WO2000036206A1 - Dry cleaning compositions containing hydrofluoroether - Google Patents

Dry cleaning compositions containing hydrofluoroether Download PDF

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Publication number
WO2000036206A1
WO2000036206A1 PCT/US1999/008562 US9908562W WO0036206A1 WO 2000036206 A1 WO2000036206 A1 WO 2000036206A1 US 9908562 W US9908562 W US 9908562W WO 0036206 A1 WO0036206 A1 WO 0036206A1
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Prior art keywords
composition
carbon atoms
groups
cosolvent
hydrofluoroether
Prior art date
Application number
PCT/US1999/008562
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English (en)
French (fr)
Inventor
Jimmie R. Baran, Jr.
John C. Newland
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3M Innovative Properties Company
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Publication date
Application filed by 3M Innovative Properties Company filed Critical 3M Innovative Properties Company
Priority to AU35697/99A priority Critical patent/AU3569799A/en
Priority to JP2000588446A priority patent/JP2002532638A/ja
Priority to EP99917619A priority patent/EP1141468B1/en
Priority to KR1020017007343A priority patent/KR20010101188A/ko
Priority to DE69935008T priority patent/DE69935008T2/de
Publication of WO2000036206A1 publication Critical patent/WO2000036206A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/28—Organic compounds containing halogen
    • C11D7/30—Halogenated hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/02—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents
    • D06L1/04—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents combined with specific additives
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5022—Organic solvents containing oxygen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/02—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • This invention relates to dry cleaning compositions and particularly to dry cleaning compositions containing hydrofluoroethers.
  • Solvent cleaning applications where contaminated articles are immersed in (or washed with) solvent liquids and/or vapors are well known. Applications involving one or more stages of immersion, rinsing, and/or drying are common. Solvents can be used at ambient temperature (often, accompanied by ultrasonic agitation) or at elevated temperatures up to the boiling point of the solvent.
  • a major concern in solvent cleaning is the tendency (especially where solvent is used at an elevated temperature) for solvent vapor loss from the cleaning system into the atmosphere. Although care is generally exercised to minimize such losses (for example, through good equipment design and vapor recovery systems), most practical cleaning applications result in some loss of solvent vapor into the atmosphere.
  • Solvent cleaning processes have traditionally utilized chlorinated solvents (for example, chlorofluorocarbons, such as l,l,2-trichloro-l,2,2-trifluoroethane, and chlorocarbons, such as 1,1,1-trichloroethane) alone or in admixture with one or more cosolvents such as aliphatic alcohols or other low molecular weight, polar compounds.
  • chlorinated solvents for example, chlorofluorocarbons, such as l,l,2-trichloro-l,2,2-trifluoroethane, and chlorocarbons, such as 1,1,1-trichloroethane
  • cosolvents such as aliphatic alcohols or other low molecular weight, polar compounds.
  • substitutes or replacements for the commonly-used cleaning solvents should have a low ozone depletion potential, should have boiling ranges suitable for a variety of solvent cleaning applications, and should have the ability to dissolve both hydrocarbon-based, fluorocarbon-based soils as well as aqueous based stains.
  • substitutes will also be low in toxicity, have no flash points (as measured by ASTM D3278-89), have acceptable stability for use in cleaning applications, and have short atmospheric lifetimes and low global warming potentials.
  • European Patent Publication No. 0 450 855 A2 (Imperial Chemical Industries PLC) describes the use of low molecular weight, fluorine-containing ethers of boiling point 20 ° - 120 °C in solvent cleaning applications.
  • U.S. Patent No. 5,275,669 (Van Der Puy et al.) describes hydrofiuorocarbon solvents useful for dissolving contaminants or removing contaminants from the surface of a substrate.
  • the solvents have 4 to 7 carbon atoms and have a portion which is fluorocarbon, the remaining portion being hydrocarbon.
  • U.S. Patent No. 3,453,333 (Litt et al.) discloses fluorinated ethers containing at least one halogen substituent other than fluorine and states that those ethers which are liquid can be used as solvents for high molecular weight resinous perhalogenated compounds such as solid polychlorotrifluoroethylene resins.
