EP0439316B1 - Detergent composition - Google Patents

Detergent composition Download PDF

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Publication number
EP0439316B1
EP0439316B1 EP91300456A EP91300456A EP0439316B1 EP 0439316 B1 EP0439316 B1 EP 0439316B1 EP 91300456 A EP91300456 A EP 91300456A EP 91300456 A EP91300456 A EP 91300456A EP 0439316 B1 EP0439316 B1 EP 0439316B1
Authority
EP
European Patent Office
Prior art keywords
sulphate
pas
sodium
surfactant
detergent 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.)
Revoked
Application number
EP91300456A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0439316A2 (en
EP0439316A3 (en
Inventor
Bryan Cecil Smith
Mohamed Sami Falou
Michael Hull
Dennis Giles
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0439316A2 publication Critical patent/EP0439316A2/en
Publication of EP0439316A3 publication Critical patent/EP0439316A3/en
Application granted granted Critical
Publication of EP0439316B1 publication Critical patent/EP0439316B1/en
Anticipated expiration legal-status Critical
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146Sulfuric acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Definitions

  • This invention relates to a detergent composition, in particular to a detergent composition for washing fabrics.
  • Fabric washing compositions contain, as an essential ingredient, a surfactant system whose role is to assist in the removal of soil from the fabric and its suspension in the wash liquor.
  • Suitable detergent active materials fall into a number of classes, including anionic, nonionic and cationic materials and marketed products contain materials selected from one or more of these classes.
  • anionic detergent active materials are the alkyl benzene sulphonates and these provide satisfactory results especially at high temperatures.
  • anionic surfactants There has been a desire to find alternative anionic surfactants for use in circumstances when alkyl benzene sulphonates are undesirable, but generally speaking the performance of other anionic detergent active materials is unsatisfactory.
  • PAS primary alcohol sulphates
  • PAS may be derived from both synthetic and natural alcohols containing from about 8 to 18 carbon atoms.
  • suitable alcohols which can be used in alkyl sulphate manufacture include decyl, lauryl, myristyl, palmityl and stearyl alcohols and the mixture of fatty alcohols derived by reducing the glycerides of tallow and coconut oil.
  • Natural alcohols, for example tallow or coconut alcohol give rise to straight chain, or linear, PAS.
  • Synthetic alcohols for example those produced by the Oxo process can give rise to straight or branched chain PAS.
  • GB 1 399 966 discloses a detergent composition in which the surfactant system is a mixture of sodium tallow alkyl sulphate and a nonionic detergent active material.
  • tallow PAS suffers from the disadvantage that its performance at low temperatures is poor. With the trend towards lower wash temperatures this becomes a serious disadvantage.
  • GB 1 399 966 referred to above also discloses the possibility of using the PAS derived from coconut oil, also linear. The performance of tallow PAS at low temperatures is poor.
  • EP 342 917A it is suggested that a PAS which has a wider spread of chain lengths than is derivable from either tallow or coconut alcohol can perform better than tallow PAS at low temperatures and better than coconut PAS at higher temperatures.
  • the PAS disclosed in EP 342 917A are derived from either synthetic or natural alcohols but are all linear PAS.
  • US 3 480 556 (Atlantic Richfield) discloses C1/C2 branched (preferably methyl- or ethyl- branched) PAS in a formulation for dishwashing.
  • JP 47 021 232B (Nissan) discloses a detergency negative for the replacement of C11 linear PAS with branched PAS of unspecified branching.
  • a detergent composition for washing fabrics the composition containing a surfactant system comprising an anionic surfactant the major ingredient of which is a primary alkyl sulphate with primary alkyl chain length between 10 and 20 carbon atoms, wherein more that 10% by weight of the total primary alkyl sulphate is branched, and more than 5% by weight of the total primary alkyl sulphate comprises material wherein the branches contain at least 4 carbon atoms.
