EP0576778B1 - Konzentriertes, wässeriges, flüssiges Reinigungsmittel - Google Patents
Konzentriertes, wässeriges, flüssiges Reinigungsmittel Download PDFInfo
- Publication number
- EP0576778B1 EP0576778B1 EP19920870098 EP92870098A EP0576778B1 EP 0576778 B1 EP0576778 B1 EP 0576778B1 EP 19920870098 EP19920870098 EP 19920870098 EP 92870098 A EP92870098 A EP 92870098A EP 0576778 B1 EP0576778 B1 EP 0576778B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- alkyl
- composition according
- anionic
- composition
- 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.)
- Expired - Lifetime
Links
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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
- C11D1/831—Mixtures of non-ionic with anionic compounds of sulfonates with ethers of polyoxyalkylenes without phosphates
-
- 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
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- 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
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
-
- 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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38618—Protease or amylase in liquid compositions only
-
- 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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
-
- 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
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
Definitions
- the present invention relates to concentrated aqueous liquid detergent compositions containing polyvinylpyrrolidone, in which the anionic surfactant majorily consists of an alkyl ethoxy sulfate salt.
- a new trend in the field of detergent compositions is the formulation of so-called concentrated detergents.
- concentrated detergents In the context of liquid aqueous detergents, this refers to products comprising less water and a higher total amount of active ingredients.
- the present invention is directed to concentrated liquid detergent compositions comprising an anionic surface-active agent, and from 2% to 35% by weight of the total composition of water, characterized in that the anionic surfactant contains at least 70%, preferably from 75% to 100% by weight of a water-soluble C 11-15 alkyl ethoxy sulfate salt containing an average per mole of from 1 to 9 ethoxy groups and that the composition comprises from 0.05% to 5% by weight of the total composition of polyvinylpyrrolidone.
- compositions preferably contain less than 6% by weight of the total composition of alkyl benzene sulfonate salt or non-ethoxylated alkyl sulfate salt.
- compositions according to the present invention are concentrated liquid detergents which comprise from 2% to 35% by weight of the total composition of water.
- compositions according to the present invention comprise from 5% to 25% by weight of the total composition of water.
- compositions according to the invention contain from 0.05% to 5% by weight of polyvinlypyrrolidone, preferably from 0.25% to 2%.
- Preferred polyvinylpyrrolidone for use herein have a molecular weight of from 1000 to 100,000, preferably from 2500 to 30,000, most preferably from 5000 to 15,000.
- compositions according to the present invention comprise a surfactant, and in particular an anionic surface active agent.
- the anionic surfactant (hereafter meant as not including soaps) contains at least 70% by weight of said anionic surfactant, of a water soluble C 11-15 alkyl ethoxy sulfate salt containing an average of from 1 to 9 ethoxy groups per mole.
- the C 11 -C 15 alkyl ethoxy sulfate salt herein comprises a primary alkyl ethoxy sulfate derived from the condensation product of a C 11 -C 15 alcohol with an average of up to 9 ethylene oxide groups.
- C 13 -C 15 alkyl ethoxy sulfate with an average of two to three ethoxy groups per mole is preferred.
- the C 11 -C 15 alcohol itself can be obtained from natural or synthetic sources.
- C 11 -C 15 alcohols, derived from natural fats, or Ziegler olefin build-up, or OXO synthesis can form suitalbe sources for the alkyl group.
- synthetically derived materials include Dobanol 23 (RTM) sold by Shell Chemicals (UK) Ltd., Ethyl 24 sold by the Ethyl Corporation, a blend of C 13 -C 15 alcohols in the ratio 67% C 13, 33% C 15 sold under the trade name Lutensol by BASF GmbH and Synperonic (RTM) by ICI Ltd., and Lial 125 sold by Liquichimica Italiana.
- Examples of naturally occurring materials from which the alcohols can be derived are coconut oil and palm kernel oil and the corresponding fatty acids.
- the alkyl ethoxy sulfate salts are preferably present in the compositions herein at levels of from 75% to 100% by weight of the anionic surfactant system.
- the anionic surfactant system may contain other types of surface-active agents, although in minor quantities; in particular, the present detergent compositions should contain less than 6% by weight of the total composition of alkyl benzene sulfonates and non-ethoxylated alkyl sulfates such as C 12-14 primary alkyl sulfate salts.
