CZ150297A3 - Micro-emulsion composition for versatile use - Google Patents

Abstract

An improvement is described in a liquid crystal composition which is more environmentally friendly. The liquid crystal cleaning composition is especially effective in the removal of oily and greasy soil and has an evidenced grease release effect, contains an anionic detergent, an ethoxylated glycerol type compound, a hydrocarbon ingredient, and water.

Description

Technical field

BACKGROUND OF THE INVENTION The present invention relates to an improved all-purpose, multi-purpose liquid cleaning composition in liquid crystal form or in the form of a microemulsion, particularly for cleaning hard surfaces, which composition is effective in removing greasy and / or bathroom soils. considering

BACKGROUND OF THE INVENTION

In recent years, multipurpose liquid detergents have been widely used for cleaning hard surfaces, such as lacquered wood products and panels, paneled walls, washing containers or bathtubs, linoleum or paving floors, washable wall paper, etc. Such multipurpose versatile liquid compositions are clear and opaque aqueous mixtures of water-soluble synthetic organic detergents and water-soluble detergent salts as fillers. In order to achieve comparable cleaning performance with granular or powdered multipurpose cleaning compositions, water-soluble inorganic phosphate salts have preferably been used in the art for this purpose in multi-purpose liquid cleaning compositions. As regards the first known publications, such phosphate-containing compositions are disclosed, for example, in U.S. Patent Nos. 2560839; 3234138; No. 3350319, and in Great Patent, 9, 9, 9, 9, 9 and 9, respectively. · S »9 ···

No. 1223739.

In view of environmentalists' requirements for reducing phosphate levels in groundwater, improved multi-purpose liquid formulations have been developed containing reduced concentrations of inorganic phosphate salts as fillers or non-phosphate salts as fillers. A particularly suitable self-opaque liquid of the latter type is described in U.S. Pat. No. 4244840.

However, these multipurpose liquid detergents, containing detergent salts as fillers or other equivalent substances, tend to leave films, stains, or smudges on the cleaned, non-washed surfaces, especially the glossy surfaces. Therefore, these fluids require washing of the surfaces to be cleaned, which is time consuming for the user.

In order to overcome the previous disadvantages of the prior art in this field of multi-purpose liquid cleaning compositions, it is proposed, according to U.S. Patent No. 4017409, to use a mixture of paraffin sulfonate and a reduced concentration of inorganic phosphate salt as a filler. However, such compositions are not environmentally acceptable due to the phosphate content. On the other hand, another alternative in the preparation of phosphate-free, multipurpose liquid cleaners was the use of a mixture of anionic and nonionic detergents with small amounts of glycol ether solvent and organic amines, which is a major proportion of the composition, such as disclosed in U.S. Pat. the solution is also not fully satisfactory, since the high levels of organic detergents necessary to achieve cleaning result in foaming which, in turn, leads to foaming, which in turn leads to foaming.

the need for careful washing, which is currently considered undesirable by the consumer.

Another solution for formulating a liquid detergent composition for hard surfaces or multipurpose compositions where product homogeneity and clarity are important requirements is to prepare oil-in-water (o / w) microemulsions containing one or more surfactant detergent compounds with a water-immiscible solvent (usually hydrocarbon solvent), water and a co-surfactant compound, or co-acting surfactant, to provide product stability.

The definition of the o / w microemulsion is a spontaneously formed colloidal dispersion of a portion of the oil phase having a particle size in the range of 25 Å (2.5 nm) to 800 Å (80 nm) in the continuous aqueous phase.

In view of the extremely small particle size of the dispersed oil phase particles, the microemulsions are transparent to light and clear, and are usually highly stable to phase separation.

Patent references relating to the use of solvents for removing grease in o / w microemulsions include, for example, European Patent Applications EP 0137615 and EP 0137616 (Herbots et al.); European Patent Application EP 0160762 (Johnston et al.); and U.S. Patent No. 4,561,991 to Herbots et al. Each of these patents also describes the use of a solvent at least 5% by weight for grease removal.

From the published British patent application

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9,999 9-9 9,999 ft ··· · ······ <

«··« Φ * · 9.9 9-4 &

No. GB 2144763A (Herbots et al.), published March 13, 1985, it is known that magnesium salts increase the grease removal efficiency of organic solvents for removing greasy impurities such as terpenes in o / w microemulsion liquid detergent compositions. The compositions of the invention described by Herbots et al. they also require a content of at least 5% of a grease removal solvent in the mixture and a 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 weakly polar solvent) and at least 0.1% magnesium salt.

However, the amount of water-immiscible and sparingly soluble ingredients that may be contained in the / w microemulsion, with a low total content of active ingredients without impairing the stability of the microemulsion, is rather limited (e.g. up to 18% by weight of the aqueous phase) The presence of such high amounts of grease-removing solvent tends to reduce the total amount of fat or oil impurities that can be removed to and into the microemulsion without causing phase separation.

The following representative patents of the prior art also relate to liquid detergent cleaning compositions in the form of microemulsions: U.S. Patent Nos. 4,472,291 (Rosario); No. 4,540,448 (Gauteer et al.), No. 3723330 (Sheflin); etc.

Liquid detergent compositions containing terpenes such as α-limonene or other grease-removing solvent, even if not described in the form of an o / w microemulsion,

T · t 9 9 9 9 tf

t?

they are at the heart of the following representative patent documents; European Patent Application 0080749; United Kingdom Patent Nos. 1603047; 4414128 and 4540505. For example, U.S. Patent No. 4,414,128 extensively discloses an aqueous liquid detergent composition which may be characterized by the following percentages by weight;

(a) from 1% to 20% of a synthetic, anionic, nonionic, amphoteric or zwitterionic surfactant or a mixture thereof (b) from 0.5% to 10% of mono- or sesquiterpene or a mixture thereof, at a weight ratio of (a): (b) from 5: 1 to 1: 3; and (c) from 0.5% to 10% of a polar solvent having a water solubility at 15 ° C of from 0.2% to 10%. Other ingredients present in the formulations described in this patent comprise from 0.05% to 2% by weight of an alkali metal, alkaline earth metal or alkanolammonium soap derived from a C13 to C24 fatty acid; a calcium sequestrant in an amount ranging from 0.5% to 13% by weight; a non-aqueous solvent such as alcohols and glycol ethers in an amount of up to 10% by weight; and hydrotropes such as urea, ethanolamines, and lower alkyl aryl sulfonate salts in amounts up to 10% by weight. All of the formulations exemplified in this patent contain relatively large amounts of detergent salts as fillers that are detrimental to surface gloss.

Furthermore, it has been observed according to the invention that in formulations containing magnesium compounds to aid in the removal of grease, the addition of small amounts of filler-containing salts, such as polyphosphates

9

Alkali metals, alkali metal carbonates, nitrilotriacetic acid salts and the like, make such compositions in the form of stable microemulsion systems more difficult.

U.S. Patent No. 5,082,584 discloses a microemulsion composition comprising an anionic surfactant, a co-surfactant (co-surfactant), a nonionic surfactant, perfume, and water; however, these compositions do not show a low ecologically acceptable toxicity profile and improved interfacial tension properties as exhibited by the compositions of the present invention.

United Kingdom Patent No. 1453385 discloses the polyesterified nonionic surfactants similar to the polyesterified nonionic surfactants of the present invention. However, these nonionic surfactants disclosed in the aforementioned United Kingdom Patent No. 1453385 do not disclose the proportion of the compound of formula (II) of the present invention. It should further be noted that the formulated compositions disclosed in the aforementioned United Kingdom Patent No. 1453385 do not meet the critical limitations of the present invention.

Furthermore, there are many patents describing esterified ethoxylated glycerol compounds for various applications. These patents include, for example, United Kingdom Patent No. 1453385; Japanese Patent No. 59-1600; and Japanese Patent No. 58-206693; and European Patent Application

0586,323Al. However, the products according to these publications do not meet the requirement that, when using a mixture of esterified ethoxylated glycerol and unesterified ethoxylated

Ί *

9 9

9999 glycerol in a cleaning composition for cleaning hard surfaces, this composition acted as a grease release agent.

SUMMARY OF THE INVENTION

The present invention relates to an improved clear, liquid cleaning composition which exhibits a better interfacial tension and which provides improved hard surface cleaning in the form of a crystalline liquid composition or a microemulsion, and the composition of the invention is suitable for cleaning hard surfaces. surfaces such as plastic, glass and metal surfaces having a glossy finish. In particular, these improved cleansing compositions exhibit good grease removal properties due to improved interfacial tension when used in undiluted (clean) form, which, when applied, results in clean surfaces being shiny and unnecessary rinse or wipe or require minimal rinsing or wiping. The latter characteristic is apparent from the fact that few or no residual residues remain on the non-rinsed cleaned surfaces, and thus one of the disadvantages of the prior art products is overcome.

More specifically, the improved cleansing compositions of the present invention exhibit good greasy soil removal properties due to improved surface tension when used in undiluted (clean) form and leave the cleaned surfaces shiny without requiring or requiring at least a minimum rinse or wipe. The latter characteristic is evident from little or no invisible residues on the non-rinsed cleaned surfaces

• ······

999 · ···· and accordingly, one of the disadvantages of prior art products is overcome. The present compositions exhibit a grease release effect by the present compositions preventing or reducing the deposition of greasy soils on surfaces that have been cleaned with the compositions of the invention as compared to surfaces cleaned with a liquid crystal composition or a commercial microemulsion composition, which means cleans the next cleaning. The instant composition of the present invention exhibits a grease removal effect by preventing or reducing or preventing the deposition of greasy soils on surfaces that have been cleaned by the instant composition of the present invention as compared to surfaces cleaned with conventional crystal. a liquid composition or a conventional prior art microemulsion composition, which means that a surface contaminated with a greasy dirt is easier to clean during subsequent cleaning. Surprisingly, it has been found that the above desired results can be achieved without the use of polyphosphates or other inorganic or organic detergent salts as builders, and also in the complete absence of solvent, or substantially complete solvent, to remove grease.

The compositions of the present invention are much more environmentally friendly due to the low ecotoxicity of the ethoxylated type compounds used in these instant compositions.

The compositions of the present invention have an ecotoxicity value measured according to the LC 50 test, which is recognized by The Organization for Economic Cooperation and 9.

99999 9 99999 999 9

9 9 9 9 9

999 9 · 9 9 9 · 9 9 ·, ······

Development (OECD) and which are US members, in OECD Test No. 202, not more than 0.18 milliliters / liter measured on Daphniae microorganisms.

According to a first aspect, the present invention relates generally to a stable, versatile and multipurpose hard surface cleaning composition which is particularly effective in removing oily and greasy dirt, wherein the composition is in the form of a substantially dilute oil-in-water microemulsion having an aqueous phase and oil phase. This diluted o / w microemulsion contains the following components, expressed as a percentage by weight:

0.1% to 20% by weight of anionic surfactant;

from 0.1% to 20% of an anionic surfactant;

from 0.1 to 50% of a water miscible co-surfactant (cosurfactant) having either limited ability or substantially no oil or greasy soil dissolution capacity;

0.1% to 20% of a compound that is a mixture of a partially esterified ethoxylated polyhydric alcohol, a fully esterified polyhydric alcohol and an unesterified ethoxylated polyhydric alcohol, hereinafter referred to as the ethoxylated glycerol type compound);

up to% magnesium sulfate heptahydrate; and up to 10.0% of a water-insoluble perfume or hydrocarbon, and

0.1 to 85% water, wherein said ratios are based on the total weight of the composition.

