EP0342917B2 - Detergent composition - Google Patents
Detergent composition Download PDFInfo
- Publication number
- EP0342917B2 EP0342917B2 EP89304919A EP89304919A EP0342917B2 EP 0342917 B2 EP0342917 B2 EP 0342917B2 EP 89304919 A EP89304919 A EP 89304919A EP 89304919 A EP89304919 A EP 89304919A EP 0342917 B2 EP0342917 B2 EP 0342917B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- chains
- surfactant
- elfan
- 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
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.
- compositions containing a C 12-14 alkyl alcohol sulphate, tallow alcohol sulphate, nonionic surfactant and detergency builder are disclosed in EP-A-0 085 448.
- 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.
- 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 adds 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 saft 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 1 0 53 12 0 Coconut ELFAN KT550 1 0 27 38 0 Coco/tallow mix SULFOPON T55 2 0 0 70 0 Tallow 1 - ex Akzo ELFAN is a Registered Trade Mark 2 - ex Henkel SULPHOPON is a Registered Trade Mark.
- 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.
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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)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB888811672A GB8811672D0 (en) | 1988-05-17 | 1988-05-17 | Detergent composition |
GB8811672 | 1988-05-17 |
Publications (4)
Publication Number | Publication Date |
---|---|
EP0342917A2 EP0342917A2 (en) | 1989-11-23 |
EP0342917A3 EP0342917A3 (en) | 1990-09-12 |
EP0342917B1 EP0342917B1 (en) | 2000-03-22 |
EP0342917B2 true EP0342917B2 (en) | 2006-10-25 |
Family
ID=10637052
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89304919A Expired - Lifetime EP0342917B2 (en) | 1988-05-17 | 1989-05-16 | Detergent composition |
Country Status (14)
Country | Link |
---|---|
EP (1) | EP0342917B2 (pt) |
JP (1) | JPH0813984B2 (pt) |
KR (1) | KR960000198B1 (pt) |
AU (1) | AU611292B2 (pt) |
BR (1) | BR8902281A (pt) |
CA (1) | CA1335488C (pt) |
DE (1) | DE68929184T3 (pt) |
ES (1) | ES2143454T5 (pt) |
GB (1) | GB8811672D0 (pt) |
IN (1) | IN168406B (pt) |
MY (1) | MY105084A (pt) |
OA (1) | OA09118A (pt) |
TR (1) | TR23981A (pt) |
ZA (1) | ZA893682B (pt) |
Families Citing this family (28)
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 |
AU7062494A (en) * | 1993-07-12 | 1995-02-13 | Procter & Gamble Company, The | Surfactant system |
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 |
GB2296919A (en) * | 1995-01-12 | 1996-07-17 | Procter & Gamble | Detergent composition |
DE19500644B4 (de) * | 1995-01-12 | 2010-09-09 | Henkel Ag & Co. Kgaa | Sprühgetrocknetes Waschmittel oder Komponente hierfür |
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 |
PH11997056158B1 (en) * | 1996-04-16 | 2001-10-15 | Procter & Gamble | Mid-chain branched primary alkyl sulphates as surfactants |
MA24136A1 (fr) * | 1996-04-16 | 1997-12-31 | Procter & Gamble | Fabrication d'agents de surface . |
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 |
US6242406B1 (en) | 1997-10-10 | 2001-06-05 | The Procter & Gamble Company | Mid-chain branched surfactants with cellulose derivatives |
ZA989155B (en) | 1997-10-10 | 1999-04-12 | Procter & Gamble | Mixed surfactant system |
EP1023425A1 (en) | 1997-10-14 | 2000-08-02 | The Procter & Gamble Company | Granular detergent compositions comprising mid-chain branched surfactants |
CN1281500A (zh) | 1997-10-14 | 2001-01-24 | 普罗格特-甘布尔公司 | 含有中链支链表面活性剂的轻垢液体或凝胶餐具洗涤剂组合物 |
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 |
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 |
CA2958319A1 (en) | 2014-09-08 | 2016-03-17 | The Procter & Gamble Company | Detergent compositions containing a branched surfactant |
WO2016040248A2 (en) | 2014-09-08 | 2016-03-17 | The Procter & Gamble Company | Detergent compositions containing a branched surfactant |
Family Cites Families (6)
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 |
FR127455A (pt) * | 1967-11-08 | |||
JPS4823643B1 (pt) * | 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 |
-
1988
- 1988-05-17 GB GB888811672A patent/GB8811672D0/en active Pending
-
1989
- 1989-05-11 CA CA000599456A patent/CA1335488C/en not_active Expired - Lifetime
- 1989-05-12 AU AU34758/89A patent/AU611292B2/en not_active Ceased
- 1989-05-16 EP EP89304919A patent/EP0342917B2/en not_active Expired - Lifetime
- 1989-05-16 OA OA59577A patent/OA09118A/xx unknown
- 1989-05-16 JP JP1122674A patent/JPH0813984B2/ja not_active Expired - Lifetime
- 1989-05-16 DE DE68929184T patent/DE68929184T3/de not_active Expired - Lifetime
- 1989-05-16 BR BR898902281A patent/BR8902281A/pt not_active IP Right Cessation
- 1989-05-16 IN IN130/BOM/89A patent/IN168406B/en unknown
- 1989-05-16 MY MYPI89000656A patent/MY105084A/en unknown
- 1989-05-16 ES ES89304919T patent/ES2143454T5/es not_active Expired - Lifetime
- 1989-05-16 KR KR1019890006516A patent/KR960000198B1/ko not_active IP Right Cessation
- 1989-05-17 TR TR89/0421A patent/TR23981A/xx unknown
- 1989-05-17 ZA ZA893682A patent/ZA893682B/xx unknown
Also Published As
Publication number | Publication date |
---|---|
AU3475889A (en) | 1989-11-23 |
EP0342917A3 (en) | 1990-09-12 |
KR960000198B1 (ko) | 1996-01-03 |
JPH0218498A (ja) | 1990-01-22 |
EP0342917A2 (en) | 1989-11-23 |
TR23981A (tr) | 1991-01-14 |
CA1335488C (en) | 1995-05-09 |
OA09118A (en) | 1991-10-31 |
ZA893682B (en) | 1991-01-30 |
DE68929184T3 (de) | 2007-02-15 |
KR890017348A (ko) | 1989-12-15 |
DE68929184T2 (de) | 2000-08-24 |
DE68929184D1 (de) | 2000-04-27 |
JPH0813984B2 (ja) | 1996-02-14 |
AU611292B2 (en) | 1991-06-06 |
GB8811672D0 (en) | 1988-06-22 |
BR8902281A (pt) | 1990-01-09 |
MY105084A (en) | 1994-08-30 |
EP0342917B1 (en) | 2000-03-22 |
ES2143454T3 (es) | 2000-05-16 |
IN168406B (pt) | 1991-03-30 |
ES2143454T5 (es) | 2007-06-16 |
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