WO1991005844A1 - Liquid detergents - Google Patents
Liquid detergents Download PDFInfo
- Publication number
- WO1991005844A1 WO1991005844A1 PCT/EP1990/001667 EP9001667W WO9105844A1 WO 1991005844 A1 WO1991005844 A1 WO 1991005844A1 EP 9001667 W EP9001667 W EP 9001667W WO 9105844 A1 WO9105844 A1 WO 9105844A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- compositions
- composition according
- preferred
- weight
- Prior art date
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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
-
- 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
-
- 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
- C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
-
- 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
- C11D3/228—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with phosphorus- or sulfur-containing groups
-
- 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
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
Definitions
- Lamellar droplets are a particular class of surfactant structures which, inter alia, are already known from a variety of references, e.g. H.A.Barnes, 'Detergents', Ch.2. in K.Walters (Ed), 'Rheometry: Industrial Applications', J. Wiley & Sons, Letchworth 1980.
- Such lamellar dispersions are used to endow properties such as consumer-preferred flow behaviour and/or turbid appearance. Many are also capable of suspending particulate solids such as detergency builders or abrasive particles. Examples of such structured liquids without suspended solids are given in US patent 4 244 840, whilst examples where solid particles ar suspended are disclosed in specifications EP-A-160 342; EP-A-38 101; EP-A-104 452 and also in the aforementioned US 4 244 840. Others are disclosed in European Patent Specification EP-A-151 884, where the lamellar droplet are called 'spherulites* .
- lamellar droplets in a liquid detergent product may be detected by means known to those skilled in the art, for example optical techniques, various rheometrical measurements. X-ray or neutron diffraction, and electron microscopy.
- the droplets consist of an onion-like configuration of concentric bi-layers of surfactant molecules, between which is trapped water or electrolyte solution (aqueous phase) .
- Systems in which such droplets are close-packed provide a very desirable combination of physical stability and solid-suspending properties with useful flow properties.
- compositions according to this patent comprise from 1-25 % of an alkali metal tripolyphosphate and from 0.1-2 % of a specific copolymer of maleic anhydride with vinylmethylether , ethylene or styrene, partially esterified with the nonionic detergent active material.
- GB 1,589,971 relates to similar compositions wherein part of the alkali metal tripolyphosphate is replaced by tetrapotassium pyrophosphate.
- the pH of the exemplified compositions is 12.5, which would generally be too low for certain purposes such as for example the industrial cleaning of fabrics, the viscosity of the products is 550 mPas or more at 30 s-1.
- Suitable deflocculating polymers are for example polymers comprising a hydrophilic backbone and one or more hydrophobic sidechains.
- the present invention relates to a liquid detergent composition
- a liquid detergent composition comprising a dispersion of lamellar droplets of detergent active materials in an aqueous continuous phase, said composition comprising a deflocculating polymer (possibly comprising a hydrophilic backbone and one or more hydrophobic side- chains) , said composition having a pH of more than 12.5.
- compositions of the invention are stable.
- stability for these systems can be defined in terms of the maximum separation compatible with most manufacturing and retail requirements. That is, the 'stable' compositions will yield no more than 10 %, preferably no more than 5 %, most preferred no more than 2% by volume phase separation as evidenced by appearance of 2 or more separate phases when stored at 25°C for 21 days from the time of preparation.
- compositions of the invention have a pH of more than 12.5, more preferred more than 13.0, especially preferred more than 13.5. These high pH values render the products of the invention especially suitable for the preparation of liquid detergent compositions intended for use in the industrial .cleaning of fabrics.
- compositions of the invention preferably have a viscosity of less than 2,500 especially less than 1,000 mPas at 21 s-1, more preferred less than 750 mPas, most preferred less than 500 mPas, especially preferred between 100 and 400 mPas at 21 s-1.
- Suitable deflocculating polymers for use in compositions of the present invention are for instance described in our copending European patent application 89201530.6 (EP 346 995) .
- the hydrophilic backbone of the polymer is predominantly linear (the main chain of the backbone constitues at least 50 %, preferably more than 75 %, most preferred more than 90% by weight of the backbone)
- suitable monomer constituents of the hydrophilic backbone are for example unsaturated C ⁇ g acids, ethers, alcohols, aldehydes, ketones or esters, sugar units, alkoxy units, maleic anhydride and saturated polyalcohols such as glycerol.
- the hydrophobic sidegroups are composed of relatively hydrophobic alkoxy groups for example butylene oxide and/or propylene oxide and/or alkyl or . alkenyl chains having from 5. to 24 carbon atoms.
