EP0656051B1 - Builder for detergents - Google Patents

Abstract

Washing and cleaning agents, especially for textiles, which contain combinations of builders like zeolithe and/or crystalline laminated silicates of the general formula (I) NaMSixO2x+1.yH2O, in which M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, and, as complex formers, polyhydroxy bicarboxylic acids or polyhydroxy bicarboxylic acid salts with 4 to 6 carbon atoms and at least 2 hydroxy groups per molecule or mixtures of these acids and/or salts, in which the ratio by weight of builders to polyhydroxy dicarboxylic acids or polyhydroxy dicarboxylic acid salts or mixtures of these acids and/or salts is 30:1 to 1:1, exhibit better secondary washing capacity than similar agents which, instead of polyhydroxy dicarboxylic acids or polyhydroxy dicarboxylic acid salts, contain polyhydroxy tricarboxylic acids or polyhydroxy tricarboxylic acid salts like citric acid or citrate. Preferred agents contain up to 15 wt % sodium and/or potassium carbonate but no phosphonates, (co)polymeric polycarboxylates and citric acid or citrate.

Description

The invention relates to a washing and cleaning agent which contains phosphate-free builders and complexing agents, as well as a phosphate-free builders combination and a process for their preparation.

In practice, zeolite, in particular zeolite NaA, and mixtures of zeolite with alkali silicates and carbonates and polymeric polycarboxylates have been used as phosphate substitutes in washing and cleaning agents. There are also complexing agents such as the salts of nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA) and phosphonic acids. The mostly selective complexing agents have the task of eliminating heavy metal ions, which can have a very negative effect on the washing process even in traces (Ullmann, 1987, Vol. 8, pages 351 to 354). It is known from the phosphonates that they also counteract the precipitation of poorly soluble calcium salts and thus the incrustation caused by poorly soluble calcium salts and the graying of the fabric ("Use of phosphonates in heavy duty liquid detergents", M. Paladini, G. Schnorbus, soap oil fats Waxes, 115th year (1989), pages 508 to 511). Finally, the combined use of phosphonates and copolymers based on acrylic acid and maleic acid, compared to formulations containing only one of these two components, results in a higher degree of whiteness of the textiles ("Use of phosphonates in household detergents with a low phosphorus content (1%)", M. Paladini, G. Schnorbus, Soap-Oil-Fat-Waxes, 114th year (1988), pages 756 to 760).

European patent application 291 869 describes phosphate-free builders combinations of zeolite, aminoalkane polyphosphonate, 1-hydroxyethane-1,1-diphosphonate (HEDP) and polymeric polycarboxylate, certain weight ratios of the last three components showing synergism with regard to preventing the formation of fiber incrustations.

European patent application 448 298 describes detergents which contain zeolite as a builder and 3 to 18% by weight of the complexing agent sodium citrate, the ratio of zeolite (calculated as anhydrous active substance) to sodium citrate (calculated as dihydrate) 2.5: 1 to 6: 1 is. The agents have a washing performance that is comparable to the washing performance of agents that contain zeolite and polyacrylates as builders.

From German patent application 40 22 005 it is known that agents which contain the complexing agent citrate and polyacrylate or copolymers of acrylic acid as builders have a better performance with regard to graying and the fabric ash than agents which contain only zeolite or a mixture of zeolite and phosphate have as a builder.

It has now been found that phosphate-free agents which contain certain complex-forming polyhydroxycarboxylic acids or their salts or mixtures thereof have a primary washing power which is comparable to the primary washing power of citrate-containing agents, the secondary washing power of these agents having great advantages over the citrate-containing agents.

Accordingly, the invention relates in a first embodiment to a phosphate-free washing and cleaning agent, in particular a textile detergent, which contains zeolite and / or crystalline phyllosilicates of the general formula (I) NaMSi _x O _{2x + 1} .yH₂O, 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 contains as complexing agent polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts with 4 to 6 carbon atoms and at least 2 hydroxyl groups per molecule or mixtures of these acids and / or salts . The content of the builders in the builders zeolite and / or crystalline phyllosilicates of the general formula (I) is 15 to 60% by weight, the weight ratio builders to polyhydroxydicarboxylic acid or polyhydroxydicarboxylic acid salt or mixtures of these acids and / or salts 30: 1 is up to 1: 1.

