PL180132B1 - Microemulsion-type versatile cleaning agent - Google Patents

Abstract

1. Micro-emulsion universal liquid agent cleaner, containing anionic surfactant, non-ionic surfactant, co-surfactant, hydrocarbon component, water and possibly other additional ingredients, characterized in that it contains in% by weight: 0.1% up to 6% anionic surfactant, 0% to 16% non-ionic surfactant, 0.1% to 50% co-surfactant, 0.1% to 20% of a mixture of a compound of Formula 1 i a compound of formula II in which w is equal to 1-4, B. is selected from the group consisting of hydrogen and o Formula 3 wherein R is an alkyl group of 6 up to 22 carbon atoms or an alkenyl group of 6 to 22 carbon atoms with at least one group B is represented by the formula 4; R is hydrogen or methyl, x, y, and z are 0-60, sub provided that (x + y + z) = 2 to 100, with the monoester / diester / triester ratio in Formula 1 is 40 to 90/5 to 35/1 to 20 and the ratio of the quantity the compound of formula 1 to the compound of formula 2 is v the range of 3-0.02; and contains 0.4% to 10% at least one water-insoluble hydrocarbon and / or fragrance and water in make-up quantity.

Description

The present invention relates to an improved microemulsion all-purpose liquid cleaner for cleaning hard surfaces that effectively removes greasy dirt and / or stains after a bath, leaving a shiny surface without rinsing.

In recent years, universal liquid detergents have been widely used for cleaning hard surfaces, e.g. painted woodwork and paneling, tiled walls, kitchen sinks, bathtubs, linoleum or floor tiles, washable wallcoverings, etc. Such universal liquid detergents are clear and opaque water mixtures. water-soluble synthetic organic detergents; and water-soluble detergent builder salts. In order to achieve a cleaning performance comparable to that of all-purpose granular or powder cleaners, known all-purpose liquid cleaners have used water-soluble inorganic phosphates as builders. For example, such some of the first phosphate-containing agents are described in US Patent Nos. 2,560,839, 3,234,138, 3,350,319 and in United Kingdom Patent No. 1,223,739.

In order to protect the environment, efforts to reduce phosphate levels in groundwater have resulted in the development of improved liquid all-purpose agents that contain fewer inorganic phosphates as builders or contain non-phosphate builders. A particularly useful self-opacifying liquid agent of the second type is described in US Patent No. 4,244,840.

However, these liquid multipurpose agents containing datergent builder salts or other equivalent agents tend to leave a film, stain or streak on the surfaces to be cleaned when not rinsed off, especially on shiny surfaces. Such measures require thorough rinsing of the cleaned surfaces, which takes additional time for the user.

According to US Patent No. 4,017,409, in order to avoid these disadvantages of known all-purpose liquid agents, a mixture of paraphmosulfonate and a lower amount of inorganic phosphate filler should be used. However, even such measures are not entirely acceptable from an environmental point of view due to their phosphate content. On the other hand, an alternative to all-purpose liquid phosphate-free agents has been to use a largely mixture of anionic and nonionic detergents with less glycol ether as solvent and organic amine, as described in U.S. Patent No. 3,935,130. This agent was also not entirely satisfactory, and the high level of organic detergents necessary to achieve the cleaning effect causes foaming which in turn leads to the need for a thorough rinsing which has proved to be undesirable by consumers.

Further advances in the formulation of liquid hard surface detergents or multipurpose agents where uniformity and transparency are important include the preparation of oil-in-water (o / w) microemulsions which contain one or more non-miscible detergent surfactants. water, a solvent (typically a hydrocarbon solvent), water and a "co-surfactant" to give a stable product. An o / w microemulsion is a spontaneously forming colloidal dispersion of "oil" phase particles ranging in size from about 25 Å to 800 Å in a continuous aqueous phase.

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Due to the extremely fine particle size of the dispersed oil phase, the microemulsions are light permeable, clear and usually very resistant to phase separation.

The use of grease-removing solvents in o / w microemulsions is known e.g. from European patent applications EP 0137615 and EP 0137616 (Herbots et al.); and European Patent Application EP 01607652 (Johnston et al.) and US Patent No. 4,651,991 (Herbots et al). Each of these descriptions also mentions the use of at least 5 wt.% Grease removal solvent.

It is known from British Patent Application No. 2144763A (Herbots et al.), Published March 13, 1985, that magnesium salts increase the grease removal capacity of organic grease-removal solvents such as terpenes in o / w microemulsion type liquid detergents. The compositions of this invention described by Herbots et al. contain at least 5% of a mixture of the degreasing solvent and magnesium salt, and preferably at least 5% of a solvent (which may be a mixture of a water-immiscible nonpolar solvent with a slightly soluble slightly polar solvent) and at least 0.1% of a magnesium salt.

However, since the amount of water-immiscible and poorly water-soluble ingredients that can be present in an o / w microemulsion with a low total amount of active ingredients without compromising the stability of the microemulsion is rather limited (e.g. up to 18 wt% of the aqueous phase) the presence of such high levels of grease-removal solvent reduces the total amount of greasy or oily soil that the microemulsion can absorb without causing phase separation.

The following patents also apply to o / w microemulsion liquid detergent cleaners: US Pat. Nos. 4,472,291 (Rosario), 4,540,448 (Gauteer et al.), 3,723,330 (Sheflin) etc.

Liquid detergent agents that contain terpenes such as d-limonene or other grease-removing solvent, albeit not disclosed as o / w microemulsion agents, are the subject of the following representative patent documents: European Patent Application 0080749; British Patent Nos. 1,603,047, 4,414,128 and 4,540,505. For example, U.S. Patent No. 4,414,128 broadly describes an aqueous liquid detergent which comprises by weight:

a) from about 1% to about 20% of a synthetic, anionic, non-ionic, amphoteric or zwitterionic surfactant, or mixtures thereof;

b) from about 0.5% to about 10% of mono- or sesquiterpene or a mixture thereof, in a weight ratio of (a) :( b) in the range of 5: 1 to 1: 3 and

c) from about 0.5% to about 10% of a polar solvent having a water solubility at 15 ° C ranging from about 0.2% to about 10%. The other ingredients of this patent include from about 0.05% to about 2% by weight. alkali metal, ammonium or alkanolammonium soaps of a C ₁₃ -C ₂₄ fatty acid; from about 0.5% to about 13% by weight. a calcium complexing compound; % to about 10 wt.% % of a non-aqueous solvent, e.g., alcohols and glycol ethers, and up to about 10 wt. hydrotropes, e.g. urea, ethanolamines, lower alkylarylsulfonate salts. All of the agents shown in the examples of this patent contain relatively high levels of detergent builders which are detrimental to the gloss of the surface.

The present inventors have noticed that the addition of small amounts of builder salts, such as alkali metal polyphosphates, alkali metal carbonates, nitrilotriacetic acid salts, etc. in magnesium fat removal agents, hinders the formation of stable microemulsion systems.

U.S. Patent No. 5,082,584 discloses a microemulsion agent that contains an anionic surfactant, a co-surfactant, a non-ionic surfactant, perfume and water; however, these measures do not demonstrate reduced toxicity to the environment (ecotoxicity) and do not

180 132 improved interfacial voltage properties like the agents of the present invention.

US Patent No. 3,776,857 discloses the use of long-chain fatty acid esters and adducts of ethylene oxide and aliphatic polyhydric alcohols as surfactants in agricultural compositions.

British Patent Specification No. 1,453,385 discloses polyesterified nonionic surfactants similar to the polyesterified nonionic compounds contained in the composition of the present invention. However, this specification does not disclose a component of the present agent of formula 2. Furthermore, this patent specification does not disclose the critical limitations of the present invention.

The present invention relates to an improved clear liquid cleaner that has improved interfacial tension and cleans hard surfaces better, and is in the form of a microemulsion that is suitable for cleaning hard surfaces such as plastic, glass and metal surfaces that have a glossy finish. These improved cleaners exhibit good greasy soil removal properties due to the improved interfacial tension when used undiluted and impart a shine to the surfaces to be cleaned with no or only minimal additional rinsing or wiping. This is evidenced by very little or invisible residue on the unrinsed cleaned surface. In this way, one of the drawbacks of the known agents is overcome. The compositions according to the invention have a grease release effect by delaying or reducing the adhesion of greasy soil to the cleaned surfaces compared to commercial microemulsion agents, which means that the greasy surface is easier to clean afterwards.

Surprisingly, such desirable effects are obtained even in the absence of polyphosphates or other inorganic or organic detergent builder salts and the complete absence or substantially complete absence of grease-removal solvent.

The subject of the invention is a stable microemulsion composition containing an anionic surfactant, non-ionic surfactant, co-surfactant, hydrocarbon component, water and optionally other additional ingredients, characterized in that it contains by weight: 0.1 to 6% anionic surfactant, 0% to 16% non-ionic surfactant, 0.1% to 50% co-surfactant, 0.1% to 20% of a mixture of a compound of formula 1 and a compound of formula 2 where w is equal to 1-4, B is selected from the group consisting of hydrogen and Is an alkyl group of 6 to 22 carbon atoms or an alkenyl group of 6 to 22 carbon atoms, at least one of the groups B is represented by the formula 4; R 'is hydrogen or methyl, x, y and z are 0-60, provided that (x + y + z) = 2 to 100, the monoester / diester / triester ratio in formula 1 is 40 to 90/5 to 35/1 to 20, and the ratio of the amount of the compound of formula 1 to the compound of formula 2 is in the range 3-0.02; and contains 0.4% to 10% of at least one water-insoluble hydrocarbon and / or fragrance and a replenishment amount of water.

