WO1996011251A1

WO1996011251A1 - Washing or cleaning agent with amorphous silicate builders

Info

Publication number: WO1996011251A1
Application number: PCT/EP1995/003821
Authority: WO
Inventors: Beatrix Kottwitz; Jörg Poethkow; Horst Upadek
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1994-10-06
Filing date: 1995-09-27
Publication date: 1996-04-18
Also published as: DE4435632A1; HUT77242A; EP0784665A1; PL318588A1; CZ104097A3

Abstract

The object of the invention is to prepare washing or cleaning agents, especially washing agents with apparent densities of over 500 g/l, which contain water-soluble silicate builders superimposed on the crystalline layered disilicates in these compositions. This is achieved by agents containing anionic and non-ionic tenside, inorganic builders and possibly organic co-builders, in which the inorganic builder in these agents is a spray-dried and then compressed and ground silicate in quantities of over 10 wt.% and organic co-builders in quantities of 0 to under 20 wt.%.

Description

O 96/11251 PC17EP95 / 03821

"Washing or cleaning agents with amorphous silicate

Builder substances "

The invention relates to a detergent which contains water-soluble amorphous silicate builder substances and has both excellent primary and secondary washing properties.

More recently, purely silicate systems, such as the crystalline layered disilicates - or combinations of such components with other ingredients of detergents or cleaning agents have been described for use as builders or co-workers. In particular, common detergents on the market today are substitutes or partial substitutes for phosphates and zeolites, crystalline, layered sodium silicates of the general formula (I) NaMSi _x θ2χ ₊ i * yHθ, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are used. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline sheet silicates of the formula (I) are those in which M represents sodium and x assumes the value 2. Such a product is commercially available, for example, as SKS ( ^R ) β from Hoechst A6, Federal Republic of Germany. These crystalline, layer-like silicates have the advantage over zeolite that they are slow, but nevertheless water-soluble. In addition, they should have advantages over the amorphous silicates of the prior art, such as the spray-dried water glasses, in the binding capacity of the hardness formers of the water.

The object of the invention was to provide modern washing or cleaning agents, in particular washing agents with bulk densities above 500 g / l, which contain water-soluble silicate builder substances which are superior to the crystalline layered disilicates in these formulations.

Surprisingly, it was found that this problem can be solved by using certain amorphous silicates.

The invention accordingly relates to a washing or cleaning agent which contains anionic and nonionic surfactants, inorganic builder substances and, if appropriate, organic cobuder, the Agent as an inorganic builder contains a spray-dried and finally compressed and coated silicate in amounts above 50% by weight and organic cobuder in amounts of 0 to less than 20 Ge.

The agents according to the invention contain the granular sodium and / or potassium sili obtained by spraying, compressing and milling with a modulus (molar SiO 2: Na 2 O ratio) of preferably 2.0 3.0, in particular sodium silicates, which can contain water. Water content is in the usual range and preferably makes up about 22% by weight. The bulk density of these silicates is above 500 g / 1, preferably above 600 g / 1 and in particular above 700 g / 1. In a preferred embodiment, these granular silicates contain less than 0.5% by weight of water-insoluble constituents. Within the scope of this invention, only granular silicates are used, since no compounds with other usual ingredients of detergents or cleaning agents, in particular no compounds with alkali carbonates. Particularly preferred are granular silicates selected from the commercially available granular Britesil ( ^R ) disilicates (commercial products from Akzo-PQ silica) of the type H20 (module 2.0), H20 Plus (module and H24 (module 2.4)), which The compositions according to the invention preferably contain at least% by weight of these granular silicates. When the zeolite and / or crystalline layered disilicates are completely exchanged, the amounts are advantageously at least 20 % By weight up to a maximum of about 50% based on the total detergent or cleaning agent formulation.

