WO1997019163A1

WO1997019163A1 - Coloured particles suitable for incorporation in washing and cleaning agents

Info

Publication number: WO1997019163A1
Application number: PCT/EP1996/004896
Authority: WO
Inventors: Fred Schambil; Eduard Smulders
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1995-11-17
Filing date: 1996-11-08
Publication date: 1997-05-29
Also published as: ES2227615T3; EP0876466A1; DE59611103D1; DE19542830A1; EP0876466B1

Abstract

Claimed are coloured particles containing surfactants, builders and/or bleaching agents and which are suitable for incorporation in washing and cleaning agents, the particles being characterized in that all or some of the dye is oxidatively destroyed by the washing process. The coloured particles make it possible to produce a coloured washing and cleaning agent which has a strong colour but which does not stain the laundry at the concentrations used, even after several washes.

Description

Colored particle suitable for incorporation into a detergent and cleaning agent

The present invention relates to a colored particle suitable for incorporation into a washing and cleaning agent, a process for its production and a process for washing textiles

Universal detergents sometimes contain colorants in the form of speckles. Frequently used color tones are green and blue. The colorants serve, for example, to compensate for the yellowing of washed fabrics or to dye the particles and to make the detergents more appealing to the consumer. The colorants used should be sufficiently alkaline and heat-resistant and do not stain the wash even after repeated washing. A colorant that was often used in the past is ultramarine blue

DE-AS 17 94 180 describes, for example, a granular blue toner mixture which contains ultramarine blue as a colorant in combination with a water-soluble inorganic hydratable alkaline salt and special canonical quaternary ammonium compounds

European patent application 0 138 410 describes a process for the production of colored detergent powder, in which a particulate colorant, for example in a screw conveyor, is intensively mixed with a detergent powder and a colored detergent powder can be obtained in this way. Ultramarine blue, Duasyn Acid Blue and Polar Bπlliant blue used

US Pat. No. 3,519,054 describes a process for producing multicolored particulate products in which two liquid streams in the form of droplets are dried in countercurrent and one colorant is added to one or both liquid streams, the droplet being converted into dried, multicolored particles For example, ultramarine blue is used as the colorant. Other examples include phthalocyanine blue, indigo, rhodamine pigment, azo ruby, chrome orange, airzarin, indanthrene yellow, phthalocyanine green, wool violet or anthraquinone violet Powdered detergents are known from the prior art which contain colored, usually green or blue, speckles in the powder. The colored particles are often colored detergent additives such as bleach activator particles

In recent years, manufacturers of foodstuffs, household items, etc. have started to color their products according to the aesthetic requirements of consumers. These products also include medical aids, which were formerly mainly offered in skin tones. It is assumed that colored products are intended for consumers are more appealing

However, the use of colored detergent powder is difficult. The colorants mentioned in the prior art are known to dye the textiles at least to a certain extent, in particular at higher temperatures. In practice, only the blue colorants which cause yellowing are usually used Compensate for the detergent They are usually contained in the detergents in such concentrations that, even with repeated washing, there is no undesirably strong blue tint or discolouration.At these concentrations, the detergents or the particles to be incorporated into the detergent powder are hardly or only very slightly colored, or the concentration of the Colorants in the colored particles are so low that they can only be seen weakly in the powder. A strong coloration of the detergent powder or larger particles to be incorporated into the detergent cannot be achieved with the colorants known from the prior art without the ge mentioned disadvantages can be achieved

The present invention is accordingly based on the object of providing a colored particle or a colored detergent and detergent suitable for incorporation into a detergent and cleaning agent, which has a strong color, but also after the washing at the application concentrations Mehrfachwascheπ not staining

The present invention relates to a colored, that is to say a particle containing particles containing surfactants, builders and / or bleaches, suitable for incorporation into a detergent and cleaning agent, characterized in that the colorant can be partially or completely oxidatively destroyed in the washing process For the purposes of this invention, colored particles which are suitable for incorporation into a detergent and cleaning agent are those which, in addition to the colorant, contain at least one further component which contributes to the washing or cleaning performance of the detergents and cleaning agents. The particles can contain all the constituents of the washing - Contain or cleaning agents or present as so-called compounds, ie contain single or several components in pre-assembled form. They can be particles that have been spray-dried by a drying tower or obtained by agglomeration or extrusion. It is also possible to use color mixtures which, in addition to the oxidatively destructible colorants for washing - and cleaning agents contain suitable blue dyes, which serve as blue toners to compensate for the yellowing of washed fabrics

