EP0658189A1 - Washing and cleaning agents with builder substances. - Google Patents

Washing and cleaning agents with builder substances.

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Publication number
EP0658189A1
EP0658189A1 EP93919191A EP93919191A EP0658189A1 EP 0658189 A1 EP0658189 A1 EP 0658189A1 EP 93919191 A EP93919191 A EP 93919191A EP 93919191 A EP93919191 A EP 93919191A EP 0658189 A1 EP0658189 A1 EP 0658189A1
Authority
EP
European Patent Office
Prior art keywords
weight
granular
acid
washing
agents
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.)
Granted
Application number
EP93919191A
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German (de)
French (fr)
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EP0658189B1 (en
Inventor
Beatrix Kottwitz
Horst Upadek
Peter Krings
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to detergents and cleaning agents which contain conventional builder substances and polymeric polycarboxylates.
  • zeolite in particular zeolite NaA, and mixtures of zeolite with alkali silicates and alkali carbonates, as well as polycarboxylates or polymeric polycarboxylates, have been used as phosphate substitutes in washing and cleaning agents.
  • the polymeric polycarboxylates are known to counteract the precipitation of poorly soluble calcium salts and thus the incrustation caused by poorly soluble calcium salts and the graying of the tissue.
  • Polymeric polycarboxylates were mostly used in the form of an aqueous solution or as a fine powder.
  • European patent application 291 869 describes phosphate-free builders combinations of zeolite and polymeric polycarboxylates, mixtures of polymeric polycarboxylates with aminoalkane polyphosphonates and l-hydroxyethane-l, l-diphosphonate (HEDP) being synergistic in preventing the formation of Show fiber incrustations.
  • HEDP l-hydroxyethane-l, l-diphosphonate
  • the object of the invention was to provide phosphate-free agents which have a primary washing and cleaning power which is comparable to the primary washing and cleaning power of conventional commercial products, but the secondary washing power of these agents at the same time has great advantages. It has now been found that this object is achieved by means of compositions which are conventional per se, but which contain polymeric polycarboxylates in a very specific form.
  • the invention accordingly relates to a detergent and cleaning agent, in particular a textile detergent, containing anionic and / or nonionic surfactants, phosphate-free builder substances and inorganic salts and polymeric polycarboxylates, the agent containing at least two granular components, the first of which is anionic and / or contains nonionic surfactants, phosphate-free builder substances and inorganic salts and the second contains an admixture component made from polymeric polycarboxyla- is in granular form.
  • agents have alkali carbonate.
  • Preferred granular polymeric polycarboxylates have a bulk density between 350 and 850 g / 1, preferably between 400 and 750 g / 1, no particles with a particle size below 50 ⁇ m, preferably no particles with a particle size below 100 ⁇ m, and a maximum of 5% of the particles a particle size above 1000 ⁇ m, preferably at most 3% by weight of the particles with a particle size above 1000 ⁇ m.
  • the granular content of monomeric polycarboxylic acids is preferably below 1% by weight.
  • the granular polymeric polycarboxylates can be prepared in a conventional manner known to the person skilled in the art, for example by drying polymer solutions, subsequent granulation and, if appropriate, size classification of the granules.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids, is generally 4,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • Sokalan ( R ) CP5 granules, Sokalan ( R ) CP45 granules and Sokalan ( R ) are very particularly preferred.
  • CP 7 granules (commercial products from BASF).
  • Zeolites are primarily considered as phosphate-free builder substances.
  • the zeolites are used in the usual hydrated, finely crystalline form. Their water content is preferably between 19 and 22% by weight. They have practically no particles larger than 30 ⁇ m and preferably consist at least 80% of particles smaller than 10 ⁇ m.
  • Their calcium binding capacity which is determined according to the information in German patent application 24 12 837, is in the range from 100 to 200 mg CaO / g.
  • Zeolite NaA is particularly suitable, as is zeolite NaX and mixtures of NaA and NaX.
  • small additions fatty alcohols g can nonionic surfactants contain as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ⁇ -C j 2 to 5 Ethylene oxide groups.
  • stabilizers for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ⁇ -C j 2 to 5 Ethylene oxide groups.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula (I) NaMSi x 02 ⁇ + ⁇ * yH20, 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 preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application 164 514.
  • Preferred crystalline sheet silicates of the formula (I) are those in which M represents sodium and x assumes the values 2 or 3.
  • both are preferably .beta.- and ⁇ 'sodium disilicates Na2S1 ⁇ 05 ⁇ 20, wherein beta-sodium disilicate, for example, by the process can be obtained, which is described in the German patent application 3,939,919th
  • the washing and cleaning agents according to the invention can also contain mixtures of zeolite and the crystalline layered silicates of the general formula (I), the mixing ratio being arbitrary.
  • zeolite is preferably used either alone or in a zeolite to crystalline layered silicate (I) weight ratio of from 10: 1 to 1: 3 and in particular from 3: 1 to 1: 1.
  • the washing and cleaning agents according to the invention contain the builders zeolite and / or crystalline layered silicates (I) and the granular polymeric polycarboxylates advantageously in a weight ratio of 30: 1 to 1: 1, preferably 20: 1 to 2 : 1 and especially from 10: 1 to 3: 1.
  • the detergents and cleaning agents according to the invention are preferably in granular form.
  • Advantageous agents contain 10 to 60% by weight, preferably 15 to 45% by weight and in particular 20 to 40% by weight of zeolite and / or crystalline layered silicates (I), in particular zeolite, and 0.5 to 15% by weight .-%, preferably 2 to 10 wt .-% and in particular 3 to 8 wt .-% granular polymeric polycarboxylates.
  • the detergents and cleaning agents according to the invention can also contain other customary builder substances and complexing agents, for example phosphonates.
  • phosphonates for example, Phosphonates and preferably the neutral reacting sodium salts of, for example, l-hydroxyethane-l, l-diphosphonate and diethylenetriapentamethylenephosphonate are frequently used as enzyme or bleach stabilizers in amounts of 0.1 to 1.5% by weight.
  • organic builder substances are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons , and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the agents according to the invention contain anionic and / or nonionic surfactants and optionally cationic and / or amphoteric surfactants and other additives usually used in detergents and cleaning agents, for example bleaching agents and bleach activators, salts which have an alkaline reaction in water, solubility improvers such as contain conventional hydrotropes or polyalkylene glycols, for example polyethylene glycols, foam inhibitors, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filler salts and colorants and fragrances, opacifiers or pearlescent agents.
  • solubility improvers such as contain conventional hydrotropes or polyalkylene glycols, for example polyethylene glycols, foam inhibitors, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filler salts and colorants and fragrances, opacifiers or pearlescent agents.
  • the anionic and nonionic surfactants, including soap, in the compositions are preferably 8 to 40% by weight, in particular 10 to 35% by weight and, in particularly preferred embodiments, 12 to 28% by weight.
  • surfactants of the sulfonate type are Cg-Ci3-alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates of the type obtained, for example, from C 1 -C 4 -monoolefins with a terminal or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkane sulfonates which are obtained from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids are also suitable.
  • esters of ⁇ -sulfo fatty acids come here, which by ⁇ -sulfonation of the alkyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and after following neutralization to water-soluble mono-salts are considered.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters.
  • the methyl esters of ⁇ -sulfo fatty acids (MES) are used with particular advantage.
  • Suitable anionic surfactants are the ⁇ -sulfofatty acids obtainable by ester cleavage of the ⁇ -sulfofatty acid alkyl esters or their di-salts.
  • the mono-salts of the ⁇ -sulfofatty acid alkyl esters are obtained in their industrial production as an aqueous mixture with limited amounts of di-salts. Mixtures of mono-salts and di-salts with other surfactants, for example with alkylbenzenesulfonate, are also preferred.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures, such as those used in the production by esterification of glycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol be preserved.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. If one starts from fats and oils, that is to say natural mixtures of different fatty acid glycerol esters, it is necessary to largely saturate the starting products with hydrogen in a known manner before the sulfonation, ie to harden them to iodine numbers less than 5, advantageously less than 2.
  • Suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, rapeseed oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or lard. Due to their high natural content of saturated fatty acids, it has proven to be particularly advantageous to start from coconut oil, palm kernel oil or beef tallow.
  • the sulfonation of saturated fatty acids with 6 to 22 carbon atoms or Mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, are preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as specified in international patent application WO 91/9009.
  • the sulfonation products are a complex mixture which essentially contains mono-, di- and triglyceride sulfonates with an ⁇ and / or internal sulfonic acid grouping.
  • sulfonated fatty acid salts glyceride sulfates, glycerol sulfates, glycerol and beefs are formed. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of the ⁇ -sulfonated fatty acid disalts can, depending on the procedure, be up to about 60% by weight.
  • alkanesulfonates obtained from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the sulfonate group is statistically distributed over the entire carbon chain, the secondary alkanesulfonates predominating.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, for example from tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the uncl those secondary alcohols of this chain length.
  • the sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-Cji alcohols with an average of 3.5 mol of ethylene oxide, are also suitable.
  • Preferred fatty alkyl sulfates are derived from fatty alcohol mixtures obtained from coconut oil, palm oil and palm kernel oil, which may additionally contain fractions of unsaturated alcohols, for example oleyl alcohol. Mixtures in which the proportion of Al-
  • alkylsulfosuccinic acid which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain Cg to CQ fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, viewed in isolation, are nonionic surfactants (for a description, see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred.
