EP0656051B2 - Adjuvants pour agents de lavage - Google Patents

Adjuvants pour agents de lavage Download PDF

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Publication number
EP0656051B2
EP0656051B2 EP93919062A EP93919062A EP0656051B2 EP 0656051 B2 EP0656051 B2 EP 0656051B2 EP 93919062 A EP93919062 A EP 93919062A EP 93919062 A EP93919062 A EP 93919062A EP 0656051 B2 EP0656051 B2 EP 0656051B2
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EP
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Prior art keywords
acids
acid
salts
polyhydroxydicarboxylic
weight
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EP93919062A
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German (de)
English (en)
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EP0656051B1 (fr
EP0656051A1 (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
    • 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
    • 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
    • C11D3/128—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 detergent and cleaning agent, the phosphate-free Contains builders and complexing agents, as well as a phosphate-free combination of builders and a process for their manufacture.
  • phosphate substitutes in detergents and cleaning agents especially zeolite, especially zeolite NaA, and mixtures of zeolite with alkali silicates and carbonates as well as polymeric polycarboxylates used.
  • complexing agents such as the salts of nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA) and phosphonic acids.
  • NTA nitrilotriacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • the mostly selective complexing agents have the task Heavy metal ions, which already have a very negative impact on traces may have to eliminate the washing process (Ullmann, 1987, vol. 8, pages 351 to 354).
  • the phosphonates are known to also precipitate poorly soluble calcium salts and thus that of poorly soluble Calcium salts caused incrustation and graying of the tissue counteract ("use of phosphonates in liquid detergents", M. Paladini, G. Schnorbus, Soap-Oil-Fat-Waxes, 115th year (1989), Pages 508 to 511). Finally, the combined use of phosphonates works and copolymers based on acrylic acid and maleic acid in comparison with formulations that contain only one of these two components, a higher degree of whiteness of the textiles ("use of phosphonates in Household detergents with a low phosphorus content (1%) ", M. Paladini, G. Schnorbus, Seifen- ⁇ le-Fette-Wwachs, 114, year (1988), pages 756 to 760).
  • European patent application 291 869 describes phosphate-free building material combinations made of zeolite.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • polymeric polycarboxylate with certain Weight ratios of the last three components related to synergism the prevention of the formation of fiber incrustations.
  • European patent application 448 298 describes detergents which are known as Builders zeolite and 3 to 18 wt .-% of the complexing agent sodium citrate contains, 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 matches the washing performance of agents that are comparable as builders zeolite and polyacrylates contain.
  • phosphate-free agents which certain complexing Polyhydroxycarboxylic acids or their salts or mixtures thereof included, have a primary wash capacity that matches the primary wash capacity citrate-containing agent is comparable, the secondary washing ability These agents have great advantages over agents containing citrate having.
  • 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 polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts with 4 to 6 carbon atoms and at least 2 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 polyhydroxydicarboxy
  • 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 polyhydroxydicarboxylic acid or polyhydroxydicarboxylic acid salt or mixtures of these acids and / or salts 30: 1 is up to 1: 1, with the proviso that no tartaric acid or tartaric acid salts are contained as complexing agents.
  • 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 is a number from 0 to 20, and as complexing agents contain polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts with 4 to 6 carbon atoms and at least 2 hydroxyl groups per molecule or mixtures of these acids and / or salts, the weight ratio of builders to polyhydroxydicarboxylic acid or polyhydroxydicarboxylic acid salt or mixtures of these acids and / or salts is 30: 1 to 1: 1, with the proviso that tartaric acid or tartaric acid salt is not present as a complexing agent.
  • complexing agents contain polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts with 4 to 6 carbon atoms and at least 2 hydroxyl groups per molecule
  • Preferred polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts are those that contain 4 to 6 carbon atoms and on each carbon atom, which has no carboxyl group, have a hydroxyl group.
  • polyhydroxydicarboxylic acids and polyhydroxydicarboxylic acid salts with 4 carbon atoms and 2 hydroxyl groups, and with 6 carbon atoms and 4 hydroxyl groups, such as galactaric acid (also called mucic acid or mucic acid) and Galactaric acid salts and glucaric acid (also called saccharic acid) and Glucaric acid salts, preferred.
  • galactaric acid also called mucic acid or mucic acid
  • Galactaric acid salts and glucaric acid also called saccharic acid
  • Glucaric acid salts preferred.
  • the salts are preferred used as sodium or potassium salts.
  • the particularly beneficial Polyhydroxydicarboxylic acid salts therefore belong to the monosodium salts and disodium salts and the monopotassium
  • the zeolites come in the usual hydrated, fine crystalline form for use. Their water content is preferably between 19 and 22 % By weight. They have practically no particles larger than 30 ⁇ m and exist preferably at least 80% smaller in size than 10 ⁇ m. Your calcium binding capacity, which according to the German Patent application 24 12 837 is determined, is in the range of 100 to 200 mg CaO / g.
