EP0646196B1 - Compositions hydrophobes et oleophobes utilisant efficacement le fluor - Google Patents

Compositions hydrophobes et oleophobes utilisant efficacement le fluor Download PDF

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EP0646196B1
EP0646196B1 EP92909526A EP92909526A EP0646196B1 EP 0646196 B1 EP0646196 B1 EP 0646196B1 EP 92909526 A EP92909526 A EP 92909526A EP 92909526 A EP92909526 A EP 92909526A EP 0646196 B1 EP0646196 B1 EP 0646196B1
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Prior art keywords
extender
weight
substrate
amount
composition according
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German (de)
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EP0646196A1 (fr
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Rudolf J. Dams
Johan E. De Witte
Christoffel C. Maes
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3M Co
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Minnesota Mining and Manufacturing Co
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them

Definitions

  • This invention relates to aqueous compositions containing fluorochemical oil- and water-repellent agents. This invention also relates to agents that improve fluorine efficiency of fluorochemical oil- and water-repellent agents. This invention also relates to processes for providing oil- and water-repellency to fibrous substrate materials.
  • This invention provides fluorine-efficient oil- and water-repellent compositions comprising:
  • This invention also provides substrates treated with a fluorine-efficient composition as described above, and methods of improving the fluorine-efficiency of a fluorochemical oil- and water-repellent agent, comprising the step of formulating the fluorochemical agent with components (B) and (C) described above.
  • compositions of the invention comprise at least one member of each of two classes of extenders.
  • the combination improves the fluorine-efficiency of fluorochemical agents, and thus reduces the cost of fluorochemical treatment, to a greater extent than would be expected based on the properties of each individual class of extenders.
  • Component (A) in a composition of the invention is a fluorochemical oil- and water-repellent agent generally comprising a plurality of fluoroaliphatic (i.e., R f ) groups.
  • fluoroaliphatic (i.e., R f ) groups are well known to those skilled in the art, and many (e.g., SCOTCHGARDTM fabric protector, 3M) are commercially available as ready-made formulations.
  • fluorochemical agents useful in this invention comprise fluorochemical compounds or polymers containing one or more fluoroaliphatic groups R f , which are fluorinated, stable, inert, non-polar, preferably saturated, monovalent and both oleophobic and hydrophobic.
  • R f preferably contains at least about 3 carbon atoms, more preferably 3 to about 20 carbon atoms, and most preferably about 6 to about 14 carbon atoms.
  • R f can contain straight chain, branched chain, or cyclic fluorinated alkylene groups or combinations thereof or combinations thereof with straight chain, branched chain, or cyclic alkylene groups.
  • R f is preferably free of polymerizable olefinic unsaturation and can optionally contain catenary heteroatoms such as oxygen, divalent or hexavalent sulfur, or nitrogen. It is preferred that R f contain about 40% to about 78% fluorine by weight, more preferably about 50% to about 78% fluorine by weight.
  • the terminal portion of the R f group contains a fully fluorinated terminal group. This terminal group preferably contains at least 7 fluorine atoms, e.g., CF 3 CF 2 CF 2 -, (CF 3 ) 2 CF-, -CF 2 SF 5 , or the like.
  • Perfluorinated aliphatic groups i.e., those of the formula C n F 2n+1 ) are the most preferred embodiments of R f .
  • fluorochemical agents include, for example, R f -containing urethanes, ureas, esters, amines (and salts thereof), amides, acids (and salts thereof), carbodiimides, guanidines, allophanates, biurets, and compounds containing two or more of these groups, as well as mixtures and blends thereof.
  • Useful fluorochemical polymers containing R f groups include copolymers of fluorochemical acrylate and/or methacrylate monomers with co-polymerizable monomers, including fluorine-containing and fluorine-free monomers, such as methyl methacrylate, butyl acrylate, octadecylmethacrylate, acrylate and methacrylate esters of poly(oxyalkylene) polyol oligomers and polymers, e.g., poly(oxyethylene)glycol dimethacrylate, glycidyl methacrylate, ethylene, vinyl acetate, vinyl chloride, vinylidenechloride, vinylidenefluoride, acrylonitrile, vinylchloroacetate, isoprene, chloroprene, styrene, butadiene, vinylpyridine, vinyl alkyl ethers, vinyl alkyl ketones, acrylic and methacrylic acid, 2-hydroxyethyl acrylate, N
