WO1991016409A1 - Liquid detergent compositions - Google Patents
Liquid detergent compositions Download PDFInfo
- Publication number
- WO1991016409A1 WO1991016409A1 PCT/EP1991/000768 EP9100768W WO9116409A1 WO 1991016409 A1 WO1991016409 A1 WO 1991016409A1 EP 9100768 W EP9100768 W EP 9100768W WO 9116409 A1 WO9116409 A1 WO 9116409A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pas
- alkyl sulphate
- composition according
- compositions
- primary alkyl
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- 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
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
Definitions
- the present invention is concerned with aqueous liquid detergent compositions which contain a primary alkyl sulphate material. More preferably the present invention relates to aqueous liquid detergent compositions which contain a primary alkyl sulphate (PAS) material, optionally in combination with other detergent-active materials and, optionally, sufficiently dissolved electrolyte to result in a structure of lamellar droplets dispersed in a continuous aqueous phase.
- PES primary alkyl sulphate
- Primary alkyl sulphates are anionic surfactant materials, which are especially preferred for use in detergent compositions for environmental reasons.
- a problem in the formulating of liquid detergent com- positions comprising a primary alkyl sulphate as deter ⁇ gent active material is sometimes the occurrence of high viscosities and/or instability after storage.
- liquid detergent com- positions comprising a primary alkyl sulphate material and having satisfactory stability and/or viscosity properties can be obtained by ensuring that the primary alkyl sulphate is present in a non-solid phase disper ⁇ sed in the system.
- compositions of the invention are structured liquid detergent compositions. Structuring is especially preferred for providing physical stability to PAS containing compositions.
- Structured compositions according to the invention may be externally structured (the structuring is provided by materials other than the main active materials) or internally structured (the structuring is provided by main active materials, e.g. detergent active materials in combination with electrolytes) .
- compositions of the invention are internally structured, more preferably compositions of the invention comprise an internal structure of lamellar droplets of detergent active material, dispersed in the aqueous phase of the composition.
- 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 droplet systems are used to endow proper ⁇ ties 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 are suspended are disclosed in specifications EP-A-160 342; EP-A-38 101; EP-A-104 452 and also in US 4 244 840.
- 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) .
- compositions of the invention comprise as part or all of the detergent active materials a PAS material, preferably a C 8 to C 20 PAS, more preferably a C 9 to C 15 PAS, most preferably a C 10 to C 14 PAS.
- Suitable materials can for example be made by sulphating primary alcohols or are for example available under the trade names Lial 125 ex Enichem, Dobanol 25 ex Shell, Empicol LX ex Albright and Wilson and Texapon LS ex Henkel.
- the level of PAS material is preferably from 0.1 to 40% by weight of the composition, more preferred from 3 to 20%, most preferably from 5 to 15%.
- the PAS is present in a non-solid dispersed phase.
- no or only minor amounts (less than 10%, more preferably less than 5%) of the PAS are present in the form of solid crystallites, also preferably no or only minor amounts (less than 10%, more preferably less than 5%) of the PAS are present in solubilised or micellar form.
- the level of PAS in the form of crystallites can be estimated by light microscopy, the level of PAS in solubilised or micellar form can be estimated by centrifuging the composition at 750G for 16 hours and then determining the level of PAS in the clear layer.
- the PAS is predominantly (for more than 80% by weight, more preferably more than 90%, most preferably more than 95%) incorporated in a non-solid dispersed phase.
- non-solid dispersed phases are liquid crystal structures, for example lamellar droplet structures.
- the PAS is part of a lamellar droplet structure either as the sole surfactant in the droplets, or more preferably in combination with other surfactant materials.
- a non-solid dispersed phase comprising the PAS materials is present, several parameters may be varied. Preferably one or more of the following conditions are fulfilled for incorporating the PAS into a non-solid phase:
- the mole ratio of sodium to other cationic counterions such as potassium and/or ammonium in the composition is from 10 : 1 to 1 : 10, more preferably from 3 : 1 to 1 : 3, most preferably from 2 : 1 to 1 : 2;
- the PAS material is a branched alkyl sulphate, wherein at least 20%, more preferably more than 30%, most preferably more than 50% of the PAS molecules are branched.
- the composition comprises a soap as part of the surfactant system, wherein preferably the soap is predominantly unsaturated. Especially preferably the iodine value of the soap is greater than 70, more preferably greater than 75, most preferably oleate soaps are used.
