RU2147312C1 - All-purpose microemulsion liquid cleansing compositions - Google Patents

Abstract

FIELD: household chemical goods. SUBSTANCE: cleansing compositions especially effective in removal of oil and fat pollution and possessing confirmed fat-repulsing effect contain, wt.%: anionic surfactant 1-20; secondary surfactant 0.1-50; compound of ethoxylated glycerol type 0.1- 20; hydrocarbon odorant 0.4-10 (amount required to form iluted oil-in-water type emulsion); water, the balance. EFFECT: improved interface tension and degreasing effect. 16 cl, 8 ex

Description

FIELD OF THE INVENTION
The invention relates to an improved universal liquid cleaning agent in the form of a liquid crystal or microemulsion, intended, in particular, for cleaning hard surfaces, which is effective in removing grease and / or contaminants on the walls of bathtubs while preserving the gloss of surfaces that have not been washed.

BACKGROUND OF THE INVENTION
In recent years, widespread use for cleaning hard surfaces, such as painted wooden products and panels, tiled walls, basins, bathtubs, linoleum or tiled floors, washable wallpaper, etc., have received universal liquid detergents. Such universal liquids contain transparent and opaque aqueous mixtures of water-soluble synthetic organic detergents and water-soluble detergent auxiliary salts. To provide a cleaning effect comparable to the cleaning effect of granular or powdery universal cleaning compositions, water-soluble inorganic auxiliary components in the form of phosphate salts were used predominantly in known universal liquids. Such known phosphate-containing compositions are described in U.S. Pat.

 Thanks to the efforts of environmentalists to reduce the level of phosphate in groundwater, improved universal fluids have appeared that contain lower concentrations of inorganic phosphate or non-phosphate auxiliary salts. A particularly useful self-dulling fluid of the latter type is described in US Pat. No. 4,244,440.

 However, these well-known universal liquid detergents containing detergent auxiliary salts or other equivalents tend to leave films, stains or streaks on cleaned surfaces that have not been washed, in particular on shiny surfaces. Therefore, such liquids require thorough washing of the cleaned surfaces, which leads to a large investment of time.

 To eliminate this drawback of the known universal fluid, US Pat. No. 4,017,409 proposes to use a mixture of an alkyl sulfonate and an inorganic auxiliary component in the form of a phosphate salt having a reduced concentration. However, due to the phosphate content, such compositions are not entirely acceptable from an environmental point of view. On the other hand, an alternative way to obtain universal phosphate-free liquids consists, as described in US Pat. No. 3,935,130, in the use of a mixture consisting mainly of anionic and nonionic detergents with small amounts of a solvent in the form of a dihydric alcohol ester and an organic amine. This approach is also not entirely satisfactory, and the high levels of organic detergents needed to ensure purification cause foaming, which in turn leads to the need for thorough washing, which has been found to be undesirable for current customers.

в непрерывной водной фазе.Another approach to the preparation of a liquid detergent composition for cleaning hard surfaces or universal, when the homogeneity and transparency of the product are important factors, is the formation of oil-in-water (m / v) microemulsions containing one or more surface-active detergent compounds, immiscible a solvent with water (usually a hydrocarbon solvent) and a secondary surfactant to ensure product stability. By definition, m / in microemulsion is a spontaneously formed colloidal dispersion of particles of the "oil" phase, having a size in the range of 25-800

in a continuous aqueous phase.

 Due to the very small size of the dispersed particles of the oil phase, the microemulsion is permeable to light and therefore transparent and usually highly resistant to phase separation.

 Descriptions of inventions regarding the use of degreasing solvents include, for example, descriptions of European Patent Applications EP 0137615 and EP 0137616 (Herbots et al.), EP 0 160 762 (Johnston et al.) And US Pat. No. 4,561,991 (Herbots et al.) . Each of these descriptions also suggests the use of at least 5% by weight of a degreasing solvent.

 It is also known from the description of GB 2144763A (Herbots et al.) For a UK patent published March 13, 1985 that magnesium salts enhance the degreasing effect of organic degreasing solvents such as terpenes in liquid detergent compositions in the form of m / v microemulsions. The compositions of this invention described by Herbots et al. Require at least 5% of a mixture of a degreasing solvent and a magnesium salt, and preferably at least 5% of a solvent (which may be a mixture of a water-immiscible non-polar solvent with a mildly soluble slightly polar solvent) and at least 0.1% magnesium salt.

 However, since the amount of water-immiscible and moderately soluble components that may be present in m / v microemulsions, with a low total content of active ingredients without reducing the stability of the microemulsion, is somewhat limited (for example, up to 18% by weight of the aqueous phase), the presence of such large amounts of degreasing solvent will reduce the total amount of fatty or oily contaminants that can be perceived by the microemulsion without phase separation.

 The following representative previously issued patents also apply to liquid detergent and cleaning compositions in the form of m / v microemulsions: US Pat. Nos. 4,472,291 (Rosario), N 4,540,448 (Gauteer et al.), N 3,723,330 (Sheflin), etc.

Liquid detergent compositions containing terpenes, such as d-limonene, or another degreasing solvent, although not disclosed as m / v microemulsions, are the subject of the following representative patent documents: European Patent Application No. 0080749, UK Patent Description N 1603047, patents N 4414128 and N 4540505. For example, in US patent N 4414128 widely disclosed aqueous liquid detergent composition containing (by weight):
(a) from 1% to 20% of a synthetic anionic, nonionic, amphoteric or zwitterionic surfactant or mixture of these substances;
(b) from 0.5% to 10% of mono- or sesquiterpene or a mixture thereof in a mass ratio of (a) :( b) in the range from 5: 1 to 1: 3;
(c) from 0.5% to 10% of a polar solvent having a solubility in water at 15 ^° C. in the range of 0.2% to 10%. Other components present in the compositions are disclosed in this patent and include from 0.05% to 2% by weight of alkali metal, ammonium or alkanolammonium soap C ₁₃ -C ₂₄ fatty acids; calcium sequestrant from 5% to 13% by weight; non-aqueous solvent, for example alcohols and glycol ethers up to 10% by weight; and hydrotropes, for example urea, ethanolamines, salts of lower alkylarylsulfonates up to 10% by weight. All of these compositions presented in the examples of the description of this patent include relatively large amounts of detergent auxiliary salts, which are harmful to the gloss of the surface.

 In addition, as established by these inventors, in compositions containing degreasing magnesium compounds, the addition of minor amounts of auxiliary salts, such as alkali metal polyphosphates, alkali metal carbonates, nitrilotriacetic acid salts, etc., makes it difficult to form stable microemulsion systems.

 US Pat. No. 5,082,584 discloses a microemulsion composition comprising an anionic surfactant, a secondary surfactant, a nonionic surfactant, perfume and water, but such compositions do not have low ecotoxicity and better interfacial tension properties as the compositions of the present invention .

 British Patent No. 1453385 discloses polyesterified nonionic surfactants similar to the polyesterified nonionic surfactants of the present invention. But these non-ionic surfactants from UK patent N 1453385 do not disclose that part of the proposed composition, which is represented by formula (II). In addition, in the compositions of the compositions described in British patent N 1453385, not disclosed important limitations (limits) described in the present invention.

 A number of patents describe esterified ethoxylated glycerol compounds for various applications. These publications include UK patent N 1453385, Japanese patent N 59-1600 and Japanese patent 58-206693, as well as European patent application N 0586323A1. Nothing is said in these publications that the mixture of esterified ethoxylated glycerol and unesterified ethoxylated glycerin acts as a grease repellent when used in a composition for cleaning hard surfaces.

Summary of the invention
The present invention provides an improved transparent liquid cleaning composition having improved interfacial tension increasing the quality of cleaning a hard surface in the form of a liquid crystal or microemulsion, which (composition) is suitable for cleaning hard surfaces such as plastic, glass and metal surfaces with a finish to shine. In particular, the improved cleaning compositions have good degreasing properties due to improved interfacial tension when used undiluted (pure) and leave the cleaned surfaces shiny without requiring or requiring only minimal additional rinsing or wiping. The last feature is indicated by the presence of minor visible residual traces or their absence on unwashed cleaned surfaces and, therefore, this distinguishing feature eliminates one of the disadvantages of the known products. The compositions of the invention have a grease repellent effect in that they prevent or reduce the possibility of fixing fatty contaminants on surfaces that have already been cleaned with the compositions as compared to surfaces that have been cleaned with a liquid crystal composition or a commercially available microemulsion composition, which means that with subsequent cleanings, it will be easier to clean the surface contaminated with fat. Surprisingly, these desirable results are achieved even in the absence of polyphosphate or other inorganic or organic auxiliary salts, as well as in the complete or almost complete absence of a degreasing solvent.

 The compositions of the present invention are more environmentally friendly due to the low ecotoxicity of the ethoxylated glycerol compounds used in the compositions of the invention.

 The compositions of the present invention have ecotoxicity measured according to the LC 50 test recommended by the Organization for Economic Co-operation and Development (OECD) (of which the United States of America is a member) in the OECD Test N 202, at least 0.18 ml / l when measured on such microorganisms like daphnia (Daphniae).

In one embodiment of the present invention, there is generally provided a stable, transparent, universal, cleansing composition for cleaning hard surfaces, particularly effective in removing oil and grease contaminants, which is in the form of a thoroughly diluted oil-in-water microemulsion having an aqueous and an oil phase. Diluted m / in microemulsion contains (by weight):
0.1 to 20% of anionic surfactant;
0.1 to 50% of a water-miscible secondary surfactant having limited ability or essentially incapable of dissolving oil or grease contaminants;
0.1 to 20% of a compound that is a mixture of a partially esterified ethoxylated polyhydric alcohol, a fully esterified ethoxylated polyhydric alcohol and a non-esterified ethoxylated polyhydric alcohol (this mixture is hereinafter referred to as a compound of the type ethoxylated glycerol);
0 - 15% magnesium sulfate heptahydrate;
0.1 - 10% of perfume or water-insoluble hydrocarbon;
10 - 85% water
moreover, the indicated proportions are taken from the total weight of the composition.

In another embodiment of the present invention, there is generally provided a stable, transparent, universal, cleansing composition for cleaning hard surfaces, particularly effective in removing oil and grease contaminants, which is in the form of a thoroughly diluted oil-in-water microemulsion having an aqueous and an oil phase. The aqueous phase of the diluted m / in the microemulsion contains (by weight):
0.1 to 20% of anionic surfactant;
0.1 to 50% of a water-miscible secondary surfactant having limited ability or essentially incapable of dissolving oil or grease contaminants;
0.4 - 1.0% of trialkyl ester of citric acid;
0.1 to 10% of a mixture of partially esterified ethoxylated polyhydric alcohol, fully esterified ethoxylated polyhydric alcohol and unesterified ethoxylated polyol (this mixture is hereinafter referred to as a compound of the type ethoxylated glycerol);
0 - 15% magnesium sulfate heptahydrate;
0.4 - 10% of perfume or a water-insoluble hydrocarbon;
10 - 85% water
moreover, the indicated proportions are taken from the total weight of the composition.

где w = 1 - 4. Два символа B представляют водород, а один B выбран из группы, состоящей из группы, представленной формулой

где R выбран из группы, состоящей из алкильной группы

имеющей 6 - 22 углеродных атомов, более предпочтительно 11 - 15 углеродных атомов, и алкенильных групп, имеющих 6 - 22 углеродных атомов, из которых наиболее предпочтительной является алкильная цепь гидрогенизированного твердого жира или алкильная цепь кокосового масла, x, y и z имеют значения в пределах между 0 и 60, более предпочтительно между 0 и 40, при условии, что (x + y + z) = ~ 2 - 100. Эта композиция может также содержать 0 - 2 масс.% сложного диэфира этоксилированного многоатомного спирта, представленного формулой

где w = 1 - 4. Один символ B представляет водород, а два B выбраны из группы, состоящей из группы, представленной формулой

где R выбран из группы, состоящей из алкильной группы, имеющей 6 - 22 углеродных атомов, и алкенильных групп, имеющих 6 - 22 углеродных атомов, из которых наиболее предпочтительной является алкильная цепь гидрогенизированного твердого жира или алкильная цепь кокосового масла, x, y и z имеют значения в пределах между 0 и 60, при условии, что (x + y + z) = 2 - 100. Эта композиция может также содержать 0 - 1,0 масс.% сложного триэфира этоксилированного многоатомного спирта, представленного формулой

где w = 1 - 4. Три B выбраны из группы, состоящей из группы, представленной формулой

где R выбран из группы, состоящей из алкильной группы

имеющей 6 - 22 углеродных атомов, и алкенильных групп, имеющих 6 - 22 углеродных атомов, из которых наиболее предпочтительной является алкильная цепь гидрогенизированного твердого жира или алкильная цепь кокосового масла, x, y и z имеют значения в пределах между 0 и 60, при условии, что (x + y + z) = ~ 2 - 100.In another embodiment of the present invention, there is generally provided a stable transparent universal cleaning composition for cleaning hard surfaces, particularly effective in removing particulate contaminants, which is in the form of a thoroughly diluted oil-in-water microemulsion having an aqueous and an oil phase. Diluted m / in microemulsion contains (by weight):
0.1 to 20% of anionic surfactant;
0.1 to 50% of a water-miscible secondary surfactant having limited ability or essentially incapable of dissolving oil or grease contaminants;
0.1 - 20% ethoxylated polyhydric alcohol;
0 - 15% magnesium sulfate heptahydrate;
0.1 - 10% of perfume or water-insoluble hydrocarbon;
10 - 85% water
moreover, the indicated proportions are taken from the total weight of the composition. This composition may also contain 0 to 10% by weight of an ethoxylated polyhydric alcohol monoester represented by the formula

where w = 1 - 4. Two B symbols represent hydrogen, and one B is selected from the group consisting of the group represented by the formula

where R is selected from the group consisting of an alkyl group

having 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, of which the hydrogenated solid fat alkyl chain or the coconut oil alkyl chain are most preferred, x, y and z have the meanings between 0 and 60, more preferably between 0 and 40, provided that (x + y + z) = ~ 2-100. This composition may also contain 0-2 wt.% diester of ethoxylated polyhydric alcohol represented by the formula

where w = 1 - 4. One B symbol represents hydrogen, and two B are selected from the group consisting of the group represented by the formula

where R is selected from the group consisting of an alkyl group having 6 to 22 carbon atoms and alkenyl groups having 6 to 22 carbon atoms, of which the hydrogenated solid fat alkyl chain or the coconut oil alkyl chain, x, y and z are most preferred have values ranging between 0 and 60, provided that (x + y + z) = 2-100. This composition may also contain 0-1.0 wt.% of a complex of ethoxylated polyhydric alcohol represented by the formula

where w = 1 - 4. Three B are selected from the group consisting of the group represented by the formula

where R is selected from the group consisting of an alkyl group

having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, of which the hydrogenated solid fat alkyl chain or the coconut oil alkyl chain are most preferred, x, y and z are between 0 and 60, provided such that (x + y + z) = ~ 2 - 100.

 The dispersed oil phase m / in the microemulsion consists mainly of perfumes that are immiscible with water or sparingly soluble in water.

 It turned out quite unexpectedly that although the fragrance is not in itself a solvent for greasy or oily contaminations (despite the fact that some fragrances may contain up to 80% terpenes, which are known as good fat solvents), the proposed diluted formulations have the ability to solubilize up to 10 or more fragrance masses of oil and grease contaminants removed from the solid surface as a result of the action of anionic and nonionic surfactants, while these contaminants turn into aslyanuyu phase o / w microemulsion.

 In yet another embodiment of the present invention, there are generally provided highly concentrated microemulsion compositions in the form of either an oil-in-water microemulsion (m / v) or a water-in-oil microemulsion (v / m) which, when diluted with additional water, is used can form diluted m / in microemulsion compositions. Concentrated microemulsion compositions contain (by weight) 0.1 to 20% anionic surfactant, 0.1 to 20% of a compound such as ethoxylated glycerol, 0 to 2.5% fatty acid, 0.1 to 10% of perfume or insoluble in water of a hydrocarbon having 6 to 18 carbon atoms, 0.1 to 50% of a secondary surfactant, and 20 to 97% of water.

 In yet another embodiment of the present invention, there are provided liquid crystal compositions containing, by weight, 0.1 to 20% of anionic surfactant, 0.1 to 20% of a compound such as ethoxylated glycerol, 0 to 2.5% fatty acid, 0.1 to 10%, and more preferably 1-10%, perfumes, 1-50% of a secondary surfactant selected from the group consisting of propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether and mixtures thereof, and the rest is water.

 In another embodiment of the present invention, there are provided highly concentrated microemulsion compositions in the form of either an oil-in-water microemulsion (m / v) or a water-in-oil microemulsion (v / m) which, when diluted with additional water, can form diluted m / in microemulsion composition. Concentrated microemulsion compositions contain (by weight) 0.1 to 20% anionic surfactant, 0.1 to 20% of a compound such as ethoxylated glycerol, 0 to 2.5% fatty acid, 0.1 to 10% of perfume or insoluble in water of a hydrocarbon having 6 to 18 carbon atoms, 0.1 to 50% of a secondary surfactant, and 20 to 97% of water.

 In a further embodiment of the present invention, there are generally provided highly concentrated microemulsion compositions in the form of either an oil-in-water microemulsion (m / v) or a water-in-oil microemulsion (v / m) which, when diluted with additional water, can form diluted m / in microemulsion compositions. Concentrated microemulsion compositions contain (by weight) 0.1 - 20% anionic surfactant, 0.1 - 20% ethoxylated polyhydric alcohol, 0.1 - 10% perfume or a water-insoluble hydrocarbon having 6 to 18 carbon atoms, 0.1 - 50% of secondary surfactant and 20 - 97% of water.

 In yet another embodiment of the present invention, liquid crystal compositions are provided containing 0.1 to 20% by weight of anionic surfactant, 0.1 to 20% ethoxylated polyhydric alcohol, 0.1 to 10% perfume, 1 to 50% secondary surfactant and the rest is water.

DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a stable liquid crystal or microemulsion composition containing by weight 0.1 to 20% anionic surfactant, 0.1 to 50% secondary surfactant, 0.1 to 20% ethoxylated glycerol type compound, 0, 1-10% water-insoluble hydrocarbon, or perfume and the rest is water, the composition having an ecotoxicity value, measured according to the LC 50 test, of at least 0.18 ml / l when measured on microorganisms such as daphniae.

 The present invention also relates to a stable liquid crystal or microemulsion composition containing by weight 0.1 to 20% anionic surfactant, 0.1 to 50% secondary surfactant, 0.4 to 1.0% citric trialkyl ester an acid such as tri-n-butyl citrate, 0.1 to 20% of a compound such as ethoxylated glycerol, 0.1 to 10% of a water-insoluble hydrocarbon, or perfume and the rest is water, the composition having an ecotoxicity value measured according to the LC 50 test at least 0.18 ml / l with measurement on microorganisms such as daphnia (Daphniae).

где w = 1 - 4. Два символа B представляют водород, а один B выбран из группы, состоящей из группы, представленной формулой

где R выбран из группы, состоящей из алкильной группы

имеющей 6 - 22 углеродных атомов, и алкенильных групп, имеющих 6 - 22 углеродных атомов, из которых наиболее предпочтительной является алкильная цепь гидрогенизированного твердого жира или алкильная цепь кокосового масла, x, y и z имеют значения в пределах между 0 и 60, при условии, что (x + y + z) = ~ 2 - 100. Эта композиция может также содержать 0 - 2 масс.% сложного диэфира этоксилированного многоатомного спирта, представленного формулой

где w = 1 - 4. Один символ B представляет водород, а два B выбраны из группы, представленной формулой

где R выбран из группы, состоящей из алкильной группы

имеющей 6 - 22 углеродных атомов, и алкенильных групп, имеющих 6 - 22 углеродных атомов, из которых наиболее предпочтительной является алкильная цепь гидрогенизированного твердого жира или алкильная цепь кокосового масла, x, y и z имеют значения в пределах между 0 и 60, при условии, что (x + y + z) = ~ 2 - 100. Эта композиция может также содержать 0 - 1,0 масс.% сложного диэфира этоксилированного многоатомного спирта, представленного формулой

где w = 1 - 4. Три B выбраны из группы, состоящей из группы, представленной формулой

где R выбран из группы, состоящей из алкильной группы

имеющей 6 - 22 углеродных атомов, и алкенильных групп, имеющих 6 - 22 углеродных атомов, из которых наиболее предпочтительной является алкильная цепь гидрогенизированного твердого жира или алкильная цепь кокосового масла, x, y и z имеют значения в пределах между 0 и 60, при условии, что (x + y + z) = 2 - 100.The present invention also relates to a stable liquid crystal or microemulsion composition containing by weight 0.1 to 20% anionic surfactant, 0.1 to 50% secondary surfactant, 0.1 to 20% ethoxylated polyol, 0, 1 - 10% water-insoluble hydrocarbon, or perfume and the rest is water. This composition may also contain 0 to 10% by weight of an ethoxylated polyhydric alcohol monoester represented by the formula

where w = 1 - 4. Two B symbols represent hydrogen, and one B is selected from the group consisting of the group represented by the formula

where R is selected from the group consisting of an alkyl group

having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, of which the hydrogenated solid fat alkyl chain or the coconut oil alkyl chain are most preferred, x, y and z are between 0 and 60, provided that (x + y + z) = ~ 2 - 100. This composition may also contain 0 - 2 wt.% diester of ethoxylated polyhydric alcohol represented by the formula

where w = 1 - 4. One B symbol represents hydrogen, and two B are selected from the group represented by the formula

where R is selected from the group consisting of an alkyl group

having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, of which the hydrogenated solid fat alkyl chain or the coconut oil alkyl chain are most preferred, x, y and z are between 0 and 60, provided that (x + y + z) = ~ 2 - 100. This composition may also contain 0 - 1.0 wt.% diester of ethoxylated polyhydric alcohol represented by the formula

where w = 1 - 4. Three B are selected from the group consisting of the group represented by the formula

where R is selected from the group consisting of an alkyl group

having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, of which the hydrogenated solid fat alkyl chain or the coconut oil alkyl chain are most preferred, x, y and z are between 0 and 60, provided such that (x + y + z) = 2 - 100.

 In accordance with the present invention, a water-insoluble fragrance is a hydrocarbon. Typically, water-based compositions require the presence of solubilizers, such as alkali metal lower alkylaryl sulfonate hydrotrop, triethanolamine, urea, etc., to dissolve the perfume, in particular when the perfume content is 1% or higher, since perfumes are usually a mixture of aromatic essential oils and aromatic compounds, generally insoluble in water. Therefore, the inclusion in the aqueous cleaning composition of a perfume in the form of an oil (hydrocarbon) phase of the final m / in the microemulsion composition provides several different important advantages.

 Firstly, the cosmetic properties of the final cleansing composition are improved: the compositions are transparent (due to the formation of a microemulsion) and highly aromatic (due to the fragrance content).

 Secondly, it eliminates the need for solubilizers that do not contribute to the cleansing effect.

 Thirdly, an improved grease repellent effect and increased degreasing ability when used in a pure (undiluted) form of a diluted version of the composition or after reconstitution of the concentrate can be achieved without auxiliary components or buffers of detergents or traditional degreasing solvents or with neutral or acidic pH and at low levels of active components, although improved purification can be achieved by using a diluted version of the composition in diluted form.

 Used in the description and the proposed claims, the term "perfume" has the usual meaning, meaning any water-insoluble aromatic substance or a mixture of substances, including natural (i.e. obtained by extraction from flowering plants, herbs, flowers or other plants), artificial ( i.e. a mixture of natural oils or oil components) and synthetic odorous substances. Typically, perfumes are complex mixtures of various organic compounds such as alcohols, aldehydes, ethers, aromatics, and varying amounts of essential oils (e.g. terpenes), for example from 0% to 80% (by weight), and the essential oils themselves are volatile odorous compounds and also serve to dissolve other fragrance components.

 In the present invention, the exact composition of the perfume does not have a particular effect on the cleaning characteristics, as long as it satisfies the criteria of immiscibility with water and has a pleasant smell. Naturally, of course, especially for cleaning compositions intended for use in everyday life, the fragrance, as well as other components should be cosmetically acceptable, i.e. non-toxic, low allergenic, etc. The compositions of the present invention are noticeably less ecotoxic compared to existing commercial products.

 A hydrocarbon, such as a perfume, is present in a diluted m / in microemulsion in an amount of from 0.1% to 10% by weight. If the amount of hydrocarbon (perfume) is less than 0.4% by mass, then this makes it difficult to form m / in the microemulsion. In the case of a liquid crystal, at least 0.5 mass% of perfume is required. When hydrocarbon (perfume) is added in amounts exceeding 10% by weight, costs increase without any additional cleaning benefit and, in fact, with a slight decrease in cleaning ability, since the total amount of grease or oil contaminants that can turn into oil will be proportionally reduced microemulsion phase.

 In addition, although perfume compositions containing no terpene solvents provide an excellent degreasing effect, it is obvious that it is difficult for perfumers to make cheap perfume compositions for products of this type (i.e. products for which the consumer is very sensitive), which includes less 20%, usually less than 30%, of such terpene solvents.

 Therefore, practically, for economic reasons, diluted m / in microemulsion detergent and cleaning compositions of the present invention can often contain from 0.2% to 7% (of the total weight of the composition) of terpene solvents introduced into the composition as an integral part of perfume. However, even when the amount of the terpene solvent in the cleaning composition is less than 1.5% by weight, for example up to 0.6% or 0.4% or less, the proposed diluted m / in microemulsions provide a satisfactory ability to remove grease and oil contaminants.

 So for a typical composition of a diluted m / in microemulsion of the present invention, a 20-milliliter sample of m / in a microemulsion containing 1% (by weight) of perfume can solubilize, for example, up to 2 to 3 ml of fat and / or oil contaminants, while remaining in the form of a microemulsion, regardless of whether the fragrance contains 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7% or 0 8% (by weight) of a terpene solvent. In other words, an important feature of the composition of the present invention is that the degreasing is the result of the action of the microemulsion as such, and not the presence or absence of a “degreasing” solvent in the microemulsion.

 As a perfume, you can use essential oil or a water-insoluble alkane or isoalkane having 6-18 hydrocarbon atoms, at a concentration of 0.4 - 8.0 wt.%.

 The water-soluble organic detergent materials used to formulate the final m / v microemulsion compositions of the present invention can be selected from the group consisting of water-soluble non-soap anionic surfactants mixed with a fatty acid and a solubilizing agent, which is a partially esterified ethoxylated polyhydric alcohol, such as partially esterified ethoxylated glycerin.

 Although the proposed compositions can use traditional non-ionic surfactants, but their use will reduce the environmental performance of the composition, and will also have a detrimental effect on such properties of the composition as the grease repellent ability and the ability to remove grease and particulate contaminants.

 As regards the anionic surfactant present in the m / in microemulsion, any conventionally used water-soluble anionic surfactants or mixtures of said anionic surfactants and nonionic surfactants can be used in the present invention. When used in this description, the term "anionic surfactant" refers to the class of anionic and mixed anionic-nonionic surfactants that provide a detergent effect.

Suitable water-soluble non-soap anionic surfactants include those surfactants or detergents that have an organic hydrophobic group containing typically 8 to 26 carbon atoms in the structure of the molecule, and at least one water-soluble group selected from the group consisting of sulfonate , sulfate and carboxylate, which provides the formation of a water-soluble detergent. Typically, a hydrophobic group includes a C ₈ -C ₂₂ alkyl, alkyl or acyl group. Such surfactants 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 and mono-, di- or tri-C ₂ -C ₃ alkanolammonium, of which sodium, magnesium cations are preferred and ammonium.

Examples of suitable sulfonated anionic surfactants are well-known higher alkyl (mononuclear aromatic) sulfonates, such as higher alkyl benzene sulfonates containing from 10 to 16 carbon atoms in a straight or branched chain alkyl group, C ₈ -C ₁₅ alkyltoluenesulfonates and C ₈ -C ₁₅ alkylphenolsulfonates.

 A preferred sulfonate is unbranched alkylbenzenesulfonate with a high content of 3- (or higher) phenyl isomers and correspondingly low (significantly lower than 50%) 2- (or lower) phenyl isomers, i.e. in which the benzene ring is preferably attached at most in position 3 or higher (for example, 4, 5, 6 or 7) of the alkyl group, wherein when the benzene ring is attached at position 2 or 1, the content of isomers is relatively low. Particularly preferred materials are those described in US patent N 3320174.

Other suitable anionic surfactants are alkenyl sulfonates, including long chain alkenyl sulfonates, long chain hydroxyalkyl sulfonates, or mixtures of alkenyl sulfonates and hydroxyalkyl sulfonates. These alkenyl sulfonates detergents can be obtained in a known manner by reacting sulfur trioxide (SO ₃ ) with long chain olefins containing 8 to 25 carbon atoms and having the formula RCH = CHR ₁ , where R represents a higher alkyl group with 6 to 23 carbon atoms and R ₁ represents an alkyl group with 1 to 17 carbon atoms, with the formation of a mixture of sultones and alkenylsulfonic acids, which is then processed to convert sultones to sulfonates. Akenylsulfonates contain from 14 to 16 carbon atoms in the alkyl group R and are obtained by sulfonation of an α-olefin.

 Other examples of suitable anionic sulfonate surfactants are alkyl sulfonates containing 10 to 20 carbon atoms. Primary alkyl sulfonates are prepared by reacting long chain alpha olefins and bisulfites. Alkyl sulfonates with a sulfonate group distributed over an alkane chain are described in US Pat. Nos. 2,532,080, 2,550,788, 3,260,744, 3,372,188 and German Patent No. 7,35096.

Examples of satisfactory anionic sulfate surfactants are salts of C ₈ -C ₁₈ alkyl sulfates and salts of C ₈ -C ₁₈ alkyl ether polyethylene sulfates having the formula R (OC ₂ H ₄ ) _n OSO ₃ M, where n = 1 - 12 and M represents solubilizing cation selected from the group consisting of sodium, potassium, ammonium, magnesium and mono-, di- or triethanolammonium ions. Alkyl sulfates can be obtained by sulfating alcohols obtained by reducing glycerides of coconut oil or solid fat or mixtures thereof, and neutralizing the resulting product. On the other hand, alkyl ether polyethylene sulphates are obtained by sulfating the product of condensation of ethylene oxide with a C ₈ -C ₁₈ alkanol and neutralizing the resulting product. Alkyl ether polyethylene sulphates differ from each other in the number of moles of ethylene oxide that have reacted with one mole of alkanol. Preferred alkyl sulfates and preferred alkyl ether polyethylene sulphates contain 10 to 16 carbon atoms and an alkyl group.

C ₈ -C ₁₂ -alkylphenyl ether polyethylene sulphates containing from 2 to 6 mol of ethylene oxide in the molecule are also suitable for use in the compositions of the invention. These detergents can be obtained by reacting alkyl phenol with 2-6 moles of ethylene oxide and sulfating and neutralizing the resulting ethoxylated alkyl phenol.

 Obviously, these anionic surfactants can be present either in the form of an acid or in the form of a salt, depending on the pH of the final composition, the salt-forming cation being the same as for other anionic surfactants.

Of the non-soap anionic surfactants described above, C ₉ -C ₁₅ - (unbranched) alkylbenzenesulfonates and C ₁₃ -C ₁₇ alkylsulfonates are preferred. Particularly preferred compounds are sodium C ₁₀ -C ₁₃ alkylbenzenesulfonates and sodium C ₁₃ -C ₁₇ alkylsulfonates.

 Typically, the proportion of non-soap anionic surfactant is in the range from 0.1% to 20.0% (by weight) of the diluted m / in the microemulsion composition.

и

где w = 1 - 4. B выбран из группы, состоящей из водорода или группы, представленной формулой

где R выбран из группы, состоящей из алкильной группы

имеющей 6 - 22 углеродных атомов, и алкенильных групп, имеющих 6 - 22 углеродных атомов, из которых наиболее предпочтительной является алкильная цепь гидрогенизированного твердого жира или алкильная цепь кокосового масла, причем по крайней мере одна из групп B представлена указанной формулой

и R' выбран из группы, состоящей из водорода и метильных групп; x, y и z имеют значения в пределах между 0 и 60, при условии, что (x + y + z) = 2 - 100, где в формуле (I) отношение сложный моноэфир/сложный диэфир/сложный триэфир составляет 45-90/5-40/1-20, где отношение соединения формулы (I) к соединению формулы (II) равно значению в пределах между 3 и 0,02, причем наиболее предпочтительным является присутствие в смеси, образующей соединение, больше соединения формулы (II), чем соединения формулы (I).The composition of the present invention contains a compound (hereinafter referred to as a compound of the ethoxylated glycerol type), which is a mixture of a fully esterified ethoxylated polyhydric alcohol, a partially esterified ethoxylated polyhydric alcohol and a non-esterified ethoxylated polyol, in which glycerol is the preferred polyhydric alcohol, and such a compound is by myself

and

where w = 1 - 4. B is selected from the group consisting of hydrogen or a group represented by the formula

where R is selected from the group consisting of an alkyl group

having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, of which the hydrogenated solid fat alkyl chain or the coconut oil alkyl chain is most preferred, at least one of the groups B is represented by the indicated formula

and R 'is selected from the group consisting of hydrogen and methyl groups; x, y and z have values between 0 and 60, provided that (x + y + z) = 2 - 100, where in the formula (I) the ratio of monoester / complex diester / complex triester is 45-90 / 5-40 / 1-20, where the ratio of the compound of formula (I) to the compound of formula (II) is equal to a value between 3 and 0.02, with the presence of more than the compound of formula (II) being present in the mixture forming the compound being more preferred than the compounds of formula (I).

 The ethoxylated glycerol type compound used in the composition of the present invention is manufactured by Kao Corporation and sold under the brand name Levenol, for example Levenol F-200, which has an average EO content of 6 and a molar ratio of coconut oil fatty acid to glycerol equal to 0.55, or Levenol V-501/2, which has an average content of EO = 17 and a molar ratio of fatty acid solid fat to glycerin equal to 1.0. It is preferred that the molar ratio of fatty acid to glycerin is less than 1.7, more preferably less than 1.5, and most preferably less than 1.0. A compound of the ethoxylated glycerol type has a molecular weight of 400-1600 and a pH (50 grams per liter of water) of 5-7. Compounds of the Levenol type essentially do not irritate human skin and have a primary biodegradability of more than 90% when measured using the Wikbold Bias method -7d.

 Two examples of compounds of the Levenol type are Levenol V-501/2, which has 17 ethoxylated groups and is derived from fatty acid solid fat with a fatty acid to glycerin ratio of 1.0 and a molecular weight of 1465, and Levenol F-200, which has 6 ethoxylated groups and obtained from coconut oil fatty acid with a fatty acid to glycerin ratio of 0.55. Both Levenol F-200 and Levenol V-501/2 are composed of a mixture of the components of formula (I) and formula (II). Levenols have the following ecotoxicity values: inhibition of algal growth> 100 mg / l; short-term toxic effect for daphnia> 100 mg / l; and short-term toxic effect for fish> 100 mg / l. Levenols are capable of rapid biochemical decomposition by more than 60% - a value that is the minimum required value when measured by OECD 301B for an acceptable biodegradability.

 Suitable for the proposed compositions are also polyesterified nonionic compounds Kolv RK-40 and Kolv RK-70 manufactured by Kroda GMBH, The Netherlands. Kolov RK-40 is a polyoxyethylene (12) coconut kernel glyceride that has 12 EO groups. Kolaw RK-70, which is the preferred compound, is a polyoxyethylene (45) coconut kernel glyceride having 45 EO groups.

 In dilute m / in microemulsion compositions or liquid crystal compositions, compounds of the ethoxylated glycerol type or polyesterified nonionic compounds are present in a mixture with an anionic detergent. The relative content of a compound such as ethoxylated glycerol or a polyesterified nonionic solubilizing agent by weight of the liquid crystal composition or the final diluted m / in the microemulsion composition is 0.1 to 20%.

 In addition, in more preferred compositions, the mass ratio of non-soap anionic detergent to the compound of the ethoxylated glycerol type is in the range of 3: 1 to 1: 3, and the mass ratio of 2: 1 gives particularly good results.

где w = 1 - 4, x, y и z имеют значение в пределах между 0 и 60, при условии, что (x + y+ z) = 2 - 100.An ethoxylated polyhydric alcohol, such as the ethoxylated glycerin of the present invention, is represented by the following formula

where w = 1 - 4, x, y and z have a value between 0 and 60, provided that (x + y + z) = 2 - 100.

 In diluted m / in microemulsion compositions or liquid crystal compositions, ethoxylated alcohol is present in admixture with an anionic surfactant. The relative content of a compound of the ethoxylated glycerol type by weight of the liquid crystal composition or the final diluted m / in the microemulsion composition is 0.1-20%.

 In addition, in more preferred compositions, the mass ratio of non-soap anionic surfactant to ethoxylated polyhydric alcohol is in the range of 3: 1 to 1: 3, and the mass ratio of 2: 1 gives particularly good results.

где w = 1 - 4. Два символа B представляют водород, а один B выбран из группы, состоящей из группы, представленной формулой

где R выбран из группы, состоящей из алкильной группы

имеющей 6 - 22 углеродных атомов, и алкенильных групп, имеющих 6 - 22 углеродных атомов, из которых наиболее предпочтительной является алкильная цепь гидрогенизированного твердого жира или алкильная цепь кокосового масла, x, y и z имеют значения в пределах между 0 и 60, при условии, что (x + y + z) = 2 - 100.The composition of the present invention may also contain 0 to 10% by weight of an ethoxylated polyhydric alcohol monoester represented by the formula

where w = 1 - 4. Two B symbols represent hydrogen, and one B is selected from the group consisting of the group represented by the formula

where R is selected from the group consisting of an alkyl group

having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, of which the hydrogenated solid fat alkyl chain or the coconut oil alkyl chain are most preferred, x, y and z are between 0 and 60, provided such that (x + y + z) = 2 - 100.

где w = 1 - 4. Один символ B представляют водород, а два B выбраны из группы, состоящей из группы, представленной формулой

где R выбран из группы, состоящей из алкильной группы

имеющей 6 - 22 углеродных атомов, и алкенильных групп, имеющих 6 - 22 углеродных атомов, из которых наиболее предпочтительной
является алкильная цепь гидрогенизированного твердого жира или алкильная цепь кокосового масла, x, y и z имеют значения в пределах между 0 и 60, при условии, что (x + y + z) = 2 - 100.The proposed composition may also contain 0 to 2 wt.% Complex diester ethoxylated polyhydric alcohol represented by the formula

where w = 1 - 4. One B symbol is hydrogen, and two B are selected from the group consisting of the group represented by the formula

where R is selected from the group consisting of an alkyl group

having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, of which the most preferred
is an alkyl chain of hydrogenated solid fat or an alkyl chain of coconut oil, x, y and z have values between 0 and 60, provided that (x + y + z) = 2 - 100.

где w = 1 - 4. Три B выбраны из группы, представленной формулой

где R выбран из группы, состоящей из алкильной группы

имеющей 6 - 22 углеродных атомов, и алкенильных групп, имеющих 6 - 22 углеродных атомов, из которых наиболее предпочтительной является алкильная цепь гидрогенизированного твердого жира или алкильная цепь кокосового масла, x, y и z имеют значения в пределах между 0 и 60, при условии, что (x + y + z) = 2 - 100.The proposed composition may also contain 0 to 1.0 wt.%, More preferably 0.02 to 0.6 wt.% Of a complex ester of ethoxylated polyhydric alcohol represented by the formula

where w = 1 - 4. Three B are selected from the group represented by the formula

where R is selected from the group consisting of an alkyl group

having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, of which the hydrogenated solid fat alkyl chain or the coconut oil alkyl chain are most preferred, x, y and z are between 0 and 60, provided such that (x + y + z) = 2 - 100.

 The compositions of the invention contain 0-1.0 wt.% Trialkyl citrate, such as tri-n-butyl citrate, tri-n-propyl citrate, triisopropyl citrate, triisobutyl citrate, tri-n-pentyl citrate, triisopentyl citrate and tri-n-hexyl citrate, of which preferred is tri-n-butyl citrate. Tri-n-butyl citrate acts as a foaming agent in the composition, providing easier sedimentation of the foam, so that the product can be washed more efficiently.

The secondary surfactant can play a significant role in the formation of a liquid crystal composition or diluted m / in microemulsion and concentrated microemulsion compositions. Three main classes of compounds have been found that give highly suitable secondary surfactants in the temperature range from 5 ^° C to 43 ^° C, for example: (1) water-soluble C ₃ -C ₄ alkanols, polypropylene glycol of the formula HO (CH ₃ CHCH ₂ O ) _n H, where n represents a number from 2 to 18, and monoalkyl ethers and ethylene glycol and propylene glycol esters having the structural formula R (X) _n OH and R ₁ (X) _n OH, where R represents C ₁ -C ₆ -alkyl, R ₁ represents a C ₂ -C ₄ acyl group, X - represents (OCH ₂ CH ₂ ) or (OCH ₂ (CH ₃ ) CH) and n represents a number from 1 to 4; (2) aliphatic mono- and dicarboxylic acids containing 2 to 10 carbon atoms, preferably 3 to 6 carbon atoms in the molecule; (3) triethyl phosphates. In addition, when specific pH is required, mixtures of two or more of these four classes of secondary surfactants can be used.

 When mono- and dicarboxylic acids are used as secondary surface-active substances in the proposed microemulsion compositions (class 2) at a concentration of 2-10% by weight, microemulsion compositions can be used as cleaning agents for bathtubs and other objects with hard surfaces that are acid resistant , for removal from surfaces of such objects of harmful deposits, plaque of soap foam and grease. If these surfaces are white zirconium enamel, then these compositions can damage them.

 Together with mono- and dicarboxylic acids, it is possible, although not necessary, to use aminoalkylene phosphonic acid at a concentration of 0.01-0.2 wt.%, Which helps prevent damage to surfaces coated with white zirconium enamel. In addition, 0.05 to 1% phosphoric acid may be used in the composition.

 Methanol and ethanol are certainly excluded from the composition due to their low flash point.

 Representatives of polypropylene glycol include dipropylene glycol and polypropylene glycol having a molecular weight of from 200 to 1000, for example polypropylene glycol 400. Other satisfactory glycol ethers are monobutyl ether of ethylene glycol (butyl cellulose) monobutyl ether of diethylene glycol (butylcarbutyl ether) monobutyl ether propylene glycol, ethylene glycol monoacetate and dipropylene glycol propionate. A liquid crystal composition can be formed at a concentration of these glycol secondary surfactants of at least 1.0 mass. % in combination with perfume at a concentration of at least 0.5 mass. %

Representatives of aliphatic carboxylic acids include monobasic and dibasic C ₃ -C ₆ -alkyl and alkenyl carboxylic acids, such as glutaric acid and mixtures of glutaric acid with adipic and succinic acids, as well as mixtures of the above acids and acrylic or propionic acid.

 Although all the above esters of glycols and acids provide the mentioned stability, the most preferred secondary surface-active substances of each type - in terms of cost and cosmetic appearance (in particular, smell) - are diethylene glycol monobutyl ether and a mixture of adipic, glutaric and succinic acids, respectively. The ratio of acids in this mixture is not particularly standardized and can be changed to provide the desired odor. Typically, in order to maximize the solubility of a mixture of acids in water, glutaric acid is used as the main component, the most water-soluble of the three saturated aliphatic dibasic acids indicated.

 In general, adipic acid: glutaric acid: succinic acid 1–3: 1–8: 1–5 can be used with equally good results.

 And yet another classes of secondary surfactants that provide microemulsion compositions that are stable at low and elevated temperatures are mono-, di- and triethyl esters of phosphoric acid, such as triethyl phosphate.

 The amount of secondary surfactant needed to stabilize the liquid crystal or microemulsion compositions depends, of course, on factors such as the surface tension characteristics of the secondary surfactant, the type and amount of primary surfactants and perfumes, and the type and amount of other additional components that may be present in the composition and which affect the thermodynamic factors listed above under the corresponding numbers . The amount of secondary surfactant in the range from 0.5% to 15% by weight gives stable diluted m / in microemulsions at the above levels of primary surfactants and perfumes and other additional components described below.

 Specialists in this field it is clear that the pH of the final microemulsion depends on the nature of the secondary surfactant, and it is chosen by cost and cosmetic properties, in particular odor. For example, in microemulsion compositions with a pH in the range of 1-10, a secondary surfactant of class 1 or class 4 can be used as the only secondary surfactant, but in the presence of a salt of a polyvalent metal, the pH range is narrowed to 1-8.5. On the other hand, at a product pH below 3.2, only a class 2 secondary surfactant can be used as the only secondary surfactant. However, when using acidic secondary surfactants in admixture with secondary surfactants such as ethers glycols, compositions having a substantially neutral pH (e.g., pH 7 ± 1.5) can be formulated.

 The ability to produce neutral and acidic products without auxiliary components having a degreasing ability is a hallmark of the present invention, since the known microemulsion formulations are highly alkaline or very multicomponent or both.

 In addition to its high ability to cleanse greasy and oily contaminants, m / v microemulsion formulations with a low pH also have an excellent cleansing effect when removing soap foam and limescale deposits when applied in pure (undiluted) or diluted form.

 The last important component in the proposed microemulsion compositions with improved interfacial tension properties is water. The relative water content in the microemulsion compositions is usually in the range of 20% to 97% by weight of the usual diluted m / in the microemulsion composition.

 It is believed that from the foregoing description it is clear that the diluted liquid universal cleansing compositions in the form of m / v microemulsions of the present invention are especially effective when used as is, that is, without additional dilution in water, since the properties of the composition in the form of m / v microemulsions are better all manifest themselves in a pure (undiluted) form. However, at the same time, it must be understood that depending on the levels of surfactants, secondary surfactants, perfumes and other components, some degree of dilution is possible without destroying the microemulsion as such. For example, at preferred low levels of active surfactants (i.e., primary anionic and nonionic surfactants), dilutions of up to 50% are generally acceptable without phase separation, that is, maintaining the microemulsion state.

 But even with a high degree of dilution, for example 2-10-fold or more, the resulting compositions are still effective in cleaning fat, oil and other contaminants. In addition, the presence of magnesium ions or other multivalent ions, for example aluminum, as will be described in more detail below, further enhances the cleaning effect of primary detergents when used in diluted form.

 On the other hand, it is also within the scope of the present invention to make highly concentrated microemulsions diluted with additional water before use.

The present invention also relates to a stable concentrated emulsion or acidic microemulsion composition containing by weight:
(a) 1-30% anionic surfactant;
(b) 0.5-15% of a compound of the ethoxylated glycerol type;
(c) 2-30% of a secondary surfactant;
(d) 0.4-10% water-insoluble hydrocarbon or perfume;
(e) 0-18% of at least one dicarboxylic acid;
(f) 0-1% phosphoric acid;
(g) 0-0.2% aminoalkylene phosphonic acid;
(h) 0-15% magnesium sulfate heptahydrate;
(i) 0-1.0% trialkyl citrate;
(j) the rest is water,
moreover, the composition has an ecotoxicity value, measured according to the LC 50 test, at least 0.18 ml / l when measured on microorganisms such as daphnia (Daphniae).

The present invention also relates to a stable liquid crystal microemulsion or acidic microemulsion composition containing, by weight:
(a) 1-30% anionic surfactant;
(b) 0.5-15% of a compound of the ethoxylated glycerol type;
(c) 0-2.5% fatty acid;
(d) 2-30% of a secondary surfactant;
(e) 0.5-10% water insoluble hydrocarbon or perfume;
(f) 0-15% magnesium sulfate heptahydrate;
(g) 0-1.0% trialkyl citrate;
(h) the rest is water,
moreover, the composition has an ecotoxicity value, measured according to the LC50 test, of at least 0.18 ml / l when measured on microorganisms such as daphnia (Daphniae).

The present invention also relates to a stable concentrated emulsion or acidic microemulsion composition containing, by weight, approximately:
(a) 1-30% anionic surfactant;
(b) 0.5-15% ethoxylated polyhydric alcohol, such as ethoxylated glycerol;
(c) 2-30% of a secondary surfactant;
(d) 0.4-10% water-insoluble hydrocarbon or perfume;
(e) 0-18% of at least one dicarboxylic acid;
(f) 0-1% phosphoric acid;
(g) 0-0.2% aminoalkylene phosphonic acid;
(h) 0-15% magnesium sulfate heptahydrate;
(i) the rest is water.

The present invention also relates to a stable liquid crystal microemulsion or acidic microemulsion composition containing, by weight, approximately:
(a) 1-30% anionic surfactant;
(b) 0.5-15% ethoxylated polyhydric alcohol, such as ethoxylated glycerol;
(c) 2-30% of a secondary surfactant;
(d) 0.5-10% water insoluble hydrocarbon or perfume;
(e) 0-15% magnesium sulfate heptahydrate;
(f) the rest is water.

 Such concentrated microemulsions can be diluted by mixing with water in an amount up to 20 times or more of their mass to form m / v microemulsions similar to the diluted microemulsion compositions described above. Although the degree of dilution is selected so that after dilution to obtain m / in the microemulsion composition, it should be understood that during the dilution it is possible to sequentially encounter both microemulsion and non-microemulsion.

 In addition to the above essential components necessary for the formation of a liquid crystal composition or microemulsion composition, the compositions of the present invention can often and preferably contain one or more additional components that serve to improve the overall characteristics of the product.

One such component is an inorganic or organic salt or oxide of a polyvalent metal cation, in particular Mg ⁺⁺ . Salt or metal oxide provides several advantages, including an improved cleaning effect when used in diluted form, in particular in areas with soft water, and extremely reduced amounts of perfume needed to obtain a microemulsion state. Magnesium sulfate, anhydrous or hydrated (e.g., heptahydrate), is a particularly preferred magnesium salt. Good results have also been obtained using magnesium oxide, magnesium chloride, magnesium acetate, magnesium propionate and magnesium hydroxide. These magnesium salts can be used with neutral or acidic pH formulations since magnesium hydroxide does not precipitate at the indicated pH levels.

 Although mania is the preferred multivalent metal from which salts are formed (including oxides and hydroxides), other multivalent metal ions can be used, provided that their salts are non-toxic and soluble in the aqueous phase of the system at the required pH level. So, depending on factors such as the pH of the system, the nature of the primary and secondary surfactants, etc., as well as availability and cost factors, other suitable multivalent metal ions include aluminum, copper, nickel, iron, calcium, etc. .d. It should be noted, for example, that when using the preferred anionic detergent in the form of an alkyl sulfonate, calcium salts will precipitate and therefore should not be used. It has also been found that aluminum salts work best at pHs below 5 or by adding a low content (e.g., 1% by weight) of citric acid to a composition that needs to have a neutral pH. In another embodiment, the aluminum salt in this case can be added directly as citrate. As the salt, one can use the same general classes of anions that are indicated for magnesium salts, such as a halide (e.g. bromide, chloride), sulfate, nitrate, hydroxide, oxide, acetate, propionate, etc.

In 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 every gram-ion of Mg ^{++ there} should be 2 gram-moles of alkyl sulfonate, alkylbenzenesulfonate, etc., and for every gram-ion of Al ^{3+ there} should be 3 gram-moles of anionic surfactant. Therefore, the relative content of the multivalent salt is usually chosen such that one equivalent of the compound neutralizes from 0.1 to 1.5 equivalents of the acidic anionic surfactant.

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

The liquid crystal composition or m / v microemulsion compositions contain from 0% to 2.5% (by weight of the composition) of a C ₈ -C ₂₂ fatty acid or fatty acid soap as an antifoam. The addition of a fatty acid or fatty acid soap increases the washing ability of the composition in both pure and diluted forms. But usually to ensure the stability of the product in the presence of a fatty acid or soap, it is necessary to increase the content of the secondary surfactant. When used in the proposed compositions more than 2.5 wt.% Fatty acid composition becomes unstable at low temperatures and has an unpleasant odor.

Examples of fatty acids that can be used on their own or in the form of soap include fatty acids of distilled coconut oil, fatty acids of the “mixed vegetable” type (for example, with a high percentage of saturated, mono- and / or polyunsaturated C ₁₈ chains ); oleic acid, stearic acid, palmitic acid, eicosanoic acid and the like, and those fatty acids having 8 to 22 carbon atoms are generally acceptable.

 If necessary, the universal liquid cleaning composition of the present invention may also contain other components that create an additional effect or make the product more attractive to the consumer. For example, the following components can be mentioned: dyes in an amount up to 0.5% by weight, bactericides in an amount up to 1% by weight, preservatives or antioxidant agents, such as formalin, 5-bromo-5-nitrodioxane-1,3, 5- chloro-2-methyl-4-isotalizolin-3-one, 2,6-di-tert-butyl-p-cresol, etc., in an amount up to 2% by weight and pH adjusting agents such as sulfuric acid or sodium hydroxide, as needed. In addition, if opaque compositions are required, then up to 4% (by weight) of a substance making the product opaque can be added.

 The compositions of the present invention certainly do not contain a zwitterionic surfactant, such as betaines, because these zwitterionic surfactants are very foaming, resulting in the proposed composition will give a very large foam, and too much foam will leave marks on the surface to be cleaned .

In the final form, universal liquid cleansing compositions are transparent oil-in-water microemulsions or liquid crystal compositions and are stable at low and high temperatures. In particular, such compositions remain transparent and stable in the range of 5 ^° C. to 50 ^° C. Such compositions have a pH in the acidic or neutral region, depending on the intended intended use. Liquid microemulsion compositions are easy to pour and have a viscosity in the range of 6-60 mPa • s when measured at 25 ^° C with a Brookfield RVT viscometer using an N 1 spindle rotating at a speed of 20 rpm.

 The compositions can be directly ready to use or can be diluted as required, and in any case do not require or require only minimal washing and, essentially, do not leave behind sediment or streaks. In addition, since the compositions do not contain auxiliary detergent components, such as polyphosphates of alkali metals, they are acceptable from the point of view of environmental protection and improve the gloss of cleaned hard surfaces.

 When the liquid compositions are intended to be used in pure form, they can be packaged under pressure in an aerosol container or in a pump-type spray gun for so-called spray and wipe applications.

 Since the compositions during preparation are aqueous liquid compositions and do not require special mixing to form m / in microemulsions, they are easily prepared simply by combining all the components in a suitable vessel. The order of mixing the components is not particularly important and usually various components can be added sequentially or all at once, either in the form of aqueous solutions of each of them, or all primary and secondary surfactants can be prepared separately and combined with each other and flavoring. A magnesium salt or other multivalent metal compound can, if present, be added as an aqueous solution or directly. At the formation stage, there is no need to use elevated temperatures, it is enough to have room temperature.

 The proposed microemulsion compositions, of course, do not contain alkali metal silicates and auxiliary additives based on alkali metals, such as alkali metal polyphosphates, alkali metal carbonates, alkali metal phosphonates and alkali metal citrates, because these materials when used in the proposed composition will lead to high pH of the composition and will leave marks on the surface being cleaned.

 It is contemplated that, within the scope of the present invention, a compound of the ethoxylated glycerol type can be used in cleaning compositions for cleaning hard surfaces, such as cleaning products for wooden products, window cleaning products and liquid cleaning products for light processing conditions where an increase in the grease repellent effect is desired.

 The following examples illustrate the liquid cleansing compositions of the present invention. Unless otherwise indicated, all percentages are by weight. The compositions shown as examples are illustrative only and do not limit the scope of the invention. Unless otherwise indicated, the relative contents in the examples and everywhere in the description are taken by weight.

 Example 1

 Were obtained compositions, wt.%, Are presented in table. 1.

 In addition, the "dissolving power" m / in the microemulsion from this example is comparable to the "dissolving power" of an identical composition, differing only in that the same amount (5 wt.%) Is used instead of the secondary surfactant in the form of diethylene glycol monobutyl ether a hydrotrop in the form of sodium cumensulfonate, in a test in which the same amount of heptane is added to both compositions. The m / v microemulsion of the present invention solubilizes 12 grams of a water-immiscible substance compared to 1.4 grams in a hydrotrop-containing liquid composition.

 In another comparative test using blue cooking oil (greasy triglyceride contamination), the composition of Example 1 remains transparent after adding 0.2 grams of cooking oil, while in a composition containing a sulfonate hydrotrope, cooking oil floats on top.

 By reducing the concentration of perfumes in the composition of example 1 to 0.4%, a stable m / in microemulsion composition is obtained. Similarly, a stable m / in microemulsion in Example 1 is obtained when the concentration of perfume is increased to 2% by weight and the concentration of the secondary surfactant is increased to 6% by weight.

и

где w = 1-4. B выбран из группы, состоящей из водорода или группы, представленной формулой

где R выбран из группы, состоящей из алкильной группы

имеющей 6-22 углеродных атомов, и алкенильных групп, имеющих 6-22 углеродных атомов, причем по крайней мере одна из групп B представлена указанной формулой

и R' выбран из группы, состоящей из водорода и метильных групп; x, y и z имеют значения в пределах между 0 и 60, при условии, что (x+y+z) = 2-100, где в формуле (I) отношение сложный моноэфир/сложный диэфир/сложный триэфир составляет 40-90/5-35/1-20, где отношение соединения формулы (I) к соединению формулы (II) равно значению в пределах между 3 и 0,02, более предпочтительно 3 и 0,1, а наиболее предпочтительно 1,5 и 0,2, причем наиболее предпочтительным является присутствие в смеси больше соединения формулы (II), чем соединения формулы (I);
(b) остальное - вода.The present invention also relates to an aqueous solution of a grease repellent system, comprising:
(a) 0.1-20.0 wt.% the mixture:

and

where w = 1-4. B is selected from the group consisting of hydrogen or a group represented by the formula

where R is selected from the group consisting of an alkyl group

having 6-22 carbon atoms, and alkenyl groups having 6-22 carbon atoms, and at least one of the groups B is represented by the indicated formula

and R 'is selected from the group consisting of hydrogen and methyl groups; x, y and z have values between 0 and 60, provided that (x + y + z) = 2-100, where in the formula (I) the ratio is complex monoester / complex diester / complex triester is 40-90 / 5-35 / 1-20, where the ratio of the compound of formula (I) to the compound of formula (II) is equal to a value between 3 and 0.02, more preferably 3 and 0.1, and most preferably 1.5 and 0.2 most preferred being the presence in the mixture of more of a compound of formula (II) than a compound of formula (I);
(b) the rest is water.

 An aqueous solution of a grease repellent agent may be applied to a solid surface. The treated hard surface will interfere with the adhesion of fat to it, thereby making it easier to clean a hard surface using a traditional cleaning composition for cleaning hard surfaces.

 Example 2

The example illustrates a typical composition of the "concentrated" m / in the microemulsion of the present invention, wt.%:
Coconut Oil Fatty Acid - 4
C ₁₃ -C _17- sodium alkyl sulfonate - 20.75
Levenol F-200 - 12
Diethylene glycol monobutyl ether - 20
Fragrance (a) - 12.5
Water - Ost. up to 100
pH: 7.0 ± 0.2
This concentrated composition can be easily diluted, for example, five times with tap water, which will give a diluted m / in microemulsion composition. Thus, using microemulsion technology, it is possible to create a product with high contents of active detergent components and perfumes, which will be very attractive to consumers in terms of transparency, odor and stability and which can be easily diluted to a concentration usual for similar universal liquid cleaning compositions for cleaning hard surfaces, preserving cosmetically attractive qualities.

 Of course, these compositions can, if necessary, be used without additional dilution and can also be used with full strength of the solution or with strength in diluted form for cleaning dirty fabrics manually or in an automatic washing machine.

 Example 3

This example illustrates a diluted m / in microemulsion composition of the present invention, which has an acidic pH and exhibits an improved cleansing effect when removing traces of soap suds and limescale and removing grease, wt.%:
C ₁₃ -C ₁₇ sodium alkyl sulfonate - 4.7
Levenol F-200 - 2.3
MgSO ₄ • 7H ₂ O - 2.2
A mixture of succinic, glutaric and adipic acids (1: 1: 1) - 5
Fragrance (d) - 1,0
Water, minor components (dye) - Remaining. up to 100
Phosphonic acid - 0.2
Aminotris- (methylenephosphonic acid) - 0.03
pH = 3 ± 0.2
(d) contains 40% (by weight) of terpene.

Example 4
Composition A of Example 1 was tested to remove a combination of fat and particulate contamination, as well as the grease repellent effect and compared with commercial Ajax ^tm NME.

 I. Removal of grease + particulate contamination.

Test method
A) Contamination composition:
70 g of mineral oil
35 g of particulate contamination (dust from a vacuum cleaner + 1% carbon black)
35 g C ₂ Cl ₄
B) Preparation of contaminants
- Weighing peeled and dried glass tiles
- Pollution of tiles with grease + solid particles
- Heat treatment of tiles for an hour at 80 ^o C
- Weighing dirty tiles after 2 hours at room temperature
C) Removal of contaminants
Contaminated tiles were soaked for 15 minutes at room temperature in the test products, after which they were thoroughly washed with tap water.

After drying for 45 minutes at 50 ^° C., the tiles were weighed again.

 The results are presented in table. 2.

Composition A shows better removal of contaminants such as fat + particles compared to commercial Ajax ^tm NME.

II. Grease repellent effect
Test method
A) Contamination composition
20% cured animal fat
80% beef fat
blue dye for fat
B) Preparation of contaminants
The fat mixture is heated and sprayed onto the cleaned and dried ceramic tiles with an automatic spray device.

C) Removal of contaminants
Undiluted product: 2.5 g per sponge
Diluted product: 1.2% solution in tap water - 10 ml of solution on a sponge
For both concentrations, the cleaning procedure is carried out using a garden tool.

results
A) On treated ceramic tiles (processed by the product before spraying contaminants) (see table 3).

B) On untreated ceramic tiles
In addition to the previous test, the following three procedures were used to verify that composition A remains on the surface after washing or wiping. After the first cleaning procedure and before the second spraying:
1) the tiles were allowed to dry in the open air;
2) the surface was wiped with a paper towel;
3) the surface was washed with a damp sponge.

 1) Drying in the open air (see table. 4).

 2) Drying by wiping the surface (see table. 5).

 3) Wet wipe the surface (see table. 6).

 The presented results clearly demonstrate the important grease repellent effect provided by composition A, especially when using a diluted product.

 Example 5

 Liquid crystal compositions were obtained by simple mixing (see table. 7).

Example 6
The following optically clear microemulsion compositions were prepared by forming the first solution by mixing at 25 ^° C. water, magnesium lauryl sulfate (ether), Levenol V-510/2 and 1-Pentanol. To this solution, dodecane was added at 25 ^° C. with stirring to form an optically transparent microemulsion. All compositions are expressed in mass percent (see table. 8).

Example 7
The following composition was obtained by simple mixing:
C ₁₃ -C ₁₇ sodium alkyl sulfonate - 4.0
Levenol F-200 - 2.0
Diethylene glycol monobutyl ether - 4.5
Fatty acid - 0.5
MgSO ₄ • 7H ₂ O - 1.8
Fragrance (a) - 0.8
Tri-n-butyl citrate - 0.5
Water - Else
pH - 7
Degreasing test
Undiluted (b)
Diluted (b)
Residual traces
Foam on hand
Water
(a) Contains 25% (by weight) of terpenes.

 (b) Fewer passes, better degreasing.

 The addition of tri-n-butyl citrate improves the washability of the surface to be washed, due to better subsidence of the foam compared to a composition not containing tri-n-butyl citrate.

 So, the present invention generally relates to the improvement of microemulsion compositions containing an anionic surfactant, a compound such as ethoxylated glycerol, a fatty acid, one of these secondary surfactants, a hydrocarbon component and water, which (improvement) contains the use of water insoluble aromatic fragrance as an essential hydrocarbon component in a proportion sufficient to form either a diluted m / in microemulsion composition, or Idcocrystalline composition containing (by weight) 0.1 - 20% of anionic surfactant, 0.1 - 10% of a compound such as ethoxylated glycerol, 0 - 50% of a secondary surfactant, 0 - 41.0% of trialkyl citrate, 0 , 4 - 10% perfumes and the rest is water.

Example 8
Were obtained compositions, wt.%, Are presented in table. 9.

Compound (a) is
CH ₂ - O (CH ₂ CH ₂ O) ₂ R ₁
CH - O (CH ₂ CH ₂ O) ₂ R ₂
CH ₂ - O (CH ₂ CH ₂ O) ₂ R ₃
where R ₁ , R ₂ and R ₃ represent the alkyl chain of coconut oil,
Compound (b) is
CH ₂ - O (CH ₂ CH ₂ O) ₂ R ₄
CH - O (CH ₂ CH ₂ O) ₂ R ₅
CH ₂ - O (CH ₂ CH ₂ O) ₂ H
where R ₄ and R ₅ are alkyl chains of coconut oil,
Compound (c) is
CH ₂ - O (CH ₂ CH ₂ O) ₂ R ₆
CH - O (CH ₂ CH ₂ O) ₂ H
CH ₂ - O (CH ₂ CH ₂ O) ₂ H
where R ₆ represents an alkyl chain of coconut oil.

Compound (d) is
CH ₂ - O (CH ₂ CH ₂ O) ₂ H
CH - O (CH ₂ CH ₂ O) ₂ H
CH ₂ - O (CH ₂ CH ₂ O) ₂ H
So, the present invention generally relates to the improvement of microemulsion compositions for removing contaminants in the form of solid particles (compositions) containing an anionic surfactant, ethoxylated polyhydric alcohol, a secondary surfactant, a hydrocarbon component and water, which (improvement) contains the use of water-insoluble aromatic fragrance as an essential hydrocarbon component in a proportion sufficient to form or diluted m / in microemulsion composition, or a liquid crystal composition containing (by weight) 0.1 - 20% anionic surfactant, 0.1 - 20% ethoxylated polyhydric alcohol, 0 - 50% secondary surfactant, 0.4 - 10% perfume and the rest is water.

 So, the present invention generally relates to the improvement of microemulsion compositions containing an anionic surfactant, a nonionic surfactant in the form of an esterified polyethoxy ether, a fatty acid, one of these secondary surfactants, a hydrocarbon component and water, which (improvement ) contains the use of a water-insoluble flavoring fragrance as an essential hydrocarbon component in a proportion sufficient to form or disperse an added m / in a microemulsion composition, or a liquid crystal composition containing (by weight) 0.1 - 20% anionic surfactant, 0.1 - 20% solubilizing agent, which is a compound of the type ethoxylated glycerol, 0 - 50% secondary surfactant -active substance, 0.4 - 10% of perfumes and the rest is water.

Claims (16)

1. Microemulsion cleansing composition for a solid surface, containing anionic and nonionic surfactants, a secondary surfactant, a water-insoluble hydrocarbon or perfume and water, characterized in that it contains a mixture of non-ionic surfactants

and

where w = 1 to 4;
B is selected from the group consisting of hydrogen or a group represented by the formula

where R is selected from the group consisting of an alkyl group

having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, with at least one of the groups B represented by the indicated formula

R 'is selected from the group consisting of hydrogen and methyl groups;
x, y and z have values between 0 and 60, provided that (x + y + z) = 2 - 100,
where in the formula I, the ratio of monoester / diester / complex triester is 45 - 90/5 - 40/1 - 20, where the ratio of the compounds of formula I to the compound of formula II is equal to a value between 3 and 0.02;
the secondary surfactant is selected from the group consisting of C ₃ -C ₄ alkanols, HO (CH ₃ CHCH ₂ O) _n H, where n ranges from 2 to 18, mono (C ₁ -C ₆ ) alkyl ethers ethylene glycol or propylene glycol, ethylene or propylene glycol esters, wherein said ethers and esters have the formula
R ₁ (X) _m OH and R ₂ (X) _p OH,
where R ₁ represents a (C ₁ -C ₆ ) alkyl group; R ₂ represents a (C ₂ -C ₄ ) acyl group; X represents (OCH ₂ CH ₂ ) or (OCH ₂ (CH ₃ ) CH); m and p each takes a value from 1 to 4,
C ₂ -C ₁₀ aliphatic mono- or dicarboxylic acids, triethyl phosphate and mixtures thereof, and further the composition contains trialkyl citrate in the following ratio, wt.%:
A mixture of nonionic surfactants I and II - 0.1 - 20
Anionic surfactant - 0.1 - 20
Secondary surfactant - 0.1 - 50
Water-insoluble hydrocarbon or perfume - 0.1 - 10
Trialkyl citrate - Not more than 1.0
Water - Else
moreover, the composition has a viscosity at 25 ^o C equal to 6 - 60 MPa • s, and does not contain zwitterionic surfactant or methanol. 2. Microemulsion cleansing composition for a solid surface containing anionic and nonionic surfactants, a secondary surfactant, a water-insoluble hydrocarbon or perfume and water, characterized in that the composition contains a mixture as a nonionic surfactant

and

where w = 1 to 4;
B is selected from the group consisting of hydrogen or a group represented by the formula

where R is selected from the group consisting of an alkyl group

having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, with at least one of the groups B represented by the indicated formula