Surprisingly, it was found that the particles according to the invention can be used as constituents of universal detergents or as universal detergents themselves and, despite their intense color as a solid, discolor very quickly in the wash liquor and do not give off any color to the wash, even at high wash temperatures

Suitable colorants are all colorants which can be oxidatively destroyed in the washing process and mixtures of these with suitable blue dyes, so-called blue toners. It has proven advantageous to use colorants which are soluble in water or in organic substances which are liquid at room temperature Preferably liquid nonionic surfactants are used, as they also contribute to the washing performance. Suitable are, for example, anionic colorants, e.g. anionic nitroso dyes. One possible colorant is, for example, naphthol green (Color Index Part 1 Acid Green 1, Part 2 10020), which is a commercial product, for example as Basacid ^® Green 970 is available from BASF, Ludwigshafen, as well as mixtures of these with suitable blue dyes

In order to rule out decomposition of the colorant already during storage, it is advantageous if the colorant is stable at temperatures up to 40 ° C. The stability of the compositions containing the particles according to the invention can be increased by the lowest possible water content. It is particularly preferred if the Colorants in the presence of water already react to a certain extent with atmospheric oxygen or with oxygen present in the water. In this case, the presence of bleaching agents can be dispensed with, which is particularly advantageous for mild detergents. The colorants should preferably have no substantivity towards textile fibers so that they do not stain. Should the colorants nevertheless react with the textile fibers, the color absorbed on the textiles should also be destroyed by reaction with the oxidizing agent, so that coloring of the textiles, in particular 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 particles according to the invention come into contact with water, as a rule a colored wash liquor is formed first, which is bleached within a short time by the bleaching agent, which also dissolves on contact with water. The colored wash liquor is decolorized at 60 ° C., preferably within 5 to 10 minutes after being dissolved 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 absorbance measurements by measuring the extinction E _{0 of} the wash liquor with a known concentration c ₀ of colorant and the extinction egg of the wash liquor after a defined time. From the extinction values determined, the amount c ₀ 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 particles or detergents and cleaning agents according to the invention which contain these particles preferably have such a low substantivity towards textiles that after 25 washing cycles for cotton textiles which have a whiteness of well 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 which are usually present in the washing and cleaning agents as bleaching agents. These include in particular the compounds which supply H ₂ 0 ₂ in water. Among these, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Other bleaches that can be used include sodium percarbonate, per- oxypyrophosphates, citrate perhydrates and H ₂ 0 ₂ providing peracidic 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 To incorporate particles into a mild detergent, with which colorful textiles in particular, the colors of which are not to be bleached, are washed, the colorant can be used without a separately added oxidizing agent. The colorant and the oxidizing agent can have a weight ratio of up to about 1 to 10 ⁴ , preferably 1 100 up to 8 x 10 ³ , whereby the amount of oxidizing agent should be kept as low as possible in order to protect the colors of the textiles

Another object of the present invention is a detergent and cleaning agent containing surfactant, builder and possibly bleach, which contains the colored particles according to the invention. The detergent and cleaning agent can be a universal, a color or a mild detergent. If the agent is a mild detergent If the colorant is not already oxidized by oxygen in the presence of water, it should not contain any other bleaching agents besides the bleaching agent required to oxidize the colorant

In detergents and cleaning agents in which the bleaching agents should also contribute to the washing power, such as for removing bleachable stains, the total bleaching agent content is preferably 5 to 30% by weight and in particular 10

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 marked with H ₂ 0 ₂ organic peracids forming N-acyl or O-acyl compounds, preferably N, N'-tetraacylated diamines, alkanoyloxybenzenesulfonates such as iso- and n-nonanoyloxybenzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Other known bleach activators are tyherte mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239 Bleach-containing agents on bleach activators are 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-diooxo-hexahydro-1, 3,5-trionazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN ^® )

The particles according to the invention can contain the components usually contained in detergents and cleaning agents, such as, for example, anionic, nonionic and / or amphoteric surfactants and / or builders. As already described, the liquid nonionic surfactants can simultaneously be used as solvents for the colorants

The particles according to the invention can contain as surfactants all surfactants commonly used in washing and cleaning agents

