EP0705328A1 - Washing agents with decolorization-inhibiting properties - Google Patents

Washing agents with decolorization-inhibiting properties

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Publication number
EP0705328A1
EP0705328A1 EP94919631A EP94919631A EP0705328A1 EP 0705328 A1 EP0705328 A1 EP 0705328A1 EP 94919631 A EP94919631 A EP 94919631A EP 94919631 A EP94919631 A EP 94919631A EP 0705328 A1 EP0705328 A1 EP 0705328A1
Authority
EP
European Patent Office
Prior art keywords
weight
acid
composition according
salts
anionic surfactants
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP94919631A
Other languages
German (de)
French (fr)
Inventor
Eduard Smulders
Günther VOGT
Gertrud Nienhaus
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0705328A1 publication Critical patent/EP0705328A1/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065High-density particulate detergent compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00Compositions of detergents, not provided for by one single preceding group
    • C11D10/04Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00Compositions of detergents, not provided for by one single preceding group
    • C11D10/04Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/045Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0021Dye-stain or dye-transfer inhibiting compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/128Aluminium silicates, e.g. zeolites
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to a solid, preferably granular detergent, which prevents the transfer of detached dyes during washing to other washed textiles without the addition of discoloration inhibitors such as polyvinylpyrrolidone.
  • the international patent application WO 92/18597 describes agents containing anionic surfactants and electrolytes which contain PVP with a low relative molecular weight between 5000 and 22000, while in the international application WO 92/18598 cellulase is additionally used to support the discoloration-inhibiting action of the PVP .
  • Weight ratios of anionic surfactants to PVP used which are usually at least 3: 1, for example in the range from 4: 1 to 16: 1 or well above. According to the older publication mentioned, however, the relatively high amounts of anionic surfactants accept a reduced effect of the PVP.
  • European patent application EP-A-0451 894 describes granular detergents with bulk densities of at least 600 g / l and improved washing-in behavior, which contain 5 to 45% by weight of a ternary surfactant system composed of anionic surfactants, nonionic surfactants and soap. wherein the weight ratio of anionic surfactants to nonionic surfactants is less than 5: 1 and the proportion of soap in the surfactant system is 10 to 90% by weight.
  • the object of the invention was to design a detergent which has discoloration-inhibiting properties without the usual color transmission inhibitor such as PVP is used.
  • the invention accordingly relates to a solid, preferably granular detergent with discoloration-inhibiting properties, which comprises 10 to 30% by weight of nonionic surfactants, 0 to 5% by weight of anionic surfactants, 1 to 6% by weight of fatty acid soaps, 20 to 60% %
  • a solid, preferably granular detergent with discoloration-inhibiting properties which comprises 10 to 30% by weight of nonionic surfactants, 0 to 5% by weight of anionic surfactants, 1 to 6% by weight of fatty acid soaps, 20 to 60% %
  • builder substances from the group of zeolites (anhydrous active substance) and layered silicates, but is free of polyvinylpyrrolidone.
  • the detergents according to the invention preferably have a weight ratio of nonionic surfactants to anionic surfactants of more than 2: 1 and in particular more than 2.5: 1, for example 3: 1 and above.
  • 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 30 moles of ethylene oxide (E0) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be, or may contain linear and methyl-branched residues in the mixture, as is usually the case in oxo alcohol most available.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 20 E0 per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C ⁇ 2-Ci4 alcohols with 3 E0 or 4 E0, Cg-Cn alcohol with 7 E0, Ci3-Ci5 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, Ci2-Ci8- Alcohols with 3 E0, 5 E0 or 7 E0 and mixtures of these, such as mixtures of Ci2-Ci4-alcohol with 3 E0 and C] .2-Ci8-alcohol with 5 E0, and alcohols of this type with 11, 14 or 16 E0.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • the compositions preferably contain 12 to 25% by weight of alkoxylated C 3 -C 10 alcohols and in particular 13 to 20% by weight of ethoxylated fatty alcohols.
  • 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, 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 described, for example, in Japanese Patent Application JP-A-58/217598 or preferably according to the process described in international patent application WO-A-90/13533 ⁇ be put.
  • the agents contain alkoxylated fatty acid alkyl esters preferably in amounts of 2 to 25% by weight, in particular in amounts of 5 to 20% by weight. Mixtures of ethoxylated fatty alcohols and alkoxylated fatty acid alkyl esters in a weight ratio of 3: 1 to 1: 3 are particularly preferred.
  • alkyl glycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18, C. -Atoms means 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, indicating the distribution of monoglycosides and oligoglycosides is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • the content of alkylglycosides in the compositions is generally about 0 to 15% by weight and preferably 2 to 10% by weight.
  • 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 alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols and the alkoxylated fatty acid alkyl esters, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • R ⁇ CO for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R ⁇ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the agents can contain anionic surfactants in amounts of preferably 0.5 to 8% by weight and in particular up to 5% by weight, preference being given, for example, to those of the sulfonate and / or sulfate type.
  • Preferred surfactants of the sulfonate type are the known C9-C13-alkylbenzenesulfonates, olefin sulfonates and alkanesulfonates. Also suitable are esters of ⁇ -sulfo fatty acids or the disalts of the ⁇ -sulfo fatty acids. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 Moles of glycerol can be obtained.
  • Suitable sulfate-type surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
  • the alk (en) yl sulfates are the sulfuric acid half-esters of the Ci2-Ci8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ⁇ o-C2 ⁇ -O ⁇ o alcohols, and those secondary alcohols this chain length preferred.
  • 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.
  • Ci6-Ci8-alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use Ci6-Ci8-alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and with relatively low detergents temperatures of, for example, room temperature to 40 ° C.
  • the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C12-C14-fatty alkyl sulfates or Ci2-Ci8-fatty alkyl sulfates with cis-Ci ⁇ -fatty alkyl sulfates and in particular Ci2-Ci6-fatty alkyl sulfates with Ci6 -Cj8 fatty alkyl sulfates.
  • not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C15 to C22 are used.
  • the sulfuric acid monoesters of the straight-chain or branched C7-C2i-alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched Cg-Cn-alcohols with an average of 3.5 mol of ethylene oxide (E0) or Ci2-Ci8 -Fatty alcohols with 2 to 4 E0 are suitable. Because of their high foaming behavior, they are only used in relatively small amounts in detergents.
  • the content of the agents in anionic surfactants and in particular in saturated and / or unsaturated fatty alk (en) yl sulfates, which are optionally ethoxylated, is preferably 0.5 to 8% by weight and in particular up to 5% by weight.
  • Suitable anionic surfactants are also 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. 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.
  • soaps preferably in amounts of 2 to 5% by weight.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated Ci2-C24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • anionic surfactants and the soaps can be present in the form of their alkali metal salts, such as the sodium, potassium or ammonium salts, and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • Preferred the anionic surfactants and soaps are present in the form of their sodium or potassium salts, in particular in the form of the sodium salts, I
  • the agents can contain so-called detergency boosters, which are known as such from the prior art.
  • Preferred detergent boosters are quaternary ammonium salts such as tri-alkyl-methylammonium halide, ethoxylated alkylamines such as cocoalkylamine with 2 EO and 1,2-alkanediols with 10 to 18 carbon atoms and 0 to 4 EO such as 1,2-dodecanediol or 1,2- Tetradecanediol.
  • builder substances which are inorganic in nature.
  • builder substances such as zeolites and layered silicates come into consideration.
  • organic builder substances are also present in the compositions.
  • the fine crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality.
  • zeolite X or zeolite P and mixtures of NaA and NaX 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.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 8 -fatty alcohols with 2 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water.
  • Suitable substitutes or partial substitutes for the zeolite are layer silicates of natural and synthetic origin. Layered silicates of this type are known, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Other suitable substitutes or partial substitutes for the zeolite are crystalline, layered sodium silicates of the general type. Formula NaMSi x ⁇ 2 ⁇ + yH2 ⁇ , where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline sheet silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ '-sodium diSilicates Na2Si2 ⁇ 5'yH2 ⁇ are preferred, ⁇ -sodium disilicate being able to be obtained, for example, by the process described in international patent application WO-A-91/08171.
