EP0813628A1 - 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

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Publication number
EP0813628A1
EP0813628A1 EP96905817A EP96905817A EP0813628A1 EP 0813628 A1 EP0813628 A1 EP 0813628A1 EP 96905817 A EP96905817 A EP 96905817A EP 96905817 A EP96905817 A EP 96905817A EP 0813628 A1 EP0813628 A1 EP 0813628A1
Authority
EP
European Patent Office
Prior art keywords
carbon dioxide
surfactant
group
alkyl
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP96905817A
Other languages
German (de)
English (en)
Inventor
Sharon Harriott Jureller
Judith Lynne Kerschner
Myongsuk Bae-Lee
Lisa Del Pizzo
Rosemarie Harris
Carol Resch
Cathy Waja
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US08/399,317 external-priority patent/US5676705A/en
Priority claimed from US08/399,318 external-priority patent/US5683977A/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0813628A1 publication Critical patent/EP0813628A1/fr
Ceased legal-status Critical Current

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Classifications

    • 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 adjunc .
  • Densified, particularly supercritical fluid, carbon dioxide has been suggested as an alternative to halo-carbon solvents used in conventional dry cleaning.
  • a dry cleaning system in which chilled liquid carbon dioxide is used to extract soils from fabrics is described in U.S. 4,012,194 issued to Maffei on March 15, 1977.
  • 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 surfactants and solvent modifiers are added.
  • a cleaning system combining particular anionic or nonionic surface active agents with supercritical fluid C0 2 is described in DE 39 04 514 Al published August 23, 1990.
  • 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 (greater than or equal to 4%) .
  • the patented system appears to combine the detergency mechanism of conventional agents with the solvent power of supercritical fluid carbon dioxide.
  • the dry cleaning systems known in the art have merely combined cleaning agents with various viscosities and polarities with supercritical fluid C0 2 generally with high amounts of water as a cosolvent.
  • the actives clean soils as in conventional washing without any synergistic effect with the C0 2 solvent.
  • 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 C0 2 - philic functional moiety connected to a supercritical fluid C0 2 -phobic functional moiety.
  • Preferred C0 2 -philic moieties of the surfactant include halocarbons such as fluorocarbons, chlorocarbons and mixed fluoro- chlorocarbons, polysiloxanes, and branched polyalkylene oxides.
  • the C0 2 -phobic groups for the surfactant contain preferably polyalkylene oxides, carboxylates, C__ 30 alkyl sulfonates, carbohydrates, glycerates, phosphates, sulfates and C-_ 3o 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 modifier such as water, or an organic solvent up to only about 5% by volume
  • enzymes up to about 10 wt.%
  • 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 surfactant to provide a total cleaning system.
  • 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.
  • n and n' are each independently 1 to 50, means that the functional group, R-,- is soluble in carbon dioxide at pressures of 500-10,000 psi and temperatures of 0-100°C to greater than 10 weight percent.
  • n and n' are each independently 1-35.
  • Such functional groups (R--) include halocarbons, polysiloxanes and branched polyalkylene oxides.
  • Z n ,- in reference to surfactants, R-Z n , means that Z n ,- will have a solubility in carbon dioxide at pressures of 500-10,000 psi and temperatures of 0-100°C of less than 10 weight percent.
  • the functional groups in Z n ,- include carboxylic acids, phosphatyl esters, hydroxys, alkyls or alkenyls, polyalkylene oxides, branched polyalkylene oxides, carboxylates, C 1-30 alkyl sulfonates, phosphates, glycerates, carbohydrates, nitrates, substituted or unsubstituted aryls and sulfates.
  • the hydrocarbon and halocarbon containing surfactants i.e., R-Z n ,, containing the C0 2 -philic functional group, R_-, and the C0 2 -phobic group, Z n .-
  • R-Z n containing the C0 2 -philic functional group, R_-, and the C0 2 -phobic group, Z n .-
  • the polymeric siloxane containing surfactants, R_Z n also designated MD x D* y M, with M representing trimethylsiloxyl end groups, D x as a dimethylsiloxyl backbone (C0 2 -philic functional group) and D* y as one or more substituted methylsiloxyl groups substituted with C0 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 insoluble solid components such as silicates, carbon black, etc.
  • 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, isopropanol, benzene, toluene, p-xylene, sulfur dioxide, chlorotrifluoromethane, trichlorofluoromethane, perfluoropropane, chlorodifluoromethane, sulfur hexafluoride and nitrous oxide.
  • 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 C0 2 -phobic group R or RM R or R' are each represented in the following formula:
  • a is 1-30, b is 0-1, C 6 H 4 is substituted or unsubstituted with a C ⁇ -- alkyl or alkenyl and A, d, L, e,
  • 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-_ 3 - 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._ s alkyl.