  • the compounds are said to be useful as hypnotic and anesthetic agents; as monomers for preparing heat-stable, fire-resistant, or self-lubricant polymers; and in phyto-sanitary and phyto-pharmaceutical fields.
  • German Patent Publication No. 1,294,949 (Farbwerke Hoechst AG) describes a technique for the production of perfluoroalkyl-alkyl ethers, said to be useful as narcotics and as intermediates for the preparation of narcotics and polymers.
  • the invention provides dry cleaning compositions comprising hydro fluoroether, a cosolvent selected from the group consisting of glycol ethers, fluorocarbon surfactants, alkanes, alkanols, and mixtures thereof, and water present in an amount of less than 1 percent by weight.
  • the compositions of the invention provide a dry cleaning composition comprising hydrofluoroether, a cosolvent selected from the group consisting of glycol ethers, alkanols, fluorocarbon surfactants, and mixtures thereof, water present in an amount of less than 1 percent by weight, and a detergent.
  • the invention provides a method of cleaning fabric articles comprising the step of contacting an effective amount of either of the above dry cleaning compositions with a fabric for a length of time sufficient to clean the article.
  • the dry cleaning compositions of the invention are generally less aggressive toward fabrics than perchloroethylene, allowing its use with a wider variety of fabrics.
  • the compositions of the invention also dry faster than perchloroethylene systems.
  • homogeneous compositions are preferred in the practice of the invention, but inhomogeneous formulations such as liquid/liquid emulsions may also be used.
  • Hydrofluoroethers suitable for use in the process are generally low polarity chemical compounds minimally containing carbon, fluorine, hydrogen, and catenary (that is, in-chain) oxygen atoms. HFEs can optionally contain additional catenary heteroatoms, such as nitrogen and sulfur. HFEs have molecular structures which can be linear , branched, or cyclic, or a combination thereof (such as alkylcycloaliphatic), and are preferably free of ethylenic unsaturation, having a total of about 4 to about 20 carbon atoms. Such HFEs are known and are readily available, either as essentially pure compounds or as mixtures.
  • Preferred hydrofluoroethers can have a boiling point in the range from about 40 °C to about 275 °C, preferably from about 50 °C to about 200 °C, even more preferably from about 50 °C to about 121 °C.
  • the HFEs of the invention have a higher vapor pressure than that of perchloroethylene, thus increasing the dry time of the cleaned fabric.
  • hydro fluoroether be non-flammable.
  • the relationship between the fluorine, hydrogen and carbon atoms of the HFE should meet the requirements of Equation I.
  • the HFEs can be relatively low in toxicity, can have very low ozone depletion potentials, for example, zero, have short atmospheric lifetimes, and have low global warming potentials relative to chlorofluorocarbons and many chlorofluorocarbon substitutes.
  • Useful hydrofluoroethers include two varieties: segregated hydrofluoroethers and omega-hydrofluoroalkylethers. Structurally, the segregated hydrofluoroethers comprise at least one mono-, di-, or trialkoxy-substituted perfluoroalkane, perfluorocycloalkane, perfluorocycloalkyl-containing perfluoroalkane, or perfluorocycloalkylene-containing perfluoroalkane compound.
  • Rf-(O-R n ) ⁇ (Formula I) wherein: x is from 1 to about 3; when x is 1, Rf is selected from the group consisting of linear or branched perfluoroalkyl groups having from 2 to about 15 carbons, perfluorocycloalkyl groups having from 3 to about 12 carbon atoms, and perfluorocycloalkyl-containing perfluoroalkyl groups having from 5 to about 15 carbon atoms; when x is 2, Rf is selected from the group consisting of linear or branched perfluoroalkanediyl groups or perfiuoroalkylidene groups having from 2 to about 15 carbon atoms, perfluorocycloalkyl- or perfluorocycloalkylene-containing perfluoroalkanediyl or perfiuoroalkylidene groups having from 6 to about 15 carbon atoms, and perfluorocycloalkylidene groups having from 3 to about 12 carbon atom
  • x is 1; Rf is defined as above; R n is an alkyl group having from 1 to about 6 carbon atoms; Rf but not R ⁇ can contain one or more catenary heteroatoms; and the sum of the number of carbon atoms in Rf and the number of carbon atoms in R ⁇ is greater than or equal to 4.