- anionic co-surfactants which may be present in minor quantities in the present compositions include C 12 -C 18 s-alkane sulfonates and alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a C 12 -C 18 fatty source.
- alkali metal sarcosinates of formula R-CON (R) CH 2 COOM wherein R is a C 9 -C 17 linear or branched alkyl or alkenyl group, R' is a C 1 -C 4 alkyl group and M is an alkali metal ion.
- R is a C 9 -C 17 linear or branched alkyl or alkenyl group
- R' is a C 1 -C 4 alkyl group
- M is an alkali metal ion.
- Preferred examples are the lauroyl, cocoyl (C 12 -C 14 ), myristyl and oleyl methyl sarcosinates in the form of their sodium salts.
- compositions preferably also contain a nonionic surfactant in combination with the alkyl ethoxy sulfate salts herein:
- Preferred nonionic surfactants for use herein are polyhydroxy fatty acid amides of the formula wherein R 1 is H, C 1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R 2 is C 5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
- R 1 is methyl
- R 2 is a straight C 11-15 alkyl or alkenyl chain or mixtures thereof
- Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
- Preferred are C 12 or C 12-14 glucosamides.
- Nonionic surfactants suitable for use herein include those produced by condensing ethylene oxide with a hydrocarbon having a reactive hydrogen atom, e.g., a hydroxyl, carboxyl, or amido group, in the presence of an acidic or basic catalyst, and include compounds having the general formula RA(CH 2 CH 2 0)nH wherein R represents the hydrophobic moiety, A represents the group carrying the reactive hydrogen atom and n represents the average number of ethylene oxide moieties. R typically contains from 8 to 22 carbon atoms. They can also be formed by the condensation of propylene oxide with a lower molecular weight compound. n usually varies from 2 to 24.
- a preferred class of such nonionic ethoxylates is represented by the condensation product of a fatty alcohol having from 12 to 15 carbon atoms and from 4 to 10 moles of ethylene oxide per mole or fatty alcohol.
- Suitable species of this class of ethoxylates include : the condensation product of C 12 -C 15 oxo-alcohols and 3 to 9 moles of ethylene oxide per mole of alcohol; the condensation product or narrow cut C 14 -C 15 oxo-alcohols and 3 to 9 moles of ethylene oxide per mole of fatty(oxo)alcohol; the condensation product of a narrow cut C 12 -C 13 fatty(oxo)alcohol and 6,5 moles of ethylene oxide per mole of fatty alcohol; and the condensation products of a C 10 -C 14 coconut fatty alcohol with a degree of ethoxylation (moles EO/mole fatty alcohol) in the range from 4 to 8.
- the fatty oxo alcohols while mainly linear can have, depending upon the processing conditions and raw material olefins, a certain degree of branching, particularly short chain such as methyl branching.
- a degree of branching in the range from 15% to 50% (weight%) is frequently found in commercial oxo alcohols.
- Nonionic surfactants comprises alkyl polyglucoside compounds of general formula RO(C n H 2n O) t Z x wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
- Compounds of this type and their use in detergent compositions are disclosed in EP-B 0 070 074, 0 070 077, 0 075 996 and 0 094 118.
- the surfactant system herein may also contain types of surfactants other than anionic and nonionic species.
- Suitable cationic surfactants include quaternary ammonium compounds of the formula R 1 R 2 R 3 R 4 N + where R 1 , R 2 and R 3 are methyl groups, and R 4 is a C 12-15 alkyl group, or where R 1 is an ethyl or hydroxy ethyl group, R 2 and R 3 are methyl groups and R 4 is a C 12-15 alkyl group.
- Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds in which the aliphatic moiety can be straight or branched chain and wherein one of the aliphatic substituents contains from 8 to 24 carbon atoms and another substituent contains, at least, an anionic water-solubilizing group.
- Particularly preferred zwitterionic materials are the ethoxylated ammonium sulfonates and sulfates disclosed in U.S. Patents 3,925,262, Laughlin et al., issued December 9, 1975 and 3,929,678, Laughlin et al., issued December 30, 1975.
- Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl or hydroxy alkyl moiety of from 8 to 28 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxy alkyl groups, containing from 1 to 3 carbon atoms which can optionally be joined into ring structures.
- the present concentrated detergent compositions typically contain from 25% to 45%, preferably 30% to 40% by weight of surfactant of which the weight ratio of anionic surfactant to nonionic surfactant is typically of 3:1 to 1:1, more preferably 2:1 to 1:1.
