EP0619368A1 - Konzentrierte flüssige Waschmittelzusammensetzungen - Google Patents
Konzentrierte flüssige Waschmittelzusammensetzungen Download PDFInfo
- Publication number
- EP0619368A1 EP0619368A1 EP93201008A EP93201008A EP0619368A1 EP 0619368 A1 EP0619368 A1 EP 0619368A1 EP 93201008 A EP93201008 A EP 93201008A EP 93201008 A EP93201008 A EP 93201008A EP 0619368 A1 EP0619368 A1 EP 0619368A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition according
- weight
- composition
- alkyl
- sodium
- 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- Withdrawn
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/201—Monohydric alcohols linear
-
- 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
-
- 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
-
- 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
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
- C11D3/2044—Dihydric alcohols linear
-
- 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
- C11D3/2068—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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid 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
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/08—Polycarboxylic acids containing no nitrogen or sulfur
Definitions
- the invention relates to concentrated liquid detergent compositions which contain a suspending solid peroxygen compound.
- EP-A-293 040 and EP-A-294 904 have described aqueous detergent compositions having a pH above 8 containing an anionic surfactant at conventional levels, i.e. above 5% by weight, typically from 15% to 40% by weight, and a solid water soluble peroxygen bleach, suspended in a specific water/solvent medium.
- Surfactant structured (neat) phases are known as means to suspend solid particles such as zeolites in liquid detergent compositions, see in particular EP-A-79 646, EP-A- 170 091 and EP-A-295 021.
- the present invention provides concentrated liquid detergent compositions formulated as a neat phase in which solid suspended peroxygen compounds, such as perborate or percarbonate, in particular percarbonate, can be stabilized chemically and physically.
- solid suspended peroxygen compounds such as perborate or percarbonate, in particular percarbonate
- the present invention provides liquid detergent bleach-containing compositions which exhibit a very good chemical stability, and are in the form of a perfectly stable structured phase.
- the present invention relates to a liquid detergent composition containing a surface-active agent, water, an organic solvent, and a solid peroxygen compound in the form of suspended particles.
- Said composition comprises at least 10% by weight of the total composition of a compound of the formula RO(CH2CH2O) y H wherein :
- structured phase refers to an essentially lamella-structured or spherulitic composition in which aqueous layers are separated by double layers of hydrophobic materials. Such a lamellar structure can be identified by observing the product through an optical microscope, between crossed Nichol prisms.
- the structured phases are characterized by specific textures which are described for instance by F.B. Rosevear, Journal of the American Oil Chemists Society, vol. 3, page 628, 1954.
- compositions herein compulsory contain a surface-active agent and an organic solvent.
- Said compositions herein can be formulated as a structured phase by incorporation of at least 10% by weight of a compound of the formula RO(CH2CH2O) y H wherein
- Preferred compounds according to this definition are nonionic surfactants consisting of condensation products of ethylene oxide with a fatty alcohol in the presence of an acidic or basic catalyst.
- Fatty alcohols having from 13 to 15 carbon atoms are preferably used to make such condensation products.
- solvents as butanol, butoxyethanol, benzylalcohol, hexyl diglycol ether, butyl diglycolether, and mixtures thereof.
- compositions herein therefore contain at least one of the organic solvents above, or a nonionic surfactant as defined above, or both types of compounds.
- the organic solvents described above should be used in combination with another solvent such as described hereinafter.
- the nonionic surfactants described above are preferably used in combination with an anionic surfactant, and/or other types of surfactants, including other nonionic surfactants, described hereinafter.
- the water level is of 5% to 20% by weight of the present composition, i.e., the present compositions are relatively concentrated.
- the organic solvent to water weight ratio is at least 0.8, preferably at least 1.0.
- Suitable solid peroxygen compounds include the perborates, persulfates, peroxydisulfates, perphosphates and the crystalline peroxyhydrates formed by reacting hydrogen peroxide with sodium carbonate (forming percarbonate) or urea.
- Preferred peroxygen bleach compounds are perborates and percarbonates. Percarbonates, known to be difficult to stabilize, have been found to be perfectly stabilized in the present composition, and are therefore the most preferred species for use herein.
- the weight-average particle diameter of the peroxygen compounds herein must be in the range from 0.1 to 350 micrometers, preferably from 0.5 to 20 micrometers.
- the required small particle size can be achieved by physical techniques, such as grinding, or any suitable chemical technique such as in-situ crystallization, especially for perborate, as it is described in detail in EP-A-294 904.
- the peroxygen compounds are present in the compositions herein at levels of from 5% to 40%, preferably from 10% to 30%, most preferably from 15% to 25%, by weight of the composition.