  • x is 1 ;
  • Rf is selected from the group consisting of linear or branched perfluoroalkyl groups having from 3 to about 8 carbon atoms, perfluorocycloalkyl-containing perfluoroalkyl or perfiuoroalkylidene groups having from 5 to about 8 carbon atoms, and perfluorocycloalkyl groups having from 5 to about 6 carbon atoms;
  • R ⁇ is an alkyl group having from 1 to about 3 carbon atoms; and Rf but not
  • Rh can contain one or more catenary heteroatoms.
  • the perfluoroalkyl and perfluorocycloalkylene groups contained within the perfluoroalkyl, perfluoroalkanediyl, perfiuoroalkylidene, and perfluoroalkanetriyl groups can optionally and independently be substituted with, for example, one or more perfluoromefhyl groups.
  • hydrofluoroether compounds described by Formula I include the following:
  • Preferred segregated hydrofluoroethers include n-C3F7OCH3 (CF3)2CFOCH3 5 n- C 4 F 9 OCH3 5 (CF3)2CFCF 2 OCH 3; n-C 4 F 9 OC H 55 (CF 3 )2CFCF2OC2H 5; (CF 3 )3COCH 3> CH 3 O(CF 2 ) 4 OCH3 5 and CH 3 O(CF 2 ) 6 OCH 3 .
  • Segregated hydrofluoroethers can be prepared by alkylation of perfluorinated alkoxides prepared by the reaction of the corresponding perfluorinated acyl fluoride or perfluorinated ketone with an anhydrous alkali metal fluoride (for example, potassium fluoride or cesium fluoride) or anhydrous silver fluoride in an anhydrous polar aprotic solvent.
  • anhydrous alkali metal fluoride for example, potassium fluoride or cesium fluoride
  • anhydrous silver fluoride in an anhydrous polar aprotic solvent.
  • a fluorinated tertiary alcohol can be allowed to react with a base (for example, potassium hydroxide or sodium hydroxide) to produce a perfluorinated tertiary alkoxide which can then be alkylated by reaction with alkylating agent, such as described in U.S. Patent No. 5,750,797.
  • a base for example, potassium hydroxide or sodium hydroxide
  • Suitable alkylating agents for use in the preparation of segregated hydrofluoroethers include dialkyl sulfates (for example, dimethyl sulfate), alkyl halides (for example, methyl iodide), alkyl p-toluene sulfonates (for example, methyl p- toluenesulfonate), alkyl perfluoroalkanesulfonates (for example, methyl perfiuoromethanesulfonate), and the like.
  • dialkyl sulfates for example, dimethyl sulfate
  • alkyl halides for example, methyl iodide
  • alkyl p-toluene sulfonates for example, methyl p- toluenesulfonate
  • alkyl perfluoroalkanesulfonates for example, methyl perfiuoromethanesulfonate
  • Suitable polar aprotic solvents include acyclic ethers such as diethyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; carboxylic acid esters such as methyl formate, ethyl formate, methyl acetate, diethyl carbonate, propylene carbonate, and ethylene carbonate; alkyl nitrites such as acetonitrile; alkyl amides such as N,N-dimethylformamide, N,N-diethylformamide, and N- methylpyrrolidone; alkyl sulfoxides such as dimethyl sulfoxide; alkyl sulfones such as dimethylsulfone, tetramethylene sulfone, and other sulfolanes; oxazolidones such as N- methyl-2-oxazolidone; and mixtures thereof.
