EP0730636B1 - Compositions nettoyantes liquides polyvalentes en microemulsion - Google Patents

Compositions nettoyantes liquides polyvalentes en microemulsion Download PDF

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Publication number
EP0730636B1
EP0730636B1 EP95904066A EP95904066A EP0730636B1 EP 0730636 B1 EP0730636 B1 EP 0730636B1 EP 95904066 A EP95904066 A EP 95904066A EP 95904066 A EP95904066 A EP 95904066A EP 0730636 B1 EP0730636 B1 EP 0730636B1
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Prior art keywords
group
microemulsion
acid
composition
formula
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EP95904066A
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German (de)
English (en)
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EP0730636A1 (fr
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Myriam Mondin
Anne-Marie Misselyn
Marianne Mahieu
Georges Yianakopoulos
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Colgate Palmolive Co
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Colgate Palmolive Co
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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
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • 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
    • C11D1/667—Neutral esters, e.g. sorbitan 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • 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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C11D1/8305—Mixtures of non-ionic with anionic compounds containing a combination of non-ionic compounds differently alcoxylised or with different alkylated chains
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof
    • 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
    • C11D3/50—Perfumes
    • 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
    • C11D1/14—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
    • C11D1/66—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
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Definitions

  • the present invention relates to a microemulsion composition containing a grease release system comprising an ethoxylated glycerol type compound (as defined below) and choline chloride.
  • This invention relates to an improved all-purpose liquid cleaning composition in the form of a microemulsion composition designed in particular for cleaning hard surfaces and which is effective in removing grease soil and in leaving unrinsed surfaces with a shiny appearance.
  • all-purpose liquid detergents have become widely accepted for cleaning hard surface, e.g., painted woodwork and panels, tiled walls, wash bowls, bathtubs, linoleum or tile floors, washable wall paper, etc.
  • Such all-purpose liquids comprise clear and opaque aqueous mixtures of water-soluble synthetic organic detergents and water-soluble detergent builder salts.
  • use of water-soluble inorganic phosphate builder salts was favored in the prior art all-purpose liquids.
  • such early phosphate-containing compositions are described in U.S. Patent Nos. 2,560,839; 3,234,138; 3,350,319; and British Patent No. 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 A 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; and 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.
  • U.S. Patent 5,082,584 discloses a microemulsion composition having an anionic surfactant, a cosurfactant, nonionic surfactant, perfume and water; however, these compositions do not possess the ecotoxicity and the improved interfacial tension properties as exhibited by the compositions of the instant invention.
  • the present invention provides an improved, clear, 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 plastic, vitreous and metal surfaces having a shiny finish, oil stained floors, automative engines and other engines. More particularly. the improved cleaning compositions exhibit good grease soil removal properties due to the improved interfacial tensions, when used in undiluted (neat) form and leave the cleaned surfaces shiny without the need of or requiring only minimal additional rinsing or wiping. The latter characteristic is evidenced by little or no visible residues on the unrinsed cleaned surfaces and, accordingly, overcomes one of the disadvantages of prior art products.
  • the instant compositions exhibit a grease release effect in that the instant compositions impede or decrease the anchoring of greasy soil on surfaces that have been cleaned with the instant compositions as compared to surfaces cleaned with a commercial microemulsion composition which means that the grease soiled surface is easier to clean upon subsequent cleanings.
  • the instant compositions are more friendly for the environment due to the low ecotoxicity of ethoxylated glycerol type compound (as defined below) used in the instant compositions.
  • compositions of the instant invention have an ecotoxocity value as measured by the LC 50 test as deferred by The Organization for Economic Cooperation and Development (OECD)(of which the United States is a member) in OECD Test No. 202 of at least 0.18 ml/L measured on Daphniae microorganisms.
  • OECD Organization for Economic Cooperation and Development
  • the invention generally provides a stable, clear all-purpose, hard surface cleaning composition especially effective in the removal of oily and greasy oil, which is in the form of a substantially diluteoil-in-water microemulsion having an aqueous phase and an oil phase;
  • the dilute o/w microemulsion includes. on a weight basis:
  • the dispersed oil phase of the o/w microemulsion is composed essentially of a water-immiscible or hardly water-soluble perfume constituting from 2% to 50% by weight of the entire composition.
  • the perfume is not, per se, a solvent for greasy or oily soil, --even though some perfumes may, in fact, contain as much as 80% of terpenes which are known as good grease solvents -- the inventive compositions in dilute form have the capacity to solubilize up to 10 times or more of the weight of the perfume of oily and greasy soil, which is removed or loosened from the hard surface by virtue of the action of the anionic and nonionic surfactants, said soil being taken up into the oil phase of the o/w microemulsion.