  • a surfactant system comprising an anionic surfactant the major ingredient of which is a primary alkyl sulphate with primary alkyl chain length between 10 and 20 carbon atoms, wherein more that 10% by weight of the total primary alkyl sulphate is branched, and more than 5% by weight of the total primary alkyl sulphate comprises material wherein the branches contain at least 4 carbon atoms.
  • the branched PAS preferably contains between 15% and 70% by weight of branching, and most preferably between 30% and 65% of branching, based on the total weight of PAS.
  • branched PAS having a range of primary alkyl chain lengths for example between 12 and 18 carbon atoms, or between 12 and 16 carbon atoms, most preferably between 13 and 15 carbon atoms.
  • the water soluble salts of these anionic surfactants are preferred, especially the alkali metal salts thereof.
  • compositions according to the invention include from 2% to 50%, such as from 4% to 30% by weight of the surfactant system.
  • PAS materials may be included in the composition, for example linear PAS.
  • compositions of the invention also preferably contain a nonionic surfactant.
  • a nonionic surfactant has an HLB of less than 10.5, preferably less than 10.
  • Suitable nonionic surfactants which may be used are 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 (C6-C22) phenols-ethylene oxide condensates, the condensation products of aliphatic (C8-C18) 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.
  • alkylene oxide adducts of fatty materials are used as the nonionic surfactants
  • the number of alkylene oxide groups per molecule has a considerable effect upon the HLB of the nonionic surfactant.
  • the chain length and nature of the fatty material is also influential, and thus the preferred number of alkylene oxide groups per molecule depends upon the nature and chain length of the fatty material.
  • the weight ratio between the anionic surfactant and the nonionic surfactant lies between 10:1 and 1:4, most preferably between 4:1 and 1:3.
  • the surfactant system may include other surfactant materials in addition to the specified alkyl sulphate and the above mentioned nonionic materials. These other surfactant materials may be selected from other anionic detergent active materials, zwitterionic or amphoteric detergent active materials or mixture thereof.
  • any such further surfactant materials should preferably be present at a level which is no more than 25% preferably not more than 10% of the total amount of surfactant in the composition.
  • the other anionic detergent active materials may be the usual 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 sodium and potassium alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonate; 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; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-olefins (C8-C20) with sodium bisulphite and those derived from reacting paraffins with SO2 and Cl2 and then hydrolysing with a base to produce a random sulphate.
  • compositions of the invention may contain a detergency builder material, this may be any material capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the compositions with other beneficial properties such as the generation of an alkaline pH and the suspension of soil removed from the fabric.
  • the amount of builder material in a composition of this invention may in particular be from 15% to 60% by weight of the composition.
  • Examples of phosphorous-containing inorganic detergency builders when present, include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates, metaphosphates, polyphosphates and phosphonates.
  • Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, orthophosphates and hexamataphosphates.
  • non-phosphorous-containing inorganic detergency builders when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminisilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate (with or without calcite seeds), sodium and potassium bicarbonates and silicates.
  • organic detergency builders when present, include the alkali 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, nitrilotriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids and citric acid.
  • compositions according to the invention be alkaline, that is at the concentration of 1 g/l in distilled water at 25°C the pH should be at least 8, preferably at least 10.
  • the compositions may include a water-soluble alkaline salt. This salt may be a detergency builder or a non-building alkaline material.