The 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 of the type obtained, for example, from C 1-4. C ^ - Monoolefins with a double bond at the end or inside by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products, are also suitable. Alkane sulfonates obtained from C ₁ -C ₂ -alkanes, for example by suifochlonation with subsequent hydrolysis, are also suitable or neutralization can also be obtained. The esters of α-sulfo fatty 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. The alkali metal and, in particular, the sodium salts of the sulfuric acid semi-esters of the C ₁ -C ₂ fatty alcohols, for example on coconut oil alcohol, tallow fatty alcohol, are used as alk (en) yl sulfates , 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 are a synthetic, straight-chain alkyl radical prepared on a petrochemical basis contain an analog Like the adequate compounds based on fatty chemical raw materials, degradation behavior has particular preference for washing technology purposes. C ₁₆ -C ₁₈ alk (en) yl sulfates are particularly preferred. It can be of particular advantage for machine detergents to use C ₁₆ -C ₁₈ alk ( To use en) yl sulfates in combination with lower melting anionic surfactants, and in particular with those anionic surfactants which have a lower power point and which have a low tendency to install at relatively low washing temperatures of, for example, room temperature to 40 ° C. In a preferred embodiment of the invention, the compositions therefore contain mixtures from 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 in particular C ₁₂ -C ₁₆ fatty alkyl sulfates ten with C _t6 -C-ig-Fett.alkylsulfat.en In a further pref According to the embodiment of the invention, not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C ₁₆ to C ₂₂ are used. In particular, mixtures of saturated, predominantly C ₁₆ sulfated fatty alcohols and unsaturated, predominantly C _18, are used sulfonated fatty alcohols preferred, for example those that differ from solid or

® derive liquid fatty alcohol mixtures of the HD-ocenol type (commercial product of the applicants). Weight ratios of alkyl sulfates to alkenyl sulfates of 10 1 to 1 2 and in particular 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 moles of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 1 -C 4 _T s-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 glycene nests. Fatty acid glycine nests are to be understood as the mono-, di- and t-esters as well as their mixtures, as they are produced by esterification of a monoglycene with 1 to 3 moles of fatty acid or in the transesterification of trigliceids with 0.3 to 2 moles of glycerol are obtained. Preferred sulfonated fatty acid glycol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, Steanic acid or behenic acid If you start from fats and oils, i.e. natural mixtures of different fatty acid glycol nests, it is necessary to largely saturate the starting products with hydrogen in a manner known per se, i.e. to iodine numbers less than 5, more advantageously less than 2 too hard, prior to sulfonation Examples of suitable feedstocks are palmol, palm kemol, palm stearin, olive oil, rubol, konanderol, sunflower oil, cotton seed oil, peanut oil, linseed oil, lardol or lard. However, because of their high natural content of saturated fatty acids, it has proven to be particularly advantageous, 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 glycene nests 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 tion with aqueous bases, as specified in international patent application WO-A-91/09009. The sulfonation products are a complex mixture which contains mono-, di- and tlyglycerol sulfonates with α-position and / or internal sulfonic acid grouping as by-products sulfonated fatty acid salts, glycne sulfates, glycene sulfates, glycerin and soaps are formed. If sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures is carried out, the proportion of α-sulfonated fatty acid disalts can, depending on the procedure, be up to about 60% by weight. be

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-is fatty alcohol residues or mixtures of These 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 whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) yl succinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof

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

The synthetic anionic surfactants and soaps 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 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. In particular, however, alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₄ alcohols with 3 EO or 4 EO, Cg-Cn alcohol with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO , 5 EO, 7 EO or 8 EO, C ₁₂ -C ₈ 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 mean values which, for a specific product, can be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow-range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more can also be used used as 12 EO. Examples of this are 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, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10, preferably x is 1.2 to 1.4

Further nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably those having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as those are described, for example, in the Japanese patent application JP 58/217598 or which are preferably produced by the process described in the international patent application WO-A-90/13533

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 fatty acid alkanolamides, may also be suitable. The amount of these nonionic surfactants is preferably no more than that of the ethoxylated ones Fatty alcohols, especially not more than half of them

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

R ³ R ² -CO-N- [Z] (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 The hydroxyl groups are known. 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

In addition to the surfactants already described in detail, the other ingredients include, in particular, inorganic and organic builder substances, components, which prevent the textile fabric from being soiled again (soil repellents), and graying inhibitors, alkaline salts, bleaching agents and bleach activators, foam inhibitors, textile softening substances, neutral salts and colorants and fragrances