In a further embodiment, the invention relates to a builder combination which comprises zeolite and / or crystalline phyllosilicates of the general formula (I) NaMSi _x O _{2x + 1} · yH₂O, 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 as complexing agents contain polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts with 4 to 6 carbon atoms and at least 2 hydroxyl groups per molecule or mixtures of these acids and / or salts, the weight ratio of builders to polyhydroxydicarboxylic acid or Polyhydroxydicarboxylic acid salt or mixtures of these acids and / or salts is 30: 1 to 1: 1.

Preferred polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts are those which contain 4 to 6 carbon atoms and have a hydroxyl group on each carbon atom which has no carboxyl group. In particular, there are polyhydroxydicarboxylic acids and polyhydroxydicarboxylic acid salts with 4 carbon atoms and 2 hydroxy groups, such as tartaric acid and tartaric acid salts, and with 6 carbon atoms and 4 hydroxy groups, such as galactaric acid (also called mucic acid or mucic acid) and galactaric acid salts and glucaric acid (also called saccharic acid) and Glucaric acid salts, preferred. Mixtures of the acids, the mono salts and / or the disalts can also be used. The salts are preferably used as sodium or potassium salts. The particularly advantageous polyhydroxydicarboxylic acid salts therefore include the monosodium and disodium salts as well as the monopotassium and dipotassium salts of tartaric acid, galactaric acid and D-glucaric acid.

The zeolites are used in the usual hydrated, finely crystalline form. Their water content is preferably between 19 and 22% by weight. They have practically no particles larger than 30 μm and preferably consist at least 80% of particles smaller than 10 μm. Their calcium binding capacity, which is determined according to the information in German patent application 24 12 837, is in the range from 100 to 200 mg CaO / g. Zeolite NaA is particularly suitable, as is zeolite NaX and mixtures of NaA and NaX. Quantities and weight ratios that relate to the builder zeolite are included in this Unless otherwise stated, the invention relates to an anhydrous active substance.

-Natriumdisilikate Na₂Si₂O₅·yH₂O bevorzugt, wobei β-Natriumdisilikat beispielsweise nach dem Verfahren erhalten werden kann, das in der deutschen Patentanmeldung 39 39 919 beschrieben ist.Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula (I) NaMSi _x O _{2x + 1} · yH₂O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from Is 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application 164 514. Preferred crystalline sheet silicates of the formula (I) are those in which M represents sodium and x assumes the values 2 or 3. In particular, both are

-Sodium disilicate Na₂Si₂O₅ · yH₂O preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in German patent application 39 39 919.

The agents or builders combinations according to the invention can also contain mixtures of zeolite and the crystalline sheet silicates of the general formula (I), the mixing ratio being arbitrary. However, zeolite is preferably used either alone or in a zeolite to crystalline layered silicate (I) weight ratio of from 10: 1 to 1: 3 and in particular from 3: 1 to 1: 1.

The agents or builders combinations according to the invention contain the builders zeolite and / or crystalline layered silicates (I) and the complexing agents polyhydroxydicarboxylic acid or polyhydroxydicarboxylic acid salt or mixtures of these acids and / or salts advantageously in a weight ratio of 20: 1 to 1: 1, preferably 10 : 1 to 1.5: 1 and especially from 5: 1 to 1.5: 1.

