WO2005035703A1 - Solution tensioactive contenant de l'oxyde de zinc - Google Patents

Solution tensioactive contenant de l'oxyde de zinc Download PDF

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Publication number
WO2005035703A1
WO2005035703A1 PCT/US2004/033195 US2004033195W WO2005035703A1 WO 2005035703 A1 WO2005035703 A1 WO 2005035703A1 US 2004033195 W US2004033195 W US 2004033195W WO 2005035703 A1 WO2005035703 A1 WO 2005035703A1
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surfactants
alkyl
surfactant
zinc oxide
composition
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PCT/US2004/033195
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English (en)
Inventor
Marc Paye
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Colgate-Palmolive Company
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Priority claimed from US10/681,935 external-priority patent/US6774096B1/en
Application filed by Colgate-Palmolive Company filed Critical Colgate-Palmolive Company
Publication of WO2005035703A1 publication Critical patent/WO2005035703A1/fr

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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27—Zinc; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/463—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/413—Nanosized, i.e. having sizes below 100 nm
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59—Mixtures
    • A61K2800/596—Mixtures of surface active compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/74—Biological properties of particular ingredients
    • A61K2800/75—Anti-irritant
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Definitions

  • This invention relates to the use of a zinc oxide suspension in a surfactant-based product to reduce its skin irritation potential and optimize its compatibility with the skin.
  • the surfactant-based product may be a hand dishwashing liquid, a liquid skin cleanser, a shower gel, a bath foam, a shampoo, liquid skin cleansing products, hand liquid soaps, a fine fabric detergent, or any type of cleaning or cleansing product based on surfactants.
  • the particularity of the zinc oxide suspension to decrease the skin irritation potential is to be highly effective even in already optimized surfactant-based product containing other types of counter-irritants such as amphoteric or nonionic secondary surfactants.
  • Background of the Invention The present invention relates to the use of zinc oxide particles in a shower gel, a bath foam, a shampoo, a liquid skin cleansing product, hand liquid soaps, a fine fabric detergent, light duty liquid detergent compositions with high foaming properties, which can contain mixtures of anionic surfactants, amine oxide surfactant and alkyl polyglucoside surfactant, in order to decrease its skin irritation potential and improve its skin compatibility.
  • Zinc oxide suspension is used for other purposes or in other types of products as shown in the following patents.
  • US5403506 describes a deodorant detergent composition containing as a deodorizing component a minor amount of zinc oxide having a particulate size no greater than about 10 microns.
  • KR9300782 describes a soap composition containing metal oxide and ethyl alcohol.
  • FR19750007063 and 19750306 describe the use of zinc oxide to prepare an opaque cleaning composition in tablet form.
  • EP20000902097 and 20000204 describe a process using ultrafine particulate zinc oxide that has a low coagulation of primary particles and can be easily dispersed or suspended in an aqueous solvent without passing through a grinding process, that provides a cosmetic material with transparency and ultraviolet shielding ability.
  • US19960590736 and 19960124 describe a deodorant soap or detergent composition containing a zinc compound and a polyamine.
  • IE 19750000469 and 19750305 describe zinc oxide-containing detergent bars.
  • US19990332007 describes photoprotective cosmetic compositions containing a metal oxide nanopigment, which may be zinc oxide, and an acrylic terpolymer, and the use of these compositions for protecting keratinous material against ultraviolet radiation.
  • WO1997EP00714 and 19970213 describe compositions containing an antifungal and a sulfur compounds for body and hair cleaning products.
  • EP00902097.5 (WO0046152) describes cosmetic products containing ultrafine particulates of zinc oxide and the process to formulate them.
  • WOEP0011713 describes a drug-tape composition containing zinc oxide.
  • WOUS0140234 describes skin protective formulations with micronized zinc oxide that allow to reduce skin damages due to light and sun exposure.
  • WOIB0100717 describes a skin protective aerosol composition containing zinc oxide to protect baby bottom from erythema.
  • WOGB0101949 describes the use of zinc oxide as a biostatic agent.
  • WOFR0200046 describes the use of zinc oxide as mineral filter for UV in cosmetic compositions.
