DE4228044A1 - 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, the phosphate-free Contains builders and complexing agents, as well as a phosphate-free scaffold fabric combination and a process for their preparation.

In practice, as phosphate substitutes in detergents and cleaners zeolite, especially zeolite NaA, and mixtures of zeolite lith with alkali silicates and carbonates and polymeric polycarboxylates used. There are also complexing agents such as the nitrilotri salts acetic acid (NTA), ethylenediaminetetraacetic acid (EDTA) and the phos phonsäuren. The most selective complexing agents have the task of Heavy metal ions, which even in trace a very negative impact on to have the wash process eliminated (Ullmann, 1987, Vol. 8, p 351 to 354). Of the phosphonates is known that they also the Aus Precipitation of sparingly soluble calcium salts and thus by sparingly soluble Calcium salts caused incrustation and graying of the tissue counteract ("use of phosphonates in liquid detergents", M. Paladini, G. Schnorbus, Soap-Oils-Fat-Waxes, Volume 115 (1989), Pages 508 to 511). Finally, the combined use of Phos phonates and copolymers based on acrylic acid and maleic acid in Ver like formulations containing only one of these two components maintain a higher whiteness of textiles ("use of phosphonates in Low Phosphorus Household Detergents (1%) ", M. Paladini, G. Schnorbus, soap-oil-grease waxes, Volume 114 (1988), pages 756 bis 760).

European Patent Application 291,869 describes phosphate-free scaffold fabric combinations of zeolite, aminoalkane polyphosphonate, 1-hydroxyethane 1,1-diphosphonate (HEDP) and polymeric polycarboxylate, with certain  Weight ratios of the last three components be a synergism show the prevention of the formation of Faserinkrustationen.

European patent application 448 298 describes detergents which are known as Builder Zeolite and 3 to 18 wt .-% of the complexing agent sodium citrate contains, the ratio of zeolite (calculated as anhydrous Active substance) to sodium citrate (calculated as dihydrate) 2.5: 1 to 6: 1 be wearing. The funds have a washing performance, with the washing performance comparable to funds used as builders Zeolite and Polyacry late included.

From the German patent application 40 22 005 it is known that means, wel as a builder the complexing agent citrate and polyacrylate or Copolymers of acrylic acid, perform better in terms of Graying and tissue ash have as an agent, the only zeolite or a mixture of zeolite and phosphate as builder.

It has now been found that phosphate-free compositions which certain kom plexbildende polyhydroxycarboxylic acids or their salts or mixtures of contain a primary washing power that matches the primary washing capacity citrate-containing agent is comparable, with the secondary The washing power of these agents has high advantages over the citrate-containing ones Has means.

The invention accordingly provides in a first embodiment form a builder combination, which as builders zeolite and / or crystalline phyllosilicates of the general formula (I) NaMSi _x O _{2x + 1} · yH ₂ O, 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 as complexing agents polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts having 4 to 6 carbon atoms and at least 2 hydroxyl groups per molecule or mixtures of these acids and / or salts, wherein the weight ratio Framework materials to polyhydroxydicarboxylic acid or polyhydroxydicarboxylic acid salt or mixtures of these acids and / or salts 30: 1 to 1: 1.

The invention in another embodiment, a phos phatfreies detergent and cleaner, in particular a Textilwaschmit tel, as builders zeolite and / or crystalline phyllosilicates of the general formula (I) 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 as complexing polyhydroxydicarboxylic or Polyhydroxydi carboxylic acid salts having 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 agents in the builders zeolite and / or crystalline sheet silicates of the general formula (I) is 15 to 60 wt .-%, wherein the weight ratio of builders to polyhydroxydicaric acid or polyhydroxydicarboxylic acid salt or mixtures of these acids and / or salts 30: 1 to 1: 1.

Preferred polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts are those containing 4 to 6 carbon atoms and on each carbon atom having no carboxyl group, a hydroxy group. In particular, in this case, polyhydroxydicarboxylic acids and polyhydroxydi are used carboxylic acid salts of 4 carbon atoms and 2 hydroxy groups, such as wine acid and tartaric acid salts, and having 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. It also mixtures of acids, the Monosalts and / or the Disalze be used. The salts are present preferably used as sodium or potassium salts. Especially for those Partial polyhydroxydicarboxylic acid salts therefore include the monosodium salts and disodium salts as well as the monopotassium and dipotassium salts of wine acid, galactaric acid and D-glucaric acid.

