DE69414779T2 - Detergent in the form of a stable microemulsion - Google Patents

Abstract

A microemulsion composition comprising approximately by weight 6 to 50% of a mixture of two different anionic surfactants, one of said anionic surfactants being a sulphonate and the other said anionic surfactant being a sulphate, a ratio of said sulphonate to said sulphate being 10:1 to 1:10; 0 to 6% of a nonionic surfactant; 1 to 20% of at least one of a water insoluble organic compound; 0 to 8% of a solubilizing agent; 0 to 20% of at least one water soluble hydroxy containing organic compound; and the balance being water, wherein the composition has a pH of 1 to 11.

Description

This invention relates to a stable microemulsion cleaning composition and methods of making and using the same. More particularly, it relates to a stable aqueous microemulsion cleaning composition in concentrated or diluted form which is particularly effective in removing oily and greasy soils from substrates such as bathroom fixtures and walls, leaving these surfaces clean and shiny without the need for extensive rinsing. The compositions described comprise a mixture of anionic surfactants, a water-insoluble organic compound which is less than 1.0% by weight soluble in water at 25°C and has a dH of 0 to 12 (MPa)1/2, dd of 14 to 19 (MPa)1/2 and dP of 0 to 6 (MPa)1/2, water and a suitable co-surfactant system, wherein the co-surfactant system adjusts the interfacial arrangement to reduce the interfacial tension at interfaces between dispersed and continuous phases of the emulsion to provide a stable, normally clear microemulsion at room temperature. When the pH of the microemulsion is in the acidic range, preferably in the range of 1 to 4, the compositions of the invention are useful for removing limescale and soap scum from hard substrates.

This invention also relates to a gelled microemulsion cleaning composition and methods of making and using the same. In particular, it relates to a stable gelled microemulsion cleaning composition in concentrated form which is particularly effective for cleaning oily and greasy soils from vertical surfaces such as bathroom fixtures and walls, leaving the surfaces clear and shiny without the need for extensive rinsing. The compositions described comprise a mixture of anionic surfactants, a water-insoluble organic compound having a dH of 0 to 1 (MPa)1/2, da of 14 to 18 (MPa)1/2 and dP of 0 to 2 (MPa)1/2, water and a suitable co-surfactant system, the co-surfactant system adjusting the interfacial arrangement to to reduce the interfacial tension at interfaces between dispersed and continuous phases of the emulsion of surfactants to provide a gelled microemulsion stable at room temperature. When the pH of the microemulsion is in the acidic range, preferably in the range of 1 to 4, the compositions of the invention are useful for removing limescale and soap scum from hard substrates.

Liquid cleaning compositions, usually in solution or emulsion form, have been used as general purpose cleaners and have been proposed for cleaning hard surfaces such as varnished wood, bathtubs, wash basins, tiled walls, tiled floors, linoleum surfaces and washable wallpaper. Many such preparations, such as those described in US-A-2,560,839, US-A-3,234,138 and US-A-3,350,319 and GB-A-1,223,739, include substantial amounts of inorganic phosphate builder salts, the presence of which is sometimes considered objectionable on environmental grounds and also because they require thorough rinsing of the liquid cleaning composition from the cleaned surface to avoid the presence of noticeable phosphate deposits thereon. Liquid detergents with reduced phosphate builder salt levels have been described in US-A-4,017,409 and US-A-4,244,840, but they may still require rinsing or may include enough phosphate to be environmentally unacceptable. Some liquid detergents have been made which are phosphate-free, such as those described in US-A-3,935,130, but these usually include higher percentages of synthetic organic detergent, and the increased detergent content may be questionable due to excessive foaming during use resulting from its presence. The liquid detergent compositions described above are emulsions, but they are not disclosed to be microemulsions such as those of the present invention.

Microemulsions have been disclosed in various patents and patent applications for liquid cleaning compositions which may be useful as hard surface cleaners or all-purpose cleaners, and such compositions sometimes include detergent, solvent, water and co-surfactant. Such disclosures include EP-A-0 137 615, EP-A-0 137 616 and EP-A-0 160 762 and US-A-4 561 448, all of which describe at least 5% by weight of solvent in the compositions. The use of magnesium salts to improve the grease removal performance of solvents in liquid microemulsion cleaning compositions is mentioned in GB-A-2 144 763. Other patents for liquid cleaning compositions in microemulsion form are US-A-3,723,330, US-A-4,472,291 and US-A-4,540,448. Additional formulations of liquid cleaning compositions in emulsion form which include hydrocarbons such as terpenes are disclosed in GB-A-1,603,047 and GB-A-2,033,421, EP-A-0,080,749 and US-A-4,017,409, US-A-4,414,128 and US-A-4,540,505. The presence of builder salt in such compositions, particularly in the presence of magnesium compounds, tends to destabilize the microemulsions and therefore such builders are considered undesirable.

US-A-4 414 128 describes liquid cleaning compositions for use as hard surface cleaners comprising 1 to 20 wt.% surfactant selected from anionic, nonionic, amphoteric and zwitterionic surfactants and mixtures of the same, 0.5 to 10 wt.% terpene and 0.5 to 10 wt.% polar solvent. This document does not suggest the specific combination of a sulfonate with a sulfate in a ratio of 10:1 to 1:10.

EP-A-384 715 describes a liquid microemulsion fine detergent composition intended in particular for washing greasy soil from dishes and comprising 20 to 40 wt.% of anionic detergent which is a mixture of a paraffin sulfonate with an alkyl diethoxy ether sulfate, 1 to 5 wt.% of co-solvent such as dipropylene monomethyl ether, 1 to 5 wt.% organic solvent such as isoparaffins and 1 to 10% by weight of a complex between anionic and cationic surfactant. It follows from this document that the cationic surfactant is essential in the complex.

It further results from EP-A-384 715 that a composition containing 8.31 wt. of sodium lauryl diethoxy ether sulfate, 24.94 wt.% of sodium C₁₄₋₁₇-paraffin sulfonate, 5 wt.% of dipropylene glycol monomethyl ether, 5 wt. of C₁₀₋₁₁-isoparaffin and water as the balance is known in the art. However, these compositions lack d-limonene.