- compositions according to the present invention may further comprise a builder.
- a builder Any conventional builder system is suitable for use herein including polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
- phosphate builders can also be used herein.
- Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R-CH(COOH)CH 2 (COOH) wherein R is C 10-20 alkyl or alkenyl, preferably C 12-16 , or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents.
- Specific examples include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenylsuccinate, 2-tetradecenyl succinate.
- Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium, and alkanolammonium salts.
- polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US-A-4,663,071.
- Suitable fatty acid builders for use herein are saturated or unsaturated C 10-18 fatty acids, as well as the corresponding soaps.
- Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain.
- the preferred unsaturated fatty acid is oleic acid.
- a preferred builder system for use herein consists of a mixture of citric acid, fatty acids and succinic acid derivatives described hereinabove.
- the builder system according to the present invention preferably represents from 5% to 35% by weight of the total composition.
- compositions according to the invention preferably comprise enzymes.
- Suitable enzymes for use herein are protease, lipases, cellulases, and amylases and mixtures thereof.
- compositions according to the present invention may still advantageously comprise an enzyme stabilizing system, although at reduced levels as compared to compositions where alkyl benzene sulfonate and/or non-ethoxylated alkyl sulfate salts are present in majority.
- Any conventional enzyme stabilizing system is suitable for use herein, and preferred enzyme stabilizing systems are based on boric acid or derivatives thereof, 1,2-propanediol, carboxylic acids such as formic acid/formate, and mixtures thereof.
- anionic surfactant system of the present invention provides improved stability of enzymes such as cellulase in presence of a protease.
- compositions herein can also advantageously contain a terphtalate-based soil release polymer at levels of from 0.05% to 2% of the total composition.
- compositions herein can contain a series of fruther, optional ingredients.
- the like additives include solvents, alkanolamines, pH adjusting agents, suds regulants, opacifiers, agents to improve the machine compatibility in relation to enamel-coated surfaces, perfumes, dyes, bactericides, brighteners, softening agents and the like.
- compositions were prepared : (weight % in formula) example 1 example 2 C13-15 Alkyl 3 ethoxylated sulfate 23 18 C13-15 alcohol 7 ethoxylated 6 5 C12-14 N-methyl glucosamide 9 9
- Builders 16 17 Ethanol 2 2 1,2 Propane diol 13 10 Mono ethanolamine 13 13 Protease 1.8 0.8 Cellulase 0.15 0.15 Sodium Formate - 1.0 Boric acid 2.5 2.0 Polyvinylpyrrolidone 0.5 0.5 Water 8 18 Minors to 100 %
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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)
- Detergent Compositions (AREA)
Claims (10)
- Konzentrierte, flüssige Waschmittelzusammensetzung, umfassend ein anionisches Tensid und 2 bis 35 Gew.-% der gesamten Zusammensetzung an Wasser, dadurch gekennzeichnet, daß das anionische Tensid mindestens 70% des anionischen Tensids aus einem wasserlöslichen C11-15-Alkylethoxysulfatsalz, welches durchschnittlich pro Mol 1 bis 9 Ethoxygruppen umfaßt, enthält. und daß die Zusammensetzung 0.05 bis 5 Gew.-% der gesamten Zusammensetzung Polyvinylpyrrolidon umfaßt.
- Konzentrierte, flüssige Waschmittelzusammensetzung nach Anspruch 1. umfassend 5 bis 25 Gew.-% der gesamten Zusammensetzung an Wasser.
- Zusammensetzung nach den Ansprüchen 1 oder 2, umfassend 0.25 bis 2 Gew.-% der gesamten Zusammensetzung an Vinylpyrrolidon.
- Zusammensetzung nach mindestens einem der vorangehenden Ansprüche, wobei das Polyvinylpyrrolidon ein Molekulargewicht von 5.000 bis 15.000 aufweist.
- Zusammensetzung nach mindestens einem der vorangehenden Ansprüche, wobei das anionische Tensid 75 bis 100 Gew.-% des anionischen Tensids aus dem Alkylethoxysulfatsalz enthält.
- Zusammensetzung nach mindestens einem der vorangehenden Ansprüche, wobei das Alkylethoxysulfatsalz ein C13-C15-Alkylethoxysulfat mit durchschnittlich 2 bis 3 Ethoxygruppen pro Mol ist.
