EP0793712B1 - Flüssige mikroemulsion-feinwaschmittelzusammensetzungen - Google Patents

Flüssige mikroemulsion-feinwaschmittelzusammensetzungen Download PDF

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Publication number
EP0793712B1
EP0793712B1 EP95940871A EP95940871A EP0793712B1 EP 0793712 B1 EP0793712 B1 EP 0793712B1 EP 95940871 A EP95940871 A EP 95940871A EP 95940871 A EP95940871 A EP 95940871A EP 0793712 B1 EP0793712 B1 EP 0793712B1
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Prior art keywords
ether
surfactant
cleaning composition
alkyl
composition
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EP95940871A
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French (fr)
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EP0793712A1 (de
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Rita Erilli
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Colgate Palmolive Co
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Colgate Palmolive Co
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Priority claimed from US08/344,059 external-priority patent/US5531938A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017—Multi-phase liquid compositions
    • C11D17/0021—Aqueous microemulsions
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • This invention relates to an improved light duty liquid cleaner in the form of a microemulsion designed in particular for cleaning hard surfaces and which is effective in removing grease soil and/or kitchen soil and in leaving unrinsed surfaces with a shiny appearance.
  • 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 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. 1,223,739.
  • 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.
  • such compositions are not completely acceptable from an environmental point of view based upon the phosphate content.
  • 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.
  • an o/w microemulsion is a spontaneously forming colloidal dispersion of "oil” phase particles having a particle size in the range of 25 to 800 ⁇ in a continuous aqueous phase.
  • microemulsions 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 microemulsions 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.
  • Liquid detergent compositions which include terpenes, such as d-limonene, or other grease-removal solvent, although not disclosed to be in the form of o/w microemulsions, are the subject matter of the following representative patent documents: European Patent Application 0080749; British Patent Specification 1,603,047; U.S. Patent Nos. 4,414,128; and 4,540,505.
  • U.S. Patent No. 4,414,128 broadly discloses an aqueous liquid detergent composition characterized by, by weight:
  • the present inventors have observed that in formulations containing grease-removal assisting magnesium compounds, the addition of minor amounts of builder salts, such as alkali metal polyphosphates, alkali metal carbonates, nitrilotriacetic acid salts, and so on, tends to make it more difficult to form stable microemulsion systems.
  • builder salts such as alkali metal polyphosphates, alkali metal carbonates, nitrilotriacetic acid salts, and so on, tends to make it more difficult to form stable microemulsion systems.
  • the present invention provides an improved, clear light duty liquid cleaning composition having improved interfacial tension which improves cleaning in the form of a microemulsion which is suitable for cleaning hard surfaces such as dishes, plastic, vitreous and metal surfaces having a shiny finish.
  • the light duty liquid microemulsion compositions of the instant invention can be generally described as comprising approximately by weight:
  • the present invention relates to a stable microemulsion composition approximately by weight: 1% to 10% of a modified polyglucoside surfactant or an alkyl ethoxy citrate, 10 % to 34% of a mixture of secondary alkane sulfonate anionic surfactant and an alkyl ether polyethenoxysulfate surfactant. 0% to 25% of a cosurfactant, 1 to 10% of a zwitterionic surfactant such as betaine , 0.4% to 8% of a water insoluble hydrocarbon essential oil or a perfume and the balance being water, said composition having a light transmission of at least 95%, more preferably at least 98%.
  • the role of the hydrocarbon is provided by a non-water-soluble perfume.
  • a solubilizers such as alkali metal lower alkyl aryl sulfonate hydrotrope, triethanolamine, urea, etc.
  • perfume dissolution especially at perfume levels of 1 % and higher, since perfumes are generally a mixture of fragrant essential oils and aromatic compounds which are generally not water-soluble. Therefore, by incorporating the perfume into the aqueous cleaning composition as the oil (hydrocarbon) phase of the ultimate o/w microemulsion composition, several different important advantages are achieved.
  • the cosmetic properties of the ultimate cleaning composition are improved: the compositions are both clear (as a consequence of the formation of a microemulsion) and highly fragranced (as a consequence of the perfume level).