  • the zeolite content of the agents (based on anhydrous active substance) and / or optionally crystalline layered sodium silicates is preferably 25 to 55% by weight and in particular 30 to 45% by weight, the use of zeolite or of zeolite and crystalline layered sodium silicates in a weight ratio of 4: 1 to 1: 2, advantageously from 3: 1 to 1: 1, particularly preferred.
  • Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their 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 sodium salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. Their content in the compositions is preferably 2 to 20% by weight.
  • zeolite-containing agents zeolite-free agents are preferred which contain crystalline layered silicates and polycarboxylates, in particular citrate, and optionally alkali metal carbonates as builders.
  • 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.
  • polymeric polycarboxylates which are biodegradable are preferred.
  • terpolymers which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomer and which are described in the earlier German patent applications P 4221 381.9 and P 4300722.4.
  • the content of the polymeric polycarboxylates and in particular of the biodegradable terpolymers is preferably 2 to 7% by weight.
  • 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.
  • Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these; in particular, alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio N ⁇ 2 ⁇ : Si ⁇ 2 of 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used.
  • the content of sodium carbonate in the agent is preferably up to 15% by weight, advantageously between 2 and 10% by weight.
  • the amorphous sodium silicate content of the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.
  • the agents can include known additives, for example graying agents, commonly used in detergents. ungsinhibitoren, foam inhibitors, salts of polyphosphonic acids, enzymes, enzyme stabilizers, small amounts of neutral filler salts as well as colors and fragrances and possibly also optical brighteners.
  • the agents may also optionally contain bleaches. It was found that compositions, in particular with bleach contents of up to, for example, about 10% by weight, have advantages in terms of primary washing power without the performance of the ink transfer inhibition of the composition being adversely affected.
  • peroxy bleaching agents such as perborate tetrahydrate, perborate monohydrate and percarbonate, if appropriate in combination with conventional bleach activators such as N, N, N ', N'-tetraacetylethylene diamine, is preferred.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin that have a high proportion of C 1 -C 24 fatty acids. The proportions of these soaps in the compositions are included in the amounts of soap specified above.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, e.g. those made of silicone, paraffins or waxes.
  • the foam inhibitors, in particular silicone 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.
  • the agents can also contain components which have a positive effect on the ability to wash off fat and fat from textiles. This effect is particularly evident when a textile is contaminated which has already been washed several times beforehand with a detergent according to the invention which contains these oil- and fat-dissolving components.
  • the preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 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.
  • nonionic cellulose ethers such as methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight
  • Graying inhibitors have the task of keeping the dirt detached from the fiber 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, e.g. degraded starch, aldehyde starches, etc.
  • cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose, and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, in particular mixtures containing cellulase, are of particular interest.
  • (Per) oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in Hü11 substances 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 up to about 2% by weight.
  • the salts of polyphosphonic acids are suitable as stabilizers. 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.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B4O7), is particularly advantageous.
  • the bulk density of the preferred granular agents is generally 300 to 1100 g / 1, in particular 500 to 1000 g / 1.
  • They can be prepared by any of the known processes, such as mixing, spray drying, granulation and extrusion, although spray drying processes are less preferred owing to the known pluming behavior of the nonionic ethoxylated alcohols. Processes in which several partial components, for example spray-dried components and granulated and / or extruded components, are mixed with one another are also particularly suitable. It is also possible for spray-dried or granulated components to be subsequently treated in the preparation, for example with nonionic surfactants, in particular ethoxylated fatty alcohols, by the customary processes.
  • anionic surfactants that may be present in the form of a spray-dried, granulated or extruded compound either as an admixture component in the process, in extrusion in particular for producing a solid premix intended for extrusion, or as an additive use other granules.
  • compositions for example carbonates, citrate or citric acid or other polycarboxylates or polycarboxylic acids, polymeric polycarboxylates, zeolite and / or layered silicates, which, if appropriate can be crystalline, subsequently mixed to spray-dried, granulated and / or extruded components, which are optionally treated with nonionic surfactants and / or other liquid to waxy ingredients at the processing temperature.
  • a method is preferred in which the surface of partial components of the agent or of the entire agent is subsequently treated to reduce the stickiness of the granules rich in nonionic surfactants and / or to improve their solubility. delt is.
  • Suitable surface modifiers are known from the prior art.
  • suitable, finely divided zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts, for example calcium stearate are particularly preferred, but mixtures of zeolite and silicas or zeolite and calcium stearate are particularly preferred.
  • Agents Ml to M7 according to the invention were produced by extrusion, the enzymes being subsequently added.
  • the anionic surfactant was premixed and extruded together with the other constituents as a granulated compound, prepared according to the teaching of application DE-A-4127323.
  • Table 1 Compositions of agents Ml to M7 and VI to V2 in% by weight
  • Sokalan DCS R ) 2 2 2 3 3 3 (dicarboxylic acid salts, hand-made product from BASF)

Abstract

Described are washing agents which possess decolorization-inhibiting properties without the need for the addition of one of the usual colour-transfer inhibitors such as PVP. These properties are due to the fact that the agents contain 10 to 30 % by wt. of non-ionic surfactants, 0 to 10 % by wt. of anionic surfactants, 1 to 6 % by wt. of fatty-acid soaps and 20 to 60 % by wt. of builders selected from the group comprising zeolites (anhydrous active substances) and phyllosilicates.

Description

"Waschmittel mit verfärbunαsinhibierenden Eigenschaften" "Detergent with discolouration-inhibiting properties"
Die Erfindung betrifft ein festes, vorzugsweise granuläres Waschmittel, das ohne Zusatz von Verfärbungsinhibitoren wie Polyvinylpyrrolidon die Übertragung von abgelösten Farbstoffen während der Wäsche auf andere mit-, gewaschene Textilien verhindert.The invention relates to a solid, preferably granular detergent, which prevents the transfer of detached dyes during washing to other washed textiles without the addition of discoloration inhibitors such as polyvinylpyrrolidone.
Beim gleichzeitigen Waschen von gefärbten Textilien oder Textilpartien mit ungefärbten oder hellfarbigen Textilien oder Textilpartien wird häufig beobachtet, daß von den stärker gefärbten Textilien oder Textilpartien Farbstoff auf die ungefärbten oder hellfarbigen Textilien oder Textilpar¬ tien übertragen und dadurch der ursprüngliche Farbton verändert wird. In gleicher Weise gilt dies auch für die Übertragung von optischen Aufhel¬ lern, mit denen Textilien häufig vom Hersteller her oder durch das Waschen mit aufhellerhaltigen Waschmitteln ausgerüstet sind. Diese unerwünschte Übertragung von Farbstoffen bzw. optischen Aufhellern zu verhindern oder zu verringern ist Gegenstand zahlreicher Patentanmeldungen. Ein für die gewünschte Verhinderung der Verfärbung gut geeignetes Mittel ist Polyvinyl¬ pyrrolidon (PVP). Ein Beispiel für Patentanmeldungen, in denen PVP alleine oder in Kombination mit anderen Wirkstoffen in Waschmitteln beschrieben wird, ist die deutsche Patentanmeldung DE-A-2232353. Dabei ist es wesent¬ lich, daß das Waschmittel mit einem Zusatz von PVP im wesentlichen frei von Aniontensiden ist. Auch die Anwesenheit von starken Elektrolyten ver¬ ringert nach der Offenbarung der deutschen Patenanmeldung DE-A-35 19 012 die Wirkung von PVP. Sowohl relativ geringe Mengen an Aniontensiden als auch an Elektrolyten weisen hingegen die PVP-haltigen Mittel in der euro¬ päischen Patentanmeldung EP-A-0262897 auf. Dabei ist es wesentlich, daß die eingesetzten nichtionischen Tenside bzw. ihre Mischung einen HLB-Wert von maximal 10,5 aufweisen. In der internationalen Patentanmeldung WO 92/18597 werden aniontensidhaltige und elektrolythaltige Mittel beschrie¬ ben, welche PVP mit einer niedrigen relativen Molekülmasse zwischen 5000 und 22000 enthalten, während in der internationalen Anmeldung WO 92/18598 zur Unterstützung der verfärbungsinhibierenden Wirkung des PVP zusätzlich Cellulase eingesetzt wird. Dabei werden in den jüngeren Anmeldungen Ge- Wichtsverhältnisse von Aniontensiden zu PVP eingesetzt, die üblicherweise mindestens 3:1, beispielsweise im Bereich von 4:1 bis 16:1 oder weit darü¬ ber betragen. Gemäß der älteren genannten Veröffentlichung wird durch die relativ hohen Mengen an Aniontensiden jedoch eine verringerte Wirkung des PVP in Kauf genommen.When washing colored textiles or textile sections with undyed or light-colored textiles or textile parts at the same time, it is frequently observed that dye is transferred from the more colored textiles or textile parts to the undyed or light-colored textiles or textile parts and the original color tone is thereby changed. In the same way, this also applies to the transmission of optical brighteners with which textiles are often equipped by the manufacturer or by washing with detergents containing brighteners. Preventing or reducing this undesired transfer of dyes or optical brighteners is the subject of numerous patent applications. A means which is well suited for the desired prevention of discoloration is polyvinyl pyrrolidone (PVP). An example of patent applications in which PVP is described alone or in combination with other active ingredients in detergents is the German patent application DE-A-2232353. It is essential that the detergent with the addition of PVP is essentially free of anionic surfactants. According to the disclosure of German patent application DE-A-35 19 012, the presence of strong electrolytes also reduces the effect of PVP. On the other hand, the PVP-containing agents in European patent application EP-A-0262897 have both relatively small amounts of anionic surfactants and electrolytes. It is essential that the nonionic surfactants used or their mixture have an HLB value of at most 10.5. The international patent application WO 92/18597 describes agents containing anionic surfactants and electrolytes which contain PVP with a low relative molecular weight between 5000 and 22000, while in the international application WO 92/18598 cellulase is additionally used to support the discoloration-inhibiting action of the PVP . In the more recent registrations, Weight ratios of anionic surfactants to PVP used, which are usually at least 3: 1, for example in the range from 4: 1 to 16: 1 or well above. According to the older publication mentioned, however, the relatively high amounts of anionic surfactants accept a reduced effect of the PVP.
