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EP0781324B1 - Composition detergente pour petits travaux sous forme de microemulsion - Google Patents

Composition detergente pour petits travaux sous forme de microemulsion Download PDF

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Publication number
EP0781324B1
EP0781324B1 EP95928799A EP95928799A EP0781324B1 EP 0781324 B1 EP0781324 B1 EP 0781324B1 EP 95928799 A EP95928799 A EP 95928799A EP 95928799 A EP95928799 A EP 95928799A EP 0781324 B1 EP0781324 B1 EP 0781324B1
Authority
EP
European Patent Office
Prior art keywords
alkyl
cleaning composition
sulfonate
ether
glycol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP95928799A
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German (de)
English (en)
Other versions
EP0781324A1 (fr
Inventor
Barbara Thomas
Ammanuel Mehreteab
Gilbert Gomes
Frank Bala, Jr.
Jiashi Tarng
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Colgate Palmolive Co
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Colgate Palmolive Co
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Publication date
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D1/02—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
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • 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

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 about 25 to about 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; 4,414,128; and 4,540,505.
  • European Patent Application 0080749 British Patent Specification 1,603,047; 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 hard surface 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 by weight:
  • the present invention relates to a stable microemulsion composition
  • a stable microemulsion composition comprising by weight: 0% to 10% of an alkyl polyglucoside surfactant, 15% to 36% of a magnesium salt of a sulfonate anionic surfactant, 1% to 20% of a metal or ammonium salt of C 8 -C 18 alkyl ether polyethenoxysulfate surfactant, 1% to 25% of a cosurfactant, 0.4% to 10% of a water insoluble hydrocarbon, essential oil or a perfume, 0 to 5% of at least one hydrotrope, 0 to 4% of magnesium sulfate, 0 to 5% of an alkyl monoalkanolamide or an alkyl dialkanol amide and mixtures thereof and water.
  • Such a composition has a light transmission of at least 95%, more preferably at least 98%.
  • the role of the hydrocarbon is provided by a water insoluble 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 water insoluble 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.
  • 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
  • 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 10% by weight, preferably from 1.0% to 8.0% 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 wihout 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 10.0 wt. percent, more preferably 2.0 to 7.0 wt. %.
  • 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 sulfonate group 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 magnesium salts.
  • 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 sulfonate detergents 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 proportion of the nonsoap-anionic sulfonate detergent will be in the range of 15% to 36%, preferably from 18% to 34%, by weight of the dilute o/w microemulsion composition.
  • anionic sulfate detergents are 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 alkali metal cations such as sodium or potassium, alkaline earth metal cations such as magnesium, ammonium, and mono-, di- and triethanol ammonium ions, wherein sodium, potassium and ammonium are preferred.
  • alkali metal cations such as sodium or potassium
  • alkaline earth metal cations such as magnesium, ammonium, and mono-, di- and triethanol ammonium ions, wherein sodium, potassium and ammonium are preferred.
  • 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 ether polyethenoxy sulfates differ from one another in the number of moles of ethylene oxide reacted with one mole of alkanol.
  • 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.
  • the preferred detergents are the magnesium C 9 -C 15 linear alkylbenzene sulfonates and the magnesium C 13 -C 17 paraffin or alkane sulfonates.
  • preferred compounds are magnesium C 10 -C 13 alkylbenzene sulfonate and magnesium C 13 -C 17 alkane sulfonate.
  • the proportion of the nonsoap-anionic alkyl ether polyethenoxy sulfate detergent will be in range 1% to 20%, preferably 2% to 18% by weight of the dilute o/w microemulsion composition, wherein the ratio of paraffin sulfonate to the alkyl ether polyethenoxy sulfate is preferably 8:1 to 1:8, more preferably 7:1 to 1:2.
  • 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. 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. e.g., a microemulsion, is formed.
  • 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).
  • the cosurfactant will (c) decrease the rigidity.
  • an increase in cosurfactant concentration results in a wider temperature range of the stability of the product.
  • the highly suitable cosurfactants of the instant composition over temperature ranges extending from 4°C to 43°C are water-soluble C 2 -C 4 alkanols, polypropylene glycol of the formula HO(CH 3 CHCH 2 O) n H wherein n is a number from 1 to 18 and monoalkyl 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, R 1 is C 2 -C 4 acyl group, X is (OCH 2 CH 2 ) or (OCH 2 CHCH 3 ) 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, propylene glycol tertiary butyl ether, ethylene glycol monoacetate and dipropylene glycol propionate.
  • 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 1% to 25%, preferably from 1% to 15%, especially preferably from 2% to 8%, 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 essential ingredients discussed above can be solubilized in one prefered embodiment of the invention in water and either an alkyl monoethanol amide such as C 12 -C 14 alkyl monoethanol amide (LMMEA) at a concentration of 0 to 5 wt. %, or an alkyl diethanol amides such as coco diethanol amide (CDEA) or lauryl diethanol amide (LDEA) at a concentration of 0 to 5 wt. %, preferably 0.5 wt. % to 3 wt. % and mixtures thereof.
  • the instant formulas can contain both alkyl monoethanol amide and alkyl diethanol amide.
  • the solubilizing ingredient can also include 0 to 5 wt. %, preferably 0.1 wt.
  • % to 3 wt. % of at least one water soluble salt of a C 1 -C 3 substituted benzene sulfonate hydrotrope such as sodium xylene sulfonate or sodium cumene sulfonate or a mixture of said sulfonates.
  • Inorganic alkali metal or alkaline earth metal salts such as sodium sulfate, magnesium sulfate. sodium chloride and sodium citrate can be added to the microemulsion at concentrations of 0.5 to 4.0 wt.%.
  • Other ingredients which have been added to the compositions at concentrations of 0.1 to 4.0 wt. percent are perfumes, preservatives, color stabilizers, sodium bisulfite, ETDA, HETDA and proteins such as lexine protein.
  • various coloring agents and perfumes sequestering agents such as ethylene diamine tetraacetates; magnesium sulfate heptahydrate; pearlescing agents and opacifiers; pH modifiers; etc.
  • the proportion of such adjuvant materials, in total will normally not exceed 15% of weight of the detergent composition, and the percentages of most of such individual components will be 0.1 to 5% by weight and preferably less than 2% by weight.
  • Sodium bisulfite can be used as a color stabilizer at a concentration of 0.01 to 0.2 wt.%.
  • Typical perservatives are dibromodicyano-butane, citric acid, benzylic alcohol and poly (hexamethylene-biguamide) hydrochloride and mixtures thereof.
  • compositions can contain 0 to 10 wt. %, more preferably 1 wt. % to 6 wt. % of an alkyl polysaccharide surfactant.
  • the alkyl polysaccharides surfactants which are used in conjunction with the aforementioned surfactant have a hydrophobic group containing from 8 to 20 carbon atoms, preferably from 10 to 16 carbon atoms, most preferably from 12 to 14 carbon atoms, and polysaccharide hydrophilic group containing from 1.5 to 10, preferably from 1.5 to 4, most preferably from 1.6 to 2.7 saccharide units (e.g., galactoside, glucoside, fructoside, glucosyl, fructosyl; and/or galactosyl units).
  • 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. 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 galactosyl as opposed to a glucoside or galactoside).
  • attachment through the 1- position 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 8 to 20, preferably from 10 to 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 30, preferably less than 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 RO(C n H 2n O) r (Z) x 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 10 to 18, preferably from 12 to 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.
  • a long chain alcohol can be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside.
  • the short chain alkylglucosde content of the final alkyl polyglucoside material should be less than 50%, preferably less than 10%, more preferably less than 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 2%, more preferably less than 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 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.
  • 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 1.09 kilograms/liter; a calculated HLB of 12.1 and a Brookfield viscosity at 35°C, 21 spindle, 5-10 RPM of 3,000 to 7,000 c Pa.s (cps).
  • 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 about 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 or 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 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 about 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 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 by the previously described process: A B C D E Mg (LAS) 2 20 24 4 30 24 NH 4 AEOS1.3EO 12 8 30 4 8 LMMEA 2 2 0 0 2 D-Limonene 4 4 4 4 0 Dipropylene glycol monomethyl ether 4 4 4 4 0 APG 625 0 0 0 0 2 Sodium cumene sulfonate 1. 1 1 1 0 Sodium xylene sulfonate 1.2 1.2 0 0 1.2 Water Bal. Bal. Bal. Bal. Bal.
  • the described invention broadly relates to an improvement in a light duty liquid microemulsion composition containing a mixture of a paraffin sulfonate surfactant and an alkyl polyethenoxy ether sulfate surfactant, a biodegradable surfactant, one of the specified cosurfactants, a hydrocarbon ingredient and water to form a light duty liquid microemulsion composition.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (12)