In addition to the conventional phosphates, suitable inorganic builders are, in particular, aluminosilicates of the zeolite type. The femcrystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quaternate, but zeolite X and zeolite P and mixtures of A and X and / or P are also suitable

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSι _x 0 _{2x + 1} yH ₂ 0, 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 is sodium and x is 2 or 3 in particular Both β and δ sodium disilicate Na ₂ Si ₂ 0 ₅ yH ₂ 0 are preferred

Usable organic scent substances 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 acid, aminocarboxylic acids, nitro-triacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures from these preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acid 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 weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid Copolymers of acrylic acid with maleic acid have been found to contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid. Their relative molecular weight, based on free acids, is generally from 5000 to 200,000, preferably from 10,000 to 12,000 and in particular 50,000 to 100,000 Particularly preferred are also biodegradable terpolymers, for example those which, as monomers, salts of acrylic acid and maleic acid, and vinyl alcohol or vinyl alcohol derivatives (DE 43 00 772), or which, as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and Sugar derivatives (DE 42 21 381) contain

Further suitable builder systems are oxidation products of carboxyl-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO-A-93/08251 or their preparation is described in international patent application WO-A-93/16110 becomes

The known polyaspartic acids or their salts and derivatives are also to be mentioned as further preferred builder substances

Further suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon 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, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid

The inorganic and / or organic builder substances are preferably used in amounts of approximately 10 to 60% by weight, in particular 15 to 50% by weight, in the washing and cleaning agents produced according to the invention

In addition, the detergents 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 with a detergent according to the invention which contains this oil- and fat-free component. 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 of hydroxypropoxyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether, 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 be effective even in small amounts. Their content is therefore preferably 0.2 to 10% by weight and in particular up to 5% by weight.

Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying of the laundry. 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 residues of cellulose or starch. Polyamides containing water-soluble acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also suitable, however, preference is given to cellulose ethers, such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 up to 5% by weight, based on the total recipe

Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures thereof, in particular alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na ₂ 0 Si0 ₂ of 1 1 to 1 4.5, preferably from 1 2 to 1.3.5. The content of sodium carbonate in the compositions is preferably up to 20% by weight, advantageously between 5 and 15% by weight. The content of sodium silicate in the compositions is generally up to 10% by weight and preferably between 2 and 8% by weight.

The amorphous silicates, like some commercially available compounds made of carbonates and amorphous silicates, are suitable for partially or completely replacing the usual builder substances such as phosphate, zeolite and crystalline phyllosilicates. If such substances are used, their content can also be higher than that specified above Quantities for carbonates and amorphous silicates go beyond this. Contents of up to 40% by weight or even 60% by weight are entirely within the scope of the invention

According to German patent application DE 43 19 578, alkali metal carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and optionally an additional carboxyl and / or amino group and amino acids and / or their salts. In the context of this invention it is preferred that a partial to 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 mixtures thereof Microfine, optionally silanized silicic acid or bistearylethylenediamide It has proven to be advantageous to use mixtures of different foam inhibitors, for example those made from silicones, paraffins or waxes. Foam inhibitors, in particular foam inhibitors containing silicone or paraffin, are preferred to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamides are preferred

The salts of polyphosphonic acids are preferably the neutral sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate

Diethylenediamine pentamethylene phosphonate or ethylenediaminetetramethylene phosphonate is used in amounts of 0.1 to 1.5% by weight

Enzymes from the class of proteases, lipases, amylases, cellulases or their mixtures are particularly suitable. Bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces gπseus are particularly suitable. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Enzyme mixtures, 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 in particular cellulase, are used. containing mixtures of special Interest Peroxidases or oxidases have also proven to be suitable in some cases.The enzymes can be adsorbed on carrier substances and / or embedded in shell substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, be about 0.1 to 5 % By weight, preferably 0.1 to 2% by weight

Components which prevent the textile fabric from being soiled again (soil repellents) are, in particular, those compounds which prevent the dirt particles detached during the washing process from settling and thus prevent the occurrence of a so-called gray haze without impairing the enzyme activity and also the washing performance usually polymeric and copolymeric compounds, such as polyesters from aliphatic and / or aromatic dicarboxylic acids and glycols and / or polyol glycols