  • perfume is used in its ordinary sense to refer to and include any non-water soluble fragrant substance or mixture of substances including natural (i.e., obtained by extraction of flower, herb, blossom or plant), artificial (i.e., mixture of natural oils or oil constituents) and synthetically produced substance) odoriferous substances.
  • perfumes are complex mixtures of blends of various organic compounds such as alcohols, aldehydes, ethers, aromatic compounds and varying amounts of essential oils (e.g., terpenes) such as from 0% to 80%, usually from 10% to 70% by weight, the essential oils themselves being volatile odoriferous compounds and also serving to dissolve the other components of the perfume.
  • the precise composition of the perfume is of no particular consequence to cleaning performance so long as it meets the criteria of water immiscibility and having a pleasing odor.
  • the perfume, as well as all other ingredients should be cosmetically acceptable, i.e., non-toxic, hypoallergenic, etc.
  • the hydrocarbon such as a perfume is present in the dilute o/w microemulsion in an amount of from 0.4% to 8% by weight, especially preferably from 2% to 7% by weight. If the amount of hydrocarbon (perfume) is less than 0.4% by weight it becomes difficult to form the o/w microemulsion. If the hydrocarbon (perfume) is added in amounts more than 10% by weight, the cost is increased without any additional cleaning benefit and, in fact, with some diminishing of cleaning performance insofar as the total amount of greasy or oily soil which can be taken up in the oil phase of the microemulsion will decrease proportionately.
  • the dilute o/w microemulsion detergent cleaning compositions of the present invention may often include as much as 0.2% to 7% by weight, based on the total composition, of terpene solvents introduced thereunto via the perfume component.
  • the amount of terpene solvent in the cleaning formulation is less than 1.5% by weight, such as up to 0.6% by weight or 0.4% by weight or less, satisfactory grease removal and oil removal capacity is provided by the inventive diluted o/w microemulsions.
  • an essential oil such as D-limonene or alpha-terpineol, a water insoluble paraffin or isoparaffin having 6 to 18 carbon at a concentration of 0.4 to 8.0 wt. %.
  • Suitable essential oils are selected from the group consisting of: Anethole 20/21 natural, Aniseed oil china star, Aniseed oil globe brand, Balsam (Peru), Basil oil (India), Black pepper oil, Black pepper oleoresin 40/20, Bois de Rose (Brazil) FOB, Borneol Flakes (China), Camphor oil, White, Camphor powder synthetic technical, Cananga oil (Java), Cardamom oil, Cassia oil (China), Cedarwood oil (China) BP, Cinnamon bark oil, Cinnamon leaf oil, Citronella oil, Clove bud oil, Clove leaf, Coriander (Russia), Coumarin 69°C (China), Cyclamen Aldehyde, Diphenyl oxide, Ethyl vanilin, Eucalyptol, Eucalyptus oil, Eucalyptus citriodora, Fennel oil, Geranium oil, Ginger oil, Ginger oleoresin (India), White grapefruit oil, Guaiacwood oil, Gurjun bals
  • Suitable water-soluble non-soap, anionic detergents include those surface-active or detergent compounds which contain an organic hydrophobic group containing generally 8 to 26 carbon atoms and preferably 10 to 18 carbon atoms in their molecular structure and at least one water-solubilizing group selected from the group of sulfonate, sulfate and carboxylate so as to form a water-soluble detergent.
  • the hydrophobic group will include or comprise a C 8 -C 22 alkyl, alkylaryl or acyl group.
  • Such detergents are employed in the form of water-soluble salts and the salt-forming cation usually is selected from the group consisting of sodium, potassium, ammonium, magnesium and mono-, di- or tri-C 2 -C 3 alkanolammonium, with the sodium, magnesium and ammonium cations again being preferred.
  • Suitable sulfonated anionic detergents are the well known higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from 10 to 16 carbon atoms in the higher alkyl group in a straight or branched chain, C 8 -C 15 alkyl toluene sulfonates and C 8 -C 15 alkyl phenol sulfonates.
  • a preferred sulfonate is linear alkyl benzene sulfonate having 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 is correspondingly low.
  • Particularly preferred materials are set forth in U.S. Patent 3,320,174.
