WO1993002169A1 - Terpene-based microemulsion cleaning composition - Google Patents
Terpene-based microemulsion cleaning composition Download PDFInfo
- Publication number
- WO1993002169A1 WO1993002169A1 PCT/US1992/005995 US9205995W WO9302169A1 WO 1993002169 A1 WO1993002169 A1 WO 1993002169A1 US 9205995 W US9205995 W US 9205995W WO 9302169 A1 WO9302169 A1 WO 9302169A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- surfactant
- cleaning composition
- weight percent
- group
- general formula
- Prior art date
Links
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
- C11D1/66—Non-ionic compounds
- C11D1/835—Mixtures of non-ionic with cationic compounds
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/835—Mixtures of non-ionic with cationic compounds
- C11D1/8355—Mixtures of non-ionic with cationic compounds containing a combination of non-ionic compounds differently alcoxylised or with different alkylated chains
-
- 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
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
-
- 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
- C11D3/2068—Ethers
-
- 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
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
- C11D1/721—End blocked ethers
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
Definitions
- the present invention relates to aqueous microemulsion cleaning compositions, to a process for their manufacture and the use of such compositions in cleaning applications. More particularly, the present invention relates to aqueous oil-in-water microemulsion cleaning compositions in concentrated or diluted form which, in the absence of any opacifying component, are clear, and which are particularly effective for cleaning oil and greasy soils from hard and flexible substrates, such as metal parts and glass surfaces.
- the cleaning compositions of the present invention comprise four essential or major components; namely, (a) a terpene hydrocarbon solvent; (b) a mixture of non-ionic surfactants including (i) a capped alkylphenol alkoxylate or alkoxylated higher aliphatic alcohol and (ii) a fatty acid alkanolamide; (c) a lower alkyl or phenyl monoether of an aliphatic glycol co-solvent; (d) and water.
- a terpene hydrocarbon solvent e.g., a mixture of non-ionic surfactants including (i) a capped alkylphenol alkoxylate or alkoxylated higher aliphatic alcohol and (ii) a fatty acid alkanolamide; (c) a lower alkyl or phenyl monoether of an aliphatic glycol co-solvent; (d) and water.
- Terpenes are known components of perfume compositions and are often incorporated into detergent compositions at low levels via the perfume. Certain terpenes have also been included in cleaning or detergent compositions at higher levels.
- U.S. Patent 4,336,151 describes a disinfectant/cleaner composition having broad spectrum germicidal activity and reduced eye irritancy by the combined use of a quaternary ammonium compound, non-ionic surfactant, d-limonene, water, and an eye-irritancy reducing compound such as ethoxylated cocodiethanolamide.
- U.S. Patent 4,336,151 describes a disinfectant/cleaner composition having broad spectrum germicidal activity and reduced eye irritancy by the combined use of a quaternary ammonium compound, non-ionic surfactant, d-limonene, water, and an eye-irritancy reducing compound such as ethoxylated cocodiethanolamide.
- Patent 4,414,128 describes liquid detergent compositions for use as hard surface cleaners of 5 1-20% surfactant, 0.5-10% mono- or sesquiterpenes, and 0.5-10% of a polar solvent, e.g., benzyl alcohol, having a solubility in water of from 0.2 to 10%.
- a polar solvent e.g., benzyl alcohol
- Water-in-oil detergent emulsions for use in laundry pre-spotting applications are described in U.S. Patent 4,438,009. These emulsions comprise from 1 to 30% of (a) certain salts, such as sodium citrate, (b) from 1 to 35% of a non-ionic surfactant mixture of (i) a non-ethoxylated sorbitan surfactant, e.g., sorbitan monolaurate, (ii) another non-ionic surfactant, e.g., ethoxylated nonylphenols or ethoxylated primary alcohols, and (iii) an ethoxylated sorbitan surfactant, (c) from 5-60% of a hydrocarbon solvent, which may be d-limonene, and (d) water.
- a non-ethoxylated sorbitan surfactant e.g., sorbitan monolaurate
- another non-ionic surfactant e.g.
- D-limonene-based aqueous cleaning compositions are described in U.S. Patent 4,511,488. Such compositions comprise from 78-96 parts of a d-limonene/surfac- tant/water mixture, 2-10 parts of coupling agent, e.g., glycols and lower alkyl glycol ethers, and 2-12 parts of additives.
- the surfactants used are anionic, non-ionic and mixtures of anionic and non-ionic surfactants.
- U.S. Patent 4,540,505 describes cleanser compositions containing from 0.4 to 1% d-limonene, quaternary ammonium compound, non-ionic surfactant, alkali builder and 4-6% of a monoether of an aliphatic glycol.
- U.S. Patent 4,704,225 (Re. 33,210) describes water-in-oil cleaning emulsion of (a) an oil phase of 95 to 85 parts by volume of an terpene and 5 to 15 parts by volume of a Cg - C]_g fatty acid alkanolamide and (b) from 5 to 8 parts by volume of water ' per part by volume of the oil phase.
- European Patent Application 80,749 describes liquid detergent compositions for use as a hard surface cleaner of terpene, surfactant and 2-(2-butoxyethoxy) ethanol.
- European Patent Application 174,711 describes a biodegradable emulsion for use in removing ink from printing presses of 50-75% d-limonene, 25-50% water, and 1-5% non-ionic surfactant, e.g., nonylphenol ethoxylates and N-substituted fatty acid amides, and 0.5-2% emulsion stabilizer, e.g., polypropylene glycol.
- Stable microemulsion cleaning compositions of synthetic organic (non-ionic/anionic) detergents (5-65%), perfume, e.g., terpenes (2-50%), water (15-85%) and co-surfactant, e.g., monoalkyl ether of a lower glycol (2-50%) are described in European Patent Application 316,726.
- the present invention concerns the discovery of certain terpene-based cleaning compositions in the form of an oil-in-water microemulsion that are particularly suitable for cleaning hard or flexible substrates of soils involving deposits of, for example, oils, grease, dirt, etc.
- the foregoing microemulsions comprise a terpene solvent, a co-solvent of a lower alkyl monoether of an aliphatic glycol, water and a mixture of certain non-ionic surfactants.
- Terpene solvents that may be used to prepare the microemulsions of the present invention are preferably the mono- and bicyclic monoterpenes, i.e., those of the hydrocarbon class, which include, for example, the terpinenes, terpinolenes, limonenes, pinenes and mixtures thereof.
- terpenes include d-limonene, dipentene, alpha-pinene, beta-pinene, the mixture of terpene hydrocarbons obtained from the essence of oranges, e.g., cold-pressed orange terpenes and orange terpene oil phase ex fruit juice, and the mixture of terpene hydrocarbons expressed from lemons and grapefruit.
- the foregoing terpene hydrocarbon solvents are derivatives of pine tree products or citrus by-products and, therefore, are naturally occurring materials. Numerous other terpene hydrocarbons are known to those skilled in the art and may be used to prepare the microemulsions of the present invention; however, those mentioned above are the most readily available and, hence, are preferred.
- auxiliary materials such as stabilizers, e.g., antioxidants such as butylated hydroxytoluene, and such auxiliary materials are included within the meaning of the term "terpene solvent”, as employed in this specification and the accompanying claims.
- D-limonene is highly preferred as the terpene component of the microemulsion. It is derived from distilled orange rind oil and 5 may be obtained in essentially pure form from citrus products companies which produce it as a by-product. An extensive discussion of d-limonene and its derivation from numerous sources is presented in a book by J.W. Kesterson et al entitled Florida Citrus Oil, published in December, 1971 by Agricultural Experiment Station, Institute of Food & Agricultural Sciences, University of Florida, Gainesville, Florida.
- the terpene component is present in the concentrated microemulsion of the present invention in the range of from about 5 to about 20 weight percent, more usually, from about 10 to about 15 weight percent, e.g., about 12 weight percent.
- Corresponding terpene contents for a microemulsion that has been diluted with nine equal parts of water, thereby to form a microemulsion containing 10 percent of the concentrated microemulsion are 0.5-2.0 weight percent, more usually, 1.0-1.5 weight percent, e.g., 1.2 weight percent.
- Another major component of the microemulsion of the present invention is a lower alkyl or phenyl monoether of a C2 or C3 aliphatic glycol, e.g., ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol, or l,5-dihydroxy-2-raethyl pentane.
- This co-solvent material may be selected from materials represented in part by the following general formula,
- R 2 may be selected from lower alkyl, e.g., C ⁇ -C ⁇ alkyl, such as methyl, ethyl, propyl, n-butyl and t-butyl, and phenyl,
- R3 is hydrogen or methyl, w is 0 or 1, and z is a number of from 1 to
- Examples of materials exemplified by general formula I that may be used to prepare the microemulsion of the present invention include, but are not limited to, the monomethyl ethers, monethyl ethers, monobutyl ethers, and the phenyl ethers of monoethylene glycol, diethylene glycol, monopropylene glycol, and dipropylene glycol; the methyl, ethyl and butyl ethers of 2-ethoxy propanol; and the methyl ether of l,5-dihydroxy-2-methyl pentane. Mixtures of such co-solvents may also be used.
- the co-solvent component may be present in the range, of from about 10 to about 35 weight percent, more usually from about 15 to about 25 weight percent, e.g., about 20 weight percent.