  • Preferred granular detergents and cleaning agents contain, as anionic surfactants, alkylbenzenesulfonates and / or alkyl sulfate, preferably fatty alkyl sulfate, and / or sulfated fatty acid glycerol esters, the weight ratio of sulfated fatty acid glycerol esters to alkylbenzenesulfonate and / or alkyl sulfate 1: 9 to 4: 1 and in particular 2 : 5 to 2: 1.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts from 0.2 to 8 and in particular from 0.5 to 5% by weight.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular 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 C 1-4 fatty acid t-acid soaps and 0 to 50% by weight of oleic acid soap.
  • the anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanola in.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts.
  • the granular detergents and cleaning agents also contain, in addition to the anionic surfactants nonionic surfactants, preferably in amounts of 1 to 15% by weight, in particular in amounts of 2 to 12% by weight.
  • the preferred nonionic surfactants are liquid ethoxylated and / or propoxylated alcohols which are derived from primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 mol of alkylene oxide, in which the alcohol radical can be linear or methyl-branched in the 2-position , or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • linear residues of alcohols of native origin with 12 to 18 carbon atoms are preferred, e.g. from coconut, tallow or oleyl alcohol.
  • Ci2-Ci4 alcohols with 3 EO or 4 EO Cg-Cn alcohol with 7 EO
  • the degrees of ethoxylation given represent statistical mean values which, for a special product, represent a whole or Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.
  • alkyl glycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms branched in the 2-position and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10.
  • Suitable ingredients of the granular agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures thereof;
  • alkali carbonate and alkali silicate especially sodium silicate with a molar ratio Na2 ⁇ : Si ⁇ 2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, optionally in combination with magnesium likate are used.
  • the content of the funds in Na Trium silicate is generally up to 10% by weight, preferably between 2 and 8% by weight and in particular 2 to 5% by weight.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 30% by weight and in particular 10 to 25% by weight, advantageously using perborate monohydrate or tetrahydrate.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose sepentaacetate.
  • the bleach activators contain bleaching agents in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
  • Graying inhibitors have the task of keeping the dirt detached from the 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, eg degraded starch, aldehyde starches etc.
  • Polyvinylpyrrolidone can also be used.
  • carboxymethyl cellulose sodium salt
  • methyl cellulose methyl hydroxyethyl cellulose and their mixtures
  • polyvinylpyrrolidone for example in amounts of 0.1 to 5% by weight, based on the composition, are preferably used.
  • the foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a reduction can also be achieved by adding non-surfactant-like substances.
  • a reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, for example sulfates and / or sulfonates with nonionic surfactants and / or with soaps.
  • soaps the foam-suppressing effect increases with the degree of saturation and the C number of the fatty acid salt. Soaps of natural or synthetic origin that contain a high proportion of C j 8-C24 fatty acids are therefore suitable as foam-inhibiting soaps.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica or bistearylethylene diamide, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes, are also advantageously used.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. At least proteases, advantageously of the subtilisin type and in particular proteases which are obtained from Bacillus lentus, are preferably used. Their proportion can be about 0.2 to about 2% by weight.
  • the enzymes can be adsorbed on carriers and / or embedded in Hü11 substances to protect them against premature decomposition.
  • the agents can contain enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used.
  • 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 agents can contain, as optical brighteners, derivatives of diaostilbenedisulfonic acid or its alkali metal salts.
  • derivatives of diaostilbenedisulfonic acid or its alkali metal salts for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazin-6-yl-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure are suitable instead of the morpholino group, a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present, for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. It has also been found that uniform white granules are obtained if, apart from the customary brighteners, the agents are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3 % By weight, also in small amounts, for example 10 ⁇ 6 to 10 ⁇ 3 % by weight, preferably around 10 * 5% by weight, of a blue dye.
  • a special ⁇ DERS preferred dye is Tinolu ⁇ (R) (commercial product of Ciba-Geigy).
  • the granular detergents and cleaning agents according to the invention can have a bulk density between about 300 and 1100 g / 1.
  • Granules are preferred which have a bulk density above 450 g / 1, in particular between 500 and 1100 g / 1, and consist of at least two granular, preferably at least three granular components, one of which contains the polymeric polycarboxylate.
  • the agents according to the invention can be prepared in a conventional manner by mixing at least two granular components, one of which contains the polymeric polycarboxylate.
  • the other granular component which is preferably anionic surfactants, optionally nonionic surfactants. contains side and builder substances as well as inorganic salts, is produced, for example, by spray drying an aqueous slurry and, if appropriate, subsequently adding temperature-sensitive components or by granulating and extruding. In the production of this other granular component by granulation or extrusion, it is preferred that this component contains anionic surfactants and nonionic surfactants as well as builder substances, inorganic salts and optionally peroxy bleaching agents.
  • the agents are produced by extrusion, the granular polymeric polycarboxylate being a constituent of the mixture to be extruded.
  • Granular detergents of the following composition were prepared and tested in a conventional manner by spray drying.
  • the polymeric polycarboxylate was used as a 40% by weight aqueous solution (Sokalan ( R ) CP 5, commercial product from BASF, Federal Republic of Germany) and as a component of the slurry to be spray-dried, and as a granular admixture in the composition according to the invention ( Sokalan ( R ) CP5 Granu ⁇ lat, commercial product from BASF, Federal Republic of Germany) subsequently added.
  • Sokalan ( R ) CP5 Granu ⁇ lat commercial product from BASF, Federal Republic of Germany
  • the constituents perborate, bleach activator and enzyme granulate were also added subsequently.
  • test was carried out under practical conditions in household washing machines.
  • the machines were loaded with 3.5 kg of clean laundry and 0.5 kg of test fabric, some of the test fabric with the usual Test soiling was impregnated (for testing the primary washing ability) and partly consisted of white fabric (for testing the secondary washing ability).
  • Strips of standardized cotton fabric (laundry research institute Krefeld; WFK), nettle (BN), knitwear (cotton jersey; B) and terry toweling fabric (FT) were used as the white test fabric.
  • Washing conditions tap water of 23 ° d (equivalent to 230 mg CaO / 1), amount of detergent used per detergent and machine 146 g, washing temperature 25 to 90 ° C (heating time 60 minutes, 15 minutes at 90 ° C), liquor ratio ( kg of laundry: liters of wash liquor in the main wash cycle) 1: 5,7, rinse 4 times with tap water, spin off and dry.
  • the agent M1 according to the invention showed, on average, better ash contents than all of the textile fabrics than Comparative Example VI.

Abstract

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

Description

"Wasch- und Reinigungsmittel mit Buildersubstanzen" "Detergents and cleaning agents with builder substances"
Die Erfindung betrifft Wasch- und Reinigungsmittel, die übliche Builder¬ substanzen und polymere Polycarboxylate enthalten.The invention relates to detergents and cleaning agents which contain conventional builder substances and polymeric polycarboxylates.
In der Praxis wurden als Phosphatsubstitute in Wasch- und Reinigungsmit¬ teln vor allem Zeolith, insbesondere Zeolith NaA, und Mischungen aus Zeo¬ lith mit Alkalisilikaten und Alkalicarbonaten sowie Polycarboxylaten oder poly eren Polycarboxylaten verwendet. Von den polymeren Polycarboxylaten ist bekannt, daß sie der Ausfällung schwerlöslicher Calciumsalze und somit der durch schwerlösliche Calciumsalze hervorgerufenen Inkrustation und der Vergrauung des Gewebes entgegenwirken. Polymere Polycarboxylate wurden dabei meist in Form einer wäßrigen Lösung oder als feinteiliges Pulver eingesetzt.In practice, zeolite, in particular zeolite NaA, and mixtures of zeolite with alkali silicates and alkali carbonates, as well as polycarboxylates or polymeric polycarboxylates, have been used as phosphate substitutes in washing and cleaning agents. The polymeric polycarboxylates are known to counteract the precipitation of poorly soluble calcium salts and thus the incrustation caused by poorly soluble calcium salts and the graying of the tissue. Polymeric polycarboxylates were mostly used in the form of an aqueous solution or as a fine powder.
So beschreibt beispielsweise die europäische Patentanmeldung 291 869 phos¬ phatfreie Gerüststoffkombinationen aus Zeolith und polymeren Polycarboxy¬ laten, wobei Mischungen aus polymeren Polycarboxylaten mit Aminoalkanpoly- phosphonaten und l-Hydroxyethan-l,l-diphosphonat (HEDP) einen Synergismus bezüglich der Verhinderung der Ausbildung von Faserinkrustationen zeigen.For example, European patent application 291 869 describes phosphate-free builders combinations of zeolite and polymeric polycarboxylates, mixtures of polymeric polycarboxylates with aminoalkane polyphosphonates and l-hydroxyethane-l, l-diphosphonate (HEDP) being synergistic in preventing the formation of Show fiber incrustations.
