EP0611392B1 - Compositions detergentes comprenant des ethers de glyceryle - Google Patents

Compositions detergentes comprenant des ethers de glyceryle Download PDF

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Publication number
EP0611392B1
EP0611392B1 EP92924209A EP92924209A EP0611392B1 EP 0611392 B1 EP0611392 B1 EP 0611392B1 EP 92924209 A EP92924209 A EP 92924209A EP 92924209 A EP92924209 A EP 92924209A EP 0611392 B1 EP0611392 B1 EP 0611392B1
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alkyl
ether
acid
ethers
composition according
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EP0611392A1 (fr
EP0611392A4 (fr
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Frederick Edward Hardy
Jean-Pol Boutique
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Procter and Gamble Co
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Procter and Gamble Co
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    • 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
    • C11D1/83—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

Definitions

  • the present invention relates to detergent compositions, especially heavy duty compositions, that contain one or more glyceryl ethers as a nonionic detersive surfactant.
  • Heavy duty detergents whether in granular or liquid form, commonly comprise an anionic detersive surfactant, for example sodium (linear alkyl) benzene sulfonate in which the alkyl group preferably has 11-13 carbon atoms, or sodium alkyl sulfate, e.g that obtained by sulfating a C 8 -C 18 alkanol.
  • an anionic detersive surfactant for example sodium (linear alkyl) benzene sulfonate in which the alkyl group preferably has 11-13 carbon atoms, or sodium alkyl sulfate, e.g that obtained by sulfating a C 8 -C 18 alkanol.
  • a nonionic detersive surfactant typically a condensation product of a (C 6 -C 15 alkyl) phenol or a C 8 -C 22 alkanol with ethylene oxide.
  • Preferred condensates are those containing 3-12 moles of ethylene oxide per mole of alkylphenol or 4-8 moles of ethylene oxide per mole of alkanol.
  • a particular preferred nonionic is a condensate of C 14 -C 15 alkanol with 7 moles of ethylene oxide per mole of alkanol.
  • ethylene oxide used in the preparation of the above discussed nonionics is, however, derived from oil and, furthermore, is a reagent that needs careful handling in order to minimise the risk of explosion.
  • the present invention relates to the use as a nonionic detersive surfactant in a detergent composition of one or more glyceryl ethers of the general formula RO - (C 3 -H 6 -O 2 ) n H wherein
  • the present invention provides a detergent composition
  • a detergent composition comprising (a) one or more glyceryl ethers of the general formula (1) as defined above and (b) an anionic detersive surfactant.
  • the glyceryl ethers of the general formula (1) defined above are effective as nonionic detersive surfactants. At least 50 mole percent and preferably at least 60 mole percent of the glyceryl ethers of the formula (1) present in the detergent composition of this invention should be constituted by diglyceryl ether and not more than 25 mole percent, preferably not more than 20 mole percent should be constituted by monoglyceryl ether. The remainder, if any, of the glyceryl ether component (a) is constituted by triglyceryl ethers and/or higher homologues.
  • diglyceryl ether should constitute 80 mole percent or more of the glyceryl ether component; it is particularly preferred that the glyceryl ether component of the present compositions should be substantially entirely composed of diglyceryl ether.
  • Diglyceryl ethers may be prepared by a process known in principle from the article by H.Sagitani et al , entitled “Solution properties of homogenious polyglycerol dodecyl ether nonionic surfactants", J.A.O.C.S., Vol. 66, No.1 ( January 1989 ) pages 146-152.
  • Sagitani et al disclose the preparation of diglyceryl dodecyl ether by a process in which sodium is added to anhydrous glycerol under a nitrogen atmosphere, the solution is heated at 130°C for 1 hour, glycidyl dodecyl ether is added dropwise to the resultant sodium glycerate over 1 hour at 180°C, the mixture is stirred for 8 hours and the product is purified on a silica gel column using chloroform/methanol (98:2) as a solvent.
  • Sagitani et al depicted the preparative process by means of the following reaction scheme: wherein R 12 represents the dodecyl radical.
  • R is usually derived from a primary or secondary alcohol.
  • the diglyceryl ether content can be worked up by conventional purification and isolation techniques.
  • the diglyceryl ether of the formula is also generally formed. Typically, about one mole of diglyceryl ether (3) is formed for every four moles of diglyceryl ether (2) that are produced.
  • the group R bonds to the first glycerol moiety at the primary site of the latter.
  • the second glycerol could, in principle, bond to the secondary site of the first glycerol; in practise, however, it has generally been found that less than 10 mole percent of the diglyceride ethers have such bonding at the said secondary site.
  • R may represent a mixture of alkyl and/or alkenyl radicals, as will be the case, for example, when the glyceryl ethers are obtained from naturally occurring fatty alcohols ROH.
  • An example is coconut alcohol, which contains primarily C 12 , C 14 and C 16 saturated alkyl radicals, with smaller amounts of C 8 , C 10 and C 18 alkenyl radicals.
  • a preferred meaning for R is cocoyl, in particular so-called “topped and tailed” and “narrow-range” cocoyl, which is predominantly n-dodecyl (C 12 ) and n-tetradecyl (C 14 ).
  • the glycidyl alkyl (or alkenyl) ethers are known compounds, some of which may be obtained commercially, or may be prepared by methods known in principle.
  • a useful starting material is the alkyl glycidyl ether available under the trade name Epoxide No. 8" from Proctor & Gamble, the alkyl groups in this epoxide being narrow-range cocoyl.
  • the diglyceryl ethers may also be prepared by a method known in principle from US-A-4,465,866 (Takaishi et al ).
  • This U.S. Patent teaches that a diglyceryl ether of the formula (2) given above can be prepared by reacting, in the presence of an acid or basic catalyst, an alkyl ( or alkenyl) glycidyl ether with an acetal or ketal derivative of glycerol in order to obtain a 1, 3-dioxolane, which is then subjected to hydrolysis.
  • Takaishi et al also mentions earlier proposals for the preparation of such diglyceryl ethers, in particular (i) the reaction of the linear dimer of glycerol with an alkali to form an alkali metal alcoholate, which is then reacted with alkyl halide, and (ii) the reaction of an alcohol with a cyclic compound of the 1, 3-dioxolane type with hydrolysis of the resultant addition product ( reference being made to Journal f. Prakt.Chemie, Band 316 (1974), 325-336).
  • the glyceryl ether components (a) will be present in the compositions of this invention in an amount usually of form 0.5 to 10%, preferably from 3 to 10% and more preferably from 5 to 10 %, by weight.
