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WO1997034973A1 - Light duty liquid cleaning compositions - Google Patents

Light duty liquid cleaning compositions Download PDF

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Publication number
WO1997034973A1
WO1997034973A1 PCT/US1997/004407 US9704407W WO9734973A1 WO 1997034973 A1 WO1997034973 A1 WO 1997034973A1 US 9704407 W US9704407 W US 9704407W WO 9734973 A1 WO9734973 A1 WO 9734973A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
surfactant
composition
glycol
solubilizing agent
Prior art date
Application number
PCT/US1997/004407
Other languages
French (fr)
Inventor
Gary Jakubicki
Leonard Zyzyck
Original Assignee
Colgate-Palmolive Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Colgate-Palmolive Company filed Critical Colgate-Palmolive Company
Priority to AU25350/97A priority Critical patent/AU2535097A/en
Publication of WO1997034973A1 publication Critical patent/WO1997034973A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/86Mixtures of anionic, cationic, and non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/52Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/662Carbohydrates or derivatives

Definitions

  • This invention relates to a light duty liquid cleaning composition which imparts mildness to the skin and is designed in particular for dishware and which is effective in removing grease soil and in leaving unrinsed surfaces with a shiny appearance. Rark ⁇ rnund of the Invention
  • all-purpose liquid detergents have become widely accepted for cleaning hard surfaces, e.g., painted woodwork and panels, tiled walls, wash bowls, bathtubs, linoleum or tile floors, washable wall paper, etc.
  • Such all-purpose liquids comprise clear and opaque aqueous mixtures of water-soluble synthetic organic detergents and water-soluble detergent builder salts.
  • use of water-soluble inorganic phosphate builder salts was favored in the prior art all-purpose liquids.
  • such early phosphate-containing compositions are described in U.S. Patent Nos. 2,560,839; 3,234,138; 3,350,319; and British Patent No.
  • an o/w microemulsion is a spontaneously forming colloidal dispersion of "oil" phase particles having a particle size in the range of about 25 to about 800 A in a continuous aqueous phase.
  • microemuisions are transparent to light and are clear and usually highly stable against phase separation.
  • Patent disclosures relating to use of grease-removal solvents in o/w microemuisions include, for example, European Patent Applications EP 0137615 and EP 0137616 - Herbots et al; European Patent Application EP 0160762 - Johnston et al; and U.S. Patent No. 4,561 ,991 - Herbots et al. Each of these patent disclosures also teaches using at least 5% by weight of grease-removal solvent.
  • compositions of this invention described by Herbots et al. require at least 5% of the mixture of grease-removal solvent and magnesium salt and preferably at least 5% of solvent (which may be a mixture of water-immiscible non-polar solvent with a sparingly soluble slightly polar solvent) and at least 0.1% magnesium salt.
  • the present invention relates to novel light duty liquid detergent compositions with high foaming properties, containing two different sulfonate surfactants, an ammonium salt of an ethoxylated alkyl ether sulfate surfactant, an alkyl polyglucoside surfactant and water.
  • 4,329,335 also discloses a shampoo containing a betaine surfactant as the major ingredient and minor amounts of a nonionic surfactant and of a fatty acid mono- or di-ethanolamide.
  • U.S. Patent No. 4,259,204 discloses a shampoo comprising 0.8-20% by weight of an anionic phosphoric acid ester and one additional surfactant which may be either anionic, amphoteric. or nonionic.
  • U.S. Patent No. 4,329.334 discloses an anionic-amphoteric based shampoo containing a major amount of anionic surfactant and lesser amounts of a betaine and nonionic surfactants.
  • 3,935.129 discloses a liquid cleaning composition based on the alkali metal silicate content and containing five basic ingredients, namely, urea, glycerin, triethanolamine, an anionic detergent and a nonionic detergent.
  • the silicate content determines the amount of anionic and/or nonionic detergent in the liquid cleaning composition.
  • U.S. Patent No. 4,129,515 discloses a heavy duty liquid detergent for laundering fabrics comprising a mixture of substantially equal amounts of anionic and nonionic surfactants, alkanolamines and magnesium salts, and, optionally, zwitterionic surfactants as suds modifiers.
  • U.S. Patent No. 4,224,195 discloses an aqueous detergent composition for laundering socks or stockings comprising a specific group of nonionic detergents, namely, an ethylene oxide of a secondary alcohol, a specific group of anionic detergents, namely, a sulfuric ester salt of an ethylene oxide adduct of a secondary alcohol, and an amphoteric surfactant which may be a betaine, wherein either the anionic or nonionic surfactant may be the major ingredient.
  • the prior art also discloses detergent compositions containing all nonionic surfactants as shown in U.S. Patent Nos.
  • U.S. Patent 4,671 ,895 teaches a liquid detergent composition containing an alcohol sulfate surfactant, a nonionic surfactant, a paraffin sulfonate surfactant, an alkyl ether sulfate surfactant and water.
  • U.S. Patent No. 4,450,091 discloses high viscosity shampoo compositions containing a blend of an amphoteric betaine surfactant, a polyoxybutylene polyoxyethylene nonionic detergent, an anionic surfactant, a fatty acid alkanolamide and a polyoxyalkylene glycol fatty ester. But, none of the exemplified compositions contains an active ingredient mixture wherein the nonionic detergent is present in major proportion, probably due to the low foaming properties of the polyoxybutylene polyoxyethylene nonionic detergent.