  1. Composition de type microémulsion liquide pour lavage délicat comprenant en poids :
    15 % à 36 % d'un sel de magnésium d'un tensioactif sulfonaté, 1 % à 20 % d'un sel d'ammonium ou métallique d'un tensioactif de type alkyle C8-C18 éther polyéthénoxy sulfate ; 0 % à 10 % d'un alkyle polyglucoside ; 0,4 % à 10 % d'un hydrocarbure non hydrosoluble, d'une huile essentielle ou d'un parfum ; 1 % à 25 % d'un cosurfactant, 0 % à 5 % d'au moins un hydrotrope ; 0 % à 4 % de sulfate de magnésium ; 0 % à 5 % d'une alkyle monoalkanol amide ou d'une alkyle dialkanol amide et leurs mélanges ; et de l'eau.
  2. Composition de type microémulsion liquide pour lavage délicat selon la revendication 1, caractérisée en ce que ledit sulfonate et ledit alkyl éther polyéthénoxy sulfate sont présents dans un rapport de 8:1 à 1:8.
  3. Composition de lavage selon la revendication 2 qui comprend en outre un sel d'un cation métallique multivalent en une quantité suffisante pour procurer de 0,5 à 1,5 équivalents dudit cation par équivalent dudit tensioactif sulfonaté.
  4. Composition de lavage selon la revendication 3 dans laquelle le cation métallique multivalent est le magnésium ou l'aluminium.
  5. Composition de lavage selon la revendication 3, caractérisée en ce que ladite composition contient de 0,9 à 1,4 équivalents dudit cation par équivalent dudit tensioactif sulfonaté.
  6. Composition de lavage selon la revendication 4, caractérisée en ce que ledit sel multivalent est le sulfate de magnésium.
  7. Composition de lavage selon la revendication 2 qui contient de 2 % à 8 % en poids dudit cosurfactant et de 2 % à 7 % en poids dudit hydrocarbure.
  8. Composition de lavage selon la revendication 2 caractérisée en ce que le cosurfactant est un glycol éther hydrosoluble.
  9. Composition de lavage selon la revendication 8 dans laquelle le glycol éther est choisi parmi le groupe consistant en l'éthylène glycol monobutyléther, le diéthylène glycol monobutyléther, le triéthylène glycol monobutyléther, le polypropylène glycol de poids moléculaire moyen variant de 200 à 1 000 et le propylène glycol tert-butyl éther et mono, di, tri propylène glycol monobutyl éther et leurs mélanges.
  10. Composition de lavage selon la revendication 9 dans laquelle le glycol éther est le dipropylène glycol monométhyl éther.
  11. Composition de lavage selon la revendication 2 dans laquelle le tensioactif sulfonaté est un alkyl benzène sulfonate en C9-C15 ou une paraffine sulfonatée en C13-C17.
  12. Composition de lavage selon la revendication 1, dans laquelle ledit métal du sel métallique dudit alkyl éther polyéthénoxy sulfate est choisi parmi le groupe consistant en le potassium et le sodium.
EP95928799A 1994-08-26 1995-08-08 Composition detergente pour petits travaux sous forme de microemulsion Expired - Lifetime EP0781324B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US29638694A 1994-08-26 1994-08-26
US296386 1994-08-26
PCT/US1995/010126 WO1996006920A1 (fr) 1994-08-26 1995-08-08 Composition detergente pour petits travaux sous forme de microemulsion

