HUT70070A - Microemulsion, all purpose liquid cleaning compositions - Google Patents

Abstract

Compositions of the present invention comprise a mixture of compounds of Formula I and Formula II, wherein w is 1-4, B is hydrogen or -CO-R, wherein R is C 6 -C 22 alkyl, or C 6 -C 22 alkenyl. with the restriction that at least one of B is -CO-R, R 'is hydrogen or methyl, x, y and z are 0-60, with the restriction x + y + z being 2-100, wherein the monoester / diester / triester ratio in the formula (I) is 40-90 / 5-35 / 1-20, and wherein the ratio of the compound of formula (I) to the compound of formula (II) is 3-0.02.

Description

FIELD OF THE INVENTION The present invention relates to an improved general purpose liquid detergent in the form of a microemulsion which is preferably used to clean hard surfaces and to remove greasy and / or bath contamination and which leaves a glossy appearance on the non-rinsed surface.

In recent years, commonly used liquid detergents have become increasingly common for cleaning hard surfaces such as painted wood surfaces and wood panels, tiled walls, washbasins, bathtubs, linoleum and tiled floors, and washable wallpaper. These commonly used liquids are generally pure or translucent aqueous mixtures of a mixture of water-soluble synthetic organic detergents and water-soluble detergent builders. In order to achieve a cleaning effect comparable to granular or powdered general cleaning compositions, known general liquid cleaners generally use a water-soluble inorganic phosphate detergent builder salt. For example, a phosphate-containing formulation is disclosed in U.S. Patents 2,560,839, 3,234,138 and 3,350,319, and GB 1 223 739.

As a result of environmental efforts to reduce the phosphate load in groundwater, commonly used liquid formulations have reduced the amount of inorganic phosphate or non-phosphate detergent builder salt used. A translucent liquid formulation of this type is described in U.S. Pat. No. 4,244,840.

Detergent builder salt or equivalent

♦ ···

Known general liquid detergents containing 3 form film coatings or leave blemishes and streaks on the cleaned but not rinsed surface, especially on a glossy surface. Thus, when using such liquid cleaners, it is necessary to rinse the cleaned surface thoroughly, which is a time-consuming process.

In order to overcome the above disadvantage of general liquid cleaners, U.S. Patent 4,017,409 utilizes a blend of paraffin sulfonate and a reduced amount of inorganic phosphate detergent builder salt. However, such a formulation is not completely environmentally satisfactory due to its phosphate content. An alternative way of developing phosphate-free general liquid cleaners is to use large amounts of anionic and nonionic detergent mixtures with a small amount of glycol ether solvent and organic amine (U.S. Pat. No. 3,935,130). However, the effect of the formulation is not fully satisfactory and causes the amount of detergent foaming required for cleaning, which again requires thorough rinsing.

Another possibility for developing liquid detergent compositions for use on hard surfaces of suitable homogeneity and purity is to form an oil-in-water type microemulsion containing one or more surfactant detergent compounds, a water-insoluble solvent, generally a hydrocarbon, water and other surfactant. , which ensures the stability of the formulation. By definition, oil-in-water

type microemulsion 25-800 Spontaneous formation of colloidal dispersion of particle size oil phase particles in the continuous aqueous phase.

Due to the particularly fine particle size of the dispersed oil phase granules, the microemulsion is transparent and pure and generally very stable to phase separation.

Various degreasing solvents may be used in oil-in-water microemulsions, such as those described in EP 0 137 615, EP 0 137 616 and EP 0 160 762 and in US 4 561 991, wherein the amount of degreasing solvent is at least 5% by weight.

GB 2 144 763 discloses that the degreasing ability of an organic solvent such as terpene is enhanced by the use of a magnesium salt in an oil-in-water microemulsion liquid detergent composition. The composition comprises at least 5% by weight of a degreasing solvent and a magnesium salt, preferably at least 5% by weight, of a water-immiscible non-polar solvent and a slightly miscible slightly polar solvent with water and at least 0.1% by weight of a magnesium salt.

Because the amount of water-immiscible and poorly miscible components present in the oil-in-water microemulsion is limited due to the low content of active ingredient due to reduced stability of the microemulsion (e.g., up to 18% w / w of the aqueous phase), the large amount of degreasing solvent and can be absorbed by the microemulsion without phase separation

the amount of greasy and oily dirt.

Liquid detergent cleaning compositions in the form of an oil-in-water microemulsion are described, for example, in U.S. Pat. No. 4,472,291, U.S. Pat. No. 4,540,448 and U.S. Pat. No. 3,723,330.

A liquid detergent composition comprising terpenes such as d-limonene or other degreasing solvent is described in EP 0 080 749, GB 1 603 047, US 4 414 128 and US 4 540 505, but it is not mentioned that the composition is in oil-in-water type microemulsion. For example, U.S. Pat. No. 4,414,128 teaches a detailed description of an aqueous liquid detergent composition which:

(a) from 1 to 20% by weight of synthetic, anionic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof;

b) 0.5 to 10% by weight of mono- or sesquiterpene or a mixture thereof, wherein the weight ratio of component a) / b) is from 5: 1 to 1: 3,

c) 0.5-20% by weight of a polar solvent having a water solubility of 0.2-10% at 15 ° C.

According to the specification, the composition further comprises 0.05 to 2% by weight of an alkali metal, ammonium or alkanolammonium soap containing from 13 to 24 carbon atoms, 0.5 to 13% by weight of calcium sequestran, up to 10% by weight of a non-aqueous solvent. such as alcohol or glycol ether and up to 10% by weight of a hydrotropic agent such as urea, ethanolamine or a lower alkylaryl sulfonate salt. The document • · ·

The formulations described in Examples 6 contain a relatively large amount of detergent builder salt which impairs the cleaned surface.

In addition, it has been observed that the use of small amounts of detergent builder salt, such as an alkali metal polyphosphate, an alkali metal carbonate or nitrilotriacetic acid salt, in compositions containing magnesium compounds to aid in fat removal reduces the stability of the microemulsion system.

US 5,082,584 discloses a microemulsion formulation containing anionic surfactant, additional surfactant, nonionic surfactant, fragrance and water, but this formulation exhibits too high an ecotoxicity and interfacial tension is unsatisfactory.

US 3,776,857 discloses the use of long chain fatty acid esters of ethylene oxide adduct of aliphatic polyhydric alcohols.

GB 1,453,385 discloses a polyesterated nonionic surfactant similar to the polyesterised nonionic surfactant of the present invention. However, the non-ionic surfactant described in GB 1 453 385 does not contain a compound of formula II, however, the disclosed composition does not have any critical limitations to the invention.

The present invention relates to an improved, clean, liquid cleaning composition having an improved boundary tension that enhances hard surfaces * · ··· · f

cleaning. The composition is in the form of a microemulsion, which is advantageous for cleaning hard surfaces such as polished plastic, glass and metal surfaces. In particular, the improved cleaning composition has good degreasing properties due to the improved interface tension and, when applied in its undiluted (original) form, leaves a shiny, clean surface without separate rinsing or wiping. This latter feature is due to the fact that the residue on the uncleaned, cleaned surface is not present or only in a small amount, and thus the composition makes it possible to eliminate the disadvantages of known products. Due to the fat-releasing effect of the instant composition, it prevents or reduces the adhesion of greasy dirt to the cleaned surface relative to the surface cleaned with the commercial microemulsion composition, and thus the greasy dirt can be removed more easily during subsequent cleaning. Surprisingly, this beneficial effect can be achieved without polyphosphate or other inorganic or organic detergent builder salts, and with or without a degreasing solvent.

