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EP0885290B1 - Compositions de detergents a cristaux liquides - Google Patents

Compositions de detergents a cristaux liquides Download PDF

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Publication number
EP0885290B1
EP0885290B1 EP97915087A EP97915087A EP0885290B1 EP 0885290 B1 EP0885290 B1 EP 0885290B1 EP 97915087 A EP97915087 A EP 97915087A EP 97915087 A EP97915087 A EP 97915087A EP 0885290 B1 EP0885290 B1 EP 0885290B1
Authority
EP
European Patent Office
Prior art keywords
composition
liquid crystal
acid
water
oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP97915087A
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German (de)
English (en)
Other versions
EP0885290A1 (fr
Inventor
Georges Yianakopoulos
Geneviève Blandiaux
Myriam Mondin
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Colgate Palmolive Co
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Colgate Palmolive Co
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Publication of EP0885290A1 publication Critical patent/EP0885290A1/fr
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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
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • 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
    • C11D3/2068—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
    • 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
    • C11D3/2086—Hydroxy carboxylic 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • This invention relates to an acidic liquid crystal detergent composition. More specifically, it is of an acidic liquid detergent composition in a liquid crystal state which when brought into contact with oily soil is superior to other liquid detergent compositions in detergency and in other physical properties.
  • Liquid aqueous synthetic organic detergent compositions have long been employed for human hair shampoos and as dishwashing detergents for hand washing of dishes (as distinguished from automatic dishwashing machine washing of dishes). Liquid detergent compositions have also been employed as hard surface cleaners, as in pine oil liquids, for cleaning floors and walls. More recently they have proven successful as laundry detergents too, apparently because they are convenient to use, are instantly soluble in wash water, and may be employed in "pre-spotting" applications to facilitate removals of soils and stains from laundry upon subsequent washing. Liquid detergent compositions have comprised anionic, cationic and nonionic surface active agents, builders and adjuvants, including, as adjuvants, lipophilic materials which can act as solvents for lipophilic soils and stains. The various liquid aqueous synthetic organic detergent compositions mentioned serve to emulsify lipophilic materials, including oily soils, in aqueous media, such as wash water, by forming micellar dispersions and emulsions.
  • microemulsions Although emulsification is a mechanism of soil removal, it has been only comparatively recently that it was discovered how to make microemulsions which are much more effective than ordinary emulsions in removing lipophilic materials from substrates.
  • microemulsions are described in British Patent Specification No. 2,190,681 and in U.S. Patents 5,075,026; 5,076,954 and 5,082,584 and 5,108,643, most of which relate to acidic microemulsions useful for cleaning hard surfaced items, such as bathtubs and sinks which microemulsions are especially effective in removing soap scum and lime scale from them.
  • microemulsions may be essentially neutral and such are also taught to be effective for microemulsifying lipophilic soils from substrates.
  • U.S. Patent application Serial No. 7/313,664 there is described a light duty microemulsion liquid detergent composition which is useful for washing dishes and removing greasy deposits from them in both neat and diluted forms.
  • Such compositions include complexes of anionic and cationic detergents as surface active components of the microemulsions.
  • the various microemulsions referred to include a lipophile, which may be a hydrocarbon, a surfactant, which may be an anionic and/or a nonionic detergent(s), a co-surfactant, which may be a poly-lower alkylene glycol lower alkyl ether, e.g., tripropylene glycol monomethyl ether, and water.
  • a lipophile which may be a hydrocarbon
  • a surfactant which may be an anionic and/or a nonionic detergent(s)
  • a co-surfactant which may be a poly-lower alkylene glycol lower alkyl ether, e.g., tripropylene glycol monomethyl ether, and water.
  • the present invention improves them still further and also increases the capacity of the detergent compositions to adhere to surfaces to which they have been applied. Thus, they drop or run substantially less than cleaning compositions of "similar" cleaning power which are in microemulsion or normal liquid detergent form. Also, because they form microemulsions with lipophilic soil or stain material spontaneously, with essentially no requirement for addition of any energy, either thermal or mechanical, they are more effective cleaners at room temperature and at higher and lower temperatures that are normally employed in cleaning operations than are ordinary liquid detergents, and are also more effective than detergent compositions in microemulsion form.
