EP1000138A1 - Aqueous microemulsions - Google Patents
Aqueous microemulsionsInfo
- Publication number
- EP1000138A1 EP1000138A1 EP98938097A EP98938097A EP1000138A1 EP 1000138 A1 EP1000138 A1 EP 1000138A1 EP 98938097 A EP98938097 A EP 98938097A EP 98938097 A EP98938097 A EP 98938097A EP 1000138 A1 EP1000138 A1 EP 1000138A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- microemulsion
- esters
- group
- mixtures
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
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- 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
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- 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
- C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
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- 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
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- 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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
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- 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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
- C11D3/2044—Dihydric alcohols linear
-
- 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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
- C11D3/2048—Dihydric alcohols branched
Definitions
- the present invention relates to microemulsions which remain stable when mixed with a variety of organic solvents and thickening agents making them particularly useful in cleaning applications involving the removal of grease, oils, paint films and other difficult to remove organic materials.
- U.S. Pat. No.'s 5,080,831 and 5,080,822 teach true solutions of non-hydrocarbon and non-hydrogenated hydrocarbon organic solvents having water solubilities of from 0.2 to 6% in a combination of water and a solubilizer .
- U.S. Pat. No. 5,158,710 teaches a microemulsion of non-hydrocarbon and non-hydrogenated hydrocarbon organic solvents having water solubilities of from 0.2 to 6% with a solubilizing additive, a builder and optionally a coupler.
- the builder is a material that enhances the cleaning efficiency of the surfactant by inactivating water hardness, supplying alkalinity to assist in cleaning and buffering the pH of the composition so that it remains above 7.
- Microemulsions have properties that make them attractive for consideration in the formulation of cleaning products.
- the object of the present invention is to provide a microemulsion characterized in that it has a wide range of compositional and thermal stabilities and that can, without loss of identity as a microemulsion, be combined with solvents and additives for formulation into various cleaning compositions.
- the present invention provides a microemulsion comprising:
- the diol of preference is 1,2- hexanediol and the preferred surfactant is sodium bis (2-ethylhexyl) sulfosuccinate.
- the microemulsion of the present invention may further comprise an organic solvent, the organic solvent being mixed with the microemulsion to form a mixture wherein the weight ratio of microemulsion to organic solvent is such that the mixture is a microemulsion .
- the present invention provides cleaning compositions formulated from the microemulsion alone or the microemulsion mixed with an organic solvent (s) and/or other additives.
- an organic solvent s
- the microemulsion retains its stability.
- Figure 1 shows a pseudo ternary phase diagram representing a microemulsion of the present invention where the weight ratio of surfactant to diol is 50/50.
- Figure 2 shows a plot of the sum of the weight percent of surfactant plus diol as a function of ⁇ at ⁇ equal to 50 and a temperature of 10°C.
- microemulsion means a single phase, microstructured equilibrium mixture of at least three components. Two of the three components of the microemulsion are sparingly soluble one in the other, for example oil and water or oil and a polar solvent .
- the third component is a substance which functions to solubilize one of the first two in the other, for example oil in water or water in oil.
- the third component may be an amphiphile, that is a molecule containing both hydrophilic and lipophilic moieties.
- a microemulsion appears clear to the eye, but it is not a solution.
- a microemulsion may be stable over a wide range of temperatures and concentrations with no loss in function or stability.
- microemulsions may be distinguished from solutions in that they are microstructured and may contain "oil” -swollen micelles, a bi-continuous structure, water-swollen inverse micelles or other structures depending on the amount of "oil” in the system. True solutions show none of these microstructural characteristics.
- oil as used in the definition above means the organic, non- surfactant, component of the microemulsion.
- microemulsions may show Tyndall scattering and have low interfacial tensions.
- a microemulsion is not an emulsion, and is distinguished from an emulsion in that the microemulsion is thermodynamically stable, that is at its lowest energy state, while an emulsion is only kinetically stable, that is the rate at which the emulsified phase is separating from the water is very slow. Although an emulsion may be stable for days, months or even longer, it will become unstable with time and separate into a layered mixture.
