EP0656050B1 - Adjuvants pour agents de lavage - Google Patents

Adjuvants pour agents de lavage Download PDF

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Publication number
EP0656050B1
EP0656050B1 EP93919063A EP93919063A EP0656050B1 EP 0656050 B1 EP0656050 B1 EP 0656050B1 EP 93919063 A EP93919063 A EP 93919063A EP 93919063 A EP93919063 A EP 93919063A EP 0656050 B1 EP0656050 B1 EP 0656050B1
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EP
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Prior art keywords
acids
salts
polyhydroxymonocarboxylic
acid
weight
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EP93919063A
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German (de)
English (en)
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EP0656050B2 (fr
EP0656050A1 (fr
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Beatrix Kottwitz
Horst Upadek
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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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof

Definitions

  • the invention relates to a washing and cleaning agent which contains phosphate-free builders and complexing agents, as well as a phosphate-free builders combination and a process for their preparation.
  • zeolite in particular zeolite NaA, and mixtures of zeolite with alkali silicates and carbonates and polymeric polycarboxylates have been used as phosphate substitutes in washing and cleaning agents.
  • complexing agents such as the salts of nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA) and phosphonic acids.
  • NTA nitrilotriacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • phosphonic acids phosphonic acids
  • European patent application 291 869 describes phosphate-free builders combinations of zeolite, aminoalkane polyphosphonate, 1-hydroxyethane-1,1-diphosphonate (HEDP) and polymeric polycarboxylate, certain weight ratios of the last three components showing synergism with regard to preventing the formation of fiber incrustations.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • polymeric polycarboxylate certain weight ratios of the last three components showing synergism with regard to preventing the formation of fiber incrustations.
  • the European patent application 448 298 describes detergents which contain zeolite as the builder and 3 to 18% by weight of the complexing agent sodium citrate, the ratio of zeolite (calculated as anhydrous active substance) to sodium citrate (calculated as dihydrate) is 2.5: 1 to 6: 1.
  • the agents have a washing performance that is comparable to the washing performance of agents that contain zeolite and polyacrylates as builders.
  • phosphate-free agents which contain certain complex-forming polyhydroxycarboxylic acids or their salts or mixtures thereof have a primary washing power which is comparable to the primary washing power of citrate-containing agents, the secondary washing power of these agents having great advantages over the citrate-containing agents.
  • the invention relates in a first embodiment to a phosphate-free washing and cleaning agent, in particular a textile washing agent, which contains zeolite and / or crystalline phyllosilicates of the general formula (I) NaMSi x O 2x + 1 .yH 2 O, where M is sodium or Hydrogen means x is a number from 1.9 to 4 and y is a number from 0 to 20, and as complexing agent polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts with 4 to 6 carbon atoms and at least 3 hydroxyl groups per molecule or mixtures of these acids and / or Contains salts.
  • a textile washing agent which contains zeolite and / or crystalline phyllosilicates of the general formula (I) NaMSi x O 2x + 1 .yH 2 O, where M is sodium or Hydrogen means x is a number from 1.9 to 4 and y is a number from 0 to 20, and as complexing agent polyhydroxymono
  • the content of the builders in the builders zeolite and / or crystalline phyllosilicates of the general formula (I) is 15 to 60% by weight, the weight ratio builders to polyhydroxymonocarboxylic acid or polyhydroxymonocarboxylic acid salt or mixtures of these acids and / or salts 30: 1 is up to 1: 1.
  • the invention relates to a builder combination which comprises zeolite and / or crystalline phyllosilicates of the general formula (I) NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number of 1, 9 to 4 and y a number from 0 to 20, and as complexing agents contain polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts with 4 to 6 carbons and at least 3 hydroxyl groups per molecule or mixtures of these acids and / or salts, the weight ratio of builders to polyhydroxymonocarboxylic acid or polyhydroxymonocarboxylic acid salt or mixtures thereof Acids and / or salts is 30: 1 to 1: 1.
  • polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts it is possible for the polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts to have one keto group per molecule, these polyhydroxymonocarboxylic acids preferably forming lactones.
  • Preferred polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts are those which contain 4 to 6 carbon atoms and have a hydroxyl group on each carbon atom which has no carboxyl group or keto group.
  • Polyhydroxymonocarboxylic acids and / or polyhydroxymonocarboxylic acid salts with 4 carbon atoms and 3 hydroxyl groups, with 5 carbon atoms and 4 hydroxyl groups and with 6 carbon atoms and 4 or 5 hydroxyl groups are particularly preferred.