Although the cited prior art relates to liquid general purpose cleaning compositions in emulsion form, and although various components of the present compositions are mentioned in the art, it is believed that the prior art does not anticipate or make obvious the present material disclosed and claimed herein. According to the invention, a stable aqueous microemulsion cleaning composition, which may be in concentrated or diluted form, comprises at least two different anionic synthetic organic cleaning agents, a water-insoluble organic compound, water, and a co-surfactant system, wherein the co-surfactant system adjusts the interfacial arrangement to reduce interfacial tension at interfaces between dispersed and continuous phases of the emulsion to provide a concentrated microemulsion stable at temperatures in the range of 5° to 50°C and having a pH in the range of 1 to 11. Such concentrated microemulsions are dilutable with at least five times their weight of water to yield dilute liquid cleaning compositions which are often also stable aqueous microemulsions useful as general purpose cleaning compositions. Both the concentrated and dilute compositions are effective for cleaning oily and greasy soils from substrates and when the compositions are acidic they are also useful for removing limescale and soap scum from hard substrates such as bathroom fixtures, floors and walls.

Also in accordance with the invention, a stable gelled microemulsion cleaning composition which is in concentrated form comprises at least two different anionic synthetic organic cleaning agents, a water-insoluble organic compound, water and a co-surfactant system, wherein the co-surfactant system adjusts the interfacial arrangement to reduce the interfacial tension at interfaces between dispersed and continuous phases of an emulsion of the surfactants to provide a concentrated gelled microemulsion stable at temperatures in the range of 5° to 50°C and having a pH in the range of 1 to 11. Such concentrated gelled microemulsions are dilutable with at least five times their weight of water to produce dilute liquid cleaning compositions which are often also stable aqueous pseudo-microemulsions useful as general purpose cleaning compositions. Both the concentrated gelled and diluted compositions are effective for cleaning oily and greasy dirt from substrates, and if the compositions are acidic, they are also useful for removing limescale and soap scum from hard surfaces such as bathroom fixtures, floors and walls.

In addition to the gelled microemulsion concentrates, the present invention also relates to diluted pseudo-microemulsions, processes for preparing such pseudo-microemulsions and processes for cleaning surfaces with them.

In addition to microemulsion concentrates, the present invention also relates to diluted microemulsions, processes for preparing such microemulsions and processes for cleaning surfaces with them.

Summary of the invention

The present invention provides an improved liquid cleaning composition in the form of a microemulsion suitable for cleaning hard surfaces having greasy deposits built up thereon, such as plastic, glass and metal surfaces, all of which have shiny surfaces While the general purpose cleaning composition may be used in other cleaning applications, such as removing oily soils and stains from fabrics, it is primarily intended for cleaning hard, shiny surfaces and desirably requires little or no rinsing. The improved cleaning compositions of the present invention exhibit excellent grease removal effects, particularly when used in concentrated form, and leave the cleaned surfaces shiny, sometimes without the need for rinsing. Little or no residue is seen on the cleaned surfaces, which overcomes one of the most significant disadvantages of various prior art products, and the surface shines even with little or no wiping. Surprisingly, this desirable cleaning is accomplished even in the absence of polyphosphates or other inorganic or organic detergent builder salts.

The present invention provides an improved liquid cleaning composition in the form of a gelled microemulsion suitable for cleaning vertical hard surfaces having greasy deposits built up thereon, such as plastic, glass and metal surfaces, all of which may have glossy surfaces. While the general purpose cleaning composition may also be used in other cleaning applications, such as removing oily dirt and stains from fabrics, it is primarily intended for cleaning hard, glossy surfaces and desirably requires little or no rinsing. The improved cleaning compositions of the invention exhibit excellent grease removal effects, particularly when used in concentrated gel form, and leave the cleaned surfaces shiny, sometimes without the need for rinsing. Little or no residue is seen on the cleaned surfaces, overcoming one of the most significant disadvantages of various prior art products, and the surface shines even with little or no wiping. Surprisingly, the general purpose cleaning composition is suitable for cleaning hard, glossy surfaces, particularly when used in concentrated gel form, and leaves the cleaned surfaces shiny, sometimes without the need for rinsing. Surprisingly, this desired cleaning is achieved even in the absence of polyphosphates or other inorganic or organic detergent builder salts.

General description of the invention

According to one aspect of the invention there is provided a stable, clear, all-purpose hard surface cleaning composition in the form of a substantially concentrated or slightly diluted microemulsion which is particularly effective for removing oily and greasy soils from hard surfaces.

According to another aspect of the invention there is provided a stable, clear, all-purpose hard surface cleaning composition in the form of a substantially concentrated gelled microemulsion or slightly diluted pseudo-microemulsion which is particularly effective for removing oily and greasy soils from vertical hard surfaces.

The compositions according to the invention, which are preferably microemulsions, which are particularly suitable for the excellent removal of grease deposits on hard surfaces, comprise, by weight,

a) 6-50% of a mixture of two different anionic surfactants, one of said anionic surfactants being a sulfonate and the other of said anionic surfactants being a sulfate, the ratio of the sulfonate to the sulfate being 10:1 to 1:10, in particular 4:1 to 2:1 and most preferably 3.3:1 to 2:7,

b) 0 to 6% non-ionic surfactant,

c) 1 to 20% d-limonene as a water-insoluble organic compound,

d) 0 to 8% solubilizing agent,

e) 1 to 14% of at least one water-soluble hydroxy containing organic compound which is a co-surfactant, and

f) the remainder being water, the composition having a pH value of 1 to 11, in particular 5 to 9, and being optically clear with at least 90%, in particular at least 95% Light transmission, wherein the interfacial tension between the lipophilic droplets of the composition and the aqueous phase is less than 10⁻⁵ N/m, in particular less than 10⁻⁶ N/m.

The compositions of the invention, which are also gelled microemulsions specifically intended for excellent removal of grease deposits from hard surfaces and also as stain pre-treatment agents for laundry, comprise, by weight,

a) 13 to 50% of a mixture of two different anionic surfactants, one of the anionic surfactants being a sulfonate and the other of the anionic surfactants being a sulfate, the ratio of the sulfonate, preferably a paraffin sulfonate, to the sulfate, preferably an alkyl ether sulfate, being 10:1 to 1:10, in particular 4:1 to 2:1 and most preferably 3.3:1 to 2:7,

b) 1 to 20%, in particular 4 to 20% d-limonene as water-insoluble organic compound,

c) 5 to 20% of at least one water-soluble, hydroxy-containing organic compound which is a co-surfactant, and

d) optionally 0 to 30 wt.% of solids suspended in the gelled microemulsion, wherein the solid is selected from the group consisting of alkali metal detergent builder salts and abrasives and mixtures thereof,

e) the remainder being water, the composition having a pH of 1 to 11, the interfacial tension between the lipophilic droplets of the composition and the aqueous phase being less than 10⁻⁵ N/m, in particular less than 10⁻⁶ N/m.