In der europäischen Patentanmeldung EP-A-0451 894 werden granuläre Wasch¬ mittel mit Schüttgewichten von mindestens 600 g/1 und einem verbesserten Einspülverhalten beschrieben, welche 5 bis 45 Gew.-% eines ternären Ten- sidsystems aus Aniontensiden, Niotensiden und Seife enthalten, wobei das Gewichtsverhältnis Aniontenside zu Niotensiden kleiner als 5:1 ist und der Anteil der Seife an dem Tensidsyste 10 bis 90 Gew.-% beträgt.European patent application EP-A-0451 894 describes granular detergents with bulk densities of at least 600 g / l and improved washing-in behavior, which contain 5 to 45% by weight of a ternary surfactant system composed of anionic surfactants, nonionic surfactants and soap. wherein the weight ratio of anionic surfactants to nonionic surfactants is less than 5: 1 and the proportion of soap in the surfactant system is 10 to 90% by weight.
Da aus dem Stand der Technik bekannt war, daß die Wirkung von PVP als Farb- übertragungsinhibitor im hohen Maße von der Rezeptur abhängig ist, bestand die Aufgabe der Erfindung darin, ein Waschmittel zu konzipieren, welches verfärbungsinhibierende Eigenschaften besitzt, ohne daß ein üblicher Farb- übertragungsinhibitor wie PVP eingesetzt wird.Since it was known from the prior art that the effect of PVP as a color transfer inhibitor depends to a large extent on the formulation, the object of the invention was to design a detergent which has discoloration-inhibiting properties without the usual color transmission inhibitor such as PVP is used.
Gegenstand der Erfindung ist dementsprechend ein festes, vorzugsweise gra¬ nuläres Waschmittel mit verfärbungsinhibierenden Eigenschaften, welches 10 bis 30 Gew.-% Niotenside, 0 bis 5 Gew.-% Aniontenside, 1 bis 6 Gew.-% Fett¬ säureseifen, 20 bis 60 Gew.-% Buildersubstanzen aus der Gruppe der Zeo- lithe (wasserfreie Aktivsubstanz) und Schichtsilikate enthält, aber frei von Polyvinylpyrrolidon ist.The invention accordingly relates to a solid, preferably granular detergent with discoloration-inhibiting properties, which comprises 10 to 30% by weight of nonionic surfactants, 0 to 5% by weight of anionic surfactants, 1 to 6% by weight of fatty acid soaps, 20 to 60% % By weight of builder substances from the group of zeolites (anhydrous active substance) and layered silicates, but is free of polyvinylpyrrolidone.
Die erfindungsgemäßen Waschmittel, weisen vorzugsweise ein Gewichtsver¬ hältnis Niotenside zu Aniontensiden von mehr als 2:1 und insbesondere von mehr als 2,5:1, beispielsweise von 3:1 und darüber auf.The detergents according to the invention preferably have a weight ratio of nonionic surfactants to anionic surfactants of more than 2: 1 and in particular more than 2.5: 1, for example 3: 1 and above.
Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhaf¬ terweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 30 Mol Ethylenoxid (E0) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2- Stellung methylverzweigt sein kann, bzw. lineare und methylverzweigte Re¬ ste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholre- sten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus -Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z.B. aus Kokos-, Palm-, Taigfett- oder Oleylalkohol, und durchschnittlich 2 bis 20 E0 pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise Cχ2-Ci4-Alkohole mit 3 E0 oder 4 E0, Cg-Cn-Alkohol mit 7 E0, Ci3-Ci5-Alkohole mit 3 E0, 5 E0, 7 E0 oder 8 E0, Ci2-Ci8-Alkoho- le mit 3 E0, 5 E0 oder 7 E0 und Mischungen aus diesen, wie Mischungen aus Ci2-Ci4-Alkohol mit 3 E0 und C].2-Ci8-Alkohol mit 5 E0, und derartige Al¬ kohole mit 11, 14 oder 16 E0. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow ränge ethoxylates, NRE). Vorzugsweise enthalten die Mittel 12 bis 25 Gew.-% alkoxylierte Cß-Cig-Al- kohole und insbesondere 13 bis 20 Gew.-% ethoxylierte Fettalkohole.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 30 moles of ethylene oxide (E0) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be, or may contain linear and methyl-branched residues in the mixture, as is usually the case in oxo alcohol most available. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 20 E0 per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, Cχ2-Ci4 alcohols with 3 E0 or 4 E0, Cg-Cn alcohol with 7 E0, Ci3-Ci5 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, Ci2-Ci8- Alcohols with 3 E0, 5 E0 or 7 E0 and mixtures of these, such as mixtures of Ci2-Ci4-alcohol with 3 E0 and C] .2-Ci8-alcohol with 5 E0, and alcohols of this type with 11, 14 or 16 E0. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). The compositions preferably contain 12 to 25% by weight of alkoxylated C 3 -C 10 alcohols and in particular 13 to 20% by weight of ethoxylated fatty alcohols.
Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit an¬ deren nichtionischen Tensiden, insbesondere zusammen mit alkoxylierten Fettalkoholen, eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxy¬ lierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugs¬ weise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fett- säuremethylester, wie sie beispielsweise in der japanischen Patentanmel¬ dung JP-A-58/217598 beschrieben sind oder die vorzugsweise nach dem in der internationalen Patentanmeldung W0-A-90/13533 beschriebenen Verfahren her¬ gestellt werden. Die Mittel enthalten alkoxylierte Fettsäurealkylester vorzugsweise in Mengen von 2 bis 25 Gew.-%, insbesondere in Mengen von 5 bis 20 Gew.-%. Dabei sind Mischungen aus ethoxylierten Fettalkoholen und alkoxylierten Fettsäurealkylestern im Gewichtsverhältnis 3:1 bis 1:3 be¬ sonders bevorzugt.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, 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 described, for example, in Japanese Patent Application JP-A-58/217598 or preferably according to the process described in international patent application WO-A-90/13533 ¬ be put. The agents contain alkoxylated fatty acid alkyl esters preferably in amounts of 2 to 25% by weight, in particular in amounts of 5 to 20% by weight. Mixtures of ethoxylated fatty alcohols and alkoxylated fatty acid alkyl esters in a weight ratio of 3: 1 to 1: 3 are particularly preferred.