- Corresponding contents of the co-solvent for a microemulsion diluted with 9 parts of water so as to form a composition containing 10 percent of the concentrated microemulsion are 1.0-3.5 weight percent, more usually 1.5-2.5 weight, e.g., about 2.0 weight percent.
- the ratio of co-solvent to terpene hydrocarbon will range from about 1.2:1 to about 4.0:1, more usually from about 1.5:1 to 2.0:1.
- a further major component of the microemulsion of the present invention is a mixture of certain non-ionic surfactants.
- the first non-ionic surfactant is a capped alkylphenol alkoxylate and/or higher aliphatic alcohol alkoxylate.
- the second non-ionic surfactant that is a part of the surfactant mixture is a fatty acid alkanolamide.
- Capped alkylphenol alkoxylates that may be used as the first non-ionic surfactant may be represented by the following general formula,
- R is a Cg-C ⁇ 2 , aliphatic group, e.g, Cg-C 10 alkyl, such as octyl, nonyl, decyl, undecyl and dodecyl
- Ph is phenylene
- A is a bivalent alkyleneoxy group selected from the group consisting of propyleneoxy, butyleneoxy and a mixture of propyleneoxy and butyleneoxy groups
- B is selected from the group consisting of benzyl, methyl, ethylchloro and polypropyleneoxy, i.e., CH 2 -CH(CH3)-0-i *t b H
- a is the integer 1 or 2
- b is a number from 3 to 4
- x is a number of from 6 to 20, e.g., 10-16
- y is a number from 0 to 4, e.g., 1-4, such as 2, 3 or 4.
- Examples of capped alkylphenol alkoxylates within the scope of general formula II include the benzyl, methyl and chloro ether of octylphenoxy polyethoxy ethanol containing from about 10 to 16 ethoxy units.
- dioctyl phenoxy 5 polyethoxy ethanols and the nonyl-, decyl- and dodecyl-phenoxy polyethoxy ethanols containing from 10 to 16, e.g., 13 to 16, ethoxy units and capped with a benzyl, methyl, ethylchlorq or polypropyleneoxy group.
- the methyl and benzyl capped alkylphenol alkoxylates may be prepared by the art recognized Williamson synthesis.
- the polypropyleneoxy capped alkylphenol alkoxylates may be prepared by the conventional alkoxylation addition reaction to the hydroxy-terrainated alkylphenol alkoxylate with propylene oxide.
- the chloro capped alkylphenol alkoxylate may be prepared by reacting the hydroxy- terminated precursor with thionyl chloride and decomposing the intermediate chlorosulfite to the organo chloride by means known in the art.
- Alkoxylated higher aliphatic alcohol non-ionic surfactants that may be used in place of (or as partial substitution for) the alkylphenol alkoxylates as the first non-ionic surfactant may be represented by the following general formula,
- R" is a C -C ⁇ 2 linear or branched chain alkyl, preferably a A » x an "i y n general formula III are as defined hereinabove with respect to the alkylphenol alkoxylates of general formula II.
- both the capped alkylphenol alkoxylate and alkoxylated aliphatic alcohol are used in combination as the first non-ionic surfactant, they may be used in a ratio of about 5:1 to 1:5, e.g., 1:1.
- Alkoxylated aliphatic alcohols within the scope of general formula III may be prepared by performing conventional alkoxylation addition reactions on commercially available aliphatic alcohols, which are commonly available as mixtures of alcohols.
- examples of such materials include ethoxylated mixed aliphatic alcohols having from 8 to 10 carbon atoms and 6 to 10 ethoxy units; ethoxylated mixed aliphatic alcohols having from 9 to 11 carbon atoms and 6 to 10 ethoxy units; ethoxylated mixed aliphatic alcohols having from 12 to 15 carbon atoms and 10 to 15 ethoxy units; an ethoxylated C ⁇ 2 aliphatic alcohol having from 10 to 15 ethoxy units; an ethoxylated isodecyl alcohol having from 8 to 10 ethoxy units; and an ethoxylated linear or branched octyl alcohol having from 2 to 10 ethoxy units.
- alkylphenol alkoxylates and alkoxylated aliphatic alcohol non-ionic surfactants may be prepared by condensing the corresponding aliphatic alcohol or alkylphenol with alkylene oxide groups, e.g., ethylene oxide, in a manner known in the art.
- alkylene oxide groups e.g., ethylene oxide
- the value for x in general formulae II and III is the average number of ethoxy groups resulting from the aforesaid condensation, as is known in the art.
- y is other than 0, the aliphatic alcohol or alkylphenol is first condensed with propylene oxide, butylene oxide or a combination of butylene oxide and propylene oxide.
- the resulting alkoxylated alkyl phenol or aliphatic alcohol is then further condensed with ethylene oxide to prepare the precursor to the surfactant material of general formulae II, and the surfactant material of general formula III.
- the resultant product may be a block polymer or random polymer, e.g., first condensing butylene oxide and then propylene oxide or condensing a mixture of butylene oxide and propylene oxide with the alkylphenol or aliphatic alcohol.
- y is other than 0 or 1, the value for y is an average number of alkoxy groups which results from the condensation reaction, as is known in the art.
- A is a mixture of butyleneoxy and propyleneoxy groups
- y represents the total number of butyleneoxy and propyleneoxy groups.
- the second non-ionic surfactant used in the surfactant mixture is a f ty acid alkanolamide, which may be represented by the following gene .1 formula,
- fatty acid alkanolamides examples include 5 cocodiethanolamide (cocoamide DEA), lauramide DEA, soyamide DEA, oleylamide DEA, stearamide DEA, linoleamide DEA, tall oil amide DEA, tallow amide DEA, and stearamide monoethanolamide (stearamide MEA).
- R'-C(O)- of general formula IV is a derivative of a fatty acid or a mixture of fatty acids.
- coconut oil fatty acids are preferred and comprise a mixture of mainly caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and linoleic acid. Derivatives of fatty acids containing from 12 to 18 carbon atoms and particularly lauric acid are preferred.
- the preferred coconut oil fatty acid diethanolamide used herein is that produced by condensing 1 mole of diethanolamine with 1 mole of the fatty acid mixture derived from coconut oil.
- the non-ionic surfactants described above may be present in the concentrated microemulsion in amounts of from about 30 to about 50 weight percent, more usually from about 35 to about 45 weight percent, e.g., about 38 weight percent.
- the weight ratio of the capped alkylphenol alkoxylate and/or alkoxylated higher aliphatic alcohol surfactant to the fatty acid alkanolamide surfactant may range from about 2:1 to about 5:1, more typically from about 2.5:1 to about 4:1, e.g. , about 3.7:1.
- the amount of non-ionic surfactants used to prepare the microemulsions of the present invention, vis-a-vis, the terpene hydrocarbon solvent is usually not less than 2 parts of non-ionic surfactant per 3 parts of terpene hydrocarbon solvent, i.e., not less than 1 part of non-ionic surfactant for each 1.5 parts of terpene hydrocarbon solvent.
- the last major ingredient of the microemulsion of the present invention is water.
- Ordinary tap water usually of less than 150 p. .m. hardness, as CaC03, distilled water or deionized water may be used.
- the microemulsion of the present invention comprises, for example, (a) the terpene hydrocarbon solvent, (b) the lower alkyl glycol monoether co-solvent, (c) a mixture of non-ionic surfactants, e.g., capped alkylphenol ethoxylate and fatty acid alkanolamide, and (d) the 10 balance water.
- non-essential (non-major) ingredients that may be added to the concentrated microemulsion of the present invention to impart desirable properties include rust inhibitors, scale inhibitors, defoa ers, chelates, preservatives, biocides, pH buffering materials 15 such as alkali metal carbonates, bicarbonates, etasilicates and orthophosphates, dyes, perfumes, enzymes and soil suspending agents such as carboxy methyl cellulose.
- These ingredients may be added in amounts of from 0 to about 30 parts by weight, based on 100 parts of the concentrated microemulsion. More typically, from about 5 to about 20 20, e.g., up to about 10 percent by weight of these additional ingredients or adjuvants may be incorporated into the concentrated microemulsion.
- the concentrated microemulsion of the present invention may be diluted by mixing one (1) part thereof with from about 1 to about 25 49 parts of water with 1 part of the concentrated microemulsion. More typically, the concentrated microemulsion may be diluted by mixing up to 20, e.g., 2 to 10, parts of water with 1 part of the concentrated microemulsion. The more dilute microemulsion may be used for light cleaning applications, while the more concentrated microemulsions, for 30 example, the concentrated microemulsion and those diluted with about 9 parts of water are used for heavier duty cleaning applications. Even when diluted, the microemulsion remains clear.
- the microemulsions of the present invention possess properties that are particularly beneficial as cleaning compositions. 5 As a microemulsion, the composition is clear and inherently stable. It is free rinsing, i.e., it does not require significant additional rinsing - little or no residue remaining on the surface cleaned with the concentrated or diluted microemulsion cleaning composition.
- the microemulsion cleaning compositions (concentrated and diluted) of the 5 present invention are highly effective in removing oils, particularly aliphatic and aromatic oils from hard surfaces, and have low VOC (volatile organic compound) values. When diluted the microemulsion has a high flash point, as measured by the Pen ⁇ ky Martens Closed Cup (P.M.C.C.) Method. For example, when diluted to 20 percent or less, the flash point of the microemulsion is greater than 212 ⁇ F.
- microemulsion cleaning composition of the present invention is compatible with high soil loads, which suggests an extended bath life.