The compositions according to the invention may contain an effective amount of component d) to bring the viscosity at 1 rad s⁻¹ to a value which is between 1 and 10³ Pa s, in particular 5 to 100 Pa s, so that the corresponding compositions are characterized by a G' value over a load range from 1 to 50% of at least 10 Pa·s, in particular at least 50 Pa·s, and a Gy value over a load range of 1 to 50% of at least 10 Pa·s, in particular at least 50 Pa·s.

Preferred concentrations of said components of the concentrated gelled microemulsion are 13 to 50 wt.% synthetic organic detergent, 14 to 20 wt.% d-limonene, 5 to 20 wt.% co-surfactant system and water as the balance. At such preferred gelled concentrations, the resulting pseudo-microemulsion when diluted one part concentrate with four parts water has a low detergent and solvent content, which may be desirable to avoid excessive foaming and to avoid destabilization of the emulsion due to too high a content of lipophilic phase therein after it dissolves in the appropriate hydrocarbon or other solvent for the oily or greasy soil to be removed from a substrate to be cleaned.

Preferred concentrations of the said components of the concentrated microemulsion are 6 to 50 wt.% synthetic organic detergent, 1 to 20 wt.% d-limonene, 1 to 14 wt.% co-surfactant system and water as the balance. At such preferred concentrations, the resulting microemulsion when diluted one part concentrate with four parts water has a low detergent and solvent content, which may be desirable to avoid excessive foaming and to avoid destabilization of the emulsion due to too high a content of lipophilic phase therein after it dissolves in the appropriate hydrocarbon or other solvent for the oily or greasy soil to be removed from a substrate to be cleaned. Due to the absence of builders, when the cleaning composition consists of or consists essentially of the described components (small amounts of compatible excipients are permissible), a chalky appearance of the cleaned surface is avoided and rinsing can be eliminated. Among the Desirable excipients which may be present in the microemulsions include, for example, divalent or polyvalent metal salts as sources of magnesium and aluminum which improve cleaning performances of the diluted compositions, and higher fatty acids and/or higher fatty acid soaps such as sodium stearate in a concentration of 1.0 to 5.0% by weight which act as foam suppressors as well as maintain the clarity of the product. Of course, where it is considered aesthetically desirable for normally clear microemulsions to be of a hazy or pearlescent appearance, an opalescent or pearlescent agent may be present, and in some cases where it is not considered disadvantageous that the builder must be rinsed off the substrate, builder salts such as polyphosphates may be present in the microemulsions, but it should be emphasized that builders are normally absent from them.

Some preferred "diluted" microemulsion cleaning compositions can be obtained by mixing four parts by weight of water with one part by weight of the previously described concentrated microemulsion. If other dilutions of 1:1 to 1:19 concentrated microemulsion:water are used, the percentages of these ranges and the preferred ranges should be adjusted accordingly. In some cases, dilutions up to 1:99 are feasible and such diluted compositions can be used as such, or further diluted in some applications, such as when used as a hand dishwashing detergent (with rinse).

Although most of these microemulsions of the invention are of the oil-in-water (o/w) type, some may be water-in-oil (w/o), particularly the concentrates. They may convert to o/w upon dilution with water, but both the o/w and w/o microemulsions are stable. The preferred detergent compositions are oil-in-water microemulsions, whether as concentrates or after dilution with water, the essential components of the same cleaning agent are water insoluble organic compound, co-surfactant and water.

The advantages of the present invention over previously known liquid cleaning compositions include the following:

1. Liquid cleaning compositions according to the invention can be prepared with comparable effectiveness and properties with lower percentages of active ingredients and comparable clarity with significantly lower percentages of solubilizing agents than disclosed in previously known compositions for removing greasy deposits.

2. Compositions of the invention can produce foam that is as good or better in both quantity and durability than that produced by prior art compositions.

3. Compositions according to the invention, when diluted to the same use concentration as compositions of the prior art, can provide significantly better performance in terms of grease removal, particularly in dishwashing.

4. Washing solutions prepared with compositions according to the invention have significantly lower surface tension than solutions of the same concentration using prior art compositions.

Additional advantages of the present invention are improved and controlled performance such as foaming and dishwashing action, viscosity and clarity, which are important factors in consumer acceptance. The sulfonate used in the present invention can be a paraffin sulfonate.

The paraffin sulfonates (A) used in the compositions according to the invention are usually mixed secondary alkyl sulfonates having 10 to 20 carbon atoms per molecule, preferably having at least 80%, usually at least 90% of the alkyl groups have 13 to 17 carbon atoms per molecule. When the majority has 14 to 15 carbon atoms per molecule, optimal foaming performance appears to be achieved with varying concentrations and water hardness. Another useful sulfonated anionic surfactant is a linear sodium alkylbenzene sulfonate (LAS) which is represented by the formula

where n is 9 to 15 and x is defined below.

The concentration of the paraffin or linear alkylbenzene sulfonate in the present non-gelled composition is 5 to 30 wt.%, in particular 15 to 30 wt.%, and the concentration of the alkyl ether sulfate is 1 to 20 wt.%, in particular 2 to 12 wt.%.

The sulfonates are generally present in amounts of 15 wt% to 50 wt%, preferably 20 wt% to 35 wt%.

The higher alkyl ether sulfates (C) that can be used in the compositions according to the invention are represented by the formula

RO(C₂H₄O)nSO₃X

in which R represents a primary or secondary alkyl group which may be straight-chain or branched having 10 to 18, preferably 12 to 15 carbon atoms, X is a suitable water-soluble cation as defined below and n is 1 to 10, preferably 1 to 6. These sulfates are prepared by sulfating the corresponding ether alcohol and subsequently neutralizing the resulting sulfuric acid ester.

The cation X of the paraffin sulfonate (A) and the alkyl ether sulfate (C) may be an alkali metal (e.g. sodium or potassium), an alkaline earth metal (e.g. magnesium), ammonium or lower amine (including alkylolamines). It is preferred to use the sodium salt of paraffin sulfonic acid and a sodium salt of the alkyl ether sulfuric acid ester.