  • Particularly advantageous properties have polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acids with 6 carbon atoms and 5 hydroxyl groups, such as D-gluconic acid (also called maltonic acid or dextronic acid) or their salts, and polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts with 6 carbon atoms, a keto group and 4 hydroxyl groups.
  • Groups such as L-ascorbic acid, which is present as a lactone, and L-ascorbic acid salts.
  • Mixtures of the acids and / or the salts can also be used, the latter preferably in the form of their sodium or potassium salts.
  • 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. Quantities and weight ratios that relate to the builder zeolite are included in this Unless otherwise stated, the invention relates to an anhydrous active substance.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula (I) NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number Number is from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application 164 514.
  • Preferred crystalline sheet silicates of the formula (I) are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • the agents or builders combinations according to the invention can also contain mixtures of zeolite and the crystalline sheet 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 agents or builders combinations according to the invention contain the builders zeolite and / or crystalline phyllosilicates (I) and the complexing agents polyhydroxymonocarboxylic acid or polyhydroxymonocarboxylic acid salt or mixtures of these acids and / or salts advantageously in a weight ratio of 20: 1 to 1: 1, preferably 10 : 1 to 1.5: 1 and especially from 5: 1 to 1.5: 1.
  • the detergents and cleaning agents according to the invention are preferably in granular form.
  • Advantageous agents contain 15 to 50% by weight of zeolite and / or crystalline phyllosilicates (I) and 1 to 20% by weight of polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts with 4 to 6 carbon atoms and at least 3 hydroxyl groups per molecule, such polyhydroxymonocarboxylic acids or Polyhydroxymonocarboxylic acid salts are preferred in which each carbon atom, which has no carboxyl group or keto group, has a hydroxy group.
  • Agents which contain 18 to 40% by weight, in particular 20 to 35% by weight, of zeolite are particularly preferred, the weight ratio of zeolite to polyhydroxymonocarboxylic acid or polyhydroxymonocarboxylic acid salt or mixtures of these acids and / or salts 20: 1 to 1: 1, preferably 10: 1 to 1.5: 1 and in particular 5: 1 to 1.5: 1.
  • those agents have advantages which contain 2 to 15% by weight and preferably 4 to 12% by weight of gluconic acid or gluconic acid salt, ascorbic acid or ascorbic acid salt or mixtures of these acids and / or salts.
  • the detergents and cleaning agents according to the invention can also contain other conventional builders and complexing agents, for example phosphonates, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is used for ecological reasons is not objectionable, as well as mixtures of these and (co) polymeric polycarboxylic acids or polycarboxylates such as 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), in particular those of acrylic acid with Methacrylic acid and the acrylic acid or methacrylic acid with maleic acid are preferred, additionally contained.
  • these additional builders and complexing agents do not further contribute to the significant improvement of the secondary washing ability.
  • Phosphonates preferably the neutral sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and diethylene triamine pentamethylene phosphonate, are frequently used as enzyme or bleach stabilizers in amounts of 0.1 to 1.5% by weight.
  • the secondary washing power of the agents according to the invention has risen to such an extent through the use of the polyhydroxymonocarboxylic acids or their salts that the use of phosphonates can be dispensed with without a loss in performance. Therefore, agents that do not contain phosphonates are preferred contain.
  • (co) polymeric polycarboxylic acids or polycarboxylates usually used in washing and cleaning agents in particular to the 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 and their relative molecular weight, based on free acids, is generally from 5,000 to 200,000, preferably from 10,000 to 120,000 and in particular from 50,000 to 100,000. Therefore, agents are preferred which do not contain (co) polymeric polycarboxylic acids or polycarboxylates. In particular, agents are preferred which contain neither phosphonate nor (co) polymeric polycarboxylates.
  • the agents according to the invention which contain polyhydroxymonocarboxylic acids, polyhydroxymonocarboxylic acid salts or mixtures thereof as complexing agents, compared to an agent which contains polyhydroxytricarboxylic acids or polyhydroxytricarboxylic acid salts such as citric acid or citrate instead of the complexing agents according to the invention, have a significantly higher secondary washing performance with the same primary washing performance exhibit.
  • the additional use of citric acid or citrate does not result in any further significant improvements in the secondary washing capacity, so that particularly preferred agents are free from citric acid or citrate.
  • the builders combinations according to the invention can also contain further constituents, for example inorganic salts which react alkaline or neutral in water.
  • inorganic salts which react alkaline or neutral in water.