- compositions of the invention contain available counterions for the PAS other than sodium, this will generally lead to less crystallisation of the PAS and therefore generally to a lower viscosity and/or increased stability.
- compositions of the invention contain mixtures of sodium and other counterions.
- the other counterions are selected from the group of monovalent cations such as potassium, lithium and ammonium, more preferably the other counterions are potassium ions.
- the mole ratio of sodium to other counterions in the total composition is preferably from 10 : 1 to 1 : 10, more preferably from 3 : 1 to 1 : 3, most preferably from 2 : 1 to 1 : 2.
- the PAS materi.als are at least partly branched, preferably at least 20% of the PAS molecules are branched, more preferably more than 30%, most preferably more than 50%. Branching is believed to be advantageous because it generally leads to less crystallisation of the PAS materials and therefore to a lower viscosity and/or increased stability.
- unsaturated soaps is believed to be advantageous, because this possibly provides a reduced formation of solid complexes of the soap and the PAS material and therefore results in a reduced viscosity and/or an increased stability.
- at least two of the three above mentioned conditions are satisfied, especially conditions (a) and (b) , most preferably all three conditions are satisfied.
- compositions of the invention are physically stable.
- physical stability for liquid systems of the invention 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 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. Especially preferred are compositions which do not yield any phase separation upon storage for 21 days at 25°C.
- compositions of the invention have a pH of between 6 and 14, more preferred from 6.5 to 13, especially preferred from 7 to 12.
- Compositions of the invention preferably have a viscosity after storage for 2 weeks of less than 2,500 Pa.s at 21 s-1, more preferred less than 2,000 mPa.s, most preferred less than 1,500 mPa.s, especially preferred between 100 and 1,000 mPa.s at 21 s-l.
- these preferred viscosities are observed after storage for at least two weeks at 25°C, but more preferably also at 15°C and most preferably also at 5°C and 0°C.
- compositions of the invention 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 50% by weight, most preferred from 10 to 40% by weight.
- At least 5% by weight of the detergent active materials are PAS materials, most preferably more than 10%, most preferably more than 20%.
- PAS constitutes less than 60% by weight of the detergent active materials, more preferred less than 50%, most preferred less than 40%.
- lamellar droplet structured liquid detergent compositions a blend of surfactants is used, the precise proportions of each component which will result in lamellar droplets will depend on the type(s) and amount(s) of the electrolytes, as is the case with conventional structured liquids.
- the detergent-active material may, in addition to the PAS material as described above, comprise one or more other surfactants, which may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof.
- Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide, either alone or with propylene oxide.
- Specific nonionic detergent compounds are alkyl (C 6 -C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
- Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long-chain tertiary phospine oxides and dialkyl sulphoxides.
- glyceryl ethers such as for example disclosed in GB 1,506,419.
- compositions of the invention may be free of nonionic surfactants, generally the level of nonionic surfactants is more than 1% by weight of the composition, preferably from 2.0 to 25.0% by weight of the composition.
- compositions of the present invention may also contain synthetic anionic surfactant ingredients other than PAS. These other synthetic anionic surfactants are preferably used in combination with the above mentioned nonionic materials.
- Suitable synthetic anionic surfactants are usually water-soluble alkali metal salts of organic 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 for example sodium and potassium alkyl (C 9 -C 2 o) 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 of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-olefins (C 8 - 20 ) with sodium bisulph
- the preferred anionic detergent compounds are sodium ( c ⁇ c i 5 ) alKyl benzene sulphonates
- the level of non-soap, non-PAS anionic surfactant materials is from 0-35% by weight of the composition, for example from 0.5 to 25%.
- 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, alk(en)yl succinates e.g. dodecyl succinate or mixtures thereof.
- the sodium or potassium soaps of these acids are preferably used.
- the level of soap in compositions of the invention is from 0-40% by weight of the composition, more preferred from 5-25%.
- the soap material is predominantly unsaturated and has a iodine value of at least 70 more preferably more than 75, most preferably the soap consists for at least 70% by weight of unsaturated soap materials such as oleate.
- the weight ratio of anionic surfactants (including the PAS material and the soap material) to the above mentioned nonionic surfactant materials is from 10 : 1 to 1 : 10, more preferred from 5 : l to 1 : 2, most preferred from 4 : 1 to 1 : 2.
- 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.