  • acyclic ethers such as diethyl ether, ethylene glyco
  • Suitable perfluorinated acyl fluorides can be prepared by electrochemical fluorination (ECF) of the corresponding hydrocarbon carboxylic acid (or a derivative thereof), using either anhydrous hydrogen fluoride (Simons ECF) or KF 2 # HF (Phillips ECF)
  • ECF electrochemical fluorination
  • KF 2 # HF Phillips
  • Perfluorinated acyl fluorides and perfluorinated ketones can also be prepared by dissociation of perfluorinated carboxylic acid esters (which can be prepared from the corresponding hydrocarbon or partially-fluorinated carboxylic acid esters by direct fluorination with fluorine gas). Dissociation can be achieved by contacting the perfluorinated ester with a source of fluoride ion under reacting conditions (see the method described in U.S. Patent No.
  • 3,900,372 (Childs) or by combining the ester with at least one initiating reagent selected from the group consisting of gaseous, nonhydroxylic nucleophiles; liquid, non-hydroxylic nucleophiles; and mixtures of at least one nonhydroxylic nucleophile (gaseous, liquid, or solid) and at least one solvent which is inert to acylating agents.
  • at least one initiating reagent selected from the group consisting of gaseous, nonhydroxylic nucleophiles; liquid, non-hydroxylic nucleophiles; and mixtures of at least one nonhydroxylic nucleophile (gaseous, liquid, or solid) and at least one solvent which is inert to acylating agents.
  • Initiating reagents which can be employed in the dissociation are those gaseous or liquid, non-hydroxylic nucleophiles and mixtures of gaseous, liquid, or solid, nonhydroxylic nucleophile(s) and solvent (hereinafter termed "solvent mixtures") which are capable of nucleophilic reaction with perfluorinated esters.
  • solvent mixtures gaseous or liquid, nonhydroxylic nucleophiles
  • Suitable gaseous or liquid, nonhydroxylic nucleophiles include dialkylamines, trialkylamines, carboxamides, alkyl sulfoxides, amine oxides, oxazolidones, pyridines, and the like, and mixtures thereof.
  • Suitable non-hydroxylic nucleophiles for use in solvent mixtures include such gaseous or liquid, non-hydroxylic nucleophiles, as well as solid, non-hydroxylic nucleophiles, for example, fluoride, cyanide, cyanate, iodide, chloride, bromide, acetate, mercaptide, alkoxide, thiocyanate, azide, trimethylsilyl difluoride, bisulfite, and bifluoride anions, which can be used in the form of alkali metal, ammonium, alkyl-substituted ammonium
  • hydrofluoroethers are the omega-hydrofluoroalkyl ethers described in U.S. Patent No. 5,658,962 (Moore et al.) which can be described by the general structure shown in Formula II: X-Rf'-(O-Rf")y-O-R"-H (Formula II)
  • X is either F or H;
  • Rf' is a divalent perfluorinated organic radical having from 1 to about 12 carbon atoms;
  • R f is a divalent perfluorinated organic radical having from 1 to about 6 carbon atoms
  • R" is a divalent organic radical having from 1 to 6 carbon atoms, and preferably, R" is perfluorinated; and y is an integer from 0 to 4; with the proviso that when X is F and y is 0, R" contains at least one F atom.
  • Representative compounds described by Formula II which are suitable for use in the processes of the invention include the following compounds:
  • omega-hydro fluoroalkyl ethers described by Formula II can be prepared by decarboxylation of the corresponding precursor fluoroalkyl ether carboxylic acids and salts thereof or, preferably, the saponifiable alkyl esters thereof, as described in U.S. Patent No.
  • omega-hydrofluoroalkyl ethers can be prepared by reduction of the corresponding omega-chlorofluoroalkyl ethers (for example, those omega- chlorofiuoroalkyl ethers described in WO 93/11868 published application), which is also described in U.S. Patent No. 5,658,962.
  • the dry cleaning compositions of the invention generally contain greater than about 70 percent by weight HFE, preferably greater than about 75 weight percent HFE, and more preferably greater than about 80 weight percent HFE. Such amounts aid in improved dry times and maintains a high flashpoint.
  • the compositions of the invention contain one or more cosolvents.
  • the purpose of a cosolvent in the dry cleaning compositions of the invention is to increase the oil solvency of the HFE.