The zeolites come in the usual hydrated, finely crystalline form for use. Their water content is preferably between 19 and 22 Wt .-%. They have virtually no particles larger than 30 microns and be are preferably at least 80% smaller in size than 10 μm. Their calcium binding capacity, which according to the data of the German Patent Application 24 12 837 is in the range of 100 to 200 mg CaO / g. Particularly suitable is the zeolite NaA, and also the  Zeolite NaX and mixtures of NaA and NaX. Quantities and weight conditions that affect the builder zeolite are in the context this invention - unless otherwise stated - to anhydrous Based on active substance.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula (I) 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 one Number is from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline sheet silicates are described, for example, in European Patent Application 164 514. Preferred crystalline layered silicates of the formula (I) are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O₅ · yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in German Patent Application 39 39 919.

The builder combinations according to the invention can also be mixtures of Zeolite and the crystalline layered silicates of the general formula (I) contain, wherein the mixing ratio is arbitrary. Preferably however, zeolite either alone or in a zeolite weight ratio crystalline layered silicate (I) of 10: 1 to 1: 3 and in particular of 3: 1 used up to 1: 1.

The builder combinations according to the invention contain the Ge Builders zeolite and / or crystalline phyllosilicates (I) and the Kom Plexbildner polyhydroxydicarboxylic acid or polyhydroxydicarboxylic acid salt or mixtures of these acids and / or salts advantageously in a weight ratio of from 20: 1 to 1: 1, preferably from 10: 1 to 1.5: 1 and in particular from 5: 1 to 1.5: 1.

The detergents and cleaners according to the invention, in particular the Tex til detergents, are preferably in granular form. advantageous Agents contain 15 to 50 wt .-% zeolite and / or crystalline layer silicates (I) and 1 to 20 wt .-% polyhydroxydicarboxylic acids or polyhydro xydicarboxylic acid salts having 4 to 6 carbon atoms and at least 2 hydro  xy groups per molecule, such polyhydroxydicarboxylic acids or poly hydroxydicarboxylic acid salts are preferred in which each carbon atom, which bears no carboxyl group, has a hydroxyl group. Especially preferred are agents which 18 to 40 wt .-%, in particular 20 to 35 Wt .-%, zeolite, wherein the weight ratio of zeolite to poly hydroxydicarboxylic 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 especially 5: 1 to 1.5: 1. These are in particular Such agents having advantages, which 2 to 15 wt .-% and before preferably 4 to 12% by weight of galactaric acid or galactaric acid salt, Glucar acid or glucaric acid salt, tartaric acid or tartaric acid salt or mixtures from these acids and / or salts.

Although the washing and cleaning agents according to the invention may still further conventional builders and complexing agents, for example phosphonates, the preferably in the form of their sodium salts used polycarboxylic acids, such as Citric acid, adipic acid, succinic acid, glutaric acid, aminocarboxylic acid nitrilotriacetic acid (NTA), if such an application from ecolog for technical reasons, as well as mixtures of these and (co) polymeric polycarboxylic acids or polycarboxylates, such as the sodium salts the polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 800 to 150000 (based on acid), wherein in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid are preferred, in addition. However, these additionally used builders and complexing agents contribute not continue to significantly improve the secondary washing power at.

Phosphonates, preferably the neutral reacting sodium salts for example, 1-hydroxyethane-1,1-diphosphonate and diethylenetriamine pentamethylene phosphonate are often used as enzyme or bleach stabilizers used in amounts of 0.1 to 1.5 wt .-%. However, it has been shown that the primary washing performance as well as the bleach and enzyme stability the means according to the invention by the use of phosphonates not he be raised. The secondary washing capacity of the agents according to the invention is by the use of polyhydroxydicarboxylic acids or their salts in such a way  increased that on the use of phosphonates without sacrificing performance can be waived. Therefore, agents which are not phosphonates are preferred contain. The same applies to the usual in washing and cleaning used referred to (co) polymeric polycarboxylic acids or poly Carboxylates, in particular for the copolymers of acrylic acid with maleic acid containing 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid and their molecular weight relative to free acids in the general 5000 to 200000, preferably 10000 to 120000 and in particular from 50,000 to 100,000. Therefore, agents are also preferred contain no (co) polymeric polycarboxylic acids or polycarboxylates. in the particular preference is given to those agents which contain neither phosphonate nor (co-) contain polymeric polycarboxylates.