- Zusammensetzung nach den Ansprüchen 5 oder 6, enthaltend weniger als 6 Gew.-% eines Alkylbenzolsulfonatsalzes oder nichtethoxylierten Alkylsulfatsalzes.
- Zusammensetzung nach mindestens einem der vorangehenden Ansprüche, wobei das Tensid ebenso ein nichtionisches Tensid in einem Gewichtsverhältnis von anionischem zu nichtionischem von 3:1 bis 1:1 enthält.
- Zusammensetzung nach Anspruch 8, wobei das nichtionische Tensid ein C12- oder C12-14-Glucosamid umfaßt.
- Zusammensetzung nach mindestens einem der vorangehenden Ansprüche, welche ein Proteaseenzym und ein Cellulaseenzym enthält.
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19920870098 EP0576778B1 (de) | 1992-07-03 | 1992-07-03 | Konzentriertes, wässeriges, flüssiges Reinigungsmittel |
CA 2139359 CA2139359A1 (en) | 1992-07-03 | 1993-06-28 | Concentrated aqueous liquid detergent comprising polyvinylpyrrolidone |
JP6503360A JPH07508788A (ja) | 1992-07-03 | 1993-06-28 | ポリビニルピロリドンを含む濃縮水性液体洗剤 |
PCT/US1993/006086 WO1994001520A1 (en) | 1992-07-03 | 1993-06-28 | Concentrated aqueous liquid detergent comprising polyvinylpyrrolidone |
TR00549/93A TR26910A (tr) | 1992-07-03 | 1993-06-30 | Konsantre, sulu sivi deterjan bilesimleri. |
IE930498A IE930498A1 (en) | 1992-07-03 | 1993-07-02 | Concentrated aqueous liquid detergent compositions. |
MX9304037A MX9304037A (es) | 1992-07-03 | 1993-07-05 | Composiciones detergentes liquidas, acuosas, concentradas. |
US08/699,175 US5723425A (en) | 1992-07-03 | 1996-08-19 | Concentrated aqueous liquid detergent comprising polyvinylpyrrolidone |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19920870098 EP0576778B1 (de) | 1992-07-03 | 1992-07-03 | Konzentriertes, wässeriges, flüssiges Reinigungsmittel |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0576778A1 EP0576778A1 (de) | 1994-01-05 |
EP0576778B1 true EP0576778B1 (de) | 1998-02-04 |
Family
ID=8212258
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19920870098 Expired - Lifetime EP0576778B1 (de) | 1992-07-03 | 1992-07-03 | Konzentriertes, wässeriges, flüssiges Reinigungsmittel |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0576778B1 (de) |
JP (1) | JPH07508788A (de) |
CA (1) | CA2139359A1 (de) |
IE (1) | IE930498A1 (de) |
MX (1) | MX9304037A (de) |
TR (1) | TR26910A (de) |
WO (1) | WO1994001520A1 (de) |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5723425A (en) * | 1992-07-03 | 1998-03-03 | Cauwberghs; Serge Gabriel Pierre | Concentrated aqueous liquid detergent comprising polyvinylpyrrolidone |
US5935922A (en) * | 1994-03-31 | 1999-08-10 | The Procter & Gamble Company | Detergent composition containing zeolite map for washing a mixture of white and colored fabrics |
GB2287949A (en) * | 1994-03-31 | 1995-10-04 | Procter & Gamble | Laundry detergent composition |
USH1513H (en) * | 1994-06-01 | 1996-01-02 | The Procter & Gamble Company | Oleoyl sarcosinate with polyhydroxy fatty acid amides in cleaning products |
JPH10501278A (ja) * | 1994-06-01 | 1998-02-03 | ザ、プロクター、エンド、ギャンブル、カンパニー | オレオイルサルコシネートを含有する染料移動抑制組成物 |
USH1514H (en) * | 1994-06-01 | 1996-01-02 | The Procter & Gamble Company | Detergent compositions with oleoyl sarcosinate and polymeric dispersing agent |
WO1995033025A1 (en) * | 1994-06-01 | 1995-12-07 | The Procter & Gamble Company | Oleoyl sarcosinate containing detergent compositions |
BR9507826A (pt) * | 1994-06-01 | 1997-09-16 | Procter & Gamble | Composição detergente líquida contendo sarcosinatos de oleoíla e tensoatívos aniõnicos |
