CN1199430A - High water content, low viscosity, oil continuous microemulsions and emulsions, and their use in cleaning applications - Google Patents
High water content, low viscosity, oil continuous microemulsions and emulsions, and their use in cleaning applications Download PDFInfo
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- CN1199430A CN1199430A CN97191142A CN97191142A CN1199430A CN 1199430 A CN1199430 A CN 1199430A CN 97191142 A CN97191142 A CN 97191142A CN 97191142 A CN97191142 A CN 97191142A CN 1199430 A CN1199430 A CN 1199430A
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- microemulsion
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- organic solvent
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/06—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using emulsions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0017—Multi-phase liquid compositions
- C11D17/0021—Aqueous microemulsions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
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
Background of the present invention
The present invention relates to microemulsion and emulsion and their various application.
Microemulsion is known.The typical component of microemulsion comprises water, organic solvent and tensio-active agent.Microemulsion is through being commonly used for cleaning formulation.United States Patent (USP) U.S.4 for example, 909,962 described clarification that the form with microemulsion, solution or gel provides, single-phase, in advance go spot composition, this composition to embody to be characterized as with water unlimited solvable and be not separated.United States Patent (USP) U.S.5,462,692 have described and have contained the water continuous phase microemulsion of spices as their the insoluble hydrocarbon component of main water.This patent has been used together with other component ready denier oil acid together as in the prescription of hard surface cleaner.United States Patent (USP) U.S.5,597,792 have described oily external phase, high water content (water-in-oil) emulsion and the microemulsion that is used to clean purpose, it contains the ionic surface active agent that dissolves in the organic solvent phase, this tensio-active agent have scope from 350～700, be preferably greater than 400 less than 600 molecular-weight average, counterion forecloses.Briefly describing and do not have one of illustrational a variety of ionic surface active agent is soap.
Other data has been described and has been cleaned the useful composition of application facet.In being described as the system of oily external phase, system has low water-content.Main the water continuous phase system is described in, United States Patent (USP) U.S.4, some embodiment in 909,962 for example understand low water content, oily external phase (water-in-oil) system.Desirable is the new composition of finding to be used for this type of purpose, and it has high water-content and is oily external phase.This type of oily external phase microemulsion especially is suitable as cleaning combination to remove oil or lubricating grease.
The present invention's general introduction
On the one hand, the present invention is the single phase external phase microemulsion as liquid cleaning compositions, and it contains:
A. based on the water of the amount of about 40wt% of being no less than of microemulsion gross weight and no more than about 75wt%;
B. the mixture of an organic solvent or two or more organic solvents, wherein the mixture of organic solvent or organic solvent embodies and is characterized as: under the situation that does not have tensio-active agent or other additive, when organic solvent is in the water saturation state, the water that contains no more than about 2wt% in the time of its 25 ℃, and wherein the amount of the mixture of organic solvent or two or more organic solvents for based on about 10wt% of being no less than of microemulsion gross weight and no more than about 60wt%;
C. be partially dissolved in one or more anion surfactants in one or more organic solvents at least, wherein one of in this tensio-active agent be at least alkene family or the saturated fatty hydrochlorate, scope with molecular-weight average is from 225～365, except the counterion group, and wherein the total amount of one or more anion surfactants be based on the microemulsion gross weight greater than about 0.1wt% and be not more than about 10wt%.
Microemulsion preferably embodies and is characterized as oily external phase microemulsion and has the specific conductivity of measuring in use temperature that is less than the little Siemens/cm of Z and the viscosity of measuring in use temperature less than 40 centistokes, and wherein Z is expressed from the next: Z=(1/3) (Φ
w)
2∑
iA
im
i, Φ wherein
wThe volume parts of water in the expression microemulsion, i represents given ionogen, A
iMolecular conductivity and the m of expression ionogen i
iThe volumetric molar concentration of expression aqueous phase ionogen i.
On the other hand, the present invention be by 25 ℃ leave standstill produce at least two-phase, wherein one be the emulsion of oily external phase microemulsion mutually, it contains:
A. based on the water of the amount of about 60wt% of being no less than of emulsion gross weight and no more than about 95wt%;
B. the mixture of an organic solvent or two or more organic solvents, wherein the mixture of organic solvent or organic solvent embodies and is characterized as: under the situation that does not have tensio-active agent or other additive, when organic solvent is in the water saturation state, the water that contains no more than 2wt% in the time of its 25 ℃, and wherein the amount of the mixture of organic solvent or two or more organic solvents for based on about 4wt% of being no less than of emulsion gross weight and no more than about 40wt%;
C. be partially dissolved in one or more anion surfactants in one or more organic solvents at least, wherein at least a this tensio-active agent be alkene family or the saturated fatty hydrochlorate, scope with molecular-weight average is from 225～365, except the counterion group, and wherein the total amount of one or more anion surfactants be based on the emulsion gross weight greater than 0.1wt% and be less than about 5wt%.
Emulsion preferably embodies and is characterized as oily external phase emulsion, wherein this emulsion has specific conductivity of measuring in use temperature that is less than the little Siemens/cm of Z (" μ S/cm ") and the viscosity of measuring in use temperature less than 40 centistokes (" cSt "), and wherein Z is expressed from the next: Z=(1/3) (Φ
w)
2∑
iA
im
i, Φ wherein
wThe volume parts of water in the expression microemulsion, i represents given ionogen, A
iMolecular conductivity and the m of expression ionogen i
iThe volumetric molar concentration of expression aqueous phase ionogen i.
Another aspect, the present invention be co-continuous mutually or water continuous phase microemulsion or emulsion, except that Z value, satisfy above-mentioned all indexs, by adding salt or molecular weight less than about 87 stable hydrocarbon perturbation enter the composition of the invention described above, and it contains:
A. the mixture of an organic solvent or two or more organic solvents, wherein the mixture of organic solvent or organic solvent embodies and is characterized as: under the situation that does not have tensio-active agent or other additive, when organic solvent is in the water saturation state, contain the water of no more than 2wt% in the time of its 25 ℃; With
B. be partially dissolved in one or more anion surfactants in one or more organic solvents at least, wherein at least a this tensio-active agent be alkene family or the saturated fatty hydrochlorate, scope with molecular-weight average is from 225～365, except the counterion group, and wherein the total amount of one or more anion surfactants is based on the about 0.1wt% of being not less than of microemulsion gross weight and is not more than about 10wt%.
Also have on the other hand, the present invention is used for the method that clean surface has the metal of lubricating grease or oily dirt, comprise that above-mentioned microemulsion or emulsion are added to the surface to be had on the metal of lubricating grease or oily dirt, to remove at least a portion lubricating grease or oily dirt from metal.
The liquid cleaning compositions that metal cleaning, hard surface cleaning, circuit card go to weld with acting on for microemulsion of the present invention and emulsion, automobile cleaning, cold rinse, dry-cleaning, paint peeling and fabric clean.In addition, microemulsion and emulsion are effective especially to removing lubricating grease and oily material.In family and personal care, composition of the present invention can be used for doing washing pretreater, detergent for washing clothes, coating, skin cleaner, hair clean and regulate prescription and be used for aerosol, wash pump liquid, spraying is with liquid or insecticidal liquid agent prescription.Said composition also can be used for industrial coating and seal gum application examples such as tackiness agent, printing ink, polishing varnish, latex neutralization as the processing solubility promoter.Composition of the present invention can be used for the desalination of soil compensation and water and increase oil recovery and with acid and other additive delivery in oil well.Composition of the present invention can be used for medicinal application for example in vaccine auxiliary, the localized drug delivery carrier and automatically in the heating combination.Composition of the present invention can be used as the medium that is used for making the ceramic applications nanometer particle, and catalyzer is for example in the application of the manufacturing of zeolite and semi-conductive manufacturing.Composition of the present invention can be used in the fuel for example alcohols of the fuel material of replacing with solubilising.Composition of the present invention can be used for stabilized enzyme, promotes the surface-area of heterogeneous reaction and increase reaction medium.Composition of the present invention can be used for producing latex and water-soluble polymers by micro-emulsion polymerization, and produces multiphase polymer for example self-enhancement plastics and manufacturing polymeric dispersions.Also may use these prescriptions to dissolve agricultural insecticide etc. on the crops by resultant composition is added to.In addition, microemulsion of the present invention and emulsion can be used for cleaning to be used, and provides SYNTHETIC OPTICAL WHITNER and enzyme in the prescription, so that limited ground of SYNTHETIC OPTICAL WHITNER degrading enzyme.Composition of the present invention also can be used as the working metal fluid, comprises cutting fluid, shaping dope, hardening liquid and protection liquid, also transmits hydraulic fluid as power.