  • fluorochemical agents include those described in Patent Nos. 2,803,615 (Ahlbrecht et al.), 2,934,450 (Brown), 3,068,187 (Bolstad et al.), 3,094,547 (Heine), 3,329,661 (Smith et al.), 3,341,497 (Sherman et al.), 3,398,182 (Guenthner et al.), 3,458,571 (Tokoli), 3,462,296 (Raynolds et al.), 3,574,791 (Sherman et al.), 3,728,151 (Sherman et al.), 3,896,251 (Landucci), 3,916,053 (Sherman et al.), 4,013,627 (Temple), 4,024,178 (Landucci), 4,029,585 (Dettre), 4,034,964 (Sherman et al.), 4,144,367 (Landucci), 4,160,777 (Loudas), 4,165,
  • Component (B) in a composition of the invention is a copolymer extender comprising
  • Examples of monomers of Formula V include general classes of ethylenic compounds capable of free-radical polymerization, such as lower olefinic hydrocarbons, optionally halogenated, such as ethylene, propylene, isobutene, 3-chloro-2-isobutene, butadiene, isoprene, chloro and dichlorobutadienes, fluoro and difluorobutadienes, 2,5-dimethyl-1,5-hexadiene; vinyl, allyl or vinylidene halides such as vinyl or vinylidene chloride, vinyl or vinylidene fluoride, allyl bromide, allyl chloride, methallyl chloride; styrene and its derivatives such as vinyltoluene, ⁇ -methylstyrene, a-cyanomethylstyrene, divinylbenene, N-vinylcarbazole; vinyl esters such as vinyl acetate, vinyl propionate, vinyl is
  • alkyl crotonates alkyl acrylates and alkyl methacrylates such as methyl acrylate, methyl methactylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isoamyl acrylate, isoamyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, cetyl acrylate, or cetyl methacrylate.
  • the copolymer extender also comprises polymerized units derived from a monomer of Formula VII.
  • Suitable monomers of Formula VII include those comprising a functional group that can interact with a fibrous substrate by, for example, physical entanglement, covalent bonding by way of nucleophilic, electrophilic, ionic, free radical or like reactions between the copolymer and the substrate, or ionic bonding.
  • Wool, leather, paper, cotton, and nylon variously comprise hydroxyl, amino, carboxyl, and carboxamido groups.
  • "a functional group that can interact with a fibrous substrate” designates a group that can interact with a fabric by any of the above-described mechanisms.
  • Such groups can be easily selected by those skilled in the art as a function of the particular fibrous substrate that is intended to be treated with the composition of the invention.
  • Representative groups suitable for interacting with a substrate include polymerizable olefin, olefin that can undergo a hydrosilation reaction, epoxy, amino, hydroxy, halo, haloformyl, aziridino, acid groups such as carboxy, sulfo, sulfino, sulfeno, dihydroxyphosphinyl, and hydroxyphosphinilidene, alkali metal and alkaline-earth metal salts thereof, amine salts thereof, quaternary ammonium salts thereof and the like, or amino and quaternary ammonium groups and salts thereof with, e.g., the above-listed types of acids.
  • Suitable functionalized monomers include N-methylol acrylamide; N-methylol methacrylamide; aziridinyl acrylate and methacrylate; diacetone acrylamide and methacrylamide; methylolated diacetone acrylamide and methacrylamide; 2-hydroxy-3-chloropropyl acrylate and methacrylate; hydroxy (C 2 to C 4 ) alkyl acrylates and methacrylates; maleic anhydride; butadiene; isoprene; chloroprene; allyl alcohol; allyl glycolate; isobutenediol; allyloxyethanol; o-allyl phenol; divinyl carbinol; glycerol ⁇ -allylether, acrylamide; methacrylamide; maleamide; maleimide; N-cyanoethyl acrylamide; N-isopropyl acrylamide; glyoxal bis-acrylamide; metal salts of acrylic acid and methacrylic acid; vinylsulfonic
  • Copolymers comprising such monomers are described in U.S. Pat. No. 3,849,521 (Kirimoto et al.) incorporated herein by reference.
  • Other suitable copolymers can be prepared by methods well known to those skilled in the art.
  • Component (C) in a composition of this invention is a blocked isocyanate.
