WO1996027704A1 - Systeme de nettoyage a sec utilisant du gaz carbonique densifie et un tensioactif comme additif - Google Patents

Systeme de nettoyage a sec utilisant du gaz carbonique densifie et un tensioactif comme additif Download PDF

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Publication number
WO1996027704A1
WO1996027704A1 PCT/EP1996/000811 EP9600811W WO9627704A1 WO 1996027704 A1 WO1996027704 A1 WO 1996027704A1 EP 9600811 W EP9600811 W EP 9600811W WO 9627704 A1 WO9627704 A1 WO 9627704A1
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WIPO (PCT)
Prior art keywords
carbon dioxide
group
compounds
alkyl
surfactant
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PCT/EP1996/000811
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English (en)
Inventor
Sharon Harriott Jureller
Judith Lynne Kerschner
Myongsuk Bae-Lee
Lisa Del Pizzo
Rosemarie Harris
Carol Resch
Cathy Waja
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Unilever N.V.
Unilever Plc
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Priority claimed from US08/399,318 external-priority patent/US5683977A/en
Priority claimed from US08/399,317 external-priority patent/US5676705A/en
Application filed by Unilever N.V., Unilever Plc filed Critical Unilever N.V.
Priority to EP96905817A priority Critical patent/EP0813628A1/fr
Priority to AU49429/96A priority patent/AU4942996A/en
Publication of WO1996027704A1 publication Critical patent/WO1996027704A1/fr
Priority to FI973603A priority patent/FI973603A/fi

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    • 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
    • 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
    • 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
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
    • 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
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/17—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen in an inert solvent