  • the present liquid crystal detergent compositions may be either clear or somewhat cloudy or milky (opalescent) in appearance but both forms thereof are stable on storage and components thereof do not settle out or become ineffective, even on storage at somewhat elevated temperatures for periods as long as six months and up to a year.
  • the presence of the cosurfactant in the liquid crystal detergent compositions helps to make such compositions resist freezing at low temperatures.
  • an acidic liquid detergent composition suitable at room temperature or colder, for pre-treating and cleaning materials soiled with lipophilic soil and soap scum, is in liquid crystal form and comprises synthetic organic surface active agent; a cosurfactant, an organic acid, a solvent for the soil, and water.
  • the invention also relates to processes for treating items and materials soiled with soap scum and/or lipophilic soil with compositions of this invention to loosen or remove such soil, by applying to the locus of such soil on such material a soil loosening or removing amount of an invented composition.
  • lipophilic soil is absorbed from the soiled surface into the liquid crystal.
  • 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.
  • U.S. Patent No. 4,017,409 teaches that a mixture of paraffin sulfonate and a reduced concentration of inorganic phosphate builder salt should be employed.
  • such compositions are not completely acceptable from an environmental point of view based upon the phosphate content.
  • another alternative to achieving phosphate-free all-purpose liquids has been to use a major proportion of a mixture of anionic and nonionic detergents with minor amounts of glycol ether solvent and organic amine as shown in U.S. Patent NO. 3,935,130. Again, this approach has not been completely satisfactory and the high levels of organic detergents necessary to achieve cleaning cause foaming which, in turn, leads to the need for thorough rinsing which has been found to be undesirable to today's consumers.
  • an o/w microemulsion is a spontaneously forming colloidal dispersion of "oil” phase particles having a particle size in the range of 25 to 800 ⁇ in a continuous aqueous phase.
  • microemulsions are transparent to light and are clear and usually highly stable against phase separation.
  • Patent disclosures relating to use of grease-removal solvents in o/w microemulsions include, for example, European Patent Applications EP 0137615 and EP 0137616 - Herbots et al; European Patent Application EP 0160762 - Johnston et al; and U.S. Patent No. 4,561,991 - Herbots et al. Each of these patent disclosures also teaches using at least 5% by weight of grease-removal solvent.
  • compositions of this invention described by Herbots et al. require at least 5% of the mixture of grease-removal solvent and magnesium salt and preferably at least 5% of solvent (which may be a mixture of water-immiscible non-polar solvent with a sparingly soluble slightly polar solvent) and at least 0.1% magnesium salt.
  • Liquid detergent compositions which include terpenes, such as d-limonene, or other grease-removal solvent, although not disclosed to be in the form of o/w microemulsions, are the subject matter of the following representative patent documents: European Patent Application 0080749; British Patent Specification 1,603,047; 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:
  • Hard surface cleaners such as bathroom cleaners and scouring cleansers
  • Scouring cleansers normally include a soap or synthetic organic detergent or surface active agent and an abrasive. Such products can scratch relatively soft surfaces and can eventually cause them to appear dull. These products are often ineffective to remove lime scale (usually encrusted calcium and magnesium carbonates) in normal use. Because lime scale can be removed by chemical reactions with acidic media various acidic cleaners have been produced and have met with various degrees of success. In some instances such cleaners have been failures because the acid employed was too strong and damaged the surfaces being cleaned. At other times, the acidic component of the cleaner reacted objectionably with other components of the product which adversely affected the detergent or perfume.
  • the described thickened microemulsion cleaner of U.S. Patent 5,076,954 is effective in removing lime scale and soap scum from hard surfaces and is easy to use, but it has been found that its mixture of acidic agents (succinic, glutaric and adipic acids) could damage the surfaces of some hard fixtures, such as those of materials which are not acid resistant.
  • acidic agents succinic, glutaric and adipic acids
  • One of such materials is an enamel that has been extensively employed in Europe as a coating for bathtubs, herein referred to as European enamel. It has been described as zirconium white enamel or zirconium white powder enamel and has the advantage of being resistant to detergents, which makes it suitable for use on tubs, sinks, shower tiles and bathroom enamelware.
  • the instant compositions of the present invention allow the cleaning of European enamel surfaces, as well as any other acid resistant surfaces of bathtubs and other bathroom surfaces.