- the organic solvent preferably contains at least one solvent corresponding to the formula RO(CH2CH2O) y H as described above, for the structured phase formation; butyl diglycol ether and hexyl diglycol ether being preferred; other organic solvents which may be used preferably in combination with such required solvents, can be selected from the group of : polyalcohols having vicinal hydroxy groups (e.g.
- 1,2-propanediol and glycerol lower monoaliphatic monoalcohols; specifically ethanol, n-propanol; iso-propanol; polyethylene glycol (e.g., PEG 150, 200, 300, 400); dipropylene glycol; ethoxymethanol; methoxyethanol; ethoxyethanol; ethyldiglycolether; benzylalcohol; butoxypropanol; butoxypropoxypropanol; and mixtures hereof.
- polyethylene glycol e.g., PEG 150, 200, 300, 400
- dipropylene glycol ethoxymethanol
- methoxyethanol ethoxyethanol
- ethyldiglycolether ethyldiglycolether
- benzylalcohol butoxypropanol; butoxypropoxypropanol; and mixtures hereof.
- the present liquid bleach compositions exhibit a pH (1% solution in distilled water) of at least 8, preferably of at least 9, more preferably of at least 9.5.
- the alkaline pH allows to get a good bleaching action of the peroxygen compound, particularly when the peroxygen is a percarbonate or perborate.
- the surface active agent is the surface active agent
- compositions of the invention contain a surface active agent selected from anionic, nonionic, zwitterionic or cationic surface-active agents, and mixtures thereof.
- compositions herein contain an anionic, synthetic or natural surfactant.
- Synthetic anionic surfactants can be represented by the general formula R1SO3M wherein R1 represents a hydrocarbon group selected from the group consisting of straight or branched alkyl radicals containing from about 8 to about 24 carbon atoms and alkyl phenyl radicals containing from about 9 to about 15 carbon atoms in the alkyl group.
- M is a salt forming cation which typically is selected from the group consisting of sodium, potassium, ammonium, and mixtures thereof.
- anionic synthetic surfactants are the water-soluble salts of alkylbenzene sulfonic acid, preferably sodium alkylbenzene sulfonates having from about 10 to 13 carbon atoms in the alkyl group.
- Suitable anionic surfactants can be represented by the water-soluble salts of an alkyl sulfate or an alkyl polyethoxylate ether sulfate wherein the alkyl group contains from about 8 to about 24, preferably from about 10 to about 20 carbon atoms, and preferably from about 1 to about 12 ethoxy groups for the alkyl polyethoxylate ether sulfates.
- alkyl sulfates containing from 12 to 15 carbon atoms in the alkyl chain.
- Natural coconut or palm kernel alkyl sulfate are especially preferred.
- the nonionic surfactants are conventionally 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(CH2CH2O) n H 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. n varies from about 4 to about 24.
- R is an alkyl, alkenyl, aryl or alkyl aryl having from about 8 to about 24, preferably from about 12 to about 20 carbon atoms.
- Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulphonium compounds in which the aliphatic moiety can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 24 carbon atoms and another substituent contains, at least, an anionic water-solubilizing group.
- Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl or hydroxy alkyl moiety of from about 8 to about 28 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxy alkyl groups, containing from 1 to about 3 carbon atoms which can optionally be joined into ring structures.
- Suitable cationic surfactants include quaternary ammonium compounds of the formula R1R2R3R4N+X ⁇ , wherein R1 is C12-C20 alkyl or hydroxyalkyl; R2 is C1-C4 alkyl or C12-C20 alkyl or hydroxyalkyl or C1-C4 hydroxyalkyl, R3 and R4 are each C1-C4 alkyl or hydroxyalkyl, or C6-C8 aryl or alkylaryl; and X ⁇ is halogen.
- R1 is C12-C20 alkyl or hydroxyalkyl
- R2 is C1-C4 alkyl or C12-C20 alkyl or hydroxyalkyl or C1-C4 hydroxyalkyl
- R3 and R4 are each C1-C4 alkyl or hydroxyalkyl, or C6-C8 aryl or alkylaryl
- X ⁇ is halogen.
- Preferred are mono-long chain qua
- the total amount of surfactant in the compositions is of from 5% to 60%, preferably 15% to 40% by weight of the total composition.
- compositions of the invention may also contain a builder.
- a builder Preferred are C10-C16 alk(en)yl substituted succinic acids, typically present at levels of from 5% to 30% by weight of the total composition.
- the preferred builder for use herein is a mixture of dodecenyl substituted succinic acid and tetradecenyl substituted succinic acid.
- Examples of other suitable organic builders for use herein are represented by polyacids such as citric acid, nitrilotriacetic acid, and mixtures of tartrate monosuccinate with tartrate disuccinate.
