EP0703970A1 - Detergents contenant des acides amines et/ou leurs sels - Google Patents

Detergents contenant des acides amines et/ou leurs sels

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Publication number
EP0703970A1
EP0703970A1 EP94920431A EP94920431A EP0703970A1 EP 0703970 A1 EP0703970 A1 EP 0703970A1 EP 94920431 A EP94920431 A EP 94920431A EP 94920431 A EP94920431 A EP 94920431A EP 0703970 A1 EP0703970 A1 EP 0703970A1
Authority
EP
European Patent Office
Prior art keywords
salts
mixtures
weight
acid
acids
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP94920431A
Other languages
German (de)
English (en)
Inventor
Beatrix Kottwitz
Hans Dolhaine
Horst Upadek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0703970A1 publication Critical patent/EP0703970A1/fr
Withdrawn legal-status Critical Current

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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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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

Definitions

  • the invention relates to a detergent which contains builder substances such as zeolite and / or silicates but essentially no alkali metal carbonates.
  • Amino acids and / or their salts are also known as ingredients of detergents. They are used in particular for the stabilization of enzymes and in particular in enzyme preparations for use in liquid detergents. Such applications are described, for example, in patent applications FR-A-2 585 363, DE-A-36 23 942, JP-A-86/133296 and JP-A-84/22998. From the German patent application DE-A-2261653, enzyme granules containing aylase and amino acids or their derivatives are known which are used in conventional detergents which contain water-soluble builder substances such as phosphates, carbonates, silicates and / or aminopolycarboxylates.
  • protein-dissolving detergents which contain sulfur-free amino acids or their salts.
  • the detergents preferably contain either anionic surfactants or nonionic surfactants as well as high amounts of phosphates as a builder substance.
  • the use of bicarbonates, carbonates and silicates is also possible.
  • the object of the invention was to provide detergents that meet the high requirements for both the primary washability and the Secondary washing capacity is sufficient, which, however, contains essentially no alkali carbonates.
  • the invention accordingly relates to a powdery to granular detergent which contains anionic and / or nonionic surfactants and zeolite and / or one or more silicates from the group of the amorphous and crystalline, layered alkali silicates and additionally sulfur-free, 2 to 11 Has carbon atoms and optionally a further carboxy and / or amino group amino acids and / or their salts, but is essentially free of alkali carbonates.
  • the detergents are said to be essentially free of alkali carbonates, i.e. they generally contain no more than about 3% by weight of alkali metal carbonate and, in a preferred embodiment of the invention, are free of additionally used alkali metal carbonates which do not result from the production process or the raw materials used.
  • the detergents according to the invention advantageously contain salts, in particular sodium or potassium salts of the amino acids or mixtures of the acids and their salts.
  • Preferred amino acids are glycine, alanine, glutamic acid, arginine, aspartic acid, leucine, isoleucine, lysine and histidine or their salts and mixtures of the salts and the amino acids mentioned.
  • the salts of glycine or mixtures of glycine and glycinate or the salts of alanine, valine, leucine and isoleucine or mixtures of the salts and the corresponding acids are very particularly preferred.
  • the amino acids and / or their salts can each by area of application contained in the detergents in a wide range.
  • alkali carbonates and in particular soda are usually used in conventional detergents.
  • Detergents containing 0.5 to 20% by weight and in particular 1 to 15% by weight of amino acids and / or their salts are preferred. Amounts of 2 to 10% by weight are very particularly preferred.
  • fine-crystalline, synthetic and bound water-containing zeolite such as zeolite NaA in detergent quality is used as builder substance.
  • zeolite NaX and mixtures of NaA and NaX are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • the zeolite may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated Ci2-Ci8 fatty alcohols with 2 up to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water.
  • Suitable substitutes or partial substitutes for zeolites are crystalline, layered sodium silicates of the general formula (I) Na Si 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 Is 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0164514.
  • Preferred crystalline sheet silicates of the formula (I) are those in which M represents sodium and x assumes the values 2 or 3.
  • both .beta.- and ⁇ '-Natriu disilicates Na2Si2 ⁇ 5 "yH2 ⁇ preferred, with .beta. Natriu disilicate for example, be obtained by the method can that is / described in International Patent Application W0-A-91 08,171th
  • the detergents according to the invention preferably contain 10 to 60% by weight of zeolite and / or crystalline layered silicates, with mixtures of zeolite and crystalline layered silicates being particularly preferred in any ratio can be advantageous.
  • the agents contain 20 to 50% by weight of zeolite and / or crystalline layered likate.
  • Particularly preferred agents contain up to 40% by weight of zeolite and in particular up to 35% by weight of zeolite, in each case based on anhydrous active substance.
  • agents water-soluble amorphous silicates; they are preferably used in combination with zeolite and / or crystalline layered silicates. Particularly preferred are agents which contain above all sodium silicate with a molar ratio Na2 ⁇ : Si ⁇ 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5.
  • the amorphous sodium silicate content of the agents is preferably up to 15% by weight and in particular between 2 and 8% by weight.
  • Phosphates such as tripolyphosphates, pyrophosphates and orthophosphates can also be present in small amounts in the compositions.
  • the content of the phosphates in the compositions is preferably up to 15% by weight, but in particular 0 to 10% by weight.
