WO1995014765A1 - Microemulsion all purpose liquid cleaning compositions - Google Patents

Microemulsion all purpose liquid cleaning compositions

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Publication number
WO1995014765A1
WO1995014765A1 PCT/US1994/013162 US9413162W WO9514765A1 WO 1995014765 A1 WO1995014765 A1 WO 1995014765A1 US 9413162 W US9413162 W US 9413162W WO 9514765 A1 WO9514765 A1 WO 9514765A1
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WO
Grant status
Application
Patent type
Prior art keywords
acid
microemulsion
water
composition
ch2ch
Prior art date
Application number
PCT/US1994/013162
Other languages
French (fr)
Inventor
Myriam Mondin
Anne-Marie Misselyn
Marianne Mahieu
Georges Yianakopoulos
Original Assignee
Colgate-Palmolive Company
Priority date (The priority date 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 date listed.)
Filing date
Publication date

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/667Neutral esters, e.g. sorbitan esters; see also C11D1/74 and C11D1/78
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/722Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/825Mixtures of compounds all of which are non-ionic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • C11D1/8305Mixtures of non-ionic with anionic compounds containing a combination of non-ionic compounds differently alcoxylised or with different alkylated chains
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/0008Detergent materials characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017Multi-phase liquid compositions
    • C11D17/0021Aqueous microemulsions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2079Monocarboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50Perfumes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143Sulfonic acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146Sulfuric acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/662Carbohydrates or derivatives
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/74Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/75Amino oxides

Abstract

An improvement is described in microemulsion compositions more environmentally friendly, which is especially effective in the removal of oily and greasy soil and having an evidenced grease release effect, contains an anionic detergent, a partially esterfied ethoxylated polyhydric alcohol, a hydrocarbon ingredient, and water which comprises the use of a water-insoluble odoriferous perfume as the essential hydrocarbon ingredient in a proportion sufficient to form a dilute o/w microemulsion composition containing, by weight, 1 % to 20 % of an anionic detergent, 0.1 to 50 % of a cosurfactant, 0.1 to 10.0 % of a grease release agent; 0.1 % to 10 % of an ethoxylated glycerol type compound, 0.4 % to 10 % of perfume and the balance being water.

Description

MICROEMULSION ALL PURPOSE LIQUID CLEANING COMPOSITIONS Field of the Invention

The present invention relates to a microemulsion composition containing a grease release system comprising an ethoxylated polyhydric alcohol type compound and choline chloride. Background of the Invention

This invention relates to an improved all-purpose liquid cleaner in the form of a microemulsion designed in particular for cleaning hard surfaces and which is effective in removing grease soil and/or bath soil and in leaving unrinsed surfaces with a shiny appearance.

In recent years 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. In order to achieve comparable cleaning efficiency with granular or powdered all-purpose cleaning compositions, use of water-soluble inorganic phosphate builder salts was favored in the prior art all-purpose liquids. For example, 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. In view of the environmentalist's efforts to reduce phosphate levels in ground water, improved all-purpose liquids containing reduced concentrations of inorganic phosphate builder salts or non-phosphate builder salts have appeared. A particularly useful self-opacified liquid of the latter type is described in U.S. Patent No. 4,244,840. However, these prior art all-purpose liquid detergents containing detergent builder salts or other equivalent tend to leave films, spots or streaks on cleaned unrinsed surfaces, particularly shiny surfaces. Thus, such liquids require thorough rinsing of the cleaned surfaces which is a time-consuming chore for the user. in order to overcome the foregoing disadvantage of the prior art all-purpose liquid, 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. However, such compositions are not completely acceptable from an environmental point of view based upon the phosphate content. On the other hand, 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.

Another approach to formulating hard surfaced or all-purpose liquid detergent composition where product homogeneity and clarity are important considerations involves the formation of oil-in-water (o/w) microemulsions which contain one or more surface-active detergent compounds, a water-immiscible solvent (typically a hydrocarbon solvent), water and a "cosurfactant" compound which provides product stability. By definition, 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.

In view of the extremely fine particle size of the dispersed oil phase particles, 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. The 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.

However, since the amount of water immiscible and sparingly soluble components which can be present in an o/w microemulsion, with low total active ingredients without impairing the stability of the microemulsion is rather limited (for example, up to 18% by weight of the aqueous phase), the presence of such high quantities of grease-removal solvent tend to reduce the total amount of greasy or oily soils which can be taken up by and into the microemulsion without causing phase separation.