Exclusive aspect of the present invention is following advantage: by using natural and the renewable unsaturated and saturated fatty hydrochlorate of lower concentration, form the high-moisture composition of low viscosity and oily external phase, produce the product that for same water-in-oil (" the w/o ") microemulsion that uses the sulfonated tensio-active agent, has enhanced environmental consistency and ionogen tolerance limit.
Microemulsion
As mentioned above, microemulsion of the present invention contains water, organic solvent and one or more anion surfactants as essential component.This type of microemulsion and emulsion embody and are characterized as oily external phase and have high water content.Microemulsion is generally considered to be the composition in the thermodynamic(al)equilibrium, has the suspended particles particle diameter from 50～1000 dusts." ionogen " meaning of herein using is some the solvation salt in microemulsion or the emulsion, comprises ionic surface active agent or adduct for example sal epsom, yellow soda ash and sodium-chlor." oily external phase " meaning of herein using is a composition, or microemulsion or emulsion, has the specific conductivity that is lower than the little Siemens/cm of Z, and wherein Z is expressed from the next: Z=(1/3) (Φ
w)
2∑
iA
im
i, Φ wherein
wThe volume parts of water in the expression composition, i represents given ionogen, A
iMolecular conductivity and the m of expression ionogen i
iThe volumetric molar concentration of expression aqueous phase ionogen i.Therefore, have the 0.02mol composition in the ionogen of 120,000 molecular conductivities (little siemens * liter/cm x mole) and 50% volume of water umber, the Z value is 200, and thereby is the oily external phase microemulsion that is lower than 200 little Siemens/cm (Z).Preferably, composition of the present invention has the specific conductivity that is lower than 0.5Z, more preferably less than 0.25Z and most preferably be lower than 0.1Z.The opposite combined thing of co-continuous is to be higher than Z and to be lower than 2Z, and the water continuous phase composition is to be higher than 2Z.
In single phase external phase microemulsion, based on the microemulsion gross weight, the amount of water is not less than about 40wt% and is not more than about 75wt%.Preferably, microemulsion contains the water that is not less than about 45wt%.Preferably, microemulsion contains the water that is not more than about 70wt%, more preferably no more than about 65wt% and even more preferably no more than about 60wt%.
In single phase external phase microemulsion, use the mixture of a kind of organic solvent or two or more organic solvents, wherein the mixture of organic solvent or organic solvent embodies and is characterized as under the situation that does not have tensio-active agent or other additive, when organic solvent is in the water saturation state, contain the water of no more than 2wt% in the time of its 25 ℃.Preferably, 25 ℃ in the mixture of organic solvent or organic solvent contains the water that is not more than 1wt% when saturated, more preferably no more than the water of 0.5wt%.The water intake of organic solvent can be changed places by the water droplet constant volume and be recorded, and for example wherein water joins in one or more organic solvents up to observing the solution muddiness or producing water.Based on the microemulsion gross weight, the amount of the mixture of organic solvent or two or more organic solvents is for being not less than about 10wt% and being not more than about 60wt%.Preferably, the amount of the mixture of organic solvent or two or more organic solvents for be not less than about 15wt%, more preferably be not less than about 20wt%, most preferably be not less than about 25wt% and preferably be not more than 50wt%.
The classification that can be used for the organic solvent of practical application of the present invention comprises fatty alcohol, aliphatic ester, aliphatic hydrocrbon, chloro aliphatic hydrocrbon, aromatic hydrocarbon, aliphatic diester, aliphatic ketone and aliphatic ether.In addition, solvent can contain the mixture that these functional groups maybe can be contained in two or more these functional groups.For example, in practical application of the present invention, can use alkylidene diol bisether, aklylene glycol monoether and alkylene glycol ether acetic ester as solvent.Operable herein alkylene glycol ether comprises two alkylene glycol ethers.Aklylene glycol monoether and alkylidene diol bisether are useful especially to the viscosity that reduces microemulsion.The preferred classification of organic solvent is aliphatic hydrocrbon, aromatic hydrocarbon, aklylene glycol monoether, alkylidene diol bisether and alkylene glycol ether acetic ester.The preferred classification of organic solvent is aliphatic hydrocrbon, aklylene glycol monoether and alkylidene diol bisether.
Fatty alcohol can be primary alconol, secondary alcohol or the tertiary alcohol.Preferred fatty alcohol has 4～24 carbon atoms.The exemplary of preferred fatty alcohol comprises 1-hexanol, iso-heptanol, octanol, 2-ethyl-hexanol, nonyl alcohol, dodecanol, hendecanol and decyl alcohol.
Preferred aliphatic ester has 4～24 carbon atoms.The exemplary of preferred aliphatic ester comprises Laurate methyl, Witconol 2301, hexyl acetate, pentyl acetate, octyl acetate, nonyl acetate and decyl acetate.
Aliphatic hydrocrbon can be straight chain, side chain, ring-type or their mixture.Preferred aliphatic hydrocrbon contains 3～24 carbon atoms, preferred 6～24 carbon atoms.The exemplary of preferred aliphatic hydrocrbon comprises for example for example 1-decene, 1-laurylene, octadecylene and hexadecylene of liquid propane gas, butane, pentane, hexane, heptane, octane, decane, dodecane, n-Hexadecane, mineral oil, paraffin oil, naphthane, bicyclohexane, hexanaphthene and alkene of paraffinic hydrocarbons.The example of commercially available aliphatic hydrocrbon is Norpar
TM12,13 and 15 (the normal paraffin solvents that Exxon Corporation sells), Naphtha SC 140 petroleum distillates (also from Exxon), Isopar
TMG, H, K, L, M and V (the different chain alkane solvents that Exxon Corporation sells) and Shellsol
TMSolvent (shell chemical company).
Preferred chloro aliphatic hydrocrbon contains 1～12 carbon atom, more preferably contains 2～6 carbon atoms.The exemplary of preferred chloro aliphatic hydrocrbon comprises methylene dichloride, tetracol phenixin, chloroform, 1, tetrachloroethylene and trieline.
Preferred aromatic hydrocarbon contains 6～24 carbon atoms.The exemplary of preferred aromatic hydrocarbon comprises toluene, naphthalene, biphenyl, ethylbenzene, dimethylbenzene, alkylbenzene for example dodecylbenzene, hot benzene and nonylbenzene.
Preferred aliphatic diester contains 6～24 carbon atoms.The exemplary of preferred aliphatic diester comprises dimethyl adipate, Succinic acid dimethylester, Methyl glutarate, diisobutyl adipate and diisobutyl maleate.
Preferred aliphatic ketone contains 4～24 carbon atoms.The exemplary of preferred aliphatic ketone comprises methyl ethyl ketone, diethyl ketone, diisobutyl ketone, methyl iso-butyl ketone (MIBK) and methyl hexyl ketone.
Preferred aliphatic ether contains 4～24 carbon atoms.The exemplary of preferred aliphatic ether comprises ether, ethyl propyl ether, hexyl ether, butyl ether and methyl tertiary butyl ether.
Preferred aklylene glycol monoether, two aklylene glycol monoethers, alkylidene diol bisether and alkylene glycol ether acetic ester comprise the propylene glycol diether with 5～25 carbon atoms, the propylene glycol acetic ester with 6～25 carbon atoms, the propylene glycol monoether with 7～25 carbon atoms, the glycol ether acetate with 6～25 carbon atoms, have the ethylene glycol diether of 6～25 carbon atoms and have the ethylene glycol mono-ether of 8～25 carbon atoms.The exemplary of preferred solvent comprises propylene glycol dimethyl ether, propylene glycol benzyl methyl ether, propylene glycol butyl methyl ether, propylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol dibutyl ether in this big class scope; Methyl proxitol acetate, dipropylene glycol methyl ether acetic ester, propylene glycol butyl ether acetic ester; Propylene glycol single-butyl ether, propylene glycol list hexyl ether, dipropylene glycol single-butyl ether, dipropylene glycol list hexyl ether; Ethylene glycol monoethyl ether acetate, ethylene glycol butyl ether acetic ester, Diethylene Glycol butyl ether acetic ester; Ethylene glycol bisthioglycolate ethyl ether, ethylene glycol bisthioglycolate butyl ether; Ethylene glycol hexyl ether, ethylene glycol Octyl Ether, ethylene glycol phenyl ether, Diethylene Glycol hexyl ether and Diethylene Glycol Octyl Ether.Most preferred aklylene glycol monoether is propylene glycol single-butyl ether, dipropylene glycol single-butyl ether, propylene glycol list propyl ether and dipropylene glycol list propyl ether.
In the preferred embodiment of the invention, use the mixture of aklylene glycol monoether and one or more other organic solvents.The preparation of low viscosity microemulsion and emulsion is convenient in the adding of aklylene glycol monoether.Based on the microemulsion gross weight, the amount of aklylene glycol monoether preferably is not less than about 10wt% for being not less than about 5wt%, more preferably is not less than about 15wt%; Be not more than about 50wt%, preferably be not more than about 40wt%, more preferably no more than about 25wt%.Generally in microemulsion and emulsion, glycol ether should be greater than 2: 1 (weight) with the ratio of total tensio-active agent.Based on the emulsion gross weight, the amount of aklylene glycol monoether in the emulsion that contains the 70-80% water of having an appointment be for being not less than about 5wt%, and be not more than about 15wt%.
