EP0746599B1 - Washing agent with amorphous silicate builder substances - Google Patents

Abstract

PCT No. PCT/EP95/00506 Sec. 371 Date Aug. 22, 1996 Sec. 102(e) Date Aug. 22, 1996 PCT Filed Feb. 13, 1995 PCT Pub. No. WO95/22592 PCT Pub. Date Aug. 24, 1995A detergent composition containing surfactants selected from anionic, cationic, nonionic, amphoteric and zwitterionic surfactants and a builder component containing 40% to 80% by weight of amorphous alkali metal silicates and 10% to 40% by weight of alkali metal carbonates in the form of a compound, with the proviso that the alkali metal carbonate content is always greater than the alkali metal silicate content, and at most 25% by weight of water, and wherein the compound does not have a homogeneous surface nor a uniform particle size distribution.

Description

The invention relates to a detergent, the amorphous silicate builder substances contains and both excellent primary and secondary Has washing properties.

From the prior art it is known that through the use of carbonates and silicates the performance of detergents can be increased. So the international patent application WO-A-93/14182 describes the subsequent Addition of both carbonates and silicates to a basic detergent granulate. However, there are also known applications relating to the manufacture and the use of carbonate-silicate compounds in detergents reveal. These include, for example, the European patent application EP-A-0 267 042 or British patent application GB-A-1 595 770 whose teaching spray-dried carbonate-silicate compounds as carriers for nonionic surfactants can be used in detergents.

More recently, carbonate-silicate compounds have also appeared in the literature described as a replacement for conventional builder substances such as zeolite, but also for newer builder substances like crystalline layered ones Sodium silicates can serve. These include compounds according to the Teachings of European patent applications EP-A-0 486 078, EP-A-0 486 079, EP-A-0 488 868 or EP-A-0 561 656, these applications only for example be mentioned and arbitrarily from the existing state of the art were selected.

Surprisingly, it has now been shown that such carbonate-silicate compounds not only as a replacement or partial replacement for zeolites and / or crystalline layered sodium silicates with regard to incrustation inhibition can serve, but that also an improved primary washing performance and improved graying inhibition can be achieved can, if used as carbonate-silicate compound, which have no homogeneous surface and no uniform grain spectrum.

The invention accordingly relates to a detergent containing surfactants from the Group of anionic, nonionic, cationic, amphoteric and zwitterionic Surfactants, silicate builder substances as well as carbonates and possibly others Ingredients of detergents, the agent being amorphous alkali silicates and alkali carbonates contains in the form of a compound, which consists of about 40 to 80 wt .-% alkali carbonate, about 10 to 40 wt .-% alkali silicate, with the proviso that the alkali carbonate content is always greater is than the alkali silicate content, and consists of a maximum of 25% by weight of water and one inhomogeneous surface, which can be seen macroscopically also by a certain roughness distinguished, has and proportionately almost spherical granules and proportionately contains cylindrical and / or splinter-like granules.

In the context of this invention, “alkali carbonates” are also understood to mean bicarbonates, however, the use of dialkali metal carbonates is preferred. Particularly preferred are sodium carbonate, potassium carbonate or mixtures of these, mostly Sodium carbonate is used.

The preferred amorphous alkali silicates include, in particular, sodium silicates with a Na ₂ O: SiO ₂ molar ratio of 1: 1 to 1: 3.5, molar ratios between 1: 2 and 1: 3 being particularly preferred. Compounds which contain disilicates have proven to be particularly advantageous.

The compounds can be produced by any process that allows inhomogeneous Generate surfaces and grain spectra. For example, it is possible that such Compounds are spray dried and / or granulated and then part of them Compounds is crushed. It is also possible that mixtures of carbonates and silicates or even spray-dried and / or granulated compounds Roll compaction or extrusion are supplied, the emerging strand optionally cut after a previous drying and / or cooling. Final roundings are not made to ensure the inhomogeneity of the Surface that is macroscopically characterized by a certain roughness, and not to destroy the grain spectrum. The compounds consist partly of almost spherical (granules, while other parts are cylindrical and / or can be splinter-like with pointed corners and edges. The size the individual particles are in a wide range. However it is preferred that a maximum of 20% by weight of the grains and in particular a maximum of 10 Wt .-% a smaller length diameter than 250 microns and a maximum of 15 wt .-% the grains, in particular a maximum of 10% by weight of a larger length diameter have than 1.5 mm.