  • the detergent compositions of this invention which may be in liquid or granular form, will also contain at least one anionic detersive surfactant.
  • the composition may also comprise at least one other detersive surfactant, preferably selected from cationic, ampholytic and zwitterionic detersive surfactants, as well as other component conventional in the art, for example a builder, an enzyme, a bleach, a bleach activator, a polymeric soil-release agent, a chelating agent, a clay soil removal/antiredeposition agent, a polymeric dispersing agent, a brightener, a suds suppressor, a pH-buffering agent, a dye or a pigment.
  • any of the above mentioned components, whether essential or optional may be constituted, if desired, by a mixture of two or more compounds of the appropriate description.
  • the other detersive surfactant(s) will typically be used in a total amount of from 0 to 50, preferably 1 to 30 and more preferably 5 to 20 percent by weight.
  • detergent compositions herin also includes dishwashing compostions, hard-surface and other household cleaners and personal care products such as shampoos.
  • anionic detersive surfactants examples of anionic detersive surfactants and of the various optional components that come into consideration are as follows.
  • the detergent compositions of the present invention can contain, in addition to the nonionic surfactant system of the present invention, one or more anionic surfactants as described below.
  • Alkyl ester sulfonate surfactants hereof include linear esters of C 8 -C 20 carboxylic acids (i.e. , fatty acids) which are sulfonated with gaseous SO 3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
  • the preferred alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula: wherein R 3 is a C 8 -C 20 hydrocarbyl, preferably an alkyl, or combination thereof, R 4 is a C 1 -C 6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with alkyl ester sulfonate.
  • Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine.
  • R 3 is C 10 -C 16 alkyl and R 4 is methyl, ethyl or isopropyl.
  • R 4 is methyl, ethyl or isopropyl.
  • methyl ester sulfonates wherein R 3 is C 10 -C 16 alkyl.
  • Alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO 3 M wherein R preferably is a C 10 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 20 alkyl component, more preferably a C 12 -C 18 alkyl or hydroxyalkyl, and M is H or a cation, e.g.
  • an alkali metal cation e.g., sodium, potassium, lithium
  • ammonium or substituted ammonium e.g., methyl-, dimethly-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethly-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • Alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m SO 3 M wherein R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C 20 alkyl or hydroxyalkyl, more preferably an alkyl group having from 12 to 18 carbon atoms, especially from 12 to 15 carbon atoms.
  • A is an ethoxy or propoxy unit
  • m is greater than zero, typically between about 0.5 and about 6, more preferably between 0.5 and about 3
  • M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cation.
  • a metal cation e.g., sodium, potassium, lithium, calcium, magnesium, etc.
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • a preferred surfactant is C 12 -C 15 alkyl polyethoxylate (3.0) sulfate (C 12 -C 15 E(3.0)M).
  • Other exemplary surfactants include C 12 -C 18 alkyl polyethoxylate (1.0) sulfate (C 12 -C 18 E(1.0)M, C 12 -C 18 alkyl polyethoxylate (2.25) sulfate (C 12 -C 18 E(2.25)M), C 12 -C 18 alkyl polyethoxylate (3.0) sulfate (C 12 -C 18 E(3.0)M), and C 12 -C 18 alkyl polyethoxylate (4.0) sulfate (C 12 -C 18 E(4.0)M), wherein M is conveniently selected from sodium and potassium.
  • anionic surfactants useful for detersive purposes can also be included in the detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C 9 -C 20 linear alkylbenzenesulfonates, C 8 -C 22 primary or secondary alkanesulfonates, C 8 -C 24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British Patent specification No.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • C 9 -C 20 linear alkylbenzenesulfonates C 8 -C 22 primary or secondary alkanesulfonates
  • alkylpolyglycethersulfates ( containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C 12 -C 18 monoesters) and diesters of sulfosuccinate (especially saturated and unsaturated C 6 -C 12 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulf
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
  • Prefered anionic surfactants systems employed in the detergent compositions of the invention are free fo alkyl benzene sulfonate salts.
  • a highly preferred system comprises a mixture of a major proportion of a C 14 -C 15 primary alkyl sulfate and a minor proportion of a C 12 -C 15 alkyl ethoxysulfate containing an average of three ethoxy groups per mole of alkyl ethoxy sulfate.
  • the detergent compositions of the present invention typically comprise from about 1% to about 20 %, preferably from about 3% to about 15% and most preferably from 5% to 10% by weight of anionic surfactants.
  • the detergent compositions of the present invention may also contain cationic, ampholytic, zwitterionic, and semi-polar surfactants, and even further nonionic surfactants.
  • Cationic detersive surfactants suitable for use in the detergent compositions of the present invention are those having one long-chain hydrocarbyl group.
  • cationic surfactants include the ammonium surfactants such as alkyldimethylammomium halogenides, and those surfactants having the formula: [R 2 (OR 3 ) y ][R 4 (OR 3 ) y ] 2 R 5 N+X - wherein R 2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R 3 is selected from the group consisting of -CH 2 CH 2 -,CH 2 CH(CH 3 )-, -CH 2 CH(CH 2 OH)-, - CH 2 CH 2 CH 2 -, and mixtures thereof; each R 4 is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl ring structures formed by joining the two R 4 groups, - CH 2 CHOHCHOHCOR 6 CHOHCH 2 OH wherein R 6 is any hexose or hexose
  • the detergent compositions of the present invention typically comprise from 0% to about 25%, preferably from about 3% to about 15% by weight of such cationic surfactants.
  • Ampholytic surfactants are also suitable for use in the detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched.
  • One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al. , issued December 30, 1975 at column 19, lines 18-35 (herein incorporated by reference) for examples of ampholytic surfactants.
  • the detergent compositions of the present invention typically comprise from 0% to about 15%, preferably from about 1% to about 10% by weight of such ampholytic surfactants.
  • Zwitterionic surfactants are also suitable for use in detergent compositions . These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al. , issued December 30, 1975 at column 19, line 38 through column 22, line 48 (herein incorporated by reference) for examples of zwitterionic surfactants.
  • the detergent compositions of the present invention typically comprise from 0% to about 15%, preferably from about 1% to about 10% by weight of such zwittarionic surfactants.
  • Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
  • Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula wherein R 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R 5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
  • the R 5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • amine oxide surfactants in particular include C 10 -C 18 alkyl dimethyl amine oxides and C 8 -C 12 alkoxy ethyl dihydroxy ethyl amine oxides.
  • the detergent compositions of the present invention typically comprise from 0% to about 15%, preferably from about 1% to about 10% by weight of such semi-polar nonionic surfactants.