The invention thus relates to a stable, clean, generally applicable and hard surface cleaning composition which is preferably used to remove oily and greasy impurities and which is present in a diluted form of an aqueous phase and an oil-in-water microemulsion consisting of an oil phase. The diluted oil-a-

• «

- the composition of the microemulsion of type 8-water is about 0-6% by weight of anionic surfactant, about 0-16% by weight of nonionic surfactant, about 0.1-50% by weight of additional surfactant which is substantially incapable or of limited ability to oily or greasy soiling from about 0% to about 8% by weight of a alkali metal dialkyl sulfosuccinate, from about 0.1% to about 20% by weight of a mixture of fully esterified ethoxylated polyhydroxy alcohol, partially esterified ethoxylated polyhydroxy alcohol and non-esterified ethoxylated polyhydroxy alcohol, 15% by weight of magnesium sulfate heptahydrate, about 0.4-10.0% by weight of at least one flavoring and / or water-insoluble hydrocarbon, and about 10-85% by weight of water, based on the total weight of the composition.

The fragrance itself does not dissolve greasy or oily impurities, even though some fragrances contain up to 80% by weight of terpene, which is known to dissolve fats well. Yet, surprisingly in its diluted form, the composition of the present invention is capable of dissolving ten times or more of the fragrance oil or greasy impurities it removes or loosens on the hard surface due to anionic and nonionic surfactants, and impurities in the oil. It is absorbed in the oil phase of a micro-emulsion of the -A-water type.

On the other hand, the present invention relates to a highly concentrated microemulsion composition in the form of an oil-in-water microemulsion or a water-in-oil microemulsion which when diluted with water forms an oil-in-water microemulsion composition. The concentrated microemulsion composition comprises 0-6% by weight of anionic detergent, 0-16% by weight of nonionic surfactant, 0-8% by weight of alkali metal dialkyl sulfosuccinate, fully esterified, ethoxylated polyhydroxy alcohol, partially esterified, ethoxylated polyhydroxy alcohol and non- a mixture of esterified ethoxylated polyhydric alcohol, 0-2.5% by weight of fatty acids, 0.4-10% by weight of perfume or water-insoluble C 6-18 hydrocarbons, 0.1-50% by weight of additional surfactant and 20-97% by weight % water.

Thus, the present invention relates to a stable microemulsion composition comprising about 0.1-6% by weight of anionic surfactant, 1.0-16% by weight of nonionic surfactant, 0.1-50% by weight of additional surfactant, 0-2.5% by weight of fatty acids 0-8% by weight of alkali metal dialkyl sulfosuccinate, 0.1-20% by weight of a mixture of fully esterified ethoxylated polyhydroxy alcohol, partially esterified ethoxylated polyhydroxy alcohol and non-esterified ethoxylated polyhydroxy alcohol, and 0.1-10 containing by weight water-insoluble hydrocarbons or fragrances in 100% water.

The detergent composition of the present invention is in the form of an oil-in-water microemulsion, alone or after dilution with water, and its essential components are water, anionic surfactant, fatty acid, esterified polyethoxy ether nonionic surfactant and hydrocarbon or perfume.

According to the invention, the role of the hydrocarbon can also be fulfilled by a water-insoluble fragrance. Aqueous compositions generally require solubilizers such as lower alkyl arylsulfonate, alkali metal hydrotropic, triethanolamine or urea to dissolve the fragrance, especially in greater than 1% by weight fragrance, since the fragrance is generally a good-smelling essential oil. and mixtures of aromatic compounds which are mostly insoluble in water. Therefore, the use of a fragrance as an oil (hydrocarbon) phase in the aqueous cleaning composition has several important advantages.

First, the cosmetic properties of the cleansing composition are improved, i.e., the composition is pure due to the formation of microemulsion and has a pleasant scent due to the presence of the perfume.

Second, there is no need to use a solubilizer that does not contribute to the cleaning effect.

Third, the liposuction effect and degreasing capacity are improved when using the diluted formulation as it is or after using the concentrate after dilution, without the use of a detergent builder or buffer or a conventional degreasing solvent with a neutral or acidic pH and low active ingredient. • · · · • · · · · · · ··· · ♦ · -. ··

can be achieved with increased cleaning effect.

The term "fragrance" is used in its usual sense and accordingly refers to water-insoluble, odoriferous substances or mixtures thereof which may be of natural origin, for example obtained by extraction of plant material such as flowers or herbs, or mixtures of artificial origin such as natural oils or oil components. and of synthetic origin. Suitable fragrances are various complex mixtures of various organic compounds, such as alcohols, aldehydes, ethers, aromatic compounds and various amounts of essential oils, e.g. terpene derivatives, preferably 0-80% by weight, particularly preferably 10-70% by weight. Essential oils are volatile odoriferous compounds which also serve as solvents for other fragrance components.

For the purposes of the present invention, the exact composition of the fragrance does not affect the cleaning effect, as long as it satisfies the requirement of water insolubility and provides a pleasant scent. Of course, a perfume which is cosmetically useful, i.e. non-toxic and hypoallergenic, is preferred. This requirement also applies to the other ingredients of the preparation and is of particular importance for household cleaning products. The formulation for direct use has improved ecotoxicity compared to known commercial products.

Hydrocarbons, so the fragrance is the oil of the dilute ······· · · 9

It is present in an amount of from 0.1 to 10% by weight, preferably from 0.4 to 3.0% by weight, more preferably from 0.5 to 3.0% by weight in a microemulsion of type 12-water. If the amount of hydrocarbon (perfume) is less than 0.4% by weight, it is difficult to form an oil-in-water microemulsion. If the amount of hydrocarbon (fragrance) is greater than 10% by weight, the cost increases without improving the cleaning effect, and in fact the cleaning effect is slightly reduced as the total amount of fatty or oily impurities that can be absorbed in the oil phase of the microemulsion decreases proportionally.

In addition, an excellent degreasing effect can be achieved with a fragrance free of terpene type solvents, but it is difficult to obtain a low cost perfume formulation containing less than 20% by weight, generally less than 30% by weight, of terpene type solvents.

From a practical point of view, therefore, for economic reasons, a thin oil-in-water microemulsion detergent cleaning composition often contains from 0.2 to 7% by weight of a terpene type solvent, based on the total weight of the composition which is introduced with the perfume. However, the microemulsion of the diluted oil-in-water type of the present invention can achieve satisfactory grease and oil removal capacity even if the amount of terpene solvent is less than 1.5% by weight, preferably up to 0.6% by weight, particularly preferably 0.4% by weight. crowd%.

For example, a typical oil-in-water diluted microemulsion of the invention is 1% by weight.

Contains a fragrance that can solubilize 2-3 ml of fatty and / or oily impurities per 20 ml sample while retaining the microemulsion form. In other words, an important feature of the composition of the invention is that fat removal is the result of microemulsion and is independent of the presence or absence of solvents to remove greasy impurities.

Instead of the perfume, water-insoluble paraffin or isoparaffin having from 6 to 18 carbon atoms can be used and is generally present in an amount of 0.4 to 8.0% by weight, preferably 0.4 to 3.0% by weight.

The water-soluble, non-soap-like anionic detergent and non-ionic surfactant which is fully esterified, ethoxylated polyhydroxy alcohol, partially esterified, ethoxylated polyhydroxy alcohol and non-esterified, can be used as water-soluble organic detergent in the oil-in-water microemulsion composition of the invention. , with a mixture of ethoxylated polyhydric alcohol.

The amount of nonionic surfactant in the instant composition is about 0-16% by weight, preferably 1-12% by weight, most preferably 1.5-10% by weight, which excellently removes oily impurities and protects human skin.