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In another aspect, the present invention relates generally to a stable, clear, versatile and versatile cleaning composition which is effective in removing oil and greasy soil and which is in the form of a substantially diluted oil-in-water microemulsion, the microemulsion having an aqueous phase and an oil phase. The aqueous phase of this diluted o / w microemulsion contains the following components, expressed as a percentage by weight:

from 0.1% to 20% of an anionic surfactant;

from 0.1 to 50% of a water-miscible co-surfactant (cosurfactant) having either limited ability or substantially no solubility to oily or greasy dirt;

0.4 to 1.0% citric acid trialkyl ester;

0.1% to 10% of a compound that is a mixture of a partially esterified ethoxylated polyhydric alcohol, a fully esterified ethoxylated polyhydric alcohol, and an unesterified polyhydric alcohol (this composition is referred to herein as an ethoxylated glycerol type compound);

up to 15% magnesium sulfate heptahydrate;

0.4 to 10.0% perfume or water insoluble hydrocarbon, and up to 85% water, wherein said ratios are based on the total weight of the composition.

In another aspect, the invention generally relates to a stable, versatile, multi-purpose hard surface cleaning composition that is particularly effective for removing dirt particles, wherein the cleaning composition of the invention is in the form of a substantially diluted oil-in-water microemulsion,

Means that it has an aqueous phase and an oil phase. The diluted microemulsion comprises the following components, the percentage by weight being from 0.1% to 20% of an anionic surfactant;

from 0.1 to 50% of a water-miscible co-surfactant (cosurfactant) having either limited ability or substantially no oil or greasy soil dissolving capacity;

0.1% to 20% of ethoxylated polyhydric alcohol;

up to% magnesium sulfate heptahydrate;

0.1 to 10.0% perfume or water-insoluble hydrocarbon, and up to 85% water, wherein said ratios are based on the total weight of the composition. The composition may also contain 0 to 10% by weight, preferably 1 to 7% by weight, of an ethoxylated polyhydric alcohol monoester of the formula

CH ₂ -O- (CH ₂ CH-O) _x -b R '

I [CH-O- (CH ₂ CH 0) _y -B] _w R '

I ch ₂ -o- (ch ₂ ch-o) _z -b in which:

W is equal to one to four, most preferably one;

two of B are hydrogen and one of B is selected from the group consisting of formula

II —C — R in which:

R is selected from the group consisting of alkyl groups of 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms, and alkenyl groups of 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms, with hydrogen tallow alkyl and coconut alkyl chain being most preferred x, y and z have a value between 0 and 60, more preferably 0 to 40, with the proviso that (x + y + z) is 2 to 100, preferably 4 to 24, and most preferably 4 to 19.

The composition may also contain 0 to 2% by weight, preferably 0.1 to 1.0% by weight, of an ethoxylated polyhydric alcohol diester of the formula

R ’

AND

CH ₂ -O- (CH ₂ CH-O) _x -b R '[CH-O- (CH ₂ CH 0) _y -B] _w R' ch ₂ -o- (CH ₂ CH-O) _z -b

··

I • · in which:

w is equal to one to four, most preferably one, one of B is hydrogen and two B are selected from the group consisting of

II —C — R in which:

R is selected from the group consisting of alkyl groups of 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms, and alkenyl groups of 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms, with hydrogen tallow alkyl and coconut alkyl chain being most preferred x, y and z have a value between 0 and 60, more preferably 0 to 40, with the proviso that (x + y + z) is 2 to 100, preferably 4 to 24, and most preferably 4 to 19.

The composition may also contain 0 to 1.0 percent by weight, more preferably 0.02 to 0.6 percent by weight, of an ethoxylated polyhydric alcohol triester of the formula 9 9 9

9 9 9 9 9 9 9 9 9 • ······ · 9 9 9999

9 9 9 9 9

9999 9 99

R ’

AND

CH ₂ -O- (CH ₂ CH-O) _x —b R '[CH-O- (CH ₂ CHO) _y -B] _w R'

I ch ₂ -o- (ch ₂ ch-o) _z —b in which:

v is equal to one to four, most preferably one. The three B's are selected from the group consisting of the formula wherein:

R is selected from the group consisting of alkyl groups of 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms, and alkenyl groups of 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms, with hydrogen tallow alkyl and coconut alkyl chain being most preferred x, y and z have a value between 0 and 60, more preferably 0 to 40, with the proviso that (x + y + z) is equal to 2 to 60, preferably 4 to 24, and most preferably 4 to 19.

This dispersed o / w oil phase of the microemulsion consists essentially of a water-immiscible or poorly perfume.

Water-soluble flflfl flflfl flflfl water-soluble

It has surprisingly been found that although the perfume itself is not a solvent for oily or oily dirt, although such perfumes may actually contain up to 80% of terpenes known as good grease solvents, the compositions of the invention in diluted form have the capacity to dissolve oily or greasy dirt up to 10 times or more the weight of the perfume, wherein the dirt is removed or released from the hard surface by the action of anionic or nonionic surfactants and entrained in the oily phase o / w of the microemulsion.

In another aspect, the present invention relates generally to a highly concentrated microemulsion composition in the form of either an oil-in-water (o / w) or a water-in-oil (w / o) microemulsion which when diluted with an additional portion of water can form an o / w microemulsion composition. In particular, these microemulsion compositions comprise the following components, expressed as a percentage by weight:

0.1% to 20% of anionic surfactant, 0.1% to 20% of ethoxylated glycerol type compound% to 2.5% of fatty acid,

0.1% to 10% of a perfume or water insoluble hydrocarbon containing from 6 to 18 carbon atoms,

0.1% to 50% of a co-surfactant (cosurfactant), and% to 97% of water.

• · ····

9 · 9 9 «• · 99 9 999 9

9

99 99 ©

In another aspect, the present invention relates to liquid crystal compositions comprising the following components, expressed in percent by weight:

0.1% to 20% of anionic surfactant,

0.1% to 20% ethoxylated glycerol type compound,% to 2.5% fatty acid,

0.1% to 10% perfume, more preferably 1% to 10%,% to 50% of a co-surfactant (cosurfactant) selected from the group consisting of propylene glycol monobutyl ether, dipropylene glycol monobutyl ether and tripropylene glycol monobutyl ether, and mixtures thereof and the remainder being water.

In a further aspect, the present invention generally relates to a highly concentrated microemulsion composition in the form of either an oil-in-water (o / w) or a water-in-oil (w / o) microemulsion, which when diluted with an additional portion of water may form o / w microemulsion composition. Generally, these microemulsion compositions contain the following components, the content of which is given in percent by weight:

0.1% to 20% of anionic surfactant,

0.1% to 10% of an ethoxylated glycerol type compound,

0.4% to 10% of a perfume or water insoluble hydrocarbon containing from 6 to 18 carbon atoms,

0.1% to 50% of a co-surfactant (cosurfactant), and% to 97% of water.

In another aspect, the present invention relates generally to a highly concentrated microemulsion composition in the form of either

99

9 9 9 9 9 9 9 9 9 9 9

9999 99 9,999 9,999 9

9 9 9 9 9

The oil-in-water microemulsion (o / w) or the water-in-oil microemulsion (w / o), which, when diluted with an additional portion of water before use, can form an o / w microemulsion composition. Generally, these microemulsion compositions contain the following components, expressed as a percentage by weight:

0.1% to 20% of anionic surfactant, 0.1% to 20% of ethoxylated polyhydric alcohol,

0.1% to 10% of a perfume or water insoluble hydrocarbon containing from 6 to 18 carbon atoms,

0.1% to 50% of a co-surfactant (cosurfactant), and 20% to 97% of water.

In a further aspect, the present invention relates to a liquid crystal composition comprising the following components, expressed in percent by weight:

0.1% to 20% of anionic surfactant, 0.1% to 20% of ethoxylated polyhydric alcohol,

0.1% to 10% perfume, more preferably 1% to 10%,% to 50% co-surfactant (cosurfactant), and the remainder being water.

The present invention relates to a stable liquid crystal or microemulsion composition comprising the following components, the content of which is expressed in percent by weight:

0.1% to 20% of anionic surfactant,

0.1% to 50% of a co-surfactant (cosurfactant),

0.1% to 20% ethoxylated glycerol compound ···· · ·

··· ·

-type

0.1% to 10% of a water or perfume insoluble hydrocarbon, the remainder being water, said composition having an ecotoxicity value as measured by an LC50 test of at least 0.18 milliliters / liter measured on Daphniae microorganisms.

The present invention also relates to a stable liquid crystal or microemulsion composition comprising the following components, the content of which is expressed in percent by weight:

0.1% to 20% of anionic surfactant,

0.1% to 50% of a co-surfactant (cosurfactant),

0.4% to 1.0% by weight of citric acid trialkyl ester in the form of tri-n-butyl citrate,

0.1% to 20% of an ethoxylated glycerol type compound

0.1% to 10% of a water or perfume insoluble hydrocarbon, and the remainder being water, wherein said composition has an ecotoxicity value measured by LC50 test of at least 0.18 milliliters / liter measured on Daphniae microorganism.

The present invention also relates to a stable liquid crystal or microemulsion composition comprising the following components, which are expressed in percent by weight:

0.1% to 50% of an anionic surfactant,

0.1% to 50% of a co-surfactant (cosurfactant),

• 9 9 9 9 9 9

99 9

1, 1% to 20% of an ethoxylated glycerol type compound,

0.1% to 10% of a water or perfume insoluble hydrocarbon, and the remainder being water.

The composition may also contain 0 to 10% by weight, preferably 1 to 7% by weight, of an ethoxylated polyhydric alcohol monoester of the formula

R 'ch ₂ -o- (ch ₂ ch-o) _x -b

R ’

I [CH-O- (CH ₂ CH 0) _y -B] _w R '

I ch ₂ -o- (ch ₂ ch-o) _z —b in which:

w is equal to one to four, most preferably one, two of B are hydrogen and one B is selected from the group consisting of the formula wherein:

II

R is selected from the group consisting of alkyl groups 99

9 9 1 • 9 9

Containing from 9 to 22 carbon atoms, more preferably from 11 to 15 carbon atoms, and alkenyl groups containing from 6 to 22 carbon atoms, more preferably from 11 to 15 carbon atoms, with a hydrogenated tallow alkyl chain and a coconut alkyl chain being most preferred, x, y and z have a value between 0 and 60, more preferably 0 to 40, with the proviso that (x + y + z) is 2 to 100, preferably 4 to 24, and most preferably 4 to 19.

The composition may also contain 0 to 2% by weight, more preferably 0.1 to 1.0% by weight, of an ethoxylated polyhydric alcohol diester of the formula

R ’

AND

CH ₂ -O- (CH ₂ CH-O) _x —b R '

I [CH-O- (CH ₂ CH 0) _y -B] _w R '

I ch ₂ -o- (ch ₂ ch-o) _z —b in which:

w is from one to four, most preferably one, one of B is hydrogen and two B are selected from the group consisting of formula f |

C-R 9 9 9

9 99

·· ···· in which :

R is selected from the group consisting of alkyl groups of 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms, and alkenyl groups of 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms, with a hydrogenated tallow alkyl chain and a coconut alkyl chain most preferred x, y and z have a value between 0 and 60, preferably 0 to 40, with the proviso that (x + y + z) is equal to 2 to 100, preferably 4 to 24, and most preferably 4 to 19.