  • EP00907548.2 (WO0050503 request) describes redispersible gels with zinc oxide nanoparticles.
  • Zinc oxide is also used in cosmetic products for the following purposes: zinc oxide may be found in facial masks to absorb excess of sebum (Ella Bache); zinc oxide may be found in Baby Balsam or cream to protect skin from redness in the diaper area (Weleda, Calidou, Mustela); zinc oxide may be found in Skin scrubbing products for its skin lightening properties (Ella Bache); zinc oxide may be used for its astringent and antiseptic properties in drugs and cosmetic products, as well as for its UV A and B radiation blocking effect Some publications describing the role of zinc oxide are hereafter: Lansdown AB.
  • the skin irritation potential of the finished is highly improved by the presence of the zinc oxide suspension in the product.
  • the zinc oxide-containing product induces much less erythematous reaction and skin barrier alteration when the products are in contact with the skin for a long period.
  • Benefits in terms of less skin drying and better respect of skin surface hydration are also expected when adding nanoparticles of zinc oxide in the product.
  • Similar anti-irritant effects are also expected in any type of surfactant-based product.
  • One object of this invention is to provide a cleaning composition which exhibits decreased skin irritation potential.
  • Another object of this invention is to provide a light duty liquid detergent composition which comprises a sulfate surfactant, a sulfonate anionic surfactant, an alkyl polyglucoside surfactant, nanoparticulates of zinc oxide having a particle size of 10-30 nm and water.
  • a cleaning composition for all purpose cleaners, dishware bars, dishware pastes, light duty liquids, shampoos such as hair cleaning, bath foams, liquid hand soaps, liquid skin cleansing products, fine fabric detergent, and shower gels which comprises approximately by weight: (a) 1 % to 50%, more preferably 2% to 40% of at least one surfactant selected from the group consisting of an alkali metal salt of a long chain fatty acid having 8 to 24 carbon atoms, sulfonated anionic surfactants, sulfated anionic surfactants, alkyl phosphate, alkyl ether carboxylate, zwitterionic surfactants, C12-C14 alkanol amide surfactants, amine oxide surfactants, ethoxylated nonionic surfactants, ethoxylated/propoxylated nonionic surfactants and alkyl polyglucoside surfactants and mixtures thereof, wherein at least one of the surfactants is an anionic surfactant; (b)
  • a preferred light duty liquid compositions of the instant invention comprises approximately by weight: (a) 0 to 20%), more preferably 3% to 15% of an alkali metal or ammonium salt of a C ⁇ -18 ethoxylated alkyl ether sulfate surfactant and/or an Cs-18 alkyl sulfate surfactant; (b) 5% to 30%, more preferably 8% to 20% of at least one alkali metal and/or alkaline earth metal salt of an anionic sulfonate surfactant; (c) 0% to 20%, more preferably 2% to 15% of an alkyl polyglucoside surfactant; (d) 0 to 10%, more preferably 0.5% to 8% of at least one solubilizer; (e) 0 to 12%), more preferably 0.5% to 11% of an amine oxide surfactant; (f) 0.01 % to 1 %, more preferably 0.03% to 0.5% of Nanoparticulates of zinc oxide which functions as an anti-irritant system for anionic surfact
  • the anionic surfactants which may be used in the instant composition of this invention are water soluble and include the magnesium, sodium, potassium, ammonium and ethanolammonium salts of linear C8-CI6 alkyl benzene sulfonates , C10-C20 paraffin sulfonates, alpha olefin sulfonates containing about 10-24 carbon atoms and C8-C18 alkyl sulfates, alkyl ether sulfates, alkyl ether carboxylates, and mixtures thereof.
  • the paraffin sulfonates may be monosulfonates or di-sulfonates and usually are mixtures thereof, obtained by sulfonating paraffins of 10 to 20 carbon atoms.
  • Preferred paraffin sulfonates are those of C12-I8 carbon atoms chains, and more preferably they are of C14.- 7 chains. Paraffin sulfonates that have the sulfonate group(s) distributed along the paraffin chain are described in U.S. Patents 2,503,280; 2,507,088; 3,260,744; and 3,372,188; and also in German Patent 735,096. Such compounds may be made to specifications and desirably the content of paraffin sulfonates outside the C14-17 range will be minor and will be minimized, as will be any contents of di- or poly-sulfonates.
  • Suitable other sulfonated anionic detergents are the well known higher alkyl mononuclear aromatic sulfonates, such as the higher alkylbenzene sulfonates containing 9 to 18 or preferably 9 to 16 carbon atoms in the higher alkyl group in a straight or branched chain, or C ⁇ -15 alkyl toluene sulfonates.
  • a preferred alkylbenzene sulfonate is a linear alkylbenzene sulfonate having a higher content of 3- phenyl (or higher) isomers and a correspondingly lower content (well below 50%) of 2- phenyl (or lower) isomers, such as those sulfonates wherein the benzene ring is attached mostly 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 is correspondingly low.