  • the invention generally provides highly concentration microemulsion compositions in the form of either an oil-in-water (o/w) microemulsion or a water-in-oil (w/o) microemulsion which when diluted with additional water before use can form dilute o/w microemulsion compositions.
  • the concentrated microemulsion compositions contain, by weight, 1% to 30% of an anionic surfactant, 0.5% to 15% of an ethoxylated glycerol type compound, 0% to 5% of a fatty acid, 0.4% to 10% of perfume or water insoluble hydrocarbon having 6 to 18 carbon atoms, 0.1% to 50% of a cosurfactant, 0.5 to 10 wt. % of a grease release agent and water being the balance.
  • the present invention relates to a stable microemulsion composition approximately by weight: 0.1% to 20% of an anionic surfactant, 0.1% to 50% of a cosurfactant, 0,5 to 8 wt % of grease release agent, 0.1% to 10% of an ethoxylated glycerol type compound, 0.1 % to 10% of a water insoluble hydrocarbon or a perfume and the balance being water, said composition having an ecotoxocity value as measured by the LC50 test of at least 0.18 ml/L measured on Daphniae microorganisms.
  • the detergent compositions of the present invention are in the form of an oil-in-water microemulsion in the first aspect or after dilution with water in the second aspect, with the essential ingredients being water, grease release agent anionic surfactant, fatty acid, ethoxylated glycerol type compound and a hydrocarbon or perfume.
  • 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).
  • an improved grease release effect and an improved grease removal capacity in neat (undiluted) usage of the dilute aspect or after dilution of the concentrate can be obtained without detergent builders or buffers or conventional grease removal solvents at neutral or acidic pH and at low levels of active ingredients while improved cleaning performance can also be achieved in diluted usage.
  • 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 instant compositions show a marked improvement in ecotoxocity as compared to existing commercial products.
  • the hydrocarbon such as a perfume is present in the dilute o/w microemulsion in an amount of from e.g. 0.4% to 10% by weight, preferably from 0.4% to 3.0% by weight, especially preferably from 0.5% to 2.0% by weight, such as weight percent. 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.
  • a 20 milliliter sample of o/w microemulsion containing 1% by weight of perfume will be able to solubilize, for example, up to 2 to 3 ml of greasy and/or oily soil, while retaining its form as a microemulsion, regardless of whether the perfume contains 0%, 0.1 %, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7% or 0.8% by weight of terpene solvent.
  • a water insoluble paraffin or isoparaffin having 6 to 18 carbon at a concentration of 0.4 to 8.0 wt. percent, more preferably 0.4 to 3.0 wt. %.
  • anionic surfactant present in the o/w microemulsions any of the conventionally used water-soluble anionic surfactants or mixtures of said anionic surfactants and anionic surfactants can be used in this invention.
  • anionic surfactant is intended to refer to the class of anionic and mixed anionic-nonionic detergents providing detersive action.
  • the water-soluble organic surfactant materials which are used in forming the ultimate o/w microemulsion compositions of this invention may be selected from the group consisting of water-soluble, non-soap, anionic surfactants mixed with a fatty acid and a partially esterfied ethoxylated glycerol.
  • Suitable water-soluble non-soap, anionic surfactants 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, alkyl or acyl group.
  • Such surfactants 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 surfactants 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 surfactants 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 a-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.
  • Examples of satisfactory anionic sulfate surfactants are the C 8 -C 18 alkyl sulfate salts and 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 surfactants can be prepared by reacting an alkyl phenol with 2 to 6 moles of ethylene oxide and sulfating and neutralizing the resultant ethoxylated alkylphenol.
  • C 9 -C 15 alkyl ether polyethenoxyl carboxylates having the structural formula R(OC 2 H 4 ) n OX COOH wherein n is a number from 4 to 12, preferably 5 to 10 and X is selected from the group consisting of CH 2 C(O)R 1 and wherein R 1 is a C 1 -C 3 alkylene group.
  • Preferred compounds include C 9 -C 11 alkyl ether polyethenoxy (7-9) C(O) CH 2 CH 2 COOH, C 13 -C 15 alkyl ether polyethenoxy (7-9) and C 10 -C 12 alkyl ether polyethenoxy (5-7) CH 2 COOH.
  • These compounds may be prepared by condensing ethylene oxide with appropriate alkanol and reacting this reaction product with chloracetic acid to make the ether carboxylic acids as shown in US Pat. No. 3,741,911 or with succinic anhydride or phtalic anhydride.
  • anionic detergents will be present either in acid form or salt form depending upon the pH of the final composition, with the salt forming cation being the same as for the other anionic detergents.
  • the preferred surfactants are the C 9 -C 15 linear alkylbenzene sulfonates and the C 13 -C 17 paraffin or alkane sulfonates.