  • U.S. Patent No. 4,595,526 describes a composition comprising a nonionic surfactant, a betaine surfactant, an anionic surfactant and a C-
  • An object of this invention is to provide a novel light duty liquid detergent composition containing two different sulfonate surfactants, an alkali metal salt or ammonium salt of an ethoxylated alkyl ether sulfate surfactant, an alkyl polygiucoside surfactant and water wherein the composition does not contain any amine oxide, betaine surfactant, silicas, abrasives, alkali metal carbonates, alkaline earth metal carbonates, alkyl giycine surfactant, cyclic imidinium surfactant, low molecular weight mono- or di-glucoside or more than 3 wt. % of a fatty acid or salt thereof or more than 0.5 wt. % of a nonionic surfactant which is an aliphatic ethoxylate or an ethylene oxide and/or propylene oxide condensates with an alkanol.
  • Another object of this invention is to provide a novel light duty liquid detergent with desirable high foaming and cleaning properties which is mild to the human skin. Additional objects, advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention. The objects and advantages of the invention may be reatized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
  • the novel, high foaming light duty liquid detergent of this invention comprises five essential surfactants: a water soluble, ethoxylated, nonionic surfactant, a betaine surfactant, an alkali metal or ammonium salt of an ethoxylated alkyl ether sulfate surfactant, a magnesium salt of a sulfonate surfactant, and a sulfonate anionic surfactant, wherein the composition does not contain any amine oxide, silicas, abrasives, alkali metal carbonates, alkaline earth metal carbonates, alkyl giycine surfactant, cyclic imidinium surfactant or more than 3 wt. % of a fatty acid or salt thereof.
  • compositions of the instant invention comprise approximately by weight:
  • the C ⁇ -18 ethoxylated alkyl ether sulfate surfactants used in the instant composition have the structure +
  • R-(OCHCH2) n OS ⁇ 3M wherein n is about 1 to about 22 more preferably 1 to 3 and R is an alkyl group having about 8 to about 18 carbon atoms, more preferably 12 to 15 and natural cuts, for example, C 12-14; C12-15 and M is an ammonium cation or an alkali metal cation, most preferably sodium or ammonium.
  • the ethoxylated alkyl ether sulfate is present in the composition at a concentration of about 0.5 wt. % to about 22 wt. %, more preferably about 1 wt. % to 20 wt. %.
  • the ethoxylated alkyl ether sulfate may be made by sulfating the condensation product of ethylene oxide and C ⁇ -10 alkanol, and neutralizing the resultant product.
  • the ethoxylated alkyl ether sulfates differ from one another in the number of carbon atoms in the alcohols and in the number of moles of ethylene oxide reacted with one mole of such alcohol.
  • Preferred ethoxylated alkyl ether polyethenoxy sulfates contain 12 to 15 carbon atoms in the alcohols and in the alkyl groups thereof, e.g., sodium myristyl (3 EO) sulfate.
  • Ethoxylated C ⁇ -18 alkylphenyl ether sulfates containing from 2 to 6 moles of ethylene oxide in the molecule are also suitable for use in the invention compositions.
  • These detergents can be prepared by reacting an alkyl phenol with 2 to 6 moles of ethylene oxide and sulfating and neutralizing the resultant ethoxylated alkylphenol.
  • a mixture of two linear alkyl benzene sulfonates containing from 10 to 16 carbon atoms in the alkyl group are used in the instant compositions wherein both of the alkyl benzene sulfonates have a high content of 3- (or higher) phenyl isomers and a correspondingly low content (well below 50%) of 2- (or lower) phenyl isomers, that is, wherein the benzene ring is preferably attached in large part at the 3 or higher (for example, 4, 5, 6 or 7) position of the alkyl group and the content of the isomers in which the benzene ring is attached in the 2 or 1 position.
  • One of these sulfonate surfactants is a sodium salt of a C10-C16 linear alkyl benzene sulfonate used at a concentration of about 0.5 wt. % to about 10 wt. %, more preferably about 1 wt. % to about 9 wt. % in the instant compositions.
  • the other sulfonate surfactant is a magnesium salt of a C10-C16 linear alkyl benzene sulfonate used at a concentration of about 2 wt. % to about 16 wt. %, more preferably about 3 wt % to about 14 wt. % in the instant compositions.
  • compositions contain about 2 wt. % to about 16 wt. %, more preferably 4 wt. % to 14 wt. % of an alkyl polysaccharide surfactant.
  • the alkyl polysacchandes surfactants which are used in conjunction with the aforementioned surfactant have a hydrophobic group containing from about 8 to about 20 carbon atoms, preferably from about 10 to about 16 carbon atoms, most preferably from about 12 to about 14 carbon atoms, and polysaccharide hydrophilic group containing from about 1 5 to about 10, preferably from about 1.5 to about 4, most preferably from about 1.6 to about 2.7 saccha de units (e.g., galactoside, glucostde, fructoside, glucosyl, fructosyl; and/or gaiactosyl units).
  • the number x indicates the number of sacchande units in a particular alkyl polysacchande surfactant.
  • x can only assume integral values.
  • the physical sample can be characterized by the average value of x and this average value can assume non-integral values. In this specification the values of x are to be understood to be average values.
  • the hydrophobic group (R) can be attached at the 2- , 3-, or 4- positions rather than at the 1 -position, (thus giving e.g.
  • glucosyl or gaiactosyl as opposed to a glucoside or galactoside).
  • attachment through the 1- position i.e., glucosides, galactoside, fructosides, etc.
  • additional sacchande units are predominately attached to the previous sacchande unit's 2-pos ⁇ tton. Attachment through the 3-, 4-, and 6- positions can also occur.
