EP0713524A1 - Detergent contenant des ethers cellulosiques non ioniques - Google Patents

Detergent contenant des ethers cellulosiques non ioniques

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Publication number
EP0713524A1
EP0713524A1 EP94925416A EP94925416A EP0713524A1 EP 0713524 A1 EP0713524 A1 EP 0713524A1 EP 94925416 A EP94925416 A EP 94925416A EP 94925416 A EP94925416 A EP 94925416A EP 0713524 A1 EP0713524 A1 EP 0713524A1
Authority
EP
European Patent Office
Prior art keywords
weight
cellulose ether
groups
mpas
acid
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Withdrawn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
EP94925416A
Other languages
German (de)
English (en)
Inventor
Fred Schambil
Peter Krings
Eduard Smulders
Gertrud Nienhaus
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 EP0713524A1 publication Critical patent/EP0713524A1/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Withdrawn legal-status Critical Current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
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC

Definitions

  • the invention relates to a detergent which contains special nonionic cellulose ethers and the use of these nonionic cellulose ethers for removing grease and oil stains.
  • Ionic and nonionic cellulose ethers have long been used as graying inhibitors (dirt carriers) in detergents.
  • the preferred cellulose ethers include salts of carboxymethyl cellulose (CMC) and methyl cellulose (MC) and mixtures of these.
  • Further known as graying inhibitors are hydroxyalkylceuloses and mixed ethers, such as methylhydroxyethylcelluloses, methylhydroxypropylcelluloses and methylcarboxymethylceuloses.
  • the invention relates in a first embodiment to a detergent which contains conventional ingredients such as surfactants, builder substances and nonionic cellulose ethers, this nonionic cellulose ether being selected from the group of methylhydroxy propyl celluloses which contain a proportion of methoxyl Groups of 15 to 35 wt .-% and of hydroxypropoxyl groups of 1 to 15 wt .-%, based on the nonionic cellulose ether. It is preferred that the agents contain methyl hydroxypropyl celluloses which contain 20 to 30% by weight of methoxyl groups and 2 to 10% by weight of hydroxypropoxyl groups, in particular 5 to 8% by weight. %, each based on the nonionic cellulose ether.
  • the nonionic cellulose ether is usually obtained in the form of a powdery to granular compound which contains sodium chloride as an impurity. It has been shown that a certain amount of sodium chloride does not have a negative effect on the improvement of fat and oil washability. However, it is preferred that the nonionic cellulose ether compound used in the agents according to the invention does not contain sodium chloride in amounts not exceeding 10% by weight. Agents which contain a nonionic cellulose ether compound with a sodium chloride content of at most 5% by weight, preferably at most 2% by weight and in particular at most 1% by weight, based in each case on the compound, are particularly advantageous.
  • the detergents contain a nonionic cellulose ether compound which, in addition to methylhydroxypropyl cellulose, contains 6 to 8% by weight of water and 4 to 10% by weight of sodium chloride.
  • the content of the methoxyl groups in the methylhydroxypropyl cellulose is 25 to 30% by weight and preferably 25 to 29% by weight, the content of hydroxypropoxyl groups is 5 to 10% by weight and preferably 5.5 up to 8% by weight.
  • the detergents contain a nonionic cellulose ether compound which, in addition to methylhydroxypropyl cellulose, contains water as stated above, but only 0.2 to 5% by weight, preferably up to a maximum of 2% by weight, of sodium chloride.
  • the content of the methoxyl groups and the hydroxypropoxyl groups in the methylhydroxypropyl cellulose is values as stated above.
  • a detergent which contains a nonionic cellulose ether compound which, in addition to methylhydroxypropyl cellulose, contains water in amounts of 5 to 10% by weight, preferably 8% by weight, and sodium chloride in the small amounts such as stated above up to a maximum of 5% by weight and preferably up to a maximum of 2% by weight contains.
  • the content of the methoxyl groups here is only in the range from 20 to 25% by weight, preferably from 21 to 24% by weight, while the content of hydroxypropoxyl groups continues to be between 5 and 10% by weight. preferably between 6 and 8% by weight.
  • the bulk density of these compounds is generally 300 to 600 g / l.
  • the aqueous solutions of nonionic cellulose ethers must not be too viscous in order to achieve optimal fat and oil washability. It is therefore preferred that the nonionic cellulose ether compound used according to the invention at 20 ° C. in a 2% by weight aqueous solution has a viscosity between 40 and 125 mPas (Brookfield viscometer, 20 ° C., spindle 3, 4 or 5, 20 revolutions per minute), preferably between 45 and 100 mPas and in particular below 100 mPas, for example 45 to 60 mPas.
  • the preferably solid, powdery to granular detergents can have a bulk density between 300 and about 1000 g / 1 and by any known production process, for example by simple mixing of the components, spray drying, granulation, roller compaction, by extrusion or by combination are produced by several of these processes.
  • the detergents can also contain all conventional known detergent ingredients.
  • anionic and nonionic, but also cationic, zwitterionic or a photic surfactants include primarily anionic and nonionic, but also cationic, zwitterionic or a photic surfactants, inorganic and organic, in particular biodegradable, organic builder substances, inorganic alkaline and neutral salts, bleaching agents, in particular peroxy bleaching agents and bleach activators, enzymes, enzyme stabilizers, Foam inhibitors, if appropriate further ionic or nonionic graying inhibitors, for example commercially available carboxymethyl celluloses, methyl celluloses and / or polyvinylpyrrolidone, optical brighteners, colorants and fragrances and pearlescent agents.
  • anionic surfactants used are those of the sulfonate and / or sulfate type.
  • the known C9-C13-alkylbenzenesulfonates, olefin sulfonates and alkanesulfonates are preferably used as surfactants of the sulfonate type Consideration.
  • Esters of ⁇ -sulfofatty acids or the disalts of ⁇ -sulfofatty acids are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0 , 3 to 2 moles of glycerol can be obtained.
  • Suitable surfactants of the sulfate type are, for example, the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ⁇ o -C2 ⁇ ⁇ 0xoalcohols, and those of secondary alcohols of this chain length.
  • the sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide, are also suitable.
  • Preferred 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.
  • soaps for example saturated fatty acid soaps, 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.
  • the anionic surfactants and soaps 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 ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (E0) per mole of alcohol, in which the alcohol radical has a methyl or linear branching, preferably in the 2-position may be, or may 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 average, are preferred in particular 2 to 8 EO per mole of alcohol is preferred.
  • alkylglycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 ° C.
  • -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.
  • Another class of preferably used 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 having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as are described, for example, in Japanese Patent Application JP 58/217598 or which are preferably described in International Patent Application WO A-90/13533 described methods can be produced.
  • 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.
  • Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • R ⁇ CO for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 is up to 10 hydroxyl groups.
  • 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 alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • Phosphates, zeolites and layered silicates are used as inorganic builder substances.
  • the preferably used fine crystalline, synthetic and bound water-containing zeolite is preferably zeolite NaA in detergent quality.
  • 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 C 12 -C 8 -fatty alcohols with 2 to 5 ethylene oxide groups, Ci2-Ci4 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measuring 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 phosphates and zeolites are crystalline, layered sodium silicates of the general formula 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.
  • Preferred crystalline layered silicates are those in which M represents sodium and x assumes the values 2 or 3.
  • both .beta.- and ⁇ '-sodium disilicates Na2S ⁇ ' 2 ⁇ 5 * yH2 ⁇ preferred.
  • Further substitutes or partial substitutes for the zeolite are non-crystalline layered silicates of natural and synthetic origin, such as bentonites and smectites.
  • 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 Ci tronic 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.
  • 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.
  • biodegradable terpolymers for example those which are salts of acrylic acid and maleic acid and vinyl alcohol as monomers or vinyl alcohol derivatives or the salts of acrylic acid and 2-alkylallylsulfonic acid as monomers and sugar derivatives.
  • biodegradable terpolymers for example those which are salts of acrylic acid and maleic acid and vinyl alcohol as monomers or vinyl alcohol derivatives or the salts of acrylic acid and 2-alkylallylsulfonic acid as monomers and sugar derivatives.
  • Further suitable builder substances are 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-0 280223.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these;
  • alkali carbonate and amorphous 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, are used.
  • the content of sodium carbonate in the middle is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
  • the content of sodium silicate in the compositions is generally up to 10% by weight and preferably between 1 and 8% by weight.
  • alkali metal carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and, if appropriate, a further carboxyl and / or amino group and amino acids and / or their salts.
  • the alkali metal carbonates are partially or completely replaced by glycine or glycinate.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • bleaching agents that 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 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or 0-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.
  • 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.
  • 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 their mixtures with siliconized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, e.g. those made of silicone, paraffins or waxes.
  • the salts of polyphosphonic acids which are preferably used are the neutral sodium salts of, for example, l-hydroxyethane-l, l-diphosphonate and Diethylene tria in pentamethylene phosphonate used in amounts of 0.1 to 1.5 wt .-%.
  • 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 for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
  • Peroxidases and oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in Hü11 substances to protect them against premature decomposition.
  • 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-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.
  • the application test was carried out in a conventional household washing machine (Miele W 717) in the entrance washing process at a temperature of 40 ° C. and a load of 3.5 kg of clean household laundry and white test strips of the fabric specified below, which had already been washed three times with the respective fabrics Pre-washed and then stained with the grease and oil-containing stains also given below (aging 3 days), and a liquor of 17 l tap water with a hardness of 16 ° d.
  • the detergent dosage in Examples 1 and 2 was 96 g each. In the first example, 99 parts by weight of a commercially available color detergent were each mixed with 1 part by weight of the cellulose ethers given below.
  • the example was tested with 96 g of the same color detergent without the addition of the specified cellulose ethers (VI).
  • these tests were repeated with a commercial universal detergent with and without the addition of cellulose ether (V2).
  • the lightening of the tissue test strips was measured at 460 nm (suppression of the brightener effect).
  • Bicycle oil 12 drops of a mass of 10 g of dusty skin fat on 100 ml of oil on PES (very dirty) (III) 6 drops of this mass on PES (slightly dirty) (IV)
  • Methyl hydroxypropyl cellulose compound (MHPC1) containing 88% by weight of MHPC with a methoxyl group content of approximately 27% by weight and a hydroxypropoxyl group content of approximately 6.5% by weight on MHPC, 5% by weight sodium chloride and 7% by weight water.
  • the viscosity of a 2% by weight aqueous solution of MHPC1 at 20 ° C. was 50 mPas.
  • Methyl hydroxypropyl cellulose compound containing 91% by weight MHPC with a content of methoxyl groups of approx. 28% by weight and a content of hydroxypropoxyl groups of approx. 6% by weight, based on MHPC , 1 wt .-% sodium chloride and 8 wt .-% water.
  • the viscosity of a 2% by weight aqueous solution of MHPC2 at 20 ° C. was 50 mPas.
  • Methyl hydroxypropyl cellulose compound containing 91% by weight MHPC with a content of methoxyl groups of approx. 22% by weight and a content of hydroxypropoxyl groups of approx. 7.5% by weight on MHPC, 1% by weight sodium chloride and 8% by weight water.
  • the viscosity of a 2% by weight aqueous solution of MHPC3 at 20 ° C. was 100 mPas.
  • Methyl cellulose compound (MC) containing 88% by weight MC, 5% by weight sodium chloride and 7% by weight water.
  • the viscosity of a 2% by weight aqueous solution of MC at 20 ° C. was 40 mPas.
  • Carboxymethyl cellulose sodium salt (CMC) commercial form of offer
  • Tables 1 and 2 show the superiority of the methyl hydroxypropyl celluloses MHPC1 and MHPC2 used according to the invention over methyl celluloses and carboxymethyl celluloses both in the case of heavy and also slight contamination of the test tissue by motor oil. With the strong lipstick stains, significant advantages over MC and CMC for MHPC 1 to 3 can be seen.
  • Table 1 Engine oil
  • V1 CMC 99: 1 43.9 43.8
  • V1 MC 99: 1 67.9 70.6
  • V1 CMC 99: 1 56.4 72.3
  • V1 MC 99: 1 59.0 74.2
  • Tables 3 to 5 show the superiority of the methyl hydroxypropyl cellulose MHPCl used according to the invention over methyl celluloses and carboxymethyl celluloses both with heavy and with slight soiling of the test fabrics by motor oil and bicycle oil.
  • MHPC2 also shows if there are significant advantages for both heavy and light soiling from bicycle oil.
  • MHPC2 and MHPC3 also show advantages when slightly contaminated by motor oil. With lipstick soiling, significant advantages over MC and CMC for MHPC 1 to 3 can be seen.
  • V1 CMC 99: 1 49.5 49.4

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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)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

L'élimination des graisses et des huiles dans les textiles peut être améliorée par l'utilisation de certains éthers cellulosiques non ioniques. Ces éthers cellulosiques non ioniques sont des méthylhydroxypropylcelluloses contenant une proportion de 15 à 35 % en poids de groupes méthoxyle et de 1 à 15 % en poids de groupes hydroxypropoxyle, rapportés à l'éther cellulosique non ionique.
EP94925416A 1993-08-09 1994-07-29 Detergent contenant des ethers cellulosiques non ioniques Withdrawn EP0713524A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4326653 1993-08-09
DE19934326653 DE4326653A1 (de) 1993-08-09 1993-08-09 Waschmittel, enthaltend nichtionische Celluloseether
PCT/EP1994/002527 WO1995004805A1 (fr) 1993-08-09 1994-07-29 Detergent contenant des ethers cellulosiques non ioniques

Publications (1)

Publication Number Publication Date
EP0713524A1 true EP0713524A1 (fr) 1996-05-29

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EP94925416A Withdrawn EP0713524A1 (fr) 1993-08-09 1994-07-29 Detergent contenant des ethers cellulosiques non ioniques

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EP (1) EP0713524A1 (fr)
DE (1) DE4326653A1 (fr)
WO (1) WO1995004805A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9426458D0 (en) * 1994-12-31 1995-03-01 Procter & Gamble A detergent compositions comprising cellulytic enzyme
KR19980015613A (ko) * 1996-08-23 1998-05-25 문정환 노광장치의 포커스 조절방법
DE10351325A1 (de) 2003-02-10 2004-08-26 Henkel Kgaa Wasch- oder Reinigungsmittel mit wasserlöslichem Buildersystem und schmutzablösevermögendem Cellulosederivat
ATE362511T1 (de) 2003-02-10 2007-06-15 Henkel Kgaa Bleichmittelhaltige wasch- oder reinigungsmittel mit wasserlöslichem buildersystem und schmutzablösevermögendem cellulosederivat
WO2008141858A2 (fr) * 2007-04-03 2008-11-27 Henkel Ag & Co. Kgaa Détergents contenant des principes actifs améliorant la détergence primaire

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2613791A1 (de) * 1975-04-02 1976-10-21 Procter & Gamble Waschmittel
SE408715B (sv) * 1975-07-17 1979-07-02 Berol Kemi Ab Rengoringsmedel innehallande minst en ytaktiv forening och en cellulosaeter
GB1534641A (en) * 1977-05-04 1978-12-06 Unilever Ltd Detergent compositions for fabric washing
US4532067A (en) * 1984-01-11 1985-07-30 Lever Brothers Company Liquid detergent compositions containing hydroxypropyl methylcellulose

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9504805A1 *

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DE4326653A1 (de) 1995-02-16
WO1995004805A1 (fr) 1995-02-16

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