  • the zeolite NaA is particularly suitable, as is the zeolite NaX and mixtures of NaA and NaX. Quantities and weight ratios, The zeolite builders are included in this Invention - unless otherwise stated - on anhydrous active substance based.
  • 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 Mixtures of zeolite and the crystalline layered silicates of the general Contain formula (I), wherein the mixing ratio is arbitrary.
  • zeolite is preferably used either alone or in a weight ratio Zeolite to crystalline layered silicate (I) from 10: 1 to 1: 3 and used in particular from 3: 1 to 1: 1.
  • the agents or builders combinations according to the invention contain the builders zeolite and / or crystalline layered silicates (I) and Complexing agent polyhydroxydicarboxylic acid or polyhydroxydicarboxylic 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.
  • Beneficial Agents contain 15 to 50 wt .-% zeolite and / or crystalline layered silicates (I) and 1 to 20 wt .-% polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts with 4 to 6 carbon atoms and at least 2 hydroxyl groups per molecule, such polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts are preferred in which each carbon atom, which does not carry a carboxyl group, has a hydroxyl group.
  • Wt .-% Especially agents which are 18 to 40% by weight, in particular 20 to 35, are preferred Wt .-%, contain zeolite, the weight ratio of zeolite to polyhydroxydicarboxylic acid or polyhydroxydicarboxylic 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.
  • Wt .-% contain zeolite, the weight ratio of zeolite to polyhydroxydicarboxylic acid or polyhydroxydicarboxylic 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.
  • Such agents have advantages which are 2 to 15% by weight and preferably 4 to 12 wt .-% galactaric acid or galactaric acid salt, glucaric acid or glucaric acid salt or mixtures contain from these acids and / or salts.
  • the detergents and cleaning agents according to the invention can still be used usual 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 from ecological Is not objectionable, as well as mixtures of these and (Co) polymeric polycarboxylic acids or polycarboxylates such as the sodium salts polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid), where especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid are preferred, additionally contained. But these additional builders and complexing agents are used no further to the significant improvement of the secondary washing ability at.
  • these additional builders and complexing agents are used no further to the significant improvement of the secondary washing ability at.
  • Phosphonates preferably the neutral sodium salts for example, 1-hydroxyethane-1,1-diphosphonate and diethylene triamine pentamethylene phosphonate are often used as enzyme or bleach stabilizers used in amounts of 0.1 to 1.5 wt .-%.
  • the secondary washing power of the agents according to the invention is through the use of the polyhydroxydicarboxylic acids or salts thereof increased that on the use of phosphonates without sacrificing performance can be dispensed with. Therefore, agents that do not contain phosphonates are preferred contain.
  • the agents according to the invention the complexing agents polyhydroxydicarboxylic acids, polyhydroxydicarboxylic acid salts or mixtures of these, compared to an agent, that instead of the complexing agents according to the invention polyhydroxytricarboxylic acids or polyhydroxytricarboxylic acid salts such as citric acid or citrate contains a significant while maintaining the primary washing performance have a higher secondary washing effect.
  • polyhydroxytricarboxylic acids or polyhydroxytricarboxylic acid salts such as citric acid or citrate
  • the builders combinations according to the invention can also contain further constituents contain, for example inorganic, alkaline in water or neutral reacting salts.
  • the builders combinations with liquid to wax-like components for example silicone oils and paraffin oils, but preferably with non-ionic surfactants are sprayed.
  • the agents according to the invention known additives commonly used in washing and cleaning agents, for example surfactants, bleaches and bleach activators, in Water alkaline salts, solubility improvers like conventional ones Hydrotropes or polyalkylene glycols, for example polyethylene glycols, Foam inhibitors, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filling salts as well as colors and fragrances, opacifiers or pearlescent agents.
  • surfactants for example surfactants, bleaches and bleach activators
  • solubility improvers like conventional ones Hydrotropes or polyalkylene glycols, for example polyethylene glycols, Foam inhibitors, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filling salts as well as colors and fragrances, opacifiers or pearlescent agents.
  • the content of the agent 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.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are the mono-, di- and triesters as well as their To understand mixtures as they are made by esterification through a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of Triglycerides with 0.3 to 2 moles of glycerin can be obtained.
  • 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.
  • Feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, Rape oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, Lard oil or lard. Because of their high natural content saturated fatty acids, however, has proven to be particularly advantageous from coconut oil, palm kernel oil or beef tallow.