Außerdem können als weitere nichtionische Tenside auch Alkylglykoside der allgemeinen Formel R0(G)x eingesetzt werden, in der R einen primären ge- radkettigen oder methylverzweigten, insbesondere in 2-Stellung methylver¬ zweigten aliphatisehen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4. Der Gehalt der Mittel an Alkylglykosiden beträgt im allgemeinen etwa 0 bis 15 Gew.-% und vorzugsweise 2 bis 10 Gew.-%.In addition, alkyl glycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18, C. -Atoms means 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, indicating the distribution of monoglycosides and oligoglycosides is any number between 1 and 10; x is preferably 1.2 to 1.4. The content of alkylglycosides in the compositions is generally about 0 to 15% by weight and preferably 2 to 10% by weight.
Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokos- alkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtio¬ nischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole und der alkoxylierten Fettsäurealkylester, insbesondere nicht mehr als die Hälfte davon.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 alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols and the alkoxylated fatty acid alkyl esters, in particular not more than half of them.
Weitere geeignete Tenside sind Polyhydroxyfettsäureamide der Formel (I),Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
R3R3
II.
R2-C0-N-[Z] (I)R 2 -C0-N- [Z] (I)
in der R^CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffato- men, R^ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydro- xyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stof¬ fe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfol¬ gende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.in the R ^ CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ^ 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. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
Die Mittel können zusätzlich zu den Niotensiden Aniontenside in Mengen von vorzugsweise 0,5 bis 8 Gew.-% und insbesondere bis zu 5 Gew.-% enthalten, wobei beispielsweise solche vom Typ der Sulfonate und/oder der Sulfate bevorzugt sind.In addition to the nonionic surfactants, the agents can contain anionic surfactants in amounts of preferably 0.5 to 8% by weight and in particular up to 5% by weight, preference being given, for example, to those of the sulfonate and / or sulfate type.
Als Tenside vom Sulfonat-Typ kommen vorzugsweise die bekannten C9-C13-AI- kylbenzolsulfonate, Olefinsulfonate und Alkansulfonate in Betracht. Geeig¬ net sind auch Ester von α-Sulfofettsäuren bzw. die Disalze der α-Sulfo- fettsäuren. Weitere geeignete Aniontenside sind sulfierte Fettsäureglyce- rinester, welche Mono-, Di- und Triester sowie deren Gemische darstellen, wie sie bei der Herstellung durch Veresterung durch ein Monoglycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden.Preferred surfactants of the sulfonate type are the known C9-C13-alkylbenzenesulfonates, olefin sulfonates and alkanesulfonates. Also suitable are esters of α-sulfo fatty acids or the disalts of the α-sulfo fatty acids. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 Moles of glycerol can be obtained.
Geeignete Tenside vom Sulfat-Typ sind die Schwefelsäuremonoester aus pri¬ mären Alkoholen natürlichen und synthetischen Ursprungs. Als Alk(en)yl- sulfate werden die Schwefelsäurehalbester der Ci2-Ci8-Fettalkohole bei¬ spielsweise aus Kokosfettalkohol, Taigfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol, oder den Cιo-C2θ-Oχoalkoholen, und diejenigen sekundärer Alkohole dieser Kettenlänge bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der Basis von fettchemischen Rohstoffen. Aus waschtechnischem Inter¬ esse sind Ci6-Ci8-Alk(en)ylsulfate insbesondere bevorzugt. Dabei kann es auch von besonderem Vorteil und insbesondere für maschinelle Waschmittel von Vorteil sein, Ci6-Ci8-Alk(en)ylsulfate in Kombination mit niedriger schmelzenden Aniontensiden und insbesondere mit solchen Aniontensiden, die einen niedrigeren Krafft-Punkt aufweisen und bei relativ niedrigen Wasch¬ temperaturen von beispielsweise Raumtemperatur bis 40 °C eine geringe Kri¬ stallisationsneigung zeigen, einzusetzen. In einer bevorzugten Ausführungs¬ form der Erfindung enthalten die Mittel daher Mischungen aus kurzkettigen und langkettigen FettalkylSulfaten, vorzugsweise Mischungen aus C12-C14- Fettalkylsulfaten oder Ci2-Ci8-Fettalkylsulfaten mit Cis-Ciβ-Fettalkyl- sulfaten und insbesondere Ci2-Ci6-Fettalkylsulfaten mit Ci6-Cj8-Fettalkyl- sulfaten. In einer weiteren bevorzugten Ausführungsform der Erfindung wer¬ den jedoch nicht nur gesättigte Alkylsulfate, sondern auch ungesättigte Alkenylsulfate mit einer Alkenylkettenlänge von vorzugsweise C15 bis C22 eingesetzt. Dabei sind insbesondere Mischungen aus gesättigten, überwie¬ gend aus Ciö bestehenden sulfierten Fettalkoholen und ungesättigten, über¬ wiegend aus Cis bestehenden sulfierten Fettalkoholen bevorzugt, beispiels¬ weise solche, die sich von festen oder flüssigen Fettalkoholmischungen des Typs HD-Ocenol (R) (Handelsprodukt des Anmelders) ableiten. Dabei sind Gewichtsverhältnisse von Alkylsulfaten zu Alkenylsulfaten von 10:1 bis 1:2 und insbesondere von etwa 5:1 bis 1:1 bevorzugt.Suitable sulfate-type surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin. The alk (en) yl sulfates are the sulfuric acid half-esters of the Ci2-Ci8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the Cιo-C2θ-O χo alcohols, and those secondary alcohols this chain length 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. Ci6-Ci8-alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use Ci6-Ci8-alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and with relatively low detergents temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize. In a preferred embodiment of the invention, the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C12-C14-fatty alkyl sulfates or Ci2-Ci8-fatty alkyl sulfates with cis-Ciβ-fatty alkyl sulfates and in particular Ci2-Ci6-fatty alkyl sulfates with Ci6 -Cj8 fatty alkyl sulfates. In a further preferred embodiment of the invention, however, not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C15 to C22 are used. Mixtures of saturated sulfated fatty alcohols consisting predominantly of Ciö and unsaturated sulfated fatty alcohols consisting predominantly of cis are particularly preferred, for example those which are derived from solid or liquid fatty alcohol mixtures of the HD-Ocenol ( R ) type (commercial product) of the applicant). Are there Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.
Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxy¬ lierten geradkettigen oder verzweigten C7-C2i~Alkohole, wie 2-Methyl-ver- zweigte Cg-Cn-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (E0) oder Ci2-Ci8-Fettalkohole mit 2 bis 4 E0, sind geeignet. Sie werden in Wasch¬ mitteln aufgrund ihres hohen Schaumverhaltens nur in relativ geringen Men¬ gen eingesetzt.The sulfuric acid monoesters of the straight-chain or branched C7-C2i-alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-Cn-alcohols with an average of 3.5 mol of ethylene oxide (E0) or Ci2-Ci8 -Fatty alcohols with 2 to 4 E0 are suitable. Because of their high foaming behavior, they are only used in relatively small amounts in detergents.
Der Gehalt der Mittel an Aniontensiden und insbesondere an gesättigten und/oder ungesättigten Fettalk(en)ylsulfaten, die gegebenenfalls ethoxy- liert sind, beträgt vorzugsweise 0,5 bis 8 Gew.-% und insbesondere bis 5 Gew.-%.The content of the agents in anionic surfactants and in particular in saturated and / or unsaturated fatty alk (en) yl sulfates, which are optionally ethoxylated, is preferably 0.5 to 8% by weight and in particular up to 5% by weight.
Geeignete Aniontenside sind auch die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeichnet werden und die Monoester und/oder Diester der Sulfobernsteinsäure mit Al¬ koholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fett¬ alkoholen darstellen. Ebenso ist es auch möglich, Alk(en)ylbernsteinsäure mit vorzugsweise 8 bis 18 Kohlenstoffatomen in der Alk(en)ylkette oder deren Salze einzusetzen.Suitable anionic surfactants are also 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. 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.