The composition may also contain 0 to 1.0 weight percent, more preferably 0.02 to 0.6 weight percent, of an ethoxylated polyhydric alcohol triester of formula

R ’

CH ₂ -O- (CH ₂ CH-O) _χ -Β R '

I [CH-O- (CH ₂ CH 0) _y -B] _in R '

I ch ₂ -o- (ch ₂ ch-o) _z —b in which:

v is one to four, most preferably one, three B are selected from the group consisting of the formula

II • · in which:

R is selected from the group consisting of alkyl groups of 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms, and alkenyl groups of 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms, with a hydrogenated tallow alkyl chain and a coconut alkyl chain most preferred x, y and z have a value between 0 and 60, more preferably 0 to 40, with the proviso that (x + y + z) is 2 to 100, preferably 4 to 24, and most preferably 4 to 19.

According to the present invention, the water-insoluble perfume functions as a hydrocarbon. Typically, in aqueous-based compositions, the presence of solubilizers such as the hydrotrope of an alkali metal lower alkylarylsulfonate, triethanolamine, urea, etc. is required to dissolve the perfume, especially at perfume concentrations of 1% or higher, relative to the perfume concentration. that perfumes are generally mixtures of essential essential oils and aromatic compounds which are usually not water-soluble. Therefore, incorporating perfume into this aqueous cleaning composition as an oil (hydrocarbon phase) in the final o / w microemulsion composition achieves several different important advantages.

Firstly, the cosmetic properties of this final cleaning composition are improved so that the compositions are not only clear (as a result of microemulsion formation) but also highly fragrant (as a result of the level of added perfume).

Secondly, the need to use solvents which do not contribute to the cleaning performance is eliminated.

··························································· • · · · · · · · · · · · · · · ·

Third, an improved grease release effect and improved grease removal capacity can be achieved when using the original (undiluted) composition, taking into account the dilution aspect, or when using a dilute concentrate without detergent builders or buffers or commonly used solvents for removal of grease at neutral or acidic pH and at low concentrations of active ingredients, and improved cleaning performance can also be achieved by using a diluted composition.

The term perfume as used herein has its usual meaning, and it is generally intended to include any water-insoluble fragrance substance or mixture of substances including natural essences (i.e. essences obtained by extracting flowers, leaves, fruit tree blossoms or artificial essences (i.e. mixtures of natural oils or oil components) and synthetically produced representing fragrant essences. Typically, these perfumes are complex mixtures of mixtures obtained by mixing various organic compounds such as alcohols, aldehydes, ethers, aromatics and varying amounts of essential oils (e.g. terpenes) in the range of, for example, 0% to 80%, usually 10% to 70% by weight, these essential oils in themselves being volatile fragrance compounds which also serve to dissolve other perfume ingredients.

In the present invention, the exact composition of the perfume is not essential from the standpoint of purifying performance if it meets the water immiscibility criteria and has a pleasant odor.

Naturally, however, with particular reference to a cleaning composition intended for domestic use, the perfume would, of course, be perfume. 9 as well as all other ingredients, should be cosmetically acceptable, that is to say, non-toxic, hypoallergenic, etc. The compositions of the present invention exhibit significantly improved ecotoxicity compared to existing commercial products.

The perfume hydrocarbon is present in the diluted o / w microemulsion in an amount of from 0.1% to 10% by weight, preferably from 0.4% to 6.0% by weight, particularly preferably from 0.5% to 3% % by weight, expressed as a percentage by weight. When the amount of hydrocarbon (perfume) is less than 0.4% by weight, it becomes more difficult to formulate it into an o / w microemulsion. In the case of a liquid crystal composition, at least 0.5% by weight of the perfume, more preferably 1% by weight, is required. If the hydrocarbon (perfume) is added in amounts greater than 10% by weight, the cost of the composition increases without further improvement in cleaning, and in fact there will be some relative reduction in cleaning efficiency in terms of the total amount of greasy or oily soil, to be removed to the oil phase of the microemulsion.

In addition, while achieving excellent grease removal performance for perfume compositions containing no terpene solvents, it is obviously difficult for perfume experts to formulate sufficiently cheap perfume compositions for products of this type (i.e., to produce conventional consumer-type products, which are very sensitive to increased cost) which contain less than 20%, usually less than 30% of such terpene solvents.

So, from a practical point of view only,

Economically, the diluted o / w microemulsion detergent cleaning compositions of the present invention can often contain up to about 0.2% to 7% by weight of terpene solvents, based on the total weight of the composition, which are incorporated by the perfume component into these compositions. However, although the amount of terpene solvent in the cleaning composition of the invention is less than 1.5% by weight, such as up to 0.6% by weight or 0.4% by weight or less, it is possible to apply diluted o / w microemulsions of the present invention yet achieve a satisfactory grease and oil removal capacity.

In a typical diluted o / w microemulsion formulation of the present invention, a 20 ml o / w microemulsion sample containing 1% by weight perfume is able to dissolve up to 2 to 3 milliliters of greasy and / or oily dirt while maintaining its microemulsion form, without whether the perfume contains 0%, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight or 0.8% by weight of a terpene solvent. In other words, an essential feature of the present invention is that the grease removal results from the composition being in the form of a microemulsion per se and not in the presence or absence of a greasy soil removal type solvent in the microemulsion.

Instead of the perfume, water-insoluble paraffin or isoparaffin containing 6 to 18 carbons in a concentration of 0.4 to 8.0% by weight, more preferably 0.4 to 3.0% by weight, can be used.

· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·· ·

The water-soluble organic detergent materials used to prepare the final o / w microemulsion compositions of the present invention may be selected from the group consisting of a water-soluble, non-soap anionic fatty acid mixed surfactant and a solubilizing agent that is partially esterified ethoxylated polyhydric alcohol such as partially esterified ethoxylated glycerol.

While conventional nonionic surfactants can be used in the compositions of the present invention, the use of such conventional nonionic surfactants in the compositions of the present invention will reduce the environmental profile of the composition and also have an adverse effect on the properties of the composition when regarding the release of grease and removal of grease + dirt particles.

With respect to the anionic surfactants contained in microemulsions o / w, any commonly used water-soluble anionic surfactants or mixtures of said anionic surfactants can be used in the compositions of the invention and thus can be used for the purposes of the invention. The term anionic surfactant as used herein means a class of anionic or mixed anionic-nonionic surfactants providing a cleansing effect.

Suitable water-soluble non-soap anionic surfactants include those surfactant or detergent compounds that contain an organic hydrophobic group containing generally from 8 to 26 generally. ······························· 9 9

9999 99 9,999 9,999 9

9 9 9 9 9

9999 9 99 99 99 9 and preferably 10 to 18 carbon atoms in their molecular structure and at least one water-soluble group selected from the group of sulfonates, sulfates and carboxylates to form a water-soluble surfactant. Typically, the hydrophobic group comprises an alkyl, an alkyl group containing 8 to 22 carbon atoms, an alkyl group or an acyl group. Such surfactants are used as water-soluble salts and the salt forming cation usually is selected from the group consisting of sodium, potassium, ammonium, magnesium and mono-, di- or _tri-C2-C3 -alkanolamonný cation, with the proviso It is preferred that sodium, magnesium and ammonium cations be used.

Examples of suitable sulfonated anionic surfactants are the commonly known higher mono-nuclear higher alkyl aromatic sulfonates, such as higher alkylbenzene sulfonates containing from 10 to 16 carbon atoms in the straight or branched chain alkyl group, alkyl toluene sulfonates containing from 8 to 15 atoms and alkylphenolsulfonates containing from 8 to 15 carbon atoms in the alkyl group.

Preferably, the sulfonate is a linear alkylbenzene sulfonate containing a higher content of 3- (or higher) phenyl isomers and a corresponding low content (below 50%) of the 2- (or lower) phenyl isomers, i.e. wherein the benzene ring is preferably attached from a large and the content of isomers in which the benzene ring is attached in the 2 or 1 position is correspondingly low. Particularly preferred compounds of this type are disclosed in the United States Patent. &Lt; RTI ID = 0.0 &gt; &quot; &quot; &lt; / RTI &gt; · No. · US No. 3320174.

Other suitable anionic surfactants include olefin sulfonates, including long alkene chain alkene sulfonates, long alkane chain hydroxyalkane sulfonates, or mixtures of alkene sulfonates and hydroxyalkane sulfonates. These olefin sulfonate detergents can be prepared in a known manner by reacting sulfur trioxide (SO ₃ ) with long chain olefins containing 8 to 25 carbon atoms, preferably 12 to 21 carbon atoms, having the general formula:

RCH = CHR- _L in which:

R is a higher alkyl group having 6 to 23 carbon atoms and

R 6 is an alkyl group having 1 to 17 carbon atoms or a hydrogen atom to form a mixture of sulfones and alkenesulfonic acids, which is then worked up to convert the sulfones to sulfonates. Preferred olefin sulfonates contain 14 to 16 carbon atoms in the R alkyl group and are obtained by sulfonation of the 2-olefin.

Other examples of suitable anionic sulfonate surfactants include paraffin sulfonates containing 10 to 20 carbon atoms, preferably 13 to 17 carbon atoms. Primary paraffin sulfonates are prepared by the reaction of long-chain alpha-olefins and bisulfites, the paraffin sulfonates having a sulfonate group distributed along the paraffin chain are disclosed in U.S. Patent Nos. 2503280; 2507088; 3260744; 3372188 and German patent 735096.

Examples of suitable anionic sulfate surfactants are alkyl sulfate salts of 8 to 18 carbon atoms in the alkyl moiety and alkyl ether polyethenoxy sulfate salts of 8 to 18 carbon atoms having the general formula:

R (OCH ₂ H ₄ ) _n OSO ₃ M in which:

n is 1 to 12, preferably 1 to 5, and

M is a solubilizing cation selected from the group consisting of sodium, potassium, ammonium, magnesium and mono-, di- or triethanolammonium ions.

These alkyl sulfates can be obtained by sulfating the alcohols obtained by reducing the glycerides of coconut oil or tallow or a mixture thereof and neutralizing the resulting product. On the other hand, the alkyl ether polyethenoxy sulfates are obtained by sulfating the condensation product of ethylene oxide with a C8 -C18 alkanol and neutralizing the resulting product. Alkyl sulfates can be obtained by sulfating alcohols obtained by reducing the glycerides of coconut oil or tallow or mixtures thereof and neutralizing the resulting product. On the other hand, the alkyl ether polyethenoxy sulfates are obtained by sulfating the condensation product of ethylene oxide with an C 8 -C 18 alkanol and neutralizing the resulting product.

These alkyl ether polyethenoxy sulfates differ in the number of moles of ethylene oxide reacted with one mole of alkanol. Preferred alkyl sulfates and preferred alkyl ether polyethenoxy sulfates contain 10 to 16 carbon atoms in the alkyl group.

