EP0241073B2 - Liquid detergents containing anionic surfactant, succinate builder and fatty acid - Google Patents
Liquid detergents containing anionic surfactant, succinate builder and fatty acid Download PDFInfo
- Publication number
- EP0241073B2 EP0241073B2 EP87200529A EP87200529A EP0241073B2 EP 0241073 B2 EP0241073 B2 EP 0241073B2 EP 87200529 A EP87200529 A EP 87200529A EP 87200529 A EP87200529 A EP 87200529A EP 0241073 B2 EP0241073 B2 EP 0241073B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- alkyl
- surfactant
- fatty acid
- acid
- 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
- C11D1/02—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
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or 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
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/08—Polycarboxylic acids containing no nitrogen or sulfur
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating compositions
-
- 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
- C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
-
- 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
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- 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
-
- 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
- C11D1/75—Amino oxides
Definitions
- the present invention relates to liquid detergent compositions, preferably heavy-duty liquid detergents, containing an anionic synthetic surfactant and a builder system comprising a C12-C14 alkyl or alkenyl succinic acid or salt thereof (hereinafter referred to as a "succinate”) and a C12-C14 fatty acid or salt thereof (hereinafter referred to as a "fatty acid”) in a molar ratio (calculated on an acid basis) of succinate to fatty acid of from 1 to 2,4.
- succinate and fatty acid mature surprisingly provides a minimum of sudsing in otherwise high sudsing detergents containing a significant amount of anionic synthetic surfactant.
- Example 10 is a low-sudsing detergent containing 2% dodecyl benzene sulfonate, 6% of an 80:20 mixture of tallow:coconut soap, and 6% disodium hexadecane-1,2-dicarboxylate. This results in a molar ratio of dicarboxylate to C12-C14 fatty acid of about 2,7.
- Examples D-M contain 0-1% LAS, 5.5-6% nonenyl succinic anhydride and 1,2-3% coconut fatty acid. The lowest ratio of suctinate to fatty acid present is about 1,7.
- U.S Patent 3,776,851 discloses detergents containing 5-70% tetrahydroxysuccinic acid builders.
- Example 4 contains 20% tetrahydroxysuccinic acid and 1.8% 80:20 tallow:coconut soap as a suds suppressor.
- the present Invention relates to a liquid detergent composition comprising, by weight:
- the detergent compositions of the present invention contain anionic synthetic surfactant and succinate and fatty acid builders in a molar ratio (calculated on an acid basis) of succinate to fatty acid of from 1 to 2.4, preferably from 1 to 1.8, more preferably from 1.0 to 1.4.
- the succinate and fatty acid provide a minimum of suds in otherwise high sudsing detergents containing a signifitant amount (e.g., greater than 10% by weight) of anionic synthetic surfactant. This is particularly surprising given that one would have expected that sudsing would gradually increase with increasing levels of succinate and decrease with increasing levels of fatty acid.
- the detergent compositions herein contain from 10% to 50%, preferably from 13% to 40%, more preferably from 16% to 30%, by weight, on an acid basis, of an anionic synthetic surfactant.
- Anionic synthetic surfactants are disclosed in U.S. Patent 4,285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent 3,919,678, Laughlin et al, issued December 30, 1975.
- Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 8 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
- water-soluble salts particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 8 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
- alkyl is the alkyl portion of aryl groups.
- alkyl sulfates especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the alkylbenzene sulfonates in which the alkyl group contains from 9 to 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in United States Patents 2,220,099 and 2,477,383.
- anionic sunfactants herein are the water-soluble salts of: paraffin sulfonates containing from 8 to 24 (preferably 12 to 18) carbon atoms; alkyl glyceryl ether sulfonates, especially those ethers of C8 ⁇ 18 alcohols (e.g., those derived from tallow and coconut oil); alkyl phenol ethylene oxide ether sulfates containing from 1 to 4 units of ethylene oxide per molecule and from 8 to 12 carbon atoms in the alkyl group; and alkyl ethylene oxide ether sulfates containing 1 to 4 units of ethylene oxide per molecule and from 10 to 20 carbon atoms in the alkyl group.