  • Suitable isocyanates for use (before blocking) include aromatic diisocyanates such as 4,4'-methylenediphenylenediisocyanate, 4,6-di-(trifluoromethyl) -1,3-benzene diisocyanate, 2,4-tolunediisocyanate, 2,6-toluene diisocyanate, o, m, and p-xylylene diisocyanate, 4,4,-diisocyanatodiphenylether, 3,3'-dichloro-4,4'-diisocyanatodiphenylmethane, 4,5'-diphenyldiisocyanate, 4,4'-diisocyanatodibenzyl, 3,3,-dimethoxy-4,4,-diisocyanatodiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodip
  • isocyanates containing internal isocyanate-derived moieties such as biuret-containing tri-isocyanates such as that available from Mobay as DESMONDURTM N-100, isocyanurate-containing tri-isocyanates such as that available from Huls AG, Germany, as IPDI-1890, and azetedinedione-containing diisocyanates such as that available from Bayer as DESMONDURTMTT.
  • triisocyanates such as tri-(4-isocyanatophenyl)-methane (available from Bayer as DESMONDURTMR) are suitable.
  • isocyanate-functional low molecular weight polyurethanes are prepared by reacting a polyfunctional, aliphatic, cycloaliphatic, araliphatic or aromatic polyisocyanate, such as, for example, hexamethylene-1,6-diisocyanate, the various isomers of tolulene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and the like, with a low molecular weight polyol having at least 2, preferably at least 3 hydroxyl groups.
  • a polyfunctional, aliphatic, cycloaliphatic, araliphatic or aromatic polyisocyanate such as, for example, hexamethylene-1,6-diisocyanate
  • the various isomers of tolulene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and the like with a low molecular weight polyol having at least 2, preferably
  • Suitable low molecular weight polyols include trimethylolpropane, 1,3,5-hexanetriol, glycerol, pentaerythritol, propylene glycol, hexylene glycol and diethylene glycol. Also suitable are other low molecular weight polyhydroxy compounds, such as triethanolamine.
  • low molecular weight polyurethanes can be prepared by reacting a polyol with an excess of polyisocyanate.
  • the equivalent ratio of hydroxyl to isocyanato groups in the reaction is preferably at least 1:1.3, more preferably 1:1.5 to 2.5.
  • isocyanates are used in a composition of the invention in the form of "blocked isocyanates", i.e., the reaction product of an isocyanate and a blocking agent, wherein the blocking agent is removable from the isocyanate under thermal conditions such as those employed during cure of a substrate treated with a compound containing the blocked isocyanato group.
  • blocked isocyanates include arylalcohols (e.g., phenol, cresols, nitrophenols, o- and p-chlorophenol, naphthols, 4-hydroxybiphenyl); C 2 to C 8 alkanone oximes (e.g.
  • acetone oxime butanone oxime
  • arylthiols e.g., thiophenol
  • organic active hydrogen compounds e.g.; diethyl malonate, acetylacetone, ethyl acetoacetate, ethyl cyanoacetate, ⁇ -caprolactam
  • sodium bisulfite and hydroxylamine.
  • Particularly preferred blocked isocyanates include those blocked with C 2 to C 8 alkanone oximes, particularly butanone oxime. Such blocked isocyanates can be de-blocked at a relatively low temperature, for example during the process of curing a substrate that has been treated with the composition comprising the blocked isocyanate.
  • a composition of the invention comprises the fluorochemical agent in an amount effective to impart repellent properties to a fibrous substrate treated with the composition.
  • the amount of fluorochemical agent that constitutes an effective amount can be easily determined by those skilled in the art and depends on the particular fluorochemical agent used and on the amounts of the copolymer and blocked isocyanate extenders used.
  • copolymer extender and the blocked isocyanate extender are present in a combined amount effective to improve the fluorine efficiency of the fluorochemical agent.
  • Each extender is preferably present in an amount such that the improvement in fluorine efficiency is greater than the improvement provided by either extender alone.
  • Immulating in fluorine efficiency designates an improvement in the repellent properties imparted by a fluorochemical agent per unit weight of fluorine in a composition comprising the agent, as those repellent properties are measured using the test procedures set forth below.
  • an extender or combination of extenders improves the fluorine efficiency of a given fluorochemical agent if performance is improved by including the extender(s) in a composition containing the same or a lesser concentration of the fluorochemical agent.
