WO2000029528A2 - Composition nettoyante liquide en microemulsion, contenant un amphiphile a chaine courte - Google Patents

Composition nettoyante liquide en microemulsion, contenant un amphiphile a chaine courte Download PDF

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Publication number
WO2000029528A2
WO2000029528A2 PCT/US1999/025155 US9925155W WO0029528A2 WO 2000029528 A2 WO2000029528 A2 WO 2000029528A2 US 9925155 W US9925155 W US 9925155W WO 0029528 A2 WO0029528 A2 WO 0029528A2
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Prior art keywords
group
carbon atoms
cleaning composition
oil
formula
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PCT/US1999/025155
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English (en)
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WO2000029528A3 (fr
Inventor
Baudouin Mertens
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Colgate-Palmolive Company
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Priority claimed from US09/191,002 external-priority patent/US6136773A/en
Priority claimed from US09/191,003 external-priority patent/US5981462A/en
Application filed by Colgate-Palmolive Company filed Critical Colgate-Palmolive Company
Priority to EP99956703A priority Critical patent/EP1129173A2/fr
Priority to AU13249/00A priority patent/AU762731B2/en
Publication of WO2000029528A2 publication Critical patent/WO2000029528A2/fr
Publication of WO2000029528A3 publication Critical patent/WO2000029528A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/18—Hydrocarbons
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • 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
    • C11D1/04—Carboxylic acids or 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
    • C11D1/02—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
    • C11D1/66—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
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols

Definitions

  • the present invention relates to liquid cleaning microemulsion composition containing short chain amphiphiles. Background of the Invention
  • This invention relates to an improved all-purpose liquid cleaning composition or a microemulsion composition having excellent foam collapse properties and excellent grease cutting properties designed in particular for cleaning hard surfaces and which is effective in removing grease soil and/or bath soil and in leaving unrinsed surfaces with a shiny appearance.
  • all-purpose liquid detergents have become widely accepted for cleaning hard surfaces, e.g., painted woodwork and panels, tiled walls, wash bowls, bathtubs, linoleum or tile floors, washable wall paper, etc.
  • Such all-purpose liquids comprise clear and opaque aqueous mixtures of water-soluble synthetic organic detergents and water-soluble detergent builder salts.
  • use of water-soluble inorganic phosphate builder salts was favored in the prior art all-purpose liquids.
  • such early phosphate-containing compositions are described in U.S. Patent Nos. 2,560,839; 3,234,138; 3,350,319; and British Patent No. 1 ,223,739.
  • 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. It also is known from British Patent Application GB 2144763A to Herbots et al, published March 13, 1985, that magnesium salts enhance grease-removal performance of organic grease- removal solvents, such as the terpenes, in o/w microemulsion liquid detergent compositions.
  • 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 cleaning compositions in the form of o/w microemulsions: U.S. Patents No. 4,472,291 - Rosario; U.S. Patent No. 4,540,448 - Gauteer et al; U.S. Patent No. 3,723,330 - Sheflin; etc.
  • 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:
  • (c ) from 0.5% 10% of a polar solvent having a solubility in water at 15°C in the range of from 0.2% to 10%.
  • Other ingredients present in the formulations disclosed in this patent include from 0.05% to 2% by weight of an alkali metal, ammonium or alkanolammonium soap of a C13-C24 fatty acid; a calcium sequestrant from 0.5% to
  • non-aqueous solvent e.g., alcohols and glycol ethers, up to 10% by weight
  • hydrotropes e.g., urea, ethanolamines, salts of lower alkylaryl sulfonates, up to 10% by weight. All of the formulations shown in the Examples of this patent include relatively large amounts of detergent builder salts which are detrimental to surface shine.
  • the present invention provides an improved, liquid cleaning composition having excellent foam collapse properties and excellent grease cutting property 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, automotive engines and other engines. More particularly, the improved cleaning compositions, with excellent foam collapse properties and excellent grease cutting property exhibit good grease soil removal properties due to the improved interfacial tensions, when used in undiluted (neat) or dilute 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 invention generally provides a stable, optically clear microemulsion, hard surface cleaning composition especially effective in the removal of oily and greasy oil, which is in the form of a substantially dilute oil-in-water microemulsion having an aqueous phase and an oil phase;
  • the dilute microemulsion composition includes, on a weight basis:
  • an ethoxylated polyhydric alcohol type compound (as defined below) an ethoxylated/propoxylated nonionic surfactant and an ethoxylated nonionic surfactant and mixtures thereof;
  • compositions does not contain a water- soluble polyethylene glycols having a molecular weight of 150 to 1000, polypropylene glycol of the formula HO(CH3CHCH2 ⁇ )nH wherein n is a number from 2 to 18, mixtures of polyethylene glycol and polypropylene glycol (Synalox) and mono and di C1 -C6 alkyl ethers and esters of ethylene glycol and propylene glycol having the structural formulas R(X) n OH, R-
  • grease release agents which are an ethoxylated maleic anhydride- alpha-olefin copolymer having a comblike structure with both hydrophobic and hydrophilic chains and is depicted by the formula:
  • 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.
  • the present invention relates to a stable optically clear microemulsion composition
  • a stable optically clear microemulsion composition comprising by weight: 0.1 % to 8% of a sulfonate anionic surfactant, 0.05% to 2% of a fatty acid; 0.5% to 8% of a short chain amphiphile; 0.25% to 6% of magnesium sulfate heptahydrate; 0.5% to 6% of a nonionic surfactant selected from the group consisting of ethoxylated nonionics, surfactants, ethoxyiated/propylated nonionic surfactant; and ethoxylated polyhydric alcohol type compound and mixtures thereof; 0.1 % to 6% of a water insoluble hydrocarbon, essential oil or a perfume, 0.05% to 2% of a fatty acid and the balance being water.
  • the role of the water insoluble hydrocarbon can be 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.
  • 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 0.1 % to 6% by weight, preferably from 0.4% to 5% by weight. If the amount of hydrocarbon (perfume) is less than 0.4% by weight it becomes difficult to form the o/w microemulsion. If the hydrocarbon (perfume) is added in amounts more than 10% by weight, the cost is increased without any additional cleaning benefit and, in fact, with some diminishing of cleaning performance insofar as the total amount of greasy or oily soil which can be taken up in the oil phase of the microemulsion will decrease proportionately. In the all purpose hard surface cleaning composition which is not a microemulsion the concentration of the perfume is 0 to 10 wt.
  • Suitable essential oils are selected from the group consisting of:
  • 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 which is sulfonate group, so as to form a water-soluble detergent.
  • the hydrophobic group will include or comprise a C8-C22 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- C2-C3 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, C8-C15 alkyl toluene sulfonates and C8-C 5 alkyl phenol sulfonates.
  • One preferred sulfonate surfactant is a 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.
  • operative anionic surfactants includes sodium dioctyl sulfosuccinate [di-(2 ethylhexyl) sodium sulfosuccinate being one ] and corresponding dihexyl and dioctyl esters.
  • the preferred sulfosuccinic acid ester salts are esters of aliphitic alcohols such as saturated alkanols of 4 to 12 carbon atoms and are normally diesters of such alkanols.
  • alkali metal salts of the diesters of alcohols of 6 to 10 carbons atoms and more preferably the diesters will be from octanol, such as 2 -ethyl hexanol, and the sulfonic acid salt will be the sodium salt.
  • Especially preferred anionic sulfonate surfactants are paraffin sulfonates containing 10 to 20, preferably 13 to 17, carbon atoms.