The detergents and cleaning agents according to the invention, in particular the textile detergents, are preferably in granular form. Advantageous agents contain 15 to 50% by weight of zeolite and / or crystalline layered silicates (I) and 1 to 20% by weight of polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts with 4 to 6 carbon atoms and at least 2 hydroxyl groups per molecule, such polyhydroxydicarboxylic acids or Polyhydroxydicarboxylic acid salts are preferred in which each carbon atom, which does not carry a carboxyl group, has a hydroxyl group. Agents which contain 18 to 40% by weight, in particular 20 to 35% by weight, of zeolite are particularly preferred, the weight ratio of zeolite to polyhydroxydicarboxylic acid or polyhydroxydicarboxylic acid salt or mixtures of these acids and / or salts 20: 1 to 1: 1, preferably 10: 1 to 1.5: 1 and in particular 5: 1 to 1.5: 1. In particular, those agents have advantages which contain 2 to 15% by weight and preferably 4 to 12% by weight of galactaric acid or galactaric acid salt, glucaric acid or glucaric acid salt, tartaric acid or tartaric acid salt or mixtures of these acids and / or salts .

The detergents and cleaning agents according to the invention can also contain other conventional builders and complexing agents, for example phosphonates, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is used for ecological reasons is not objectionable, as well as mixtures of these and (co) polymeric polycarboxylic acids or polycarboxylates such as 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), in particular those of acrylic acid with Methacrylic acid and the acrylic acid or methacrylic acid with maleic acid are preferred, additionally contained. However, these additional builders and complexing agents do not further contribute to the significant improvement of the secondary washing ability.

Phosphonates, preferably the neutral sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and diethylene triamine pentamethylene phosphonate, are frequently used as enzyme or bleach stabilizers in amounts of 0.1 to 1.5% by weight. However, it has been shown that the primary washing performance and the bleach and enzyme stability of the agents according to the invention are not increased by the use of phosphonates. The secondary washing power of the agents according to the invention has risen to such an extent through the use of the polyhydroxydicarboxylic acids or their salts that the use of phosphonates can be dispensed with without loss of performance. Therefore, agents that do not contain phosphonates are preferred contain. The same applies to the (co) polymeric polycarboxylic acids or polycarboxylates usually used in washing and cleaning agents, in particular to the 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 and their relative molecular weight, based on free acids, is generally from 5,000 to 200,000, preferably from 10,000 to 120,000 and in particular from 50,000 to 100,000. Therefore, agents are preferred which do not contain (co) polymeric polycarboxylic acids or polycarboxylates. In particular, agents are preferred which contain neither phosphonate nor (co) polymeric polycarboxylates.

Surprisingly, it was found that the agents according to the invention, which contain polyhydroxydicarboxylic acids, polyhydroxydicarboxylic acid salts or mixtures thereof as complexing agents, compared to an agent which contains polyhydroxytricarboxylic acids or polyhydroxytricarboxylic acid salts, such as citric acid or citrate, instead of the complexing agents according to the invention, have a significantly higher secondary washing performance exhibit. The additional use of citric acid or citrate does not result in any further significant improvements in the secondary washing capacity, so that particularly preferred agents are free from citric acid or citrate.

The builders combinations according to the invention can also contain further constituents, for example inorganic salts which react alkaline or neutral in water. In particular, however, it is preferred that the builder combinations are sprayed with liquid to wax-like components, for example silicone oils and paraffin oils, but preferably with nonionic surfactants.

In addition to the ingredients mentioned, the agents according to the invention can contain known additives commonly used in detergents and cleaning agents, for example surfactants, bleaching agents and bleach activators, salts which have an alkaline reaction in water, solubility improvers such as conventional hydrotropes or polyalkylene glycols, for example polyethylene glycols, foam inhibitors, optical brighteners, enzymes, enzyme stabilizers , contain small amounts of neutral filling salts as well as colors and fragrances, opacifiers or pearlescent agents.

The content of the agents in anionic and nonionic surfactants including soap is preferably 10 to 35% by weight, advantageously 12 to 28% by weight and in particular 15 to 25% by weight.

