EP0658189B1 - Washing and cleaning agents with builder substances - Google Patents

Abstract

The object of the invention is to obtain granulated washing and cleaning agents having the usual composition, a primary washing and cleaning power comparable to the primary washing and cleaning power of usual commercially-available products, but whose secondary washing power has big advantages. For that purpose, agents are used which contain determined polymer polycarboxylates as granulated builder components. Preferred textile washing agents contain 8 to 40 % by weight anionic and non-ionic surfactants, including soap, 15 to 45 % by weight zeolite and/or crystalline layered silicates, in particular zeolite, 0.5 to 8 % by weight sodium or potassium carbonate and 0.5 to 15 % by weight, preferably 2 to 10 % by weight, in particular 3 to 5 % by weight, granulated polymer polycarboxylates. These agents may be produced in the usual manner by mixing at least two granulated components, of which one contains the polymer polycarboxylate.

Description

The invention relates to detergents and cleaning agents which contain customary builder substances and polymeric polycarboxylates.

In practice, zeolite, in particular zeolite NaA, and mixtures of zeolite with alkali silicates and alkali carbonates as well as polycarboxylates or polymeric polycarboxylates were used as phosphate substitutes in washing and cleaning agents.

The European patent application EP-A-0 221 777 describes washing and cleaning agents which contain anionic and / or nonionic surfactants, phosphate-free builder substances, inorganic salts and polymeric polycarboxylates. These agents are spray dried.

The polymeric polycarboxylates are known to counteract the precipitation of poorly soluble calcium salts and thus the incrustation caused by poorly soluble calcium salts and the graying of the tissue. Polymeric polycarboxylates were mostly used in the form of an aqueous solution or as a fine powder.

For example, European patent application 291 869 describes phosphate-free builders combinations of zeolite and polymeric polycarboxylates, mixtures of polymeric polycarboxylates with aminoalkane polyphosphonates and 1-hydroxyethane-1,1-diphosphonate (HEDP) showing a synergism in preventing the formation of fiber incrustations.

From the international patent application W0-A-92/07928, phosphate-free building material combinations are known which contain zeolite, polymeric polycarboxylates and crystalline layered silicates.

International patent application W0-A-91/02047 describes the use of polymeric polycarboxylates as plasticizers in extruded washing and cleaning agents.

European patent application EP-A-0 421 664 discloses granules which contain at least 10% by weight of polymeric polycarboxylates and at least 20% by weight contain a water-soluble inorganic component and which can be used as an additive in washing or cleaning agents. These washing or cleaning agents preferably contain other builders such as zeolite or sodium carbonate. The content of sodium carbonate can make up to 80% by weight in these agents.

The object of the invention was to provide phosphate-free agents which have a primary washing and cleaning power which is comparable to the primary washing and cleaning power of conventional commercial products, but the secondary washing power of these agents at the same time has great advantages. It has now been found that this object is achieved by compositions which are conventional per se, but which contain polymeric polycarboxylates in a very specific form.

The invention accordingly relates to a detergent and cleaning agent, in particular a textile detergent, containing anionic and / or nonionic surfactants, phosphate-free builder substances and inorganic salts and polymeric polycarboxylates, the agent containing at least two granular components, the first of which is anionic and / or nonionic surfactants contains phosphate-free builder substances and inorganic salts and the second contains an admixture of polymeric polycarboxylates is in granular form. Agents which contain alkali carbonate in amounts below 10% by weight, based on the total agent, have an improved incrustation inhibition.

