MXPA98002355A - High water content, low viscosity, oil continuous microemulsions and emulsions, and their use in cleaning applications - Google Patents

Abstract

Superior high water-containing, oil continuous microemulsions and emulsions, useful for cleaning, contain defined amounts of water, one or more anionic surfactants from a group of selected molecular weight carboxylic acid salts, and one or more organic solvents so that the compositions have low conductivity and low viscosity.

Description

MICROEMULSIONS AND CONTINUOUS EMULSIONS IN OIL, OF LOW VISCOSITY, WITH HIGH CONTENT OF WATER AND ITS USE IN APPLICATIONS OF CLEANING. BACKGROUND OF THE INVENTION This invention relates to microemulsions and emulsions, and their use in various applications. The microemulsions are well known. The normal components of microemulsions include water, an organic solvent and surfactants. Microemulsions are often used as cleaning formulations. For example, the Patent of E.U.A. No. 4,909,962 discloses a transparent, single-phase composition, prior to spotting provided in the form of a microemulsion, solution or gel, this composition characterized by being infinitely di iu b le in water without separating from the phase. The Patent of E.U.A. 5,462,692 describes continuous microemulsions of water containing a perfume as its water-insoluble hydrocarbon component first. The patent employs, among other components, bait oil fatty acids, in formulations useful as hard surface cleaners. The Patent of E.U.A. 5,597,792 describes emulsions and microemulsions with high water content (water-in-oil) continuous oily useful for cleaning purposes, containing ionic surfactants soluble in the phase of organic solvents, said surfactant having an average molecular weight that would give 350 to 700, preferably greater than 400 and less than 600, exclusive of counterions. One of the different categories of surfactants described in summary and not amplified is the salt of fatty acids. Other references describe compositions useful in cleaning applications. The systems described as being continuous oil, the systems have low water contents. While continuous water systems are predominantly described, some of the examples in the U.A. 4,909,962 exemplifies continuous oil (water in oil) systems with low water content. It is desired to find new compositions for these purposes which will have high water contents and continuous in oil. Said continuous microemulsions in oil are especially suitable to function as cleaning compositions in order to remove oil or grease. SUMMARY OF THE INVENTION This invention, in one aspect, is a continuous single-phase oil microemulsion useful as a liquid cleaning composition, comprising: A. Water in an amount of not less than about 40 weight percent and not more than about 75 weight percent based on the total weight of the microemulsion; B. An organic solvent or a mixture of two organic solvents, wherein the organic solvent or mixture of organic solvents are characterized as containing no more than about 2 weight percent water at 25 ° C when the organic solvent is with water in the absence of surfactants or other additives and wherein the organic solvent or mixture of two or more organic solvents is in an amount of not less than about 10 percent and not more than about 60 percent by weight based on the total weight of the microemulsion . C. One or more anionic surfactants which are at least partially soluble in one or more of the organic solvents, wherein at least one of said surfactants is an olefinic or saturated fatty acid salt, having an average molecular weight in the range of 225 to 365 exclusive of the group of counterions, and wherein one or more anionic surfactants are present in a total amount greater than about 0.1 percent and not more than about 10 weight percent based on the total weight of the microemulsion. Preferably the microemulsion is characterized by being a microemulsion continuous in oil and having an electrical conductivity less than Z microSiemens / centimeter when measured at temperatures of use and at a viscosity of less than 40 centistokes as measured at temperatures of use, where Z is represented by the following formula: Z = (1/3) (? w) 2 ?? Aim, where? W represents the volume fraction of water in the microemulsion, i represents a given electrolyte, A | represents the electrolyte conductivity, i and m, represents the molarity of electrolyte in the aqueous phase. In another aspect, this invention is an emulsion, which, when at rest at 25 ° C, forms at least two phases wherein one phase is a continuous microemulsion in oil, comprising: A. Water in an amount of not less than about 60 weight percent and not more than about 95 weight percent based on the total weight of the emulsion; B. An organic solvent or a mixture of two or more organic solvents, wherein the organic solvent or mixture of organic solvents are characterized as containing no more than about 2 weight percent water at 25 ° C when the organic solvent is saturated with water in the absence of surfactants or other additives and wherein the organic solvent or mixture of two or more organic solvents is present in an amount of not less than about 4 percent and not more than about 40 percent by weight based on the total weight of the emulsion; C. One or more anionic surfactants which are at least partially soluble in one or more of the organic solvents, wherein at least one of said surfactants is an olefinic salt or saturated fatty acid salt, which has a weight average molecular scale from 225 to 365 exclusive of the counterion group, and wherein one or more anionic surfactants are present in a total amount greater than 0.1 percent and less than about 5 percent by weight based on the total weight of the emulsion. Preferably the emulsion is characterized as a continuous emulsion in oil where the emulsion has an electrical conductivity less than Z microSiemens / centimeter ("μS / Cm") when measured at temperatures of use and at a viscosity of less than 40 centistokes ("cSt ") as measured at temperatures of use, where Z is represented by the following formula: Z = (1/3) (fw) 2 ?? Airrii where? W represents the volume fraction of water in the microemulsion, i represents a given electrolyte, A represents the electrolyte conductivity, i and mt represents the molarity of electrolyte and in the aqueous phase. In yet another aspect, this invention is a microemulsion, or a bicontinuous or continuous microemulsion in water, meeting the criteria mentioned above except the Z value which can be disturbed in the compositions of the invention described above, through the addition of salt or a saturated hydrocarbon of molecular weight less than about 87, and comprising: A. An organic solvent or a mixture of two or more organic solvents, wherein the organic solvent or a mixture of organic solvents are characterized as containing no more than 2 percent by weight of water at 25 ° C when the organic solvent is saturated with water in the absence of surfactants or other additives; and B. U n or more anionic surfactants which are at least partially soluble in one or more organic solvents, wherein at least one of said surfactants is an olefinic salt or saturated fatty acid, which has an average molecular weight in the scale from 225 to 365 exclusive of the counter-ion stream, and wherein one or more anionic surfactants are present in a total amount not less than 0.1 percent and no greater than about 10 percent by weight based on the total weight of the microemulsion. In yet another aspect, this invention is a method for cleaning metal having grease or oil stains on a metal surface comprising applying the microemulsion or emulsion described above to the metal which has grease or oil stains on the metal surface to remove at least a portion of the grease or oil stains from the metal. The microemulsions and emulsions of this invention find utility as liquid cleaning compositions for use in metal cleaning, hard surface cleaning, deflection of circuit boards, automotive cleaning, cold cleaning, dry cleaning, paint separation and cleaning. fabrics In addition, microemulsions and emulsions are particularly effective in removing oily and fatty substances. In housekeeping and personal care, the compositions of this invention can be used as pretreators of clothes, laundry detergents, coatings, skin cleansers, hair cleansers and conditioning formulations and in aerosol, pumping, spray or liquid pesticide formulations. The compositions can also be used in industrial coatings and sealant applications such as adhesives, inks, polishes, latexes and as process solvents. The compositions of this invention can be used to remove stains and desalinate