EP0986627A1

EP0986627A1 - Washing or cleaning agents with greater cleaning power

Info

Publication number: EP0986627A1
Application number: EP98936279A
Authority: EP
Inventors: Eduard Smulders; Peter Sandkühler; Thomas Müller-Kirschbaum
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1997-06-02
Filing date: 1998-05-22
Publication date: 2000-03-22
Also published as: JP2002510342A; WO1998055568A1; DE19722767A1

Abstract

The invention relates to granular washing or cleaning agents presenting exceptional cleaning powers when they contain between 20 and 55 weight % tensides from the group of anionic tensides, nonioninc tensides and soaps as well as one or several builders from the group of inorganic and organic builders, where the ratio by weight of total tensides used to total quantity of builders used is between 1.2:1 and 1:1.2. Said agents are especially advantageous at wash temperatures below 50 °C.

Description

Detergents or cleaning agents with increased cleaning performance

The invention relates to granular detergents or cleaning agents, in particular those with bulk densities above 500 g / l, which have an increased washing performance compared to conventional detergents or cleaning agents, in particular when cleaning soiled textiles.

While in the past, detergents or cleaning agents had surfactant contents of 10 to approx. 16% by weight, the content of surfactants, especially in the so-called heavy powders or compactates, has risen to usually above 16% by weight to about 30% by weight . Detergents are known from the Asian region which even contain up to 40% by weight of surfactants.

International application WO-A-94/13771 describes detergents, in particular extrudates, which have 20 to 55% by weight of surfactants with a weight ratio of anionic surfactants: nonionic surfactants of 10: 1 to 1: 2.5. Example 2 of the abovementioned application describes an agent which contains a total of 28.3% by weight of surfactants, which are composed of 18% by weight of alkyl sulfate, 9.5% by weight of nonionic surfactants and 0.8% by weight of soap put together. The total amount of builder substances used, consisting of zeolite, copolymeric polycarboxylate, sodium carbonate, sodium silicate and citrate, is 36% by weight. This represents a weight ratio of surfactant: builder of 1: 1.29.

Although the recipe already has excellent washing performance, it has now been found that this washing performance at 30 ° C, 40 ° C and 60 ° C, especially at 30 ° C and 40 ° C, can be improved if the surfactants used in one certain weight ratio to the builder substances used.

In a first embodiment, the invention therefore relates to a granular washing or cleaning agent containing 20 to 55% by weight of surfactants from the group of anionic surfactants, nonionic surfactants and soaps, and one or more builder substances from the group of inorganic and organic builder substances , in which the weight ratio of the total surfactants used to the total amount of builder substances used is between 1.2: 1 and 1: 1.2.

Preferred anionic 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 an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. The use of the alkylbenzenesulfonates mentioned is particularly preferred.

Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), e.g. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well as their mixtures, such as those produced 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 be preserved.

The alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. From the washing are C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ - C ₁₅ alkyl sulfates are particularly preferred. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN ^(R) , are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂ -alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-C ^ -alcohols with an average of 3.5 mol of ethylene oxide (EO) or C ₁₂ -C ₁₈ -Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight. Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent 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. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Fatty acid derivatives of amino acids, for example of N-methyl taurine (taurides) and / or of N-methyl glycine (sarcosides) are suitable as further anionic surfactants. The sarcosides or sarcosinates, and in particular sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate, are particularly preferred.

The anionic surfactants are preferably used in relatively high amounts, i.e. in amounts above 15% by weight. Anionic surfactants are advantageously present in the compositions in amounts between 16 and 30% by weight, based on the finished compositions.

Suitable surfactants also include soaps, which are preferably present in amounts of 0.5 to 3% by weight, based on the finished agent. Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. The known alkenyl-succinic acid salts can also be used together with these soaps or as a substitute for soaps. The proportion of soaps and alkenylsuccinic acid salts in the total surfactant system is preferably below 10% by weight and in particular at most 5% by weight.

The anionic surfactants and soaps 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, available. The anionic surfactants are preferably in the form of their sodium and / or potassium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, palm kernel, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, Cg-C, -, alcohols 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 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as are described, for example, in Japanese patent application JP 58/217598 or preferably according to the method described in the international patent The method described in WO-A-90/13533 can be produced. C ₁₂ -C ₁₈ fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO, are particularly preferred.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanol amides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

R ³

I.