  • Primary paraffin sulfonates are made by reacting long-chain alpha olefins and bisulfites and paraffin sulfonates having the sulfonate group distributed along the paraffin chain are shown in U.S. Patents Nos. 2,503,280; 2,507,088; 3,260,744; 3,372,188; and German Patent 735,096.
  • the preferred surfactants are the magnesium salt of the C13-C17 paraffin or alkane sulfonates.
  • the proportion of the nonsoap-anionic surfactant will be in the range of 0.1 % to 8%, preferably from 1% to 6%, by weight of the dilute microemulsion composition.
  • the instant composition contains 0.5 wt. % to 6 wt. %, more preferably 1.0 wt. % to 5 wt. % of a nonionic surfactant selected from the group of an aliphatic ethoxylated nonionic surfactant, an ethoxylated polyhydric alcohol and an aliphatic ethoxylated/propoxylated nonionic surfactant.
  • a nonionic surfactant selected from the group of an aliphatic ethoxylated nonionic surfactant, an ethoxylated polyhydric alcohol and an aliphatic ethoxylated/propoxylated nonionic surfactant.
  • the water soluble aliphatic ethoxylated nonionic surfactants utilized in this invention are commercially well known and include the primary aliphatic alcohol ethoxylates and secondary aliphatic alcohol ethoxylates.
  • the nonionic surfactant class includes the condensation products of a higher alcohol (e.g., an alkanol containing 8 to 16 carbon atoms in a straight or branched chain configuration) condensed with 4 to 20 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with 16 moles of ethylene oxide (EO), tridecanol condensed with 6 to 15 moles of EO, myristyl alcohol condensed with 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to 14 carbon atoms in length and wherein the condensate contains either 6 moles of EO per mole of total alcohol or 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO
  • a higher alcohol e.g., an alkanol containing 8 to 16 carbon atoms in
  • Neodol ethoxylates which are higher aliphatic, primary alcohol containing 9-15 carbon atoms, such as C9-C11 alkanol condensed with 4 to 10 moles of ethylene oxide (Neodol 91-8 or Neodol 91-5), C-
  • ethoxamers (Neodol 25-12), C14-15 alkanol condensed with 13 moles ethylene oxide (Neodol 45- 13), and the like.
  • HLB hydrophobic lipophilic balance
  • ethoxamers with HLB values below 7 contain less than 4 ethyleneoxide groups and tend to be poor emulsifiers and poor detergents.
  • Additional satisfactory water soluble alcohol ethylene oxide condensates are the condensation products of a secondary aliphatic alcohol containing 8 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide.
  • Examples of commercially available nonionic detergents of the foregoing type are C11-C15 secondary alkanol condensed with either 9 EO (Tergitol
  • the ethoxylated polyhydric alcohol type compound such as an ethoxylated glycerol type compound
  • ethoxylated polyhydric alcohol 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 ula
  • w equals one to four, most preferably one, and B is selected from the group consisting of hydrogen or a group represented by:
  • 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
  • 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 (I) 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, preferably 3 to 0.1 , most preferably 1.5 to 0.2, wherein it is most preferred that there is more of Formula (II) than Formula (I) in the mixture that forms the compound.
  • 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 301 B 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 water soluble nonionic surfactants which can be utilized in this invention are an aliphatic ethoxylated/propoxylated nonionic surfactants which are depicted by the formula:
  • R is a branched chain alkyl group having 10 to 16 carbon atoms, preferably an isotridecyl group and x and y are independently numbered from 1 to 20.
  • a preferred ethoxylated/propoxylated nonionic surfactant is Plurafac ® 300 manufactured by BASF.
  • the composition contains 0.5 wt. % to 8 wt. %, more preferably 1 wt. % to 6 wt. % of a short chain amphiphile which is not a surfactant and is characterized by the formula:
  • R1 or R2 or R3 are a straight or branched chain alkyl group having 2 to 6 carbon atoms and x or w is a number from 2 to 5, more preferably 2 to 4 and n is a number from 2 to 8, more preferably 3 to 6 and y or z is a number from 1 to 4, more preferably 1 to 3 and the amphiphile has an HLB of 6 to 9, preferably 7 to 8.
  • Preferred amphiphiies have a C6 alkyl group and 2 to 5 EO such as hexanol 5EO.
  • the composition also contains an inorganic or organic salt of oxide of a multivalent metal cation, particularly Mg ++ .
  • the metal salt or oxide provides several benefits including improved cleaning performance in dilute usage, particularly in soft water areas, and minimized amounts of perfume required to obtain the microemulsion state.
  • Magnesium sulfate either anhydrous or hydrated (e.g., heptahydrate), is especially preferred as the magnesium salt.
  • Good results also have been obtained with magnesium oxide, magnesium chloride, magnesium acetate, magnesium propionate and magnesium hydroxide.
  • These magnesium salts can be used with formulations at neutral or acidic pH since magnesium hydroxide will not precipitate at these pH levels.
  • magnesium is the preferred multivalent metal from which the salts (inclusive of the oxide and hydroxide) are formed
  • other polyvalent metal ions also can be used provided that their salts are nontoxic and are soluble in the aqueous phase of the system at the desired pH level.
  • other suitable polyvalent metal ions include aluminum, copper, nickel, iron, calcium, etc. 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 microemulsion compositions can include from 0.05% to 2.0% by weight of the composition of a C8-C22 fatty acid or fatty acid soap as a foam suppressant.
  • the addition of 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-
  • the final essential ingredient in the inventive microemulsion compositions or all purpose hard surface cleaning compositions having improved interfacial tension properties is water.
  • the proportion of water in the microemulsion or all purpose hard surface cleaning composition compositions generally is in the range of 20% to 97%, preferably 70% to 97% by weight.
  • the liquid cleaning composition of this invention may, if desired, also contain other components either to provide additional effect or to make the product more attractive to the consumer.
  • 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.
  • the microemulsions exhibit stability at reduced and increased temperatures. More specifically, such compositions remain clear and stable in the range of 4°C to 50°C, especially 2°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 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 surfactants and amphiphiles 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.
  • compositions in wt. % were prepared by simple mixing at 25°C:
  • Example 2 The following compositions in wt. % were prepared by simple mixing at 25°C:

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Abstract

L'invention concerne une amélioration de composition nettoyante liquide universelle et de composition en microémulsion, compositions particulièrement efficaces dans l'élimination de salissures huileuse et grasses et contenant un détergent anionique, un surfactant non-ionique, un amphiphile à chaîne courte, un ingrédient hydrocarboné et de l'eau.
PCT/US1999/025155 1998-11-12 1999-10-27 Composition nettoyante liquide en microemulsion, contenant un amphiphile a chaine courte WO2000029528A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP99956703A EP1129173A2 (fr) 1998-11-12 1999-10-27 Composition nettoyante liquide en microemulsion, contenant un amphiphile a chaine courte
AU13249/00A AU762731B2 (en) 1998-11-12 1999-10-27 Microemulsion liquid cleaning composition containing a short chain amphiphile

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US09/191,002 US6136773A (en) 1998-11-12 1998-11-12 Microemulsion liquid cleaning composition containing a short chain amphiphile and mixtures of partially esterified fully esterified and non-esterified polyhydric alcohols
US09/191,002 1998-11-12
US09/191,003 US5981462A (en) 1998-11-12 1998-11-12 Microemulsion liquid cleaning composition containing a short chain amphiphile
US09/191,003 1998-11-12

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WO2000029528A2 true WO2000029528A2 (fr) 2000-05-25
WO2000029528A3 WO2000029528A3 (fr) 2000-10-05

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1159393A1 (fr) * 1999-03-05 2001-12-05 Cognis Corporation Composition de nettoyage pour surfaces dures
WO2003064578A1 (fr) * 2002-01-28 2003-08-07 Colgate-Palmolive Company Composition de nettoyage liquide contenant un agent de chelation biodegradable efficace
WO2003080781A1 (fr) * 2002-03-21 2003-10-02 Colgate-Palmolive Company Liquide de nettoyage contenant un agent conservateur et un agent chelateur
WO2003080780A1 (fr) * 2002-03-21 2003-10-02 Colgate-Palmolive Company Composition nettoyante liquide contenant un systeme de conservation ameliore
WO2003083024A1 (fr) * 2002-03-27 2003-10-09 Colgate-Palmolive Company Compositions de liquide vaisselle presentant un systeme de conservation ameliore
WO2006021329A1 (fr) * 2004-08-23 2006-03-02 Henkel Kommanditgesellschaft Auf Aktien Agent de nettoyage a residus reduits et sechage ameliore
WO2013110682A1 (fr) * 2012-01-26 2013-08-01 Henkel Ag & Co. Kgaa Micro-émulsions à force de dissolution optimisée des graisses