  • the terms “polyalkylene oxide”, “alkyl” and “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 C0 2 -philic functional groups extending into a continuous phase and the C0 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.%.
  • the C0 2 -philic moieties of the surfactants are groups exhibiting low Hildebrand solubility parameters, as described in Grant, D. J. . et al. "Solubility Behavior of Organic Compounds", Techniques of Chemistry Series, J. Wiley & Sons, NY (1990) pp. 46-55 which describes the Hildebrand solubility equation, herein incorporated by reference. These C0 2 -philic moieties also exhibit low polarizability and some electron donating capability allowing them to be solubilized easily in densified fluid carbon dioxide.
  • C0 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 C0 2 -philic functional groups include halocarbons (such as fluoro-, chloro- and fluoro- chlorocarbons) , polysiloxanes and branched polyalkylene oxides.
  • the C0 2 -phobic portion of the surfactant molecule is obtained either by a hydrophilic or a hydrophobic functional group which is less than 10 weight percent soluble in densified C0 2 , preferably less than 5 wt. %, at a pressures of 500-10,000 psi and temperatures of 0-100°C.
  • moieties contained in the C0 2 -phobic groups include polyalkylene oxides, carboxylates, branched acrylate esters, C- ⁇ - hydrocarbons, aryls which are unsubstituted or substituted, sulfonates, glycerates, phosphates, sulfates and carbohydrates.
  • Especially preferred C0 2 -phobic groups include C 2 _ 20 straight chain or branched alkyls, polyalkylene oxides, glycerates, carboxylates, phosphates, sulfates and carbohydrates.
  • the C0 2 -philic and C0 2 -phobic groups may be directly connected or linked together via a linkage group.
  • Such groups include ester, keto, ether, amide, amine, thio, alkyl, alkenyl, fluoroalkyl or fluoroalkenyl .
  • Surfactants which are useful in the invention may be selected from four groups of compounds.
  • the first group of compounds has the following formula: [ (CX 3 (CX 2 ) a (CH 2 ) b ) c (A) d —[ (L) e — (A- ) f ] n —(L' ) g ] 0 Z (G) h (I)
  • X is F, Cl, Br, I and mixtures thereof, preferably F and Cl;
  • 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 X .
  • d is 0 or 1;
  • L and L' are each independently a C-_ 30 straight chained or branched alkyl or alkenyl or an aryl which is unsubstituted or substituted and mixtures thereof; e is 0-3; f is 0 or 1; n is 0-10, preferably 0-5, most preferably 0-3; g is 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-_ 30 alkyl or alkenyl, (preferably C 1-25 alkyl) , a carbohydrate unsubstituted or substituted with a C ⁇ - o 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
  • 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 straight chain or branched alkyl or unsubstituted aryl; and Z is a hydrogen, carboxylic acid, hydroxyl, a phosphato, a sulfonyl, a sulfate, an ammonium, a polyalkylene oxide, or a carbohydrate, preferably unsubstituted.
  • G groups which are preferred include H + , Li + , Na + , NH + 4 , Cl " , Br " and tosylate.
  • Most preferred compounds within the scope of formula I include those compounds wherein A and A" are each independently an ester, ether, an amido, a polyoxyalkylene oxide and mixtures thereof; L and L' are each independently a i. jo 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; and G is H ⁇ Na * or NH 4 * •
  • Non-limiting examples of compounds within the scope of 'formula I include the following: Perhalogenated Surfactants
  • CF 3 (CF 2 ) a CH 2 CH 2 C (O) N [ (CH 2 ) m CU 3 ] 2 G H + , Na ⁇ K ⁇ NH 4 + , CF 3 (CF 2 ) _CH 2 C (O) N [ (CH 2 ) a CH 3 ] 2 Mg +2 ,Ca* 2 , etc. CF 3 (CF 2 ) a C (0) N [ (CH 2 ),_CH 3 ] 2 Perhalogenated Surfactants (cont.)
  • G H ⁇ Na * , K ⁇ NH 4 ⁇ Mg +2 , Ca* 2 , etc.
  • G H + , Na*, K ⁇ Li * , Ca* 2 , Mg *2 , NH 4 * , etc Perhalogenated Surfactants (cont.)
  • CClF j (CCIF). CH J CH J S (CH J ). ,C(0)0(CH J ) B CH J CClF j (CCIF) .CH J S (CH J ) a .C (0) O (CH 2 ) B CH 3 CClF j (CCIF) a S (CH j ) a .C (O) 0 (CH j ) a CH 3 Perhalogenated Surfactants (cont.)