Die Aufgabe der Erfindung bestand darin, phosphatfreie Mittel bereitzu¬ stellen, die ein Primärwasch- und Reinigungsvermögen aufweisen, das mit dem Primärwasch- und Reinigungsvermögen üblicher Handelsprodukte ver¬ gleichbar ist, wobei das Sekundärwaschvermögen dieser Mittel aber gleich¬ zeitig hohe Vorteile aufweist. Es wurde nun gefunden, daß diese Aufgabe durch Mittel an sich üblicher Zusammensetzung gelöst wird, die aber poly¬ mere Polycarboxylate in einer ganz bestimmten Form enthalten.The object of the invention was to provide phosphate-free agents which have a primary washing and cleaning power which is comparable to the primary washing and cleaning power of conventional commercial products, but the secondary washing power of these agents at the same time has great advantages. It has now been found that this object is achieved by means of compositions which are conventional per se, but which contain polymeric polycarboxylates in a very specific form.
Gegenstand der Erfindung ist dementsprechend ein Wasch- und Reinigungs¬ mittel, insbesondere ein Textilwaschmittel, enthaltend anionische und/oder nichtionische Tenside, phosphatfreie Buildersubstanzen sowie anorganische Salze und polymere Polycarboxylate, wobei das Mittel mindestens zwei gra¬ nuläre Komponenten enthält, wovon die erste anionische und/oder nichtioni¬ sche Tenside, phosphatfreie Buildersubstanzen sowie anorganische Salze enthält und die zweite eine Zumischkomponente aus polymeren Polycarboxyla- ten in granulärer Form ist. Dabei weisen Mittel, welche Alkalicarbonat. inThe invention accordingly relates to a detergent and cleaning agent, in particular a textile detergent, containing anionic and / or nonionic surfactants, phosphate-free builder substances and inorganic salts and polymeric polycarboxylates, the agent containing at least two granular components, the first of which is anionic and / or contains nonionic surfactants, phosphate-free builder substances and inorganic salts and the second contains an admixture component made from polymeric polycarboxyla- is in granular form. In doing so, agents have alkali carbonate. in
Mengen unterhalb 10 Gew.-%, bezogen auf das gesamte Mittel, enthalten, eine verbesserte Inkrustationsinhibierung auf.Amounts below 10 wt .-%, based on the total agent, contain an improved incrustation inhibition.
Bevorzugte granuläre polymere Polycarboxylate weisen ein Schüttgewicht zwischen 350 und 850 g/1, vorzugsweise zwischen 400 und 750 g/1, keine Partikel mit einer Teilchengröße unter 50 μm, vorzugsweise keine Partikel mit einer Teilchengröße unter 100 μm, und maximal 5 % der Partikel mit einer Teilchengröße oberhalb 1000 μm, vorzugsweise maximal 3 Gew.-% der Partikel mit einer Teilchengröße oberhalb 1000 μm auf. Der Gehalt der Gra¬ nulate an onomeren Polycarbonsäuren liegt vorzugsweise unter 1 Gew.-%. Die granulären polymeren Polycarboxylate können auf übliche, dem Fachmann bekannte Weise, beispielsweise durch Trocknung von Polymerlösungen, an¬ schließende Granulierung und gegebenenfalls Größenklassierung der Granula¬ te hergestellt werden. Dabei ist es bevorzugt, Polymerlösungen in einem Sprühturm oder in einer Wirbelschicht zu trocknen und das getrocknete Pul¬ ver mit Wasser, insbesondere mit wäßrigen Lösungen der polymeren Polycarb¬ oxylate und vorteilhafterweise ohne weitere Hilfsmittel zu granulieren. Besonders bevorzugt ist dabei eine Fließbettgranulation. Geeignete poly¬ mere Polycarboxylate sind beispielsweise die Natriumsalze der Polyacryl- säure oder der Polymethacrylsäure, beispielsweise solche mit einer relati¬ ven Molekülmasse von 800 bis 150000 (auf Säure bezogen). Geeignete copoly- mere Polycarboxylate sind insbesondere solche der Acrylsäure mit Meth- acrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 4000 bis 200000, vorzugsweise 10000 bis 120000 und insbe¬ sondere 50000 bis 100000. Ganz besonders bevorzugt sind Sokalan(R) CP5 Granulat, Sokalan(R) CP45 Granulat und Sokalan(R) CP 7 Granulat (Handels¬ produkte der BASF).Preferred granular polymeric polycarboxylates have a bulk density between 350 and 850 g / 1, preferably between 400 and 750 g / 1, no particles with a particle size below 50 μm, preferably no particles with a particle size below 100 μm, and a maximum of 5% of the particles a particle size above 1000 μm, preferably at most 3% by weight of the particles with a particle size above 1000 μm. The granular content of monomeric polycarboxylic acids is preferably below 1% by weight. The granular polymeric polycarboxylates can be prepared in a conventional manner known to the person skilled in the art, for example by drying polymer solutions, subsequent granulation and, if appropriate, size classification of the granules. It is preferred to dry polymer solutions in a spray tower or in a fluidized bed and to granulate the dried powder with water, in particular with aqueous solutions of the polymeric polycarboxylates, and advantageously without further auxiliaries. Fluid bed granulation is particularly preferred. Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 4,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. Sokalan ( R ) CP5 granules, Sokalan ( R ) CP45 granules and Sokalan ( R ) are very particularly preferred. CP 7 granules (commercial products from BASF).
Eine Erklärung für die verbesserte Inkrustationsinhibierung und damit ein¬ hergehend für das bessere Sekundärwaschvermögen von Mitteln, welche die polymeren Polycarboxylate in granulärer Form enthalten, im Vergleich zu Mitteln, in welche dieselben polymeren Polycarboxylate in wäßriger oder pulvriger Form eingearbeitet wurden, liegt nicht vor. Es wird lediglich vermutet, daß dieser Effekt auf die unregelmäßige und keineswegs geschlos¬ sene Oberfläche der einzelnen Granulate zurückzuführen ist, die aufgrund ihrer räumlichen Anordnung eine stabilere Bindung der Härtebildner im Ver¬ gleich zu den pulverförmigen Polycarboxylaten und insbesondere im Ver¬ gleich zu den in der Lösung doch recht beweglich vorliegenden Polymerket¬ ten ermöglicht.An explanation for the improved incrustation inhibition and concomitant for the better secondary washing ability of agents which contain the polymeric polycarboxylates in granular form compared to agents in which the same polymeric polycarboxylates are used in aqueous or powdered form were not available. It is only assumed that this effect can be attributed to the irregular and by no means closed surface of the individual granules, which, owing to their spatial arrangement, ensures a more stable bond between the hardening agents in comparison to the powdery polycarboxylates and, in particular, in comparison to those in FIGS the solution allows the polymer chains to be quite mobile.
Als phosphatfreie Buildersubstanzen kommen in erster Linie Zeolithe in Be¬ tracht. Die Zeolithe kommen dabei in der üblichen hydratisierten, feinkri¬ stallinen Form zum Einsatz. Ihr Wassergehalt liegt vorzugsweise zwischen 19 und 22 Gew.-%. Sie weisen praktisch keine Teilchen größer als 30 μm auf und bestehen vorzugsweise zu wenigstens 80 % aus Teilchen einer Größe kleiner als 10 μm. Ihr Calciumbindevermögen, das nach den Angaben der deutschen Patentanmeldung 24 12 837 bestimmt wird, liegt im Bereich von 100 bis 200 mg CaO/g. Geeignet ist insbesondere der Zeolith NaA, ferner auch der Zeolith NaX sowie Mischungen aus NaA und NaX. 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.-%, bezogen auf Zeolith, an ethoxylierten C^-Cjg-Fettalkoholen mit 2 bis 5 Ethylenoxidgruppen. Mengenangaben und Gewichtsverhältnisse, die den Gerüststoff Zeolith betreffen, werden im Rahmen dieser Erfindung - sofern nichts anderes angegeben ist - auf wasserfreie Aktivsubstanz bezo¬ gen.Zeolites are primarily considered as phosphate-free builder substances. The zeolites are used in the usual hydrated, finely crystalline form. Their water content is preferably between 19 and 22% by weight. They have practically no particles larger than 30 μm and preferably consist at least 80% of particles smaller than 10 μm. Their calcium binding capacity, which is determined according to the information in German patent application 24 12 837, is in the range from 100 to 200 mg CaO / g. Zeolite NaA is particularly suitable, as is zeolite NaX and mixtures of NaA and NaX. In the case that the zeolite is used as a suspension, small additions fatty alcohols g can nonionic surfactants contain as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ^ -C j 2 to 5 Ethylene oxide groups. Quantities and weight ratios which relate to the zeolite builder are - within the scope of this invention - unless otherwise stated - based on anhydrous active substance.
Geeignete Substitute bzw. Teilsubstitute für Phosphate und Zeolithe sind kristalline, schichtförmige Natriumsilikate der allgemeinen Formel (I) NaMSix02χ+ι*yH20, 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 Schichts likate werden beispiels¬ weise in der europäischen Patentanmeldung 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate der Formel (I) sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch δ'-Natriumdisilikate Na2S1^05^20 bevorzugt, wobei ß-Natrium- disilikat beispielsweise nach dem Verfahren erhalten werden kann, das in der deutschen Patentanmeldung 3939919 beschrieben ist. Die erfindungsgemäßen Wasch- und Reinigungsmittel können auch Mischungen aus Zeolith und den kristallinen Schichtsilikaten der allgemeinen Formel (I) enthalten, wobei das Mischungsverhältnis beliebig ist. Vorzugsweise wird jedoch Zeolith entweder allein oder in einem Gewichtsverhältnis Zeo¬ lith zu kristallinem Schichtsilikat (I) von 10:1 bis 1:3 und insbesondere von 3:1 bis 1:1 eingesetzt.Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula (I) NaMSi x 02χ + ι * yH20, 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 preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application 164 514. Preferred crystalline sheet silicates of the formula (I) are those in which M represents sodium and x assumes the values 2 or 3. In particular, both are preferably .beta.- and δ 'sodium disilicates Na2S1 ^ 05 ^ 20, wherein beta-sodium disilicate, for example, by the process can be obtained, which is described in the German patent application 3,939,919th The washing and cleaning agents according to the invention can also contain mixtures of zeolite and the crystalline layered silicates of the general formula (I), the mixing ratio being arbitrary. However, zeolite is preferably used either alone or in a zeolite to crystalline layered silicate (I) weight ratio of from 10: 1 to 1: 3 and in particular from 3: 1 to 1: 1.