The water-soluble or water-dispersible nonionic synthetic organic detergents optionally used in the non-gelled composition at a concentration of 0 to 6%, preferably 0.1 to 6%, by weight of the non-gelled microemulsion cleaning compositions of the invention are typically condensation products of an organic aliphatic or alkyl aromatic hydrophobic compound and ethylene oxide, which is hydrophilic. Almost any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free hydrogen present can be condensed with ethylene oxide or with polyethylene glycol to form a nonionic cleaning agent. The length of the polyethyleneoxy chain of the condensation product can be adjusted to achieve the desired balance between hydrophobic and hydrophilic elements (hydrophilic/lipophilic balance, or HLB), and such balances can be estimated as HLB numbers.

Particularly suitable non-ionic cleaning agents are the condensation products of higher aliphatic alcohol with 8 to 18 carbon atoms in straight-chain or branched configuration, which is condensed with 2 to 30, preferably 2 to 10 moles of ethylene oxide. A particularly preferred compound is C9-11 alkanol ethoxylate of five ethylene oxides per mole (5 EO), which may also be referred to as C9-11 alcohol EO 5:1, C12-15 alkanol ethoxylate (7 EO), or C12-15 alcohol EO 7:1 is also preferred, such non-ionic detergents are commercially available from Shell Chemical Co. under the trade names Dobanol® 91-5 and Neodol® 25-7.

Other suitable non-ionic detergents are the polyethylene oxide condensates of one mole of alkylphenol containing 6 to 12 carbons in straight chain or branched configuration, with 2 to 30, preferably 2 to 15 moles of ethylene oxide, such as nonylphenol condensed with 9 moles of ethylene oxide, dodecylphenol condensed with 15 moles of ethylene oxide, and dinonylphenol condensed with 15 moles of ethylene oxide. These aromatic compounds are not as desirable as the aliphatic alcohol ethoxylates in the compositions of the invention because they are not as biodegradable.

Another well-known group of useful non-ionic detergents is marketed under the trade name "Pluronic"®. These compounds are block copolymers formed by condensing ethylene oxide with a hydrophobic base formed by condensing propylene oxide with propylene glycol. The molecular weight of the hydrophobic portion of the molecule is on the order of 950 to 4000, preferably 1200 to 2500. Condensation of ethylene oxide with the hydrophobic portion increases the water solubility of the molecule. The molecular weight of these polymers is in the range of 1000 to 15000 and the polyethylene oxide content can be 20 to 80% of the same.

Still other satisfactory nonionic detergents are a condensation of C₁₀₋₁₆ alkanol with a heteric mixture of ethylene oxide and propylene oxide. The molar ratio of ethylene oxide to propylene oxide is 1:1 to 4:1, preferably 1.5:1 to 3.0:1, the total weight of the ethylene oxide and propylene oxide content (including the terminal ethanol group or propanol group) being 60% to 85%, preferably 70% to 80% of the molecular weight of the nonionic detergent. Preferably, the higher alkanol contains 12 to 15 carbon atoms and a preferred compound is the condensation product of C₁₃₋₁₅ alkanol with 4 moles of propylene oxide and 7 moles of ethylene oxide. Such preferred compounds are commercially available from BASF Company under the trade name Lutensol® LF.

Also suitable for incorporation into the cleaning compositions according to the invention are the non-ionic detergents which are obtained by the condensation of ethylene oxide with the product which resulting from the reaction of propylene oxide and ethylenediamine. For example, satisfactory ones of these compounds contain 40 to 80% by weight of polyoxyethylene having a molecular weight of 5,000 to 11,000 and result from the reaction of ethylene oxide with a hydrophobic base which is a reaction product of ethylenediamine and propylene oxide in excess and has a molecular weight in the range of 2,500 to 3,000.

In addition, the generally non-polar non-ionic detergents described above can be replaced by polar non-ionic detergents. Such polar detergents include those in which a hydrophilic group contains a semi-polar bond directly between two atoms, for example N-O and P-O. There is charge separation between such directly bonded atoms, but the detergent molecule carries no net charge and does not dissociate into ions. Suitable such polar non-ionic detergents include open-chain aliphatic amine oxides having the general formula R⁷R⁸R⁹N-O, in which R⁷ is an alkyl, alkenyl or monohydroxyalkyl radical having 10 to 16 carbon atoms and R⁸ and R⁹ are each hydrogen. are each selected from the group consisting of methyl, ethyl, propyl, ethanol and propanol radicals. Preferred amine oxides are the C10-16 alkyl dimethyl and dihydroxyethyl amine oxides, e.g. lauryl dimethyl amine oxide and lauryl myristyl dihydroxyethyl amine oxide. Other useful polar nonionic cleaning agents are the related open-chain aliphatic phosphine oxides having the general formula R10R11R12P-O, where R10 is an alkyl, alkenyl or monohydroxyalkyl radical having a chain length in the range of 10 to 18 carbon atoms and R11 and R12 are each alkyl or monohydroxyalkyl radicals having 1 to 3 carbon atoms. As with the amine oxides, the preferred phosphine oxides are the C10-16 alkyldimethyl and dihydroxyethylphosphine oxides.

In diluted o/w microemulsions according to the invention, the non-ionic cleaning agent can be present mixed with the anionic cleaning agent. The proportion of the non-ionic cleaning agent in such mixed cleaning agent compositions, based on the finished diluted o/w microemulsion sion composition may be in the range of 0 to 6 wt.%, preferably 0.1 to 6 wt.%.

Many other suitable anionic and nonionic detergents which can be cleaning components of the present microemulsion cleaning compositions are described in the tests concerning cleaning effectiveness, cleaner compositions and components, including Surface Active Agents (Their Chemistry and Technology), by Schwartz and Perry, and the various annual issues of John W. McCutcheon's Detergents and Emulsifiers.

The viscosity and clarity control system for the non-gelled composition comprises a solubilizing agent such as urea and a lower aliphatic alcohol which is a co-surfactant and optionally a water-soluble hydrotrope effective to promote compatibility of the ingredients in the microemulsion composition and which can replace a portion of the urea or alcohol. Generally, the viscosity and clarity control system is required in concentrated liquid cleaning compositions containing at least 30% by weight of active ingredients, namely the sum of paraffin sulfonate and alkyl ether sulfate.