In the case of detergents in particular, combinations of water-soluble amorphous granular silicates with zeolite are preferred in the case of partial substitutions. The zeolites which are used here are the customary zeolites in detergent qualities, in particular zeolite A, zeolite P or mixtures of these in betra less than 25% by weight, advantageously even less than% by weight and in particular even less than 15% by weight. Particularly advantageous embodiments of the invention even have less than 15% by weight of zeolite. The zeolite content can, for example, be reduced to amounts which are usually no longer used to remove the water hardness, but for other purposes, such as powdering granules, etc. In a particularly preferred embodiment of the invention, the compositions, in particular the detergents, contain more than 20% by weight of water-soluble amorphous granular silicates of the type described above, preferably at least 25% by weight of Britesü ( ^R ) H20, H20 Plus or H24, and also 0 up to 5% by weight of zeolite.

Usable organic cobuids are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons , and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polyethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. Also particularly preferred are biodegradable terpolymers and quadropolymers, for example those which are monomers according to DE-A-4300772 Salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-4221381, which contain salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives as monomers. Further suitable builder systems are oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application WO-A-93/16110.

Likewise to be mentioned as further preferred builder substances are the known polyaspartic acids or their salts and derivatives.

Other 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, glutaldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.

The amounts of cobuder in the agents according to the invention are preferably a maximum of 15% by weight, of which in particular up to 15% by weight of polycarboxylates, preferably citrates, salts of sugar acid and mixtures of the salts of adipic acid, succinic acid and gluta acid, and 0 to 10 wt .-%, advantageously 0 to 5 wt .-% polyme polycarboxylates including polyaspartic acid and / or the oxidation products of carboxyl-containing polyglucosans or the water-soluble salts.

The agents according to the invention can contain bicarbonates and carbonates, preferably their sodium salts, as further alkaline salts. However, based on the total composition, their content is preferably less than 10% by weight and in particular a maximum of 5% by weight. In a further embodiment, no alkali metal carbonates are added, so that the agents do not contain any carbonates than is entered as a minor component by the raw materials used.

According to the teaching of German patent application DE 43 19 578, alkali carbonates can also be formed by sulfur-free, 2 to 11 carbon atoms optionally a further carboxyl and / or amino group amino acids and / or their salts are replaced. Within the scope of this invention it is possible for the alkali metal carbonates to be partially or completely replaced by glycine or glycinate.

In addition to anionic and nonionic surfactants, the agents may also contain cationic, amphoteric and / or zwitterionic surfactants. The surfactant content of the agents is preferably 10 to 40% by weight and in particular 15 to 30% by weight.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are Cg-Ci3-alkylbenzenesulfonates, olefin sulfonates, i.e. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from Ci2-Ci8 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which are obtained from Ci2-Ci8-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfo fatty acids (ester sulfonates), e.g. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. Further suitable anionic surfactants are the α-sulfofatty acids obtainable by ester cleavage of the α-sulfofatty acid alkyl esters or their di-salts. The mono-salts of the α-sulfofatty acid alkyl esters are obtained already in their industrial production as an aqueous mixture with limited amounts of di-salts. The salt content of such surfactants is usually below 50% by weight of the anionic surfactant, for example up to about 30% by weight.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example the Caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmic acid, stearic acid or behenic acid. If one starts from fats and oils, i.e. natural mixtures of different fatty acid glycerol residues, it is necessary to largely saturate the starting products with hydrogen in a known manner before the sulfonation, ie to harden iodine numbers less than 5, advantageously less than 2. Typical examples of suitable feedstocks are palm oil, palm kernel oil, palm stearin olive oil, turnip oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or lard. Due to their high natural content of saturated fatty acids, it has proven to be particularly advantageous to start from coconut oil, palm kernel oil or beef tallow. The sulfonation of the saturated fatty acids with 6 to 22 carbon atoms or the mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, is preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as described in the international patent message W0-A-91/09009 is specified.