- the hydrophobic groups may be connected to the hydrophilic backbone via relatively hydrophilic bonds for example a poly ethoxy linkage.
- Preferred polymers are of the formula:
- Q 2 is a molecular entity of formula (la) :
- R 1 represents -CO-O-, -0-, -O-CO-, -CH 2 -, -CO-NH- or is absent; especially it has been found that a -CO-0 linkage is more stable at high pH values than a -O-CO- link.
- R 2 represents from 1 to 50 independently selected alkyleneoxy groups preferably ethylene oxide or propylene oxide groups, or is absent , provided that when R 3 is absent and R 4 represents hydrogen or contains no more than 4 carbon atoms, then R 2 must contain an alkyleneoxy group preferably more than 5 alkyleneoxy groups with at least 3 carbon atoms;
- R ⁇ represents hydrogen or a group of formula -COOA ;
- R 6 represents hydrogen or C j .4 alkyl
- a 1 , A 2 , A 3 and A 4 are .independently selected from hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases and C ⁇ - ⁇ , or (C 2 H 4 0)tH wherein t is from 1-50, and wherein the monomer units may be in random order.
- Q 1 is a multifunctional monomer, allowing the branching of the polymer, wherein the monomers of the polymer may be connected to Q 1 in any direction, in any order, therewith possibly resulting in a branched polymer.
- Q 1 is trimethyl propane triacrylate (TMPTA) , methylene bisacrylamide or divinyl glycol.
- n is at least 1, z and v are 1; and (x + y + p + q + r) : z is from 4 : 1 to 1,000 : 1, preferably from 6 : 1 to 250 : l; in which the monomer units may be in random order; and preferably either p and q are zero, or r is zero;
- R 7 and R 8 represent -CH 3 or -H
- R 9 and R 10 represent substituent groups such as amino, amine, amide, sulphonate, sulphate, phophonate, phosphate, hydroxy, carboxyl and oxide groups, preferably they are selected from -S0 3 Na, -CO-O-C 2 H4- OS0 3 Na, -CO-0-NH-C(CH 3 ) 2 -S0 3 Na, -C0-NH 2 , -0-CO-CH 3 , -QH;
- R 3 and R 4 represent hydrogen or C-L_ 4 alkyl
- R 1 represents -C 3 H 6 -N + -(CH 3 ) 3 (Cl " ) , -C 2 H 4 -OS0 3 ⁇ (Na + ) , -SQ 3 " (Na + ),
- R 3 represents form 1 to 50 independently selected alkylene oxide groups, preferably ethylene oxide groups or is absent;
- R c represents -OH or -H; and wherein if R ,R a and R b are absent, then R c is preferably not -H.
- Other preferred polymers have the formula:
- R 2 represents -CH 2 COO ⁇ Na+ or -C 3 H 6 ON + (CH 3 ) 3 C1-
- R 3 and R 4 represent -OH, CH 2 OH, -0(C 3 H 6 0) p -H, -CH 2 -0(C 3 H 6 0) p -H or -OCH 2 COO " Na + or
- R 5 represents -OH, -NH-CO-CH 3 or -0(C 3 H 6 0) p -H
- R 6 represents -OH,-CH 2 OH, -CH 2 -OCH 3 , -0(C 3 H 6 0) p -H or -CH 2 -0-(C 3 H 6 0) p -H - p is from 1 - 10.
- polymers for use in compositions have a molecular weight (as determined as in our co-pending European patent application 346 995) of between 500 and 100,000, more preferred from 1,000 to 20,000, especially preferred from 1,500 to 10,000.
- Polymers for use in compositions of the invention may for example be prepared by using conventional aqueous polymerisation procedures, suitable methods are for example described in the above mentioned co-pending European patent application.
- the deflocculating polymer will be used at from 0.01 to 5 % by weight of the composition, more preferably from 0.1 to 3.0, especially preferred from 0.25 to 2.0 %.
- compositions of the invention also comprise detergent active materials, preferably at a level of from 1 to 70% by weight of the composition, more preferred a level of 5 to 40 % by weight, most preferred from 10 to 35 % by weight.
- the detergent-active material in general, may comprise one or more surfactants, and may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof.