  • the detergent compositions of this invention may contain a nonionic surfactant in addition to the glyceryl ether component discussed above.
  • Suitable nonionic surfactants include the polyethylene oxide condensates of alkly phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from 6 to 8 carbon atoms, in either a straight-chain or branched-chain configuration, with from 1 to 12 moles of ethylene oxide per mole of alkyl phenol.
  • Suitable nonionics also include the condensation products of aliphatic alcohols containing from 8 to 22, preferably 12 to 18, carbon atoms, in either straight-chain or branched-chain configuration, with from 2 to 12, preferably 3 to 7, moles of ethylene oxide per mole of alcohol.
  • Suitable nonionic surfactants also include the fatty acyl or alkyl condensation products of carbohydrates and their derivatives such as glycosides, aminodeoxy forms, and polyols. Examples include coco-alkyl polyglucosides and tallow-acyl-N-methyl-glucamides.
  • the additional nonionic surfactants if used, will generally be present at a level of up to 15 percent, usually from 1 to 6 precent, by weight of the composition.
  • the detergent compositions of the present invention can comprise inorganic or organic detergent builders to assist in mineral hardness control.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form.
  • Liquid formulations typically comprise at least about 1%, more typically from about 5% to about 50%, preferably from about 5% to about 30% by weight of the detergent builder.
  • Granular formulations typically comprise at least about 1%, more typically from about 10% to about 80%, preferably from about 15% to about 50% by weight of the detergent builder. Lower or higher levies of builder, however, are not meant to be excluded.
  • Inorganic detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions can also be used but are not preferred at wash conditions less than about 50°C, especially less than about 40°C.
  • Preferred builder systems are also free of phosphates.
  • silicate builders are the alkali metal silicates, particularly those having a SiO 2 :Na 2 O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck, incorporated herein by reference.
  • layered silicates such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck, incorporated herein by reference.
  • other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesquicarbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973, the disclosure of which is incorporated herein by reference.
  • Aluminosilicate builders are useful in the present invention.
  • Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations.
  • Aluminosilicate builders include those having the empirical formula: M z (zAlO 2 ⁇ ySiO 2 ) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2; and y is 1; this material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO 3 hardness per gram of anhydrous aluminosilicate.
  • Preferred aluminosilicates are zeolite builders which have the formula: Na z [(AlO 2 ) z (SiO 2 ) y ].xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, el at , issued October 12, 1976, incorporated herein by reference. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula: Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ] ⁇ xH 2 O wherein x is from about 20 to about 30, especially about 27.
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
  • polyphosphates are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta phosphate in which the degree of polymerization ranges from about 6 to about 21, and salts of phytic acid.
  • phosphonate builder salts are the water-soluble salts of ethane 1-hydroxy-1, 1-diphosphonate particularly the sodium and potassium salts, the water-soluble salts of methylene diphosphonic acid e.g.
  • Phosphonate builder salts of the aforementioned types are disclosed in U.S. Patent Nos. 3,159,581 and 3,213,030 issued December 1, 1964 and October 19, 1965, to Diehl; U.S. Patent No. 3,422,021 issued January 14, 1969, to Roy; and U.S. Patent Nos. 3,400,148 and 3,422,137 issued September 3, 1968, and January 14, 1969 to Quimby, said disclosures being incorporated herein by reference.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt.
  • alkali metals such as sodium, potassium, and lithium salts, especially sodium salts, or ammonium and substituted ammonium ( e.g., alkanolammonium ) salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates.
  • a number of ether polycarboxylates have been disclosed for use as detergent builders.
  • Examples of useful ether polycarboxylates include oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al. , U.S. Patent 3,635,830, issued January 18, 1972, both of which are incorporated herein by reference.
  • a specific type of ether polycarboxylates useful as builders in the present invention also include those having the general formula: CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX) (B) wherein A is H or OH; B is H or -O-CH(COOX)-CH2(COOX); and X is H or a salt-forming cation.
  • a and B are both H, then the compound is oxydissuccinic acid and its water-soluble salts. If A is OH and B is H, then the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts.
  • TDS tartrate disuccinic acid
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903, all of which are incorporated herein by reference.
  • ether hydroxypolycarboxylates represented by the structure: HO-[C(R) (COOM)-C(R) (COOM)-O] n -H wherein M is hydrogen or a cation wherein the resultant salt is water-soluble, preferably an alkali metal, ammonium or substituted ammonium cation, n is from about 2 to about 15 (preferably n is from about 2 to about 10, more preferably n averages from about 2 to about 4) and each R is the same or different and selected from hydrogen, C 1-4 alkyl or C 1-4 substituted alkyl (preferably R is hydrogen).
  • Still other ether polycarboxylates include copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid.
  • Organic polycarboxylate builders also include the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids.
  • polyaceatic builder salts are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, and nitrilotriacetic acid.
  • polycarboxylates such as mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, benezene pentacarboxylic acid, and carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citric builders e.g., citric acid and soluble salts thereof, is a polycarboxylate builders of particular importance for heavy duty liquid detergent formulations, but can also be used in granular compositions.
  • Suitable salts include the metal salts such as sodium, lithium, and potassium salts, as well as ammonium and substituted ammonium salts.
  • carboxylate builders include the carboxylated carbohydrates disclosed in U.S. Patent 3,723,322, Diehl, issued March 28, 1973, incorporated herein by reference. Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986, incorporated herein by reference.
  • Useful succinic acid builders include the C 5 -C 20 alkyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • Alkyl succinic acids typically are of the general formula R-CH(COOH)CH 2 (COOH) i.e., derivatives of succinic acid, wherein R is hydrocarbon, e.g., C 10 -C 20 alkyl or alkenyl, preferably C 12 -C 16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
  • the succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • useful builders also include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclo-hexane-hexacarboxylate,cis-cyclopentane-tetracarboxylate, water-soluble polyacrylates (these polyacrylates having molecular weights to above about 2,000 can also be effectively utilized as dispersants), and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
  • suitable polycarboxylates are the polyacetal carboxylates disclosed in U.S. Patent 4,144,226, Crutchfield et al , issued March 13, 1979, incorporated herein by reference.
  • polyacetal carboxylates can be prepared by bringing together, under polymerization conditions, an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.
  • Polycarboxylate builders are also disclosed in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, incorporated herein by reference. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
  • the hydrocarbyls can be saturated or unsaturated.
  • Detersive enzymes can be included in the detergent compositions of the present invention for a variety of reasons including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and prevention of refugee dye transfer.
