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WO1994005764A1 - Produits de lavage et de nettoyage contenant des adjuvants - Google Patents

Produits de lavage et de nettoyage contenant des adjuvants Download PDF

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Publication number
WO1994005764A1
WO1994005764A1 PCT/EP1993/002310 EP9302310W WO9405764A1 WO 1994005764 A1 WO1994005764 A1 WO 1994005764A1 EP 9302310 W EP9302310 W EP 9302310W WO 9405764 A1 WO9405764 A1 WO 9405764A1
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WIPO (PCT)
Prior art keywords
weight
granular
acid
washing
agents
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PCT/EP1993/002310
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German (de)
English (en)
Inventor
Beatrix Kottwitz
Horst Upadek
Peter Krings
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6467292&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1994005764(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP93919191A priority Critical patent/EP0658189B1/fr
Priority to DE59303899T priority patent/DE59303899D1/de
Publication of WO1994005764A1 publication Critical patent/WO1994005764A1/fr

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Classifications

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

Definitions

  • the invention relates to detergents and cleaning agents which contain conventional builder substances and polymeric polycarboxylates.
  • zeolite in particular zeolite NaA, and mixtures of zeolite with alkali silicates and alkali carbonates, as well as polycarboxylates or polymeric polycarboxylates, have been used as phosphate substitutes in washing and cleaning agents.
  • the polymeric polycarboxylates are known to counteract the precipitation of poorly soluble calcium salts and thus the incrustation caused by poorly soluble calcium salts and the graying of the tissue.
  • Polymeric polycarboxylates were mostly used in the form of an aqueous solution or as a fine powder.
  • European patent application 291 869 describes phosphate-free builders combinations of zeolite and polymeric polycarboxylates, mixtures of polymeric polycarboxylates with aminoalkane polyphosphonates and l-hydroxyethane-l, l-diphosphonate (HEDP) being synergistic in preventing the formation of Show fiber incrustations.
  • HEDP l-hydroxyethane-l, l-diphosphonate
  • the object of the invention was to provide phosphate-free agents which have a primary washing and cleaning power which is comparable to the primary washing and cleaning power of conventional commercial products, but the secondary washing power of these agents at the same time has great advantages. It has now been found that this object is achieved by means of compositions which are conventional per se, but which contain polymeric polycarboxylates in a very specific form.
  • the invention accordingly relates to a detergent and cleaning agent, in particular a textile detergent, containing anionic and / or nonionic surfactants, phosphate-free builder substances and inorganic salts and polymeric polycarboxylates, the agent containing at least two granular components, the first of which is anionic and / or contains nonionic surfactants, phosphate-free builder substances and inorganic salts and the second contains an admixture component made from polymeric polycarboxyla- is in granular form.
  • agents have alkali carbonate.
  • Preferred granular polymeric polycarboxylates have a bulk density between 350 and 850 g / 1, preferably between 400 and 750 g / 1, no particles with a particle size below 50 ⁇ m, preferably no particles with a particle size below 100 ⁇ m, and a maximum of 5% of the particles a particle size above 1000 ⁇ m, preferably at most 3% by weight of the particles with a particle size above 1000 ⁇ m.
  • the granular content of monomeric polycarboxylic acids is preferably below 1% by weight.
  • the granular polymeric polycarboxylates can be prepared in a conventional manner known to the person skilled in the art, for example by drying polymer solutions, subsequent granulation and, if appropriate, size classification of the granules.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids, is generally 4,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • Sokalan ( R ) CP5 granules, Sokalan ( R ) CP45 granules and Sokalan ( R ) are very particularly preferred.
  • CP 7 granules (commercial products from BASF).
  • Zeolites are primarily considered as phosphate-free builder substances.
  • the zeolites are used in the usual hydrated, finely crystalline form. Their water content is preferably between 19 and 22% by weight. They have practically no particles larger than 30 ⁇ m and preferably consist at least 80% of particles smaller than 10 ⁇ m.
  • Their calcium binding capacity which is determined according to the information in German patent application 24 12 837, is in the range from 100 to 200 mg CaO / g.
  • Zeolite NaA is particularly suitable, as is zeolite NaX and mixtures of NaA and NaX.
  • small additions fatty alcohols g can nonionic surfactants contain as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ⁇ -C j 2 to 5 Ethylene oxide groups.
  • stabilizers for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ⁇ -C j 2 to 5 Ethylene oxide groups.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula (I) NaMSi x 02 ⁇ + ⁇ * yH20, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application 164 514.
  • Preferred crystalline sheet silicates of the formula (I) are those in which M represents sodium and x assumes the values 2 or 3.
  • both are preferably .beta.- and ⁇ 'sodium disilicates Na2S1 ⁇ 05 ⁇ 20, wherein beta-sodium disilicate, for example, by the process can be obtained, which is described in the German patent application 3,939,919th
  • the washing and cleaning agents according to the invention can also contain mixtures of zeolite and the crystalline layered silicates of the general formula (I), the mixing ratio being arbitrary.
  • zeolite is preferably used either alone or in a zeolite to crystalline layered silicate (I) weight ratio of from 10: 1 to 1: 3 and in particular from 3: 1 to 1: 1.
  • the washing and cleaning agents according to the invention contain the builders zeolite and / or crystalline layered silicates (I) and the granular polymeric polycarboxylates advantageously in a weight ratio of 30: 1 to 1: 1, preferably 20: 1 to 2 : 1 and especially from 10: 1 to 3: 1.
  • the detergents and cleaning agents according to the invention are preferably in granular form.
  • Advantageous agents contain 10 to 60% by weight, preferably 15 to 45% by weight and in particular 20 to 40% by weight of zeolite and / or crystalline layered silicates (I), in particular zeolite, and 0.5 to 15% by weight .-%, preferably 2 to 10 wt .-% and in particular 3 to 8 wt .-% granular polymeric polycarboxylates.