Die erfindungsgemäßen Wasch- und Reinigungsmittel enthalten dabei die Ge¬ rüststoffe Zeolith und/oder kristalline Schichtsilikate (I) und die granu¬ lären polymeren Polycarboxylate vorteilhafterweise in einem Gewichtsver¬ hältnis von 30:1 bis 1:1, vorzugsweise von 20:1 bis 2:1 und insbesondere von 10:1 bis 3:1.The washing and cleaning agents according to the invention contain the builders zeolite and / or crystalline layered silicates (I) and the granular polymeric polycarboxylates advantageously in a weight ratio of 30: 1 to 1: 1, preferably 20: 1 to 2 : 1 and especially from 10: 1 to 3: 1.
Die erfindungsgemäßen Wasch- und Reinigungsmittel, insbesondere die Tex- tilwaschmittel, liegen vorzugsweise in granulärer Form vor. Vorteilhafte Mittel enthalten 10 bis 60 Gew.-%, vorzugsweise 15 bis 45 Gew.-% und ins¬ besondere 20 bis 40 Gew.-% Zeolith und/oder kristalline Schichtsilikate (I), insbesondere Zeolith, und 0,5 bis 15 Gew.-%, vorzugsweise 2 bis 10 Gew.-% und insbesondere 3 bis 8 Gew.-% granuläre polymere Polycarboxylate.The detergents and cleaning agents according to the invention, in particular the textile detergents, are preferably in granular form. Advantageous agents contain 10 to 60% by weight, preferably 15 to 45% by weight and in particular 20 to 40% by weight of zeolite and / or crystalline layered silicates (I), in particular zeolite, and 0.5 to 15% by weight .-%, preferably 2 to 10 wt .-% and in particular 3 to 8 wt .-% granular polymeric polycarboxylates.
Die erfindungsgemäßen Wasch- und Reinigungsmittel können zwar noch weitere übliche Buildersubstanzen und Komplexbildner, beispielsweise Phosphonate, enthalten. Doch ist der Effekt der Verbesserung der Inkrustationsinhibie¬ rung bzw. des Sekundärwaschvermögens durch den erfindungsgemäßen Einsatz von polymeren Polycarboxylaten als granuläre Zumischkomponente derart gra¬ vierend, daß es insbesondere bevorzugt ist, auf den Einsatz von Phospho- naten zu verzichten. Phosphonate und zwar vorzugsweise die neutral reagie¬ renden Natriumsalze von beispielsweise l-Hydroxyethan-l,l-diphosphonat und Diethylentria inpentamethylenphosphonat werden häufig als Enzym- oder Bleichstabilisatoren in Mengen von 0,1 bis 1,5 Gew.-% verwendet. Es hat sich jedoch gezeigt, daß die Primärwaschleistung sowie die Bleichmittel- und Enzymstabilität der erfindungsgemäßen Mittel durch den Einsatz von Phosphonaten nicht signifikant erhöht werden, so daß auf den Einsatz von Phosphonaten insgesamt ohne Leistungseinbußen verzichtet werden kann. Weitere brauchbare organische Buildersubstanzen sind beispielsweise die bevorzugt in Form ihrer Natriumsalze eingesetzten Polycarbonsäuren, wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuk- kersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), sofern ein der¬ artiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäu¬ ren wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäu¬ re, Zuckersäuren und Mischungen aus diesen.The detergents and cleaning agents according to the invention can also contain other customary builder substances and complexing agents, for example phosphonates. However, the effect of improving the incrustation inhibition or the secondary washing ability through the use according to the invention of polymeric polycarboxylates as granular admixture component is so grave that it is particularly preferred to forego the use of phosphonates. Phosphonates and preferably the neutral reacting sodium salts of, for example, l-hydroxyethane-l, l-diphosphonate and diethylenetriapentamethylenephosphonate are frequently used as enzyme or bleach stabilizers in amounts of 0.1 to 1.5% by weight. However, it has been shown that the primary washing performance and the bleach and enzyme stability of the agents according to the invention are not significantly increased by the use of phosphonates, so that the use of phosphonates can be dispensed with overall without any loss in performance. Further usable organic builder substances are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons , and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
Außer den genannten Inhaltsstoffen enthalten die erfindungsgemäßen Mittel anionische und/oder nichtionische Tenside sowie gegebenenfalls kationische und/oder amphotere Tenside und weitere üblicherweise in Wasch- und Reini¬ gungsmitteln eingesetzte Zusatzstoffe, beispielsweise Bleichmittel und Bleichaktivatoren, in Wasser alkalisch reagierende Salze, Löslichkeitsver- besserer wie herkömmliche Hydrotrope oder Polyalkylenglykole, beispiels¬ weise Polyethylenglykole, Schauminhibitoren, optische Aufheller, Enzyme, Enzymstabilisatoren, geringe Mengen an neutralen Füllsalzen sowie Farb- und Duftstoffe, Trübungsmittel oder Perlglanzmittel enthalten.In addition to the ingredients mentioned, the agents according to the invention contain anionic and / or nonionic surfactants and optionally cationic and / or amphoteric surfactants and other additives usually used in detergents and cleaning agents, for example bleaching agents and bleach activators, salts which have an alkaline reaction in water, solubility improvers such as contain conventional hydrotropes or polyalkylene glycols, for example polyethylene glycols, foam inhibitors, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filler salts and colorants and fragrances, opacifiers or pearlescent agents.
Der Gehalt der Mittel an anionischen und nichtionischen Tensiden ein¬ schließlich Seife beträgt vorzugsweise 8 bis 40 Gew.-%, insbesondere 10 bis 35 Gew.-% und in besonders bevorzugten Ausführungsformen 12 bis 28 Gew.-%.The anionic and nonionic surfactants, including soap, in the compositions are preferably 8 to 40% by weight, in particular 10 to 35% by weight and, in particularly preferred embodiments, 12 to 28% by weight.
Als Tenside vom Sulfonat-Typ kommen beispielsweise Cg-Ci3-Alkylbenzolsul- fonate, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfona- ten sowie Disulfonaten, wie man sie beispielsweise aus C^-Cig-Monoolefi- nen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gas¬ förmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch Alkan- sulfonate, die aus Ci2-Ci8-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation gewon¬ nen werden. Geeignet sind auch die Ester von α-Sulfofettsäuren (Estersul- fonate). Insbesondere kommen hierbei Ester von α-Sulfofettsäuren, die durch α-Sulfonierung der Alkylester von Fettsäuren pflanzlichen und/oder tierischen Ursprungs mit 8 bis 20 C-Atomen im Fettsäuremolekül und nach- folgende Neutralisation zu wasserlöslichen Mono-Salzen hergestellt werden, in Betracht. Vorzugsweise handelt es sich hierbei um die α-sulfonierten Ester der hydrierten Kokos-, Palmkern- oder Taigfettsäuren, wobei auch Sulfonierungsprodukte von ungesättigten Fettsäuren, beispielsweise Ölsäu- re, in geringen Mengen, vorzugsweise in Mengen nicht oberhalb etwa 2 bis 3 Gew.-%, vorhanden sein können. Insbesondere sind α-Sulfofettsäurealkyl- ester bevorzugt, die eine Alkylkette mit nicht mehr als 4 C-Atomen in der Estergruppe aufweisen, beispielsweise Methylester, Ethylester, Propylester und Butylester. Mit besonderem Vorteil werden die Methylester der α-Sulfo¬ fettsäuren (MES) eingesetzt. Weitere geeignete Aniontenside sind die durch Esterspaltung der α-Sulfofettsäurealkylester erhältlichen α-Sulfofettsäu¬ ren bzw. ihre Di-Salze. Die Mono-Salze der α-Sulfofettsäurealkylester fal¬ len schon bei ihrer großtechnischen Herstellung als wäßrige Mischung mit begrenzten Mengen an Di-Salzen an. Auch Mischungen von Mono-Salzen und Di-Salzen mit weiteren Tensiden, beispielsweise mit Alkylbenzolsulfonat, sind bevorzugt.Examples of surfactants of the sulfonate type are Cg-Ci3-alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates of the type obtained, for example, from C 1 -C 4 -monoolefins with a terminal or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkane sulfonates which are obtained from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates) are also suitable. In particular, esters of α-sulfo fatty acids come here, which by α-sulfonation of the alkyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and after following neutralization to water-soluble mono-salts are considered. These are preferably the α-sulfonated esters of hydrogenated coconut, palm kernel or tallow fatty acids, with sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight. , may be present. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters. The methyl esters of α-sulfo fatty acids (MES) are used with particular advantage. Other suitable anionic surfactants are the α-sulfofatty acids obtainable by ester cleavage of the α-sulfofatty acid alkyl esters or their di-salts. The mono-salts of the α-sulfofatty acid alkyl esters are obtained in their industrial production as an aqueous mixture with limited amounts of di-salts. Mixtures of mono-salts and di-salts with other surfactants, for example with alkylbenzenesulfonate, are also preferred.