The following representative prior art patents also relate to liquid detergent cleaning compositions in the form of o/w microemulsions: U.S. Patents Nos.. 4,472,291 - Rosario; 4,540,448 - Gauteer et al; 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; 4,414,128; and 4,540,505. For example, U.S. Patent No. 4,414,128 broadly discloses an aqueous liquid detergent composition characterized by, by weight: (a) from 1 % to 20% of a synthetic anionic, nonionic, amphoteric or zwitte onic surfactant or mixture thereof;

(b) from 0.5% to 10% of a mono- or sesquiterpene or mixture thereof, at a weight ratio of (a):(b) being in the range of 5:1 to 1 :3; and (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 13% by weight; non-aqueous solvent, e.g., alcohols and glycol ethers, up to 10% by weight; and 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. Furthermore, 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. 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.

A number of patents teach esterified ethoxylated glycerol compounds for various applications. These patents are Great Britain 1 ,453,385; Japan 59-1600 and Japan 58- 206693 and European Patent Application 0586,323A1. These publications fail to appreciate that a mixture of esterified ethoxylated glycerol and nonesterified ethoxylated glycerol, when used in a hard surface cleaning composition, functions as a grease release agent. Summary of the 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.

Surprisingly, these desirable results are accomplished even in the absence of polyphosphate or other inorganic or organic detergent builder salts and also in the complete absence or substantially complete absence of grease-removal solvent. The instant compositions are more friendly for the environment due to the low ecotoxicity of ethoxylated glycerol type compound used in the instant compositions.

The 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.

In one aspect, 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 dilute oil-in-water microemulsion having an aqueous phase and an oil phase; The dilute o/w microemulsion includes, on a weight basis:

0.1% to 20% of an anionic surfactant;

0.1 to 10% of a grease release agent;

0.1% to 50% of a water-mixable cosurfactant having either limited ability or substantially no ability to dissolve oily or greasy soil; 0.1 % to 10% of a compound which is a mixture of a partially esterified polyhydric alcohol, a fully esterified ethoxylated polyhydric alcohol and a nonesterified ethoxylated polyhydric alcohol (said mixture being herein after referred to as an ethoxylated glycerol type compound); 0 to 15% of magnesium sulfate heptahydrate;

0.4 to 10.0% of a perfume or water insoluble hydrocarbon; and 10 to 85% of water, said proportions being based upon the total weight of the composition.

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.

Quite surprisingly although 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.

In second aspect, 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. Broadly, the concentrated microemulsion compositions contain, by weight, 0.1% to 20% of an anionic surfactant, 0.1 % to 10% 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 to 10 wt. % of a grease release agent and 20% to 97% of water. Detailed Description of the Invention

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 to 10.0 wt % of grease release agent, 0.1 % to 20% 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.

According to the present invention, the role of the hydrocarbon is provided by a non-water-soluble perfume. Typically, in aqueous based compositions the presence of a solubilizers, such as alkali metal lower alkyl aryl sulfonate hydrotrope, triethanolamine, urea, etc., is required for 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.

First, 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). Second, the need for use of solubilizers, which do not contribute to cleaning performance, is eliminated.

Third, 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.

The use of 0.5 to 15 wt. % of the ethoxylated glycerol type compound in combination with 0.1 to 10.0 wt. % of a grease release agent in the instant composition yields a composition having excellent grease soil release properties, when the composition is used in neat or dilute form.

As used herein and in the appended claims the term "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. Typically, 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.

In the present invention 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. Naturally, of course, especially for cleaning compositions intended for use in the home, 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 0.4% 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.

Furthermore, although superior grease removal performance will be achieved for perfume compositions not containing any terpene solvents, it is apparently difficult for perfumers to formulate sufficiently inexpensive perfume compositions for products of this type (i.e., very cost sensitive consumer-type products) which includes less than 20%, usually less than 30%, of such terpene solvents.

Thus, merely as a practical matter, based on economic consideration, 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. However, even when 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.

Thus, for a typical formulation of a diluted o/w microemulsion according to this invention 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. In other words, it is an essential feature of the compositions of this invention that grease removal is a function of the result of the microemulsion, per se, and not of the presence or absence in the microemulsion of a "greasy soil removal" type of solvent.

In place of the perfume one can employ 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. %.

Regarding the 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. As used herein the term "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. Usually, 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.

Examples of 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-C15 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.