Alkylphenyl ether polyethenoxy sulfates containing from 8 to 12 carbon atoms in the alkyl moiety containing from 2 to 6 moles of ethylene oxide per molecule are also suitable for use in the compositions of the invention. These detergents can be prepared by reacting alkylphenols with 2 to 6 moles of ethylene oxide and sulfating and neutralizing the resulting ethoxylated alkylphenols.

It is understood that these anionic surfactants will be present either in acid or salt form depending on the pH of the final composition, with the salt-forming cation being the same as in other anionic detergents.

Of these non-soap anionic surfactants, preferred surfactants are C8-C15 linear alkylbenzene sulfonates and C13-C18-paraffin or alkane sulfonates. Particularly preferred compounds are

C 1-6 -C-11-alkylbenzenesulfonates and sodium salts

C ₁₃ -C 6 -alkane sulfonates.

Generally, the proportion of non-soap anionic surfactant is in the range of 0.1% to 20.0%, preferably 1% to 7% by weight of the diluted o / w microemulsion composition.

The product of the present invention comprises a composition (hereinafter referred to as an ethoxylated glycerol type compound) that is a mixture of a fully esterified ethoxylated polyhydric alcohol, a partially esterified polyhydric alcohol and a non-esterified ethoxylated polyhydric alcohol, wherein the preferred polyhydric alcohol is glycerol, the compound is a compound of formula I

9 9 9

9 99

9 9 9

9 9

99

·· · · · · ····

R ’

I ch ₂ -o- (CH ₂ CH-O) _x -b R '

I [CH-O- (CH ₂ CHO) _y -B] _w (I)

R ’

I ch ₂ -o- (ch ₂ ch-o) _z -b a compound of formula II:

R ’

I ch ₂ -o- (CH ₂ CH-O) _x -h R '

I [CH-O- (CH ₂ CH 0) _y -H] _w (II)

R ’

AND

CH ₂ -O- (CH ₂ CH-O) _z -h in which:

w is equal to one to four, most preferably one,

B is selected from the group consisting of hydrogen or a group of formula

II

99

9

9

9,999 9 9

9 9 9

99 99 • · ···· · · ···· · · · · 9

9 • · in which:

R is selected from the group consisting of alkyl groups of 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms, and alkenyl groups of 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms, with hydrogen tallow alkyl and coconut alkyl chain being most preferred wherein at least one of the B groups has the formula

II

CR and R 'are selected from the group consisting of hydrogen and methyl, x, y and z have a value between 0 and 60, more preferably 0 to 40, with the proviso that (x + y + z) is 2 to 100, preferably 4 to 24 and most preferably 4 to 19, wherein in formula I the monoester / diester / triester ratio is 45 to 90/5 to 40/1 to 20, more preferably 50 to 90/9 to 32/1 to 12, wherein the ratio of formula I to formula II it has a value of between 3 and 0.02, preferably 3 to 0.1, most preferably 1.5 to 0.2, and most preferably the compound of formula (II) is greater than the compound of formula (I) .>

The ethoxylated glycerol type compound used in the composition of the present invention is a product of Kao Corporation and is commercially available under the trade name Levenol such as Levenol F-200 having an average EO of 6 and a molar ratio of coconut fatty acids to glycerol. 0.55, or Levenol V501 / 2, which has an average EO value of 17 and a molar ·· ····

9 ·

9 9 ·· ♦

999 9 ratio of tallow fatty acid to glycerol 1.0. preferably, the molar ratio of fatty acid to glycerol is less than 1.7, more preferably less than 1.5, and most preferably less than 1.0. This ethoxylated glycerol type compound has a molecular weight in the range of 400 to 1600 and a pH value (50 grams / liter of water) in the range of 5 to 7. These compounds, known under the Levenol trademark, are substances that are substantially non-irritating human skin and having a primary biodegradability greater than 90% as measured by the Vickbold method of Bias-7d.

Two examples of Levenol compounds include Levenol V-501/2 having 17 ethoxylated groups and derived from a tallow fatty acid having a fatty acid to glycerol ratio of 1.0 and a molecular weight of 1465, and Levenol F-200 having 6 ethoxylated groups and is derived from a coconut fatty acid having a fatty acid to glycerol ratio of 0.55. Both Levenol F-200 and Levenol V-501/2 consist of a mixture of compounds of Formula I and Formula II. The levenol compounds have ecotoxic values of algal growth inhibition > 100 mg / liter; acute toxicity to Daphniae> 100 mg / liter and acute toxicity to fish> 100 mg / liter. Levenol compounds have an easy biodegradability of greater than 60%, which is the minimum required value according to OECD 301B for acceptable biodegradability.

Also suitable for instant compositions of the present invention are the non-ionic compounds Crovol PK-40 and Crovol PK-70, manufactured by Croda GMBH, The Netherlands. Crovol PK-40 is a polyoxyethylene (12) Palm Kernel Glyceride that has 12 EO groups. Crovol PK-70, which is a preferred compound for this purpose, is polyoxyethylene (45) Palm. · · · ··· · ··· · · · · · · · · · · · · ·

Kernel Glyceride containing 45 EO groups.

In diluted o / w microemulsion compositions or liquid crystal compositions, ethoxylated glycerol type compounds or polyesterified nonionic compounds are present in admixture with an anionic detergent. The proportion of the ethoxylated glycerol type compound or polyesterified nonionic solubilizing agent in the liquid crystal composition or the final diluted o / w microemulsion composition ranges from 0.1% to 20% by weight, preferably from 0.5% to 10% by weight. most preferably in the range from 0.5% to 6% by weight.

Further, in preferred compositions of the present invention, the weight ratio of the non-soap anionic detergent to the ethoxylated glycerol type compound is in the range of 3; 1 to 1: 3 with particularly good results obtained using a 2: 1 weight ratio.

The ethoxylated polyhydric alcohol of the present invention, such as ethoxylated glycerol, can be represented by the following formula:

99

9 9 9

9

9 9999

9 9 9 9 9

9

9

9

9

R ’

AND

CH ₂ -O- (CH ₂ CH-O) _x -h R '

I [CH-O- (CH ₂ CHO) _y -H] _in R '

I ch ₂ -o- (CH ₂ CH-O) _z —h in which:

w is equal to one to four, most preferably one x, y and z are between 0 and 60, more preferably 0 to 40, with the proviso that the sum (x + y + z) is equal to 2 to 100, preferably 4 to 24 and most preferably 4 to 19.

In diluted o / w microemulsion compositions or liquid crystal compositions, the ethoxylated alcohol is present in admixture with an anionic surfactant. The proportion of the ethoxylated glycerol type compound in the weight of the liquid crystal composition or final diluted o / w of the microemulsion composition is in the range of 0.1% to 20% by weight, preferably in the range of 0.5% to 10% by weight, most preferably 0.5% to 6% by weight.

Further, in preferred compositions of the invention, the weight ratio of the non-soap anionic surfactant to the ethoxylated polyhydric alcohol ranges from 3: 1 to 1: 3, with particularly good results being obtained at a weight ratio of 2: 1.

The compositions of the present invention may also

99

9

9

9,999 9 9

9 9 9

99 99

9 • 9 9

9 9

9999 9

9 • 999 8

9999

9

9

9

9 contain 0 to 10% by weight, preferably 1 to 7% by weight, of the monoester of the ethoxylated polyhydric alcohol represented by the formula

R ’

AND

CH ₂ -O- (CH ₂ CH-O) _x —b R '

I [CH-O- (CH ₂ CH 0) _y -B] _w R '

I ch ₂ -o- (ch ₂ ch-o) _z -b in which:

w is one to four, most preferably one, two of B are hydrogen and one B is selected from the group consisting of the formula

II

C-R in which:

is selected from the group consisting of alkyl groups of 6 to 22 carbon atoms, preferably 11 to 15 carbon atoms, and alkenyl groups of 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms, most preferably the alkyl chain of hydrogenated tallow and coconut alkyl chain, ··

9 9 9 9 • 9 9 99

9 9 9

99 99

·· • ·

9 x, y and z have a value between 0 and 60, preferably 0 to 40, with the proviso that (x + y + z) is 2 to 100, preferably 4 to 24 and most preferably 4 to 19.

The composition of the invention may also contain 0 to 2% by weight, preferably 0.1 to 1.0% by weight, of an ethoxylated polyhydric alcohol diester of the formula

R ’

AND

CH ₂ -O- (CH ₂ CH-O) _x -b R '

I [CH-O- (CH ₂ CH 0) _y -B] _w R '

I ch ₂ -o- (ch ₂ ch-o) _z -b in which:

w is one to four, most preferably one, one of B is hydrogen and two B are selected from the group consisting of

-R in which:

R is selected from the group consisting of alkyl groups containing 6 to 22 carbon atoms, preferably 11 to 10 carbon atoms;

# · · · · · · · · · * * * * · · ·

Carbon atoms and alkenyl groups having 6 to 22 carbon atoms, preferably 11 to 15 carbon atoms, most preferably a hydrogenated tallow alkyl chain and a coconut alkyl chain, x, y and z are between 0 and 60, more preferably 0 to 40, with the proviso that (x + y + z) is 2 to 100, preferably 4 to 24, and most preferably 4 to 19.

The composition of the present invention may also contain 0 to 1.0 wt%, preferably 0.02 to 0.6 wt%, of an ethoxylated polyhydric alcohol triester of formula

R ’

AND

CH ₂ -O- (CH ₂ CH-O) _x —β R '

I [CH-O- (CH ₂ CH 0) _y -B] _w R 'ch ₂ -o- (CH ₂ CH-O) _z -b wherein:

w is equal to one to four, most preferably one, three B are selected from the group consisting of the formula

·· ···· in which :

R is selected from the group consisting of alkyl groups of 6 to 22 carbon atoms, preferably 11 to 15 carbon atoms, and alkenyl groups of 6 to 22 carbon atoms, preferably 11 to 15 carbon atoms, with the alkyl chain hydrogenated most preferred tallow and a coconut alkyl chain, x, y and z have a value between 0 and 60, more preferably 0 to 40, with the proviso that (x + y + z) is 2 to 100, preferably 4 to 24, and most preferably 4 to 19.

The compositions of the present invention optionally contain 0 to 1.0% by weight, preferably 0.4 to 0.8% by weight, of a trialkyl citrate such as tri-n-butyl citrate, tri-n-propyl citrate, triisopropyl citrate, tri-isobutyl citrate, tri n-pentyl citrate and tri-n-hexyl, with tri-n-butyl citrate being preferred. Tri-n-butyl citrate acts as a foam control agent in the composition in that the foam is more easily degradable, so that the article can be washed more efficiently.

The co-acting surfactant (cosurfactant) may play an essential role in formulating the above liquid crystal compositions or diluted o / w microemulsions and concentrated microemulsion compositions.