In single phase external phase microemulsion, use the anion surfactant that is partially dissolved in one or more particular chemical structures in one or more organic solvents at least.One or more anion surfactants also preferably embody and are characterized as, in one or more organic solvents than in water, having bigger solubleness, and in the mixture of water and organic solvent priority allocation in organic solvent.Preferably, one or more anion surfactants only are a spot of water-soluble.Here the term solvability does not comprise dispersiveness or emulsifying property.One or more anion surfactants have greater than 225 and less than 365 molecular weight.If use two or more anion surfactants, " molecular weight " that use above is based on the mean value calculation of two or more anion surfactant molecular weight.The natural acid that is used to prepare anion surfactant is commercially available with the blend of the various molecular weight components of various degrees of unsaturation and carbon content usually.
A preferred analog anion surfactants be general formula (R '-COO)
yThe anion surfactant of M (formula I), the unsaturated or saturated alkyl of R ' expression olefinic wherein, y is 1 or 2, wherein M represent the cation balance ion and wherein the middle carbon sum of R ' be 13～23.Preferred R ' be alkyl inner undersaturated and neither α, β-unsaturated neither be unsaturated with carboxyl conjugated olefinic.The molecular weight of the anion surfactant of the weight calculating formula (I) of eliminating M promptly only calculates molecular weight to R '-COO-.
Contain M and can be prepared at an easy rate by their acid precursor as the anion surfactant of counterion, wherein M is a hydrogen, for example by making the metal hydroxides reaction of carboxylic acid and the oxyhydroxide that comprises ammonium, lithium, sodium, potassium, magnesium, calcium etc.The selection of special M counterion is not strict, and is solvable and preferred only a small amount of water-soluble and the anion surfactant that can prepare microemulsion of the present invention and emulsion is provided as long as resulting tensio-active agent is retained to small part in organic solvent.Preferably, M is a unit price, and more preferably is selected from sodium, potassium and " " (for example quaternary nitrogen in the ammonium etc.) positively charged ion.Preferably, anion surfactant has molecular-weight average at least about 250, and more preferably at least 280, most preferably at least about 295.Preferably, anion surfactant has molecular weight and is not more than 345, more preferably no more than 340, and most preferably is not more than 337, except the counterion M.
Being used for concrete examples of anionic surfactants of the present invention is following alkene family and radical of saturated aliphatic and alicyclic carboxylic acid: alkene family lipid acid: Oleomyristic acid (suitable-the 9-tetradecenoic acid); Zoomeric acid (suitable-palmitoleic acid); Linolenic acid (9,12, the 15-punicic acid); Linolic acid (9,12 or 13-octadecadienoic acid); Oleic acid (suitable-the 9-octadecenic acid); Arachidonic acid (5,8,11, the 14-arachidonic acid); Erucic acid (suitable-the 13-Decosahedaenoic acid); With unsaturated 5-carbon alicyclic acid: hydnocarpic acid (C
16H
28O
2); Chaulmoogric acid (C
18H
32O
2); Gorlic acid (C
18H
30O
2); And saturated fatty acid: tetradecanoic acid (tetradecanoic acid-C
14H
20O
2); Palmitinic acid (hexadecanoic acid-C
16H
32O
2); Stearic acid (octadecanoic acid-C
18H
36O
2); Arachic acid (eicosanoic acid-C
20H
40O
2); With docosanoic acid (docosoic C
22H
44O
2).
Using the benefit of preferred anionic surfactants tensio-active agent is to need the preferred anionic tensio-active agent of relatively small amount so that high water content of the present invention, oily external phase microemulsion and emulsion to be provided.Therefore, be extremely low in the amount of the lip-deep remaining anion surfactant that cleans with microemulsion and emulsion, and the problem of speckle etc. also is minimum.Another benefit is because acid is the derivative of natural product basically, and how much more they be considered to than synthetic anion surface active agent commonly used " useful to environment ".
Preferably, the amount of preferred anionic surfactants tensio-active agent and more preferably is not less than about 1wt% for being not less than about 0.5wt% in the microemulsion.Preferably, the amount of preferred anionic surfactants tensio-active agent is for being not more than about 6wt%, and more preferably no more than about 5wt% in the microemulsion.When comprising carboxylic acid (and salt) in the prescription, the effect of acid does not resemble tensio-active agent and more resembles fatty alcohol organic solvent above-mentioned.But because the general higher molecular weight of acid is more less than the effect of such alcohol with the acid of weight opinion.
In single phase external phase microemulsion, above-mentioned concrete carboxylate surface active agent can be supplemented with other typical anion sulfoacid salt surfactant of sulfonated alkyl benzene/methylbenzene/naphthalene type commonly used.For example by general formula R
xB-SO
3Those that M represents, wherein R represents alkyl, x is 1 or 2, when x is 1 B be divalent group or when x is 2 B be the trivalent group, its derive from aromatics part and wherein M represent cation balance ion same as described above, and R wherein
xIn the carbon sum be from 18～30.Formula R
xB-SO
3The estimating of molecular weight of the anion surfactant of M has been got rid of the molecular weight of counterion M; Be that molecular weight only calculates R
xB-SO
3 -This type of additional sulfosalt surfactant that contains M as counterion can be by their precursor sulfonic acid by making it the metal hydroxides reaction preparation at an easy rate with the oxyhydroxide that comprises ammonium, lithium, sodium, potassium, magnesium, calcium.The selection of special M counterion is not strict, as long as resulting tensio-active agent is retained to small part in organic solvent solvable, and preferably only water-soluble on a small quantity, and can help the anion surfactant of concrete carboxylic acid derivatives to prepare microemulsion of the present invention and emulsion.Preferably, M is monovalent.Preferably, B derives from benzene, toluene or naphthalene.Preferably, additional sulfosalt surfactant has the molecular weight greater than 400.Preferably, these additional surfactant have molecular weight less than 600 and be more preferably less than 550.
In single phase external phase microemulsion, one or more nonionogenic tensides also can be used for replenishing or strengthening the effectiveness of anion surfactant.The amount of using one or more nonionogenic tensides is based on 0 of microemulsion gross weight～about 6wt%.Preferably, use the amount of one or more nonionogenic tensides for being not more than about 3wt%, more preferably no more than about 2wt%.The gross weight of preferred anionic tensio-active agent and nonionogenic tenside is not more than about 10wt% of microemulsion altogether, and more preferably no more than about 8wt%.
Operable ionic surfactant pack is drawn together alkylphenol alcoxylates and primary alconol and secondary alcohol alkoxylates among the present invention, and wherein alcoxylates can be oxyethyl group, propoxy-, butoxy or their mixture.Can use the mixture of alcohol alkoxylate.Preferred nonionic is alkyl phenol ethoxylate and primary alconol and secondary alcohol ethoxyl compound.Alkyl phenol ethoxylate and primary alconol and secondary alcohol ethoxyl compound are expressed from the next:
R-O-(CH
2CH
2O)
n-H wherein R is the hydrocarbon that contains 9～24 carbon atoms, and n is the mean number from 1～9.Commercially available nonionogenic tenside is sold by shell chemical company, is named as Neodol
TMAnd, be named as Tergitol by Union CarbideCorporation sale
TMThe exemplary of preferred commercially available nonionogenic tenside comprises Tergitol
TM15-s-series and Neodol
TM91 or 25 series.The other exemplary of useful nonionogenic tenside comprises the glyceryl of the ethylating polypropylene glycol of polyoxy, the ethylating polytetramethylene glycol of polyoxy, the ethylating mercaptan of polyoxy, natural acid and polyglyceryl ester, the Sorbitol Powder of polyoxyethyleneization, lipid acid, alkanolamide, uncle acetylinic glycol, N-alkyl-pyrrolidone and the alkylpolyglycosides of polyoxyethyleneization.The preferred nonionogenic tenside that uses among the present invention is a secondary alcohol ethoxyl compound.The exemplary of preferred commercially available secondary alcohol ethoxyl compound comprises Tergitol
TM15-s-3, Tergitol
TM15-s-5 and Tergitol
TM15-s-7.
Microemulsion of the present invention can further contain the tensio-active agent of other type, for example molecular weight surpasses 350 amphoterics, betaine is N-alkyl betaine for example, comprise N, N, N-dimethyl-hexadecyl-amino-(3-propionic ester) and sulfo group betaine be N for example, N, N-dimethyl-hexadecyl-amino-propylidene sulphonate.