- Microemulsions have the following identifying characteristics: they are easily prepared by gentle mixing or shaking the components together; they are thermodynamically stable and will not separate into separate phases or settle out, as long as they retain their chemical identity, without some change in temperature; and if they become unstable because of a change in the temperature, the microemulsion is easily restored by heating or cooling the mixture until it is again at a temperature within the range of the microemulsion' s thermodynamic stability.
- microemulsion generally involves the two mutually insoluble or sparingly soluble substances and a surfactant or surfactant/co- surfactant mixture.
- the formation of a microemulsion may be proved by any one of the following test methods: Tyndall scattering, dynamic light scattering, X-ray scattering, and small angle neutron scattering; all well known scattering techniques.
- Other important methods include conductivity, NMR and fluorescence techniques described in Surfactant Solutions, New
- surfactant means a surface active substance of an anionic, cationic or nonionic type which lowers the surface tension of water.
- functionalized hydrocarbon means a hydrocarbon molecule having substituted for at least one hydrogen, or in the case of heterocyclic compounds substitution for at least one carbon, a group containing at least one non-carbon atom, at least one non-hydrogen atom or non-halogen atoms.
- Such groups include those having oxygen, nitrogen, sulfur, and/or phosphorous atoms present, for example, acids, esters, ethers, amines, amides, ketones, nitriles, nitro functional organic compounds, aldehydes, alcohols, organic carbonates, organic phosphates, organic sulfoxide and heterocyclic compounds having oxygen or nitrogen incorporated into the ring structure .
- Preferred functionalized hydrocarbons which form the microemulsions of the present invention include esters, diesters, triesters, tetraesters, acetates and diacetates, and lactones . Of these, the functionalized hydrocarbons preferred for formulating cleaning compositions are the dibasic esters.
- the functionalized hydrocarbon of the present invention is sparingly soluble in water.
- sparingly soluble is meant that the solubility of the functionalized hydrocarbon in water is less than 10% by weight, and conversely the solubility of water in the functionalized hydrocarbon is less than 10% by weight.
- Surfactants useful in the microemulsions of the present invention are anionic sulfosuccinates .
- Preferred surfactants are sodium salts of bis (2- ethylhexyl) sulfosuccinate, (bEHSs) , di (1, 3-dimethyl- butyl) -sulfosuccinate, and diamylsulfo-succinate .
- These surfactants are available commercially neat or in solution form (in alcohol or water) under the AEROSOL trademark of Cytec, Inc. of West Patterson, NJ as AEROSOL-OT (AOT) or AEROSOL-GPG, AEROSOL-MA-80 (MA-80) and AEROSOL-AY (AY) , respectively.
- MACKANATE DOS-75 Another source of surfactant is MACKANATE DOS-75 (MACKANATE is a trademark of the Mclntyre Group Ltd. of University Park, IL, and the DOS-75 product is a mixture of sodium bis (2-ethylhexyl) sulfosuccinate, water, ethanol and propylene glycol) .
- bEHSs is most preferred followed in order by sodium diamylsulfosuccinate and sodium di (1, 3-dimethylbutyl) - sulfosuccinate .
- Diols useful in the present invention are those diols having from 2 to 10 carbons and preferably having the OH groups present in the 1,2 positions.
- the diols may be linear or branched and include a functionality in addition to the OH groups.
- Useful diols include 1, 2-butanediol, 1, 2-pentanediol, hexanediols, octanediols, 1, 2 , 3-propanetriol monoacetate, heptanediols, decanediols, neopentyl glycol, 2-methyl-2 , 4-pentanediol (commonly known as hexylene glycol) and 2-methyl-l, 3-propanediol .
- the function of the diol in the present invention is particularly surprising in the case of 1, 2-hexanediol and bEHSs since the corresponding alcohol, hexanol, shows no synergy in combination with the surfactants of the present invention.
- synergy does exist between the lower chain alcohols and the surfactant. This is of particular importance since many commercially available surfactants are sold as solutions in lower chain alcohols.