According to the invention, three main classes of compounds have been found which are highly suitable co-acting surfactants (cosurfactants) for microemulsions over a temperature range ranging from 5 ° C to 5 ° C. ° C, for example;

(1) water-soluble C 3 -C 4 alkanols, propylene glycol of the formula HO (CH 2 CHCl 4 O) _n H, where n is a number from 2 to 18, and monoalkyl ethers and esters of ethylene glycol and propylene glycol having the structural formulas:

R (X) _n OH and R-1CXIhOH in which:

R represents an alkyl group having 1 to 6 carbon atoms,

R 1 is an acyl group having 2 to 4 carbon atoms,

X is (OCH ₂ CH ₂ ) or (OCH ₂ (CH ₃ ) CH) and n is a number from 1 to 4;

(2) aliphatic mono- and di-carboxylic acids containing 2 to 10 carbon atoms, preferably 3 to 6 carbon atoms per molecule;

(3) triethylphosphate.

Furthermore, mixtures of two or more of the three classes of co-active surfactants can be used, if a specific pH is desired.

When mono-dicarboxylic acids (class 2) are used as co-surfactants (cosurfactants) in the microemulsion compositions of the present invention at a concentration of 2 to 10% by weight, the microemulsion compositions can be used as cleaners for bathtubs and other hard surfaces that are resistant against acid, thereby removing lime deposits, soapy dirt and greasy dirt from surfaces so contaminated without damaging them. If these surfaces are zirconium white enamel, they can be damaged by these compositions.

• ·

Aminoalkylenephosphonic acid at a concentration of 0.01 to 0.2% by weight can optionally be used in conjunction with mono- and dicarboxylic acids, wherein the aminoalkylenephosphonic acid helps prevent damage to the zirconium white enamel surfaces. In addition, 0.05 to 1% by weight of phosphoric acid may be used in the composition.

Methanol and ethanol are explicitly excluded from the composition of the invention because of their low flash point.

Representative examples of polypropylene glycol include dipropylene glycol and polypropylene glycol having molecular weights ranging from 200 to 1000, for example polypropylene glycol 400. Other suitable glycol ethers are ethylene glycol monobutyl ether (butylcellosolve), diethylene glycol monobutyl ether (butylcarbitol), triethylene glycol monobutyl ether, tripropylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol tert-butyl ether, ethylene glycol monoacetate and dipropylene glycol propionate. When glycol type cosurfactants are used at a concentration of at least 1.0% by weight, preferably at least 2.0% by weight in combination with the perfume at a concentration of at least 0.5% by weight, more preferably 1.5% by weight then a liquid crystal composition can be formed.

Representative examples of aliphatic carboxylic acids include monobasic and dibasic, monobasic and dibasic acids. Alkyl and alkenyl acids of 3 to 6 carbon atoms, such as glutaric acid and mixtures of glutaric acid with adipic acid and succinic acid as well as mixtures of the abovementioned acids as well as acrylic acid or propionic acid.

While all of the above glycol ether compounds and acidic compounds can achieve the described stability, the most preferred co-surfactants (cosurfactants) of any type, taking into account price and cosmetic appearance (especially odor), are diethylene glycol monobutyl ether and an acid mixture. adipic, glutaric and amber. The ratio of acids in the above mixture is not particularly substantial and can be modified to achieve the desired odor.

In general, to maximize the water solubility of this glutaric acid mixture, the most water soluble of the three saturated aliphatic dibasic acids will be used as the main constituent.

Generally, the weight ratio of adipic acid: glutaric acid: succinic acid is in the range 1-3: 1-8: 1-5, preferably in the range of

1-2: 1-6: 1-3 such as ratios of 1: 1: 1,1: 2: 1, 2: 2: 1, 1: 2: 1,5, 1: 2: 2, 2: 3 : 2 etc. that can be used with equally good results.

Yet other classes of co-acting surfactants (cosurfactants) providing stable microemulsion compositions at low and elevated temperatures are the above-mentioned alkyl ether polyethenoxycarboxylic acids and mono-, di- and triethyl phosphoric esters such as triethyl phosphate.

9 9 9 9

9 9 9 9 9 9 9 ·

9999 999 999 9,999 9

9 9 9 9 9

9 9 9 9 9 9 9 9 9 ·

The amount of co-surfactant (cosurfactant) required to stabilize the liquid crystal compositions and microemulsion compositions of the invention will of course depend on such factors as the surface tension characteristics of the co-surfactant (cosurfactant), the type and amount of primary surfactants used. and perfumes and the type and amount of any other components which may be present in the composition and which affect the thermodynamic factors mentioned above. Generally, the amount of co-surfactant (cosurfactant) is in the range of 0.5% to 15% by weight, particularly preferably in the range of 1% to 7% by weight, these amounts providing stable dilutions of / w microemulsion for the above-described levels of primary surfactants and perfume and any other components as described below.

It is particularly valuable for the end use that the pH of the final microemulsion will depend on the nature of the co-surfactant (cosurfactant), the choice of the co-surfactant (cosurfactant) being made with respect to cost and cosmetic properties, in particular odor. For example, either class 1 or class 4 of co-surfactants (cosurfactants) may be used to prepare microemulsion compositions having a pH in the range of 1 to 10 and may be used as the sole co-surfactants (cosurfactants). ), but in the presence of a polyvalent metal salt, the pH range is reduced to 1 to 8.5. Conversely, co-acting surfactant 9 9 9 9 9 9 9

9999 99 9,999 9,999 9

9 9 9 9 9

9999 9 99 99 99 9 (cosurfactant) of Class 2 may be used as the sole co-surfactant (cosurfactant) when the pH of the product is below 3.2. However, if acidic co-surfactants (cosurfactants) are used in admixture with a glycol ether co-surfactant (cosurfactant), then the compositions may be formulated at a substantially neutral pH (e.g., pH + 1.5, preferably at pH 7 + 0.2).

The ability to formulate neutral and acidic products having grease removal capacities without the use of builders is a feature of the present invention since o / w microemulsion formulations are most often highly alkaline or have a high builder content or both.

In addition to excellent grease or oily dirt cleaning capacity, these low pH microemulsion formulations also exhibit excellent cleaning performance and removal of soap and lime deposits when used for cleaning as they are (undiluted) as well as diluted form.

The last essential component in the microemulsion compositions of the invention having improved interfacial voltage properties is water. The proportion of water in the microemulsion compositions is generally in the range of 20% to 97% by weight, preferably in the range of 70% to 97% by weight in the commonly diluted o / w microemulsion composition.

On the basis of the foregoing, it is possible to draw a conclusion: 9 9 9 9 9

9999 99 9 999 It is clear that dilute liquid versatile cleaning compositions of the present invention in the form of microemulsion o / w are particularly effective when used as such, i.e. without further dilution with water, since the properties of the o / w microemulsion composition are best reflected in pure (undiluted) form. However, it should be noted at the same time that, depending on the amount of surfactants, co-surfactants (cosurfactants), perfumes and other ingredients, a certain degree of dilution is possible without disrupting the microemulsion as such. For example, when using preferred low levels of active surfactants (i.e., primary anionic and nonionic surfactants) dilutions of up to about 50% are generally well tolerated without inducing phase separation, i.e., the microemulsion state will be maintained.

However, even when diluting the composition to a greater extent, such as a 2 to 10 fold dilution or even greater dilution, the resulting compositions will still be effective for cleaning grease, oil and other types of dirt. In addition, the presence of magnesium ions or other polyvalent ions such as aluminum ions, as described in more detail below, serves to increase the cleaning performance of the primary detergents in the diluted state.

On the other hand, the present invention also encompasses the formulation of highly concentrated microemulsions that are diluted with additional water before use.

The present invention also relates to a stable concentrated microemulsion or acidic microemulsion composition comprising:

Φ Φ Φ Φ Φ ·

Následující Φ následující následující následující · následující · následující následující následující následující následující následující následující následující následující následující následující následující následující následující následující následující následující následující následující následující následující následující následující následující následující následující následující následující weight:

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

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

(c) 2 to 30% of a co-surfactant (cosurfactant);

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

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

(f) 0 to 1% phosphoric acid;

(g) 0 to 0.2% aminoalkylene phosphonic acid;

(h) 0-15% magnesium sulfate heptahydrate;

(i) 0 to 1.0%, preferably 0.4 to 0.8% of trialkyl citrate; and (j) the remainder being water, wherein the composition has an ecotoxicity as measured by an LC 50 assay of at least 0.18 mL / L as measured on Daphniae microorganisms.

The present invention also relates to a stable liquid crystal microemulsion composition comprising the following components, the content of which is expressed in percentages by weight:

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

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

(c) 0 to 2.5% fatty acid;

(d) 2 to 30% of a co-surfactant (cosurfactant);

(e) 0.5 to 10% water-insoluble hydrocarbon or perfume;

(f) 0-15% magnesium sulfate heptahydrate;

(g) 0 to 1.0%, preferably 0.4 to 0.8%, of trialkyl citrate, and (h) the remainder is water, the composition having ecotoxicity measured by LC 50 assay of at least 0.18 ml / l measured on Daphniae microorganisms.

The present invention also relates to a stable concentrated microemulsion or acidic microemulsion composition comprising the following components, their content being approximately expressed in percent by weight:

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

(b) 0.5 to 15% of ethoxylated polyhydric alcohol such as ethoxylated glycerol;

(c) 2 to 30% of a co-surfactant (cosurfactant);

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

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

(f) 0 to 1% phosphoric acid;

(g) 0 to 0.2% aminoalkylene phosphoric acid;

(h) 0-15% magnesium sulfate heptahydrate;

(i) the remainder being water.

The present invention also relates to a stable liquid crystal microemulsion or an acidic microemulsion composition comprising the following components, the content of which is approximately given in percent by weight:

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

(b) 0.5 to 15% ethoxylated polyhydric alcohol such as ethoxylated glycerol;

(c) 2 to 30% of a co-surfactant (cosurfactant);

(d) 0.5 to 10% water insoluble hydrocarbon or perfume;

99 · 99 · »99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 (E) up to 15% magnesium sulfate heptahydrate; and (j) the balance being water.

These concentrated microemulsions can be diluted by mixing with up to 20 times the amount or even more, preferably four to ten times the amount of their weight with water to form o / w microemulsions similar to the diluted microemulsion compositions described above. Although the degree of dilution is suitably selected so as to obtain an o / w of the microemulsion composition upon dilution, it should be understood that both the microemulsion and the non-microemulsion forms may gradually develop during the dilution.

In addition to the aforementioned essential components necessary for preparing a liquid crystal composition or microemulsion composition, the compositions of the present invention, and often this variant is one of the preferred embodiments, may contain one or more additional components to improve the overall efficiency of the composition.

One such component is an inorganic or organic salt of a polyvalent metal cation oxide, in particular Mg ⁺⁺ . The metal salt or oxide provides the advantages of improving the cleaning performance when the composition is used in a diluted state, especially in the case of soft water, and minimizing the amount of perfume required to obtain the microemulsion state. Magnesium sulphate, either anhydrous or hydrated (e.g. heptahydrate), is particularly preferred in the form of the magnesium salt. Good results were also obtained with magnesium oxide, magnesium chloride, magnesium acetate, magnesium propionate, and magnesium hydroxide. These magnesium salts can be used in combination with formulations at neutral or acidic pH because:

9999

9999 99 9,999 9,999 9

9 9 9 9 9

9999 9 99 99 99 9 Magnesium hydroxide will not precipitate at these pH values.