  • the extenders are present in relative amounts between about 1:20 to about 20:1, preferably abut 1:4 to about 4:1, more preferably about 2:1 to abut 1:2, and most preferably about 1:1.
  • the fluorochemical agent is present in an amount of about 20 to about 2000, preferably 40 to about 900, and most preferably about 100 to about 400, parts by weight based on 100 parts by weight of the copolymer and the blocked isocyanate extenders combined.
  • a treated substrate comprises the fluorochemical agent in an amount of abut 0.1% to about 0.6% by weight based on the weight of the untreated substrate. Further, it is preferred that a treated substrate comprise the fluorochemical agent, the copolymer extender, and the blocked isocyanate extender in a total combined amount of about 0.1% to about 1% by weight based on the weight of the untreated substrate.
  • a composition of the invention can be applied to a substrate by any suitable method.
  • a composition can be prepared in the form of an aqueous dispersion and the substrate treated therewith.
  • a dispersion will generally contain water, an amount of composition effective to provide repellent properties to a substrate treated therewith, and an emulsifier in an amount effective to stablilize the dispersion.
  • Water is preferably present in an amount of about 70 to about 900 parts by weight based on 100 parts by weight of the composition of the invention.
  • the emulsifier is preferably present in an amount of about 1 to about 25 parts by weight, preferably about 5 to about 10 parts by weight, based on 100 parts by weight of the composition of the invention.
  • Conventional cationic, nonionic, anionic, and zwitterionic emulsufiers are suitable.
  • the substrate can be immersed in the dispersion and agitated until it is saturated.
  • the saturated substrate can then be run through a padder/roller to remove excess dispersion, dried in an oven at a relatively low temperature (e.g., 70°C) for a time sufficient to remove the dispersion medium (e.g., water, ethylene glycol, or a mixture thereof), and cured at a temperature and for a time sufficient to provide a cured treated substrate.
  • a relatively low temperature e.g., 70°C
  • the dispersion medium e.g., water, ethylene glycol, or a mixture thereof
  • This curing process can be carried out at temperatures between 40°C and about 200°C depending on the particular composition used. In general, a temperature of about 155°C for period of about 5 minutes is suitable.
  • the cured treated substrate can be cooled to room temperature and used as desired, e.g., incorporated or fashioned into a garment such as rainwear.
  • thermo-condensable products capable of promoting interaction with the substrate.
  • additives include in the dispersion certain additives, polymers, thermo-condensable products and catalysts capable of promoting interaction with the substrate.
  • these include in the dispersion certain additives, polymers, thermo-condensable products and catalysts capable of promoting interaction with the substrate.
  • these include the condensates or precondensates of urea or melamine with formaldehyde (sometimes referred to herein as resins).
  • auxilliary extenders can be used, either alone or in combination with each other.
  • Suitable auxilliary extenders include paraffin; compositions containing alkylketenes or derivatives thereof; siloxanes; chlorohydrates of stearamidomethylpyridinium; condensates of fatty acids with melamine or urea derivatives (such as the product obtained on reacting stearic acid with hexamethoxymethylmelamine), condensates of fatty acids with polyamides (such as the reaction product of stearic acid with diethylenetriamine) and their epichlorohydrin adducts. It is also possible to use salts of inorganic or organic acids such as aluminum stearate, zirconium acetate, zirconium oxychloride or Werner complexes such as chromium stearatochloride.
  • softeners such as certain polyethylenes, polydimethylsiloxanes, modified hydrogenalkylpolysiloxanes, or other materials known to those skilled in the art.
  • auxilliary products such as polyglycols, colloids such as starch, dextrin, casein, sizing agents, fixing or retaining agents, materials to improve stain resistance, cleaning ability, fire proofing or antistatic properties, buffering agents, fungicidal agents, optical bleaching agents, sequestering agents, mineral salts, surface-activity agents, or swelling agents to promote penetration.