Suitable hydrotropes are the organic sulfonated alkali metal salts (including sulfated salts) having an alkyl group of up to 6 carbon atoms. The preferred sulfonated hydrotropes are alkylarylsulfonates having up to 3 carbon atoms in the alkyl group, e.g. the sodium and potassium xylene, toluene, ethylbenzene and isopropylbenzene (cumene)sulfonates. Sulfonates prepared from xylene include ortho-xylenesulfonate, meta-xylenesulfonate, para-xylenesulfonate and ethylbenzenesulfonate. Commercial xylenesulfonates usually contain meta-xylenesulfonate as the major component. Analysis of typical commercial xylene sulfonate products shows 40 to 50% meta-xylene sulfonate, 10 to 35% ortho-xylene sulfonate and 15 to 30% para-xylene sulfonate with 0 to 20% ethylbenzene sulfonate. However, any suitable isomeric mixture can be used. Sodium cumene sulfonate and sodium xylene sulfonate are preferred alkylarylsulfonated hydrotropes for use in the compositions of the invention. It is also permissible to use suitable alkyl sulfate salts having 5 or 6 carbon atoms in the alkyl group, such as alkali metal n-amyl and n-hexyl sulfates.

The use of the viscosity and clarity control system imparts excellent low temperature clarity to the non-gelled liquid cleaning composition and provides control of the viscosity of the product over a wider range for each specific concentration of active ingredients, as described in more detail below. The alcohols preferably have 2 or 3 carbon atoms. Thus, ethyl alcohol, propyl alcohol, isopropyl alcohol or propylene glycol can be used, preferably ethyl alcohol is used.

The proportions of urea, alcohol and hydrotrope most suitable for any particular non-gelled composition will depend on the active ingredient components and proportions and can be determined by the formulator by conventional testing. The weight content of this viscosity and control system, based on the total composition, varies from 0 to 22% and preferably 0.5 to 10%. Within this range, the solubilization varies within the ranges of 0 to 8.0%, preferably 0.5 to 6% and the co-surfactant is 0 to 14%, preferably 0.15 to 10%. The ratio of alcohol to urea is kept below 1.3:1, preferably below 1:1 and is most preferably in the range of 0.37:1 to 0.85:1 when using an active ingredient content above 30% by weight, preferably 35 to 45%. Various amounts of hydrotrope such as xylene sulfonate can be added or partially replace the alcohol or urea to form a ternary system with special properties such as significantly increasing the viscosity. The amount should be chosen to maintain a satisfactory viscosity and cloud point and to maintain other desirable properties. In general, the Hydrotrope can make up to 15 wt.% of the total viscosity and control system.

The co-surfactant component plays an essential role in the concentrated and dilute gelled and non-gelled microemulsions of the present invention. In the absence of co-surfactant, the water, detergent(s) and water-insoluble organic compound, when mixed in appropriate proportions, form either a micellar solution at lower concentrations, a microemulsion or a conventional oil-in-water emulsion. In the presence of the co-surfactant in such systems, the interfacial tension or surface tension at the interfaces between the lipophilic droplets and the continuous aqueous phase is substantially reduced, to a value close to (10-6 N/m). This reduction in interfacial tension results in the spontaneous disintegration of the spheres or droplets of the dispersed phase until they become so small that they cannot be perceived by the unaided human eye and a clear microemulsion is formed which appears to be transparent. In such a microemulsion state, thermodynamic factors come into equilibrium, with varying degrees of stability associated with the total free energy of the microemulsion. Some of the thermodynamic factors involved in determining the total free energy of the system are (1) particle-particle potential, (2) interfacial tension or free energy (stretching and bending), (3) droplet dispersion entropy, and (4) chemical potential changes upon formation of the microemulsion. A thermodynamically stable system is achieved when interfacial tension or free energy is minimized and when droplet dispersion entropy is maximized. Thus, the role of the co-surfactant in the formation of a stable o/w microemulsion appears to be to reduce the interfacial tension and modify the microemulsion structure and increase the number of possible configurations. It also seems likely that the co-surfactant serves to reduce the rigidity of the dispersed phase with respect to the continuous phase and with respect to on the oily and greasy dirt that is removed from surfaces that are to be contacted with the microemulsions.

The amount of cosurfactant used to stabilize the gelled or non-gelled microemulsion compositions depends on such factors as the surface tension characteristics of the cosurfactant, the types and proportions of detergents and fragrances, and the types and proportions of any additional components present in the composition which have an impact on the thermodynamic factors previously enumerated. Generally, amounts of cosurfactant in a preferred range of 1 to 14%, more preferably 1 to 10%, and most preferably 1 to 8%, provide stable non-gelled dilute o/w emulsions for the above-described levels of major surfactants, water-insoluble organic compound, and any other additives as described below in the dilute microemulsions. Related ranges for concentrated microemulsions are obtained by multiplying the extremes of the given ranges by five.

Generally, amounts of cosurfactants in a preferred range of 5 to 20%, especially 6 to 18%, and most preferably 8 to 18% provide stable gelled o/w microemulsions for the above-described levels of main surfactants, water-insoluble organic compound, and any other additives as described below in the gelled microemulsions. The preferred cosurfactants of the present gelled compositions are at least water-soluble hydroxy compounds having at least one hydroxyl group and 2 to 12 hydroxyl groups, preferably 2 to 10, and most preferably 2 to 8 or 2 to 4. Particularly preferred cosurfactants are butyl carbitol, propylene glycol monobutyl ether, propylene glycol, isopropyl alcohol, propanol, and ethanol, and mixtures thereof.

The water-insoluble organic compound of the present non-gelled composition is d-limonene, which has an average dH (hydrogen bond solubility parameter) of 0 to 12 (Mpa)1/2, an average dP (polar soluble ity parameter) of 0 to 6 (Mpa)1/2 and an average dd (dispersion solubility parameter) of 14 to 19 (Mpa)1/2. Due to the presence of d-limonene, the non-gelled microemulsion composition of the invention exhibits maximum grease cleaning capacity for removing grease deposits on hard surfaces.

Similarly, due to the presence of d-limonene, the pseudo-microemulsion composition of the invention exhibits a maximum grease cleaning capacity for the removal of grease deposits on hard surface.

The concentration of water-insoluble organic compound in the non-gelled microemulsion is 1 to 20 wt.%, in particular 2 to 15 wt.%.

The concentration of water-insoluble organic compound in the gelled microemulsion is 1 to 20 wt.%, especially 4 to 20 wt.%, most preferably 5 to 10 wt.%.

