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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/162—Organic compounds containing Si
• • 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
• • 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
  • D06L1/22—Processes involving successive treatments with aqueous and organic agents

Definitions

• the present invention is directed to a dry cleaning composition, more specifically, to a siloxane fluid based composition, for use in dry cleaning and to a dry cleaning process using the composition.
• PERC perchloroethylene
• petroleum-based materials as the cleaning solvent.
• PERC suffers from toxicity and odor issues.
• the petroleum-based products are not as effective as PERC in cleaning garments.
• Cyclic siloxanes have been reported as spot cleaning solutions, see US 4,685,930, and as dry cleaning fluids in dry cleaning machines, see US 5,942,007.
• Other patents disclose the use of silicone soaps in petroleum solvents, see JP 09299687, and the use of silicone surfactants in super critical carbon dioxide solutions has been reported, see, for example, US 5,676,705 and Chem. Mark. Rep., 15 Dec 1997, 252(24), p. 15.
• Non-volatile silicone oils have also been used as the cleaning solvent requiring removal by a second washing with perfluoroalkane to remove the silicone oil, see JP 06327888.
• the present invention is directed to a dry cleaning composition, comprising a volatile cyclic, linear or branched siloxane and one or more organic surfactants.
• the present invention is directed to a method for dry cleaning an article, comprising contacting the article with a composition comprising a cyclic, linear or branched siloxane and an organic surfactant which may be chosen from the classes of nonio ⁇ ic, cationic, anionic or amphoteric.
• the process of the present invention exhibits improved performance, such as for example, removal of water soluble stains from the article, for example a garment, being cleaned.
• the process of the present invention also effectively removes most soluble stains, including oil stains and grease stains.
• the composition comprises, based on 100 parts by weight ("pbw") of the composition, from greater than 90 pbw to 99.99 pbw, more preferably from 92 pbw to 99.9 pbw and even more preferably from 95 pbw to 99.5 pbw of the siloxane and from 0.001 pbw to less than 10 pbw, more preferably from 0.01 pbw to 8 pbw and even more preferably from 0.1 pbw to 5 pbw of the surfactant.
• pbw 100 parts by weight
• the composition optionally further comprises water, preferably from 0.01 pbw to 15 pbw, more preferably from 0.1 pbw to less than 12 pbw and even more preferably from 0.2 pbw to 10 pbw of water.
• the composition does not include siloxane resins or crosslihking agents.
• the water may be added as "free" water or may be delivered by an emulsion containing other components such as siloxanes, hydrocarbons, surfactants, or other suitable additives. If the water is delivered by an emulsion, the emulsion may be prepared by either homogenization of the components or by mechanically stirring the mixture.
• linear or branched, volatile siloxane solvent of the present invention are those containing a polysiloxane structure that includes from 2 to 20 silicon atoms.
• the linear or branched, volatile siloxanes are relatively volatile materials, having, for example, a boiling of below about 300°C point at a pressure of 760 millimeters of mercury ("mm Hg").
• the linear or branched, volatile siloxane comprises one or more compounds of the structural formula (I):
• T is R Si0 3 /2;
• R 1 , R 2 , R 3 and R 4 are each independently a monovalent hydrocarbon radical
• x and y are each integers, wherein 0 ⁇ x ⁇ 10 and 0 ⁇ y ⁇ 10 and 0 ⁇ z ⁇ 10.
• Suitable monovalent hydrocarbon groups include acyclic hydrocarbon radicals, monovalent alicyclic hydrocarbon radicals, monovalent and aromatic or fluoro containing hydrocarbon radicals.
• Preferred monovalent hydrocarbon radicals are monovalent alkyl radicals, monovalent aryl radicals and monovalent aralkyl radicals.
• (C 1 -C6)alkyl means a, linear or branched alkyl group containing from 1 to 6 carbons per group, such as, for example, methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl, preferably methyl.
• aryl means a monovalent unsaturated hydrocarbon ring system containing one or more aromatic or fluoro containing rings per group, which may optionally be substituted on the one or more aromatic or fluoro containing rings, preferably with one or more (Q- Ce)alkyl groups and which, in the case of two or more rings, may be fused rings, including, for example, phenyl, 2,4,6-trimethylphenyl, 2- isopropylmethylphenyl, 1-pentalenyl, naphthyl, anthryl, preferably phenyl.