- paraffin sulfonates containing from 8 to 24 (preferably 12 to 18) carbon atoms
- alkyl glyceryl ether sulfonates especially those ethers of C8 ⁇ 18 alcohols (e.g., those derived from tallow and coconut oil)
- Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane- 1-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety.
- Preferred anionic surfactants herein are the alkyl sulfates of the formula RO(C2H4O) x SO - 3 M+ wherein R is an alkyl chain having from 12 to 18 carbon atoms, saturated or unsaturated, M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x is from 0 to 4.
- R is a C12-C16 alkyl or hydroxyalkyl group, especially a C12-C15 alkyl, and x is from 0 to 3.
- anionic surfactants are the C12 ⁇ 15 alcohol sulfates containing from 0 to 3 ethylene oxide units, as described above. These anionics form hardness, preferably magnesium, surfactants that are particularly effective at lowering interfacial tension and removing greasy/oily soils.
- the detergent compositions herein also contain from 2% to 25%, preferably from 3% to 20%, more preferably from 5% to 15%, by weight of a succinate builder of the general formula R-CH(COOH)CH2(COOH), wherein R is C12-C14 alkyl or alkenyl group.
- succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts (e.g., mono-, di-, or tri-ethanolammonium).
- succinate builders include: lauryl succinate, myristyl succinate, 2-dodecenyl succinate (preferred) and 2-tetradecenyl succinate.
- compositions of the present invention further contain from 1% to 15%, preferably from 2% to 10%, more preferably from 3% to 6%, by weight of a C12-C14 fatty acid, or salt thereof.
- Suitable fatty acids can be obtained from natural sources such as plant or animal esters (e.g., palm kernel oil, palm oil and coconut oil) or synthetically prepared (e.g., via the oxidation of petroleum or by hydrogenation of carbon monoxide via the Fisher-Tropsch process).
- suitable fatty acids for use in the compositions of this invention include lauric, myristic, coconut and palm kernel fatty acid.
- Preferred are saturated coconut fatty acids, from 5:1 to 1:1 (preferably about 3:1) weight ratio mixtures of lauric and myristic acid, and palm kernel fatty acid.
- the succinate and fatty acid builders herein are calcium-selective builders, which means they preferentially control calcium ion in the wash solution, rather than magnesium or other hardness ions. It is believed that these calcium-selective builders adequately control wash water hardness, preventing excessive interactions with the anionic surfactant herein and with soils, while allowing sufficient free hardness to complex some of the anionic surfactant to produce a hardness surfactant (such as magnesium linear alkylbenzene sulfonate) that is highly effective at removing greasy and oily soils. Such hardness-surfactants pack at the oil/water interface where they lower interfacial tension and enhance removal of greasy/oily soils.
- a hardness surfactant such as magnesium linear alkylbenzene sulfonate
- the liquid detergent compositions herein can optionally contain any of the auxiliary ingredients known for use in detergent compositions. These include cosurfactants, cobuilders, neutralizing agents, buffering agents, phase regulants, solvents, hydrotropes, enzymes, enzyme stabilizing agents, polyacids, suds regulants, opacfiers, antioxidants, bactericides, dyes, perfumes, and brighteners, such as those described in U.S. Patent 4,285,841, Barrat et al, issued August 25, 1981.
- compositions herein include those described in U.S. Patent 4,561,998, Wertz et al, issued December 31, 1985, and U.S. Patent 4,507,219, Hughes, issued March 26, 1985.