The water-soluble nonionic surfactants used in the present invention are generally known and include, for example, primary, aliphatic alcohol ethoxylates, secondary aliphatic alcohol ethoxylates, alkyl phenol ethoxylates, primary alkanols by ethylene oxide / propylene oxide condensation.

14 such as Plurafax (BASF) and condensates of ethylene oxide with sorbitan fatty acid esters such as Tween (ICI). Examples of synthetic nonionic organic surfactants include condensation products of organic aliphatic or alkyl aromatic hydrophobic compounds and hydrophilic ethylene oxide groups. Virtually any hydrophobic compound containing a carboxyl group, a hydroxyl group, an amido group or an amino group and a free hydrogen atom attached to a nitrogen atom can be condensed with ethylene oxide or a polyhydrated product thereof, such as polyethylene glycol, to form a water-soluble nonionic detergent. In addition, adjusting the length of the polyethylene oxide chain can be used to control the ratio of hydrophobic to hydrophilic in any way.

Examples of nonionic surfactants are the condensation products of higher alcohols, such as C8-C18 straight or branched chain alkanols with about 5 to about 30 moles of ethylene oxide, such as lauryl alcohol or myristyl alcohol with about 16 moles ethylene oxide (EO). condensation product of tridecanol with about 6 moles of E0, condensation product of myristyl alcohol with about 10 moles of EO, coconut fatty alcohol containing about 10 moles of EO or about 9 moles of EO containing a mixture of C 10 -C 14 fatty alcohols. condensation product and ethoxylated product containing 6-11 EO units of tallow alcohol.

A preferred group of the above nonionic surfactants

neodol ethoxylates (Shell Co.) ₍ which are 8 molar EO condensates of aliphatic primary alcohols having about 9 to 15 carbon atoms, such as 9 to 11 carbon atoms, (Neodol 91-18),

Condensates of C12-C13 alkanols with 6.5 M EO (Neodol 23-6.5), C12-C15 alkanols with 12 M EO (Neodol 25-12), C14-C15 alkanols with 13 M EO Containing condensates (Neodol 45-13) and similar products. Such ethoxamers have an HLB (hydrophobic / lipophilic balance) of about 8 to 15 and exhibit good oil-in-water type emulsifiers, while ethoxamers below HLB = = 8 have less than 5 ethyleneoxy groups and are therefore weak emulsifiers and weak surfactants (at least for current purposes).

Other suitable water-soluble alcohol / ethylene oxide condensates are the condensates of C8-C18 straight or branched secondary aliphatic alcohols with 5 to 30 moles of ethylene oxide. Examples of commercial nonionic detergents of this type are the condensates of C11-C15 secondary alkanols containing 9 EO (Tergitol 15-S-9) or 12 EO (Tergitol 15-S-12) (Unión Carbide).

Also suitable as nonionic surfactants are polyethylene oxide condensates of 1 mol of alkylphenol with about 5 to 30 mol of ethylene oxide in the alkyl moiety thereof having from 8 to 18 carbon atoms in the alkyl moiety. Examples of alkyl phenol ethoxylates include nonylphenol condensate containing about 9.5 EO, dinonylphenol condensate containing about 12 mole EO, dinonylphenol about 15 mole EO ····

- a condensate of 16 and a condensate of isooctylphenol containing about 15 moles of E0. An example of this type of nonionic surfactant is Igepal CO-630 (GAF Corporation), which is a nonyl phenol ethoxylate.

Suitable nonionic surfactants are further water-soluble condensation products of C8-20 alkanols with a heterogeneous mixture of ethylene oxide and propylene oxide, wherein the ethylene oxide / propylene oxide weight ratio in the mixture is 2.5: 1-4-1, preferably 2, 8: 1-3.3: 1, and the proportion of ethylene oxide and propylene oxide (including the temple ethanol or propanol moiety) is 60-85% by weight, preferably 70-80% by weight. Such a detergent is commercially available from BASF-Wyandotte, with ethylene oxide / propylene oxide condensate having from 10 to 16 carbon atoms having a weight ratio of ethylene oxide / propylene oxide of 3: 1 and a total alkoxy content of about 75% by weight.

Further, non-ionic surfactants of the general purpose detergent of the present invention can be used in the alkyl portion of 2-30 moles of ethylene oxide with 10-20 carbon atoms of sorbitan mono and trialkanoic acid, where the HLB is 8-15. Such surfactants are generally known and are commercially available under the name Tween (ICI). Within this, polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (20) sorbitan trioleate and polyoxyethylene (20) sorbitan tristearate are preferred.

They may also be used, although less preferred is Pluronix

water soluble nonionic surfactants marketed under the name of. The hydrophobic base obtained by condensing propylene oxide with propylene glycol is condensed with ethylene oxide to prepare the compounds. The molecular weight of the hydrophobic moiety of the molecule is generally 950-4000, preferably 200-2500. Addition of polyoxyethylene groups to the hydrophobic moiety increases the solubility of the molecule and the water solubility of the surfactant. The block polymer generally has a molecular weight of 1000-15000 and a polyethylene oxide content of 20-80% by weight. Of this type of surfactant, liquid surfactants of L-62 and L-64 are preferred.

Any conventional water-soluble anionic detergent or mixture thereof with a nonionic surfactant may be used as the anionic detergent in the oil-in-water microemulsion of the present invention. By anionic surfactant is meant anionic detergents having a cleaning effect and mixed anionic nonionic detergents.

Examples of water-soluble, non-soap-like anionic detergents include surfactants and detergents having an organic hydrophobic group having from 8 to 26 carbon atoms, preferably from 10 to 18 carbon atoms, and at least one water solubilizing moiety in their molecular structure. The hydrophobic moiety is generally, or contains, C 8 -C 22 alkyl, alkenyl or acyl. These types of detergent compounds are soluble in water ···. ··· ♦ · ·.

18, wherein the salt-forming cation is generally sodium, potassium, ammonium, magnesium, or mono-, di-, or trialkanol ammonium containing 2 to 3 carbon atoms, preferably sodium, magnesium or ammonium.

Examples of sulfonated anionic detergents include sulfonates having a lower alkyl group and a monocyclic aromatic group, such as alkyl moieties having 10 to 16 carbon atoms in the alkyl moiety, alkyl toluenesulfonates of 8 to 15 carbon atoms, and 8 to 15 carbon atoms. C 1 -C 6 alkylphenol sulfonates.

The sulfonates are preferably used in large amounts

Linear alkylbenzene sulfonates containing 3- (or higher) phenyl isomers and correspondingly less (preferably less than 50%) 2- (or lower) phenyl isomers, i.e. those wherein the benzene ring is preferably predominantly alkyl 3- or higher (e.g., 4-, 5-, 6- or 7-) and the amount of isomers containing benzene ring attached to the 2- or 1-position of the alkyl group is accordingly low. Particularly preferred materials are those disclosed in US 3,320,174.

Also suitable as anionic detergents are olefin sulfonates, such as long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates. Such olefin sulfonate-type detergents may be prepared by conventional means such as sulfur trioxide (SO3) and RCH = CHR _{X having} from 8 to 25 carbon atoms,

preferably by reaction of C12-C21 long chain olefins in the formula

R is C 6 -C 23 alkyl and

R _x is C 1 -C 17 alkyl or hydrogen.

The reaction results in a mixture of sultons and alkanesulfonic acids which are treated in the usual way to convert the sultones to sulfonates. Preferred olefin sulfonates are compounds wherein

R is a C 14 -C 16 alkyl group prepared by sulfonation of an α-olefin.

They can also be used as an anionic sulfonate detergent

Paraffin sulfonates having from 10 to 20 carbon atoms, preferably from 13 to 17 carbon atoms. Primary paraffin sulfonates are generally prepared by reaction of long chain α-olefins and bisulfites. Paraffin sulfonates having a sulfonate group distributed along the paraffin chain are described in U.S. Pat. No. 2,503,280;

U.S. Patent Nos. 507,088; US 3,260,744; US 3,372,188; and DE 735,096.