• aralkyl means an aryl derivative of an alkyl group, preferably a (C2-C 6 )alkyl group, wherein the alkyl portion of the aryl derivative may, optionally, be interrupted by an oxygen atom, such as, for example, phenylethyl, phenylpropyl, 2-(l-naphthyl)ethyl, preferably phenylpropyl, phenyoxypropyl, biphenyloxypropyl.
• the monovalent hydrocarbon radical is a monovalent (C ⁇ -C 6 )alkyl radical, most preferably, methyl.
• the linear or branched, volatile siloxane comprises one or more of, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane or hexadecamethylheptasiloxane or methyltris(trimethylsiloxy)silane.
• the linear or branched, volatile siloxane of the present invention comprises octamethyltrisiloxane, decamethyltetrasiloxane, or dodecamethylpentasiloxane or methyltris(trimethylsiloxy)silane.
• the siloxane component of the composition of the present invention consists essentially of decamethyltetrasiloxane.
• Suitable linear or branched volatile siloxanes are made by known methods, such as, for example, hydrolysis and condensation of one or more of tetrachlorosilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, or by isolation of the desired fraction of an equilibrate mixture of hexamethyldisiloxane and octamethylcyclotetrasiloxane or the like and are commercially available.
• cyclic siloxane component of the present invention are those containing a polysiloxane ring structure that includes from 2 to 20 silicon atoms in the ring.
• the linear, volatile siloxanes and cyclic siloxanes are relatively volatile materials, having, for example, a boiling point of below about 300°C at a pressure of 760 millimeters of mercury ("mm Hg").
• the cyclic siloxane component comprises one or more compounds of the structural formula (II):
• R 5 , R 6 , R 7 and R 8 are each independently a monovalent hydrocarbon group; and a and b are each integers wherein 0 ⁇ a ⁇ 10 and 0 ⁇ b ⁇ 10, provided that 3 ⁇ (a + b) ⁇ 10.
• the cyclic siloxane comprises one or more of, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetradecamethylcycloheptasiloxane.
• the cyclic siloxane of the present invention comprises octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane.
• the cyclic siloxane component of the composition of the present invention consists essentially of decamethylcyclopentasiloxane.
• Suitable cyclic siloxanes are made by known methods, such as, for example, hydrolysis and condensation of dimethyldichlorosilane and are commercially available.
• the organic surfactant of the present invention comprises one or more surfactants selected from nonionic, cationic, anionic and amphoteric surfactants.
• the organic surfactant comprises a mixture of two or more surfactants of the same or different classes, as long as they are compatible, such as, for example, a mixture of two or more nonionic, cationic, anionic or amphoteric surfactants, a mixture of nonionic and cationic surfactants, a mixture of nonionic and anionic surfactants, a mixture of nonionic and amphoteric surfactants, a mixture of cationic and anionic surfactants, a mixture of cationic and amphoteric surfactants, a mixture of anionic and amphoteric surfactants, a mixture of anionic and amphoteric surfactants, a mixture of nonionic, cationic and anionic surfactants, a mixture of nonionic, anionic and amphoteric surfactants, a mixture of cationic anionic and am
• Nonionic surfactants are generally known in the art and include, for example, alkanol amides (such as, for example, coco, lauric, oleic and stearic monoethanolamides, diethanolamides and monpisopropanolamides), amine oxides (such as, for example, polyoxyethylene ethanolamides and polyoxyethylene propanolamides), polyalkylene oxide block copolymers (such as, for example, poly(oxyethylene-co-o ⁇ ypropylene)), ethoxylated alcohols, (such as, for example, isostearyl polyoxyethylene alcohol, lauryl, cetyl, stearyl, oleyl, tridecyl, trimethylnonyl, isodecyl, tridecyl), ethoxylated alkylphenols (such as, for example, nonyl), ethoxylated alkylphenols (such as, for example, nonyl), ethoxylated alkylphenols
• fatty esters such as lauric, isostearic, pelargonic, oleic, coco, stearic, and ricinoleic, and oils such as castor oil and tall oil
• fatty esters fluorocarbon containing materials
• glycerol esters such as, for example, glycerol monostearate, glycerol monolaurate, glycerol dilaurate, glycerol monoricinoleate, and glycerol oleate
• glycol esters such as, for example, propylene glycol monostearate, ethylene glycol monostearate, ethylene glycol distearate, diethylene glycol monolaurate, diethylene glycol monolaurate, diethylene glycol monooleate, and diethylene glycol stearate
• lanolin-based surfactants such as lauric, isostearic, pelargonic, oleic, coco, stearic, and ricinoleic,
• one component of the present invention comprises one or more nonionic surfactants according to one or more of the structural formulas III and IN: R Q -0-(CH 2 -CH_-0)n-R 10 (HI)
• R 9 is a monovalent hydrocarbon group of 1-30 carbons that may be linear, cyclic, branched, unsaturated, aromatic or fluoro containing
• R 10 is hydrogen or a monovalent hydrocarbon group of 1 to 30 carbons that may be linear, cyclic, branched, unsaturated, aromatic or fluoro containing
• n is from about 1 to about 100, more preferably from about 1 to about 40.
