JP2002510342A - Cleaning or cleaning agents with improved cleaning performance - Google Patents

Abstract

  (57) [Summary] The present invention relates to a composition comprising 20 to 55% by weight of a surfactant selected from the group of anionic surfactants, nonionic surfactants and soaps and one or more builders selected from the group of inorganic and organic builders. The present invention relates to a granular detergent having high detergency, wherein the weight ratio of the total amount of the surfactant to the total amount of the builder is 1.2: 1 to 1: 1.2. The detergents of the present invention are particularly useful at washing temperatures below 50 ° C.

Description

DETAILED DESCRIPTION OF THE INVENTION                    Cleaning or cleaning agents with improved cleaning performance   The present invention is particularly improved in cleaning dirty textiles compared to conventional detergents Granular detergents with improved cleaning performance (especially those with a bulk density exceeding 500 g / l) About.   Conventionally, detergents have a surfactant content of about 10-16% by weight, but especially The surfactant content of loose heavy powder or compact typically ranges from 16 to about 3 It is as high as 0% by weight. Detergents containing as much as 40% by weight of surfactants have been Is known.   International Patent Application WO-A-94-13773 includes an anionic surfactant: Noni When the weight ratio of the on-surfactant is 10: 1 to 1: 2.5, the surfactant is used in an amount of 20 to 2%. Detergents (particularly extrudates) containing 5% by weight are described. Implementation of the international application Example 2 has a total surfactant content of 28.3% by weight, which comprises alkylsulfate 18% by weight, 9.5% by weight of nonionic surfactant and 0.8% by weight of soap Certain detergents have been described. Builders used (zeolites, copolymer poly) Carboxylate, sodium carbonate, sodium silicate and citrate) The amount is 36% by weight. That is, the weight ratio of surfactant: builder is 1: 1. . 29.   Although the above preparations already have excellent cleaning performance, surfactants and builders Is used at a certain weight ratio, it is possible to obtain 30 ° C., 40 ° C. and 60 ° C. (0 ° C.).   That is, the present invention provides, as a first embodiment, an anionic surfactant and a nonionic surfactant. 20 to 55% by weight of a surfactant selected from the group of surfactants and soaps; And one or more builders selected from the group of organic builders and organic builders. The weight ratio of the total amount of surfactant used to the total amount of builder used is 1.2: 1 to 1: 1. . 2. The granular detergent according to item 2.   Suitable anionic surfactants of the sulfonate type are preferably C_9-13Alkyl Benzenesulfonates, olefinsulfonates, i.e. Is a C having a non-terminal double bond_12-18Sulfur monoolefin with gaseous sulfur trioxide By sulfonation and then alkali or acid hydrolysis of the sulfonated product. Alkene and hydroxyalkane sulfonate and disulfo obtained by A mixture of catenates. The above-mentioned alkylbenzene sulfonates are particularly preferred.   Esters of α-sulfo fatty acids (ester sulfonates), such as hydrogenated palm Α-Sulfonated methyl esters of fatty acids of oil, palm kernel oil or tallow are also suitable. You.   Other suitable anionic surfactants are the sulfonated fatty acid glycerol esters. Ter, i.e., monoglycerol, is esterified with 1-3 moles of fatty acids, or Or transesterification of triglycerides with 0.3 to 2 moles of glycerol Mono-, di- and triesters and mixtures thereof.   Preferred alkyl (alkenyl) sulfates are C_12-18Fatty alcohol, eg For example, coconut oil fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetir Or stearyl alcohol, or C_10-20Semi-sulfuric acid of oxo alcohol Esters, and sulfuric acid semiesters of secondary alcohols having a similar chain length, Alkali metal salts, especially sodium salts. Other preferred alkyls (alkes Nyl) sulfate is the above-mentioned chain length having a synthetic linear alkyl chain derived from petrochemicals. An alkyl (alkenyl) sulfate having the formula It has a degradability comparable to that of the compound. C_12-16Alkylsulfe G, C_12-15Alkyl sulfate, and C_14-15Alkyl sulfate is washed Particularly preferred in terms of purification performance. Other suitable anionic surfactants are 2,3-alkyl Rusulfate, for example US Pat. No. 3,234,258 or US Pat. And commercially available from Shell Oil Company under the name DAN ™ I have.   Linear or branched C ethoxylated with 1 to 6 moles of ethylene oxide_7-21Al Cole, for example, 2-methyl branched C_9-11Alcohol + 3.5 mol average EO (ethylene Oxide) or C_12-18Fatty alcohol + 1 to 4 EO sulfuric acid monoester is also suitable It is. Since these are highly foamable, a relatively small amount (for example, 1 to 5) is contained in the detergent. (% By weight).   Other preferred anionic surfactants are sulfosuccinic acid and alcohols (preferably Or fatty alcohols, more preferably ethoxylated fatty alcohols) Sulfosuccinates or sulfochels which are stels and / or diesters It is a salt of alkyl sulfosuccinic acid, also known as succinate. Preferred Lephosuccinate is a C_8-18It has a fatty alcohol residue or a mixture thereof. Particularly preferred sulfosuccinates are themselves nonionic surfactants (described below). Fatty acid residues derived from ethoxylated fatty alcohols. That Ethoxylated fatty alcohols with a narrow homolog range among such sulfosuccinates Particularly preferred are those having a fatty alcohol residue derived from thiol. Alkyl ( Alkyl (alkenyl) having preferably 8 to 18 carbon atoms in the chain. R) Succinic acid or a salt thereof may be used.   