Other suitable anionic surfactants are the olefin sulfonates, including long-chain alkene sulfonates, long-chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates. These olefin sulfonate detergents may be prepared in a known manner by the reaction of sulfur trioxide (SO3) with long-chain olefins containing 8 to 25, preferably 12 to 21 carbon atoms and having the formula RCH=CHRι where R is a higher alkyl group of 6 to 23 carbons and R1 is an alkyl group of 1 to 17 carbons or hydrogen to form a mixture of sultones and alkene sulfonic acids which is then treated to convert the sultones to sulfonates. Preferred olefin sulfonates contain from 14 to 16 carbon atoms in the R alkyl group and are obtained by sulfonating an a-olefin.

Other examples of 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 C8-C1 β alkyl sulfate salts and the C8-C18 alkyl sulfate salts and the Cs-C-|8 alkyl ether polyethenoxy sulfate salts having the formula R(OC2H4)n OSO3M 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.

On the other hand, the alkyl ether polyethenoxy sulfates are obtained by sulfating the condensation product of ethylene oxide with a C8-C18 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. On the other hand, the alkyl ether polyethenoxy sulfates are obtained by sulfating the condensation product of ethylene oxide with a Cβ- C18 alkanol and neutralizing the resultant product. The alkyl ether polyethenoxy sulfates differ from one another in the number of moles of ethylene oxide reacted with one mole of alkanol. Preferred alkyl sulfates and preferred alkyl ether polyethenoxy sulfates contain 10 to 16 carbon atoms in the alkyl group.

The C8-C12 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.

Other suitable anionic surfactants are the C9-C15 alkyl ether polyethenoxyl carboxylates having the structural formula R(OC2H4)nOX COOH wherein n is a number from 4 to 12, preferably 5 to 10 and X is selected from the group consisting of

CH2, (C(O)Rι and

wherein R1 is a C1 -C3 alkylene group. Preferred compounds include C9-C11 alkyl ether polyethenoxy (7-9) C(0) CH2CH2COOH, C13-C15 alkyl ether polyethenoxy (7-9)

and C10-C12 alkyl ether polyethenoxy (5-7) CH2COOH. These compounds may be prepared by considering 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. Obviously, these anionic detergents will be present either in acid form or salt form depending upon the pH of the final composition, with salt forming cation being the same as for the other anionic detergents. Of the foregoing non-soap anionic surfactants, the preferred surfactants are the C9-C15 linear alkylbenzene sulfonates and the C13-C17 paraffin or alkane sulfonates. Particularly, preferred compounds are sodium C10-C13 alkylbenzene sulfonate and sodium C13-C17 alkane sulfonate.

Generally, 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

R' CH2 O (CH2CH O )X B

R' [ CH O (CH2CH O )y β]w Formula

R' (I) CH2 O (CH2CH O )Z B and

R'

CH2 O (CH2CH O )x H

R' [ CH O (CH2CH O )y H]W Formula

R- (II)

CH2 O (CH2CH O )z H wherein w equals one to four, most preferably one. B is selected from the group consisting of hydrogen or a group represented by:

O C R 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

O C R, 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 (I) the ratio of moπoester / diester / triester is 45 to 90 / 5 to 40 / 1 to 20, more preferably 50 to 90 / 9 to 32 / 1 to 12, wherein the 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. 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 prefered is a polyoxyethylene (45) Palm Kernel Glyceride have 45 EO groups.

In the dilute o/w microemulsion compositions or liquid crystal compositions the ethoxylated glycerol type compounds or the polyesterified nonionic compounds will be present in admixture with the anionic detergent. The proportion of the ethoxylated glycerol type compound or the polyesterified nonionic compound based upon the weight of the liquid crystal composition or the final dilute o/w microemulsion composition will be 0.1% to 20%, more preferably 0.5% to 10%, most preferably 0.5% to 6% by weight.

In the more preferred compositions the weight ratio of nonsoap anionic detergent to the ethoxylated glycerol type 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 mixture of a grease release agent and the compound which is the mixture of the fully esterified ethoxylated polyhydric alcohol, the partially esterified ethoxylated polyhydric alcohol and the nonesterified ethoxylated polyhydric alcohol.