- Polymeric carboxylate builders inclusive of polyacrylates, polydydroxy acrylates and polyacrylates/polymaleates copolymers can also be used.
- detergent enzymes include the detergent proteases, amylases, lipases and cellulases. Enzymatic stabilizing agents for use in aqueous liquid detergents can also be used herein.
- salts of formic acid such as sodium formate, which is a typical enzyme stabilizing agent, be used at levels not exceeding 0.5% by weight of the total composition.
- compositions of the invention may also contain chelants, especially chelants for transition metal ions, since such ions can have a detrimental effect on the chemical stability of the compositions, the peroxygen bleaching agents being sensitive to these ions.
- chelants include ethylenediaminotetracetic acid, diethylenetriaminopentacetic acid, ethylenediamino disuccinic acid or the water-soluble alkali metals thereof.
- chelants include organophosphonic acids; particularly preferred are ethylenediamino tetramethylenephosphonic acid, hexamethylenediamino tetramethylenephosphonic acid, diethylenetriamino pentamethylenephosphonic acid, aminotrimethylenephosphonic acid and hydroxyethylidene 1,1 diphosphonic acid.
- compositions make it possible to include only very small levels of such chelants, typically 0.2%.
- compositions herein can contain further optional ingredients which are mostly used in additive levels, usually below about 5%.
- additives include : suds regulants, opacifiers, agents to improve the machine compatibility in relation to enamel-coated surfaces, bactericides, dyes, perfumes, brighteners and the like.
- compositions under various usage conditions can require the utilization of a suds regulant like polysiloxanes such as dimethylpolysiloxane, also frequently used in a level not exceeding 1.5%, most preferably between 0.1% and 1.0%
- compositions herein are kept to a minimum.
- preferred compositions according to the present invention contain no more than 0.5% by weight of the total composition of added electrolytes such as sodium or potassium salts of bromide, chloride, iodide, nitrate and C1-4 alkyl carboxylates. Accordingly, the liquid detergent formulations of the present invention are substantially free of electrolytes.
- compositions are designed to be used as is and are not diluted before use.
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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)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP93201008A EP0619368A1 (de) | 1993-04-06 | 1993-04-06 | Konzentrierte flüssige Waschmittelzusammensetzungen |
JP6523284A JPH08511288A (ja) | 1993-04-06 | 1994-04-05 | 懸濁ペルオキシゲン漂白剤、有機溶媒および5〜20%の水を含有する濃縮液体洗剤 |
PCT/US1994/003739 WO1994024247A1 (en) | 1993-04-06 | 1994-04-05 | Concentrated liquid detergent containing suspended peroxygen bleach, organic solvent and 5-20 % water |
CN 94192141 CN1123558A (zh) | 1993-04-06 | 1994-04-05 | 含有悬浮的过氧漂白剂、有机溶剂和5-20%水的浓缩液体洗涤剂 |
CA 2159983 CA2159983A1 (en) | 1993-04-06 | 1994-04-05 | Concentrated liquid detergent containing suspended peroxygen bleach, organic solvent and 5-20% water |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP93201008A EP0619368A1 (de) | 1993-04-06 | 1993-04-06 | Konzentrierte flüssige Waschmittelzusammensetzungen |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0619368A1 true EP0619368A1 (de) | 1994-10-12 |
Family
ID=8213748
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93201008A Withdrawn EP0619368A1 (de) | 1993-04-06 | 1993-04-06 | Konzentrierte flüssige Waschmittelzusammensetzungen |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0619368A1 (de) |
JP (1) | JPH08511288A (de) |
CN (1) | CN1123558A (de) |
CA (1) | CA2159983A1 (de) |
WO (1) | WO1994024247A1 (de) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996030485A1 (en) * | 1995-03-24 | 1996-10-03 | Warwick International Group Limited | Alkaline isotropic liquid detergent with peroxide |
EP0826771A2 (de) * | 1996-08-30 | 1998-03-04 | Clariant GmbH | Flüssige Bleichmittelsuspension |
WO1999025801A1 (de) * | 1997-11-14 | 1999-05-27 | Henkel Kommanditgesellschaft Auf Aktien | Wässrige bleichmittel |