  • the product can be used on various other materials that are especially susceptible to attack by acidic media, such as marble.
  • the instant compositions are stable at 25°C for at least 3 months and are shear thinning.
  • the present invention relates to a thickened acidic aqueous liquid crystal cleaner for bathtubs and other hard surfaced items, which are acid resistant or are of zirconium white enamel, wherein the cleaner has a pH in the range of 1 to 4 and the cleaner removes lime scale, soap scum and greasy soil from surfaces of such items without damaging such surfaces.
  • the present invention provides an improved acidic liquid crystal detergent composition having improved interfacial tension which improves cleaning hard surface in the form of a liquid crystal 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 exhibit good grease soil removal properties due to the improved interfacial tensions 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 provides a stable, liquid crystal, hard surface cleaning composition especially effective in the removal of oily and greasy oil.
  • the liquid crystal composition includes, on a weight basis:
  • the present invention relates to a stable acidic liquid crystal detergent composition
  • a stable acidic liquid crystal detergent composition comprising approximately by weight 1% to 15% of an ethoxylated alkyl ether sulfate surfactant, 1% to 30% of a cosurfactant, 1% to 30% of an ethoxylated nonionic surfactant, 0.6% to 10% of a water insoluble hydrocarbon, essential oil or a perfume, 1% to 5% of an aliphatic carboxylic acid, 0.1 % to 3% of weak base, 0.48% to 8% of a magnesium salt and the balance being water, wherein the acidic liquid crystal composition does not contain any sulfonate surfactant, and the liquid detergent composition has a storage modulus equal to or higher than one Pascal (1 Newton/sq.m.), more preferably higher than 10 Pascal at a temperature of 20°C to 40°C at a strain of 0.1 % to 5% at a frequency of 10 radians/second as measured on a Carr-MedTM CS
  • 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.
  • 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 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 precise composition of the perfume is of no particular consequence to cleaning performance so long as it meets the criteria of water immiscibility and having a pleasing odor.
  • the perfume, as well as all other ingredients should be cosmetically acceptable, i.e., non-toxic, hypoallergenic, etc.
  • the hydrocarbon such as a perfume is present in the liquid crystal composition in an amount of from 0.6% to 10% by weight, preferably from 0.8% to 8% by weight, especially preferably from 1% to 6% by weight. If the amount of hydrocarbon (perfume) is less than 0.6% by weight it becomes difficult to form the liquid crystal. 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 liquid crystal 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 compositions.
  • an essential oil or a water insoluble organic compound such as a water insoluble hydrocarbon having 6 to 18 carbon such as a paraffin or isoparaffin such as isoparH, isodecane, alpha-pinene, beta-pinene, decanol and terpineol.
  • Suitable essential oils are selected from the group consisting of: Anethole 20/21 natural, Aniseed oil china star, Aniseed oil globe brand, Balsam (Peru), Basil oil (India), Black pepper oil, Black pepper oleoresin 40/20, Bois de Rose (Brazil) FOB, Borneol Flakes (China), Camphor oil, White, Camphor powder synthetic technical, Cananga oil (Java), Cardamom oil, Cassia oil (China), Cedarwood oil (China) BP, Cinnamon bark oil, Cinnamon leaf oil, Citronella oil, Clove bud oil, Clove leaf, Coriander (Russia), Coumarin 69°C (China), Cyclamen Aldehyde, Diphenyl oxide, Ethyl vanilin, Eucalyptol, Eucalyptus oil, Eucalyptus citriodora, Fennel oil, Geranium oil, Ginger oil, Ginger oleoresin (India), White grapefruit oil, Guaiacwood oil, Gurjun bals
  • the nonionic surfactant is present in amounts of 1% to 30%, preferably 3% to 18% by weight of the liquid crystal composition and provides superior performance in the removal of oily soil and mildness to human skin.
  • the water soluble ethoxylated nonionic surfactants utilized in this invention are commercially well known and include the primary aliphatic alcohol ethoxylates and secondary aliphatic alcohol ethoxylates.
  • the lengtn of the polyethenoxy chain can be adjusted to achieve the desired balance between the hydrophobic and hydrophilic elements.