  • suitable auxilliary products and amounts thereof can be easily selected by those skilled in the art.
  • compositions of the invention can also be used to provide anti-adhesion properties and to protect substrates against solvents or certain aggresive chemicals. They can also be used for applications such as stain resistance, soil resistance, soil release and stain release on textiles, paper, or leather. Further, they can be used for imparting properties such as antistatic, antipilling, mold release, corrosion inhibition, or anti-fouling properties.
  • the resistance of a treated substrate to wetting with water was measured using AATCC Test Method 22-1977, "Water Repellency: Spray Test” as described in American Association of Textile Chemists and Colorists Technical Manual, 1977, 53 , 245. Samples are rated on a scale of 0 to 100, with 0 indicating complete wetting of the upper and lower surfaces of the substrate and 100 indicating no wetting.
  • oil repellency of a substrate treated with a compound of the invention was measured using AATCC Test Method 118-1975, "Oil Repellency: Hydrocarbon Resistance Test” as described in AATCC Technical Manual, 1977, 53, 223. This test measures the resistance of a substrate to wetting by a series of hydrocarbon liquids with a range of surface tensions. The values reported range from 0 (least repellent) to 8 (most repellent).
  • a 230 g sample of generally square, 400 cm 2 to about 900 cm 2 sheets of treated substrate was placed in a washing machine along with a ballast sample (1.9 Kg of 8 oz fabric in the form of generally square, hemmed 8100 cm 2 sheets).
  • Conventional detergent ("TIDE", 46 g) is added and the washer is filled to high water level with hot water (49°C ⁇ 3°C).
  • the substrate and ballast load is washed five times using a 12-minute normal wash cycle and the substrate and the ballast are dried together in a conventional clothes dryer set on the "heat" setting for about 45 minutes.
  • the dry substrate is pressed using a hand iron set at the temperature recommended for the particular substrate fabric.
  • reaction temperature was increased to 60°C and maintained for two hours.
  • the reaction mixture was then diluted to 40% solids in ethyl acetate using about 86 g ethyl acetate. A clear, brown organic solution was obtained.
  • MARLOWETTM 5401 cationic emulsifier (5.7 g, 10 percent by weight based on total solids, Hüls, Germany), ethylene gylcol (35 g, 60% by weight on total solids) and deionized water (171 g, 300% by weight on total solids).
  • This solution was warmed to about 40°C and under very vigorous mixing added to the organic solution, also at about 40°C.
  • a milky pre-emulsion was obtained, which was passed three times through a MANTON-GAULINTM emulsifier at about 40°C and 300 bar pressure. The solvent was removed under reduced pressure. A slightly brown dispersion was obtained. This dispersion was diluted to 20% solids and filtered and stored.
  • 2-Ethylhexyl methacrylate (59,4 g, 0.3 mol), N-methylolacrylamide (1.5 g, 0.014 mol), ETHOQUADTM 18/25 cationic emulsifier (Akzo, the Netherlands, 3 g, about 5% by weight on total solids), tertiary dodecyl mercaptan (.15 g, about 0.25% by weight on total solids) and V-50TM initiator ([2,2'-azobis[2-methylpropanimidamide]-dihydrochloride, Wako, Japan] 0.12 g, about 0.2% by weight on total solids) and deionized water (140 g) were mixed. The mixture was deaereated and then heated at 75°C for 16 hours. A nearly transparent dispersion was obtained.
  • a dispersion was prepared as described in U.S. Pat. No. 3,068,187 (Bolstad et al., Example 5), containing a graft copolymer of a fluorinated monomer and a fluorine-free comonomer.
  • the mixture was warmed to 62°C and a solution of VAZOTM 52 initiator [(2,2'-azobis-(2,4-dimethylvaleronitrile), 5 g, Du Pont)] in 10 g of dichloromethane was added over a period of 4 hours.
  • N-Methylperfluorooctylsulfonamidoethyl acrylate (61.1 g, 0.1 mol), 2-mercaptoethanol (1.95 g, 0.025 mol), ethyl acetate 40 g and AIBN (0.12 g, 0.2% by weight on total solids) were mixed, deaerated, and heated at reflux (about 80°C) for 16 hours.
  • the reaction mixture was cooled to room temperature.
  • PAPI (10.2 g, 0.075 equivalent) was added together with 2 drops of dibutyltin dilaureate catalyst.