Weitere geeignete Aniontenside sind sulfierte Fettsäureglycerinester. Un¬ ter Fettsäureglycerinestern sind die Mono-, Di- und Triester sowie deren Gemische zu verstehen, wie sie bei der Herstellung durch Veresterung von Glycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceri- den mit 0,3 bis 2 Mol Glycerin erhalten werden. Bevorzugte sulfierte Fett¬ säureglycerinester sind dabei die Sulfierprodukte von gesättigten Fettsäu¬ ren mit 6 bis 22 Kohlenstoffatomen, beispielsweise der Capronsäure, Ca- prylsäure, Caprinsäure, Myristinsäure, Laurinsäure, Palmitinsäure, Stearinsäure oder Behensäure. Geht man dabei von Fetten und Ölen, also natürlichen Gemischen unterschiedlicher Fettsäureglycerinester aus, so ist es erforderlich, die Einsatzprodukte vor der Sulfierung in an sich be¬ kannter Weise mit Wasserstoff weitgehend abzusättigen, d.h. auf Iodzahlen kleiner 5, vorteilhafterweise kleiner 2 zu härten. Typische Beispiele ge¬ eigneter Einsatzstoffe sind Palmöl, Palmkernöl, Palmstearin, Olivenöl, Rüböl, Korianderöl, Sonnenblumenöl, Bau wollsaatöl , Erdnußöl, Leinöl, Lardöl oder Schweineschmalz. Aufgrund ihres hohen natürlichen Anteils an gesättigten Fettsäuren hat es sich jedoch als besonders vorteilhaft erwie¬ sen, von Kokosöl, Palmkernöl oder Rindertalg auszugehen. Die Sulfierung der gesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen oder der Mischungen aus Fettsäureglycerinestern mit Iodzahlen kleiner 5, die Fett¬ säuren mit 6 bis 22 Kohlenstoffatomen enthalten, erfolgt vorzugsweise durch Umsetzung mit gasförmigem Schwefeltrioxid und anschließender Neutra¬ lisierung mit wäßrigen Basen, wie sie in der internationalen Patentanmel¬ dung WO 91/9009 angegeben ist.Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures, such as those used in the production by esterification of glycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol be preserved. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. If one starts from fats and oils, that is to say natural mixtures of different fatty acid glycerol esters, it is necessary to largely saturate the starting products with hydrogen in a known manner before the sulfonation, ie to harden them to iodine numbers less than 5, advantageously less than 2. Typical examples of suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, rapeseed oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or lard. Due to their high natural content of saturated fatty acids, it has proven to be particularly advantageous to start from coconut oil, palm kernel oil or beef tallow. The sulfonation of saturated fatty acids with 6 to 22 carbon atoms or Mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, are preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as specified in international patent application WO 91/9009.
Die Sulfierprodukte stellen ein komplexes Gemisch dar, das im wesentlichen Mono-, Di- und Triglyceridsulfonate mit α-ständiger und/oder innenstän¬ diger Sulfonsäuregruppierung enthält. Als Nebenprodukte bilden sich sulfo- nierte Fettsäuresalze, Glyceridsulfate, Glycerinsulfate, Glycerin und Sei¬ fen. Geht man bei der Sulfierung von gesättigten Fettsäuren oder gehärte¬ ten Fettsäureglycerinestergemischen aus, so kann der Anteil der α-sulfo- nierten Fettsäure-Disalze je nach Verfahrensführung durchaus bis etwa 60 Gew.-% betragen.The sulfonation products are a complex mixture which essentially contains mono-, di- and triglyceride sulfonates with an α and / or internal sulfonic acid grouping. As by-products, sulfonated fatty acid salts, glyceride sulfates, glycerol sulfates, glycerol and beefs are formed. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of the α-sulfonated fatty acid disalts can, depending on the procedure, be up to about 60% by weight.
Geeignet sind auch Alkansulfonate, die aus Ci2-Ci8~Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation gewonnen werden. Die Sulfonatgruppe ist dabei über die gesamte Kohlenstoffkette statistisch verteilt, wobei die sekundären Alkan¬ sulfonate überwiegen.Also suitable are alkanesulfonates obtained from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The sulfonate group is statistically distributed over the entire carbon chain, the secondary alkanesulfonates predominating.
Geeignete Tenside vom Sulfat-Typ sind die Schwefelsäuremonoester aus pri¬ mären Alkoholen natürlichen und synthetischen Ursprungs, insbesondere aus Fettalkoholen, z.B. aus Taigfettalkohol, Oleylalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol, oder den uncl diejenigen sekundärer Alkohole dieser Kettenlänge. Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten Alkohole, wie 2-Methyl-ver- zweigte Cg-Cji-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid, sind ge¬ eignet. Bevorzugte Fettalkylsulfate leiten sich von aus Kokosöl, Palm- und Palmkernöl gewonnenen Fettalkoholgemischen, die zusätzlich noch Anteile an ungesättigten Alkoholen, z.B. an Oleylalkohol, enthalten können, ab. Eine bevorzugte Verwendung finden dabei Gemische, in denen der Anteil der Al-Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, for example from tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the uncl those secondary alcohols of this chain length. The sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-Cji alcohols with an average of 3.5 mol of ethylene oxide, are also suitable. Preferred fatty alkyl sulfates are derived from fatty alcohol mixtures obtained from coconut oil, palm oil and palm kernel oil, which may additionally contain fractions of unsaturated alcohols, for example oleyl alcohol. Mixtures in which the proportion of Al-
kylreste zu 50 bis 70 Gew.-% auf C12, zu 18 bis 30 Gew.-% auf C14, zu 5 bis 15 Gew.-% auf C15, unter 3 Gew.-% auf CJQ und unter 10 Gew.-% auf C^g verteilt sind. Ebenso bevorzugte Aniontenside sind die Salze der Alkylsulfobernsteinsäu- re, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeich¬ net werden und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fett¬ alkoholen darstellen. Bevorzugte Sulfosuccinate enthalten Cg- bis C Q- Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sul¬ fosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside dar¬ stellen (Beschreibung siehe unten). Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit einge¬ engter HomologenVerteilung ableiten, besonders bevorzugt.50 to 70% by weight of alkyl radicals on C12, 18 to 30% by weight on C14, 5 to 15% by weight on C15, less than 3% by weight on CJQ and less than 10% by weight C ^ g are distributed. Likewise preferred anionic surfactants are the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain Cg to CQ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, viewed in isolation, are nonionic surfactants (for a description, see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred.
Bevorzugte granuläre Wasch- und Reinigungsmittel enthalten als anionische Tenside Alkylbenzolsulfonate und/oder Alkylsulfat, vorzugsweise Fettalkyl- sulfat, und/oder sulfierte Fettsäureglycerinester, wobei das Gewichtsver¬ hältnis sulfierte Fettsäureglycerinester zu Alkylbenzolsulfonat und/oder Alkylsulfat 1 : 9 bis 4 : 1 und insbesondere 2 : 5 bis 2 : 1 beträgt.Preferred granular detergents and cleaning agents contain, as anionic surfactants, alkylbenzenesulfonates and / or alkyl sulfate, preferably fatty alkyl sulfate, and / or sulfated fatty acid glycerol esters, the weight ratio of sulfated fatty acid glycerol esters to alkylbenzenesulfonate and / or alkyl sulfate 1: 9 to 4: 1 and in particular 2 : 5 to 2: 1.
Als weitere anionische Tenside kommen insbesondere Seifen, vorzugsweise in Mengen von 0,2 bis 8 und insbesondere von 0,5 bis 5 Gew.-%, in Betracht. Geeignet sind gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure oder Stearinsäure, sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkern- oder Taigfettsäuren, abge¬ leitete Seifengemische. Insbesondere sind solche Seifengemische bevorzugt, die zu 50 bis 100 Gew.-% aus gesättigten C^-Ciδ-Fet-t-säureseifen und zu 0 bis 50 Gew.-% aus Ölsäureseife zusammengesetzt sind.Other suitable anionic surfactants are, in particular, soaps, preferably in amounts from 0.2 to 8 and in particular from 0.5 to 5% by weight. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular 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 C 1-4 fatty acid t-acid soaps and 0 to 50% by weight of oleic acid soap.
Die anionischen Tenside können in Form ihrer Natrium-, Kalium- oder Ammo¬ niumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanola in, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze vor.The anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanola in. The anionic surfactants are preferably in the form of their sodium or potassium salts.
In einer weiteren bevorzugten Ausführungsform enthalten die granulären Wasch- und Reinigungsmittel zusätzlich zu den anionischen Tensiden auch nichtionische Tenside, vorzugsweise in Mengen von 1 bis 15 Gew.-%, ins¬ besondere in Mengen von 2 bis 12 Gew.-%.In a further preferred embodiment, the granular detergents and cleaning agents also contain, in addition to the anionic surfactants nonionic surfactants, preferably in amounts of 1 to 15% by weight, in particular in amounts of 2 to 12% by weight.
