EP0200263B2 - Homogeneous concentrated liquid detergent compositions containing ternary surfactant system - Google Patents
Homogeneous concentrated liquid detergent compositions containing ternary surfactant system Download PDFInfo
- Publication number
- EP0200263B2 EP0200263B2 EP86200690A EP86200690A EP0200263B2 EP 0200263 B2 EP0200263 B2 EP 0200263B2 EP 86200690 A EP86200690 A EP 86200690A EP 86200690 A EP86200690 A EP 86200690A EP 0200263 B2 EP0200263 B2 EP 0200263B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- weight
- acid
- accordance
- surfactant system
- 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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
-
- 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
- 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
-
- 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
- C11D1/143—Sulfonic 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
- C11D1/12—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
- C11D1/12—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
- C11D1/66—Non-ionic 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
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- compositions herein are characterized by the utilization of a ternary surfactant system and contain less than 50% water.
- the ternary surfactant system contains a majority of an anionic surfactant which is represented by a binary mixture of an alkyl(aryl) sulfonated surface-active agent and an alk(en)yl succinate in a weight ratio of sulfonate to succinate in the range of from 3:1 to 1:4, and a nonionic surfactant component.
- the inventive compositions exhibit excellent and highly desirable detergency, they can be manufactured easily and furthermore display excellent stability during prolonged periods of storage.
- Homogeneous concentrated heavy duty liquid detergents are well-known in the art and have found commercial application.
- the like compositions can comprise a ternary active system, namely: synthetic anionic sulfonates or sulfates in combination with nonionic ethoxylates and soaps.
- Such prior art compositions are difficultly processable, particularly depending upon alkalinity.
- the prior art concentrated liquid detergents are in that respect vulnerable to phase separation under neutral to mildly alkaline conditions.
- U.S. Patent 4.285.841 discloses builder-free concentrated homogeneous liquid compositions containing a combination of anionic synthetic surface-active compounds, nonionic surface-active compounds and fatty acids.
- the manufacture of the like compositions containing less than 50% water requires the utilization of substantial amounts of solvents and/or compatibilizing agents and even under those circumstances, remain of borderline stability having particularly regard to levels and type of nonionics, fatty acids, particularly saturated species, and optional electrolytes such as low levels of organic builders.
- the succinate ingredient is well-known in the detergent art and has been disclosed in combination with all kinds of detergent executions, mostly granular compositions. While, the like succinates have been recommended for utilization in liquid compositions, it is well-known that substantial formulation difficulties will originate from their use in such compositions, particularly in presence of low levels of water and substantial amounts of nonionics.
- German Patent 17 68 851 relates to the utilization of specific succinate derivatives as suds boosters. These compositions contain solely anionic surface-active agents and furthermore substantial levels of water in combination with additional hydrotropes.
- German Patent 19 56 671 discloses binary liquid preparations containing substantial levels of alk(en)yl succinates in combination with nonionic surface-active agents.
- German Patent Application 30 13 904 relates to alkaline cleaning agent compositions, solid or liquid, containing a partially neutralized succinic acid derivative which seems to be utilized for its foaming properties.
- EP-A-0 017 951 relates to the utilization of alk(en)yl succinic acid salts or monoesters thereof with polyvalent alcohols for hydrotroping perfumes in liquid detergent compositions containing high levels of electrolytes.
- EP-A-0 028 850 relates to the utilization of monoalkyl or alkenyl C7 ⁇ 12, preferably C8 and C9 succinates, as hydrotropes in nonionic-based liquid detergent compositions.
- GB-A-2 049 723 discloses the use of partially neutralized alkyl succinates in replacement for conventional surfactants, in liquid detergent compositions.
- compositions herein are characterized by the presence of:
- the invention herein can be embodied by highly concentrated homogeneous liquid detergent compositions containing a ternary surfactant system and having a pH in the neutral to mildly alkaline range.
- the anionic surfactant component amounts to from 50% to 90% of the ternary surfactant system and is represented by a binary combination of:
- the anionic sulfonate surfactant can be represented by all alkyl(aryl) sulfonated surface-active agents which are known to be suitable for use in liquid detergent compositions and have been used in fact, extensively, in commercial detergent executions.
- anionic synthetic sulfonates can be represented by the general formula R1SO3M wherein R1 represents a hydrocarbon moiety selected from the group consisting of straight or branched alkyl radicals containing from 8 to 24 carbon atoms and alkyl phenyl radicals containing from 10 to 18 carbon atoms in the alkyl group.