- compositions herein contain from 1% to 20%, more preferably from 3% to 15%, most preferably from 5% to 10%, by weight of an ethoxylated nonionic surfactant of the formula R1(OC2H4) n OH, wherein R1 is a C10-C16 alkyl group (preferred) or a C8-C12 alkyl phenyl group, n is from 3 to 9, and said nonionic surfactants has an HLB (hydrophile-lipophile balance) of from 9 to 13, preferably from 10 to 13.
- HLB hydrophile-lipophile balance
- ethoxylated nonionic surfactants suspend hardness-surfactants in the wash water solution. They are used a a level high enough to prevent extessive precipitation of hardness-surfactants at the oil/water interface (which makes soil removal more difficult), but low enough to allow for the desired adsorption and packing at the interface.
- compositions herein can be formulated to have a pH of from 7,5 to 12, more preferably from 8 to 11.
- Certain preferred compositions herein are alkaline compositions that are particularly useful in combination with peroxyacid bleach compositions, which generally have a pH of from 2 to 5 for best bleach stability.
- Such alkaline compositions have a pH of from 9 to 12, preferably from 9,5 to 11.5, more preferably from 10 to 11. They preferably contain from 2% to 15%, more preferably from 4% to 10%, by weight of monoethanolamine.
- the combination of such an alkaline composition and peroxyacid bleach preferably delivers a wash water pH of from 7.8 to 9, preferably from 7.9 to 8.5, which is desired for good bleaching performance, a minimum of fabric yellowing, and a minimum of bleach decomposition by the monoethanolamine.
- composition was prepared by adding the components to a mixing tank in the order listed with continuous mixing.
- the above composition is preferably used in combination with the following liquid diperoxyacid bleach composition.
- the liquid bleach composition was prepared by high shear mixing of the components in an Eppenbach mixer while in an ice bath.
- the DPDA and water were added to the mixer before turning the mixer on.
- the suds suppressor was added to minimize foaming while mixing and to minimize air entrapment in the finished composition.
- the other components were added in the order listed at the indicated times after turning on the mixer.
- the pH of the composition was determined to be 3.20 at 20°C. After 4 hr. 10 min., the pH was again determined to be 3.20 at 20°C and the mixer was turned off.
- the composition was a stable suspension of the ingredients and had a viscosity of about 350 mPa ⁇ s at about 20°C.
- the DPDA had an average particle size of about 2-5 »m.
- the compositions are preferably used in a volume ratio of detergent composition to liquid bleach of about 5.5:1.
- the detergent composition is designed for a usage level of about 0,55 cups in a typical U.S. laundering process. This delivers a concentration of product in the wash water of about 0,22% by weight. Usage of about 0.1 cups (i.e., about 25 ml) of the liquid bleach delivers about 10 ppm of available oxygen to the wash water.
- the detergent composition and liquid bleach are preferably simultaneously codispersed from a dual compartment bottle at a volume ratio of detergent to bleach of about 5.5:1.
- the mixture of the succinate and fatty acid builders in the above detergent composition is preferred because it causes less fabric yellowing and measuring cup residue than an all fatty acid formula when used with the above liquid bleach.
- compositions of the invention which can be prepared by adding the components to a mixing tank in the order listed with continuous mixing, are as follows.