  • Suitable anionic detergents are the olefin sulfonates, including long-chain alkene sulfonates, long-chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates.
  • Preferred olefin sulfonates contain from 14 to 16 carbon atoms in the R alkyl group and are obtained by sulfonating an 2 olefin.
  • Suitable anionic sulfonate surfactants are the paraffin sulfonates containing 10 to 20, preferably 13 to 17, carbon atoms.
  • Primary paraffin sulfonates are made by reacting long-chain alpha olefins and bisulfites and paraffin sulfonates having the sulfonate group distributed along the paraffin chain are shown in U.S. Patents Nos.. 2,503,280; 2,507,088; 3,260,744; 3,372,188; and German Patent 735,096.
  • the preferred anionic sulfonate surfactants used in the instant compositions are the C 13 -C 17 secondary alkane sulfonate surfactants.
  • Examples of satisfactory anionic sulfate detergents are the C 8 -C 18 alkyl sulfate salts and the C 8 -C 18 alkyl ether polyethenoxy sulfate salts having the formula R(OC 2 H 4 ) n OSO 3 M wherein n is 1 to 12, preferably 1 to 5, and M is a solubilizing cation selected from the group consisting of sodium, potassium, ammonium, magnesium and mono-, di- and triethanol ammonium ions.
  • the alkyl sulfates may be obtained by sulfating the alcohols obtained by reducing glycerides of coconut oil or tallow or mixtures thereof and neutralizing the resultant product.
  • the alkyl ether polyethenoxy sulfates are obtained by sulfating the condensation product of ethylene oxide with a C 8 -C 18 alkanol and neutralizing the resultant product.
  • the alkyl sulfates may be obtained by sulfating the alcohols obtained by reducing glycerides of coconut oil or tallow or mixtures thereof and neutralizing the resultant product.
  • the alkyl ether polyethenoxy sulfates are obtained by sulfating the condensation product of ethylene oxide with a C 8 -C 18 alkanol and neutralizing the resultant product.
  • alkyl ether polyethenoxy sulfates differ from one another in the number of moles of ethylene oxide reacted with one mole of alkanol.
  • Preferred alkyl sulfates and preferred alkyl ether polyethenoxy sulfates contain 10 to 16 carbon atoms in the alkyl group.
  • the C 8 -C 12 alkylphenyl ether polyethenoxy sulfates containing from 2 to 6 moles of ethylene oxide in the molecule also are suitable for use in the inventive 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.
  • anionic detergents will be present either in acid form or salt form depending upon the pH of the final composition, with salt forming cation being the same as for the other anionic detergents.
  • the preferred detergents are the C 9 -C 15 linear alkylbenzene sulfonates and the C 13 -C 17 paraffin or secondary alkane sulfonates.
  • preferred compounds are sodium C 10 -C 13 alkylbenzene sulfonate and sodium C 13 -C 17 secondary alkane sulfonate.
  • the proportion of the nonsoap-anionic sulfonate detergent will be in the range of 1.0% to 25 %, preferably from 1 % to 7%, by weight of the dilute o/w microemulsion composition.
  • the proportion of the nonsoap-anionic alkyl ether polyethonoxy sulfate detergent will be in the range of 1 % to 20 %, preferably from 2% to 10%, by weight of the dilute o/w microemulsion composition, wherein the ratio of anionic sulfonate to the alkyl ether polyethenoxy sulfate is preferably 1.2:1 to 14:1, more preferably 1.3:1 to 5:1.
  • the water-soluble zwitterionic surfactant which is also an essential ingredient of present liquid detergent composition, constitutes 1% to 10%, by weight and provides good foaming properties and mildness to the present nonionic based liquid detergent.
  • the zwitterionic surfactant is a water soluble betaine having the general formula: wherein X - is selected from the group consisting of CO 2 - and SO 3 - and R 1 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; R 2 and R 3 are each alkyl groups having 1 to 3 carbons and preferably 1 carbon; R 4 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 (C 8 -C 18 ) amidopropyl dimethyl betaine.