Surprisingly, it has been found that the agents according to the invention, as complexing agents polyhydroxydicarboxylic, Polyhydroxydicarbonsäu resalts or mixtures of these, compared to a co-containing tel, which instead of the complexing agent according to the invention Polyhydroxytricar Bonsäuren or Polyhydroxytricarbonsäuresalze such as citric acid or Ci contains a significant, with the same primary washing performance have higher secondary washing effect. Due to the additional use of Citric acid or citrate are no significant significant Improvements of the secondary washing power achieved, so that particularly be preferred means are free of citric acid or citrate.

The builder combinations according to the invention can be further Be contain constituents, for example inorganic, alkaline in water or neutral salts. In particular, however, it is preferred that the builder combinations with liquid to waxy components, For example, silicone oils and paraffin oils, but preferably with nonionic surfactants are sprayed.

In addition to the ingredients mentioned, the compositions of the invention known, commonly used in detergents and cleaners Ingredients, for example surfactants, bleaching agents and bleach activators, in Water alkaline salts, Löslichkeitsverbesserer as conven Liche hydrotropes or polyalkylene glycols, for example polyethylene glycol  kole, foam inhibitors, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filler salts as well as dyes and fragrances, Trü or pearlescent agent.

The content of the agents in anionic and nonionic surfactants Finally, soap is preferably 10 to 35 wt .-%, more advantageous Wise 12 to 28 wt .-% and in particular 15 to 25 wt .-%.

Examples of suitable surfactants of the sulfonate type are C ₉ -C ₁₃ -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates, such as are obtained, for example, from C ₁₂ -C ₁₈ -monoolefins having terminal or internal double bonds Sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained, into consideration. Also suitable are alkane sulfonates which are obtained from C ₁₂ -C ₁₈ -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfo fatty acids (Estersul fonate). In particular, esters of α-sulfo fatty acids, which are prepared by α-sulfonation of the alkyl esters of fatty acids of plant and / or animal origin having 8 to 20 carbon atoms in the fatty acid molecule and following neutralization to water-soluble mono-salts, come into consideration. These are preferably the α-sulfonated esters of hydrogenated coconut, palm kernel or tallow fatty acids, although sulfonation of unsaturated fatty acids, for example Ölsäu re, in small amounts, preferably in amounts not above about 2 to 3 wt .-%, can be present. In particular, preferred are α-sulfofatty acid alkyl esters which have an alkyl chain having not more than 4 carbon atoms in the ester group, for example, methyl ester, ethyl ester, propyl ester and butyl ester. With particular advantage, the methyl esters of α-sulfo fatty acids (MES) are used. 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 .alpha.-sulfofatty acid alkyl esters fall as early as their industrial production as an aqueous mixture with limited amounts of di-salts. Mixtures of mono-salts and di-salts with further surfactants, for example with alkylbenzenesulfonate, are also preferred.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Un fatty acid glycerol esters are the mono-, di- and triesters and their Mixtures to understand how they are produced by esterification a monoglycerine with 1 to 3 moles of unsaturated fatty acid or in the Um esterification of unsaturated triglycerides with 0.3 to 2 moles of glycerol to hold. Preferred sulfated fatty acid glycerol esters are the Sulfur 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 you go there of fats and oils, so natural mixtures of different fat acid glycerol esters, it is necessary to prepare the feedstock the sulfonation in a conventional manner with hydrogen largely from to saturate, d. H. to iodine numbers less than 5, advantageously less than 2 to cure. Typical examples of suitable starting materials are palm oil, palm kernel oil, palm stearin, olive oil, rapeseed oil, coriander oil, sunflower oil, tree wollseaatöl, peanut oil, linseed oil, lard oil or lard. Because of her However, it has proved to be a high natural content of saturated fatty acids proved particularly advantageous from coconut oil, palm kernel oil or beef tallow go out. The sulfation of saturated fatty acids with 6 to 22 Koh lenstoffatomen or mixtures of fatty acid glycerol esters with iodine less than 5 containing fatty acids of 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 inter national patent application WO 91/9009.