In a preferred embodiment of the invention, the carbonate-silicate compounds used according to the invention have a bulk density of between approximately 600 and 1100 g / l, in particular between 700 and 1000 g / l. The carbonate content, preferably sodium carbonate, is advantageously between 45 and 75% by weight, in particular between 50 and 70% by weight. At the same time, advantageous carbonate-silicate compounds have a silicate content, preferably a content of sodium silicate and in particular sodium disilicate, of 15 to 40% by weight and with particular advantages of 20 to 35% by weight, the water content being 22% by weight and in particular should not exceed 20% by weight. Particularly advantageous embodiments of the carbonate-silicate compounds have weight ratios of carbonate to silicate, in each case based on the sodium salts, of 2.2: 1 to 1.8: 1. A carbonate-silicate compound that meets all of these requirements is, for example, Gransil ^(R) , which is commercially available from Colin Stewart, Minchem (Great Britain).

The carbonate-silicate compounds mentioned can be used as a partial substitute or as a full substitute for conventional builder substances. Their content in the detergents according to the invention can therefore be about 2 to 50% by weight, but preferably 5 to 40% by weight and in particular 10 to about 35% by weight. In a preferred embodiment of the invention, the detergents are free of zeolite. However, if the compositions contain a combination of zeolite and the carbonate-silicate compounds mentioned, a preferred embodiment has zeolite and carbonate-silicate compounds in a weight ratio of 3: 1 to 1: 3, in particular 2: 1 to 1: 2 on. The carbonate-silicate compound content of the agents according to the invention preferably does not exceed 30% by weight. The zeolite used is preferably NaA zeolite in detergent quality. However, zeolite X or zeolite P and mixtures of A and X and P are also suitable, for example. 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 may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 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.

In a further preferred embodiment of the invention, the detergent contains 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 Is 20 and are preferred values for x 2, 3 or 4, in combination with the carbonate-silicate compounds mentioned. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline sheet silicates of the above formula are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171 . The combinations of crystalline layered sodium silicates and carbonate-silicate compounds can be used in a broad weight ratio of about 10: 1 to 1:10, but again weight ratios of 3: 1 to 1: 3 and in particular 2: 1 to 1: 2 are preferred.

In a further preferred embodiment of the invention, the detergents contain carbonate-silicate compounds in combination with 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 are preferred values for x 2, 3 or 4, and additionally also zeolite. Particularly advantageous detergents have a carbonate-silicate compound content of about 5 to 30% by weight, a crystalline layered sodium silicate content of about 2 to 15% by weight and a zeolite content also of about 2 to 15% by weight .-%, the weight information in all cases refer to the detergent. The weight ratios between crystalline layered sodium silicates of the type mentioned and zeolite can vary in a range from 7.5: 1 to 1: 7.5, weight ratios above 1: 1 being particularly preferred.

Anionic, nonionic, cationic, amphoteric and / or zwitterionic surfactants can be mentioned as further ingredients of the detergents according to the invention. Preferred anionic surfactants of the sulfonate type are the known C ₉ -C ₁₃ alkylbenzenesulfonates, α-olefin sulfonates and alkanesulfonates. Esters of α-sulfofatty acids or the disalts of α-sulfofatty acids are also suitable. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol be preserved.

In particular, however, anionic sulfate-type surfactants are preferred. The alk (en) yl sulfates used are the alkali metal salts, preferably the sodium salts, the sulfuric acid semiesters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ₁₀ -C ₂₀ - Oxoalcohols, and those 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, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds 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 can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C ₁₆ -C ₁₈ -alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones 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 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 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 HD-Ocenol ^(R) fatty alcohol mixtures (commercial product of the applicant) . Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 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 of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol of ethylene oxide (EO) or C ₁₂ - C ₁₈ fatty alcohols with 2 to 4 EO are suitable. Due to their high foaming behavior, they are only used in relatively small amounts in detergents for machine washing.

Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, also known as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols represent. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or use their salts.

Other ingredients can be soaps, for example, in amounts of 0.5 to 5 % By weight. Saturated fatty acid soaps, such as the salts of Lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid or behenic 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 C ₁₂ -C ₂₄ fatty acid soaps.

The anionic surfactants and the soaps can be in the form of their alkali salts such as the sodium, potassium or ammonium salts and as soluble organic salts Bases, such as mono-, di- or triethanolamine, are present. Preferably are the anionic surfactants and soaps in the form of their sodium or Potassium salts, especially in the form of the sodium salts.

The content of anionic surfactants in the detergents according to the invention is preferably 5 to 35% by weight, in particular 10 to 30% by weight, the use of fatty alk (en) yl sulfates and / or alkylbenzenesulfonate is preferred.

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 alcohols 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). The detergents according to the invention preferably contain 2 to 15% by weight of alkoxylated C ₈ -C ₁₈ alcohols and in particular 5 to 10% by weight of ethoxylated C ₁₂ -C ₁₈ fatty alcohols.

Another class of preferred non-ionic surfactants that either as the sole nonionic surfactant or in combination with others nonionic surfactants, especially together with alkoxylated Fatty alcohols used 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 ester, as for example in the Japanese patent application JP-A-58/217598 are described or which are preferably according to the in the international patent application WO-A-90/13533 become.

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; x is preferably 1.2 to 1.4. The content of alkylglycosides in the detergents is generally about 0 to 5% by weight and preferably 0.5 to 3% by weight.

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 may be suitable. The amount of this nonionic Surfactants are preferably no more than that of the ethoxylated ones Fatty alcohols and the alkoxylated fatty acid alkyl esters, in particular not more than half of it.

in der R²CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R³ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 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 Polyhydroxyfettsäureamiden 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 the R ² CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ³ 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 stands. The polyhydroxy 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, organic builder substances can also be used. Useful organic builder substances are preferred, for example polycarboxylic acids used in the form of their salts, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided such use ecological reasons are not objectionable, as well as mixtures of these. Preferred salts are the sodium 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 detergents can generally 0 to 15 wt .-%.

Suitable polymeric polycarboxylates are, for example, the sodium salts 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 proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain. Their relative molecular mass, 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 also preferred terpolymers in the older German patent applications DE 42 21 381 and DE 43 00 722 are described. The salary of the polymeric polycarboxylates and including the terpolymers preferably 2 to 7% by weight.

Other suitable builder systems are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts as they described for example in the international patent application WO-A-93/08251 be or their production, for example, in the international Patent application WO-A-93/16110 or the older German patent application P 43 30 393.0 is described.

Other suitable builder substances are polyacetals, which by reaction of dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and have at least 3 hydroxyl groups, for example as in European Patent application EP-A-0 280 223 can be obtained. Preferred polyacetals are derived from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

The detergents according to the invention can be used in addition to those Carbonate-silicate compounds still further amounts of carbonates and bicarbonates contain. Depending on the recipe, this may even be preferred his.

In addition to the ingredients mentioned, the detergents can contain other known additives commonly used in detergents, for example Bleaching agents and bleach activators, graying inhibitors, salts of polyphosphonic acids, Enzymes, enzyme stabilizers, small amounts of neutral Filling salts and, if necessary, colors and fragrances, opacifiers or Pearlescent agents and optical brighteners included.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate and / or percarbonate.

Examples of suitable bleach activators are the N-acyl or O-acyl compounds which form H ₂ O ₂ organic peracids, preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate . Particularly preferred bleach activators are N, N, N'N'-tetraacetylethylene diamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.