  • the nonionic surfactant class includes the condensation products of a higher alcohol (e.g., an alkanol containing about 8 to 16 carbon atoms in a straight or branched chain configuration) condensed with about 4 to 20 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with about 16 motes of ethylene oxide (EO), tridecanol condensed with about 6 to moles of EO, myristyl alcohol condensed with about 10 moles of ED 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 about 14 carbon atoms in length and wherein the condensate contains either about 6 moles of EO per mole of total alcohol or about 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol.
  • a higher alcohol e.g.
  • NeodolTM ethoxylates which are higher aliphatic, primary alcohol containing about 9-15 carbon atoms, such as C 9 -C 11 alkanol condensed with 4 to 10 moles of ethylene oxide (NeodolTM 91-8), C 12-13 alkanol condensed with 6.5 moles ethylene oxide (NeodolTM 23-6.5), C 12-15 alkanol condensed with 12 moles ethylene oxide (NeodolTM 25-12). C 14-15 alkanol condensed with 13 moles ethylene oxide (NeodolTM 45-13), and the like.
  • NeodolTM ethoxylates such as C 9 -C 11 alkanol condensed with 4 to 10 moles of ethylene oxide (NeodolTM 91-8), C 12-13 alkanol condensed with 6.5 moles ethylene oxide (NeodolTM 23-6.5), C 12-15 alkanol condensed with 12 moles ethylene
  • Such ethoxamers have an HLB (hydrophobic lipophilic balance) value of about 8 to 15 and give good O/W emulsification, whereas ethoxamers with HLB values below 7 contain less than 4 ethyleneoxide groups and tend to be poor emulsifiers and poor detergents.
  • HLB hydrophobic lipophilic balance
  • Additional satisfactory water soluble alcohol ethylene oxide condensates are the condensation products of a secondary aliphatic alcohol containing 8 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide.
  • Examples of commercially available nonionic detergents of the foregoing type are C 11 -C 15 secondary alkanol condensed with either 9 EO (TergitolTM 15-S-9) or 12 EO (TergitolTM 15-S-12) marketed by Union Carbide.
  • the ethoxylated alkyl ether sulfate is present in the composition at a concentration of about 1% to about 20% by weight, more preferably about 2% to 15% by weight.
  • the ethoxylated alkyl ether sulfate may be made by sulfating the condensation product of ethylene oxide and C 8-10 alkanol, and neutralizing the resultant product.
  • the ethoxylated alkyl ether sulfates differ from one another in the number of carbon atoms in the alcohols and in the number of moles of ethylene oxide reacted with one mole of such alcohol.
  • Preferred ethoxylated alkyl ether polyethenoxy sulfates contain 12 to 15 carbon atoms in the alcohols and in the alkyl groups thereof, e.g., sodium myristyl (3 EO) sulfate.
  • Ethoxylated C 8-18 alkylphenyl ether sulfates containing from 2 to 6 moles of ethylene oxide in the molecule are also suitable for use in the invention compositions.
  • These detergents can be prepared by reacting an alkyl phenol with 2 to 6 moles of ethylene oxide and sulfating and neutralizing the resultant ethoxylated alkylphenol.
  • the concentration of the ethoxylated alkyl ether sulfate surfactant is about 1 to about B wt. %.
  • the cosurfactants are mono C 1 -C 6 alkyl ethers of ethylene glycol and propylene glycol having the structural formula R(X) n OH wherein R is a C 1 -C 6 alkyl group, X is (OCH 2 CH 2 ) or (OCH 2 (CH 3 )CH) and n is a number from 1 to 4, and mono C 1-6 alkyl ethers of mono-, di- or tri-butylene glycol.
  • Representative members of the polypropylene glycol include dipropylene glycol and polypropylene glycol having a molecular weight of 200 to 1000, e.g., polypropylene glycol 400.
  • Other satisfactory glycol ethers are ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monobutyl ether, mono, di, tri propylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, mono, di, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, propylene glycol tertiary butyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monopentyl ether, diethylene glycol mono
  • the amount of cosurfactant required to stabilize the liquid crystal 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 used in the liquid crystal composition are in the range of from 1% to 30%, preferably from 2% to 20%, especially preferably from 3% to 16%, by weight provide stable liquid crystal composition for the above-described levels of primary surfactants and perfume and any other additional ingredients as described below.
  • the aliphatic carboxylic acid having about 2 to about 10 carbon atoms is present in the composition at a concentration of 1 wt. % to 5 wt. %, more preferably about 1.25 wt. % to about 4 wt. %.