- microemulsions of the present invention provide a microemulsion having a greater range of thermal stability at a lower concentration of surfactant.
- Practical microemulsions of the present invention may be formulated at lower levels of volatile organic content (VOC) and at higher flash points than known solution or emulsion products. This is of particular interest when the microemulsion is used in formulating cleaning compositions.
- VOC volatile organic content
- These microemulsions are stable over the temperature range of from at least 5°C to a temperature of about 100°C.
- An important advantage of the microemulsions of the present invention are that they may be diluted with organic solvents without loss of function or stability, that is the mixture of the microemulsion and the solvent is also a microemulsion.
- Organic solvents that may be used in diluting the microemulsions of the present invention are solvents selected from the group consisting of alcohols, ketones, esters, acyclic amides, cyclic amides, glycol ethers, acetates, glycol ether acetates, lactones, sulfoxides, cyclic carbonates, aromatic hydrocarbons, terpenes, N-methylpyrrolidone and other N-alkyl pyrrolidones, dimethylpiperidone, dipropylene glycol monomethyl ether, propylene carbonate, alkylbenzenes , d-limonene and mixtures of any combination of these compounds.
- Preferred organic solvents include N-methylpyrrolidone; dimethyl piperidone; ethylene and propylene glycol based ethers and their esters, such as propylene glycol methyl ether acetate; propylene carbonate; alkyl acetates such as those sold under the EXXATE trademark of EXXON
- the functionalized hydrocarbons of the present invention include dibasic esters preferably those esters of adipic, glutaric and succinic acids and alcohols having from 1 to 12 carbons and mixtures of these esters.
- dibasic esters preferably those esters of adipic, glutaric and succinic acids and alcohols having from 1 to 12 carbons and mixtures of these esters.
- Dimethyl adipate, dimethyl glutarate, dimethyl succinate are sold individually and as mixtures under the DBE product name by E.I. DuPont de Nemours , Inc . , located in
- DBE mixtures include DBE, a mixture of each of the three esters with the major component being dimethyl glutarate; DBE-2, a mixture of dimethyl adipate in dimethyl glutarate; DBE-3, a mixture of dimethyl glutarate in dimethyl adipate; DBE-4, dimethyl succinate; DBE-5 dimethyl glutarate; DBE-6, dimethyl adipate; DBE-9 dimethyl glutarate in dimethyl succinate, and DBE-IB, a mixture of diisobutyl esters adipate, glutarate and succinate.
- the microemulsions of the present invention are of particular interest in the formulation of cleaning compositions and especially those containing the dibasic esters.
- Microemulsions offer advantages as cleaning compositions over solutions and two phase emulsions. Microemulsions have greater stability and the unique property in the ease of re-forming with heating or cooling if the microemulsion is broken due to changes in storage temperatures. Microemulsions may have better cleaning power than emulsions or solutions in given situations and may be formulated at lower VOC and sometimes lower costs than true solutions.
- Cleaning applications for which the microemulsions of the present invention are of use include metal cleaning, degreasing and paint stripping.
- cleaning composition includes, for example, compositions for degreasing and paint stripping.
- a cleaning composition of the present invention may be formulated by mixing the microemulsion of the present invention with a organic solvent and optionally a thickener.
- Thickeners that may be used in this formulation include unmodified and hydrophobically modified cationic cellulose ether polymers, polyurethanes and polyacrylic acids and polyacrylics .
- Inorganic thickeners may also be used.
- layered hydrous magnesium silicates sold as LAPONITE, a trademark of Southern Clay Products of Gonzales, TX is useful in the present invention.
- a preferred organic thickener is a polyacrylic acid thickener sold under the B.F. Goodrich trademark PEMULEN.
- Useful diols in the formulating of cleaning compositions are 2 -methyl- 1,3- propanediol, 2-methyl-2 , 4-pentanediol and neopentyl glycol .