Preferred granular polymeric polycarboxylates have a bulk density between 350 and 850 g / l, preferably between 400 and 750 g / l, no particles with a particle size below 50 μm, preferably no particles with a particle size below 100 μm, and a maximum of 5% of the particles a particle size above 1000 microns, preferably a maximum of 3 wt .-% of the particles with a particle size above 1000 microns. The content of monomeric polycarboxylic acids in the granules is preferably below 1% by weight. The granular polymeric polycarboxylates can be prepared in a conventional manner known to the person skilled in the art, for example by drying polymer solutions, subsequent granulation and, if appropriate, size classification of the granules. It is preferred to dry polymer solutions in a spray tower or in a fluidized bed and to granulate the dried powder with water, in particular with aqueous solutions of the polymeric polycarboxylates and advantageously without further auxiliaries. Fluid bed granulation is particularly preferred. Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and 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 4,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. Sokalan ^(R) CP5 granules, Sokalan ^(R) CP45 granules and Sokalan ^(R) CP 7 are very particularly preferred Granules (commercial products from BASF).

An explanation for the improved incrustation inhibition and concomitant for the better secondary washing ability of agents which contain the polymeric polycarboxylates in granular form compared to agents in which the same polymeric polycarboxylates are used in aqueous or powdered form were not available. It is only assumed that this effect can be attributed to the irregular and by no means closed surface of the individual granules, which, owing to their spatial arrangement, ensures a more stable binding of the hardness formers compared to the powdered polycarboxylates and, in particular, to those that are quite mobile in the solution Polymer chains.

Zeolites are primarily considered as phosphate-free builder substances. The zeolites are used in the usual hydrated, fine 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 Ca0 / g. Zeolite NaA is particularly suitable, as is zeolite NaX and mixtures of NaA and NaX. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups . Quantities and weight ratios which relate to the zeolite builder are based on anhydrous active substance in the context of this invention, unless stated otherwise.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula (1) 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 Number is from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application 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 β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in German patent application 39 39 919.

The washing and cleaning agents according to the invention can also contain mixtures of zeolite and the crystalline layered 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 washing and cleaning agents according to the invention contain the builders zeolite and / or crystalline layered silicates (I) and the granular polymeric polycarboxylates advantageously in a weight ratio of 30: 1 to 1: 1, preferably 20: 1 to 2: 1 and in particular 10 : 1 to 3: 1.

The detergents and cleaning agents according to the invention, in particular the textile detergents, are preferably in granular form. Advantageous agents contain 10 to 60% by weight, preferably 15 to 45% by weight and in particular 20 to 40% by weight of zeolite and / or crystalline layered silicates (I), in particular zeolite, and 0.5 to 15% by weight. %, preferably 2 to 10 wt .-% and in particular 3 to 8 wt .-% granular polymeric polycarboxylates.

Although the detergents and cleaning agents according to the invention may contain other customary builder substances and complexing agents, for example phosphonates, the effect of improving incrustation inhibition or secondary washing capacity by using polymeric polycarboxylates as granular admixture component according to the invention is so serious that it is particularly preferred to refrain from using phosphonates. 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 bleaching agent and enzyme stability of the agents according to the invention are not significantly increased by the use of phosphonates, so that the use of phosphonates can be dispensed with overall without loss of performance.

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

In addition to the ingredients mentioned, the agents according to the invention contain anionic and / or nonionic surfactants and optionally cationic and / or amphoteric surfactants and other additives usually used in detergents and cleaning agents, for example 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, small amounts of neutral filler salts and colorants and fragrances, opacifiers or pearlescent agents.

The content of the agents in anionic and nonionic surfactants including soap is preferably 8 to 40% by weight, in particular 10 to 35% by weight and in particularly preferred embodiments 12 to 28% by weight.

Examples of surfactants of the sulfonate type are C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C ₁₂ -C ₁₈ monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C ₁₂ -C ₁₈ 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 come from 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 ones Neutralization to water-soluble mono-salts are considered. 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 as well as their mixtures as obtained in the production by esterification of glycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfonated 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, that is to say 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, ie to harden them 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 saturated fatty acids with 6 to 22 carbon atoms or Mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, are preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as specified in international patent application WO 91/9009.