The sulfonation products represent a complex mixture that is essentially Mono-, di- and triglyceride sulfonates with α-standing and / or Innenstän contains a th sulphonic acid grouping. By-products form sulfonated fatty acid salts, glyceride sulfates, glycerol sulfates, glycerol and Soap. If one goes in the sulfation of saturated fatty acids or ge hardened Fettsäureglycerinestergemischen, so the proportion of α sulfonated fatty acid Disalze depending on the procedure well to about 60 wt .-% amount.

Also suitable are alkanesulfonates which are obtained from C ₁₂ -C ₁₈ -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The sulfonate group is distributed randomly over the entire carbon chain, with the secondary alkanesulfonates predominating.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols of natural and synthetic origin, in particular of fatty alcohols, eg. Example, from tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ₁₀ -C ₂₀ -oxo alcohols, and those of secondary alcohols of this chain length. Also, the sulfuric monoesters of ethoxylated with 1 to 6 moles of ethylene oxide alcohols, such as 2-methyl-branched branched C ₉ -C ₁₁ alcohols having an average of 3.5 moles of ethylene oxide, ge are suitable. Preferred fatty alkyl sulfates are derived from fatty alcohol mixtures obtained from coconut oil, palm oil and palm kernel oil, which additionally contain amounts of unsaturated alcohols, eg. B. of oleyl alcohol may contain, from. A preferred use are mixtures in which the proportion of Al kylreste to 50 to 70 wt .-% to C ₁₂ , to 18 to 30 wt .-% to C ₁₄ , to 5 to 15 wt .-% to C ₁₆ , less than 3% by weight to C ₁₀ and less than 10% by weight to C ₁₈ .

Likewise preferred anionic surfactants are the salts of alkyl sulfosuccinic acids which are also characterized as sulfosuccinates or as sulfosuccinic 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 C ₈ to C ₁₈ fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.

Preferred granular detergents and cleaners contain as anionic Surfactants Alkylbenzenesulfonates and / or alkylsulfate, preferably Fatty alkyl sulfate, and / or sulfated fatty acid glycerol esters, wherein the Ge Weight ratio sulfated Fettsäureglycerinester to alkylbenzenesulfonate  and / or alkyl sulfate 1: 9 to 4: 1 and in particular 2: 5 to 2: 1 be wearing.

As further anionic surfactants are in particular soaps, preferably in amounts of from 0.2 to 8 and in particular from 0.5 to 5 wt .-%, into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, for. As coconut, palm kernel or tallow fatty acids, derived soap mixtures. In particular, those soap mixtures are preferred which are composed of 50 to 100 wt .-% of saturated C ₁₂ -C ₁₈ fatty acid soaps and 0 to 50 wt .-% of oleic acid soap.

The anionic surfactants may be in the form of their sodium, potassium or ammo niumsalze and as soluble salts of organic bases, such as mono-, di- or Triethanolamine. Preferably, the anionic surfactants are in Form their sodium or potassium salts.

In a further preferred embodiment, the granular contain Detergents and cleaners in addition to the anionic surfactants as well nonionic surfactants, preferably in amounts of 1 to 15 wt .-%, in particular in amounts of 2 to 12 wt .-%, included.

As nonionic surfactants are preferably liquid ethoxylated and / or propoxylated alcohols derived from primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles Alky lenoxid in which the alcohol radical may be methyl linear or linear in the 2-position, respectively may contain linear and methyl-branched radicals in the mixture, as usually present in oxo alcohol residues. In particular, however, linear radicals of alcohols of native origin having 12 to 18 carbon atoms are preferred, such as. B. from coconut oil, tallow or oleyl alcohol. In particular, 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 used.

The stated degrees of ethoxylation represent statistical averages, which for a particular product may be a whole or a fractional number can. Preferred alcohol ethoxylates have a restricted Homologenver division (narrow range ethoxylates, NRE). In particular, are alcohol ethoxylates which average 2 to 8 ethylene oxide groups respectively.

In addition, as other nonionic surfactants and alkyl glycosides of the general formula RO (G) _x are used in which R is a primary ge radkettigen or methyl-branched in the 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably 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 metal carbonate and alkali metal silicate, above all sodium silicate with a molar ratio of Na ₂ O: SiO _{2 of} from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used. The content of the sodium silicate compositions is generally up to 10% by weight, preferably between 2 and 8% by weight and in particular from 2 to 5% by weight. However, particularly preferred are agents containing sodium and / or potassium carbonate in amounts up to about 20 wt .-%, advantageously between between 2 and 15 wt .-% and in particular between 5 and 14 wt .-%.