Other suitable anionic surfactants are fatty acid derivatives of amino acids, such as N-meth Tiltaurin (tauride) and / or N-methylglycine (sarcoside) . Sarcosides or sarcosinates, especially mono- or poly- Sarcosinates of saturated higher fatty acids (e.g., oleyl sarcosinate) are particularly preferred. New   Anionic surfactants are used in relatively large amounts, ie in amounts exceeding 15% by weight. Is preferred. The anionic surfactant is 16-30 times the final detergent. Advantageously, it is present in the detergent in an amount of% by weight.   Another suitable surfactant is soap, preferably 0.5-3% by weight with respect to the final detergent. Use in% amount. Suitable soaps are, inter alia, saturated fatty acid soaps, such as lauric acid , Myristic, palmitic, stearic, hydrogenated erucic and behenic acids Salts, and especially natural fatty acids such as coconut oil fatty acids, palm kernel oil fatty acids or animal Soap fatty acid). With or with such a soap Alternatively, known alkenyl succinates may be used. For the entire surfactant system The proportion of soap and alkenyl succinate in the mixture is preferably less than 10% by weight, More preferably, it is up to 5% by weight.   Anionic surfactants and soaps are sodium, potassium or ammonium In the form of a salt, and with an organic base (e.g., mono, di or triethanolamine) May be present in the form of soluble salts. Anionic surfactants include sodium salts and It is preferably in the form of a potassium salt.   Preferred nonionic surfactants are alkoxylated (preferably ethoxylated) Particularly preferred are alcohols having 8 to 18 carbon atoms. And an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol Can the alcohol residue be straight-chain or preferably 2-methyl-branched? Or straight and methyl branching groups as in normal oxo alcohol residues. Can have a mixture. However, C derived from natural products_12-18Alcohol (e.g. coconut oil (Coal, palm oil alcohol, tallow alcohol or oleyl alcohol) Alcohol ethoxy having chain groups and an average of 2 to 8 EO per mole of alcohol Rates are particularly preferred. Preferred ethoxylated alcohols are, for example, C_12-14A Lecol + 3EO or 4EO, C_9-11Alcohol + 7EO, C_13-15Alcow + 3EO, 5EO, 7EO or 8EO, C_12-18Alcohol + 3EO, 5E O or 7EO, and mixtures thereof (eg, C_12-14Alcohol + 3EO and C_12-18 Mixtures with alcohols + 7EO). The above ethoxylation degree is It is a statistical average that can be integer or non-integer depending on the entity. Narrow homolog distribution Alcohol ethoxylates (narrow range ethoxylates, NRE) are preferred. this Fatty alcohols having an EO of more than 12 in addition to such nonionic surfactants Can also be used. Examples are (tallow) fatty alcohols + 14EO, 16EO, 20 EO, 25EO, 30EO or 40EO.   Further, the alkyl glycoside represented by the formula RO (G) x is also a nonionic surfactant. Can be used. Wherein R is a primary straight chain or methyl branch (especially 2-methyl A branched) aliphatic group (having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms); 5 or 6 glucose units (preferably glucose). Oligomerization degree x represents the distribution of monoglycosides and oligoglycosides, and 1 to 10, preferably Is a number from 1.2 to 1.4.   As the only nonionic surfactant or other nonionic surfactant (for (E.g., alkoxylated fatty alcohols and / or alkyl glycosides) Another preferred group of nonionic surfactants used in combination are fatty acid alkyl esters. Ster (preferably having 1 to 4 carbon atoms in the alkyl chain), especially fatty acid methyl ester Of alkoxylated, especially ethoxylated or ethoxylated / propoxy, Silylated product, which is described, for example, in Japanese Patent Application JP58 / 217598. Or preferably as described in International Patent Application WO-A-90 / 13533 It is manufactured by the method described above. C_12-18Fatty acid methyl ester + average 3-15 EO (especially 5-12 EO) are particularly preferred.   Nonionic surfactants of the amine oxide type, such as N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxy Nonionic surfactants of tylamine oxide and fatty acid alkanolamide type Agents are also suitable. The amount of these nonionic surfactants used is preferably Do not exceed the amount of toxylated fatty alcohol used, more preferably half No.   Other suitable surfactants are of formula (I): [Wherein, R^TwoCO is an aliphatic acyl group having 6 to 22 carbon atoms;¹Is hydrogen, carbon number An alkyl or hydroxyalkyl group having 1 to 4 carbon atoms, and [Z] has 3 to 10 carbon atoms. / A linear or branched polyhydroxyalkyl group having 3 to 10 hydroxyl groups You. ] Is a polyhydroxy fatty acid amide represented by Polyhydroxy fatty acid amide Preferably derived from a reducing sugar having 5 or 6 carbon atoms, especially glucose. .   