Three major classes of compounds have been found to provide highly suitable cosurfactants over temperature ranges extending from 5°C to 43°C for instance; (1 ) water-soluble C3-C4 alkanols, polypropylene glycol of the formula HO(CH3CHCH2θ)nH wherein n is a number from 2 to 18 and monoalkyl ethers and esters of ethylene glycol and propylene glycol having the structural formulas R(X)nOH and R1 (X)nOH wherein R is C1 -C6 alkyl, R1 is C2-C4 acyl group, X is (OCH2CH2) or (OCH2 (CH3)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. Additionally, mixtures of two or more of the four classes of cosurfactant compounds may be employed where specific pH's are desired. When the mono- and di-carboxylic acid (Class 2) cosurfactants are employed in the instant microemulsion compositions at a concentration of 2 to 10 wt. %, the microemulsion compositions can be used as a cleaners for bathtubs and other hard surfaced items, which are acid resistant thereby removing lime scale, soap scum and greasy soil from the surfaces of such items damaging such surfaces. If these surfaces are of zirconium white enamel, they can be damaged by these compositions.

An aminoalkylene phophoric 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, tetraethyiene glycol monobutyl ether, propylene glycol tertiary butyl ether, ethylene glycol monoacetate and dipropylene glycol propionate.

Representative members of the aliphatic carboxylic acids include C3-C6 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.

While all of the aforementioned glycol ether compounds and acid compounds provide the described stability, 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. Generally, 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. Generally, 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. As will be appreciated by the practitioner, 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. For example, microemulsion compositions which have a pH in the range of 1 to 10 may employ either the class 1 or the class 4 cosurfactant as the sole cosurfactant, but the pH range is reduced to 1 to 8.5 when the polyvalent metal salt is present. On the other hand, the class 2 cosurfactant can only be used as the sole cosurfactant where the product pH is below 3.2. However, where 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 ability to formulate neutral and acidic products without builders which have grease removal capacities is a feature of the present invention because the prior art o/w microemulsion formulations most usually are highly alkaline or highly built or both..

In addition to their excellent capacity for cleaning greasy and oily soils, 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.

One of the grease release agent of the instant invention used in the grease release system is characterized by the formula:

R2

R1 N+ R4 X

R3 wherein Ri is a methyl group and R2, R3 and R4 are independently selected from the group consisting of methyl, ethyl and CH2CH2Y, wherein Y is selected from the group consisting of Cl, Br, CO2H, (CH2θ)n OH wherein n=1 to 10, OH, CH2CH2OH and X" is selected from the group consisting of Cl, Br, methosulfate

O CH3-OS-0"

O and -HCO3". Preferred grease release agents are B- hydroxyethyltrimethyl ammonium chloride (choline chloride), B-chloroethylthmethyl ammonium chloride, and tri(B-hydroxyethyl) methyl ammonium methosulfate

(Stepanquat T), wherein the choline chloride is preferred.

It is theorized that 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. The concentration of the grease release agent in the instant microemulsion composition is 0.1 to 10 wt. % and more preferably 0.5 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(CH2CH2θ)nH wherein n is 11 to 52. The concentration of the polyethylene glycol in the instant composition is 0 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-alpha- olefin 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: C02H

(CH-CH) (CH2-CH)

C=0 (CH2)x y

O

(CH2-CH2-0)nH CH3 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 to 10 wt. %, more preferably 0.5 to 8.0 wt. %, is a polymer depicted by the formula: O Rι

II I

HO - C - C - C - C - C

I I C = 0 R2

O

I (EO)n I

R3 wherein n is a number from 2 to 16, preferably 2 to 10, Ri is selected from the group consisting of methyl or hydrogen, R2 is a C1 to C12, preferably C4 to Cδ, linear or branched chained alkyl group and R3 is a C2 to C16, preferably C2 to C12 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. As believed to have been made clear from the foregoing description, 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. However, at the same time it should be understood that depending on the levels of surfactants, cosurfactants, perfume and other ingredients, some degree of dilution without disrupting the microemulsion, per se, is possible. For example, at the preferred low levels of active surfactant compounds (i.e., primary anionic and nonionic detergents) dilutions up to 50% will generally be well tolerated without causing phase separation, that is, the microemulsion state will be maintained. However, even when diluted to a great extent, such as a 2- to 10-fold or more dilution, for example, the resulting compositions are still effective in cleaning greasy, oily and other types of soil. Furthermore, 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. On the other hand, it is also within the scope of this invention to formulate highly concentrated microemulsions which will be diluted with additional water before use. The present invention also relates to a stable concentrated microemulsion or acidic microemulsion composition comprising approximately by weight: (a) 1 to 30% of an anionic surfactant;

(b) 0.5 to 15% of an ethoxylated glycol type compound;

(c) 2 to 30% of a cosurfactant;

(d) 0.4 to 10% of a water insoluble hydrocarbon or perfume;

(e) 0 to 18% of at least one dicarboxylic acid; (f) 0 to 1 % of phosphoric acid;

(g) 0 to 0.2% of an aminoalkylene phosphoric acid;

(h) 0 to 15% of magnesium sulfate heptahydrate;

(i) 0.1 to 10% of a grease release agent and;

(j) balance being water, wherein the composition has an ecotoxocity as measured by the LC 50 test of at least 0.18 ml/L measured on Daphniae microorganisms.