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, such as H ₂ O _2- delivering peracidic salts or peracids, such as perbenzoates, peroxaphthalates, diperazelaic acid or diperdodecanedioic acid. The content of the bleaching agent is preferably 5 to 25 wt .-% and in particular 10 to 20 wt .-%, wherein advantageously perborate monohydrate is 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 thereof are N-acyl or O-acyl compounds which form organic peracids with H ₂ O ₂ , preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols, such as glucose pentaacetate. The content of the bleach-containing agents in bleach activators is in the usual range, preferably between 1 and 10 wt .-% and in particular between 3 and 8 wt .-%. 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 removing the fiber To keep dirt suspended in the liquor and thus to prevent graying prevent. For this purpose, water-soluble colloids are mostly organic in nature is suitable, 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 esters of Cellulose or starch. Also water-soluble, containing acidic groups Polyamides are suitable for this purpose. Furthermore, can be soluble Use starch preparations and other than the starch products mentioned above, z. B. degraded starch, aldehyde levels, etc. , Also polyvinylpyrrolidone is useful. However, preference is given to carboxymethylcellulose (Na salt), Methylcellulose, methylhydroxyethylcellulose and mixtures thereof as well Polyvinylpyrrolidone, for example in amounts of 0.1 to 5 wt .-%, be relied on the funds, used.

The foaming power of the surfactants can be increased or decreased by combining suitable surfactant types; a reduction can just be achieved by adding additives nichttensidartiger. A verrin siege foaming, which is desirable when working in machines, it is often enough by combining different types of surfactants, eg. As sulfates and / or sulfonates with nonionic surfactants and / or with soaps. For soaps, the foam-damping effect increases with the degree of saturation and the C number of the fatty acid salt. Suitable foam-inhibiting soaps are therefore those soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanier ter silica. Advantageously, mixtures of different foam inhibitors are used, for. As those of silicones, paraffins or waxes. Preferably, the foam inhibitors are bound to a granular, water-soluble or dispersible carrier substance.

Enzymes are those from the class of proteases, lipases, amylases, Cellulases or mixtures thereof in question. Especially suitable are Bacterial strains or fungi, such as Bacillus subtilis, Bacillus lichenifor mis and Streptomyces griseus derived enzymatic agents. virtue example be proteases of the subtilisin type and in particular proteases, the from Bacillus lentus are used. Their share can be about 0.2 to about 2 wt .-% amount. The enzymes can be adsorbed to carriers and / or embedded in encasing substances to protect them against premature decomposition protect it.

In addition, the agents may contain enzyme stabilizers. For example, 0.5 to 1 wt .-% sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and with a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of Borver compounds, such as boric acid, boron oxide, borax and other Alka limetallboraten such as the salts of orthoboric acid (H ₃ BO ₃ ), the metaboric acid (HBO ₂ ) and the pyroboric acid (tetraboric H ₂ B ₄ O ₇ ).

The agents may contain as optical brighteners derivatives of Diaminostilbendi sulfonic acid or their alkali metal salts. Suitable z. B. salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) stil ben-2,2'-disulfonic acid or compounds of similar construction, the place in place the morpholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted 4,4'-distyryl-di-phenyl type may be present, e.g. As the compound 4,4'-bis (4-chloro-3-sulfosty ryl) -diphenyl. Mixtures of the aforementioned brightener can be used. It has also been found that uniformly white granules he will keep when the means except the usual brighteners in conventional amounts, for example, between 0.1 and 0.5 wt .-%, preferably between 0.1 and 0.3 wt. %, even small amounts, for example 10 ^-6 to 10 ^-3 wt .-%, preferably 10 to ⁵ wt .-%, of a blue dye. A particularly preferred dye is Tinolux® (commercial product of Ciba-Geigy).

The granular detergents and cleaners according to the invention can be Have apparent bulk density between about 300 and 1100 g / l. Here are Gra preferably having a bulk density above 450 g / l, in particular between 500 and 1100 g / l.