  • the builder combinations are sprayed with liquid to wax-like components, for example silicone oils and paraffin oils, but preferably with nonionic surfactants.
  • the agents according to the invention can contain known additives commonly used in detergents and cleaning agents, for example surfactants, bleaching agents and bleach activators, salts which have an alkaline reaction in water, solubility improvers such as conventional hydrotropes or polyalkylene glycols, for example polyethylene glycols, foam inhibitors, optical brighteners, enzymes, enzyme stabilizers , contain small amounts of neutral filling salts as well as colors and fragrances, opacifiers or pearlescent agents.
  • solubility improvers such as conventional hydrotropes or polyalkylene glycols, for example polyethylene glycols, foam inhibitors, optical brighteners, enzymes, enzyme stabilizers , contain small amounts of neutral filling salts as well as colors and fragrances, opacifiers or pearlescent agents.
  • the content of the agents in anionic and nonionic surfactants including soap is preferably 10 to 35% by weight, advantageously 12 to 28% by weight and in particular 15 to 25% by weight.
  • surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfofatty acids are also suitable.
  • esters of ⁇ -sulfo fatty acids which are produced by ⁇ -sulfonation of the alkyl esters of fatty acids of plant and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts are suitable.
  • These are preferably the ⁇ -sulfonated esters of hydrogenated coconut, palm kernel or tallow fatty acids, and sulfonation products of unsaturated fatty acids, for example oleic acid, are also present in small amounts, preferably in amounts not above about 2 to 3% by weight could be.
  • ⁇ -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 ⁇ -sulfofatty acids (MES) are used with particular advantage.
  • Further 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.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • fats and oils i.e. natural mixtures of different fatty acid glycerol esters
  • suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, turnip oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or lard. Due to their high natural content of saturated fatty acids, it has proven to be particularly advantageous to start from coconut oil, palm kernel oil or beef tallow.
  • the sulfonation of the saturated fatty acids with 6 to 22 carbon atoms or the mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, is preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as described in the international patent application WO 91/9009 is specified.
  • the sulfonation products are a complex mixture which essentially contains mono-, di- and triglyceride sulfonates with an ⁇ -position and / or internal sulfonic acid grouping.
  • sulfonated fatty acid salts glyceride sulfates, glycerine sulfates, glycerin and soaps are formed. If one starts out 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 made from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization can be obtained.
  • the sulfonate group is statistically distributed over the entire carbon chain, with the secondary alkanesulfonates predominating.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, for example from tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and those secondary alcohols of this chain length.
  • the sulfuric acid monoesters of alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 moles of ethylene oxide, are also suitable.
  • Preferred fatty alkyl sulfates are derived from fatty alcohol mixtures obtained from coconut oil, palm oil and palm kernel oil, which may additionally contain fractions of unsaturated alcohols, for example oleyl alcohol. Mixtures in which the proportion of the alkyl radicals is 50 to 70% by weight on C 12 , 18 to 30% by weight on C 14 , 5 to 15% by weight on C 16 , are preferred 3% by weight on C 10 and less than 10% by weight on C 18 are distributed.
  • anionic surfactants are the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred.
  • Preferred granular detergents and cleaning agents contain, as anionic surfactants, alkylbenzenesulfonates and / or alkyl sulfate, preferably fatty alkyl sulfate, and / or sulfated fatty acid glycerol esters, the weight ratio of sulfated fatty acid glycerol esters to alkylbenzenesulfonate and / or alkyl sulfate 1: 9 to 4: 1 and in particular 2: 5 to 2 : 1 is.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts from 0.2 to 8 and in particular from 0.5 to 5% by weight.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12 -C 24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts.
  • the granular detergents and cleaning agents also contain nonionic surfactants in addition to the anionic surfactants, preferably in amounts of 1 to 15% by weight, in particular in amounts of 2 to 12% by weight.
  • the nonionic surfactants used are preferably liquid ethoxylated and / or propoxylated alcohols which are derived from primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 mol of alkylene oxide, in which the alcohol radical can be linear or methyl-branched in the 2-position, or linear and May contain methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals.
  • linear residues of alcohols of native origin with 12 to 18 carbon atoms such as, for example, coconut oil, tallow oil or oleyl alcohol, are particularly preferred.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution on (narrow range ethoxylates, NRE).