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

Graying inhibitors have the task of detaching from the fiber Keep dirt suspended in the fleet and prevent 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 Starch or the cellulose or salts of acidic sulfuric acid esters Cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Furthermore, soluble ones Use starch preparations and other starch products than those mentioned above, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, cellulose ethers such as carboxymethyl cellulose are preferred. Methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures used. Carboxymethyl cellulose (sodium salt), Methyl cellulose, methyl hydroxyethyl cellulose and their mixtures and polyvinyl pyrrolidone are preferred, for example in amounts of 0.1 to 5 % By weight, based on the detergent.

The agents can, as optical brighteners, 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 similarly constructed connections that instead the morpholino group is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present be, 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 also be used.

Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. They are particularly well suited from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens obtained enzymatic Active ingredients. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Here are enzyme mixtures, for example of 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, in particular cellulase-containing and protease-containing mixtures of particular Interest. (Per) oxidases can also be suitable. The enzymes can adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition. It is also possible Use of proteases with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme, is stabilized are. Surprisingly, it was found that in particular the Effect of the enzymes through the use of the compounds mentioned above Use of conventional builder substances such as zeolite or crystalline layered sodium silicates could be significantly increased.

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

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. 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, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example 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 bistearylethylenediamides are particularly preferred.

The bulk density of the advantageously granular agents is preferably at least about 600 g / l, in particular 650 to 1100 g / l. It can however, means are also produced which are lower Have bulk density.

They can be produced by any of the known processes, such as mixing, Spray drying, granulating and extruding take place. Are particularly suitable such processes in which several sub-components, for example spray-dried components and granulated and / or extruded Components are mixed together. It is also possible that spray-dried or granulated components after processing for example with nonionic surfactants, especially ethoxylated fatty alcohols the usual procedures are applied. Especially in granulation and Extrusion processes, it is preferred to form the anionic surfactants that may be present of a spray dried, granulated or extruded compound either as Additive component in the process or as an additive to other granules to use. It is also possible and can be advantageous depending on the recipe be if further individual components of the agent, for example carbonates, citrate or Citric acid or other polycarboxylates or polycarboxylic acids, polymers Polycarboxylates, zeolite and / or layered silicates, for example layered crystalline ones Disilicates, subsequently spray-dried, granulated and / or extruded Components, if necessary, with nonionic surfactants and / or others in the Processing temperature are applied to liquid to waxy ingredients, be mixed in. A method is preferred in which the surface of Partial components of the agent or the entire agent for reducing the stickiness of the granules rich in nonionic surfactants are subsequently treated. Suitable Surface modifiers are known from the prior art. Among others finely divided zeolites, silicas, amorphous silicates, fatty acids or are suitable Fatty acid salts, for example calcium stearate, but especially mixtures of zeolite and silicas or zeolite and calcium stearate are particularly preferred.

In particular, a method is preferred in which a basic detergent is more common Composition is produced by conventional methods and a carbonate-silicate compound, which consists of about 40 to 80% by weight of alkali carbonate, about 10 to 40% by weight Alkali silicate, with the proviso that the alkali carbonate content is always greater than that Alkali silicate content, and consists of a maximum of 25 wt .-% water and an inhomogeneous Surface that is macroscopically characterized by a certain roughness, has and partly almost spherical granules and partly cylindrical and / or contains splinter-like granules, is subsequently mixed, optionally after the Adding the carbonate-silicate compound, further processing of the detergent, preferably with finely divided powder and / or liquid to pasty Detergent ingredients.