  • Representative 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 having 2 to 10 carbon atoms such as glutaric acid and mixtures of glutaric acid with adipic acid and succinic acid, as well as mixtures of the foregoing acids.
  • 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.
  • dicarboxylic acids having 2 to 10 carbon atoms from oxalic acid through sebacic acid, suberic, azelaic and sebacic acids are of lower solubilities and therefore are not as useful in the present emulsions as the other dibasic aliphatic fatty acids, all of which are preferably saturated and straight chained.
  • Oxalic and malonic acids although useful as reducing agents too, may be too strong for delicate hard surface cleaning.
  • Preferred such dibasic acids are those of the middle portion of the 2 to 10 carbon atom acid range, succinic, glutaric, adipic and pimelic acids, especially the first three thereof, which inevitably are available commercially, in mixture.
  • Citric acid can also be employed as the acid.
  • the preferred aliphatic carboxylic acid is an alpha hydroxy aliphatic acid which is strong enough to lower the pH of the microemulsion to one in the range of one to four.
  • Various such carboxylic acids can perform this function but those which have been found effectively to remove soap scum and lime scale from bathroom surfaces best, while still not destabilizing the emulsion, are alpha hydroxy aliphatic acids having the structure: wherein Y is selected from the group consisting of hydroxy or a COOH group and X is (CH 2 ) n W, wherein W is selected from the group consisting of CH3 or COOH and n is 0, 1, or 2.
  • Preferred alpha hydroxy aliphatic acids are citric acid, lactic acid and malic acid, wherein a mixture of lactic acid and malic acid is preferred, wherein the weight ratio of lactic acid to malic acid is preferred to be 5:1 to 1:1, more preferably 4:1 to 1:1.
  • the at least one alpha hydroxy aliphatic acid is incorporated in the composition in an amount of 1 to 9 wt. %, more preferably 2 to 7 wt. %.
  • the alpha hydroxy aliphatic acid after being incorporated in the acidic emulsion, may be partially neutralized to produce effectiveness, with safety.
  • Phosphoric acid can be used at a concentration of 0 to 1 wt. % and is one of the additional acids that helps to protect acid-sensitive surfaces being cleaned with the present emulsion cleaner. Being a tribasic acid, it too may be partially neutralized to obtain an emulsion pH in the desired range. For example. It may be partially neutralized to the biphosphate, e.g., N a H 2 PO 4 , or NH 4 H 2 PO 4 .
  • Phosphonic acid used at a concentration of 0 to 1 wt. % can also be used for protecting acid-sensitive surfaces from the dissolving action of the dicarboxylic acids of the present thickened emulsions, apparently exists only theoretically, but its derivatives are stable and are useful in the practice of the present invention.
  • Such are considered to be phosphonic acids as that term is used in this specification.
  • the phosphonic acids are of the structure. wherein Y is any suitable substituent, but preferably Y is alkylamino or N-substituted alkylamino.
  • a preferred phosphonic acid component of the present thickened acidic emulsions is aminotris (methylenephosphonic) acid which is of the formula N (CH 2 PH x O 3 )
  • aminotris (methylenephosphonic) acid which is of the formula N (CH 2 PH x O 3 )
  • other useful phosphonic acids are ethylene diamine tetra-(methylenephosphonic) acid, hexamethylenediamine tetra-(methylenephosphonic) acid, ad diethylenetriamine penta-(methylenephosphonic) acid.
  • Such class of compounds may be described as aminoalkylenephosphonic acids containing in the ranges of 1 to 3 amino nitrogen, 3 or 4 lower alkylenephosphonic acid groups in which the lower alkylene is of 1 or 2 carbon atoms, and 0 to 2 alkylene groups of 2 to 6 carbon atoms each, which alkylene(s) is/are present and join amino nitrogen when a plurality of such amino nitrogen is present in the aminoalkylenephosphonic acid.
  • aminoalkylenephosphonic acids which also may be partially neutralized at the desired pH of the microemulsion cleaner, are of desired stabilizing and protecting effect in the invented cleaner, especially when present with phosphate acid, preventing harmful attacks on European enamel surfaces by the diacid(s) components of the cleaner.
  • the phosphorus acid salts if present, will be monosalts of each of the phosphoric and/or phosphonic acid groups present.