  • the agents can also contain layered silicates of natural and synthetic origin.
  • Layered silicates of this type are known, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here.
  • Suitable layered silicates which belong to the group of water-swellable smectites, are e.g. those of the general formulas
  • the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca ++ .
  • the amount of water of hydration is usually in the range from 8 to 20% by weight and is of the swelling state or of the Depending on the type of processing.
  • Useful sheet silicates are known, for example, from US Pat. No. 3,966,629, US Pat. No. 4,062,647, EP-A-0 026 529 and EP-A-0028432.
  • Layered silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
  • Usable organic builders 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.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • polymeric polycarboxylates are not absolutely necessary. However, if polymeric polycarboxylates are used, agents are preferred which are biodegradable polymers, for example terpolymers, the monomers acrylic acid and maleic acid or salts thereof, and vinyl alcohol or vinyl alcohol derivatives or the monomers acrylic acid and 2-alkylallylsulfonic acid or their salts and sugar derivatives contain ent. Terpolymers which are obtained according to the teaching of the older German patent applications P 4221 381.9 and P 43 00 772.4 are particularly preferred.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0280 223.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the agents contain, in particular, anionic, nonionic, cationic, amphoteric and / or zwitterionic surfactants as further ingredients.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Preferred surfactants of the sulfonate type are Cg-Ci3-alkylbenzenesulfonates, olefin sulfonates, i.e. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from Ci2-Ci8 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkane sulfonates which are obtained from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of oc-sulfo fatty acids e.g. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, and their salts (disalts).
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as 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 become.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example capric 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, 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 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, such as it is specified in international patent application WO-A-91/09009.
  • the sulfonation products are a complex mixture containing mono-, di- and triglyceride sulfonates with an ⁇ -position and / or internal sulfonic acid grouping.
  • Sulfonated fatty acid salts, glyceride sulfates, glycerol sulfates, glycerol and soaps are formed as by-products. 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.
  • Suitable surfactants of the sulfate type and particularly preferred anionic surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
  • Alk (en) yl sulfates from fatty alcohols for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 1 -C 2 -oxo alcohols, and those of secondary alcohols of this chain length are particularly preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • Ci6-C ⁇ s- alk (en) yl sulfates are particularly preferred for reasons of washing technology. It can also be special Advantage and especially advantageous for machine washing agents, Ci6-Ci8-Alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and at relatively low washing temperatures of for example room temperature to 40 ° C show a low tendency to crystallize.
  • the agents therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of Ci2-Ci4-fatty alkyl sulfates or Ci2-Ci8-fatty alkyl sulfates with Ci6-C ⁇ 8-fatty alkyl sulfates and in particular Ci2-Ci6 -Fatty alkyl sulfates with Ci6-Ci8 fatty alkyl sulfates.
  • not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably CIOE to C22 are used.
  • Mixtures of saturated sulfonated fatty alcohols consisting predominantly of Ci6 and unsaturated sulfated fatty alcohols consisting predominantly of Ci8 are particularly preferred, for example those derived from solid or liquid fatty alcohol mixtures of the HD-Oenol ( R ) type (commercial product of the applicant) .
  • Weight ratios of alkyl sulfates to alkenyl sulfates of 10: 1 to 1: 2 and in particular of about 5: 1 to 1: 1 are preferred.
  • the sulfuric acid monoesters of the straight-chain or branched C7-C2i-alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched Cg-Cn-alcohols with an average of 3.5 mol of ethylene oxide (E0) or Ci2-Ci8 -Fatty alcohols with 2 to 4 E0 are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain CQ to Ci8 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. (see description below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts of up to 4% 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 particularly preferred which are composed of 50 to 100% by weight of saturated Ci2-C24- ' : acidic 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 triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the nonionic surfactants used are preferably alkoxylated, advantageously liquid ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably in 2 Position can be methyl-branched, or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 C atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, 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-Ci8 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages that can be an integer or a fractional number for a special product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • alkyl glycosides of the general formula R0 (G) x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C., can also be used as further nonionic surfactants -Atoms means and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain , in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP-A-58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • surfactants are polyhydroxy fatty acid amides of the formula (II),