Weitere Bestandteile der erfindungsgemäßen Mittel sind Seifen vorzugsweise in Mengen von 2 bis 5 Gew.-%. Geeignet sind gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure oder Stearin¬ säure, sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palm¬ kern- oder Taigfettsäuren, abgeleitete Seifengemische. Insbesondere sind solche Seifengemische bevorzugt, die zu 50 bis 100 Gew.-% aus gesättigten Ci2-C24-Fettsäureseifen und zu 0 bis 50 Gew.-% aus Ölsäureseife zusammen¬ gesetzt sind.Other components of the agents according to the invention are soaps, preferably in amounts of 2 to 5% by weight. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. In particular, those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated Ci2-C24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
Die anionischen Tenside sowie die Seifen können in Form ihrer Alkalisalze wie der Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze or¬ ganischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugs- weise liegen die anionischen Tenside und Seifen in Form ihrer Natrium¬ oder Kaliumsalze, insbesondere in Form der Natriumsalze vor, IThe anionic surfactants and the soaps can be present in the form of their alkali metal salts, such as the sodium, potassium or ammonium salts, and as soluble salts of organic bases, such as mono-, di- or triethanolamine. Preferred the anionic surfactants and soaps are present in the form of their sodium or potassium salts, in particular in the form of the sodium salts, I
Zusätzlich können die Mittel sogenannte Waschkraftverstärker enthalten, die als solche aus dem Stand der Technik bekannt sind. Bevorzugte Wasch¬ kraftverstärker sind quartäre Ammoniumsalze wie TriaIkyl-methylammonium- halogenid, ethoxylierte Alkylamine wie Kokosalkylamin mit 2 EO und 1,2- Alkandiole mit 10 bis 18 Kohlenstoffatomen und 0 bis 4 EO wie 1,2-Dodecan- diol oder 1,2-Tetradecandiol.In addition, the agents can contain so-called detergency boosters, which are known as such from the prior art. Preferred detergent boosters are quaternary ammonium salts such as tri-alkyl-methylammonium halide, ethoxylated alkylamines such as cocoalkylamine with 2 EO and 1,2-alkanediols with 10 to 18 carbon atoms and 0 to 4 EO such as 1,2-dodecanediol or 1,2- Tetradecanediol.
Ein weiteres wesentliches Merkmal ist durch den Gehalt an Buildersubstan- zen gegeben, welche anorganischer Natur sind. Hierbei kommen Buildersub- stanzen wie Zeolithe und Schichtsilikate in Betracht. In einer bevorzugten Ausführungsform der Erfindung liegen neben diesen anorganischen auch orga¬ nische Buildersubstanzen in den Mitteln vor.Another essential feature is the content of builder substances, which are inorganic in nature. Here, builder substances such as zeolites and layered silicates come into consideration. In a preferred embodiment of the invention, in addition to these inorganic, organic builder substances are also present in the compositions.
Der eingesetzte feinkristalline, synthetische und gebundenes Wasser ent¬ haltende Zeolith ist vorzugsweise Zeolith NaA in Waschmittelqualität. Ge¬ eignet sind jedoch auch beispielsweise Zeolith X oder Zeolith P sowie Mi¬ schungen aus NaA und NaX. Der Zeolith kann als sprühgetrocknetes Pulver oder auch als ungetrocknete, von ihrer Herstellung noch feuchte, stabili¬ sierte Suspension zum Einsatz kommen. Für den Fall, daß der Zeolith als Suspension eingesetzt wird, kann diese geringe Zusätze an nichtionischen Tensiden als Stabilisatoren enthalten, beispielsweise 1 bis 3 Gew.-%, be¬ zogen auf Zeolith, an ethoxylierten Ci2-Ci8-Fettalkoholen mit 2 bis 5 Ethylenoxidgruppen oder ethoxylierte Isotridecanole. Geeignete Zeolithe weisen eine mittlere Teilchengröße von weniger als 10 μm (VolumenVertei¬ lung; Meßmethode: Coulter Counter) auf und enthalten vorzugsweise 18 bis 22, insbesondere 20 bis 22 Gew.-% an gebundenem Wasser.The fine crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. However, zeolite X or zeolite P and mixtures of NaA and NaX 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 may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 8 -fatty alcohols with 2 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, in particular 20 to 22% by weight of bound water.
Geeignete Substitute bzw. Teilsubstitute für den Zeolith sind Schichtsi¬ likate natürlichen und synthetischen Ursprungs. Derartige Schichtsilikate sind beispielsweise aus den Patentanmeldungen DE-B-23 34 899, EP-A-0 026 529 und DE-A-35 26 405 bekannt. Ihre Verwendbarkeit ist nicht auf eine spezielle Zusammensetzung bzw. Strukturformel beschränkt. Bevorzugt sind hier jedoch Smectite, insbesondere Bentonite. Weitere geeignete Substitute bzw. Teilsubstitute für den Zeolith sind kri¬ stalline, schichtförmige Natriumsilikate der allgemeinen,. Formel NaMSixθ2χ+ yH2θ, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Derartige kristalline Schichtsilikate werden beispiels¬ weise in der europäischen Patentanmeldung EP-A-0 164 514 beschrieben. Be¬ vorzugte kristalline Schichtsilikate der angegebenen Formel sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt. Insbeson¬ dere sind sowohl ß- als auch δ'-NatriumdiSilikate Na2Si2θ5'yH2θ bevorzugt, wobei ß-Natriumdisilikat beispielsweise nach dem Verfahren erhalten werden kann, das in der internationalen Patentanmeldung W0-A-91/08171 beschrieben ist.Suitable substitutes or partial substitutes for the zeolite are layer silicates of natural and synthetic origin. Layered silicates of this type are known, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Other suitable substitutes or partial substitutes for the zeolite are crystalline, layered sodium silicates of the general type. Formula NaMSi x θ2χ + yH2θ, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline sheet silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ'-sodium diSilicates Na2Si2θ5'yH2θ are preferred, β-sodium disilicate being able to be obtained, for example, by the process described in international patent application WO-A-91/08171.
Der Gehalt der Mittel an Zeolith (bezogen auf wasserfreie Aktivsubstanz) und/oder gegebenenfalls kristallinen schichtförmigen Natriumsilikaten be¬ trägt vorzugsweise 25 bis 55 Gew.-% und insbesondere 30 bis 45 Gew.-%, wobei der Einsatz von Zeolith oder von Zeolith und kristallinen schicht¬ förmigen Natriumsilikaten im Gewichtsverhältnis 4:1 bis 1:2, vorteilhafter¬ weise von 3:1 bis 1:1, insbesondere bevorzugt ist.The zeolite content of the agents (based on anhydrous active substance) and / or optionally crystalline layered sodium silicates is preferably 25 to 55% by weight and in particular 30 to 45% by weight, the use of zeolite or of zeolite and crystalline layered sodium silicates in a weight ratio of 4: 1 to 1: 2, advantageously from 3: 1 to 1: 1, particularly preferred.
Brauchbare organische Gerüstsubstanzen sind beispielsweise die bevorzugt in Form ihrer Salze eingesetzten Polycarbonsäuren, wie Citronensäure, Adi- pinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren, Aminocar- bonsäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus die¬ sen. Bevorzugte Salze sind die Natriumsalze der Polycarbonsäuren wie Ci¬ tronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zucker¬ säuren und Mischungen aus diesen. Ihr Gehalt in den Mitteln beträgt vor¬ zugsweise 2 bis 20 Gew.-%. Dabei sind neben zeolithhaltigen Mitteln auch zeolithfreie Mittel bevorzugt, die als Gerüststoffe kristalline Schicht¬ silikate und Polycarboxylate, insbesondere Citrat, sowie gegebenenfalls Alkalicarbonate enthalten.Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their 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 sodium salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. Their content in the compositions is preferably 2 to 20% by weight. In addition to zeolite-containing agents, zeolite-free agents are preferred which contain crystalline layered silicates and polycarboxylates, in particular citrate, and optionally alkali metal carbonates as builders.
Geeignete polymere Polycarboxylate sind beispielsweise die Natriumsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 800 bis 150000 (auf Säure bezogen). Ge- eignete copolymere Polycarboxylate sind insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäu¬ re erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Malein¬ säure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 5000 bis 200000, vorzugsweise 10000 bis 120000 und insbesondere 50000 bis 100000. Insbesondere sind auch polymere Polycarb¬ oxylate bevorzugt, die biologisch abbaubar sind. Hierzu zählen beispiels¬ weise Terpolymere, die als Monomere Salze der Acrylsäure und der Malein¬ säure sowie Vinylalkohol bzw. Vinylalkohol-Derivate oder die als Monomere Salze der Acrylsäure und der 2-Alkylallylsulfonsäure sowie Zucker-Derivate enthalten und die in den älteren deutschen Patentanmeldungen P 4221 381.9 und P 4300722.4 beschrieben werden. Der Gehalt der poly eren Polycarb¬ oxylate und insbesondere der biologisch abbaubaren Terpolymere beträgt vorzugsweise 2 bis 7 Gew.-%.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. In particular, polymeric polycarboxylates which are biodegradable are preferred. These include, for example, terpolymers which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomer and which are described in the earlier German patent applications P 4221 381.9 and P 4300722.4. The content of the polymeric polycarboxylates and in particular of the biodegradable terpolymers is preferably 2 to 7% by weight.