The pH values of the final concentrated or diluted microemulsion depend largely on the identity of the cosurfactant compound, with the choice of cosurfactant also being influenced by cost and cosmetic properties, often specifically fragrance or perfume. For example, microemulsion compositions intended to have a pH in the range of 1 to 10 may use either an alkanol, a propylene glycol, an ethylene glycol or propylene glycol ether or ester as the sole cosurfactant, but the pH range may be restricted to 1 to 8.5 if a polyvalent metal salt is present.

In addition to their excellent capacity for cleaning greasy and oily dirt, the low pH o/w microemulsion formulations according to the invention also exhibit excellent other cleaning properties. They satisfactorily remove soap scum and lime scale from hard surfaces when applied in pure (undiluted) form and also when diluted. For such applications on originally hard, shiny surfaces with lime scale and/or soap scum, which may also be additionally soiled with oil and grease deposits, the microemulsions can be used. sions have a pH in the range of 0.5 to 6, preferably 1 to 4 and in particular 1.5 to 3.5. For general-purpose cleaning of oily and greasy surfaces without limescale or soap scum deposits, the pH can be in the range of 1 to 11, and sometimes 6 to 11 is preferred or 6 to 8 is particularly preferred (due to mildness and effectiveness).

The last essential component of the microemulsions of the invention is water. This water can be tap water, usually having less than 150 ppm hardness as CaCO3, but is preferably deionized water or water having a hardness of less than 50 ppm as CaCO3. The proportion of water in the gelled or non-gelled o/w microemulsion compositions is generally in the range of 15 to 85%.

The gel composition may comprise 0 to 30 wt.%, in particular 1 to 20 wt.% of at least one alkali metal detergent builder salt, wherein the detergent builder salt is selected from the group consisting of alkali metal polyphosphates, alkali metal pyrophosphates, alkali metal silicates, alkali metal carbonates, alkali metal bicarbonates and alkali metal gluconates and mixtures thereof.

The abrasive used in the gelled composition of the present invention may be inorganic or polymeric. The inorganic abrasives are selected from the group consisting of quartz, pumice, samicite, titanium dioxide, alumina, silica sand, feldspar, silicon carbide and the like and mixtures thereof. The inorganic abrasives may be used alone or in combination with polymeric abrasives. The inorganic abrasives having a Mohr hardness of less than 3, especially less than 2.75 are used in the composition at 0% to 30%, especially 1 to 15% by weight.

The polymeric abrasive may be any material derived from a polymerizable composition such as polyethylene, polypropylene, polystyrene, polyester, polyvinyl chloride, polyvinyl acetate, polymethyl methacrylate and various copolymers and interpolymers of the foregoing. The criterion for the suitability is that the material is polymethyl methacrylate and that the average particle size is in the range of 10 to 150 µm, and preferably 25 to 100 µm, and most preferably 30 to 75 µm, e.g. 60 µm. For optimum performance it is most desirable to use a polyvinyl chloride scouring powder whose average particle size is 60 µm, with a greater amount being in the range of 30 to 75 µm. The molecular weight ranges of the polymeric abrasives can vary widely as long as the above physical properties are met. Generally, molecular weights range from several thousand (e.g., 2000, 5000, 20000) to several hundred thousand (e.g., 125000, 250000, 400000) and up to several million (e.g., 1000000, 2000000, 4000000, 6000000). The amount of this abrasive may range from 2% to 30% or more (e.g., 40%, 50%). A preferred range in the preferred formulations is 5% to 25% and a particularly preferred range is 5% to 15%, such as 7%, 10% or 12%.

The concentrated and diluted, clear, liquid, o/w microemulsion general purpose cleaning compositions described herein are effective when used as such without further dilution with water, but it should be noted that some dilution without disturbing the microemulsion is possible and may often be preferred depending on the levels of surfactants, cosurfactants, water-insoluble organic compounds and other components present in the composition. For example, with preferred low levels of anionic components, dilutions of up to 50% occur without any phase separation (the microemulsion state is maintained) and much greater dilutions often work. Even when diluted to a large extent, such as 2- to 10-fold or more, the resulting compositions are often still effective for cleaning greasy, oily and other lipophilic soils.

It is within the scope of the invention to formulate various concentrated microemulsions that can be diluted with additional water prior to use.

The concentrated microemulsions, like other such emulsions mentioned above, can be diluted by mixing them with up to 20 times or more, sometimes even 100 times, but preferably 3 or 4 or 10 times their weight of water, e.g. 4 times, to form microemulsions similar to the diluted microemulsion compositions described above. Although the degree of dilution is suitably chosen to yield a microemulsion composition after dilution, it should be recognized that microemulsion stages may occur during and at the end of dilutions, particularly when diluting from concentrated emulsions.

Optionally, the o/w microemulsion compositions may include minor amounts, e.g., 0.1 to 5.0%, preferably 0.25 to 4.0%, based on a diluted product, of C8-22 fatty acid or fatty acid soap as a suds suppressor. The addition of free higher fatty acid or fatty acid soap provides an improvement in the rinsability of the composition whether the microemulsion is applied in neat or diluted form. However, it is generally desirable to increase the co-surfactant content to between 1.1 and 1.5 times its otherwise normal concentration in order to maintain product stability when the free fatty acid or soap is present.

Examples of fatty acids that can be used as such or in the form of soaps include distilled coconut oil fatty acids, "mixed vegetable" type fatty acids (e.g., those with higher percentages of saturated, mono- and/or polyunsaturated C18 chains), oleic acid, stearic acid, palmitic acid, eicosanoic acid, and the like. Generally, such fatty acids with 8 to 22 carbon atoms will function.

The gelled or non-gelled microemulsion composition may optionally contain 0 to 5.0% by weight of an alkylolamide as a foaming agent. Its presence results in a Product which, in use, exhibits high foaming power, particularly in terms of the persistence of foam generated during dishwashing or laundry operations. It should not be used in an amount sufficient to impair the desired physical properties. The acyl moiety of the alkylolamide is selected from the class of fatty acids having 8 to 18 carbon atoms and each alkylol group usually has up to 3 carbon atoms. It is preferred to use the monoethanolamides of lauric and myristic acid, but diethanolamides and isopropanolamides as well as monoethanolamides of fatty acids having 10 to 14 carbon atoms in the acyl moiety are satisfactory. Examples are capric, lauric, myristic and "heart cut" coconut (C₁₂ to C₁₄) monoethanolamides, diethanolamides and isopropanolamides and mixtures thereof. Also the alkylolamides substituted with additional ethyleneoxy groups can be used, suitable examples can be the above amides condensed with 1 to 4 moles of ethylene oxide.