R ² -CO-N- [Z] (I)

in the R ^ CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ³ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands. The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

R ⁴ -OR ⁵

(II)

R -CO-N- [Z]

in which R ^{3 represents} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{5 represents} a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C ₁ -C ₄ -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is here also preferably by reductive amination of a sugar such as glucose, fructose, Get maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

So-called gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are generally separated from one another by a so-called “spacer”. This spacer is generally a carbon chain which should be long enough that the hydrophilic groups are sufficiently far apart that they can act independently of one another. Such surfactants are distinguished generally by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water, but in exceptional cases the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.

Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE-A-43 21 022 or dimer alcohol bis and trimeral alcohol trisulfates and ether sulfates according to older German patent application P 195 03 061.3. End group-capped dimeric and trimeric mixed ethers according to the earlier German patent application P 195 13 391.9 are distinguished in particular by their bi- and multifunctionality. The end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.

Gemini-polyhydroxyfatty acid amides or poly-polyhydroxyfatty acid amides, as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO95-A- / 19955, can also be used.

Advantageously, the content of the finished agents in nonionic surfactants is at least 2% by weight, preferably at least 4% by weight, contents of the finished agents in nonionic surfactants between 5 and 12% by weight being particularly preferred, especially if the Agents are used at low temperatures below 50 ° C. A content of nonionic surfactants above 12% by weight of the agents can in principle lead to a further increase in the performance of the agents, but it has become in Several cases have shown that, at such high levels of nonionic surfactants, the granular agents increasingly lose their free-flowing properties and can tend to stick or even clump together. For this reason, amounts of nonionic surfactants above 12% by weight are not particularly preferred.

Weight ratios of anionic surfactants: nonionic surfactants of at least 1: 1, preferably of 2; 5: 1 to 1.1: 1, have proven to be particularly advantageous, especially when the soap content, based on the total surfactant content, is at most 5% by weight .

The total content of surfactants in the compositions is preferably 22 to 35% by weight, advantageously at least one anionic surfactant and at least one nonionic surfactant and optionally soap are contained in the compositions.

In addition to the substances already mentioned, the conventional phosphates, in particular sodium tripolyphosphates, can of course also be used as builder substances; however, their presence in the agents is less preferred for ecological reasons

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, for example, zeolite MAP ^(R) (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production. In the event that the zeolite is used as a suspension, it can 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, C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x 0 _{2x +} ι'yH ₂ O, 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 EP-A-0 164 514. Preferred crystalline Layered silicates of the formula given are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ yH ₂ O are preferred.

The preferred builder substances also include amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can have been brought about in various ways, for example by surface treatment, compounding, compaction / compaction or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

It is also possible to use the conventional alkali silicates without special builder properties, the so-called water glasses, which were usually used in detergents or cleaning agents before the technical production of crystalline layered disilicates and amorphous silicates with delayed dissolving properties. In the context of this invention, for the sake of simplicity, these water glasses are also to be added to the builder substances which are used according to the invention or which may be contained in the compositions.

Carbonates, bicarbonates and sesquicarbonates, in particular the sodium salts and / or the potassium salts, are particularly worth mentioning as further possible ingredients of the agents having a builder effect. Carbonates can also be present in compounded form, for example together with silicates with delayed dissolving properties. In a pre- Preferred embodiment of the invention, the content of carbonates, in particular sodium carbonate and / or sodium bicarbonate, is 5 to 20% by weight, in particular 10 to 15% by weight. High amounts of carbonates are particularly advantageous when the zeolite content of the compositions, based on anhydrous active substance, is below 20% by weight, preferably from 10 to 18% by weight.

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

The acids themselves can also be used. In addition to their builder effect, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000. A polysaccha d with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure for the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both Maltodexthne with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 can be used.

Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO-A-95/20029.

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 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred.

Polymers of more than two different monomer units are also particularly preferred, for example those which, according to DE-A-43 00 772, are monomers as salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.

Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Other suitable builder substances are oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application WO-A-93/16110. Oxidized oligosaccharides according to the older German patent application P 196 00 018.1 are also suitable.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which those in the German patent application DE-A-195 40 086 discloses that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.