R 'is selected from the group consisting of hydrogen and methyl groups;
x, y and z have values between 0 and 60, provided that (x + y + z) = 2 - 100,
where in the formula I, the ratio of monoester / diester / complex triester is 45 - 90/5 - 40/1 - 20, where the ratio of the compounds of formula I to the compound of formula II is equal to a value between 3 and 0.02;
the secondary surfactant is selected from the group consisting of C ₃ -C ₄ alkanols, HO (CH ₃ CHCH ₂ O) _n H, where n ranges from 2 to 18, mono (C ₁ -C ₆ ) alkyl ethers , ethylene glycol or propylene glycol, ethylene or propylene glycol esters, wherein said ethers and esters have the formula
R ₁ (X) _m OH and R ₂ (X) _p OH,
where R ₁ represents a (C ₁ -C ₆ ) alkyl group;
R ₂ represents a (C ₂ -C ₄ ) acyl group;
X represents (OCH ₂ CH ₂ ) or (OCH ₂ (CH ₃ ) CH);
m and p each takes a value from 1 to 4,
C ₂ -C ₁₀ aliphatic mono- or dicarboxylic acids, triethyl phosphate and mixtures thereof in the following ratio of components, wt.%:
A mixture of nonionic surfactants I and II - 0.1 - 20
Anionic surfactant - 0.1 - 20
Secondary surfactant - 0.1 - 50
Water-insoluble hydrocarbon or perfume - 0.1 - 10
Water - Else
moreover, the composition has a viscosity at 25 ^o C equal to 6 - 60 MPa • s, and does not contain zwitterionic surfactant or methanol.  3. The composition according to claims 1 and 2, characterized in that it further comprises a salt of a multivalent metal cation in an amount sufficient to provide from 0.5 to 1.5 equivalents of the specified cation per equivalent of anionic surfactant.  4. The composition according to claim 3, characterized in that the multivalent metal cation is magnesium or aluminum.  5. The composition according to claim 3, which contains 0.9 to 1.4 equivalents of said cation per equivalent of anionic surfactant.  6. The composition according to claim 4, characterized in that it contains chloride, or magnesium sulfate, or magnesium oxide.  7. The composition according to claims 1 and 2, characterized in that it further comprises a fatty acid having 8 to 22 carbon atoms.  8. The composition according to claims 1 and 2, characterized in that it contains 0.5 - 7 wt.% Secondary surfactant and 0.4 - 3.0 wt.% Of the specified hydrocarbon.  9. The composition according to claims 1 and 2, characterized in that the secondary surfactant is a water-soluble ether of ethylene or propylene glycol.  10. The composition according to claim 9, characterized in that the glycol ether is selected from the group consisting of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, polypropylene glycol, propylene glycol tert-butyl ether and monobutyl ether tri-butyl ether.  11. The composition of claim 10, wherein the glycol ether is ethylene glycol monobutyl ether or diethylene glycol monobutyl ether. 12. The composition according to claims 1 and 2, characterized in that the secondary surfactant is a C ₃ -C ₆ aliphatic ionic or dicarboxylic acid selected from the group consisting of acrylic acid, propionic acid, glutaric acid, glutaric mixtures, succinic and adipic acids and mixtures of any of the above acids.  13. The composition according to p. 12, characterized in that the aliphatic carboxylic acid is a mixture of adipic, glutaric and succinic acids. 14. A stable concentrated microemulsion composition for cleaning a solid surface, containing an anionic surfactant selected from the group consisting of sulfates and sulfonates, and a nonionic surfactant, a secondary surfactant, a water-insoluble hydrocarbon or perfume and water, characterized in that as a non-ionic surfactant it contains a mixture

and

where w = 1 to 4;
B is selected from the group consisting of hydrogen or a group represented by the formula

where R is selected from the group consisting of an alkyl group

having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, with at least one of the groups B represented by the indicated formula

R 'is selected from the group consisting of hydrogen and methyl groups;
x, y and z have values between 0 and 60, provided that (x + y + z) = 2 - 100,
where in the formula I the ratio of the monoester / diester / complex triester is 45 - 90/5 - 40/1 - 20, where the ratio of the compound of formula I to the compound of the formula to the compound of formula II is equal to a value between 3 and 0.02;
the secondary surfactant is selected from the group consisting of C ₃ -C ₄ alkanols, HO (CH ₃ CHCH ₂ O) _n H, where n ranges from 2 to 10, mono C ₁ -C ₆ ethylene glycol alkyl ethers, or propylene glycol, ethylene or propylene glycol esters, wherein said ethers and esters have the formula
R ₁ (X) _m OH and R ₂ (X) _p OH,
where R ₁ represents a (C ₁ -C ₆ ) alkyl group;
R ₂ represents a (C ₂ -C ₄ ) acyl group;
X represents (OCH ₂ CH ₂ ) or (OCH ₂ (CH ₃ ) CH);
m and p each takes a value from 1 to 4,
C ₂ -C ₁₀ aliphatic mono- or dicarboxylic acids, triethyl phosphate and mixtures thereof, and additionally the composition contains at least one dicarboxylic acid, aminoalkylene phosphonic acid, phosphoric acid, magnesium sulfate heptahydrate, trialkyl citrate in the following ratio, wt. %:
Anionic Surfactant - 1 - 30
A mixture of nonionic surfactants I and II - 0.5 - 15
Secondary Surfactant - 2 - 30
Water-insoluble hydrocarbon or perfume - 0.4 - 10
Dicarboxylic acid - Not more than 18
Aminoalkylene phosphonic acid - Not more than 0.2
Phosphoric Acid - Not more than 1
Magnesium sulfate heptahydrate - Not more than 15
Trialkyl Citrate - Not more than 1
Water - Else
moreover, the composition has an ecotoxicity value, measured according to the LC 50 test of at least 0.18 ml / l when measured on microorganisms such as daphnia (Daphniae), has a viscosity at 25 ^° C. of 6-60 mPa · s and does not contain zwitterionic surfactant or methanol. 15. A stable concentrated microemulsion composition for cleaning a solid surface, containing an anionic surfactant selected from the group consisting of sulfates or sulfonates, a nonionic surfactant, a secondary surfactant, a water-insoluble hydrocarbon or perfume and water, characterized in that it contains a mixture as a non-ionic surfactant

and

where w = 1 to 4;
B is selected from the group consisting of hydrogen or a group represented by the formula

where R is selected from the group consisting of an alkyl group

having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, with at least one of the groups B represented by the indicated formula

R 'is selected from the group consisting of hydrogen and methyl groups;
x, y and z have values between 0 and 60, provided that (x + y + z) = 2 - 100,
where in the formula I, the ratio of monoester / diester / complex triester is 45 - 90/5 - 40/1 - 20, where the ratio of the compounds of formula I to the compound of formula II is equal to a value between 3 and 0.02;
the secondary surfactant is selected from the group consisting of C ₃ -C ₆ alkanols, HO (CH ₃ CHCH ₂ O) _n H, where n ranges from 2 to 18, mono (C ₁ -C ₆ ) alkyl ethers , ethylene glycol or propylene glycol, ethylene or propylene glycol esters, wherein said ethers and esters have the formula
R ₁ (X) _m OH and R ₂ (X) _p OH,
where R ₁ represents a (C ₁ -C ₆ ) alkyl group;
R ₂ represents a (C ₂ -C ₄ ) acyl group;
X represents (OCH ₂ CH ₂ ) or (OCH ₂ (CH ₃ ) CH);
m and p each takes a value from 1 to 4,
C ₂ -C ₁₀ aliphatic mono- or dicarboxylic acids, triethyl phosphate and mixtures thereof in the following ratio of components, wt.%:
Anionic Surfactant - 1 - 30
A mixture of nonionic surfactants I and II - 0.5 - 15
Secondary Surfactant - 2 - 30
Water-insoluble hydrocarbon or perfume - 0.4 - 10
Water - Else
moreover, the composition has an ecotoxicity value, measured according to the LC 50 test of at least 0.18 ml / l when measured on microorganisms such as daphnia (Daphniae), has a viscosity at 25 ^o C, equal to 6 - 60 MPa · s, and does not contain zwitterionic surfactant or methanol. 16. A liquid crystal composition for cleaning a solid surface, containing an anionic surfactant selected from the group consisting of sulfates and sulfonates, a nonionic surfactant, a secondary surfactant, a water-insoluble hydrocarbon or perfume and water, characterized in that it contains a mixture as a non-ionic surfactant

where w = 1 to 4;
B is selected from the group consisting of hydrogen or a group represented by the formula

where R is selected from the group consisting of an alkyl group

having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, with at least one of the groups B represented by the indicated formula

R 'is selected from the group consisting of hydrogen and methyl groups;
x, y and z have values between 0 and 60, provided that (x + y + z) = 2 - 100,
where in the formula I, the ratio of monoester / diester / complex triester is 45 - 90/5 - 40/1 - 20, where the ratio of the compounds of formula I to the compound of formula II is equal to a value between 3 and 0.02;
the secondary surfactant is selected from the group consisting of propylene glycol monobutyl ether, dipropylene glycol monobutyl ether and tripropylene glycol monobutyl ether and mixtures thereof in the following ratio, wt.%:
Anionic surfactant - 0.1 - 20
Secondary Surfactant - 2 - 50
A mixture of nonionic surfactants I and II - 0.1 - 20
Water-insoluble hydrocarbon or perfume - 0.5 - 10
Water - Else
moreover, the composition has a viscosity at 25 ^o C equal to 6 - 60 MPa • s, and does not contain zwitterionic surfactant or methanol. Priority on points:
11/15/94 according to claims 1 to 14;
02/05/95 according to claims 15-16.

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