Examples of surfactants of the sulfonate type are C₉-C₁₃ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C₁₂-C₁₈ monoolefins with terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkali or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C₁₂-C₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates) are also suitable. In particular, esters of α-sulfo fatty acids which are produced by α-sulfonation of the alkyl esters of fatty acids of plant and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts are suitable. These are preferably the α-sulfonated esters of hydrogenated coconut, palm kernel or tallow fatty acids, and sulfonation products of unsaturated fatty acids, for example oleic acid, are also present in small amounts, preferably in amounts not above about 2 to 3% by weight could be. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters. The methyl esters of α-sulfofatty acids (MES) are used with particular advantage. 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 in their industrial production as an aqueous mixture with limited amounts of di-salts. Mixtures of mono-salts and di-salts with other surfactants, for example with alkylbenzenesulfonate, are also preferred.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol 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, stearic acid or behenic acid. If one starts from fats and oils, i.e. natural mixtures of different fatty acid glycerol esters, it is necessary to largely saturate the starting products with hydrogen in a manner known per se, i.e. to harden to iodine numbers less than 5, advantageously less than 2. Typical examples of suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, 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 application WO 91/9009 is specified.

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

Also suitable are alkanesulfonates made from C₁₂-C₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization can be obtained. The sulfonate group is statistically distributed over the entire carbon chain, with the secondary alkanesulfonates predominating.

Suitable sulfate-type surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, especially from fatty alcohols, e.g. from tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C₁₀-C₂₀ oxo alcohols, and those secondary alcohols of this chain length. The sulfuric acid monoesters of alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C₉-C₁₁ alcohols with an average of 3.5 moles of ethylene oxide, are suitable. Preferred fatty alkyl sulfates are derived from fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil, which additionally contain proportions of unsaturated alcohols, e.g. of oleyl alcohol. Mixtures in which the proportion of the alkyl radicals are 50 to 70% by weight on C₁₂, 18 to 30% by weight on C₁₄, 5 to 15% by weight on C₁₆, less than 3% are preferred. -% on C₁₀ and less than 10 wt .-% are distributed on C₁₈.

Likewise preferred anionic surfactants are 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 especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C₈ to C₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred.

Preferred granular detergents and cleaning agents contain, as anionic surfactants, alkylbenzenesulfonates and / or alkyl sulfate, preferably fatty alkyl sulfate, and / or sulfated fatty acid glycerol esters, the weight ratio of sulfated fatty acid glycerol esters to alkylbenzenesulfonate and / or alkyl sulfate 1: 9 to 4: 1 and in particular 2: 5 to 2 : 1 is.

Other suitable anionic surfactants are, in particular, soaps, preferably in amounts from 0.2 to 8 and in particular from 0.5 to 5% by weight. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. In particular, such soap mixtures are preferred which are composed of 50 to 100 wt .-% of saturated C₁₂-C₂₄ fatty acid soaps and 0 to 50 wt .-% of oleic acid soap.

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

In a further preferred embodiment, the granular detergents and cleaning agents also contain nonionic surfactants in addition to the anionic surfactants, preferably in amounts of 1 to 15% by weight, in particular in amounts of 2 to 12% by weight.

The nonionic surfactants used are preferably liquid ethoxylated and / or propoxylated alcohols which are derived from primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 mol of alkylene oxide, in which the alcohol radical can be linear or methyl-branched in the 2-position, or linear and May contain methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals. In particular, linear residues of alcohols of native origin with 12 to 18 carbon atoms are preferred, e.g. made from coconut, tallow or oleyl alcohol. In particular, C₁₂-C₁₄ alcohols with 3 E0 or 4 E0, C₉-C₁₁ alcohol with 7 E0, C₁₃-C₁₅ alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C₁₂-C₁₈ alcohols with 3 E0, 5 E0 or 7 E0 and mixtures of these, such as mixtures of C₁₂-C₁₄ alcohol with 3 E0 and C₁₂-C₁₈ alcohol with 5 E0.

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 on (narrow range ethoxylates, NRE). In particular, alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.

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 aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms branched in the 2-position and G denotes 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.