  • the cosolvent also enables the formation of a homogeneous solution containing a cosolvent, an HFE, and an oil; or a cosolvent, an HFE and an optional detergent.
  • a "homogeneous composition” is a single phased composition or a composition that appears to have only a single phase, for example, a solution or a microemulsion.
  • Useful cosolvents of the invention are soluble in HFEs or water, are compatible with typical dry cleaning detergents, and can solubilize oils typically found in stains on clothing, such as vegetable, mineral, or animal oils, and aqueous-based stains. Any cosolvent or mixtures of cosolvents meeting the above criteria may be used.
  • cosolvents include alcohols, ethers, glycol ethers, alkanes, alkenes, perfluorocarbons, perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters, ketones, aromatics, siloxanes, hydrochlorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, and fluorinated surfactants.
  • the cosolvent is selected from the group consisting of alcohols, alkanes, alkenes, cycloalkanes, esters, aromatics, hydrochlorocarbons, and hydrofluorocarbons.
  • cosolvents which can be used in the dry cleaning compositions of the invention include methanol, ethanol, isopropanol, t-butyl alcohol, methyl t-butyl ether, methyl t-amyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, propylene glycol methyl ether, ethylene glycol monobutyl ether, 1 ,2-dimethoxyethane, cyclohexane, 2,2,4- trimethylpentane, n-decane, terpenes (for example, ⁇ -pinene, camphene, and limonene), trans- 1,2-dichloroethylene, methylcyclopentane, decalin, methyl decanoate, t-butyl acetate, ethyl acetate, glycol methyl ether acetate, diethyl
  • fluorinated nonionic surfactants having the tradenames FLUORAD FC-171 and FC-170C, commercially available from Minnesota Mining and Manufacturing Co., St. Paul, MN, or ZONYL FSO and FSN, commercially available from E.I DuPont de Nemours and Co.,
  • the cosolvent is present in the compositions of the invention in an effective amount by weight to form a homogeneous composition with HFE.
  • the effective amount of cosolvent will vary depending upon which cosolvent or cosolvent blends are used and the HFE or blend of HFEs used in the composition. However, the preferred maximum amount of any particular cosolvent present in a dry cleaning composition should not be above the amount needed to make the composition inflammable.
  • cosolvent may be present in the compositions of the invention in an amount of from about 1 to about 30 percent by weight, preferably from about 5 to about 25 percent by weight, and more preferably from about 5 to about 20 percent by weight.
  • Water may be present in the compositions of the invention at a level of less than 1 percent by weight of the composition.
  • the amount of water present in the compositions of the invention is affected by the amount of water present in detergents or other additives. Water may be directly added to the compositions of the invention, if desired.
  • the compositions of the invention contain from 0 to less than 1 percent by weight water and more preferably, about 0.1 to less than 1 percent by weight water.
  • the dry cleaning compositions of the invention may contain one or more optional detergents.
  • Detergents are added to dry cleaning compositions to facilitate the cleaning of aqueous-based stains.
  • Useful detergents are those which can form a homogeneous solution with HFE and a cosolvent as defined above. These can be easily selected by one of ordinary skill in the art from the numerous known detergents used in the dry cleaning industry.
  • Examples of preferred commercially available detergents include those having the tradenames V ARI-CLEAN, ST ATICOL and NUTOUCH, commercially available from
  • the amount of detergent present in the compositions of the invention is only limited by the compatibility of the detergent. Any desired amount of a detergent may be used provided that the resulting dry cleaning composition is homogeneous as defined above.
  • An effective amount of a detergent is that amount which is compatible with or soluble in either the dispersed or continuous phase.
  • the detergents may be present in the compositions of the invention in an amount of about 2 percent by weight or less.
  • the dry cleaning compositions may also optionally contain other additives that would alter the physical properties of the fabric in a desired way, after the cleaning process. These would include materials that would increase the hand, or softness, of the fabric, repellency, etc.
  • the cleaning compositions of the invention can be made by simply mixing the components together to form either a solution or a microemulsion.