The protein optionally used in the gelled or non-gelled microemulsion compositions of the invention is a water-soluble, partially degraded protein and may be a partially enzymatically hydrolysed protein or a heat-derived protein product. This material may be used as an agent to overcome the skin irritating effect of surfactants. When the partially degraded protein is applied together with or after contact with the surfactants, it has also been found that a prophylactic effect is present. The partially degraded protein is characterized by a gel strength of 0 to 200 Bloom grams. The partially degraded protein may also provide rinsing and draining properties to the composition. Such hydrolysis occurs, for example, by the action of trypsin or pancreatic enzymes on protein material. The partially degraded protein may also be a heat-derived protein degradation product. Partially heat-degraded proteins having the required Bloom strength for use in the compositions can be prepared by heating proteinaceous materials such as pork or beef bones, hooves or hide which have been reduced to small pieces and immersed in water by autoclaving. A preferred hydrolyzed protein is a partially enzymatically hydrolyzed protein derived from bovine collagen. Typical proteins which may be partially hydrolyzed for use in the compositions include casein, gelatin, collagen, albumin, zein, keratin, fibroin, globulin and glutenin. Typical commercially available partially enzymatically hydrolyzed proteins include bacto-proteose, proteose-peptone, casein-peptone, gelatin-peptone, bacto-peptone, vegetable peptones such as soybean peptones, the solubilized collagen being derived from heating pork or beef bones, hooves or hide. The preferred proteins are solubilized bovine collagen and solubilized porcine collagen. The partially hydrolyzed protein may have a relatively wide range of molecular weights ranging from 500 to 70,000, preferably 500 to 10,000 for hand conditioning effects and 25,000 to 70,000 for good drainage properties. The lower molecular weight proteins may contain some fully degraded polypeptides, such as dipeptides and tripeptides, and even some amino acids, as a result of the degradation process. The protein, when used, is generally used in amounts ranging from 0.1 to 2.0% by weight, preferably 0.3 to 0.8% by weight.

The liquid gelled or non-gelled microemulsion cleaning compositions of the present invention may also contain any of the additives used in other liquid cleaning compositions such as sequestering agents, e.g. salts of ethylenediaminetetraacetic acid such as the sodium and potassium salts, and salts of hydroxyethylethylenediaminetriacetate. If it is desired to colour or dye the liquid cleaning composition, any suitable dye may be used for this purpose. Perfume may also be added to the compositions to impart a pleasant fragrance.

In the final diluted form, the non-gelled general purpose fluids are clear microemulsions and exhibit satisfactory stability at reduced and elevated temperatures. When the concentrated gel microemulsion is diluted, the general purpose fluids are clear pseudo-microemulsions and exhibit satisfactory stability at reduced and elevated temperatures. Specifically, such compositions remain clear and stable in the range of 5ºC to 50ºC, particularly 10ºC to 43ºC. They exhibit a pH in the acidic, neutral or alkaline range, e.g. 1 to 11, depending on the intended end use, with acidic and neutral pHs, e.g. 2 to 7 or 2 to 8, being preferred and acidic pHs, e.g. 1 to 4 or 2 to 3.5, being considered best for limescale and soap scum removal applications. The liquids are easily pourable and exhibit a viscosity in the range of 5 x 10⁻³ Pa s to 0.15 Pa s or 0.2 Pa s [5 or 150 or 200 centipoise], preferably 6 x 10⁻³ Pa s to 6 x 10⁻² Pa s [6 to 60 centipoises (cps)], and especially 1 x 10⁻² Pa s to 4 x 10⁻² Pa s [10 to 40 cps], measured at 25ºC with a Brookfield RVT Viscometer® using a No. 1 spindle rotating at 20 rpm. Typically, the viscosity of the product in the absence of thickener is not greater than 0.1 Pa·s (100 cps), even for the lower microemulsions.

The liquid non-gelled microemulsion compositions are preferably packaged in hand-operated spray dispensing containers made of synthetic organic polymeric plastic, e.g., PVC, polyethylene or polypropylene, which may include nylon closure, valve and nozzle parts, but they may also be pressure packed into aerosol containers. Such products, including the dispensers provided, are particularly suitable for so-called spray-and-wipe applications, but in the present operations, wiping may be omitted and replaced by relatively little rinsing.

The liquid gelled compositions are preferably packaged in containers made of synthetic organic polymeric plastic, e.g. PVC, polyethylene or polypropylene.

Because the compositions as prepared are aqueous liquid formulations, often no special mixing procedure needs to be followed to bring about the formation of the desired microemulsions. The compositions are readily prepared, often simply by combining the entire components thereof in a suitable vessel or container. The order of mixing the ingredients in such cases is not particularly important and generally the various materials may be added sequentially or all at once or in the form of aqueous solutions, or each or all of the main detergents and co-surfactants may be prepared separately and combined together followed by the water-insoluble organic compound. However, to avoid any problems with the microemulsion breaking or not forming properly, a solution of the synthetic detergent(s) in water can be prepared, the co-surfactant dissolved therein and then the water-insoluble organic compound mixed in, whereby the concentrated or diluted microemulsion spontaneously forms, the operations being carried out at a temperature in the range of 5ºC to 50ºC, preferably 10ºC to 43ºC and especially 20ºC to 30ºC. If fatty acid is to be used for its antifoaming effect, it is preferably melted and added to the surfactant-co-surfactant solution followed by the water-insoluble organic compound. Diluted microemulsions can be prepared from the concentrated microemulsion by diluting at least 50% of it with water, with both the microemulsion and the water being in the described temperature range. The resulting products have droplet sizes of the dispersed lipophilic phase in the range of 50 to 500 Å, preferably 100 to 500 Å, with the smaller particle sizes providing better absorption of oily soil from soiled substrates to be cleaned.

Detailed description of the preferred embodiment

The following examples illustrate liquid cleaning compositions according to the invention. Unless otherwise indicated, all percentages and parts given in these examples in the specification and appended claims are by weight and all temperatures are in degrees Celsius. The exemplified compositions illustrate the invention. It should be noted that among the exemplified compositions, only those comprising d-limonene and the essential mixture of anionic sulfonate surfactant with anionic sulfate surfactant illustrate the invention.

example 1

The following examples were prepared at room temperature by dissolving the anionic and/or non-ionic surfactants in the water, subsequently dissolving the urea and then the alcohol solvents, followed by mixing the d-limonene, Isopar® H, Exxate® 1000, Exxate® 1300, isooctanol, decane and/or C₁₃ acetate into the water solution to form a stable homogeneous o/w microemulsion. The formulations were tested for appearance, olive oil uptake, mini-plate and foam volume in milliliters at the start and end. The examples and test results are as follows:

* Compositions according to the invention are marked with I, comparative examples with C

* Compositions according to the invention are marked with I, comparative examples with C

The testing procedures are as follows:

Foam long-lasting adhesion - mini-plate test A) Foam durability - mini plate test principle

The test is designed to evaluate the foam stability of an LDLD solution in the presence of greasy soil.

dirt

Vegetable margarine: (Crisco (own product))

This fat is injected into the LDLD solution using a syringe at a flow rate of 0.6 g/minute.