Other suitable ingredients of the granular agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous or crystalline silicates or mixtures of these; in particular, alkali carbonate and alkali silicate, especially sodium silicate with a molar ratio Na₂O: SiO₂ from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used. The sodium silicate content of the agents is generally up to 10% by weight, preferably between 2 and 8% by weight and in particular 2 to 5% by weight. However, agents containing sodium and / or potassium carbonate in amounts of up to about 20% by weight, advantageously between 2 and 15% by weight and in particular between 5 and 14% by weight, are particularly preferred.

Of the compounds used as bleaching agents, which supply H₂O₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H₂O₂-delivering peracidic salts or peracids, such as perbenzoates, peroxaphthalates, 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, with perborate monohydrate being advantageously 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 this are organic peracids with H₂O₂ forming N-acyl or O-acyl compounds, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. The bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.

Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying. Water-soluble colloids, mostly of an 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, carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition, are preferably used.

The foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a reduction can also be achieved by adding non-surfactant-like substances. A reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, for example sulfates and / or sulfonates with nonionic surfactants and / or with soaps. In the case of soaps, the foam-suppressing effect increases with the degree of saturation and the C number of the fatty acid salt. Soaps of natural or synthetic origin that contain a high proportion of C₁₈-C₂₄ fatty acids are therefore suitable as foam-inhibiting soaps. 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. Mixtures of various foam inhibitors are also advantageously used, for example those made of silicone, paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Their proportion can be about 0.2 to about 2% by weight. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.

In addition, the agents can contain enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H₃BO₃), metaboric acid (HBO₂) and pyroboric acid (tetraboric acid H₂B₄O₇) is particularly advantageous.

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-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which are used instead of Morpholino group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Brighteners of the substituted 4,4'-distyryl-diphenyl type can also be present, for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. It has also been found that uniform white granules are obtained if, apart from the customary brighteners, the agents are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, also in small amounts, for example 10⁻⁶ to 10⁻³% by weight, preferably around 10⁻⁵% by weight, of a blue dye. A particularly preferred dye is Tinolux ^(R) (commercial product from Ciba-Geigy).

The granular washing and cleaning agents according to the invention can have a bulk density between about 300 and 1100 g / l. Granules are preferred which have a bulk density above 450 g / l, in particular between 500 and 1100 g / l.

Both the builders combinations according to the invention and the washing and cleaning agents according to the invention can be prepared in a conventional manner, for example by mixing, granulating, extruding and / or by spray drying an aqueous slurry and optionally subsequently adding temperature-sensitive components. In the case of detergents and cleaning agents, separately manufactured builders combinations in the form of a spray-dried or granulated compound can be used as admixing components with other granular constituents of the detergents and cleaning agents. It is also possible to incorporate the builders and complexing agents into the agents individually in a conventional manner and in any order.

Examples

Granular detergents of the following composition (comparative examples V1 to V3 and agents M1 / 1 to M3 / 2 according to the invention) were prepared and tested in a conventional manner by spray drying. The constituents perborate, bleach activator and enzyme granulate and the complexing agents including the copolymeric polyacrylate and 1-hydroxyethane-1,1-diphosphonate (HEDP) were subsequently mixed in comparative example C3. Basic composition (in parts by weight) Sodium dodecylbenzenesulfonate 7.5 C₁₂-C₁₈ fatty acid soap 1.5 C₁₂-C₁₈ fatty alcohol with 5 E0 4.5 Tallow fatty alcohol with 5 E0 0.8 Zeolite 25.0 sodium 13.2 Sodium silicate (1: 2) 3.5 Magnesium silicate 1.0 Perborate tetrahydrate 25.0 Tetraacetylethylenediamine 3.0 CMC / MC 0.8 opt. Brightener 0.2 Enzyme granules 1.5 Silicone oil 0.5 water 7.5 Sodium sulfate (and other salts from solutions) 4.0

Addition of complexing agents:

The test was carried out under practical conditions in household washing machines. For this purpose, the machines were loaded with 3.5 kg of clean laundry and 0.5 kg of test fabric, some of the test fabric being impregnated with conventional test soiling (for testing the primary washing ability) and some consisting of white fabric (for testing the secondary washing ability). Strips of standardized cotton fabric (Krefeld laundry research institute; 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 CaO / l), amount of detergent used per detergent and machine 146 g, washing temperature 25 to 90 ° C (heating time 60 minutes, 15 minutes at 90 ° C), liquor ratio (kg laundry: liter Wash water in the main wash cycle) 1: 5,7, rinse 4 times with tap water, spin off and dry.

The primary washing performance of agents V1 to V3 and M1 / 1 or M1 / 2 to M3 / 1 or M3 / 2 were comparable. There were also no significant differences in the graying of the fabrics.

After 25 washing cycles, the ash content of the textile samples was determined quantitatively. The agents M1 / 1 or M1 / 2 to M3 / 1 or M3 / 2 according to the invention showed, on average, better ash contents than all the comparative examples V1 to V3.

Analogous results have been obtained with agents which have been produced by granulation or extrusion and / or which contain another surfactant base. Wt% ash FT BN B WFK φ Initial value 0.25 0.46 0.19 0.99 0.47 V1 2.75 4.61 1.94 8.83 4.53 M1 / 1 0.80 1.04 0.50 3.10 1.36 M2 / 1 0.97 1.11 0.41 3.20 1.42 M3 / 1 0.85 0.72 0.51 2.17 1.06 V2 2.73 3.69 1.70 7.81 3.98 M1 / 2 0.74 0.84 0.51 2.75 1.21 M2 / 2 1.17 1.07 0.64 3.27 1.53 M3 / 2 1.13 0.80 0.63 2.72 1.32 V3 1.22 1.76 2.34 6.09 2.85 % By weight of total incrustation B WFK φ Initial value 1.99 2.69 2.34 V1 9.10 15.44 12.52 M1 / 1 2.64 5.62 4.13 M2 / 1 2.80 6.05 4.42 M3 / 1 2.16 4.50 3.33 V2 7.90 13.60 10.75 M1 / 2 2.33 5.49 3.91 M2 / 2 2.69 6.05 4.37 M3 / 2 2.18 4.87 3.52 V3 3.78 8.81 6.29

When determining the ashes, the combustion of organic constituents usually results in a lower value than the actual incrustation. As a control, the total incrustation was therefore also determined (1st weighing of the untreated fabric, 2nd weighing of the fabric after 25 washing cycles, 3rd weighing of the fabric after extraction with EDTA, 4th determination of the so-called "soluble ash" from the difference in weighing 2 and 3rd, 5th ashing of the extracted tissue to determine the residual ash, 6. determination of the total incrustation (sum of soluble ash and residual ash)).

Claims (17)