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

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, for example from tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ₁₀ -C ₂₀ oxo alcohols, and those secondary alcohols of this chain length. The sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol of ethylene oxide, are also suitable. Preferred fatty alkyl sulfates are derived from fatty alcohol mixtures obtained from coconut oil, palm oil and palm kernel oil, which may additionally contain fractions of unsaturated alcohols, for example oleyl alcohol. Mixtures in which the proportion of the alkyl radicals is 50 to 70% by weight on C ₁₂ , 18 to 30% by weight on C ₁₄ , 5 to 15% by weight on C ₁₆ , are preferred 3% by weight on C ₁₀ and less than 10% by weight on C _{18 are} distributed.

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 in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ 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 soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. In particular, those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C ₁₂ -C ₁₈ fatty acid soaps and 0 to 50% by weight 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, in addition to the anionic surfactants nonionic 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. However, linear residues of alcohols of native origin with 12 to 18 carbon atoms, such as, for example, coconut oil, tallow oil or oleyl alcohol, are particularly preferred. 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 E0, 7 EO or 8 EO, C ₁₂ - C ₁₈ alcohols with 3 EO, 5 EO or 7 E0 and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). 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 silicates or mixtures of these; In particular, alkali carbonate and alkali silicate, especially sodium silicate with a Na ₂ O: SiO ₂ molar ratio of 1: 1 to 1: 4.5, preferably 1: 2 to 1: 3.5, optionally in combination with magnesium silicate, are used. The content of the means in sodium silicate 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 0 to about 8% by weight, advantageously between 0.5 and 8% by weight and in particular between 2 and 6% by weight are particularly preferred.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 30% by weight and in particular 10 to 25% by weight, advantageously using perborate monohydrate or tetrahydrate.

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 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 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 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, eg 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 which contain a high proportion of C ₁₈ -C ₂₄ 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 or bistearylethylenediamide, as well as paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. 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. At least proteases, advantageously 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 (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), 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 contains 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 and consist of at least two granular, preferably at least three granular components, one of which contains the polymeric polycarboxylate.

The agents according to the invention can be prepared in a conventional manner by mixing at least two granular components, one of which contains the polymeric polycarboxylate. The other granular component, which is preferably anionic surfactants, optionally nonionic surfactants and contains builder substances and inorganic salts is produced, for example, by spray drying an aqueous slurry and, if appropriate, then adding temperature-sensitive components, or by granulating and extruding. In the production of this other granular component by granulation or extrusion, it is preferred that this component contains anionic surfactants and nonionic surfactants as well as builder substances, inorganic salts and optionally peroxy bleaching agents.

In a further embodiment of the invention, the compositions are produced by extrusion, the granular polymeric polycarboxylate being a constituent of the mixture to be extruded.

Examples

Granular detergents of the following composition (comparative examples V1 and agent M1 according to the invention) were prepared and tested in a conventional manner by spray drying. In the comparative example, the polymeric polycarboxylate was used as a 40% strength by weight aqueous solution (Sokalan ^(R) CP 5, commercial product from BASF, Federal Republic of Germany) and as part of the slurry to be spray-dried and in the composition according to the invention as a granular admixture component (Sokalan ^(R) CP5 granules, commercial product from BASF, Federal Republic of Germany) added afterwards. The constituents perborate, bleach activator and enzyme granulate were also added subsequently. Basic composition (in% by weight) Sodium dodecylbenzenesulfonate 7.5 C ₁₂ -C ₁₈ fatty acid soap 1.5 C ₁₂ -C ₁₈ fatty alcohol with 5 EO 4.5 Tallow fatty alcohol with 5 EO 0.8 Zeolite 28.0 Copolymeric salt of acrylic acid with maleic acid 3.8 (Sokalan ^(R) CP5) sodium 5.5 Sodium silicate (Na ₂ O: SiO ₂ 1: 2) 3.5 Perborate tetrahydrate 25.0 Tetraacetylethylenediamine 4.0 CMC / MC 0.8 opt. Brightener 0.2 Enzyme granules 1.5 Silicone oil 0.2 water 8.0 Sodium sulfate (and other salts from solutions) rest

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 with the usual Test soiling was impregnated (for testing the primary washing ability) and partly consisted 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.