water as well as in applications to improve oil recovery and in the supply of acids and other additives to oil wells. The compositions of this invention can be used in pharmaceutical applications such as in vaccine adjuvants, topical drug delivery vehicles and in self-heating compositions. The compositions of this invention can be used as a means for producing nanoparticles in ceramic applications as well as in applications for manufacturing catalysts such as zeolites and semiconductors. The compositions of this invention can be used in fuels to solubilize alternative combustible materials such as alcohols. The compositions of this invention can be used to stabilize enzymes, facilitate heterophase reactions and increase the surface area in applications of reaction media. The compositions of this invention can be used to produce latex and water soluble polymers by polymerization, by microemulsion as well as to produce heterophase polymers such as self-reinforcing plastic and to form polymer dispersions. It may also be possible to employ these formulations to dissolve agricultural and similar pesticides using the resulting composition to be applied to crops. In addition, the microemulsions and emulsions of this invention can be used to clean applications for the purpose of supplying bleaching agent and enzyme in a formulation so that the bleaching agent depletes the enzyme in a limited manner. The compositions of this invention can also be employed as fluids for metal working including cutting fluids, forming fluids, cooling fluids and protective fluids and as hydraulic force transmitting fluids. A unique aspect of this invention is the advantage of forming compositions containing high water content that have low viscosity and are continuous in oil, using salts of unsaturated and saturated fatty acids present in nature and renewable, in low concentrations to give products They have increased environmental compatibility and electrolyte tolerance over similar water-in-oil ("a / ac") mroemulsions employing sulphonated surfactants. Microemulsions As described above, the microemulsions of this invention contain as essential components, water, an organic solvent and one or more anionic surfactants. Said microemulsions and emulsions are characterized by being continuous in oil and having a high water content. Microemulsions are generally considered to be thermodynamic equilibrium compositions having particle sizes suspended in the range of 50 to 1000 angstroms. As used herein "electrolyte" means any solvated salt in the microemulsions or emulsion including ionic surface active agent or added salts such as magnesium sulfate, sodium carbonate and sodium chloride. As used herein, "continuous in oil" means compositions, either microemulsions or emulsions, which have an electrical conductivity below Z micro Siemens / centimeter where Z is represented by the following formula: Z = (1/3 ) (fw) 2 ?? A? M (where? W represents the volume fraction of water in the microemulsion, i represents a given electrolyte, Ai represents the electrolyte conductivity, i and mi represents the molarity of electrolyte and in the aqueous phase., a composition of 0.02 molar in an electrolyte that has a molar conductivity of 120,000 (microSiemens x liter / centimeter x mole) and a water volume fraction of 50 percent has a Z value of 200 and is therefore a microemulsion Continue in oil below 200 microSiemens / centimeter (Z). Preferably, the compositions of this invention have an electrical conductivity of below 0.5 Z, more preferably below 0.25 Z and even more preferably below 0.1 Z. In contrast bicontinuous compositions are above Z and below 2Z. and the continuous compositions in water are above 2Z. In continuous single-phase oil microemulsions, water is present in an amount of not less than about 40 weight percent and no greater than about 75 weight percent based on the total weight of the microemulsion. Preferably, the microemulsion contains not less than about 45 weight percent water. Preferably, the microemulsions contain no more than about 70 weight percent water, more preferably no more than about 65 weight percent and even more preferably no more than about 60 weight percent. In the continuous microemulsions in single-phase oil, an organic solvent or a mixture of two or more organic solvents is used, wherein the organic solvent or mixture of organic solvents are characterized by containing no more than 2 weight percent water. at 25 ° C when the organic solvent is saturated with water in the absence of surfactants or other additives. Preferably, the organic solvent or mixture of organic solvents contains no more than 1 weight percent water at 25 ° C when saturated, more preferably no more than 0.5 weight percent water. The absorption of water from an organic solvent can be easily determined by water filtration, for example, where water is added to one or more organic solvents until the solution is observed to be nebulized or an excess water phase develops. The organic solvent or mixture of two or more organic solvents are present in an amount of not less than about 10 percent and not more than about 60 percent by weight based on the total weight of the microemulsion. Preferably, the organic solvent or mixture of two or more organic solvents are present in an amount of not less than about 15 weight percent, more preferably not less than about 20 weight percent, still more preferably not less than about 25 weight percent. hundred in weight; and preferably not greater than 50 percent by weight. The classes of organic solvents that can be used in the practice of this invention include aliphatic alcohols, aliphatic esters, aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, aromatic hydrocarbons, aliphatic diesters, aliphatic ketones and aliphatic ethers. In addition, a solvent may contain two or more of these functional groups or may contain combinations of these functional groups. For example, alkylene glycol diethers, alkylene glycol monoethers, and alkylene glycol ether acetates may be employed as solvents in the practice of this invention. As used herein, the alkylene glycol ethers include dialkylene glycol ethers. Alkylene glycol monoethers and alkylene glycol diethers are particularly useful for decreasing the viscosity of a microemulsion. Preferred classes of organic solvents are aliphatic hydrocarbons, aromatic hydrocarbons, alkylene glycol monoethers, alkylene glycol diethers, and alkylene glycol ether acetates. The most preferred classes of organic solvents are aliphatic hydrocarbons, alkylene glycol monoethers and alkylene glycol diethers. The aliphatic alcohols can be primary, secondary or tertiary. Preferred aliphatic alcohols have from 4 to 24 carbon atoms. Representative examples of more preferred aliphatic alcohols include 1-hexanol, isopentyl alcohol, octane! , 2-ethyl-hexanol, nonanol, dodecanol, undecanol and decanol. Preferred aliphatic esters have from 4 to 24 carbon atoms. Representative examples of more aliphatic esters include methyl laurate, methyl oleate, hexyl acetates, pentyl acetates, octyl acetates, nonyl acetates and decyl acetates. The aliphatic hydrocarbons can be linear, branched cyclic or combinations thereof. Preferred aliphatic hydrocarbons contain from 3 to 24 carbon atoms, preferably from 6 to 24 carbon atoms. Representative examples of more preferred aliphatic hydrocarbons include alkanes such as propane, butane, pentane, hexane, heptane, octane, decano, dodecane, hexadecane, mineral oils, paraffinic oils, decahydronaphthalene, bicyclohexane, cyclohexane, and olefins such as 1 -decene, octadecene and hexadecene liquids. Examples of aliphatic hydrocarbons commercially available with Norpar ™ 12, 12 and 15 (standard paraffin solvents available from Exxon Corporation), petroleum distillate Naphtha SC 140 (also from Exxon Corporation), Isopar ™ G, H, K, L, M and V (isoparaffin solvents available from Exxon Corporation), and Shellsol ™ solvents (Shell Chemical Company). Preferred chlorinated aliphatic hydrocarbons contain from 1 to 12 carbon atoms, more preferably they contain from 2 to 6 carbon atoms. Representative examples of more more preferred chlorinated aliphatic hydrocarbons include methylene chloride, carbon tetrachloride, chloroform 1,1,1-trichloroethane, perchlorethylene and trichlorethylene. Preferred aromatic hydrocarbons contain from 6 to 24 carbon atoms. Representative examples of more preferred aromatic hydrocarbons include toluene, naphthalene, biphenyl, ethylbenzene, xylene, alkyl benzenes such as dodecyl benzene, octyl benzene and nonylbenzene. Preferred aliphatic diesters contain from 6 to 24 carbon atoms. Representative examples of more preferred aliphatic