The invention also relates to a permanent, transparent all-purpose cleaner for hard surfaces, containing an anionic surfactant, non-ionic surfactant, co-surfactant, hydrocarbon component, water and possibly other additional ingredients, particularly effective at removing oily and greasy soil, in the form of an oil-in-water microemulsion, characterized by in that the aqueous phase of this emulsion contains by weight: 0.1 to 6% anionic surfactant, 0% to 16% non-ionic surfactant, 0.1% to 20% of a mixture of a compound of formula 1 and a compound of formula 2, w is equal to 1-4, B is selected from the group consisting of hydrogen and the group of formula 3 in which R is an alkyl group of about 6 to 22 carbon atoms or an alkenyl group of about 6 to 22 carbon atoms, with at least one of groups B is represented by formula 4; R 'is hydrogen or methyl, x, y and z are 0-60, provided that (x + y + z) = 2 to 100, the monoester / diester / triester ratio in formula 1 is 40 to 90/5 to 35/1 to 20, and the ratio of the amount of compound

Formula 1 to Formula 2 is in the range 3-0.02; and contains from 0.1% to 50% of a co-surfactant, which is substantially incapable of dissolving oily or greasy soil, selected from the group consisting of C ₃ -C ₅ alcohols, polypropylene glycol and C ₁ -C ₆ alkyl ethers and esters of ethylene or propylene glycol , aliphatic mono- and dicarboxylic acids with 3 to 6 carbon atoms per molecule and mono-, di-, and triethyl phosphate and water; and the oil phase of the microemulsion consists essentially of at least one water-immiscible or poorly water-soluble hydrocarbon component in an amount of 0.1% to 10% by weight. entire composition.

The agent preferably additionally comprises a salt or oxide of the multivalent metal cation to provide 0.5 to 1.5 equivalents of cation per equivalent of anionic detergent.

The agent preferably comprises a salt or an oxide of magnesium or aluminum as the salt or oxide of the multivalent metal cation, in particular it comprises magnesium sulphate as the multivalent metal salt or it comprises magnesium oxide as the multivalent metal oxide.

The agent preferably contains 0.9 to 1.4 equivalents of cation per one equivalent of anionic detergent.

The agent preferably comprises a fatty acid with about 8 to about 22 carbon atoms.

The agent preferably comprises from about 0.5 to 15 wt. co-surfactant and from about 0.4% to about 3.0% by weight. hydrocarbon.

The agent preferably comprises a glycol ether as a co-surfactant, the alkyl chain of which has 1 to 6 carbon atoms.

The agent preferably comprises a glycol ether selected from the group consisting of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, polypropylene glycol with an average molecular weight of about 200 to 1000, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, diethylene glycol monohexyl ether and propylene glycol t-butyl ether and mono-, di- and tripropylene glycol monobutyl ether, in particular as glycol ether it comprises ethylene glycol monobutyl ether, diethylene glycol monobutyl ether or ethylene glycol monohexyl ether.

The agent preferably comprises a C ₉ -C ₁₅ alkyl benzene sulphonate or C 1 as anionic surfactant. _O- C ₂₀ alkylsulfonate.

The invention also relates to a stable concentrated microemulsion agent containing an anionic surfactant, a non-ionic surfactant, a co-surfactant, a hydrocarbon component, water and optionally other additional ingredients, characterized in that it comprises in% by weight:

a) 1% to 30% of an anionic surfactant;

b) 0.1% to 20% of a mixture of a compound of Formula 1 and a compound of Formula 2 wherein w is equal to 1-4, B is selected from the group consisting of hydrogen and Formula 3 where R is an alkyl group of 6 up to 22 carbon atoms or an alkenyl group of 6 to 22 carbon atoms, at least one of the groups B is represented by the formula 4; R 'is hydrogen or methyl, x, y and z are 0-60, provided that (x + y + z) = 2 to 100, the monoester / diester / triester ratio in formula 1 is 40 to 90/5 to 35/1 to 20, and the ratio of the amount of the compound of formula 1 to the compound of formula 2 is in the range 3-0.02;

c) 0.1% to 50% co-surfactant;

d) 0.4% to 10% of at least one water-insoluble hydrocarbon or fragrance;

e) 0% to 18% of at least one mono- or dicarboxylic acid;

f) 0% to 0.2% of aminoalkylene phosphonic acid;

g) 0% to 1.0% phosphoric acid;

h) 0% to 15% magnesium sulfate heptahydrate;

i) 0% to 16% of a non-ionic surfactant i

j) water in a supplementary quantity.

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The invention also relates to a stable microemulsion comprising an anionic surfactant, nonionic surfactant, co-surfactant, hydrocarbon component, water and optionally other additional ingredients, characterized in that it comprises, by weight%: 0.25% to 8% of an alkali metal salt of a dialkylsulfosuccinate; 0.1% to 50% co-surfactant; 0.1% to 20% of a mixture of a compound of Formula 1 and a compound of Formula 2 wherein w is equal to 1-4, B is selected from the group consisting of hydrogen and Formula 3 in which R is an alkyl group of 6 to 22 carbon atoms or an alkenyl group of 6 to 22 carbon atoms, at least one of the groups B is represented by the formula 4; R 'is hydrogen or the methyl group x, y and z are 0-60, provided that (x + y + z) = 2 to 100, with the monoester / diester / triester ratio in formula 1 being 40 to 90/5 to 35/1 to 20, and the ratio of the amount of the compound of formula 1 to the compound of formula 2 is in the range of 3-0.02; 0.4% to 10% of at least one water-insoluble hydrocarbon and / or fragrance, and a make-up amount of water.

According to the invention, a permanent transparent all-purpose hard surface cleaner containing an anionic surfactant, non-ionic surfactant, co-surfactant, hydrocarbon component, water and optionally other additives, particularly effective at removing oily or greasy soil, in the form of an oil-in-water microemulsion, is characterized by: that the aqueous phase of the microemulsion contains from 0.25% to 8% by weight of an alkali metal salt of a dialkyl sulfosuccinate; 0.1% to 20% of a mixture of a compound of Formula 1 and a compound of Formula 2 wherein w is equal to 1-4, B is selected from the group consisting of hydrogen and Formula 3 in which R is an alkyl group of 6 to 22 carbon atoms or an alkenyl group of 6 to 22 carbon atoms, at least one of the groups B is represented by the formula 4; R 'is hydrogen or the methyl group x, y and z are 0-60, provided that (x + y + z) = 2 to 100, with the monoester / diester / triester ratio in formula 1 being 40 to 90/5 to 35/1 to 20, and the ratio of the amount of the compound of formula 1 to the compound of formula 2 is in the range of 3-0.02; 0.1% to about 50% of a water-miscible co-surfactant that is substantially incapable of dissolving oily or greasy soil, selected from the group consisting of C ₃ -C ₅ alcohols, polypropylene glycol and C] -C ₆ alkyl ethers and glycol esters ethylene or propylene, aliphatic mono- and dicarboxylic acids with 3 to 6 carbon atoms per molecule and mono-, di- and triethyl phosphate and water; and the oil phase of the microemulsion consists essentially of at least one water-immiscible or poorly water-soluble hydrocarbon component in an amount of 0.1% to 10% by weight. of the entire composition, the composition being particularly effective at removing oily or greasy soil from hard surfaces by solubilizing it in the oil phase of the emulsion.

The agent preferably further comprises a salt of the multivalent metal cation in an amount to provide 0.5 to 1.5 equivalents of cation per equivalent of anionic detergent.

The agent preferably comprises a salt or oxide of magnesium or aluminum as a salt or oxide of a multivalent metal cation, in particular it comprises magnesium sulfate as a multivalent metal salt or magnesium oxide as a multivalent metal oxide.

The agent preferably contains 0.9 to 1.4 equivalents of cation per one equivalent of anionic detergent.

The agent preferably comprises a fatty acid having about 8 to about 22 carbon atoms as a co-surfactant.

The agent preferably comprises from about 0.5-15 wt. co-surfactant and from about 0.4% to about 3.0% by weight. hydrocarbon.

The co-surfactant preferably comprises a glycol ether whose alkyl chain has 1 to 6 carbon atoms.

The agent preferably comprises a glycol ether selected from the group consisting of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, polypropylene glycol with an average molecular weight of about 200 to 1000, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, diethylene glycol monohexyl ether and propylene glycol t-butyl ether

180 132 and mono-, di- and tripropylene glycol monobutyl ether, in particular as glycol ether it comprises ethylene glycol monobutyl ether, diethylene glycol monobutyl ether or ethylene glycol monohexyl ether.

The agent preferably comprises a lithium, potassium or sodium salt as the alkali metal salt of the dialkyl sulfosuccinate, and each alkyl group in the salt contains about 4 to about 12 carbon atoms.