Both the builder combinations according to the invention and the inventions Detergents and cleaning agents according to the invention can be used in a conventional manner, for example, by mixing, granulating, extruding and / or by Spray-drying an aqueous slurry and optionally subsequently ßende admixture of temperature-sensitive components made who the. In the case of detergents and cleaners can herge separately presented builder combinations in the form of a spray-dried or granulated compounds as Zumischkomponente to other granular Be components of the washing and cleaning agent are used. Likewise is it is possible to use the builders and complexing agents individually in themselves to incorporate into the means any way and any order.

Examples

Granular detergents of the following composition (comparative Examples V1 to V3 and inventive agents M1 / 1 to M3 / 2) in her conventionally prepared and tested by spray drying. It was wur the ingredients perborate, bleach activator and enzyme granules as well the complexing agents including the copolymeric polyacrylate and 1-Hy droxyethan-1,1-diphosphonate (HEDP) in Comparative Example V3 later admixed.

Base composition (in parts by weight) sodium dodecyl benzene sulfonate 7.5 C₁₂-C₁₈ fatty acid soap 1.5 C₁₂-C₁₈ fatty alcohol with 5 EO 4.5 Tallow fatty alcohol with 5 EO 0.8 zeolite 25.0 sodium 13.2 Sodium silicate (1: 2) 3.5 magnesium silicate 1.0 perborate 25.0 tetraacetylethylenediamine 3.0 CMC / MC 0.8 opt. brighteners 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 V1 trisodium citrate dihydrate 5.0 M1 / 1 disodium tartrate dihydrate 5.0 M2 / 1 galactaric acid disodium salt 5.0 M3 / 1 D-glucaric acid monopotassium salt 5.0 V2 trisodium citrate dihydrate 10.0 M1 / 2 disodium tartrate dihydrate 10.0 M2 / 2 galactaric acid disodium salt 10.0 M3 / 2 D-glucaric acid monopotassium salt 10.0 V3 Sokalan CP5® (copolymer of acrylic acid with maleic acid, commercial product of BASF) 4.0 HEDP 0.5

The test was carried out under practical conditions in household washing machines. For this purpose, the machines were equipped with 3.5 kg of clean linen and 0.5 kg of test tissue fed, the test tissue in part with conventional Impregnated with test contaminants (to test the primary washing power) and partly of white fabric (for testing the secondary washer mögens). As a white test fabric, strips of standardized tree wool fabric (laundry research institute Krefeld, WFK), nettle (BN), Wirk ware (cotton jersey; B) and terry cloth (FT). Waschbedingun : tap water of 23 ° d (equivalent to 230 mg CaO / l), used Detergent amount per medium and machine 146 g, washing temperature 25 to 90 ° C (heating time 60 minutes, 15 minutes at 90 ° C), liquor ratio (kg Wash: 1 liter of wash liquor in the main wash cycle) 1: 5.7, rinse 4 times with tap water, centrifuging and drying.

The primary washing capacities of means V1 to V3 and M1 / 1 and M1 / 2 to M3 / 1 and M3 / 2 were comparable. Also at the graying of the tissues no significant differences were achieved.

After 25 washing cycles, the ash content of the textile samples became quantitative certainly. The agents according to the invention M1 / 1 or M1 / 2 to M3 / 1 or M3 / 2 showed on average over all textile fabrics better ash content than Comparative Examples V1 to V3.

Analogous results were obtained by means of granulation or Extrusion were prepared and / or contained a different surfactant base.  

In the determination of the ashes is by the combustion of organic Be usually a lower value than the owner corresponds to incrustation. As a control, therefore, the Ge velvet enrammation determined (1st weighing of the untreated tissue, 2nd weighing tissue after 25 washing cycles, 3. weighing the tissue after extraction with EDTA, 4. Determination of the so-called "soluble ash" from the difference weighing 2nd and 3rd, 5th ashing of the extracted tissue to Be mood of the residual ash, 6. Determination of the total ingestion (sum of soluble ash and residual ash)).