diesters include dimethyl adipate, dimethyl succinate, dimethyl glutarate, diisobutyl adipate, and diisobutyl maleate. Preferred aliphatic ketones have from 4 to 24 carbon atoms. Representative examples of more preferred aliphatic ketones include methyl ethyl ketone, dimethyl ketone, diisobutyl ketone, methyl isobutyl ketone, and methyl hexyl ketone. Preferred aliphatic ethers have from 4 to 24 carbon atoms. Representative examples of the most preferred isathether ethers include diethyl ether, ethyl propyl ether, hexyl ether, butyl ether, and methyl t-butyl ether. Preferred alkylene glycol monoethers, dialkylene glycol monoethers, alkylene glycol diethers, and alkylene glycol ether acetates include propylene glycol diethers having from 5 to 25 carbon atoms, glycol ether acetates from propylene having from 6 to 25 carbon atoms, propylene glycol monoethers having from 7 to 25 carbon atoms, glycol ether acetates having from 6 to 25 carbon atoms, ethylene glycol diethers or having 6 to 25 carbon atoms; to 25 carbon atoms and ethylene glycol monoethers having from 8 to 25 carbon atoms. Representative examples of more preferred solvents within this broad class include propylene glycol dimethyl ether, propylene glycol benzyl methyl ether, propylene glycol butyl methyl ether, propylene glycol dibutyl ether, dipropylene glycol demethyl ether, ether dipropylene butyl methyl, dipropylene glycol dibutyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol butyl ether acetate; propylene glycol monobutyl ether, propylene glycol monohexyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether; ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, ethylene glycol butyl ether acetate; ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol hexyl ether, ethylene glycol octyl ether, ethylene glycol phenyl ether, diethylene glycol hexyl ether and diethylene glycol octyl ether. The most preferred alkylene glycol monoethers are propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, propylene glycol monopropyl ether and dipropylene glycol monopropyl ether. In preferred embodiments of the present invention, the alkylene glycol monoethers are employed mixed with one or more organic solvents. The addition of alkylene glycol monoethers facilitates the preparation of microemulsions and low viscosity emulsions. The alkylene glycol monoether is present in an amount of not less than 5 percent by weight based on the total weight of the microemulsion, preferably not less than about 10 weight percent, more preferably not less than about 15 weight percent; not more than about 50 weight percent, preferably not more than about 40 weight percent and more preferably not more than about 25 weight percent. In general, the ratio of glycol ether to total surfactants should be greater than 2 to 1 by weight, both in microemulsions and emulsions. The alkylene glycol monoether is present in the emulsions containing about 70-80 weight percent water in an amount of not less than 5 weight percent based on the total weight of the emulsion, and not greater than about 15 weight percent. hundred. In continuous single-phase oil microemulsions, one or more anionic surfactants of specified chemical structure are employed which are at least partially soluble in one or more organic solvents. One or more anionic surfactants are preferably also characterized as having greater solubility in one or more organic solvents than in water and preferentially being divided in the organic solvent in a mixture of water and organic solvent. Preferably, one or more anionic surfactants are no more than sparingly soluble in water. Here the term solubility does not include dispersibility or emulsification. One or more surfactants have a molecular weight greater than 225 and less than 365. If one more anionic surfactants are employed, the "molecular weight" as used above is calculated based on the average molecular weights of two or more anionic surfactants. Frequently the fatty acids present in nature used to prepare the anionic surfactants are commercially available as mixtures of various molecular weight components, in various degrees of unsaturation and carbon content. A preferred class of anionic surfactants are anionic surfactants of the formula (R 1 -COO) and (formula I) wherein R 1 represents an olefinically unsaturated or saturated alkyl, and is 1 2 2, wherein M represents a cationic counterion and The total number of carbons in R 1 is 13 to 23. Preferably R 1 is internally unsaturated in the alkyl group and is not alpha, beta-unsaturated, nor is the conjugate of olefinic unsaturation with the carboxyl group. The molecular weight of an anionic surfactant of formula (I) is calculated exclusive of the weight of M; that is, the molecular weight is calculated for R1-COO only. Anionic surfactants containing M as a counterion can be easily prepared from their acid precursors wherein M is hydrogen, such as by reacting the carboxylic acid with metal hydroxide including ammonium hydroxides., lithium, sodium, potassium, magnesium, calcium, etc. The selection of a particular M counter ion is not critical as long as the resulting surfactant remains at least partially soluble in the organic solvent preferably not more sparingly soluble in water and provides surfactants anionics that are capable of producing the microemulsions and emulsions of this invention. Preferably, M is monovalent, and more preferably selected from sodium, potassium and "onium" cations (e.g., quaternary nitrogen such as in ammonium, etc.). preferably, the anionic surfactants have an average molecular weight of at least 250, more preferably at least 280 and even more preferably at least about 295. Preferably, the anionic surfactants have a molecular weight not greater than 340 and more preferably not greater than 340, and even more preferably not greater than 337, exclusive of counterion M. Examples of specific anionic surfactants useful in the invention are salts of the following olefinic and saturated aliphatic and alicyclic carboxylic acids: Olefinic fatty acids: acid myristoleic (cis-tetradec-9-enoic); palmitoleic acid (cis-9-hexadecenoic); linoleic acid (9, 12, 15-octadecatrienoic); linoleic acid (9, 12, or 13-octadecadienoic); oleic acid (cis-9-octadecanoic); arachidonic acid (5,8,11,14-eicosatetraenoic acid); erucic acid (cis-13-docosenoic acid); and unsaturated alicyclic acid of 5 carbons; Hydrocarpal acid (C? 6H28O2); caulmo-ogric acid (C? 8H32O2); and gorlic acid (C? ßH30O2); and Saturated fatty acids: myristic acid (tetradecanoic -C? 4H28O2); palmitic acid (hexadecanoic C? ßH32O2); stearic acid (octadecanoic - C22H44? 2); eicosanoic acid (arachidic C20H40O2); and docosanoic acid (behenic - C22H44O2). An advantage of using preferred anionic surfactants is that relatively small amounts of the preferred anionic surfactants are necessary to provide the continuous high emulsion microemulsions and oil emulsions of this invention. Consequently, the amount of residual anionic surfactant left on a surface cleaned with the microemulsions and emulsions is minimal and marking problems are also minimal and so on. An additional advantage is that because acids are derived mostly from natural products, it is considered by some to be more "environmentally friendly" than normal synthetic anionic surfactants. Preferably, the preferred anionic surfactants are present in the microemulsions in an amount of not less than about 0.5 weight percent and more preferably not less than about 1 weight percent. Preferably, the preferred anionic surfactants are present in the microemulsions in an amount of not more than about 6 percent and more preferably in an amount of not more than about 5 percent by weight. While a carboxylic acid (in addition to its salt) can be included in the formulation the acid does not act as a surface active agent but as organic solvents of aliphatic alcohols mentioned above. However, the acids act less effectively on a weight basis than said alcohol due to the generally higher molecular weight of acids. In continuous microemulsions in single-phase oils, the specific carboxylic acid salt surfactants described above may be supplemented with other commonly available anionic sulphonate surfactants of the commonly available alkylbenzene / toluene / sulfonated naphthalene type. For example, those represented by the formula RxB-SO3M wherein R represents alkyl, x is 1 or 2, B is a biradical when x is 1 or is a triradical when x is 2 and which is derived from an aromatic portion and wherein M represents the same cationic counterion mentioned previously and wherein the number of carbons in Rx is from 18 to 30. The molecular weight of a surfactant of the formula RxB-SO3M is