Als nichtionische Tenside dienen vorzugsweise flüssige ethoxylierte und/ oder propoxylierte Alkohole, die sich von primären Alkoholen mit vorzugs¬ weise 8 bis 18 Kohlenstoffatomen und durchschnittlich 1 bis 12 Mol Alky- lenoxid ableiten, in denen der Alkoholrest linear oder in 2-Stellung methylverzweigt sein kann, beziehungsweise lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkohol- resten vorliegen. Insbesondere sind jedoch lineare Reste aus Alkoholen nativen Ursprungs mit 12 bis 18 Kohlenstoffatomen bevorzugt, wie z.B. aus Kokos-, Taigfett- oder Oleylalkohol. Insbesondere werden Ci2-Ci4-Alkohole mit 3 EO oder 4 EO, Cg-Cn-Alkohol mit 7 EO, Ci3-Ci5-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, Ci2-Ci8-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischun¬ gen aus diesen, wie Mischungen aus Ci2~Ci4-Alkohol mit 3 EO und Ci2-Cl8" Alkohol mit 5 EO eingesetzt. 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). Insbesondere sind Alkoholethoxylate bevorzugt, die durchschnittlich 2 bis 8 Ethylenoxidgruppen aufweisen.The preferred nonionic surfactants are liquid ethoxylated and / or propoxylated alcohols which are derived from primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 mol of alkylene oxide, in which the alcohol radical can be linear or methyl-branched in the 2-position , or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, linear residues of alcohols of native origin with 12 to 18 carbon atoms are preferred, e.g. from coconut, tallow or oleyl alcohol. In particular, Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Cn alcohol with 7 EO, Ci3-Ci5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-Ci8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2-Ci4-alcohol with 3 EO and Ci2-Cl8 "alcohol with 5 EO. The degrees of ethoxylation given represent statistical mean values which, for a special product, represent a whole or Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In particular, alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.
Außerdem können als weitere nichtionische Tenside auch Alkylglykoside der allgemeinen Formel R0(G)x eingesetzt werden, in der R einen primären ge- radkettigen oder in 2-Stellung methylverzweigten aliphatischen 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.In addition, alkyl glycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms branched in the 2-position and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10.
Weitere geeignete Inhaltsstoffe der granulären Mittel sind wasserlösliche anorganische Salze wie Bicarbonate, Carbonate, amorphe Silikate oder Mi¬ schungen aus diesen; insbesondere werden Alkalicarbonat und Alkalisilikat, vor allem Natriumsilikat mit einem molaren Verhältnis Na2θ : Siθ2 von 1 : 1 bis 1 : 4,5, vorzugsweise von 1 : 2 bis 1 : 3,5, gegebenenfalls in Kom¬ bination mit Magnesiums likat eingesetzt. Der Gehalt der Mittel an Na- triumsilikat beträgt im allgemeinen bis zu 10 Gew.-%, vorzugsweise zwi¬ schen 2 und 8 Gew.-% und insbesondere 2 bis 5 Gew.-%. Besonders bevorzugt sind jedoch Mittel, die Natrium- und/oder Kaliumcarbonat in Mengen von 0 bis etwa 8 Gew.-%, vorteilhafterweise zwischen 0,5 und 8 Gew.-% und ins¬ besondere zwischen 2 und 6 Gew.-% enthalten.Other suitable ingredients of the granular agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures thereof; In particular, alkali carbonate and alkali silicate, especially sodium silicate with a molar ratio Na2θ: Siθ2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, optionally in combination with magnesium likate are used. The content of the funds in Na Trium silicate is generally up to 10% by weight, preferably between 2 and 8% by weight and in particular 2 to 5% by weight. However, agents which contain sodium and / or potassium carbonate in amounts of from 0 to about 8% by weight, advantageously between 0.5 and 8% by weight and in particular between 2 and 6% by weight, are particularly preferred.
Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbin¬ dungen haben das Natriumperborattetrahydrat und das Natriumperboratmono- hydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind bei¬ spielsweise Natriu percarbonat, Peroxypyrophosphate, Citratperhydrate so¬ wie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Per- oxophthalate, Diperazelainsäure oder Diperdodecandisäure. Der Gehalt der Mittel an Bleichmitteln beträgt vorzugsweise 5 bis 30 Gew.-% und insbeson¬ dere 10 bis 25 Gew.-%, wobei vorteilhafterweise Perboratmonohydrat oder -tetrahydrat eingesetzt wird.Among the compounds which serve as bleaching agents and supply H2O2 in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 30% by weight and in particular 10 to 25% by weight, advantageously using perborate monohydrate or tetrahydrate.
Um beim Waschen bei Temperaturen von 60 °C und darunter eine verbesserte Bleichwirkung zu erreichen, können Bleichaktivatoren in die Präparate ein¬ gearbeitet werden. Beispiele hierfür sind mit H2O2 organische Persäuren bildende N-Acyl- bzw. O-Acyl-Verbindungen, vorzugsweise N,N'-tetraacylier- te Diamine, ferner Carbonsäureanhydride und Ester von Polyolen wie Gluco- sepentaacetat. Der Gehalt der bleichmittelhaltigen Mittel an Bleichaktiva¬ toren liegt in dem üblichen Bereich, vorzugsweise zwischen 1 und 10 Gew.-% und insbesondere zwischen 3 und 8 Gew.-%. Besonders bevorzugte Bleichakti¬ vatoren sind N,N,N' ,N'-Tetraacetylethylendiamin und l,5-Diacetyl-2,4-di- oxo-hexahydro-1,3,5-triazin.In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the preparations. Examples of this are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose sepentaacetate. The bleach activators contain bleaching agents in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
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.. Auch Polyvinylpyrrolidon ist brauchbar. Bevorzugt werden jedoch Carboxymethylcellulose (Na-Salz), Me- thylcellulose, Methylhydroxyethylcellulose und deren Gemische sowie Poly¬ vinylpyrrolidon, beispielsweise in Mengen von 0,1 bis 5 Gew.-%, bezogen auf die Mittel, 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, eg degraded starch, aldehyde starches etc. Polyvinylpyrrolidone can also be used. However, carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and their mixtures and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition, are preferably used.
Das Schäumvermögen der Tenside läßt sich durch Kombination geeigneter Ten- sidtypen steigern oder verringern; eine Verringerung läßt sich ebenfalls durch Zusätze nichttensidartiger Substanzen erreichen. Ein verringertes Schäumvermögen, das beim Arbeiten in Maschinen erwünscht ist, erreicht man vielfach durch Kombination verschiedener Tensidtypen, z.B. von Sulfaten und/oder Sulfonaten mit nichtionischen Tensiden und/oder mit Seifen. Bei Seifen steigt die schaumdämpfende Wirkung mit dem Sättigungsgrad und der C-Zahl des Fettsäuresalzes an. Als schauminhibierende Seifen eignen sich daher solche Seifen natürlicher oder synthetischer Herkunft, die einen hohen Anteil an Cj8-C24-Fettsäuren aufweisen. Geeignete nichttensidartige Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemi¬ sche mit mikrofeiner, ggf. silanierter Kieselsäure oder Bistearylethylen- diamid sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure oder Bistearylethylendiamid. Mit Vorteil wer¬ den auch Gemische aus verschiedenen Schauminhibitoren verwendet, z.B. sol¬ che aus Silikonen, Paraffinen oder Wachsen. Vorzugsweise sind die Schaum¬ inhibitoren an eine granuläre, in Wasser lösliche bzw. dispergierbare Trägersubstanz gebunden.The foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a reduction can also be achieved by adding non-surfactant-like substances. A reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, for example sulfates and / or sulfonates with nonionic surfactants and / or with soaps. In the case of soaps, the foam-suppressing effect increases with the degree of saturation and the C number of the fatty acid salt. Soaps of natural or synthetic origin that contain a high proportion of C j 8-C24 fatty acids are therefore suitable as foam-inhibiting soaps. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica or bistearylethylene diamide, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes, are also advantageously used. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
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- is und Streptomyces griseus gewonnene enzymatische Wirkstoffe. Vorzugs¬ weise werden zumindest Proteasen, vorteilhafterweise vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, ein¬ gesetzt. Ihr Anteil kann etwa 0,2 bis etwa 2 Gew.-% betragen. Die Enzyme können an Trägerstoffen adsorbiert und/oder in Hü11Substanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen. Zusätzlich können die Mittel Enzymstabilisatoren enthalten. Beispielsweise können 0,5 bis 1 Gew.-% Natriumformiat eingesetzt werden. Möglich ist auch der Einsatz von Proteasen, die mit löslichen Calciumsalzen und einem Cal- ciumgehalt von vorzugsweise etwa l,2-Gew.-%, bezogen auf das Enzym, sta¬ bilisiert sind. Besonders vorteilhaft ist jedoch der Einsatz von Borver¬ bindungen, beispielsweise von Borsäure, Boroxid, Borax und anderen Alkali- metallboraten 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. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. At least proteases, advantageously of the subtilisin type and in particular proteases which are obtained from Bacillus lentus, are preferably used. Their proportion can be about 0.2 to about 2% by weight. The enzymes can be adsorbed on carriers and / or embedded in Hü11 substances to protect them against premature decomposition. In addition, the agents can contain enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B4O7), is particularly advantageous.