- M is a salt forming cation which typically is selected from the group consisting of sodium, potassium, magnesium, ammonium, monoalkanolammonium, dialkanolammonium, trialkanolammonium and mixtures thereof.
- a preferred synthetic anionic sulfonate surfactant is a water-soluble salt of an alkylbenzene sulfonic acid containing from 10 to 18 carbon atoms in the alkyl group, the most preferred species for use herein having from C12 to C16 carbon atoms in the alkyl chain.
- the alk(en)yl succinate has the formula referred to hereinbefore wherein R1 is either a saturated or unsaturated radical having from 10 to 20 carbon atoms, preferably an unsaturated derivative having from 12 to 16 carbon atoms in the alkenyl moiety.
- R2 can be hydrogen or C1-C4 alkyl, although hydrogen is preferred.
- succinate and “succinic acid” are used interchangeably.
- Suitable succinic acid salts include the sodium, potassium, lithium, ammonium, mono-, di- and tri-alkanol amine salts and mixtures thereof.
- Preferred succinic acid derivatives for use herein include 2-dodecenylsuccinic acid, 2-tetradecenylsuccinic acid, 2-hexadecenylsuccinic acid, decyl succinic acid, dodecyl succinic acid and tetradecyl succinic acid and the water- soluble salts thereof.
- the alkyl or alkenyl chain attached to succinic acid can be either straight or branched. Preferred are the straight-chain alk(en)yl moieties.
- the weight ratio of sulfonate to succinate surfactant in the binary mixture is in the range from 3:1 to 1:4, preferably from 2:1 to 1:2.
- the ternary surfactant system represents usually from 35% to 75% of the composition.
- the anionic surfactant component is defined in the salt form.
- the nonionic surfactant component contains a hydrophobic organic radical condensed with an ethylene oxide hydrophilic moiety.
- All ethoxylated nonionic surfactants which are known to be suitable for use in detergent application can be used in the compositions of this invention.
- Preferred nonionic species herein are polyethoxylates derived from primary and secondary aliphatic alcohols having from 8 to 24 carbon atoms, and having a HLB (hydrophilic- lipophilic balance) in the range from 8 to 15. These preferred ethoxylates frequently contain from 2 to about 14 moles of ethylene oxide per mole of hydrophobic moiety.
- the hydrocarbyl chain (hydrophobic moiety) can be represented by linear or branched fatty alcohols.
- a preferred class of nonionic ethoxylates is represented by the condensation product of a fatty alcohol having from 12 to 15 carbon atoms and from 4 to 10 moles of ethylene oxide per mole of fatty alcohol.
- Suitable species of this class of ethoxylates include: the condensation product of C12-C15 oxo-alcohols and 7 moles of ethylene oxide per mole of alcohol; the condensation product of C13 ⁇ 15 oxoalcohols and 5 moles of ethylene oxide; the condensation product of narrow cut C14-C15 oxo-alcohols and 7 or 9 moles of ethylene oxide per mole of fatty (oxo)alcohol; the condensation product of a narrow cut C12-C13 fatty (oxo)alcohol and 6.5 moles of ethylene oxide per mole of fatty alcohol; and the conden- sation products of a C10-C14 coconut fatty alcohol with a degree of ethoxylation (moles EO/mole fatty
- the fatty oxo alcohols while mainly linear can have, depending upon the processing conditions and raw material olefins, a certain degree of branching, particularly short chain such as methyl branching.
- a degree of branching in the range from 15% to 50% (weight %) is frequently found in commercial oxo-alcohols.
- Preferred nonionic ethoxylated components can also be represented by a mixture of 2 separately ethoxylated nonionic surfactants having a different degree of ethoxylation.
- the nonionic ethoxylate can be represented by mixtures of a first ethoxylated surfactant containing from 3 to 7 moles of ethylene oxide per mole of hydrophobic moiety and a second ethoxylated species having from 8 to 14 moles of ethylene oxide per mole of hydrophobic moiety.
- a preferred nonionic ethoxylated mixture contains a lower ethoxylate which is the condensation product of a C12-C15 oxo-alcohol, with up to 50% (wt) branching, and from 3 to 7 moles of ethylene oxide per mole of fatty oxo-alcohol, and a higher ethoxylate which is the condensation product of a C16-C19 oxo-alcohol with more than 50% (wt) branching and from 8 to 14 moles of ethylene oxide per mole of branched oxo-alcohol.
- the nonionic surfactant component represents from 50% to 10%, preferably from 15% to 40% of the ternary surfactant system.