  • the enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • proteases are the subtilisins which are obtained from particular strains of B.subtilis and B.licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name Esperase @ . The preparation of this enzyme and analogous enzymes is described in British patent specification No. 1,243,784 of Novo.
  • protealytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASETM and SAVINASETM by Novo Industries A/S (Denmark) and MAXATASETM by International Bio-Synthetics, Inc. (The Netherlands).
  • Protease A and Protease B are enzymes referred to herein as Protease A and Protease B.
  • Protease A and methods for its preparation are described in European Patent Application 130,756, published January 9, 1985, incorporated herein by reference.
  • Protease B is a proteolytic enzyme which differs from Protease A in that it has a leucine substituted for tyrosine in position 217 in its amino acid sequence.
  • Protease B is described in European Patent Application Serial No. 87303761.8, filed April 28, 1987, incorporated herein by reference.
  • Methods for preparation of Protease B are also disclosed in European Patent Application 130,756, Bott et al. , published January 9, 1985, incorporated herein by reference.
  • Amylases include, for example, a-amylases obtained from a special strain of B.licheniforms, described in more detail in British patent specification No. 1,296,839 (Novo), previously incorporated herein by reference.
  • Amylolytic proteins include, for example RAPIDASETM, International Bio-Synthetics, Inc. and TERMAMYLTM, Novo Industries.
  • the cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4, 435, 307, Barbesgoard et al. , issued March 6, 1984, incorporated herein by reference, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermo idea ) , particularly the Humicola strain DSM 1800, and cellulases produced by a fungas of Bacillus N or a cellulase 212-producing fungas belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusc (Dolabella Auricula Solander).
  • Suitable lipase enzymes for detergent usage include those produced by micro-organisms of the of the Pseudomonas groups, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034, incorporated herein by reference.
  • Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase and a method for its purification have been described in Japanese Patent Application 53-20487, laid open on February 24, 1978. This lipase is available from Amano Pharmaceutical Co.
  • Lipase P Lipase P
  • Amano-P Lipase P
  • Such lipases of the present invention should show a positive immunological cross reaction with the Amano-P antibody, using the standard and well-known immunodiffusion procedure according to Ouchterlony (Acta. Med. Scan., 133, pages 76-79 (1950)).
  • Ouchterlony Acta. Med. Scan., 133, pages 76-79 (1950)
  • These lipases, and a method for their immunological cross-reaction with Amano-P are also described in U.S. Patent 4,707,291, Thom et al. , issued November 17, 1987, incorporated herein by reference.
  • Typical examples thereof are the Amano-P lipase, the lipase ex Pseudomonas fragi FERM P 1339 (available under the trade name Amano-B), lipase ex Pseudomonas nitroreducens var. lipolyticum FERM P 1338 (available under the trade name Amano-CES), lipases ex Chromobacter viscosum , e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli .
  • Amano-P lipase the lipase ex Pseudomonas fragi FERM P 1339 (available under the trade name Amano-B
  • Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perbonate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzvmes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application Wo 89/099813, published October 19, 1989, by O.Kirk, assigned to Novo Industries A/S, incorporated herein by reference.
  • Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.5 mg to about 3 mg, of active enzyme per gram of the composition.
  • the enzymes are preferably coated or prilled with additives inert toward the enzymes to minimize dust formation and improve storage stability. Techniques for accomplishing this are well known in the art.
  • an enzyme stabilisation system is preferably utilized.
  • nzyme stabilization techniques for aqueous detergent compositions are well known in the art.
  • one technique for enzyme stabilization in aqueous solutions involves the use of free calcium ions from sources such as calcium acetate, calcium formate, and calcium propionate. Calcium ions can be used in combination with short chain carboxylic acid salts, preferably formates. See. for example, U.S. Patent 4,318,818, Letton et al. , issued March 9, 1982, incorporated herein by reference.
  • Non-boric acid and borate stabilizers are preferred. Enzyme stabilization systems are also described, for example, in U.S Patents 4,261,868, 3,600,391, and 3,519,570.
  • the detergent composition of the present invention may contain bleaching agents or bleaching compositions, containing bleaching agent or one or more bleach activators.
  • present bleaching compounds will typically comprise from about 1% to about 20%, more typically from about 1% to about 10%, of such laundry detergent composition.
  • bleaching compounds are optional components in non-liquid formulations, e.g., granular detergents. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
  • the compositions hereof not contain borate or material which can form borate in situ (i.e. borate-forming material) under detergent storage or wash conditions.
  • borate-forming material i.e. borate-forming material
  • detergents to be used at these temperatures are substantially free of borate or borate-forming material.
  • substantially free or borate or borate-forming material shall mean that the composition contains not more than about 2% by weight of borate-containing and borate-forming material of any type, preferably, no more than 1%, more preferably 0%.
  • One category of bleaching agent which can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al. ,filed June 3, 1985, European Patent Application 0,133,354, Banks et al. ,published February 20, 1985, and U.S. Patent 4,412,934, Chung et al.
  • Highly preferred bleaching agents also include 6-nonlyamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6.1987 to Burns et al. , incorporated herein by reference.
  • Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, and subject to the wash condition limitation perviously mentioned, sodium perborate monohydrate and tetrahydrate.
  • Peroxygen bleaching agents are preferably combined with bleach activators, which lead to the in situ production in aqueous solution ( i.e., during the washing process ) of the peroxy acid corresponding to the bleach activator.
  • bleach activators include the tetraacetyl alkylene diamines, particularly tetraacetyl ethylene diamine (TAED) and tetraacetyl glycouril (TAGU).
  • R is the alkyl group containing from about 1 to about 18 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from about 6 to about 10 carbon atoms and L is a leaving group, the conjugate acid of which has a pK a in the range from about 4 to 13.
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photo-activated bleaching agents such as the sulfonated zinc and/or aluminimu phthalocyanines. These materials can be deposited upon the substrate during the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached.
  • Preferred zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. ,incorporated herein by reference.
  • detergent compositions will contain about 0.025% to about 1.25% by weight, of sulfonated zinc phthalocyanine.
  • polymeric soil release agents Any polymeric soil release agents known to those skilled in the art can be employed in the detergent compositions of the present invention.
  • Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • Polymeric soil release agents include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polyrropylene oxide terephthalate, and the like.
  • Cellulosic derivatives that are functional as soil release agents are commercially available and include hydroxyethers of cellulose such as Methocel R (Dow).
  • Cellulosic soil release agents also include those selected from the group consisting of C 1 -C 4 alkyl and C 4 hydroxyalkyl cellulose such as methylcellulose, ethylcellulose, hydroxypropyl methycellulose, and hydroxybutyl methylcellulose.