  • the liquid crystal composition contains a weak base such as diethanolamine or triethanol amine at a concentration of 0.1 wt. % to 3 wt. %.
  • the weak base is employed in the composition to adjust the pH of the composition.
  • the instant composition contains 0.48 to 8 wt. %, more preferably 1 to 6 wt. % of a magnesium salt such as magnesium chloride and/or magnesium sulfate heptahydrate and mixtures thereof.
  • a magnesium salt such as magnesium chloride and/or magnesium sulfate heptahydrate and mixtures thereof.
  • the low pH liquid crystal formulations In addition to their excellent capacity for cleaning greasy and oily soils, the low pH liquid crystal formulations also exhibit excellent cleaning performance and removal of soap scum and lime scale in neat (undiluted) as well as in diluted usage.
  • the final essential ingredient in the inventive acidic liquid crystal compositions having improved interfacial tension properties is water.
  • the proportion of water in the liquid crystal detergent composition generally is in the range of 20% to 97%, preferably 70% to 97% by weight.
  • a composition of this invention is in a liquid crystal state when it is of lypotropic structure, is transparent or slightly turbid (opalescent) but no opaque, and has a storage modulus equal to or higher than one Pascal (1 Newton/sq. m.), more preferably higher than 10 Pascal and most preferably higher than 20 Pascal and when measured at a temperature of 20 to 40°C, at a frequency of ten radians per second and at a strain of 0.1 to 5%.
  • the rheological behavior of the compositions of this invention were measured at 25°C by means of a Carri-MedTM CS Rheometer.
  • a cone and plate are used at a cone angle of 2 degrees: 0 minutes: 0 seconds with a cone diameter of 6.0 cm, measurement system gap of 52.0 micro m and a measurement system inertia of 17.02 micro Nm sec -2 .
  • liquid crystal compositions of the invention is relatively simple because they tend to form spontaneously with little need for the addition of energy to promote transformation to the liquid crystal state.
  • mixing will normally be undertaken and it has been found desirable first to mix the surfactants and cosurfactant with the water, followed by admixing of the lipophilic component, usually a hydrocarbon (but esters or mixtures of hydrocarbons and esters may also be employed). It is not necessary to employ heat and most mixings are preferably carried out at about room temperature (20-25°C).
  • compositions may be applied to such surfaces by pouring onto them, by application with a cloth or sponge, or by various other contacting means but it is preferred to apply them in the form of a spray by spraying them onto the substrate from a hand or finger pressure operated sprayer or squeeze bottle.
  • Such application may be onto hard surfaces, such as dishes, walls or floors, from which lipophilic (usually greasy or oily) soil is to be removed, or may be onto fabrics, such as laundry, which has previously been stained with lipophilic soils, such as motor oil.
  • the invented compositions may be used as detergents and as such may be employed in the same manner in which liquid detergents are normally utilized in dishwashing, floor and wall cleaning and laundering, but it is preferred that they be employed as pre-spotting agents too, in which applications they are found to be extremely useful in loosening the adhesions of lipophilic soils to substrates, thereby promoting much easier cleaning with application of more of the same invented detergent compositions or by applications of different commercial detergent compositions, in liquid, bar or particulate forms.
  • the invention relates to the important discovery that effective liquid detergent compositions can be made in the liquid crystal state and that because they are in such state they are especially effective in removing lipophilic soils from substrates and also are effective in removing from substrates non-lipophilic materials.
  • Such desirable properties of the liquid crystal detergent compositions of this invention make them ideal for use as pre-spotting agents and detergents for them ideal for use as pre-spotting agents and detergents for removing hard-to-remove soils from substrates in various hard and soft surface cleaning operations.
  • the cleaning easiness index is expressed as: [1-(strokes number A, PROTO)/strokes number expert bathroom products)]
  • strokes number proto strokes number ref., then the index is 0 (cleaning equivalence between prototype and reference).
  • the index is characterised by a negative value (the more negative the index, the less efficient the prototype).
  • the index is characterised by a positive value (the more positive the index, the more efficient the prototype).
  • the soap scum is generated by direct spraying of Oleate Na and and stoechiometric quantity of calcium chloride on ceramic tile.
  • the cleaning easiness index of A vs different references was calculated by indirect comparison between the neutral proto (A) and the references. In other words, A and references were not directly evaluated in the same tile.