Examples of anionic sulfate detergents are: a

C8-C18 alkyl sulfate salts and C (C18-C8) alkyl ether polyethyleneoxysulfate salts of formula R (OC2 H4) _n -OSC3M wherein n is from 1 to 12, preferably from 1 to 5,

M is a solubilizing cation, preferably sodium, potassium, ammonium, magnesium or mono-, di- or triethanolammonium.

· ♦ · «· * · · · · · ·; ** · * ..... · * .. ·

Alkyl sulfates may be prepared by sulfating the alcohols obtained by reduction of glycerides in coconut oil, antifreeze, or mixtures thereof, and neutralizing the resulting product. On the other hand, the alkyl ether polyethylene oxysulfates can be prepared by sulfating the condensation product of ethylene oxide with a C8-C18 alkanol and neutralizing the resulting product. The alkyl ether polyethylene oxysulfates differ in the number of moles of ethylene oxide reacted with 1 mole of alkanol. Preferred alkylsulphates and alkyl ether polyethylene oxysulphates in the alkyl group are compounds having from 10 to 16 carbon atoms.

C 8 -C 12 alkylphenyl ether polyethyleneoxysulfates containing from 2 to 6 moles of ethylene oxide per molecule may also be used in the composition of the invention. These detergents may be prepared by reacting the alkylphenol with 2-6 moles of ethylene oxide, and sulfurizing and neutralizing the resulting ethoxylated alkylphenol.

Also suitable as anionic surfactants are C 9 -C 15 alkyl ether polyethyleneoxycarboxylates of the formula R (OC 2 H 4) _n OX-COOH wherein n is 4 to 12, preferably 5 to 10,

X is CH ₂ , CO-R ¹ and a) wherein

R ¹ is C 1-3 alkylene.

Preferred examples include C9-C11 alkyl ether polyethylene (7-9) COCH2CH2COOH, C13-C15 alkyl ether polyethylene (7-9) (b), and C10-C12 alkyl. -ether-polyethyloxy (5-7) CH ₂ COOH. These compounds ·· ·

- · · · ·%. · «::

They can be prepared by treating ethylene oxide with a suitable alkanol and reacting the reaction product with chloroacetic acid to form ether carboxylic acid (U.S. Pat. No. 3,741,911) or with succinic anhydride or phthalic anhydride.

Of course, these anionic detergents are present in acid or salt form depending on the pH of the final formulation, where other cations referred to as other anionic detergents may be present as salt-forming cations.

Preferred anionic surfactants in the oil-in-water emulsion include alkali metal salts of alkyl sulfates, alkaline earth metal salts of alkyl sulfates, alkali metal salts of dialkyl sulfosuccinic acid and mixtures thereof.

The amount of non-soap-like anionic detergent in the dilute oil-in-water microemulsion composition is generally from 0 to 6.0% by weight, preferably from 0.1 to 5% by weight.

The instant composition is about 0-8% by weight, preferably

0.25 to 7% by weight of an alkali metal salt of a dialkyl sulfosuccinate, wherein the dialkyl groups may be the same or different and each have about 4 to 12 carbon atoms, preferably about 7 to 9 carbon atoms, and the alkali metal is sodium, potassium and lithium. Preferably the alkali metal salt of dialkyl sulfosuccinate is sodium dioctyl sulfosuccinate.

A further component (hereinafter ethoxylated glycerol-type compound) of the present invention is a fully esterified ethoxylated polyhydric alcohol, partially esterified

It consists of a mixture of a tertiary ethoxylated polyhydroxy alcohol and a non-esterified ethoxylated polyhydroxy alcohol, wherein the polyhydroxy alcohol is preferably glycerol. Preferably said mixture of compounds of formula (I) and (II)

R ¹

I ch ₂ -o- (CH ₂ CH-O) _x B

R

I [CH-O- (CH ₂ CH-O) _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 CH-O) _y H] w (II),

R

I

CH ₂ -O- (CH ₂ CH-O) _z where w is 1-4, preferably 1,

B is hydrogen or -CO-R wherein

R is C 6 -C 22 alkyl, preferably C 11 -C 15 alkyl, or C 6 -C 22 alkyl, preferably C 11 -C 15 alkenyl, particularly preferably derived from hydrogenated tallow or coconut oil, wherein at least one B is -CO-R .

R 'is hydrogen or methyl, x, y and z are 0-60, preferably 0-40, with the proviso that x + y + z is 2-100, preferably 4-24, especially 4-19.

In the formula (I), the monoester / diester / triester ratio is 45-90: 5-40: 1-20, preferably 50-90: 9-32: 1-12 and the ratio of the compound (I) / (II) The ratio of the compound of formula I is 3-0.02, preferably 1.5-0.2, wherein the mixture preferably contains more compounds of formula II than the compound of formula I.

Preferred glycerol esters of ethoxylate include those of Kao Corporation, such as Levenol, such as Levenol F200, which has an average EO of 6 and a mole ratio of coconut fatty acid to glycerol of 0.55, and Levenol V501 / 2, having an average EO of is 17 and the molar ratio of tallow to glycerol is 1.0. The fatty acid / glycerol molar ratio is up to about 1.7, preferably up to about 1.5, most preferably up to about 1.0. The ethoxylated glycerol-type compound has a molecular weight of 400-1600 and a pH of 5-7 (50 g / l water). Levenol is non-irritating to the human skin and has a primary biodegradability of at least 90% as measured by the Wickbold Bias-7d method.

An example of a surfactant named Levenol is Levenol V-501/2, which has seventeen ethoxylated tubing 24 ports and is derived from tallow fatty acid, with a fatty acid / glycerol ratio of 1.0 and a molecular weight of 1465; and Levenol F 200, which contains six ethoxylated groups and is derived from coconut fatty acid with a fatty acid / glycerol ratio of 0.55. It is a mixture of both Levenol F200 and Levenol V-501/2 compounds I and II. Levenol has an ecotoxicity of greater than 100 mg / L in inhibition of algae growth, an acute toxicity in Daphniae of greater than 100 mg / L and a fish of greater than 100 mg / L. Levenol has a biodegradability of at least 60%, which is above the OECD 301B threshold.

Other suitable polyesterified nonionic surfactants are Crovol PK-40 and Crovol PK-70 (Croda GmbH, The Netherlands). Crovol PK-40 is a polyoxyethylene (12) palm kernel glyceride containing twelve EO groups, Crovol PK-70 is a polyoxyethylene (45) palm kernel glyceride containing forty-five EO groups.

In the dilute oil-in-water microemulsion composition or liquid crystal composition, the ethoxylated glycerol type compound or the polyesterated nonionic compound is present together with the anionic detergent. The amount of the ethoxylated glycerol type compound or the polyesterated nonionic solubilizing agent is 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the weight of the liquid crystalline composition or the diluted oil-in-water microemulsion composition. -6% by weight.

Further polyesterified as nonionic surfactant

• «·

- 25 applicable to Crovol PK-40 and Crovol PK-70 (Croda GmbH, The Netherlands). Crovol PK-40 is a polyoxyethylene (12) palm kernel glyceride containing 12 EO groups, Crovol PK-70 is a polyoxyethylene (45) palm kernel glyceride containing 45 EO groups.

In the dilute oil-in-water microemulsion composition, the esterified ethoxylated glycerol compound is present together with the anionic detergent. The amount of esterified ethoxylated glycerol type compound is 0.1 to 20.0% by weight, preferably 0.5 to 10% by weight, based on the weight of the diluted oil-in-water microemulsion composition.