- surfactants may be chosen from any of the classes, sub-classes and specific materials described in 'Surface Active Agents' Vol.I, by Schwartz & Perry, Interscience 1949 and •Surface Active Agents' Vol.II by Schwartz, Perry & Berch (Interscience 1958) , in the current edition of "McCutcheon's Emulsifiers & Detergents" published by the McCutcheon division of Manufacturing Confectioners
- salting out resistant active materials such as for example described in EP 328 177, especially the use of alkyl poly glycoside surfactants such as for example disclosed in EP 70 074. Also alkyl mono glucosides may be used.
- compositions of the present invention may contain synthetic anionic surfactant ingredients, which are preferably present in combination with the above mentioned nonionic materials.
- Suitable anionic surfactants are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
- suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C 8 -C 18 ) alcohols produced, for example, from tallow or coconut oil, sodium and potassium alkyl (Cg-C 20 ) benzene sulphonates, particularly sodium linear secondary alkyl (C 10 -C 15 ) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty.monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C 8 -C 18 ) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides
- the preferred anionic detergent compounds are sodium ( ll ⁇ 15) alkyl benzene sulphonates, sodium (C ⁇ g-C 18 ) alkyl sulphates and primary (CIQ ⁇ C 24) alkyl sodium or potassium sulphate.
- the level of the above mentioned anionic surfactant materials is from 1-15 % by weight of the composition.
- low levels of these anionic materials are used, for example less than 5 %, more preferred less than 3 % by weight of the composition, especially preferred less than 2.5 %.
- the weight ratio of the above mentioned synthetic anionic surfactant materials to the nonionic surfactant materials is less than 1:2, more preferred less than 1:3, especially preferred from 1:4 to 1:10.
- an alkali metal soap of a mono- or di-carboxylic acid especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, and fatty acids derived from castor oil, rapeseed oil, groundnut oil,coconut oil, palmkernel oil or mixtures thereof.
- the sodium or potassium soaps of these acids can be used.
- the level of soap in compositions of the invention is from 5-35 % by weight of the composition, more preferred from 10-25 %.
- compositions optionally also contain electrolyte in an amount sufficient to bring about lamellar structuring of the detergent-active material.
- the compositions contain from 1% to 60%, especially from 10 to 45% of a salting-out electrolyte.
- Salting-out electrolyte has the meaning ascribed to in specification EP-A-79 646, that is those electrolytes which have a lyotropic number of less than 9.5.
- some salting-in electrolyte (as defined in the latter specification) may also be included.
- compositions according to the present invention include detergency builder material, some or all of which may be electrolyte.
- some detergent active materials such as for example soaps, also have builder properties.
- phosphorus-containing inorganic detergency builders include the water-soluble salts, especially alkali metalpyrophosphates, orthophosphates, polyphosphates and phosphonates.
- Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates. Phosphonate sequestrant builders may also be used. For many reasons, including environmental reasons it is however preferred to minimise the amount of phosphate builders.
- alkali metal phosphate builders such as sodium tripolyphosphate is preferably less than 0.5 % by weight of the composition, more preferred less than 0.1 %, especially preferred compositions of the invention are substantially free of phosphate builder materials.
- Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilitriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids, CMOS, tartrate mono succinate, tartrate di succinate and citric acid.
- compositions of the present invention are of low viscosity (less than 500 mPas at 21 s-l) and are substantially free of suspended solid materials such as undissolved builder materials.
- level of less soluble builder materials such as sodium tripolyphosphate is less than 1 %, more preferred less than 0.5 %, more preferred less than 1 %, most preferred the builder material for use in compositions of the invention are completely water- soluble.
- the level of non-soap builder material is from 5-40 % by weight of the composition, more preferred from 5 to 25 % by weight of the composition. Especially preferred is the use of from 5-20 % by weight of the composition of a silicate builder material, preferably a metasilicate builder material.
- compositions of the invention comprise from 5 to 99 % by weight of water, more preferred from 10- 50 %, most preferred from 15 to 40 %.
- lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, fabric softeners such as clays, amines and amine oxides, lather depressants, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases, amylases and lipases (including Lipolase (Trade Mark) ex Novo) , anti-redeposition agents, germicides and colourants.
- lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids
- fabric softeners such as clays, amines and amine oxides
- lather depressants oxygen-releasing bleaching agents such as sodium perborate and sodium
- compositions of the invention may be prepared by any conventional method for the preparation of liquid detergent compositions.
- a preferred method involves the dispersing of the electrolyte ingredient together with the minor ingredients except for the temperature sensitive ingredients -if any- in water of elevated temperature, followed by the addition of the builder material, the deflocculating polymer and the detergent active material under light stirring and finally cooling the mixture and adding any temperature sensitive minor ingredients such as enzymes perfumes etc.