The invention also relates to a stable, concentrated microemulsion agent containing an anionic surfactant, a non-ionic surfactant, a co-surfactant, a hydrocarbon component, water and optionally other additional ingredients, characterized in that it comprises in% by weight:

a) 0.1% to 20% of a mixture of a compound of formula 1 and a compound of formula 2 in which w is equal to 1-4, B is selected from the group consisting of hydrogen and a group of formula 3 in which R is an alkyl group of 6 up to 22 carbon atoms or an alkenyl group of 6 to 22 carbon atoms, at least one of the groups B is represented by the formula 4; R is hydrogen or methyl, x, y and z are from 0-60, provided that (x + y + z) = 2 to 100, the monoester / diester / triester ratio in formula 1 is 40 to 90/5 to 35/1 to 20, and the ratio of the amount of the compound of formula 1 to the compound of formula 2 is in the range of 3-0.02;

b) 0.1% to 50% co-surfactant;

c) 0.4% to 10% of at least one water-insoluble hydrocarbon or fragrance;

d) 0% to 18% of at least one mono- or dicarboxylic acid;

e) 0% to 0.2% of aminoalkylene phosphonic acid;

f) 0% to 1.0% of phosphoric acid;

g) 0% to 15% magnesium sulfate heptahydrate;

h) 0.25% to 8% of an alkali metal salt of a dialkylsulfosuccinate wherein each alkyl group contains 4 to 12 carbon atoms and the alkali metal is lithium, potassium or sodium, and a make-up of water.

The composition of the present invention is a permanent clear all purpose hard surface cleaner, and is in the form of a substantially dilute oil-in-water microemulsion that includes an aqueous phase and an oil phase. The diluted o / w microemulsion contains by weight:

0% to about 6% of an anionic surfactant;

0% to about 16.0% of a non-ionic surfactant;

about 0.1% to about 50% of a co-surfactant that has limited or essentially no ability to dissolve oily or greasy soil,

0% to about 8% of an alkali metal salt of a dialkyl sulfosuccinate, about 0.1% to about 20% of a mixture of fully esterified ethoxylated polyol, partially esterified ethoxylated polyhydric alcohol, and unesterified ethoxylated polyol,

0% to about 15% of magnesium sulfate heptahydrate;

about 0.4% to about 10% of at least one perfume and / or water-insoluble hydrocarbon and about 10% to about 85% water, said proportions being based on the total weight of the agent.

While fragrances as such are not a solvent for greasy or oily soil, although some may contain up to 80% terpenes, which are known to be good fat solvents, it is quite surprising that the agent of the invention in diluted form has the ability to solubilize oily and greasy soil in an amount up to about 10 times or more of the weight of the fragrances. This dirt is removed from the hard surface by the action of anionic and nonionic surfactants and is absorbed into the oil phase of the o / w microemulsion.

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Also included within the scope of the invention are highly concentrated oil-in-water (o / w) or water-in-oil (w / o) microemulsions which, when diluted with additional water prior to use, may form dilute o / w microemulsions. Concentrated microemulsions contain 0% to 6% by weight of anionic surfactant, 0% to 16% of a non-ionic surfactant, 0% to 8% of an alkali metal salt of a dialkylsulfosuccinate, about 0.1% to about 20% of a mixture of fully esterified ethoxylated polyhydric alcohol, partially esterified ethoxylated a polyhydric alcohol and a non-esterified ethoxylated polyhydric alcohol, 0% to 2.5% fatty acid, 0.4% to 10% of a fragrance or a water-insoluble hydrocarbon containing about 6 to 18 carbon atoms, 0.1% to 50% of a co-surfactant, and 20% to 97% water.

The invention relates to a stable microemulsion agent which approximately comprises by weight: 0.1% to 6% anionic surfactant, 1.0% to 16% non-ionic surfactant, 0.1% to 50% co-surfactant, 0% to 2.5% fatty acid. , 0% to 8% alkali metal salt of a dialkylsulfosuccinate, 0.1% to 20% of a mixture of fully esterified ethoxylated polyol, partially esterified ethoxylated polyol, and non-esterified ethoxylated polyhydric alcohol, 0.1% to 10% water-insoluble hydrocarbon or substance fragrance and in the amount of replenishing water.

In one aspect the invention relates to a detergent which is in the form of an oil-in-water microemulsion, and in a second aspect, the detergent when diluted with water, the essential ingredients of which are: water, an anionic surfactant, a fatty acid, an esterified polyethoxyether nonionic surfactant, and a hydrocarbon or perfume.

According to the invention, the role of the hydrocarbon is played by a water-insoluble fragrance. Typically in aqueous compositions a solubilizing agent such as an alkali metal lower alkylaryl sulfonate salt hydrotrope, triethanolamine, urea etc. is required to dissolve the fragrance, especially about 1% and greater, as perfumes are usually a mixture of flavoring oils and compounds aromatics, which are usually insoluble in water.

Thus, by incorporating perfume in the aqueous liquid cleaner as the oily phase (hydrocarbon) in the final o / w microemulsion, several different important advantages are achieved.

First, the cosmetic properties of the agent are better: the agents are transparent (as a result of microemulsion formation) and highly perfumed (as a result of the fragrance level).

Second, the need for solubilizing agents that do not contribute to cleaning performance is eliminated.

Third, a better fat release effect and an improved fat removal capacity can be obtained when the agent is used neat or after dilution of the concentrate, without builders or buffers or conventional fat-removing solvents at neutral or acidic pH and at low levels of active ingredients.

The term "fragrance" as used in the description and claims is used in the usual sense and refers to and includes water-insoluble aromatics or mixtures thereof including natural substances (i.e. obtained by extracting flowers, herbs, flowers of fruit trees or plants) and artificial (ie mixtures of natural oils or their ingredients and synthetically produced substances) odorants. Typically the fragrances are complex mixtures of various organic compounds such as alcohols, aldehydes, ethers, aromatics and various amounts of essential oils (e.g. terpenes) from about 0% to about 80%, usually from about 10% to about 70% by weight. the essential oils themselves are volatile odorants and also serve to dissolve other components of the fragrance.

In the compositions according to the invention, the exact composition of the perfume is not of particular importance for cleaning performance as long as it is water-immiscible and has a pleasant smell. The fragrance as well as the other ingredients should be acceptable

Cosmetically, i.e., they should be non-toxic, hypoallergenic etc., especially when the cleaning products are intended for domestic use.

The agent according to the invention shows a clear improvement in ecotoxicity compared to commercial products.

A hydrocarbon such as a perfume is present in the diluted o / w microemulsion in an amount of from about 0.1% to about 10%, preferably from about 0.4% to 3% by weight, particularly preferably from about 0.5% to 2% by weight. . If the amount of hydrocarbon (perfume) is less than about 0.4 wt%, it is more difficult to form an o / w microemulsion. If the hydrocarbon (perfume) is added in an amount greater than about 10 wt.%, The cost increases without any additional benefit in cleaning performance, and indeed with some reduction in cleaning performance, since the total amount of greasy and oily soil that can be absorbed by the oil phase this microemulsion will be proportionally smaller.

In addition, while excellent grease removal properties are achieved in flavoring agents that do not contain terpene solvents, it is difficult to formulate a suitably inexpensive fragrance for products of this type (i.e. products that are highly price sensitive) containing less than about 20% and usually less than about 30% of such terpene solvents.

Thus, from a practical economic point of view, the dilute o / w microemulsion detergent cleaners of the invention can often contain as much as about 0.2% to about 7% by weight of the present invention. for the whole agent, the terpene solvents that are introduced through the fragrance ingredient. However, even when the amount of terpene solvent in the cleaner is less than 1.5 wt.%. % and is up to about 0.6 wt.%. or 0.4 wt.%. or less, the dilute o / w microemulsions of the invention have a satisfactory grease and oil removal capacity.

Thus, for a typical agent of the invention which is an o / w dilute microemulsion, a 20 ml microemulsion sample containing 1 wt. the fragrance will be able to solubilize e.g. up to about 2-3 ml of greasy and / or oily soil while maintaining the form of a microemulsion. In other words, it is an essential feature of the composition of the invention that fat removal is due to the fact that the agent is a microemulsion as such, and not to the presence or absence of a "soil release" type solvent in the microemulsion.

Water-insoluble paraffinic or isoparaffic hydrocarbons containing about 6 to about 18 carbon atoms in a concentration of about 0.4 to 8 wt.%, More preferably 0.4 to 3 wt.% May be used in place of the fragrance.

The water-soluble organic detergent substances which are used to prepare the o / w compositions of the invention can be selected from the group consisting of non-soap water-soluble anionic detergents and non-ionic surfactants mixed with a mixture of fully esterified polyethoxylated polyhydric alcohol, partially esterified ethoxylated alcohol. a polyhydric alcohol and a non-esterified ethoxylated polyhydric alcohol.

The nonionic surfactant of the present invention is present in an amount of about 0% to 16%, preferably 1% to 12%, more preferably 1.5% to 10% by weight. and provides excellent oil removal capacity and gentle character to human skin.

The water-soluble nonionic surfactants used in the present invention are well known and commercially available and include ethoxylated primary aliphatic alcohols, ethoxylated secondary aliphatic alcohols, ethoxylated alkylphenols, and ethylene oxide-propylene oxide and primary alcohol condensation products such as Plurafac (BASF) and products condensation of ethylene oxide with sorbitol fatty acid esters such as Tween (ICI).

The nonionic synthetic organic surfactants are typically the condensation products of organic aliphatic or alkyl aromatic hydrophobic compounds and hydrophytic ethylene oxide groups. Virtually any hydrophobic compound containing a carboxyl, hydroxyl, amide or amino group with a free hydrogen atom attached to the nitrogen atom.

180 132 can be condensed with ethylene oxide or with its hydration product, polyethylene glycol, to produce a water-soluble non-ionic detergent. The length of the polyethoxyethylene chain can be adjusted to achieve the desired balance of hydrophobic and hydrophilic elements.