As expected, the primary washing performance of agents V1 and M1 were comparable.

After 25 washing cycles, the ash content of the textile samples was determined quantitatively. Agent M1 according to the invention showed on average better ash contents than all comparative example V1 over all textile fabrics.

Analogous results were achieved with agents which were produced by granulation or extrusion, the polymeric polycarboxylate in the comparative example being used as an aqueous solution and / or as a finely divided powder, and / or containing another surfactant base, for example fatty alkyl sulfates instead of alkylbenzenesulfonate. Wt% ash FT BN B WFK 0̸ Initial value 0.19 0.39 0.46 0.75 0.45 V1 2.27 3.28 3.65 7.30 4.12 M1 1.63 2.37 2.39 5.09 2.87

Claims (11)

1. A detergent, more particularly a laundry detergent, containing anionic and/or nonionic surfactants and phosphate-free builders, inorganic salts and polymeric polycarboxylates, characterized in that it contains at least two granular components of which the first contains anionic and/or nonionic surfactants, phosphate-free builders and inorganic salts and the second is an added component of polymeric polycarboxylates in granular form, the detergent containing alkali metal carbonates in quantities below 10% by weight, based on the detergent as a whole, and showing an improved incrustation-inhibiting effect.
2. A detergent as claimed in claim 1, 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, in quantities of 10 to 60% by weight as phosphate-free builders, the ratio by weight of builders to granular polymeric polycarboxylates being 30:1 to 1:1, preferably 20:1 to 2:1 and more preferably 10:1 1 to 3:1.
3. A detergent as claimed in claim 1 or 2, characterized in that the granular polymeric polycarboxylates have an apparent density of 350 to 850 g/l and preferably 400 to 750 g/l and contain no particles below 50 µm in size and preferably no particles below 100 µm in size, at most 5% of the particles being lager than 1,000 µm in size and preferably at most 3% by weight of the particles being larger than 1,000 µm in size.
4. A detergent as claimed in any of claims 1 to 3, characterized in that it contains granular polymeric polycarboxylates in the form of copolymeric salts of acrylic acid with maleic acid.
5. A detergent as claimed in any of claims 1 to 4, characterized in that it contains 8 to 40% by weight, preferably 10 to 35% by weight and more preferably 12 to 28% by weight of anionic and nonionic surfactants, including soap, 15 to 45% by weight and preferably 20 to 40% by weight of zeolite and/or crystalline layer silicates, more especially zeolite, 0.5 to 8% by weight of sodium or potassium carbonate and 0.5 to 15% by weight, preferably 2 to 10% by weight and more preferably 3 to 8% by weight of granular polymeric polycarboxylates.
6. A detergent as claimed in any of claims 1 to 5, characterized in that it contains other typical ingredients of detergents, preferably peroxy bleaching agents, bleach activators, inorganic salts, enzymes and polycarboxylates, in the usual quantities, but is preferably free from phosphonates.
7. A detergent as claimed in any of claims 1 to 6, characterized in that it has an apparent density of 300 to 1,100 g/l and preferably between 500 and 1,000 g/l and consists in particular of at least three granular components of which one contains the polymeric polycarboxylate.
8. A process for the production of the granular detergent claimed in any of claims 1 to 7, characterized in that it is obtained by mixing at least two granular components of which one contains the polymeric polycarboxylate.
9. A process as claimed in claim 8, characterized in that the other granular component, which preferably contains anionic surfactants, optionally nonionic surfactants, builders and inorganic salts, is produced by spray drying.
10. A process as claimed in claim 8, characterized in that the other granular component, which preferably contains anionic surfactants and nonionic surfactants, builders, inorganic salts and optionally peroxy bleaching agents, is produced by a granulation or extrusion process.
11. A process for the production of a granular detergent as claimed in any of claims 1 to 7, characterized in that it is produced by extrusion, the granular polymeric polycarboxylate being part of the mixture to be extruded.