Die Mittel können als optische Aufheller Derivate der Dia inostilbendi- sulfonsäure bzw. deren Alkalimetallsalze enthalten. Geeignet sind z.B. Salze der 4,4'-Bis(2-anilino-4-morpholino-l,3,5-triazin-6-yl-amino)stil- ben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die an¬ stelle der Morpholino-Gruppe eine Diethanolaminogruppe, eine Methylamino- gruppe, eine Anilinogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ des substituierten 4,4'-Distyryl-di- phenyls anwesend sein, z.B. die Verbindung 4,4'-Bis(4-chlor-3-sulfosty- ryl)-diphenyl. Auch Gemische der vorgenannten Aufheller können verwendet werden. Es wurde außerdem gefunden, daß einheitlich weiße Granulate erhal¬ ten werden, wenn die Mittel außer den üblichen Aufhellern in üblichen Men¬ gen, beispielsweise zwischen 0,1 und 0,5 Gew.-%, vorzugsweise zwischen 0,1 und 0,3 Gew.-%, auch geringe Mengen, beispielsweise 10~6 bis 10~3 Gew.-%, vorzugsweise um 10*5 Gew.-%, eines blauen Farbstoffs enthält. Ein beson^ ders bevorzugter Farbstoff ist Tinoluχ(R) (Handelsprodukt der Ciba-Geigy).The agents can contain, as optical brighteners, derivatives of diaostilbenedisulfonic acid or its alkali metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazin-6-yl-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure are suitable instead of the morpholino group, a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present, for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. It has also been found that uniform white granules are obtained if, apart from the customary brighteners, the agents are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3 % By weight, also in small amounts, for example 10 ~ 6 to 10 ~ 3 % by weight, preferably around 10 * 5% by weight, of a blue dye. A special ^ DERS preferred dye is Tinoluχ (R) (commercial product of Ciba-Geigy).
Die erfindungsgemäßen granulären Wasch- und Reinigungsmittel können ein Schüttgewicht zwischen etwa 300 und 1100 g/1 aufweisen. Dabei werden Gra¬ nulate bevorzugt, die ein Schüttgewicht oberhalb 450 g/1, insbesondere zwischen 500 und 1100 g/1 aufweisen und aus mindestens zwei granulären, vorzugsweise aus mindestens drei granulären Komponenten bestehen, wovon die eine das polymere Polycarboxylat enthält.The granular detergents and cleaning agents according to the invention can have a bulk density between about 300 and 1100 g / 1. Granules are preferred which have a bulk density above 450 g / 1, in particular between 500 and 1100 g / 1, and consist of at least two granular, preferably at least three granular components, one of which contains the polymeric polycarboxylate.
Die erfindungsgemäßen Mittel können in an sich üblicher Weise durch Mi¬ schen von mindestens zwei granulären Komponenten hergestellt werden, wovon die eine das polymere Polycarboxylat enthält. Die andere granuläre Kompo¬ nente, welche vorzugsweise Aniontenside, gegebenenfalls nichtionische Ten- side und Buildersubstanzen sowie anorganische Salze enthält, wird bei¬ spielsweise durch Sprühtrocknung einer wäßrigen Aufschlämmung und gegebe¬ nenfalls anschließende Zumischung von temperaturempfindlichen Komponenten oder durch Granulieren und Extrudieren hergestellt. Bei der Herstellung dieser anderen granulären Komponente durch Granulieren oder Extrudieren ist es bevorzugt, daß diese Komponente Aniontenside und nichtionische Ten¬ side sowie Buildersubstanzen, anorganische Salze und gegebenenfalls Per- oxybleichmittel enthält.The agents according to the invention can be prepared in a conventional manner by mixing at least two granular components, one of which contains the polymeric polycarboxylate. The other granular component, which is preferably anionic surfactants, optionally nonionic surfactants. contains side and builder substances as well as inorganic salts, is produced, for example, by spray drying an aqueous slurry and, if appropriate, subsequently adding temperature-sensitive components or by granulating and extruding. In the production of this other granular component by granulation or extrusion, it is preferred that this component contains anionic surfactants and nonionic surfactants as well as builder substances, inorganic salts and optionally peroxy bleaching agents.
In einer weiteren Ausführungsfoπn der Erfindung werden die Mittel durch Extrusion hergestellt, wobei das granuläre polymere Polycarboxylat einen Bestandteil der zu extrudierenden Mischung darstellt. In a further embodiment of the invention, the agents are produced by extrusion, the granular polymeric polycarboxylate being a constituent of the mixture to be extruded.
B e i s p i e l eB e i s p i e l e
Es wurden granuläre Waschmittel nachstehender Zusammensetzung (Vergleichs¬ beispiele VI sowie erfindungsgemäßes Mittel Ml) in herkömmlicher Weise durch Sprühtrocknung hergestellt und getestet. Dabei wurde das polymere Polycarboxylat im Vergleichsbeispiel als 40 Gew.-%ige wäßrige Lösung (So- kalan(R) CP 5, Handelsprodukt der BASF, Bundesrepublik Deutschland) und als Bestandteil des sprühzutrocknenden Slurries eingesetzt und im erfin¬ dungsgemäßen Mittel als granuläre Zumischkomponente (Sokalan(R) CP5 Granu¬ lat, Handelsprodukt der BASF, Bundesrepublik Deutschland) nachträglich zugemischt. Die Bestandteile Perborat, Bleichaktivator und Enzym-Granulat wurden ebenfalls nachträglich zugemischt.Granular detergents of the following composition (comparative examples VI and agent Ml according to the invention) were prepared and tested in a conventional manner by spray drying. In the comparative example, the polymeric polycarboxylate was used as a 40% by weight aqueous solution (Sokalan ( R ) CP 5, commercial product from BASF, Federal Republic of Germany) and as a component of the slurry to be spray-dried, and as a granular admixture in the composition according to the invention ( Sokalan ( R ) CP5 Granu¬ lat, commercial product from BASF, Federal Republic of Germany) subsequently added. The constituents perborate, bleach activator and enzyme granulate were also added subsequently.
Die Prüfung erfolgte unter praxisnahen Bedingungen in Haushaltswaschma¬ schinen. Hierzu wurden die Maschinen mit 3,5 kg sauberer Füllwäsche und 0,5 kg Testgewebe beschickt, wobei das Testgewebe zum Teil mit üblichen Testanschmutzungen imprägniert war (zur Prüfung des Primärwaschvermögens) und zum Teil aus weißem Gewebe bestand (zur Prüfung des Sekundärwaschver¬ mögens). Als weiße Testgewebe wurden Streifen aus standardisiertem Baum- wollgewebe (Wäschereiforschungsanstalt Krefeld; WFK), Nessel (BN), Wirk¬ ware (Baumwolltrikot; B) und Frottiergewebe (FT) verwendet. Waschbedingun¬ gen: Leitungswasser von 23°d (äquivalent 230 mg CaO/1), eingesetzte Wasch¬ mittelmenge pro Mittel und Maschine 146 g, Waschtemperatur 25 bis 90 °C (Aufheizzeit 60 Minuten, 15 Minuten bei 90 °C), Flottenverhältnis (kg Wä¬ sche : Liter Waschlauge im Hauptwaschgang) 1:5,7, 4maliges Nachspülen mit Leitungswasser, Abschleudern und Trocknen.The test was carried out under practical conditions in household washing machines. For this purpose, the machines were loaded with 3.5 kg of clean laundry and 0.5 kg of test fabric, some of the test fabric with the usual Test soiling was impregnated (for testing the primary washing ability) and partly consisted of white fabric (for testing the secondary washing ability). Strips of standardized cotton fabric (laundry research institute Krefeld; WFK), nettle (BN), knitwear (cotton jersey; B) and terry toweling fabric (FT) were used as the white test fabric. Washing conditions: tap water of 23 ° d (equivalent to 230 mg CaO / 1), amount of detergent used per detergent and machine 146 g, washing temperature 25 to 90 ° C (heating time 60 minutes, 15 minutes at 90 ° C), liquor ratio ( kg of laundry: liters of wash liquor in the main wash cycle) 1: 5,7, rinse 4 times with tap water, spin off and dry.
Die Primärwaschleistungen der Mittel VI sowie Ml waren erwartungsgemäß vergleichbar.As expected, the primary washing performance of agents VI and Ml were comparable.
Nach 25 Waschzyklen wurde der Aschegehalt der Textilproben quantitativ be¬ stimmt. Das erfindungsgemäße Mittel Ml zeigte im Durchschnitt über alle Textilgewebe bessere Aschegehalte als das Vergleichsbeispiel VI.After 25 washing cycles, the ash content of the textile samples was determined quantitatively. The agent M1 according to the invention showed, on average, better ash contents than all of the textile fabrics than Comparative Example VI.
Analoge Ergebnisse wurden mit Mitteln erzielt, die durch Granulierung oder Extrusion hergestellt wurden, wobei das polymere Polycarboxylat im Ver¬ gleichsbeispiel als wäßrige Lösung und/oder als feinteiliges Pulver einge¬ setzt wurde, und/oder eine andere Tensidbasis, beispielsweise Fettalkyl¬ sulfate anstelle von Alkylbenzolsulfonat, enthielten.Analogous results were achieved with agents which were produced by granulation or extrusion, the polymeric polycarboxylate in the comparative example being used as an aqueous solution and / or as a finely divided powder, and / or a different surfactant base, for example fatty alkyl sulfates instead of Alkylbenzenesulfonate, contained.