  • the formula of the gel bath is: Wt.% Xanthan gum 5.0 Paraffin sulfonate 4.0 LF400 Plurafac nonionic 3.0 H 3 PO 4 (85%) 0.26 Amino trimethyl phosphonic acid 0.05 Perfume 0.75 Water Balance
  • AjaxTM AME 1:1 is the same formula as the gel bath except there is no xanthan gum and in there is an addition 1.5 wt. % of MgSO 4 ⁇ 7H 2 O.

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  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Claims (7)

  1. Composition détergente à cristal liquide acide qui comprend en poids :
    (a) 1 à 30 % d'un agent tensioactif non ionique éthoxylé contenant des groupes oxydes d'éthylène;
    (b) 1 à 5 % d'un acide carboxylique aliphatique comportant de 2 à 10 atomes de carbone ;
    (c) 1 à 15 % d'un sel soluble dans l'eau d'un agent tensioactif alkyl éther sulfate en C8-18 éthoxylé ou un agent tensioactif alkyl phényl éther sulfate en C8-18 éthoxylé comportant de 2 à 6 moles d'oxyde d'éthylène ou le lauryl sulfate de sodium;
    (d) de 0,1 à 3 % d'une base faible ;
    (e) 0,6 à 10 % d'un composé organique insoluble dans l'eau choisi dans le groupe constitué des parfums, huiles essentielles et hydrocarbures insolubles dans l'eau ;
    (f) 1 à 30 % d'un cosurfactant glycol éther mélangeable à l'eau qui est un mono-, di-, tri- ou tetra-éthylène ou propylène glycol ou mono alkyle en C1- 6 ou un mono-, di-, ou tri-butylène glycol mono alkyle en C1-6 ;
    (g) 0,48 à 8 % d'un sel de magnésium ; et
    (h) le reste étant de l'eau, ladite composition détergente à cristal liquide ne contient pas d'agent tensioactif sulfonate et présente un module de stockage mesuré à une température entre 20°C à 40°C, à une contrainte de 0,1 à 5 % et une fréquence de 10 radians/s égale à ou supérieure à un pascal et est thermiquement stable et existe sous forme de cristal liquide à la température de 8°C à 43°C.
  2. Composition selon la revendication 1, dans laquelle l'agent tensioactif non ionique est un produit de condensation d'une mole d'un alcool gras supérieur comportant environ 9 à environ 11 atomes de carbone avec de 2 à 5 moles desdits groupes oxyde d'éthylène.
  3. Composition selon la revendication 2, dans laquelle ledit sel soluble dans l'eau dudit agent tensioactif alkyl C8-18 éther sulfate éthoxylé comporte un cation choisi dans le groupe constitué du sodium, du potassium et de l'ammonium.
  4. Composition selon la revendication 3, dans laquelle ledit acide carboxylique aliphatique est l'acide citrique.
  5. Composition selon la revendication 3, dans laquelle ledit hydrocarbure insoluble dans l'eau est choisi dans le groupe constitué de d-limonène, alpha-terpinéol, alpha-pinène et béta-pinène et leurs mélanges.
  6. Composition selon la revendication 1, dans laquelle l'acide carboxylique est l'acide citrique.
  7. Procédé pour enlever l'un ou plus parmi les écailles de chaux, les écumes de savon et les salissures grasses de baignoires ou d'autres produits à surfaces dures, qui sont résistants aux acides ou sont constitués d'émail blanc de zirconium, qui comprend les étapes constituant à appliquer à une telle surface une composition en conformité avec la revendication 1 et à enlever une telle composition et les écailles de chaux et/ou les écumes de savon et/ou les salissures grasses d'une telle surface.