  • biodegradable anionic surfactants useful in the instant invention is a sodium salt of a di-alcohol ethoxy citrate which is depicted by the formula: wherein R is an alkyl group of 10 to 16 carbon atoms.
  • An especially preferred biodegradable anionic surfactant is a di-laureth citrate, sodium salt manufactured by Auschem wherein X + is selected from the group consisting of sodiu, potassium, ammonium, triethanol amine diethanol amine and monoethanol amine, wherein sodium is preferred and m and n are each a number from 1 to 12, more preferably 5 to 9, most preferably 7.
  • Another biodegradable anionic surfactant is a modified alkyl polyglycoside depicted by the formula wherein R is a C 10 to C 16 alkyl group,m is a number average which is less than 4 and is of such a value to provide a number molecular weight of 500 to 1000, preferably 1 to 4, and X is selected from the group consisting of (sold under the tradename of Eucarol tm APG/SS), (sold under the tradename of Eucarol tm APG/EC) and (sold under the tradename of Eucarol tm APG/ET) wherein Z is selected from the group consisting of sodium, potassium, ammonium, triethanol amine, diethanol amine and monoethanol amine.
  • Euacarol is a trade name of Auschem
  • the cosurfactant may play an essential role in the formation of the microemulsion compositions.
  • the water, detergent(s) and hydrocarbon e.g., perfume
  • the cosurfactant added to this system, the interfacial tension at the interface between the emulsion droplets and aqueous phase is reduced to a very low value (never negative). This reduction of the interfacial tension results in spontaneous break-up of the emulsion droplets to consecutively smaller aggregates until the state of a transparent colloidal sized emulsion.
  • thermodynamic factors come into balance with varying degrees of stability related to the total free energy of the microemulsion.
  • Some of the thermodynamic factors involved in determining the total free energy of the system are (1) particle-particle potential; (2) interfacial tension or free energy (stretching and bending); (3) droplet dispersion entropy; and (4) chemical potential changes upon formation.
  • a thermodynamically stable system is achieved when (2) interfacial tension or free energy is minimized and (3) droplet dispersion entropy is maximized.
  • the role of cosurfactant in formation of a stable o/w microemulsion is to (a) decrease interfacial tension (2); and (b) modify the microemulsion structure and increase the number of possible configurations (3). Also, the cosurfactant will (c) decrease the rigidity.
  • the major class of compounds found to provide highly suitable cosurfactants for the microemulsion over temperature ranges extending from 5°C to 43°C for instance are glycerol, ethylene glycol, water-soluble polyethylene glycols having a molecular weight of 300 to 1000, polypropylene glycol of the formula HO(CH 3 CHCH 2 O) n H wherein n is a number from 2 to 18, mixtures of polyethylene glycol and polypropyl glycol (Synalox) and mono C 1 -C 6 alkyl ethers and esters of ethylene glycol and propylene glycol having the structural formulas R(X) n OH and R 1 (X) n OH wherein R is C 1 -C 6 alkyl group, R 1 is C 2 -C 4 acyl group, X is (OCH 2 CH 2 ) or (OCH 2 (CH 3 )CH) and n is a number from 1 to 4, diethylene glycol, triethylene glycol, an alkyl lactate,
  • 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 mono
  • glycol type cosurfactants When these glycol type cosurfactants are at a concentartion of 1.0 to 14 weight %, more preferably 2.0 weight % to 10 weight % in combination with a water insoluble hydrocarbon at a concentration of at least 0.5 weight %, more preferably 1.5 weight % one can form a microemulsion composition.
  • glycol ether compounds While all of the aforementioned glycol ether compounds provide the described stability, the most preferred cosurfactant compounds of each type, on the basis of cost and cosmetic appearance (particularly odor), are glycerol, dipropylene glycol monomethyl ether and propylene glycol. Less preferred cosurfactants are ethanol, propanol isopropanol, butanol, isobutanol and alkanols having 5 to 7 carbon atoms.
  • the amount of cosurfactant required to stabilize the microemulsion compositions will, of course, depend on such factors as the surface tension characteristics of the cosurfactant, the type and amounts of the primary surfactants and perfumes, and the type and amounts of any other additional ingredients which may be present in the composition and which have an influence on the thermodynamic factors enumerated above.