calculated exclusive of the molecular weight of the counterion M; that is, the molecular weight is calculated for RxB-SO3 only. Said adjunct sulfonate agents containing M as a counterion can be easily prepared from their precursor sulfonic acid by reacting it with a metal hydroxide including ammonium hydroxide, lithium, sodium, potassium, magnesium, calcium. The selection of a particular counter ion M is not critical as long as the resulting surfactant remains at least partially soluble in the organic solvent and, preferably, not more than sparingly soluble in water and probes capable of aiding the anionic surfactants derived from carboxylic acid specific for producing the microemulsions and emulsions of this invention. Preferably, M is monovalent. Preferably, B is derived from benzene, toluene or naphthalene. Preferably, the attached sulphonate surfactants have a molecular weight greater than 400. Preferably these adjunct surfactants have a molecular weight of less than 600 and more preferably less than 550. In continuous microemulsions in single-phase oil, one or more nonionic surfactants may also be employed to supplement or increase the effectiveness of the apionic surfactant (s). One or more nonionic surfactants are employed in an amount of from 0 to about 6 weight percent based on the total weight of the microemulsion. Preferably, one or more nonionic surfactants are employed in an amount of not more than about 3, more preferably not greater than about 2 weight percent. Preferably, the combined weight of the ammonium surfactants and nonionic surfactants amount to no more than about 10, and more preferably no more than about 8 weight percent of the microemulsion. The nonionic surfactants that can be usefully employed in this invention include alkylphenol alkoxylates and primary and secondary alcohol alkoxylates wherein the alkoxylate can be ethoxy, propoxy, butoxy or combinations thereof. Mixtures of alcohol alkoxylates can be used. Preferred nonionic surfactants are alkylphenol ethoxylates and primary and secondary alcohol ethoxylates. Alkylphenol ethoxylates and primary and secondary alcohol ethoxylates are represented by the formula: RO- (CH2CH2O) "- H Where R is a hydrocarbon containing 9 to 24 carbon atoms and n is a number that averages from 1 to 9 The commercially available nonionic surfactants are sold by Shell Chemical Company under the name Neodol ™ and by Union Carbide Corporation under the name Tergitol ™. Representative examples of preferred commercially available nonionic surfactants include Tergitol ™ series 15-s and Neodol ™ series 91 or 25. Further representative examples of useful nonionic surfactants include polyoxyethylated polypropylene glycols, polyoxyethylated polybutylene glycols, polyoxyethylated mercaptans, esters of glyceryl and polyglycerol of natural fatty acids, polyoxyethylated sorbitol esters, polyoxyethylated fatty acids, alcohol amides, tertiary acetic acid glycols, N-alkyl-pyrrolidones and alkyl polyglycosides. The most preferred nonionic surfactants employed in this invention are secondary alcohol ethoxylates. Representative examples of preferred commercially available secondary alcohol ethoxylates include Tergitol ™ 15-S-3, Terigitol ™ 15-s-d and Tergitol ™ 15-S-7.

The microeimulsions of this invention may also contain other types of surfactants such as amphoteric surfactants with molecular weights above 350, betaines such as N-alkylbetaines including N, N, N-dimethyl-hexadecyl-amino- (3-propionate) , and sulfobetaines such as N, N, N-dimethyl-hexadecyl-amino-propylene sulfonate. The conductivity of a microemulsion of this invention is measured at temperatures of use, since the conductivity can vary with temperature, because the phase behavior of the microemulsion also changes with temperature. It is further possible to form a microemulsion which is not continuous in oil and does not fall within the scope of this invention at room temperature, but which when heated to higher use temperature is continuous in oil and falls within the scope of this invention. Electrical conductivity can be measured using standard techniques and conventional equipment, using, for example, a Model 326 conductivity meter from the Fisher brand that has a space of centimeters between the anode and the cathode in the probe. When such a device is used, the probe is simply immersed in the solution, the instrument is allowed to equilibrate and the conductivity value of the device is observed. It should be understood that the device should be calibrated using normal electrolyte solutions of known conductivity before measuring the conductivity of compositions of this invention.

The microemulsions of this invention have a viscosity of less than 40 centistokes as measured at temperatures of use. The viscosity is measured at temperatures of use since the viscosity can vary with temperature. It is therefore possible to form a microemulsion which is not within the scope of this invention at room temperature, but which when heated to a higher use temperature has a viscosity which falls within the scope of this invention. Preferably, the continuous single-phase oil microemulsions have a viscosity of less than 30 centistokes, more preferably less than 20 centistokes and still more preferably less than 10 centistokes and even more preferably less than about 8 centistokes. An advantage of the preferred microemulsions of this invention is that upon dilution to at least 10 percent by weight of water or oil, the viscosity of the resulting composition does not increase above 40 centistokes. Viscosity can be measured by well-known methods using conventional equipment designed for that purpose. For example, a capillary viscometer such as the Cannon-Fenske capillary viscometer equipped with a capillary size of 350 can be used following the procedure of ASTM DD 445. Alternatively, a Brookfield viscometer model LVT can be used with a UL adapter for Measure the viscosities in centipoise. Subsequently, one or more surfactants are employed in an amount effective to form a continuous micro-emulsion in oil. The amount varies depending on the amount and nature of the components throughout the composition of the microemulsion. However, it is equally important that the microemulsions contain a higher water content, generally above 40 weight percent based on the total weight of the composition. This being the case, the microemulsions of the invention are characterized as being compositions that are not bicontinuous or are not continuous in water. A generalized methodology for designing single-phase, high-water microemulsion cleaning systems is as follows: (A) selecting an organic solvent or mixture of organic solvents that has the desired low water content absorption; (B) determining the relationship between the structure of the surfactant agent (eg, hydrophilicity) and conductivity, viscosity and phase behavior (eg, the presence of liquid crystals) of compositions with the desired level of water , surfactants, organic solvent and additive content by varying only the surfactant composition or surfactant mixture; (C) The procedure of steps A and B may be repeated as necessary at various concentrations of solvent and surfactant until the amount and types of solvent and surfactant necessary to give a continuous structure in oil of a single agent are determined. phase to the desired level of water based on the information generated in step B); (D) Determine the viscosity or conductivity of the continuous microemulsion in oil; (E) if the viscosity is very high, it can be adjusted by reducing the concentration of surfactant, changing the composition of the solvent (eg, increasing the level of an oxygenated solvent such as glycol ether or alcohol), adding a second class of surface-active agent (e.g., nonionic to an ammonium-based system) or by adding electrolytes of up to 0.6, preferably up to 0.2 percent by weight (excluding surfactant) or by changing the organic solvent to the surfactant agent ratio; (F) if necessary, adjusting the surfactant composition or surfactant mixture (repeating steps B, C and D with new formulation) of step E to provide a continuous microemulsion in oil of a single phase; and (H) confirming that the viscosity and conductivity of the continuous microemulsion in oil are within the scope of this invention. It should be noted that some steps can be suppressed or repeated depending on the circumstances. In general, optimum cleaning performance is obtained when the microemulsion systems are prepared with a minimum amount of surfactant. This leads to low residues and lower inherent viscosity (in the absence of liquid crystals). In order to determine the minimum amount of surfactant