  • C 1 -C 4 alkyl and C 4 hydroxyalkyl cellulose such as methylcellulose, ethylcellulose, hydroxypropyl methycellulose, and hydroxybutyl methylcellulose.
  • a variety of cellulose derivatives useful as soil release polymers are disclosed in U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al. , incorporated herein by reference.
  • Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g. C 1 -C 6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylen oxide backbones.
  • poly(vinyl ester) e.g. C 1 -C 6 vinyl esters
  • poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylen oxide backbones.
  • Such materials are known in the art and are described in European Patent Application 0,219,048, published April 22, 1987 by Kud, et al .
  • Suitable commercially available soil release agents of this kind include the SokalanTM type of material, e.g., SokalanTM HP-22, available from BASF (West Germany).
  • One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. More specifically, these polymers are comprised of repeating units of ethylene terephthalate and PEO terephthalate in a mole ratio of ethylene terephthalate units to PEO terephthalate units of from about 25:75 to about 35:65, said PEO terephthalate units containing polyethylene oxide having molecular weights of from about 300 to about 2000.
  • the molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976, which is incorporated by reference. See also U.S. Patent 3,893,929 to Basadur issued July 8, 1975 (incorporated by reference) which discloses similar copolymers.
  • Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethlyene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000, and the mole ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the polymeric compound is between 2:1 and 6:1.
  • this polymer include the commercially available material Zelcon R 5126 (from Dupont) and Milease R T (from ICI). These polymers and methods of their preparation are more fully described in U.S. Patent 4,702,857, issued October 27, 1987, to Gosselink, which is incorporated herein by reference.
  • Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyaleneoxy repeat units and terminal moieties covalently attached to the backbone, said soil release agent being derived from a allyl alcohol ethoxylate, dimethtlterephthalate, and 1,2 propylene diol, wherein the terminal moieties of each oligomer have, on average, a total of from about 1 to about 4 sulfonate groups.
  • These soil release agents are described fully in U.S. Patent 4,968,451, issued 6 November, 1990 to J. J. Scheibel and E. P. Gosselink, U.S.
  • Suitable polymeric soil release agents include the ethyl- or methyl-capped 1,2-propylene terephthalate-polyoxy- ethylene terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987, to Gosselink et al., the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988, to Gosselink, wherein the anionic end-caps comprise sulfo-polyethoxy groups derived from polyethylene glycol (PEG), the block polyester oligomeric compounds of U.S.
  • PEG polyethylene glycol
  • Patent 4,702,857 issued October 27, 1987 to Gosselink, having polyethoxy end-caps of the formula X-(OCH 2 CH 2 ) n - wherein n is from 12 to about 43 and X is a C 1 -C 4 alkyl, or preferably methyl, all of these patents being incorporated herein by reference.
  • Additional soil release polymers include soil release polymers of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al., which discloses anionic, especially sulfoaroyl, end-capped terephthalate esters, said patent being incorporated herein by reference.
  • the terephthalate esters contain unsymmetrically substituted oxy-1,2-alkyleneoxy units.
  • soil release agents will generally comprise from about 0.01% to about 10.0%, preferably from about 0.1% to about 5.0%, more preferably from about 0.2% to about 3.0% by weight of the laundry detergent compositions of the present invention.
  • the detergent compositions of the present invention may also contain one or more iron and manganese chelating agents as a builder adjunct material.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents in compositions of the invention can have one or more, preferably at least two, units of the substructure wherein M is hydrogen, alkali metal, ammonium or substituted ammonium (e.g. ethanolamine) and x is from 1 to about 3, preferably 1.
  • these amino carboxylates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Operable amine carboxylates include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexa-acetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof.
  • Amino phosphonates are also suitable for use as chelating agents in the detergent compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions.
  • Compounds with one or more, preferably at least two, units of the substructure wherein M is hydrogen, alkali metal, ammonium or substituted ammonium and x is from 1 to about 3, preferably 1, are useful and include ethylenediaminetetrakis (methylenephosphonates), nitrilotris (methylenephosphonates) and diethylenetriaminepentakis (methylenephosphonates).
  • these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Alkylene groups can be shared by substructures.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. These materials can comprise compounds having the general formula: wherein at least one R is -SO 3 H or -COOH or soluble salts thereof and mixtures thereof.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5-disulfo- benzene.
  • Alkaline detergent compositions can contain these materials in the form of alkali metal, ammonium or substituted ammonium (e.g. mono-or triethanolamine) salts.
  • these chelating agents will generally comprise from about 0.1% to about 10% by weight of the laundry detergent compositions of the present invention. More preferably chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.
  • Clay soil removal/anti-redeposition agents useful in the detergent compositions of the present invention include polyethylene glycols and water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties.
  • Polyethylene glycol compounds useful in the detergent compositions of the present invention typically have a molecular weight in the range of from about 400 to about 100,000, preferably from about 1,00 to about 20,000, more preferably from about 2,000 to about 12,000, most preferably from about 4,000 to about 8,000.
  • Such compunds are commercially available and are sold as Carbowax @ , which is available from Union Carbide, located in Danbury, Conn.
  • the water soluble ethoxylated amines are preferably selected from the group consisting of :
  • the most preferred soil release and anti-redeposition agent are ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986, incorporated herein by reference.
  • Another group of preferred clay soil removal/anti-redeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984, incorporated herein by reference.
  • clay soil removal/anti-redeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985, all of which are incorporated herein by reference.
  • the most preferred soil release and anti-deposition agents are ethoxylated tetraethylenepentamine and the polythylene glycols having a molecular weight in the range of from about 4,000 to about 8,000.
  • Granular detergent compositions which contain such compounds typically contain from about 0.01% to about 10.0% by weight of the clay removal agent; liquid detergent compositions typically contain from about 0.01% to about 5.0% by weight.
  • Polymeric polycarboxylate dispersing agents can advantageously be utilized in the detergent compositions of the present invention. These materials can aid in calcium and magnesium hardness control. In addition to acting as a builder adjunt analogously to the poycarboxylate described above in the Builder description, it is believed, though it is not intended to be limited by theory, that these higher molecular weight dispersing agents can further enhance overall detergnet builder performance by inhibiting crystal growth of inorganics, by particulate soil peptization, and by antiredeposition, when used in combination with other builders including lower molecular weight polycarboxylates.