- the detergent compositions of the invention will be diluted with wash water to form a wash liquor for instance for use in a washing machine.
- concentration of liquid detergent composition in the wash liquor is preferably from 0.1 to 10 %, more preferred from 0.1 to 3% by weight.
- compositions were made by adding the KOH plus the silicate ingredients to water of ambient temperature under stirring followed by the addition of the deflocculating polymer.
- the detergent active materials are premixed and subsequently added to the aqueous mixture. Finally the remaining ingredients are added.
- the pH of the compositions is around 14.0.
- composition A had a viscosity of-280 mPas at 21 s- 1
- composition B of 490 mPas at 21s"-l
- compositions C-F had viscosities of about 300 mPas.
- Composition G (comparison) was unstable (more than 10 % phase separation upon storage for three weeks) , no viscosity was measured of this composition.
- Compositions A-F were stable lamellar dispersions of active materials in the aqueous base. The lamellar phase volume of these compositions was from 0.5 to 0.67.
- the pH of the compositions was 14 or more.
- compositions were tested by washing at 60 °C at a dosage of 5 g/1 in the presence of standard stained clothes AS 9. The following scores were obtained:
- Both compositions had a viscosity of 14 or more.
- compositions had a pH of 14 or more, all formulations were physically stable for more than 1 month upon storage at 37°C.
- compositions had a pH of more than 14.
- the viscosity of composition A was 504 mPas at 21 s -1
- the viscosity of composition B was 384 mPas at 21 s -1 .
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002066623A CA2066623C (en) | 1989-10-12 | 1990-10-04 | Liquid detergents containing deflocculating polymers |
AU65406/90A AU651797B2 (en) | 1989-10-12 | 1990-10-04 | Liquid detergents |
DE69016449T DE69016449T2 (en) | 1989-10-12 | 1990-10-04 | LIQUID CLEANING AGENTS. |
EP90915470A EP0495858B1 (en) | 1989-10-12 | 1990-10-04 | Liquid detergents |
FI921570A FI921570A0 (en) | 1989-10-12 | 1992-04-09 | FLYTANDE TVAETTMEDEL. |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP89202580 | 1989-10-12 | ||
EP89202580.0 | 1989-10-12 | ||
GB898927728A GB8927728D0 (en) | 1989-12-07 | 1989-12-07 | Liquid detergents |
GB8927728.9 | 1989-12-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1991005844A1 true WO1991005844A1 (en) | 1991-05-02 |
Family
ID=26121323
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1990/001667 WO1991005844A1 (en) | 1989-10-12 | 1990-10-04 | Liquid detergents |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0495858B1 (en) |
AU (1) | AU651797B2 (en) |
CA (1) | CA2066623C (en) |
DE (1) | DE69016449T2 (en) |
ES (1) | ES2067766T3 (en) |
FI (1) | FI921570A0 (en) |
NZ (1) | NZ235599A (en) |
WO (1) | WO1991005844A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5312427A (en) * | 1992-10-16 | 1994-05-17 | Shturman Cardiology Systems, Inc. | Device and method for directional rotational atherectomy |
US5314438A (en) * | 1992-12-17 | 1994-05-24 | Shturman Cardiology Systems, Inc. | Abrasive drive shaft device for rotational atherectomy |
US5356418A (en) * | 1992-10-28 | 1994-10-18 | Shturman Cardiology Systems, Inc. | Apparatus and method for rotational atherectomy |
EP0623670A2 (en) | 1993-05-07 | 1994-11-09 | ALBRIGHT & WILSON UK LIMITED | Aqueous based surfactant compositions |
WO2006127394A2 (en) | 2005-05-20 | 2006-11-30 | Rhodia Inc. | Structured surfactant compositions |
WO2009060312A3 (en) * | 2007-08-17 | 2009-11-05 | Rhodia Asia Pacific Pte, Limited | Structured soap compositions |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BR9007902A (en) * | 1989-12-07 | 1992-09-15 | Unilever Nv | DETERGENT COMPOSITION AND PROCESS FOR ITS PREPARATION |