  • preferred compounds are sodium C 10 -C 13 alkylbenzene sulfonate and sodium C 13 -C 17 alkane sulfonate.
  • the proportion of the nonsoap-anionic surfactant will be in the range of 0.1 % to 20.0%, preferably from 1 % to 7%, by weight of the dilute o/w microemulsion composition.
  • the instant composition contains a composition (herein after referred to as ethoxylated glycerol type compound) which is a mixture of a fully esterified ethoxylated polyhydric alcohol, a partially esterified ethoxylated polyhydric alcohol and a nonesterified ethoxylated polyhydric alcohol, wherein the preferred polyhydric alcohol is glycerol, and the compound is and wherein w equals one to four, most preferably one.
  • ethoxylated glycerol type compound is a mixture of a fully esterified ethoxylated polyhydric alcohol, a partially esterified ethoxylated polyhydric alcohol and a nonesterified ethoxylated polyhydric alcohol, wherein the preferred polyhydric alcohol is glycerol, and the compound is and wherein w equals one to four, most preferably one.
  • B is selected from the group consisting of hydrogen or a group represented by: wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms and alkenyl groups having 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, wherein at least one of the B groups is represented by said and R' is selected from the group consisting of hydrogen and methyl groups; x, y and z have a value between 0 and 60, more preferably 0 to 40, provided that (x+y+z) equals 2 to 100, preferably 4 to 24 and most preferably 4 to 19, wherein in Formula(l) the weight ratio of monoester/diester/triester is 40 to 90/5 to 35/1 to 20, more preferably 50 to 90/9 to 32/1 to 12, wherein the weight ratio of Formula(I) to Formula(II) is a value between 3 to 0.02,
  • the ethoxylated glycerol type compound used in the instant composition is manufactured by the Kao Corporation and sold under the trade name Levenol such as Levenol F-200 which has an average EO of 6 and a molar ratio of coco fatty acid to glycerol of 0.55 or Levenol V501/2 which has an average EO of 17 and a molar ratio of tallow fatty acid to glycerol of 1.0. It is preferred that the molar ratio of the fatty acid to glycerol is less than 1.7, more preferably less than 1.5 and most preferably less than 1.0.
  • the ethoxylated glycerol type compound has a molecular weight of 400 to 1600, and a pH (50 grams / liter of water) of 5-7.
  • the Levenol compounds are substantially non irritant to human skin and have a primary biodegradabillity higher than 90% as measured by the Wickbold method Bias-7d.
  • Levenol V-501/2 Two examples of the Levenol compounds are Levenol V-501/2 which has 17 ethoxylated groups and is derived from tallow fatty acid with a fatty acid to glycerol ratio of 1.0 and a molecular weight of 1465 and Levenol F-200 has 6 ethoxylated groups and is derived from coco fatty acid with a fatty acid to glycerol ratio of 0.55.
  • Both Levenol F-200 and Levenol V-501/2 are composed of a mixture of Formula (I) and Formula (II).
  • the Levenol compounds has ecoxicity values of algae growth inhibition > 100 mg/liter; acute toxicity for Daphniae > 100 mg/liter and acute fish toxicity > 100 mg/liter.
  • the Levenol compounds have a ready biodegradability higher than 60 % which is the minimum required value according to OECD 301B measurement to be acceptably biodegradable.
  • Polyesterified nonionic compounds also useful in the instant compositions are Crovol PK-40 and Crovol PK-70 manufactured by Croda GMBH of the Netherlands.
  • Crovol PK-40 is a polyoxyethylene (12) Palm Kernel Glyceride which has 12 EO groups.
  • Crovol PK-70 which is preferred is a polyoxyethylene (45) Palm Kernel Glyceride have 45 EO groups.
  • the weight ratio of nonsoap anionic surfactant to the ethoxylated polyhydric alcohol compound will be in the range of 3:1 to 1:3 with especially good results being obtained at a weight ratio of 2:1.
  • the grease release system of the instant composition comprises a compound which is the mixture of the fully esterified ethoxylated polyhydric alcohol, the partially esterified ethoxylated polyhydric alcohol, and the nonesterified ethoxylated polyhydric alcohol, and the nonesterified ethoxylated polyhydric alcohol.
  • Three major classes of compounds found to provide highly suitable cosurfactants for the microemulsion over temperature ranges extending from 5°C to 43°C for instance are water soluble C 3 -C 4 alkanols, polypropylene glycol of the formula HO(CH 3 CHCH 2 O) n H wherein n is a number from 2 to 18 and mono 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, 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, (2) aliphatic mono- and di-carboxylic acids containing 2 to 10 carbon atoms, preferably 3 to 6 carbons in the molecule; and (3) triethyl phosphate.