The group of polyhydroxy fatty acid amides has the formula (II):[Wherein, R^ThreeIs a linear or branched alkyl or alkenyl having 7 to 12 carbon atoms And R is^FourIs a linear, branched or cyclic alkyl group having 2 to 8 carbon atoms or An aryl group;^FiveIs a linear, branched or cyclic alkyl having 1 to 8 carbon atoms Or an aryl or oxyalkyl group, preferably C_1-4Alkyl group Is a phenyl group, and [Z] is at least two hydroxyl groups on the alkyl chain. Is a straight-chain polyhydroxyalkyl group or its alkoxylation (preferably Or ethoxylated or propoxylated) derivatives. ] The compound represented by is also included. Also in this case, preferably, [Z] is a sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose Induced by reductive amination of sugar or xylose. Then, N-alkoxy -Or N-aryloxy-substituted compounds are described, for example, in International Patent Application WO-A-9. Fatty acid methyl ester in the presence of alkoxide as catalyst according to 5/07331 Can be converted to the desired polyhydroxy fatty acid amide.   Other suitable surfactants are the so-called Gemini surfactants. The Emini surfactants usually have two hydrophilic groups and two hydrophobic groups per molecule. Is understood to be a compound having These groups are usually called “spacers” Are separated from each other. Spacers typically have a hydrophilic group attached to each other. It is a carbon chain that must have a sufficient length to function independently. Gemini interface Activators typically have very low critical micelle concentrations and can significantly reduce the surface tension of water Characterized by nature. Gemini surfactants are not only dimeric surfactants, but also trimeric It is also sometimes understood to be a body surfactant.   Suitable gemini surfactants are described, for example, in German patent application DE-A-43 210 22 mixed sulfated ethers, as well as the earlier German patent application P195 Dimer alcohol bis- and trimer alcohol tris according to 03061.3 Sulphate and -ether sulphate. Earlier German Patent Application P19 The end-capped dimer and trimer mixed ether according to 513291.9 is It is characterized, inter alia, by its bifunctional and multifunctional nature. That is, like that Endcap surfactants have good wettability and low foaming properties, Particularly suitable for use in washing or cleaning methods.   International patent applications WO-A-95 / 19953, WO-A-95 / 19954 and And gemini polyhydroxy fatty acid amides described in WO-A-95 / 19955. Alternatively, a poly-polyhydroxy fatty acid amide may be used.   In an advantageous embodiment, the nonionic surfactant content in the final detergent is low. 2% by weight, preferably at least 4% by weight, and 5 to 12% by weight of nonio. Surfactant content is particularly preferred (especially detergents are used at low temperatures below 50 ° C.) Case). Basically, when the nonionic surfactant content in the detergent exceeds 12% by weight, Detergent performance can be further improved, but nonionic surfactants can be used at such high levels If so, often the granular detergent tends to lose fluidity and adhere to each other Or a tendency to form clumps. Therefore, the nonionic interface It is less preferred that the activator content exceeds 12% by weight.   The weight ratio between the anionic surfactant and the nonionic surfactant is at least 1: 1 (preferably 2.5: 1 to 1.1: 1). won. This is especially true when the soap content is up to 5% by weight relative to the total surfactant content. It is.   The total surfactant content of the detergent is preferably between 22 and 35% by weight. Detergent At least one anionic surfactant and at least one nonionic surfactant It is preferable to include a stimulant and optionally a soap.   In principle, besides the substances mentioned above, conventional phosphates, in particular tripolyphosphate sodium Thorium is naturally also suitable as a builder. However, in the detergents of the invention such The presence of a good builder is less preferred for ecological reasons.   The microcrystalline synthetic zeolite containing bound water used according to the invention is preferably a zeolite. Light A and / or zeolite P. As the zeolite P, for example, Ze olite MAP ™ (Crosfield) is particularly preferred. Zeolite X and zeolite Mixtures of lights A, X and / or P are also suitable. Zeolite is spray-dried Can be used in the form of a powder or in the form of an undried suspension that is still wet after manufacture . If the zeolite is used in the form of a suspension, the suspension may be used as a small stabilizer. Amount of nonionic surfactant, such as 1-3% by weight of ethoxy, based on zeolite Silylated C_12-18Fatty alcohol (2 to 5 ethylene oxide groups), ethoxylated C_{1 2-14} Fatty alcohol (4 to 5 ethylene oxide groups) or ethoxylated isoto It may contain lidecanol. Suitable zeolite has an average particle size of less than 10 μm (Volume distribution, measured by the Coulter Counter method), and bound water is preferably 18 -22% by weight, more preferably 20-22% by weight.   Suitable or partial substitutes for phosphates and zeolites have the formula: NaMSi_x O_{2x + 1}・ YH_TwoO [wherein M is sodium or hydrogen and x is a number from 1.9 to 4. And y is a number from 0 to 20, preferably x is 2, 3 or 4. ] Is a crystalline layered sodium silicate represented by Such crystalline layered silicates For example, it is described in European Patent Application EP-A-0164514. Shown by the above formula Preferred crystalline layered silicates are those wherein M is sodium and x is 2 or 3. is there. β- and δ-sodium disilicate sodium_TwoSi_TwoO_Five・ YH_TwoAny of O Particularly preferred.   