The additional surfactant plays an important role in the formulation of the diluted oil-in-water microemulsion and the concentrated microemulsion formulation. Briefly, in the absence of additional surfactant, the water, the one or more detergents and the hydrocarbon (e.g., a perfume) are mixed together in an appropriate ratio to form either a micellar solution (low concentration) or an oil-in-water emulsion of the first aspect. As a result of the additional excipient, the interface tension between the emulsion droplets and the water phase in the system is reduced to a very low value. As a result of the reduction in interfacial tension, the emulsion droplets spontaneously disintegrate into smaller aggregates during formation of a transparent colloidal size emulsion, such as a microemulsion. In the microemulsion state, thermodynamic factors are equilibrated with varying degrees of stability associated with the total free energy of the microemulsion. THE

- Examples of various thermodynamic factors determined by the total free energy of 26 systems are:

(1) particle-to-particle potential, (2) interfacial tension or free energy (stretching and bending), (3) drop dispersion entropy, and (4) chemical change due to formation.

A thermodynamically stable system can be achieved by (1) minimizing interfacial tension or free energy and (2) maximizing drop dispersion entropy.

Accordingly, the role of the additional excipient in forming a stable oil-in-water type microemulsion is (a) reducing interface tension (1), and (b) modifying the microemulsion structure and increasing the number of possible configurations (2).

Another function of the additional surfactant is to (c) reduce the stiffness of the surface between the micelles.

Increasing the concentration of further surfactant generally broadens the temperature range within which the product is stable.

In the range of from 5 to 43 ° C, three groups of compounds are preferably used as further surfactants in the microemulsion formulation:

(1) water-soluble C 3 -C 5 alkanol,

HO (CH 3 CHCH 2 O) _n is a polypropylene glycol of the formula:

- 27 n is from 2 to 18 and ethylene glycol and propylene glycol monoalkyl ether or ester of the formulas R (X) _n OH and R ₁ (X) _n OH, wherein

R is C 1-6 alkyl,

R-L is C2-C4 acyl,

X is (OCH 2 CH 2) or (OCH 2 CH 3 CH) and n is 1-4;

(2) aliphatic, mono- and dicarboxylic acids having from 2 to 10 carbon atoms, preferably from 3 to 6 carbon atoms;

(3) triethyl phosphate.

Further surfactants are mixtures of the aforementioned compounds which can be used to adjust a specific pH.

When used as an additional surfactant, the mono and dicarboxylic acid of group (2) is used in the ready-to-use microemulsion composition at a concentration of 2 to 10% by weight, the microemulsion composition can be used removal of lime deposits, soap foam and greasy dirt. If such a surface is made of white zirconium enamel, it can be damaged by such a composition.

In addition to the mono- and dicarboxylic acids, 0.01-0.2% by weight of aminoalkylene phosphonic acid can also be used to promote damage to white zirconium enamel surfaces.

- 28 blocking. 0.05 to 1% by weight of phosphoric acid may also be used.

Suitable polypropylene glycols are, for example, dipropylene glycol or 200-1000 molar polypropylene glycol, such as polypropylene glycol (400). Also used as glycol ether are ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), ethylene glycol monohexyl ether (hexyl cellosolve), diethylene glycol monohexyl ether ( hexylcarbitol), triethylene glycol monobutyl ether, mono-, di- or tripropylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol terobutyl ether, ethylene glycol monoacetate and dipropylene glycol propionate.

Suitable aliphatic carboxylic acids are, for example, C3-C6 alkyl or alkenyl monobasic acids and dibasic acids such as glutaric acid, glutaric acid / adipic acid and succinic acid, and mixtures thereof.

The aforementioned glycol ether compounds and acid compounds provide sufficient stability, preferably because of their cost and cosmetic properties (primarily odor) as diethylene glycol monobutyl ether or diethylene glycol monohexyl ether or adipic acid / glutaric acid / succinic acid as further surfactants. mixture. The proportion of each acid in the mixture is not critical and can be modified to the desired odor. Of the three saturated aliphatic dibasic acids, the most water-soluble glutaric acid is used to maximize the water solubility of the acid mixture.

- 29 components. The weight ratio of adipic acid / glutaric acid to succinic acid is generally 1-3: 1-8: 1-5, preferably 1-2: 1-6: 1-3, for example 1: 1: 1, 1: 2: 1, 2: 2: 1: 1: 2: 1.5, 1: 2: 2, or 2: 3: 2.

The amount of additional surfactant required to stabilize the microemulsion composition will, of course, depend on various factors. These include, for example, the surface-tension characteristics of the additional surfactant, the type and amount of primary surfactants and fragrances, and the type and amount of other components present in the composition that influence the listed thermodynamic factors. The amount of additional surfactant is generally from 0.1 to 50% by weight, preferably from 0.5 to 15% by weight, particularly preferably from 1 to 7% by weight, which is the above-mentioned amount of primary surfactants and fragrances, and any additional surfactant described below. forming a stable, dilute oil-in-water type microemulsion in the presence of the component.

The pH of the final microemulsion will depend on the amount of additional surfactant used, but the latter will be selected based on the cost and cosmetic properties, in particular the fragrance. For example, in the microemulsion composition in the pH range of 1 to 10, the compounds of the group (1) or (3) can be used as additional surfactants alone, but in the presence of a polyvalent metal salt, the pH falls to the range of 1 to 8.5. On the other hand, the additional surfactant of group (2) can be used alone if the pH is less than 3.2. However, if the acidic additional surfactant is a glycol ether type additional surfactant

When used in combination, the pH of the composition is substantially neutral, e.g. pH 7 + 1.5, preferably 7 + 0.2.

It is a feature of the present invention that a detergent with a degreasing capacity without a builder can be produced in a neutral or acidic product, since known oil-in-water microemulsion formulations are either highly alkaline or contain large amounts of detergent builder or both.

In addition to their excellent cleaning performance against greasy and oily soils, low pH oil-in-water microemulsion formulations have excellent cleaning performance and removal capacity for soap foam and lime scale, both in the original (undiluted) and diluted state.

Water is the last essential component of the microemulsion composition of the present invention with improved interfacial tension. The amount of water in the microemulsion composition is generally 20-97% by weight, preferably 70-97% by weight of the conventionally diluted oil-in-water type microemulsion composition.

As described above, the liquid oil-in-water microemulsion liquid cleaning composition of the present invention is thus particularly effective when used alone, i.e. without further dilution with water, since the properties of the composition, i.e. oil-in-water microemulsion its nature prevails in its original (undiluted) form. However, depending on the amount of surfactants, additional surfactants, fragrance, and other components, some dilution is possible without losing the microemulsion character. For example, at preferred low concentrations of active surfactants (e.g. primary anionic and nonionic detergents), dilution of up to 50% is well tolerated, does not cause phase separation, and maintains the microemulsion state.

However, the composition is more effective and, after dilution of 2 to 10 times or more, it can be used effectively for cleaning greasy and oily or other types of impurities. In addition, the presence of magnesium ions or other polyvalent ions, such as aluminum ions, upon dilution, contributes to enhancing the cleaning performance of the primary detergents.

On the other hand, however, the invention also encompasses highly concentrated microemulsion formulations which are diluted with additional water before use.