  • the compositions can be used for hard surfaced items, which are acid resistant thereby removing lime scale, soap scum and greasy soil from the surfaces of such items without damaging such surfaces. If these surfaces are of zirconium white enamel, they can be damaged by these compositions.
  • An aminoalkylene phosphoric acid at a concentration of 0.01 to 0.2 wt. % can be optionally used in conjunction with the mono- and di-carboxylic acids, wherein the aminoalkylene phosphoric acid helps prevent damage to zirconium white enamel surfaces. Additionally, 0.05 to 1 % of phosphoric acid can be used in the composition.
  • 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.
  • Reprentative members of the aliphatic carboxylic acids include C 3 -C 6 alkyl and alkenyl monobasic acids such as acrylic acid and propionic acid and dibasic acids such as glutaric acid and mixtures of glutaric acid with adipic acid and succinic acid, as well as mixtures of the foregoing acids.
  • the aforementioned glycol ether compounds and acid compounds provide the described stability, but the most preferred cosurfactant compounds of each type, on the basis of cost and cosmetic appearance (particularly odor), are diethylene glycol monobutyl ether and a mixture of adipic, glutaric and succinic acids, respectively.
  • the ratio of acids in the foregoing mixture is not particularly critical and can be modified to provide the desired odor. Generally, to maximize water solubility of the acid mixture glutaric acid. the most water-soluble of these three saturated aliphatic dibasic acids, will be used as the major component.
  • weight ratios of adipic acid: glutaric acid:succinic acid is 1-3:1-8:1-5. preferably 1-2:1-6:1-3, such as 1:1:1, 1:2:1, 2:2:1, 1:2:1.5, 1:2:2. 2:3:2, etc. can be used with equally good results.
  • Still other classes of cosurfactant compounds providing stable microemulsion compositions at low and elevated temperatures are the mono-, di- and triethyl esters of phosphoric acid such as triethyl phosphate.
  • 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 0.1 % to 50%, preferably from 0.5% to 15%, especially preferably from 1% to 7%, 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 pH of the final microemulsion will be dependent upon the identity of the cosurfactant compound, with the choice of the cosurfactant being effected by cost and cosmetic properties, particularly odor.
  • microemulsion compositions which have a pH in the range of 1 to 10 may employ either the class 1 or the class 3 cosurfactant as the sole cosurfactant, but the pH range is reduced to 1 to 8.5 when the polyvalent metal salt is present.
  • the class 2 cosurfactant can only be used as the sole cosurfactant where the product pH is below 3.2.
  • the acidic cosurfactants are employed in admixture with a glycol ether cosurfactant.
  • compositions can be formulated at a substantially neutral pH (e.g., pH 7 ⁇ 1.5. preferably 7 ⁇ 0.2).
  • the low pH o/w microemulsion formulations also exhibit excellent cleaning performance and removal of soap scum and lime scale in neat (undiluted) as well as in diluted usage.
  • Preferred grease release agents are Beta-hydroxyethyltrimethyl ammonium chloride (choline chloride),Beta-chloroethyltrimethyl ammonium chloride, and tr(Beta-hydroxyethyl) methyl ammonium methosulfate (Stepanquat T), wherein the choline chloride is preferred.
  • the positively charged grease release agent is electrostatically bonded to the negatively charged groups on the surface of the surface to be cleaned such as a ceramic thereby preventing bonding of calcium ions contained in grease to the negative charged surface of the ceramic tile.
  • concentration of the grease release agent in the instant microemulsion composition is 0.5 to 10 wt. %, more preferably 0.5 wt. % to 8.0 wt. %.
  • the grease release agents of the present invention can also be an anionic surfactant being associated in the composition with a polyethylene glycol having a molecular weight of 500 to 1,000. wherein the polyethylene glycol has the structure HO(CH 2 CH 2 O) n H wherein n is 11 to 52.
  • the concentration of the polyethylene glycol in the instant composition is 0.5 to 10.0 wt. %. more preferably 0.5 to 8.0 wt. %. wherein the ratio of anionic surfactant to the polyethylene glycol is 5:1 to 1:5.
  • Another class of grease release agents used in the grease release system of the present invention are an ethoxylated maleic anhydride -alpha- olefin copolymer having a comblike structure with both hydrophobic and hydrophilic chains.
  • the polymer is made by Akzo Chemie America and has a number average molecular weight of 10.000 to 30,000. most preferably 15,000 to 25,000.
  • the ethoxylated maleic anhydride-alphaolefin copolymer which is used at a concentration of 0.5 to 10.0 wt. %, more preferably 1.0 to 8.0 wt. %, is depicted by the formula: wherein n is 5 to 14, preferably 7 to 9, x is 7 to 19, preferably 8 to 19 and y is of such a value as to provide a molecular weight 10,000 to 30,000.