  • the preferred alkoxide moiety is ethoxide.
  • Typical hydrophobic groups include alkyl groups, either saturated or unsaturated. branched or unbranched containing from about 8 to about 20, preferably from about 10 to about 18 carbon atoms.
  • the alkyl group is a straight chain saturated alkyl group.
  • the alkyl group can contain up to 3 hydroxy groups and or the polyalkoxide chain can contain up to about 30, preferably less than about 10, alkoxide moieties.
  • Suitable alkyl polysaccharides are decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl, di-, tn-, tetra-, pe ⁇ ta-, and hexaglucosides, galactosides, lactosides, fructosides, fructosyls, lactosyls, glucosyls and/or gaiactosyls and mixtures thereof.
  • the alkyl monosaccharides are relatively less soluble in water than the higher alkyl polysaccharides. When used in admixture with alkyl polysaccharides. the alkyl monosaccharides are solubilized to some extent.
  • the use of alkyl monosaccharides in admixture with alkyl polysaccharides is a preferred mode of carrying out the invention Suitable mixtures include coconut alkyl, d ⁇ -, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.
  • the preferred alkyl polysaccharides are alkyl polyglucosides having the formula wherein Z is derived from glucose, R is a hydrophobic group selected from the group consisting of alkyl, alkylphenyl, hydroxyalkylphenyl, and mixtures thereof in which said alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14 carbon atoms; n is 2 or 3 preferably 2, r is from 0 to 10, preferably 0; and x is from 1.5 to 8, preferably from 1.5 to 4, most preferably from 1.6 to 2.7.
  • R2OH long chain alcohol
  • the alkyl polyglucosides can be prepared by a two step procedure in which a short chain alcohol (R1 OH) can be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside.
  • the short chain alkylgiucosde content of the final alkyl poiyglucoside material should be less than 50%, preferably less than 1 %, more preferably less than about 5%, most preferably 0% of the alkyl poiyglucoside.
  • the amount of unreacted alcohol (the free fatty alcohol content) in the desired alkyl polysaccharide surfactant is preferably less than about 2%, more preferably less than about 0.5% by weight of the total of the alkyl polysaccharide. For some uses it is desirable to have the alkyl monosaccharide content less than about 10%.
  • alkyl polysaccharide surfactant is intended to represent both the preferred glucose and galactose derived surfactants and the less preferred alkyl polysaccharide surfactants.
  • alkyl poiyglucoside is used to include alkyl polyglycosides because the stereochemistry of the saccharide moiety is changed during the preparation reaction.
  • APG glycoside surfactant is APG 625 glycoside manufactured by the Henkel Corporation of Ambler, PA.
  • APG 625 has: a pH of 6 to 10 (10% of APG 625 in distilled water); a specific gravity at 25°C of 1.1 g/ml; a density at 25°C of 9.1 lbs/gallon; a calculated HLB of 12.1 and a Brookfield viscosity at 35°C. 21 spindle, 5-10 RPM of 3,000 to 7,000 cps.
  • the instant compositions contain about 1 wt. % to about 6 wt. %, more preferably about 1.5 wt. % to about 5 wt. % of a Cl 2-C14 alkyl monoalkanol amide such as lauryl monoalkanol amide (LMMEA).
  • the instant compositions contain about 0 wt. % to about 12 wt. %, more preferably about 1 wt. % to about 10 wt. %, of at least one solubilizing agent which can be sodium xylene sulfonate, sodium cumene sulfonate.
  • solubilizing agents are included in order to control low temperature cloud clear properties.
  • Urea can be optionally employed in the instant composition as a supplemental solubilizing agent at a concentration of 0 to about 10 wt. %, more preferably about 0.5 wt. % to about 8 wt. %.
  • solubilizing agents are glycerol.
  • n is a number from 2 to 18, mixtures of polyethylene glycol and polypropylene glycol (Synalox) and mono Ci -C ⁇ alkyl ethers and esters of ethylene glycol and propylene glycol having the structural formulas R(X) n OH and Rl (X) n OH wherein R is C1-C6 alkyl group, Ri is C2-C4 acyl group, X is (OCH2CH2) or (OCH2(CH3)CH) and n is a number from 1 to 4.
  • Representative members of the polypropylene glycol include dipropylene glycol and polypropylene glycol having a molecular weight of 200 to 1000, e.g., polypropylene glycol 400.
  • Other satisfactory glycol ethers are ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monobutyl ether, mono, di, tri propylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, mono, di, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, propylene glycol tertiary butyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monopentyl ether.
  • tributylene glycol mono methyl ether mono, di, tributylene glycol monoethyl ether, mono, di, tributylene glycol monopropyl ether, mono, di. tributylene glycol monobutyl ether, mono, di, tributylene glycol monopentyl ether and mono, di. tributylene glycol monohexyl ether, ethylene glycol monoacetate and dipropylene glycol propionate.
  • the instant formulas explicitly exclude alkali metal silicates and alkali metal builders such as alkali metal polyphosphates, alkali metal carbonates, alkali metal phosphonates and alkali metal citrates because these materials, if used in the instant composition, would cause the composition to have a high pH as well as leaving residue on the surface being cleaned.
  • alkali metal silicates and alkali metal builders such as alkali metal polyphosphates, alkali metal carbonates, alkali metal phosphonates and alkali metal citrates because these materials, if used in the instant composition, would cause the composition to have a high pH as well as leaving residue on the surface being cleaned.
  • the final essential ingredient in the inventive compositions having improved interfacial tension properties is water.