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EP0781324A1 EP0781324A1 (fr) 1997-07-02
EP0781324B1 true EP0781324B1 (fr) 1999-02-24

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EP (1) EP0781324B1 (fr)
AU (1) AU3241995A (fr)
DE (1) DE69507960D1 (fr)
WO (1) WO1996006920A1 (fr)
ZA (1) ZA956932B (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5874393A (en) * 1994-12-15 1999-02-23 Colgate-Palmolive Co. Microemulsion light duty liquid cleansing composition
US5840676A (en) * 1994-12-15 1998-11-24 Colgate-Palmolive Company Microemulsion light duty liquid cleaning compositions
AU2535097A (en) * 1996-03-21 1997-10-10 Colgate-Palmolive Company, The Light duty liquid cleaning compositions
CO4771111A1 (es) * 1996-03-25 1999-04-30 Colgate Palmolive Co Composiciones limpiadoras liquidas de trabajo ligero
US5696073A (en) * 1996-04-08 1997-12-09 Colgate-Palmolive Co. Light duty liquid cleaning composition
AU2661597A (en) * 1996-04-08 1997-10-29 Colgate-Palmolive Company, The Light duty liquid cleaning compositions
US5700773A (en) * 1996-04-08 1997-12-23 Colgate-Palmolive Co. Light duty liquid cleaning compositions
US5714454A (en) * 1996-08-07 1998-02-03 Colgate-Palmolive Co. Light duty liquid cleaning compositions comprising alkyl sulroglycerides
US5780417A (en) * 1997-07-31 1998-07-14 Colgate-Palmolive Company Light duty liquid cleaning compositions
US5905064A (en) * 1998-01-08 1999-05-18 Colgate-Palmolive Co. Microemulsion cleaning compositions
WO2009029046A1 (fr) * 2007-08-29 2009-03-05 Agency For Science, Technology And Research Microémulsions d'agent tensio-actif à base de sucre contenant des huiles essentielles pour une utilisation cosmétique et pharmaceutique
GB2578278B (en) 2018-08-17 2021-04-21 Arrival Ltd Two-component adhesive dispenser with mixing unit replacement system

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0070074B2 (fr) * 1981-07-13 1997-06-25 THE PROCTER & GAMBLE COMPANY Compositions moussantes contenant des agents tensio-actifs
GB2144763B (en) * 1983-08-11 1987-10-28 Procter & Gamble Liquid detergent compositions with magnesium salts
US5076954A (en) * 1986-05-21 1991-12-31 Colgate-Palmolive Company Stable microemulsion cleaning composition
US4919839A (en) * 1989-02-21 1990-04-24 Colgate Palmolive Co. Light duty microemulsion liquid detergent composition containing an aniocic/cationic complex
AU690553B2 (en) * 1993-07-14 1998-04-30 Colgate-Palmolive Company, The Stable microemulsion cleaning composition

Also Published As

Publication number Publication date
WO1996006920A1 (fr) 1996-03-07
DE69507960D1 (de) 1999-04-01
ZA956932B (en) 1997-02-18
AU3241995A (en) 1996-03-22
EP0781324A1 (fr) 1997-07-02

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