  • Another class of grease release agents manufactured by BASF that are used in the grease release system of the present invention at a concentration of 0.5 to 10 wt. %, more preferably 0.5 to 8.0 wt. %. is a polymer depicted by the formula: wherein n is a number from 2 to 16, preferably 2 to 10, R 1 is selected from the group consisting of methyl or hydrogen, R 2 is a C 1 to C 12 , preferably C 4 to C 8 , linear or branched chained alkyl group and R 3 is a C 2 to C 16 , preferably C 2 to C 12 linear or branched chained alkyl group.
  • the final essential ingredient in the inventive 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 dilute o/w microemulsion liquid all-purpose cleaning 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 an o/w microemulsion are best manifested in the neat (undiluted) form.
  • the properties of the composition as an o/w microemulsion are best manifested in the neat (undiluted) form.
  • some degree of dilution without disrupting the microemulsion, per se is possible.
  • active surfactant compounds i.e., primary anionic and nonionic detergents
  • 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.
  • the present invention also relates to a stable concentrated microemulsion or acidic microemulsion composition comprising approximately by weight:
  • Such concentrated microemulsions can be diluted by mixing with up to 20 times or more, preferably 4 to 10 times their weight of water to form o/w microemulsions similar to the diluted microemulsion compositions described above. While the degree of dilution is suitably chosen to yield an o/w microemulsion composition after dilution, it should be recognized that during the course of dilution both microemulsion and non-microemulsions may be successively encountered.
  • compositions of this invention may often and preferably do 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.
  • polyvalent metal ions include aluminum, copper, nickel, iron, calcium, etc. It should be noted, for example, that with the preferred paraffin sulfonate anionic detergent calcium salts will precipitate and should not be used. It has also been found that 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. Alternatively, 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 surfactant.
  • the amount of multivalent salt will be in range of 0.5 to 1 equivalents per equivalent of anionic surfactant.
  • the o/w microemulsion compositions will include from 0% to 2.5%, preferably from 0.1 % to 2.0% by weight of the composition of a C 8 -C 22 fatty acid or fatty acid soap as a foam suppressant.
  • fatty acid or fatty acid soap provides an improvement in the rinseability of the composition whether applied in neat or diluted form. Generally, however, it is necessary to increase the level of cosurfactant to maintain product stability when the fatty acid or soap is present. If more than 2.5 wt. % of a fatty acid is used in the instant compositions, the composition will become unstable at low temperatures as well as having an objectionable smell.
  • fatty acids which can be used as such or in the form of soap, mention can be made of distilled coconut oil fatty acids, "mixed vegetable” type fatty acids (e.g. high percent of saturated, mono-and/or polyunsaturated C 18 chains); oleic acid, stearic acid, palmitic acid, eiocosanoic acid, and the like, generally those fatty acids having from 8 to 22 carbon atoms being acceptable.
  • the all-purpose 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.
  • 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-bromo-5-nitro-dioxan-1,3; 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.
  • up to 4% by weight of an opacifier may be added.
  • the all-purpose liquids are clear oil-in-water microemulsions and exhibit stability at reduced and increased temperatures. More specifically, such compositions remain clear and stable in the range of 5°C to 50°C, especially 10°C to 43°C. Such compositions exhibit a pH in the acid or neutral range depending on intended end use.
  • the liquids are readily pourable and exhibit a viscosity in the range of 6 to 60 milliPascal . second (mPas.) as measured at 25°C. with a Brookfield RVT Viscometer using a #1 spindle rotating at 20 RPM.
  • the viscosity is maintained in the range of 10 to 40 mPas.
  • compositions are directly ready for use or can be diluted as desired and in either case no or only minimal rinsing is required and substantially no residue or streaks are left behind. Furthermore, because the compositions are free of detergent builders such as alkali metal polyphosphates they are environmentally acceptable and provide a better "shine" on cleaned hard surfaces.
  • liquid compositions When intended for use in the neat form, the liquid compositions can be packaged under pressure in an aerosol container or in a pump-type sprayer for the so-called spray-and-wipe type of application.
  • 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.
  • the instant microemulsion formulas explicitly exclude alkali metal silicates and alkali metal builders such as alkali metal polyphosphates, alkali metal carbonates, alkali metal phosphonates and alkali metal citrates because these materials, if used in the instant composition, would cause the composition to have a high pH as well as leaving residue on the surface being cleaned.
  • alkali metal silicates and alkali metal builders such as alkali metal polyphosphates, alkali metal carbonates, alkali metal phosphonates and alkali metal citrates because these materials, if used in the instant composition, would cause the composition to have a high pH as well as leaving residue on the surface being cleaned.
  • the instant partially esterified ethoxylated glycol type compound can be employed in hard surface cleaning compositions such as wood cleaners, window cleaners and light duty liquid cleaners.