  • ingredients which may be present in the composition include fabric softening agents such as fatty amines, fabric softening clay materials, 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 tricloroisocyanuric acid, inorganic salts such as sodium sulphate, and; usually present in very minor amounts, fluorescent agents, perfumes including deodorant perfumes, enzymes such as proteases, cellulases and amylases, lipases germicides and colourants.
  • fabric softening agents such as fatty amines, fabric softening clay materials
  • 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
  • detergent compositions generally include sodium sulphate it may sometimes be desirable to have compositions which are sulphate free or contain low levels of sulphate.
  • the detergent compositions according to the invention may be prepared by a number of different methods according to their physical form.
  • they may be prepared by dry-mixing or coagglomeration.
  • a preferred physical form is a granule incorporating a detergency builder salt and this is most conveniently manufactured by spray-drying at least part of the composition.
  • a slurry is prepared containing the heat-insensitive components of the composition such as the surfactant system, builder material and filler.
  • the slurry is spray-dried to form base powder granules with which any solid heat-sensitive ingredients may be mixed, such ingredients including bleaches and enzymes.
  • the specified nonionic surfactants can be liquidified by melting or solvent dissolution and sprayed onto the base powder granules, rather than including them in the slurry for spray-drying.
  • wash liquors were prepared in water having a hardness of 24°FH (equivalent to a free calcium ion concentration of 2.4 x 10 ⁇ 3 molar).
  • the wash liquor contained the equivalent of 6g/l of a composition containing (by weight) 1 2 3 4
  • the sodium metaborate was included as being equivalent in ionic strength to 8% sodium perborate monohydrate which would be present in practice.
  • the bleach is left out of these experiments to avoid confusion between detergency and bleaching effects in the interpretation of the results.
  • the anionic surfactants used were as set out in the following table: Example No.
  • ELFAN 280 none none (12/14/16/18) 2 SYNPROL SULPHATE 46 2.3 (13/15) 3 DOBANOL 45 SULPHATE 18 8.8 14/15 4 LIAL 145 SULPHATE 61 30 14/15 ELFAN 280 is ex Akzo, SYNPROL SULPHATE is ex ICI, DOBANOL 45 SULPHATE is the sulphate of DOBANOL 45 alcohol ex Shell, LIAL 145 SULPHATE is the sulphate of LIAL 145 alcohol ex Enichem.
  • nonionic surfactant was SYNPERONIC A7 (ex ICI) which is principally C13/C15 alcohol ethoxylated with an average of 7 moles of ethylene oxide mixed with SYNPERONIC A3 (ex ICI) which is principally C13/15 alcohol ethoxylated with an average of 3 moles of ethylene oxide.
  • This mixture has an HLB of approximately 9.
  • the wash liquors were used to wash a fabric load at liquor to cloth ratio of 50:1.
  • the load included a number of polyester monitors to which had previously been applied an amount of H3 tagged triolein. Measurement of the level of tagged triolein after washing, using standard radio-tracer techniques, gives an indication of the degree of detergency, i.e. soil removal, obtained.
  • wash time was 20 minutes with an agitation of 70 rpm. Washes were isothermal at 40°C.
  • sodium chloride was included as being equivalent in ionic strength to 8% sodium perborate monohydrate.
  • nonionic surfactant mixture had an HLB of approximately 9.
  • Wash liquors were prepared in water having a hardness of 24°FH to give a product concentration of 6g/l from a composition containing (by weight) 12 13 SYNPROL SULPHATE (PAS)1 13 ACROPOL SULPHATE (PAS)2 13 Zeolite 24 24 Sokalan CP5 4 4 Sodium carbonate 12 12 Sodium sulphate 10 10 Sodium metaborate 11 11 1 is C13/C15 sulphate with 46% branching of which 78% is methyl and 5% is butyl or higher. 2 is a sulphate with 35% branching of which 50% is methyl and 21% is butyl or higher.
  • wash liquors were used to wash a fabric load as in Example 1.
  • Examples 12 and 13 were repeated with nonionic detergent active in the formulation.
  • 14 15 SYNPROL SULPHATE (PAS) 6 - ACROPOL SULPHATE (PAS) - 6 SYNPERONIC A7 2 2 SYNPERONIC A3 6 6 ZEOLITE 24 24 SOKALAN CP5 4 4 SODIUM CARBONATE 12 12 SODIUM SULPHATE 10 10 SODIUM METABORATE 11 11
  • Example 12 was repeated using three different PASs in place of SYNPROL SULPHATE. The results obtained were as follows: Example No. Anionic % soil removal 16 C16 straight chain PAS 4.1 ⁇ 0.8 17 C15-2-methyl PAS 58.9 ⁇ 2.3 18 C12-2-butyl PAS 60.2 ⁇ 2.5