  • amounts of cosurfactant in the range of from 0% to 25%, preferably from 0.5% to 15%, especially preferably from 2% to 13%, by weight provide stable dilute o/w microemulsions for the above-described levels of primary surfactants and perfume and any other additional ingredients as described below.
  • the final essential ingredient in the inventive light duty liquid microemulsion compositions having improved interfacial tension properties is water.
  • the proportion of water in the microemulsion compositions generally is in the range of 20% to 97%, preferably 70% to 97% by weight of the usual diluted o/w microemulsion composition.
  • the light duty liquid microemulsion compositions of this invention are especially effective when used as is, that is, without further dilution in water, since the properties of the composition as a microemulsion are best manifested in the neat (undiluted) form.
  • the properties of the composition as a microemulsion are best manifested in the neat (undiluted) form.
  • some degree of dilution without disrupting the microemulsion, per se is possible.
  • active surfactant compounds dilutions up to 50% will generally be well tolerated without causing phase separation, that is, the microemulsion state will be maintained.
  • the resulting compositions are still effective in cleaning greasy, oily and other types of soil.
  • the presence of magnesium ions or other polyvalent ions, e.g., aluminum, as will be described in greater detail below further serves to boost cleaning performance of the primary detergents in dilute usage.
  • compositions of this invention may possibly contain one or more additional ingredients which serve to improve overall product performance.
  • One such ingredient is an inorganic or organic salt of oxide of a multivalent metal cation, particularly Mg ++ .
  • the metal salt or oxide provides several benefits including improved cleaning performance in dilute usage, particularly in soft water areas, and minimized amounts of perfume required to obtain the microemulsion state.
  • Magnesium sulfate either anhydrous or hydrated (e.g., heptahydrate), is especially preferred as the magnesium salt.
  • Good results also have been obtained with magnesium oxide, magnesium chloride, magnesium acetate, magnesium propionate and magnesium hydroxide.
  • These magnesium salts can be used with formulations at neutral or acidic pH since magnesium hydroxide will not precipitate at these pH levels.
  • magnesium is the preferred multivalent metal from which the salts (inclusive of the oxide and hydroxide) are formed
  • other polyvalent metal ions also can be used provided that their salts are nontoxic and are soluble in the aqueous phase of the system at the desired pH level.
  • other suitable polyvalent metal ions include aluminum, copper, nickel, iron, calcium, etc. can be employed. It should be noted, for example, that with the preferred paraffin sulfonate anionic detergent calcium salts will precipitate and should not be used.
  • the aluminum salts work best at pH below 5 or when a low level, for example 1 weight percent, of citric acid is added to the composition which is designed to have a neutral pH.
  • the aluminum salt can be directly added as the citrate in such case.
  • the same general classes of anions as mentioned for the magnesium salts can be used, such as halide (e.g., bromide, chloride), sulfate, nitrate, hydroxide, oxide, acetate, propionate, etc.
  • the metal compound is added to the composition in an amount sufficient to provide at least a stoichiometric equivalent between the anionic surfactant and the multivalent metal cation.
  • the proportion of the multivalent salt generally will be selected so that one equivalent of compound will neutralize from 0.1 to 1.5 equivalents, preferably 0.9 to 1.4 equivalents, of the acid form of the anionic detergent.
  • the amount of multivalent salt will be in range of 0.5 to 1 equivalents per equivalent of anionic detergent.
  • the concentration of the magnesium sulfate is 0 to 4%, more preferably 0.1 to 2% by weight.
  • the light duty liquid microemulsion 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.
  • Colors or dyes in amounts up to 0.5% by weight; bactericides in amounts up to 1% by weight; preservatives or antioxidizing agents, such as formalin, 5-chloro-2-methyl-4-isothaliazolin-3-one, 2,6-di-tert.butyl-p-cresol, etc., in amounts up to 2% by weight; and pH adjusting agents, such as sulfuric acid or sodium hydroxide, as needed.
  • compositions as prepared are aqueous liquid formulations and since no particular mixing is required to form the o/w microemulsion, the compositions are easily prepared simply by combining all the ingredients in a suitable vessel or container.