1. A detergent, more particularly a laundry detergent, containing zeolite and/or crystalline layer silicates corresponding to general formula (I): NaMSi_xO_2x+1·yH₂O, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, as phosphate-free builders together with complexing agents, characterized in that it contains the builders in quantities of 15 to 60% by weight and complexing agents selected from polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts containing 4 to 6 carbon atoms and at least 2 hydroxy groups per molecule or mixtures of these acids and/or salts, the ratio by weight of builders to polyhydroxydicarboxylic acid or polyhydroxydicarboxylic acid salt or mixtures of these acids and/or salts being 30:1 to 1:1.
2. A detergent as claimed in claim 1, characterized in that it contains 15 to 50% by weight of zeolite and/or crystalline layer silicates and 1 to 20% by weight of polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts containing 4 to 6 carbon atoms, each carbon atom that does not carry a carboxyl group bearing a hydroxy group.
3. A detergent as claimed in claim 1 or 2, characterized in that it contains 10 to 35% by weight, preferably 12 to 28% by weight and more preferably 15 to 25% by weight of anionic and nonionic surfactants, including soap, and 18 to 40% by weight and preferably 20 to 35% by weight of zeolite, the ratio by weight of zeolite to polyhydroxydicarboxylic acid or polyhydroxydicarboxylic acid salt or mixtures of these acids and/or salts being 20:1 to 1:1, preferably 10:1 to 1.5:1 and more preferably 5:1 to 1.5:1.
4. A detergent as claimed in any of claims 1 to 3, characterized in that it contains 2 to 15% by weight and preferably 4 to 12% by weight of galactosaccharic acid or galactosaccharic acid salt, glucaric acid or glucaric acid salt, tartaric acid or tartaric acid salt or mixtures of these acids and/or salts.
5. A detergent as claimed in any of claims 1 to 4, characterized in that it does not contain any phosphonates.
6. A detergent as claimed in any of claims 1 to 5, characterized in that it does not contain any (co)polymeric polycarboxylic acids or polycarboxylates.
7. A detergent as claimed in any of claims 1 to 6, characterized in that it does not contain any citrate.
8. A detergent as claimed in any of claims 1 to 7, characterized in that it contains sodium carbonate and/or potassium carbonate in quantities of 2 to 15% by weight and preferably in quantities of 5 to 14% by weight.
9. A detergent as claimed in any of claims 1 to 8, characterized in that it has an apparent density of 300 to 1100 g/l and preferably 500 to 1000 g/l.
10. A builder combination containing builders and a complexing agent, characterized in that it contains zeolite and/or crystalline layer silicates corresponding to general formula (I): NaMSi_xO_2x+1·yH₂O, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, as builders and polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts containing 4 to 6 carbon atoms and at least 2 hydroxy groups per molecule or mixtures of these acids and/or salts as complexing agents, the ratio by weight of builders to polyhydroxydicarboxylic acid or polyhydroxydicarboxylic acid salt or mixtures of these acids and/or salts being 30:1 to 1:1.
11. A builder combination as claimed in claim 10, characterized in that it contains polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts with 4 to 6 carbon atoms which contain a hydroxy group at each carbon atom that does not carry a carboxyl group, the ratio by weight of builders, more particularly zeolite, to polyhydroxydicarboxylic acid or polyhydroxydicarboxylic acid salt or mixtures of these acids and/or salts being 20:1 to 1:1, preferably 10:1 to 1.5:1 and more preferably 5:1 to 1.5:1.
12. A builder combination as claimed in claim 10 or 11, characterized in that it contains galactosaccharic acid or galactosaccharic acid salt, glucaric acid or glucaric acid salt, tartaric acid or tartaric acid salt or mixtures of these acids and/or salts as the polyhydroxydicarrboxylic acids or polyhydroxydicarboxylic acid salts.
13. A builder combination as claimed in any of claims 10 to 12, characterized in that the builder combination is sprayed with liquid to wax-like components, preferably with nonionic surfactants.
14. A process for the production of a builder combination containing zeolite and/or crystalline layer silicates corresponding to general formula (I): NaMSi_xO_2x+1. yH₂O, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, as builders and polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts with 4 to 6 carbon atoms and at least 2 hydroxy groups per molecule or mixtures of these acids and/or salts as complexing agents, characterized in that the builder combination is produced by mixing, granulation and/or by spray drying.
15. A process for the production of the granular detergent claimed in any of claims 1 to 9, characterized in that the granules are produced by spray drying.
16. A process for the production of the granular detergent claimed in any of claims 1 to 9, characterized in that the granules are produced by granulation or extrusion.
17. A process for the production for the granular detergent claimed in any of claims 1 to 9, characterized in that the builder combination of zeolite and/or crystalline layer silicates corresponding to general formula (I): NaMSi_xO_2x+1· yH₂O, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, and polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts containing 4 to 6 carbon atoms and at least 2 hydroxy groups or mixtures of these acids and/or salts is used in the form of a spray-dried or granulated compound for mixing with other granular constituents of detergents.