While magnesium is preferably the polyvalent metal used to prepare salts (including oxide and hydroxide), other polyvalent metal ions may also be used provided their salts are non-toxic and soluble in the aqueous phase of the system at the desired pH level. Depending on factors such as the pH of the system, the nature of the primary surfactant and the co-surfactant (cosurfactant) and the like, as well as the availability and financial factors, other suitable polyvalent metal ions could also be used, among which aluminum, copper, nickel, iron, calcium, etc. may be included. In this context, it should be noted that, for example, when the preferred paraffin sulfonate is used as an anionic detergent, precipitation occurs in combination with calcium salts and thus cannot be used. It has been found that aluminum salts work best at a pH below 5 or, for example, when 1 weight percent of citric acid is added to a pH neutral composition.

Alternatively, an aluminum salt such as citrate may be added. In the case of a salt, generally the same classes of anions as mentioned in connection with the above-mentioned magnesium salts can be used, such as halides (e.g. bromide, chloride) sulfate, nitrate, hydroxide, oxide, acetate, propionate, etc.

Preferably, a metal compound is added to the diluted compositions of the invention in an amount sufficient to achieve at least an equivalent stoichiometric content between the anionic surfactant and the polyvalent metal cation. For example, based on this stoichiometric equivalence, each gram-ion of Mg ⁺⁺ corresponds to 2 grammols of paraffin sulphonate, alkylbenzenesulfonate, etc., whereas each gram-ion of Al ²⁺ corresponds to 3 grammols of anionic surfactant. Thus, the proportion of polyvalent salt is generally chosen such that one equivalent of the compound neutralizes 0.1 to 1.5 equivalents, preferably 0.9 to 1.4 equivalents of the acid in the form of an anionic surfactant.

At higher concentrations of anionic detergents, the amount of polyvalent salt will be in the range of 0.5 to 1 equivalent per equivalent of anionic surfactant.

The liquid crystal composition or o / w composition of the invention comprises from 0% to 2.5% by weight, preferably from 0.1% to 2% by weight of the composition, of a C 8 -C 22 fatty acid or a fatty acid soap as a suds suppressor. . Addition of a fatty acid or fatty acid soap results in improved rinsability of the composition when applied in its original form or in diluted form. In general, however, it is necessary to increase the level of co-surfactant (cosurfactant) to maintain product stability when a fatty acid or soap is present. When more than 2.5% by weight of a fatty acid is used in the composition of the present invention, the composition becomes unstable at low temperatures and has an unpleasant odor.

Examples of fatty acids that may be used as such or in the form of soap include those obtained from distilled coconut oil fatty acids, mixed vegetable types of fatty acids (e.g., substances containing a high percentage of saturated, mono- and / or poly- unsaturated C18 chains); acid

Oleic acid, stearic acid, palmitic acid, eicosanoic acid and the like are generally acceptable, fatty acids having from 8 to 22 carbon atoms are generally acceptable.

The liquid cleaning versatile and multipurpose composition of the present invention may also, if desired, also contain other ingredients, either to provide additional effect or to make the product more attractive to the consumer. Examples include: dyes or coloring agents in amounts up to 0.5% by weight; bactericides in an amount of up to 1% by weight; preservatives or antioxidants such as formalin, 5-bromo-5-nitro-dioxane-1,3: 5-chloro-2-methyl-4-isothiazolin-3-one, 2,6-di-tert-butylp-cresol, etc. in an amount of up to 2% by weight; in addition, pH adjusting agents such as sulfuric acid or sodium hydroxide may be used if desired. In addition, if opaque compositions are desired, up to 4% by weight of opacifying agent may be added.

The compositions of the present invention exclude the use of zwitterionic surfactants, such as betaines, as these zwitterionic surfactants, when used in the composition of the present invention, are extremely foaming and could give a high foaming profile to the compositions of the present invention. this would mean that the foam could leave too much residue on the surface to be cleaned.

In the final form, these versatile and multipurpose oil-in-water microemulsions or liquid crystal compositions exhibit stability at elevated and reduced temperatures. In particular, such compositions remain clear and stable in the range of 5 ° C to 50 ° C, especially at temperatures in the range of 5 ° C to 50 ° C. • · · · · ·

9 9 9

9 9 9

9999 999 9

9 9

99 9 from 10 ° C to 43 ° C. Such compositions exhibit a pH in the acid or neutral range, depending on the intended end use. These liquids are readily pourable and have a viscosity in the range of 6 to 60 milliPascal.seconds (mPa.s) measured at 25 ° C on a Brookfield RVT Viscometer using a No. 1 spindle rotating at 20 rpm. minute". In a preferred embodiment, the viscosity is maintained in the range of 10 to 40 mPa.s.

The compositions are in a form in which they can be used directly or can be diluted, with no or minimal rinsing required in both cases, with substantially no residue or streaks left. In addition, as the compositions are free from detergent builders such as alkali metal polyphosphates, they are environmentally acceptable and provide better brightness on the cleaned hard surfaces.

Where intended to be used in base form (i.e., undiluted), the liquid compositions may be packaged under pressure in an aerosol container or pump type spray for the type of application where spraying and wiping of the surface is performed.

Since the compositions of the present invention are in the form in which they are prepared, they are in the form of an aqueous liquid formulation and since no particular mixing is required to form the microemulsion o / w, these compositions are readily prepared by simply combining the ingredients in a suitable container or container. The order of mixing of the components is not particularly important, and in general, it is possible to state that it is possible to mix the components. · Add different folders one at a time or you can add all folders at once or these can be added components in the form of aqueous solutions in a primary detergent or co-surfactant or all primary detergents and co-surfactants, which may be prepared separately and combined with each other and with a perfume. The magnesium salt, or other polyvalent metal compound, if used, can be added in the form of its aqueous solution or can be added directly. It is not necessary to use elevated temperatures during the preparation phase, and the room temperature is sufficient.

The instant microemulsion compositions of the present invention explicitly exclude the use of alkali metal silicates and builders based on alkali metals such as alkali metal polyphosphates, alkali metal carbonates, alkali metal phosphonates and alkali metal citrates, When used in the composition of the present invention, they could induce high pH compositions as well as leaving residues on the surface to be cleaned.

The present invention encompasses variants in which an ethoxylated glycerol type compound can be used in hard surface cleaning compositions such as wood cleaners, window cleaners, and gentle liquid cleaners to improve the fat release effect.

• · <

··· 9 · ····

DETAILED DESCRIPTION OF THE INVENTION

The following examples illustrate the liquid cleaning compositions of the present invention. Unless otherwise indicated, all percentages are by weight. The compositions set forth in these examples are illustrative only and do not limit the scope of the present invention. Unless otherwise indicated, the ratios are by weight, not only in the examples but also in the preceding description.

Example 1

According to this example, the following compositions were prepared, whose composition is expressed in percent by weight:

• · ······ · · · · · · · · · · ·

AND (B) C D C - ^ - C- ^ paraffin- sodium sulfonate 4.7 4.3 4 4.3 EO / PO non-ionic - - - - Levenol F-200 2.3 2.2 2 2.2 C13-C15 EO 14 - - - - nonionic DEGMBE 4 4 3.5 4 fatty acid 0.75 0.5 0.4 0.75 MgSO ₄ .7H ₂ 0 2.2 2 1.9 2.2 perfume (a) 0.8 0.75 0.9 0.7 sodium citrate - - - - water residue residue residue residue pH 7 7 7 7 degreasing test basic comp. (b) 30 35 35 35 diluted (b) 45 60 60 60 residue same same same same jako u j as u jako u jako u refer. refer. refer. refer. foaming the same the same same the same in hard water jako u j as u jako u j as u refer. refer. refer. refer. LC50-ecotoxicity 0.18 - - - on Daphnia (c) ml / l

• · ···· continued

E F Mr. Proper St Marc Lemon Sodium C- ₃ -C-yparaph insulfonate 14.1 7.05 2.9 EO / PO non-ionic - - - 3.2 Levenol F-200 6.3 3.45 - - C13-C15 EO 14 - - 3.3 - nonionic DEGMBE 12 6 4.4 3 fatty acid 2.25 1,125 0.65 0.3 MgSO ₄ .7H ₂ 0 6.3 3.15 - - perfume (a) 2.4 1,2 present present sodium citrate - - 3.2 - water residue residue residue residue pH 7 7 9.5 7 degreasing test basic comp. (b) 30 30 70 > 100 diluted (b) 45 45 > 90 90 residue same same not good same j as u j as u j as u refer. refer. refer. foaming the same the same the same the same in hard water jako u jako u j as u jako u refer. refer. refer. refer. LC50-ecotoxicity - - 0.1 0,033 on Daphnia (c) ml / l ml / l

• * β · ♦ · ··· · continued

G H AND linear alkylbenzene- sulfonic acid 4.7 4,5 5 NaOH to pH7 0.6 0.57 0.64 Levenol F-20 2.3 2.5 2 DEGMBE 5.6 6 6.2 fatty acid 0.75 0.75 0.75 MgSO ₄ .7H ₂ 0 2.15 2.06 2.3 perfume (a) 0.8 0.8 0.8 water residue residue residue PH 7 7 7

(a) contains 25% terpenes by weight (b) fewer smudges, better degreasing performance (c) higher results, lower ecotoxicity

In addition, the dissolution force of the microemulsion of this example was compared to the dissolution force of the same composition except that the same amount (5% by weight) of the cumene sulfonate hydrotrope sodium salt was used instead of the diethylene glycol monobutyl ether co-surfactant. (cosurfactant), the same amounts of heptane being added to both compositions. In the case of the o / w microemulsion of the present invention, 12 grams of the water immiscible substance was dissolved compared to 1.4 grams for the hydrotrope-containing liquid composition.

·················································· · · · ···· · ·· ♦ ·· ··

According to another comparative test using blue-colored cooking oil (triglyceride impurity test), the composition of Example 1 was clear after addition of 0.2 g of cooking oil while, when using a composition containing a sulfonate hydrotrope, cooking oil floated on the surface of this composition.

When the perfume concentration is reduced to 0.4% in the composition of Example 1, a stable microemulsion composition o / w is obtained. Similarly, a stable o / w microemulsion is obtained when the perfume concentration is increased to 2% by weight and the concentration of co-surfactant (cosurfactant) is increased to 6% by weight in Example 1

The present invention also relates to an aqueous solution of a grease release system comprising:

(a) 0.1 to 20.0% by weight of the composition

R ’

AND

CH ₂ -O- (CH ₂ CH-O) _x -b R '

I [CH-O- (CH ₂ CH 0) _y -B] _w (I)

R ’

CH ₂ -O- (CH ₂ CH-O) _Z -B • ·· φ

Φ Φ · · · · φ φ · φ φ φ φ φ φ · · φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ

R ’

AND

CH ₂ -O- (CH ₂ CH-O) _χ -η R '

I [CH-O- (CH ₂ CHO) _y -H] _w (II)

R ’

AND

CH ₂ -O- (CH ₂ CH-O) _{Ζ -Η} in which:

v is equal to one to four,

B is selected from hydrogen or formula

1.1

C-R in which:

R is selected from the group consisting of alkyl groups of 6 to 22 carbon atoms and alkenyl groups of 6 to 22 carbon atoms, wherein at least one of the B groups is represented by said

II • · 9 • 9 9 • ···

R 'is selected from the group consisting of hydrogen and methyl, x, y and z are between 0 and 60, with the proviso that (x + y + z) is from 2 to 100, wherein in formula I the monoester / diester ratio the triester 40 to 90/5 to 35/1 to 20, while the ratio of formula I to formula II has a value in the range of 3 to 0.02, preferably 3 to 0.1, and most preferably 1.5 to 0, 2, wherein, most preferably, there is more of Formula II than Formula I in the mixture, and (b) the balance is water.