- Phase boundary determination and construction of the phase diagrams Samples were prepared by individually weighing the water (A) , DBE (B) , bEHSs (C) , and C n -diol (D) into graduated cylinders having sealable closures and magnetic stirring bars. The samples were sealed, and the graduated cylinders were placed in a constant temperature bath(s) . Samples were then equilibrated in constant-temperature baths to within ⁇ 0.05°C of the desired temperature. While the samples were coming to thermal equilibrium, they were stirred using the stirring bars to agitate the mixtures .
- phase boundary was determined ⁇ 0.1°C, and the numerical average of the temperature before and after the phase boundary crossed was used as the boundary point .
- the present invention is illustrated by the following non-limiting examples.
- Figure 1 shows the microemulsion of the present invention at 20°C for a composition containing water, DBE-5 and a mixture of bEHSs and 1 , 2 , hexanediol at a weight ratio of 50:50.
- the region of the microemulsion is the larger shaded portion of the pseudo ternary phase diagram.
- Microemulsions of the present invention are stable over a wide temperature range .
- microemulsions may be formulated having stabilities over the entire temperature range of from about 5 to about 100°C or having stabilities within any range of temperatures between about 5 and 100°C.
- the temperature range is limited to 5 to 100°C only at atmospheric pressure. At higher pressures, the range of stability of the microemulsion is extended beyond this temperature range at both the upper and the lower temperature limits.
- the region of the microemulsion is area marked 1 in the Figure .
- the region of the microemulsion is the area to the right of the plotted phase boundary line.
- Each Figure illustrates the extensive compositional range of the microemulsion of the present invention.
- a particular advantage of the present invention is that one can prepare microemulsions consisting of equal fractions of functionalized hydrocarbon and water making these microemulsions suitable for a variety of different applications.
- Formulations that is mixtures of the microemulsions with organic solvents and/or other additives, formed from the microemulsion of the present invention can be used as effective replacements for organic solvents in applications such as paint stripping, degreasing, resin clean-up, aircraft and vehicle cleaning, electronic cleaning and other general cleaning applications.
- Suitable diols for use in the present invention include those having from 2 to 10 carbon atoms, for example 1, 2-butanediol (BD) , 1,2- pentanediol (PD) , 1, 2-octanediol and 2-methyl-l, 3- propanediol .
- BD 2-butanediol
- PD pentanediol
- 2-octanediol 2-methyl-l
- 2-methyl-l 3- propanediol
- the preferred diol is 1,2- hexanediol, but in specific cleaning formulations other diols may be preferred over the hexanediol .
- This example illustrates a microemulsion containing water, DBE-5, 1, 2-hexanediol and several commercial surfactants .
- AY65 is a mixture of sodium diamylsulfosuccinate, water, ethanol and methanol . It was of interest to understand if the synergistic effect of the diol would be effected by the presence of the alcohol, especially ethanol since ethanol is a common diluent found in commercial surfactants. It was found that presence of ethanol in the commercial surfactant decreases the amount of hexanediol needed to form the microemulsion.
- GPG surfactant composed of sodium di(2- ethylhexyl) sulfosuccinate (66-72%) , ethanol (7-9%) and water (19-27%) , sold by Cytec under the trademark GPG was tested in the microemulsions of the present invention. Again the microemulsions showed were acceptable over the temperature range of 5 to 100 °C and were readily diluted by "oil” or water to form microemulsions having a broad range of compositions.
- This example illustrates the use of a thickener in the microemulsion of the present invention.
- the microemulsion made according to Example 1 was mixed with about 1% by weight of JR-400, an unmodified cationic cellulose ether polymer available as UCARE from Amerchol Corporation of Edison, New Jersey.
- JR-400 an unmodified cationic cellulose ether polymer available as UCARE from Amerchol Corporation of Edison, New Jersey.
- the additions of the thickener were below 1.25%, the mixture remained a clear single phase microemulsion.
- a viscous emulsion was formed.
- the 1% JR-400 by weight thickened microemulsions had a zero shear viscosity of 0.2 Pa-s (200 times more viscous than water) measured using a Rheometrics Dynamic Stress Model SR500 rheometer .