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanol and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the agents according to the invention preferably contain surfactants in amounts of 5 to 40% by weight and in particular in amounts of at least 10% by weight. It is particularly advantageous if the agents include anionic surfactants including soaps, preferably alkylbenzenesulfonate and / or alk (en) yl sulfate, and nonionic surfactants, of which alkoxylated fatty alcohols and alkylglycosides are particularly preferred, in weight ratios between 10: 1 and 1: 5 contain.
  • anionic surfactants including soaps, preferably alkylbenzenesulfonate and / or alk (en) yl sulfate
  • nonionic surfactants of which alkoxylated fatty alcohols and alkylglycosides are particularly preferred, in weight ratios between 10: 1 and 1: 5 contain.
  • the agents can include known additives commonly used in detergents, for example foam inhibitors, salts of polyphosphonic acids, optical brighteners, enzymes, small amounts of neutral filler salts, and colorants and fragrances, opacifiers or pearlescent agents contain.
  • 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 peracid salts or peracids providing H2O2, such as perbenzoates, peroxophthalates, 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, advantageously using perborate monohydrate.
  • bleach activators can be incorporated into the preparations. be worked.
  • 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.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin which have a high proportion of Ci8-C24 fatty acids:
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica or bistearylethylenediamide.
  • Mixtures of different foam inhibitors are also used with advantages, e.g. those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • the salts of polyphosphonic acids which are preferably used are the neutral-reacting sodium salts of, for example, l-hydroxyethane-l, l-diphosphonate and diethylenetriaminepentamethylenephosphonate in amounts of 0.1 to 1.5% by weight.
  • agents which do not contain phosphonates are particularly preferred.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures are gene, for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, of particular interest.
  • (Per) oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • 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 ande ren alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) ur, d of pyroboric acid (tetraboric acid H2B4O7).
  • H3BO3 orthoboric acid
  • HBO2 metaboric acid
  • tetraboric acid H2B4O7 tetraboric acid
  • 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, for example degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethy1ce11u1ose, methylhydroxypropy1ce11u1ose, methcarboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the Medium.
  • the agents can contain derivatives of diaminost ibensisulfonic acid or their alkali metal salts.
  • Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which contain an replace the morpholino group with a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, and also in small amounts, for example Contain 10 "6 to 10" 3% by weight, preferably around 10 ⁇ 5% by weight, of a blue dye.
  • a particularly preferred dye is Tinolu ⁇ ( R ) (commercial product from Ciba-Geigy).
  • the bulk density of the preferred granular agents is generally 300 to 1200 g / 1, in particular 500 to 1100 g / 1.
  • the preferred heavier granules with bulk densities above 600 g / l preferably contain components which improve the induction behavior and / or the dissolving behavior of the granules.
  • alkoxylated fatty alcohols with 12 to 80 mol Ethylene oxide per mole of alcohol for example tallow fatty alcohol with 14 EO, 30 EO or 40 EO, and polyethylene glycols with a relative molecular weight between 200 and 12000, preferably between 200 and 600, are used.
  • the counter ⁇ can also be crystalline, are subsequently mixed into spray-dried, granulated and / or extruded components, which may have non-ionic surfactants and / or other ingredients which are liquid to waxy at the processing temperature, added.
  • a method is preferred in which the surface of partial components of the agent or of the entire agent is subsequently treated to reduce the stickiness of the granules rich in nonionic surfactants and / or to improve their solubility.
  • Suitable surface modifiers are known from the prior art.
  • suitable finely divided zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts for example calcium stearate, but in particular mixtures of zeolite and silicas or zeolite and calcium stearate are particularly preferred.
  • Granular detergents of the following composition were prepared in a conventional manner by spray drying and with respect to their primary and secondary washing ability tested.
  • the constituents perborate, bleach activator, enzyme granulate and defoamer granulate were subsequently mixed in.
  • the sodium glycinate in the agents according to the invention was also subsequently added.
  • Vl / 2 sodium carbonate 12 polymeric polycarboxylate (Sokalan CP ⁇ ( R ), 5.5 commercial product from BASF, Federal Republic of Germany)
  • the test was carried out under the following application conditions in a household washing machine (type Miele W 717).
  • a household washing machine type Miele W 717
  • the machines were charged with 3.5 kg of clean laundry and 0.5 kg of test fabric
  • the test fabric for testing the primary washing ability was partially impregnated with conventional test soiling and for testing the secondary washing ability consisted partly of white fabric.
  • Strips of standardized cotton fabric laundry research institute Krefeld; WFK), nettle (BN), knitwear (cotton jersey; B) and terry fabric (FT) were used as the white test fabric.
  • the soiling consisted of dust-wool fat on cotton (SW-B), dust-skin fat on cotton (SH-B), dust-skin fat on refined cotton (SH-BV), dust-skin fat on a blend of polyester and refined cotton ( SH-PBV), as well as lipstick (LS-PBV) and make-up (MU-PBV) each on mixed fabrics made of polyester and finished cotton.
  • Washing conditions Washing program: Cottons without prewash at 90 ° C (heating up time 60
  • the ash content of the textile samples and the total incrustation were determined after 25 washing cycles.
  • the combustion of organic constituents usually gives 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 2nd and 3rd, 5th ashing of the extracted tissue to determine the residual ash, 6. determination of the total incrustation from the sum of the soluble ash and the residual ash).
  • Table 1 Remission for soiling