  • dissolution power of the o/w microemulsion of this example is compared to the “dissolution power" of an identical composition except that an equal amount (5 weight percent) of sodium cumene sulfonate hydrotrope is used in place of the diethylene glycol monobutyl ether cosurfactant in a test wherein equal concentrations of heptane are added to both compositions.
  • the o/w microemulsion of this invention solubilizes 12 grams of the water immiscible substance as compared to 1.4 grams in the hydrotrope containing liquid composition.
  • Example 1 In a further comparative test using blue colored cooking oil--a fatty triglyceride soil --, the composition of Example 1 is clear after the addition of 0.2 grams of cooking oil whereas the cooking oil floats on the top of the composition containing the sulfonate hydrotrope.
  • Example 1 When the concentration of perfume is reduced to 0.4% in the composition of Example 1, a stable o/w microemulsion composition is obtained. Similarly, a stable o/w microemulsion is obtained when the concentration of perfume is increased to 2% by weight and the concentration of cosurfactant is increased to 6% by weight in Example 1.
  • Formula 1-E of example 1 was tested for grease release.
  • the combination of Levenol plus Choline chloride provides a superior grease release effect to the microemulsion composition.
  • 1.a.Treated with the neat product drying in open air before spraying the soil number of strokes for first cleaning number of strokes for second cleaning after drying in open air Formula 1-E 24 23 current AJAX tm NME 46 40 1.a.Treated with the neat product ; wiping with wet sponges before spraying the soil number of strokes for first cleaning number of strokes for second cleaning after drying in open air Formula 1-E 32 19 current AJAX tm NME 53 27 1.a.Treated with the diluted product ; drying in open air before spraying the soil number of strokes for first cleaning number of strokes for second cleaning after drying in open air Formula 1-E 3 2 current AJAX tm NME 18 19 1.a.Treated with the diluted product ; wiping with wet sponges before spraying the soil number of strokes for first cleaning number of strokes for second cleaning after drying
  • the described invention broadly relates to an improvement in microemulsion compositions containing an anionic surfactant, a partially esterified ethoxylated polyhydric alcohol, a fatty acid, a grease release agent, one of the specified cosurfactants, a hydrocarbon ingredient and water which comprise the use of a water-insoluble, odoriferous perfume as the essential hydrocarbon ingredient.

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Claims (11)

  1. Composition nettoyante en microémulsion comprenant :
    (a) 0,1 % en poids à 10 % en poids d'un mélange de
    Figure 00400001
    et
    Figure 00400002
    où :
    w est égal à un à quatre,
    B est choisi dans la classe formée par un atome d'hydrogène et un groupe représenté par :
    Figure 00400003
    où R est choisi dans la classe formée par les groupes alkyle ayant 6 à 22 atomes de carbone et les groupes alcényle ayant 6 à 22 atomes de carbone, au moins l'un des groupes B étant représenté par ledit
    Figure 00400004
    R' est choisi dans la classe formée par un atome d'hydrogène et un groupe méthyle ; x, y et z ont des valeurs comprises entre 0 et 60, à condition que (x + y + z) soit égal à 2 à 100, dans lequel, dans la Formule (I), le rapport en poids monoester/diester/triester est de 40 à 90/5 à 35/1 à 20, et le rapport en poids de la Formule (I) et de la Formule (II) est une valeur comprise entre 3 et 0,02 ;
    (b) 0,5 à 8 % en poids d'un agent d'élimination des graisses complémentaire, ledit agent d'élimination des graisses étant choisi dans la classe formée par
    (a)
    Figure 00410001
    où R1 est un groupe méthyle et R2, R3 et R4 sont choisis indépendamment dans la classe formée par les groupes méthyle, éthyle et CH2CH2Y, où Y est choisi dans la classe formée par Cl, Br, CO2H, (CH2O)nOH où n = 1 à 10, OH, CH2CH2OH, et X- est choisi dans la classe formée par Cl, Br, l'ion métho-sulfate
    Figure 00410002
    et HCO3 - ;
    (b) un polyéthylène-glycol ayant un poids moléculaire de 500 à 1000, le polyéthylène-glycol ayant la structure HO(CH2CH2O)nH où n est de 11 à 52 ;
    (c) un copolymère anhydride maléique éthoxylé/alpha-oléfine ayant la formule
    Figure 00410003
    où n est de 5 à 14, et y a une valeur convenant pour donner un poids moléculaire de 10 000 à 30 000 ; et
    (d) un polymère ayant la formule
    Figure 00420001
    où n est un nombre de 2 à 16, R1 est choisi dans la classe formée par un groupe méthyle ou un atome d'hydrogène, R2 est un groupe alkyle à chaíne linéaire ou ramifiée en C1 à C12 et R3 est un groupe alkyle à chaíne linéaire ou ramifiée en C2 à C16 ;
    (c) 0,1 % en poids à 20 % en poids d'un agent tensio-actif anionique ;
    (d) 0,1 % en poids à 50 % en poids d'un agent co-tensio-actif choisi dans la classe formée par l'éther monobutylique d'éthylène-glycol, l'éther monobutylique de diéthylène-glycol, l'éther monobutylique de triéthylène-glycol, un polypropylène-glycol ayant un poids moléculaire moyen de 200 à 1000 et l'éther tert-butylique de propylène-glycol, l'éther monobutylique de mono-, di-, tripropylène-glycol et un acide carboxylique aliphatique en C3 à C6 choisi dans la classe formée par l'acide acrylique, l'acide propionique, l'acide glutarique, les mélanges d'acide glutarique avec l'acide succinique et l'acide adipique, et les mélanges de n'importe lesquels des précédents ;
    (e) 0,1 % en poids à 10 % en poids d'un hydrocarbure insoluble dans l'eau, d'une huile essentielle ou d'un parfum ; et
    (f) le reste étant de l'eau.