  • the instant compositions exhibit stability at reduced and increased temperatures. More specifically, such compositions remain clear and stable in the range of 5°C to 50°C, especially 10°C to 43°C.
  • the instant compositions have a light transmission of at least 95%.
  • Such compositions exhibit a pH of 5 to 8.
  • the liquid compositions are readily pourable and exhibit a viscosity in the range of 100 to 600 cps as measured at 25°C. with a Brookfield RVT Viscometer using a #2 spindle rotating at 30 RPM. Preferably, the viscosity is maintained in the range of 300 to 500 cps.
  • the instant compositions have a minimum foam height of 110 mis after 55 rotation at 40°C as measured by the foam volume test using 0.75 grams of the composition per liter of water and 1 gram of corn oil per liter of water having a hardness of 300 ppm.
  • composition in wt. % was prepared by simple mixing procedure at °C:

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Abstract

A light duty liquid detergent with desirable cleansing properties and mildness to the human skin comprising: two different sulfonate surfactants, and alkali metal or ammonium salt of a C8-18 ethoxylated alkyl ether sulfate anionic surfactant, an alkyl polyclucoside surfactant, and water.

Description

LIGHT DUTY LIQUID CLEANING COMPOSITIONS FiPlri of Invention
This invention relates to a light duty liquid cleaning composition which imparts mildness to the skin and is designed in particular for dishware and which is effective in removing grease soil and in leaving unrinsed surfaces with a shiny appearance. Rarkπrnund of the Invention
In recent years all-purpose liquid detergents have become widely accepted for cleaning hard surfaces, e.g., painted woodwork and panels, tiled walls, wash bowls, bathtubs, linoleum or tile floors, washable wall paper, etc. Such all-purpose liquids comprise clear and opaque aqueous mixtures of water-soluble synthetic organic detergents and water-soluble detergent builder salts. In order to achieve comparable cleaning efficiency with granular or powdered all-purpose cleaning compositions, use of water-soluble inorganic phosphate builder salts was favored in the prior art all-purpose liquids. For example, such early phosphate-containing compositions are described in U.S. Patent Nos. 2,560,839; 3,234,138; 3,350,319; and British Patent No. 1 ,223,739. In view of the environmentalist's efforts to reduce phosphate levels in ground water, improved all-purpose liquids containing reduced concentrations of inorganic phosphate builder salts or non-phosphate builder salts have appeared. A particularly useful self-opacified liquid of the latter type is described in U.S. Patent No. 4,244.840. However, these prior art all-purpose liquid detergents containing detergent builder salts or other equivalent tend to leave films, spots or streaks on cleaned unrinsed surfaces, particularly shiny surfaces. Thus, such liquids require thorough rinsing of the cleaned surfaces which is a time-consuming chore for the user. In order to overcome the foregoing disadvantage of the prior art all-purpose liquid, U.S. Patent No. 4,017,409 teaches that a mixture of paraffin sulfonate and a reduced concentration of inorganic phosphate builder salt should be employed. However, such compositions are not completely acceptable from an environmental point of view based upon the phosphate content. On the other hand, another alternative to achieving phosphate-free all-purpose liquids has been to use a major proportion of a mixture of anionic and nonionic detergents with minor amounts of glycol ether solvent and organic amine as shown in U.S. Patent No. 3,935,130. Again, this approach has not been completely satisfactory and the high levels of organic detergents necessary to achieve cleaning cause foaming which, in turn, leads to the need for thorough rinsing which has been found to be undesirable to today's consumers.
Another approach to formulating hard surface or all-purpose liquid detergent composition where product homogeneity and clarity are important considerations involves the formation of oil-in-water (o/w) microemuisions which contain one or more surface-active detergent compounds, a water-immiscible solvent (typically a hydrocarbon solvent), water and a "cosurfactant" compound which provides product stability. By definition, an o/w microemulsion is a spontaneously forming colloidal dispersion of "oil" phase particles having a particle size in the range of about 25 to about 800 A in a continuous aqueous phase.
In view of the extremely fine particle size of the dispersed oil phase particles, microemuisions are transparent to light and are clear and usually highly stable against phase separation.
Patent disclosures relating to use of grease-removal solvents in o/w microemuisions include, for example, European Patent Applications EP 0137615 and EP 0137616 - Herbots et al; European Patent Application EP 0160762 - Johnston et al; and U.S. Patent No. 4,561 ,991 - Herbots et al. Each of these patent disclosures also teaches using at least 5% by weight of grease-removal solvent.
It also is known from British Patent Application GB 21 4763A to Herbots et al, published March 13, 1985, that magnesium salts enhance grease-removal performance of organic grease-removal solvents, such as the terpenes, in o/w microemulsion liquid detergent compositions. The compositions of this invention described by Herbots et al. require at least 5% of the mixture of grease-removal solvent and magnesium salt and preferably at least 5% of solvent (which may be a mixture of water-immiscible non-polar solvent with a sparingly soluble slightly polar solvent) and at least 0.1% magnesium salt.
However, since the amount of water immiscible and sparingly soluble components which can be present in an o/w microemulsion, with low total active ingredients without impairing the stability of the microemulsion is rather limited (for example, up to about 18% by weight of the aqueous phase), the presence of such high quantities of grease-removal solvent tend to reduce the total amount of greasy or oily soils which can be taken up by and into the microemulsion without causing phase separation. The present invention relates to novel light duty liquid detergent compositions with high foaming properties, containing two different sulfonate surfactants, an ammonium salt of an ethoxylated alkyl ether sulfate surfactant, an alkyl polyglucoside surfactant and water.