Product concentration

10 ml of 5% LDLD solution is added to 400 ml of water (+1.25 g/l LDLD).

Test procedure

Foam is generated with a brush for 1 minute (according to a hypocycloidal pattern). The brush continues to move to assist in fat emulsification. Fatty dirt is then injected into the solution at a constant flow rate until the foam disappears. Foam generation and disappearance are evaluated by a photoelectric cell and automatically recorded.

Results

Mini plate number: MP = (GC X GF X ΔT)/0.12

GC = fat coefficient

GF = fat flow equal to (total injected fat weight)(T2-T0)

ΔT = time measured from the start of fat injection (T0) to the end of foam detection (T1)

0.12 = correlation coefficient to link the calculated mini-plate number with the number of plates washed by hand under similar conditions

T2 = End of test, fat injection is stopped

Extrapolation

Actual plate count can easily be extrapolated from mini plate count by assuming that each large plate is contaminated with 3 g of fat.

(Number of mini plates) · (Product weight) · 0.8

B) Foam test - foam volume principle

Foam is generated by rotating a graduated cylinder containing a detergent solution. This process allows defining the speed of foam generation and the maximum foam height generated in the presence of fat.

dirt

Corn oil

Product concentration

0.75 g/l cleaning solution

method

2 different products (including a reference sample) were evaluated simultaneously. 100 ml of a solution of 0.75 g/l cleaner at 47ºC was poured into a graduated cylinder. 1 g of corn oil was added to the solution. The graduated cylinders were mounted on the rotation device and allowed to make 5 complete revolutions. The foam height was read from the cylinder graduation. The 5 complete revolutions were repeated 10 times (foam height was recorded after every 5 complete revolutions).

Results

Initial foam volume (ml), final foam volume (ml)

(D) Olive oil intake principle

Oil absorption from dishwashing liquid

dirt

olive oil

Product concentration

Product as such

method

In 50 ml of pure (undiluted) product, the addition of drops of olive oil was started. After each drop was added, the solution was allowed to clear again by mixing with a magnetic stirrer. If after 5 minutes the solution was not clear, the addition of olive oil was stopped and the amount of olive oil added was recorded.

Results

g of olive oil to saturate 100 ml of product.

Example 2

The following compositions were prepared at room temperature by dissolving the anionic surfactants in water, followed by Dissolving the co-surfactant followed by mixing the water insoluble organic compound into the water solution to form a stable gelled homogeneous o/w emulsion. The formulations were tested for appearance and mini-plate. The examples and test results are as follows:

The test procedures are identical to those of Example 1.

Claims (19)

1. A microemulsion composition comprising, by weight: a) 6-50% of a mixture of two different anionic surfactants, one of these anionic surfactants being a sulfonate and the other of these anionic surfactants being a sulfate, the ratio of the sulfonate to the sulfate being 10:1 to 1:10, b) 0 to 6% non-ionic surfactant, c) 1 to 20% d-limonene, d) 0 to 8% solubilizing agent, e) 1 to 14% of at least one water-soluble hydroxy-containing organic compound and f) the balance being water, the composition having a pH of 1 to 11 and being optically clear with at least 90% light transmission, the interfacial tension between the lipophilic droplets of the composition and the aqueous phase being less than 10⁻⁵ N/m. 2. The composition of claim 1 wherein the sulfonate is a paraffin sulfonate and the sulfate is an alkyl ether sulfate wherein the ratio of the sulfonate to the sulfate is 4:1 to 2:1. 3. A composition according to claim 2, wherein the water-soluble hydroxyorganic compound contains 2 to 4 carbon atoms. 4. A composition according to claim 3, wherein the water-soluble hydroxyorganic compound is selected from the group consisting essentially of ethanol, propanol, isopropanol and propylene glycol and mixtures thereof. 5. A composition according to claim 2, wherein the solubilizing agent is urea. 6. The composition of claim 1, further comprising a partially degraded protein. 7. The composition of claim 5 further comprising a hydrotrope which is an aryl sulfonate. 8. A composition according to claim 1, wherein the concentration of the nonionic surfactant is 0.1 to 6.0 wt.%. 9. The composition of claim 1 further comprising an alkylol amide. 10. The composition of claim 1, further comprising a sequestering agent. 11. A gelled microemulsion composition comprising, by weight: a) 13 to 50% of a mixture of two different anionic surfactants, one of the anionic surfactants being a sulfonate and the other of the anionic surfactants being a sulfate, the ratio of the sulfonate to the sulfate being 10:1 to 1:10, b) 1 to 20% d-limonene, c) 5 to 20% of at least one water-soluble, hydroxy-containing organic compound and d) the balance being water, the composition having a pH of 1 to 11 and a complex viscosity at 1 rad s⁻¹ of 1 to 10³ Pascal seconds, the interfacial tension between the lipophilic droplets of the composition and the aqueous phase being less than 10⁻⁵ N/m. 12. The composition of claim 1 wherein the sulfonate is a paraffin sulfonate and the sulfate is an alkyl ether sulfate wherein the ratio of the paraffin sulfonate to the alkyl ether sulfate is 4:1 to 2:1. 13. A composition according to claim 12, wherein the water-soluble hydroxyorganic compound has 2 to 12 carbon atoms. 14. The composition of claim 13, wherein the water-soluble hydroxyorganic compound is selected from the group consisting of butyl carbitol, propylene glycol, ethanol and isopropanol, and mixtures thereof. 15. The composition of claim 11, further comprising a partially degraded protein. 16. The composition of claim 11 further comprising an alkylolamide or the ethoxylated species. 17. The composition of claim 11, further comprising a sequestering agent. 18. The composition of claim 11 further comprising an abrasive. 19. The composition of claim 11 further comprising at least one alkali metal detergent builder salt.