  • Preferred materials are set forth in U.S. Patent 3,320,174, especially those in which the alkyls are of 10 to 13 carbon atoms.
  • Suitable anionic surfactants are the olefin sulfonates, including long-chain alkene sulfonates, long-chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates.
  • olefin sulfonate detergents may be prepared in a known manner by the reaction of sulfur trioxide (SO3) with long-chain olefins containing 8 to 25, preferably 12 to 21 carbon atoms and having the formula where R is a higher alkyl group of 6 to 23 carbons and R1 is an alkyl group of 1 to 17 carbons or hydrogen to form a mixture of sultones and alkene sulfonic acids which is then treated to convert the sultones to sulfonates.
  • Preferred olefin sulfonates contain from 14 to 16 carbon atoms in the R alkyl group and are obtained by sulfonating an a-olefin.
  • ethoxylated alkyl ether sulfate surfactants examples include the alkyl sulfate salts and the and the alkyl ether polyethenoxy sulfate salts
  • the C ⁇ -18 ethoxylated alkyl ether sulfate surfactants have the structure - + R-(OCHCH2)nOSO3 M 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 2-14 or C12-16 and M is an ammonium cation or a metal cation, most preferably sodium.
  • the ethoxylated alkyl ether sulfate may be made by sulfating the condensation product of ethylene oxide and C8-10 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 C8-18 alkylphenyl ether sulfates containing from 2 to 6 moles of ethylene oxide in the molecule are also suitable for use in the invention compositions.
  • 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.
  • suitable anionic detergents are the C9-C15 alkyl ether polyethenoxyl carboxylates having the structural formula R(OC2H4)nOX COOH wherein n is a number from 4 to 12, preferably 6 to 11 and X is selected from the group consisting of CH2,
  • Ri is a C1-C3 alkylene group.
  • Preferred compounds include C9-C11 alkyl ether polyethenoxy (7-9) C(O) CH2CH2COOH, C13-C15 alkyl ether polyethenoxy (7-9)
  • the amine oxide semi-polar nonionic surfactants used in the instant compositions comprise compounds and mixtures of compounds having the formula
  • is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from 8 to 18 carbon atoms
  • R2 and R3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or
  • n is from 0 to 10.
  • Particularly preferred are amine oxides of the formula:
  • is a C12-I6 alkyl and R2 and R3 are methyl or ethyl.
  • ethylene oxide condensates, amides, and amine oxides are more fully described in U.S. Pat. No. 4,316,824 which is hereby incorporated herein by reference.
  • An especially preferred amine oxide is depicted by the formula:
  • R1 is a saturated or unsaturated alkyl group having about 6 to about 24 carbon atoms
  • R2 is a methyl group
  • R3 is a methyl or ethyl group.
  • the preferred amine oxide is cocoamidopropyl-dimethylamine oxide.
  • the alkyl polysaccharides surfactants which are used in conjunction with the aforementioned surfactants 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 saccharide units (e.g., galactoside, glucoside, fructoside, glucosyl, fructosyl; and/or galactosyl units). Mixtures of saccharide moieties may be used in the alkyl polysaccharide surfactants.
  • the number x indicates the number of saccharide units in a particular alkyl polysaccharide 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.
  • 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 galactosyl as opposed to a glucoside or galactoside).
  • glucosides i.e., glucosides, galactoside, fructosides, etc.
  • additional saccharide units are predominately attached to the previous saccharide unit's 2-position. 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-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, fructosides, fructosyls, lactosyls, glucosyls and/or galactosyls 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, di-, 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, preferable 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 (R-]OH) can be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside.
  • R-]OH short chain alcohol
  • the short chain alkylglucosde content of the final alkyl polyglucoside material should be less than 50%, preferably less than 10%), more preferably less than about 5%, most preferably 0% of the alkyl polyglucoside.
  • 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 polyglucoside 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.
  • 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 water soluble nonionic surfactants which can be utilized in this invention are commercially well known and include the primary aliphatic alcohol ethoxylates, secondary aliphatic alcohol ethoxylates, alkylphenol ethoxylates and ethylene-oxide- propylene oxide condensates on primary alkanols, such a Plurafacs (BASF) and condensates of ethylene oxide with sorbitan fatty acid esters such as the Tweens (ICI).