Definitions

  • the invention pertains to a dry cleaning system utilizing densified carbon dioxide and a surfactant adjunct.
  • the invention also pertains to a method of dry cleaning fabrics utilising densified carbon dioxide and a surfactant
  • Supercritical fluid carbon dioxide provides a nontoxic, inexpensive, recyclable and environmentally acceptable solvent to remove soils in the dry cleaning process.
  • the solvent has been shown to be effective in removing nonpolar stains such as motor oil, when combined with a viscous cleaning solvent, particularly mineral oil or petrolatum as described in US S/N 715,299, filed June 14, 1991, assigned to The Clorox Company and corresponding to EP 518,653.
  • Supercritical fluid carbon dioxide has been combined with other components, such as a source of hydrogen peroxide and an organic bleach activator as described in US S/N 754,809, filed September 4, 1991 and owned by The Clorox Company, corresponding to EP 530,949.
  • the solvent power of densified carbon dioxide is low relative to ordinary liquid solvents and the carbon dioxide solvent alone is less effective on hydrophilic stains such as grape juice, coffee and tea and on compound hydrophobic stains such as lipstick and red candle wax, unless
  • anionic and nonionic agents such as alkylbenzene sulfates and sulfonates, ethoxylated alkyl phenols and ethoxylated fatty alcohols, were particularly effective when combined with a relatively large amount of water
  • the dry cleaning systems known in the art have merely combined cleaning agents with various viscosities and polarities with supercritical fluid CO 2 generally with high amounts of water as a cosolvent.
  • the actives clean soils as in conventional washing without any synergistic effect with the CO 2 solvent.
  • Another object of the invention is to provide a dry
  • the dry cleaning system used for cleaning a variety of soiled fabrics comprises densified carbon dioxide and about 0.001% to about 5% of a surfactant in supercritical fluid carbon dioxide.
  • the surfactant has a supercritical fluid CO 2 -philic functional moiety connected to a supercritical fluid CO 2 -phobic functional moiety.
  • Preferred CO 2 -philic moieties of the surfactant include halocarbons such as
  • the CO 2 -phobic groups for the surfactant contain preferably polyalkylene oxides, carboxylates, C 1-30 alkyl sulfonates, carbohydrates, glycerates, phosphates, sulfates and C 1-30 hydrocarbons.
  • the dry cleaning system may also be designed to include a modifier, such as water, or an organic solvent up to only about 5% by volume; enzymes up to about 10 wt.% and a bleaching agent such as a peracid.
  • a method for dry cleaning a variety of soiled fabrics wherein a selected surfactant and optionally a modifier, an enzyme, bleaching agent or mixtures thereof are combined and the cloth is contacted with the mixture.
  • Densified carbon dioxide is introduced into a cleaning vessel which is then pressurized from about 700 psi to about 10,000 psi and heated to a range of about 20°C to about 100°C. Fresh densified carbon dioxide is used to flush the cleaning vessel.
  • Figure 1 is a diagrammatic flow chart of the supercritical fluid carbon dioxide dry cleaning process according to the invention.
  • the invention provides a dry cleaning system which replaces conventional solvents with densified carbon dioxide in combination with selected cleaning surfactants.
  • modifiers, enzymes, bleaching agents and mixtures thereof are combined with the solvent and
  • Defined carbon dioxide means carbon dioxide in a gas form which is placed under pressures exceeding about 700 psi at about 20°C.
  • Supercritical fluid carbon dioxide means carbon dioxide which is at or above the critical temperature of 31°C and a critical pressure of 71 atmospheres and which cannot be condensed into a liquid phase despite the addition of further pressure.
  • denotesified carbon dioxide-philic in reference to surfactants R n Z n , wherein n and n' are each independently 1 to 50, means that the functional group, R n - is soluble in carbon dioxide at pressures of 500-10,000 psi and
  • n and n' are each independently 1-35.
  • Such functional groups (R n -) include halocarbons, polysiloxanes and branched polyalkylene oxides.
  • temperatures of 0-100°C of less than 10 weight percent are temperatures of 0-100°C of less than 10 weight percent.
  • the functional groups in Z n ,- include carboxylic acids, phosphatyl esters, hydroxys, C 1-30 alkyls or alkenyls, polyalkylene oxides, branched polyalkylene oxides,
  • carboxylates C 1-30 alkyl sulfonates, phosphates,
  • R n Z n (i.e., R n Z n ,, containing the CO 2 -philic functional group, R n -, and the CO 2 -phobic group, Z n ,-) will have an HLB of less than 15, preferably less than 13 and most preferably less than 12.
  • the polymeric siloxane containing surfactants, R n Z n also designated MD x D* y M, with M representing trimethylsiloxyl end groups, D x as a dimethylsiloxyl backbone (C O2 -philic functional group) and D* y as one or more substituted methylsiloxyl groups substituted with CO 2 -phobic R or R' groups as described in the Detailed Description Section will have a D x D* y ratio of greater than 0.5:1, preferably greater than 0.7:1 and most preferably greater than 1:1.
  • nonpolar stains refers to those which are at least partially made by nonpolar organic compounds such as oily soils, sebum and the like.
  • polar stains is interchangeable with the term “hydrophilic stains” and refers to stains such as grape juice, coffee and tea.
  • compound hydrophobic stains refers to stains such as lipstick and red candle wax.
  • particulate soils means soils containing
  • Densified carbon dioxide preferably supercritical fluid carbon dioxide
  • Densified carbon dioxide is used in the inventive dry cleaning system. It is noted that other densified molecules having supercritical properties may also be employed alone or in mixture. These molecules include methane, ethane, propane, ammonia, butane, n-pentane, n-hexane, cyclohexane, n-heptane, ethylene, propylene, methanol, ethanol,
  • the temperature range is between about 20°C and about 100°C, preferably 20°C to 60°C and most preferably 30°C to about 60°C.
  • the pressure during cleaning is about 700 psi to about 10,000 psi, preferably 800 psi to about 7,000 psi and most preferably 800 psi to about 6,000 psi.
  • a "substituted methylsiloxyl group” is a methylsiloxyl group substituted with a CO 2 -phobic group R or RM R or R' are each represented in the following formula:
  • A', F, n L', g, Z, G and h are defined below, and mixtures of R and R'.