Claims (17)

1. washing and cleaning agents, especially a laundry detergent, ent holding as phosphate-free builders zeolite and / or crystalline layered silicates of the general formula (I) NaMSi _x O _{2x + 1} · yH ₂ O, 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 complexing agent, characterized in that it contains the builders in amounts of 15 to 60 wt .-% and complexing agent selected from Polyhydroxydicarbonsäuren or polyhydroxy dicarboxylic acid salts with 4 to 6 Carbon atoms and at least 2 hydroxyl groups per molecule or mixtures of these acids and / or salts, wherein the weight ratio of builders to Polyhy droxydicarbonsäure or Polyhydroxydicarbonsäuresalz or mixtures of these acids and / or salts is 30: 1 to 1: 1. 2. Composition according to claim 1, characterized in that it is 15 to 50 % By weight of zeolite and / or crystalline sheet silicates and 1 to 20 % By weight of polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts containing from 4 to 6 carbon atoms, where each carbon atom, which carries no carboxyl group, has a hydroxyl group. 3. Composition according to claim 1 or 2, characterized in that it is 10 bis 35 wt .-%, 12 to 28 wt .-% and in particular 15 to 25 wt .-% anio niche and nonionic surfactants including soap, 18-40 Wt .-%, preferably 20 to 35 wt .-%, zeolite, wherein the Ge weight ratio of zeolite to polyhydroxydicarboxylic acid or polyhydroxy dicarboxylic 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. 4. Composition according to one of claims 1 to 3, characterized in that from 2 to 15% by weight and preferably from 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 ent holds.   5. Composition according to one of claims 1 to 4, characterized in that it does not contain phosphonates. 6. Composition according to one of claims 1 to 5, characterized in that it contains no (co) polymeric polycarboxylic acids or polycarboxylates. 7. Composition according to one of claims 1 to 6, characterized in that it does not contain citrate. 8. Composition according to one of claims 1 to 7, characterized in that it is sodium carbonate and / or potassium carbonate in quantities of 2 to 15, preferably 5 to 14 wt .-%. 9. Composition according to one of claims 1 to 8, characterized in that it has a bulk density between 300 and 1100 g / l, preferably between 500 and 1000 g / l. 10. builder combination containing builders and a complexing agent, characterized in that as builders zeolite and / or crystalline phyllosilicates of the general formula (I) 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 as the complexing agent polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts having 4 to 6 carbon atoms and at least 2 hydroxyl groups per molecule or mixtures of these acids and / or salts are contained and Weight ratio builders to polyhydroxydicarboxylic acid or polyhydroxydicarboxylic acid salt or mixtures of these acids and / or salts 30: 1 to 1: 1. 11. builder combination according to claim 10, characterized in that Polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts with 4 to 6 carbon atoms present on each carbon atom, which carries no carboxyl group, a hydroxy group, wherein the weight ratio of builders, especially zeolite, to poly hydroxydicarboxylic acid or polyhydroxydicarboxylic acid salt or mixtures  from these acids and / or salts 20: 1 to 1: 1, preferably 10: 1 to 1.5: 1 and especially 5: 1 to 1.5: 1. 12. builder combination according to claim 10 or 11 characterized gekennzeich net, that as polyhydroxydicarboxylic acid or polyhydroxydicarboxylic acid salt galactaric acid or galactaric acid salt, glucaric acid or glucar acid salt, tartaric acid or tartaric acid salt or mixtures thereof Acids and / or salts are included. 13. builder combination according to any one of claims 10 to 12, characterized characterized in that the builder combination with liquid up to waxy components, preferably with nonionic surfactants, is sprayed. 14. A process for preparing a builder combination containing as builders zeolite and / or crystalline phyllosilicates of the general my formula (I) 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 as complexing polyhydroxydicarboxylic or Polyhydroxydi carboxylic acid salts having 4 to 6 carbon atoms and at least 2 Hy droxy groups per molecule or mixtures of these acids and / or salts, characterized in that the builder combination Mixing, granulating and / or produced by spray drying. 15. A process for the preparation of a granular detergent Tels according to one of claims 1 to 9, characterized in that the granules are prepared by spray drying. 16. A process for the preparation of a granular detergent Tels according to one of claims 1 to 9, characterized in that the granules produced by a granulation or extrusion process becomes. 17. A process for the preparation of a granular detergent and Reinigungsmit means according to one of claims 1 to 9, characterized in that the builder combination of zeolite and / or crystalline layer silicates of the general formula (I) 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 polyhydroxydicarboxylic or polyhydroxydicarboxylic acid salts having 4 to 6 carbon atoms and at least 2 Hy droxy groups or mixtures of these acids and / or salts in the form of a spray-dried or granulated compound as admixing component to other granular components of detergents and cleaners is used.