  • the nonionic synthetic organic detergents generally are the condensation products of an organic aliphatic or alkyl aromatic hydrophobic compound and hydrophilic ethylene oxide groups.
  • any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a water-soluble nonionic detergent. Further, the length of the polyethenoxy chain can be adjusted to achieve the desired balance between the hydrophobic and hydrophilic elements.
  • the nonionic detergent class includes the condensation products of a higher alcohol (e.g., an alkanol containing 8 to 18 carbon atoms in a straight or branched chain configuration) condensed with 5 to 30 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with 16 moles of ethylene oxide (EO), tridecanol condensed with 6 to moles of EO, myristyl alcohol condensed with about 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to 14 carbon atoms in length and wherein the condensate contains either 6 moles of EO per mole of total alcohol or 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol.
  • a higher alcohol e.g., an alkanol containing 8
  • Neodol ethoxylates which are higher aliphatic, primary alcohols containing about 9- 15 carbon atoms, such as Cg-C-n alkanol condensed with 8 moles of ethylene oxide (Neodol 91-8), C-
  • Such ethoxamers have an HLB (hydrophobic lipophilic balance) value of 8-15 and give good/W emulsification, whereas ethoxamers with HLB values below 8 contain less than
  • Additional satisfactory water soluble alcohol ethylene oxide condensates are the condensation products of a secondary aliphatic alcohol containing 8 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide.
  • Examples of commercially available nonionic detergents of the foregoing type are C-
  • Nonionic detergents include the polyethylene oxide condensates of one mole of alkyl phenol containing from 8 to 18 carbon atoms in a straight- or branched chain alkyl group with 5 to 30 moles of ethylene oxide.
  • alkyl phenol ethoxylates include nonyl condensed with 9.5 moles of EO per mole of nonyl phenol, dinonyl phenol condensed with 12 moles of EO per mole of phenol, dinonyl phenol condensed with 15 moles of EO per mole of phenol and di-isoctylphenol condensed with 15 moles of EO per mole of phenol.
  • nonionic surfactants of this type include Igepal CO-630 (nonyl phenol ethoxylate) marketed by
  • nonionic detergents are the water-soluble condensation products of a C8-C20 alkanol with a heteric mixture of ethylene oxide and propylene oxide wherein the weight ratio of ethylene oxide to propylene oxide is from
  • Such detergents are commercially available from BASF-Wyandotte and a particularly preferred detergent is a C-
  • Other suitable water-soluble nonionic detergents which are less preferred are marketed under the trade name "Pluronics.”
  • the compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
  • the molecular weight of the hydrophobic portion of the molecule is of the order of 950 to 4000 and preferably 200 to 2,500.
  • polyoxyethylene radicals to the hydrophobic portion tends to increase the solubility of the molecule as a whole so as to make the surfactant water-soluble.
  • the molecular weight of the block polymers varies from 1 ,000 to 15,000 and the polyethylene oxide content may comprise 20% to 80% by weight.
  • these surfactants will be in liquid form and satisfactory surfactants are available as grades L62 and L64.
  • Condensates of 2 to 30 moles of ethylene oxide with sorbitan mono- and tri-C-io- C20 alkanoic acid esters having a HLB of 8 to 15 also may be employed as the nonionic detergent ingredient in the described composition.
  • These surfactants are well known and are available from Imperial Chemical Industries under the Tween trade name.
  • Suitable surfactants include polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (20) sorbitan trioleate and polyoxyethylene (20) sorbitan tristearate.
  • the water-soluble zwitterionic surfactant which can also be used provides good foaming properties and partial mildness to the present anionic based liquid detergent.
  • the zwitterionic surfactant is a water soluble betaine having the general formula:
  • is an alkyl group having 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms, or the amido radical: wherein R is an alkyl group having 9 to 19 carbon atoms and a is the integer 1 to 4; R2 and R3 are each alkyl groups having 1 to 3 carbons and preferably 1 carbon; R4 is an alkylene or hydroxyalkylene group having from 1 to 4 carbon atoms and, optionally, one hydroxyl group.
  • Typical alkyldimethyl betaines include decyl dimethyl betaine or 2-(N- decyl-N, N-dimethyl-ammonia) acetate, coco dimethyl betaine or 2-(N-coco N, N- dimethylammonio) acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, lauryl dimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine, etc.
  • the amidobetaines similarly include cocoamidoethylbetaine, cocoamidopropyl betaine and the like.