- alkyl mono glucosides may be used. Preferred levels of these materials are from 0-20% by weight, more preferably from 1 to 15%.
- the compositions optionally also contain electrolyte, preferably in an amount sufficient to bring about lamellar droplet structuring of the detergent-active material.
- the compositions contain from 1% to 60%, especially from 2 to 45% of a salting-out electrolyte. Salting-out electrolyte has the meaning ascribed to in specification EP-A-79 646.
- salting-in electrolyte (as defined in the latter specification) may also be included.
- level of salting-out electrolyte it is sometimes preferred to use relatively low amounts of salting-out electrolytes, say from 2-10% by weight. These levels are generally sufficiently high to provide structuring of the composition, and do not provide viscosity problems.
- compositions according to the present invention include detergency builder material, some or all of which may be electrolyte.
- detergency builder material some or all of which may be electrolyte.
- some detergent active materials such as for example soaps, also have builder properties.
- Examples of phosphorous-containing inorganic deter- gency 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. Sometimes it is however preferred to minimise the amount of phosphate builders.
- non-phosphorus-containing inorganic detergency builders when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous alu inosilicates. Specific examples include sodium carbonate (with or without calcite seeds) , potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites.
- organic detergency builders when present, include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates. Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilitriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylie acids, CMOS, tartrate mono succinate, tartrate di succinate and citric acid. Citric acids or salts thereof are preferred builder materials for use in compositions of the invention.
- 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.
- compositions of the present invention alternatively, or in addition to the partly dissolved polymer, yet another polymer which is substantially totally soluble in the aqueous phase.
- use of such polymers is generally described in our EP 301,883. Typical levels are from 0.5 to 4.5% by weight.
- lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, 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
- 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
- a preferred further ingredient -which is especially preferred for incorporation in internally structured compositions according to the invention- is a deflocculating polymer e.g one having a hydrophilic backbone and at least one hydrophobic side chain.
- a deflocculating polymer e.g one having a hydrophilic backbone and at least one hydrophobic side chain.
- Such polymers are described in our copending British patent applications 8924479.2, 8924478.4 and 8924477.6 and in our European patent application EP 346 995. Typical levels of these ingredients are from 0.5 to 4.5% by weight.
- 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 -if any- 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- if any-, the detergent active materials (preferably as a non-aqueous premix containing the PAS in acid-form) under stirring and thereafter cooling the mixture and adding any temperature sensitive minor ingredients such as enzymes perfumes etc.
- the deflocculating polymer -if any- may advantageously be added after the electrolyte ingredients, the builder ingredients or just before cooling.
- a particularly preferred method of making a aqueous liquid detergent composition which contains a PAS material is to use a premix of PAS with nonionic surfactants, said premix containing little or no water.
- Preferred premixes contain 10 - 50% by weight more preferably 15 - 40% most preferably 20 - 35% of PAS, and 50 - 90% more preferably 60 - 80% of nonionic surfactant.
- the water level is preferably less than 20% by weight, more preferably less than 10% most preferably the premix is substantially free of water.
- the PAS in the premix may be present in acid form, but generally the PAS will be present in salt form for example in its sodium salt form.
- the premixes can easily be handled and do not suffer from high viscosities. They can for example be supplied as a feedback raw material from as sulphonation or sulphation plant.
- 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 0.05 to 10%, more preferred from 0.1 to 3% by weight.
- compositions were made by adding the ingredients in the listed order to the water at a temperature of 40 °C.
- a coconut PAS ex A&W (as 100% ammonium salt) .
- compositions A and B This example illustrates that PAS containing compositions of satisfactory viscosity after storage at 25 °C can be obtained by using a Dobanol 91 or Lial 145 PAS (compositions A and B) . Further viscosity benefits can be obtained by using mixed counterions (Compositions C and D) or by using unsaturated soap materials (Composition E) , especially advantageous results can be obtained by using mixed counterions in combination with unsaturated soaps (Composition F) .
- compositions A-C This example illustrates that the viscosity after storage is less, when more potassium counterions are present (Compositions A-C) . From compositions D-E it follows that higher levels of PAS may cause viscosity problems after storage.
- compositions were made in the following way: A premix of PAS with nonionic surfactants was made. This premix had a water content of about 6%. Oleic acid was mixed with the premix.
- Borax and citric acid and KOH were added to water under stirring followed by the addition of the Zeolyte, polymer, antifoam, the above active mix and the remaining ingredients.