Examples

Granular detergents of the compositions below (Table 1) were prepared. Due to the different raw materials, the funds had a different water content. The exchange took place over sodium sulfate. In the agent M1 according to the invention, a carbonate-silicate compound Gransil ^(R) from Colin Stewart, Minchem (Great Britain) was used, which contained 54% by weight sodium carbonate, 27% by weight amorphous sodium disilicate and 19% by weight water. The bulk density of this compound was above 800 g / l. In Comparative Example V1, instead of this compound, the same amount of zeolite NaA, based on anhydrous active substance, was used in Comparative Example V2, the same amount of crystalline layered β-sodium disilicate, which had been prepared according to the teaching of international patent application WO-A-91/08171. Composition of agents M1, V1 and V2 (in% by weight) M1 V1 V2 C ₁₆ -C ₁₈ alkyl sulfate 8th 8th 8th C ₁₂ -C ₁₈ fatty acid soap 1 1 1 C ₁₂ -C ₁₈ fatty alcohol with 5 EO 5.5 5.5 5.5 Gransil ^(R) 27 ---- ---- Zeolite NaA (anhydrous active substance) ---- 27 ---- β-disilicate ---- ---- 27 sodium 8th 8th 8th amorphous sodium silicate (1: 3.0) 1.5 1.5 1.5 Perborate tetrahydrate 20th 20th 20th Tetraacetylethylenediamine 5.5 5.5 5.5 Copolymer of acrylic acid 5 5 5 CMC / MC 0.1 0.1 0.1 Phosphonate 0.5 0.5 0.5 Protease granules 1 1 1 Foam inhibitor based on silicone oil 0.7 0.7 0.7 Sodium sulfate and water rest rest rest

The application test was carried out under practical conditions in Household washing machines. The machines were cleaned with 3.0 kg Loaded laundry and 0.5 kg test fabric, the test fabric for testing of the primary detergent impregnated with usual test soiling was and consisted of white tissue to test the graying inhibition Strips of standardized cotton fabric were used as the white test fabric (Krefeld laundry research institute, WFK), nettle (BN), knitwear (cotton jersey; B) and terry cloth (FT) used.

Anschmutzungen:

Staub-Wollfett auf Baumwolle (SW-B)
Staub-Hautfett auf Baumwolle (SH-B)
Staub-Hautfett auf veredelter Baumwolle (SH-BV)
Staub-Hautfett auf Mischgewebe aus Polyester und veredelter Baumwolle (SH-PBV)
Milch-Ruß auf Baumwolle (MR-B)
Milch-Kakao auf Baumwolle (MK-B)
Rotwein auf Baumwolle (R-B)
Tee auf Baumwolle (T-B)

Washing conditions for primary washing capacity: tap water of 23 ° d (equivalent to 230 mg CaO / l), amount of detergent used per detergent and machine 98 g, washing temperatures 60 ° C and 90 ° C, liquor ratio (kg washing: liters of washing solution in the main wash) 1: 5, 7, 3 rinsing with tap water, centrifuging and drying.

Soiling:

Dust-wool grease on cotton (SW-B)
Dust skin fat on cotton (SH-B)
Dust skin grease on refined cotton (SH-BV)
Dust-skin grease on blended fabrics made of polyester and finished cotton (SH-PBV)
Milk soot on cotton (MR-B)
Milk cocoa on cotton (MK-B)
Red wine on cotton (RB)
Tea on Cotton (TB)

Washing conditions for graying inhibition:

Tap water of 23 ° d (equivalent to 230 mg CaO / l), amount of detergent used per detergent and machine 98 g, wash temperature 90 ° C, liquor ratio (kg of laundry: liters of wash solution in the main wash cycle) 1: 5.7, rinsed 3 times with tap water, spun off and drying, number of washes: 25. Surprisingly, after 25 washes with agent M1 according to the invention, the initial white values of the test fabrics used were almost reached. Primary washing power (reflectance in%) at 90 ° C M1 V1 V2 SW-B 79.0 76.8 77.7 SH-B 74.2 72.2 74.8 SH-BV 78.4 77.5 77.2 SH-PBV 70.0 64.3 64.6 MR-B 81.4 74.9 79.7 MK-B 84.8 79.3 83.9 RB 81.9 80.6 79.8 TB 80.8 78.8 79.1 Primary washing power (reflectance in%) at 60 ° C M1 V1 V2 SH-BV 69.1 68.7 67.1 SH-PBV 58.7 58.8 54.3 MR-B 79.5 70.4 77.0 MK-B 79.9 73.1 77.9 Graying inhibition (remission in%) WFK BN B FT Initial value 84.7 86.8 87.2 87.2 M1 82.1 86.0 86.0 86.7 V1 79.3 84.1 82.1 82.4 V2 76.9 82.1 80.7 82.3