  • the detergents and cleaning agents according to the invention can also contain other customary builder substances and complexing agents, for example phosphonates.
  • phosphonates for example, Phosphonates and preferably the neutral reacting sodium salts of, for example, l-hydroxyethane-l, l-diphosphonate and diethylenetriapentamethylenephosphonate are frequently used as enzyme or bleach stabilizers in amounts of 0.1 to 1.5% by weight.
  • organic builder substances are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons , and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the agents according to the invention contain anionic and / or nonionic surfactants and optionally cationic and / or amphoteric surfactants and other additives usually used in detergents and cleaning agents, for example bleaching agents and bleach activators, salts which have an alkaline reaction in water, solubility improvers such as contain conventional hydrotropes or polyalkylene glycols, for example polyethylene glycols, foam inhibitors, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filler salts and colorants and fragrances, opacifiers or pearlescent agents.
  • solubility improvers such as contain conventional hydrotropes or polyalkylene glycols, for example polyethylene glycols, foam inhibitors, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filler salts and colorants and fragrances, opacifiers or pearlescent agents.
  • the anionic and nonionic surfactants, including soap, in the compositions are preferably 8 to 40% by weight, in particular 10 to 35% by weight and, in particularly preferred embodiments, 12 to 28% by weight.
  • surfactants of the sulfonate type are Cg-Ci3-alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates of the type obtained, for example, from C 1 -C 4 -monoolefins with a terminal or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkane sulfonates which are obtained from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids are also suitable.
  • esters of ⁇ -sulfo fatty acids come here, which by ⁇ -sulfonation of the alkyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and after following neutralization to water-soluble mono-salts are considered.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters.
  • the methyl esters of ⁇ -sulfo fatty acids (MES) are used with particular advantage.
  • Suitable anionic surfactants are the ⁇ -sulfofatty acids obtainable by ester cleavage of the ⁇ -sulfofatty acid alkyl esters or their di-salts.
  • the mono-salts of the ⁇ -sulfofatty acid alkyl esters are obtained in their industrial production as an aqueous mixture with limited amounts of di-salts. Mixtures of mono-salts and di-salts with other surfactants, for example with alkylbenzenesulfonate, are also preferred.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures, such as those used in the production by esterification of glycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol be preserved.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. If one starts from fats and oils, that is to say natural mixtures of different fatty acid glycerol esters, it is necessary to largely saturate the starting products with hydrogen in a known manner before the sulfonation, ie to harden them to iodine numbers less than 5, advantageously less than 2.
  • Suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, rapeseed oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or lard. Due to their high natural content of saturated fatty acids, it has proven to be particularly advantageous to start from coconut oil, palm kernel oil or beef tallow.
  • the sulfonation of saturated fatty acids with 6 to 22 carbon atoms or Mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, are preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as specified in international patent application WO 91/9009.
  • the sulfonation products are a complex mixture which essentially contains mono-, di- and triglyceride sulfonates with an ⁇ and / or internal sulfonic acid grouping.
  • sulfonated fatty acid salts glyceride sulfates, glycerol sulfates, glycerol and beefs are formed. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of the ⁇ -sulfonated fatty acid disalts can, depending on the procedure, be up to about 60% by weight.
  • alkanesulfonates obtained from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the sulfonate group is statistically distributed over the entire carbon chain, the secondary alkanesulfonates predominating.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, for example from tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the uncl those secondary alcohols of this chain length.
  • the sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-Cji alcohols with an average of 3.5 mol of ethylene oxide, are also suitable.
  • Preferred fatty alkyl sulfates are derived from fatty alcohol mixtures obtained from coconut oil, palm oil and palm kernel oil, which may additionally contain fractions of unsaturated alcohols, for example oleyl alcohol. Mixtures in which the proportion of Al-
  • alkylsulfosuccinic acid which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain Cg to CQ fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, viewed in isolation, are nonionic surfactants (for a description, see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred.
  • Preferred granular detergents and cleaning agents contain, as anionic surfactants, alkylbenzenesulfonates and / or alkyl sulfate, preferably fatty alkyl sulfate, and / or sulfated fatty acid glycerol esters, the weight ratio of sulfated fatty acid glycerol esters to alkylbenzenesulfonate and / or alkyl sulfate 1: 9 to 4: 1 and in particular 2 : 5 to 2: 1.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts from 0.2 to 8 and in particular from 0.5 to 5% by weight.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 1-4 fatty acid t-acid soaps and 0 to 50% by weight of oleic acid soap.
  • the anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanola in.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts.
  • the granular detergents and cleaning agents also contain, in addition to the anionic surfactants nonionic surfactants, preferably in amounts of 1 to 15% by weight, in particular in amounts of 2 to 12% by weight.
  • the preferred nonionic surfactants are liquid ethoxylated and / or propoxylated alcohols which are derived from primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 mol of alkylene oxide, in which the alcohol radical can be linear or methyl-branched in the 2-position , or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • linear residues of alcohols of native origin with 12 to 18 carbon atoms are preferred, e.g. from coconut, tallow or oleyl alcohol.