  • the reaction mixture was heated at reflux for 5 hours.
  • the reaction was then cooled to about 60°C and 4.35 g of 2-butanone oxime (0.05 mol) was added.
  • the reaction was continued for 2 hours at 70°C.
  • the reaction product was emulsified at 70°C using the procedure described in Intermediate A. A slightly brown dispersion was obtained, filtered, and stored.
  • FC-217 a fluorochemical acrylate copolymer commercially available from 3M Company.
  • FC-352 a fluorochemical carbodiimide containing composition commercially available from 3M Company.
  • FC-353 a fluorochemical containing ester commercially available from 3M Company.
  • N-Allylperfluorooctylsulfonamide 54 g, 0.1 equivalent
  • the mixture was heated to 110°C and 1 mL of 1% solution of H 2 Pt 116 in 2-butanone is added. After 30 minutes Monylvinylester (2 g, 0.01 mol, VEORATM 10, Shell) and 0.3 mL of the 1% catalyst solution was added.
  • the reaction was heated at 126°C for 1 hour. A slightly brown solution was obtained.
  • the material was emulsified at 30°C using the procedure, ingredients, and amounts decribed in Intermediate H. A slightly brown dispersion was obtained, the pH was adjusted to 7, and the emulsifion was filtered and stored.
  • FC-247 a composition containing a blend of a fluorochemical ester, a fluorochemical urethane, and a fluorochemical acrylate copolymer, commercially available from 3M Company.
  • FC-214 a composition containing a blend of a fluorochemical urethane and a fluorochemical copolymer, and commercially available from 3M Company.
  • FC-270 a composition containing a blend of a fluorochemical carbodiimide and a fluorochemical acrylate copolymer, commercially available from 3M Company.
  • N-methyl perfluorooctylsulfonamidoethyl acrylate 30.6 g, about 0.050 mol, MeFOSEA
  • 2-ethylhexyl acrylate 8.1, about 0.044 mol
  • 2-hydroxyethyl acrylate 0.7 g, about 0.006 mol
  • 2 g ETHOQUADTM 18/25 emulsifier.
  • Hexamethoxymethylmelamine 39 g, 0.1 mol, CYMELTM 303, American Cyanamid
  • a fluorochemical mercaptan with general formula C n F 2n+1 CH 2 CH 2 SH 232 g, 0.4 mol, average n is about 10, average molecular weight is about 580, Atochem, France
  • para-toluenesulfonic acid 0.42 g
  • Methanol was evolved and removed by distillation. Over a 2 hour period the temperature was further raised to 180°C and kept at that temperature for 4 hours.
  • hexafluoroxylene solvent was added to make a 40% solids solution (in total, 348 g hexafluoroxylene was used).
  • a dispersion was prepared of this solution according to the procedure set forth in Intermediate F. The dispsersion was filtered and stored.
  • a fluorochemical agent as described in Intermediates C-Q above is provided and formulated into a treatment bath containing a predetermined amount of each of the appropriate fluorochemical agent, the copolymer extender, and the blocked isocyanate extender such that the treatment can be made by a padding application at the indicated percent solids on fabric.
  • the substrate is dried and cured at 150°C for 10 min.
  • Fluorochemical agents were formulated with single extenders and combinations of extenders to treat a polyester/cotton 50/50 fabric at 0.4% total solids on fabric.
  • FC designates fluorochemical agent and weight percents indicate percent based on the combined weight of the fluorochemical agent and the extender or extenders.
  • compositions of the invention comprising any of a wide variety of fluorochemical agents in combination with a member of each of the two extender classes, give superior results compared to the compositions of the Comparative Examples comprising only one extender. Superior oil and water repellencies were obtained, and fluorine efficiency was improved relative to the Comparative Examples.
  • formulations were prepared and used to treat 100% cotton fabrics at 0.6% total solids on fabric.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Compositions contenant un agent fluorochimique, un diluant copolymère, et un diluant à base d'isocyanate séquencé. La combinaison de diluants permet d'utiliser plus efficacement la teneur en fluor de l'agent fluorochimique que chaque diluant inclus séparément. On décrit aussi des substrats traités au moyen de telles compositions, des procédés permettant de conférer des caractéristiques hydro- et oléophobes à un substrat et des procédés permettant d'utiliser plus efficacement la teneur en fluor d'un agent fluorochimique.