  • a preferred betaine is coco (Cs-Ci ⁇ ) amidopropyl dimethyl betaine.
  • the cleaning composition can contain at least one solubilizer selected from the group consisting of a C2-C5 mono, dihydroxy or polyhydroxy alkanols such as ethanol, isopropanol, glycerol, ethylene glycol, diethylene glycol, propylene glycol, and hexylene glycol and mixtures thereof, urea, and alkali metal salts of cumene, toluene or xylene sulfonates such as sodium cumene sulfonate and sodium xylene sulfonate and mixtures thereof.
  • the nanoparticles suspended in the instant composition are of zinc oxide.
  • An especially preferred Zinc Oxide particulate is manufactured by Sumitomo Osaka Cement (distributed in Europe by Maprecos) as Ultra fine zinc Oxide ZnO-350. Their appearance is white to pale yellow powder, with a particle size between 10 and 30 nm and a purity of at least 99.5 %. As alternatives, other zinc Oxide particles of a size in the range of 5 to 2000 nm may be used, more preferably from 5 to 350 nm.
  • a viscosity building system or 3-D structuring agent may be optionally added at a concentration of 0.1 wt. % to 4 wt. % to the composition to help suspending the zinc oxide particulates.
  • some potentially thickening systems are selected from the group consisting of: - Polymers such as polyacrylates (linear or cross-linked), cellulose ethers (eg those derived from hydroxyethyl or hydroxypropyl cellulose), natural polysaccharides and gums (eg Carrageenan, Xanthan, etc); - associative thickeners (eg hydrophobically modified modified polymers and Inorganic thickeners (eg clay, Iaponite, etc) and mixtures thereof - Self thickened surfactant systems (eg containing alcohol ethoxy sulfates and/or betaines and/or amine oxides, etc., with or without salting out agent) can also be used Inorganic salts such as sodium sulfate, magnesium sulfate, sodium chloride and sodium citrate can be optionally added at concentrations of 0.1 to 4.0 wt.
  • - Polymers such as polyacrylates (linear or cross-linked), cellulose ethers (eg those derived from
  • the magnesium inorganic salt which can be used in the instant composition is selected from the group consisting of magnesium oxide, magnesium chloride, and magnesium sulfate hepta hydrate and mixtures thereof.
  • the final essential ingredient in the inventive cleaning compositions is water.
  • the proportion of water in the compositions generally is in the range of 35% to 90%, preferably 50% to 85% by weight of the cleaning composition.
  • the liquid cleaning composition of this invention may, if desired, also contain other components either to provide additional effect or to make the product more attractive to the consumer. The following are mentioned by way of example: Colors or dyes or perfumes in amounts up to 3.0%> by weight; sodium bisulfite in amounts up to 0.2%), and pH adjusting agents, such as sulfuric acid or sodium hydroxide, as needed.
  • compositions of the present invention have a pH of about 4 to about 8, more preferably about 5 to 7. Thus, they may comprise as an optional ingredient a source of acidity or alkalinity for the purpose of pH adjustment. Suitable sources of acidity for use herein are lactic acid, citric acid, sulfuric acid and hydrochloric acid.
  • Suitable sources of alkalinity for use herein are the caustic alkalis such as sodium hydroxide or potassium hydroxide or also triethanolamine.
  • Preservatives can be optionally used in the instant compositions at a concentration of 0.005 wt. % to 3 wt. %, more preferably 0.01 wt. % to 2.5 wt. %.
  • preservatives are: benzalkonium chloride; formalin, benzethonium chloride,5-bromo-5- nitro-1 ,3dioxane; 2-bromo-2-nitropropane-1 ,3-diol; alkyl trimethyl ammonium bromide; N-(hydroxymethyl)-N-(1 ,3-dihydroxy methyl-2,5-dioxo-4-imidaxolidinyl-N'-(hydroxy methyl) urea; 1-3-dimethyol-5,5-dimethyl hydantoin; formaldehyde; iodopropynl butyl carbamata, butyl paraben; ethyl paraben; methyl paraben; propyl paraben, mixture of methyl isothiazolinone/methyl-chloroisothiazoline in a 1 :3 wt.
  • 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. Examples The following compositions in wt. % were prepared by simple mixing procedure. ZnO-350 is a white to pale yellow powder. The ZnO-350 powder is gently and homogeneously incorporated in the products at the end of the process.
  • Such compositions remain clear and stable in the range of 15°C to 35°C, especially 20°C to 30°C.
  • the liquid cleaning compositions exhibits a viscosity around 4500 centipoise (cps) as measured at 25°C with a Brookfield RVT Viscometer using a # 5 spindle rotating at 20 RPM (example 1) or 500-700 cps as measured at 25°C with a Brookfield RVT Viscosimeter using a # 2 spindle rotating at 50 RPM (example 2).
  • the Examples demonstrate excellent skin compatibility that is much better than the same compositions without the ZnO suspension, good foaming properties during hand washing, and good dish cleaning performance.