- a diluted aqueous microemulsion cleaning composition of the present invention containing 10 percent of the concentrated microemulsion has been found capable of performing additional cleaning even in the presence of a 10 percent contamination load.
- the cleaning compositions described herein are compatible with materials of construction such as elastomers, rubber, and thermoset resins, i.e., they do not swell, attack or craze many of such materials used for articles such as gaskets and piping.
- the microemulsion compositions of the present invention are particularly useful for cleaning oily and greasy soils from substrates, e.g., hard surfaces. It also may be adapted for cleaning textiles, for example, woven or knit cotton or cellulose-synthetic blend, e.g., cotton-polyester textile materials. It is also contemplated that the cleaning compositions of the present invention may be used as a laundry pre-spotting composition.
- the microemulsion cleaning compositions of the present invention may be prepared by simply combining all of the organic components thereof in a suitable vessel or container with sufficient agitation and then adding the amount of water required to make up 100 parts.
- the order of mixing the organic components is not particularly important and generally the various organic materials may be added sequentially or all at once.
- the compositions of the present invention are prepared by mixing the organic components until the mixture is clear and then add slowly the required amount of water.
- good manufacturing procedures involve adding the largest (in amount) component first, and adding the most volatile component last.
- the pH of the microemulsion is from about 6 to 9 for cleaning applications. Diluted microemulsions may be made from the concentrated microemulsion by dilution with the appropriate amount of water.
- microemulsion cleaning compositions of the present invention may be used in a wide variety of methods which will vary according to the amount of soil to be removed and the size and shape of the article to be cleaned.
- Application of the cleaning composition can, for example, be by brushing, spraying, air or immersion dipping, hosing and wiping. Cleaning may be by batch or continuous methods.
- the diluted microemulsions of the present invention are effective when used with ultrasonic cleaning methods.
- the cleaning compositions of the present invention are used at temperatures up to 160 ⁇ F., e.g., from ambient temperatures, e.g., about 70°F., to 160°F.
- a concentrated microemulsion cleaning solution was prepared by mixing the following organic ingredients and then adding the water: 5
- 15 13.5 gallons of the concentrated microemulsion were diluted with tap water having a total hardness of 156 p.p.m. as combined Ca/MgC0 to a total of 135 gallons.
- the diluted microemulsion was used to clean metal parts in a 4 stage tester designed to simulate commercial degreasing equipment. The four stages were (1) wash, (2) first rinse, 0 (3) second rinse, and (4) forced hot air (157"F.) dry.
- the cleaning conditions (temperature (T) and spray pressures (P), psi) for each of the first three stages and the parts cleaned are tabulated in Table 1.
- the surfaces of the parts cleaned were soiled with non-aqueous metal working fluids, e.g., lubricating, rolling and machine oils.
- Tests 1 and 2 the parts were placed in a metal cage and rotated in the cleaning composition at a speed of 5 rpm/minute.
- Tests 3 and 4 the parts were dipped in the cleaning composition, and in Test 5 the fittings were sprayed with the cleaning composition.
- Rinsing in the second stage was by immersion in water and liquid spray 0 below liquid level.
Abstract
Oil-in-water microemulsion cleaning compositions comprising four principal components are described. These four components are a terpene solvent, e.g., d-limonene, an aliphatic glycol monoether co-solvent, e.g., dipropylene glycol monomethyl ether, a mixture of non-ionic surfactants selected from (1) a capped alkylphenol ethoxylate or an ethoxylated higher aliphatic alcohol, and (2) a fatty acid alkanolamide, and water. The cleaning composition may be used in concentrated form or in a diluted form. The composition may be used for cleaning soil from among other glass and metal parts.
Description
TERPENE-BASED MICROE ULSION CLEANING COMPOSITION
DESCRIPTION OF THE INVENTION The present invention relates to aqueous microemulsion cleaning compositions, to a process for their manufacture and the use of such compositions in cleaning applications. More particularly, the present invention relates to aqueous oil-in-water microemulsion cleaning compositions in concentrated or diluted form which, in the absence of any opacifying component, are clear, and which are particularly effective for cleaning oil and greasy soils from hard and flexible substrates, such as metal parts and glass surfaces. The cleaning compositions of the present invention comprise four essential or major components; namely, (a) a terpene hydrocarbon solvent; (b) a mixture of non-ionic surfactants including (i) a capped alkylphenol alkoxylate or alkoxylated higher aliphatic alcohol and (ii) a fatty acid alkanolamide; (c) a lower alkyl or phenyl monoether of an aliphatic glycol co-solvent; (d) and water.
In the manufacture of various articles, such as glass, metal parts or, for example, iron, steel, brass, aluminum, copper, etc., coated and uncoated automobile parts and circuit boards, a need arises during the manufacturing process to clean such articles of manufacture of soils involving deposits of oils, e.g., rolling oil, cutting oil and stamping oil, grease, dirt, waxes, silicones, etc. In the past, it has been customary to employ cleaning compositions based primarily upon the use of petroleum derived hydrocarbon solvents, e.g., petroleum distillates, such as n-hexane, or halogenated hydrocarbon solvents, e.g., methyl chloroform and CFC solvents. While these solvents are effective for the purposes for which they have been developed, they have become environmentally undesirable. Terpenes are known components of perfume compositions and are often incorporated into detergent compositions at low levels via the perfume. Certain terpenes have also been included in cleaning or detergent compositions at higher levels. For instance, U.S. Patent 4,336,151 describes a disinfectant/cleaner composition having broad spectrum germicidal activity and reduced eye irritancy by the combined
use of a quaternary ammonium compound, non-ionic surfactant, d-limonene, water, and an eye-irritancy reducing compound such as ethoxylated cocodiethanolamide. U.S. Patent 4,414,128 describes liquid detergent compositions for use as hard surface cleaners of 5 1-20% surfactant, 0.5-10% mono- or sesquiterpenes, and 0.5-10% of a polar solvent, e.g., benzyl alcohol, having a solubility in water of from 0.2 to 10%.
Water-in-oil detergent emulsions for use in laundry pre-spotting applications are described in U.S. Patent 4,438,009. These emulsions comprise from 1 to 30% of (a) certain salts, such as sodium citrate, (b) from 1 to 35% of a non-ionic surfactant mixture of (i) a non-ethoxylated sorbitan surfactant, e.g., sorbitan monolaurate, (ii) another non-ionic surfactant, e.g., ethoxylated nonylphenols or ethoxylated primary alcohols, and (iii) an ethoxylated sorbitan surfactant, (c) from 5-60% of a hydrocarbon solvent, which may be d-limonene, and (d) water. D-limonene-based aqueous cleaning compositions are described in U.S. Patent 4,511,488. Such compositions comprise from 78-96 parts of a d-limonene/surfac- tant/water mixture, 2-10 parts of coupling agent, e.g., glycols and lower alkyl glycol ethers, and 2-12 parts of additives. The surfactants used are anionic, non-ionic and mixtures of anionic and non-ionic surfactants.
U.S. Patent 4,540,505 describes cleanser compositions containing from 0.4 to 1% d-limonene, quaternary ammonium compound, non-ionic surfactant, alkali builder and 4-6% of a monoether of an aliphatic glycol. U.S. Patent 4,704,225 (Re. 33,210) describes water-in-oil cleaning emulsion of (a) an oil phase of 95 to 85 parts by volume of an terpene and 5 to 15 parts by volume of a Cg - C]_g fatty acid alkanolamide and (b) from 5 to 8 parts by volume of water ' per part by volume of the oil phase.
European Patent Application 80,749 describes liquid detergent compositions for use as a hard surface cleaner of terpene, surfactant and 2-(2-butoxyethoxy) ethanol. European Patent Application 174,711 describes a biodegradable emulsion for use in removing ink from printing presses of 50-75% d-limonene, 25-50% water, and 1-5%
non-ionic surfactant, e.g., nonylphenol ethoxylates and N-substituted fatty acid amides, and 0.5-2% emulsion stabilizer, e.g., polypropylene glycol. Stable microemulsion cleaning compositions of synthetic organic (non-ionic/anionic) detergents (5-65%), perfume, e.g., terpenes (2-50%), water (15-85%) and co-surfactant, e.g., monoalkyl ether of a lower glycol (2-50%) are described in European Patent Application 316,726.
The present invention concerns the discovery of certain terpene-based cleaning compositions in the form of an oil-in-water microemulsion that are particularly suitable for cleaning hard or flexible substrates of soils involving deposits of, for example, oils, grease, dirt, etc. The foregoing microemulsions comprise a terpene solvent, a co-solvent of a lower alkyl monoether of an aliphatic glycol, water and a mixture of certain non-ionic surfactants.
DETAILED DESCRIPTION OF THE INVENTION Terpene solvents that may be used to prepare the microemulsions of the present invention are preferably the mono- and bicyclic monoterpenes, i.e., those of the hydrocarbon class, which include, for example, the terpinenes, terpinolenes, limonenes, pinenes and mixtures thereof. Particularly preferred terpenes include d-limonene, dipentene, alpha-pinene, beta-pinene, the mixture of terpene hydrocarbons obtained from the essence of oranges, e.g., cold-pressed orange terpenes and orange terpene oil phase ex fruit juice, and the mixture of terpene hydrocarbons expressed from lemons and grapefruit. The foregoing terpene hydrocarbon solvents are derivatives of pine tree products or citrus by-products and, therefore, are naturally occurring materials. Numerous other terpene hydrocarbons are known to those skilled in the art and may be used to prepare the microemulsions of the present invention; however, those mentioned above are the most readily available and, hence, are preferred. Such materials are often formulated with small amounts, e.g., 0.1 weight percent, of auxiliary materials, such as stabilizers, e.g., antioxidants such as butylated hydroxytoluene, and such auxiliary materials are included within the meaning of the term
"terpene solvent", as employed in this specification and the accompanying claims.