required, the methodology described above should be repeated at various levels of surfactant for a given solvent system and water content. Normally, the level of minimal surfactant is defined as the lowest level of surfactant where the region of microemulsion structures can be traversed continuously in continuous water in oil without the generation of any excess phase. In practice it has been found that efficient systems (lower surfactant levels) are obtained when predominantly an anionic surfactant is used from the upper end of the specified molecular weight scale and adjusts the phase behavior using a second component (either by the decision of small amounts of electrolyte or by adjusting the composition of the solvent phase, for example by the addition of the low molecular weight hydrocarbon described below). Another consideration when designing optimal continuous oil microemulsions is to avoid regions of high viscosity during the cleaning process. When used, the microemulsions described herein can be transformed from their continuous structure in oil through the ntinuous region into the continuous in water via, v. gr. , evaporation of solvent components giving a new balance of solvents; dirt cleaning that can favor the continuous structure in water; or adding water during a rinsing procedure with water. For this reason the most preferred systems should maintain low viscosities not only in the continuous region in oil but also in the ntinuous or continuous regions in water. The addition of electrolytes is an effective method to adjust the behavior of phases; however, the increase in electrolyte content decreases the efficiency of surfactants. Therefore, the total electrolyte content (excluding surfactants) should be minimized. In another embodiment of the invention, a microemulsion having a conductivity, measured at its use temperature, of more than its Z number (a ntinuous or oil in water microemulsion) can be disturbed, comprising the components mentioned above (also referred to as weakly as "titrated" with aqueous sodium carbonate electrolyte) to generate microemulsions. This disturbance is achieved through the introduction, by total weight of the composition, up to about 0.5 percent of an electrolyte as mentioned above, or up to about 20 percent, preferably up to 10 percent or less of an aliphatic or alicyclic hydrocarbon not greater than a molecular weight of 100. Normally, the electrolyte selected for this purpose can be one or more of the above-mentioned salts or a soluble polymer electrolyte, for example, a polyacrylic acid or water-soluble polyacrylate salt. The low molecular weight hydrocarbon, for example, may be propane, butane, pentane, hexane, or cyclohexane. Generally, while the hydrocarbon weight is lower, it will be more effective in disturbance. The use of the electrolyte is described below in all Examples and the effective use of the lower hydrocarbon (cyclohexane) in Example 8 (samples E-1 to E-3) and Example 9 (samples H-1 to HI-4). In Example 13, a number of sample formulations were prepared using the methodology noted above, until the properties were adjusted appropriately by varying the levels and types of the Carb Na formula and electrolyte components in samples S-1 to S-5, where the microemulsion of a / c of conductivity less than Z was finally prepared by perturbation. Emulsions The cleaning emulsions of this invention are dispersed when they are mixed sufficiently; however, when at rest the emulsions form at least two phases in which a phase is a continuous microemulsion in oil. Normally, only two phases are formed when the emulsions are allowed to stand. As used herein "at rest" means to let sit undisturbed for 7 days at 25 ° C. The emulsions of this invention contain water in an amount greater than 60 weight percent and less than 95 weight percent based on the total weight of the emulsion. Preferably, the emulsions contain water in an amount greater than 70 percent by weight, more preferably greater than 75 percent by weight; preferably less than 90 percent by weight, more preferably less than 88 percent by weight. The types of organic solvents used in the emulsions of this invention are the same as those described above under the heading of Microemulsions, including all kinds of solvents, physical characteristics of the solvents, representative examples and preferred solvents. However, the amount of solvent employed in the emulsions of this invention is greater than 4 percent and less than 40 percent by weight based on the total weight of the emulsion. Preferably, the amount of solvent employed for an emulsion is greater than 8 weight percent, more preferably greater than 10 weight percent; preferably less than 25 percent by meso, and more preferably less than 15 percent by weight. The descriptions of useful ionic surfactants and nonionic surfactants are the same as those described above under the heading of Microemulsions. However, the amount of ionic surface active agent employed is about 0.1 percent about 5 weight percent based on the total weight of the emulsion. Preferably, the amount employed is less than about 3 weight percent. The definition used above to describe "continuous oil" compositions is also used to describe emulsions. Conductivity is measured, then agitation and before phase separation occurs, at temperatures of use since the conductivity can vary with temperature because the phase behavior of the invention can also change with temperature. Thus it is possible to form an emulsion which is not continuous in oil and does not fall within the scope of this invention at room temperature, but which when heated to a higher use temperature is continuous in oil and fell within the scope of that invention.

In addition, the emulsions have a viscosity of less than 40 centistokes as measured at temperatures of use. The viscosity was measured at temperatures of use since the viscosity can vary with temperature, i.e. it is possible to form a microemulsion which is not within the scope of this invention at room temperature, but which when heated to a higher use temperature it has a viscosity that fell within the scope of this invention. Preferably, the emulsions have a viscosity of less than 20 centistokes, more preferably less than 10 centistokes. A generalized methodology used to designate emulsion cleaning systems with high water content is as follows: (A) select an organic solvent or mixture of organic solvents having the desired absorption of low water content; (B) determining the relationship between the structure of the surface active agent (e.g., hydrophilicity) and conductivity of a composition with water, surfactants, organic solvent and content of desired additives by varying only the composition of the surfactant or mixture of agents surfactants; (C) The procedure of steps A and B may be repeated as necessary at various concentrations of solvent and surfactant until the amount and types of solvent and surfactant necessary to give a continuous emulsion structure in oil at the level are determined. desired water based on the information generated in step B; (D) Determine the viscosity, conductivity and water content of the stability emulsion (type of phase separation) or the continuous emulsion in oil; (E) if the viscosity is very high, it can be adjusted by varying the concentration of surfactant, ratio of organic solvent to surfactant, or by the addition of an additional organic solvent such as a glycol ether, to decrease the viscosity; (F) if necessary, adjust the surfactant composition or surfactant mixture (repeat steps B, C and D with the new formulation of step E) to provide a continuous microemulsion in oil; and (H) confirming that the viscosity and conductivity of the continuous microemulsion in oil are within the scope of this invention. It should be noted that some may be suppressed or repeated depending on circumstance. Optional Further, of the required components listed above for microemulsions and emulsions, respectively, a variety of optional materials may be added depending on the end use, desired physical properties of the microemulsion or emulsion, and the like. Therefore, various detergent additives, chelating agents (such as tetrasodium ethylenediamine tetra-acetate "EDTA"), sequestering agents, suspending agents, perfumes, enzymes (such as those of the invention) can be included in a microemulsion or emulsion of this invention. lipases and proteases), flavorings, preservatives, corrosion inhibitors, phosphatization agents, UV absorbers, disinfectants, biologically active components such as pesticides, herbicides, fungicides, and drugs filled and dyes. Before use, any sodium alkyl toluene sulfonates used