The specific conductivity of microemulsion of the present invention is measured under use temperature, because specific conductivity can change with temperature, the phase behaviour of microemulsion also can change with temperature.This shows that preparation at room temperature is not oily external phase and does not fall into the scope of the invention but be that oily external phase and the microemulsion that falls into the scope of the invention are possible when being heated to higher use temperature.With standard method and habitual instrument, for example using has the conductance instrument in one centimetre of gap can testing conductivity between Fisher brand326 type probe positive pole and negative pole.When using such device, probe immerses solution simply, the appliance requires balance, and from device, observe specific conductivity.Should be understood that before the specific conductivity of the test present composition this device must be calibrated with the standard electrolyte solution of known conductivity.
When testing under use temperature, the viscosity of microemulsion of the present invention is less than 40 centistokes.Because viscosity can change with temperature, viscosity will be tested under use temperature.This shows that preparation is not at room temperature not within the scope of the present invention but the microemulsion that has the viscosity in the scope of the invention of falling into when being heated to higher use temperature is possible.Preferably, single phase external phase microemulsion has the viscosity less than 30 centistokes, is more preferably less than 20 centistokes, especially preferably less than 10 centistokes and most preferably less than 8 centistokes.The benefit of the preferred microemulsion of the present invention is that the viscosity of resultant composition improves can not surpass 40 centistokes by water or the oil of 10wt% dilute with reaching at least.Viscosity can be used the habitual instrument test of design for this purpose with known method.For example, can use the capillary viscosimeter capillaceous that is equipped with No. 350 according to ASTM D 445 methods as the Cannon-Fenske capillary viscosimeter.In addition, the Bu Shi LVT type viscometer that has a UL setter can be used to the centipoise tested viscosity.
This shows, use the amount of one or more tensio-active agents will be enough to form oily external phase microemulsion.This amount changes according to the amount and the kind of component in whole microemulsion compositions.It is no less important that but microemulsion contains the general high water content that surpasses based on composition total weight 40wt%.Under a kind of situation, microemulsion of the present invention embody be characterized as neither co-continuous mutually neither water continuous phase composition.
The general method that is used to design high water content, Monophase microemulsion cleaning system is as follows: the organic solvent or the organic solvent blend of (A) selecting to have suitable low water intake; (B) form by only changing tensio-active agent or surfactant blend, determine to have the surfactant structure (for example wetting ability) of composition of suitable water, tensio-active agent, organic solvent content and additive level and the relation between specific conductivity, viscosity and the phase behaviour (for example existence of liquid crystal); (C) if essential, the method of steps A and B can repeat under all kinds of SOLVENTS and surfactant concentration, and (information that produces in based on step B) produces the amount and the type of single phase necessary solvent of external phase structure and tensio-active agent when determining at suitable water-content; (D) viscosity and the specific conductivity of the oily external phase microemulsion of mensuration; (E) if viscosity is too high, can be by reducing surfactant concentrations, change solvent composition (for example by improving for example content of glycol ether or alcohol of oxo solvent), adding the second class tensio-active agent (for example nonionic is to the anion-radicals system) or by adding ionogen 0.6wt% at the most, preferred 0.2wt% (eliminating tensio-active agent) or adjusted with the ratio of tensio-active agent at the most by the change organic solvent; (F) if desired, by step e adjustment sheet surface-active agent or surfactant blend composition (with new prescription repeating step B, C and D) so that single phase external phase microemulsion to be provided; (H) viscosity of the oily external phase microemulsion of confirmation and specific conductivity are within the scope of the invention.Should be noted that according to circumstances and can delete or repeat some steps.
General when microemulsion system prepares with minimum tensio-active agent, can obtain optimal clean usefulness.This causes low residue and lower limiting viscosity (not having under the situation of liquid crystal).In order to determine the minimum of required tensio-active agent, should repeat aforesaid method with various surfactant content to given solvent system and water-content.General least surface active agent content is defined as from water continuous phase to oily external phase through the microemulsion structural region and without any the excessive minimum surface active agent content that produces mutually.In fact find, when mainly using the anion surfactant of specified molecular weight range limit and use second kind of component, people (or add the small amount of electrolyte or the composition of adjustment solvent phase, for example add following low molecular weight hydrocarbon) when adjusting phase behaviour, can obtain efficient system (low surfactant content).
When designing optimal oil external phase microemulsion, another consideration is the high viscosity district that avoids in cleaning process.When using, microemulsion described here can become water continuous phase through the co-continuous phase region from their oily external phase structure, the evaporation of the solvent composition by for example producing new solvent balance; The solubilising of the impurity of the favourable water continuous phase structure of possibility; Or the adding of water in the water rinse program.For this reason, most preferred system should not only keep low viscosity at the continuous phase region of oil but also in two and water continuous phase district.
Electrolytical adding is an effective means for adjusting phase behaviour; Yet improve electrolyte content and can reduce tensio-active agent effectiveness.Therefore, total electrolyte content (not comprising tensio-active agent) should be minimum.In another program of the present invention, the microemulsion that comprises aforementioned component that has greater than its Z value (co-continuous mutually or oil-in-water microemulsion) specific conductivity (testing when its use temperature) can be by disturbance (also strictly not being referred to as with yellow soda ash aqueous electrolyte liquid " titration ") to form microemulsion.By add based on composition total weight or the above-mentioned ionogen of about 0.5wt% at the most, or about at the most 20wt%, preferably 10wt% or molecular weight still less are not more than 100 aliphatic series or clicyclic hydrocarbon at the most, realize this disturbance.The general ionogen of selecting for this purpose can be one or more aforesaid salt or water-soluble polymers ionogen, for example water-soluble polyacrylic acid or polyacrylate.Low molecular weight hydrocarbon can for example be propane, butane, pentane, hexane and hexanaphthene.General hydrocarbon weight is low more, and is effective more in the disturbance.Described electrolytical effect among all below embodiment, described useful effect among embodiment 8 (sample E-1 is to E-3) and the embodiment 9 (sample H-1 is to H-4) than lower hydrocarbon.In embodiment 13, some sample prescriptions are by using method for preparing, up to suitably adjusting its character by changing recipe ingredient and sample S-1 to electrolytical content of the yellow soda ash among the S-5 and type, wherein specific conductivity is mainly prepared by disturbance less than the w/o microemulsion of Z.
Emulsion
Cleaning emulsion of the present invention can be disperseed when thorough mixing well; Yet produce two-phase at least by leaving standstill emulsion, wherein one is oily external phase microemulsion mutually.The general two-phase that when emulsion leaves standstill, only produces." leaving standstill " meaning of herein using is 25 ℃ of static placements 7 days.
Emulsion of the present invention contain based on the emulsion gross weight greater than 60wt% and less than the water of 95wt%.The amount that preferred emulsion contains water is greater than 70wt%, more preferably greater than 75wt%; Preferably, be more preferably less than 88wt% less than 90wt%.
With an organic solvent type is identical with under the above-mentioned microemulsion title those in the emulsion of the present invention, comprises the solvent of all classes, physical properties, exemplary embodiments and the preferred solvent of solvent.But amount in the emulsion of the present invention with an organic solvent be based on the emulsion gross weight greater than 4wt% and less than 40wt%.The amount that is preferred for the solvent of emulsion is greater than 8wt%, more preferably greater than 10wt%; Preferably, be more preferably less than 15wt% less than 25wt%.
Useful ionic surface active agent and the explanation of nonionogenic tenside and above-mentioned identical under the microemulsion title.But the amount of used ionic surface active agent be based on the emulsion gross weight from about 0.1wt%～about 5wt%.Preferred institute consumption is less than about 3wt%.
Above also can be in order to describe emulsion in order to describe defining of " oily external phase " composition.Stir the back and be separated produce before under use temperature testing conductivity because specific conductivity can change with temperature, the phase behaviour of emulsion also can change with temperature.This shows that preparation at room temperature is not oily external phase and does not fall in the scope of the invention but be that oily external phase and the emulsion that falls in the scope of the invention are possible when being heated to higher use temperature.
In addition, when under use temperature when test emulsion have viscosity less than 40 centistokes.Viscosity is tested under use temperature, because viscosity can change with temperature.This shows that preparation is not at room temperature not within the scope of the present invention but the emulsion that has the viscosity in the scope of the invention of falling into when being heated to higher use temperature is possible.Preferred emulsion has the viscosity less than 20 centistokes, is more preferably less than 10 centistokes.