Another preferred builder is modulus (Na_TwoO: SiO_TwoRatio) is 1: 2 to 1 : 3.3, preferably 1: 2 to 1: 2.8, more preferably 1: 2 to 1: 2.6 non-quality sodium silicate that dissolves slowly and exhibits secondary detergency You. Dissolution retardation for normal amorphous sodium silicate is, for example, surface treatment, compounding , Compression or overdrying. In the present invention, It is understood that “crystalline” also includes “X-ray amorphous”. In other words, X-ray diffraction analysis Silicate does not show the sharp X-ray reflection characteristic of crystalline materials, and has a diffraction angle width of several degrees. Mean only one or more scattered X-ray maxima. However , Silicate particles show weak or sharp diffraction maximum in electron diffraction analysis In some cases, particularly good builder performance can also be achieved. This means that there are not enough silicates Can be interpreted to mean having a microcrystalline portion of several hundred nm in size. This value Is preferably up to 50 nm, especially up to 20 nm. Such, Iwayu X-ray amorphous silicates that dissolve slowly compared to ordinary water glass are, for example, It is described, for example, in German Patent Application DE-A-4400024. Compressed amorphous silicon Salts, compounded amorphous silicates, and over-dried X-ray amorphous silicates are particularly preferred. No.   In particular, conventional alkali metal silicates that exhibit no builder action (so-called water It is also possible to use Water glass is a crystalline layered disilicate, and Before amorphous silicates with delayed solubility can be manufactured on an industrial scale Used in detergents. In the present invention, such water glass is also referred to as (simple type). ), A builder which can be used according to the invention, or can be present in the detergent according to the invention Intended to be included in builders.   Additional components that may be present in the builder-containing detergent include, among others, carbonates , Hydrogen carbonate and sesquicarbonate (especially sodium salts and / or Is a potassium salt). For example, carbonates having delayed solubility can be used. It may be in the form of a blend with the silicate. In a preferred embodiment of the present invention Means that the detergent is a carbonate, especially sodium carbonate and / or hydrogen carbonate. It contains 5 to 20% by weight, especially 10 to 15% by weight of thorium. Detergent zeo Light content of less than 20% by weight (preferably 10 to 18% by weight) ), A high carbonate content is particularly advantageous.   Suitable organic builders are, for example, polycarboxylic acids which can be used as sodium salts. Acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, amino acids Carboxylic acid, nitrilotriacetic acid (NTA), whose use is ecologically inconvenient And mixtures thereof. Preferred salts are polycarboxylic acids, For example, salts of citric, adipic, succinic, glutaric, tartaric, sugar acids, and And mixtures thereof.   The acid itself may be used. Such acids, besides builder action, are customarily Since it also acts as an acidifying component, the pH of the detergent or cleaner is relatively high. Also helps to keep it low and calm. Where citric acid, succinic acid, glutaric acid, Particular mention is made of adipic acid, gluconic acid and mixtures thereof.   Other suitable organic builders are for the partial hydrolysis of dextrins, such as starch. Thus, carbohydrate oligomers and polymers obtainable. Hydrolysis is , Standard methods such as acid or enzyme catalyzed methods. That Most The end product is preferably a hydrolysis product having an average molecular weight of 400 to 500,000. You. Polysaccharides with a dextrose equivalent (DE) of 0.5 to 40, especially 2 to 30, are preferred. No. DE is a measure of the reduction of polysaccharides compared to dextrose with a DE of 100 It is recognized that there is. Maltodextrin of DE 3-20 and DE 20-3 7, a relatively high molecular weight (2000-3000) Either yellow dextrin or white dextrin May be used.   Other suitable auxiliary builders are oxydisuccinates and other disuccinates A derivative, preferably ethylenediaminedisuccinate.   Other useful organic auxiliary builders are, for example, acetylated hydroxycarboxylic acids and And salts thereof, optionally in lactone form, having at least 4 carbon atoms. , The number of hydroxyl groups is at least 1, and the number of acid groups is up to 2. Such an auxiliary Ruder is described, for example, in International Patent Application WO-A-95 / 20029.   Suitable polymeric polycarboxylates include, for example, polyacrylic acid or polyacrylic acid. Sodium salt of methacrylic acid (for example, the relative molecular weight is 800 to 15,000 0). Suitable copolymer polycarboxylates are, inter alia, Consisting of lylic acid and methacrylic acid, and acrylic or methacrylic acid It is composed of oleic acid. Acrylic acid 50-90% by weight and maleic acid 5 Acrylic / maleic copolymers of from 0 to 10% by weight are particularly suitable. all right. Its relative molecular weight is usually 5,000 to 200,000 in terms of free acid, and Or 10,000 to 120,000, more preferably 50,000 to 100,000 is there.   The (co) polymer polycarboxylate may be used as a powder or an aqueous solution. A 20-55% by weight aqueous solution is preferred.   