  • a "substituted aryl” is an aryl substituted with a C 1-30 alkyl, alkenyl or hydroxyl, preferably a C 1-20 alkyl or alkenyl.
  • a “substituted carbohydrate” is a carbohydrate substituted with a C 1-10 alkyl or alkenyl, preferably a C 1-5 alkyl.
  • polyalkylene oxide alkyl
  • alkenyl each contain a carbon chain which may be either straight or branched unless otherwise stated.
  • a surfactant which is effective for use in a densified carbon dioxide dry cleaning system requires the combination of densified carbon dioxide-philic functional groups with densified carbon dioxide-phobic functional groups (see definitions above).
  • the resulting compound may form reversed micelles with the CO 2 -philic functional groups extending into a continuous phase and the CO 2 -phobic functional groups directed toward the center of the micelle.
  • the surfactant is present in an amount of from 0.001 to 10 wt.%, preferably 0.01 to 5 wt.%.
  • CO 2 -philic moieties of the surfactants are groups exhibiting low Hildebrand solubility parameters, as
  • CO 2 -philic functional groups are soluble in densified carbon dioxide to greater than 10 weight percent, preferably greater than 15 weight percent, at pressures of 500-10,000 psi and temperatures of 0-100°C.
  • Preferred densified CO 2 -philic functional groups include halocarbons (such as fluoro-, chloro- and fluorochlorocarbons), polysiloxanes and branched polyalkylene oxides.
  • the CO 2 -phobic portion of the surfactant molecule is obtained either by a hydrophilic or a hydrophobic
  • moieties contained in the CO 2 -phobic groups include polyalkylene oxides, carboxylates, branched acrylate esters, C 1-30 hydrocarbons, aryls which are
  • CO 2 -phobic groups include C 2-20 straight chain or branched alkyls, polyalkylene oxides, glycerates,
  • CO 2 -philic and CO 2 -phobic groups may be directly
  • the first group of compounds has the following formula:
  • a is 1 - 30, preferably 1-25, most preferably 5-20;
  • b is 0 - 5, preferably 0 - 3;
  • c is 1 - 5, preferably 1 - 3;
  • a and A' are each independently a linking moiety representing an ester, a keto, an ether, a thio, an amido, an amino, a C 1-4 fluoroalkyl, a C 1-4 fluoroalkenyl, a
  • d is 0 or 1;
  • L and L' are each independently a C 1-30 straight
  • e 0-3;
  • f is 0 or 1;
  • n is 0-10, preferably 0-5, most preferably 0-3;
  • g 0-3;
  • o is 0-5, preferably 0-3;
  • Z is a hydrogen, a carboxylic acid, a hydroxy, a phosphato, a phosphato ester, a sulfonyl, a sulfonate, a sulfate, a branched or straight-chained polyalkylene oxide, a nitryl, a glyceryl, an aryl unsubstituted or substituted with a C 1-30 alkyl or alkenyl, (preferably C 1-25 alkyl), a carbohydrate unsubstituted or substituted with a C 1-10 alkyl or alkenyl (preferably a C 1-5 alkyl) or an ammonium;
  • G is an anion or cation such as H + , Na + , Li + , K + , NH 4 + Ca +2 , Mg +2 ; Cl-, Br-, I-, mesylate, or tosylate; and h is 0-3, preferably 0-2.
  • Preferred compounds within the scope of the formula I include those having linking moieties A and A' which are each independently an ester, an ether, a thio, a
  • polyalkylene oxide an amido, an ammonium and mixtures thereof;
  • L and L' are each independently a C 1-25 straight chain or branched alkyl or unsubstituted aryl; and Z is a
  • G groups which are preferred include H + , Li + , Na + , NH + 4 , Cl-, Br- and tosylate.
  • L and L' are each independently a C 1-20 straight chain or branched alkyl or an unsubstituted aryl;
  • Z is a hydrogen, a phosphato, a sulfonyl, a
  • carboxylic acid a sulfate, a polyalkylene oxide and mixtures thereof;
  • G is H + , Na + or NH 4 + .
  • Non-limiting examples of compounds within the scope of 'formula I include the following: Compounds of formula I are prepared by any conventional preparation method known in the art such as the one
  • fluorinated compounds include compounds supplied as the ZonylTM series by Dupont.
  • the second group of surfactants useful in the dry cleaning system are those compounds having a polyalkylene moiety and having a formula (II). wherein R and R' each represent a hydrogen, a C 1-5 straight chained or branched alkyl or alkylene oxide and mixtures thereof;
  • i 1 to 50, preferably 1 to 30, and
  • A, A', d, L, L', e f, n, g, o, Z, G and h are as defined above.
  • R and R' are each independently a hydrogen, a C 1-3 alkyl, or alkylene oxide and mixtures thereof. Most preferably R and R' are each independently a hydrogen, C 1-3 alkyl and mixtures thereof.
  • Non-limiting examples of compounds within the scope of formula II are:
  • a third group of surfactants useful in the invention contain a fluorinated oxide moiety and the compounds have a formula:
  • r is 1-50, preferably 1-25, most preferably 5-20, T is a straight chained or branched haloalkyl or haloaryl,
  • s is 0 to 5, preferably 0-3,
  • Non-limiting examples of halogenated oxide containing compounds include:
  • x is 1- 50 .
  • the fourth group of surfactants useful in the invention include siloxanes containing surfactants of formula IV
  • MD x D* y M (IV) wherein M is a trimethylsiloxyl end group, D x is a dimethylsiloxyl backbone which is CO 2 -philic and D * y is one or more methylsiloxyl groups which are substituted with a CO 2 -phobic R or R' group,
  • R and R' each independently have the following formula:
  • b 0 or 1
  • C 6 H 4 is unsubstituted or substituted with a C 1-10 alkyl or alkenyl
  • A, A', d, L, e, f, n, L', g, Z, G and h are as defined above and mixtures of R and R' thereof.
  • the D x :D* y ratio of the siloxane containing surfactants should be greater than 0.5:1, preferably greater than 0.7:1 and most preferably greater than 1:1.
  • the siloxane compounds should have a molecular weight ranging from 100 to 100,000, preferably 200 to 50,000, most preferably 500 to 35,000.
  • Silicones may be prepared by any conventional method such as the method described in Hardman, B. "Silicones" the
  • siloxane containing compounds which may be used in the invention are those supplied under the ABIL series by Goldschmidt.
  • Suitable siloxane compounds within the scope of formula IV are compounds of formula V:
  • the ratio of x:y and y' is greater than 0.5:1,
  • R and R' are as defined above.
  • Preferred CO 2 -phobic groups represented by R and R' include those moieties of the following formula:
  • A, A', d, L, e, f, n, g, Z, G and h are as defined above, and mixtures of R and R'.
  • Non-limiting examples of polydimethylsiloxane surfactants substituted with CO 2 -phobic R or R' groups are:
  • Enzymes may additionally be added to the dry cleaning system of the invention to improve stain removal.
  • Such enzymes include proteases (e.g., Alcalase ® , Savinase ® and Esperase ® from Novo Industries A/S); amylases (e.g.,
  • Termamyl ® from Novo Industries A/S lipases (e.g.,
  • Lipolase ® from Novo Industries A/S); and oxidases.
  • the enzyme should be added to the cleaning drum in an amount from 0.001% to 10%, preferably 0.01% to 5%.
  • the type of soil dictates the choice of enzyme used in the system.
  • the enzymes should be delivered in a conventional manner, such as by preparing an enzyme solution, typically of 1% by volume (i.e., 3 mls enzyme in buffered water or solvent). Modifiers
  • a modifier such as water, or a useful organic solvent may be added with the stained cloth in the cleaning drum in a small volume.
  • Preferred amounts of modifier should be 0.0% to about 10% by volume, more preferably 0.0% to about 5% by volume, most preferably 0.0% to about 3%.
  • Preferred solvents include water, ethanol, acetone, hexane, methanol, glycols, acetonitrile, C 1-10 alcohols and C 5-15 hydrocarbons.
  • Especially preferred solvents include water, ethanol and methanol.
  • Organic peracids which are stable in storage and which solubilize in densified carbon dioxide are effective at bleaching stains in the dry cleaning system.
  • the selected organic peracid should be soluble in carbon dioxide to greater than 0.001 wt . % at pressures of 500-10,000 psi and temperatures of 0-100°C.
  • the peracid compound should be present in an amount of about 0.01% to about 5%, preferably 0.1% to about 3%.
  • the organic peroxyacids usable in the present invention can contain either one or two peroxy groups and can be either aliphatic or aromatic.
  • the unsubstituted acid has the general formula: where Y can be, for example, H, CH 3 , CH 2 Cl, COOH, or COOOH; and n is an integer from 1 to 20.
  • unsubstituted acid has the general formula: wherein Y is hydrogen, alkyl, alkylhalogen, halogen, or COOH or COOOH.
  • Typical monoperoxyacids useful herein include alkyl
  • peroxybenzoic acid e.g. peroxy- ⁇ -naphthoic acid
  • aliphatic, substituted aliphatic and arylalkyl monoperoxy acids e.g. peroxylauric acid, peroxystearic acid, and N,N-phthaloylaminoperoxycaproic acid (PAP); and
  • amidoperoxy acids e.g. monononylamide of either peroxysuccinic acid (NAPSA) or of peroxyadipic acid (NAPAA).
  • NAPSA peroxysuccinic acid
  • NAPAA peroxyadipic acid
  • Typical diperoxy acids useful herein include alkyl diperoxy acids and aryldiperoxy acids, such as:
  • TPCAP N,N'-terephthaloyl-di(6-aminoperoxycaproic acid)
  • Particularly preferred peroxy acids include PAP, TPCAP, haloperbenzoic acid and peracetic acid.
  • a process of dry cleaning using densified carbon dioxide as the cleaning fluid is schematically represented in Figure 1.
  • the cleaning vessel may also be referred to as an autoclave, particularly as described in the examples below.
  • Densified carbon dioxide such as supercritical fluid carbon dioxide, is introduced into the cleaning vessel from a storage vessel 1. Since much of the CO 2 cleaning fluid is recycled within the system, any losses during the dry cleaning process are made up through a CO 2 liquid supply vessel 2.
  • the CO 2 fluid is pumped into the cleaning vessel by a pump 3 at pressures ranging between 700 and 10,000 psi, preferably 800 to 6000 psi.
  • the CO 2 fluid is heated to its supercritical range of about 20°C to about 60°C by a heat exchanger 4.
  • the densified CO 2 is transferred from the supply vessel 2 to the cleaning vessel 5 through line 7 for a dry cleaning cycle of between about 15 to about 30 minutes.
  • surfactants, modifiers, enzymes, peracid and mixtures thereof as discussed above are introduced into the cleaning vessel, preferably through a line and pump system connected to the cleaning vessel.
  • dirty CO 2 , soil and spent cleaning agents are transferred through an expansion valve 6, a heat exchanger 8 by way of a line 9 into a flash drum 10.
  • pressures are reduced to between about 800 and about 1,000 and psi and to a
  • Gaseous CO 2 is separated from the soil and spent agents and transferred via line 11 through a filter 12 and condenser 13 to be recycled back to the supply vessel 2.
  • the spent agents and residue CO 2 are transferred via line 14 to an atmospheric tank 15, where the remaining CO 2 is vented to the
  • Hydrocarbon and fluorocarbon containing surfactants useful in the invention must exhibit a hydrophilic/lipophilic balance of less than 15.
  • This example describes the calculation of HLB values for various surfactants to determine their effectiveness in supercritical carbon dioxide. This calculation for various hydrocarbon and fluorocarbon surfactants is reported in the literature 1 and is represented by the following equation:
  • HLB 7 + ⁇ (hydrophilic group numbers) - ⁇ (lipophilic group numbers)
  • hydrophilic and lipophilic group numbers have been assigned to a number of common surfactant functionalities including hydrophilic groups such as carboxylates, sulfates and ethoxylates and lipophilic groups such as -CH 2 , CF 2 and PPG's. 1 These group numbers for the functional groups in surfactants were utilized to calculate the HLB number for the following hydrocarbon or fluorocarbon surfactant:
  • the conventional surfactants exhibit an HLB value of greater than 15 and are not effective as dry cleaning components in the invention.
  • Example 2
  • the stained fabrics were prepared by taking a two inch by three inch cloth and applying the stain directly to the cloths. The cloths were allowed to dry.
  • the stained fabrics were then placed in a 300 ml autoclave having a gas compressor and an extraction system.
  • the stained cloth was hung from the bottom of the autoclave's overhead stirrer using a copper wire to promote good agitation during washing and extraction.
  • liquid CO 2 at a tank pressure of 850 psi was allowed into the system and was heated to reach a temperature of about 40°C to 45°C.
  • the pressure inside the autoclave was increased to 4,000 psi by pumping in more CO 2 with a gas compressor.
  • the stirrer was then turned on for 15 minutes to mimic a wash cycle. At the completion of the wash cycle, 20 cubic feet of fresh CO 2 were passed through the system to mimic a rinse cycle. The pressure of the autoclave was then released to
  • Colorguard The R scale, which measures darkness from black to white, was used to determine stain removal.
  • hydrophilic stain, grape juice was dry cleaned using supercritical fluid carbon dioxide, a polydimethylsiloxane surfactant, water as a modifier and mixtures thereof according to the invention.