D-limonene is highly preferred as the terpene component of the microemulsion. It is derived from distilled orange rind oil and 5 may be obtained in essentially pure form from citrus products companies which produce it as a by-product. An extensive discussion of d-limonene and its derivation from numerous sources is presented in a book by J.W. Kesterson et al entitled Florida Citrus Oil, published in December, 1971 by Agricultural Experiment Station, Institute of Food & Agricultural Sciences, University of Florida, Gainesville, Florida.
The terpene component is present in the concentrated microemulsion of the present invention in the range of from about 5 to about 20 weight percent, more usually, from about 10 to about 15 weight percent, e.g., about 12 weight percent. Corresponding terpene contents for a microemulsion that has been diluted with nine equal parts of water, thereby to form a microemulsion containing 10 percent of the concentrated microemulsion, are 0.5-2.0 weight percent, more usually, 1.0-1.5 weight percent, e.g., 1.2 weight percent. Another major component of the microemulsion of the present invention is a lower alkyl or phenyl monoether of a C2 or C3 aliphatic glycol, e.g., ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol, or l,5-dihydroxy-2-raethyl pentane. This co-solvent material may be selected from materials represented in part by the following general formula,
R20 CH2-CH(R3)-0^z CH2-CH(CH3)-0^wH (I)
In general formula I, R2 may be selected from lower alkyl, e.g., C^-Cή alkyl, such as methyl, ethyl, propyl, n-butyl and t-butyl, and phenyl,
R3 is hydrogen or methyl, w is 0 or 1, and z is a number of from 1 to
2; provided that z is 1 and R is hydrogen when w is 1.
Examples of materials exemplified by general formula I that may be used to prepare the microemulsion of the present invention include, but are not limited to, the monomethyl ethers, monethyl
ethers, monobutyl ethers, and the phenyl ethers of monoethylene glycol, diethylene glycol, monopropylene glycol, and dipropylene glycol; the methyl, ethyl and butyl ethers of 2-ethoxy propanol; and the methyl ether of l,5-dihydroxy-2-methyl pentane. Mixtures of such co-solvents may also be used.
The co-solvent component may be present in the range, of from about 10 to about 35 weight percent, more usually from about 15 to about 25 weight percent, e.g., about 20 weight percent. Corresponding contents of the co-solvent for a microemulsion diluted with 9 parts of water so as to form a composition containing 10 percent of the concentrated microemulsion are 1.0-3.5 weight percent, more usually 1.5-2.5 weight, e.g., about 2.0 weight percent. Typically the ratio of co-solvent to terpene hydrocarbon will range from about 1.2:1 to about 4.0:1, more usually from about 1.5:1 to 2.0:1. A further major component of the microemulsion of the present invention is a mixture of certain non-ionic surfactants. The first non-ionic surfactant is a capped alkylphenol alkoxylate and/or higher aliphatic alcohol alkoxylate. The second non-ionic surfactant that is a part of the surfactant mixture is a fatty acid alkanolamide. Capped alkylphenol alkoxylates that may be used as the first non-ionic surfactant may be represented by the following general formula,
(R)a-Ph-0 A-0}y4CH2-CH2-0}χB (II)
wherein R is a Cg-C^2, aliphatic group, e.g, Cg-C10 alkyl, such as octyl, nonyl, decyl, undecyl and dodecyl, Ph is phenylene, A is a bivalent alkyleneoxy group selected from the group consisting of propyleneoxy, butyleneoxy and a mixture of propyleneoxy and butyleneoxy groups, B is selected from the group consisting of benzyl, methyl, ethylchloro and polypropyleneoxy, i.e., CH2-CH(CH3)-0-i*t bH, a is the integer 1 or 2, b is a number from 3 to 4, x is a number of from 6 to 20, e.g., 10-16, and y is a number from 0 to 4, e.g., 1-4, such as 2, 3 or 4.
Examples of capped alkylphenol alkoxylates within the scope of general formula II include the benzyl, methyl and chloro ether of octylphenoxy polyethoxy ethanol containing from about 10 to 16 ethoxy units. Similarly, there can be mentioned the dioctyl phenoxy 5 polyethoxy ethanols, and the nonyl-, decyl- and dodecyl-phenoxy polyethoxy ethanols containing from 10 to 16, e.g., 13 to 16, ethoxy units and capped with a benzyl, methyl, ethylchlorq or polypropyleneoxy group. The methyl and benzyl capped alkylphenol alkoxylates may be prepared by the art recognized Williamson synthesis. The polypropyleneoxy capped alkylphenol alkoxylates may be prepared by the conventional alkoxylation addition reaction to the hydroxy-terrainated alkylphenol alkoxylate with propylene oxide. The chloro capped alkylphenol alkoxylate may be prepared by reacting the hydroxy- terminated precursor with thionyl chloride and decomposing the intermediate chlorosulfite to the organo chloride by means known in the art.
Alkoxylated higher aliphatic alcohol non-ionic surfactants that may be used in place of (or as partial substitution for) the alkylphenol alkoxylates as the first non-ionic surfactant may be represented by the following general formula,
R"-0(A-0)v(CH2-CH2-0)χH (III)
wherein R" is a C -C^2 linear or branched chain alkyl, preferably a
A» x an"i y n general formula III are as defined hereinabove with respect to the alkylphenol alkoxylates of general formula II. When both the capped alkylphenol alkoxylate and alkoxylated aliphatic alcohol are used in combination as the first non-ionic surfactant, they may be used in a ratio of about 5:1 to 1:5, e.g., 1:1.
Alkoxylated aliphatic alcohols within the scope of general formula III may be prepared by performing conventional alkoxylation addition reactions on commercially available aliphatic alcohols, which are commonly available as mixtures of alcohols. Examples of such materials include ethoxylated mixed aliphatic alcohols having from 8
to 10 carbon atoms and 6 to 10 ethoxy units; ethoxylated mixed aliphatic alcohols having from 9 to 11 carbon atoms and 6 to 10 ethoxy units; ethoxylated mixed aliphatic alcohols having from 12 to 15 carbon atoms and 10 to 15 ethoxy units; an ethoxylated C^2 aliphatic alcohol having from 10 to 15 ethoxy units; an ethoxylated isodecyl alcohol having from 8 to 10 ethoxy units; and an ethoxylated linear or branched octyl alcohol having from 2 to 10 ethoxy units.
The above-described alkylphenol alkoxylates and alkoxylated aliphatic alcohol non-ionic surfactants may be prepared by condensing the corresponding aliphatic alcohol or alkylphenol with alkylene oxide groups, e.g., ethylene oxide, in a manner known in the art. The value for x in general formulae II and III is the average number of ethoxy groups resulting from the aforesaid condensation, as is known in the art. In those embodiments wherein y is other than 0, the aliphatic alcohol or alkylphenol is first condensed with propylene oxide, butylene oxide or a combination of butylene oxide and propylene oxide. The resulting alkoxylated alkyl phenol or aliphatic alcohol is then further condensed with ethylene oxide to prepare the precursor to the surfactant material of general formulae II, and the surfactant material of general formula III. When mixtures of butylene oxide and propylene oxide are used, the resultant product may be a block polymer or random polymer, e.g., first condensing butylene oxide and then propylene oxide or condensing a mixture of butylene oxide and propylene oxide with the alkylphenol or aliphatic alcohol. When y is other than 0 or 1, the value for y is an average number of alkoxy groups which results from the condensation reaction, as is known in the art. When A is a mixture of butyleneoxy and propyleneoxy groups, y represents the total number of butyleneoxy and propyleneoxy groups. The second non-ionic surfactant used in the surfactant mixture is a f ty acid alkanolamide, which may be represented by the following gene .1 formula,
R'-C(0)-N(R1)CH2CH20H (IV)
wherein R' is a C12-Clg aliphatic group, and Rj^ is hydrogen or hydroxyethyl. Preferably, Rj^ is hydroxyethyl.
Examples of fatty acid alkanolamides that may be used to prepare the microemulsions of the present invention include 5 cocodiethanolamide (cocoamide DEA), lauramide DEA, soyamide DEA, oleylamide DEA, stearamide DEA, linoleamide DEA, tall oil amide DEA, tallow amide DEA, and stearamide monoethanolamide (stearamide MEA).
As described, R'-C(O)- of general formula IV is a derivative of a fatty acid or a mixture of fatty acids. Coconut oil fatty acids are preferred and comprise a mixture of mainly caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and linoleic acid. Derivatives of fatty acids containing from 12 to 18 carbon atoms and particularly lauric acid are preferred. The preferred coconut oil fatty acid diethanolamide used herein is that produced by condensing 1 mole of diethanolamine with 1 mole of the fatty acid mixture derived from coconut oil.