to supplement the anionic carboxylate surfactant in the preparation of microemulsions shall be treated to remove salts of residual sulfate and toluene from alkyl disulfonate by extracting a surfactant solution in PnB using aqueous hydrogen peroxide followed by neutralization using aqueous sodium hydroxide. "Pnb" denotes the n-butyl ether of propylene glycol (PnB DOWA NO ™ obtained from The Dow Chemical Company), "PnP" denotes the n-propyl ether of propylene glycol (Pn B DOWANO ™ obtained from The Dow Chemical Company), "a / ac" denotes continuous microemulsions in oil, "acia" denotes continuous microemulsions in water, Nafta SC 140 is a commercial petroleum distillate obtained from Exxon Corporation and Exxal ™ 7 is a commercial isoheptyl alcohol (5-methyl hexanol) ), also obtained from Exxon. Sodium erucate ("Erucato Na") is the sodium salt of erucic acid and is prepared in situ by the neutralization of erucic acid with 5 N aqueous sodium hydroxide solution. Similately. the other acid salts were prepared by neutralization of their respective carboxylic acid with sodium hydroxide or other aqueous alkaline or alkaline earth metal base, v. g r. , potassium hydroxide or the like. The term "Na oleate", "Na stearate", "Na linoleate", "Na palitate", etc., represents the sodium salt of each of the respective carboxylic acids. The following examples are included for the purposes of illustration only and should not be construed as limiting the scope of the invention or claims. Unless otherwise indicated, all parts and percentages are by weight. All examples, viscosities were measured at 25 ° C using ASTM D 445 on a Cannon Fenske capillary viscometer using a 350 size capillary or a Brookfield Model LVT viscometer with a UL adapter. Example 1. Concentrate A solution of concentrates was prepared by mixing 16.2 parts of Exxal ™ 7 isoheptyl alcohol with 16.2 parts of DOWANOL ™ propylene glycol n-propyl ether PnP ("PnP"), and 41.7 parts of n-butyl ether of DOWANOL ™ PnB propylene glycol ("PnB"), in which the erucic acid is combined and then neutralized by a 5N aqueous sodium hydroxide solution to give 16.2 parts of Na erucate and 9.7 parts of water. The result is a single-phase, transparent, stable solution of low viscosity. This concentrated solution can subsequently be "disturbed", by the addition of electrolyte, water and organic solvent in an a / c microemulsion resulting from the invention. Example 2. Microemulsion of Water in Oil A sample of 3.08 parts of the solution prepared as described in Example 1, is mixed with 2.2 parts of n-heptane and 4.72 parts of DI water to give a two phase product with oil phase in excess and a conductivity of 4040 microSiemens / centimeters ("μS / cm") (where Z = 1374) which has the overall composition of 5 parts of Na erucate, 22 parts of heptane, 12.9 parts of PnB, 5 parts of PnP , 5 parts of Exxal 7, and 50.1 parts of water. The two-phase product is "titrated" with a 10 percent sodium carbonate solution ("Carb Na") by adding a part of a Carb Na solution, forming liquid crystals ("CL") and giving As a result, conductivity drops of the sample at 1770μS / cm (Z = 1475). After a total of 1.25 parts of Carb Na solution was added, a clear single-phase microemulsion product is formed having a conductivity of 1430μS / cm (Z = 1490) and then a Carb solution is added. Na of 1.5 parts total, the resulting transparent single-phase bluish oil water microemulsion has a conductivity of 430 μS / cm (Z = 1590) and a viscosity of 9.7 centistokes ("cSt") measured by the viscometer Brookfield LVT with a UL adapter. Example 3. Disturbing Microemulsion and Microemulsion of A / AC In the manner of Example 1, a sample of the same components was prepared in slightly modified ratios, varying amounts of the two glycol esters using instead 14.9 parts of PnB and 3 parts. of PnP. The resulting ac / a microemulsion contains LC and have conductivity of 4250 μS / cm (Z = 1375). This is a disturbing microemulsion that can be converted into a microemulsion of a / c by the addition of electrolyte. When titrated with a 10 percent Nab Carb solution (the electrolyte), as described in Example 2, the ac / a microemulsion was converted to a bluish or clear single phase water / oil microemulsion. In addition to 1 part of the solution of Carb Na gives a microemulsion that has a conductivity of 530 μS / cm (Z = 1472) and a viscosity 9.5 cSt. Example 4. Product based on Naphtha v Disturbing Microemulsion In the manner of Example 1, a sample was prepared, replacing an oil distillate - Naphtha SC 140 supplied by Exxon Chemical, for the previous base of organic heptane solvent. The components of the sample and their respective quantities are: Naphtha SC 140 = 22 parts, Pnb = 15 parts, PnP = 3 parts, Exxal 7 = 5 parts, erucate of Na = 5 parts and water of Di = 50 parts. The resulting sample is a perturbable microemulsion in ac / a of a single phase, transparent having a conductivity of 4420 μS / cm (Z = 1459). When treating this disturbing ac / a microemulsion was filtered with 10 percent Na Carb solution, the following results were observed: 1 part of Na Carb solution, a single phase transparent product with conductivity of 3620 μS / cm (Z = 1547); 1.75 parts of Carb Na solution gives a milky emulsion with excess water phase having a conductivity of 1030 μS / cm (Z = 1620) and viscosity of 11.5 cSts. After that emulsion, an additional quantity of the organic solvent naphtha SC 140 was added to adjust the water / oil balance in order to produce the desired microemulsion of a / c. When a total of 4.78 parts of Naphtha SC 140 have been added, a single-phase transparent bluish a / c microemulsion is formed, which exhibits conductivity of 1 1 10 μS / cm (Z = 1370) and a viscosity of 7.5 cSt. It is an excellent fat removal product. Example 5. Cleaning Process The low viscosity a / c microemulsion with a conductivity of 1 1 10 μS / cm prepared as described in Example 4 was contacted with steel coupons coated with lithium grease according to the Normal Conoco cleaning test. The removal and excellent cleansing of fat was observed. Example 6. Product based on d-Limonene In the same manner as the previous examples, a sample was prepared substituting d-limonene for an organic base component commonly employed in a wide range of cleaning products. The prepared sample comprises the following quantities of each respective component: d-limonene = 22 parts, PnB = 14.9 parts, PnP = 3 parts, Exxal 7 = 5 parts, and water of Dl = 40.1 parts, and the microemulsion of ac / a The resultant contains CL and has a conductivity of 4670 μS / cm (Z = 1527). When the composition is "titrated" with the 10 percent Na Carb solution, 0.5 parts of Na Carb solution provides a resulting microemulsion containing a CL with conductivity of 1 180 μS / cm (Z = 1573). The additional titration to a total of one part of Na Carb solution converts the sample to a transparent single-phase a / c microemulsion with conductivity of 375 μS / cm (Z = 1613) and having a viscosity of 12.5 cSt . Example 7. Emulsions with High Water Content In the same manner as Example 2, a formulation was prepared using: erucate of Na = 2.5 parts, heptane = 10.5 parts, PnB = 3.5 parts; PnP = 3.5 parts, water of Dl = 80 parts. To that emulsion of disturbing ac / a containing an excess of oil phase, variable amounts of Nab Carb were added, passing through intermediate bicontinuous formulations, until a transparent a / c microemulsion with some excess water phase results. . Upon stirring, there is an emulsion having a conductivity of about 0.5Z and a viscosity of 12.5 cSt. The different stages of this preparation are shown graphically in Table 1, Samples A-1 to A-4. Examples 8-13 Use of Other Na Carboxylates as the Surfactant Component In a similar manner to the preceding Examples, various formulations were prepared using a variety of sodium carboxylic acid salts in place of Na erucate found in the previous Examples . The other components of the formulations were selected from Na carb, n-heptane, PnB, 1-hexanol and DI water, and in some formulations, cyclohexane. With each different Na carboxylate, a series of formulations were prepared by adjusting the ratios of the different components to obtain the desired conductivity properties of less than 1 Z and a low viscosity. From these series, it can be observed how the methodology described in the previous teachings is used for the preparation and then the fine tuning of each formulation. The properties of each microemulsion or emulsion can be observed in these examples. The compositions of different formulations and their respective resulting physical properties and calculated Z numbers are presented in Tables 2-7, found below.