  • the sulfation saturated fatty acids with 6 to 22 carbon atoms or mixtures from fatty acid glycerol esters with iodine numbers less than 5, the fatty acids containing 6 to 22 carbon atoms, is preferably carried out by Reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as described in international patent application WO 91/9009 is specified.
  • the sulfonation products are a complex mixture that essentially Mono-, di- and triglyceride sulfonates with ⁇ and / or internal Contains sulfonic acid grouping.
  • Sulfonated form as by-products Fatty acid salts, glyceride sulfates, glycerine sulfates, glycerin and soaps. Goes with the sulfation of saturated fatty acids or hydrogenated ones Fatty acid glycerol ester mixtures, so the proportion of ⁇ -sulfonated Depending on the procedure, fatty acid disalts can be up to about 60 % By weight.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • 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 alkyl benzene sulfonates and / or alkyl sulfate, preferably fatty alkyl sulfate, and / or sulfonated fatty acid glycerol esters, the weight ratio sulfonated fatty acid glycerol esters to alkylbenzenesulfonate and / or Alkyl sulfate is 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 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 as well as soluble salts of organic bases, such as mono-, di- or Triethanolamine.
  • the anionic surfactants are preferably in Form of their sodium or potassium salts.
  • the granular ones contain Detergents and cleaning agents 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 nonionic surfactants used are preferably liquid ethoxylated and / or propoxylated alcohols which are derived from primary alcohols preferably having 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, that are an integer or a fraction for a specific product can.
  • Preferred alcohol ethoxylates have a narrow homolog distribution on (narrow range ethoxylates, NRE).
  • NRE narrow range ethoxylates
  • alcohol ethoxylates 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;
  • alkali carbonate and alkali silicate especially sodium silicate with a molar ratio Na 2 O: SiO 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.
  • 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 removing the fiber Keep dirt suspended in the fleet and prevent 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 Starch or the cellulose or salts of acidic sulfuric acid esters Cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose.
  • soluble ones Use starch preparations and other starch products than those mentioned above, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.
  • carboxymethyl cellulose Na salt
  • Methyl cellulose methyl hydroxyethyl cellulose and mixtures thereof
  • polyvinyl pyrrolidone for example in amounts of 0.1 to 5% by weight on the means.
  • 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-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. 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.
  • Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. Are particularly well suited Strains of bacteria or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably become proteases of the subtilisin type and in particular proteases that are obtained from Bacillus lentus. Their share can be about 0.2 up to about 2% by weight.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances to prevent them from premature decomposition to protect.
  • 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 (HBO 2 ) and pyrobic 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. 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 be a Have bulk density between about 300 and 1100 g / l. Thereby granules preferred, which has a bulk density above 450 g / l, in particular have between 500 and 1100 g / l.
  • Detergents and cleaning agents can be used in a conventional manner, for example by mixing, granulating, extruding and / or by Spray drying an aqueous slurry and optionally subsequent Admixture of temperature-sensitive components can be produced.
  • detergents and cleaning agents they can be manufactured separately Builders combinations in the form of a spray-dried or granulated Compounds as an admixture to other granular components of the detergent and cleaning agent are used. It is the same possible, the builders and complexing agents individually in a conventional manner To incorporate into the funds in a 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 filled with 3.5 kg of clean laundry and 0.5 kg of test fabric is loaded, some of the test fabric with usual Test soiling was impregnated (for testing the primary washing ability) and consisted partly of white fabric (for testing the secondary washing ability).
  • Strips of standardized cotton fabric were used as the white test fabric (Krefeld laundry research institute; WFK), Nessel (BN), knitwear (Cotton jersey; B) and terry fabric (FT) are used.
  • Washing conditions Tap water of 23 ° d (equivalent to 230 mg CaO / l) Amount of detergent per detergent and machine 146 g, washing temperature 25 to 90 ° C (heating up time 60 minutes, 15 minutes at 90 ° C), liquor ratio (kg Wash: liters of wash water in the main wash cycle) 1: 5,7, rinse 4 times with tap water, centrifuging and drying.
  • the agents M1 / 1 or M1 / 2, M2 / 1 or M2 / 2 according to the invention showed better ash contents on average across all textile fabrics than the comparative examples V1 to V3.
  • the total incrustation was therefore used as a control determined (1st weighing of the untreated tissue, 2nd weighing of the Tissue after 25 washing cycles, 3rd weighing of the tissue after extraction with EDTA, 4. Determination of the so-called "soluble ash” from the difference weighing 2nd and 3rd, 5th ashing of the extracted tissue for determination the remaining ash. 6. Determination of the total incrustation (sum of soluble Ash and residual ash)).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (17)