- Oleic acid could equally well be added separately after addition of the blends.
- compositions were made in the following way: The ingredients were mixed in the listed order, with PAS added as the last active, followed by 20 minutes mixing.
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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)
- Crystallography & Structural Chemistry (AREA)
- Detergent Compositions (AREA)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3508143A JPH0776356B2 (ja) | 1990-04-25 | 1991-04-22 | 液体洗剤組成物 |
DE91908596T DE69101007T2 (de) | 1990-04-25 | 1991-04-22 | Flüssige waschmittelzusammensetzungen. |
BR919106381A BR9106381A (pt) | 1990-04-25 | 1991-04-22 | Composicao detergente liquida aquosa e processo de preparacao da mesma |
AU77781/91A AU651825B2 (en) | 1990-04-25 | 1991-04-22 | Liquid detergent compositions |
KR92702638A KR950013220B1 (en) | 1990-04-25 | 1992-10-24 | Liquid detergent composition |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT90304440.2 | 1990-04-25 | ||
EP90304440 | 1990-04-25 | ||
EP90312402 | 1990-11-14 | ||
AT90312402.2 | 1990-11-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1991016409A1 true WO1991016409A1 (en) | 1991-10-31 |
Family
ID=26126442
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1991/000768 WO1991016409A1 (en) | 1990-04-25 | 1991-04-22 | Liquid detergent compositions |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP0526539B1 (zh) |
JP (1) | JPH0776356B2 (zh) |
KR (1) | KR950013220B1 (zh) |
CN (1) | CN1031890C (zh) |
AU (1) | AU651825B2 (zh) |
BR (1) | BR9106381A (zh) |
CA (1) | CA2080688C (zh) |
DE (1) | DE69101007T2 (zh) |
ES (1) | ES2062787T3 (zh) |
MY (1) | MY105315A (zh) |
WO (1) | WO1991016409A1 (zh) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994004639A1 (en) * | 1992-08-11 | 1994-03-03 | Unilever Plc | Liquid compositions |
EP0636689A2 (en) * | 1993-07-30 | 1995-02-01 | National Starch And Chemical Limited | Bleach compositions |
EP0684300A2 (en) * | 1994-05-27 | 1995-11-29 | Unilever Plc | Surfactant composition and cleaning composition comprising the same |
WO1996010625A1 (en) * | 1994-09-30 | 1996-04-11 | Unilever N.V. | Detergent composition |
US5529724A (en) * | 1995-02-06 | 1996-06-25 | Lever Brothers Company, Division Of Conopco, Inc. | Structured liquid compositions comprising selected secondary alcohol sulfates and a deflocculating polymer |
EP0874041A1 (en) * | 1997-04-22 | 1998-10-28 | The Procter & Gamble Company | Detergent compositions |
US5858950A (en) * | 1993-06-28 | 1999-01-12 | The Procter & Gamble Company | Low sudsing liquid detergent compositions |
WO1999019443A1 (en) * | 1997-10-10 | 1999-04-22 | The Procter & Gamble Company | Mid-chain branched surfactants with potassium ions |
US6194364B1 (en) | 1996-09-23 | 2001-02-27 | The Procter & Gamble Company | Liquid personal cleansing compositions which contain soluble oils and soluble synthetic surfactants |
WO2001014507A1 (de) * | 1999-08-24 | 2001-03-01 | Henkel Kommanditgesellschaft Auf Aktien | Tensidzusammensetzung |
EP1111031A1 (en) * | 1999-12-22 | 2001-06-27 | The Procter & Gamble Company | cleaning composition |
US7781390B2 (en) | 1996-11-26 | 2010-08-24 | Shell Oil Company | Highly branched primary alcohol compositions, and biodegradable detergents made therefrom |
WO2014190131A1 (en) * | 2013-05-24 | 2014-11-27 | The Procter & Gamble Company | Compact fluid laundry detergent composition |
US9267095B2 (en) | 2013-05-24 | 2016-02-23 | The Procter & Gamble Company | Low pH detergent composition comprising nonionic surfactants |