- compositions herein contain less than 50%, usually from 15% to 40% water.
- the claimed compositions are further characterized by a pH, measured in 1% aqueous solution at 20°C, in the range from 7 to 9.
- This pH range implies that the anionic surfactant component, i.e., the binary mixture of sulfonate and succinate, particularly the succinate, is substantially completely (i.e., more than 90%) neutralized in the claimed composition as is.
- compositions herein frequently contain a series of optional ingredients which are used for their known functionality in conventional quantities.
- optional ingredients can include fatty acids, saturated and/or unsaturated, and the corresponding soaps, synthetic anionic surfactants which are different from sulfonates (non-sulfonate anionics), water-insoluble solvents, enzymes, enzyme stabilizers, polyacids, suds regulants, brighteners, perfumes, dyes, antioxidants, bactericides, corrosion inhibitors, fabric-softening agents, phase regulants and the like.
- Suitable fatty acids saturated or unsaturated, have from 10 to 18 carbon atoms in the alkyl chain. Preferred are unsaturated species having from 14 to 18 carbon atoms in the alkyl chain, most preferably oleic acid.
- the corresponding soaps can equally be used.
- the optional fatty acid/soaps are used in levels up to 10%, preferably from 1% to 8%, (of the composition).
- the fatty acids/soaps among others, act as suds modifiers/regulants.
- Synthetic non-sulfonate anionics can also be used in the composition in relatively minor levels, e.g. in levels not exceeding 25% of the ternary surfactant system.
- suitable non-sulfonate anionics include the salts of sulfated fatty alcohols having from 12 to 20 carbon atoms in the alcohol chain.
- Water-insoluble solvents such as terpenes, phthalic acid esters and liquid paraffins can also be used in levels generally below 5%.
- Detergent enzymes generally aid and augment the removal of specific stains.
- Suitable enzymes can be represented by proteases, amylases, lipases, glucose-oxidases, cellulase, or mixtures thereof.
- Proteases and amylases are preferred in the claimed liquid concentrated compositions. They are frequently employed in a level from about 0.01% to about 1%.
- Suitable stabilizing systems include short C1 ⁇ 4 chain carboxylic acid, particularly formic acid in combination with low level of calcium, boric acid and the water-soluble salts thereof possibly in combination with polyols.
- polyacid or mixture of polyacids in an amount from 0.05% to 2%.
- Suitable polyacids are those having one pK value of at least 5.
- Preferred polyacid species for use herein can be represented by organo-phosphonic acids, particularly alkylene-polyamino-polyalkylene phosphonic acids such as ethylene diamine tetramethylenephosphonic acid, and diethylene triaminepentamethylenephosphonic acid or the salts thereof.
- Suitable polyamino-polyalkylene ethoxylate polymers are disclosed in European Patent Application number 0 112 593.
- Non-fatty acid detergent suds regulants can also be used.
- Preferred species include alkylated polysiloxanes such as dimethylpolysiloxane also frequently termed silicone.
- the silicones are frequently used in a level not exceeding 0.5%, most preferably between 0.01% to 0.2%.
- compositions herein can also contain known antioxidants for their known utility, frequently radical scavengers, in the art established levels i.e. 0.01% to 0.25% (by reference to total composition). These antioxidants are frequently introduced in conjunction with unsaturated organic acids. While many suitable antioxidants are readily known and available for that purpose, especially preferred for use in the compositions herein are: 2,6 ditertiary butyl-p-cresol, more commonly known as butylated hydroxytoluene, BHT, and 2-tertiarybutyl-4-hydroxyanisole. Other suitable antioxidants are: 4,4'thiobis(6-ter-butyl-m-cresol) and 2-methyl-4,6-dinonyl phenol.
- Soil release polymers can also be incorporated in the compositions herein. Suitable species of such release polymers are described in U.S. Patent Application Serial Number 684.511, filed December 21, 1984. However compositions comprising at least 0,01% by weight of a soil release polymer which is an alkoxylated ester of phthalic acid are excluded from the present invention.
- phase regulant is a further optional ingredient in the compositions herein.
- This component together with water can constitute the solvent matrix for the claimed concentrated liquid compositions.
- Suitable ingredient classes include lower aliphatic alcohols having from 2 to 6 carbon atoms and from 1 to 3 hydroxyl groups, ethers of diethyleneglycol and lower aliphatic monoalcohols having from 1 to 4 carbon atoms.