Biodegradable polymers composed of two or more different monomer units, such as acrylic acid And maleic acid salts, with vinyl alcohol or vinyl alcohol derivatives (DE-A-4300772), or a polymer containing Sulfonic acid and 2-alkylallylsulfonic acid salts and sugar derivatives as monomers. Also having polymers (DE-C-4221381) are particularly preferred.   Other preferred copolymers are German Patent Application DE-A-4303320 and DE-A-4417734, preferably acrolein and Lylic acid / acrylate, or acrolein and vinyl acetate as monomers Including.   Other suitable builders are carboxy-containing polyglucosan and / or its water It is an oxidation product of a soluble salt. This is described, for example, in International Patent Application WO-A-93 / 082. 51 and its production method is described, for example, in WO-A-93 / 16110. Have been. Oxidized oligosaccharides according to the earlier German patent application 196 008.1 are also suitable. It is.   Other preferred builders are polymeric aminodicarboxylic acids, salts or precursors thereof. It is. Polyaspartic acid and salts or derivatives thereof (German Patent Application 195 According to 4086.0, it has a bleaching stabilizing effect in addition to the auxiliary builder effect.) Is particularly preferred.   Other suitable builders are described, for example, in European Patent Application EP-A-0280223. As described above, the dialdehyde is converted to a polyalkylene having 5 to 7 carbon atoms / at least 3 hydroxyl groups. It is a polyacetal obtained by reacting with a thiol carboxylic acid. Preferred polyacetals are glyoxal, glutaraldehyde, terephthalate Dialdehydes such as aldehydes and mixtures thereof with gluconic acid and / or Or a polyol carboxylic acid such as glucoheptonic acid.   The total builder content of the detergent is determined by the amount of surfactant and the prescribed surfactant: builder weight Determined from the ratio. The surfactant: builder ratio is preferably from 1.1: 1 to 1: 1.1, especially 1: 1 to 1: 1.1. Usually inorganic building in detergent Builder content is higher than organic builder content, inorganic builder: organic builder weight The ratio is particularly preferably from 10: 1 to 3: 1.   The detergent may also contain, in addition to the above ingredients, known additives commonly used in detergents. You. Examples of additives include bleaching agents and bleaching activators or bleaching catalysts, foam inhibitors, polyphophates. Sulfonates, optical brighteners, enzymes, enzyme stabilizers, antifouling and anti-redeposition agents, small amounts And neutralizing salts, as well as pigments and fragrances, opacifiers or pearlescent agents.   H in water, acting as a bleach_TwoO_TwoOf the compounds that produce Lium tetrahydrate and monohydrate are of particular interest. Other useful bleaching agents are, for example, , Sodium percarbonate, peroxypyrophosphate, citrate perhydrate and H_TwoO_TwoFormed persalts or peracids (e.g. perbenzoate, peroxophthalate, diacid) Perazellaic acid, phthaloimino peracid or diperdocanedioic acid). Of the present invention The peroxy bleach content of the detergent is preferably 5 to 25% by weight, more preferably 1 to 25% by weight. 0 to 20% by weight. Perborate monohydrate or percarbonate may be used. It is profitable.   In order to improve the bleaching action when washing at a temperature of 60 ° C. or lower, A bleach activator may be combined with the formulations of the present invention. Examples of bleach activators are H_TwoO_TwoWith N-acyl or O-acyl compounds producing organic peracids, preferably polyacyl Alkylatediamines (eg, N, N'-tetraacylated diamines), Recalluril (especially tetraacetyl glycoluril), N-acylated arsenic Dantin, hydrazide, triazole, triazine, urazole, diketopipe Razine, sulfurylamide and cyanurate, and carboxylic esters (eg, For example, p- (alkanoyloxy) benzenesulfonate, especially sodium iso- Nonanoyloxybenzenesulfonate, and p- (alkenoyloxy)- Benzene sulfonate); caprolactam derivatives, carboxylic acid anhydrides (eg, anhydrous Phthalic acid) and polyol esters (eg glucose pentaacetate) is there. Other known bleach activators are described, for example, in European Patent Application EP-A-0525239. An acetylated mixture of sorbitol and mannitol, as described in Acetylated pentaerythritol. The bleach activator content of the bleach-containing detergent, It exceeds the usual range, preferably 1 to 10% by weight, more preferably 3% by weight. Special Preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine ( TAED) 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-to Riadine (DADHT) and acetylated sorbitol / mannitol mixture ( SOLMAN).   The bleach activator may be coated with the shell forming material in a known manner, or may be granulated. Alternatively, it may be extruded / pelletized. At this time, if necessary, Use methylcellulose and / or carboxymethylcellulose If so, other additives (for example, dyes) may be included. Such granules have bleaching activity The agent preferably contains more than 70% by weight, more preferably 90-99% by weight. You. It is preferred to use a bleach activator that produces peracetic acid under washing conditions.   