The non-ionic surfactants described above may be present in the concentrated microemulsion in amounts of from about 30 to about 50 weight percent, more usually from about 35 to about 45 weight percent, e.g., about 38 weight percent. The weight ratio of the capped alkylphenol alkoxylate and/or alkoxylated higher aliphatic alcohol surfactant to the fatty acid alkanolamide surfactant may range from about 2:1 to about 5:1, more typically from about 2.5:1 to about 4:1, e.g. , about 3.7:1. The amount of non-ionic surfactants used to prepare the microemulsions of the present invention, vis-a-vis, the terpene hydrocarbon solvent is usually not less than 2 parts of non-ionic surfactant per 3 parts of terpene hydrocarbon solvent, i.e., not less than 1 part of non-ionic surfactant for each 1.5 parts of terpene hydrocarbon solvent.
The last major ingredient of the microemulsion of the present invention is water. Ordinary tap water, usually of less than 150 p. .m. hardness, as CaC03, distilled water or deionized water may be used. Tap water of less than 50 p.p.m. hardness, as CaCθ3, " preferred for reasons of cost. The amount of dissolved impurities
- 9 -
normally in tap water does not appear to affect adversely the microemulsion cleaning compositions of the present invention.
Water is used in the described and claimed concentrated microemulsions in amounts and quantities sufficient so that the total 5 of all four major components adds to 100 percent. Thus, the microemulsion of the present invention comprises, for example, (a) the terpene hydrocarbon solvent, (b) the lower alkyl glycol monoether co-solvent, (c) a mixture of non-ionic surfactants, e.g., capped alkylphenol ethoxylate and fatty acid alkanolamide, and (d) the 10 balance water.
Other suitable non-essential (non-major) ingredients that may be added to the concentrated microemulsion of the present invention to impart desirable properties include rust inhibitors, scale inhibitors, defoa ers, chelates, preservatives, biocides, pH buffering materials 15 such as alkali metal carbonates, bicarbonates, etasilicates and orthophosphates, dyes, perfumes, enzymes and soil suspending agents such as carboxy methyl cellulose. These ingredients may be added in amounts of from 0 to about 30 parts by weight, based on 100 parts of the concentrated microemulsion. More typically, from about 5 to about 20 20, e.g., up to about 10 percent by weight of these additional ingredients or adjuvants may be incorporated into the concentrated microemulsion.
The concentrated microemulsion of the present invention may be diluted by mixing one (1) part thereof with from about 1 to about 25 49 parts of water with 1 part of the concentrated microemulsion. More typically, the concentrated microemulsion may be diluted by mixing up to 20, e.g., 2 to 10, parts of water with 1 part of the concentrated microemulsion. The more dilute microemulsion may be used for light cleaning applications, while the more concentrated microemulsions, for 30 example, the concentrated microemulsion and those diluted with about 9 parts of water are used for heavier duty cleaning applications. Even when diluted, the microemulsion remains clear.
The microemulsions of the present invention possess properties that are particularly beneficial as cleaning compositions. 5 As a microemulsion, the composition is clear and inherently stable.
It is free rinsing, i.e., it does not require significant additional rinsing - little or no residue remaining on the surface cleaned with the concentrated or diluted microemulsion cleaning composition. The microemulsion cleaning compositions (concentrated and diluted) of the 5 present invention are highly effective in removing oils, particularly aliphatic and aromatic oils from hard surfaces, and have low VOC (volatile organic compound) values. When diluted the microemulsion has a high flash point, as measured by the Penβky Martens Closed Cup (P.M.C.C.) Method. For example, when diluted to 20 percent or less, the flash point of the microemulsion is greater than 212βF.
In most cleaning applications using the microemulsion of the present invention, low foaming is experienced during the cleaning operation. In high pressure washing applications, the foam produced is low to moderate. Further, the microemulsion cleaning composition of the present invention is compatible with high soil loads, which suggests an extended bath life. For example, a diluted aqueous microemulsion cleaning composition of the present invention containing 10 percent of the concentrated microemulsion has been found capable of performing additional cleaning even in the presence of a 10 percent contamination load.
Finally, the cleaning compositions described herein are compatible with materials of construction such as elastomers, rubber, and thermoset resins, i.e., they do not swell, attack or craze many of such materials used for articles such as gaskets and piping. The microemulsion compositions of the present invention are particularly useful for cleaning oily and greasy soils from substrates, e.g., hard surfaces. It also may be adapted for cleaning textiles, for example, woven or knit cotton or cellulose-synthetic blend, e.g., cotton-polyester textile materials. It is also contemplated that the cleaning compositions of the present invention may be used as a laundry pre-spotting composition.
The microemulsion cleaning compositions of the present invention may be prepared by simply combining all of the organic components thereof in a suitable vessel or container with sufficient agitation and then adding the amount of water required to make up 100
parts. The order of mixing the organic components is not particularly important and generally the various organic materials may be added sequentially or all at once. Preferably, the compositions of the present invention are prepared by mixing the organic components until the mixture is clear and then add slowly the required amount of water. Typically, good manufacturing procedures involve adding the largest (in amount) component first, and adding the most volatile component last. Preferably, the pH of the microemulsion is from about 6 to 9 for cleaning applications. Diluted microemulsions may be made from the concentrated microemulsion by dilution with the appropriate amount of water.
The microemulsion cleaning compositions of the present invention may be used in a wide variety of methods which will vary according to the amount of soil to be removed and the size and shape of the article to be cleaned. Application of the cleaning composition can, for example, be by brushing, spraying, air or immersion dipping, hosing and wiping. Cleaning may be by batch or continuous methods. It has been surprisingly found that the diluted microemulsions of the present invention are effective when used with ultrasonic cleaning methods. Preferably, the cleaning compositions of the present invention are used at temperatures up to 160βF., e.g., from ambient temperatures, e.g., about 70°F., to 160°F. Contact times of the article with the cleaning composition are usually for from about 1 to 5 minutes, e.g., 3 minutes. The present invention is more particularly described in the following example, which is intended as illustrative only, since numerous modifications and variations therein will be apparent to one skilled in the art.
EX MELE
A concentrated microemulsion cleaning solution was prepared by mixing the following organic ingredients and then adding the water: 5
Cocodiethanolamide 6.66 parts
Benzyl capped octyl phenol ethoxylate* 24.99 parts Dipropylene glycol monomethyl ether 16.66 parts D-limonene 9.99 parts
10 Mazon® RI 6 corrosion inhibitor 16.7 parts
Water 25.00 parts
* Contains about 16 ethoxy units
15 13.5 gallons of the concentrated microemulsion were diluted with tap water having a total hardness of 156 p.p.m. as combined Ca/MgC0 to a total of 135 gallons. The diluted microemulsion was used to clean metal parts in a 4 stage tester designed to simulate commercial degreasing equipment. The four stages were (1) wash, (2) first rinse, 0 (3) second rinse, and (4) forced hot air (157"F.) dry. The cleaning conditions (temperature (T) and spray pressures (P), psi) for each of the first three stages and the parts cleaned are tabulated in Table 1. The surfaces of the parts cleaned were soiled with non-aqueous metal working fluids, e.g., lubricating, rolling and machine oils. 5 In Tests 1 and 2, the parts were placed in a metal cage and rotated in the cleaning composition at a speed of 5 rpm/minute. In Tests 3 and 4, the parts were dipped in the cleaning composition, and in Test 5 the fittings were sprayed with the cleaning composition. Rinsing in the second stage was by immersion in water and liquid spray 0 below liquid level. In the third stage, air bubbled up from the bottom of the vessel through the water rinse bath in which the parts were immersed.
TABLE 1
STAGES Test First/Wash Secpnd/Rinse
K£L__ Parts Cleaned -∑-. f/PSJ I»T. P«P8J TVFt fiPSJ Minutes' Result
1 Steel Bearing
Cases 140 78 128 50 66 15 1 Clean
2 Steel Bearing
Cases 99 35 99 52 68 15 3 99%Clean
96 50 68 15 3 90%Clean
90 54 70 15 3 Clean
.
93 50 72 15 3 Clean * Ultrasonically cleaned using a 40 Megahertz Ultrasonic Generator a. Used a 2 percent cleaning solution b. 35 psi air spray c. Time in each stage The data of Table 1 shows that excellent cleaning of the metal parts was obtained in a short time at moderate temperatures using a 10% aqueous microemulsion of the present invention rather than halohydrocarbons.
No appreciable foam was observed after two days of continuous operation in the tank used for the second rinse stage, which confirms the free rinsing properties of the cleaning composition. The data also shows that the dilute microemulsion of the present invention was effective using ultrasonic cleaning. The data of Test 2 shows that the cleaning composition of the present invention is relatively effective at lower temperatures and pressures, vis-a-vis , Test 1 and that longer times in each stage, e.g., 4 minutes is needed to comp..etely clean the parts.
Although the present invention has been described with reference to the specific details of certain embodiments thereof, it is not intended that such details should be regarded as limitations upon the scope of the invention except as and to the extent that they are included in the accompanying claims.