US5916865A (en) * | 1996-08-30 | 1999-06-29 | Clariant Gmbh | Liquid bleaching agent suspension |
WO2001007557A1 (de) * | 1999-07-27 | 2001-02-01 | Henkel Kommanditgesellschaft Auf Aktien | Bleichmittelzusammensetzungen |
US6194364B1 (en) | 1996-09-23 | 2001-02-27 | The Procter & Gamble Company | Liquid personal cleansing compositions which contain soluble oils and soluble synthetic surfactants |
WO2011088089A1 (en) | 2010-01-12 | 2011-07-21 | The Procter & Gamble Company | Intermediates and surfactants useful in household cleaning and personal care compositions, and methods of making the same |
WO2012112828A1 (en) | 2011-02-17 | 2012-08-23 | The Procter & Gamble Company | Bio-based linear alkylphenyl sulfonates |
WO2012138423A1 (en) | 2011-02-17 | 2012-10-11 | The Procter & Gamble Company | Compositions comprising mixtures of c10-c13 alkylphenyl sulfonates |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0293040A1 (de) * | 1987-05-27 | 1988-11-30 | The Procter & Gamble Company | Flüssiges Reinigungsmittel, welches festes Peroxy-Bleichmittel enthält |
EP0385522A2 (de) * | 1989-02-27 | 1990-09-05 | Unilever N.V. | Flüssiges Reinigungsmittel |
EP0430330A2 (de) * | 1989-11-24 | 1991-06-05 | The Procter & Gamble Company | Suspendierfähige, flüssige Reinigungsmittel |
WO1991012309A2 (en) * | 1990-02-08 | 1991-08-22 | Unilever N.V. | Liquid bleach composition |
-
1993
- 1993-04-06 EP EP93201008A patent/EP0619368A1/de not_active Withdrawn
-
1994
- 1994-04-05 JP JP6523284A patent/JPH08511288A/ja active Pending
- 1994-04-05 CA CA 2159983 patent/CA2159983A1/en not_active Abandoned
- 1994-04-05 WO PCT/US1994/003739 patent/WO1994024247A1/en active Application Filing
- 1994-04-05 CN CN 94192141 patent/CN1123558A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0293040A1 (de) * | 1987-05-27 | 1988-11-30 | The Procter & Gamble Company | Flüssiges Reinigungsmittel, welches festes Peroxy-Bleichmittel enthält |
EP0385522A2 (de) * | 1989-02-27 | 1990-09-05 | Unilever N.V. | Flüssiges Reinigungsmittel |
EP0430330A2 (de) * | 1989-11-24 | 1991-06-05 | The Procter & Gamble Company | Suspendierfähige, flüssige Reinigungsmittel |
WO1991012309A2 (en) * | 1990-02-08 | 1991-08-22 | Unilever N.V. | Liquid bleach composition |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996030485A1 (en) * | 1995-03-24 | 1996-10-03 | Warwick International Group Limited | Alkaline isotropic liquid detergent with peroxide |
EP0826771A2 (de) * | 1996-08-30 | 1998-03-04 | Clariant GmbH | Flüssige Bleichmittelsuspension |
EP0826771A3 (de) * | 1996-08-30 | 1998-09-16 | Clariant GmbH | Flüssige Bleichmittelsuspension |
US5916865A (en) * | 1996-08-30 | 1999-06-29 | Clariant Gmbh | Liquid bleaching agent suspension |
US6194364B1 (en) | 1996-09-23 | 2001-02-27 | The Procter & Gamble Company | Liquid personal cleansing compositions which contain soluble oils and soluble synthetic surfactants |
WO1999025801A1 (de) * | 1997-11-14 | 1999-05-27 | Henkel Kommanditgesellschaft Auf Aktien | Wässrige bleichmittel |
WO2001007557A1 (de) * | 1999-07-27 | 2001-02-01 | Henkel Kommanditgesellschaft Auf Aktien | Bleichmittelzusammensetzungen |
WO2011088089A1 (en) | 2010-01-12 | 2011-07-21 | The Procter & Gamble Company | Intermediates and surfactants useful in household cleaning and personal care compositions, and methods of making the same |
US8933131B2 (en) | 2010-01-12 | 2015-01-13 | The Procter & Gamble Company | Intermediates and surfactants useful in household cleaning and personal care compositions, and methods of making the same |
WO2012112828A1 (en) | 2011-02-17 | 2012-08-23 | The Procter & Gamble Company | Bio-based linear alkylphenyl sulfonates |
WO2012138423A1 (en) | 2011-02-17 | 2012-10-11 | The Procter & Gamble Company | Compositions comprising mixtures of c10-c13 alkylphenyl sulfonates |
US9193937B2 (en) | 2011-02-17 | 2015-11-24 | The Procter & Gamble Company | Mixtures of C10-C13 alkylphenyl sulfonates |
Also Published As
Publication number | Publication date |
---|---|
CN1123558A (zh) | 1996-05-29 |
CA2159983A1 (en) | 1994-10-27 |
WO1994024247A1 (en) | 1994-10-27 |
JPH08511288A (ja) | 1996-11-26 |
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