The prior art is replete with light duty liquid detergent compositions containing nonionic surfactants in combination with anionic and/or betaiπe surfactants wherein the nonionic detergent is not the major active surfactant, as shown in U.S. Patent No. 3,658,985 wherein an anionic based shampoo contains a minor amount of a fatty acid alkanolamide. U.S. Patent No. 3,769.398 discloses a betaine-based shampoo containing minor amounts of nonionic surfactants. This patent states that the low foaming properties of nonionic detergents renders its use in shampoo compositions non-preferred. U.S. Patent No. 4,329,335 also discloses a shampoo containing a betaine surfactant as the major ingredient and minor amounts of a nonionic surfactant and of a fatty acid mono- or di-ethanolamide. U.S. Patent No. 4,259,204 discloses a shampoo comprising 0.8-20% by weight of an anionic phosphoric acid ester and one additional surfactant which may be either anionic, amphoteric. or nonionic. U.S. Patent No. 4,329.334 discloses an anionic-amphoteric based shampoo containing a major amount of anionic surfactant and lesser amounts of a betaine and nonionic surfactants. U.S. Patent No. 3,935.129 discloses a liquid cleaning composition based on the alkali metal silicate content and containing five basic ingredients, namely, urea, glycerin, triethanolamine, an anionic detergent and a nonionic detergent. The silicate content determines the amount of anionic and/or nonionic detergent in the liquid cleaning composition. However, the foaming property of these detergent compositions is not discussed therein. U.S. Patent No. 4,129,515 discloses a heavy duty liquid detergent for laundering fabrics comprising a mixture of substantially equal amounts of anionic and nonionic surfactants, alkanolamines and magnesium salts, and, optionally, zwitterionic surfactants as suds modifiers.
U.S. Patent No. 4,224,195 discloses an aqueous detergent composition for laundering socks or stockings comprising a specific group of nonionic detergents, namely, an ethylene oxide of a secondary alcohol, a specific group of anionic detergents, namely, a sulfuric ester salt of an ethylene oxide adduct of a secondary alcohol, and an amphoteric surfactant which may be a betaine, wherein either the anionic or nonionic surfactant may be the major ingredient. The prior art also discloses detergent compositions containing all nonionic surfactants as shown in U.S. Patent Nos. 4,154,706 and 4,329,336 wherein the shampoo compositions contain a plurality of particular nonionic surfactants in order to effect desirable foaming and detersive properties despite the fact that nonionic surfactants are usually deficient in such properties. U.S. Patent No. 4,013,787 discloses a piperazine based polymer in conditioning and shampoo compositions which may contain all nonionic surfactant or all anionic surfactant.
U.S. Patent 4,671 ,895 teaches a liquid detergent composition containing an alcohol sulfate surfactant, a nonionic surfactant, a paraffin sulfonate surfactant, an alkyl ether sulfate surfactant and water.
U.S. Patent No. 4,450,091 discloses high viscosity shampoo compositions containing a blend of an amphoteric betaine surfactant, a polyoxybutylene polyoxyethylene nonionic detergent, an anionic surfactant, a fatty acid alkanolamide and a polyoxyalkylene glycol fatty ester. But, none of the exemplified compositions contains an active ingredient mixture wherein the nonionic detergent is present in major proportion, probably due to the low foaming properties of the polyoxybutylene polyoxyethylene nonionic detergent.
U.S. Patent No. 4,595,526 describes a composition comprising a nonionic surfactant, a betaine surfactant, an anionic surfactant and a C-| 2-C-] 4 fatty acid monethanolamide foam stabilizer.
However, none of the above-cited patents discloses a liquid detergent composition containing two different sulfonate surfactants, an alkali metal or ammonium salt of an ethoxylated alkyl ether sulfate surfactant, an alkyl polyglucqside surfactant and water, wherein the composition does not contain any amine oxide, betaine surfactant, low molecular weight mono- or di-glucoside, abrasives, silicas, alkaline earth metal carbonates, alkyl giycine surfactant, cyclic imidinium surfactant, alkali metal carbonates or more than 3 wt. % of a fatty acid or its salt thereof or more than 0.5 wt. % of a nonionic surfactant which is an aliphatic ethoxylate or an ethylene oxide and/or propylene oxide condensate with an alkanol. Summary of the Invention
It has now been found that a light duty liquid composition which has desirable cleaning properties together with mildness to the human skin.
An object of this invention is to provide a novel light duty liquid detergent composition containing two different sulfonate surfactants, an alkali metal salt or ammonium salt of an ethoxylated alkyl ether sulfate surfactant, an alkyl polygiucoside surfactant and water wherein the composition does not contain any amine oxide, betaine surfactant, silicas, abrasives, alkali metal carbonates, alkaline earth metal carbonates, alkyl giycine surfactant, cyclic imidinium surfactant, low molecular weight mono- or di-glucoside or more than 3 wt. % of a fatty acid or salt thereof or more than 0.5 wt. % of a nonionic surfactant which is an aliphatic ethoxylate or an ethylene oxide and/or propylene oxide condensates with an alkanol.
Another object of this invention is to provide a novel light duty liquid detergent with desirable high foaming and cleaning properties which is mild to the human skin. Additional objects, advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention. The objects and advantages of the invention may be reatized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
To achieve the foregoing and other objects and in accordance with the purpose of the present invention, as embodied and broadly described herein the novel, high foaming light duty liquid detergent of this invention comprises five essential surfactants: a water soluble, ethoxylated, nonionic surfactant, a betaine surfactant, an alkali metal or ammonium salt of an ethoxylated alkyl ether sulfate surfactant, a magnesium salt of a sulfonate surfactant, and a sulfonate anionic surfactant, wherein the composition does not contain any amine oxide, silicas, abrasives, alkali metal carbonates, alkaline earth metal carbonates, alkyl giycine surfactant, cyclic imidinium surfactant or more than 3 wt. % of a fatty acid or salt thereof.