• R 9 contains from 2 to about 24 carbons, even more preferably from 8 to 24 carbons
• R 10 is H and n is from about 2 to about 20.
• one component of the present invention comprises one or more nonionic surfactants that may be a sugar- based surfactant according to one or more of the structural formulas V and VI:
• RU RW R 20 / RH R_ ⁇ R23 ⁇ R24 and R 2_ is independently H or a monovalent hydrocarbon group of 1 to 30 carbons that may be linear, cyclic, branched, an oxygenated alkane or other chalcogen containing group.
• Chalcogens are herein specifically defined as oxygen, sulfur, selenium, tellurium and polonium. These surfactants may also be the open-chain analogs.
• R 17 , R « RW R20, RH R ⁇ R23 / 2 an d R ⁇ are each H or a hydrocarbon group of 1 to 24 carbons, preferably a polyether or ester, even more preferably, one of R 17 and R 20 is a hydrocarbon of from 8 to 24 carbons while the other is H or a hydrocarbon of from 1 to 4 carbons, such as -CH2OH or -CH2CH3, and one of R 21 and R 25 is H or a hydrocarbon of from 8 to 24 carbons while the other is a hydrocarbon of from 1 to 4 carbons, such as -CH2OH or -CH2CH3.
• the surfactant or surfactants are chosen from sucrose esters, glucose esters, monoglycerides, polysaccharide ethers and sorbitan-based surfactants.
• one component of the present invention comprises one or more nonionic surfactants that may be an amine- based or phosphate ester-based surfactant according to one or more of the structural formulas VII and VIII:
• each R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 is independently H or a monovalent hydrocarbon group of 1 to 30 carbons that may be linear, cyclic, branched, unsaturated, aromatic, fluoro containing, an oxygenated alkane or other chalcogen containing group.
• R 11 , R 12 and R 13 are H or hydrocarbon groups of 1 to 4 carbons, and one is a hydrocarbon group of from 8 to 24 carbons, and R 14 and R 15 are either H or hydrocarbon groups of from 1 to 4 carbons while R 16 is a hydrocarbon group of from 8 to 24 carbons, or R 14 and R 15 are hydrocarbon groups of from 8 to 24 carbons while R 16 is a hydrocarbon group of from 1 to 4 carbons.
• the surfactant or surfactants are chosen from alkanol amides, amine oxides, ethoxylated amines, ethoxylated amides and phosphate esters.
• Anionic surfactants are generally known in the art and include, for example, alkyl aryl sulfonates (such as, for example, alkylbenzenesulfonates), alkyl aryl sulfonic acids (such as, for example, sodium and ammonium salts of toluene-, xylene- and isopropylbenzenesulfonic acids), sulfonated amines and sulfonated amides (such as, for example, amidosulfonates), carboxylated alcohols and carboxylated alkylphenol ethoxylates, diphenyl sulfonates, fatty esters, isethionates, lignin-based surfactants, olefin sulfonates (such
• one component of the present invention comprises one or more anionic surfactants that may be a sulfosuccinate, sulfate, sulfonate, carboxylate, or phosphorous containing surfactant according to one or more of the structural formulas IX to XIII:
• each R 26 , R 27 , R 28 , R 29 and R 30 is independently a monovalent hydrocarbon group of 1 to 30 carbons that may be linear, cyclic, branched, unsaturated, aromatic, fluoro containing, an oxygenated alkane or other chalcogen containing radical, and X is H or an alkali metal, alkaline earth element or a chalcogen containing counterion or other suitable cation that does not unduly interfere with the functioning of the molecule as a surfactant where the subscript q is the valence or oxidation state of the cation X.