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.

In addition to the above-described essential ingredients required for the formation of the microemulsion composition, the 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.

Although 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.

Thus, depending on such factors as the pH of the system, the nature of the primary surfactants and cosurfactant, and so on, as well as the availability and cost factors, 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. As the salt, 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.

Preferably, in the dilute compositions 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. For example, for each gram-ion of Mg++ there will be 2 gram moles of paraffin sulfonate, alkylbenzene sulfonate, etc., while for each gram-ion of A13+ there will be 3 gram moles of anionic surfactant. Thus, 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. At higher concentrations of 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 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.

As example of the 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 C18 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. The following are mentioned by way of example: 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. Furthermore, if opaque compositions are desired, up to 4% by weight of an opacifier may be added.

In final form, 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. Preferably, the viscosity is maintained in the range of 10 to 40 mPas. The 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. 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.

Because the 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.

It is contemplated within the scope of the instant invention that 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.

The following examples illustrate liquid cleaning compositions of the described invention. Unless otherwise specified, all percentages are by weight. The exemplified compositions are illustrative only and do not limit the scope of the invention. Unless otherwise specified, the proportions in the examples and elsewhere in the specification are by weight.

Example 1 The following compositions in wt. % were prepared:

(a) contains 25% by weight of terpenes.

(b) the lower the number of strokes, the better the degreasing performance.

(c) the higher the results, the lower the ecotoxicity.

Furthermore, "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. 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.

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.

Example 2 The example illustrates a typical formulation of a "concentrated" o/w microemulsion based on the present invention:

% bv weight

Coco fatty acid 5

Sodium C13-C17 Paraffin Sulfonate 25 Levenol F-200 14.5 diethylene glycol monobutyl ether 20

Perfume (a) 15

Water Bal to 100 pH: 7.0 ± 0.2

This concentrated formulation can be easily diluted, for example, five times with tap water, to yield a diluted o/w microemulsion composition. Thus, by using microemulsion technology it becomes possible to provide a product having high levels of active detergent ingredients and perfume, which has high consumer appeal in terms of clarity, odor and stability, and which is easily diluted at the usual usage concentration for similar all-purpose hard surface liquid cleaning compositions, while retaining its cosmetically attractive attributes. Naturally, these formulations can be used, where desired, without further dilution and can also be used at full or diluted strength to clean soiled fabrics by hand or in an automatic laundry washing machine.

Example 3 This example illustrates a diluted o/w microemulsion composition according to the invention having an acidic pH and which also provides improved cleaning performance on soap scum and lime scale removal as well as for cleaning greasy soil.

% bv weight

Coco fatty acid 0.75

Sodium C13-C17 paraffin sulfonate 4.7

Levenol F-200 2.3

Mg SO47H20 2.2

Mixture of succinic acid/glutaric acid/adipic acid (1 :1 :1 ) 5

Perfume (d) 1.0

Water, minors (dye) balance to 100

Phosphoric acid 0.2

Amino tris - (methylene-phosphonic acid) 0.03 pH = 3 ± 0.2 (d) contains 40% by weight of terpene

Example 4 Formula A of Example I was tested for the removal of a combination of grease and particulate soil as well as for a grease release effect and compared to commercial AjaxtmNME I. Grease + particulate soil removal;

Test Method

A) Soil composition:

70 g of mineral oil

35 g of particulate soil (vacuum cleaner dust + 1 % of carbon black) 35 g C2CI4

B) Soil preparation:

- Weigh cleaned/dried glass tiles

- Soil the tiles with the grease + particulate soil - Bake the tiles 1 hour at 80°C

- Weigh the soiled tiles which aged 2 hours at RT. C) Soil removal:

The soiled tiles are soaked for 15 minutes at RT in the test products, then they are delicately rinsed with tap water. After drying 45 minutes at 50°C, the tiles are weighed again.