  2. Composition nettoyante selon la revendication 1, qui contient, de plus, un sel d'un cation métallique polyvalent en une quantité suffisante pour fournir 0,5 à 1,5 équivalent dudit cation par équivalent dudit agent tensio-actif anionique.
  3. Composition nettoyante selon la revendication 2, dans laquelle le cation métallique polyvalent est le magnésium ou l'aluminium.
  4. Composition nettoyante selon la revendication 2, dans laquelle ladite composition contient 0,9 à 1,4 équivalent dudit cation par équivalent de détergent anionique.
  5. Composition nettoyante selon la revendication 3, dans laquelle ledit sel de cation polyvalent est l'oxyde de magnésium ou le sulfate de magnésium.
  6. Composition nettoyante selon la revendication 1, contenant, de plus, un acide gras ayant 8 à 22 atomes de carbone.
  7. Composition en microémulsion selon la revendication 1, qui contient 0,5 à 15 % en poids dudit agent co-tensio- actif et 0,4 % à 3,0 % en poids dudit hydrocarbure.
  8. Composition en microémulsion selon la revendication 1, dans laquelle l'éther de glycol est l'éther monobutylique d'éthylène-glycol ou l'éther monobutylique de diéthylène-glycol.
  9. Composition nettoyante selon la revendication 1, dans laquelle l'acide carboxylique aliphatique est un mélange d'acide adipique, d'acide glutarique et d'acide succinique.
  10. Composition nettoyante selon la revendication 1, dans laquelle l'agent tensio-actif anionique est un (alkyle en C9 à C15) benzène-sulfonate ou un alcanesulfonate en C10 à C20.
  11. Composition en microémulsion concentrée stable, comprenant, en poids :
    (a) 1 à 30 % d'un agent tensio-actif anionique ;
    (b) 0,5 à 15 % d'un mélange de
    Figure 00440001
    et
    Figure 00440002
    où w est égal à un à quatre, et B est choisi dans la classe formée par un atome d'hydrogène et un groupe représenté par :
    Figure 00440003
    où R est choisi dans la classe formée par les groupes alkyle ayant 6 à 22 atomes de carbone et les groupes alcényle ayant 6 à 22 atomes de carbone, au moins l'un des groupes B étant représenté par ledit
    Figure 00440004
    R' est choisi dans la classe formée par un atome d'hydrogène et un groupe méthyle ; x, y et z ont des valeurs comprises entre 0 et 60, à condition que (x + y + z) soit égal à 2 à 100, dans lequel, dans la Formule (I), le rapport en poids monoester/diester/triester est de 40 à 90/5 à 35/1 à 20, et le rapport en poids de la Formule (I) et de la Formule (II) est une valeur comprise entre 3 et 0,02 ;
    (c) 2 à 30 % d'un agent, co-tensio-actif,
    (d) 0,4 à 10 % d'un hydrocarbure insoluble dans l'eau ou d'un parfum ;
    (e) 0 à 18 % d'au moins un acide dicarboxylique ;
    (f) 0 à 0,2 % d'un acide aminoalkylène-phosphorique;
    (g) 0 à 1,0 % d'acide phosphorique ;
    (h) 0 à 15 % de sulfate de magnésium heptahydraté ;
    (i) 0,5 à 10 % d'un agent d'élimination des graisses, choisi dans la classe formée par
    (a)
    Figure 00450001
    où R1 est un groupe méthyle et R2, R3 et R4 sont choisis indépendamment dans la classe formée par les groupes méthyle, éthyle et CH2CH2Y, où Y est choisi dans la classe formée par Cl, Br, CO2H, (CH2O)nOH où n = 1 à 10, OH, CH2CH2OH et X- est choisi dans la classe formée par Cl, Br, l'ion métho-sulfate
    Figure 00450002
    et HCO3 -;
    (b) un polyéthylène-glycol ayant un poids moléculaire de 500 à 1000, le polyéthylène-glycol ayant la structure HO(CH2CH2O)nH où n est de 11 à 52 ;
    (c) un copolymère anhydride maléique éthoxylé/alpha oléfine ayant la formule
    Figure 00450003
    où n est de 5 à 14, et y a une valeur convenant pour donner un poids moléculaire de 10 000 à 30 000 ; et
    (d) un polymère ayant la formule
    Figure 00460001
    où n est un nombre de 2 à 16, R1 est choisi dans la classe formée par un groupe méthyle ou un atome d'hydrogène, R2 est un groupe alkyle à chaíne linéaire ou ramifiée en C1 à C12 et R3 est un groupe alkyle à chaíne linéaire ou ramifiée en C2 à C16 ; et
    (j) le reste étant de l'eau, la composition ayant un indice d'écotoxicité, tel que mesuré par le test LC50, d'au moins 0,18 ml/ℓ mesuré sur des microorganismes du genre Daphniae.
