EP0342917B1 - Detergenszusammensetzung - Google Patents

Detergenszusammensetzung Download PDF

Info

Publication number
EP0342917B1
EP0342917B1 EP89304919A EP89304919A EP0342917B1 EP 0342917 B1 EP0342917 B1 EP 0342917B1 EP 89304919 A EP89304919 A EP 89304919A EP 89304919 A EP89304919 A EP 89304919A EP 0342917 B1 EP0342917 B1 EP 0342917B1
Authority
EP
European Patent Office
Prior art keywords
alkyl
chains
weight
surfactant
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.)
Expired - Lifetime
Application number
EP89304919A
Other languages
English (en)
French (fr)
Other versions
EP0342917A3 (de
EP0342917A2 (de
EP0342917B2 (de
Inventor
Michael Hull
Dennis Giles
Reginald Vear Scowen
Bryan Cecil Smith
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
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=10637052&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0342917(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0342917A2 publication Critical patent/EP0342917A2/de
Publication of EP0342917A3 publication Critical patent/EP0342917A3/de
Application granted granted Critical
Publication of EP0342917B1 publication Critical patent/EP0342917B1/de
Publication of EP0342917B2 publication Critical patent/EP0342917B2/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic 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
    • 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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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

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.
  • anionic surfactants are the primary alcohol sulphates (PAS) otherwise known as alkyl sulphates.
  • PAS primary alcohol sulphates
  • the PAS derived from tallow fat has been recommended for use.
  • GB-A-1399966 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.
  • PAS's have been proposed in the art.
  • GB-A-1399966 also discloses the possibility of using the PAS derived from coconut oil.
  • coconut PAS can perform better than tallow PAS at low temperatures, but under such circumstances its performance at higher temperatures is significantly poorer than the tallow derived material.
  • the replacement of tallow PAS by coconut PAS is not an attractive option.
  • An objective of the present invention is to provide a surfactant system based on PAS and which is able to give a good combination of performance levels at a range of temperatures.
  • the spread of chain lengths may be characterised by the presence of alkyl chains of twelve and eighteen carbon atoms in amounts or a ratio which does not occur when the alkyl chains come from a single natural source.
  • composition for washing fabrics, which composition contains
  • the percentages of C 12 and C 18 alkyl are typically 53% and 12%, amounting to a ratio over 3:1 (and indeed over 4:1) while in a tallow feedstock the alkyl chains can be 70% C 18 alkyl with C 12 almost entirely absent.
  • compositions of this invention preferably at least 15% by weight of the alkyl chains present in the alkyl sulphate are C 12 while the C 18 alkyl chains are at least 25% by weight of the alkyl chains in the alkyl sulphate.
  • the alkyl sulphate of mixed chain lengths is at least 80% of the anionic surfactant present. Of course it may constitute the whole of the anionic surfactant present.
  • Alkyl sulphates are also known as sulphated fatty alcohol salts.
  • the alkyl sulphates which are particularly envisaged for this invention, are normally produced from natural alcohols, such as those produced by reducing the glycerides of naturally occurring fats and oils.
  • Natural alcohols rich in C 12 alkyl chains include those derived from babassu, coconut, ouri-coury and palm kernel while alcohols rich in C 18 chains include those derived from beef tallow, kapok, olive, peanut, sesame, tall oil and teaseed.
  • Natural alcohols may be hardened, in which case unsaturated alkyl chains will be absent.
  • PAS from unhardened materials such as unhardened tallow alcohol, may be employed so that unsaturated chains are present.
  • C 18 unsaturated chains will normally be oleyl but further unsaturation may be present e.g. linoleic chains may be present.
  • alkyl and unsaturated chains may be present. These chains will normally have between 8 and 18 carbon atoms. Materials which contain more than a small amount, i.e. more than 2%, of chains containing more than 18 carbon atoms or less than 8 carbon atoms are less preferred.
  • PAS derived from a mixture of tallow and coconut in the weight ratio of from 3:1 to 1:3, most preferably from 2:1 to 1:2.
  • water-soluble salts of these anionic surfactants specifically the alkali metal (sodium or potassium) salts thereof.
  • compositions according to the invention contain from 4% to 30% by weight of the surfactant system.
  • compositions of the invention also contain a nonionic surfactant.
  • a nonionic surfactant has an HLB of less than 10.5, although there is benefit even if the nonionic surfactant has an HLB greater than this.
  • 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 (C 6 - c 22 ) phenols-ethylene oxide condensates, the condensation products of aliphatic (C 8 - 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.
  • 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 1:2.
  • 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 mixtures thereof.