  • NRE narrow range ethoxylates
  • alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms branched in the 2-position and G denotes the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10.
  • Suitable ingredients of the granular agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous or crystalline silicates or mixtures of these; in particular, alkali carbonate and alkali silicate, especially sodium silicate with a molar ratio Na 2 0: Si0 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
  • the sodium silicate content of the agents 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 H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxaphthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used. Since, as is known, peroxy compounds react with ascorbic acid and this results in a loss of active oxygen, agents which contain ascorbic acid or ascorbic acid salts are preferably free from peroxy bleaching agents.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
  • Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying.
  • Water-soluble colloids mostly of an organic nature, are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • carboxymethyl cellulose sodium salt
  • methyl cellulose methyl hydroxyethyl cellulose and mixtures thereof
  • 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 which contain a high proportion of C 18 -C 24 fatty acids are therefore suitable as foam-inhibiting soaps.
  • Suitable non-surfactant Foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of various foam inhibitors are also advantageously used, for example those made of silicone, paraffins or waxes.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Their proportion can be about 0.2 to about 2% by weight. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the agents can contain enzyme stabilizers.
  • 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.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HB0 2 ) and pyroboric acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which are used instead of Morpholino group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted 4,4'-distyryl-diphenyl type can also be present, for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used will. It has also been found that uniform white granules are obtained if, apart from the customary brighteners, the agents are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight. , also contains small amounts, for example 10 -6 to 10 -3 % by weight, preferably around 10 -5 % by weight, of a blue dye.
  • a particularly preferred dye is Tinolux (R) (commercial product from Ciba-Geigy).
  • the granular washing and cleaning agents according to the invention can have a bulk density between about 300 and 1100 g / l.
  • Granules are preferred which have a bulk density above 450 g / l, in particular between 500 and 1100 g / l.
  • Both the builders combinations according to the invention and the washing and cleaning agents according to the invention can be prepared in a conventional manner, for example by mixing, granulating, extruding and / or by spray drying an aqueous slurry and optionally subsequently adding temperature-sensitive components.
  • detergents and cleaning agents separately manufactured builders combinations in the form of a spray-dried or granulated compound can be used as admixing components with other granular constituents of the detergents and cleaning agents. It is also possible to incorporate the builders and complexing agents into the agents individually in a conventional manner and in any order.
  • Granular detergents of the following composition were prepared and tested in a conventional manner by spray drying.
  • the constituents perborate, bleach activator and enzyme granulate and the complexing agents including the copolymeric polyacrylate and 1-hydroxyethane-1,1-diphosphonate (HEDP) were subsequently mixed in Comparative Example C3.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • 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 being impregnated with conventional test soiling (for testing the primary washing ability) and some consisting of white fabric (for testing the secondary washing ability).
  • Strips of standardized cotton fabric (Krefeld laundry research institute; WFK), nettle (BN), knitwear (cotton jersey; B) and terry toweling fabric (FT) were used as the white test fabric.
  • Washing conditions tap water of 23 ° d (equivalent to 230 mg CaO / l), amount of detergent used per detergent and machine 146 g, washing temperature 25 to 90 ° C (heating time 60 minutes, 15 minutes at 90 ° C), liquor ratio (kg laundry: liter Wash water in the main wash cycle) 1: 5,7, rinse 4 times with tap water, spin off and dry.
  • Agents M1 / 1 or M1 / 2 to M2 / 1 or M2 / 2 according to the invention showed, on average, better ash contents than all comparative examples V1 and V2 over all textile fabrics.
  • the combustion of organic constituents usually results in a lower value than the actual incrustation.
  • the total incrustation was therefore also determined (1st weighing of the untreated fabric, 2nd weighing of the fabric after 25 washing cycles, 3rd weighing of the fabric after extraction with EDTA, 4th determination of the so-called "soluble ash” from the difference in weighing 2 and 3rd, 5th ashing of the extracted tissue to determine the residual ash, 6. determination of the total incrustation (sum of soluble ash and residual ash)).