Detailed Description of the Invention
The light duty liquid compositions of the instant invention comprise approximately by weight:
(a) 0.5% to 22% of an alkali metal salt or ammonium salt of a Cβ-18 ethoxylated alkyl ether sulfate;
(b) 0.5% to 10% of a sodium salt of a linear alkyl benzene sulfonate surfactant;
(c) 1 % to 6% of a C 12-14 alkyl monoalkanol amide ;
(d) 2% to 16% of a magnesium salt of a linear alkyl benzene sulfonate surfactant;
(e) 2% to 15% of an alkyl polyglucoside surfactant; and
(f) the balance being water.
The Cβ-18 ethoxylated alkyl ether sulfate surfactants used in the instant composition have the structure +
R-(OCHCH2)nOSθ3M wherein n is about 1 to about 22 more preferably 1 to 3 and R is an alkyl group having about 8 to about 18 carbon atoms, more preferably 12 to 15 and natural cuts, for example, C 12-14; C12-15 and M is an ammonium cation or an alkali metal cation, most preferably sodium or ammonium. The ethoxylated alkyl ether sulfate is present in the composition at a concentration of about 0.5 wt. % to about 22 wt. %, more preferably about 1 wt. % to 20 wt. %.
The ethoxylated alkyl ether sulfate may be made by sulfating the condensation product of ethylene oxide and Cβ-10 alkanol, and neutralizing the resultant product. The ethoxylated alkyl ether sulfates differ from one another in the number of carbon atoms in the alcohols and in the number of moles of ethylene oxide reacted with one mole of such alcohol. Preferred ethoxylated alkyl ether polyethenoxy sulfates contain 12 to 15 carbon atoms in the alcohols and in the alkyl groups thereof, e.g., sodium myristyl (3 EO) sulfate.
Ethoxylated Cβ-18 alkylphenyl ether sulfates containing from 2 to 6 moles of ethylene oxide in the molecule are also suitable for use in the invention compositions. These detergents can be prepared by reacting an alkyl phenol with 2 to 6 moles of ethylene oxide and sulfating and neutralizing the resultant ethoxylated alkylphenol. A mixture of two linear alkyl benzene sulfonates containing from 10 to 16 carbon atoms in the alkyl group are used in the instant compositions wherein both of the alkyl benzene sulfonates have a high content of 3- (or higher) phenyl isomers and a correspondingly low content (well below 50%) of 2- (or lower) phenyl isomers, that is, wherein the benzene ring is preferably attached in large part at the 3 or higher (for example, 4, 5, 6 or 7) position of the alkyl group and the content of the isomers in which the benzene ring is attached in the 2 or 1 position.
One of these sulfonate surfactants is a sodium salt of a C10-C16 linear alkyl benzene sulfonate used at a concentration of about 0.5 wt. % to about 10 wt. %, more preferably about 1 wt. % to about 9 wt. % in the instant compositions. The other sulfonate surfactant is a magnesium salt of a C10-C16 linear alkyl benzene sulfonate used at a concentration of about 2 wt. % to about 16 wt. %, more preferably about 3 wt % to about 14 wt. % in the instant compositions.
The instant compositions contain about 2 wt. % to about 16 wt. %, more preferably 4 wt. % to 14 wt. % of an alkyl polysaccharide surfactant. The alkyl polysacchandes surfactants, which are used in conjunction with the aforementioned surfactant have a hydrophobic group containing from about 8 to about 20 carbon atoms, preferably from about 10 to about 16 carbon atoms, most preferably from about 12 to about 14 carbon atoms, and polysaccharide hydrophilic group containing from about 1 5 to about 10, preferably from about 1.5 to about 4, most preferably from about 1.6 to about 2.7 saccha de units (e.g., galactoside, glucostde, fructoside, glucosyl, fructosyl; and/or gaiactosyl units). Mixtures of sacchande moieties may be used in the alkyl polysacchande surfactants. The number x indicates the number of sacchande units in a particular alkyl polysacchande surfactant. For a particular alkyl polysacchande molecule x can only assume integral values. In any physical sample of alkyl polysacchande surfactants there will be in general molecules having different x values The physical sample can be characterized by the average value of x and this average value can assume non-integral values. In this specification the values of x are to be understood to be average values. The hydrophobic group (R) can be attached at the 2- , 3-, or 4- positions rather than at the 1 -position, (thus giving e.g. a glucosyl or gaiactosyl as opposed to a glucoside or galactoside). However, attachment through the 1- position, i.e., glucosides, galactoside, fructosides, etc., is preferred. In the preferred product the additional sacchande units are predominately attached to the previous sacchande unit's 2-posιtton. Attachment through the 3-, 4-, and 6- positions can also occur. Optionally and less desirably there can be a polyalkoxide chain joining the hydrophobic moiety (R) and the polysacchande chain The preferred alkoxide moiety is ethoxide.
Typical hydrophobic groups include alkyl groups, either saturated or unsaturated. branched or unbranched containing from about 8 to about 20, preferably from about 10 to about 18 carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group can contain up to 3 hydroxy groups and or the polyalkoxide chain can contain up to about 30, preferably less than about 10, alkoxide moieties. Suitable alkyl polysaccharides are decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl, di-, tn-, tetra-, peπta-, and hexaglucosides, galactosides, lactosides, fructosides, fructosyls, lactosyls, glucosyls and/or gaiactosyls and mixtures thereof.