In addition to or instead of the above-mentioned conventional bleach activators, EP 044 6982 and sulfonimines known from EP 0453003, and / or Or a transition metal salt or complex having a bleach-enhancing effect is called a bleaching catalyst. It may be present as a medium. Suitable transition metal compounds include, among others: Manganese-, iron-, Kovar known from German Patent Application DE 195 29 905 To-, ruthenium- or molybdenum-Salen complexes, and N-analogue thereof known from patent application DE 19620267, German patent application D Manganese-, iron-, cobalt-, ruthenium known from E19536082 Or a molybdenum-carbonyl complex, as described in German Patent Application DE 196 05 688. Manganese, iron, cobalt, ruthenium with the described nitrogen-containing tridentate ligands, Molybdenum, titanium, vanadium and copper complexes, German Patent Application DE19620 411, cobalt-, iron-, copper- and ruthenium-amine complexes, Manganese, copper and koval described in German Patent Application DE 44 16 438 Complex, the cobalt complex described in EP 0 272 030, the European patent Manganese complexes known from application EP0695550, EP 0 925 Manganese, iron, cobalt and copper complexes known by N.92 and / or Europe Patent EP0444351 or European patent applications EP0458397, EP0458 398, EP 0549271, EP 0549272, EP 0544490 and A manganese complex described in EP0544519. Bleaching activators and transition metals Combinations of bleaching catalysts are described, for example, in German Patent Application DE 19613103 and It is known from the international patent application WO 95/27775. Bleach-enhancing transition metal complex, In particular, the central atom is Mn, Fe, Co, Cu, Mo, V, Ti and / or What is Ru, the amount normally used, based on the total detergent / cleaner, is preferred. Up to 1% by weight, more preferably from 0.0025 to 0.25% by weight, most preferably Or 0.01 to 0.1% by weight.   If the detergent of the present invention is used in a washing machine, it is advantageous to add a conventional foam inhibitor. Can be Suitable foam inhibitors are, for example, C_18-24Natural and synthetic with high fatty acid content It is a soap derived from a product. Suitable non-surfactant foam inhibitors include, for example, organopolysiloxanes. Sun and mixtures thereof with fine, optionally silanized silica; and Paraffins, waxes, microcrystalline waxes and silanized silica or It is a mixture with su-stearylethylenediamine. Mixtures of various foam inhibitors, e.g. For example, it is advantageous to use a mixture of silicone, paraffin and wax. Can get. Foam inhibitors, especially silicone- and / or paraffin-containing foam inhibitors Is preferably fixed on a granular water-soluble or water-dispersible carrier. paraffin And mixtures of bis-stearylethylenediamine.   Suitable enzymes are, inter alia, hydrolases such as proteases, esterases, Lipase or lipolytic enzyme, amylase, cellulase or other glycosyl Selected from the group consisting of drolase and mixtures thereof. These hydrolases Are all soils (such as proteins, fats or starches) in the washing process. ) And discoloration. Cellulases and other glycos Silhydrolases can contribute to color retention and improved textile flexibility (pills) And by removal of microfibers). Use oxyreduct to prevent bleaching and transfer. A enzyme may be used.   Bacteria or fungi, such as Bacillus subtilis, Bacillus Bacillus Iicheniformis, Streptomyces glyce Hus (Streptomyces griseus) and Humicola insole ns) are particularly suitable. Subtilisin type protease Preferably used, obtained from Bacillus lentus Proteases are particularly preferred. Enzyme mixtures, such as protease / amylase, Or protease / lipase (or lipolytic enzyme), or Protease / cellulase mixture, or cellulase / lipase (or fat Degradation enzyme) mixture, or protease / amylase / lipase (or fat) Protease / lipase (or lipolytic enzyme) / cell Particularly preferred are mixtures of lase, mixtures containing protease and / or lipase. Or mixtures with lipolytic enzymes are more preferred. Of such lipolytic enzymes Examples are the known cutinases. Suitable for peroxidase or oxidase In some cases. Suitable amylases are, inter alia, α-amylases, isoamylases, Includes pullulanase and pectinase. A preferred cellulase is cellobio Hydrolases, endoglucanases and β-glucosidases (with cellobiase and ), And mixtures thereof. C depending on the type of cellulase Since the MCase and avicelase activities are different, mix the cellulases in appropriate ratios. By doing so, the desired activity can be achieved.   Enzymes may be adsorbed on a carrier and / or encapsulated in shell-forming material for early Can be protected from solution. The content of enzymes, enzyme mixtures or enzyme granules For example, it may be about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.   Stabilizers, especially those for per compounds and enzymes (heavy metal ion sensitive) Suitable are polyphosphonates, especially 1-hydroxyethane-1,1 Diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or a salt of ethylenediaminetetramethylenephosphonic acid .   