Weitere geeignete Buildersubstanzen sind Polyacetale, welche durch Umset¬ zung von Dialdehyden mit Polyolcarbonsäuren, welche 5 bis 7 C-Atome und mindestens 3 Hydroxylgruppen aufweisen, beispielsweise wie in der europä¬ ischen Patentanmeldung EP-A-0 280 223 beschrieben erhalten werden können. Bevorzugte Polyacetale werden aus Dialdehyden wie Glyoxal, Glutaraldehyd, Terephthalaldehyd sowie deren Gemischen und aus Polyolcarbonsäuren wie Gluconsäure und/oder Glucoheptonsäure erhalten.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.
Weitere geeignete Inhaltsstoffe der Mittel sind wasserlösliche anorgani¬ sche Salze wie Bicarbonate, Carbonate, amorphe Silikate oder Mischungen aus diesen; insbesondere werden Alkalicarbonat und amorphes Alkalisilikat, vor allem Natriumsilikat mit einem molaren Verhältnis Nβ2θ : Siθ2 von 1:1 bis 1:4,5, vorzugsweise von 1:2 bis 1:3,5, eingesetzt. Der Gehalt der Mit¬ tel an Natriumcarbonat beträgt dabei vorzugsweise bis zu 15 Gew.-%, vor¬ teilhafterweise zwischen 2 und 10 Gew.-%. Der Gehalt der Mittel an amor¬ phem Natriumsilikat beträgt im allgemeinen bis zu 10 Gew.-% und vorzugs¬ weise zwischen 2 und 8 Gew.-%.Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these; in particular, alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Nβ2θ: Siθ2 of 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used. The content of sodium carbonate in the agent is preferably up to 15% by weight, advantageously between 2 and 10% by weight. The amorphous sodium silicate content of the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.
Außer den genannten Inhaltsstoffen können die Mittel bekannte, in Wasch¬ mitteln üblicherweise eingesetzte Zusatzstoffe, beispielsweise Vergrau- ungsinhibitoren, Schauminhibitoren, Salze von Polyphosphonsäuren, Enzyme, Enzymstabilisatoren, geringe Mengen an neutralen Füllsalzen sowie Farb- und Duftstoffe und gegebenfalls auch optische Aufheller enthalten. Eben¬ falls fakultativ können die Mittel Bleichmittel enthalten. Dabei wurde festgestellt, daß Mittel insbesondere mit Gehalten an Bleichmittel bis beispielsweise etwa 10 Gew.-% Vorteile bezüglich des Primärwaschvermögens aufweisen, ohne daß die Leistung der Farbübertragungsinhibierung des Mittels negativ beeinflußt wird. Insbesondere ist dabei der Einsatz von Peroxybleichmitteln wie Perborattetrahydrat, Perboratmonohydrat und Per- carbonat gegebenenfalls in Kombination mit üblichen Bleichaktivatoren wie N,N,N' ,N'-Tetraacetylethylendiamin bevorzugt.In addition to the ingredients mentioned, the agents can include known additives, for example graying agents, commonly used in detergents. ungsinhibitoren, foam inhibitors, salts of polyphosphonic acids, enzymes, enzyme stabilizers, small amounts of neutral filler salts as well as colors and fragrances and possibly also optical brighteners. The agents may also optionally contain bleaches. It was found that compositions, in particular with bleach contents of up to, for example, about 10% by weight, have advantages in terms of primary washing power without the performance of the ink transfer inhibition of the composition being adversely affected. In particular, the use of peroxy bleaching agents such as perborate tetrahydrate, perborate monohydrate and percarbonate, if appropriate in combination with conventional bleach activators such as N, N, N ', N'-tetraacetylethylene diamine, is preferred.
Beim Einsatz in maschinellen Waschverfahren kann es von Vorteil sein, den Mitteln übliche Schauminhibitoren zuzusetzen. Als Schauminhibitoren eignen sich beispielsweise Seifen natürlicher oder synthetischer Herkunft, die einen hohen Anteil an Cιs-C24-Fettsäuren aufweisen. Die Anteile dieser Seifen in den Mitteln sind in die oben angegebenen Seifenmengen einbezo¬ gen. Geeignete nichttensidartige Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, ggf. silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemi¬ sche mit silanierter Kieselsäure oder Bistearylethylendiamid. Mit Vortei¬ len werden auch Gemische aus verschiedenen Schauminhibitoren verwendet, z.B. solche aus Silikonen, Paraffinen oder Wachsen. Vorzugsweise sind die Schauminhibitoren, insbesondere Silikon- oder Paraffin-haltige Schauminhi¬ bitoren, an eine granuläre, in Wasser lösliche bzw. dispergierbare Träger¬ substanz gebunden. Insbesondere sind dabei Mischungen aus Paraffinen und Bistearylethylendiamiden bevorzugt.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 that have a high proportion of C 1 -C 24 fatty acids. The proportions of these soaps in the compositions are included in the amounts of soap specified above. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, e.g. those made of silicone, paraffins or waxes. The foam inhibitors, in particular silicone 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.
Zusätzlich können die Mittel auch Komponenten enthalten, welche die 01- und Fettauswaschbarkeit aus Textilien positiv beeinflussen. Dieser Effekt wird besonders deutlich, wenn ein Textil verschmutzt wird, das bereits vorher mehrfach mit einem erfindungsgemäßen Waschmittel, das diese öl- und fettlösenden Komponenten enthält, gewaschen wird. Zu den bevorzugten öl- und fettlösenden Komponenten zählen beispielsweise nichtionische Cellulose- ether wie Methylhydroxypropylcellulose mit einem Anteil an Methoxyl-Gruppen von 15 bis 30 Gew.-% und an Hydroxypropoxyl-Gruppen von 1 bis 15 Gew.-%, jeweils bezogen auf den nichtionischen Celluloseether, sowie die aus dem Stand der Technik bekannten Polymere der Phthalsäure und/oder der Ter- ephthalsäure bzw. von deren Derivaten, insbesondere Polymere aus Ethylen- terephthalaten und/oder Polyethylenglykol-terephthalaten.In addition, the agents can also contain components which have a positive effect on the ability to wash off fat and fat from textiles. This effect is particularly evident when a textile is contaminated which has already been washed several times beforehand with a detergent according to the invention which contains these oil- and fat-dissolving components. The preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 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.
Vergrauungsinhibitoren haben die Aufgabe, den von der Faser abgelösten Schmutz in der Flotte suspendiert zu halten und so das Vergrauen zu ver¬ hindern. Hierzu sind wasserlösliche Kolloide meist organischer Natur ge¬ eignet, beispielsweise die wasserlöslichen Salze polymerer Carbonsäuren, Leim, Gelatine, Salze von Ethercarbonsäuren oder Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren SchwefelSäureestern der Cellulose oder der Stärke. Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet. Weiterhin lassen sich lösliche Stärkepräparate und andere als die obengenannten Stärkeprodukte verwenden, z.B. abgebaute Stärke, Aldehydstärken usw.. Bevorzugt werden jedoch Cellu¬ loseether, wie Carboxymethylcellulose, Methylcellulose, Hydroxyalkylcellu¬ lose und Mischether, wie Methylhydroxyethylcellulose, Methylhydroxypropyl- cellulose, Methylcarboxymethylcellulose und deren Gemische, eingesetzt.Graying inhibitors have the task of keeping the dirt detached from the fiber 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, e.g. degraded starch, aldehyde starches, etc. However, preference is given to using cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose, and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.
Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen, Cellulasen bzw. deren Gemische in Frage. Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus lichenifor- mis und Streptomyces griseus gewonnene enzymatische Wirkstoffe. Vorzugs¬ weise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Dabei sind Enzymmischun¬ gen, beispielsweise aus Protease und Amylase oder Protease und Lipase oder Protease und Cellulase oder aus Cellulase und Lipase oder aus Protease, Amylase und Lipase oder Protease, Lipase und Cellulase, insbesondere Cel- lulase-haltige Mischungen von besonderem Interesse. Auch (Per-)Oxidasen haben sich in einigen Fällen als geeignet erwiesen. Die Enzyme können an Trägerstoffen adsorbiert und/oder in Hü11Substanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen. Der Anteil der Enzyme, En¬ zymmischungen oder Enzymgranulate kann beispielsweise etwa 0,1 bis 5 Gew.-%, vorzugsweise bis etwa 2 Gew.-% betragen. Als Stabilisatoren kommen die Salze von Polyphosphonsäuren, insbesondere l-Hydroxyethan-l,l-diphos- phonsäure (HEDP) in Betracht. Möglich ist auch der Einsatz von Proteasen, die mit löslichen Calciumsalzen.und einem Calciumgehalt von vorzugsweise etwa l,2-Gew.-%, bezogen auf das Enzym, stabilisiert sind. Besonders vor¬ teilhaft ist jedoch der Einsatz von Borverbindungen, beispielsweise von Borsäure, Boroxid, Borax und anderen Alkalimetallboraten wie den Salzen der Orthoborsäure (H3BO3), der Metaborsäure (HBO2) und der Pyroborsäure (Tetraborsäure H2B4O7).Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, in particular mixtures containing cellulase, are of particular interest. (Per) oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in Hü11 substances 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 up to about 2% by weight. The salts of polyphosphonic acids, in particular l-hydroxyethane-l, l-diphosphonic acid (HEDP), are suitable as stabilizers. It is also possible to use proteases, which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B4O7), is particularly advantageous.
Das Schüttgewicht der bevorzugten granulären Mittel beträgt im allgemeinen 300 bis 1100 g/1, insbesondere 500 bis 1000 g/1. Ihre Herstellung kann nach jedem der bekannten Verfahren wie Mischen, Sprühtrocknung, Granulie¬ ren und Extrudieren erfolgen, wobei jedoch Sprühtrocknungsverfahren auf¬ grund des bekannten pluming-Verhaltens der nichtionischen ethoxylierten Alkohole weniger bevorzugt sind. Geeignet sind insbesondere auch solche Verfahren, in denen mehrere Teilkomponenten, beispielsweise sprühgetrock¬ nete Komponenten und granulierte und/oder extrudierte Komponenten mitein¬ ander vermischt werden. Dabei ist es auch möglich, daß sprühgetrocknete oder granulierte Komponenten nachträglich in der Aufbereitung beispiels¬ weise mit nichtionischen Tensiden, insbesondere ethoxylierten Fettalko¬ holen, nach den üblichen Verfahren beaufschlagt werden. Insbesondere in Granulations- und Extrusionsverfahren ist es bevorzugt, die gegebenenfalls vorhandenen Aniontenside in Form eines sprühgetrockneten, granulierten oder extrudierten Compounds entweder als Zumischkomponente in dem Verfah¬ ren, bei der Extrusion insbesondere zur Herstellung eines zur Extrusion bestimmten festen Vorgemisches, oder als Additiv nachträglich zu anderen Granulaten einzusetzen. Ebenso ist es möglich und kann in Abhängigkeit von der Rezeptur von Vorteil sein, wenn weitere einzelne Bestandteile des Mit¬ tels, beispielsweise Carbonate, Citrat bzw. Citronensäure oder andere Po¬ lycarboxylate bzw. Polycarbonsäuren, polymere Polycarboxylate Zeolith und/oder Schichtsilikate, die gegebenenfalls kristallin sein können, nach¬ träglich zu sprühgetrockneten, granulierten und/ oder extrudierten Kompo¬ nenten, die gegebenenfalls mit nichtionischen Tensiden und/oder anderen bei der Verarbeitungstemperatur flüssigen bis wachsartigen Inhaltsstoffen beaufschlagt sind, hinzugemischt werden. Bevorzugt ist dabei ein Verfah¬ ren, bei dem die Oberfläche von Teilkomponenten des Mittels oder des ge¬ samtem Mittels zur Reduzierung der Klebrigkeit der an Niotensiden reichen Granulate und/oder zu ihrer verbesserten Löslichkeit nachträglich behan- delt wird. Geeignete Oberflächenmodifizierer sind dabei aus dem Stand der Technik bekannt. Neben weiteren geeigneten sind dabei feinteiüge Zeo¬ lithe, Kieselsäuren, amorphe Silikate, Fettsäuren oder Fettsäuresalze, beispielsweise Calciumstearat, insbesondere, jedoch Mischungen aus Zeolith und Kieselsäuren oder Zeolith und Calciumstearat besonders bevorzugt. The bulk density of the preferred granular agents is generally 300 to 1100 g / 1, in particular 500 to 1000 g / 1. They can be prepared by any of the known processes, such as mixing, spray drying, granulation and extrusion, although spray drying processes are less preferred owing to the known pluming behavior of the nonionic ethoxylated alcohols. Processes in which several partial components, for example spray-dried components and granulated and / or extruded components, are mixed with one another are also particularly suitable. It is also possible for spray-dried or granulated components to be subsequently treated in the preparation, for example with nonionic surfactants, in particular ethoxylated fatty alcohols, by the customary processes. In granulation and extrusion processes in particular, it is preferred to add the anionic surfactants that may be present in the form of a spray-dried, granulated or extruded compound either as an admixture component in the process, in extrusion in particular for producing a solid premix intended for extrusion, or as an additive use other granules. It is also possible and, depending on the recipe, to be advantageous if further individual constituents of the composition, for example carbonates, citrate or citric acid or other polycarboxylates or polycarboxylic acids, polymeric polycarboxylates, zeolite and / or layered silicates, which, if appropriate can be crystalline, subsequently mixed to spray-dried, granulated and / or extruded components, which are optionally treated with nonionic surfactants and / or other liquid to waxy ingredients at the processing temperature. A method is preferred in which the surface of partial components of the agent or of the entire agent is subsequently treated to reduce the stickiness of the granules rich in nonionic surfactants and / or to improve their solubility. delt is. 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, are particularly preferred, but mixtures of zeolite and silicas or zeolite and calcium stearate are particularly preferred.
BeispieleExamples
Die erfindungsgemäßen Mittel Ml bis M7 wurden durch Extrusion hergestellt, wobei die Enzyme nachträglich hinzugemischt wurden. Das Aniontensid wurde als granuliertes Compound, hergestellt nach der Lehre der Anmeldung DE-A-4127323, zusammen mit den übrigen Bestandteilen vorgemischt und ex- trudiert.Agents Ml to M7 according to the invention were produced by extrusion, the enzymes being subsequently added. The anionic surfactant was premixed and extruded together with the other constituents as a granulated compound, prepared according to the teaching of application DE-A-4127323.