- Components A Sodium C14 ⁇ 15 alkyl polyethoxylate (2.25) sulfate 12.7 Sodium C13 linear alkylbenzene sulfonate 8.5 Sodium diethylenetriamine pentaacetate 0.3 Propylene glycol 8.5 Monoethanolamine 2.0 C12 ⁇ 13 alcohol polyethoxylate (6.5)* 5.0
- Ethanol 4.0 Sodium 2-dodecenyl succinate 11.0 C12 ⁇ 14 fatty acid 7.0
- Citric acid 4.0 Calcium formate 0.12 Sodium formate 0.87 TEPA-E15 ⁇ 18** 2.0 Protease enzyme (2.0 AU/g) 0.75 Amylase enzyme (375 AM. U/g) 0.16 Water and minors Balance to 100%
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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)
- Cosmetics (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT87200529T ATE69260T1 (de) | 1986-03-31 | 1987-03-23 | Fluessige reinigungsmittel, welche einen anionischen oberflaechenaktiven stoff, ein salz der bernsteinsaeure als gerueststoff und eine fettsaeure enthalten. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US84638286A | 1986-03-31 | 1986-03-31 | |
US846382 | 1986-03-31 |
Publications (4)
Publication Number | Publication Date |
---|---|
EP0241073A2 EP0241073A2 (en) | 1987-10-14 |
EP0241073A3 EP0241073A3 (en) | 1989-03-15 |
EP0241073B1 EP0241073B1 (en) | 1991-11-06 |
EP0241073B2 true EP0241073B2 (en) | 1995-03-08 |
Family
ID=25297769
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87200529A Expired - Lifetime EP0241073B2 (en) | 1986-03-31 | 1987-03-23 | Liquid detergents containing anionic surfactant, succinate builder and fatty acid |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP0241073B2 (es) |
JP (1) | JPH07113120B2 (es) |
KR (1) | KR950004927B1 (es) |
AT (1) | ATE69260T1 (es) |
AU (1) | AU612317B2 (es) |
CA (1) | CA1332137C (es) |
DE (1) | DE3774312D1 (es) |
GB (1) | GB2188645A (es) |
GR (1) | GR3003069T3 (es) |
HK (1) | HK50294A (es) |
IE (1) | IE60012B1 (es) |
MX (1) | MX169254B (es) |
NZ (1) | NZ219812A (es) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2523341B2 (ja) * | 1987-11-09 | 1996-08-07 | 花王株式会社 | 非イオン界面活性剤の強アルカリ性水溶液 |
DE3834181A1 (de) * | 1988-10-07 | 1990-04-12 | Henkel Kgaa | Fluessiges waschmittel |
EP0430330A3 (en) * | 1989-11-24 | 1991-12-18 | The Procter & Gamble Company | Suspending liquid detergent compositions |
DE19540373A1 (de) * | 1995-10-30 | 1997-05-07 | Henkel Kgaa | Reinigung mit Ultraschall und dazu geeignete Reinigungsmittel |
DE19635070A1 (de) * | 1996-08-30 | 1998-03-05 | Clariant Gmbh | Flüssige Bleichmittelsuspension |
US5972869A (en) * | 1996-12-17 | 1999-10-26 | Colgate-Palmolive Co | Mildly acidic laundry detergent composition providing improved protection of fine fabrics during washing and enhanced rinsing in hand wash |
GB9816377D0 (en) * | 1998-07-29 | 1998-09-23 | Dow Corning Sa | Foam control agents |
US6352966B1 (en) | 2000-05-19 | 2002-03-05 | Albemarle Corporation | Cleansing bars |
PL2130897T3 (pl) * | 2008-06-02 | 2012-01-31 | Procter & Gamble | Koncentrat środka powierzchniowo czynnego |
JP2011213992A (ja) * | 2010-03-15 | 2011-10-27 | Kao Corp | 液体洗浄剤組成物 |
JP2013076054A (ja) * | 2011-09-15 | 2013-04-25 | Kao Corp | 液体洗浄剤組成物 |
WO2016196555A1 (en) * | 2015-06-02 | 2016-12-08 | Stepan Company | Cold-water cleaning method |
EP3101101B1 (en) * | 2015-06-05 | 2018-01-10 | The Procter and Gamble Company | Compacted liquid laundry detergent composition |