- Specific examples of phase regulants are: ethanol; n-propanol; isopropanol; butanol; 1,2-propanediol; 1,3-propanediol; monomethyl-, ethyl-, propyl-, and monobutyl ethers of di-ethylene glycol.
- a liquid detergent composition in accordance with the invention is prepared by mixing the listed ingredients in the stated proportions.
- the preceeding composition is, from a detergency performance standpoint, compared to ARIEL, R a granular tripolyphos- phate built detergent containing oxygen bleach.
- the tests are carried out in a horizontal drum washing machine in an up-to-60°C cycle. Comparative performances are measured on cotton strips, stained with various types of artificial soils inclusive of bleach-builder sensitive soils, enzyme- sensitive soils, particulate soils and greasy-oily soils. It is found that the composition in accordance with this invention provides textile cleaning performance on all types of soils comparable to what is obtained from ARIEL.
- Example I It was also found that the liquid composition of Example I remained homogeneous and stable after at least 2 weeks storage at temperatures varying from 4°C to 50°C and also following exposure to several freeze-thaw cycles.
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)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT86200690T ATE73840T1 (de) | 1985-05-03 | 1986-04-23 | Ein ternaeres oberflaechenaktives system enthaltende homogene konzentrierte fluessige reinigungsmittel. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8511303 | 1985-05-03 | ||
GB858511303A GB8511303D0 (en) | 1985-05-03 | 1985-05-03 | Liquid detergent compositions |
Publications (4)
Publication Number | Publication Date |
---|---|
EP0200263A2 EP0200263A2 (en) | 1986-11-05 |
EP0200263A3 EP0200263A3 (en) | 1989-05-10 |
EP0200263B1 EP0200263B1 (en) | 1992-03-18 |
EP0200263B2 true EP0200263B2 (en) | 1995-10-04 |
Family
ID=10578612
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86200690A Expired - Lifetime EP0200263B2 (en) | 1985-05-03 | 1986-04-23 | Homogeneous concentrated liquid detergent compositions containing ternary surfactant system |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0200263B2 (fi) |
JP (1) | JPH0735517B2 (fi) |
AT (1) | ATE73840T1 (fi) |
CA (1) | CA1284446C (fi) |
DE (1) | DE3684355D1 (fi) |
DK (1) | DK167155B1 (fi) |
FI (1) | FI85380C (fi) |
GB (1) | GB8511303D0 (fi) |
GR (1) | GR861143B (fi) |
IE (1) | IE58673B1 (fi) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6790814B1 (en) | 1999-12-03 | 2004-09-14 | Procter & Gamble Company | Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes |
US7790664B2 (en) | 2008-10-27 | 2010-09-07 | The Procter & Gamble Company | Methods for making a nil-phosphate liquid automatic dishwashing composition |
Families Citing this family (22)
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 |
GB2245000B (en) * | 1987-09-17 | 1992-06-03 | Colgate Palmolive Co | Liquid detergent composition |
JP2559448B2 (ja) * | 1988-02-26 | 1996-12-04 | 花王株式会社 | 液体洗剤組成物 |
GB8817726D0 (en) * | 1988-07-26 | 1988-09-01 | Unilever Plc | Detergent composition with fabric softening properties |
EP0430330A3 (en) * | 1989-11-24 | 1991-12-18 | The Procter & Gamble Company | Suspending liquid detergent compositions |
DE4134078A1 (de) * | 1991-10-15 | 1993-04-22 | Henkel Kgaa | Konzentriertes waesseriges fluessigwaschmittel |
USH1468H (en) | 1994-04-28 | 1995-08-01 | Costa Jill B | Detergent compositions containing cellulase enzyme and selected perfumes for improved odor and stability |
GB2297978A (en) | 1995-02-15 | 1996-08-21 | Procter & Gamble | Detergent compositions containing amylase |
DE69524212T2 (de) | 1995-06-12 | 2002-07-25 | Procter & Gamble | Reinigungszusammensetzung und Verfahren zum Reinigen von empfindlichen Oberflächen |
EP0753571A1 (en) | 1995-07-10 | 1997-01-15 | The Procter & Gamble Company | Process for making granular detergent composition |
ATE211728T1 (de) | 1995-11-02 | 2002-01-15 | Procter & Gamble | Aminoester von parfümalkoholen und ihre verwendung in reinigungs- und waschmittelzusammensetzungen |
EP0778342A1 (en) | 1995-12-06 | 1997-06-11 | The Procter & Gamble Company | Detergent compositions |
AU5725996A (en) | 1996-05-03 | 1997-11-26 | Procter & Gamble Company, The | Detergent compositions comprising polyamine polymers with improved soil dispersancy |