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

The total content of builder substances in the composition results from the amount of surfactants and the claimed weight ratio of surfactants and builder substances, a preferred ratio of surfactants: builder between 1.1: 1 to 1: 1.1 and in particular between 1: 1 and 1: 1, 1 lies. Usually it also applies that the content of inorganic builders is greater than that of organic builders, weight ratios of inorganic builders: organic builders between 10: 1 and 3: 1 being particularly advantageous.

In addition to the ingredients mentioned, the agents can contain known additives commonly used in detergents or cleaning agents, for example bleaching agents and bleach activators or bleaching catalysts, foam inhibitors, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, soil repellents and graying inhibitors, and small amounts of neutral filler salts as well as dyes and fragrances, opacifiers or pearlescent agents.

Of the compounds used as bleaching agents and providing H ₂ 0 ₂ in water, the sodium perborate tetrahydrate and the sodium perborate monohydrate are of particular importance. Other bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphate, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.

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 for this are N-acyl or O-acyl compounds which form organic peracids with H ₂ O ₂ , preferably multiply acylated alkylenediamines such as N, N'-tetraacylated diamines, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, Triazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid esters such as p- (alkanoyloxy) benzenesulfonate, in particular sodium isononanoyloxy-benzenesulfonate, and the p- (alkenoyloxy) benzenesulfonate, furthermore caprolactam derivatives, carboxylic acid anhydrides such as phthalic acid anhydrides such as phthalate pentacids . Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239, and acetylated pentaerythritol. The bleach activator content of the bleach-containing agents is in the usual range, preferably between 1 and 10% by weight and in particular above 3% by weight. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).

The bleach activator can be coated with coating substances in a known manner or, if appropriate using auxiliaries, in particular methyl celluloses and / or carboxymethyl celluloses, may have been granulated or extruded / pelletized and, if desired, contain further additives, for example dye. Such granules preferably contain more than 70% by weight, in particular 90 to 99% by weight, of bleach activator. A bleach activator is preferably used which forms peracetic acid under washing conditions.

In addition to the conventional bleach activators listed above or in their place, the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0 446 982 and EP 0 453 003 may also be present as so-called bleaching catalysts. The transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum salen complexes known from German patent application DE 195 29 905 and their N-analog compounds known from German patent application DE 196 20 267, which are known from German Patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum-carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium described in German patent application DE 196 05 688 -, Vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium-amine complexes known from German patent application DE 196 20 411, which are described in German Pa Mangan, copper and cobalt complexes described in DE 44 16 438, the cobalt complexes described in European patent application EP 0 272 030, the manganese complexes known from European patent application EP 0 693 550, which are known from European patent EP 0 392 592 known manganese, iron, cobalt and copper complexes and / or those described in European patent EP 0 443 651 or European patent applications EP 0 458 397, EP 0 458 398, EP 0 549 271, EP 0 549 272, EP 0 544 490 and EP 0 544 519 described manganese complexes. Combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 196 13 103 and international patent application WO 95/27775. Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, possibly signed silica, and paraffins, waxes, microcrystalline waxes and their mixtures with signed silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

Particularly suitable enzymes are those from the class of hydrolases, such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases, and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can help maintain color and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus cheniformis, Streptomyces gπseus and Humicola msolens are particularly suitable. Proteases of the subtihsin type and in particular proteases obtained from Bacillus lentus are preferably used. Enzyme mixtures are used here , for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, in particular however, protease- and / or lipase-containing mixtures or mixtures with lipolytically active enzymes are of particular interest. Examples of such lipolytically active enzymes are the known cutinases. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable Amy Read in particular α-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures of these, are preferably used as cellulases, since the various cellulase types differ by their CMCase and avicelase -Activities differ, the desired activities can be set by targeted mixtures of the cellulases

The enzymes can be adsorbed on carriers and / or embedded in shell substances in order to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight. be

Suitable stabilizers, in particular for per-compounds and enzymes which are sensitive to heavy metal ions, are the salts of polyphosphonic acids, in particular 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), diethylenedaminopentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid

In addition, the detergents can also contain components which have a positive influence on the oil and fat washability from textiles. This effect becomes particularly clear when a textile is contaminated which has already been washed several times with a detergent according to the invention which contains these oils and contains fat-free component, was washed Among the preferred oil-free and fat-free components are, for example, non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropoxyl groups 1 to 15% by weight, in each case based on the nonionic cellulose ether and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

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

As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure, which instead of the Morphoiino group have a diethanolamino group , a methylamino group, an amino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4'- (2- sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can also be used.