  • the surfactant, linear alkylbenzene sulfonate is a solid and has an HLB value of 20.
  • the LAS was added to the bottom of the autoclave with varying amounts of water. The following cleaning results were observed and are reported in Table 3 below.
  • DE 3904514 describes dry cleaning using supercritical fluid carbon dioxide in combination with a conventional surfactant.
  • the publication exemplifies cleaning results with LAS.
  • the experimental conditions in the examples state that the stained cloth has only minimal contact with supercritical fluid carbon dioxide, namely a 10 minute rinse only. It appears that the cleaning obtained with LAS and the large amount of water is similar to spot or wet cleaning, since the cloth remains wet at the end of the process. There appears to be little to minimal
  • a hydrophilic stain namely grape juice, was dry cleaned using polydimethylsiloxane surfactants with water and supercritical fluid carbon dioxide according to the
  • Polyester cloths were stained with 7% grape juice stain as described in Example 3 above. Two different
  • polydimethylsiloxane surfactants were used with varying amounts of water and supercritical fluid carbon dioxide.
  • LAS the conventional surfactant, used with the same amounts of water was used to remove the grape juice stains.
  • the cleaning results for the two types of surfactants are reported in Table 4 below.
  • modified polydimethylsiloxane surfactants according to the invention are more effective in the presence of less water (0.5 ml vs. 6.0 ml) as cleaning was reduced from 50% to 40% when the water levels were increased.
  • the opposite effect was observed with LAS, as stain removal increased from 0% to 75% as the water levels were increased to 6.0 ml.
  • the claimed siloxane surfactants provide better cleaning results with less water which is beneficial for water sensitive fabrics.
  • Polydimethylsiloxanes having varying molecular weights and alkyl substituted moieties were tested as surfactants with supercritical fluid carbon dioxide in the inventive dry cleaning process.
  • a compound hydrophobic stain, red candle wax, was placed on both cotton fabrics as follows. A candle was lit and approximately 40 drops of melted wax were placed on each cloth so that a circular pattern was achieved. The cloths were then allowed to dry and the crusty excess wax layer was scraped off the top and bottom of each stain so that only a flat waxy colored stain was left.
  • the pressure of the autoclave during the washing cycle was 6000 psi at a temperature of 40°C with a 15 minute cycle. Twenty cubic feet of supercritical fluid carbon dioxide was used for the rinse cycle.
  • D* y M(C z ) wherein M represents the trimethylsiloxyl end groups, D x represents the dimethylsiloxane backbone (CO 2 - philic), D* y represents the substituted methylsiloxyl group (CO 2 -phobic) and (C z ) represents the carbon length of the alkyl chain of R.
  • Molecular weights of the siloxanes ranged from 1,100 to 31,000.
  • the polydimethylsiloxanes straight chain alkyl group ranged from C 8 to C 18 carbons.
  • the red wax stained cloths were cleaned and the cleaning results were observed and are reported in Table 5 below. No modifier was used.
  • a glycerated siloxane surfactant having a formula MD x D* y M wherein D* y is substituted by -(CH 2 ) 3 OCH 2 CH(OH)CH 2 OH was used to dry clean a grape juice stain on a polyester cloth under the dry cleaning conditions described in Example 2 above. About 0.2 gram of the surfactant was combined with 0.5 ml. water.
  • the glycerated siloxane is a polydimethylsiloxane with a glycerol side chain having a molecular weight of 870 and prepared as described in Hardman, Supra.
  • the pressure in the autoclave was 4000 psi and the temperature was 40°C to 45°C.
  • FSO-100 and FSN were more effective than the fluorinated nonionic having a lithium carboxylate salt (FSA).
  • the bleaching peracids tested include m-chloroperbenzoic acid (m-CPBA), p-nitroperbenzoic acid (p-NPBA) and 6-phthalimidoperoxy hexanoic acid (PAP) in an amount of about 0.2 to 0.5 grams each.
  • m-CPBA m-chloroperbenzoic acid
  • p-NPBA p-nitroperbenzoic acid
  • PAP 6-phthalimidoperoxy hexanoic acid
  • Protease enzyme was used in supercritical carbon dioxide to clean spinach stains from cotton cloth.
  • Three (3) mls of protease enzyme (Savinase supplied by Novo, Inc.) was added to buffered water to form a 1% solution and then added to each cloth. The cloths were then washed and rinsed as described in Example 2 above. The cleaning results
  • Lipolase enzyme 1% enzyme solution of 3 mls in buffered wear was used in supercritical carbon dioxide to clean red candle wax stains from rayon cloth. The procedure used was identical to that of Example 10. The results are
  • Amylase enzyme 1% enzyme solution of 3 mls enzyme in buffered water was used to dryclean starch/azure blue stains on wool cloth in supercritical carbon dioxide. The blue dye is added to make the starch stain visible so that its removal may be detected by the reflectometer.
  • the drycleaning procedure used was identical to that of example 10, and the results are presented in Table 10 below.
  • polydimethylsiloxane surfactant Abil 88184 is added to the supercritical carbon dioxide dry cleaning system.
  • Dry cleaning of red candle wax stains was conducted on several different types of fabric, using an alkyl modified polydimethylsiloxane surfactant, MD 15.3 D * 1.5 M (C 12 ), having a molecular weight of 1475 g/mole.
  • the surfactant was synthesized as described in Hardman, Supra.
  • the dry cleaning procedure used was the same as that used in example 5, and the cleaning results are presented in the following table.
  • the dry cleaning results show significantly enhanced cleaning of the red candle wax stain on all fabrics except for rayon, which shows no cleaning enhancement from addition of the surfactant.
  • the cleaning results for the silk cloth are especially high, giving a cloth which looks very clean to the eye.
  • Dry cleaning of grape juice on polyester cloth and of red candle wax on cotton cloth was investigated at different pressures to determine the effect of the pressure of supercritical carbon dioxide on the cleaning effectiveness of the system.
  • the dry cleaning procedures used were the same as those used in examples 3 and 6 except for the variations in pressure, and the results are presented in the following table.
  • Example 3 identical to that of Example 3, including the use of 0.5 ml water on each cloth prior to cleaning.