US9840681B2 (en) | 2013-05-24 | 2017-12-12 | The Procter & Gamble Company | Concentrated surfactant composition |
US10519400B2 (en) | 2013-05-24 | 2019-12-31 | The Procter & Gamble Company | Low PH detergent composition |
EP3623459A1 (en) * | 2018-09-11 | 2020-03-18 | The Procter & Gamble Company | Water-soluble unit dose article |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5723426A (en) * | 1996-02-29 | 1998-03-03 | Zhen; Yueqian | Liquid laundry detergent compositions containing surfactants and silicone emulsions |
US5759208A (en) * | 1996-02-29 | 1998-06-02 | The Procter & Gamble Company | Laundry detergent compositions containing silicone emulsions |
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FR2325639A1 (fr) * | 1974-01-16 | 1977-04-22 | Albright & Wilson | Solutions aqueuses concentrees d'alkyl-sulfates et procede d'obtention |
FR2390497A1 (fr) * | 1977-05-10 | 1978-12-08 | Colgate Palmolive Co | Composition de nettoyage liquide |
GB2021141A (en) * | 1977-12-09 | 1979-11-28 | Albright & Wilson | Concentrated aqueous surfactant compositions |
EP0120638A2 (en) * | 1983-03-11 | 1984-10-03 | Albright & Wilson Limited | Concentrated aqueous surfactant |
EP0346993A2 (en) * | 1988-06-13 | 1989-12-20 | Unilever N.V. | Liquid detergent compositions |
EP0346994A2 (en) * | 1988-06-13 | 1989-12-20 | Unilever N.V. | Liquid detergent compositions |
EP0359308A2 (en) * | 1988-09-16 | 1990-03-21 | Unilever N.V. | Liquid detergents |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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GB8334250D0 (en) * | 1983-12-22 | 1984-02-01 | Albright & Wilson | Liquid detergent compositions |
JPS6114300A (ja) * | 1984-06-29 | 1986-01-22 | ライオン株式会社 | 液体洗浄剤組成物の製造方法 |
GB8803036D0 (en) * | 1988-02-10 | 1988-03-09 | Unilever Plc | Liquid detergents |
-
1991
- 1991-04-22 AU AU77781/91A patent/AU651825B2/en not_active Ceased
- 1991-04-22 DE DE91908596T patent/DE69101007T2/de not_active Expired - Fee Related
- 1991-04-22 EP EP91908596A patent/EP0526539B1/en not_active Expired - Lifetime
- 1991-04-22 WO PCT/EP1991/000768 patent/WO1991016409A1/en active IP Right Grant
- 1991-04-22 ES ES91908596T patent/ES2062787T3/es not_active Expired - Lifetime
- 1991-04-22 CA CA002080688A patent/CA2080688C/en not_active Expired - Fee Related
- 1991-04-22 BR BR919106381A patent/BR9106381A/pt not_active IP Right Cessation
- 1991-04-22 JP JP3508143A patent/JPH0776356B2/ja not_active Expired - Fee Related
- 1991-04-23 MY MYPI91000665A patent/MY105315A/en unknown
- 1991-04-24 CN CN91103233.9A patent/CN1031890C/zh not_active Expired - Fee Related
-
1992
- 1992-10-24 KR KR92702638A patent/KR950013220B1/ko not_active IP Right Cessation
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2325639A1 (fr) * | 1974-01-16 | 1977-04-22 | Albright & Wilson | Solutions aqueuses concentrees d'alkyl-sulfates et procede d'obtention |
FR2390497A1 (fr) * | 1977-05-10 | 1978-12-08 | Colgate Palmolive Co | Composition de nettoyage liquide |
GB2021141A (en) * | 1977-12-09 | 1979-11-28 | Albright & Wilson | Concentrated aqueous surfactant compositions |
EP0120638A2 (en) * | 1983-03-11 | 1984-10-03 | Albright & Wilson Limited | Concentrated aqueous surfactant |
EP0346993A2 (en) * | 1988-06-13 | 1989-12-20 | Unilever N.V. | Liquid detergent compositions |
EP0346994A2 (en) * | 1988-06-13 | 1989-12-20 | Unilever N.V. | Liquid detergent compositions |
EP0359308A2 (en) * | 1988-09-16 | 1990-03-21 | Unilever N.V. | Liquid detergents |
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WO1994004639A1 (en) * | 1992-08-11 | 1994-03-03 | Unilever Plc | Liquid compositions |