Claims
1. A cleaning composition in concentrated form comprising an oil-in-water microemulsion of: (a) from about 5 to about 20 weight percent of terpene hydrocarbon solvent,
(b) from about 30 to about 50 weight percent of a non-ionic surfactant mixture of:
(1) a first surfactant selected from the group consisting of:
(i) capped alkylphenol alkoxylate surfactant represented by the general formula,
(R)aPh-0 A-0 y CH2-CH2-0^χ-B, wherein R is a C -C^2 alkyl, Ph is phenylene, A is a bivalent alkyleneoxy group selected from the group consisting of propyleneoxy, butyleneoxy and mixtures of propyleneoxy and butyleneoxy groups, B is selected from the group consisting of benzyl, methyl, ethylchloro and CH2-CH(CH3)-0-zt DH, a is the integer 1 or 2, b is a number from 3 to 4, x is a number of from 6 to 20, and y is a number from 0 to 4, and
(ii) an alkoxylated aliphatic alcohol surfactant represented by the general formula, R"-0- A-0 y CH2-CH2-0^χH, wherein R" is a Cg-C^g alkyl, and A, x and y are as defined hereinabove, and (2) a second surfactant comprising a fatty acid alkanolamide represented by the general formula, R,-C(0)-N(R1)CH2CH20H, wherein R' is a C12-C18 aliphatic group and R is hydrogen or hydroxyethyl, the weight ratio of surfactant (1) to surfactant (2) being from about 2:1 to about 5:1, and
- 16 -
(c) from about 10 to about 35 weight percent of a monoether co-solvent represented by the general formula,
R20 CH2-CH(R3)-0^Z CH2-CH(CH3)-0^WH, wherein R2 is selected from the group consisting of a C^-C^ alkyl and phenyl, 3 is a hydrogen or methyl, w is 0 or 1, and z is a number of from 1 to 2, provided that z is.1 and R3 is hydrogen when w is 1, and
(d) the balance water.
2. The cleaning composition of claim 1 comprising:
(a) from about 10 to about 15 weight percent of terpene hydrocarbon solvent,
(b) from about 35 to 45 weight percent of the non-ionic surfactant mixture, (c) from about 15 to about 25 weight percent of the monoether co-solvent, and (d) the balance water.
3. The cleaning composition of claim 2 wherein the terpene hydrocarbon solvent is d-limonene; the first non-ionic surfactant is a monoalkylphenol ethoxylate wherein a is 1, y is 0, and B is benzyl; the second non-ionic surfactant is a diethanolamide and R^ is hydroxyethyl; and the monoether co-solvent is one wherein R2 and R3 are each methyl.
4. A cleaning composition comprising one part of the concentrated composition of claim 3 diluted with 9 parts of water.
5. The cleaning composition of claim 3 wherein the first non-ionic surfactant is a benzyl capped octyl phenol ethoxylate containing from about 10 to 16 ethoxy units, the second non-ionic surfactant is cocodiethanolamide, and the monoether co-solvent is the monomethyl ether of dipropylene glycol.
6. A method of cleaning metal parts, comprising contacting said parts with the cleaning composition of claim 3 for a time, and temperature sufficient to remove the soil contained on the surface of said parts.
7. The method of claim 6 wherein the time is from.about 1 to 5 minutes.
8. The method of claim 6 wherein the parts are ultrasonically cleaned.
AMENDED CLAIMS
[received by the International Bureau .on 28 December 1992, (28.12.92); original claim 1 amended; remaining claims unchanged (1page)0
1. A cleaning composition in concentrated form consisting essentially of an oil-in-water microemulsion of: (a) from about 5 to about 20 weight percent of terpene hydrocarbon solvent,
(b) from about 30 to about 50 weight percent of a non-ionic surfactant mixture of:
(1) a first surfactant selected from the group consisting of:
(i) capped alkylphenol alkoxylate surfactant represented by the general formula,
(R)aPh-0 A-0^y CH2-CH2-0^χ-B, wherein R is a C -C^2 alkyl, Ph is phenylene, A is a bivalent alkyleneoxy group selected from the group consisting of propyleneoxy, butyleneoxy and mixtures of propyleneoxy and butyleneoxy groups, B is selected from the group consisting of benzyl, methyl, ethylchloro and CH2-CH(CH3)-0-ή.H, a is the integer 1 or 2, b is a number from 3 to 4, x is a number of from 6 to 20, and y is a number from 0 to 4, and
(ii) an alkoxylated aliphatic alcohol surfactant represented by the general formula, R"-0-(A-0^CH2-CH2-0 χH, wherein R" is a Cg-C^g alkyl, and A, x and y are as defined hereinabove, and (2) a second surfactant comprising a fatty acid alkanolamide represented by the general formula, R'-C(0)-N(R1)CH2CH20H, wherein R1 is a Cj^-C^ aliphatic group and R^ is hydrogen or hydroxyethyl, the weight ratio of surfactant (1) to surfactant (2) being from about 2:1 to about 5:1, and
STATEMENT UNDER ARTICLE19
Enclosed herewith is a replacement for page 15 of the subject application in which amendments to claim 1 are made. The difference between the claims as filed and the claims as amended are as follows:
(a) Claim 1 has been amended.
(b) Claims 2-8 remain unchanged.
Claim 1 has been amended by defining the claimed cleaning composition as "consisting essentially of" the recited components, and by specifying that the first and second surfactant of the non-ionic surfactant mixture are "nonionic". Such amendment is based on the disclosure on page 5, lines 16-17, and page 7, line 30, of the specification.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/732,565 US5213624A (en) | 1991-07-19 | 1991-07-19 | Terpene-base microemulsion cleaning composition |
US732,565 | 1991-07-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1993002169A1 true WO1993002169A1 (en) | 1993-02-04 |
Family
ID=24944048
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1992/005995 WO1993002169A1 (en) | 1991-07-19 | 1992-07-17 | Terpene-based microemulsion cleaning composition |
Country Status (2)
Country | Link |
---|---|
US (1) | US5213624A (en) |
WO (1) | WO1993002169A1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2266725A (en) * | 1992-04-30 | 1993-11-10 | Kao Corp | Composition for removing oil & grease. |
WO1996017052A1 (en) * | 1994-12-02 | 1996-06-06 | Daewoo Electronics Co., Ltd. | Detergent composition and method for washing using the same |
US5818399A (en) * | 1994-02-09 | 1998-10-06 | Terumo Kabushiki Kaisha | Image communication apparatus |
US5910455A (en) * | 1995-09-01 | 1999-06-08 | Kimberly Clark Corp. | Hand cleanser |
WO2005111185A1 (en) * | 2004-05-07 | 2005-11-24 | Croda Uniqema Inc. | Solvated nonionic surfactants |
EP2857362A4 (en) * | 2012-07-31 | 2015-12-30 | Orientnano Co Ltd | Microbial flora activator, anti-filamentous fungi agent comprising said microbial flora activator as active ingredient, and method for treating waste water containing oil, fat, etc. using said microbial flora activator |
EP2841540A4 (en) * | 2012-04-24 | 2016-02-10 | Stepan Co | Aqueous hard surface cleaners based on terpenes and fatty acid derivatives |
CN110582559A (en) * | 2017-07-05 | 2019-12-17 | Jxtg能源株式会社 | W/O emulsion detergent composition, cleaning method using W/O emulsion detergent composition, and method for producing W/O emulsion detergent composition |
Families Citing this family (74)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU3781793A (en) * | 1992-02-26 | 1993-09-13 | Arrow Engineering, Inc | Process and compositions for dyeing hydrophobic polymer products |
WO1994017144A1 (en) * | 1993-01-25 | 1994-08-04 | Dotolo Research Corporation | All-in-one offset printing solution composition |
CA2120375A1 (en) * | 1993-04-02 | 1994-10-03 | John Klier | A laundry pretreater having enhanced oily soil removal |
US6020296A (en) * | 1993-08-04 | 2000-02-01 | Colgate Palmolive Company | All purpose liquid cleaning composition comprising anionic, amine oxide and EO-BO nonionic surfactant |
US5330673A (en) * | 1993-08-12 | 1994-07-19 | Dotolo Research Corp. | Auto body cleaner and all purpose adhesive and urethane cleaner |
US5494611A (en) * | 1993-11-24 | 1996-02-27 | Armor All Products Corporation | Dual-purpose cleaning composition for painted and waxed surfaces |
AU1332195A (en) * | 1993-11-24 | 1995-06-13 | Penetone Corporation | Cleaning composition |
CA2173136A1 (en) * | 1994-03-31 | 1995-10-12 | Peter Robert Garrett | Detergent compositions |
HU218036B (en) * | 1994-03-31 | 2000-05-28 | Unilever Nv. | Water containing liquid cleaning compositions and process for cleaning hard surfaces |
WO1995032275A1 (en) * | 1994-05-19 | 1995-11-30 | Penetone Corporation | Cleaning compositions |
US5514294A (en) * | 1994-11-22 | 1996-05-07 | Alliedsignal Inc. | Limonene and tetrahydrofurfuryl alcohol cleaning agent |
US5670469A (en) * | 1995-01-06 | 1997-09-23 | Texas Research Institute | Methods and compositions for cleaning and decontamination |