  • the polycarboxylate materials which can be employed as the polymeric polycarboxylate dispersing agent are these polymers or copolymers which contain at least about 60% by weight of segments with the general formula : wherein X, Y, and Z are each selected from the group consisting fo hydrogen, methyl, carboxy, carboxmethyl, hydroxy and hydroxymethyl; a salt forming cationand n is from about 30 to about 400.
  • Y is hydrogent or carboxy
  • Z is hydrogen
  • M is hydrogen, alkali metal, ammonia or substituted ammonium.
  • Polymeric polycarboxylate materials of this type can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
  • Water soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions have been disclosed, for example, in Diehl, U.S. Patent No. 3,308,067, issued March 7, 1967. This patent is incorporated herein by reference.
  • Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing agent.
  • Such materials include the water soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form ranges from about 5,000 to 100,000, preferably from about 6,000 to 60,000, more preferably from about 7,000 to 60,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, moe preferably from about 10:1 to 2:1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are knwon materials which are described in European Patent Application No. 66915, published December 15, 1982, which publication is incorporated herein by reference.
  • the polymeric dispersing agents will generally comprise from about 0.2% to about 10%, preferably form about 1% to about 5% by weight of the detergent compositions.
  • Optical brighteners or other brightening or whitening agents known to those skilled in the art can be incorporated into the laundry detergent compositions of the present invention.
  • the choice of brightener will depend upon a number of factors, such as the type of detergnt, the nature of other components present in the detergent composition, the temperatures of wahs wash, the degree of agitation, and the ratio of the material washed to tub size.
  • the brightener selection is also dependent upon the type of material to be cleaned, e.g. cottons, synthetics, etc. Since most laundry detergent products are used to clean a variety of fabrics, the detergent compositions should contain a mixture of brighteners which will be effective for a variety of fabrics. It is of course necessary that the individual components of such a brightener mixture be compatible.
  • optical brighteners can be classified into subgroups which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982), the disclosure of which is incorporated herein by reference.
  • Stilbene derivatives include, but are not necessarily limited to, derivatives of stilbene; triazole derivatives of stilbene; oxadiazole derivatives of stilbene; oxazole derivatives fo stilbene; and stryl of stilbene.
  • Certain derivatives of bis(triazinly) aminostilbene may be prepared from 4,4'-diamine-stilbene-2,2'-disulfonic acid.
  • Coumarin derivatives include, but are not necessarily limited to, derivatives substituted in the 3-position, in the 7-position, and in the 3- and 7-positions.
  • Carboxylic acid derivatives include, but are not necessarily limited to, fumaric acid derivatives; benzoic acid derivatives; p-phenylene-bis-acrylic acid derivatives; naphthalenedicarboxylic acid derivatives; heterocyclic acid derivatives; and cinnamic acid derivatives.
  • Cinnamic acid derivatives can be further subclassified into groups which include, but are not necessarily limited to, cinnamic acid derivatives, styrylazoles, styrylbenzofurans, styryloxadiazoles, styryltriazoles, and styrylpolyphenyls, as disclosed on page 77 of the Zahradnik reference.
  • the styrylazoles can be further subclassified into styrylbenzoxazoles, styrylimidazoles and styrylthiazoles, as disclosed on page 78 of the Zahradnik reference. It will be understood that these three identified subclasses may not necessarily reflect an exhaustive list of subgroups into which styrylazoles may be subclassified.
  • optical brighteners are the derivatives of dibenzothiophene-5,5-dioxide disclosed at page 741-749 of The Kirk-Othmer Encyclopedia of Chemical Technology, Volume 3, pages 737-750 (John Wiley & Son, Inc., 1962), the disclosure of which is incorporated herein by reference, and include 3,7-daiminodibenzothiophene-2, 8-disulfonic acid5, 5 dioxide.
  • optical brighteners are azoles, which are derivatives of 6-membered ring heterocycles. These can be further subcategorized into monoazoles and bisazoles. Examples of monazoles and bisazoles are disclosed in the Kirk-Othmer reference.Still other optical brigteners are the derivatives of 6-membered-ring heterocycles disclosed in the Kirk-Othmer reference. Examples of such compounds include brighteners derived from pyrazine and brighteners derived from 4-aminonaphthalamide.
  • miscellaneous agents may also be useful as brighteners.
  • miscellaneous agents are disclosed at pages 93-95 of the Zahradnik reference, and include 1-hydroxy-3,6,8-pyrenetrisulfonic acid; 2,4-dimethoxy-1,3,5-triazin-6-yl-pyrene; 4,5-diphenylimidazolonedisulfonic acid; and derivatives of pyrazolinequinoline.
  • optical brightener examples include those identified in U.S. Patent 4,790,856, issued to Wixon on December 13,1988, the disclosure of which is incorporated herein by reference. Thse brighteners include the PhorwhiteTM series of brighteners from Verona.
  • Tinopal UNPA Tinopal CBS adn Tinopal 5BM; available from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis, located in Italy; the 2-(4-styrylphenyl)-2H-naphthol(1,2-d)triazoles; 4,4'-bis-(1,2,3-triazol-2-yl)-stilbene; 4,4'-bis(styryl)bisphenyls; and the y-amino-coumarins.
  • these brighteners include 4-methyl-7-diethylamino coumarin; 1,2-bis (-bensimidazol-2-yl)-ethylene; 1,3-diphenylphrazolines; 2,5-bis(benzoxazol-2-yl)-thiophene; 2-styryl-naphth-(1,2-d)-oxazole; and 2-(stilbene-4-yl)-2H-naphtho(1,2-d)triazole.
  • Still other optical brighteners include those disclosed in U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton, the disclosure of which is incorporated herein by reference.
  • the optical brighteners will generally comprise from about 0.05% to about 2.0%, preferably from about 0.1% to about 1.0% by weight of the laundry detergent compositions.
  • Suds supressor can be desirable because the polyhydroxy fatty acid amide surfactants hereof can increase suds stability of the detergent compositions. Suds suppression can be of particular importance when the detergent compositons include a relatively high sudsing surfactant in combination with the polyhydroxy fatty acid amide surfactant. Suds suppression is particularly desirable for compositions intended for use in front loading automatic washing machines. These machines are typically characterized by having drums, for containing the laundry and wash water, which have a horizontal axis and rotary action about the axis. This type of agitation can result in high suds formation and, consquently, in reduced cleaning performance. The use of suds suppressors cna also be of particular importance under hot water wahsing conditions and under high surfactant concentration conditions.
  • suds suppressors are well known to those skilled in the art. They are generally described, for example, in Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
  • One categroy of suds suppressor of particular interest encompasses monocarboxylic fatty acids and soluble salts thereof. These materials are discussed in U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John, said patent being incorporated herein by reference.