  • Ci2-Ci4 alcohols with 3 EO or 4 EO Cg-Cn alcohol with 7 EO
  • the degrees of ethoxylation given represent statistical mean values which, for a special product, represent a whole or Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.
  • alkyl glycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms branched in the 2-position and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10.
  • Suitable ingredients of the granular agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures thereof;
  • alkali carbonate and alkali silicate especially sodium silicate with a molar ratio Na2 ⁇ : Si ⁇ 2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, optionally in combination with magnesium likate are used.
  • the content of the funds in Na Trium silicate is generally up to 10% by weight, preferably between 2 and 8% by weight and in particular 2 to 5% by weight.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 30% by weight and in particular 10 to 25% by weight, advantageously using perborate monohydrate or tetrahydrate.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose sepentaacetate.
  • the bleach activators contain bleaching agents in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, eg degraded starch, aldehyde starches etc.
  • Polyvinylpyrrolidone can also be used.
  • carboxymethyl cellulose sodium salt
  • methyl cellulose methyl hydroxyethyl cellulose and their mixtures
  • polyvinylpyrrolidone for example in amounts of 0.1 to 5% by weight, based on the composition, are preferably used.
  • the foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a reduction can also be achieved by adding non-surfactant-like substances.
  • a reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, for example sulfates and / or sulfonates with nonionic surfactants and / or with soaps.
  • soaps the foam-suppressing effect increases with the degree of saturation and the C number of the fatty acid salt. Soaps of natural or synthetic origin that contain a high proportion of C j 8-C24 fatty acids are therefore suitable as foam-inhibiting soaps.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica or bistearylethylene diamide, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes, are also advantageously used.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. At least proteases, advantageously of the subtilisin type and in particular proteases which are obtained from Bacillus lentus, are preferably used. Their proportion can be about 0.2 to about 2% by weight.
  • the enzymes can be adsorbed on carriers and / or embedded in Hü11 substances to protect them against premature decomposition.
  • the agents can contain enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B4O7), is particularly advantageous.
  • the agents can contain, as optical brighteners, derivatives of diaostilbenedisulfonic acid or its alkali metal salts.
  • derivatives of diaostilbenedisulfonic acid or its alkali metal salts for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazin-6-yl-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure are suitable instead of the morpholino group, a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present, for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. It has also been found that uniform white granules are obtained if, apart from the customary brighteners, the agents are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3 % By weight, also in small amounts, for example 10 ⁇ 6 to 10 ⁇ 3 % by weight, preferably around 10 * 5% by weight, of a blue dye.
  • a special ⁇ DERS preferred dye is Tinolu ⁇ (R) (commercial product of Ciba-Geigy).
  • the granular detergents and cleaning agents according to the invention can have a bulk density between about 300 and 1100 g / 1.
  • Granules are preferred which have a bulk density above 450 g / 1, in particular between 500 and 1100 g / 1, and consist of at least two granular, preferably at least three granular components, one of which contains the polymeric polycarboxylate.
  • the agents according to the invention can be prepared in a conventional manner by mixing at least two granular components, one of which contains the polymeric polycarboxylate.
  • the other granular component which is preferably anionic surfactants, optionally nonionic surfactants. contains side and builder substances as well as inorganic salts, is produced, for example, by spray drying an aqueous slurry and, if appropriate, subsequently adding temperature-sensitive components or by granulating and extruding. In the production of this other granular component by granulation or extrusion, it is preferred that this component contains anionic surfactants and nonionic surfactants as well as builder substances, inorganic salts and optionally peroxy bleaching agents.
  • the agents are produced by extrusion, the granular polymeric polycarboxylate being a constituent of the mixture to be extruded.
  • Granular detergents of the following composition were prepared and tested in a conventional manner by spray drying.
  • the polymeric polycarboxylate was used as a 40% by weight aqueous solution (Sokalan ( R ) CP 5, commercial product from BASF, Federal Republic of Germany) and as a component of the slurry to be spray-dried, and as a granular admixture in the composition according to the invention ( Sokalan ( R ) CP5 Granu ⁇ lat, commercial product from BASF, Federal Republic of Germany) subsequently added.
  • Sokalan ( R ) CP5 Granu ⁇ lat commercial product from BASF, Federal Republic of Germany
  • the constituents perborate, bleach activator and enzyme granulate were also added subsequently.
  • test was carried out under practical conditions in household washing machines.
  • the machines were loaded with 3.5 kg of clean laundry and 0.5 kg of test fabric, some of the test fabric with the usual Test soiling was impregnated (for testing the primary washing ability) and partly consisted of white fabric (for testing the secondary washing ability).
  • Strips of standardized cotton fabric (laundry research institute Krefeld; WFK), nettle (BN), knitwear (cotton jersey; B) and terry toweling fabric (FT) were used as the white test fabric.
  • Washing conditions tap water of 23 ° d (equivalent to 230 mg CaO / 1), amount of detergent used per detergent and machine 146 g, washing temperature 25 to 90 ° C (heating time 60 minutes, 15 minutes at 90 ° C), liquor ratio ( kg of laundry: liters of wash liquor in the main wash cycle) 1: 5,7, rinse 4 times with tap water, spin off and dry.
  • the agent M1 according to the invention showed, on average, better ash contents than all of the textile fabrics than Comparative Example VI.