Preferred is a stable concentrated microemulsion or acid microemulsion composition having a composition of about

a) 0-6% by weight of anionic surfactant,

b) 0.1-20% by weight of a mixture of fully esterified ethoxylated polyhydroxy alcohol, partially esterified ethoxylated polyhydroxy alcohol and non-esterified ethoxylated polyhydroxy alcohol,

c) 0.1-50% by weight of additional surfactant;

(d) 0,4 to 10% by weight of water-insoluble hydrocarbons or perfumes,

e) 0-18% by weight of at least one mono- or dicarboxylic acid,

f) 0-1.0% by weight of phosphoric acid,

g) 0-0.2% by weight of aminoalkylene phosphonic acid,

h) 0-15% by weight of magnesium sulfate heptahydrate,

i) 0-16% by weight of a nonionic surfactant,

j) 0-8% by weight of alkali metal dialkyl sulfosuccinate and

j) 100% by weight water.

Such a concentrated microemulsion composition can be diluted with up to 20 times more water or more, preferably 4 to 10 times by weight water, to form an oil-in-water microemulsion similar to the above diluted microemulsion composition. Although the degree of dilution is determined to give an oil-in-water microemulsion formulation after dilution, it should be noted that both microemulsion and non-microemulsion formulation can be obtained during dilution.

In addition to the essential components described above for the preparation of the microemulsion composition, the composition of the invention may, preferably, contain one or more additional components that improve the overall performance of the product.

Examples of such further components are polyvalent metal cations such as oxide of magnesium and inorganic or organic salts thereof. The metal salt or oxide has a number of beneficial effects, for example, when diluted, it improves the cleaning performance, especially in soft water, and reduces the amount of fragrance needed to form a microemulsion state. Preferably, the magnesium salt is magnesium sulfate, in anhydrous or hydrated form, such as heptahydrate. Also preferred are magnesium oxide, magnesium chloride, magnesium acetate, magnesium propionate and magnesium hydroxide. These magnesium salts can be used in formulations having a neutral or acidic pH, since no magnesium hydroxide is precipitated at this pH.

Although the salts, oxides, and hydroxides of polyvalent metals are preferred, magnesium compounds may be used, as long as these polyvalent metal ions are non-toxic and are soluble in the aqueous phase of the system at a given pH. Accordingly, depending on the above factors, such as the pH of the system, the nature of the primary surfactant and further surfactant, and the availability and cost, other useful polyvalent metal ions include aluminum, copper, nickel, iron and calcium. It is noted, for example, that the preferred paraffin sulfonate anionic detergent precipitates the calcium salts and cannot be used. Similarly, aluminum salts are most effective at pH below 5 or in the presence of a small amount, for example 1% by weight of citric acid, which adjusts to the desired pH. Alternatively, the aluminum salt can also be used directly in the form of its citrate salt. The anions mentioned for each of these salts are the anions mentioned for the magnesium salts.

34 glazing agents such as halides (bromide and chloride) as well as sulfate, nitrate, hydroxide, oxide, acetate and propionate.

In the case of a diluted composition, the metal compound is preferably added in an amount such that at least a stoichiometric equilibrium is formed between the anionic surfactant and the polyvalent metal cation. For example, two grams of paraffin sulfonate, alkylbenzene sulfonate, or alkylsulfate is counted per gram of magnesium, while each gram ion contains 3 grams of anionic surfactant. Accordingly, the amount of polyvalent salt is generally selected such that one equivalent of compound will neutralize 0.1 to 1.5 equivalents, preferably 0.9 to 1.4 equivalents, of the acidic anionic detergent.

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

The oil-in-water microemulsion composition contains from 0 to 2.5% by weight, preferably from 0.1 to 2.0% by weight, of C8-C22 fatty acids or fatty acid soaps as anti-foaming agents.

The use of fatty acid or fatty acid soap improves the rinsability of the composition used in its original form or in diluted form. However, when a fatty acid or fatty acid soap is used, it is generally necessary to increase the amount of additional surfactant to maintain stability.

As fatty acids, which can be used alone or in the form of soaps, for example, distilled coconut oil fatty acids, mixed vegetable fatty acids (e.g.

saturated mono- and / or polyunsaturated C 18 fatty acids), oleic acid, stearic acid, palmitic acid, eicosanoic acid, preferably an C 8-22 fatty acid.

The general-purpose liquid cleansing composition of the present invention optionally contains additional components that enhance the effect or utility of the composition. Examples include coloring agents or dyes up to 0.5%, bactericides up to 1%, preservatives up to 2%, or antioxidants such as formaline, 5-chloro-2-methyl-4-isothiazole, 3-one, 2,6-di-tert-butyl p-cresol, and pH adjusting agents such as sulfuric acid or sodium hydroxide. If desired, up to 4% by weight of a translucent is added to produce a translucent composition.

The composition according to the invention does not contain alkali metal silicates or alkali metal detergent builders such as alkali metal phosphonates, alkali metal carbonates, alkali metal polyphosphates or alkali metal cephrates, since these substances produce high pH values in the formulation used, on the surface to be cleaned.

The use of zwitterionic surfactants, such as betaines, in the ready-to-use composition of the present invention is explicitly excluded as they result in strong foaming and highly foaming composition deposits.

- 36 leaves on the cleaned surface. The concentration of fatty acids in the composition is up to 2.5% by weight, because at higher concentrations the composition has an unpleasant odor. In addition, due to their low flash point, no methanol or ethanol is used in the formulation to be used.

In its final form, the generally applicable liquid is a pure oil-in-water microemulsion formulation which exhibits good stability at low or high temperatures. In particular, the composition remains pure and stable at a temperature of 5 to 50 ° C, preferably 10 to 43 ° C. The pH of such a formulation will be in the acidic or neutral range, depending on the intended use. The liquid microemulsion composition is easy to pour and has a viscosity of 6-60 mPas, preferably 10-40 mPas, measured at 25 ° C on a single axis Brookfield RVT viscometer at 20 rpm.

The composition can be used directly or, if desired, diluted, and in both cases, can be applied with minimal rinsing without substantially settling or staining. In addition, the composition is free of detergent builders such as alkali metal polyphosphates and is therefore environmentally friendly and provides better light on the cleaned hard surface.

For direct use, the liquid formulation may be packaged under pressure in an aerosol can or pumped sprayer and used for direct spraying.

Because the composition is an aqueous liquid preparation and does not require special mixing to form an oil-in-water microemulsion, it can be readily prepared by mixing the required components in a suitable vessel. The order of mixing the components is virtually arbitrary and the individual components may be added sequentially, either simultaneously or in aqueous solution. The primary detergent and the additional surfactant may be added separately or in combination or in combination with the perfume. The magnesium salt or other polyvalent metal compound which may be used may be added in the form of an aqueous solution or directly. It is not necessary to produce at elevated temperatures during production, usually room temperature.

According to the present invention, the esterified ethoxylated glycerol type compound can be used in all or part of the compositions for cleaning hard surfaces such as wood surfaces, windows and toilets to replace conventional anionic and / or nonionic surfactants where it is necessary to improve the lipid release effect.

The liquid cleaning composition of the present invention is illustrated in more detail by the following examples. The examples given are for information only and are not intended to limit the scope of protection.

Example 1

Formulations of various compositions are prepared, wherein the amount of each component, by weight, is given in the following table:

THE B C D Ajax Frais Magnesium lauryl sulphate 0.1 Nonionic surfactant substance- Neodol 45-7 2.0 1.2 Esterified polyethoxy ether nonionic surfactant- - Levenol F200 4.0 4.5 3.6 4.5 Sodium dioctyl szulfoszuk- succinate 1.5 1.5 Diethylene glycol monohexil- -ether 3 3 3 4 Tallow PKO Soap 0.2 0.15 MgSO ₄ x 7H ₂ O 0.25 0.5 0.25 Nicky LCV fragrance (a) 0.8 0.8 0.8 0.8 Na lauryl sulfate 1.2 dodecane 0.2 0.15 Water + additive the d 1 0 0 PH 7 7 7 7 Liposuction effect - direct use (b), 10 deletions 80 100 40 100 100 -diluted use (b), 50 deletions 50 40 35 40 35

·· ♦ • · »« · · · · · · · · · · · · ···

- 39 new matches:

(a): Contains 25% by weight of terpene (b): The higher the percentage purification, the better the fat removal.