Claims (11)

1. A detergent containing surfactants from the group of anionic, nonionic, cationic, amphoteric and zwitterionic surfactants, silicate-based builders and carbonates and, optionally, other ingredients of detergents, characterized in that the detergent contains amorphous alkali metal silicates and alkali metal carbonates in the form of a compound which consists of about 40 to 80% by weight of alkali metal carbonate, about 10 to 40% by weight of alkali metal silicate, with the proviso that the alkali metal carbonate content is always greater than the alkali metal silicate content, and at most 25% by weight of water and has an inhomogeneous surface, which ― macroscopically ― is also distinguished by a certain roughness, and contains partly substantially spherical granules and partly cylindrical and/or splinter-like granules.
2. A detergent as claimed in claim 1, characterized in that the carbonate/silicate compound has a particle size distribution in which at most 20% by weight of the particles and preferably at most 10% have a smaller length diameter than 250 µm and at most 15% of the particles and preferably at most 10% have a larger length diameter than 1.5 mm.
3. A detergent as claimed in claim 1 or 2, characterized in that the carbonate/silicate compound has a content of carbonates, preferably sodium carbonate, of 45 to 75% by weight and, more particularly, 50 to 70% by weight and a silicate content, preferably a content of sodium silicate and, more particularly, sodium disilicate, of 15 to 40% by weight and, with particular advantage, 20 to 35% by weight, the water content not exceeding 22% by weight and, more particularly, 20% by weight.
4. A detergent as claimed in any of claims 1 to 3, characterized in that it contains about 2 to 50% by weight, preferably 5 to 40% by weight and more preferably 10 to about 35% by weight of the carbonate/silicate compound.
5. A detergent as claimed in any of claims 1 to 4, characterized in that it contains zeolite and carbonate/silicate compounds in a ratio by weight of 3:1 to 1:3 and preferably 2:1 to 1:2, the content of sodium/silicate compound in the detergent not exceeding 30% by weight.
6. A detergent as claimed in any of claims 1 to 4, characterized in that it is zeolite-free.
7. A detergent as claimed in any of claims 1 to 4 or 6, characterized in that it contains carbonate/silicate compounds in combination with crystalline layer-form sodium silicates with the general formula NaMSi_xO_2x+1AyH₂O, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or 4.
8. A detergent as claimed in any of claims 1 to 5, characterized in that it contains carbonate/silicate compounds in combination with crystalline layer-form sodium silicates with the general formula NaMSi_xO_2x+1AyH₂O, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or 4, and zeolite, the content of carbonate/silicate compound, based on the detergent, preferably being 5 to 30% by weight, the content of crystalline layer-form sodium silicates, based on the detergent, being 2 to 15% by weight and the content of zeolite, based on the detergent, also being 2 to 15% by weight.
9. A detergent as claimed in any of claims 1 to 8, characterized in that it contains enzymes from the class of proteases, lipases, amylases, cellulases and mixtures thereof.
10. A detergent as claimed in any of claims 1 to 9, characterized in that it contains peroxy bleaching agents.
11. A process for the production of the detergent claimed in any of claims 1 to 8, characterized in that a basic detergent of standard composition is produced by conventional methods and a carbonate/silicate compound which consists of about 40 to 80% by weight of alkali metal carbonate, about 10 to 40% by weight of alkali metal silicate, with the proviso that the alkali metal carbonate content is always greater than the alkali metal silicate content, and at most 25% by weight of water and has an inhomogeneous surface, which ― macroscopically ― is also distinguished by a certain roughness, and contains partly substantially spherical granules and partly cylindrical and/or splinter-like granules, is subsequently incorporated, the detergent being further processed, preferably with fine-particle powder-form and/or liquid to paste-form detergent ingredients, optionally after addition of the carbonate/silicate compound.