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'objet de l'invention est d'obtenir des produits granulés de lavage et de nettoyage ayant la composition usuelle, avec un pouvoir de lavage et de nettoyage primaires comparable au pouvoir de lavage et de nettoyage primaires des produits disponibles dans le commerce, mais dont le pouvoir de lavage secondaire présente de grands avantages. A cet effet, on utilise des produits qui contiennent des polycarboxylates polymères déterminés sous forme d'adjuvants granulés. Les produits de lavage de textiles préférés contiennent 8 à 40 % en poids d'agents tensio-actifs anioniques et non ioniques, y compris du savon, 15 à 45 % en poids de zéolithes et/ou de silicates stratifiés cristallins, notamment des zéolithes, 0,5 à 8 % en poids de carbonate de sodium ou de potassium et 0,5 % à 15 % en poids, de préférence 2 à 10 % en poids, notamment 3 à 8 % en poids, de polycarboxylates polymères granulés. Ces produits peuvent être préparés de la manière usuelle par mélange d'au moins deux composants granulés dont l'un contient le polycarboxylate polymère.
PCT/EP1993/002310 1992-09-04 1993-08-26 Produits de lavage et de nettoyage contenant des adjuvants WO1994005764A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP93919191A EP0658189B1 (fr) 1992-09-04 1993-08-26 Produits de lavage et de nettoyage contenant des adjuvants
DE59303899T DE59303899D1 (de) 1992-09-04 1993-08-26 Wasch- und reinigungsmittel mit buildersubstanzen