  • the level of any such further surfactant materials will not exceed 50% of the composition. It is preferably not more than 40% of the total amount of surfactant in the composition, and may perhaps be not over 5% by weight of the whole composition.
  • the other anionic detergent active materials which may be present may be the usual water-soluble alkali metal salts of organic sulphonates having alkyl radicals containing from 8 to 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 (C 9 - 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 to C 18 ) fatty alcohol-ethylene oxide reaction products; 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 (C 8 -C 20 ) with sodium bisulphite and those derived from reacting paraffin
  • compositions of the invention also 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 phosphorus-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 hexametaphosphates.
  • non-phosphorus-containing inorganic detergency builders when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates. 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, mellitic 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 trichloroisocyanuric 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, amylases and lipase, 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 perbor
  • 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 salt.
  • 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 liquified 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 25° FH (equivalent to a free calcium ion concentration of 2.5 x 10 -3 molar).
  • the wash liquor contained the equivalent of 6 g/l of a composition containing (by weight): Specified anionic surfactant 9% Specified nonionic surfactant 4% Sodium tripolyphosphate 23% Sodium carbonate 6% Sodium alkaline silicate 5.5% Sodium sulphate 30.8% Sodium chloride 2.93% Water balance
  • the sodium chloride was included as being equivalent in ionic strength to 5% sodium perborate monohydrate which would be present in practice.
  • the bleach is left out of these experiments in order to avoid confusion between detergency and bleaching effect in the interpretation of the results.
  • 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 C 14 tagged triolein. Measurement of the level of tagged triolein after washing, using standard radiotracer 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 temperatures as specified below.
  • the anionic surfactants used were as set out in the following table: Chain Length Distribution (%) Surfactant ⁇ C 8 C 12 C 18 ⁇ C 18 Origin ELFAN 280 0 53 12 0 Coconut ELFAN KT550 0 27 38 0 Coco/tallow mix SULFOPON T55 0 0 70 0 Tallow
  • nonionic surfactant was SYNPERONIC A7 (ex ICI) which is principally C 13 /C 15 alcohol ethoxylated with an average of 7 moles of ethylene oxide. This nonionic surfactant has an HLB of 11.7. SYNPERONIC is a Registered Trade Mark
  • nonionic surfactant was a mixture of 1 part SYNPERONIC A7 with 3 parts of SYNPERONIC A3, which is a similar material in which the alcohol is ethoxylated with an average of 3 moles ethylene oxide per molecule.
  • This nonionic surfactant mixture has an HLB of approximately 9.0.
  • Examples 1 to 3 were repeated but the levels and proportions of the surfactants were varied. The variations in composition and the results are set out in the list below in which "A3" and "A7” denote SYNPERONIC A3 and SYNPERONIC A7.
  • the wash temperature was 30°C in each instance, as with Examples 1 to 3.
  • wash liquors were prepared in water of 30°FH (equivalent to a free calcium ion concentration of 3.0 x 10 -3 molar).
  • the wash liquor contained the equivalent of 6g/l of a composition containing (by weight): Specified surfactant 13% Zeolite 24% Polyacrylate 4% Sodium sulphate 20.6% Sodium carbonate 12% Water balance
  • Each wash liquor composition was employed to launder several test cloths in a Tergotometer, in a heat-up cycle to 60°C. After laundering the increase in reflectance of the test cloths was measured.
  • test cloths employed had various stains as follows:
  • the specified surfactant(s) consisted of some or all of hardened tallow alcohol sulphate (TAS) and/or coconut alcohol sulphate (CAS) and mixtures with nonionic surfactant (NI) which was SYNPERONIC A3, i.e. C 13 /C 15 fatty alcohol ethoxylated with an average of 3 moles of ethylene oxide per molecule.
  • TAS hardened tallow alcohol sulphate
  • CAS coconut alcohol sulphate
  • NI nonionic surfactant
  • wash liquors were prepared in water having a hardness of 25° FH.
  • the wash liquors contained the equivalent of 6 g/l of a composition containing (by weight): Ingredient % by weight Specified anionic 9 SYNPERONIC A7 1 SYNPERONIC A3 3 Zeolite 26.6 Sodium sulphate 19.5 Sodium carbonate 14.0 Sodium silicate 1.3 Sodium chloride 3.0 Moisture balance to 100%
  • Example 32 the anionic surfactant was ELFAN KT550.
  • Example 33 the anionic surfactant was PAS derived from myristyl alcohol (i.e. C 14 alcohol). The wash liquors were tested as in Examples 1 to 6, although a different grade of polyester was used for the test cloths.
  • This composition was used to wash a variety of stained fabrics under a variety of conditions, results being assessed by measuring the reflectance of treated monitors.
  • the anionic surfactants used were tallow PAS, coconut PAS and a 50/50 mixture of the two.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (5)