  • articles of clothing are cleaned by contacting a sufficient amount of the dry cleaning composition of the invention with the clothing articles for a sufficient period of time to clean the articles or otherwise remove stains.
  • the amount of dry cleaning composition used and the amount of time the composition contacts the article can vary based on equipment and the number of articles being cleaned.
  • the reactor was then resealed and water (6.0 kg) was added slowly to the reactor. After the exothermic reaction of the water with unreacted heptafluorobutyryl fluoride had subsided, the reactor was cooled to 25 °C and the reactor contents were stirred for 30 minutes. The reactor pressure was carefully vented, and the lower organic phase was removed, affording 22.6 kg of material which was
  • propylene glycol n-propyl ether having the tradename DOWANOL PnP ether, commercially available from Dow Chemical Co.,
  • STATICOL surfactant commercially available from R. R. Streets, a proprietary detergent formulation used in dry cleaning formulations based on perchloroethylene
  • Dry Cleaning Simulation Test a laboratory scale test designed to mimic conditions in a dry cleaning shop, used to evaluate the effectiveness of dry cleaning compositions in removing oil- and water-based stains from fabrics.
  • the water-based stains consisted of 3 drops each of HEINZ ketchup and red wine (Cabernet Sauvignon, E.J. Gallo Wineries, Modesto, CA).
  • the stains were each covered with a piece of wax paper, and a five pound weight was applied to each of the stains on the fabric for one minute to simulate grinding the stain into the garment.
  • the weight and wax paper were then removed, and the stained fabric was exposed to ambient air for 20 minutes.
  • the pieces of fabric were then each placed in an 8 ounce (236 mL) glass jar filled with a cleaning solution. Then the jars were capped and shaken for 20 minutes, the fabric swatches were removed, and excess cleaning solution was squeezed out by running the fabric swatch through a roller press.
  • the swatches were then hung in a forced air oven and dried at 160 °F (71 °C) for 15 minutes.
  • the degree of staining was measured immediately after drying using a compact tristimulus color analyzer, having the tradename MINOLTA 310 Chroma Meter. The reported values in the Tables are an average of three measurements.
  • the analyzer measures the degree of staining as a Delta E ( ⁇ E) value, a mathematical calculation which describes the total color space relative to unstained fabric. The smaller the number, the smaller the difference in color change, that is, the less noticeable the stain. Differences of less than 1 cannot be detected by the human eye.
  • a cosolvent was considered useful if it produced a clear solution when added at a certain minimum percent by weight (even if it produced a cloudy solution at lesser concentrations).
  • a STATICOL-based concentrate was formulated which contained 75 g of CZ1F9OCH3, 0.75 g of STATICOL surfactant and 0.8 g of water.
  • TOUCH-based concentrate was formulated which contained 75 g of C F9OCH3 and 1.0 g of NU TOUCH surfactant (the NU TOUCH surfactant contains some water).
  • the minimum weight percent of each cosolvent required to form compatible mixtures with each concentrate was determined, and the results are presented in TABLE 2.
  • the Dry Cleaning Simulation Test Procedure was used to evaluate several of the C 4 F9OCH3/cosolvent blends listed in TABLE 1 for removal of ketchup, red wine, mineral oil, and com oil stains from yellow crepe.
  • the amount of cosolvent used was the minimum amount listed in Table 1 to produce a homogeneous solution.
  • Also evaluated as comparative examples were C 4 F9OCH3 (C3) and perchloroethylene (C4).
  • the Dry Cleaning Simulation Test Procedure was used to evaluate several of the C 4 F9OCH 3 /cosolvent/STATICOL surfactant/water blends listed in TABLE 2 for removal of ketchup, red wine, mineral oil and com oil stains from peach twill. This time the cosolvent was incorporated at a constant 18 percent by weight into each blend, rather than at the concentration shown in TABLE 2. This is the minimum amount of cosolvent required for all of the compositions in TABLE 2 to be homogeneous, and thus could be compared at equal cosolvent amounts. Also evaluated as a comparative example was a standard dry cleaning formulation containing 75 g of perchloroethylene, 0.75 g of STATICOL surfactant and 0.8 g of water (C5).