The general method that is used to design high water content emulsion cleaning system is as follows: the organic solvent or the organic solvent blend of (A) selecting to have suitable low water intake; (B), determine to have the surfactant structure (for example wetting ability) of composition of suitable water, tensio-active agent, organic solvent content and additive level and the relation between the specific conductivity by only changing tensio-active agent or surfactant blend composition; (C) if essential, the method of steps A and B can repeat under all kinds of SOLVENTS and surfactant concentration, and (information that produces in based on step B) produces the amount and the type of necessary solvent of oily external phase emulsion structure and tensio-active agent when determining at suitable water-content; (D) viscosity, specific conductivity and the water-content of mensuration emulsion, the stability of oily external phase emulsion (time that is separated); (E) if viscosity is too high, ratio that can be by changing surfactant concentrations, organic solvent and tensio-active agent or by add additional organic solvents for example glycol ether adjusted to reduce viscosity; (F) if desired, adjustment sheet surface-active agent or surfactant blend composition (using new prescription repeating step B, C and D by step e) are to provide oily external phase emulsion; (H) viscosity of the oily external phase microemulsion of confirmation and specific conductivity are within the scope of the invention.Should be noted that according to circumstances and can delete or repeat some steps.
Selection condition
Except the required component of listing above that is used for microemulsion and emulsion, can add various optional material according to the end-use of microemulsion or emulsion, suitable physical properties etc.Therefore can comprise various detergent additives, sequestrant (for example tetrasodium ethylenediamine tetraacetate " EDTA "), sequestering agent, suspension agent, spices, enzyme (for example lipase and proteolytic enzyme), whitening agent, sanitas, inhibiter, phosphorization agent, UV absorption agent, disinfectant, bioactive compounds for example agricultural chemicals, weedicide, sterilant and medicine, filler and dyestuff in microemulsion of the present invention and the emulsion.
Before the use, should pass through with surfactant soln among the aqueous hydrogen peroxide solution extraction PnB then with aqueous sodium hydroxide solution neutralizing treatment all alkyl toluene sodium sulfonates in the preparation microemulsion, to remove residual vitriol and disulfonic acid alkyl toluene ester in order to additional anionic carboxylic acid salt surfactant." PnB " expression propylene glycol n-butyl ether is (by the DOWANOL of Dow chemical company acquisition
TMPnB), " PnP " expression propylene glycol n-propyl ether is (by the DOWANOL of Dow chemical company acquisition
TMPnP), " w/o " represents oily external phase microemulsion, " o/w " expression water continuous phase microemulsion, and Naphtha SC140 is commercial petroleum distillate and the Exxal that is obtained by Exxon Corporation
TMThe 7th, commercial iso-heptanol (5-methyl-n-amyl carbinol) also is to be obtained by Exxon.
Erucic acid sodium (" Na Erucate ") is the neutralization reaction on-site preparation of the sodium salt of erucic acid and the aqueous sodium hydroxide solution by erucic acid and 5N.Similarly, other hydrochlorate is by for example neutralization reaction preparation of potassium hydroxide etc. of their corresponding carboxylic acid and sodium hydroxide or other basic metal or the alkaline-earth metal-based aqueous solution.The sodium salt of each of those corresponding carboxylic acids of expression such as term " sodium oleate ", " sodium stearate ", " linolic acid sodium ", " Sodium pentadecanecarboxylate ".
The following examples are as illustrative purposes only rather than in order to the scope of restriction the present invention or claim.
Except as otherwise noted, all umber and percentage ratios all are by weight.In all embodiment, with the viscosity of ASTM D 445 when using on No. 350 Cannon-Fenske capillary viscosimeters capillaceous or having 25 ℃ of tests on the Bu Shi LVT type viscometer of UL setter.Embodiment 1. enriched materials
By mixing 16.2 parts of Exxal
TM7 iso-heptanols and 16.2 parts of DOWANOL
TMPnP propylene glycol n-propyl ether (" PnP ") and 41.7 parts of DOWANOL
TMPnB propylene glycol n-butyl ether (" PnB ") preparation strong solution, erucic acid are sneaked into wherein and with the neutralization of 5N aqueous sodium hydroxide solution, are produced 16.2 parts of erucic acid sodium and 9.7 parts of water.Product is low viscosity, stable, limpid a single phase soln.Then by ionogen, water and organic solvent are added, this strong solution is become w/o microemulsion of the present invention by " disturbance ".Embodiment 2. water-in-oil microemulsions
3.08 part is the sample of the solution of preparation as described in example 1 above, mix with 2.2 portions of normal heptanes and 4.72 parts of deionized waters, obtain having the two-phase product of oil phase, specific conductivity is 4040 little Siemens/cm (" μ s/cm ") (wherein Z=1374), and this product has whole compositions of 5 parts of erucic acid sodium, 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 with 10% yellow soda ash (" Na Carb ") " titration ".By adding 1 part of sodium carbonate solution, the specific conductivity that forms dispersive liquid crystal (" LCs ") and resultant sample drops to 1770 μ s/cm (Z=1475).After ading up to 1.25 parts of sodium carbonate solutions addings, formation has limpid, the Monophase microemulsion product of 1430 μ s/cm specific conductivity (Z=1490), and after ading up to 1.5 parts of sodium carbonate solutions addings, resulting limpid, single-phase, light blue oil/water microemulsion has the specific conductivity (Z=1590) of 430 μ s/cm, and the viscosity that records with the Bu Shi LVT type viscometer that has the UL setter is 9.7 centistokes (" cSt ").But embodiment 3. turbulent microemulsions and W/O microemulsion
Press the method for embodiment 1,, use 14.9 parts of PnB and 3 parts of PnP to prepare sample by changing two glycol ethers-replace by the same composition of slight modification ratio.Resulting o/w microemulsion contains LCs and has the specific conductivity (Z=1375) of 4250 μ s/cm.But this is the disturbance microemulsion that can change the w/o microemulsion by the adding ionogen into.When with 10% sodium carbonate solution (ionogen) titration, as described in example 2 above, the o/w microemulsion changes low viscous single-phase, limpid light blue oil/water microemulsion into.The adding of 1 part of sodium carbonate solution has produced the specific conductivity (Z=1472) with 530 μ s/cm and the microemulsion of 9.5cSt viscosity.But embodiment 4. petroleum naphtha based articles and disturbance microemulsion
Press the method for embodiment 1, the oil distillate-Naphtha SC140 that provides with Exxon Chemical replaces the organic solvent based preparation sample of aforesaid heptane.The corresponding amount in the component of sample and their is: Naphtha SC 140=22 part, PnB=15 part, PnP=3 part, Exxal 7=5 part, erucic acid sodium=5 part and deionized water=50 part.But resulting sample is clarification, single-phase o/w disturbance microemulsion, has the specific conductivity (Z=1459) of 4420 μ s/cm.But when this disturbance o/w microemulsion during with 10% sodium carbonate solution titration, can be observed following result: it is limpid, the single-phase product of 3620 μ s/cm (Z=1547) that 1 part of sodium carbonate solution produces specific conductivity; 1.75 it is that 1030 μ s/cm (Z=1620) and viscosity are the milk of the water excessively shape emulsion of 11.5cSt that part sodium carbonate solution generation has specific conductivity.In order to prepare suitable w/o microemulsion, in this emulsion, add a certain amount of Naphtha SC 140 organic solvents more then to adjust water/oily balance.When adding the Naphtha SC 140 that adds up to 4.76 parts, formed single-phase, the light blue w/o microemulsion of clarification, having specific conductivity is that 1110 μ s/cm (Z=1370) and viscosity are 7.5cSt.It is the excellent grease product that removes.Embodiment 5. cleanings
According to standard C onoco washing test, 1110 μ s/cm specific conductivity, low viscosity w/o microemulsion with preparation as described in example 4 above contact with the steel part that is coated with lithium soap grease.Can be observed excellent lubricating grease removes and cleans.Embodiment 6.d-limonene based articles
Press method same in the foregoing description, substitute the heptane that uses previously with the d-limonene and prepare sample.The d-limonene is the organic radical solvent composition that generally uses in the wide range cleaning article.The amount that the sample of preparation comprises following each respective components is: d-limonene=22 part, PnB=14.9 part, PnP=3 part, Exxal 7=5 part and deionized water=50.1 part, resulting o/w microemulsion contains LCs and has specific conductivity 4670 μ s/cm (Z=1527).When said composition during with 10% sodium carbonate solution " titration ", 0.5 part of sodium carbonate solution provides and has still contained the microemulsion of LCs, and has specific conductivity 1180 μ s/cm (Z=1573).With the further titration of the sodium carbonate solution that adds up to 1 part, it is that 375 μ s/cm (Z=1613) and viscosity are limpid, the single-phase w/o microemulsion of 13.5cSt that sample is transformed into specific conductivity.Embodiment 7. high water content emulsions
With method similarly to Example 2, use following material to make prescription: erucic acid sodium=2.5 part, heptane=10.5 part, PnB=3.5 part, PnP=3.5 part, deionized water=80 part.But contained the yellow soda ash that adds various amounts in the disturbance o/w emulsion of oil phase to this, filled a prescription mutually, had the limpid w/o microemulsion of water up to formation through the intermediary co-continuous.Having specific conductivity by the stirring generation is that about 0.5Z and viscosity are the emulsion of 12.5cSt.The various stages of this preparation are shown in the Sample A-1 of table 1 in A-4 with table.Embodiment 8-13. is as the application of other carboxylic acid sodium of anion surfactant component
With method same as the previously described embodiments, use various carboxylic acid sodium salts to substitute the erucic acid sodium that appears among the embodiment of front, prepare various prescriptions.Other component of prescription is selected from yellow soda ash, normal heptane, PnB, 1-hexanol and deionized water, uses hexanaphthene in some components.Use each different carboxylic acid sodium to prepare the ratio of a series of prescriptions-each component of adjustment to obtain specific conductivity less than 1Z and low viscous suitable character.People can see from these series, and how the method for describing in the top instruction is used to prepares and each prescription is finely tuned.Also can see the character of every kind of microemulsion or emulsion formulations in these embodiments.The Z value of the various compositions of prescription and their corresponding physical propertiess and calculating is listed among the table 2-7 that occurs below.