Results

Grease + particulate soil

% of removal mean of 6 tiles

Commercial Ajaxtm NME 60

Formula A of Example I 95

Formula A exhibits improved grease + particulate soil removal over the Commercial Ajaxtm NME

II. Grease release effect Test Method

A) Soil composition:

20% hardened tallow 80% beef tallow fat blue dye

B) Soil preparation:

The fat mixture is heated and sprayed with an automatic spraying device on cleaned and dried ceramic tiles.

C) Soil removal:

Product used neat: 2.5 g on sponge

Product used dilute: 1.2% sol in tap water - 10 ml of the solution on the sponge

The cleaning procedure is done with the gardner device for both product concentrations.

Results

A) On treated ceramic tiles (treated with the product before spraying the soil)

Neat | Dilute

Number of Strokes

First grease layer deposition mean of 4 mean of 6 tiles tiles

Commercial Current Ajaxtm NME 27 19

19 5 *

Second grease layer deposition on the mean of 4 mean of 6 same tile tiles tiles

Commercial Ajax*m NME 25 48

25 18* B) On untreated ceramic tiles

In addition to the previous test, the 3 following procedures were used to verify that Formula A remains on the surface after rinsing or wiping. After the first cleaning procedure and before the second spraying:

1 ) the tiles were allowed to dry in open air

2) the surface was wiped with paper towel

3) the surface was rinsed with wet sponge 1) dry in open air

Neat I Dilute

Number of Strokes

First grease layer deposition mean of 4 mean of 6 tiles tiles

Commercial Ajaxtm NME 29 30

Formula A 27 32

Second grease layer deposition on the mean of 4 mean of 6 same tile tiles tiles

Commercial Ajaxtm NME 33 21

Formula A 30 6*

2) wipe dry the surface

Neat Dilute

Number of Strokes

First grease layer deposition mean of 4 mean of 6 tiles tiles

Commercial Ajaxtm NME 29 30

Formula A 27 32

Second grease layer deposition on the mean of 4 mean of 6 same tile tiles tiles

Commercial Ajaxtm NME 35 46

Formula A 30 48.5

3) wet wiping the surface

Neat | Dilute

Number of Strokes

First grease layer deposition mean of 4 mean of 6 tiles tiles

Commercial Aiaxtm NME 29 30

Formula A 27 32

Second grease layer deposition on the mean of 4 mean of 6 same tile tiles tiles

Commercial Ajaxtm NME 34 58

Formula A 27 41 ** * highly significant difference

** after 5 strokes, 65% of the grease is already removed These results clearly demonstrate the important grease release effect obtained with Formula A especially when the product is used dilute.

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.

La.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 AJAXtm 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 AJAXtm NME 53 27

La.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*"1 NME 18 19

La.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 in open air

Formula 1-E 9 12

current AJAX* NME 20 21 2. Non pretreated tiles Cleaning with diluted products. number of strokes for first cleaning number of strokes for second cleaning after drying in open air

Formula 1-E 27 3

current AJAXtm NME 30 14

In summary, 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 in a proportion sufficient to form a dilute o/w microemulsion composition containing, by weight, 0.1% to 20% of an anionic detergent, 0.1% to 10% an ethoxylated glycerol type compound, 0.1 to 10% of a grease release agent, 0% to 50% of cosurfactant, 0.4% to 10% of perfume and the balance being water.