  • the monocarboxylic fatty acids, and salts thereof, for use as suds suppressors typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts. These materials are a preferred category of suds suppressor for detergent compositions.
  • the detergent compositions of the present invention may also contain non-surfactant suds suppressors.
  • non-surfactant suds suppressors include, for example, high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C 18 -C 40 ketones (e.g. stearone), etc.
  • suds inhititors include N-alkylated amino triazines such as tri- to hexa-alkylemlamines or di- to tetra-alkyldaimine chlortriazines formed as products of cyanuric choloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., sodium, potassium, lithium) phosphates and phosphate esters.
  • the hydrocarbons, such as paraffin and haloparaffin can be utilized in liquid form.
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40°C and about 5°C, and a minimum boiling point not less than about 100°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C.
  • the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described for example in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al., incorporated herein by reference.
  • hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms.
  • the term "parrafin”, as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Non-surfactant suds comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethysiloxane, dispersions or emulsions fo polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed of fused onto the silica.
  • Silicone suds suppressors are well known in the art and are, for example disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al., and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M.S., both incorporated herein by reference.
  • silicone suds suppressors are disclosed in U.S. Patent 3,455,839, which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids. Mixtures of silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al., and in U.S. Patent 4,652,392, Baginski et al., issued March 24, 1987.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of :
  • Suds suppressors when utilized, are present in a “suds suppressing amoung".
  • Suds suppressing amount is meant that he formulator of the composition can select an amount of this suds controlling agent that will control the suds to the extent desired. Teh amount of suds control will vary with the detergent surfactant selected. Fro example, with high sudsing surfactants, relatively more of the suds controlling agent is used to achieve the desired suds control than with low foaming surfactants.
  • the detergent compositions of the present invention will generally comprise from 0% to about 5% of suds suppressor.
  • monocarboxylic fatty acids, and salts thereof When utilized as suds suppressors, monocarboxylic fatty acids, and salts thereof, will be present typically in amounts up to about 5%, by weight, of the detergent composition.
  • from about 0.5% to about 3% of fatty monocarboxylate suds suppressor is utilized.
  • Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
  • from about 0.01% to about 1% of silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%.
  • these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized.
  • Monostearyl phosphates are generally utilized in amounts ranging from about 0.1% to about 2% by weight of the compositions.
  • Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used.
  • ingredients which can be included in the detergent compositions of the present invention include other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulation.
  • Liquid detergent compositions can contain water and other solvents as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, and polyols such as those containing from about 2 to about 6 carbon atoms and from about 2 to about 6 hydroxy groups ( e.g.propylene glycol, ethylene glycol, glycerine, and 1,3-propandiol ) can also be used.
  • the detergent composition of the present invention will preferably be formulated such that during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and 11, preferably between about 7.5 and about 10.5.
  • Liquid product formulations preferably have a pH between about 7.5 and about 9.5, more preferably between about 7.5 and about 9.0.
  • Techniques for controlling pH at recommended usage levels include the use of buffers, alkali,acids, etc., and are well known to those skilled in the art.
  • This invention further provides a method for cleaning substrates, such as fibres, fabrics, hard surfaces, skin, etc., by contacting said substrate with a detergent composition containing the glyceryl ether component (a) and the anionic detersive surfactant component (b), in the presence of a solvent such as water or a water-misile solvent (e.g. a primary or secondary alcohol ).
  • a solvent such as water or a water-misile solvent (e.g. a primary or secondary alcohol ).
  • Agitation is preferably provided for enhancing cleaning.
  • Suitable means for providing agitation include rubbing by hand, preferably with the aid of a brush, or other cleaning device, automatic laundry washing machine, automatic dish washer or the like.
  • the glyceryl ethers employed as component (a) allow the replacement of polyethoxylate nonionic surfactants, thereby obviating the need to use ethylene oxide, whilst obtaining excellent cleaning characteristics.
  • the glyceryl ethers of the formula (1) are very effective against greasy stains whilst showing no significant weaknesses against other, e.g. particulate, stains: furthermore, the glyceryl ethers are satisfactory with regard to redeposition of soils.
  • the glyceryl ethers exhibit further advantages, for example the stabilization of enzyme in heavy duty detergent liquids.
  • the glyceryl ethers have comparatively low melting points and their use as agglomerating agents comes into consideration.
  • Cocoyl diglyceryl ether was prepared by a method analogous to that described by Sagitani et al. , J.O.A.C.S, Vol. 66, No.1 (January 1989) page 146, using the following reagents:
  • the sodium and glyceryl were reacted together at 130°C for one hour under nitrogen.
  • the epoxide was added dropwise over one hour to the reaction mixture and 180°C, the mixture then being stirred at that temperature for 8 hours.
  • the reaction mix was dissolved in ethanol and treated with pellets of carbon dioxide in order to neutralize the sodium.
  • the mix was freed of ethanol on a rotary evaporator and then distilled (1.75 mmHg (233 Pa);140°C head temperature) to remove a fore-fraction of glycerol dimer ( identified as such using gas-liquid chromatography).
  • the dodecyl diglyceryl ether as produced was a low-melting (44-46°C) solid comprising 92% diglyceryl ethers, 1.5% monoglyceryl ethers and 2% triglyceryl ethers.
  • the diglyceryl ether contained approximately 4 moles of the "linear” ether of the general formula (2) per mole of the "branched” ether of the general formula (3).
  • the above synthesis may also be carried using Epoxide No. 8 to which a small amount of sodium borohydride has been added, in order to obtain the end product of improved color.
  • Cocoyl diglyceryl ether was prepared by the method of Takaishi et al. ,US-A-4,465,866, using the following reagents:
  • the acetone glycerol ketal and tetramethyldiaminohexane were mixed together and heated to 100°C.
  • the epoxide was added dropwise over a period of 30 minutes, keeping the temperature between 100 and 110°C.
  • the resultant mixture was then heated at that temperature for 6 hours.
  • the product was distilled (1mm Hg (133Pa) at 52°C head temperature) to remove the excess acetone glycerol ketal, and was vacuum distilled further (4.5 mmHg (600 Pa) at a head temperature of 230°C) to collect the product (dioxolane intermediate).
  • a series of heavy duty liquid detergent compositions, A-C were prepared, these compositions having the surfactant components shown in the following Table, in which the amount of each component is shown in percent by weight of the composition.