US5798330A (en) * | 1995-07-20 | 1998-08-25 | Colgate-Palmolive Co | Liquid cleaning compositions |
EP0781837A1 (de) * | 1995-12-29 | 1997-07-02 | Colgate-Palmolive Company | Waschmittelzusammensetzung mit verbesserter Reinigungsleistung |
US6025316A (en) * | 1995-12-29 | 2000-02-15 | Colgate-Palmolive Co. | Detergent composition having improved cleaning power |
DE19601365A1 (de) * | 1996-01-16 | 1997-07-17 | Planttec Biotechnologie Gmbh | Nucleinsäuremoleküle aus Pflanzen codierend Enzyme, die an der Stärkesynthese beteiligt sind |
DE19626338A1 (de) * | 1996-07-01 | 1998-01-08 | Vorwerk Co Interholding | Teppich-Fleckentfernungsmittel |
US5880081A (en) * | 1997-04-07 | 1999-03-09 | Gopalkrishnan; Sridhar | Concentrated built liquid detergents containing a dye-transfer inhibiting additive |
WO1999033942A1 (en) * | 1997-12-29 | 1999-07-08 | Colgate-Palmolive Company | Detergent composition having improved cleaning power |
CN101297025B (zh) * | 2005-09-02 | 2012-10-24 | 诺维信公司 | 浓缩的液体酶添加剂的稳定化 |
GB0911294D0 (en) * | 2009-06-30 | 2009-08-12 | Reckitt Benckiser Nv | Composition |
US9840681B2 (en) | 2013-05-24 | 2017-12-12 | The Procter & Gamble Company | Concentrated surfactant composition |
EP3004310B1 (de) | 2013-05-24 | 2021-07-14 | The Procter & Gamble Company | Reinigungsmittelzusammensetzung mit geringem ph-wert |
CN105209587A (zh) | 2013-05-24 | 2015-12-30 | 宝洁公司 | 包含非离子表面活性剂的低ph洗涤剂组合物 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3860536A (en) * | 1970-01-02 | 1975-01-14 | Cpc International Inc | Enzyme-detergent combination |
US4304680A (en) * | 1973-02-05 | 1981-12-08 | Colgate-Palmolive Company | Laundry soap |
US3970594A (en) * | 1975-03-18 | 1976-07-20 | The Procter & Gamble Company | Hard surface cleaning compositions |
US4368146A (en) * | 1979-01-12 | 1983-01-11 | Lever Brothers Company | Light duty hand dishwashing liquid detergent composition |
NZ192549A (en) * | 1979-01-12 | 1981-11-19 | Unilever Ltd | Liquid detergent comprising a copolymer of n-vinylpyrrolidone |
GB8618635D0 (en) * | 1986-07-30 | 1986-09-10 | Unilever Plc | Detergent composition |
US4954292A (en) * | 1986-10-01 | 1990-09-04 | Lever Brothers Co. | Detergent composition containing PVP and process of using same |
GB8821282D0 (en) * | 1988-09-12 | 1988-10-12 | Unilever Plc | Liquid cleaning products |
DE3840056A1 (de) * | 1988-11-28 | 1990-05-31 | Henkel Kgaa | Verfahren zum waschen von verfaerbungsempfindlichen textilien |
EP0508034B1 (de) * | 1991-04-12 | 1996-02-28 | The Procter & Gamble Company | Polyvinylpyrrolidon enthaltendes Kompaktwaschmittel |
-
1992
- 1992-07-03 EP EP19920870098 patent/EP0576778B1/de not_active Expired - Lifetime
-
1993
- 1993-06-28 JP JP6503360A patent/JPH07508788A/ja active Pending
- 1993-06-28 WO PCT/US1993/006086 patent/WO1994001520A1/en active Application Filing
- 1993-06-28 CA CA 2139359 patent/CA2139359A1/en not_active Abandoned
- 1993-06-30 TR TR00549/93A patent/TR26910A/xx unknown
- 1993-07-02 IE IE930498A patent/IE930498A1/en not_active IP Right Cessation
- 1993-07-05 MX MX9304037A patent/MX9304037A/es unknown
Also Published As
Publication number | Publication date |
---|---|
IE930498A1 (en) | 1994-01-12 |
CA2139359A1 (en) | 1994-01-20 |
WO1994001520A1 (en) | 1994-01-20 |
MX9304037A (es) | 1994-05-31 |
JPH07508788A (ja) | 1995-09-28 |
EP0576778A1 (de) | 1994-01-05 |
TR26910A (tr) | 1994-08-22 |
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