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  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

L'invention concerne un système pour le nettoyage à sec de tissus souillés, comprenant du gaz carbonique densifié et un tensioactif dans ce CO2 densifié. Le tensioactif comporte un polysiloxane, un oxyde de polyalkylène ramifié ou un groupe halocarboné qui est une fraction CO2-phile liée à une fraction fonctionnelle CO2-phobe. Le tensioactif présente un HLB de moins de 15 ou il présente un rapport de groupes siloxyle sur groupes siloxyle substitués supérieur à 0,5:1.
PCT/EP1996/000811 1995-03-06 1996-02-26 Systeme de nettoyage a sec utilisant du gaz carbonique densifie et un tensioactif comme additif WO1996027704A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP96905817A EP0813628A1 (fr) 1995-03-06 1996-02-26 Systeme de nettoyage a sec utilisant du gaz carbonique densifie et un tensioactif comme additif
AU49429/96A AU4942996A (en) 1995-03-06 1996-02-26 Dry cleaning system using densified carbon dioxide and a surfactant adjunct
FI973603A FI973603A (fi) 1995-03-06 1997-09-05 Kuivapesujärjestelmä, jossa käytetään tiivistettyä hiilidioksidia ja pinta-aktiivista apuainetta

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US08/399,318 1995-03-06
US08/399,318 US5683977A (en) 1995-03-06 1995-03-06 Dry cleaning system using densified carbon dioxide and a surfactant adjunct
US08/399,317 1995-03-06
US08/399,317 US5676705A (en) 1995-03-06 1995-03-06 Method of dry cleaning fabrics using densified carbon dioxide

Publications (1)

Publication Number Publication Date
WO1996027704A1 true WO1996027704A1 (fr) 1996-09-12

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PCT/EP1996/000811 WO1996027704A1 (fr) 1995-03-06 1996-02-26 Systeme de nettoyage a sec utilisant du gaz carbonique densifie et un tensioactif comme additif

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Country Link
EP (1) EP0813628A1 (fr)
AU (1) AU4942996A (fr)
CA (1) CA2211412A1 (fr)
FI (1) FI973603A (fr)
TR (1) TR199700901T1 (fr)
TW (1) TW338067B (fr)
WO (1) WO1996027704A1 (fr)

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997018234A2 (fr) * 1995-11-13 1997-05-22 Genencor International, Inc. Extraction de proteines dans du dioxyde de carbone
US5783082A (en) * 1995-11-03 1998-07-21 University Of North Carolina Cleaning process using carbon dioxide as a solvent and employing molecularly engineered surfactants
US5784905A (en) * 1996-12-03 1998-07-28 Hughes Electronics Liquid carbon dioxide cleaning system employing a static dissipating fluid
US5858022A (en) * 1997-08-27 1999-01-12 Micell Technologies, Inc. Dry cleaning methods and compositions
WO1999010587A1 (fr) * 1997-08-29 1999-03-04 Micell Technologies Tensioactifs a base de polysiloxane a extremite fonctionnelle utilises dans des formulations de dioxyde de carbone
WO1999057358A1 (fr) * 1998-05-06 1999-11-11 Unilever N.V. Systeme de nettoyage a sec utilisant du gaz carbonique et un auxiliaire d'agent tensioactif
US6120613A (en) * 1998-04-30 2000-09-19 Micell Technologies, Inc. Carbon dioxide cleaning and separation systems
WO2000065018A1 (fr) * 1999-04-26 2000-11-02 3M Innovative Properties Company Composition liquide de dioxyde de carbone stabilisee et utilisation de celle-ci
US6200352B1 (en) 1997-08-27 2001-03-13 Micell Technologies, Inc. Dry cleaning methods and compositions
US6218353B1 (en) 1997-08-27 2001-04-17 Micell Technologies, Inc. Solid particulate propellant systems and aerosol containers employing the same
US6235701B1 (en) 1998-12-11 2001-05-22 3M Innovative Properties Company Stabilized carbon dioxide fluid composition and use thereof
US6248136B1 (en) 2000-02-03 2001-06-19 Micell Technologies, Inc. Methods for carbon dioxide dry cleaning with integrated distribution
WO2002050364A1 (fr) * 2000-12-20 2002-06-27 Unilever N.V. Systeme nettoyant les tissus textiles
WO2002050365A1 (fr) * 2000-12-20 2002-06-27 Unilever N.V. Systeme de nettoyage de tissus
US6506259B1 (en) 1998-04-30 2003-01-14 Micell Technologies, Inc. Carbon dioxide cleaning and separation systems
WO2003057811A1 (fr) * 2001-12-31 2003-07-17 Advanced Technology Materials, Inc. Nettoyage de substrats semi-conducteurs a l'aide de fluide supercritique
EP1328610A1 (fr) * 2000-09-26 2003-07-23 University Of North Carolina At Chapel Hill Fluorosurfactifs phosphate utilisable dans du dioxyde de carbone
EP1368360A2 (fr) * 2001-01-25 2003-12-10 University Of North Carolina At Chapel Hill Tensioactifs gemini zwitterioniques utilisables dans du dioxyde de carbone
DE10359721B3 (de) * 2003-12-19 2005-08-11 Forschungszentrum Karlsruhe Gmbh Verfahren zur Ablösung von Mikro- und Nanopartikeln von zu reinigenden Oberflächen
US6953041B2 (en) 2002-10-09 2005-10-11 Micell Technologies, Inc. Compositions of transition metal species in dense phase carbon dioxide and methods of use thereof
EP2014344A2 (fr) 2003-11-19 2009-01-14 SCF Technologies A/S Procédé et processus pour le contrôle de profils de température, de pression et de densité dans des processus à fluides denses
US7557073B2 (en) 2001-12-31 2009-07-07 Advanced Technology Materials, Inc. Non-fluoride containing supercritical fluid composition for removal of ion-implant photoresist
WO2012146304A1 (fr) 2011-04-29 2012-11-01 Ecolab Usa Inc. Méthode d'application d'un agent de finition de lessive sur des pièces de lessive
WO2012159679A1 (fr) 2011-05-26 2012-11-29 Ecolab Usa Inc. Procédé utilisant du dioxyde de carbone solide comme support pour appliquer un agent de finissage de blanchisserie à des articles de blanchisserie
CN113318521A (zh) * 2021-07-12 2021-08-31 苏州远浩新纺织科技有限公司 一种活性炭纤维空气过滤材料的清洗方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6875709B2 (en) 2003-03-07 2005-04-05 Taiwan Semiconductor Manufacturing Comapny, Ltd. Application of a supercritical CO2 system for curing low k dielectric materials