TABLE 1 Eiem.7 Erucato Heptane PnB PnP Water Cycle- Na2CO3 Comp. Conductivity- Viscosity of Na hexane Phase (üS / cm) (CSL) sample A-1 2.5 10.5 3.5 3.5 80 0 0 2080 nm 690 A \ r? - ¿ ¿D 10.5 3.5 3.5 79.4 0 0.8 8160 nm 2400 A-3 2.5 10.5 3.5 3.5 78.8 0 1.2 1 f.cl 4400 nm 3920 A-4 2.5 10.5 3.5 3.5 78.6 0 1.4 2450 12.5 4490 00 tD TABLE 2 Eiem.8 Erucate Heptane PnB PnP Water Cycle- Na2CO3 Comp. Conductivi- Viscosi- Z of Na hexane Phase nity Sample (uS / cm) (CSL) B 5.5 21.5 23 0 49.8 0 0.2 1 f .cl. 5360 nm 1880 C-1 5.5 22 17.5 5 50 0 0 1f.cl. 4550 nm 1600 C-2 5.44 21.78 17.33 4.95 50.4 0 0.1 1f.cl. 4120 nm 1740 C-3 5.39 21.57 17.16 4.9 50.8 0 0.2 1f.cl. 1950 6.5 1880 4w O D-1 5.39 21.57 17.16 6.86 49 0 0 LCs nm Na 1840 D-2 5.37 21.46 17.07 6.82 49.2 0 0.05 CL nm Na 1910 D-3 5.35 21.36 17 6.8 49.4 0 0.1 1f.cl. 2640 Na 1980 D-4 5.33 21.25 16.9 6.76 49.6 0 0.15 1f.cl. 1270 Na 2050 D-5 5.32 21.2 16.83 6.74 49.74 0 0.17 1 f.cl. 620 7 2080 E-1 5.42 21.67 17.24 4.92 50.6 0 0.15 1f.cl. 3060 Na 1810 E-2 4.93 19.73 15.69 4.48 46.06 8.97 0.14 1 f.cl. 1920 Na 1630 E-3 4.53 18.11 14.4 4.1 42.24 16.5 0.12 1f.cl. 1380 7 1450 1 f.cl. = 1 clear phase nm = not measured CL = liquid crystals TABLE 3 Ahem.9 Erucate Heptane PnB PnP Water Cycle- Na2CO3 Comp. Conductivi- Viscosi- Z of Na hexane Phase of the sample Sample (iiS / cm) (CSL) F 5.5 22 22.5 0 49.8 0 0.2 1 f.cl. 5600 nm 1870 G-1 5.5 22 17.5 5 50 0 0 1 f.cl. 4200 nm 1600 G-2 5.44 21.78 17.33 4.95 50.4 0 0.1 CL nm nm 1740 G-3 5.39 21.57 17.16 4.9 50.8 0 0.2 1 f.cl. 2000 7 1880 H-1 5.5 22 17.5 5 49.8 0 0.2 1 f.cl. 2500 nm 1880 H-2 5.24 20.95 16.67 4.76 47.43 4.76 0.19 1 f.cl. 1780 nm 1690 H-3 5 20 15.91 4.54 45.27 9.1 0.18 1 f.cl. 1140 nm 1500 H-4 4.58 18.33 14.58 4.17 41.5 16.67 0.17 1 f.cl. 340 nm 1130 1-1 5.5 22 15 7.5 50 0 0 CL nm nm 1610 I-2 5.5 22 15 7.5 49.95 0 0.05 CL nm nm 1680 I-3 5.5 22 15 7.5 49.9 0 0.1 1 f.cl. 600 8.5 1750 TABLE 4 Ahem 10 Erucato Heptane PnB PnP ja. Cycle-? 2C03 Comp. ConductiviViscosiZ of Na hexane Phase of the sample Sample (uS / cm) (CSL) 5.5 22 22.5 49.8 0.2 1 f.cl. 4800 nm 1870 K-1 5.5 22 17.5 5 50 0 0 CL nm nm 1600 K-2 5.44 21.78 17.33 4.95 50.4 or 0.1 CL nm nm 1740 K-3 5.39 21.57 17.16 4.9 50.8 or 0.2 1 f.cl. 1500 7 1880 t 1 f.cl. = 1 clear phase nm = not measured CL = liquid crystals TABLE 5 Ahem.11 Erucate Heptane PnB PnP Water Cycle- Na2C03 Comp. Conductivi- Viscoside Na hexa n o Phase quality Sample (μS / cm) (CSL) 5.5 22 22.5 49.8 0.2 1 f.cl. 1080 8 1800 M-1 5.5 22 17.5 5 50 0 0 CL nm nm 1530 M-2 5.44 21.78 17.33 4.95 50.4 0 0.1 1 f.cl. 280 11.5 1670 o o o O O O Ni co o • < 3- CM < o CO O) co • < * CD CJ) or CM CN t- CM CN Q. 0) e (??? O C O Ü_ co O CN? O CN CO m O LO CO CN O CU 2 O co O c co? X or o or < b CD -1 m SI or -s < r- cs r- ~ m 3 co m 00 o CD cr s cn m co c < - < r - r M- f cc (A 0_ c m LO LO LO? 0. II O o m m m m lO LO m c CN CN CN h- h- r- ~ r ^ -s CL CN CN e CN co • < ~ II CN CN CN CO T a > a > 3 2 2 o o? o o Lll ooooooo OOOOOOOO - CO OO 00 O) CO ffi lO r lD O ^ CO N cn m CD ~ - n T - CN - - t - cO - t LO tv - Ni t - CN CN - t - CN CN t- t- CN CN CN CN C \ J CO O O O LO - CN CO cn O o CN co co CN co co CM o o O o O ro 2 o r > - O c rco O X o o o < in CO O O O O O _? or F tn CQ or TJ < r oo o LO LO CD 3 00 N (D 3 co CD or CO CO n o s s < n cn cn LO cn n LO T-LO s > cn cn cn < 5 i "vt T -vf f • + ro- * Q. CD c WHAT THE WHAT? 0_. "f? - -. r- II _ l O o WHAT WHAT IS WHAT IS WHAT IS WHAT IS WHAT IS MUC CN CM CM f» r »r- r- LO- WHAT IT LO CN CN CN r-? Ofe O o c c CM CN CN CN CN CN CN CN O CO o o o O O II CN CN CM CN CN CN CN CN CN CN X c co e C? CN CO CN CO CN CN CN CO O F 3 o. o_ o o s s s tJ üí tr o c w O o UJ e

Claims (32)

1. CLAIMS 1. A continuous microemulsion in oil of a single phase, comprising: A. Water in an amount not less than about 40 weight percent and not more than about 75 percent based on the total weight of the microemulsion; B. An organic solvent or a mixture of two organic solvents, wherein the organic solvent or mixture of organic solvents are characterized as containing no more than about 2 weight percent water at 25 ° C when the organic solvent is with water in it. absence of surfactants or other additives and wherein the organic solvent or mixture of two or more organic solvents is in an amount of not less than about 10 percent and not more than about 60 percent by weight based on the total weight of the microemulsion. C. One or more anionic surfactants which are at least partially soluble in one or more of the organic solvents, wherein at least one of said surfactants is an olefinic or saturated fatty acid salt, having an average molecular weight in the range of 225 to 365 exclusive of the group of counterions, and wherein one or more anionic surfactants are present in a total amount greater than about 0.1 percent and not more than about 10 weight percent based on the total weight of the microemulsion.
2. 2. The microemulsion of claim 1, characterized in that it is a continuous microemulsion in oil having an electrical conductivity of less than Z microSiemens / centimeter when measured at temperatures of use and a viscosity of less than 40 centistokes as measured at temperatures of use , where Z is represented by the following formula: (1/3) (? w) 2 ?? A (m? Where? W represents the volume fraction of water in the microemulsion, i represents a given electrolyte, A | represents the molar conductivity of the electrolyte, i and mi represents the molarity of the electrolyte i in the aqueous phase. microemulsion of the preceding claims wherein one or more organic solvents is an aliphatic alcohol, an aliphatic ester, an aliphatic hydrocarbon, a chlorinated aliphatic hydrocarbon, an aromatic hydrocarbon, an aliphatic diester, an aliphatic ketone, an aliphatic ether, a glycol monoether of alkylene, an alkylene glycol diether, an alkylene glycol ether acetate or combinations thereof 4. The microemulsion of any of the preceding claims, wherein one or more organic solvents is present in an amount not less than 30 weight percent and not more than 50 weight percent 5. The microemulsion of any of the preceding claims, wherein water is present in an amount not less than 45 percent by weight and not more than 70 percent by weight.