As alk (en) yl sulfates, the alkali and in particular the sodium salt of the sulfuric acid semiesters of the Ci2-Cιβ fatty alcohols, for example au coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Cιn-C20-0x ° alcohol 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, straight-chain alkyl radical produced on a petrochemical basis, which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. Ci6-Ci8 ~ alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be of particular advantage, and particularly advantageous for machine washing detergents, Ci6-Ci8-alk (en) yl sulfates in combination with low melting anionic surfactants and especially with such anionic surfactants that have a lower Krafft point and at relatively low washing temperatures from, 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 Ci2-Ci4-fatty alkyl sulfates or Ci2-Ci8-fatty alkyl sulfates with Ci-Ciβ-pettalkyl sulfates and in particular Ci2-Ci6-fatty alkyl sulfates with

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 1 to C 22 are used. Mixtures of saturated sulfonated fatty alcohols predominantly consisting of C15 and unsaturated sulfated fatty alcohols predominantly consisting of C 8 are particularly preferred, for example those derived from solid or liquid HD-0cenol ( ^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 C7-C2i alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol of ethylene oxide (E0) or C ^ - Ciβ fatty alcohols with 1 to 4 E0 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.

Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain Cs to Cχ8 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, viewed in isolation, are nonionic surfactants (for a description, see below). 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) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. β

Preferred anionic surfactant mixtures contain combinations of alcohol sulfates, in particular mixtures of saturated and unsaturated fatty alcohol sulfates, and alkylbenzenesulfonates and / or sulfated fatty acid glycerol esters. In particular, mixtures which contain alcohol sulfates and alkylbenzenesulfonate and / or sulfated fatty acid glycerol esters as anionic surfactants are preferred.

The content of anionic surfactants in the compositions is preferably 10 to 30% by weight and in particular 15 to 25% by weight.

In addition to the anionic surfactants, the agents can also contain soaps, preferably in amounts of 0.5 to 5% by weight. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, pal itic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. In particular, such mixtures are preferred which are composed of 50 to 100% by weight of saturated C12-C2 fatty acid soaps and 0 to 50% by weight of oleic acid soap.

The anionic surfactants such as the 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 of the sodium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably up to 18 C atoms and an average of 1 to 12 mol ethylene oxide (E0) per mo alcohol, in which the alcohol radical can be linearly or preferably 2-branched methyl 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 or oleyl alcohol, and an average of 2 to 8 E0 per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols are 3 for example Ci2-Ci4-alcohols with 3 EO or 4 EO, Cg-Cn-alcohol with 7 EO, Ci3-Ci5-alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-Ci8-alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Cχ2 ~ Ci4 alcohol with 3 EO and Cj2- i8-Al ohol 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula R0 (G) _x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18, C. -Atoms means 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.

Another class of preferably used 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 with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-NN-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them. Other suitable surfactants are polyhydroxy fatty acid amides of the formula (II),

R3

I.

R2-C0-N- [Z] (II)

in the R ^ CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ^ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. With regard to the processes for their preparation, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798 and international patent application WO-A-92/06984. The polyhydroxyfatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.

The content of the nonionic surfactants in the agents according to the invention is preferably 1 to 15% by weight and in particular 2 to 10% by weight.

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

Polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof.

The agents can also contain components which improve the solubility of the heavy granules. Components of this type are described, for example, in international patent application WO-A-93/02176 and in German patent application DE-A-4203031. The preferred ingredients include in particular fatty alcohols with 20 to 80 moles of ethylene oxide per mole of fatty alcohol, for example tallow fatty alcohol with 30 E0 and tallow alcohol with 40 E0, but also fatty alcohols with 14 E0 and polyethylene glycols with a relative molecular weight between 200 and 2000.

The other constituents which may be contained in the compositions include graying inhibitors (dirt carriers), foam inhibitors, bleaching agents and bleach activators, optical brighteners, enzymes, text-softening substances, colorants and fragrances, and neutral salts such as sulfates and chlorides in the form their sodium or potassium salts.

Among the compounds which serve as bleaching agents and supply H2O2 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 peroxide salts which deliver H2O2 or peracids such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodeeandioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate onohydrate advantageously being used.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ^° C. and below, bleach activators can be incorporated into the preparations. Examples of these are N-acyl or 0-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as used, for example, in Europe Patent application EP-A-0525239 can be described. The content of bleach activators in the lead-containing agents is, in the usual range, preferably between 1 and 10% by weight and in particular between 3 u% by weight. Particularly preferred bleach activators are N, N, N ', N'-Te acetylethylened a in (TAED), l, 5-diacetyl-2,4-dioxo-hexahydro-l, 3,5-tri (DADHT) and acetylated sorbitol Mannitol mixtures (SORMAN).