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Abstract

L'invention concerne des détergents qui contiennent des acides aminés et/ou leurs sels à la place de carbonates de métaux alcalins. De tels détergents ont un meilleur pouvoir détergent secondaire, sans perdre leur pouvoir détergent primaire.
EP94920431A 1993-06-14 1994-06-06 Detergents contenant des acides amines et/ou leurs sels Withdrawn EP0703970A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4319578 1993-06-14
DE19934319578 DE4319578A1 (de) 1993-06-14 1993-06-14 Waschmittel, enthaltend Aminosäuren und/oder deren Salze
PCT/EP1994/001828 WO1994029419A1 (fr) 1993-06-14 1994-06-06 Detergents contenant des acides amines et/ou leurs sels

Publications (1)

Publication Number Publication Date
EP0703970A1 true EP0703970A1 (fr) 1996-04-03

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EP94920431A Withdrawn EP0703970A1 (fr) 1993-06-14 1994-06-06 Detergents contenant des acides amines et/ou leurs sels

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EP (1) EP0703970A1 (fr)
DE (1) DE4319578A1 (fr)
WO (1) WO1994029419A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4324396A1 (de) * 1993-07-21 1995-01-26 Henkel Kgaa Reinigungsmittel mit hohem Benetzungsvermögen
DE4329988A1 (de) * 1993-09-04 1995-03-09 Henkel Kgaa Sprühgetrocknetes Granulat mit hohem Schüttgewicht
DE4403323A1 (de) * 1993-09-23 1995-08-10 Henkel Kgaa Extrudierte Wasch- oder Reinigungsmittel mit verbesserten Löseeigenschaften
DE4400024A1 (de) * 1994-01-03 1995-07-06 Henkel Kgaa Silikatische Builder und ihre Verwendung in Wasch- und Reinigungsmitteln sowie Mehrstoffgemische für den Einsatz auf diesem Sachgebiet
DE4406592A1 (de) * 1994-03-01 1995-09-07 Henkel Kgaa Verbesserte Mehrstoffgemische auf Basis wasserlöslicher Alkalisilikatverbindungen und ihre Verwendung, insbesondere zum Einsatz als Builder in Wasch- und Reinigungsmitteln
DE4415362A1 (de) * 1994-05-02 1995-11-09 Henkel Kgaa Verfahren zur Herstellung silikatischer Buildergranulate mit erhöhtem Schüttgewicht
DE4429550A1 (de) * 1994-08-19 1996-02-22 Henkel Kgaa Verfahren zur Herstellung von Wasch- oder Reinigungsmitteltabletten
DE19600466A1 (de) * 1996-01-09 1997-07-10 Henkel Kgaa Verfahren zur Herstellung von granularen Wasch- oder Reinigungsmitteln bzw. Komponenten hierfür
DE19709411A1 (de) 1997-03-07 1998-09-10 Henkel Kgaa Waschmittelformkörper

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51114406A (en) * 1975-04-01 1976-10-08 Dai Ichi Kogyo Seiyaku Co Ltd Transparent and stable detergents
SE467827B (sv) * 1985-07-26 1992-09-21 Colgate Palmolive Co Stabiliserad enzyminnehaallande foerstaerkt flytande detergentkomposition och dess anvaendning vid tvaettning av textilier
DE4029297A1 (de) * 1990-09-15 1992-03-19 Huels Chemische Werke Ag Aminodicarbonsaeuren und deren derivate als stabilisatoren fuer die sauerstoffbleiche bei der textilwaesche

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9429419A1 *

Also Published As

Publication number Publication date
WO1994029419A1 (fr) 1994-12-22
DE4319578A1 (de) 1994-12-15

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