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Abstract

La présente invention concerne une composition de liquide vaisselle pour travaux légers comprenant des nanoparticules d'oxyde de zinc en suspension, laquelle composition comprend approximativement en poids :: (a) de 0 à 20 % d'un métal alcalin ou d'un sel d'ammonium d'un tensioactif à base de sulfate d'alkyle éther éthoxylé C8-C18 et/ou d'un tensioactif à base de sulfate d'alkyle C8-C18; (b) de 5 % à 30 % d'un métal terreux alcalin ou d'un sel métallique alcalin d'un tensioactif anionique à base d'alkyle benzène sulfonate C9-C18; (c) de 0,01 % à 1 % de particules solides d'oxyde de zinc, présentant une granulométrie comprise entre 5 et 2000 nm; et (d) le reste étant de l'eau.
PCT/US2004/033195 2003-10-09 2004-10-08 Solution tensioactive contenant de l'oxyde de zinc WO2005035703A1 (fr)

Applications Claiming Priority (4)

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US10/681,935 2003-10-09
US10/681,935 US6774096B1 (en) 2003-10-09 2003-10-09 Zinc oxide containing surfactant solution
US10/777,734 2004-02-12
US10/777,734 US20050079983A1 (en) 2003-10-09 2004-02-12 Zinc oxide containing surfactant solution

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009143091A1 (fr) 2008-05-23 2009-11-26 Colgate-Palmolive Company Compositions nettoyantes liquides et procédés et fabrication

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0987314A1 (fr) * 1998-09-16 2000-03-22 The Procter & Gamble Company Compositions de blanchiment
US6043204A (en) * 1997-11-07 2000-03-28 Kaufman; Stacy R. Body cleansing composition providing protection against sunburn after rinsing
US6172022B1 (en) * 2000-04-17 2001-01-09 Colgate-Palmolive Company High foaming, grease cutting light duty liquid detergent comprising poly (oxyethylene) diamine
GB2358638A (en) * 1999-12-22 2001-08-01 Reckitt & Colmann Prod Ltd Cleaning compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6043204A (en) * 1997-11-07 2000-03-28 Kaufman; Stacy R. Body cleansing composition providing protection against sunburn after rinsing
EP0987314A1 (fr) * 1998-09-16 2000-03-22 The Procter & Gamble Company Compositions de blanchiment
GB2358638A (en) * 1999-12-22 2001-08-01 Reckitt & Colmann Prod Ltd Cleaning compositions
US6172022B1 (en) * 2000-04-17 2001-01-09 Colgate-Palmolive Company High foaming, grease cutting light duty liquid detergent comprising poly (oxyethylene) diamine

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009143091A1 (fr) 2008-05-23 2009-11-26 Colgate-Palmolive Company Compositions nettoyantes liquides et procédés et fabrication

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