US5858950A (en) * | 1993-06-28 | 1999-01-12 | The Procter & Gamble Company | Low sudsing liquid detergent compositions |
EP0636689A2 (en) * | 1993-07-30 | 1995-02-01 | National Starch And Chemical Limited | Bleach compositions |
EP0636689A3 (en) * | 1993-07-30 | 1996-05-01 | Nat Starch Chem Corp | Whitening compositions. |
EP0684300A2 (en) * | 1994-05-27 | 1995-11-29 | Unilever Plc | Surfactant composition and cleaning composition comprising the same |
EP0684300A3 (en) * | 1994-05-27 | 1999-08-04 | Unilever Plc | Surfactant composition and cleaning composition comprising the same |
WO1996010625A1 (en) * | 1994-09-30 | 1996-04-11 | Unilever N.V. | Detergent composition |
US5529724A (en) * | 1995-02-06 | 1996-06-25 | Lever Brothers Company, Division Of Conopco, Inc. | Structured liquid compositions comprising selected secondary alcohol sulfates and a deflocculating polymer |
WO1996024658A1 (en) * | 1995-02-06 | 1996-08-15 | Unilever N.V. | Liquid compositions |
US6194364B1 (en) | 1996-09-23 | 2001-02-27 | The Procter & Gamble Company | Liquid personal cleansing compositions which contain soluble oils and soluble synthetic surfactants |
US7781390B2 (en) | 1996-11-26 | 2010-08-24 | Shell Oil Company | Highly branched primary alcohol compositions, and biodegradable detergents made therefrom |
US7888307B2 (en) | 1996-11-26 | 2011-02-15 | Shell Oil Company | Highly branched primary alcohol compositions, and biodegradable detergents made therefrom |
US7871973B1 (en) | 1996-11-26 | 2011-01-18 | Shell Oil Company | Highly branched primary alcohol compositions, and biodegradable detergents made therefrom |
WO1998047990A1 (en) * | 1997-04-22 | 1998-10-29 | The Procter & Gamble Company | Detergent composition |
EP0874041A1 (en) * | 1997-04-22 | 1998-10-28 | The Procter & Gamble Company | Detergent compositions |
WO1999019443A1 (en) * | 1997-10-10 | 1999-04-22 | The Procter & Gamble Company | Mid-chain branched surfactants with potassium ions |
WO2001014507A1 (de) * | 1999-08-24 | 2001-03-01 | Henkel Kommanditgesellschaft Auf Aktien | Tensidzusammensetzung |
WO2001046370A1 (en) * | 1999-12-22 | 2001-06-28 | The Procter & Gamble Company | Cleaning composition |
EP1111031A1 (en) * | 1999-12-22 | 2001-06-27 | The Procter & Gamble Company | cleaning composition |
WO2014190131A1 (en) * | 2013-05-24 | 2014-11-27 | The Procter & Gamble Company | Compact fluid laundry detergent composition |
US9267095B2 (en) | 2013-05-24 | 2016-02-23 | The Procter & Gamble Company | Low pH detergent composition comprising nonionic surfactants |
US9840681B2 (en) | 2013-05-24 | 2017-12-12 | The Procter & Gamble Company | Concentrated surfactant composition |
US10519400B2 (en) | 2013-05-24 | 2019-12-31 | The Procter & Gamble Company | Low PH detergent composition |
EP3623459A1 (en) * | 2018-09-11 | 2020-03-18 | The Procter & Gamble Company | Water-soluble unit dose article |
US11692152B2 (en) | 2018-09-11 | 2023-07-04 | The Procter & Gamble Company | Water-soluble unit dose article |
Also Published As
Publication number | Publication date |
---|---|
JPH05508427A (ja) | 1993-11-25 |
DE69101007T2 (de) | 1994-05-05 |
AU651825B2 (en) | 1994-08-04 |
KR930700631A (ko) | 1993-03-15 |
EP0526539B1 (en) | 1994-01-12 |
BR9106381A (pt) | 1993-04-27 |
JPH0776356B2 (ja) | 1995-08-16 |
CN1056707A (zh) | 1991-12-04 |
AU7778191A (en) | 1991-11-11 |
EP0526539A1 (en) | 1993-02-10 |
KR950013220B1 (en) | 1995-10-26 |
CN1031890C (zh) | 1996-05-29 |
MY105315A (en) | 1994-09-30 |
DE69101007D1 (de) | 1994-02-24 |
ES2062787T3 (es) | 1994-12-16 |
CA2080688A1 (en) | 1991-10-26 |
CA2080688C (en) | 1998-11-03 |
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