  1. Agent de lavage et de nettoyage, en particulier agent de lavage pour les textiles contenant comme adjuvants sans phosphates, de la zéolithe et/ou des silicates lamellaires cristallins de la formule générale (I) NaMSixO2x+1.yH2O, dans laquelle M représente le sodium ou l'hydrogène, x, un nombre de 1,9 à 4 et y, un nombre de 0 à 20, ainsi que des complexants, caractérisé en ce qu'il renferme les adjuvants en proportions de 15 à 60 % en poids et des complexants sélectionnés parmi des acides ou des sels d'acides polyhydroxydicarboxyliques comportant 4 à 6 atomes de carbone et au moins 2 groupes hydroxyle par molécule, ou des mélanges de ces acides et/ou sels, le rapport pondéral entre les adjuvants et l'acide ou le sel d'acide polyhydroxydicarboxylique ou les mélanges de ces acides et/ou sels étant compris entre 30:1 et 1:1, à condition que l'acide ou le sel d'acide tartrique ne soit pas contenu comme agent complexant.
  2. Agent selon la revendication 1, caractérisé en ce qu'il contient 15 à 50 % en poids de zéolithe et/ou de silicates lamellaires cristallins et 1 à 20 % en poids d'acides ou de sels d'acides polyhydroxydicarboxyliques comportant 4 à 6 atomes de carbone, chaque atome de carbone, qui ne porte pas de groupe carboxyle présentant un groupe hydroxyle.
  3. Agent 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, en particulier, 15 à 25 % en poids de surfactifs anioniques et non ioniques, y compris du savon, 18 à 40 % en poids, de préférence 20 à 35 % en poids de zéolithe, le rapport pondéral entre la zéolithe et l'acide ou le sel d'acide polyhydroxydicarboxylique ou les mélanges de ces acides ou sels, atteignant 20:1 à 1:1, de préférence 10:1 à 1,5:1 et, en particulier, 5:1 à 1,5:1.
  4. Agent selon 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 ou de sel d'acide galactarique, d'acide ou de sel d'acide glucarique ou de mélanges de ces acides et/ou sels.
  5. Agent selon une des revendications 1 à 4, caractérisé en ce qu'il ne contient pas de phosphonates.
  6. Agent selon une des revendications 1 à 5, caractérisé en ce qu'il ne contient pas d'acides polycarboxyliques ni de polycarboxylates (co-)polymères.
  7. Agent selon une des revendications 1 à 6, caractérisé en ce qu'il ne contient pas de citrate.
  8. Agent selon une des revendications 1 à 7, caractérisé en ce qu'il contient du carbonate de sodium et/ou du carbonate de potassium en quantités de 2 à 15, de préférence, de 5 à 14 % en poids.
  9. Agent selon une des revendications 1 à 8, caractérisé en ce qu'il présente une densité en vrac comprise entre 300 et 1100 g/l, de préférence comprise entre 500 et 1000 g/l.
  10. Association d'adjuvants contenant des adjuvants et un complexant, caractérisée en ce qu'elle contient comme adjuvants, de la zéolithe et/ou des silicates lamellaires cristallins de la formule générale (I) NaMSixO2x+1.yH2O, dans laquelle M représente le sodium ou l'hydrogène, x, un nombre de 1,9 à 4 et y, un nombre de 0 à 20, et comme complexants, des acides ou des sels d'acides polyhydroxydicarboxyliques comportant 4 à 6 atomes de carbone et au moins 2 groupes hydroxyle par molécule, ou des mélanges de ces acides et/ou sels, et en ce que le rapport pondéral entre les adjuvants et l'acide ou le sel d'acide polyhydroxydicarboxylique ou les mélanges de ces acides et/ou sels est compris entre 30:1 et 1:1, à condition que l'acide ou un sel d'acide tartrique ne soit pas contenu comme agent complexant.