  • CClF j (CClF) CH J CH J O (CH J ) .. (OCH j CH (CH,) ) p OH CClF j (CClF) CH j O (CH j ) .. (OCH j CH (CH 3 ) ) p OH CClF j (CClF) 0 (CH j ) .. (OCH j CH (CH,) ) p OH
  • CClF j (CClF) CH J CH J C (0) (CH j ) B N(CH 3 ) 3 G CClF j (CClF) CH j C(O) (CH j ) B N(CH 3 ) 3 G CClF j (CClF) C(O) (CH j ) B N(CH 3 ) 3 G
  • 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) .
  • R and R' each represent a hydrogen, a Cj. ⁇ straight chained or branched alkyl or alkylene oxide and mixtures thereof; i is 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 Ci. 3 alkyl, or alkylene oxide and mixtures thereof.
  • R and R' are each independently a hydrogen, C ⁇ alkyl and mixtures thereof.
  • Non-limiting examples of compounds within the scope of formula II are: Polypropylene Glycol Surfactants
  • G H*, Na * , K * ,NH 4 * , Ca* 2 , Mg* 2 , Cl Br “ , " OTs, “ OMs, etc Polypropylene Glycol Surfactants (cont.)
  • Examples of commercially available compounds of formula II may be obtained as the Pluronic series from BASF, Inc.
  • a third group of surfactants useful in the invention contain a fluorinated oxide moiety and the compounds have a formula:
  • XO is a halogenated alkylene oxide having C 1-6 straight or branched halocarbons, preferably C x _ 3 , 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, X, A, A', c, d, L, L", e, f, n, g, o, Z, G and hare as defined above.
  • Non-limiting examples of halogenated oxide containing compounds include:
  • G H*, Na*, K*, Li*, NH 4 ⁇ Ca* 2 , Mg* 2 , Cl “ , Br “ , " OTs, " OMs, etc.
  • G H*, Na*, Li*,NH 4 *, Ca* Mg ⁇ 2 Cl “ , Br “ , * OTs, " OMs, etc
  • CClF j (CC1FCC1FO) r (CH 2 CH a O) t H CClF j (CC1FCC1FO) r (CH j CH (CH,) 0) t H CClF j (CCIFCF (CClF j ) 0 r (CH j CH j ) O) t H CClF j (CCIFCF (CClF j ) O r (CH 2 CH (CH,) O) t H
  • CC1F 2 (CC1FCC1F0) r C (O) OG CClF j (CC1FCC1F0) r (CH 2 ) C (O) OG CC1F 2 (CC1FCC1F0) r (CH (CF 3 ) C (0) OG CC1F 2 (CCIFCF (CC1F 2 ) O) r C (O) OG CClF a (CCIFCF (CClF j ) O) _CF 2 C (O) OG CCIF- (CCIFCF (CClF j ) 0) r CF (CF 3 ) C (0) OG
  • G H ⁇ Na*, Li*, K ⁇ NH 4 ⁇ Mg* 2 , Ca* Cl “ , Br “ , " OTs, " OMs, etc.
  • Examples of commercially available compounds within the scope of formula III include those compounds supplied under the KrytoxTM series by DuPont having a formula:
  • x is 1-50 .
  • the fourth group of surfactants useful in the invention include siloxanes containing surfactants of formula IV
  • M is a trimethylsiloxyl end group
  • D x is a dimethylsiloxyl backbone which is C0 2 -philic
  • D * y is one or more methylsiloxyl groups which are substituted with a C0 2 -phobic R or R' group, wherein R and R' each independently have the following formula:
  • a is 1-30, preferably 1-25, most preferably 1-
  • C ⁇ H 4 is unsubstituted or substituted with a C ⁇ -- 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 Hard an, 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, preferably greater than 0.7:1 and most preferably greater than 1:1, and
  • R and R' are as defined above.
  • Preferred C0 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 C0 2 -phobic R or R' groups are:
  • G H * , Na * , K * ,
  • 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 mis enzyme in buffered water or solvent) .
  • 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 ⁇ . Q 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. When the organic peroxyacid is aliphatic, the unsubstituted acid has the general formula:
  • Y can be, for example, H, CH 3 , CH 2 C1, COOH, or COOOH; and n is an integer from 1 to 20.
  • the organic peroxy acid is aromatic
  • the unsubstituted acid has the general formula:
  • Y is hydrogen, alkyl, alkylhalogen, halogen, or COOH or COOOH.
  • Typical monoperoxyacids useful herein include alkyl peroxyacids and aryl peroxyacids such as:
  • peroxybenzoic acid and ring-substituted 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)
  • PAP N,N-phthaloylaminoperoxycaproic acid
  • amidoperoxy acids e.g. monononylamide of either peroxysuccinic acid (NAPSA) or of peroxyadipic acid (NAPAA) .
  • Typical diperoxy acids useful herein include alkyl diperoxy acids and aryldiperoxy acids, such as:
  • 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.