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EP0518653A1 (fr) * 1991-06-14 1992-12-16 The Clorox Company Procédé et composition pour le nettoyage de tissus, utilisant le dioxyde de carbone densifié et des additifs de nettoyage
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US4012194A (en) * 1971-10-04 1977-03-15 Maffei Raymond L Extraction and cleaning processes
US4219333A (en) * 1978-07-03 1980-08-26 Harris Robert D Carbonated cleaning solution
US4219333B1 (fr) * 1978-07-03 1984-02-28
DE4004111A1 (de) * 1989-02-15 1990-08-23 Deutsches Textilforschzentrum Verfahren zur vorbehandlung von textilen flaechengebilden oder garnen
DE3904514A1 (de) * 1989-02-15 1990-08-23 Oeffentliche Pruefstelle Und T Verfahren zum reinigen bzw. waschen von bekleidungsteilen o. dgl.
DE3906735A1 (de) * 1989-03-03 1990-09-06 Deutsches Textilforschzentrum Verfahren zum bleichen
EP0518653A1 (fr) * 1991-06-14 1992-12-16 The Clorox Company Procédé et composition pour le nettoyage de tissus, utilisant le dioxyde de carbone densifié et des additifs de nettoyage
EP0530949A1 (fr) * 1991-09-04 1993-03-10 The Clorox Company Nettoyage par perhydrolyse menée dans un médium fluide dense