Claims

What Is Claimed:
1. A microemulsion composition comprising: (a) 0.1 wt. % to 20 wt. % of a mixture of R' CH2 O (CH2CH O )χ B
R' [ CH O (CH2CH O )y β]w
R' (I)
CH2 O (CH2CH O )z B and
R' CH2 O (CH2CH 0 )χ H
R' R' (II)
CH2 O (CH2CH O )z H wherein w equals one to four. B is selected from the group consisting of hydrogen or a group represented by: O C R wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein at least one of the B groups is represented by said O C R,
R' is selected from the group consisting of hydrogen and methyl groups; x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100, wherein in Formula (I) the ratio of monoester / diester /triester is 40 to 90 / 5 to 35 / 1 to 20, wherein the ratio of Formula (I) to Formula (II) is a value between 3 to 0.02; (b) 0 to 10 wt. % of a grease release agent;
(c) 0.1 wt. % to 20 wt. % of an anionic surfactant;
(d) 0.1 wt. % to 50 wt. % of a cosurfactant;
(e) 0.1 wt. % to 10 wt. % of a water insoluble hydrocarbon or a perfume; and (f) the balance being water.
2. The cleaning composition of Claim 1 which further contains a salt of a multivalent metal cation in an amount sufficient to provide from 0.5 to 1.5 equivalents of said cation per equivalent of said anionic detergent.
3. The cleaning composition of Claim 2 wherein the multivalent metal cation is magnesium or aluminium.
4. The cleaning composition of Claim 2, wherein said composition contains 0.9 to 1.4 equivalents of said cation per equivalent of anionic detergent.
5. The cleaning composition of Claim 3 wherein said multivalent salt is magnesium oxide or magnesium sulfate.
6. The cleaning composition of Claim 1 wherein said fatty acid has 8 to 22 carbon atoms.
7. The cleaning composition of Claim 1 which contains from 0.5 to 15% by weight of said cosurfactant and from 0.4% to 3.0% by weight of said hydrocarbon.
8. The cleaning composition of Claim 1 wherein the cosurfactant is a water soluble glycol ether.
9. The cleaning composition of Claim 8 wherein the glycol ether is selected from the group consisting of ethylene glycol monobutylether, diethylene glycol monobutyl ether, triethylene glycol monobutylether, poly-propylene glycol having an average molecular weight of from 200 to 1 ,000 and propylene glycol tert.butyl ether, mono, di, tri propylene glycol monobutyl ether.
10. The cleaning composition of Claim 7 wherein the glycol ether is ethylene glycol monobutyl ether or diethylene glycol monobutyl ether.
11. The cleaning composition of Claim 1 wherein the cosurfactant is a C3-C6 aliphatic carboxylic acid selected from the group consisting of acrylic acid, propionic acid, glutaric acid, mixtures of glutaric acid and succinic acid and adipic acid and mixtures of any of the foregoing.
12. The cleaning composition of Claim 11 wherein the aliphatic carboxylic acid is a mixture of adipic acid, glutaric acid and succinic acid.
13. The cleaning composition of Claim 1 wherein the anionic surfactant is a
C9-C15 alkyl benzene sulfonate or a C10-C20 alkane sulfonate.
14. A stable concentrated microemulsion composition comprising approximately by weight:
(a) 1 to 30% of an anionic surfactant; (b) 0.5 to 15% of a mixture of
R' CH2 O (CH2CH 0 )X B
R' [ CH O (CH2CH O )y β]w R' (I)
CH2 O (CH2CH O )z B and
R' CH2 O (CH2CH O )χ H R'
[ CH O (CH2CH O )y H]W
R' (II)
CH2 O (CH2CH O )z H wherein w equals one to four. B is selected from the group consisting of hydrogen or a group represented by:
O C R wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein at least one of the B groups is represented by said O C R,
R' is selected from the group consisting of hydrogen and methyl groups; x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100, wherein in Formula (I) the ratio of monoester / diester / triester is 40 to 90 / 5 to 35 / 1 to 20, wherein the ratio of Formula (I) to Formula (II) is a value between 3 to 0.02; (c) 2 to 30% of a cosurfactant;
(d) 0.4 to 10% of a water insoluble hydrocarbon or perfume;
(e) 0 to 18% of at least one dicarboxylic acid;
(f) 0 to 0.2% of an aminoalkylene phosphoric acid;
(g) 0 to 1.0% of phosphoric acid; (h) 0 to 15% of magnesium sulfate heptahydrate;
(i) 0 to 10.0% of a grease release agent; and
(j) balance being water, wherein the composition has an ecotoxicity value as measured by the LC50 test of at least 0.18 ml/L measured on Daphniae microorganisms.
PCT/US1994/013162 1993-11-22 1994-11-18 Microemulsion all purpose liquid cleaning compositions WO1995014765A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US15534593 true 1993-11-22 1993-11-22
US08/155,345 1993-11-22
US28863894 true 1994-08-10 1994-08-10
US08/288,638 1994-08-10
US33693494 true 1994-11-15 1994-11-15
US08/336,934 1994-11-15

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
CA 2177067 CA2177067A1 (en) 1993-11-22 1994-11-18 Microemulsion all purpose liquid cleaning compositions
DE1994627154 DE69427154T2 (en) 1993-11-22 1994-11-18 Microemulsion liquid all purpose cleaning compositions
EP19950904066 EP0730636B1 (en) 1993-11-22 1994-11-18 Microemulsion all purpose liquid cleaning compositions
DK95904066T DK0730636T3 (en) 1993-11-22 1994-11-18 Liquid cleaning compositions of microemulsion
DE1994627154 DE69427154D1 (en) 1993-11-22 1994-11-18 Microemulsion liquid all purpose cleaning compositions

Publications (1)