  1. Eine Detergenszuammensetzung für das Waschen von Geweben, welche Zusammensetzung enthält
    (i) von 4 bis 30 Gewichtsprozent eines Tensid-Systems, enthaltend ein anionisches Tensid und auch ein nichtionisches Tensid, worin das Gewichtsverhältnis zwischen dem anionischen Tensid und dem nichtionischen Tensid zwischen 10 : 1 und 1 : 2 liegt, und
    (ii) Waschkraftbuilder
    dadurch gekennzeichnet, daß das anionische Tensid zumindest 80 Gewichtsprozent Alkylsulfat von gemischter Alkylkettenlänge derart enthält, daß zumindest 10 Gewichtsprozent der in dem Alkylsulfat vorhandenen Alkylketten C12-Ketten sind, zumindest 20 Gewichtsprozent der erwähnten Alkylketten C18-Ketten sind und das Gewichtsverhältnis von C12-Alkylketten zu C18-Alkylketten in dem Bereich von 9 : 4 bis 1 : 6 ist.
  2. Eine Zusammensetzung nach Anspruch 1, worin das Gewichtsverhältnis von C12- zu C18-Alkylketten in dem Bereich von 2 : 1 bis 1 : 5 liegt.
  3. Eine Zusammensetzung nach Anspruch 1 oder Anspruch 2, worin zumindest 15 Gewichtsprozent der Alkylketten C12-Ketten sind, während zumindest 25% C18-Ketten sind.
  4. Eine Detergenszusammensetzung nach Anspruch 1, in welcher das Alkylsulfat eine Mischung von Talgalkylsulfat und Kokosnußalkylsulfat in einem Gewichtsverhältnis von 3 : 1 bis 1 : 3, bevorzugterweise von 2 : 1 bis 1 : 2, ist.
  5. Eine Detergenszusammensetzung nach irgendeinem der vorstehenden Ansprüche, in welcher das nichtioniche Tensid einen HLB-Wert von weniger als 10,5 hat.
EP89304919A 1988-05-17 1989-05-16 Detergenszusammensetzung Expired - Lifetime EP0342917B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8811672 1988-05-17
GB888811672A GB8811672D0 (en) 1988-05-17 1988-05-17 Detergent composition

Publications (4)

Publication Number Publication Date
EP0342917A2 EP0342917A2 (de) 1989-11-23
EP0342917A3 EP0342917A3 (de) 1990-09-12
EP0342917B1 true EP0342917B1 (de) 2000-03-22
EP0342917B2 EP0342917B2 (de) 2006-10-25

Family

ID=10637052

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89304919A Expired - Lifetime EP0342917B2 (de) 1988-05-17 1989-05-16 Detergenszusammensetzung

Country Status (14)