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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)
EP91300456A 1990-01-22 1991-01-21 Detergent composition Revoked EP0439316B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9001404 1990-01-22
GB909001404A GB9001404D0 (en) 1990-01-22 1990-01-22 Detergent composition

Publications (3)

Publication Number Publication Date
EP0439316A2 EP0439316A2 (en) 1991-07-31
EP0439316A3 EP0439316A3 (en) 1992-03-04
EP0439316B1 true EP0439316B1 (en) 1995-11-02

Family

ID=10669691

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91300456A Revoked EP0439316B1 (en) 1990-01-22 1991-01-21 Detergent composition

Country Status (11)

Country Link
EP (1) EP0439316B1 (ar)
JP (1) JPH04218598A (ar)
AU (1) AU631714B2 (ar)
BR (1) BR9100241A (ar)
CA (1) CA2034666C (ar)
DE (1) DE69114149T2 (ar)
ES (1) ES2079559T3 (ar)
GB (1) GB9001404D0 (ar)
IN (1) IN171886B (ar)
MX (1) MX173914B (ar)
ZA (1) ZA91453B (ar)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6281181B1 (en) 1997-10-14 2001-08-28 The Procter & Gamble Company Light-duty liquid or gel dishwashing detergent compositions comprising mid-chain branched surfactants
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
US9493726B2 (en) 2014-09-08 2016-11-15 The Procter & Gamble Company Detergent compositions containing a predominantly C15 branched alkyl alkoxylated surfactant
US9493725B2 (en) 2014-09-08 2016-11-15 The Procter & Gamble Company Detergent compositions containing a predominantly C15 alkyl branched surfactant