Cited By (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5944996A (en) * 1995-11-03 1999-08-31 The University Of North Carolina At Chapel Hill Cleaning process using carbon dioxide as a solvent and employing molecularly engineered surfactants
US5783082A (en) * 1995-11-03 1998-07-21 University Of North Carolina Cleaning process using carbon dioxide as a solvent and employing molecularly engineered surfactants
US5866005A (en) * 1995-11-03 1999-02-02 The University Of North Carolina At Chapel Hill Cleaning process using carbon dioxide as a solvent and employing molecularly engineered surfactants
US6224774B1 (en) 1995-11-03 2001-05-01 The University Of North Carolina At Chapel Hill Method of entraining solid particulates in carbon dioxide fluids
WO1997018234A3 (fr) * 1995-11-13 1997-08-28 Genencor Int Extraction de proteines dans du dioxyde de carbone
WO1997018234A2 (fr) * 1995-11-13 1997-05-22 Genencor International, Inc. Extraction de proteines dans du dioxyde de carbone
US6638749B1 (en) 1995-11-13 2003-10-28 Genencor International, Inc. Carbon dioxide soluble surfactant having two fluoroether CO2-philic tail groups and a head group
US5784905A (en) * 1996-12-03 1998-07-28 Hughes Electronics Liquid carbon dioxide cleaning system employing a static dissipating fluid
WO1999010585A1 (fr) * 1997-08-27 1999-03-04 Micell Technologies, Inc. Procedes et compositions pour le nettoyage a sec
US6258766B1 (en) 1997-08-27 2001-07-10 Micell Technologies, Inc. Dry cleaning methods and compositions
US5858022A (en) * 1997-08-27 1999-01-12 Micell Technologies, Inc. Dry cleaning methods and compositions
AU736088B2 (en) * 1997-08-27 2001-07-26 Micell Technologies, Inc. Dry cleaning methods and compositions
US6200352B1 (en) 1997-08-27 2001-03-13 Micell Technologies, Inc. Dry cleaning methods and compositions
US6218353B1 (en) 1997-08-27 2001-04-17 Micell Technologies, Inc. Solid particulate propellant systems and aerosol containers employing the same
US6270531B1 (en) 1997-08-29 2001-08-07 Micell Technologies, Inc. End functionalized polysiloxane surfactants in carbon dioxide formulations
WO1999010587A1 (fr) * 1997-08-29 1999-03-04 Micell Technologies Tensioactifs a base de polysiloxane a extremite fonctionnelle utilises dans des formulations de dioxyde de carbone
US6228826B1 (en) 1997-08-29 2001-05-08 Micell Technologies, Inc. End functionalized polysiloxane surfactants in carbon dioxide formulations
US6200393B1 (en) 1998-04-30 2001-03-13 Micell Technologies, Inc. Carbon dioxide cleaning and separation systems
US6413574B1 (en) 1998-04-30 2002-07-02 Micell Technologies, Inc. Deposition methods utilizing carbon dioxide separation systems
US6120613A (en) * 1998-04-30 2000-09-19 Micell Technologies, Inc. Carbon dioxide cleaning and separation systems
US6506259B1 (en) 1998-04-30 2003-01-14 Micell Technologies, Inc. Carbon dioxide cleaning and separation systems
WO1999057358A1 (fr) * 1998-05-06 1999-11-11 Unilever N.V. Systeme de nettoyage a sec utilisant du gaz carbonique et un auxiliaire d'agent tensioactif
US6235701B1 (en) 1998-12-11 2001-05-22 3M Innovative Properties Company Stabilized carbon dioxide fluid composition and use thereof
WO2000065018A1 (fr) * 1999-04-26 2000-11-02 3M Innovative Properties Company Composition liquide de dioxyde de carbone stabilisee et utilisation de celle-ci
WO2001057303A1 (fr) * 2000-02-03 2001-08-09 Micell Technologies, Inc. Procedes et dispositifs de nettoyage a sec au dioxyde de carbone avec distribution integree
US6332342B2 (en) 2000-02-03 2001-12-25 Mcclain James B. Methods for carbon dioxide dry cleaning with integrated distribution
US6248136B1 (en) 2000-02-03 2001-06-19 Micell Technologies, Inc. Methods for carbon dioxide dry cleaning with integrated distribution
EP1328610A4 (fr) * 2000-09-26 2004-09-01 Univ North Carolina State Fluorosurfactifs phosphate utilisable dans du dioxyde de carbone
EP1328610A1 (fr) * 2000-09-26 2003-07-23 University Of North Carolina At Chapel Hill Fluorosurfactifs phosphate utilisable dans du dioxyde de carbone
US7122060B2 (en) 2000-09-26 2006-10-17 The University Of North Carolina Phosphate fluorosurfactants for use in carbon dioxide
JP2004509756A (ja) * 2000-09-26 2004-04-02 ユニヴァーシティ・オヴ・ノース・キャロライナ・アト・チャペル・ヒル 二酸化炭素に使用するためのホスフェートフルオロ界面活性剤
WO2002050365A1 (fr) * 2000-12-20 2002-06-27 Unilever N.V. Systeme de nettoyage de tissus
WO2002050364A1 (fr) * 2000-12-20 2002-06-27 Unilever N.V. Systeme nettoyant les tissus textiles
EP1368360A4 (fr) * 2001-01-25 2006-05-17 Univ North Carolina Tensioactifs gemini zwitterioniques utilisables dans du dioxyde de carbone
EP1368360A2 (fr) * 2001-01-25 2003-12-10 University Of North Carolina At Chapel Hill Tensioactifs gemini zwitterioniques utilisables dans du dioxyde de carbone
WO2003057811A1 (fr) * 2001-12-31 2003-07-17 Advanced Technology Materials, Inc. Nettoyage de substrats semi-conducteurs a l'aide de fluide supercritique
US7326673B2 (en) 2001-12-31 2008-02-05 Advanced Technology Materials, Inc. Treatment of semiconductor substrates using long-chain organothiols or long-chain acetates
US7557073B2 (en) 2001-12-31 2009-07-07 Advanced Technology Materials, Inc. Non-fluoride containing supercritical fluid composition for removal of ion-implant photoresist
US6953041B2 (en) 2002-10-09 2005-10-11 Micell Technologies, Inc. Compositions of transition metal species in dense phase carbon dioxide and methods of use thereof
EP2014344A2 (fr) 2003-11-19 2009-01-14 SCF Technologies A/S Procédé et processus pour le contrôle de profils de température, de pression et de densité dans des processus à fluides denses
DE10359721B3 (de) * 2003-12-19 2005-08-11 Forschungszentrum Karlsruhe Gmbh Verfahren zur Ablösung von Mikro- und Nanopartikeln von zu reinigenden Oberflächen
WO2012146304A1 (fr) 2011-04-29 2012-11-01 Ecolab Usa Inc. Méthode d'application d'un agent de finition de lessive sur des pièces de lessive
WO2012159679A1 (fr) 2011-05-26 2012-11-29 Ecolab Usa Inc. Procédé utilisant du dioxyde de carbone solide comme support pour appliquer un agent de finissage de blanchisserie à des articles de blanchisserie
CN113318521A (zh) * 2021-07-12 2021-08-31 苏州远浩新纺织科技有限公司 一种活性炭纤维空气过滤材料的清洗方法

Also Published As

Publication number Publication date
TR199700901T1 (xx) 1998-02-21
FI973603A0 (fi) 1997-09-05
FI973603A (fi) 1997-09-05
EP0813628A1 (fr) 1997-12-29
AU4942996A (en) 1996-09-23
TW338067B (en) 1998-08-11
CA2211412A1 (fr) 1996-09-12

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