WO2021108307A1 (en) | 2019-11-27 | 2021-06-03 | The Procter & Gamble Company | Improved alkylbenzenesulfonate surfactants |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2220099A (en) | 1934-01-10 | 1940-11-05 | Gen Aniline & Flim Corp | Sulphonic acids |
US2477383A (en) | 1946-12-26 | 1949-07-26 | California Research Corp | Sulfonated detergent and its method of preparation |
GB1215498A (en) | 1967-06-13 | 1970-12-09 | Unilever Ltd | Succinic acid derivatives and their use in detergent compositions |
DK130417A (es) | 1968-08-08 | |||
GB1380390A (en) * | 1970-12-16 | 1975-01-15 | Unilever Ltd | Detergent compositions |
US3776851A (en) | 1972-09-25 | 1973-12-04 | Colgate Palmolive Co | Detergents containing tetrahydroxysuccinic acid and salts thereof |
US3919678A (en) | 1974-04-01 | 1975-11-11 | Telic Corp | Magnetic field generation apparatus |
DE3063434D1 (en) | 1979-05-16 | 1983-07-07 | Procter & Gamble Europ | Highly concentrated fatty acid containing liquid detergent compositions |
DE3062842D1 (en) | 1979-11-09 | 1983-05-26 | Unilever Nv | Liquid detergent composition |
US4561998A (en) | 1982-05-24 | 1985-12-31 | The Procter & Gamble Company | Near-neutral pH detergents containing anionic surfactant, cosurfactant and fatty acid |
US4507219A (en) | 1983-08-12 | 1985-03-26 | The Proctor & Gamble Company | Stable liquid detergent compositions |
GB2179669B (en) * | 1985-08-15 | 1988-12-29 | Procter & Gamble | Built liquid detergents |
JP3470354B2 (ja) * | 1993-07-21 | 2003-11-25 | 大同特殊鋼株式会社 | 加熱走行部材の寸法測定装置 |
-
1987
- 1987-03-23 DE DE8787200529T patent/DE3774312D1/de not_active Expired - Fee Related
- 1987-03-23 EP EP87200529A patent/EP0241073B2/en not_active Expired - Lifetime
- 1987-03-23 AT AT87200529T patent/ATE69260T1/de not_active IP Right Cessation
- 1987-03-30 GB GB08707572A patent/GB2188645A/en not_active Withdrawn
- 1987-03-30 CA CA000533361A patent/CA1332137C/en not_active Expired - Fee Related
- 1987-03-30 AU AU70781/87A patent/AU612317B2/en not_active Ceased
- 1987-03-30 IE IE81587A patent/IE60012B1/en not_active IP Right Cessation
- 1987-03-30 NZ NZ219812A patent/NZ219812A/xx unknown
- 1987-03-30 KR KR1019870002922A patent/KR950004927B1/ko active IP Right Grant
- 1987-03-31 MX MX005811A patent/MX169254B/es unknown
- 1987-03-31 JP JP62076555A patent/JPH07113120B2/ja not_active Expired - Lifetime
-
1991
- 1991-11-07 GR GR91401150T patent/GR3003069T3/el unknown
-
1994
- 1994-05-19 HK HK50294A patent/HK50294A/xx not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
KR950004927B1 (ko) | 1995-05-16 |
MX169254B (es) | 1993-06-28 |
JPS63397A (ja) | 1988-01-05 |
EP0241073A2 (en) | 1987-10-14 |
AU612317B2 (en) | 1991-07-11 |
GR3003069T3 (en) | 1993-02-17 |
IE60012B1 (en) | 1994-05-18 |
EP0241073B1 (en) | 1991-11-06 |
HK50294A (en) | 1994-05-27 |
EP0241073A3 (en) | 1989-03-15 |
CA1332137C (en) | 1994-09-27 |
AU7078187A (en) | 1987-10-08 |
GB8707572D0 (en) | 1987-05-07 |
IE870815L (en) | 1987-09-30 |
JPH07113120B2 (ja) | 1995-12-06 |
GB2188645A (en) | 1987-10-07 |
NZ219812A (en) | 1989-06-28 |
ATE69260T1 (de) | 1991-11-15 |
DE3774312D1 (de) | 1991-12-12 |
KR870009007A (ko) | 1987-10-22 |
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