Citations (7)

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US4861516A (en) * 1987-04-25 1989-08-29 Henkel Kommanditgesellschaft Auf Aktien Laundry pretreatment composition for oily and greasy soil
EP0616028A1 (fr) * 1993-03-19 1994-09-21 The Procter & Gamble Company Compositions de nettoyage comprenant des agents tensioactifs non-ioniques à chaînes courtes
EP0616026A1 (fr) * 1993-03-19 1994-09-21 The Procter & Gamble Company Compositions de nettoyage concentrées
EP0668346A1 (fr) * 1994-02-07 1995-08-23 Colgate-Palmolive Company Compositions de nettoyage liquides d'usage général en micro-émulsion
WO1995027034A1 (fr) * 1994-03-31 1995-10-12 Unilever Plc Compositions detergentes
US5462690A (en) * 1994-09-09 1995-10-31 Colgate-Palmolive Co. Liquid cleaning compositions
US5776880A (en) * 1993-08-04 1998-07-07 Colgate-Palmolive Co. Aqueous cleaning compositions which may be in microemulsion form comprising ethoxylated secondary alcohol cosurfactant

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Publication number Priority date Publication date Assignee Title
US4861516A (en) * 1987-04-25 1989-08-29 Henkel Kommanditgesellschaft Auf Aktien Laundry pretreatment composition for oily and greasy soil
EP0616028A1 (fr) * 1993-03-19 1994-09-21 The Procter & Gamble Company Compositions de nettoyage comprenant des agents tensioactifs non-ioniques à chaînes courtes
EP0616026A1 (fr) * 1993-03-19 1994-09-21 The Procter & Gamble Company Compositions de nettoyage concentrées
US5776880A (en) * 1993-08-04 1998-07-07 Colgate-Palmolive Co. Aqueous cleaning compositions which may be in microemulsion form comprising ethoxylated secondary alcohol cosurfactant
EP0668346A1 (fr) * 1994-02-07 1995-08-23 Colgate-Palmolive Company Compositions de nettoyage liquides d'usage général en micro-émulsion
WO1995027034A1 (fr) * 1994-03-31 1995-10-12 Unilever Plc Compositions detergentes
US5462690A (en) * 1994-09-09 1995-10-31 Colgate-Palmolive Co. Liquid cleaning compositions

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1159393A1 (fr) * 1999-03-05 2001-12-05 Cognis Corporation Composition de nettoyage pour surfaces dures
EP1159393A4 (fr) * 1999-03-05 2003-05-02 Cognis Corp Composition de nettoyage pour surfaces dures
WO2003064578A1 (fr) * 2002-01-28 2003-08-07 Colgate-Palmolive Company Composition de nettoyage liquide contenant un agent de chelation biodegradable efficace
WO2003080781A1 (fr) * 2002-03-21 2003-10-02 Colgate-Palmolive Company Liquide de nettoyage contenant un agent conservateur et un agent chelateur
WO2003080780A1 (fr) * 2002-03-21 2003-10-02 Colgate-Palmolive Company Composition nettoyante liquide contenant un systeme de conservation ameliore
WO2003083024A1 (fr) * 2002-03-27 2003-10-09 Colgate-Palmolive Company Compositions de liquide vaisselle presentant un systeme de conservation ameliore
WO2006021329A1 (fr) * 2004-08-23 2006-03-02 Henkel Kommanditgesellschaft Auf Aktien Agent de nettoyage a residus reduits et sechage ameliore
WO2013110682A1 (fr) * 2012-01-26 2013-08-01 Henkel Ag & Co. Kgaa Micro-émulsions à force de dissolution optimisée des graisses

Also Published As

Publication number Publication date
AU762731B2 (en) 2003-07-03
AU1324900A (en) 2000-06-05
EP1129173A2 (fr) 2001-09-05
WO2000029528A3 (fr) 2000-10-05

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