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9012612D0 (en) * 1990-06-06 1990-07-25 Unilever Plc Detergents compositions
CA2083331C (en) * 1991-11-26 1998-08-11 Johannes H. M. Akkermans Detergent compositions
GB9313878D0 (en) * 1993-07-05 1993-08-18 Unilever Plc Detergent composition or component containing anionic surfactant and process for its preparation
GB9324129D0 (en) * 1993-11-24 1994-01-12 Unilever Plc Detergent compositions and process for preparing them
BR9408118A (pt) * 1993-11-24 1997-08-05 Unilever Nv Composição detergente em particulas processo para a preparação da mesa e uso de um sal de ácido cítrico
GB9410678D0 (en) * 1994-05-27 1994-07-13 Unilever Plc Surfactant composition and cleaning composition comprising the same
EP0693549A1 (en) 1994-07-19 1996-01-24 The Procter & Gamble Company Solid bleach activator compositions
EG21623A (en) * 1996-04-16 2001-12-31 Procter & Gamble Mid-chain branced surfactants
EG21174A (en) * 1996-04-16 2000-12-31 Procter & Gamble Surfactant manufacture
WO1997039090A1 (en) * 1996-04-16 1997-10-23 The Procter & Gamble Company Detergent compositions containing selected mid-chain branched surfactants
MA24136A1 (fr) * 1996-04-16 1997-12-31 Procter & Gamble Fabrication d'agents de surface .
EG22088A (en) * 1996-04-16 2002-07-31 Procter & Gamble Alkoxylated sulfates
PH11997056158B1 (en) * 1996-04-16 2001-10-15 Procter & Gamble Mid-chain branched primary alkyl sulphates as surfactants
CN1093876C (zh) * 1996-04-16 2002-11-06 普罗格特-甘布尔公司 含有选择的中链支化的表面活性剂的液体清洗组合物
US6150322A (en) 1998-08-12 2000-11-21 Shell Oil Company Highly branched primary alcohol compositions and biodegradable detergents made therefrom
US6093856A (en) * 1996-11-26 2000-07-25 The Procter & Gamble Company Polyoxyalkylene surfactants
US5780694A (en) 1996-11-26 1998-07-14 Shell Oil Company Dimerized alcohol compositions and biodegradible surfactants made therefrom having cold water detergency
US5849960A (en) * 1996-11-26 1998-12-15 Shell Oil Company Highly branched primary alcohol compositions, and biodegradable detergents made therefrom
ZA989155B (en) 1997-10-10 1999-04-12 Procter & Gamble Mixed surfactant system
US6242406B1 (en) 1997-10-10 2001-06-05 The Procter & Gamble Company Mid-chain branched surfactants with cellulose derivatives
JP2001519376A (ja) 1997-10-14 2001-10-23 ザ、プロクター、エンド、ギャンブル、カンパニー 中間鎖分岐界面活性剤を含んでなるパーソナルクレンジング組成物
EP1023425A1 (en) 1997-10-14 2000-08-02 The Procter & Gamble Company Granular detergent compositions comprising mid-chain branched surfactants
DE19939991A1 (de) * 1999-08-24 2001-03-01 Henkel Kgaa Tensidzusammensetzung
US6765106B2 (en) * 2001-02-15 2004-07-20 Shell Oil Company Process for preparing a branched olefin, a method of using the branched olefin for making a surfactant, and a surfactant
EP3298119B2 (en) 2015-05-22 2022-05-25 The Procter & Gamble Company Surfactant and detergent compositions containing ethoxylated glycerine
WO2017079958A1 (en) * 2015-11-13 2017-05-18 The Procter & Gamble Company Cleaning compositions containing a branched alkyl sulfate surfactant and a short-chain nonionic surfactant
CN108350392B (zh) 2015-11-13 2022-04-15 宝洁公司 具有很少或没有烷氧基化的烷基硫酸盐的包含支链的烷基硫酸盐表面活性剂的清洁组合物
WO2017079959A1 (en) 2015-11-13 2017-05-18 The Procter & Gamble Company Detergent compositions
CA3173147A1 (en) * 2020-06-05 2021-12-09 Phillip Kyle Vinson Detergent compositions containing a branched surfactant

Family Cites Families (5)

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US3480556A (en) * 1966-09-29 1969-11-25 Atlantic Richfield Co Primary alcohol sulfate detergent compositions
GB1257679A (ar) * 1969-02-20 1971-12-22
JPS492962A (ar) * 1972-05-08 1974-01-11
JPS529006A (en) * 1975-07-14 1977-01-24 Kao Corp Liquid bleaching detergent composition
GB8811672D0 (en) * 1988-05-17 1988-06-22 Unilever Plc Detergent composition

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6281181B1 (en) 1997-10-14 2001-08-28 The Procter & Gamble Company Light-duty liquid or gel dishwashing detergent compositions comprising mid-chain branched surfactants
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
US9493726B2 (en) 2014-09-08 2016-11-15 The Procter & Gamble Company Detergent compositions containing a predominantly C15 branched alkyl alkoxylated surfactant
US9493725B2 (en) 2014-09-08 2016-11-15 The Procter & Gamble Company Detergent compositions containing a predominantly C15 alkyl branched surfactant

Also Published As

Publication number Publication date
JPH04218598A (ja) 1992-08-10
IN171886B (ar) 1993-01-30
EP0439316A2 (en) 1991-07-31
GB9001404D0 (en) 1990-03-21
DE69114149D1 (de) 1995-12-07
ZA91453B (en) 1992-09-30
EP0439316A3 (en) 1992-03-04
AU6943091A (en) 1991-07-25
AU631714B2 (en) 1992-12-03
ES2079559T3 (es) 1996-01-16
BR9100241A (pt) 1991-10-22
MX173914B (es) 1994-04-08
CA2034666A1 (en) 1991-07-23
DE69114149T2 (de) 1996-03-21
CA2034666C (en) 1996-09-03

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