- Example 4 This example illustrates the addition of various organic solvents to the microemulsion.
- Base microemulsions were made by mixing 3.9 g of DBE, 1.2 g of Aerosol-OT, 3.9 g water, 0.5 g ethanol and 0.5 g 1, 2-hexanediol .
- the mixtures with solvent formed a single phase and were stable microemulsions over the range of 5 to 100°C.
- the microemulsion formed including Aromatic 150 was stable from 20 to 75°C. At temperatures below 20°C, phase separation occurred.
- Aromatic 150 1 20-75
- This example illustrates the utility of the microemulsion of the present invention in paint stripping.
- the microemulsion was formed by mixing a DBE, water, surfactant and diol to give the following composition by weight: 37.5% DBE, 37.5% water, 15% sodium bis (2 -ethylhexyl) sulfosuccinate and 10% 2-methyl-1,3 -propanediol .
- a small amount (2-3 mL) of this microemulsion was placed on pine boards with the following surfaces for 60 minutes at 25°C: a) Marine Paint in three fully cured layers, a primer coating formed from Pettit Specialty Fiberglass
- This example illustrates a degreasing composition using the microemulsion of the present invention.
- This example illustrates another degreasing formulation using the microemulsion of the present invention.
- the formulation was made as described below and tested as described in Example 6. Data shown below is for the weight removed by the formulation.
- the weight removed by water is the same as shown in the table in Example 6.
- a microemulsion was prepared from 115.5 g DBE, 115.6 g water, 77.0 g d-limonene, 46.2 g sodium bis (2- ethylhexyl) sulfosuccinate, and 30.8 g 2 -methyl-1, 3- propanediol .
- This Example illustrates the utility of neopentyl glycol in a microemulsion of the present invention.
- a microemulsion was formed by mixing 56.4 grams of DBE, 30 grams of MACKANATE DOS-75 (MACKANATE is a trademark of the Mclntyre Group Ltd. of University Park, IL; the DOS- 75 product is a mixture of sodium bis (2-ethylhexyl) sulfo- succinate, water, ethanol and propylene glycol), 13.5 grams of neopentyl glycol and 50.4 grams of water. The components mixed together easily with stirring to form a clear microemulsion .
- Example 9 This Example illustrates the utility of 2 -methyl-
- 4-pentanediol (commonly known as hexylene glycol) as the diol in a microemulsion of the present invention.
- a microemulsion was prepared from mixing together 4.0 grams of DBE 1.0 gram of MACKANATE DOS-75, 1.0 gram of 2-methyl-2 , 4-pentanediol, and 4 grams of water. The components mixed together easily with stirring to form a clear microemulsion.
- Example 10 This Example illustrates the utility of PEMULEN, a polyacrylic acid, in thickening the microemulsions of the present invention.
- PEMULEN is a trademark of the B.F. Goodrich Company of Cleveland, OH.
- a microemulsion was prepared by mixing 3.36 grams of DBE, 1.0 grams of NMP, 1,79 grams of MACKANATE DOS-75, 0.81 grams of neopentyl glycol and 3 grams of water. To this microemulsion was added 0.3 grams of PEMULEN 1622. The resulting combination was stirred vigorously using a magnetic stirrer until it became uniform, clear and extremely viscous. Approximately 2 grams of this thickened formulation was placed on a vertical surface and observed for a period of 60 minutes. During the observation time the formulation remained in its original position on the surface without showing any evidence of downward flow.
- This Example shows the use of the formulation of Example 10 in paint stripping.