The particles according to the invention can contain optical brighteners, for example derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are, for example, salts of 4,4'-Bιs (2-anιlιno-4-morpholιno-1, 3,5-tπazιnyl-6-amιno) -2,2'- disulfonic acid or similarly structured compounds which, instead of the morphohno group, carry a diethanoiamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali metal salts of 4'-Bιs (2-sulfostyryl) diphenyls 4,4'-Bιs (4-chloro-3-sulfostyryl) diphenyls, or 4- (4-chlorostyryl) -4'- (2-sulfostyryl) diphenyls. Also mixtures the aforementioned brighteners can be used

The colored particles suitable for incorporation into a detergent and cleaning agent according to the invention can be any particles which can contain one or more of the components described above. The particles according to the invention preferably exist as compounds, ie as pre-assembled mixtures of individual starting materials. Surfactant is particularly preferred - Compounds used, in particular compounds containing anionic surfactants, which may 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 inventive Particles also contain oxidizing agents in addition to the coloring agent. If the coloring agent is not already oxidized by the oxygen present in the water, this can be present as a separate component

In a preferred embodiment of the invention, the particles according to the invention are compounds containing anionic surfactants which contain various anionic surfactants - for example alkyl sulfates and alkylbenzenesulfonates and / or soap or alkyl sulfates and sulfated fatty acid glycol esters - and / or anionic surfactants in combination with nonionic surfactants - for example alkyl sulfates and ethoxylated fatty alcohols or alkylsulfonates , ethoxylated fatty alcohols and / or alkyl glycosides or alkyl sulfates, soap, ethoxylated fatty alcohols and glucamides - these are preferably compounds which contain anionic surfactants and nonionic surfactants in a weight ratio of 10 1 to 1 1

In a further embodiment of the invention, the particles according to the invention are compounds containing nonionic surfactants, which contain various nonionic, generally liquid surfactants in a mixture with solid constituents, such as, for example, builders and inorganic salts. Preferred nonionic surfactants are ethoxylated fatty alcohols and / or alkyl glycosides Builders are suitable for the builders described above, such as, for example, zeolites, amorphous and crystalline silicates and polycarboxylates

The particles suitable for incorporation into a detergent and cleaning agent according to the invention can be prepared by known processes for the production of

Powdered washing and cleaning agents are produced, such as spray drying, granulating and extruding

The spray drying process is a known process which is particularly suitable for the production of powdered detergents and cleaning agents with debris weights of about 300 to 700 g / l. In spray drying, the colorant can be added to the slurry before the spraying process and then dried together with the other constituents With this method it is possible to obtain particularly uniformly colored particles. However, it is also possible to dissolve the colorant in nonionic surfactant and to color the spray-dried particles to 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 purpose, the individual components and the colorant are placed in a conventional mixer and subjected to the agglomeration

It is also possible to produce the particles according to the invention by extrusion molding, as described, for example, in European patent applications EP-A-0 339 996, EP-A-0 420 317 or international patent application WO-A-93/23523 or European patent EP -B-0 486 592 is described. In this process variant, the colorant is added to the extrusion compound

In a further embodiment of the invention, the particles are produced by granulation with simultaneous drying possibility, advantageously by a process which takes place in a fluidized bed, as described in international application WO 93/04162

Another object of the present invention is a method for washing laundry in the presence of water, which is characterized in that a washing and cleaning agent is used which contains colored particles, whereby the washing liquor is colored after dissolving the washing agent, and this Coloring at temperatures of 30 ° C. to 95 ° C. customary in washing processes disappears after a period of 5 to 10 minutes. To carry out this process, a washing and cleaning agent which contains the particles colored according to the invention or consists of these in a manner known per se in given the induction chamber of a conventional washing machine. The water supplied dissolves the detergent, the wash liquor is initially colored by the colorant. After a short time, about 5 to 10 minutes, the wash liquor decolorises, which is due to the reaction between the colorant and the oxidizing agent

Another object of the present invention relates to the use of water-soluble colorants, which can be oxidatively destroyed in the presence of water and oxidizing agents at temperatures of from 30 ° C. to 95 ° C., for incorporation into detergents and cleaning agents preferably soluble in water or liquid organic substances such as non-ionic surfactants and has no or only a very low substantivity towards textile fibers. As described above, it can be incorporated during the manufacturing process for detergents and cleaning agents. During the washing process, the colorant dissolves and reacts with decolorization with an oxidizing agent, which can either be oxygen in the air or in water or a bleaching agent in washing and cleaning agents