The lipid removal effect is tested as follows:

x 15 cm white Formica tiles are washed with soap and warm water, rinsed with water, deionized water, and then ethanol and dried at room temperature for at least 4 hours. Once used, the tiles are discarded. The tiles are then sprayed with a solution of dye grease in chloroform using a laboratory chromatographic sprayer. Compressed air at a pressure of about 2 x 10 ⁵ Pa is used for spraying. The following components are used to prepare the spray solution: undiluted: 5% hard fat, 5% soft fat, 0.01% D + C in red 17 chloroform; Diluted: 1.0% Hard Fat, 1.0% Soft Fat, 0.01% D + C Red 17. To remove contamination, prepare a stock solution of chloroform containing 1% dye by adding 1.0 g of this solution to 1000 g. diluted to give the desired final dye concentration. The tiles are sprayed with a reflection coefficient of about 63-70 for the contaminated tiles. The tiles were allowed to dry for 15 minutes after spraying until the chloroform evaporated.

Contaminated tiles are placed in a Gardner Abrader equipped with a two-way / two-boat sled. The two boats40

The sponge is compressed and the boats are filled with 300 g of lead ball to ensure the same pressure on the sponges.

For the diluted preparation, two preparations are tested

A 1.2% solution was prepared and approximately 50 ml of each solution was placed in separate 14 x 7 cm Pyrex bowls. Place the boat with the compressed sponge in the solution. Allow the solutions to be absorbed into the sponges and, after 1 to 2 minutes, remove the excess by pressing the sponge against the edge of the dish. The boats are then returned to the abrasion machine and subjected to 15 deletions. The boats are removed, the sponges are pressed to the edge of the sink and saturated with fresh solution. The excess is removed and the abrasion is repeated. This process is repeated after every 15 deletions, and a total of 105 deletions are made. The tiles measure the reflection coefficient before testing, after contamination, and after every 15 wipes using a Photovolt 575 reflectometer. The reflection coefficient is read without removing the tiles from the abrasive machine. The measurement is made at three points in the purified section and averaged.

To test for undiluted cleaning, two boats are equipped with compressed sponges and placed in separate 14 x 7 cm Pyrex bowls containing approximately 50 ml of tap water. Allow the sponges to saturate and then press the sponge over the edge of the pan

- 41 removed. 1.0 ml of cleaning agent was added to each sponge. The boats are placed in the abrasion machine and operated until 1, 3, 5, 10, 20, 35, and 50 wipes, between which the reflection coefficient is measured. Again, the measurement is performed without removing the tile from the abrasive machine. The measurement is made at three points on the cleaned surface and averaged. During the test, the solutions are not refreshed

The percentage cleaning effect is calculated by the following equation:

Reflection coefficient of cleaned tile - Reflection coefficient of dirty tile cleaning (%) = --------------------------------- x 100.

reflection coefficient of unpolluted tiles - reflection coefficient of dirty tiles

In summary, the present invention significantly improves the properties of a microemulsion composition comprising an anionic surfactant, an esterified ethoxylated glycerol compound, an additional surfactant, a hydrocarbon component, and water, wherein the essential hydrocarbon component is a water-insoluble fragrance oil. in an amount required for the preparation of a micro-emulsion composition of the a-water type. Typically, the composition will comprise from 0.1 to 6.0% by weight of anionic detergent, from 0 to 16% by weight of nonionic surfactant, from 0.1 to 20% by weight of esterified ethoxylated glycerol, 0.1 to 50% by weight of additional surfactant, and Containing 4-10% by weight of perfume or hydrocarbon in 100% water.

Claims (6)