  • the Dry Cleaning Simulation Test Procedure was used to evaluate several of the C 4 F9OCH3/cosolvent/STATICOL surfactant/water blends listed in TABLE 2 for removal of ketchup, red wine, mineral oil and com oil stains from yellow crepe. Again the cosolvent was incorporated at a constant 18 percent by weight into each blend, rather than at the concentration shown in TABLE 2. This is the minimum amount of cosolvent required for all of the compositions in TABLE 2 to be homogeneous, and thus could be compared at equal cosolvent amounts. Also evaluated as a comparative example was a standard dry cleaning formulation containing 75 g of perchloroethylene, 0.75 g of STATICOL surfactant and 0.8 g of water (C6).
  • the Dry Cleaning Simulation Test Procedure was used to evaluate several of the C 4 F9OCH 3 /cosolvent/NU TOUCH surfactant blends listed in TABLE 2 for removal of ketchup, red wine, mineral oil and com oil stains from peach twill. Again the cosolvent was incorporated at a constant 18 percent by weight into each blend, rather than at the concentration shown in TABLE 2. This is the minimum amount of cosolvent required for all of the compositions in TABLE 2 to be homogeneous, and thus could be compared at equal cosolvent amounts. Also evaluated as a comparative example was a standard dry cleaning formulation consisting of 75 g of perchloroethylene and 1.0 g of NU TOUCH surfactant (C7).
  • the Dry Cleaning Simulation Test Procedure was used to evaluate several of the C 4 F 9 OCH3/cosolvent/NU TOUCH surfactant blends listed in TABLE 2 for removal of ketchup, red wine, mineral oil and com oil stains from yellow crepe. Again the cosolvent was incorporated at a constant 18 percent by weight into each blend, rather than at the concentration shown in TABLE 2. This is the minimum amount of cosolvent required for all of the compositions in TABLE 2 to be homogeneous, and thus could be compared at equal cosolvent amounts. Also evaluated as a comparative example was a standard dry cleaning formulation consisting of 75 g of perchloroethylene and 1.0 g of NU TOUCH surfactant (C8).
  • the Dry Cleaning Simulation Test Procedure was used to evaluate several of the C 4 F9OCH3/cosolvent/STATICOL surfactant/water blends listed in TABLE 2 for removal of ketchup, red wine, mineral oil and com oil stains from peach twill. This time each cosolvent was incorporated at the same level as shown in TABLE 2 (that is, a sufficient cosolvent level to produce a homogeneous solution). Also evaluated as a comparative example was a standard dry cleaning formulation containing 75 g of perchloroethylene, 0.75 g of STATICOL surfactant and 0.8 g of water (C9).
  • the Dry Cleaning Simulation Test Procedure was used to evaluate several of the C 4 F9OCH3/cosolvent/NU TOUCH surfactant blends listed in TABLE 2 for removal of ketchup, red wine, mineral oil and com oil stains from peach twill. This time each cosolvent was incorporated at the same level as shown in TABLE 2 (that is, a sufficient cosolvent level to produce a homogeneous solution). Also evaluated as a comparative example was a standard dry cleaning formulation consisting of 75 g of perchloroethylene and 1.0 g of NU TOUCH surfactant (Cl 1). Average ⁇ E values for each stain and solvent/surfactant blend are presented in TABLE 11.
  • the Dry Cleaning Simulation Test Procedure was used to evaluate several of the C 4 F9OCH3/cosolvent/NU TOUCH surfactant blends listed in TABLE 2 for removal of ketchup, red wine, mineral oil, and com oil stains from yellow crepe. This time each cosolvent was incorporated at the same level as shown in TABLE 2 (that is, a sufficient cosolvent level to produce a homogeneous solution). Also evaluated as a comparative example was a standard dry cleaning formulation consisting of 75 g of perchloroethylene and 1.0 g of NU TOUCH surfactant (C12).