The bulk density of the granular compositions according to the invention can vary within a wide range, but is preferably 500 to 1100 g / l.

The agents can be produced by any of the known processes, such as mixing, spray drying, granulating and extruding. Processes in which several partial components, for example spray-dried components and granulated and / or extruded components, are mixed with one another are particularly suitable. It is also possible for spray-dried or granulated components to be subsequently treated, for example with non-ionic surfactants, in particular ethoxylated fatty alcohols, by the customary processes. In granulation and extrusion processes in particular, it is preferred to use the anionic surfactants which may be present in the form of a spray-dried, granulated or extruded compound, either as an additive component in the process or as an additive to other granules. It is also possible and, depending on the recipe, to be advantageous if further individual constituents of the agent, for example carbonates, citrate or citric acid or other polycarboxylates or polycarboxylic acids, polymeric polycarboxylates, zeolite and / or layered silicates, for example layered crystalline disilicates, subsequently to spray-dried, granulated and / or extruded components, which are optionally charged with nonionic surfactants and / or other liquid to waxy ingredients at the processing temperature, are added. A method is preferred in which the surface of partial components of the composition or of the entire composition is subsequently treated to reduce the stickiness of the granules rich in nonionic surfactants and / or to improve their solubility. Suitable surface modifiers are known from the prior art. In addition to other suitable, finely divided zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts, for example calcium stearate, but in particular mixtures of zeolite and silicas or zeolite and calcium stearate are particularly preferred.

A preferred method for producing the detergents or cleaning agents according to the invention with bulk densities above 600 g / l are conventional granulation methods. Granulation in a slow-running mixer / compressor or in two consecutive mixers / granulators / compressors, which preferably have different stirring speeds, are examples here , called. It is possible, for example, for the granulation to be carried out first in a so-called high-speed mixer and then in a slower-running mixer or else first in a slower-running mixer and then in a high-speed mixer, in which case it must be ensured that the resulting granules not be smashed again. The so-called roll granulation, in which the agglomerates accumulate under rolling conditions, is particularly preferred. be built and compacted. Almost spherical end products are obtained as finished granules. Such roll granulation is possible, for example, in high-quality fillets (Marumerizers). Another roll granulation process is described in international patent application WO-A-94/13779.

Another preferred method for producing the washing or cleaning agents according to the invention is extrusion, in particular the extrusion of a solid and free-flowing premix with the addition of a plasticizer and / or lubricant at pressures between 25 and 200 bar. Such an extrusion process is described, for example, in European patent EP-B-0 486 592 or in German patent application P 196 38 599.7.

In a further embodiment of the invention, the use of an above-mentioned agent according to the invention for manual or machine washing at washing temperatures below 50 ° C., in particular at a maximum of 40 ° C., advantageously at temperatures of at least 30 ° C. to a maximum of 40 ° C. Surprisingly, the agents according to the invention show outstanding performances precisely at these relatively low washing temperatures, some of which are considerably better than the performances of conventional agents on the market.

Examples

A granular agent of the composition given below was extruded and tested against a commercially available detergent from the market (V, Ariel futur, commercial product from April 1996). The bulk density of M was 720 g / l.

Composition of agent M (in% by weight):

Anionic surfactants (alkyl benzene sulfonate and C ₁₂ -C ₁₈ alkyl sulfate) 20

C ₁₂ -C ₁₈ sodium fatty acid soap 1

C ₁₂ -C ₁₈ fatty alcohol with 7 EO 10

Zeolite (anhydrous active substance) 13

Sodium carbonate 12

Sodium silicate (1: 2.0) 2.5

Maleic acid-acrylic acid copolymer 4

Perborate monohydrate 15

Tetraacetylethylenediamine 8

Enzymes (protease, lipase, cellulase, amylase) 2.4

Phosphonate 0.5

Foam inhibitor granulate 15% based on silicone oil 4

Silicic acid (powdering agent) 0.5 optical brightener 0.3

Water and salts from solutions rest

The application test was carried out under practical conditions in Miele Novotronic W918 (17 liter) household washing machines. For this purpose, the machines were loaded with 3.5 kg of clean household laundry and 0.5 kg of soiled test fabric.