EP97915087A 1996-03-06 1997-03-06 Compositions de detergents a cristaux liquides Expired - Lifetime EP0885290B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US61123196A 1996-03-06 1996-03-06
US611231 1996-03-06
PCT/US1997/004065 WO1997032968A1 (fr) 1996-03-06 1997-03-06 Compositions de detergents a cristaux liquides

Publications (2)

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EP0885290A1 EP0885290A1 (fr) 1998-12-23
EP0885290B1 true EP0885290B1 (fr) 2002-02-06

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EP (1) EP0885290B1 (fr)
AR (1) AR006129A1 (fr)
AT (1) ATE213016T1 (fr)
AU (1) AU711740B2 (fr)
CA (1) CA2247902A1 (fr)
DE (1) DE69710315T2 (fr)
DK (1) DK0885290T3 (fr)
ES (1) ES2174243T3 (fr)
NZ (1) NZ331726A (fr)
PL (1) PL187384B1 (fr)
PT (1) PT885290E (fr)
WO (1) WO1997032968A1 (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6046148A (en) * 1999-10-01 2000-04-04 Colgate-Palmolive Co. Acidic light duty liquid cleaning compositions
US6159925A (en) * 2000-04-06 2000-12-12 Colgate-Palmolive Co. Acidic liquid crystal compositions
EP1167500A1 (fr) * 2000-06-29 2002-01-02 The Procter & Gamble Company Procédé pour le nettoyage d'une surface dure
WO2004090085A1 (fr) * 2003-04-03 2004-10-21 Vocfree, Inc. Decapants sans cov
US8888926B2 (en) 2010-06-08 2014-11-18 Innovation Services, Inc. Medical instrument cleaning solution and method of cleaning contaminated surfaces
US8536105B2 (en) 2010-06-08 2013-09-17 Innovation Services, Inc. Method of cleaning contaminated surfaces
DE102012206707A1 (de) * 2012-04-24 2013-10-24 Henkel Ag & Co. Kgaa Wasch-, Reinigungs- oder Spülmittel mit verbessertem Schaumverhalten
EP3118300A1 (fr) * 2015-07-13 2017-01-18 The Procter and Gamble Company Compositions acides de nettoyage de surfaces dures comprenant un solvant
ES2704087T3 (es) 2015-07-13 2019-03-14 Procter & Gamble Producto de limpieza
PL3118301T3 (pl) 2015-07-13 2019-04-30 Procter & Gamble Produkt czyszczący
PL3118299T3 (pl) 2015-07-13 2019-04-30 Procter & Gamble Produkt czyszczący
ES2827229T3 (es) 2015-07-13 2021-05-20 Procter & Gamble Producto de limpieza
RU2762277C2 (ru) * 2017-06-29 2021-12-17 Кемира Ойй Композиция, ее применение и способ удаления и предотвращения загрязнений бумагоделательного оборудования влагопрочными смолами
US10626355B2 (en) 2017-06-29 2020-04-21 Kemira Oyj Composition, its use and method for removing and preventing wet strength resins from contaminating papermaking equipment
WO2019002682A1 (fr) * 2017-06-29 2019-01-03 Kemira Oyj Composition, son utilisation et procédé permettant d'éliminer et d'empêcher la contamination d'un équipement de fabrication de papier par des résines résistantes à l'humidité

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Publication number Priority date Publication date Assignee Title
GB8310529D0 (en) * 1983-04-19 1983-05-25 Unilever Plc General-purpose cleaning composition
ATE122383T1 (de) * 1988-02-10 1995-05-15 Colgate Palmolive Co Saurer reiniger für harte oberflächen.
US5035826A (en) * 1989-09-22 1991-07-30 Colgate-Palmolive Company Liquid crystal detergent composition
EP0656936B1 (fr) * 1992-08-25 1997-05-14 Unilever Plc Compositions de nettoyage liquides contenant du sulfate d'alcool primaire et des surfactants non-ioniques
DE69329782T2 (de) * 1992-09-09 2001-05-03 Unilever N.V., Rotterdam Verbesserung von Reinigern für harte Oberflächen
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

Also Published As

Publication number Publication date
ATE213016T1 (de) 2002-02-15
WO1997032968A1 (fr) 1997-09-12
DE69710315D1 (de) 2002-03-21
DK0885290T3 (da) 2002-05-27
CA2247902A1 (fr) 1997-09-12
PL328696A1 (en) 1999-02-15
PT885290E (pt) 2002-07-31
AU2212197A (en) 1997-09-22
AR006129A1 (es) 1999-08-11
DE69710315T2 (de) 2003-01-16
EP0885290A1 (fr) 1998-12-23
ES2174243T3 (es) 2002-11-01
NZ331726A (en) 1999-01-28
PL187384B1 (pl) 2004-06-30
AU711740B2 (en) 1999-10-21

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