Publication Number Publication Date
WO1995014765A1 true true WO1995014765A1 (en) 1995-06-01

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CA (1) CA2177067A1 (en)
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WO (1) WO1995014765A1 (en)

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EP0672747A2 (en) * 1994-03-14 1995-09-20 Colgate-Palmolive Company Microemulsion all purpose liquid cleaning compositions
WO1996015217A1 (en) * 1994-11-15 1996-05-23 Colgate-Palmolive Company Microemulsion all purpose liquid cleaning compositions
WO1998006818A1 (en) * 1996-08-16 1998-02-19 Colgate-Palmolive Company Microemulsion all purpose liquid cleaning compositions
WO1998006819A2 (en) * 1996-08-16 1998-02-19 Colgate-Palmolive Company Microemulsion all purpose liquid cleaning compositions
WO1998028391A1 (en) * 1996-12-20 1998-07-02 Unilever Plc Cleaning composition comprising monoalkyl cationic surfactants
WO1998059031A1 (en) * 1997-06-23 1998-12-30 Colgate-Palmolive Company Microemulsion all purpose liquid cleaning compositions
WO1999035227A1 (en) * 1998-01-12 1999-07-15 The Procter & Gamble Company Acidic aqueous cleaning compositions
EP0637629B1 (en) * 1993-08-04 2002-01-09 Colgate-Palmolive Company Microemulsion all purpose liquid cleaning compositions
EP0677578B1 (en) * 1994-04-15 2002-02-06 Colgate-Palmolive Company (a Delaware corporation) Microemulsion all purpose liquid cleaning compositions with insect repellent
EP0677579B1 (en) * 1994-04-15 2002-03-20 Colgate-Palmolive Company Microemulsion liquid cleaning compositions with insect repellent
WO2007141120A1 (en) * 2006-06-08 2007-12-13 Unilever N.V. Liquid laundry detergent with an alkoxylated ester surfactant and urea
EP3015539A4 (en) * 2013-06-28 2017-02-15 Kao Corporation, S.A. Liquid detergent composition

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EP0637629B1 (en) * 1993-08-04 2002-01-09 Colgate-Palmolive Company Microemulsion all purpose liquid cleaning compositions
EP0672747A3 (en) * 1994-03-14 1996-07-17 Colgate Palmolive Co Microemulsion all purpose liquid cleaning compositions.
EP0672747A2 (en) * 1994-03-14 1995-09-20 Colgate-Palmolive Company Microemulsion all purpose liquid cleaning compositions
EP0677579B1 (en) * 1994-04-15 2002-03-20 Colgate-Palmolive Company Microemulsion liquid cleaning compositions with insect repellent
EP0677578B1 (en) * 1994-04-15 2002-02-06 Colgate-Palmolive Company (a Delaware corporation) Microemulsion all purpose liquid cleaning compositions with insect repellent
WO1996015217A1 (en) * 1994-11-15 1996-05-23 Colgate-Palmolive Company Microemulsion all purpose liquid cleaning compositions
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WO1998006818A1 (en) * 1996-08-16 1998-02-19 Colgate-Palmolive Company Microemulsion all purpose liquid cleaning compositions
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WO1998028391A1 (en) * 1996-12-20 1998-07-02 Unilever Plc Cleaning composition comprising monoalkyl cationic surfactants
WO1998059031A1 (en) * 1997-06-23 1998-12-30 Colgate-Palmolive Company Microemulsion all purpose liquid cleaning compositions
WO1999035227A1 (en) * 1998-01-12 1999-07-15 The Procter & Gamble Company Acidic aqueous cleaning compositions
WO2007141120A1 (en) * 2006-06-08 2007-12-13 Unilever N.V. Liquid laundry detergent with an alkoxylated ester surfactant and urea
US7635393B2 (en) 2006-06-08 2009-12-22 The Sun Products Corporation Liquid laundry detergent with an alkoxylated ester surfactant and urea
EP3015539A4 (en) * 2013-06-28 2017-02-15 Kao Corporation, S.A. Liquid detergent composition

Also Published As

Publication number Publication date Type
EP0730636A1 (en) 1996-09-11 application
DK0730636T3 (en) 2001-08-13 grant
EP0730636B1 (en) 2001-04-25 grant
DE69427154D1 (en) 2001-05-31 grant
ES2158072T3 (en) 2001-09-01 grant
CA2177067A1 (en) 1995-06-01 application
DK730636T3 (en) grant
DE69427154T2 (en) 2001-11-29 grant

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