Washing conditions:

Tap water of 16 ° d (equivalent to 160 mg CaO / l), amount of detergent used per detergent and machine 76 g of agent M according to the invention or 84 g of comparative agent V (dosage recommendation given on the package), washing temperature 30 ° C (1-course drive, short wash program, ie 20 minutes wash time), 40 ° C and 60 ° C (1-cycle process, colored wash program, ie 60 minutes wash time), drying, 5-fold determination.

Soiling: - Dust-wool grease on cotton (SW-B)

- Dust skin fat on cotton (SH-B)

- Dust skin fat on refined cotton (SH-BV)

- red wine on cotton (R-B)

- cocoa on cotton (K-B)

- Tea on processed cotton (T-BV)

- Lipstick on mixed fabric made of polyester and refined cotton (LS-PBV)

Table: Primary washing power (reflectance in%) at 30 ° C, 40 ° C and 60 ° C (suppression of the brightener effect)

30 ° C 40 ° C 60 ° C

M V M V M V

SW-B 53.7 49.6 61, 4 56.2 67.8 65.2

SH-B 47.5 42.9 62.2 52.1 61, 9 56.1

SH-BV 69.2 62.2 76.9 70.9 76.8 75.7

R-B 50.6 47.9 63.9 62.5 72.9 73.0

K-B 67.6 66.6 74.2 73.0 77.9 76.7

T-BV 48.4 41, 2 61, 6 58.0 72.3 67.8

LS-PBV 58.3 50.3 67.1 64.3 69.1 64.8

Claims

claims

1. Granular detergent or cleaning agent containing 20 to 55 wt .-% surfactants from the group of anionic surfactants, nonionic surfactants and soaps and one or more builder substances from the group of inorganic and organic builder substances, characterized in that the weight ratio of the total surfactants used for the total amount of builder substances used is between 1.2: 1 and 1: 1, 2.

2. Agent according to claim 1, characterized in that the total content of surfactants in the agent is 22 to 35 wt .-%, advantageously at least one anionic surfactant and at least one nonionic surfactant and optionally soap are contained in the agent.

3. Composition according to claim 1 or 2, characterized in that it contains at least 2 wt .-%, preferably at least 4 wt .-% of nonionic surfactants, with contents of the finished nonionic surfactants between 5 and 12 wt .-% particularly are preferred.

4. Composition according to one of claims 1 to 3, characterized in that it has weight ratios of anionic surfactants: nonionic surfactants of at least 1: 1, preferably of 2; 5: 1 to 1: 1.

5. Composition according to claim 4, characterized in that the soap content, based on the total surfactant content, is a maximum of 5 wt .-%.

6. Agent according to one of claims 1 to 5, characterized in that the content of carbonate, in particular sodium carbonate and / or sodium bicarbonate, is 5 to 20% by weight, in particular 10 to 15% by weight.

7. Composition according to claim 6, characterized in that the content of the agent in carbonates 10 to 15 wt .-% and the content of the agent in zeolite, based on anhydrous active substance, below 20 wt .-%, preferably at 10 to 18 wt .-%, lies.

8. Composition according to one of claims 1 to 7, characterized in that the weight ratio of surfactants: builder is between 1.1: 1 to 1: 1.1 and in particular between 1: 1 and 1: 1.1.

9. Agent according to one of claims 1 to 8, characterized in that the content of the agent in inorganic builders is greater than in organic builders, wherein weight ratios of inorganic builders: organic builders between 10: 1 and 3: 1 are particularly advantageous.

10. A method for producing a granular detergent or cleaning agent containing 20 to 55 wt .-% surfactants from the group of anionic surfactants, the nonionic surfactants and soaps, and one or more builder substances from the group of inorganic and organic builder substances, the Weight ratio of the total surfactants used to the total amount of builder substances used is between 1.2: 1 and 1: 1.2 by mixing, spray drying, granulating and / or extruding.

11. Use of a granular washing or cleaning agent containing 20 to 55% by weight of surfactants from the group of anionic surfactants, nonionic surfactants and soaps, and one or more builder substances from the group of inorganic and organic builder substances, the weight ratio of total surfactants used for the total amount of builder substances used is between 1: 2: 1 and 1: 1, 2, for manual or machine washing at washing temperatures below 50 ° C, in particular at a maximum of 40 ° C, advantageously at temperatures of at least 30 ° C up to a maximum of 40 ° C.