Nonionic surfactants include the condensation products of a higher alcohol (e.g., having about 8 to 18 carbon atoms in a straight or branched chain) with about 5 to 30 moles of ethylene oxide, e.g., lauryl or myristyl alcohol condensed with about 16 moles of ethylene oxide (EO), tridecanol condensed with about 6 moles EO, myristyl alcohol condensed with about 10 moles EO per mole alcohol, EO condensation product with a coconut fatty alcohol fraction, containing a mixture of fatty alcohols with an alkyl chain of 10 to about 14 carbon atoms, containing about 6 moles EO per mole of all alcohols, or about 9 moles of EO per mole of alcohol, and tallow ethoxylated alcohols containing 6 EO to 11 EO per mole of alcohol.

A preferred group of these nonionic surfactants are Neodol (Shell Co.), which are condensation products of higher aliphatic primary alcohols containing about 9-15 carbon atoms, such as a C ₉ -C _n alcohol condensed with 8 moles of ethylene oxide (Neodol 91- 18), C ₁₂ -C ₁₃ alcohol condensed with 6.5 moles of ethylene oxide (Neodol 23-6.5), C ₁₂ -C ₁₅ alcohol condensed with 12 moles of ethylene oxide (Neodol 25-12), C ₁₄ -C alcohol ₁₅ condensed with 13 moles of ethylene oxide (Neodol 45-13) etc. Such ethoxylated products have an HLB (hydrophilic-lipophilic balance) value of about 8-15 and give a good o / w emulsion, while products with HLB below 8 contain less than 5 groups oxyethylene and are rather poor emulsifiers and poor surfactants (at least for the purposes of the present invention).

Other satisfactory water-soluble alcohol ethylene oxide condensation products include the condensation products of secondary aliphatic alcohols containing 8 to 18 carbon atoms in a straight or branched chain with 5 to 30 moles of ethylene oxide. Commercial examples of nonionic detergents of this type is the condensation product of a secondary alcohol C _{15 H} -C 9 EO (Tergitol 15-S-9) or 12 EO (Tergitol 15-S-12) marketed by Union Carbide.

Other suitable nonionic surfactants include the condensation products of one mole of an alkylphenol containing from about 8 to 18 carbon atoms in a straight or branched chain alkyl group with about 5 to 30 moles of ethylene oxide. Specific examples of such condensation products include nonylphenol condensed with about 9.5 moles EO per mole of nonylphenol, dinonylphenol condensed with about 12 moles EO per mole of phenol, dinonylphenol condensed with about 15 moles EO per mole of phenol, and isooctylphenol condensed with about 15 moles EO per mole. phenol. Commercially available non-ionic surfactants of this type include Igepal CO-630 (a nonylphenol ethylene oxide condensation product) sold by GAF Corporation.

Also suitable as nonionic surfactants are the water-soluble condensation products of C ₈ -C ₂₀ alcohols with a mixture of ethylene oxide and propylene oxide in a weight ratio of 2.5: 1 to 4: 1, preferably 2.8: 1 - 3.3: 1. with a total content of ethylene oxide and propylene oxide (including ethanol or propanol end group) of 60-85%, preferably 70-80% by weight. These detergents from BASF-Wyandotte are commercially available. Particularly preferred is the condensation product of a C ₁₀ -C ₁₆ alcohol with a mixture of ethylene oxide and propylene oxide in a weight ratio of 3: 1 and a total alkoxy content of about 75% by weight.

Condensates of 2 to 30 moles of ethylene oxide with mono- and tri-C ₁₀ -C ₂₀ alkanoic acid esters with sorbitol having an HLB value in the range 8 to 15 can also be used as nonionic surfactants in the present invention. Such surfactants are well known and are available. commercially available from Imperial Chemical Industries under the tradename Tween. Suitable surfactants include polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (4)

180 132 sorbitan monostearate, polyethoxylated (20) sorbitan trioleate and polyethoxylated (20) sorbitan tristearate.

Other suitable, but less preferred, nonionic surfactants are sold under the name "Pluronics". These compounds are produced by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The molecular weight of the hydrophobic portion of the molecule is in the order of 950 to 4,000, and preferably 200 to 2,500. The addition of polyethoxylene radicals to the hydrophobic portion increases the solubility of the molecule as a whole and renders the surfactant water-soluble. The molecular weight of the block polymers varies from 1,000 to 15,000 and the polyethylene oxide content may be 20% to 80% by weight. Preferably the compositions are in liquid form, grades L62 and L64 being preferred among them.

Any of the conventionally used water-soluble anionic detergents or mixtures of anionic and nonionic surfactants can be used as the anionic surfactants in the o / w microemulsion of the invention. The term "anionic surfactant" as used herein refers to the class of anionic and mixed anionic-nonionic surfactants which impart detersive action.

Suitable non-soap water-soluble anionic surfactants include surface-active or detergent compounds that contain an organic hydrophobic group of 8 to 26 carbon atoms, preferably 10 to 18 carbon atoms, and at least one water solubilizing group selected from the group sulfonate, sulfate and carboxylate. Typically, the hydrophobic group comprises or is a C ₈ -C ₂₂ alkyl, alkenyl or acyl group. Such detergents are used in the form of water-soluble salts, and the salt-forming cation is usually selected from the group consisting of sodium, potassium, magnesium, ammonium and mono- di- or tri-C ₂ -C ₃ alkanolammonium cations and is preferably sodium, magnesium and ammonium.

Examples of suitable sulfonated anionic surfactants are the well known single ring aromatic higher alkyl sulfonates such as higher alkyl benzene sulfonates containing 10 to 16 carbon atoms in a higher straight or branched chain alkyl group, C ₈ -C ₁₅ alkyl toluenesulfonates and C ₈ -C ₁₅ alkyl phenols sulfonates.

A preferred sulfonate is a linear alkylbenzene sulfonate with a high content of 3- (or higher) phenyl isomers and suitably low content (well below 50%) of the 2- (or lower) phenyl isomers, i.e. where the benzene ring is preferably bound to a large extent the 3-position or higher (e.g. 4, 5, 6 or 7) portion of the alkyl group and the content of isomers in which the benzene ring is attached to the 2 or 1 position is low. Particularly advantageous agents are described in US Patent No. 3,320,174.

Other suitable anionic surfactants are olefin sulfonates, including long chain alkenesulfonates, long chain hydroxyalkanesulfonates, or mixtures of alkenesulfonates and hydroxyalkanesulfonates. Such olefin sulfonate detergents can be prepared in a known manner by reacting sulfur trioxide (SO ₃ ) ₂ with long-chain olefins having 8 to 25, preferably 12 to 21 carbon atoms of the formula RCH = CHRj, in which R is a higher alkyl group of 6 to 23 carbon atoms and R, is an alkyl group of 1 to 17 carbon or hydrogen atoms in which a mixture of sultones and alkene sulfonic acids is formed which is then reacted to convert the sultons to sulfonates. Preferred olefin sulfonates contain from 14 to 16 carbon atoms in the R alkyl group and are prepared by sulfonating an alpha olefm.

Other examples of suitable anionic sulfonate surfactants are paraffin sulfonates containing about 10 to 20, preferably 13 to 17 carbon atoms. Primary paraffin sulfonates are produced by the reaction of long-chain α-olefins and bisulfites. Paraffin sulfonates containing sulfonate groups distributed along the paraffinic chain are described in U.S. Patent Nos. 2,503,280, 2,507,088, 3,260,744, 3,372,188 and German Patent No. 735,096.

180 132

An example of satisfactory anionic sulfate surfactants are the salts of C ₁₈ -C _g alkyl sulfates and salts of C ₈ -C _lg alkiloeteropolietenoksysiarczanów the formula R (OC ₂ H _{4) n} OSO ₃ M wherein n is 1 to 12, preferably 1 to 5, and M is a solubilizing cation selected from the group consisting of sodium, potassium, magnesium, ammonium, and mono-, di- and triethanolammonium ions. The alkyl sulfates can be prepared by sulfating the alcohols obtained by reducing the glycerides from coconut oil or tallow or mixtures thereof and neutralizing the resulting product.

While the alkyl is prepared by sulfating the condensation product of ethylene oxide with an alcohol C ₈ -C _lg and neutralizing the resultant product. The alkyl ether polyethenoxy sulfates differ from one another in the number of moles of ethylene oxide that react with one mole of alcohol. Preferred alkyl sulfates and preferred alkyl ether polyethenoxy sulfates contain 10 to 16 carbon atoms in the alkyl group.

Also suitable for use in the composition of the invention are C ₈ -C ₁₂ alkylphenyl ether polyethenoxy sulfates containing from 2 to 6 moles of ethylene oxide per molecule. These surfactants can be prepared by reacting an alkylphenol with 2 to 6 moles of ethylene oxide and sulfating and neutralizing the resultant ethoxylated alkylphenol.

Other suitable anionic surfactants are C ₉ -C ₁₅ alkyl ether polyethenoxy carboxylates of the structural formula R (OC ₂ H ₄ ) _n OXCOOH where n is from 4 to 12, preferably 5 to 10, and X is selected from the group consisting of CH ₂ , C (O) R ₁₅ , wherein R] is a C] -C ₃ alkylene group and including the group of formula 5.

Preferred compounds include C ₉ -C _H alkyl ether polyethenoxy (7-9) C (O) CH ₂ CH ₂ COOH, C ₁₃ -C ₁₅ alkyl ether polyethenoxy (7-9) -group of formula 6 and C ₁₀ -C ₁₂ alkyl ether polyethenoxy (5- 7) CH ₂ COOH.

These compounds can be prepared by condensing ethylene oxide with the appropriate alcohol and reacting the product with chloroacetic acid to form ether carboxylic acids as described in US Patent No. 3,741,911 or with succinic or phthalic anhydride.

Such anionic surfactants will be in the form of an acid or a salt, depending on the pH of the final composition, the salt-forming cation being the same as for other anionic detergents.

Preferred anionic surfactants present in the o / w microemulsion are selected from the group consisting of alkali metal salts of alkyl sulfates, alkaline earth metal salts of alkyl sulfates and alkali metal salts of dialkyl sulfosuccinic acid and mixtures thereof.

Typically the amount of the non-soap anionic surfactant is 0% to 6.0%, preferably 0.1% -5% by weight. diluted microemulsion o / w center.

An agent of the invention may contain about 0% to about 8% by weight, and more preferably 0.25% to about 7% by weight. The alkali metal dialkylsulfosuccinate salt surfactant, wherein the alkyl groups may be the same or different and each alkyl group contains about 4 to about 12 carbon atoms, more preferably about 7 to about 9 carbon atoms, and the alkali metal is sodium, potassium or lithium. The preferred alkali metal salt of the dialkyl sulfosuccinate to be used as a component of the agent of the invention is sodium dioctyl sulfosuccinate.

The composition of the invention comprises an ingredient (hereinafter referred to as an ethoxylated glycerin type component) which is a mixture of a fully esterified ethoxylated polyol, a partially esterified ethoxylated polyol and an unesterified ethoxylated polyol, in which glycerin is the preferred polyol. Component is a mixture of a compound of Formula 1 and Formula 2 wherein w is 1 to 4, most preferably 1. B is hydrogen or Formula 3 wherein R is an alkyl group of about 6 to 22 carbon atoms, more preferably about 11 up to 15 carbon atoms or an alkenyl group having about 6 to 22 carbon atoms, more preferably about 11 to 15 carbon atoms, with an alkyl chain derived from a hydrogenated

180 132 tallow or coconut oil; and at least one group B is represented by the formula 4; R 'represents a hydrogen atom or a methyl group; x, y, and z are 0-60, more preferably 0-40, provided that (x + y + z) = about 2 to about 100, preferably 4 to about 24, and most preferably about 4 to 19; and the monoester / diester / triester ratio in formula 1 is 45 to 90/5 to 40/1 to 20, more preferably 50 to 90/9 to 32/1 to 12, while the molar ratio of the compound of formula 1 to the compound of formula 2 is a value in the range of about 3 to about 0.02, preferably 3 to 0.1, and most preferably about 1.5 to about 0.2, most preferably there is more of the compound of Formula 2 in the mixture that forms the component than the compound of Formula 1.

The ethoxylated glycerin type component of the present invention is manufactured by Kao Corporation and marketed under the trade name Levenol such as Levenol F-200 which has an average of 6 EO and wherein the molar ratio of coconut oil fatty acids to glycerin is 0.55 or Levenol V501 / 2 containing an average of 17 EO in which the molar ratio of tallow fatty acids to glycerin is 1.0. Preferably, the molar ratio of fatty acid to glycerin is less than about 1.7, more preferably less than about 1.5, and most preferably less than about 1.0.

The ethoxylated glycerin type compound has a molecular weight of about 400 to about 1600 and a pH (50 g / L of water) of about 5-7. Compounds called Levenol are essentially non-irritating to human skin and are more than 90% biodegradable as measured by the Wickbold Bias-7d method.

Two examples of ingredients called Levenol are: Levenol V-501/2, which has 17 ethoxy groups, is a tallow fatty acid derivative with a molar ratio of fatty acid to glycerin of 1.0 and a molecular weight of 1465, and Levenol F- 200, which has 6 ethoxy groups, is derived from coconut fatty acids and wherein the molar ratio of fatty acid to glycerin is 0.55. Both Levenol F-200 and Levenol V-501/2 are composed of a mixture of a compound of formula 1 and a compound of formula 2. Levenol has the following ecotoxicity values: inhibition of algae growth> 100 mg / 1; acute toxicity to Daphniae> 100 mg / l and acute toxicity to fish> 100 mg / l. Levenol is more than 60% biodegradable which is the required minimum value according to OECD 301 B which is acceptable.

Suitable polyesterified nonionic surfactants in the inventive compositions are Crovol PK-40 and Crovol PK-70, manufactured by Croda GMBH, The Netherlands. Crovol PK-40 is a polyethoxylated (12) palm oil glyceride that contains 12 EO groups. Crovol PK-70, which is a benefit agent, is a polyethoxylated (45) glyceride from palm oil and contains 45 EO groups.

In dilute o / w microemulsion agents or in liquid crystalline agents, ethoxylated glycerol compounds or polyesterified nonionic compounds are mixed with the anionic detergent. The amount of ethoxylated glycerin type compound or polyesterified nonionic solubilizing agent based on the weight of the liquid crystalline agent or the final o / w dilute microemulsion is 0.1% to 20.0%, more preferably 0.5% to 10%, and most preferably about 0, 5% to 6% by weight

In preferred dilute microemulsions the o / w component of the ethoxylated glycerin type is in admixture with the anionic surfactant. The amount of ethoxylated glycerin type component based on the weight of the final diluted o / w microemulsion is 0.1% to 20.0%, more preferably 0.5% to 10% by weight.

The co-surfactant may play an important role in the preparation of dilute o / w microemulsions and concentrated microemulsions. Briefly, when co-surfactant is absent, water, detergent (s) and hydrocarbon (e.g. perfume) when mixed in appropriate proportions will form either a micellam solution (low concentration) or an "oil in water" emulsion according to the first aspect of the invention. When a co-surfactant is added to such a system, the interfacial tension at the surface between the emulsion droplets and the aqueous phase is lowered to a very low value. This reduction of the interfacial tension leads to the spontaneous rupture of the emulsion droplets into smaller aggregates until they become transparent

180 132 emulsions with colloidal particle size, e.g. microemulsions. In the microemulsion state, the thermodynamic factors balance with varying degrees of stability related to the total free energy of the microemulsion. Some of the thermodynamic factors that determine the total free energy of a system are: 1) particle-particle potential, 2) interfacial tension or free energy (stretching and bending), 3) droplet dispersion entropy, and 4) chemical potential changes after formation. A thermodynamically stable system is obtained when (1) the interfacial tension or free energy is minimal and (2) the droplet dispersion entropy is maximum.

Thus, the role of the co-surfactant in forming a stable o / w microemulsion is to (a) reduce the interfacial tension (1) and (b) modify the structure of the microemulsion and increase the number of possible configurations (2). The co-surfactant will also (c) reduce the stiffness at the interfacial micelle layer.

Typically, increasing the concentration of co-surfactant leads to a wider range of temperatures at which the product is stable.

Three main classes of compounds have been found which are very suitable co-surfactants, e.g. in the temperature ranges from 5 ° C to 43 ° C: (1) water-soluble C ₃ -C ₅ alcohols, polypropylene glycol of formula HO (CH ₃ CHCH ₂ O) _n H, where n is a number from 2 to 18 and mono-CpCg alkyl ethers and esters of ethylene glycol and propylene glycol of the formulas R (X) _n OH and Rj (X) _n OH, where R is a C ₁ -C ₆ alkyl group , R 1 is C ₂ -C ₄ acyl, X is (OCH ₂ CH ₂ ) or (OCH ₂ CH ₃ CH) and n is from 1 to 4; (2) aliphatic mono- and dicarboxylic acids containing 2 to 10 carbon atoms, preferably 3 to 6 carbon atoms, and (3) triethyl phosphate. In addition, mixtures of two or more of these three classes of compounds may be used when a specific pH is desired.

When the microemulsion according to the invention contains mono- and dicarboxylic acids (class 2) as co-surfactants in a concentration of about 2 to 10% by weight, it can be used as a cleaner for bathtubs and other objects with hard surfaces which are acid and scale resistant. boiler, lime soap scum and greasy dirt from such surfaces are removed without damaging them. If the surface is white zirconium enamel, such agents may damage it.

An aminoalkylene phosphonic acid at a concentration of about 0.01 to about 0.2 wt.% May optionally be used along with the mono- and dicarboxylic acids to prevent damage to such white enamel surfaces. The agent may further contain 0.05% to 1% of phosphonic acid.

Representative examples of polypropylene glycol include dipropylene glycol and polypropylene glycol with a molecular weight of 200 to 1000, e.g. polypropylene glycol 400. Other suitable glycol ethers are ethylene glycol monobutyl ether (available as Butyl Cellosolve from Union Carbide), diethylene glycol monobutyl ether (Butyl Carbitol ), ethylene glycol monohexyl ether (Hexyl Cellosolve), diethylene glycol monohexyl ether (Hexyl Carbitol), triethylene glycol monobutyl ether, mono-, di-, tripropylene glycol monobutyl ether, tetraethylene glycol tetraethylene glycol monobutyl ether, glycol tetraethylene glycol butyl ether ethylene glycol and dipropylene glycol propionate.

Representative examples of aliphatic carboxylic acids include C ₃ -C ₆ alkyl and alkenyl monobasic and dibasic acids such as glutaric acid and mixtures of glutaric acid with adipic and succinic acid, and mixtures of the above acids.

While all of the aforementioned glycol ethers and acid compounds impart the described stability, the most preferred co-surfactant in terms of cost and cosmetic properties (especially fragrance) is diethylene glycol monobutyl ether or diethylene glycol monohexyl ether and a mixture of adipic, glutaric and succinic acids. respectively. The ratio of the acids in such a mixture is not particularly critical and may be modified to provide the desired fragrance.

180 132

To ensure maximum water solubility of the acid mixture, glutaric acid is used as the main component, which is the most water-soluble of the three saturated aliphatic dibasic acids.

In general, weight ratios of adipic acid: glutaric acid: succinic acid 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. with equally good results.

The amount of co-surfactant needed to stabilize the microemulsion agents will, of course, be dependent upon factors such as the surface tension of the co-surfactant, the type and amount of major surfactants and flavors, and the type and amount of other additional ingredients that the agent may contain and which affect the thermodynamic factors mentioned above. In general, the amount of co-surfactant ranges from 0.1% to 50%, preferably from about 0.5% to 15%, and particularly preferably from about 1% to 7% by weight. gives stable dilute o / w microemulsions with the above stated levels of major surfactants and flavors and other additional ingredients as described above.

The pH of the final microemulsion depends on the nature of the co-surfactant compound, the choice of the co-surfactant being dependent on cost and cosmetic properties, especially odor. For example, microemulsion agents which have a pH in the range 1 to 10 may contain a class 1 or 3 co-surfactant as the sole co-surfactant, but when a multivalent metal salt is present, the pH range is reduced to 1 to 8.5. On the other hand, a class 2 co-surfactant can be used as the sole co-surfactant when the pH of the product is below 3.2. However, when acidic co-surfactants are used in admixture with a glycol ether type co-surfactant, the pH of the agent may be substantially neutral (e.g., pH 7 1.5, preferably 7 0.2).

It is a feature of the present invention that it is possible to produce neutral or acid products without builders, which products have the ability to remove greasy soil, whereas known microemulsion agents most often contain strong alkaline substances or strong builders or both.

In addition to their excellent ability to wash off greasy and oily soil, the low pH o / w microemulsion agents also show excellent washing and removal capacity of limescale soap and limescale, both when used neat or after dilution.

The last essential ingredient of the inventive microemulsion compositions which have improved interfacial tension properties is water. The amount of water in o / w microemulsions is typically 20% to 97%, preferably 70% to 97% by weight. ordinary diluted o / w microemulsion.

As is clear from the above description, the diluted microemulsion (o / w) liquid all-purpose cleaners of the invention are particularly effective when used as such, i.e. without further dilution with water, since the properties of the o / w microemulsion are best seen in the form of undiluted. However, depending on the level of surfactants, co-surfactants, fragrances and other ingredients, some degree of dilution is possible without destroying the microemulsion. For example, with a favorable low level of active surfactants (i.e. mainly anionic and nonionic detergents), dilution of up to about 50% will usually be tolerated and will not result in phase separation, i.e. the microemulsion state will be maintained.

However, even a highly diluted agent, e.g. 2-10 times or more, will still be effective in removing greasy, oily or other types of soil. In addition, the presence of magnesium ions or other multivalent ions, e.g. aluminum, as described in detail hereinafter, serves to enhance the cleaning capacity of the main detergents when used in a dilute state.

On the other hand, highly concentrated microemulsions which are diluted with additional water before use are also within the scope of the invention.

The invention also relates to a stable concentrated microemulsion or acidic microemulsion agent containing approximately by weight:

180 132

a) 0% to 6% of an anionic surfactant;

b) 0.1 to 20% of a mixture of fully esterified ethoxylated polyols, partially esterified ethoxylated polyols and non-esterified ethoxylated polyols;

c) 0.1% to 50% co-surfactant;

d) 0.4% to 10% of a water-insoluble hydrocarbon or fragrance;

e) 0% to 18% of at least one mono- or dicarboxylic acid;

f) 0% to 1% phosphoric acid;

g) 0% to 0.2% of aminoalkylene phosphonic acid;

h) 0% to 15% magnesium sulfate heptahydrate;

i) 0% to 16% of a non-ionic surfactant;

j) 0% to 8% of an alkali metal salt of a dialkylsulfosuccinate and

k) water in a supplementary quantity.

Such concentrated microemulsions can be diluted by mixing with water in an amount up to about 20 times or more, preferably about 4 to about 10 times their weight, and produce o / w microemulsions similar to the dilute microemulsion agents described above. Although the degree of dilution is chosen so as to obtain an o / w microemulsion upon dilution, both the microemulsion and the non-microemulsion occur sequentially upon dilution.

In addition to the essential ingredients described above that are required to form the microemulsion agent, the agent of the invention can often and preferably does contain one or more additional ingredients that serve to improve the overall product characteristics.

One such component is an inorganic or organic salt or oxide with a multivalent metal cation, especially Mg3. The metal salt or oxide offers significant benefits including better cleaning ability when using dilute agents, especially with soft water, and less perfume is then needed to create a microemulsion state. As the magnesium salt, magnesium sulfate, either anhydrous or hydrated (e.g. heptahydrate) is particularly preferred. Good results are also obtained with magnesium oxide, magnesium chloride, magnesium acetate, magnesium propionate and magnesium hydroxide. These magnesium salts can be used at the neutral or acidic pH of the agent as magnesium hydroxide will not precipitate at these pH values.

While magnesium is the preferred multivalent metal from which salts (including oxide and hydroxide) are formed, other polyvalent metal ions may also be used provided the salts thereof are non-toxic and are soluble in the aqueous phase of the system at the desired pH level. Thus, depending on factors such as the pH of the system, the nature of the major surfactants and co-surfactants, etc., as well as the availability and cost, other multivalent metal ions may be suitable which include aluminum, copper, nickel, iron, calcium, etc. note that, for example, in the presence of the preferred paraffosulfonate or alkyl sulfate anionic detergent, calcium salts will precipitate and should not be used. Aluminum salts have also been found to perform best at a pH below 5, or when little, e.g., about 1 wt.%, Has been added to the agent intended to be neutral pH. citric acid. Alternatively, in such a case, the aluminum salt can be directly added in the form of the citrate. As the salt, salts with anions of the same general class as for magnesium salts can be used, such as halide (e.g. bromide, chloride), sulfate, nitrate, hydroxide, oxide, acetate, propionate, etc.

Preferably, in the case of dilute media, a metal compound is added in an amount sufficient to provide an at least stoichiometric ratio of equivalents between the anionic surfactant and the multivalent metal cation. For example, for every gramion of Mg ⁺⁺ there will be 2 gmoles of paraffosulphonate, alkyl benzene sulphonate, alkyl sulphate, etc., while for each Al ³⁺ gion there will be 3 gmoles of anionic surfactant. Thus, the amount of the multivalent salt will usually be selected such that one equivalent

The compound will neutralize from 0.1 to 1.5 equivalents, preferably 0.9 to 1.4 equivalents, of the acid form of the anionic detergent.

At higher anionic detergent concentrations, the amount of multivalent salt is in the range of 0.5 to 1 equivalent per equivalent of the anionic detergent.

The o / w microemulsion agent may also contain from 0% to 2.5%, preferably from 0.1% to 2.0% by weight. a C ₈ -C ₂₂ fatty acid composition or fatty acid soap as foam depressant. The addition of fatty acid or fatty acid soap improves the flushability of the undiluted or diluted product. Typically, however, when the composition comprises fatty acid or soap, the co-surfactant content must be increased to maintain the stability of the product.

As an example of fatty acids that can be used as such or in the form of soap, distilled coconut oil fatty acids, "mixed vegetable" type fatty acids (eg containing a high percentage of saturated, mono and / or polyunsaturated C ₁₈ chains); oleic acid, stearic acid, palmitic acid, ejicosanoic acid and the like, usually those fatty acids having 8 to 22 carbon atoms are preferred.

The all-purpose liquid cleaner according to the invention may, if desired, also contain other ingredients that provide additional effects or make the product more attractive to the consumer. Examples include: coloring agents or dyes up to 0.5 wt.%, Bactericides up to 1 wt.%, Preservatives or antioxidants, such as formalin, 5-chloro-2-methyl-4-isothiazolin-3. -one, 2,6-di-tert-butyl-p-cresol etc. in an amount up to 2 wt.%, and pH adjusting agents such as sulfuric acid or sodium hydroxide as required. In addition, if the agent is to be opaque, it may contain up to 4 wt.% Of an opacifying agent.

The compositions according to the invention do not contain alkali metal silicates or alkali metal salts which are builders for detergents such as alkali metal phosphonates, alkali metal carbonates, alkali metal polyphosphates or alkali metal citrates, because the compositions containing these compounds are too corrosive and their remnants remain on the cleaned surfaces.

The compositions according to the invention do not contain betaine surfactants because the foam profile of the compositions containing them would be too high. The concentration of the fatty acid in the compositions according to the invention must be lower than 2.5 wt.%, Because at concentrations higher than 2.5 wt.%. the inside would have a bad smell. The compositions according to the invention do not contain methanol or ethanol due to their extremely low flash point.

In their final form, all-purpose liquids are clear oil-in-water microemulsions and are stable at low and elevated temperatures, in particular, remain clear and stable at temperatures ranging from 5 ° C to 50 ° C, especially from 10 ° C to 43 ° C. Such agents have a pH range of acidic or neutral, depending on the end use. Such liquids are pourable and have a viscosity in the range of 6 to 60 mPa s as measured at 25 ° C with a Brookfield RVT viscometer with a No. 1 spindle rotating at 20 rpm. Preferably, the viscosity is kept in the range of 10 to 40 mPa s.

The products are ready-to-use or can be diluted if necessary and in any case do not require or require only minimal rinsing and leave essentially no residue or streaks after cleaning. Moreover, since the agents do not contain detergent builders such as alkali metal polyphosphates, they are ecologically acceptable and give a better shine to the cleaned hard surfaces.

Liquid agents to be used undiluted can be packaged under pressure in aerosol canisters or in pump or "trigger" type sprayers. spray and wipe application.

Since the compositions are aqueous liquid agents and no special mixing is required to form an o / w microemulsion, the compositions are readily prepared simply by combining all ingredients in a suitable vessel or container. The order in which the ingredients are mixed is not particularly important, and usually different ingredients can be added

In sequence, or all at once, or each as an aqueous solution, or primary detergents and co-surfactants may be prepared separately and combined with each other and with the fragrance. If a magnesium salt or other multivalent metal compound is used, it can be added as an aqueous solution or directly. No elevated temperature is necessary for the production, room temperature is sufficient.

Also within the scope of the invention is the possibility of using esterified ethoxylated glycerol compounds in hard surface cleaners such as wood surface cleaners, window cleaners, mild liquid cleaners as substitutes for wholly or partially anionic and / or nonionic surfactants when it is necessary to improve greasy dirt release effect.

The following examples illustrate the liquid cleaners of the invention. The agents in the examples are provided for the purpose of illustration only and are not intended to limit the scope of the invention. Unless otherwise stated, the proportions in the examples and throughout the specification are percentages by weight.

Example 1 The following compositions were prepared with the composition given in% by weight:

AND B C. D Ajax Frais Magnesium lauryl sulfate 0.1 The non-ionic surfactant Neodol 45-7 2.0 1.2 Esterified polyethoxyether-thone surfactant Levenol F200 4.0 4.5 3.6 4.5 Sodium dioctylsulfosuccinate 1.5 1.5 Diethylene glycol monohexyl ether 3 3 3 4 PKO tallow soap 0.2 0.15 MgSO ₄ -7H ₂ O 0.25 0.5 0.25 Fragrance Nicky LCV (a) 0.8 0.8 0.8 0.8 Lauryl Sulfate - Na 1.2 Dodecan 0.2 0.15 Water + secondary additives Ball. Ball. Ball. Ball. pH 7 7 7 7 Fat absorption test Undiluted (b) 10 strokes 80 100 40 100 100 Dilute, (b) 50 strokes 50 40 35 40 35

Ball. = in the supplementary amount (a) about 25 wt. terpenes (b) higher washing percentage, better degreasing

The cleaning performance was tested according to the following procedure:

The 15 cm x 15 cm white Formica ceramic tiles were washed with soap and warm water, rinsed with deionized water and finally with ethanol, then dried at room temperature for at least 4 hours. After a single use, the plates were discarded. They were sprayed with a chloroform solution of dye and fat using a laboratory chromatographic sprayer. Compressed air at approximately 30 psi was used for the spraying. The spray solution is prepared with the following ingredients:

180 132 for the undiluted agent: 5% hard tallow, 5% soft tallow, 0.01% D&C Red 17 in chloroform; for the diluted agent: 1.0% of hard tallow, 1.0% of soft tallow, 0.01% of D&C red 17. To facilitate the preparation of the soil, first make a stock solution of 1% of the dye in chloroform so that 1.0 g of such a solution is in 100 g it gave the correct final dye concentration. The plates were sprayed to such an extent that their reflectance (Rd) was 63-70. The plates were left for 15 minutes after spraying to evaporate the chloroform.

The soiled plates were placed in a Gardner Abrader equipped with a two-track two-boat sleigh. Squeezed sponges were put into two boats. Each boat was filled with 300 g of lead shot, which provided equal pressure to each sponge.

1.2% solutions with two recipes were prepared for the dilute cleanup test and approximately 50 ml of each solution was placed in separate 14 cm x 7 cm Pyrex glass vessels. A boat was placed in each solution with a compressed sponge inserted into it. The sponges were left for 1-2 minutes to saturate with the solution, then the excess solution was removed by rubbing the sponge against the edge of the vessel. The boats were placed in the sled of the abrasive device and set for 15 strokes. The boats were removed, the sponges squeezed against the edge of the sink and re-saturated with fresh solution from the vessel. The excess was removed and the abrasion process was repeated. This cycle of 15 strokes was repeated up to a total of 105 strokes. Before and after staining, and after each 15 strokes, the Rd value of the plaques was read with a Photovolt model 575 reflectometer. The Pd value was read without removing the plaques from the instrument. The values for three areas on each cleaned surface were read and averaged.

For the undiluted cleaning test, compressed sponges were placed in two boats and placed in separate 14 cm x 7 cm Pyrex vessels filled with approximately 50 ml of tap water. The sponges were allowed to saturate with water and the excess was removed by rubbing the sponge against the rim of the vessel. On each sponge, 1.0 ml of one of the two cleaning agents was placed. The boats were placed in a scrubber and set for 1, 3, 5, 10, 20, 35, and 50 strokes with intervals between cycles for measuring Rd. The readings, as before, were taken without removing the plates from the device. Three values were read for three areas of each part cleaned and averaged. The solution was not refilled during the test.

The purification degree in% was calculated according to the following equation:

% oc puppy - ^re ^ ^e ^ ^tanc J ^{a of} the cleaned plate - reflectance of the dirty plate * reflectance of the dirty plate - reflectance of the dirty plate

In summary, the described invention generally relates to the improvement of microemulsion agents containing an anionic surfactant, an esterified ethoxylated glycerin type component, one of certain co-surfactants, a hydrocarbon component and water, which consists in the use of a water-insoluble odorizing fragrance as the essential hydrocarbon component in an amount sufficient to form a dilute o / w microemulsion containing 0.1 to 6.0 wt.%. % of an anionic detergent, 0% to 16 wt. nonionic surfactant, 0.1% to 20% by weight of an esterified ethoxylated glycerin type component, 0.1% to 50% by weight. co-surfactant, 0.4% to 10% by weight fragrance or hydrocarbon and replenishment water.

180 132

R '

CH ₂ -04CH ₂ CH-0 -) - _x B

R ¹

[CH-04CH ₂ CH-04yB] _w

R 'ch ₂ -o + ch ₂ ch-o-w

Formula 1

R 'ch ₂ -o-ch ₂ -h-ooh

R '

[CH-O-i CH ₂ CH-OHyH] _w

R '

And ch ₂ -ch ₂ ch-o

Formula 2

180 132

Formula 3

Formula 4

Pattern

Publishing Department of the UP RP. Circulation of 70 copies. Price PLN 4.00.

Claims (26)

Patent claims 1. Micro-emulsion universal liquid cleaner, containing an anionic surfactant, non-ionic surfactant, co-surfactant, hydrocarbon component, water and optionally other additional ingredients, characterized in that it contains by weight: 0.1% to 6% anionic surfactant, 0% to 16 % non-ionic surfactant, 0.1% to 50% co-surfactant, 0.1% to 20% of a mixture of a compound of formula 1 and a compound of formula 2 where w is equal to 1-4, B is selected from the group consisting of hydrogen and Formula 3 wherein R is an alkyl group of 6 to 22 carbon atoms or an alkenyl group of 6 to 22 carbon atoms, at least one of the groups B is represented by the formula 4; R 'is hydrogen or the methyl group x, y and z are 0-60, provided that (x + y + z) = 2 to 100, with the monoester / diester / triester ratio in formula 1 being 40 to 90/5 to 35/1 to 20, and the ratio of the amount of the compound of formula 1 to the compound of formula 2 is in the range of 3-0.02; and contains 0.4% to 10% of at least one water-insoluble hydrocarbon and / or fragrance and a replenishment amount of water. 2. Hard surface cleaner, containing an anionic surfactant, non-ionic surfactant, co-surfactant, hydrocarbon component, water and optionally other additives, particularly effective at removing oily and greasy soil, in the form of an oil-in-water microemulsion, characterized in that the water phase of this of the emulsion contains by weight: 0.1% to 6% anionic surfactant, 0% to 16% non-ionic surfactant, 0.1% to 20% of a mixture of a compound of formula 1 and a compound of formula 2 in which w is equal to 1-4 , B is selected from the group consisting of hydrogen and the group of formula 3 in which R is an alkyl group of 6 to 22 carbon atoms or an alkenyl group of 6 to 22 carbon atoms, at least one of the groups B being represented by formula 4; R 'is hydrogen or the methyl group x, y and z are 0-60, provided that (x + y + z) = 2 to 100, with the monoester / diester / triester ratio in formula 1 being 40 to 90/5 to 35/1 to 20, and the ratio of the amount of the compound of formula 1 to the compound of formula 2 is in the range of 3-0.02; and contains from 0.1% to 50% of a co-surfactant, which is substantially incapable of dissolving oily or greasy soil, selected from the group consisting of C ₃ -C ₅ alcohols, polypropylene glycol and C 1-8 alkyl ethers and esters of ethylene or propylene glycol, aliphatic acids mono- and dicarboxylic acids containing 3 to 6 carbon atoms per molecule and mono-, di- and triethyl phosphate and water; and the oil phase of the microemulsion consists essentially of at least one water-immiscible or poorly water-soluble hydrocarbon component in an amount of 0.1% to 10% by weight. entire composition. 3. The agent according to claim The method of claim 2, further comprising a salt or oxide of the multivalent metal cation to provide 0.5 to 1.5 equivalents of cation per equivalent of anionic detergent. 4. The agent according to claim 1 The process of claim 3, wherein the multivalent metal cation salt or oxide is a magnesium or aluminum salt or oxide. 5. The agent according to claim 1 The process of claim 3, comprising 0.9 to 1.4 equivalents of cation per one equivalent of anionic detergent. 6. The agent according to p. The process of claim 4, wherein the multivalent metal salt is magnesium sulphate or the polyvalent metal oxide is magnesium oxide. 7. The agent according to p. The co-surfactant of claim 2, wherein the co-surfactant is a fatty acid having about 8 to about 22 carbon atoms. 8. The agent according to claim 1 The process of claim 2, characterized in that it contains from about 0.5% - 15% by weight of co-surfactant and from about 0.4% to about 3.0% by weight. hydrocarbon. 9. The agent according to claim 1 A process according to claim 2, characterized in that the co-surfactant is a glycol ether whose alkyl chain has 1 to 6 carbon atoms. 180 132 10. The agent according to claim 1 The process of claim 9, wherein the glycol ether is selected from the group consisting of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, polypropylene glycol with an average molecular weight of about 200 to 1000, ethylene glycol monohexyl ether, diethylene glycol monobutyl ether triethylene glycol monohexyl ether and propylene glycol t-butyl ether; and mono-, di- and tripropylene glycol monobutyl ether. 11. The agent according to claim 1 The process of claim 10, wherein the glycol ether is ethylene glycol monobutyl ether, diethylene glycol monobutyl ether or ethylene glycol monohexyl ether. 12. An agent according to claim 1 The process of claim 2, wherein the anionic surfactant is a C ₉ -C ₁₅ alkyl benzene sulphonate or a C ₁₀ -C ₂₀ alkyl sulphonate. 13. A concentrated microemulsion cleaner containing an anionic surfactant, a non-ionic surfactant, a co-surfactant, a hydrocarbon component, water and optionally other additional ingredients, characterized in that it comprises in% by weight: a) 1% to 30% of an anionic surfactant; b) 0.1% to 20% of a mixture of a compound of Formula 1 and a compound of Formula 2 wherein w is equal to 1-4, B is selected from the group consisting of hydrogen and Formula 3 where R is an alkyl group of 6 up to 22 carbon atoms or an alkenyl group of 6 to 22 carbon atoms, at least one of the groups B is represented by the formula 4; R 'is hydrogen or methyl, x, y and z are 0-60, provided that (x + y + z) = 2 to 100, the monoester / diester / triester ratio in formula 1 is 40 to 90/5 to 35/1 to 20, and the ratio of the amount of the compound of formula 1 to the compound of formula 2 is in the range 3-0.02; c) 0.1% to 50% co-surfactant; d) 0.4% to 10% of at least one water-insoluble hydrocarbon or fragrance; e) 0% to 18% of at least one mono- or dicarboxylic acid; f) 0% to 0.2% of aminoalkylene phosphonic acid; g) 0% to 1.0% phosphoric acid; h) 0% to 15% magnesium sulfate heptahydrate; i) 0% to 16% of a non-ionic surfactant i j) water in a supplementary quantity. 14. A microemulsion cleaner comprising an anionic surfactant, a nonionic surfactant, a co-surfactant, a hydrocarbon component, water and optionally other adjunct ingredients, characterized in that it comprises by weight%: 0.25% to 8% of a dialkyl sulfosuccinate alkali metal salt; 0.1% to 50% co-surfactant; 0.1% to 20% of a mixture of a compound of Formula 1 and a compound of Formula 2 wherein w is equal to 1-4, B is selected from the group consisting of hydrogen and Formula 3 in which R is an alkyl group of 6 to 22 carbon atoms or an alkenyl group of 6 to 22 carbon atoms, at least one of the groups B is represented by the formula 4; R 'is hydrogen or methyl, x, y and z are 0-60, provided that (x + y + z) = 2 to 100, the monoester / diester / triester ratio in formula 1 is 40 to 90/5 to 35/1 to 20, and the ratio of the amount of the compound of formula 1 to the compound of formula 2 is in the range 3-0.02; 0.4% to 10% of at least one water-insoluble hydrocarbon and / or fragrance, and a make-up amount of water. 15. A transparent all-purpose cleaner for hard surfaces, containing an anionic surfactant, non-ionic surfactant, co-surfactant, hydrocarbon component, water and possibly other additional ingredients, particularly effective at removing oily or greasy dirt, in the form of an oil-in-water microemulsion, characterized in that the phase the aqueous microemulsion comprises by weight% from 0.25% to 8% of an alkali metal salt of a dialkylsulfosuccinate; 0.1% to 20% of a mixture of a compound of Formula 1 and a compound of Formula 2 wherein w is equal to 1-4, B is selected from the group consisting of hydrogen and Formula 3 in which R is an alkyl group of 6 to 22 carbon atoms or an alkenyl group of 6 to 22 atoms Carbon 180 132, wherein at least one of groups B is represented by Formula 4; R 'is hydrogen or methyl, x, y and z are 0-60, provided that (x + y + z) = 2 to 100, the monoester / diester / triester ratio in formula 1 is 40 to 90/5 to 35/1 to 20, and the ratio of the amount of the compound of formula 1 to the compound of formula 2 is in the range 3-0.02; 0.1% to 50% of a water-miscible co-surfactant which is substantially incapable of dissolving oily or greasy soil, selected from the group consisting of C ₃ -C ₅ alcohols, polypropylene glycol and C ₁ -C ₆ alkyl ethers and ethylene glycol esters or propylene, aliphatic mono- and dicarboxylic acids with 3 to 6 carbon atoms per molecule and mono-, di- and triethyl phosphate and water; and the oil phase of the microemulsion consists essentially of at least one water-immiscible or poorly water-soluble hydrocarbon component in an amount of 0.1% to 10% by weight. entire composition. 16. An agent according to claim 1 The process of claim 15, further comprising a salt of the multivalent metal cation in an amount to provide 0.5 to 1.5 equivalents of cation per equivalent of anionic detergent. 17. The agent according to claim 1 The process of claim 16, wherein the multivalent metal cation salt or oxide is a magnesium or aluminum salt or oxide. 18. The agent according to claim 1 The process of claim 16, comprising 0.9 to 1.4 equivalents of cation per one equivalent of anionic detergent. 19. The agent according to claim 1 The method of claim 17, wherein the multivalent metal salt is magnesium sulphate or the polyvalent metal oxide is magnesium oxide. 20. The agent according to claim 1 The co-surfactant of claim 15, wherein the co-surfactant is a fatty acid having about 8 to about 22 carbon atoms. 21. An agent according to claim 1 The method of claim 15, comprising from about 0.5% to 15% by weight of co-surfactant and from about 0.4% to about 3.0% by weight. hydrocarbon. 22. An agent according to claim 22 The process of claim 15, wherein the co-surfactant is a glycol ether whose alkyl chain has 1 to 6 carbon atoms. 23. The agent according to claim 1 The method of claim 22, wherein the glycol ether is selected from the group consisting of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, polypropylene glycol with an average molecular weight of about 200 to 1000, ethylene glycol monohexyl ether, diethylene glycol monobutyl ether triethylene glycol monohexyl ether and propylene glycol t-butyl ether; and mono-, di- and tripropylene glycol monobutyl ether. 24. An agent according to claim 24 The process of claim 23, wherein the glycol ether is ethylene glycol monobutyl ether, diethylene glycol monobutyl ether or ethylene glycol monohexyl ether. 25. The agent according to claim 25 The process of claim 15, wherein the alkali metal salt of the dialkyl sulfosuccinate is a lithium, potassium, or sodium salt, and each alkyl group in the salt contains about 4 to about 12 carbon atoms. 26. A concentrated microemulsion cleaner containing an anionic surfactant, non-ionic surfactant, co-surfactant, hydrocarbon component, water and optionally other additional ingredients, characterized in that it comprises in% by weight: a) 0.1% to 20% of a mixture of a compound of formula 1 and a compound of formula 2 in which w is equal to 1-4, B is selected from the group consisting of hydrogen and a group of formula 3 in which R is an alkyl group of 6 up to 22 carbon atoms or an alkenyl group of 6 to 22 carbon atoms, at least one of the groups B is represented by the formula 4; R 'is hydrogen or methyl, x, y and z are 0-60, provided that (x + y + z) = 2 to 100, the monoester / diester / triester ratio in formula 1 is 40 to 90/5 to 35/1 to 20, and the ratio of the amount of the compound of formula 1 to the compound of formula 2 is in the range 3-0.02; b) 0.1% to 50% co-surfactant; c) 0.4% to 10% of at least one water-insoluble hydrocarbon or fragrance; d) 0% to 18% of at least one mono- or dicarboxylic acid; 180 132 e) 0% to 0.2% of aminoalkylene phosphonic acid; f) 0% to 1.0% of phosphoric acid; g) 0% to 15% magnesium sulfate heptahydrate; h) 0.25% to 8% of an alkali metal salt of a dialkylsulfosuccinate where each alkyl group contains 4 to 12 carbon atoms and the alkali metal is lithium, potassium or sodium; and i) water in a supplementary quantity. * * *