• R 26 and R 27 are linear hydrocarbon groups of from 4 to 20 carbons, more preferably 6 to 13 carbons
• R 28 is a hydrocarbon group of from 6 to 20 carbons, more preferably from 8 to 16 carbons
• R 29 is a hydrocarbon group of from 8 to 26 carbons, more preferably from 10 to 20 carbons
• R 30 is a hydrocarbon of from 8 to 30 carbons.
• Compounds suitable for use as the cationic surfactant of the present invention are those having a positive charge when dissolved in aqueous media, which resides on an amino or quaternary nitrogen.
• Cationic surfactants are generally known in the art and include, for example, amine acetates, amines (such as, for example, oxygen-free amines such as monoalkylamines, dialkylamines and N-alkyltrimethylene diamines, and oxygen-containing amines such as amine oxides, ethoxylated alkylamines, 1- (2-hydroxyethyl)-2-imidazolines, and alkoxylates of ethylenediamine), and quaternary ammonium salts (such as, for example, dialkyldim ⁇ thylammonium salts, alkylbenzyldimethylammonium chlorides, alkyltrimethylammonium salts and alkylpyridium halides), and quaternary ammonium esters (such as
• one component of the present invention comprises one or more cationic surfactants that may be a quaternary amine- based surfactant according to the structural formula XIV:
• each R 31 , R 32 , R 33 , and R 34 is independently H or a monovalent hydrocarbon group of 1 to 30 carbons that may be linear, cyclic, branched, unsaturated, aromatic, fluoro containing, an oxygenated alkane or other chalcogen containing group, and J is a suitable anion having an oxidation state or valence p that does not unduly interfere with the functioning of the molecule as a surfactant.
• R 31 and R 32 are hydrocarbon groups of from 1 to 4 carbons, more preferably, methyl
• R 33 and R 34 are hydrocarbon groups of from 6 to 30 carbons, more preferably from 8 to 24 carbons.
• Amphoteric surfactants are compatible with anionic and cationic surfactants.
• Amphoteric surfactants are generally known in the art and include, for example, betaine derivatives such as alkylbetaines and amidopropylbetaines, block copolymers, imidazolines and lecithins.
• one component of the present invention comprises one or more amphoteric surfactants according to the structural formula XV:
• each R 35 , R 36 and R 37 is independently H or a monovalent hydrocarbon group of 1 to 30 carbons that may be linear, cyclic, branched, unsaturated, aromatic, fluoro containing, an oxygenated alkane or other chalcogen containing group
• G is a divalent spacer group
• Y is a carboxylate, sulfonate, sulfate, phosphonate or other similar group.
• R 35 is a hydrocarbon of from 1 to 4 carbons
• R 36 and R 37 are hydrocarbons of from 6 to 24 carbons.
• Surfactants are known in the art and are commercially available under many trade names from many sources, such as for example, Akzo Chemical Co., Calgene Chemical Inc., Emkay Chemical Co, Hercules, Inc., ICI Americas Inc., Lonza, Inc., Rhone Poulenc, Inc., Union Carbide Corp. and Witco Corp.
• the dry cleaning composition of the present invention further comprises a minor amount, preferably, less than 50 pbw per 100 pbw of the composition, more preferably, less than 10 pbw per 100 pbw of the composition, of one or more non-siloxane fluids.
• Suitable non- siloxane fluids include aqueous fluids, such as, for example, water, and organic fluids, for example, hydrocarbon fluids and halogenated hydrocarbon fluids.
• an article such as for example, a textile or leather article, typically, a garment, is dry cleaned by contacting the article with the composition of the present invention.
• the articles to be cleaned include textiles made from natural fibers, such as for example, cotton, wool, linen and hemp, from synthetic fibers, such as, for example, polyester fibers, polyamide fibers, polypropylene fibers and elastomeric fibers, from blends of natural and synthetic fibers, from natural or synthetic leather or natural or synthetic fur.
• the article and dry cleaning composition are then separated, by, for example, one or more of draining and centrifugation.
• separation of the article and dry cleaning composition is followed by the application of heat, preferably, heating to a temperature of from 15°C to 120°C, preferably from 20°C to 100°Q or reduced pressure, preferably, a pressure of from 1 mm Hg to 750 mm Hg, or by application of both heat and reduced pressure, to the article.
• This color difference represents the relative amount of cleaning, with the higher ⁇ E indicative of better cleaning performance.
• a cleaning composition according to the present invention containing a cyclic siloxane (Ds) and one or more nonionic surfactants was made. Fabric swatches were cleaned using the above procedure, and the color difference was measured to determine the effectiveness of the cleaning composition. A solution of cyclic siloxane (D5) without a surfactant was used as a control.