Tabelle 1: Zusammensetzungen der Mittel Ml bis M7 und VI bis V2 in Gew.-%Table 1: Compositions of agents Ml to M7 and VI to V2 in% by weight
Fortsetzung der Tabelle 1: Continuation of table 1:
r Ml M2 M3 M4 M5 M6 M7 VI V2r Ml M2 M3 M4 M5 M6 M7 VI V2
BASF, Bundesrepu¬ blik DeutschlandBASF, Federal Republic of Germany
Sokalan DCS(R) 2 2 2 3 3 3 (Dicarbonsäure- salze, Handespro¬ dukt der BASF)Sokalan DCS ( R ) 2 2 2 3 3 3 (dicarboxylic acid salts, hand-made product from BASF)
Natriumsilikat, 4 4 3 2 3 7 6 1,5 1,5 amorph a2θ:Siθ21:2,0Sodium silicate, 4 4 3 2 3 7 6 1.5 1.5 amorphous a2θ: Siθ21: 2.0
Perboratmonohy- - - - 8 5 - - - - dratPerborate monohy- - - - 8 5 - - - - third
Protease 0,2 0,5 0,2 0,3 0,1 0,2 0,2 0,4 0,4 Lipase 0,2 0,2 0,1 0,3 0,2 0,2 Cellulase 0,2 0,2 0,3 0,1 0,2 1,0 0,2 0,2 Amylase 0,1 0,1 0,1 0,2Protease 0.2 0.5 0.2 0.3 0.1 0.2 0.2 0.4 0.4 Lipase 0.2 0.2 0.1 0.3 0.2 0.2 Cellulase 0, 2 0.2 0.3 0.1 0.2 1.0 0.2 0.2 Amylase 0.1 0.1 0.1 0.2
Polyvinyl¬ 1 pyrrolidonPolyvinyl 1 pyrrolidone
Natriumsulfat 1 2 6 - 2 8 4 6 5Sodium sulfate 1 2 6 - 2 8 4 6 5
Wasser und Sal¬ Rest ze aus LösungenWater and salt residue from solutions
Zur Bestimmung der Farbübertragungsinhibierung wurden weiße Teststreifen aus Baumwolle, Polyester, Baumwolle und Viskose und aus Viskose mit Farb¬ geweben, die blaue, rote, braune, schwarze und grüne Farbstoffe enthielten in einem Launderometer (60 °C, 16 °d, Waschmitteldosierung: 5,0 g/1) mit Ml und M3 sowie den Vergleichsmitteln VI und V2 gewaschen. Anschließend wurde der Weißwert der Teststreifen ermittelt. Das aniontensidhaltige Ml wies dabei wesentlich bessere Weißwerte als VI und im Durchschnitt etwa gleich gute Weißwerte wie V2 auf. Das aniontensidfreie M3 wies bei blauen und roten Farbstoffen deutlich bessere Weißwerte auf als Ml und VI, war jedoch insgesamt etwas schlechter als Ml und V2. To determine the color transfer inhibition, white test strips made from cotton, polyester, cotton and viscose and from viscose with colored fabrics containing blue, red, brown, black and green dyes in a launderometer (60 ° C, 16 ° d, detergent dosage: 5 , 0 g / 1) with Ml and M3 and the comparative VI and V2. The white value of the test strips was then determined. The anionic surfactant-containing Ml had significantly better white values than VI and, on average, about the same good white values as V2. With blue and red dyes, the anionic surfactant-free M3 had significantly better whiteness values than Ml and VI, but was overall somewhat worse than Ml and V2.

Claims

Patentansprüche claims
1. Festes, vorzugsweise granuläres Waschmittel mit verfärbungsinhibieren¬ den Eigenschaften, dadurch gekennzeichnet, daß es 10 bis 30 Gew.- Niotenside, 0 bis 10 Gew.-% Aniontenside, 1 bis 6 Gew.-% Fettsäuresei¬ fen, 20 bis 60 Gew.-% Buildersubstanzen aus der Gruppe der Zeolithe (wasserfreie Aktivsubstanz) und Schichtsilikate enthält, aber frei von Polyvinylpyrrolidon ist.1. Solid, preferably granular detergent with discoloration-inhibiting properties, characterized in that it contains 10 to 30% by weight nonionic surfactants, 0 to 10% by weight anionic surfactants, 1 to 6% by weight fatty acid soap, 20 to 60% by weight .-% contains builders from the group of zeolites (anhydrous active substance) and layered silicates, but is free of polyvinylpyrrolidone.
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß es 0,5 bis 8 Gew.-3 und insbesondere bis 5 Gew.-% Aniontenside enthält.2. Composition according to claim 1, characterized in that it contains 0.5 to 8% by weight and in particular up to 5% by weight of anionic surfactants.
3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß es ein Ge¬ wichtsverhältnis Niotenside zu Aniontensiden von oberhalb 2:1, vor¬ zugsweise von mehr als 2,5:1, insbesondere von 3:1 und darüber auf¬ weist.3. Composition according to claim 1 or 2, characterized in that it has a weight ratio of nonionic surfactants to anionic surfactants of above 2: 1, preferably of more than 2.5: 1, in particular of 3: 1 and above.
4. Mittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es 12 bis 25 Gew.-% alkoxylierte Cs-Ciβ-Alkohole und insbesondere 13 bis 20 Gew.-% ethoxylierte Fettalkohole, 2 bis 5 Gew.-% Alkalisalze von Fettsäureseifen und 25 bis 55 Gew.-%, vorzugsweise 30 bis 45 Gew.-3 Buildersubstanzen aus der Gruppe der Zeolithe (wasserfreie Aktivsub¬ stanz) und Schichtsilikate, insbesondere Zeolith NaA, Bentonit und kristallinen schichtförmige Natriumsilikate, enthält.4. Composition according to one of claims 1 to 3, characterized in that there are 12 to 25 wt .-% alkoxylated Cs-Ciβ alcohols and in particular 13 to 20 wt .-% ethoxylated fatty alcohols, 2 to 5 wt .-% alkali salts of Fatty acid soaps and 25 to 55% by weight, preferably 30 to 45% by weight, of 3 builders from the group of the zeolites (anhydrous active substance) and layered silicates, in particular zeolite NaA, bentonite and crystalline layered sodium silicates.
5. Mittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es als Aniontenside Alk(en)ylsulfate, insbesondere gesättigte und/oder ungesättigte Fettalkoholsulfate, die gegebenenfalls ethoxyliert sind, enthält.5. Composition according to one of claims 1 to 4, characterized in that it contains alk (en) yl sulfates, in particular saturated and / or unsaturated fatty alcohol sulfates, which are optionally ethoxylated, as anionic surfactants.
6. Mittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es 2 bis 20 Gew.-% Salze von Polycarbonsäuren, insbesondere Salze der Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, von Zuckersäuren und Mischungen aus diesen enthält. 6. Composition according to one of claims 1 to 5, characterized in that it contains 2 to 20 wt .-% salts of polycarboxylic acids, in particular salts of citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, of sugar acids and mixtures of these.
7. Mittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es 0,1 bis 5 Gew.-% Cellulase oder eine Enzymmischung aus Cellulase und einem oder mehreren Enzymen aus der Gruppe der Proteasen, Lipasen, Amylasen und (Per-)Oxidasen enthält.7. Composition according to one of claims 1 to 6, characterized in that it contains 0.1 to 5 wt .-% cellulase or an enzyme mixture of cellulase and one or more enzymes from the group of proteases, lipases, amylases and (per) Contains oxidases.
8. Mittel nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß es bis zu 10 Gew.-% Peroxybleichmittel, vorzugsweise Perborat oder Percarbonat enthält. 8. Agent according to one of claims 1 to 7, characterized in that it contains up to 10 wt .-% peroxy bleach, preferably perborate or percarbonate.
EP94919631A 1993-06-23 1994-06-15 Washing agents with decolorization-inhibiting properties Withdrawn EP0705328A1 (en)

Applications Claiming Priority (3)

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DE19934320851 DE4320851A1 (en) 1993-06-23 1993-06-23 Detergent with discoloration-inhibiting properties
DE4320851 1993-06-23
PCT/EP1994/001942 WO1995000627A1 (en) 1993-06-23 1994-06-15 Washing agents with decolorization-inhibiting properties

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FR2743085B1 (en) * 1995-12-29 1999-02-26 Rhone Poulenc Chimie DETERGENT COMPOSITION FOR THE WASHING OF LAUNDRY CONTAINING SODIUM SILICATE AS A MAIN DETERGENCE ADJUVANT
GB0030671D0 (en) 2000-12-15 2001-01-31 Unilever Plc Detergent compositions
GB0030669D0 (en) 2000-12-15 2001-01-31 Unilever Plc Detergent compositions
GB0124308D0 (en) 2001-10-10 2001-11-28 Unilever Plc Detergent compositions
GB0124307D0 (en) * 2001-10-10 2001-11-28 Unilever Plc Detergent compositions

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AT338948B (en) * 1974-10-10 1977-09-26 Henkel & Cie Gmbh POWDERED DETERGENTS AND CLEANING AGENTS AND METHOD FOR THEIR PRODUCTION
DE3545947A1 (en) * 1985-12-23 1987-07-02 Henkel Kgaa PHOSPHATE-FREE, GRANULAR DETERGENT
DE3711267A1 (en) * 1987-04-03 1988-10-13 Henkel Kgaa PHOSPHATE-FREE, TEXTILE SOFTENING DETERGENT
GB8927362D0 (en) * 1989-12-04 1990-01-31 Unilever Plc Process for manufacturing a granular detergent composition
GB9008013D0 (en) * 1990-04-09 1990-06-06 Unilever Plc High bulk density granular detergent compositions and process for preparing them
AU660101B2 (en) * 1992-08-07 1995-06-08 Colgate-Palmolive Company, The Heavy duty laundry detergent compositions of reduced dye transfer properties

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