The aqueous solution of the grease releasing agent may be applied to a hard surface. The treated hard surface will be protected from grease adhering to the hard surface, thereby facilitating easier cleaning of the hard surface with a conventional hard surface cleaning composition.

Example 2

This example illustrates the composition of a typical concentrated o / w microemulsion formulation of the present invention.

♦ · · · ♦ φ ♦ ♦ ♦ • • • φ

% by weight coconut fatty acids 4 Sodium C 1 -C 6 -paraphinsulfonate 20.75 Levenol F-200 12 diethylene glycol monobutyl ether 20 May perfume (a) 12.5 water the remainder to 100

pH: 7.0 + 0.2

This concentrated formulation can be readily diluted, for example, five times tap water to give a microemulsion composition o / w. Thus, using the microemulsion method, it is possible to obtain a product having a high level of active detergent ingredients and perfume which is met with a favorable consumer response since a composition of this type achieves appropriate clarity, odor and stability while at the same time easily diluting the product. to the usual concentration used for similar versatile and multipurpose liquid cleaning compositions used for hard surfaces while maintaining its cosmetically attractive attributes.

Naturally, these formulations may be used, if necessary, without further dilution, and may also be used in base form or in diluted form for cleaning soiled materials manually or in automatic washing machines.

Example 3

This example illustrates a diluted microemulsion composition of the invention having an acidic pH and also provides improved cleaning performance with respect to soaps and calcareous deposits, as well as the cleaning of greasy soils.

% by weight Sodium C 1 -C 4 -parapine sulfonate 4.7 Levenol F-200 2.3 MgSO ₄ .7H ₂ 0 2.2 succinic acid / acid mixture glutaric / adipic acid (1: 1: 1) 5 perfume (d) 1.0 water, low (dye) the remainder to 100 phosphonic acid 0.2 amino-tris- (methylene-phosphonic acid) 0.03

pH = 3 + 0.2 (d) contains 40% by weight terpene

Example 4

The composition of composition A of Example 1 was tested for removal of the combination of grease and particulate soiling as well as for the effect of grease release, and the results were compared with the commercial preparation Ajax ® NME.

I. Removal of grease + particulate impurities

«· ·· 999 · ··· · • ·

Test method (A) Composition of dirt g mineral oil g particulate impurities (dust from vacuum cleaner + 15% soot) g C2CI4 (B) Preparation of dirt

- cleaned / dried glass tiles are weighed

- the tiles get dirty with grease + particulate dirt

- the tiles are baked at 80 ° C for 1 h

- soiled tiles are weighed after aging for 2 hours at room temperature (C) Dirt removal

Soiled tiles are soaked for 15 minutes at room temperature in the test preparations, then carefully washed with tap water.

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

Results grease + particle dirt% removal diameter 6 tiles commercial Aj ax ^ NME composition A from example 1 • · ·· ····

• «• · ··· • ·

Formulation A shows improved grease + particulate soil removal compared to the commercially available Ajax ⁱⁿ NME.

II. Effect on grease release

Test method (A) Composition of dirt

20% hardened tallow

80% beef tallow fat blue color (B) Preparation of dirt

The grease mixture is heated and sprayed with an automatic sprayer onto cleaned and dried ceramic tiles.

(C) Dirt removal Base used: 2.5 g per sponge diluted product used: 1.2% dissolved in tap water - 10 ml sponge solution

The purification procedure is carried out with a conventional apparatus for both product concentrations.

Results (A) On treated ceramic tiles (treated with dirt spray) ·· ····

basic diluted number smudges first depositing an oily layer average 4 average 6 on the tile on the tile rp-iur commercially available Ajax ⁱⁿ NME 27 Mar: 19 Dec 19 Dec 5 * second deposition of the greasy layer average 4 average 6 on the same tile on the tile on the tile 'Τ' commercially available Ajax ^iP1 NME 25 48 25 18 *

(B) On untreated ceramic tiles

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

(1) the tiles were allowed to air dry (2) the surface was wiped with a paper towel (3) the surface was wetted with a damp sponge ·· ···· (1) Air drying

basic diluted number smudges first depositing an oily layer average 4 on the tile average 6 on the tile TM commercially available Ajax NME 29 30 means A 27 Mar: 32 a second deposition of an oily layer on the same tile average 4 on the tile average 6 on the tile TM commercially available Ajax NME 33 21 means A 30 6 *

(2) Wipe the surface dry ·· ····

basic diluted number smudges first depositing an oily layer average 4 on the tile average 6 on the tile commercially available λ ax NM NME 29 30 means A 27 Mar: 32 a second deposition of an oily layer average 4 average 6 on the same tile on the tile on the tile TM commercially available Ajax NME 35 46 means A 30 48.5

··· (3) Wet wiping of the surface

basic diluted number smudges first depositing an oily layer average 4 on the tile average 6 on the tile commercially available Ajax NME 29 30 means A 27 Mar: 32 a second deposition of an oily layer average 4 average 6 on the same tile on the tile on the tile commercially available Ajax ^1P1 NME 34 58 means A 27 Mar: 41 **

* Highly significant difference ** After 5 streaks, 65% grease is removed

These results clearly demonstrate an important enhancement of the grease release effect of the composition A composition when the diluted product is used.

• 9 • 9 • 9 • 9

Example 5

The following liquid crystal compositions were prepared by a simple mixing procedure:

AND (B) C Sodium C 1 -C 4 -paraphinsulfonate 4.3 4.3 4.3 Levenol F-200 2.2 2.2 2.2 propylene glycol monobutyl ether 3.5 - - dipropylene glycol monobutyl ether - 3.5 - tripropylene glycol monobutyl ether - - 3.5 fatty acid 0.5 0.5 0.5 MgSO ₄ .7H ₂ 0 1.6 1.6 1.6 perfume (a) 1 1.5 1.5 water remn. remn. remn. pH 7 7 7

Example 6

The following optically clear microemulsion compositions were prepared by first preparing a solution by mixing water, magnesium lauryl ether sulfate, Levenol V-510/2 and 1-pentanol at 25 ° C. To this solution was added dodecane under stirring at 25 ° C to obtain an optically clear microemulsion. The compositions are expressed in weight percent.

·· 9 * 9

9 9 * 9999

····

AND (B) C D E lauryl sulfate magnesium 7 2.04 3.04 4.99 3.01 Levenol V-501/2 3.2 8.15 7.1 5.1 7.06 1-Pentanol 1.19 1.03 4.1 4.05 5,05 dodekan 1.29 0.73 17.36 11.26 20.07 water residue residue residue residue residue

continuation F G H AND lauryl sulfate magnesium 6.38 5.01 4.02 2.99 Levenol V-501/2 3.9 5.06 6.24 7.2 1-Pentanol 5.67 1.07 1.05 1.13 dodekan 15.2 2.86 3.05 2.9 water residue residue residue residue

· · · Φ φ · · · · · · · · · · · · · · · · · · · · · ·

Example Ί

The following composition was prepared by a simple mixing procedure:

C 1-8 -C-γ-Parafosulfonate sodium 4.0 Levenol F-200 2,0 DEGMBE 4,5 fatty acid 0.5 MgSO ₄ .7H ₂ 0 1,8 perfume (a) 0.8 tri-n-butyl citrate 0.5 water residue pH 7

degreasing test basic (6) diluted (6) residue foam in hand water (a) contains 25% by weight terpenes (b) fewer smudges, better degreasing efficiency

The addition of tri-n-butyl citrate improves the washability of the wash surface by improving foam disintegration compared to the tri-n-butyl citrate-free composition.

In summary, the present invention relates generally to improved microemulsion compositions containing anionic surface

an active substance, an ethoxylated glycerol type compound, a fatty acid, one of the specified co-surfactants (cosurfactants), a hydrocarbon component and water in which a water-insoluble, fragrant perfume is used as the basic hydrocarbon component in an amount sufficient to form either a dilute o / w of a microemulsion composition or a liquid crystal composition comprising from 0.1% to 20.0% by weight of an anionic detergent, from 0.1% to 10% by weight of an ethoxylated glycerol type compound, from 0% to 50% by weight of a co-surfactant (cosurfactant) 0 to 1.0% by weight of trialkyl citrate, 0.4% to 10% by weight of perfume and the remainder being water

Example 8

The following compositions were prepared in which the content of the individual components is expressed in percent by weight.

• · ···· ·

AND (B) C C13-17 paraffin- 4.7 4.7 4.7 sodium sulfonate DEGMBE 4 4 4 coconut fatty 0.75 0.75 0.75 acid MgSO ₄ 2.2 2.2 2.2 perfume 0.8 0.8 0.8 Compound (s) 0,023 0.017 0.011 Compound (b) 0,115 0,086 0,056 Compound (c) 0,897 0,673 0.449 Compound (d) 1,265 1,525 1.78 Neodol 91-5 - - - water remn. remn. remn. behavior phase j edna j edna j edna phase phase phase particle dirt 71.0 79.8 84.0 (kaolin removal)

D E F C13-17 paraffin- 4.7 4.7 4.7 sodium sulfonate DEGMBE 4 4 4 coconut fatty 0.75 0.75 0.75 acid MgSO ₄ 2.2 2.2 2.2 perfume 0.8 0.8 0.8 Compound (s) 0.006 - - Compound (b) 0,028 - - Compound (c) 0.024 - - Compound (d) 2,066 2.3 - Neodol 91-5 - - 2.3 water remn. remn. remn. behavior phase one j edna one phase phase phase particle dirt 86.0 88.7 51.0 (kaolin removal)

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 are cocoalkyl chains

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 g j are cocosalkyl chains

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 g is a cocosalkyl chain

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

In summary, the present invention relates generally to the improvement of particulate soil removal microemulsion compositions comprising an anionic surfactant, ethoxylated polyhydric alcohol, a co-surfactant (cosurfactant), a hydrocarbon component, and water, comprising the use of a water-insoluble, fragrant perfume as a basic hydrocarbon a component in a proportion sufficient to form either a diluted o / w microemulsion composition or a liquid crystal composition comprising 0.1% to 20.0% by weight of an anionic detergent, 0.1% to 10% by weight of an ethoxylated polyhydric alcohol type compound, 0.1% up to 20.0% by weight of ethoxylated polyhydric alcohol, 0% to 50% by weight of the co-surfactant (cosurfactant), 0.4 to 10% of perfume and the remainder being water.

In summary, the present invention relates to improved microemulsion compositions comprising an anionic surfactant, esterified polyethoxyether nonionic surfactant, one of the specified co-surfactants (cosurfactants), a hydrocarbon component and water in which water-insoluble fragrance perfume is used as essential a hydrocarbon component in a proportion sufficient to form either a diluted o / w microemulsion composition or a liquid crystal composition containing from 0.1% to 20% by weight of an anionic detergent, from 0.1% to 20.0% by weight of a solubilizing agent which is an ethoxylated compound glycerol, 0% to 50% by weight of the co-surfactant (cosurfactant), 0.4% to 10% by weight of the perfume, and the remainder being water.