The alkyl monosaccharides are relatively less soluble in water than the higher alkyl polysaccharides. When used in admixture with alkyl polysaccharides. the alkyl monosaccharides are solubilized to some extent. The use of alkyl monosaccharides in admixture with alkyl polysaccharides is a preferred mode of carrying out the invention Suitable mixtures include coconut alkyl, dι-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.
The preferred alkyl polysaccharides are alkyl polyglucosides having the formula
Figure imgf000011_0001
wherein Z is derived from glucose, R is a hydrophobic group selected from the group consisting of alkyl, alkylphenyl, hydroxyalkylphenyl, and mixtures thereof in which said alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14 carbon atoms; n is 2 or 3 preferably 2, r is from 0 to 10, preferably 0; and x is from 1.5 to 8, preferably from 1.5 to 4, most preferably from 1.6 to 2.7. To prepare these compounds a long chain alcohol (R2OH) can be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside. Alternatively the alkyl polyglucosides can be prepared by a two step procedure in which a short chain alcohol (R1 OH) can be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside. Alternatively the alkyl polyglucosides can be prepared by a two step procedure in which a short chain alcohol (C1-6) is reacted with glucose or a poiyglucoside (x=2 to 4) to yield a short chain alkyl glucoside (x=1 to 4) which can in turn be reacted with a longer chain alcohol (R2OH) to displace the short chain alcohol and obtain the desired alkyl poiyglucoside. If this two step procedure is used, the short chain alkylgiucosde content of the final alkyl poiyglucoside material should be less than 50%, preferably less than 1 %, more preferably less than about 5%, most preferably 0% of the alkyl poiyglucoside.
The amount of unreacted alcohol (the free fatty alcohol content) in the desired alkyl polysaccharide surfactant is preferably less than about 2%, more preferably less than about 0.5% by weight of the total of the alkyl polysaccharide. For some uses it is desirable to have the alkyl monosaccharide content less than about 10%.
The used herein, "alkyl polysaccharide surfactant" is intended to represent both the preferred glucose and galactose derived surfactants and the less preferred alkyl polysaccharide surfactants. Throughout this specification, "alkyl poiyglucoside" is used to include alkyl polyglycosides because the stereochemistry of the saccharide moiety is changed during the preparation reaction.
An especially preferred APG glycoside surfactant is APG 625 glycoside manufactured by the Henkel Corporation of Ambler, PA. APG25 is a nonionic alkyl polyglycoside characterized by the formula:
Figure imgf000012_0001
wherein n=10 (2%); n=12 (65%); n=14 (21-28%); n=16 (4-8%) and n=18 (0.5%) and x (degree of polymerization) = 1.6. APG 625 has: a pH of 6 to 10 (10% of APG 625 in distilled water); a specific gravity at 25°C of 1.1 g/ml; a density at 25°C of 9.1 lbs/gallon; a calculated HLB of 12.1 and a Brookfield viscosity at 35°C. 21 spindle, 5-10 RPM of 3,000 to 7,000 cps.
The instant compositions contain about 1 wt. % to about 6 wt. %, more preferably about 1.5 wt. % to about 5 wt. % of a Cl 2-C14 alkyl monoalkanol amide such as lauryl monoalkanol amide (LMMEA). The instant compositions contain about 0 wt. % to about 12 wt. %, more preferably about 1 wt. % to about 10 wt. %, of at least one solubilizing agent which can be sodium xylene sulfonate, sodium cumene sulfonate. a C2-3 mono or dihydroxy alkanols such as ethanol, isopropanol and propylene glycol and mixtures thereof. The solubilizing agents are included in order to control low temperature cloud clear properties. Urea can be optionally employed in the instant composition as a supplemental solubilizing agent at a concentration of 0 to about 10 wt. %, more preferably about 0.5 wt. % to about 8 wt. %.
Other solubilizing agents are glycerol. water-soluble polyethylene glycols having a molecular weight of 300 to 600, polypropylene glycol of the formula
HO(CH3CHCH2θ)nH wherein n is a number from 2 to 18, mixtures of polyethylene glycol and polypropylene glycol (Synalox) and mono Ci -Cβ alkyl ethers and esters of ethylene glycol and propylene glycol having the structural formulas R(X)nOH and Rl (X)nOH wherein R is C1-C6 alkyl group, Ri is C2-C4 acyl group, X is (OCH2CH2) or (OCH2(CH3)CH) and n is a number from 1 to 4.
Representative members of the polypropylene glycol include dipropylene glycol and polypropylene glycol having a molecular weight of 200 to 1000, e.g., polypropylene glycol 400. Other satisfactory glycol ethers are ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monobutyl ether, mono, di, tri propylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, mono, di, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, propylene glycol tertiary butyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monopentyl ether. diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monopentyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monopentyl ether, triethylene glycol monohexyl ether, mono, di, tripropylene glycol monoethyl ether, mono, di tripropylene glycol monopropyl ether, mono, di, tripropylene glycol monopentyl ether, mono, di, tripropylene glycol monohexyl ether, mono, di. tributylene glycol mono methyl ether, mono, di, tributylene glycol monoethyl ether, mono, di, tributylene glycol monopropyl ether, mono, di. tributylene glycol monobutyl ether, mono, di, tributylene glycol monopentyl ether and mono, di. tributylene glycol monohexyl ether, ethylene glycol monoacetate and dipropylene glycol propionate.