Further, the detergents of the present invention are positive for the removal of oils and fats from textiles by washing. It may contain a component exhibiting an effect. This effect reduces such oil and fat dissolving ingredients. Particularly evident when soiling textiles that have already been washed repeatedly with a detergent according to the invention become. Preferred oil and fat dissolving components include, for example, nonionic cellulose acetate. Ter (e.g., for methylcellulose, and nonionic cellulose ethers) It has 15-30% by weight of methoxyl group / 1-15% by weight of hydroxyproxyl group Methylhydroxypropylcellulose), and the known phthalic acid and / or Are terephthalic acid polymers or their derivatives (especially ethylene terephthalate And / or a polymer of polyethylene glycol terephthalate or Anionic and / or nonionic modified derivative). Among them, Particularly preferred are the sulfonated derivatives of tallic and terephthalic acid polymers.   The function of the anti-redeposition agent is to keep dirt separated from the fiber suspended in This prevents dirt from being reabsorbed into the laundry. Appropriate reprecipitation Anti-adhesion agents are water-soluble and usually organic colloids, such as water-soluble polymeric carboxylic acids Salt, glue, gelatin, cellulose or starch ether carboxylic acid or Salts of ether sulfonic acids or acid sulfate esters of cellulose or starch Le salt. Water-soluble polyamides having acid groups are also suitable. Made of soluble starch And starch products other than those mentioned above, such as starch degradation products, aldehyde starch A pin or the like may be used. Polyvinylpyrrolidone is also suitable. Cellulose For example, carboxymethylcellulose (Na salt), methylcellulose, Droxyalkylcellulose, mixed ethers (e.g. Lurose, methylhydroxypropylcellulose, methylcarboxymethylcell Loin), and mixtures thereof, and polyvinylpyrrolidone, for example, 0.1 It is preferably used in an amount of up to 5% by weight.   The detergent of the present invention can be used as an optical brightener to induce diaminostilbene disulfonic acid. Body or an alkali metal salt thereof. Suitable optical brighteners are, for example, 4, 4'-bis- (2-anilino-4-morpholino-1,3,5-triazinyl-6-a A salt of (mino) -stilbene-2,2'-disulfonic acid, or a similar structure, A diethanolamino group, a methylamino group, an anilino group or 2 -A compound having a methoxyethylamino group. Of substituted diphenylstyryl type Brighteners, for example 4,4'-bis- (2-sulfostyryl) -diphenyl, 4,4'-biphenyl S- (4-chloro-3-sulfostyryl) -diphenyl or 4- (4-chloros Using an alkali metal salt of (tyryl) -4 '-(2-sulfostyryl) -diphenyl Is also good. Mixtures of the above whitening agents may be used.   The bulk density of the granular detergents of the present invention can vary within a wide range, but is preferably 0 to 1100 g / l.   The detergents of the present invention can be prepared by any known method, such as mixing, spray drying, granulating and extruding. It may be manufactured by a method.   In a particularly suitable method, a plurality of components, such as a spray-dried component, and granulation and And / or mix the extruded ingredients. Standard for spray dried or granulated ingredients Non-ionic surfactants (eg, especially ethoxylated fatty alcohols) Impregnation may be performed as a blend with C.I. Especially in granulation and extrusion processes The optional anionic surfactant is spray dried, granulated or extruded It is preferably used as a blend, which is added as a component during the process, Alternatively, it is used later as an additive for other granules. Spray drying, granulating and / or The extruded components may optionally be mixed with nonionic surfactants and / or liquids at processing temperatures. Other detergent components, such as carpet, impregnated with body or other components like wax Bonate, citrate or citric acid or other polycarboxylate or Are polycarboxylic acids, polymeric polycarboxylates, zeolites and / or Later addition of layered silicate (eg crystalline layered disilicate) It is possible and advantageous depending on the formulation. In a preferred embodiment of this method In this case, the surface of the detergent component or the entire detergent is then treated to obtain a nonionic surfactant. It reduces the adhesion of granules with a high content of active ingredient and / or improves the solubility. suitable Various surface treatment agents are conventionally known. Suitable surface treatment agents include fine particle Light, silica, amorphous silicates, fatty acids or fatty acid salts (eg, stearin Calcium oxide), a mixture of zeolite and silica, or zeolite and steel Mixtures of calcium phosphates are particularly preferred.   A preferred method for producing the detergent of the present invention having a bulk density of more than 600 g / l is granulation. Any of the standard methods may be used. For example, low-speed rotating mixer / compactor Mixer / granulator / compactor in or in tandem (preferably Or different stirring speeds). In the latter case, for example, first the so-called Performing the granulation step in a high speed mixer and then in a lower speed mixer, or It is possible to carry out the granulation step first in a low speed, then high speed mixer. the latter In this case, it is important that the granules formed are not ground again. Rotation conditions So-called tumbling granulation, in which an aggregate is formed below and compressed, is particularly preferred. This way The more finally obtained granules are substantially spherical. Rolling granulation, e.g. This can be done in a granulator (Marumerizer). International Patent Application WO-A-94 / 13779 May be performed.   