GB2371307B (en) | 2001-01-19 | 2003-10-15 | Reckitt Benckiser Nv | Packaged detergent compositions |
US8361946B2 (en) | 2004-04-08 | 2013-01-29 | Akzo Nobel N.V. | Detergent composition |
US20070015674A1 (en) | 2005-06-30 | 2007-01-18 | Xinbei Song | Low phosphate automatic dishwashing detergent composition |
CA2642970C (en) | 2006-03-22 | 2013-09-24 | The Procter & Gamble Company | Liquid treatment compositions comprising pearlescent agents |
DE602006020845D1 (de) | 2006-05-09 | 2011-05-05 | Procter & Gamble | Flüssigkeitsgefüllter wasserlöslicher Beutel |
WO2007131860A1 (en) * | 2006-05-12 | 2007-11-22 | Unilever N.V. | Aqueous liquid cleaning compositions and their use |
ES2377160T3 (es) | 2007-03-20 | 2012-03-23 | The Procter & Gamble Company | Método para lavar ropa o limpiar superficies duras |
JP5425929B2 (ja) | 2008-12-18 | 2014-02-26 | ザ プロクター アンド ギャンブル カンパニー | 液状処理組成物のための真珠光沢剤スラリー |
CN106661501A (zh) * | 2014-08-01 | 2017-05-10 | 宝洁公司 | 包含高脂肪酸的清洁组合物 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3579453A (en) * | 1968-11-12 | 1971-05-18 | Rohm & Haas | Alkali-soluble surfactant consisting of substituted succinic acid-nonionic ethoxylate blends |
PH11320A (en) * | 1973-07-05 | 1977-11-02 | Procter & Gamble | Liquid detergent compositions |
EP0019315B1 (en) * | 1979-05-16 | 1983-05-25 | Procter & Gamble European Technical Center | Highly concentrated fatty acid containing liquid detergent compositions |
DE3062842D1 (en) * | 1979-11-09 | 1983-05-26 | Unilever Nv | Liquid detergent composition |
JPS6039719B2 (ja) * | 1982-05-11 | 1985-09-07 | 花王株式会社 | 液体洗浄剤組成物 |
JPS5915495A (ja) * | 1982-07-19 | 1984-01-26 | 花王株式会社 | 界面活性剤の曇点上昇法 |
NZ214410A (en) * | 1984-12-18 | 1988-07-28 | Colgate Palmolive Co | Built aqueous detergent compositions containing nonionic and amphoteric detergents |
-
1985
- 1985-05-03 GB GB858511303A patent/GB8511303D0/en active Pending
-
1986
- 1986-04-23 DE DE8686200690T patent/DE3684355D1/de not_active Expired - Fee Related
- 1986-04-23 AT AT86200690T patent/ATE73840T1/de not_active IP Right Cessation
- 1986-04-23 EP EP86200690A patent/EP0200263B2/en not_active Expired - Lifetime
- 1986-04-29 GR GR861143A patent/GR861143B/el unknown
- 1986-05-02 IE IE117986A patent/IE58673B1/en not_active IP Right Cessation
- 1986-05-02 JP JP61101277A patent/JPH0735517B2/ja not_active Expired - Lifetime
- 1986-05-02 CA CA000508194A patent/CA1284446C/en not_active Expired - Fee Related
- 1986-05-02 DK DK203586A patent/DK167155B1/da not_active IP Right Cessation
- 1986-05-02 FI FI861846A patent/FI85380C/fi not_active IP Right Cessation
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6790814B1 (en) | 1999-12-03 | 2004-09-14 | Procter & Gamble Company | Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes |
US7790664B2 (en) | 2008-10-27 | 2010-09-07 | The Procter & Gamble Company | Methods for making a nil-phosphate liquid automatic dishwashing composition |
Also Published As
Publication number | Publication date |
---|---|
IE58673B1 (en) | 1993-11-03 |
EP0200263A2 (en) | 1986-11-05 |
FI85380B (fi) | 1991-12-31 |
EP0200263A3 (en) | 1989-05-10 |
FI861846A (fi) | 1986-11-04 |
FI85380C (fi) | 1992-04-10 |
GR861143B (en) | 1986-08-11 |
GB8511303D0 (en) | 1985-06-12 |
IE861179L (en) | 1986-11-03 |
DK203586D0 (da) | 1986-05-02 |
CA1284446C (en) | 1991-05-28 |
EP0200263B1 (en) | 1992-03-18 |
FI861846A0 (fi) | 1986-05-02 |
DE3684355D1 (de) | 1992-04-23 |
DK203586A (da) | 1986-11-04 |
DK167155B1 (da) | 1993-09-06 |
JPS6225196A (ja) | 1987-02-03 |
JPH0735517B2 (ja) | 1995-04-19 |
ATE73840T1 (de) | 1992-04-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0200263B2 (en) | Homogeneous concentrated liquid detergent compositions containing ternary surfactant system | |
US4285841A (en) | Highly concentrated fatty acid containing liquid detergent compositions | |
US4302364A (en) | Liquid detergent compositions comprising anionic, nonionic and cationic surfactants | |
US4608189A (en) | Detergents and liquid cleaners free of inorganic builders | |
US3914185A (en) | Method of preparing liquid detergent compositions | |
US4714565A (en) | Homogeneous concentrated liquid detergent compositions containing a monoester of a dicarboxylic acid | |
US3579453A (en) | Alkali-soluble surfactant consisting of substituted succinic acid-nonionic ethoxylate blends | |
EP0125854B1 (en) | Liquid detergent compositions | |
NZ213655A (en) | Light duty detergent compositions containing organic diamine diacid salts | |