  11. Association d'adjuvants selon la revendication 10, caractérisée en ce qu'elle contient des acides ou des sels d'acides polyhydroxydicarboxyliques comportant 4 à 6 atomes de carbone, qui présentent un groupe hydroxyle sur chaque atome de carbone ne portant pas de groupe carboxyle, le rapport pondéral entre les adjuvants, en particulier la zéolithe, et l'acide ou le sel d'acide polyhydroxydicarboxylique ou les mélanges de ces acides ou sels, atteignant 20:1 à 1:1, de préférence 10:1 à 1,5:1 et, en particulier, 5:1 à 1,5:1.
  12. Association d'adjuvants selon la revendication 10 ou 11, caractérisée en ce qu'elle contient comme acide ou sel d'acide polyhydroxydicarboxylique, de l'acide ou du sel d'acide galactarique, de l'acide ou du sel d'acide glucarique ou des mélanges de ces acides et/ou sels.
  13. Association d'adjuvants selon une des revendications 10 à 12, caractérisée en ce que l'association d'adjuvants est pulvérisée par des composants liquides à cireux, de préférence par des tensioactifs non ioniques.
  14. Procédé de fabrication d'une association d'adjuvants contenant comme adjuvants, de la zéolithe et/ou des silicates lamellaires cristallins de la formule générale (I) NaMSixO2x+1.yH2O, dans laquelle M représente le sodium ou l'hydrogène, x, un nombre de 1,9 à 4 et y, un nombre de 0 à 20, et comme complexants, des acides ou des sels d'acides polyhydroxydicarboxyliques comportant 4 à 6 atomes de carbone et au moins 2 groupes hydroxyle par molécule, ou des mélanges de ces acides et/ou sels, caractérisé en ce que ladite association d'adjuvants est fabriquée par mélangeage, granulation et/ou séchage par pulvérisation, à condition que l'acide ou un sel d'acide tartrique ne soit pas contenu comme agent complexant.
  15. Procédé de fabrication d'un agent de lavage et de nettoyage granulaire conformément à une des revendications 1 à 9, caractérisé en ce que le granulé est fabriqué par séchage par pulvérisation.
  16. Procédé de fabrication d'un agent de lavage et de nettoyage granulaire conformément à une des revendications 1 à 9, caractérisé en ce que le granulé est fabriqué par un procédé de granulation ou d'extrusion.
  17. Procédé de fabrication d'un agent de lavage et de nettoyage granulaire conformément à une des revendications 1 à 9, caractérisé en ce que l'association d'adjuvants constituée de zéolithe et/ou de silicates lamellaires cristallins de la formule générale (I) NaMSixO2x+1.yH2O, dans laquelle M représente le sodium ou l'hydrogène, x, un nombre de 1,9 à 4 et y, un nombre de 0 à 20, ainsi que d'acides ou de sels d'acides polyhydroxydicarboxyliques comportant 4 à 6 atomes de carbone et au moins 2 groupes hydroxyle, ou de mélanges de ces acides et/ou sels est mise en oeuvre sous la forme d'un "compound" séché par pulvérisation ou granulé, comme composant d'addition par mélange à d'autres constituants granulaire des agents de lavage et de nettoyage.
EP93919062A 1992-08-24 1993-08-16 Adjuvants pour agents de lavage Expired - Lifetime EP0656051B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4228044 1992-08-24
DE4228044A DE4228044A1 (de) 1992-08-24 1992-08-24 Gerüststoff für Waschmittel
PCT/EP1993/002171 WO1994004650A1 (fr) 1992-08-24 1993-08-16 Adjuvants pour agents de lavage