US5942484A (en) * | 1995-03-30 | 1999-08-24 | The Procter & Gamble Company | Phase-stable liquid fabric refreshment composition |
MX9707450A (en) * | 1995-03-30 | 1997-12-31 | Procter & Gamble | Dry cleaning article. |
US5630847A (en) * | 1995-03-30 | 1997-05-20 | The Procter & Gamble Company | Perfumable dry cleaning and spot removal process |
US5632780A (en) * | 1995-03-30 | 1997-05-27 | The Procter & Gamble Company | Dry cleaning and spot removal proces |
US5547476A (en) * | 1995-03-30 | 1996-08-20 | The Procter & Gamble Company | Dry cleaning process |
US5591236A (en) * | 1995-03-30 | 1997-01-07 | The Procter & Gamble Company | Polyacrylate emulsified water/solvent fabric cleaning compositions and methods of using same |
US5630848A (en) * | 1995-05-25 | 1997-05-20 | The Procter & Gamble Company | Dry cleaning process with hydroentangled carrier substrate |
US5687591A (en) * | 1995-06-20 | 1997-11-18 | The Procter & Gamble Company | Spherical or polyhedral dry cleaning articles |
US5912408A (en) * | 1995-06-20 | 1999-06-15 | The Procter & Gamble Company | Dry cleaning with enzymes |
US5817186A (en) * | 1995-08-10 | 1998-10-06 | Corpex Technologies, Inc | Cleaning composition for metal objects |
US5817187A (en) * | 1995-08-10 | 1998-10-06 | Corpex Technologies, Inc. | Composition for grease removal |
US5663135A (en) * | 1995-08-10 | 1997-09-02 | Corpex Technologies, Inc. | Terpene-based cleaning composition |
US5681355A (en) * | 1995-08-11 | 1997-10-28 | The Procter & Gamble Company | Heat resistant dry cleaning bag |
JPH0966266A (en) * | 1995-08-31 | 1997-03-11 | Zenken:Kk | Cleaning method and device used for the method |
US6316399B1 (en) | 1995-12-27 | 2001-11-13 | Envirox, L.L.C. | Surfactants based aqueous compositions with D-limonene and hydrogen peroxide and methods using the same |
US5811380A (en) * | 1996-01-11 | 1998-09-22 | Rainbow Technology Corporation | Cleaner, preservative and antioxidant compositions |
US5789368A (en) * | 1996-01-26 | 1998-08-04 | The Procter & Gamble Company | Fabric care bag |
US6233771B1 (en) | 1996-01-26 | 2001-05-22 | The Procter & Gamble Company | Stain removal device |
US5840675A (en) * | 1996-02-28 | 1998-11-24 | The Procter And Gamble Company | Controlled released fabric care article |
DE69718772T2 (en) | 1996-03-19 | 2003-11-27 | Procter & Gamble | GLASS CLEANING AGENT CONTAINING VOLATILE HYDROPHOBIC FRAGRANCE ("BLOOMING PERFUME") |
US5753605A (en) * | 1996-04-05 | 1998-05-19 | Finger Lakes Chemical, Inc. | High Temperature flash point stable microemulsion cleaning composition |
US5679628A (en) * | 1996-06-14 | 1997-10-21 | Arco Chemical Technology, L.P. | Microemulsion cleaner compositions |
US5891197A (en) * | 1996-08-02 | 1999-04-06 | The Proctor & Gamble Company | Stain receiver for dry cleaning process |
EP0834550A1 (en) * | 1996-10-01 | 1998-04-08 | The Procter & Gamble Company | Laundry detergent compositions |
US5872090A (en) * | 1996-10-25 | 1999-02-16 | The Procter & Gamble Company | Stain removal with bleach |
US5762648A (en) * | 1997-01-17 | 1998-06-09 | The Procter & Gamble Company | Fabric treatment in venting bag |
US5849039A (en) * | 1997-01-17 | 1998-12-15 | The Procter & Gamble Company | Spot removal process |
JP3666709B2 (en) | 1997-06-12 | 2005-06-29 | 日本エム・アイ・シー株式会社 | Anti-shrink agent for water washing |
US5922277A (en) * | 1997-07-22 | 1999-07-13 | Donhoff; Ron | Recycling system for hazardous waste disposal |
US5866527A (en) * | 1997-08-01 | 1999-02-02 | Colgate Palmolive Company | All purpose liquid cleaning compositions comprising anionic EO nonionic and EO-BO nonionic surfactants |
US5858956A (en) * | 1997-12-03 | 1999-01-12 | Colgate-Palmolive Company | All purpose liquid cleaning compositions comprising anionic, EO nonionic and EO-BO nonionic surfactants |
US5958857A (en) * | 1997-09-04 | 1999-09-28 | The United States Of America As Represented By The Secretary Of The Navy | Thixotropic low-solvent, non-hap wheel well cleaner |
US5814594A (en) * | 1997-11-17 | 1998-09-29 | Citra Science Ltd. | Heavy oil remover |
ZA991371B (en) * | 1998-02-20 | 1999-12-23 | Procter & Gamble | Carpet stain removal product which uses sonic or ultrasonic waves. |
US6063206A (en) * | 1998-05-04 | 2000-05-16 | C. J. Latta & Associates | De-oiling process using enzymes |
DE19824236A1 (en) * | 1998-05-29 | 1999-12-02 | Basf Ag | Process for cleaning printing machines and printing forms |
US6136778A (en) * | 1998-07-22 | 2000-10-24 | Kamiya; Akira | Environment safeguarding aqueous detergent composition comprising essential oils |
US5958149A (en) * | 1998-09-17 | 1999-09-28 | S. C. Johnson & Son, Inc. | Method of cleaning surfaces, composition suitable for use in the method, and of preparing the composition |
US6153571A (en) * | 1999-01-29 | 2000-11-28 | Sports Care Products, Inc. | Terpene based aqueous cleaning gel for sporting equipment |
DE19908434A1 (en) * | 1999-02-26 | 2000-10-05 | Wack O K Chemie Gmbh | Process and cleaning liquid for liquid cleaning objects |
US6369016B1 (en) * | 1999-11-08 | 2002-04-09 | Dotolo Research Ltd. | Heavy oil remover |
US6486115B1 (en) | 1999-11-09 | 2002-11-26 | Baker Hughes Incorporated | Microemulsion cleaning composition |
FR2819201B1 (en) * | 2001-01-09 | 2003-02-21 | Atofina | PROCESS FOR CLEANING A SOLID SURFACE BY REMOVING ORGANIC AND / OR MINERAL SOILING BY MEANS OF A MICROEMULSION |
AU2002340501A1 (en) * | 2001-11-20 | 2003-06-10 | Unilever N.V. | Process for cleaning a substrate |
WO2003074833A2 (en) * | 2002-03-01 | 2003-09-12 | Cesi Chemical, A Flotek Company | Composition and process for well cleaning |
US7220712B1 (en) | 2002-03-04 | 2007-05-22 | Maggi Anthony G | Compositions and methods for cleaning and conditioning |
US20070004615A1 (en) * | 2005-06-30 | 2007-01-04 | Brian Phillips | Cleaning composition |
US8222194B2 (en) * | 2008-05-09 | 2012-07-17 | Rhodia Operations | Cleaning compositions incorporating green solvents and methods for use |
US8512481B2 (en) * | 2010-10-22 | 2013-08-20 | Presstek, Inc. | Press cleaning with low-VOC solvent compositions |
RU2013125289A (en) | 2010-11-01 | 2014-12-10 | КОГНИС АйПи МЭНЕДЖМЕНТ ГМБХ | Biodegradable Quaternary Compounds as Emulsifiers for Microemulsions |
CN102277239A (en) * | 2011-07-20 | 2011-12-14 | 天津鎏虹科技发展有限公司 | Natural plant aqueous cleaning agent and preparation method thereof |
MX360865B (en) * | 2012-01-02 | 2018-11-09 | Environmetal Development Products Endevpro Ltd Star | Composition of biodegradable surfactants for separating hydrocarbon impurities. |
US9068108B2 (en) | 2013-03-14 | 2015-06-30 | Cesi Chemical, Inc. | Methods and compositions for stimulating the production of hydrocarbons from subterranean formations |
US10000693B2 (en) * | 2013-03-14 | 2018-06-19 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
US9428683B2 (en) | 2013-03-14 | 2016-08-30 | Flotek Chemistry, Llc | Methods and compositions for stimulating the production of hydrocarbons from subterranean formations |
US9868893B2 (en) | 2013-03-14 | 2018-01-16 | Flotek Chemistry, Llc | Methods and compositions for use in oil and/or gas wells |
US11180690B2 (en) | 2013-03-14 | 2021-11-23 | Flotek Chemistry, Llc | Diluted microemulsions with low surface tensions |
US10060073B2 (en) * | 2013-05-23 | 2018-08-28 | Washing Systems, Llc | Method of laundering industrial garments |
CN105238578B (en) * | 2015-10-30 | 2017-12-15 | 深圳市新纶科技股份有限公司 | A kind of microemulsion-type cleaning agent and preparation method thereof |
US10119099B2 (en) | 2017-01-10 | 2018-11-06 | Envirox, L.L.C. | Peroxide based multi-purpose cleaner, degreaser, sanitizer/virucide and associated solutions and methods for preparing the same |
GB2573546B (en) * | 2018-05-09 | 2021-03-31 | Twi Ltd | A method of diffusion bonding |
US11518966B2 (en) | 2019-11-07 | 2022-12-06 | Envirox, L.L.C. | Peroxide-based multi-purpose cleaning, degreasing, sanitizing, and disinfecting solutions and methods for preparing the same |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3728265A (en) * | 1970-02-09 | 1973-04-17 | Alberto Culver Co | High-foaming liquid detergent compositions |
EP0129987A1 (en) * | 1983-05-27 | 1985-01-02 | Optikon Limited | Cleaning compositions |
GB2144763A (en) * | 1983-08-11 | 1985-03-13 | Procter & Gamble | Liquid detergent compositions with magnesium salts |
US4511488A (en) * | 1983-12-05 | 1985-04-16 | Penetone Corporation | D-Limonene based aqueous cleaning compositions |