Country Link
EP (1) EP0342917B2 (de)
JP (1) JPH0813984B2 (de)
KR (1) KR960000198B1 (de)
AU (1) AU611292B2 (de)
BR (1) BR8902281A (de)
CA (1) CA1335488C (de)
DE (1) DE68929184T3 (de)
ES (1) ES2143454T5 (de)
GB (1) GB8811672D0 (de)
IN (1) IN168406B (de)
MY (1) MY105084A (de)
OA (1) OA09118A (de)
TR (1) TR23981A (de)
ZA (1) ZA893682B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9001404D0 (en) * 1990-01-22 1990-03-21 Unilever Plc Detergent composition
GB9012613D0 (en) * 1990-06-06 1990-07-25 Unilever Plc Soap powder compositions
KR0170424B1 (ko) * 1990-07-05 1999-01-15 호르스트 헤를레,요한 글라슬 세제 및 청정제용 표면 활성제 과립의 제조방법
DE4024657A1 (de) * 1990-08-03 1992-02-06 Henkel Kgaa Verfahren zur trocknung und granulierung waessriger pasten waschaktiver wirkstoffgemische
DE4038476A1 (de) * 1990-12-03 1992-06-04 Henkel Kgaa Feste waschmittel
DE4241473A1 (de) * 1992-12-09 1994-06-16 Henkel Kgaa Wasserlösliche Tensidgemische für Flüssigwaschmittel
GB9313878D0 (en) * 1993-07-05 1993-08-18 Unilever Plc Detergent composition or component containing anionic surfactant and process for its preparation
EP0708633A4 (de) * 1993-07-12 1999-04-07 Procter & Gamble Tensichsystem
DE4403323A1 (de) * 1993-09-23 1995-08-10 Henkel Kgaa Extrudierte Wasch- oder Reinigungsmittel mit verbesserten Löseeigenschaften
DE4415369C1 (de) * 1994-05-02 1995-08-31 Henkel Kgaa Heterogene Tensidgranulate
DE4432365A1 (de) * 1994-09-12 1996-03-14 Henkel Kgaa Wasserfreie Tensidgemische
DE19500644B4 (de) * 1995-01-12 2010-09-09 Henkel Ag & Co. Kgaa Sprühgetrocknetes Waschmittel oder Komponente hierfür
GB2296919A (en) * 1995-01-12 1996-07-17 Procter & Gamble Detergent composition
MA24136A1 (fr) * 1996-04-16 1997-12-31 Procter & Gamble Fabrication d'agents de surface .
ES2185936T3 (es) * 1996-04-16 2003-05-01 Procter & Gamble Composiciones liquidas de limpieza que contienen tensioactivos ramificados en mitad de la cadena seleccionados.
PH11997056158B1 (en) * 1996-04-16 2001-10-15 Procter & Gamble Mid-chain branched primary alkyl sulphates as surfactants
EG21174A (en) * 1996-04-16 2000-12-31 Procter & Gamble Surfactant manufacture
EG22088A (en) * 1996-04-16 2002-07-31 Procter & Gamble Alkoxylated sulfates
WO1998018889A2 (de) * 1996-10-30 1998-05-07 Henkel Kommanditgesellschaft Auf Aktien Wasserfreie tensidgemische
US6093856A (en) * 1996-11-26 2000-07-25 The Procter & Gamble Company Polyoxyalkylene surfactants
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
EP1023426B1 (de) 1997-10-14 2005-02-09 The Procter & Gamble Company flüssige oder gelförmige spülmittelzusammensetzungen enthaltend in der mitte der kette verzweigte tenside
EP1023042A1 (de) 1997-10-14 2000-08-02 The Procter & Gamble Company Tensiden mit verzweigungen in der kettenmitte enthaltende körperreinigungszusammensetzung
ZA989342B (en) 1997-10-14 1999-07-01 Procter & Gamble Granular detergent compositions comprising mid-chain branched surfactants.
JP5000991B2 (ja) * 2006-11-28 2012-08-15 三洋化成工業株式会社 エレクトロニクス材料用洗浄剤