The instant formulas explicitly exclude alkali metal silicates and alkali metal builders such as alkali metal polyphosphates, alkali metal carbonates, alkali metal phosphonates and alkali metal citrates because these materials, if used in the instant composition, would cause the composition to have a high pH as well as leaving residue on the surface being cleaned. The final essential ingredient in the inventive compositions having improved interfacial tension properties is water.
In final form, the instant compositions exhibit stability at reduced and increased temperatures. More specifically, such compositions remain clear and stable in the range of 5°C to 50°C, especially 10°C to 43°C. The instant compositions have a light transmission of at least 95%. Such compositions exhibit a pH of 5 to 8. The liquid compositions are readily pourable and exhibit a viscosity in the range of 100 to 600 cps as measured at 25°C. with a Brookfield RVT Viscometer using a #2 spindle rotating at 30 RPM. Preferably, the viscosity is maintained in the range of 300 to 500 cps. The instant compositions have a minimum foam height of 110 mis after 55 rotation at 40°C as measured by the foam volume test using 0.75 grams of the composition per liter of water and 1 gram of corn oil per liter of water having a hardness of 300 ppm.
The following examples illustrate liquid cleaning compositions of the described invention. Unless otherwise specified, all percentages are by weight. The exemplified compositions are illustrative only and do not limit the scope of the invention. Unless otherwise specified, the proportions in the examples and elsewhere in the specification are by weight. Example 1
The following composition in wt. % was prepared by simple mixing procedure at °C:
A B C D E F G
Sodium salt of a C10-C16 linear alkyl 5 5 4.7 4.9 3.7 4.83 3.79 benzene sulfonate
Magnesium salt of a C 10-C16 linear 5 5 4.7 4.9 3.7 4.83 3.79 alkyl benzene sulfonate
LMMEA 1.6 2.1 1.5 2 2.5 1.54 2.58
APG625 6 6 8.46 6.7 6.5 8.7 6.6
NH4AEOSH .3EO) 15.5 14 13.2 14.3 16 13.53 16.41
Water Bal. Bal. Bat. Bal. Bal. Bal. Bal.
Lard 1% mqs 35 75 65 80 55 40 30
Crisco 1 % mqs 100 90 85 100 100 90 85
Shell Foam % FPR 103 103 104 102 107 107 114
Foam volume initial (ml) 440 435 425 420 425 415 420 with soil (ml) 215 205 200 200 215 200 215

Claims

What Is Claimed:
1. A clear light duty liquid cleaning composition which comprises approximately by weight:
(a) 0.5% to 22% of an alkali metal or ammonium salt of a Cβ-18 ethoxylated alkyl ether sulfate;
(b) 0.5% to 10% of a sodium salt of a C 10-C16 alkyl benzene sulfonate surfactant;
(c) 2% to 16% of a magnesium salt of a Ci 0-C16 alkyl benzene sulfonate surfactant; (d) 0% to 12% of at least one solubilizing agent;
(e) 2% to 16% of an alkyl poiyglucoside surfactant;
(f) 1 % to 6% of a C 12-C 14 alkyl monoalkanol amide; and
(g) the balance being water.
2. The composition of Claim 1 , wherein said solubilizing agent is a C2-4 mono or dihydroxy alkanol.
3. The composition of Claim 1 , wherein said solubilizing agent is selected from the group consisting of isopropanol. ethanol and propylene glycol and mixtures thereof.
4. The composition of Claim 1 , wherein said solubilizing agent is selected from the group consisting of glycerol, polyethylene glycols, polypropylene glycol of the formula HO(CH3)CHCH2θ)nH, wherein n is 2 to 18, mono C1 -C6 alkyl ethers and esters of ethylene glycol and propylene glycol having the formulas of R(X)nOH and Rl (X)nOH wherein R is a C1-6 alkyl group, R1 is a C2-4 acyl group, X is (OCH2CH2) or (OCH2CHCH3) and n is from 1 to 4.
5. The composition of Claim 1 , wherein said solubilizing agent is sodium xylene sulfonate or sodium cumene sulfonate.
PCT/US1997/004407 1996-03-21 1997-03-19 Light duty liquid cleaning compositions WO1997034973A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999006508A1 (en) * 1997-07-31 1999-02-11 Colgate-Palmolive Company Light duty liquid cleaning compositions
WO2002066590A1 (en) * 2000-12-12 2002-08-29 Colgate-Palmolive Company Grease cutting light duty liquid detergent

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990002164A1 (en) * 1988-08-19 1990-03-08 Colgate Palmolive Company Light duty liquid detergent compositions
EP0509608A2 (en) * 1991-04-15 1992-10-21 Colgate-Palmolive Company Light duty liquid detergent compositions
WO1996006920A1 (en) * 1994-08-26 1996-03-07 Colgate-Palmolive Company Microemulsion light duty liquid cleaning compositions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990002164A1 (en) * 1988-08-19 1990-03-08 Colgate Palmolive Company Light duty liquid detergent compositions
EP0509608A2 (en) * 1991-04-15 1992-10-21 Colgate-Palmolive Company Light duty liquid detergent compositions
WO1996006920A1 (en) * 1994-08-26 1996-03-07 Colgate-Palmolive Company Microemulsion light duty liquid cleaning compositions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999006508A1 (en) * 1997-07-31 1999-02-11 Colgate-Palmolive Company Light duty liquid cleaning compositions
WO2002066590A1 (en) * 2000-12-12 2002-08-29 Colgate-Palmolive Company Grease cutting light duty liquid detergent

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