  • Surfactant A B C NaCnAS 12.9 12.9 12.9 Nat. NI E07 8.4 - - Nat. NI E05 - 8.4 - CnDGE - - 8.4
  • compositions were tested against a variety of stains, wherein soiled loads were washed in a miniwasher at 60°C using city water ( 5 moles total hardness ), at 1 percent usage.
  • the soiled loads were prepared by staining cotton or polyester/cotton (PC) swatches in conventional manner.
  • the composition C which is according to the present invention, exhibited an excellent cleaning performance, especially against greasy stains and particulate stains.
  • a reference composition was prepared in the form of a heavy duty detergent liquid containing 7.25 percent by weight of linear alkyl benzene sulfonate, 1,75 percent coconut-alkyl sulfate, 9 percent of citric builder, 5 percent of other builder and 10 percent of condensate of fatty alkyl alcohol with, per mole,7 moles of ethylene oxide.
  • test composition was then prepared, this being essentially similar to the reference composition but with only 6 percent of the said fatty alkyl alcohol/ethylene oxide condensate but with 4 percent of coconut alkyl diglyceryl ether (prepared as in Example 1 above).
  • test composition which was formulated according to the present invention, showed improved performance against greasy stains with comparable performance against other stains.

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Claims (10)

  1. Composition détergente comprenant:
    (a) un ou plusieurs éthers de glycéryle de fonnule générale RO - (C3H6O2)nH dans laquelle
    R représente un groupe alkyle ou alcényle de 12 à 18 atomes de carbone,
    C3H6O2 représente un radical divalent formé par l'élimination d'un groupe hydroxyle d'un glycérol et de l'atome d'hydrogène du groupe hydroxyle restant, et
    n est un nombre entier,
    présents à raison de 0.5% à 10% en poids de la composition détergente, au moins 50 pour cent en moles du constituant (a) étant constitués d'éther de diglycéryle et pas plus de 25 pour cent en moles du constituant (a) étant constitués d'éther de monoglycéryle, et
    (b) un tensioactif détersif anionique.
  2. Composition selon la revendication 1, dans laquelle au moins 60 pour cent en moles du constituant (a) sont constitués d'éther de diglycéryle et pas plus de 20 pour cent en moles du constituant (a) sont constitués d'éther de monoglycéryle.
  3. Composition selon la revendication 1 ou 2, dans laquelle l'éther de diglycéryle du constituant (1) est un mélange comprenant les éthers de diglycéryle de formules générales: R-OCH2CHOHCH2-OCH2CHOHCH2OH et
    Figure 00540001
  4. Composition selon la revendication 3, dans laquelle les éthers de formules (2) et (3) sont présents dans un rapport molaire d'environ 4:1.
  5. Composition selon l'une quelconque des revendications 1 à 4, dans laquelle le constituant (a) est pratiquement entièrement de l'éther de diglycéryle.
  6. Composition selon l'une quelconque des revendications 1 à 5, dans laquelle R est un groupe alkyle de coprah.
  7. Composition selon l'une quelconque des revendications 1 à 6, qui comprend aussi au moins un autre constituant choisi parmi les tensioactifs détersifs cationiques, ampholytes, zwittérioniques et semi-polaires, les adjuvants de détergence, les enzymes, les agents de blanchiment et les agents chélatants.
  8. Composition selon l'une quelconque des revendications 1 à 7, sous forme d'un liquide détergent pour usage intensif ou de granulés détergents pour usage intensif.
  9. Procédé de préparation d'un éther de diglycéryle de formule (1) donnée dans la revendication 1, ou d'un mélange de tels éthers, dans lequel on fait réagir un composé de formule générale:
    Figure 00550001
       dans laquelle R a la signification donnée dans la revendication 1,
       avec du glycérol en présence d'une base et/ou avec un glycérate et les impuretés du produit sont éliminées par distillation.
  10. Utilisation comme tensioactif détersif d'un éther de diglycéryle de formule (1) selon la revendication 1, ou d'un mélange de tels éthers.
EP92924209A 1991-11-08 1992-11-02 Compositions detergentes comprenant des ethers de glyceryle Expired - Lifetime EP0611392B1 (fr)

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GB919123734A GB9123734D0 (en) 1991-11-08 1991-11-08 Detergent composition
GB9123734 1991-11-08
PCT/US1992/009386 WO1993009214A1 (fr) 1991-11-08 1992-11-02 Compositions detergentes comprenant des ethers de glyceryle

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JP3759345B2 (ja) * 1999-08-09 2006-03-22 花王株式会社 液体洗浄剤
JP3371098B2 (ja) * 1999-11-04 2003-01-27 花王株式会社 洗浄剤組成物
DE19959000B4 (de) 1999-12-08 2018-07-05 Cognis Ip Management Gmbh Verwendung primärer Monoalkylether von Eigenkondensationsprodukten des Glycerins
US7098181B2 (en) 2002-05-22 2006-08-29 Kao Corporation Liquid detergent composition
EP1405669B1 (fr) * 2002-08-29 2007-11-28 Kao Corporation Procédé de fabrication d'adduit de glycidylether et catalyseur utilisé dans ce procédé
JP4423237B2 (ja) * 2005-06-13 2010-03-03 太陽化学株式会社 洗浄剤用増粘剤
JP4348319B2 (ja) * 2005-06-13 2009-10-21 太陽化学株式会社 洗浄剤組成物
JP4348329B2 (ja) * 2005-10-21 2009-10-21 太陽化学株式会社 液体洗浄剤組成物
AU2007232772B2 (en) * 2006-03-31 2012-03-08 Kao Corporation Softening detergent composition
WO2008081990A1 (fr) * 2006-12-28 2008-07-10 Kao Corporation Composition détersive
JP5046714B2 (ja) 2007-04-06 2012-10-10 花王株式会社 衣料用洗剤組成物
JP5101997B2 (ja) * 2007-11-09 2012-12-19 花王株式会社 高嵩密度洗剤組成物
WO2009084729A1 (fr) 2007-12-28 2009-07-09 Kao Corporation Composition détergentes pour lessive
JP2009227583A (ja) * 2008-03-19 2009-10-08 Daicel Chem Ind Ltd ポリグリセリンアルキルエーテル型非イオン界面活性剤
KR101789284B1 (ko) 2011-11-25 2017-10-24 주식회사 엘지생활건강 일반 세탁 및 드라이클리닝용 친환경 용제 및 이를 포함한 조성물
CN113980747B (zh) * 2021-11-10 2023-08-25 重庆臻宝科技股份有限公司 一种半导体材料表面脱脂处理的清洗剂

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MX9206421A (es) 1994-05-31

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