- Example 10 A portion of the Example 10 formulation was placed on a pine board which was coated with Marine paint as described in Example 5. The board was held vertically for 60 minutes, the sample of the formulation was then removed by gently scraping the surface of the board with a flat metal spatula.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- Health & Medical Sciences (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
- Colloid Chemistry (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
Abstract
Description
Claims
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
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US90416697A | 1997-07-31 | 1997-07-31 | |
US904166 | 1997-07-31 | ||
US50307 | 1998-03-30 | ||
US09/050,307 US6165962A (en) | 1997-07-31 | 1998-03-30 | Aqueous microemulsions |
PCT/US1998/015744 WO1999006520A1 (en) | 1997-07-31 | 1998-07-30 | Aqueous microemulsions |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1000138A1 true EP1000138A1 (en) | 2000-05-17 |
EP1000138B1 EP1000138B1 (en) | 2003-09-17 |
Family
ID=26728132
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98938097A Expired - Lifetime EP1000138B1 (en) | 1997-07-31 | 1998-07-30 | Aqueous microemulsions |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP1000138B1 (en) |
JP (1) | JP4271366B2 (en) |
AT (1) | ATE250119T1 (en) |
AU (1) | AU740364B2 (en) |
BR (1) | BR9810847A (en) |
DE (1) | DE69818271T2 (en) |
DK (1) | DK1000138T3 (en) |
ES (1) | ES2202881T3 (en) |
PT (1) | PT1000138E (en) |
WO (1) | WO1999006520A1 (en) |
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FR2795088B1 (en) * | 1999-06-21 | 2002-05-24 | Atofina | COLD CLEANING COMPOSITIONS OF THE MICROEMULSION TYPE |
US6511952B1 (en) | 2000-06-12 | 2003-01-28 | Arco Chemical Technology, L.P. | Use of 2-methyl-1, 3-propanediol and polycarboxylate builders in laundry detergents |
US6624128B1 (en) | 2001-03-30 | 2003-09-23 | Dixie Chemical Company | Water miscible composition containing a carboxylic acid diester and a fatty acid salt |
KR100779296B1 (en) * | 2001-12-12 | 2007-11-27 | 애경산업(주) | Oil-in-water microemulsion type detergent compositions containning aliphatic hydrocarbon oil |
JP4629354B2 (en) * | 2004-02-25 | 2011-02-09 | 三洋化成工業株式会社 | Surfactant composition |
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GB0605157D0 (en) * | 2006-03-15 | 2006-04-26 | Gramos Applied Ltd | Decontaminant formulations |
JP5066881B2 (en) | 2006-09-27 | 2012-11-07 | 住友化学株式会社 | Emulsion composition |
EP2045320B1 (en) * | 2007-09-19 | 2012-04-25 | Bubbles & Beyond Gmbh | Cleaning agent for removing paint layers on surfaces, method for manufacturing the agent and cleaning method |
JP5256749B2 (en) | 2008-01-23 | 2013-08-07 | 住友化学株式会社 | Emulsion composition |
JP5262131B2 (en) | 2008-01-24 | 2013-08-14 | 住友化学株式会社 | Emulsion composition |
JP2009173578A (en) | 2008-01-24 | 2009-08-06 | Sumitomo Chemical Co Ltd | Emulsion composition |
DE102009013469B4 (en) * | 2009-03-19 | 2014-04-17 | Bubbles And Beyond Gmbh | Preparation for external use |
DE102009014380A1 (en) | 2009-03-26 | 2010-10-07 | Bubbles And Beyond Gmbh | Method and composition for cleaning objects |
EP2491102A2 (en) * | 2009-10-19 | 2012-08-29 | Rhodia Operations | Auto-emulsifying cleaning systems and methods for use |
CN102655930B (en) * | 2009-12-15 | 2014-12-24 | 因温斯特技术公司 | Emulsion compositions and a method for selecting surfactants |
US9109191B2 (en) | 2009-12-15 | 2015-08-18 | Invista North America S.A.R.L. | Emulsion compositions and a method for selecting surfactants |