  • the order of mixing the ingredients is not particularly important and generally the various ingredients can be added sequentially or all at once or in the form of aqueous solutions of each or all of the primary detergents and cosurfactants can be separately prepared and combined with each other and with the perfume.
  • the magnesium salt, or other multivalent metal compound when present, can be added as an aqueous solution thereof or can be added directly. It is not necessary to use elevated temperatures in the formation step and room temperature is sufficient.
  • compositions in wt. % were prepared:
  • the described invention broadly relates to an improvement in a light duty liquid microemulsion composition containing a mixture of a C 13 -C 17 secondary alkane sulfonate surfactant and an alkyl polyethenoxy ether sulfate surfactant, a biodegradable anionic surfactant, optionally a betaine surfactant, one of the specified cosurfactants, a hydrocarbon ingredient and water to form a microemulsion light duty liquid composition.

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  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Claims (11)

  1. Flüssige Mikroemulsion-Feinreinigungszusammensetzung, die bezogen auf das Gewicht ungefähr 10 bis 34 % einer Mischung aus Sulfonattensid und Alkyletherpolyethenoxysulfattensid, 1 bis 10 % zwitterionisches Tensid, 1 bis 10 % biologisch abbaubares anionisches Tensid ausgewählt aus der Gruppe bestehend aus Alkylethoxycitrat und modifiziertem Alkylpolyglukosid, 0,4 bis 8,0 % wasserunlöslichen Kohlenwasserstoff, essentielles Öl oder Parfüm, 0 bis 25 % Cotensid und als Rest Wasser umfaßt, wobei die Zusammensetzung eine Brookfield Viskosität bei 25°C und 30 UpM unter Verwendung einer Spindel Nr. 2 von 20 bis 500 cps, bevorzugter 200 bis 450 cps, einen pH-Wert von 5 bis 7 und eine Lichttransmission von mindestens 95 %, bevorzugter 98 % aufweist.
  2. Flüssige Mikroemulsion-Feinreinigungszusammensetzung nach Anspruch 1, bei der das Sulfonattensid und das Alkyetherpolyethenoxysulfat in einem Verhältnis von 1,2:1 bis 14:1 vorliegen.
  3. Reinigungszusammensetzung nach Anspruch 2, die ferner ein Salz eines mehrwertigen Metallkations in einer Menge enthält, die ausreicht, um 0,5 bis 1,5 Äquivalente des Kations pro Äquivalent des anionischen Reinigungsmittels zu liefern.
  4. Reinigungszusammensetzung nach Anspruch 3, bei der das mehrwertige Metallkation Magnesium oder Aluminium ist.
  5. Reinigungszusammensetzung nach Anspruch 3, bei der die Zusammensetzung 0,9 bis 1,4 Äquivalente des Kations pro Äquivalent an anionischem Reinigungsmittel enthält.
  6. Reinigungszusammensetzung nach Anspruch 4, bei der das mehrwertige Salz Magnesiumsulfat ist.
  7. Reinigungszusammensetzung nach Anspruch 2, die etwa 0,5 bis 15 Gew.-% des Cotensids und 0,4 bis 8,0 Gew.-% des Kohlenwasserstoffs enthält.
  8. Reinigungszusammensetzung nach Anspruch 2, bei der das Cotensid in wasserlöslicher Glykolether ist.
  9. Reinigungszusammensetzung nach Anspruch 8, bei der der Glykolether ausgewählt ist aus der Gruppe bestehend aus Ethylenglykolmonobutylether, Diethylenmonobutylether, Triethylenglykolmonobutylether, Polypropylenglykol mit einem durchschnittlichen Molekulargewicht von 200 bis 1000 und Propylenglykoltert.-butylether, Mono-, Di- oder Tripropylenglykolmonobutylether.
  10. Reinigungszusammensetzung nach Anspruch 9, bei der Glykolether Ethylenglykolmonobytolether oder Diethylenmonobytolether ist.
  11. Reinigungszusammensetzung nach Anspruch 2, bei der das anionische Tensid ausgewählt ist aus der Gruppe bestehend aus C9- bis C15- Alkylbenzolsulfonattensid oder C10- bis C20- sekundäres Alkansulfonattensid.