• Nonionic surfactants used in the example are those represented by formula III above, where R 9 and n are as described in Table 1, and R 10 is H.
• Table 1 shows that nonionic surfactants enhance the cleaning and dye removal of the base cyclic siloxane (D5) solvent.
• Example 2 Anionic Surfactants
• a cleaning composition according to the present invention containing a cyclic siloxane (D 5 ) and one or more anionic surfactants was made. Fabric swatches were cleaned using the above procedure, and the color difference was measured to determine the effectiveness of the cleaning composition. A solution of cyclic siloxane (D5) without a surfactant was used as a control.
• Table 2 shows that the anionic sulfosuccinate surfactants enhanced the water soluble dye removal of the base cyclic siloxane (D5) solvent.
• Surfactant TR is a solution in 20% ethanol and 10% water
• GPG is a solution in 8% ethanol and 22% water.
• a cleaning composition according to the present invention containing a cyclic siloxane (D5) and one or more anionic and cationic surfactants was made. Fabric swatches were cleaned using the above procedure, and the color difference was measured to determine the effectiveness of the cleaning composition. A solution of cyclic siloxane (D 5 ) without a surfactant was used as a control.
• Table 3 shows that the ionic surfactants enhanced the water soluble dye removal of the base cyclic siloxane (D5) solvent. (R 2 Me 2 N + Cl-came as a solution in water.)
• a cleaning composition according to the present invention containing a cyclic siloxane (D5), water and a nonionic surfactant was made. Fabric swatches were cleaned using the above procedure, and the color difference was measured to determine the effectiveness of the cleaning composition. A solution of cyclic siloxane (D5) without a surfactant was used as a control.
• Nonionic surfactants used in the example are those represented by formula III above, where R 9 and n are as described in Table 4, and R 10 is H. Table 4 - Nonionic Surfactants
• Tables 4 and 4A show that nonionic surfactants in the presence of water enhance the cleaning and dye removal of the base cyclic siloxane (D5) solvent.
• a cleaning composition according to the present invention containing a cyclic siloxane (D5), water and an ionic surfactant was made. Fabric swatches were cleaned using the above procedure, and the color difference was measured to determine the effectiveness of the cleaning composition. A solution of cyclic siloxane (D5) and water without a surfactant was used as a control.
• Table 5 shows that the ionic surfactants in the presence of water enhanced the water soluble dye removal of the base cyclic siloxane (D5) solvent.
• Table 6 Ionic surfactants with and without water
• 1,2-diols were efficient at removing the dye at the 5% level, although significant cleaning was seen at
• Table 5 shows the results from using sugar based surfactants and alkanol amides as water-based stain removers.
• the cationic surfactants tested were all quaternary ammonium salts of the type 6 below. As one can see, the quat salts were effective at the 1% level in all cases. Additional water was sometimes advantageous.
• Vari-Soft 300 30% ( es Cl “ : Ethoquad C/25: C I2 - 15 (Me)N((EO) 25 H) 2 + Cl '
• amphoteric materials examined were of the betaine class as illustrated below (table7). These were quatemized glycine derivatives. All these materials were supplied as aqueous solutions and performed moderately well at high levels and even better at lower, 1% loading.
• a wide variety of organic anionic surfactants are available in the fo ⁇ ns of sulfosuccinates, sulfonates, phosphonates and the like.
• One set examined were the sulfosuccinates as shown in Table 8. Best results were seen with high levels of added water.
• One beneficial feature of the Aerosol OT was that it was soluble in D 5 to at least 5 weight percent.
• A ⁇ -Ph-O ⁇ EO ⁇ CV
• ATPHOS 3226 C l Ph-0-(EO) 6 -P 2 0 5 -
• Yelkin and Ultralec are lecithin based.
• Triton X-200 C 12 -Ph-0-(EO) 3 -OS0 3 ' Na ; Witconate AOS : C, 4 . 16 -S0 4 _ Na + ; Bio-Soft D-62: Na DDBSA, 50% .
• Fluoro-surfactants were also examined as shown in Table 11. Of all the varieties tried, the fluorinated quat salts and the fluoroalkyl alkoxide displayed the best performance.
• the present invention exhibits improved performance of dry cleaning agents for stain removal, particularly water soluble stains, through the addition of a surfactant, and optionally water.

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