EP95904066A 1993-11-22 1994-11-18 Compositions nettoyantes liquides polyvalentes en microemulsion Expired - Lifetime EP0730636B1 (fr)

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US15534593A 1993-11-22 1993-11-22
US155345 1993-11-22
US28863894A 1994-08-10 1994-08-10
US288638 1994-08-10
US33693494A 1994-11-15 1994-11-15
US336934 1994-11-15
PCT/US1994/013162 WO1995014765A1 (fr) 1993-11-22 1994-11-18 Compositions nettoyantes liquides polyvalentes en microemulsion

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NZ264113A (en) * 1993-08-04 1996-06-25 Colgate Palmolive Co Liquid crystal or microemulsion liquid cleaners containing esterified polyethoxyether nonionic surfactant, anionic surfactant, cosurfactant, optionally a fatty acid, and water-insoluble hydrocarbon or perfume
US5759983A (en) * 1993-08-04 1998-06-02 Colgate-Palmolive Co. Aqueous cleaning composition which may be in microemulsion form comprising polyalkylene oxide -polydimethyl siloxane and ethoxylated secondary alcohol
US5741760A (en) * 1993-08-04 1998-04-21 Colgate-Palmolive Company Aqueous cleaning composition which may be in microemulsion form comprising polyalkylene oxide-polydimethyl siloxane
US5486307A (en) * 1993-11-22 1996-01-23 Colgate-Palmolive Co. Liquid cleaning compositions with grease release agent
AU1355995A (en) * 1994-03-14 1995-09-21 Colgate-Palmolive Company, The Microemulsion all purpose liquid cleaning compositions
ZA952386B (en) * 1994-04-15 1996-09-23 Colgate Palmolive Co Microemulsion liquid cleaning compositions with insect repellent
AU681487B2 (en) * 1994-04-15 1997-08-28 Colgate-Palmolive Company, The Microemulsion all purpose liquid cleaning compositions with insect repellent
HUT77481A (hu) * 1994-11-15 1998-05-28 Colgate-Palmolive Company Sok célra felhasználható folyékony tisztítókompozíciók
GB9626610D0 (en) * 1996-12-20 1997-02-05 Unilever Plc Cleaning composition comprising monoalkyl cationic surfactants
AU7975598A (en) * 1997-06-23 1999-01-04 Colgate-Palmolive Company, The Microemulsion all purpose liquid cleaning compositions
EP1047763B1 (fr) * 1998-01-12 2005-12-07 The Procter & Gamble Company Compositions aqueuses acides de nettoyage
ATE486921T1 (de) * 2006-06-08 2010-11-15 Unilever Nv Flüssigwaschmittel mit esteralkoxylat als tensid sowie harnstoff
ES2539732B1 (es) * 2013-06-28 2016-02-05 Kao Corporation, S.A. Composición detergente líquida

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BR9408122A (pt) 1997-08-05
GR3036281T3 (en) 2001-10-31
ATE200793T1 (de) 2001-05-15
DE69427154T2 (de) 2001-11-29
AU1289195A (en) 1995-06-13
CA2177067A1 (fr) 1995-06-01
NZ277602A (en) 1997-09-22
ES2158072T3 (es) 2001-09-01
DK0730636T3 (da) 2001-08-13
EP0730636A1 (fr) 1996-09-11
PT730636E (pt) 2001-10-30
WO1995014765A1 (fr) 1995-06-01
PL314622A1 (en) 1996-09-16
AU680087B2 (en) 1997-07-17

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