US20130146545A1 (en) * | 2010-06-02 | 2013-06-13 | Rhodia Operations | Use of eco-friendly microemulsions in oil cleaning applications |
US8569218B2 (en) * | 2011-03-07 | 2013-10-29 | Illinois Tool Works, Inc. | Cleaning composition containing polymer microemulsion |
JP6199013B2 (en) * | 2012-07-19 | 2017-09-20 | 株式会社トクヤマMetel | Cleaning agent and cleaning method |
DE102018123858A1 (en) * | 2018-09-27 | 2020-04-02 | BÜFA GmbH & Co. KG | Solvent and application for a solvent |
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US2606874A (en) * | 1947-06-23 | 1952-08-12 | Shell Dev | Water in oil emulsions containing 1, 2-alkanediols as coupling agents |
US4781848A (en) * | 1987-05-21 | 1988-11-01 | Aluminum Company Of America | Metalworking lubricant comprising an oil-in-water microemulsion |
US4927556A (en) * | 1987-06-04 | 1990-05-22 | Minnesota Mining And Manufacturing Company | Aqueous based composition containing dibasic ester and thickening agent for removing coatings |
US4934391A (en) * | 1988-02-08 | 1990-06-19 | 501 Petroleum Fermentations N.V. | Dibasic esters for cleaning electronic circuits |
US5158710A (en) * | 1989-06-29 | 1992-10-27 | Buckeye International, Inc. | Aqueous cleaner/degreaser microemulsion compositions |
US5080831A (en) * | 1989-06-29 | 1992-01-14 | Buckeye International, Inc. | Aqueous cleaner/degreaser compositions |
US5035826A (en) * | 1989-09-22 | 1991-07-30 | Colgate-Palmolive Company | Liquid crystal detergent composition |
BR9405958A (en) * | 1993-04-02 | 1995-12-12 | Dow Chemical Co | Continuous microemulsion of single phase oil concentrated cleaning emulsion and method for cleaning metal with grease |
US5401326A (en) * | 1993-07-29 | 1995-03-28 | Drew Chemical Corporation | Microemulsion cleansers and their uses |
ES2143030T3 (en) * | 1993-11-12 | 2000-05-01 | Procter & Gamble | LIQUID DETERGENT COMPOSITIONS FOR HARD SURFACES, CONTAINING AMPHOTERO AND PERFUME DETERGENT SURFACTANT. |
US5691289A (en) * | 1994-11-17 | 1997-11-25 | Kay Chemical Company | Cleaning compositions and methods of using the same |
AU3980197A (en) * | 1996-08-14 | 1998-03-06 | Colgate-Palmolive Company, The | Light duty liquid microemulsion cleaning compositions |
-
1998
- 1998-07-30 DE DE69818271T patent/DE69818271T2/en not_active Expired - Lifetime
- 1998-07-30 WO PCT/US1998/015744 patent/WO1999006520A1/en active IP Right Grant
- 1998-07-30 AT AT98938097T patent/ATE250119T1/en active
- 1998-07-30 PT PT98938097T patent/PT1000138E/en unknown
- 1998-07-30 ES ES98938097T patent/ES2202881T3/en not_active Expired - Lifetime
- 1998-07-30 EP EP98938097A patent/EP1000138B1/en not_active Expired - Lifetime
- 1998-07-30 JP JP2000505264A patent/JP4271366B2/en not_active Expired - Fee Related
- 1998-07-30 DK DK98938097T patent/DK1000138T3/en active
- 1998-07-30 AU AU86699/98A patent/AU740364B2/en not_active Ceased
- 1998-07-30 BR BR9810847-6A patent/BR9810847A/en not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
See references of WO9906520A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE69818271T2 (en) | 2004-06-03 |
JP2002501087A (en) | 2002-01-15 |
DE69818271D1 (en) | 2003-10-23 |
DK1000138T3 (en) | 2004-02-02 |
EP1000138B1 (en) | 2003-09-17 |
WO1999006520A1 (en) | 1999-02-11 |
AU740364B2 (en) | 2001-11-01 |
AU8669998A (en) | 1999-02-22 |
JP4271366B2 (en) | 2009-06-03 |
PT1000138E (en) | 2004-01-30 |
ES2202881T3 (en) | 2004-04-01 |
BR9810847A (en) | 2000-07-25 |
ATE250119T1 (en) | 2003-10-15 |
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