US6090762A (en) * | 1993-05-07 | 2000-07-18 | Albright & Wilson Uk Limited | Aqueous based surfactant compositions |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3235505A (en) * | 1961-09-20 | 1966-02-15 | Monsanto Co | Detergent processes |
FR2309629A1 (en) * | 1975-04-29 | 1976-11-26 | Unilever Nv | LIQUID DETERGENT COMPOSITION AND ITS PREPARATION PROCESS |
EP0151884A2 (en) * | 1983-12-22 | 1985-08-21 | Albright & Wilson Limited | Liquid detergent compositions |
EP0301883A1 (en) * | 1987-07-31 | 1989-02-01 | Unilever Plc | Liquid detergent compositions |
EP0346995A2 (en) * | 1988-06-13 | 1989-12-20 | Unilever N.V. | Liquid detergents |
-
1990
- 1990-10-04 WO PCT/EP1990/001667 patent/WO1991005844A1/en active IP Right Grant
- 1990-10-04 AU AU65406/90A patent/AU651797B2/en not_active Expired
- 1990-10-04 EP EP90915470A patent/EP0495858B1/en not_active Expired - Lifetime
- 1990-10-04 ES ES90915470T patent/ES2067766T3/en not_active Expired - Lifetime
- 1990-10-04 CA CA002066623A patent/CA2066623C/en not_active Expired - Lifetime
- 1990-10-04 DE DE69016449T patent/DE69016449T2/en not_active Expired - Fee Related
- 1990-10-08 NZ NZ23559990A patent/NZ235599A/en unknown
-
1992
- 1992-04-09 FI FI921570A patent/FI921570A0/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3235505A (en) * | 1961-09-20 | 1966-02-15 | Monsanto Co | Detergent processes |
FR2309629A1 (en) * | 1975-04-29 | 1976-11-26 | Unilever Nv | LIQUID DETERGENT COMPOSITION AND ITS PREPARATION PROCESS |
EP0151884A2 (en) * | 1983-12-22 | 1985-08-21 | Albright & Wilson Limited | Liquid detergent compositions |
EP0301883A1 (en) * | 1987-07-31 | 1989-02-01 | Unilever Plc | Liquid detergent compositions |
EP0346995A2 (en) * | 1988-06-13 | 1989-12-20 | Unilever N.V. | Liquid detergents |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5312427A (en) * | 1992-10-16 | 1994-05-17 | Shturman Cardiology Systems, Inc. | Device and method for directional rotational atherectomy |
US5360432A (en) * | 1992-10-16 | 1994-11-01 | Shturman Cardiology Systems, Inc. | Abrasive drive shaft device for directional rotational atherectomy |
US5356418A (en) * | 1992-10-28 | 1994-10-18 | Shturman Cardiology Systems, Inc. | Apparatus and method for rotational atherectomy |
US5314438A (en) * | 1992-12-17 | 1994-05-24 | Shturman Cardiology Systems, Inc. | Abrasive drive shaft device for rotational atherectomy |
EP0623670A2 (en) | 1993-05-07 | 1994-11-09 | ALBRIGHT & WILSON UK LIMITED | Aqueous based surfactant compositions |
WO2006127394A2 (en) | 2005-05-20 | 2006-11-30 | Rhodia Inc. | Structured surfactant compositions |
EP1882029A2 (en) * | 2005-05-20 | 2008-01-30 | Rhodia Inc. | Structured surfactant compositions |
EP1882029A4 (en) * | 2005-05-20 | 2009-02-25 | Rhodia | Structured surfactant compositions |
CN101223267B (en) * | 2005-05-20 | 2011-04-13 | 罗迪亚公司 | Structured surfactant compositions |
AU2006249418B2 (en) * | 2005-05-20 | 2011-08-18 | Rhodia Inc. | Structured surfactant compositions |
WO2009060312A3 (en) * | 2007-08-17 | 2009-11-05 | Rhodia Asia Pacific Pte, Limited | Structured soap compositions |
US9090861B2 (en) | 2007-08-17 | 2015-07-28 | Rhodia Asia Pacific Ltd. | Structured soap compositions |
Also Published As
Publication number | Publication date |
---|---|
FI921570A (en) | 1992-04-09 |
FI921570A0 (en) | 1992-04-09 |
DE69016449D1 (en) | 1995-03-09 |
EP0495858B1 (en) | 1995-01-25 |
NZ235599A (en) | 1992-05-26 |
AU651797B2 (en) | 1994-08-04 |
EP0495858A1 (en) | 1992-07-29 |
DE69016449T2 (en) | 1995-06-08 |
CA2066623C (en) | 2001-03-06 |
CA2066623A1 (en) | 1991-04-13 |
AU6540690A (en) | 1991-05-16 |
ES2067766T3 (en) | 1995-04-01 |
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