Table 1 embodiment 7
Erucic acid sodium heptane PnB PnP water ring hexane Na
2CO
3Phase behaviour specific conductivity viscosity Z
(μ s/cm), (cSt) Sample A-1 2.5 10.5 3.5 3.5 80 00 excessive oil 2080 na 690 A-2 2.5 10.5 3.5 3.5 79.4 0 0.6 excessive oil 8160 na 2400 A-3 2.5 10.5 3.5 3.5 78.8 0 1.2 1p.c1. 4400 na 3920 A-4 2.5 10.5 3.5 3.5 78.6 0 1.4 excessive waters 2,450 12.5 4490
Table 2 embodiment 8
Sodium oleate heptane PnB 1-hexanol water ring hexane Na
2CO
3Phase behaviour specific conductivity viscosity Z
( μs/cm ) ( cSt ) B 5.5 21.5 23 0 49.8 0 0.2 1p.c1. 5360 na 1880 C-1 5.5 22 17.5 5 50 0 0 1p.c1. 4550 na 1600 C-2 5.44 21.78 17.33 4.95 50.4 0 0.1 1p.c1. 4120 na 1740 C-3 5.39 21.57 17.16 4.9 50.8 0 0.2 1p.c1. 1950 6.5 1880 D-1 5.39 21.57 17.16 6.86 49 0 0 LCs na na 1840 D-2 5.37 21.46 17.07 6.82 49.2 0 0.05 LCs na na 1910 D-3 5.35 21.36 17 6.8 49.4 0 0.1 1p.c1. 2640 na 1980 D-4 5.33 21.25 16.9 6.76 49.6 0 0.15 1p.c1. 1270 na 2050 D-5 5.32 21.2 16.83 6.74 49.74 0 0.17 1p.c1. 620 7 2080 E-1 5.42 21.67 17.24 4.92 50.6 0 0.15 1p.c1. 3060 na 1810 E-2 4.93 19.73 15.69 4.48 46.06 8.97 0.14 1p.c1. 1920 na 1630 E-3 4.53 18.11 14.4 4.1 42.24 16.5 0.12 1p.c1. 1380 7 14501p.c1.＝1 na＝ Lcs＝
Table 3 embodiment 9
Stearic heptane PnB 1-hexanol water ring hexane Na
2CO
3Phase behaviour specific conductivity viscosity Z
Acid sodium (μ s/cm) is sample F 5.5 22 22.5 0 49.8 0 0.2 1p.c1. 5600 na 1870 G-1 5.5 22 17.5 5 50 00 1p.c1. 4200 na 1600 G-2 5.44 21.78 17.33 4.95 50.4 0 0.1 LCs na na 1740 G-3 5.39 21.57 17.16 4.9 50.8 0 0.2 1p.c1. 2,000 7 1880 H-1 5.5 22 17.5 5 49.8 0 0.2 1p.c1. 2500 na 1880 H-2 5.24 20.95 16.67 4.76 47.43 4.76 0.19 1p.c1. 1780 na 1690 H-3 5 20 15.91 4.54 45.27 9.1 0.18 1p.c1. 1140 na 1500 H-4 4.58 18.33 14.58 4.17 41.5 16.67 0.17 1p.c1. 340 na 1130 I-1 5.5 22 15 7.5 50 00 LCs na na 1610 I-2 5.5 22 15 7.5 49.95 0 0.05 LCs na na 1680 I-3 5.5 22 15 7.5 49.9 0 0.1 1p.c1. 600 8.5 1750 (cSt)
Table 4 embodiment 10
Inferior oily heptane PnB 1-hexanol water ring hexane Na
2CO
3Phase behaviour specific conductivity viscosity Z
Acid sodium (μ s/cm) (cSt) sample J 5.5 22 22.5 0 49.8 0 0.2 1p.c1. 4800 na 1870 K-1 5.5 22 17.5 5 50 00 LCs na na 1600 K-2 5.44 21.78 17.33 4.95 50.4 0 0.1 LCs na na 1740 K-3 5.39 21.57 17.16 4.9 50.8 0 0.2 1p.c1. 1,500 7 18801p.c1.=1 is clarified mutually na=and is not tested the Lcs=liquid crystal
Table 5 embodiment 11
Erucic acid sodium heptane PnB 1-hexanol water ring hexane Na
2CO
3Phase behaviour specific conductivity viscosity Z
(μ s/cm) be sample L 5.5 22 22.5 0 49.8 0 0.2 1p.c1. 1,080 8 1800 M-1 5.5 22 17.5 5 50 00 LCs na na 1530 M-2 5.44 21.78 17.33 4.95 50.4 0 0.1 1p.c1. 280 11.5 1670 (cSt)
Table 6 embodiment 12
Palm heptane PnB 1-hexanol water ring hexane Na
2CO
3Phase behaviour specific conductivity viscosity Z
Acid sodium (μ s/cm) (cSt) sample N-1 5.5 22 22.5 0 49.8 0 0.2 excessive oil na na 1910 N-2 5.5 22 22.5 0 49.5 0 0.5 1p.c1. 6000 na 2330 N-3 5.5 22 22.5 0 49.45 0 0.55 excessive water na na 2400 O-1 5.5 22 17.5 5 50 00 excessive oil na na 1640 O-2 5.5 22 17.5 5 49.8 0 0.2 1p.c1. 4600 na 1920 O-3 5.5 22 17.5 5 49.7 0 0.3 1p.c1. 2800 na 2060 O-4 5.5 22 17.5 5 49.65 0 0.35 excessive water na na 21301p.c1.=1 is clarified mutually na=and is not tested the Lcs=liquid crystal
Table 7 embodiment 13
Semen Myristicae heptane PnB 1-hexanol water ring hexane Na
2CO
3Phase behaviour specific conductivity viscosity Z
( μs/cm ) ( cSt ) P-1 5.5 22 22.5 0 49.8 0 0.2 4800 na 1970 P-2 5.5 22 22.5 0 49.4 0 0.6 1p.c1. 8000 na 2530 P-3 5.5 22 22.5 0 49.35 0 0.65 na na 2600 Q-1 5.5 22 17.5 5 50 0 0 na na 1700 Q-2 5.5 22 17.5 5 49.8 0 0.2 1p.c1. 5600 na 1980 Q-3 5.5 22 17.5 5 49.65 0 0.35 1p.c1. 3900 na 2190 Q-4 5.5 22 17.5 5 49.6 0 0.4 na na 2260 R-1 5.5 22 17.5 5 49.65 0 0.35 1p.c1. 3900 na 2190 R-2 5 20 15.91 4.54 45.14 9.1 0.31 1p.c1. 4210 na 1750 R-3 4.58 18.32 14.58 4.16 41.36 16.7 0.29 1p.c1. 4340 na 1310 S-1 7 20 15.5 7.5 50 0 0 LCs na na 2160 S-2 7 20 15.5 7.5 49.9 0 0.1 LCs na na 2300 S-3 7 20 15.5 7.5 49.8 0 0.2 1p.c1. 3670 na 2440 S-4 7 20 15.5 7.5 49.7 0 0.3 1p.c1. 2760 na 2580 S-5 7 20 15.5 7.5 49.6 0 0.4 1p.c1. 1630 na 27201p.c1.＝1 na＝ Lcs＝
Claims (32)
1. single phase external phase microemulsion, comprising: A. is based on the water of the amount of about 40wt% of being no less than of microemulsion gross weight and no more than about 75wt%; B. the mixture of an organic solvent or two or more organic solvents, wherein the mixture of organic solvent or organic solvent embodies and is characterized as: under the situation that does not have tensio-active agent or other additive, when organic solvent is in the water saturation state, the water that contains no more than 2wt% in the time of its 25 ℃, and wherein the amount of the mixture of organic solvent or two or more organic solvents for based on about 10wt% of being no less than of microemulsion gross weight and no more than about 60wt%; At least be partially dissolved in one or more anion surfactants in one or more organic solvents with C., wherein at least a this anion surfactant be selected from by general formula (R '-COO)
yAliphatic series that M represents and alicyclic carboxylic acid salt, and molecular weight is from 225 to about 365, except the M group, R ' is the alkyl of 14～23 carbon atoms, M is 1 or the basic metal or the alkaline earth metal cation of divalent, y is 1 or 2 integer, and wherein the total amount of this anion surfactant be based on the microemulsion gross weight greater than about 0.1wt% and less than about 10wt%.