When used in machine washing processes, it can be advantageous to add customary foam inhibitors to agents. As foam inhibitors, for example, soaps of natural or synthetic origin have a high proportion of C 1 -C 24 fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes, their mixtures with microfine, optionally purified silica, and fine, waxes, microcrystalline waxes, and their mixtures with silica, or bistearylethylenediamide. Advantages are also used of various foam inhibitors, e.g. S cones, paraffins or waxes. The foam inhibitors are preferably, in particular, silicone and / or paraffin-containing foam inhibitors bound to granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethyl diam are preferred.

Enzymes from the class of proteases, lipases, Amyla cellulases or mixtures thereof are possible. Bacterial strains or fungi such as Bacülus subtilis, Bacülus lichem ^' mis, Streptomyces griseus and Humicola insolens are particularly suitable enzymatic active ingredients. Proteases of the subtüisin type and in particular proteases which are obtained from Bacülus lentus are preferably used. Enzyme mixtures, for example from protease and amylase, protease and lipase or protease and cellulase or from cellulase lipase or from protease, amylase and lipase or protease, Lipase cellulase, but in particular cellulase-containing mixtures of particular interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carrier substances and / embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

The salts of polyphosphonic acids, in particular l-hydroxyethane-l, l-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid are suitable as stabilizers, in particular for per compounds and enzymes.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the detergent, are preferred used.

As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anino-4-morpholino-l, 3,5-triazinyl-6-amino), 2,2'-disulfonic acid or compounds of the same structure which contain an replace the morpholino group with a diethanolamino 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 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. The bulk density of the preferred granular agents is generally 500 to 1100 g / l. They can be produced by any of the known methods such as mixing, granulating and extruding. Processes are particularly suitable in which several partial components, for example spray-dried components and granular and / or extruded components, are mixed with one another. It is also possible for spray-dried or granulated components to be subsequently treated in the preparation, for example with nonionic surfactants, in particular ethoxylated fatty alcohols, by the customary processes. In granulation and extrusion processes in particular, it is preferred to use the anionic surfactants which may be present in the form of a spray-dried, granulated or extruded compound either as a mixing component in the process or as an additive to other granules. It is also possible and, depending on the recipe, to be advantageous if further individual constituents d agent, for example the water-soluble amorphous granular silicate citrate or citric acid or other polycarboxylates or polycarboxylic acids, polymeric polycarboxylates, zeolite and / or layered silicate, for example layered ones Crystalline disilicates, subsequently to spray-dried, granulated and / or extruded components, which are optionally coated with nonionic surfactants and / or other ingredients which are liquid to waxy at the processing temperature, are added. A method is preferred in which the surface of partial components of the composition or of the entire composition is subsequently treated to reduce the stickiness of the granules rich in nonionic surfactants and / or to improve their solubility. Suitable surface modifiers are known from the prior art. In addition to other suitable, fine zeolites, silicic acids, amorphous silicates, fatty acids or fatty acid salts, for example calcium stearate, but especially mixtures of zeolite and silicic acids or zeolite and calcium stearate or silicas and calcium stearate are particularly preferred. Examples

The detergent granules M1 and M2 according to the invention were produced by mixing, which had the compositions below (Table 1). The Britesü ( ^R ) H20 Plus and Britesü ( ^R ) H24 used as builder in the agents Ml and M2 are sodium silicates with a modulus of 2.0 and 2.4, respectively, and are obtained from Akzo-PQ Silica ¬ Lich. In Comparative Example V, the crystalline layered sodium disilicate available under the name SKS ( ^R ) 6 from Hoechst AG was used instead of the amorphous silicates.