Examples

The recipe shown in the table was used to decolorize color solutions. The time until complete decolorization, ie until no further coloration was visible to the eye, was measured

Table 1

1 Sasil® (manufacturer Henkel KGaA)

2 Sokalan® CP 5 (manufacturer BASF AG)

3 Turpinal® 2 NZ (manufacturer Henkel KGaA)

4 BLAP® 200 (manufacturer Biozym GmbH)

Decolorization of color solutions

Solutions of various colorants were used as color solutions. The time until decolorization, that is to say until no further coloration was visible to the eye, is shown in Table 2 below

Table 2

^* after 4 minutes the green colorant was no longer visible

Discoloration of the wash

A detergent containing the components shown in Table 1 and one of each of the colorants listed in Table 2 was prepared by a conventional spray drying process. The colorant was added to the slurry to be sprayed in such an amount that the final product contained 0.005% by weight

White cotton textiles were washed 25 times at 90 ° C. using 150 g of the detergent per wash cycle. The discoloration was determined visually and by measurement in accordance with DIN 5033 and the RAL-RG 992 guideline “Good laundry care” With colorant a), no green discoloration of the textiles was found in comparison to the washing result with colorant-free powder

With colorant b), the wash became intensely green. With colorant c), the wash got a clear green tinge, which was not acceptable from a consumer point of view

No visually recognizable effect was found with the colorants d) and e). The added blue toner Sandolan® Blue E-HRL had a brightening effect, and a green coloration due to the Basacid® green 970 was not visible

Claims

claims

Colored particles suitable for incorporation into a washing and cleaning agent, containing surfactants, builders and / or bleaching agents, characterized in that the coloring agent can be partially or completely destroyed by oxidation in the washing process

Particles according to claim 1, characterized in that the colorant is soluble in water or liquid organic substances

Particles according to claim 1 or 2, characterized in that the colorant and the bleaching agent for decoloring the colorant are present in a weight ratio of up to about 1 in 500

Particles according to one of claims 1 to 3, characterized in that they contain anionic, nonionic and / or amphoteric surfactants as surfactants

Particles according to one of claims 1 to 4, characterized in that it is an anionic surfactant compound containing one or more anionic surfactants, possibly in a mixture with inorganic salts or builder materials

Particles according to one of Claims 1 to 5, characterized in that it is a compound containing nonionic surfactants, comprising one or more nonionic surfactants in a mixture with solid builders and / or inorganic salts

A process for the preparation of colored particles suitable for incorporation into a washing and cleaning agent, which contain surfactants, builders and / or bleaching agents and a coloring agent which can be partially or completely destroyed by oxidation in the washing process, characterized in that the individual components and the Colorants slurried in water to a slurry and subjected to spray drying

Process for the preparation of colored particles suitable for incorporation into a detergent and cleaning agent, the surfactants, builders and / or Contain bleach and a colorant which can be partially or completely destroyed by oxidation in the washing process, characterized in that the individual components and the colorant are agglomerated in a manner known per se

A process for the preparation of colored particles suitable for incorporation into a washing and cleaning agent, which contain surfactants, builders and / or bleaching agents and a coloring agent which can be partially or completely destroyed by oxidation in the washing process, characterized in that the individual components and the Colorants are added to an extruder and subjected to extrusion in a manner known per se

A process for the production of colored particles suitable for incorporation into a detergent and cleaning agent, which contain anionic, nonionic and / or amphoteric surfactants, builders, bleaching agents and / or bleach activators and a coloring agent which can be oxidatively destroyed in the washing process, characterized in that that the individual components and the colorant are granulated in a manner known per se

Surfactant, builder and bleach-containing washing and cleaning agent which contains colored particles according to one of Claims 1 to 6

Agent according to claim 11, characterized in that it contains bleach activator

Process for washing laundry in the presence of water, characterized in that a washing and cleaning agent is used which contains a particle according to any one of claims 1 to 6, and the washing liquor is colored after dissolving the washing and cleaning agent and this coloring at temperatures of 30 ° C. to 95 ° C. customary in washing processes disappears after a time of 5 to 10 minutes

Use of water-soluble colorants, which are used in washing processes at temperatures of 30 ° C to 95 ° C in the presence of water and Oxidizing agents are partially or completely destroyed by oxidation, for incorporation in detergents and cleaning agents