2. the microemulsion of claim 1 embodies being characterized as oily external phase microemulsion, and when having when use temperature is tested less than the specific conductivity of the little Siemens/cm of Z with less than the viscosity of 40 centistokes, wherein Z is expressed from the next: Z=(1/3) (Φ
w)
2∑
iA
im
i, Φ wherein
wThe volume parts of water in the expression microemulsion, i represents given ionogen, A
iMolecular conductivity and the m of expression ionogen i
iThe volumetric molar concentration of expression aqueous phase ionogen i.
3. the microemulsion that requires of aforesaid right, wherein one or more organic solvents are fatty alcohol, aliphatic ester, aliphatic hydrocrbon, chloro aliphatic hydrocrbon, aromatic hydrocarbon, aliphatic diester, aliphatic ketone, aliphatic ether, aklylene glycol monoether, alkylidene diol bisether, alkylene glycol ether acetic ester or their mixture.
4. aforesaid right requires each microemulsion, and wherein the amount of one or more organic solvents is for being not less than 30wt% and being not more than 50wt%.
5. aforesaid right requires each microemulsion, and wherein the amount of water is for being not less than 45wt% and being not more than 70wt%.
6. aforesaid right requires each microemulsion, and wherein at least a anion surfactant is that molecular weight is not less than 250 and be not more than about 345 anion surfactant, except the M counterion.
7. each microemulsion of claim 6 wherein has at least a second analog anion surfactants, has general formula R
xB-SO
3M, wherein R represents alkyl, x is 1 or 2, when x is 1 B be divalent group or when x is 2 B be the trivalent group, its derive from aromatics part and wherein M represent the cation balance ion, and R wherein
xIn the carbon sum be from 18～30.
8. aforesaid right requires each microemulsion, and wherein specific conductivity is less than the little Siemens/cm of 0.5Z.
9. aforesaid right requires each microemulsion, and its medium viscosity is less than 20 centistokes.
10. aforesaid right requires each microemulsion, and wherein specific conductivity is less than the little Siemens/cm of 0.25Z.
11. aforesaid right requires each microemulsion, wherein at least a organic solvent is the aklylene glycol monoether.
12. an emulsion leaves standstill at 25 ℃ and to produce two-phase at least, wherein one is oily external phase microemulsion mutually, comprising: A. is based on the water of the amount of about 60wt% of being no less than of emulsion gross weight and no more than about 95wt%; B. the mixture of an organic solvent or two or more organic solvents, wherein the mixture of organic solvent or organic solvent embodies and is characterized as: under the situation that does not have tensio-active agent or other additive, when organic solvent is in the water saturation state, the water that contains no more than 2wt% in the time of its 25 ℃, and wherein the amount of the mixture of organic solvent or two or more organic solvents for being no less than 4wt% and no more than 40wt% based on the emulsion gross weight; C. be partially dissolved in one or more anion surfactants in one or more organic solvents at least, wherein at least a this anion surfactant be selected from by general formula (R '-COO)
yAliphatic series that M represents and alicyclic carboxylic acid salt, and molecular weight is from 225 to about 365, except the M group, R ' is the alkyl of 14～23 carbon atoms, M is 1 or the basic metal or the alkaline earth metal cation of divalent, y is 1 or 2 integer, and wherein the total amount of one or more ionic surface active agents is based on the about 0.1wt% of being not less than of emulsion gross weight and is not more than about 5wt%; Emulsion embodies and to be characterized as oily external phase emulsion, wherein has less than the specific conductivity of the little Siemens/cm of Z with less than the viscosity of 40 centistokes when emulsion when use temperature is tested, and wherein Z is with previously defined identical.
13. the emulsion of claim 12, wherein one or more organic solvents are fatty alcohol, aliphatic ester, aliphatic hydrocrbon, chloro aliphatic hydrocrbon, aromatic hydrocarbon, aliphatic diester, aliphatic ketone, aliphatic ether, aklylene glycol monoether, alkylidene diol bisether, alkylene glycol ether acetic ester or their mixture.
14. the emulsion of claim 12 or 13, wherein the amount of one or more organic solvents is for being not less than 8wt% and being not more than 25wt%.
15. each emulsion of claim 12-14, wherein the amount of water is for being not less than about 70wt% and being not more than about 90wt%.
16. each emulsion of claim 12-15, wherein anion surfactant has and is not more than about 345 molecular weight.
17. each emulsion of claim 12-16, wherein anion surfactant has and is not less than 250 molecular weight.
18. the emulsion of claim 17 wherein has at least a other anion surfactant, has general formula R
xB-SO
3M, wherein R represents alkyl, x is 1 or 2, when x is 1 B be divalent group or when x is 2 B be the trivalent group, its derive from aromatic group and wherein M represent the cation balance ion, and R wherein
xIn the carbon sum be from 18～30.
19. each emulsion of claim 12-18, wherein specific conductivity is less than the little Siemens/cm of 0.5Z.
20. each emulsion of claim 12-19, its medium viscosity is less than 20 centistokes.
21. each emulsion of claim 12-20, wherein specific conductivity is less than the little Siemens/cm of 0.25Z.
22. each emulsion of claim 12-21, wherein at least a organic solvent is the aklylene glycol monoether.
23. each emulsion of claim 12-22, wherein the amount of water is for being not less than about 80wt% and being not more than about 90wt%.
24. cleaning concentrate, it can form each microemulsion of claim 1-11 when dilute with water, it comprises: the mixture of an A. organic solvent or two or more organic solvents, wherein the mixture of organic solvent or organic solvent embodies and is characterized as: under the situation that does not have tensio-active agent or other additive, when organic solvent is in the water saturation state, contain the water of no more than 2wt% in the time of its 25 ℃; At least be partially dissolved in one or more anion surfactants in one or more organic solvents with B., wherein at least a this anion surfactant be selected from by general formula (R '-COO)
yAliphatic series that M represents and alicyclic carboxylic acid salt, and molecular weight is from 225 to about 365, except the M group, R ' is the alkyl of 14～23 carbon atoms, M is 1 or the basic metal or the alkaline earth metal cation of divalent, y is 1 or 2 integer, and wherein the amount of one or more anion surfactants is based on the about 0.1wt% of being not less than of microemulsion gross weight and is not more than about 10wt%.
25. one kind is used for the method that clean surface has the metal of lubricating grease or oily dirt, comprise each microemulsion or each emulsion of claim 12-23 of claim 1-11 is applied on the metal that the surface has lubricating grease or oily dirt, to remove from the metallic surface to small part lubricating grease or oily dirt.
26. the microemulsion of claim 1 or the emulsion of claim 12, the carboxylate salt of wherein getting rid of M has the molecular weight between 250～345, the valence state of M be 1 and y be integer 1.
27. the microemulsion of claim 26 or emulsion, the carboxylic acid that wherein derives carboxylate salt is selected from erucic acid, oleic acid and stearic acid.
28. but disturbance composition, comprise: the mixture of a component A. organic solvent or two or more organic solvents, wherein the mixture of organic solvent or organic solvent embodies and is characterized as: under the situation that does not have tensio-active agent or other additive, when organic solvent is in the water saturation state, contain the water of no more than 2wt% in the time of its 25 ℃; And B component. be partially dissolved in one or more anion surfactants among the component A at least, wherein at least a anion surfactant be selected from by general formula (R '-COO)
yAliphatic series that M represents and alicyclic carboxylic acid salt, R ' are the alkyl of 14～23 carbon atoms, and M is 1 or the basic metal or the alkaline earth metal cation of divalent, and y is 1 or 2 integer, and the scope that this salt has a molecular weight is from 225～365, except the counterion M; By adding ionogen or low molecular weight hydrocarbon, said composition can form to embody and be characterized as the microemulsion of specific conductivity less than the oily external phase of Z, and this microemulsion comprises: based on the microemulsion gross weight, the amount of water is greater than 45wt% and less than 70wt%; Based on the microemulsion gross weight, the amount of component A. is greater than 15wt% and less than 50wt%; With based on microemulsion gross weight, B component. amount be greater than 0.1wt% and less than 10wt%.
29. the composition of claim 28, wherein component A. is aklylene glycol monoether and alkylidene diol bisether or their mixture.
30. the composition of claim 28, wherein B component. at least a anion surfactant have greater than 250 and less than 345 molecular weight.