Another preferred method of making the detergents of the present invention is extrusion. Above all, a plasticizer At a pressure of 25 to 200 bar in the presence of a lubricant and / or Extrude the mix or blend. Such extrusion methods are described, for example, in EP-EP- B-0486592 or German Patent Application P1963859.7. I have.   In another aspect, the present invention provides a method for washing a detergent as described above, Cleaning temperature, especially at the highest temperature 40 ° C, especially at the lowest 30 ° C up to 40 ° C. Or for use in mechanical cleaning. Just such a relatively low wash At temperatures, the detergents according to the invention are better (in some cases very Good cleaning performance).                                  Example   A granular detergent M having the following composition is extruded to produce a commercially available detergent (C: Ariel futu r; commercially available from April 1996). The bulk density of detergent M is 720 g / L.Composition of detergent M (% by weight) Anionic surfactant (alkylbenzene sulfonate And C_12-18Alkyl sulfate) 20 C_12-18Sodium fatty acid soap 1 C_12-18Fatty alcohol 7EO 10 Zeolite (in terms of water-free 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 Antifoam granules (15% silicone oil) 4 Silica (powdering agent) 0.5 Optical brightener 0.3 Water and salt (from solution) balance   Miele Novotronic W918 (171) type home washing machine, simulated hands-on A performance test was performed under the conditions. For this purpose, 3.5 kg of clean household laundry And 0.5 kg of soiled test fiber product was put into a washing machine.   Washing conditions:   Tap water with a hardness of 16 ° d (equivalent to 160 mg CaO / l); applied once for each detergent The amounts used are 76 g of the detergent M of the present invention and 84 g of the comparative detergent C (designated as appropriate for packaging). Washing temperature 30 ° C (1 cycle method, short-time washing program, ie washing Time 20 minutes), 40 ° C and 60 ° C (one cycle method, multiple washing (Buntwasch) Program, i.e., washing time 60 minutes); drying; 5 measurements.   Dirt: ・ Dust / wool fat-cotton (SW-B) ・ Dust / Sebum-Cotton (SH-B) ・ Dust / sebum-anti-wrinkled cotton (SH-BV) ・ Red wine-cotton (RB) -Cocoa-cotton (KB) ・ Black tea-anti-wrinkled cotton (T-BV) ・ Lipstick-polyester / wrinkled cotton blend (LS-PBV)   table   One-cycle cleaning performance at 30 ° C, 40 ° C and 60 ° C (reflectance%) (fluorescence (Excluding the effect of brightener)

Claims (1)

[Claims]   1. Select from the group of anionic surfactants, nonionic surfactants and soaps 20 to 55% by weight of a surfactant selected from the group consisting of inorganic and organic builders Or more builders, the total amount of surfactant used and the total builders A granular detergent whose weight ratio to the amount used is 1.2: 1 to 1: 1.2.   2. The detergent has a total surfactant content of 22-35% by weight, preferably at least Also one anionic surfactant and at least one nonionic surfactant 2. The detergent according to claim 1, further comprising a soap.   3. At least 2% by weight of nonionic surfactant, preferably at least 4% % Nonionic surfactant content in the final detergent is in particular 5 to 12% by weight The detergent according to claim 1 or 2, wherein   4. The weight ratio between the anionic surfactant and the nonionic surfactant is at least 4. The method according to claim 1, wherein the ratio is 1: 1, preferably 2.5: 1 to 1.1: 1. The detergent according to item 1.   5. The soap content of up to 5% by weight relative to the total surfactant content. detergent.   6. Carbonates, especially sodium carbonate and / or sodium bicarbonate 5. The composition according to claim 1, wherein the composition contains 5 to 20% by weight of the solvent. Detergent according to any of the above.   7. Contains 10 to 15% by weight of carbonate and converts zeolite to anhydrous active substance Detergent according to claim 6, containing less than 20% by weight, preferably 10 to 18% by weight.   8. The weight ratio of surfactant to builder is from 1.1: 1 to 1: 1.1, The detergent according to any one of claims 1 to 7, wherein the ratio is 1: 1 to 1: 1.1.   9. The detergent has a higher inorganic builder content than the organic builder content, The weight ratio between the organic builder and the organic builder is particularly preferably from 10: 1 to 3: 1. A detergent according to any one of claims 1 to 8.   10. Select from the group of anionic surfactants, nonionic surfactants and soaps 20 to 55% by weight of a surfactant to be selected from the group of inorganic and organic builders Contains one or more builders, the total amount of surfactant used and the builders Mixing a granular detergent having a weight ratio of 1.2: 1 to 1: 1.2 with respect to the total amount, A method of producing by spray drying, granulation and / or extrusion.   11. Select from the group of anionic surfactants, nonionic surfactants and soaps 20 to 55% by weight of a surfactant to be selected from the group of inorganic and organic builders Contains one or more builders, the total amount of surfactant used and the builders The use of a granular detergent having a weight ratio of 1.2: 1 to 1: 1.2 with respect to the total amount used. Therefore, a cleaning temperature of less than 50 ° C., especially a maximum temperature of 40 ° C., especially a minimum of Use in hand or machine cleaning at temperatures up to ° C.