US4704225A (en) * | 1986-05-01 | 1987-11-03 | Stoufer Wilmer B | Cleaning composition of terpene hydrocarbon and a coconut oil fatty acid alkanolamide having water dispersed therein |
EP0316726A2 (en) * | 1987-11-12 | 1989-05-24 | Colgate-Palmolive Company | Stable microemulsion cleaning composition |
USRE33210E (en) * | 1986-05-01 | 1990-05-08 | Cleaning composition of terpene hydrocarbon and a coconut oil fatty acid alkanolamide having water dispersed therein |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3642644A (en) * | 1969-12-16 | 1972-02-15 | Procter & Gamble | Stable dry cleaning compositions |
US4199482A (en) * | 1977-03-31 | 1980-04-22 | Colgate-Palmolive Company | Laundry pre-spotter composition and method of using same |
JPS5414406A (en) * | 1977-07-05 | 1979-02-02 | Dotolo V | Deterging compositions |
US4256661A (en) * | 1978-05-09 | 1981-03-17 | Mobay Chemical Corporation | Production of thiosemicarbazide |
CA1120820A (en) * | 1978-06-28 | 1982-03-30 | Morris A. Johnson | Pine oil cleaner disinfectant compositions containing quaternary ammonium compound |
US4362638A (en) * | 1980-07-28 | 1982-12-07 | S. C. Johnson & Son, Inc. | Gelled laundry pre-spotter |
US4455250A (en) * | 1981-01-12 | 1984-06-19 | American Cyanamid Company | Stable liquid hard surface cleanser composition containing DGH and a quaternary germicide |
US4540505A (en) * | 1981-05-22 | 1985-09-10 | American Cyanamid Company | Disinfectant spray cleanser containing glycol ethers |
US4414128A (en) * | 1981-06-08 | 1983-11-08 | The Procter & Gamble Company | Liquid detergent compositions |
US4336151A (en) * | 1981-07-06 | 1982-06-22 | American Cyanamid Company | Disinfectant/cleanser compositions exhibiting reduced eye irritancy potential |
US4336152A (en) * | 1981-07-06 | 1982-06-22 | American Cyanamid Company | Disinfectant/cleanser compositions exhibiting reduced eye irritancy potential |
US4438009A (en) * | 1981-08-14 | 1984-03-20 | S. C. Johnson & Son, Inc. | Low solvent laundry pre-spotting composition |
DE3270670D1 (en) * | 1981-11-12 | 1986-05-22 | Procter & Gamble | Liquid detergent compositions |
EP0174711A1 (en) * | 1984-08-28 | 1986-03-19 | Varn Products Company, Inc. | Biodegradable emulsion for removing printing ink from printing press component parts |
US4620937A (en) * | 1985-02-11 | 1986-11-04 | Joseph Dellutri | All purpose cleaner containing D-Limonene |
US4640719A (en) * | 1985-07-01 | 1987-02-03 | Petroleum Fermentations N.V. | Method for printed circuit board and/or printed wiring board cleaning |
US4859359A (en) * | 1988-03-25 | 1989-08-22 | Dyna-5, Inc. | Hard surface cleaning and polishing compositions |
US4867800B1 (en) * | 1988-07-21 | 1995-02-14 | Du Pont | Cleaning composition of terpene compound and dibasic ester |
-
1991
- 1991-07-19 US US07/732,565 patent/US5213624A/en not_active Expired - Lifetime
-
1992
- 1992-07-17 WO PCT/US1992/005995 patent/WO1993002169A1/en active Application Filing
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3728265A (en) * | 1970-02-09 | 1973-04-17 | Alberto Culver Co | High-foaming liquid detergent compositions |
EP0129987A1 (en) * | 1983-05-27 | 1985-01-02 | Optikon Limited | Cleaning compositions |
GB2144763A (en) * | 1983-08-11 | 1985-03-13 | Procter & Gamble | Liquid detergent compositions with magnesium salts |
US4511488A (en) * | 1983-12-05 | 1985-04-16 | Penetone Corporation | D-Limonene based aqueous cleaning compositions |
US4511488B1 (en) * | 1983-12-05 | 1990-09-11 | Penetone Corp | |
US4704225A (en) * | 1986-05-01 | 1987-11-03 | Stoufer Wilmer B | Cleaning composition of terpene hydrocarbon and a coconut oil fatty acid alkanolamide having water dispersed therein |
USRE33210E (en) * | 1986-05-01 | 1990-05-08 | Cleaning composition of terpene hydrocarbon and a coconut oil fatty acid alkanolamide having water dispersed therein | |
EP0316726A2 (en) * | 1987-11-12 | 1989-05-24 | Colgate-Palmolive Company | Stable microemulsion cleaning composition |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2266725A (en) * | 1992-04-30 | 1993-11-10 | Kao Corp | Composition for removing oil & grease. |
GB2266725B (en) * | 1992-04-30 | 1996-07-03 | Kao Corp | Detergent composition for precision parts or jigs |
US5567348A (en) * | 1992-04-30 | 1996-10-22 | Kao Corporation | Detergent composition for precision parts or jigs |
US5818399A (en) * | 1994-02-09 | 1998-10-06 | Terumo Kabushiki Kaisha | Image communication apparatus |
WO1996017052A1 (en) * | 1994-12-02 | 1996-06-06 | Daewoo Electronics Co., Ltd. | Detergent composition and method for washing using the same |
US5910455A (en) * | 1995-09-01 | 1999-06-08 | Kimberly Clark Corp. | Hand cleanser |
WO2005111185A1 (en) * | 2004-05-07 | 2005-11-24 | Croda Uniqema Inc. | Solvated nonionic surfactants |
US7456139B2 (en) | 2004-05-07 | 2008-11-25 | Croda Uniqema, Inc. | Solvated nonionic surfactants |
CN1961064B (en) * | 2004-05-07 | 2013-03-27 | 尤利凯玛美国有限责任公司 | Solvated nonionic surfactants |
EP2841540A4 (en) * | 2012-04-24 | 2016-02-10 | Stepan Co | Aqueous hard surface cleaners based on terpenes and fatty acid derivatives |
US9758751B2 (en) | 2012-04-24 | 2017-09-12 | Stepan Company | Aqueous hard surface cleaners based on terpenes and fatty acid derivatives |
US10233412B2 (en) | 2012-04-24 | 2019-03-19 | Stepan Company | Aqueous hard surface cleaners based on terpenes and fatty acid derivatives |
EP2857362A4 (en) * | 2012-07-31 | 2015-12-30 | Orientnano Co Ltd | Microbial flora activator, anti-filamentous fungi agent comprising said microbial flora activator as active ingredient, and method for treating waste water containing oil, fat, etc. using said microbial flora activator |
CN110582559A (en) * | 2017-07-05 | 2019-12-17 | Jxtg能源株式会社 | W/O emulsion detergent composition, cleaning method using W/O emulsion detergent composition, and method for producing W/O emulsion detergent composition |
CN110582559B (en) * | 2017-07-05 | 2021-05-11 | Jxtg能源株式会社 | W/O emulsion detergent composition, cleaning method using the same, and method for producing the same |
Also Published As
Publication number | Publication date |
---|---|
US5213624A (en) | 1993-05-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5213624A (en) | Terpene-base microemulsion cleaning composition | |
US4316824A (en) | Liquid detergent composition containing alkyl sulfate and alkyl ethoxylated sulfate | |
US6228830B1 (en) | Heavy oil remover | |
CA1305640C (en) | Low foam surfactant mixtures | |
EP3470506B1 (en) | Alkyl amides for enhanced food soil removal | |
US5277836A (en) | Terpene cleaning compositions and methods of using the same | |
CA2265407C (en) | Aqueous cleaning and disinfecting compositions which include quaternary ammonium compounds, block copolymer surfactants and further mitigating compounds which compositions featurereduced irritation | |
WO2008091753A1 (en) | Cleaning composition | |
CN102242369A (en) | Metal bearing water-based cleaning agent and preparation method and application thereof | |
EP0904344A1 (en) | Germicidal dishwashing detergent compositions | |
US3507798A (en) | Built detergents containing nonionic polyoxyalkylene surface active materials | |
CN102018490A (en) | D-limonene contained cleaning moist wipe used in kitchens and production method thereof | |
CA2265363C (en) | Aqueous cleaning and disinfecting compositions having reduced irritation characteristics based on quaternary ammonium compounds including block copolymer surfactants and further surfactants | |
CN112094703B (en) | Oil-removing environment-friendly kitchen wet tissue immersion liquid composition and preparation method thereof | |
JP2001020000A (en) | Microemulsion type low-temperature detergent composition | |
US6191099B1 (en) | Method for cleaning hydrocarbon-containing soils from surfaces | |
JP3610434B2 (en) | Nonionic surfactant | |
US4822514A (en) | Compositions and methods for cleaning surfaces while selectively imparting gloss or shine thereto | |
JPH0647677B2 (en) | Liquid detergent composition | |
EP0715646B1 (en) | Surfactants | |
JPH0461916B2 (en) | ||
JP2003336092A (en) | Concentrated liquid detergent composition | |
US10233406B2 (en) | Nonionic surfactant composition and surface cleaning formulation | |
US5837667A (en) | Environmentally safe detergent composition and method of use | |
JP2003013092A (en) | Detergent |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): BR CA JP KR |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IT LU MC NL SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
NENP | Non-entry into the national phase |
Ref country code: CA |
|
122 | Ep: pct application non-entry in european phase |