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4229660A DE4229660A1 (de) 1992-09-04 1992-09-04 Wasch- und Reinigungsmittel mit Buildersubstanzen
DEP4229660.9 1992-09-04

Publications (1)

Publication Number Publication Date
WO1994005764A1 true WO1994005764A1 (fr) 1994-03-17

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AT (1) ATE143048T1 (fr)
DE (2) DE4229660A1 (fr)
WO (1) WO1994005764A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5654265A (en) * 1992-03-12 1997-08-05 Kao Corporation Nonionic powdery detergent composition
EP1529834A1 (fr) * 2003-11-10 2005-05-11 The Procter & Gamble Company Particules de détergent
WO2005047442A1 (fr) * 2003-11-10 2005-05-26 The Procter & Gamble Company Particules de detergents

Families Citing this family (11)

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Publication number Priority date Publication date Assignee Title
GB9711356D0 (en) 1997-05-30 1997-07-30 Unilever Plc Particulate detergent composition
DE19847569A1 (de) * 1998-10-15 2000-04-20 Henkel Kgaa Phosphonathaltige Granulate
DE19850100A1 (de) 1998-10-29 2000-05-04 Henkel Kgaa Polymer-Granulate durch Wirbelschichtgranulation
GB9825560D0 (en) 1998-11-20 1999-01-13 Unilever Plc Particulate laundry detergent compositons containing nonionic surfactant granules
GB9825558D0 (en) 1998-11-20 1999-01-13 Unilever Plc Granular detergent components and particulate detergent compositions containing them
GB9825563D0 (en) 1998-11-20 1999-01-13 Unilever Plc Particulate laundry detergent compositions containing anionic surfactant granules
US6726362B1 (en) 1999-10-22 2004-04-27 The Procter & Gamble Company Shoe bags for use in laundering process
WO2001030955A1 (fr) 1999-10-22 2001-05-03 The Procter & Gamble Company Compositions destinees au traitement des chaussures et procedes et articles dans lesquels ces compositions sont utilisees
DE19959914A1 (de) * 1999-12-11 2001-07-05 Henkel Kgaa Granulate durch Wirbelschichtgranulation
KR100376620B1 (ko) * 2000-09-19 2003-03-19 씨제이 주식회사 정제형 세제 및 그 제조방법
US6861396B2 (en) 2000-10-20 2005-03-01 The Procter & Gamble Company Compositions for pre-treating shoes and methods and articles employing same

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EP0221777A2 (fr) * 1985-11-01 1987-05-13 Unilever Plc Compositions détergentes
EP0368137A1 (fr) * 1988-11-10 1990-05-16 Henkel Kommanditgesellschaft auf Aktien Méthode de préparation de granules en zéolite de haute densité
WO1991002047A1 (fr) * 1989-08-09 1991-02-21 Henkel Kommanditgesellschaft Auf Aktien Fabrication de granules comprimes pour produits de lavage
EP0421664A2 (fr) * 1989-10-02 1991-04-10 Rohm And Haas Company Granulés contenant des polymères
WO1991009927A1 (fr) * 1989-12-27 1991-07-11 Henkel Kommanditgesellschaft Auf Aktien Additif d'agent de lavage granulaire, a effet avivant et procede pour sa fabrication
WO1992007928A1 (fr) * 1990-10-26 1992-05-14 Henkel Kommanditgesellschaft Auf Aktien Adjuvant pour produit de lavage

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DE3545947A1 (de) * 1985-12-23 1987-07-02 Henkel Kgaa Phosphatfreies, granulares waschmittel
DE3916629A1 (de) * 1989-05-22 1990-11-29 Henkel Kgaa Granulares, nichtionische tenside enthaltendes waschmitteladditiv

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0221777A2 (fr) * 1985-11-01 1987-05-13 Unilever Plc Compositions détergentes
EP0368137A1 (fr) * 1988-11-10 1990-05-16 Henkel Kommanditgesellschaft auf Aktien Méthode de préparation de granules en zéolite de haute densité
WO1991002047A1 (fr) * 1989-08-09 1991-02-21 Henkel Kommanditgesellschaft Auf Aktien Fabrication de granules comprimes pour produits de lavage
EP0421664A2 (fr) * 1989-10-02 1991-04-10 Rohm And Haas Company Granulés contenant des polymères
WO1991009927A1 (fr) * 1989-12-27 1991-07-11 Henkel Kommanditgesellschaft Auf Aktien Additif d'agent de lavage granulaire, a effet avivant et procede pour sa fabrication
WO1992007928A1 (fr) * 1990-10-26 1992-05-14 Henkel Kommanditgesellschaft Auf Aktien Adjuvant pour produit de lavage

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5654265A (en) * 1992-03-12 1997-08-05 Kao Corporation Nonionic powdery detergent composition
EP1529834A1 (fr) * 2003-11-10 2005-05-11 The Procter & Gamble Company Particules de détergent
WO2005047442A1 (fr) * 2003-11-10 2005-05-26 The Procter & Gamble Company Particules de detergents

Also Published As

Publication number Publication date
ATE143048T1 (de) 1996-10-15
EP0658189A1 (fr) 1995-06-21
DE59303899D1 (de) 1996-10-24
DE4229660A1 (de) 1994-03-10
EP0658189B1 (fr) 1996-09-18

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