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3598747A (en) * 1963-05-01 1971-08-10 Ethyl Corp Alcohol mixtures adapted for use in making detergent sulfates
FR96188E (fr) * 1967-11-08 1972-05-19 Helene Curtis France Nouvelle composition détergente solide.
JPS4823643B1 (de) * 1968-04-13 1973-07-16
PH10800A (en) * 1972-10-31 1977-09-07 Procter & Gamble Detergent composition
JPS62240397A (ja) * 1986-04-11 1987-10-21 花王株式会社 洗浄剤組成物
JPS62273300A (ja) * 1986-05-21 1987-11-27 花王株式会社 洗浄剤組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
ES2143454T3 (es) 2000-05-16
MY105084A (en) 1994-08-30
TR23981A (tr) 1991-01-14
IN168406B (de) 1991-03-30
CA1335488C (en) 1995-05-09
AU611292B2 (en) 1991-06-06
EP0342917A3 (de) 1990-09-12
ES2143454T5 (es) 2007-06-16
EP0342917A2 (de) 1989-11-23
DE68929184T3 (de) 2007-02-15
DE68929184D1 (de) 2000-04-27
EP0342917B2 (de) 2006-10-25
BR8902281A (pt) 1990-01-09
KR960000198B1 (ko) 1996-01-03
JPH0813984B2 (ja) 1996-02-14
DE68929184T2 (de) 2000-08-24
GB8811672D0 (en) 1988-06-22
AU3475889A (en) 1989-11-23
ZA893682B (en) 1991-01-30
OA09118A (en) 1991-10-31
JPH0218498A (ja) 1990-01-22
KR890017348A (ko) 1989-12-15

Similar Documents

Publication Publication Date Title
EP0342917B1 (de) Detergenszusammensetzung
CA2034666C (en) Detergent composition
CA1312419C (en) Composition for softening fabrics
JPH0559394A (ja) 洗剤組成物
AU624577B2 (en) Detergent compositions
JPH0415840B2 (de)
GB2236538A (en) Detergent compositions
CA1122094A (en) Built liquid detergent composition
CA1334919C (en) Liquid detergent compositions
AU619266B2 (en) Detergent composition
US5180515A (en) Granular detergent compositions having low levels of potassium salt to provide improved solubility
CA1318471C (en) Composition for softening fabrics
EP0423968A1 (de) Waschmittelzusammensetzung
AU621374B2 (en) Liquid detergent compositions
EP0330337A1 (de) Waschmittelzusammensetzung
US4881940A (en) Granulated magnesium monoperoxyphthalate coated with fatty acid for prevention of dye damage of bleach sensitive fabrics
EP0328361A2 (de) Reinigungsmittel
CA2022321C (en) Granular laundry detergent compositions having improved solubility
JPH0753999A (ja) 高嵩密度粒状洗剤組成物
GB2265908A (en) Fabric washing detergents.
JPH09501977A (ja) 噴霧乾燥洗浄もしくは清浄組成物またはその成分
EP0306493A1 (de) Waschmittelzusammensetzung
GB2221694A (en) Detergent composition
GB1599560A (en) Detergency booster

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): CH DE ES FR GB IT LI NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): CH DE ES FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19900731

RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNILEVER PLC

Owner name: UNILEVER N.V.

17Q First examination report despatched

Effective date: 19930506

APAA Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOS REFN

APAB Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPE

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE ES FR GB IT LI NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000322

Ref country code: SE

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 20000322

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20000322

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000322

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 68929184

Country of ref document: DE

Date of ref document: 20000427

ITF It: translation for a ep patent filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2143454

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 20001220

Opponent name: HENKEL KGAA

Effective date: 20001215

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: HENKEL KGAA * 20001220 THE PROCTER & GAMBLE COMPAN

Effective date: 20001215

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20061025

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): CH DE ES FR GB IT LI NL SE

ET3 Fr: translation filed ** decision concerning opposition
REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Date of ref document: 20070123

Kind code of ref document: T5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20080526

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20080630

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20080528

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20080529

Year of fee payment: 20

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20090515

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20090518

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20090518

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20090515

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20080519

Year of fee payment: 20