GB1562801A (en) | Liquid detergent composition | |
GB1569617A (en) | Liquid detergent composition | |
EP0028865B2 (en) | Homogeneous enzyme-containing liquid detergent compositions containing saturated fatty acids | |
JPS61166895A (ja) | 液体洗剤組成物 | |
US4298492A (en) | Built liquid detergent composition | |
EP0593841A1 (en) | Detergent composition with suds suppressing system | |
EP0223306B1 (en) | Liquid detergent compositions containing binary anionic surfactant system | |
IE59407B1 (en) | Built liquid detergents | |
CA1109355A (en) | Liquid detergent composition | |
GB2123847A (en) | Liquid detergent compositions | |
GB1572605A (en) | Liqid enzyme containing detergent composition | |
GB1600018A (en) | Liquid detergent composition | |
US5668095A (en) | Detergent composition with suds suppressing system | |
EP0815188A1 (en) | Alkaline detergent having high contents of nonionic surfactant and complexing agent, and use of an amphoteric compound as solubiliser | |
EP0306493A1 (en) | Detergent composition | |
AU7513687A (en) | Detergent composition |
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): AT BE CH DE 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): AT BE CH DE FR GB IT LI NL SE |
|
17P | Request for examination filed |
Effective date: 19891030 |
|
17Q | First examination report despatched |
Effective date: 19900928 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 19920318 |
|
REF | Corresponds to: |
Ref document number: 73840 Country of ref document: AT Date of ref document: 19920415 Kind code of ref document: T |
|
ITF | It: translation for a ep patent filed |
Owner name: ING. C. GREGORJ S.P.A. |
|
REF | Corresponds to: |
Ref document number: 3684355 Country of ref document: DE Date of ref document: 19920423 |
|
ET | Fr: translation filed | ||
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
26 | Opposition filed |
Opponent name: UNILEVER N.V. Effective date: 19921216 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: UNILEVER N.V. |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
EAL | Se: european patent in force in sweden |
Ref document number: 86200690.5 |
|
R26 | Opposition filed (corrected) |
Opponent name: UNILEVER N.V. Effective date: 19921216 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19950412 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19950425 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19950430 Year of fee payment: 10 |
|
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: 19951004 |
|
AK | Designated contracting states |
Kind code of ref document: B2 Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
ET3 | Fr: translation filed ** decision concerning opposition | ||
ITF | It: translation for a ep patent filed |
Owner name: ING. C. GREGORJ S.P.A. |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: AEN Free format text: AUFRECHTERHALTUNG DES PATENTES IN GEAENDERTER FORM |
|
NLR2 | Nl: decision of opposition | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Effective date: 19960104 |
|
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 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI 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: 19960430 Ref country code: CH 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: 19960430 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20000405 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20000512 Year of fee payment: 15 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010424 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010430 |
|
BERE | Be: lapsed |
Owner name: PROCTER & GAMBLE EUROPEAN TECHNICAL CENTER Effective date: 20010430 |
|
EUG | Se: european patent has lapsed |
Ref document number: 86200690.5 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20030313 Year of fee payment: 18 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20030403 Year of fee payment: 18 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20030430 Year of fee payment: 18 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 20040423 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041103 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20040423 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041231 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050423 |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |