid as monomers and maleic acid and vinyl alcohol or vinyl alcohol derivatives (DE 43 00 772) or the monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives (DE 42 21 381) included.

Other suitable builder systems are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts, as described, for example, in the international Patent application WO-A-93/08251 can be described or their preparation in international patent application WO-A-93/16110.

Also known as other preferred builder substances are the known polyaspartic acids or to name their salts and derivatives.

Other suitable builder substances are polyacetals, which are produced by the implementation of Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups, for example as in the European patent application EP-A-0 280 223 can be obtained. Preferred polyacetals will be from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their Mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid receive.

The inorganic and / or organic builder substances are preferably in Amounts of about 10 to 60 wt .-%, in particular from 15 to 50 wt .-%, in the invention manufactured detergents and cleaning agents used.

In addition, the agents can also contain components that make the oil and fat washable made of textiles. This effect is particularly evident if a textile is soiled that has already been washed several times with one detergent according to the invention, which contains this oil and fat-dissolving component, is washed. The preferred oil and fat dissolving components include for example nonionic cellulose ethers such as methyl cellulose and in particular methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and on hydroxypropoxyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ethers, as well as those known from the prior art Polymers of phthalic acid and / or terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionically and / or nonionically modified Derivatives of these. They can take effect in small quantities. Your salary is therefore preferably 0.2 to 10% by weight and in particular up to 5% by weight.

Graying inhibitors have the task of removing the dirt detached from the fiber to keep the fleet suspended and thus prevent the laundry from turning gray. Water-soluble colloids of mostly organic nature are suitable for this purpose, 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 acid Sulfuric acid esters of cellulose or starch. Also water-soluble acidic groups containing polyamides are suitable for this purpose. Furthermore, soluble ones Use starch preparations and starch products other than the above, e.g. mined Starch, aldehyde starches etc. Polyvinylpyrrolidone is also suitable. Prefers However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, Hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the overall recipe.

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 Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used. The sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight. The sodium silicate content of the compositions is generally up to 10% by weight and preferably between 2 and 8% by weight.

The amorphous silicates as well as some commercially available compounds are made of Carbonates and amorphous silicates suitable, the usual builder substances like Partly or entirely to replace phosphate, zeolite and crystalline layered silicates. Become If such substances are used, their content can also exceed those specified above Go beyond amounts for carbonates and amorphous silicates. Levels here are up to 40 % By weight or even 60% by weight within the scope of the invention.

According to German patent application DE 43 19 578, alkali carbonates can also by sulfur-free, 2 to 11 carbon atoms and optionally one more Amino acids and / or salts thereof having carboxyl and / or amino groups be replaced. In the context of this invention, it is preferred that a partial until the alkali carbonates are completely replaced by glycine or glycinate.

When used in machine washing processes, it may be advantageous to add conventional foam inhibitors to the formulations. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica or bistearylethylenediamide. It has proven to be advantageous to use mixtures of different foam inhibitors, for example those made of silicone, paraffins or waxes. 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 bistearylethylenediamides are particularly preferred.

The salts of polyphosphonic acids are preferably the neutral ones Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, Diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate used in amounts of 0.1 to 1.5 wt .-%.

Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. Are particularly well suited Strains of bacteria or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic active ingredients obtained. Preferably be Subtilisin-type proteases, and in particular proteases derived from Bacillus lentus won, used. Enzyme mixtures are, for example, from Protease and amylase or protease and lipase or protease and cellulase or from Cellulase and lipase or from protease, amylase and lipase or protease, lipase and Cellulase, but especially cellulase-containing mixtures of particular Interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules, for example, about 0.1 to 5 wt .-%, preferably 0.1 to 2 wt .-%.

Components that prevent re-soiling of the textile fabric (soil repellents) are in particular those compounds that stop settling during the washing process Prevent detached dirt particles and so the appearance of a so-called gray haze avoid without affecting enzyme activity and washing performance. Such components are usually polymeric and copolymeric compounds, such as polyester from aliphatic and / or aromatic dicarboxylic acids and glycols and / or polyol glycols.

The colored particles can be optical brighteners e.g. B. Derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar built-up compounds that instead of the morpholino group a diethanolamino group, carry a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned Brighteners can be used.

The solid-colored ones suitable for incorporation in a detergent and cleaning agent Particles can be any particles that are one or more of those described above Components can contain. The particles are preferably present as compounds, i.e. H. as pre-assembled mixtures of individual raw materials. Particularly preferred surfactant compounds are used, in particular compounds containing anionic surfactants which can also contain nonionic, amphoteric or cationic surfactants. The Surfactant compounds usually have a surfactant content of at least 10% by weight, preferably at least 40% by weight, particularly preferably 60 to 95% by weight, based on the compound, on. It is not necessary that the colored Particles also contain oxidizing agents in addition to the colorant. This can be done as a separate Component.

In a preferred embodiment of the invention, the colored particles Compounds containing anionic surfactants, which various anionic surfactants - for example Alkyl sulfates and alkyl benzene sulfonates and / or soap or alkyl sulfates and sulfated fatty acid glycerol esters - and / or anionic surfactants in combination with nonionic surfactants - for example Alkyl sulfates and ethoxylated fatty alcohols or alkyl sulfates, alkylbenzenesulfonates, ethoxylated Fatty alcohols and / or alkyl glycosides or alkyl sulfates, soap, ethoxylated fatty alcohols and Glucamide - included. These are preferably compounds which are anionic surfactants and nonionic surfactants in a weight ratio of 10: 1 to 1: 1.

In a further embodiment of the invention, the colored particles Compounds containing nonionic surfactants, which are different nonionic, usually liquid Surfactants in a mixture with solid components, such as. B. Buildem and inorganic salts contain. Preferred nonionic surfactants are ethoxylated fatty alcohols and / or alkyl glycosides contain. The builders described above are suitable as builders, such as, for. B. zeolites, amorphous and crystalline silicates and polycarboxylates.

The colored particles suitable for incorporation in a detergent and cleaning agent can by known methods for the production of powdered washing and Cleaning agents are made, such as. B. spray drying, granulating and Extrusion.

The spray drying process is a known process which is particularly suitable for the production of powdered detergents and cleaning agents with bulk weights of approx 300 to 700 g / l is suitable. In spray drying, the colorant can be used before the spraying process added to the slurry and then dried together with the other ingredients become. This process can be used to color through uniformly Particles are obtained. But it is also possible to stain the spray-dried Particles to dissolve the colorant in nonionic surfactant and spray this solution onto the spray-dried particles in a manner known per se.

In a further embodiment, the particles can be produced by agglomeration. For this, the individual components and the colorant are put in a customary Mixer added and subjected to agglomeration.

It is also possible to extrude the colored particles, such as this for example in European patent applications EP-A-0 339 996, EP-A-0 420 317 or the international patent application WO-A-93/23523 or the European patent EP-B-0 486 592. In this process variant, the colorant becomes Given extrusion compound.

In a further embodiment of the invention, the particles are obtained by granulation with simultaneous drying option, advantageously after one in a fluidized bed ongoing process, as described in international application WO 93/04162 is produced.

Another object of the present invention is a method for washing Wash in the presence of water, which is characterized in that a inventive washing and cleaning agent is used, the wash liquor after the dissolving of the detergent and cleaning agent is colored and this coloring at in Washing process usual temperatures of 30 ° C to 95 ° C after a time of 5 to 10 Minutes disappears. To carry out this method, a washing and Detergent containing or consisting of the colored particles in itself known way in the dispenser of a conventional washing machine. The supplied water dissolves the agent, the wash liquor is initially by the colorant colored. After a short time, about 5 to 10 minutes, the wash liquor discolors what is due to the reaction between the colorant and the oxidizing agent.

Examples

The recipe shown in the table was used to decolorize color solutions. The time until complete decolorization, ie until no more color was visible to the eye, was measured. component Quantity / wt .-% C _12-18 fatty alcohol sulfate Na salt 10 C _12-18 fatty alcohol + 7 EO units 8th C _12/18 fatty acid _soap , Na salt 2 zeolite 25 soda 15 polycarboxylate 5 complexing 0.5 Na-perborate tetrahydrate 25 TAED (powder crystal) 6 Silicone foam inhibitor 0.6 protease 0.4 Water, salts from raw materials ad 100

Decolorization of color solutions

Solutions of different colorants were used as color solutions. The time until decolorization, ie until no further coloration was visible to the eye, is shown in Table 2 below. dye Time / min. a) Basacid® green 970 (0.01% by weight) 4 b) Pigmosol® green 870 (0.005% by weight) no discoloration c) Basovit® green 876 (0.005% by weight) no discoloration d) Basacid® green 970 (0.01% by weight) + Sandolan® Blue E-HRL (0.005% by weight) blue coloring e) Basacid® green 970 (0.005% by weight) + Sandolan® Blue E-HRL (0.0015% by weight) blue coloring *

Discoloration of the laundry

A detergent containing the components shown in Table 1 as well as each contained one of the colorants mentioned in Table 2 was, according to a conventional Spray drying process made. The colorant became the one to be sprayed Slurry added in an amount such that 0.005% by weight in the final product were included.

White cotton fabrics were washed 25 times at 90 ° C using 150 g of Detergent washed per wash. The discoloration was visual and metrological according to DIN 5033 and the guideline RAL-RG 992 "Quality assurance appropriate Laundry care ".

With colorant a) there was no green discoloration of the textiles compared to the washing result determined with colorant-free powder.

With dye b) the laundry became intensely green. With dye c) received the laundry a clear green tinge that is unacceptable from a consumer perspective.

No visually recognizable effect was found with the colorants d) and e). The added blue tones Sandolan® Blue E-HRL had a brightening effect, one Green discoloration from the Basacid® green 970 was not visible.

Claims (11)

1. Surfactant-, builder-, bleach- and bleach- activator-containing washing and cleaning composition which comprises a coloured particle comprising a colorant which is partially or completely oxidatively destroyed in the washing process, characterized in that the coloured particle comprises surfactant and optionally builder, bleach and/or bleach activator.
2. Composition according to Claim 1, characterized in that the colorant present in the coloured particle is soluble in water or liquid organic substances.
3. Composition according to Claim 1 or 2, characterized in that the colorant and the bleach for decolouring the colorant are present in a weight ratio up to about 1 to 500.
4. Composition according to one of Claims 1 to 3, characterized in that the coloured particle comprises anionic, nonionic and/or amphoteric surfactants.
5. Composition according to one of Claims 1 to 4, characterized in that the coloured particle is an anionic surfactant compound comprising one or more anionic surfactants, optionally in a mixture with inorganic salts or builder materials.
6. Composition according to one of Claims 1 to 5,
   characterized in that the coloured particle is a nonionic surfactant-containing compound comprising one or more nonionic surfactants in a mixture with solid builders and/or inorganic salts.
7. Composition according to one of Claims 1 to 6, characterized in that the coloured particle is obtainable by suspending the individual components and the colorant in water to give a slurry and subjecting it to spray-drying.
8. Composition according to one of Claims 1 to 6, characterized in that the coloured particle is obtainable by agglomerating the individual components including the colorant in a manner known per se.
9. Composition according to one of Claims 1 to 6, characterized in that the coloured particle is obtainable by placing the individual components including the colorant into an extruder and subjecting them to extrusion in a manner known per se.
10. Composition according to one of Claims 1 to 6, characterized in that the coloured particle is obtainable by granulating the individual components including the colorant in a manner known per se.
11. Process for washing laundry in the presence of water, characterized in that a washing and cleaning composition according to one of Claims 1 to 10 is used, the wash liquor becomes coloured following dissolution of the washing and cleaning composition and this coloration disappears at temperatures, customary in the washing process, of from 30°C to 95°C after a time of from 5 to 10 minutes.