Claims CLAIMS 1. A stable microemulsion formulation comprising 0.1-6% by weight of anionic surfactant, 0-16% by weight of nonionic surfactant, 0.1-50% by weight of additional surfactant and 0.1-20.0% by weight. in an amount of a mixture of compounds of formula (I) and (II) R I CH ₂ -O- (CH ₂ CH-O) _x B R I [CH-O- (CH ₂ CH-O) _y B] w (I) R I CH ₂ -O- (CH ₂ CH-O) ₂ b and R I CH ₂ -O- (CH ₂ CH-O) _x H R I [CH-O- (CH ₂ CH-O) _y H] w (II), R I CH ₂ -O- (CH ₂ CH-O) _z where w is 1-4, B is hydrogen or -CO-R wherein R is C 6 -C 22 alkyl, or C 6 -C 22 alkenyl, with the proviso that at least one B has the meanings of R, ··········· - 44 -CO-R, R 'is hydrogen or methyl, x, y and z are 0-60, with the proviso that x + y + z is 2-100, wherein the monoester / diester / triester ratio of formula (I) is 40-90 / 5-35 / 1-20, and wherein the ratio of compound of formula I to compound of formula II is 3-0.02; 0.4 to 10% by weight with at least one water-insoluble hydrocarbon and / or perfume and 100% water. 2. A stable, clean, general-purpose hard surface cleaner that is particularly effective at removing oily or greasy dirt and forms an oil-in-water microemulsion, wherein the aqueous phase of the microemulsion composition is about 0.1 to about 6% by weight. % anionic surfactant, 0-16% by weight nonionic surfactant and 0.1-20% by weight mixture of compounds of formula I and II, wherein w is 1-4, B is hydrogen or -CO-R wherein R is C 6 -C 22 alkyl, or C 6 -C 22 alkenyl, with the proviso that at least one B is -CO-R, - 45 R 'is hydrogen or methyl, x, y and z are 0-60, with the proviso that x + y + z is 2-100, wherein the monoester / diester / triester ratio in the formula (I) is 40- 90 / 5-35 / 1-20 and wherein the ratio of compound of formula I to compound of formula II is 3-0.02; from about 0.1% to about 50% by weight of a further surfactant that is substantially incapable of dissolving oily or greasy impurities, and may be a C 1-6 alkyl ether of C 3 -C 5 alkanol, polypropylene glycol, ethylene glycol or propylene glycol; its ester, C3-C6 aliphatic mono- and dicarboxylic acids, and mono-, di-triethyl phosphate, and water; and the oily phase of the microemulsion composition comprises from about 0.1% to about 10% by weight of the composition of at least one water-immiscible or water-miscible hydrocarbon; wherein the composition is particularly effective in removing oily or greasy impurities from hard surfaces by solubilizing the oily or greasy impurity in the oil phase of the microemulsion. 3. The detergent composition of claim 2, further comprising a cationic salt of a polyvalent metal in an amount of 0.5 to 1.5 equivalents of cation per equivalent of anionic detergent. • · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · exc exc 4. The cleaning agent according to claim 3, wherein the polyvalent metal cation is magnesium or aluminum. 5. A detergent composition according to claim 3, characterized in that it contains 0.9 to 1.4 equivalents of cation per equivalent of anion detergent. The detergent according to claim 4, wherein the polyvalent salt is magnesium oxide or magnesium sulfate. 7. The detergent according to claim 2, wherein the fatty acid has from about 8 to about 22 carbon atoms. 8. The detergent composition of claim 2, wherein it contains from about 0.5 to about 15% by weight of additional surfactant and from about 0.4 to about 3.0% by weight of hydrocarbon. The detergent according to claim 2, characterized in that it further contains a C 1 -C 6 glycol ether as an additional surfactant. 10. The cleaning agent of claim 9, wherein the glycol ether is selected from the group consisting of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, polypropylene pilene having an average molecular weight of about 200-1000. glycol, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, triethylene glycol monohexyl ether, propylene glycol tert-butyl ether, and mono-, di- or tripropylene glycol monobutyl- ether. 11. The cleaning agent of claim 10, wherein the glycol ether is selected from the group consisting of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and diethylene glycol monohexyl ether. 12. The detergent composition of claim 2, wherein the further surfactant is selected from the group consisting of C3-C6 aliphatic carboxylic acids such as acrylic acid, propionic acid, glutaric acid, glutaric acid and succinic acid and adipic acid, or a mixture thereof. 13. A detergent composition according to claim 12, characterized in that it is a mixture of aliphatic carboxylic acid, adipic acid, glutaric acid and succinic acid. 14. The cleaning agent of claim 2, wherein the anionic surfactant is selected from the group consisting of C 9 -C 15 alkyl benzene sulfonate and C 10 -C 20 alkane sulfonate. 15. A stable, concentrated microemulsion formulation, characterized in that a) 1-30% by weight of anionic surfactant, b) from 0.1 to 20% by weight of a mixture of the compounds of the formulas I and II, wherein w is 1-4, B is hydrogen or -CO-R wherein R is C 6 -C 22 alkyl, or C 6 -C 22 alkenyl, with the proviso that at least one B is -CO-R, R 'is hydrogen or methyl, x, y and z are 0-60, with the proviso that x + y + z is 2-100, wherein the monoester / diester / triester ratio of formula (I) is 40-90 / 5-35 / 1-20, and wherein the ratio of the compound of formula I to the compound of formula II is 3-0.02, c) 0.1 to 50% by weight of additional surfactant, (d) 0.4 to 10% by weight of at least one water-insoluble hydrocarbon or perfume, e) 0-18% by weight of at least one mono- or dicarboxylic acid, f) 0-0.2% by weight of aminoalkylene phosphonic acid, g) 0 to 1.0% by weight of phosphoric acid, h) 0-15% by weight of magnesium sulfate heptahydrate, (i) 0 to 16% by weight of a nonionic surfactant, and (j) it contains 100% water. • · ············································································································································ · · · · · 16. A stable microemulsion formulation comprising from about 0.25 to about 8% by weight of an alkali metal dialkyl sulfosuccinate, from about 0.1 to about 50% by weight of additional surfactant, and from about 0.1% to about 20% by weight of a mixture of compounds of Formulas I and II. , where w is 1-4, B is hydrogen or -CO-R wherein R is C 6 -C 22 alkyl, or C 6 -C 22 alkenyl, with the proviso that at least one B is -CO-R, R ¹ is hydrogen or methyl, x, y and z are 0-60, with the proviso that x + y + z is 2-100, wherein the monoester / diester / triester ratio in the formula (I) is 40-90 / 5-35 / 1-20, and wherein the ratio of compound of formula I to compound of formula II is 3-0.02; 0.4-10% by weight of at least one water-insoluble hydrocarbon and / or perfume and 100% water. 17. A stable, clean, generally applicable, and hard surface cleaning composition which is preferably used to remove oil or greasy impurities and which is an oil-in-water microemulsion, - 50, wherein the aqueous phase of the microemulsion composition comprises from about 0.25 to about 8% by weight of an alkali metal dialkyl sulfosuccinate and from about 0.1% to about 20% by weight of a mixture of compounds of Formulas I and II wherein w is 1-4, B is hydrogen or -CO-R wherein R is C 6 -C 22 alkyl, or C 6 -C 22 alkenyl, with the proviso that at least one B is -CO-R, R 'is hydrogen or methyl, x, y and z are 0-60, with the proviso that x + y + z is 2-100, wherein the monoester / diester / triester ratio of formula (I) is 40-90 / 5-35 / 1-20, and wherein the ratio of compound of formula I to compound of formula II is 3-0.02; from about 0.1% to about 50% by weight of water-insoluble additional surfactant which is substantially incapable of dissolving oily or greasy impurities, which may be C3-C5 alkanol, polypropylene glycol, ethylene glycol or propylene glycol C 1-6 alkyl its ether or ester, C3-C6 aliphatic mono- or dicarboxylic acid, mono-, di- and triethylphosphate, and water; the oily phase of the microemulsion in an amount of from about 0.1% to about 10% by weight based on the total weight of the composition, at least · · · · · · · · · · · · · · · 51 contains a hydrocarbon which is insoluble in water or miscible with water; which composition is preferably used to remove oily or greasy impurities from hard surfaces by solubilizing the oily or greasy impurity in the oil phase of the microemulsion. 18. The composition of claim 19, further comprising from 0.5 to 1.5 equivalents of a cation salt of a polyvalent metal cation relative to the equivalent of the anionic detergent. 19. The composition of claim 18, wherein the polyvalent metal cation is magnesium or aluminum. 20. The composition of claim 18, wherein the composition comprises from 0.9 to 1.4 equivalents of cation per equivalent of detergent anine. 21. The composition of claim 19, wherein the polyvalent salt is magnesium oxide or magnesium sulfate. 22. The composition of claim 17, wherein the composition comprises about 8 to about 22 carbon fatty acids. 23. A composition according to claim 17, characterized in that: 52, comprising about 0.5% to about 15% by weight of additional surfactant and about 0.4% to about 3.0% by weight of hydrocarbons. 24. The composition of claim 17, wherein the additional surfactant has a C 1-6 glycol ether in the alkyl portion. 25. The composition of claim 24, wherein the glycol ether is selected from the group consisting of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, polypropylene having an average molecular weight of about 200-1000. glycol, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, triethylene glycol monohexyl ether, propylene glycol tert-butyl ether, and mono-, di- or tripropylene glycol monobutyl ether . 26. The composition of claim 25, wherein the glycol ether is selected from the group consisting of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and diethylene glycol monohexyl ether. 27. The composition of claim 17, wherein the additional surfactant is selected from the group consisting of C 3 -C 6 aliphatic carboxylic acids such as acrylic acid, propionic acid, glutaric acid, glutaric acid and succinic acid and adipic acid, and mixtures thereof. · «··· ♦ · 29. The composition of claim 27, wherein the aliphatic carboxylic acid is a mixture of adipic acid, glutaric acid and succinic acid. 30. The composition of claim 17, wherein the alkali metal present in the alkali metal dialkyl sulfosuccinate is lithium, potassium and sodium, and the alkyl groups each contain from about 4 to about 12 carbon atoms. 31. Stable, concentrated microemulsion formulation, characterized in that it has a composition of ca. a) 0.1 to 20% by weight of a mixture of compounds of formula I and II, wherein w is 1-4, B is hydrogen or -CO-R wherein R is C 6 -C 22 alkyl, or C 6 -C 22 alkenyl, with the proviso that at least one B is -CO-R, R 'is hydrogen or methyl, x, y and z are 0-60, with the proviso that x + y + z is 2-100, wherein the monoester / diester / triester ratio of formula (I) is 40-90 / 5-35 / 1-20, and wherein the ratio of the compound of formula I to the compound of formula II is 3-0.02, b) 0.1 to 50% by weight of additional surfactant, (c) 0.4 to 10% by weight of at least one water-insoluble hydrocarbon or perfume, d) 0-18% by weight of at least one mono- or dicarboxylic acid, e) 0-0.2% by weight of aminoalkylene phosphonic acid, f) 0-1.0% by weight of phosphoric acid, g) 0-15% by weight of magnesium sulfate heptahydrate, h) from 0.25 to 8% by weight of an alkali metal dialkyl sulfosuccinate wherein the alkyl group is from about 4 to about 12 carbon atoms and the alkali metal may be lithium, potassium and sodium, and (i) 100% volume of water.