Gew.-% Asche FT BN B WFKWt% ash FT BN B WFK
Anfangswert 0,19 0,39 0,46 0,75 0,45Initial value 0.19 0.39 0.46 0.75 0.45
VI 2,27 3,28 3,65 7,30 4,12VI 2.27 3.28 3.65 7.30 4.12
Ml 1,63 2,37 2,39 5,09 2,87 Ml 1.63 2.37 2.39 5.09 2.87

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Wasch- und Reinigungsmittel, insbesondere ein Textilwaschmittel , ent¬ haltend anionische und/oder nichtionische Tenside sowie phosphatfreie Buildersubstanzen, anorganische Salze und polymere Polycarboxylate, dadurch gekennzeichnet, daß es mindestens zwei granuläre Komponenten enthält, wovon die erste anionische und/oder nichtionische Tenside und phosphatfreie Buildersubstanzen sowie anorganische Salze aufweist und die zweite eine Zu ischkomponente aus polymeren Polycarboxylaten in granulärer Form ist, wobei das Mittel Alkalicarbonate in Mengen unter¬ halb 10 Gew.-%, bezogen auf das gesamte Mittel, enthält und eine ver¬ besserte Inkrustationsinhibierung aufweist.1. Detergents and cleaning agents, in particular a textile detergent, containing anionic and / or nonionic surfactants and phosphate-free builder substances, inorganic salts and polymeric polycarboxylates, characterized in that it contains at least two granular components, the first of which is anionic and / or nonionic surfactants and phosphate-free builder substances and inorganic salts, and the second is an add-on component of polymeric polycarboxylates in granular form, the agent containing alkali carbonates in amounts below 10% by weight, based on the total agent, and having an improved incrustation inhibition .
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß es als phosphat¬ freie Buildersubstanzen Zeolith und/oder kristalline Schichtsilikate der allgemeinen Formel (I) NaMSixθ2χ+ι*yH2θ, wobei M Natrium oder Was¬ serstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist, in Mengen von 10 bis 60 Gew.-% enthält, wobei das Gewichtsver¬ hältnis Buildersubstanzen zu granulären polymeren Polycarboxylaten 30:1 bis 1:1, vorzugsweise 20:1 bis 2:1 und insbesondere 10:1 bis 3:1 beträgt.2. Composition according to claim 1, characterized in that it as a phosphate-free builder zeolite and / or crystalline phyllosilicates of the general formula (I) NaMSi x θ2χ + ι * yH2θ, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number from 0 to 20, in amounts of 10 to 60% by weight, the weight ratio of builder substances to granular polymeric polycarboxylates being 30: 1 to 1: 1, preferably 20: 1 to 2: 1 and in particular 10: 1 to 3: 1.
3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die granu¬ lären polymeren Polycarboxylate ein Schüttgewicht zwischen 350 und 850 g/1, vorzugsweise zwischen 400 und 750 g/1 aufweisen und keine Parti¬ kel mit einer Teilchengröße unter 50 μm, vorzugsweise keine Partikel mit einer Teilchengröße unter 100 μm, enthalten und maximal 5 % der Partikel eine Teilchengröße oberhalb 1000 μm, vorzugsweise maximal 3 Gew.-% der Partikel eine Teilchengröße oberhalb 1000 μm aufweisen.3. Composition according to claim 1 or 2, characterized in that the granular polymeric polycarboxylates have a bulk density between 350 and 850 g / 1, preferably between 400 and 750 g / 1 and no particles with a particle size below 50 μm, preferably contain no particles with a particle size below 100 μm, and a maximum of 5% of the particles have a particle size above 1000 μm, preferably a maximum of 3% by weight of the particles have a particle size above 1000 μm.
4. Mittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es granuläre polymere Polycarboxylate enthält, die copolymere Salze der Acrylsäure mit Maleinsäure darstellen.4. Composition according to one of claims 1 to 3, characterized in that it contains granular polymeric polycarboxylates which are copolymeric salts of acrylic acid with maleic acid.
5. Mittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es 8 bis 40 Gew.-%, vorzugsweise 10 bis 35 Gew.-% und insbesondere 12 bis 28 Gew.-% anionische und nichtionische Tenside einschließlich5. Composition according to one of claims 1 to 4, characterized in that it is 8 to 40 wt .-%, preferably 10 to 35 wt .-% and in particular 12th up to 28% by weight of anionic and nonionic surfactants
Seife, 15 bis 45 Gew.-%, vorzugsweise 20 bis 40 Gew.-% Zeolith und/oder kristalline Schichtsilikate, insbesondere Zeolith, 0,5 bis 8 Gew.-% Natrium- oder Kaliumcarbonat und 0,5 bis 15 Gew.-%, vorzugs¬ weise 2 bis 10 Gew.-% und insbesondere 3 bis 8 Gew.-% granuläre poly¬ mere Polycarboxylate enthält.Soap, 15 to 45% by weight, preferably 20 to 40% by weight of zeolite and / or crystalline layered silicates, in particular zeolite, 0.5 to 8% by weight of sodium or potassium carbonate and 0.5 to 15% by weight %, preferably 2 to 10% by weight and in particular 3 to 8% by weight of granular polymeric polycarboxylates.
6. Mittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es weitere übliche Bestandteile von Wasch- und Reinigungsmitteln, vorzugsweise Peroxybleichmittel, Bleichaktivatoren, anorganische Salze, Enzyme und Polycarboxylate in an sich üblichen Mengen enthält, aber vorzugsweise frei von Phosphonaten ist.6. Composition according to one of claims 1 to 5, characterized in that it contains other conventional components of detergents and cleaning agents, preferably peroxy bleach, bleach activators, inorganic salts, enzymes and polycarboxylates in conventional amounts, but is preferably free of phosphonates.
7. Mittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es ein Schüttgewicht zwischen 300 und 1100 g/1, vorzugsweise zwischen 500 und 1000 g/1 aufweist und insbesondere aus mindestens drei granu¬ lären Komponenten besteht, wovon die eine das polymere Polycarboxylat enthält.7. Composition according to one of claims 1 to 6, characterized in that it has a bulk density between 300 and 1100 g / 1, preferably between 500 and 1000 g / 1 and in particular consists of at least three granular components, one of which is the contains polymeric polycarboxylate.
8. Verfahren zur Herstellung eines granulären Wasch- und Reinigungsmit¬ tels gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß es durch Mischen von mindestens zwei granulären Komponenten erhalten wird, wovon die eine das polymere Polycarboxylat enthält.8. A method for producing a granular washing and cleaning agent according to one of claims 1 to 7, characterized in that it is obtained by mixing at least two granular components, one of which contains the polymeric polycarboxylate.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß die andere granuläre Komponente, welche vorzugsweise Aniontenside, gegebenenfalls nichtionische Tenside, Buildersubstanzen und anorganische Salze ent¬ hält, durch Sprühtrocknung hergestellt wird.9. The method according to claim 8, characterized in that the other granular component, which preferably contains anionic surfactants, optionally nonionic surfactants, builder substances and inorganic salts, is produced by spray drying.
10. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß die andere granuläre Komponente, welche vorzugsweise Aniontenside und nichtio¬ nische Tenside sowie Buildersubstanzen, anorganische Salze und gege¬ benenfalls Peroxybleichmittel enthält, durch ein Granulier- oder Extrudierverfahren hergestellt wird. 10. The method according to claim 8, characterized in that the other granular component, which preferably contains anionic surfactants and non-ionic surfactants and builder substances, inorganic salts and, if appropriate, peroxy bleaching agent, is produced by a granulation or extrusion process.
11. Verfahren zur Herstellung eines granulären Wasch- und Reinigungsmit¬ tels gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß es durch Extrusion hergestellt wird, wobei das granuläre polymere Poly¬ carboxylat einen Bestandteil der zu extrudierenden Mischung darstellt. 11. A process for the preparation of a granular washing and cleaning agent according to one of claims 1 to 7, characterized in that it is produced by extrusion, the granular polymeric polycarboxylate being a constituent of the mixture to be extruded.
EP93919191A 1992-09-04 1993-08-26 Washing and cleaning agents with builder substances Revoked EP0658189B1 (en)

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ATE107352T1 (en) * 1989-08-09 1994-07-15 Henkel Kgaa PRODUCTION OF COMPACT GRANULES FOR DETERGENT.
GB8922179D0 (en) * 1989-10-02 1989-11-15 Rohm & Haas Polymer-containing granulates
DE3943019A1 (en) * 1989-12-27 1991-07-04 Henkel Kgaa GRANULAR, AVIVATING ACTIVITY OF DETERGENT ADDITIVE AND METHOD FOR THE PRODUCTION THEREOF
DE4034131C2 (en) * 1990-10-26 1999-08-26 Henkel Kgaa Builders for detergents

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Title
See references of WO9405764A1 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6841614B1 (en) 1998-10-29 2005-01-11 Henkel Kommanditgesellschaft Auf Aktien Polymer granules produced by fluidized bed granulation
EP1529834A1 (en) * 2003-11-10 2005-05-11 The Procter & Gamble Company Detergent particles
WO2005047442A1 (en) * 2003-11-10 2005-05-26 The Procter & Gamble Company Detergent particles

Also Published As

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DE4229660A1 (en) 1994-03-10
DE59303899D1 (en) 1996-10-24
WO1994005764A1 (en) 1994-03-17
EP0658189B1 (en) 1996-09-18
ATE143048T1 (en) 1996-10-15

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