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Claims (18)

  1. Produit de lavage et de nettoyage, notamment un produit de lavage de textiles, contenant comme substances adjuvants sans phosphates une zéolithe et/ou des silicates feuilletés cristallins de formule générale (I) NaMSixO2x+1·yH2O, où M représente le sodium ou l'hydrogène, x est un nombre de 1,9 à 4 et y est un nombre de 0 à 20, et des complexants,
    caractérisés en ce qu'
    il contient les adjuvants en des quantités de 15 à 60 % en poids et comme des complexants choisis parmi poly(hydroxyacides monocarboxyliques) ou des sels de poly(hydroxyacides monocarboxyliques) de 4 à 6 atomes de carbone et au moins 3 groupes hydroxy par molécule ou des mélanges de ces acides et/ou de ces sels, où le rapport pondéral des adjuvants aux poly(hydroxyacides monocarboxyliques) ou aux sels de poly(hydroxyacides monocarboxyliques) ou aux mélanges de ces acides et/ou sels représente 30:1 à 1:1.
  2. Produit selon la revendication 1,
    caractérisé en ce qu'il contient 15 à 50 % en poids de zéolithe et/ou de silicates feuilletés cristallins (I) et 1 à 20 % en poids de poly(hydroxyacides monocarboxyliques) ou de sels de poly(hydroxyacides monocarboxyliques) de 4 à 6 atomes de carbone, où chaque atome de carbone qui ne porte pas de groupe carboxyle ni de groupe céto présente un groupe hydroxy.
  3. Produit selon la revendication 1 ou 2,
    caractérisé en ce qu'
    il contient 10 à 35 % en poids, de préférence 12 à 28 % en poids et notamment 15 à 25 % en poids de tensioactifs anioniques et non ioniques y compris des savons, 18 à 40 % en poids de préférence 20 à 35 % en poids de zéolithe, où le rapport pondéral de la zéolithe au poly(hydroxyacide monocarboxylique) ou au sel de poly(hydroxyacide monocarboxylique) ou aux mélanges de ces acides et/ou sels représente 20:1 à 1:1, de préférence 10:1 à 1,5:1 et notamment 5:1 à 1,5:1.
  4. Produit selon l'une des revendications 1 à 3,
    caractérisé en ce qu'
    il contient 2 à 15 % en poids et de préférence 4 à 12 % en poids d'acide gluconique ou de sel d'acide gluconique, de l'acide ascorbique ou du sel d'acide ascorbique ou des mélanges de ces acides et/ou de ces sels.
  5. Produit selon l'une des revendications 1 à 4,
    caractérisé en ce qu'
    il ne contient pas de phosphonates.
  6. Produit selon l'une des revendications 1 à 5,
    caractérisé en ce qu'
    il ne contient pas de poly(acide carboxyliques) ou de sels de poly(acides carboxyliques).
  7. Produit selon l'une des revendications 1 à 6,
    caractérisé en ce qu'
    il ne contient pas de citrate.
  8. Produit selon l'une des revendications 1 à 7,
    caractérisé en ce qu'
    il contient du carbonate de sodium et/ou du carbonate de potassium en des quantités de 2 à 15, de préférence de 5 à 14 % en poids.
  9. Produit selon l'une des revendications 1 à 8,
    caractérisé en ce qu'
    il contient de l'acide gluconique ou des sels d'acide gluconique ou de l'acide ascorbique ou des sels d'acide ascorbique, où en cas de présence d'acide ascorbique ou d'un sel d'acide ascorbique le produit est de préférence exempt d'agents blanchissants peroxy.
  10. Produit selon l'une des revendications 1 à 9,
    caractérisé en ce qu'
    il a une densité apparente comprise entre 300 et 1100 g/l, de préférence entre 500 et 1100 g/l.
  11. Combinaison d'adjuvants, contenant des adjuvants et un complexant,
    caractérisée en ce qu'