   6. The microemulsion of any of the preceding claims, wherein at least one of the anionic surfactants is an anionic surfactant having a molecular weight of not less than 250 and not more than about 345, exclusive of counterion M. 7. The microemulsion according to claim 6, wherein at least one second anionic surfactant of the formula RxB-SO3M is present wherein R represents alkyl, x is 1 or 2, B is a biradical when x is 1 or is a triradical when x is 2 and that it is derived from an aromatic portion and where M represents a cationic counterion and where the total number of carbons in Rx is 18 to 30. The microemulsion of any of the preceding claims, wherein The electrical conductivity is less than 0.5Z microSiemens / centimeter. 9. The microemulsion of any of the preceding claims, wherein the viscosity is less than 20 centistokes. The microemulsion of any of the preceding claims, wherein the electrical conductivity is less than 0.25 microSiemeps / centimeters. The microemulsion of any of the preceding claims, wherein at least one organic solvent is an alkylene glycol monoether.

   12. An emulsion, which when at rest at 25 ° C form at least two phases wherein one phase is a continuous microemulsion in oil, comprising: A. Water in an amount not less than about 60 weight percent and no greater to about 95 percent based on the total weight of the emulsion; B. An organic solvent or a mixture of two or more organic solvents, wherein the organic solvent or mixture of organic solvents are characterized as containing no more than about 2 weight percent water at 25 ° C when the organic solvent is saturated with water in the absence of surfactants or other additives and wherein the organic solvent or mixture of two or more organic solvents is present in an amount of not less than about 4 percent and not more than about 40 percent by weight based on the total weight of the emulsion; C. U or more anionic surfactants which are at least partially soluble in one or more of the organic solvents, wherein at least one of said surfactants is an olefinic salt or saturated fatty acid salt, having an average molecular weight in the range of 225 to 365 exclusive of the group of counterions, and wherein one or more anionic surfactants are present in a total amount greater than 0. 1 percent and less than about 5 percent by weight based on the total weight of the emulsion; the emulsion is characterized by being a continuous emulsion in oil where the emulsion has an electrical conductivity of less than Z microSiemens / centimeter when measured at temperatures of use and a viscosity of less than 40 centistokes as measured at temperatures of use, where Z is as described above. The emulsion of claim 12, wherein one or more organic solvents is an aliphatic alcohol, an aliphatic ester, an aliphatic hydrocarbon, a chlorinated aliphatic hydrocarbon, an aromatic hydrocarbon, an aliphatic diester, an aliphatic ketone, an aliphatic ether, an alkylene glycol monoether, an alkylene glycol diether, an alkylene glycol ether acetate or combinations thereof. The emulsion of claims 12 or 13, wherein one or more organic solvents are present in an amount of not less than 8 weight percent and not more than 25 weight percent. 15. The emulsion of claims 12-14, wherein the water is present in an amount of not less than about 70 weight percent and not more than about 90 weight percent. 16. The emulsion of claims 12-15, wherein the anionic surfactant has a molecular weight not greater than about 345. 17. The emulsion of claims 12-16, wherein the anionic surfactant has a not lesser molecular weight. to 250.

   18. The emulsion of claim 17, wherein at least one additional anionic surfactant is present, of the formula: RxB-SO3M wherein R represents alkyl, x is 1 or 2, B is a biradical when x is 1 or is a triradical when x is 2 and which is derived from an aromatic portion and wherein M represents a cationic counterion and where the total number of carbons in Rx is 18 to 30. 19. The solution of any of claims 12-18. , where the electrical conductivity is less than 0.5 Z microSiemens / centimeter. 20. The emulsion of any of claims 12-9, wherein the viscosity is less than 20 centistokes. twenty-one . The emulsion of any of claims 12-20, wherein the electrical conductivity is less than 0.25Z microSiemens / centimeter. 22. The emulsion of any of claims 12-21, wherein by an organic solvent is an alkylene glycol monoether. The emulsion of any of claims 12-22, wherein the water is in an amount of not less than about 80 weight percent and not more than about 90 weight percent. 24. A cleaning concentrate, which when diluted with water can form the microemulsion of any of claims 1-11, which comprises: A. An organic solvent or a mixture of two or more organic solvents, wherein the organic solvent or a mixture of organic solvents are characterized as containing no more than 2 weight percent water at 25 ° C when the organic solvent is saturated with water in the absence of surfactants or other additives; and B. One or more anionic surfactants which are at least partially soluble in one or more organic solvents, wherein at least one of said surfactants is an olefinic salt or saturated fatty acid, which has an average molecular weight in the 225 to 365 scale exclusive of the group of counterions, and wherein one or more anionic surfactants are present in a total amount not less than 0.1 percent and no greater than about 10 percent by weight based on the total weight of the microemulsion. 25. A method for cleaning metal having a grease or oil stain on a metal surface comprising applying the microemulsion to any of claims 1-11 or the emulsion of any of claims 12-23 to the metal which has a Grease or oil stain on the metal surface to remove at least a portion of the grease or oil stain from the metal surface. The microemulsion of claim 1 or the emulsion of claim 12, wherein the salt of the carboxylic acid, exclusive of the group M has a molecular weight between 250 and 345, the valence of M is 1 and y is the integer 1

   27. The microemulsion or emulsion of claim 26, wherein the carboxylic acid from which the salt is derived is selected from erucic, oleic and stearic acid. 28. A disturbing composition comprising: Component A. An organic solvent or a mixture of two or more organic solvents, wherein the organic solvent or a mixture of organic solvents are characterized as containing no more than 2 weight percent of water. 25 ° C when the organic solvent is saturated with water in the absence of surfactants or other additives; and Component B. One or more anionic surfactants which are at least partially soluble in Component A, wherein at least one of said surfactants is selected from the group of aliphatic and alicyclic carboxylic acid salts represented by the formula (R '-COO) and M where R' is a hydrocarbyl group of 14 to 23 carbon atoms, where M is an alkali metal or alkaline earth metal cation with a valence of 1 or 2 and y is the integer 1 or 2 and where the salt has a molecular weight on the scale of 225 to 365, exclusive of the counterion M; whose composition, by adding an electrolyte or hydrocarbon of low molecular weight forms a microemulsion characterized by being continuous in oil with a conductivity less than Z, said microemulsion comprising: water present in an amount greater than 45 percent and less than 70 percent percent in weight, based on the total weight of the microemulsion; Component A, present in an amount greater than 15 percent and less than 50 percent by weight based on the total weight of the microemulsion; and Component B, present in an amount greater than 0.1 percent and less than 10 percent by weight based on the total weight of the microemulsion. The composition of claim 28, wherein Component A is a monoether of alkylene glycol and alkylene glycol diether, or combinations thereof. The composition of claim 28, wherein at least one anionic surfactant of Component B has a molecular weight greater than 250 and less than 345. 31. A process for preparing a continuous microemulsion in oil, comprising the steps of Step 1. Select a disturbing composition of claim 28. Step 2. Add to said composition an amount of a salt or other electrolyte sufficient to induce said composition to become a continuous microemulsion in oil of conductivity less than Z. 32 The process of claim 31, wherein one or more organic solvents of the composition is an alkylene glycol monoether, an alkylene glycol diether or combinations thereof. RESU MEN Higher microemulsions and emulsions, continuous in oil, with high water content, useful for cleaning, contain defined amounts of water, one or more anionic surfactants from a group of carboxylic acid salts with selected molecular weight and one or more organic solvents so that the compositions have low conductivity and low viscosity.