31. a method that is used to prepare oily external phase microemulsion comprises that step is as follows:
But step 1. is selected the disturbance composition of claim 28,
Step 2. adds salt or other ionogen in said composition, present in an amount at least sufficient to cause said composition to be transformed into the oily external phase microemulsion of specific conductivity less than Z.
32. the method for claim 31, wherein one or more organic solvents of composition are aklylene glycol monoether, alkylidene diol bisether or their mixture.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2266496P | 1996-07-26 | 1996-07-26 | |
| US60/022,664 | 2008-01-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1199430A true CN1199430A (en) | 1998-11-18 |
Family
ID=21810780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97191142A Pending CN1199430A (en) | 1996-07-26 | 1997-07-24 | High water content, low viscosity, oil continuous microemulsions and emulsions, and their use in cleaning applications |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0866889B1 (en) |
| JP (1) | JPH11513077A (en) |
| KR (1) | KR19990063712A (en) |
| CN (1) | CN1199430A (en) |
| AU (1) | AU711474B2 (en) |
| BR (1) | BR9702359A (en) |
| CA (1) | CA2232976A1 (en) |
| DE (1) | DE69708459T2 (en) |
| ES (1) | ES2163188T3 (en) |
| WO (1) | WO1998004761A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101948682A (en) * | 2010-08-20 | 2011-01-19 | 中国石油天然气股份有限公司 | Oil well anti-eccentric wearing, corrosion-inhibiting and scale-removing agent with reversed phase accumulation |
| CN108817059A (en) * | 2018-07-19 | 2018-11-16 | 昆明理工大学 | A method of utilizing microemulsion renovation of organic pollution soil |
| CN110144594A (en) * | 2019-06-18 | 2019-08-20 | 雅思汀娜（北京）科技有限公司 | A kind of detergent and its preparation method and application |
| CN114258426A (en) * | 2019-08-21 | 2022-03-29 | 横浜油脂工业株式会社 | Good-applicability foaming cleaning agent for car washer of water-repellent coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19920907A1 (en) * | 1999-05-06 | 2000-11-09 | Basf Ag | Preparation of cyclohexylglycine ester derivatives comprises reacting cyclohexylglycine derivatives with methanesulfonic acid and benzyl alcohol derivative in organic solvent |
| DE19951635A1 (en) * | 1999-10-26 | 2001-05-17 | Henkel Kgaa | Aqueous multiphase detergent |
| NO20001693L (en) * | 2000-03-31 | 2001-10-02 | Bj Services As | Method and washing liquid for use in well washing and subsequent treatment of the used washing liquid, as well as the use of a special liquid mixture |
| JP4801841B2 (en) * | 2001-02-19 | 2011-10-26 | 東レ東燃機能膜合同会社 | Method for cleaning thermoplastic resin microporous membrane and method for producing thermoplastic resin microporous membrane using the same |
| KR100779296B1 (en) * | 2001-12-12 | 2007-11-27 | 애경산업(주) | Oil-in-water microemulsion type detergent compositions containning aliphatic hydrocarbon oil |
| DE10206795A1 (en) * | 2002-02-19 | 2003-08-28 | Beiersdorf Ag | Two-phase cosmetic or dermatological compositions useful as sunscreen, artificial tanning or insect repellent products comprise a microemulsion phase and a lipophilic phase |
| US6878184B1 (en) | 2002-08-09 | 2005-04-12 | Kovio, Inc. | Nanoparticle synthesis and the formation of inks therefrom |
| US7078276B1 (en) | 2003-01-08 | 2006-07-18 | Kovio, Inc. | Nanoparticles and method for making the same |
| US7547670B2 (en) * | 2005-10-25 | 2009-06-16 | Cognis Ip Management Gmbh | Low odor ester-based microemulsions for cleaning hard surfaces |
| JP2014151295A (en) * | 2013-02-13 | 2014-08-25 | Harutoshi Nishikido | W/o-type emulsion manufacturing method and emulsion manufacturing apparatus |
| DE102014202990A1 (en) * | 2014-02-19 | 2015-08-20 | Henkel Ag & Co. Kgaa | concentrates |
| JP2017031326A (en) * | 2015-07-31 | 2017-02-09 | Ｊｘエネルギー株式会社 | Method for evaluating detergency of w/o microemulsion-type detergent, cleaning method by w/o microemulsion-type detergent, and method for forming film |
| EP3170884A1 (en) * | 2015-11-20 | 2017-05-24 | The Procter and Gamble Company | Alcohols in liquid cleaning compositions to remove stains from surfaces |
| UY37323A (en) | 2016-07-12 | 2018-02-28 | Monsanto Technology Llc | PESTICIDED MICROEMULSIONS |
| EP3399013B1 (en) | 2017-05-05 | 2022-08-03 | The Procter & Gamble Company | Laundry detergent compositions with improved grease removal |
| EP3399012A1 (en) | 2017-05-05 | 2018-11-07 | The Procter & Gamble Company | Liquid detergent compositions with improved rheology |
| WO2021033717A1 (en) * | 2019-08-21 | 2021-02-25 | 横浜油脂工業株式会社 | Foamable cleaning agent for car-washing machine and highly compatible with water-repellent coating |
| CN110387245B (en) * | 2019-08-28 | 2021-06-08 | 浙江海洋大学 | Diesel oil contaminated soil remediation method based on conductivity |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3723330A (en) * | 1970-10-05 | 1973-03-27 | Tri D Corp | Detergent composition |
| DE3469037D1 (en) * | 1983-08-11 | 1988-03-03 | Procter & Gamble | Liquid detergents with solvent |
| US5171475A (en) * | 1990-10-25 | 1992-12-15 | Penetone Corporation | Soil-removal microemulsion compositions |
| CA2120375A1 (en) * | 1993-04-02 | 1994-10-03 | John Klier | A laundry pretreater having enhanced oily soil removal |
| AU6528694A (en) * | 1993-04-02 | 1994-10-24 | Dow Chemical Company, The | Microemulsion and emulsion cleaning compositions |
| US5462690A (en) * | 1994-09-09 | 1995-10-31 | Colgate-Palmolive Co. | Liquid cleaning compositions |
-
1997
- 1997-07-24 BR BR9702359A patent/BR9702359A/en unknown
- 1997-07-24 KR KR1019980702179A patent/KR19990063712A/en not_active Application Discontinuation
- 1997-07-24 WO PCT/US1997/013145 patent/WO1998004761A1/en not_active Application Discontinuation
- 1997-07-24 CN CN97191142A patent/CN1199430A/en active Pending
- 1997-07-24 EP EP97935130A patent/EP0866889B1/en not_active Expired - Lifetime
- 1997-07-24 AU AU38147/97A patent/AU711474B2/en not_active Ceased
- 1997-07-24 DE DE69708459T patent/DE69708459T2/en not_active Expired - Lifetime
- 1997-07-24 ES ES97935130T patent/ES2163188T3/en not_active Expired - Lifetime
- 1997-07-24 JP JP10509025A patent/JPH11513077A/en active Pending
- 1997-07-24 CA CA002232976A patent/CA2232976A1/en not_active Abandoned
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948682A (en) * | 2010-08-20 | 2011-01-19 | 中国石油天然气股份有限公司 | Oil well anti-eccentric wearing, corrosion-inhibiting and scale-removing agent with reversed phase accumulation |
| CN101948682B (en) * | 2010-08-20 | 2012-12-12 | 中国石油天然气股份有限公司 | Oil well anti-eccentric wearing, corrosion-inhibiting and scale-removing agent with reversed phase accumulation |
| CN108817059A (en) * | 2018-07-19 | 2018-11-16 | 昆明理工大学 | A method of utilizing microemulsion renovation of organic pollution soil |
| CN110144594A (en) * | 2019-06-18 | 2019-08-20 | 雅思汀娜（北京）科技有限公司 | A kind of detergent and its preparation method and application |
| CN114258426A (en) * | 2019-08-21 | 2022-03-29 | 横浜油脂工业株式会社 | Good-applicability foaming cleaning agent for car washer of water-repellent coating |
Also Published As
| Publication number | Publication date |
|---|---|
| KR19990063712A (en) | 1999-07-26 |
| WO1998004761A1 (en) | 1998-02-05 |
| DE69708459T2 (en) | 2002-05-23 |
| CA2232976A1 (en) | 1998-02-05 |
| JPH11513077A (en) | 1999-11-09 |
| AU711474B2 (en) | 1999-10-14 |
| BR9702359A (en) | 1999-07-20 |
| AU3814797A (en) | 1998-02-20 |
| DE69708459D1 (en) | 2002-01-03 |
| EP0866889B1 (en) | 2001-11-21 |
| MX9802355A (en) | 1998-08-30 |
| EP0866889A1 (en) | 1998-09-30 |
| ES2163188T3 (en) | 2002-01-16 |
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