Claims (20)

PATENT CLAIMS 1. A microemulsion composition comprising: (a) 0.1% to 20% by weight of the composition R ’ AND CH ₂ -O- (CH ₂ CH-O) _x —b R ' I [CH-O- (CH ₂ CH 0) _y -B] _w R ' I ₂ -O- (CH ₂ CH-O) _z -ba R ’ AND CH ₂ -O- (CH ₂ CH-O) _x -h R '[CH-O- (CH ₂ CH 0) _y -H] _w R' I ch ₂ -o- (ch ₂ ch-o) _z -h (II) in which: w is equal to one to four, B is selected from the group consisting of hydrogen or a group of the formula wherein: R is selected from the group consisting of alkyl groups of 6 to 22 carbon atoms and alkenyl groups of 6 to 22 carbon atoms, wherein at least one of the B groups has the formula II -CR and R 'are selected from the group consisting of hydrogen and methyl, x, y and z are between 0 and 60 with the proviso that (x + y + z) is 2 to 100, wherein in formula I the monoester / the diester / triester is 45 to 90/5 to 35/1 to 20, wherein the ratio of Formula I to Formula II is between 3 and 0.02; (b) 0.1% to 20% by weight of anionic surfactant; (c) 0.1% to 50% by weight of the co-surfactant cosurfactant; (d) 0.1% to 10% by weight of a water insoluble hydrocarbon or perfume; (e) 0 to 1.0% by weight of trialkyl citrate; and (f) the remainder being water. The cleaning composition of claim 1, further comprising a polyvalent metal cation salt in an amount sufficient to provide from 0.5 to 1.5 equivalents of said cation per equivalent of said anionic detergent. Cleaning composition according to claim 2, characterized in that the polyvalent metal cation is magnesium or aluminum. The cleaning composition of claim 2, wherein said composition comprises 0.9 to 1.4 equivalents of said cations per equivalent of anionic detergent. 5. The cleaning composition of claim 3 wherein said polyvalent salt is magnesium oxide, magnesium chloride, or magnesium sulfate. The cleaning composition of claim 1, wherein said fatty acid contains 8 to 22 carbon atoms. 7. A cleaning composition according to claim 1 comprising from 0.5 to 15% to 7% by weight of said co-surfactant or cosurfactant and from 0.4% to 3.0% by weight of said hydrocarbon. The cleaning composition of claim 1, wherein the co-acting surfactant or cosurfactant is a water-soluble glycol ether. ·· ·· The cleaning composition of claim 8, 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 having an average molecular weight of from 200 to 1000, and propylene glycol tert-butyl ether, mono-, di-, tripropylene glycol. Cleaning composition according to claim 9, characterized in that the glycol ether is ethylene glycol monobutyl ether or diethylene glycol monobutyl ether. Cleaning composition according to claim 1, characterized in that the co-acting surfactant or cosurfactant is a C 3 -C 6 aliphatic carboxylic acid selected from the group consisting of acrylic acid, propionic acid, glutaric acid, a mixture of glutaric acid and succinic acid and mixtures of any of the above. 12. The cleaning composition of claim 11 wherein the aliphatic carboxylic acid is a mixture of adipic acid, glutaric acid, and succinic acid. The cleaning composition of claim 1, wherein the anionic surfactant is an alkylbenzene sulfonate containing from 9 to 15 carbon atoms or an alkane sulfonate containing from 10 to 20 carbon atoms. 14. A stable concentrated microemulsion composition comprising the following components, the approximate content of which is given in percent by weight: (a) 1 to 30% of an anionic surfactant; (B) 0.5 to 15% of the mixture R ’ AND CH ₂ -O- (CH ₂ CH-O) _x —b R ' I [CH-O- (CH ₂ CHO) _y -B] _in (I) R ’ I ₂ -o- (CH ₂ CH-O) _{z -} b R ’ AND CH ₂ -O- (CH ₂ CH-O) _x —h R ' I [CH-O- (CH ₂ CHO) _y -H] _in (II) R ’ AND CH ₂ -O- (CH ₂ CH-O) _Z -H in which: w is equal to one to four, B is selected from the group consisting of hydrogen or a group of formula II € -R in which: R is selected from the group consisting of alkyl groups of 6 to 22 carbon atoms and alkenyl groups of 6 to 22 carbon atoms, wherein at least one of the B groups has the formula AND -C-R and R 'is selected from the group consisting of hydrogen and methyl, x, y and z are between 0 and 60 with the proviso that (x + y + z) is equal to 2 to 100, wherein in formula I the monoester / diester / triester ratio is 40 to 90/5 to 35/1 to 20, wherein the ratio of formula I to formula II is in the range of 3 to 0.02; (c) 2 to 30% of a co-acting cosurfactant surfactant; (d) 0.4 to 10% water insoluble hydrocarbon or perfume; (e) 0 to 18% of at least one dicarboxylic acid; (f) 0 to 0.2% aminoalkylenephosphonic acid; (g) 0 to 1.0% phosphoric acid; (h) 0-15% magnesium sulfate heptahydrate; (i) 0 to 1.0 wt% trialkyl citrate; and (j) the balance is water, the composition having an ecotoxicity measured by LC 50 assay of at least 0.18 milliliters / liter measured on Daphniae microorganisms. • · · 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 99 9 9999 9 9 9 9 9 9 9 9 9 9 999 9 9 9 9 9 9 9 9 9 99 9999 15. A liquid crystal composition comprising about 0 to 2.5% by weight of a fatty acid; 0.1% to 20% by weight of the composition R ’ AND CH ₂ -O- (CH ₂ CH-O) _x —b R ' I [CH-O- (CH ₂ CH 0) _y -B] _w (I) R ’ AND CH ₂ -O- (CH ₂ CH-O) ₂ -B a R ’ AND CH ₂ -O- (CH ₂ CH-O) _x -h R ' I [CH-O- (CH ₂ CH 0) _y -H] _w (II) R ’ I ch ₂ -o- (ch ₂ ch-o) _z -h in which: w is equal to one to four, B is selected from hydrogen or hydrogen; 999 formula in which: R is selected from the group consisting of alkyl groups of 6 to 22 carbon atoms and alkenyl groups of 6 to 22 carbon atoms, wherein at least one of the B groups has the formula II -CR and R 'are selected from the group consisting of hydrogen and methyl, x, y and z are between 0 and 60 with the proviso that (x + y + z) is 2 to 100, wherein in formula I the monoester / the diester / triester is 40 to 90/5 to 35/1 to 20 and the ratio of the compound of formula I to the compound of formula II is between 3 and 0.02; 0.5% to 10% of a water insoluble hydrocarbon and the remainder being water. 16. A grease releasing agent, comprising an aqueous solution (a) of 0.1 to 20% by weight of the composition. 9 9 9 9 9 9 9 9 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 R 'ch ₂ -o- (ch ₂ ch-o) _{χ -} Β R' I [CH-O- (CH ₂ CHO) _y -B] _w (I) R ’ I ch ₂ -o- (ch ₂ ch-o) _z -b R ’ I ch ₂ -o- (ch ₂ ch-o) _x -h R ’ I [CH-O- (CH ₂ CHO) _y -H] _w (II) R ’ I ch ₂ -o- (ch ₂ ch-o) _z -h in which: w is equal to one to four, B is selected from the group consisting of hydrogen or a group of the formula 9 9 9 9 99 99 · * * které které které které které které které které které které které které které které R is selected from the group consisting of alkyl groups of 6 to 22 carbon atoms and alkenyl groups of 6 to 22 carbon atoms, wherein at least one of the B groups has the formula -CR and R 'are selected from the group consisting of hydrogen and methyl, x, y and z are between 0 and 60 with the proviso that (x + y + z) is 2 to 100, wherein in formula I the monoester / the diester / triester is 40 to 90/5 to 35/1 to 20, wherein the ratio of Formula I to Formula II is between 3 and 0.02; and (b) the remainder being water. 17. A microemulsion composition comprising: (a) 0.1% to 20% by weight of a compound of the formula: ΦΦ · • φ φ φ φ · ΦΦΦΦ Φ Φ Φ Φ 9 9 9 «• Φ 9 · · Φ ΦΦΦ Φ ΦΦΦΦ ΦΦΦ Φ ΦΦΦ ΦΦΦ ΦΦ Φ ΦΦ Φ ΦΦ ΦΦ R ’ AND CH ₂ -O- (CH ₂ CH-O) _χ -η R ' I [CH-O- (CH ₂ CHO) y H] _w R ' I ch ₂ -o- (ch ₂ ch-o) _z —h in which: w is equal to one to four and x, y and z are between 0 and 60 with the proviso that (x + y + z) is equal to 2 to 100; (b) from 0.1% to 20% by weight of anionic surfactant; (c) from about 0.1% to about 50%, by weight of the co-acting surfactant; (d) 0.1% to 10% by weight of a water insoluble hydrocarbon or perfume; and (e) the balance being water. A stable concentrated microemulsion composition comprising the following components, the approximate content of which is given in percent by weight: (a) 1 to 30% of an anionic surfactant; (b) 0j5 to 15% of the compound · · · · · · · · · · · · · · · · · · · · · · · · · · R ’ AND CH ₂ -O- (CH ₂ CH-O) _χ -Η R ' I [CH-O- (CH ₂ CHO) _y -H] _w R ' I ch ₂ -o- (ch ₂ ch-o) _z —h in which: w is equal to one to four, x, y and z are between 0 and 60 with the proviso that (x + y + z) is 2 to 100, (c) 2 to 30% of the co-surfactant, cosurfactant; (d) 0.4 to 10% water insoluble hydrocarbon or perfume; (e) 0 to 18% of at least one dicarboxylic acid; (f) 0 to 0.2% aminoalkylene phosphonic acid; (g) 0 to 0.1% phosphoric acid, (h) 0 to 15% magnesium sulfate heptahydrate, and (i) the remainder is water, the composition having an ecotoxicity value measured by LC50 of at least 0.18 milliliters / liter measured on Daphniae microorganisms . 19. A liquid crystal composition comprising the following components, the approximate content of which is approximately expressed in percent by weight: • · · · · · Ο 1% to 20% of an anionic surfactant; 2% to 50% of a co-acting cosurfactant surfactant; 0% to 2.5% fatty acid; 0.1% to 20% of the compound R ’ AND CH ₂ -O- (CH ₂ CH-O) _x —h R ' I [CH-O- (CH ₂ CH 0) _y -H] _w (II) R ’ AND CH ₂ -O- (CH ₂ CH-O) _z -h in which: w is equal to one to four, x, y and z are between 0 and 60, with the proviso that (x + y + z) is equal to 2 to 100. 20. A soil release agent comprising: (a) 0.1% by weight to 20.0% by weight of the compound: ·· · 9 9 »tr r ·· 9999 9999 8 9 9 9 9 9 9 9 99 9 9 9 9,999 9 · CH ₂ -O- (CH ₂ CH-O) _x -h R '[CH-O- (CH ₂ CHO) _y -H] _w (II) R 'ch ₂ -o- (ch ₂ ch-o) _z —h in which: w is one to four, x, y and z are between 0 and 10 with the proviso that (x + y + z) is 2 to 100 and (b) the rest is water.