  • a cleaning vessel 5 preferably a rotatable drum, receives soiled fabrics as well as the selected surfactant, modifier, enzyme, peracid and mixtures thereof.
  • 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
  • a storage vessel 1 Since much of the C0 2 cleaning fluid is recycled within the system, any losses during the dry cleaning process are made up through a C0 2 liquid supply vessel 2.
  • the C0 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 C0 2 fluid is heated to its supercritical range of about 20°C to about 60°C by a heat exchanger 4.
  • the densified C0 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 C0 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 temperature of about 20°C to about 60°C.
  • Gaseous C0 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 C0 2 are transferred via line 14 to an atmospheric tank 15, where the remaining C0 2 is vented to the atmosphere.
  • 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) - ⁇ dipophilic 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- 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 C0 2 with a gas compressor.
  • the stirrer was then turned on for 15 minutes to mimic a wash cycle.
  • 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.
  • Two different polydimethylsiloxane surfactants were used alone or in combination with 0.5 ml of water and supercritical fluid carbon dioxide.
  • the control was supercritical fluid carbon dioxide alone.
  • a polydimethylsiloxane having a molecular weight of 7,100 and 14% of its siloxyl group substituted with a 75/25 ethylene oxide/propylene oxide chain also supplied by Goldschmidt.
  • 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. 2_al_l______,
  • 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 influence of the supercritical fluid carbon dioxide on spot removal under these conditions.
  • a hydrophilic stain namely grape juice, was dry cleaned using polydimethylsiloxane surfactants with water and supercritical fluid carbon dioxide according to the invention.
  • 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.
  • a polydimethylsiloxane having a molecular weight of 7,100 and 14% of its siloxyl group substituted with a 75/25 ethylene oxide/propylene oxide chain also supplied by Goldschmidt. It was observed that the 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. Thus, 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.
  • Various types of stained cloths were tested under the dry cleaning conditions described in Example 2 above.
  • 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.
  • Red candle wax was placed on the wool cloth by predissolving the red candle in hexane and then pipetting an amount of the hexane solution onto the fabric.
  • the fabric was dried and the resulting fabric contained about 10 wt.% stain.
  • 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.
  • x:y and y' ratio is ⁇ 0.5:1 and R and R' are each independently a straight or branched C-_ 30 alkyl chain were prepared.
  • the compound formula is represented as MD X D* y M(C_) wherein M represents the trimethylsiloxyl end groups, D x represents the dimethylsiloxane backbone (C0 2 - philic) , D* y represents the substituted methylsiloxyl group (C0 2 -phobic) and (C_) 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 ⁇ to C l ⁇ 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 withdrawD* 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.
  • fluorinated surfactants equalled or improved dry cleaning of the tested stains over the use of supercritical fluid carbon dioxide alone. It was further observed that the fluorinated nonionic surfactants (FSO-100 and FSN) were more effective than the fluorinated nonionic having a lithium carboxylate salt (FSA) .
  • FSO-100 and FSN fluorinated nonionic surfactants
  • 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) mis 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 observed and calculated are as shown in Table 8 below:
  • Lipolase enzyme 1% enzyme solution of 3 mis 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 summarized in Table 9 below.
  • Amylase enzyme 1% enzyme solution of 3 mis 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.
  • Dry cleaning of red candle wax stains was conducted on several different types of fabric, using an alkyl modified polydimethylsiloxane surfactant, MD 153 D * . 5 M (C 12 ) , having a molecular weight of 1475 g/mole.
  • the surfactant was synthesized as described in Hardman, Supr .
  • 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.
  • the following tables show dry cleaning results on grape juice stains made on polyester cloth where the stained cloths were prepared by dipping the entire cloth in the staining solution.
  • the cloths are prepared with 2 wt . % stain, and otherwise, the drycleaning procedure is identical to that of Example 3, including the use of 0.5 ml water on each cloth prior to cleaning.

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  • Engineering & Computer Science (AREA)
  • 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.
EP96905817A 1995-03-06 1996-02-26 Systeme de nettoyage a sec utilisant du gaz carbonique densifie et un tensioactif comme additif Ceased EP0813628A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US399318 1995-03-06
US08/399,317 US5676705A (en) 1995-03-06 1995-03-06 Method of dry cleaning fabrics using densified carbon dioxide
US399317 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
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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EP (1) EP0813628A1 (fr)
AU (1) AU4942996A (fr)
CA (1) CA2211412A1 (fr)
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TR (1) TR199700901T1 (fr)
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FI973603A0 (fi) 1997-09-05
FI973603A7 (fi) 1997-09-05
AU4942996A (en) 1996-09-23
TR199700901T1 (xx) 1998-02-21
WO1996027704A1 (fr) 1996-09-12
TW338067B (en) 1998-08-11
CA2211412A1 (fr) 1996-09-12

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