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PCT/US1999/008562 1998-12-16 1999-04-19 Dry cleaning compositions containing hydrofluoroether WO2000036206A1 (en)

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AU35697/99A AU3569799A (en) 1998-12-16 1999-04-19 Dry cleaning compositions containing hydrofluoroether
JP2000588446A JP2002532638A (ja) 1998-12-16 1999-04-19 ヒドロフルオロエーテルを含有するドライクリーニング組成物
EP99917619A EP1141468B1 (en) 1998-12-16 1999-04-19 Dry cleaning compositions containing hydrofluoroether
KR1020017007343A KR20010101188A (ko) 1998-12-16 1999-04-19 히드로플루오로에테르를 포함하는 드라이 클리닝 조성물
DE69935008T DE69935008T2 (de) 1998-12-16 1999-04-19 Hydrofluorether enthaltende trockenreinigungsmittel

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WO2003033805A1 (en) * 2001-10-12 2003-04-24 Unilever N.V. Non-toxic cleaning composition
WO2003033637A1 (en) * 2001-10-12 2003-04-24 Unilever N.V. Cleaning compositon with an immiscible liquid system
WO2003038179A1 (en) * 2001-10-26 2003-05-08 Unilever N.V. Dry cleaning process
WO2003044149A1 (en) * 2001-11-20 2003-05-30 Unilever N.V. Process for cleaning a substrate
WO2003068175A1 (en) * 2002-02-11 2003-08-21 Arrow Pharmaceuticals As A method of cleaning a contact lens
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JP2002080893A (ja) * 2000-06-23 2002-03-22 Asahi Kasei Corp 不燃性洗浄剤、洗浄方法および洗浄装置
WO2003033805A1 (en) * 2001-10-12 2003-04-24 Unilever N.V. Non-toxic cleaning composition
WO2003033637A1 (en) * 2001-10-12 2003-04-24 Unilever N.V. Cleaning compositon with an immiscible liquid system
US6706678B2 (en) 2001-10-12 2004-03-16 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Non-toxic cleaning composition
US6727218B2 (en) 2001-10-12 2004-04-27 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Delivery of benefit agents
WO2003038179A1 (en) * 2001-10-26 2003-05-08 Unilever N.V. Dry cleaning process
US6900166B2 (en) 2001-10-26 2005-05-31 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Dry cleaning process comprising a dry cleaning step and a regeneration step
WO2003044149A1 (en) * 2001-11-20 2003-05-30 Unilever N.V. Process for cleaning a substrate
WO2003068175A1 (en) * 2002-02-11 2003-08-21 Arrow Pharmaceuticals As A method of cleaning a contact lens
WO2004057093A1 (en) * 2002-12-19 2004-07-08 Unilever N.V. Dry cleaning process
WO2004057092A1 (en) * 2002-12-19 2004-07-08 Unilever N.V. Dry cleaning process
WO2004057096A1 (en) * 2002-12-19 2004-07-08 Unilever N.V. Dry cleaning process
WO2004057097A1 (en) * 2002-12-19 2004-07-08 Unilever N.V. Dry cleaning process
WO2004057095A1 (en) * 2002-12-19 2004-07-08 Unilever N.V. Dry cleaning process
WO2004057094A1 (en) * 2002-12-19 2004-07-08 Unilever N.V. Dry cleaning process
WO2004057098A1 (en) * 2002-12-19 2004-07-08 Unilever N.V. Dry cleaning process
WO2004057091A1 (en) * 2002-12-19 2004-07-08 Unilever N.V. Dry cleaning process
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US7452383B2 (en) 2002-12-19 2008-11-18 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Dry cleaning process
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WO2018128514A1 (ko) * 2017-01-09 2018-07-12 엘지전자 주식회사 드라이세정제 조성물
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US6159917A (en) 2000-12-12
EP1141468B1 (en) 2007-01-24
DE69935008T2 (de) 2007-11-15
AU3569799A (en) 2000-07-03
EP1141468A1 (en) 2001-10-10
KR20010101188A (ko) 2001-11-14
DE69935008D1 (de) 2007-03-15

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