Table 1: Compositions of agents Ml. M2 and V (in parts by weight)

Ml M2 V

Alkylbenzenesulfonate 17.0 17.0 17.0

Ci2-Ci8 sodium fatty acid soap 0.7 0.7 0.7

Ci3-Ci5 alcohol with 5 E0 2.5 2.5 2.5

Britsü ( ^R ) H20 Plus 30.0

British menu ( ^R ) H24 30.0

SKS ( ^R ) 6 30.0

Copolymer of acrylic acid 5.0 5.0 5.0

Sodium carbonate 3.8 3.8 3.8

Perborate monohydrate 18.0 18.0 18.0

Zeolite A 2.8 2.8 2.8 granular foam inhibitor

Silicone oil base 4.0 4.0 4.0

Tetraacetylethylenediamine granules 6.3 6.3 6.3

Enzyme granules (protease) 1.0 1.0 1.0

The application-related testing of agents Ml, M2 and V was carried out under practical conditions in household washing machines. For this purpose, the machines were charged with 3.0 kg of clean laundry and 0.5 kg of test fabric, the test fabric being used to test the primary washing ability with conventional Test soiling was impregnated and consisted of white fabric for testing the graying in-test. Strips of standardized cotton fabric (laundry research institute Krefeld, WFK), nettle (BN), knitwear (cotton jersey; B) and terry toweling fabric (FT) were used as the white test fabric.

Washing conditions:

Tap water of 23 ° d (equivalent to 230 mg Ca0 / 1), amount of detergent used per detergent and machine 80 g, 90 ° C wash program (including heating phase), liquor ratio (kg of laundry: liters of detergent in the main wash) 1: 5.7, Rinsing three times with tap water, centrifuging and drying.

The primary washing capacity was comparable for the agents M1 and M2 and V.

After 25 wash cycles, the ash content of the textile samples was determined quantitatively. Agents M1 and M2 according to the invention showed comparative example V (table 2) both on the individual samples and on average much better ash contents.

Table 2:

Average wt% ash

WFK BN FT B 0

Initial value 0.41 0.15 0.63 0.61 0.45

Ml 4.47 2.50 2.40 2.39 2.94

M2 4.46 3.00 3.17 3.08 3.47

4.99 3.59 3.90 3.74 4.06

Claims

IT claims

1. washing or cleaning agents containing anionic and nonionic surfactants, inorganic builder substances and optionally organic cobuder, characterized in that it is a spray-dried and subsequently compressed and ground silicate in amounts above 10% by weight and organic as an inorganic builder substance Cobuüder contains in amounts of 0 to less than 20 wt .-%.

2. Composition according to claim 1, characterized in that it contains, as a substitute or as a partial substitute for zeolite and / or crystalline layered disilicates, granular silicates selected from granular Britesü ( ^R ) di-silicates of the types H20, H20 Plus and H24.

3. Composition according to claim 1 or 2, characterized in that it contains the granular silicates in amounts of at least 15 wt .-%, preferably from at least 20 wt .-% to a maximum of about 50 wt .-%.

4. Agent, in particular detergent, according to one of claims 1 to 3, characterized in that it has a zeolite content of less than 25 wt .-%, preferably less than 20 wt .-% and in particular less than 15 wt. -% contains.

5. Detergent, in particular detergent, according to one of claims 1 to 4, characterized in that it contains more than 20% by weight of water-soluble amorphous granular silicates, preferably at least 25% by weight of Britesü ( ^R ) H20, H20 Plus or H24, and contains 0 to 5% by weight of zeolite.

6. Composition according to one of claims 1 to 5, characterized in that it contains a maximum of 15 wt .-% as organic cobuuder, of which in particular 1 to 15 wt .-% polycarboxylates, preferably citrates, salts of sugar acids and mixtures of the salts adipic acid, succinic acid and glutaric acid, and 0 to 10% by weight, advantageously 0 to 5% by weight, of polymeric polycarboxylates, including polyaspartic acid 19 and / or the oxidation products of carboxyl-containing polyglucosans or their water-soluble salts.

7. Composition according to one of claims 1 to 6, characterized in that it contains less than 10 wt .-% and preferably at most 5 wt .-% of bicarbonates and alkali carbonates.