Publications (3)

Publication Number Publication Date
EP0656051A1 EP0656051A1 (fr) 1995-06-07
EP0656051B1 EP0656051B1 (fr) 1996-04-03
EP0656051B2 true EP0656051B2 (fr) 1998-12-23

Family

ID=6466269

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Application Number Title Priority Date Filing Date
EP93919062A Expired - Lifetime EP0656051B2 (fr) 1992-08-24 1993-08-16 Adjuvants pour agents de lavage

Country Status (7)

Country Link
EP (1) EP0656051B2 (fr)
JP (1) JPH08500373A (fr)
AT (1) ATE136327T1 (fr)
DE (2) DE4228044A1 (fr)
ES (1) ES2086236T5 (fr)
PL (1) PL307588A1 (fr)
WO (1) WO1994004650A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW240243B (fr) * 1992-03-12 1995-02-11 Kao Corp
FR2736636B1 (fr) * 1995-07-11 1997-09-19 Roquette Freres Procede de fabrication de l'acide xylarique et utilisations de celui-ci
FR2844525B1 (fr) 2002-09-18 2005-06-03 Roquette Freres Procede de preparation d'une composition polycarboxylique comprenant une etape d'oxydation electrochimique d'une composition monosaccharidique
ES2373300B1 (es) 2011-12-14 2012-12-20 Soro Internacional, S.A. Detergente para lavavajillas.

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4876195A (en) * 1985-12-26 1989-10-24 Takeda Chemical Industries, Ltd. Process for producing 2-keto-D-glucaric acid
DE3838086A1 (de) * 1988-11-10 1990-05-17 Henkel Kgaa Verfahren zur herstellung zeolithhaltiger granulate hoher dichte
DE4034131C2 (de) * 1990-10-26 1999-08-26 Henkel Kgaa Gerüststoff für Waschmittel

Also Published As

Publication number Publication date
ES2086236T3 (es) 1996-06-16
JPH08500373A (ja) 1996-01-16
EP0656051B1 (fr) 1996-04-03
EP0656051A1 (fr) 1995-06-07
PL307588A1 (en) 1995-05-29
ATE136327T1 (de) 1996-04-15
ES2086236T5 (es) 1999-03-01
WO1994004650A1 (fr) 1994-03-03
DE59302126D1 (de) 1996-05-09
DE4228044A1 (de) 1994-03-03

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