    elle contient comme substances d'adjuvants une zéolithe et/ou des silicates feuilletés cristallins de formule générale (I) NaMSixO2x+1·yH2O, où M représente le sodium ou l'hydrogène, x est un nombre de 1,9 à 4 et y est un nombre de 0 à 20, et comme des complexants des poly(hydroxyacides monocarboxyliques) ou des sels de poly(hydroxyacides monocarboxyliques) de 4 à 6 atomes de carbone et au moins 3 groupes hydroxy par molécule ou des mélanges de ces acides et/ou de ces sels, où le rapport pondéral des adjuvants aux poly(hydroxyacides monocarboxyliques) ou aux sels de poly(hydroxyacides monocarboxyliques) ou aux mélanges de ces acides et/ou sels représente 30:1 à 1:1.
  12. Combinaison d'adjuvants selon la revendication 11,
    caractérisée en ce qu'
    elle contient des poly(hydroxyacides monocarboxyliques) de 4 à 6 atomes de carbone qui présentent sur chaque atome de carbone qui ne contient pas de groupe carboxyle ni de groupe céto, un groupe hydroxy, où le rapport pondéral des substances adjuvants, notamment la zéolithe, au poly(hydroxyacides monocarboxyliques) ou au sel de poly(hydroxyacide monocarboxylique) ou aux mélanges de ces acides et/ou sels représente 20:1 à 1:1, de préférence 10:1 à 1,5:1 et notamment 5:1 à 1,5:1.
  13. Combinaison d'adjuvants selon la revendication 11 ou 12,
    caractérisée en ce qu'
    elle contient comme poly(hydroxyacides monocarboxyliques) ou au sel de poly(hydroxyacide monocarboxylique) de l'acide gluconique ou un gluconate, de l'acide ascorbique ou un ascorbate ou des mélanges de ces acides et/ou de ces sels.
  14. Combinaison d'adjuvants selon l'une des revendications 11 à 13,
    caractérisée en ce qu'
    on pulvérise la combinaison de substances d'adjuvants avec des composants liquides à cireux, de préférence en présence de tensioactifs non ioniques.
  15. Procécé de production d'une combinaison d'adjuvants contenant :
    comme substances d'adjuvants, une zéolithe et/ou des silicates feuilletés cristallins de formule générale (I) NaM-SixO2x+1·yH2O, où M représente le sodium ou l'hydrogène, x est un nombre de 1,9 à 4 et y est un nombre de 0 à 20, et comme complexants des poly(hydroxyacides monocarboxyliques) ou des sels de poly(hydroxyacides monocarboxyliques) de 4 à 6 atomes de carbone et au moins 3 groupes hydroxy par molécule ou des mélanges de ces acides et/ou de ces sels,
    caractérisé en ce qu'
    on produit la combinaison de substances d'adjuvants par mélange, granulation et/ou par atomisation.
  16. Procédé de fabrication d'un produit de lavage et de nettoyage en granulés selon l'une des revendications 1 à 10,
    caractérisé en ce qu'
    on produit le granulé par atomisation.
  17. Procédé de fabrication d'un produit de lavage et de nettoyage en granulés selon l'une des revendications 1 à 10,
    caractérisé en ce qu'
    on produit le granulé par un procédé de granulation ou d'extrusion.
  18. Procedé de fabrication d'un produit de lavage et de nettoyage en granulés selon l'une des revendications 1 à 10,
    caractérisé en ce qu'
    on utilise la combinaison de substances d'adjuvants une zéolithe et/ou des silicates feuilletés cristallins de formule générale (I) NaMSixO2x+1·yH2O, où M représente le sodium ou l'hydrogène, x est un nombre de 1,9 à 4 et y est un nombre de 0 à 20, et des poly(hydroxyacides monocarboxyliques) ou des sels de poly(hydroxyacides monocarboxyliques) de 4 à 6 atomes de carbone et au moins 3 groupes hydroxy par molécule ou des mélanges de ces acides et/ou de ces sels, sous forme d'une composition atomisée ou granulée comme composant d'addition à d'autres composants en granulés de produits de lavage et de nettoyage.
EP93919063A 1992-08-24 1993-08-16 Adjuvants pour agents de lavage Expired - Lifetime EP0656050B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4228043 1992-08-24
DE4228043A DE4228043A1 (de) 1992-08-24 1992-08-24 Gerüststoff für Waschmittel
PCT/EP1993/002172 WO1994004649A1 (fr) 1992-08-24 1993-08-16 Adjuvants pour agents de lavage