EP95940871A 1994-11-23 1995-11-13 Flüssige mikroemulsion-feinwaschmittelzusammensetzungen Expired - Lifetime EP0793712B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US344059 1994-11-23
US08/344,059 US5531938A (en) 1994-11-23 1994-11-23 Microemulsion light duty liquid cleaning compositions
US51705095A 1995-08-21 1995-08-21
US517050 1995-08-21
PCT/US1995/015522 WO1996016160A1 (en) 1994-11-23 1995-11-13 Microemulsion light duty liquid cleaning compositions

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EP0793712B1 true EP0793712B1 (de) 1998-10-14

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DE (1) DE69505414D1 (de)
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US5741769A (en) * 1994-11-23 1998-04-21 Colgate Palmolive Company Microemulsion light duty liquid cleaning compositions
BR9609727A (pt) * 1995-07-20 1999-03-16 Colgate Palmolive Co Composição de limpeza
EP0987319A3 (de) * 1995-07-20 2000-03-29 Colgate-Palmolive Company Flüssige Reinigungszusammensetzungen
AU3906097A (en) * 1996-08-06 1998-02-25 Colgate-Palmolive Company, The High foaming nonionic surfactant based liquid detergent
US5767051A (en) * 1997-02-13 1998-06-16 Colgate Palmolive Company Light duty liquid cleaning compositions
GB9707718D0 (en) * 1997-04-16 1997-06-04 Unilever Plc Light duty cleaning composition
US5929023A (en) * 1997-05-08 1999-07-27 Colgate Palmolive Company Cleaning composition containing a N-octyl ribonamide
DE19916335A1 (de) * 1999-04-12 2000-10-19 Schwarzkopf Gmbh Hans Kosmetisches Mittel und Verwendung
WO2009029046A1 (en) * 2007-08-29 2009-03-05 Agency For Science, Technology And Research Sugar-based surfactant microemulsions containing essential oils for cosmetic and pharmaceutical use
US20100009888A1 (en) * 2008-07-14 2010-01-14 Freddy Arthur Barnabas Microemulsion or protomicroemulsion cleaning composition with disrupting surfactants
US10952950B2 (en) 2015-04-23 2021-03-23 The Procter And Gamble Company Concentrated personal cleansing compositions and methods
MX2017013537A (es) 2015-04-23 2018-03-01 Procter & Gamble Composiciones concentradas para la limpieza personal y metodos.
MX371306B (es) 2015-04-23 2020-01-24 Procter & Gamble Composiciones concentradas para la limpieza personal y usos.
EP3285725B1 (de) 2015-04-23 2019-12-04 The Procter and Gamble Company Konzentrierte körperreinigungszusammensetzungen
US11179301B2 (en) 2016-10-21 2021-11-23 The Procter And Gamble Company Skin cleansing compositions and methods
US11185486B2 (en) 2016-10-21 2021-11-30 The Procter And Gamble Company Personal cleansing compositions and methods
US10675231B2 (en) 2017-02-17 2020-06-09 The Procter & Gamble Company Packaged personal cleansing product

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GB226045A (en) * 1924-01-09 1924-12-18 George Buckley Williams Ventilating the ovens of gas cookers
DE3011550A1 (de) * 1980-03-26 1981-10-01 Henkel KGaA, 4000 Düsseldorf Fluessige reinigungsmittel
US5192460A (en) * 1988-02-10 1993-03-09 Colgate-Palmolive Company Safe acidic hard surface cleaner
DE4315810A1 (de) * 1993-05-12 1994-11-17 Henkel Kgaa Wäßrige Detergensgemische

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BR9509761A (pt) 1998-07-07
DE69505414D1 (de) 1998-11-19
WO1996016160A1 (en) 1996-05-30
PL320415A1 (en) 1997-09-29
MX9703824A (es) 1998-02-28
ATE172242T1 (de) 1998-10-15
AU4247896A (en) 1996-06-17
CA2205854A1 (en) 1996-05-30
EP0793712A1 (de) 1997-09-10

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