Publications (3)

Publication Number Publication Date
EP0656050A1 EP0656050A1 (fr) 1995-06-07
EP0656050B1 true EP0656050B1 (fr) 1997-05-14
EP0656050B2 EP0656050B2 (fr) 2000-03-08

Family

ID=6466268

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93919063A Expired - Lifetime EP0656050B2 (fr) 1992-08-24 1993-08-16 Adjuvants pour agents de lavage

Country Status (7)

Country Link
EP (1) EP0656050B2 (fr)
JP (1) JPH08500378A (fr)
AT (1) ATE153055T1 (fr)
DE (2) DE4228043A1 (fr)
ES (1) ES2102674T5 (fr)
PL (1) PL307589A1 (fr)
WO (1) WO1994004649A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2796389A1 (fr) * 1999-07-15 2001-01-19 Roquette Freres Procede de lavage contenant de l'acide arabinonique et/ou l'un, au moins, de ses sels

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2254885T3 (es) 2002-06-20 2006-06-16 L'oreal Utilizacion cosmetica y/o dermatologica de una composicion que contiene al menos un agente hidrofilo sensible a la oxidacion por al menos un copolimero de anhidrido maleico.
FR2886845B1 (fr) * 2005-06-13 2009-07-03 Oreal Produit cosmetique solide
ITCR20060016A1 (it) * 2006-06-07 2007-12-08 Silvia Palladini Formulazioni di detersivi a basso impatto ambientale

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT337326B (de) * 1974-08-02 1977-06-27 Henkel & Cie Gmbh Verfahren zum waschen, reinigen bzw. bleichen der oberflachen fester werkstoffe, insbesondere von textilien, und mittel zur durchfuhrung dieses verfahrens
AT375393B (de) * 1974-10-04 1984-07-25 Henkel Kgaa Verfahren zum waschen bzw. bleichen von textilien sowie mittel dazu
DE4034131C2 (de) * 1990-10-26 1999-08-26 Henkel Kgaa Gerüststoff für Waschmittel

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2796389A1 (fr) * 1999-07-15 2001-01-19 Roquette Freres Procede de lavage contenant de l'acide arabinonique et/ou l'un, au moins, de ses sels

Also Published As

Publication number Publication date
WO1994004649A1 (fr) 1994-03-03
DE59306463D1 (de) 1997-06-19
ES2102674T3 (es) 1997-08-01
PL307589A1 (en) 1995-05-29
ATE153055T1 (de) 1997-05-15
JPH08500378A (ja) 1996-01-16
DE4228043A1 (de) 1994-03-03
ES2102674T5 (es) 2000-05-01
EP0656050B2 (fr) 2000-03-08
EP0656050A1 (fr) 1995-06-07

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