Claims (23)

  1. Composition oléofuge et hydrofuge utilisant efficacement le fluor, comprenant:
    (A) un agent chimique fluoré oléofuge et hydrofuge;
    (B) un diluant copolymère comprenant:
    (i) des motifs polymérisés dérivés d'un monomère de formule:

            CR1R2=CR3R4

    dans laquelle chacun des radicaux R1, R2, R3 et R4 représente indépendamment un atome d'hydrogène, un atome d'halogène, ou un groupe organique; et
    (ii) des motifs polymérisés dérivés d'un monomère de formule:

            CH2=CR5X

    dans laquelle R5 représente un atome d'hydrogène ou un groupe méthyle, et X représente un groupement comprenant un groupe fonctionnel pouvant interagir avec un substrat fibreux; et
    (C) un diluant isocyanate bloqué,
    dans laquelle l'agent chimique fluoré est présent dans une proportion efficace pour conférer des propriétés repoussantes à un substrat fibreux traité avec la composition, et dans laquelle le diluant copolymère et le diluant isocyanate bloqué sont présents dans une proportion combinée efficace pour améliorer l'efficacité en fluor de l'agent chimique fluoré, et chaque diluant est présent dans une proportion telle que l'amélioration de l'efficacité en fluor soit plus grande que l'amélioration apportée par l'un ou l'autre des diluants seul.
  2. Composition selon la revendication 1, dans laquelle le diluant copolymère comprend:
    (i) des motifs polymérisés dérivés d'un monomère de formule:

            CR6R7=CR8COOR9

    dans laquelle R6, R7 et R8 représentent indépendamment un atome d'hydrogène ou un groupe méthyle, et R9 représente un groupe alkyle en C1-C18; et
    (ii) des motifs polymérisés dérivés d'un monomère de formule:

            CH2=CR5CONHCH2OH

    dans laquelle R5 représente un atome d'hydrogène ou un groupe méthyle.
  3. Composition selon la revendication 1, dans laquelle le diluant copolymère comprend:
    (i) des motifs polymérisés dérivés d'un monomère choisi dans le groupe constitué par un crotonate d'alkyle, un acrylate d'alkyle et un méthacrylate d'alkyle; et
    (ii) des motifs polymérisés dérivés d'un monomère de formule:

            CH2=CR5CONHCH2OH

    dans laquelle R5 représente un atome d'hydrogène ou un groupe méthyle.
  4. Composition selon la revendication 1, dans laquelle le diluant isocyanate bloqué est un polyuréthane de faible masse moléculaire à fonction isocyanate bloquée.
  5. Composition selon la revendication 1, dans laquelle le diluant isocyanate bloqué est un isocyanate aromatique bloqué.
  6. Composition selon la revendication 1, dans laquelle le diluant isocyanate bloqué est un polyphénylpolyisocyanate bloqué par un 2-butanone-oxime.
  7. Composition selon la revendication 1, dans laquelle le diluant copolymère comprend des motifs polymérisés dérivés du méthacrylate de 2-éthylhexyle et des motifs polymérisés dérivés du N-méthylolacrylamide.
  8. Composition selon la revendication 1, dans laquelle les diluants sont présents en proportions relatives comprises entre environ 1:20 et environ 20:1.
  9. Composition selon la revendication 1, dans laquelle les diluants sont présents en proportions relatives comprises entre environ 1:4 et environ 4:1.
  10. Composition selon la revendication 1, dans laquelle les diluants sont présents en proportions relatives comprises entre environ 2:1 et environ 1:2.
  11. Composition selon la revendication 1, dans laquelle les diluants sont présents en proportions relatives d'environ 1:1.
  12. Composition selon la revendication 1, dans laquelle l'agent chimique fluoré est présent dans une proportion d'environ 20 à environ 2 000 parties en poids, pour 100 parties en poids du diluant copolymère et du diluant isocyanate bloqué combinés.
  13. Composition selon la revendication 1, dans laquelle l'agent chimique fluoré est présent dans une proportion d'environ 40 à environ 900 parties en poids, pour 100 parties en poids du diluant copolymère et du diluant isocyanate bloqué combinés.
  14. Composition selon la revendication 1, dans laquelle l'agent chimique fluoré est présent dans une proportion d'environ 100 à environ 400 parties en poids, pour 100 parties en poids du diluant copolymère et du diluant isocyanate bloqué combinés.
  15. Substrat ayant des propriétés oléofuges et hydrofuges, comprenant un substrat fibreux dont la surface comporte une quantité de composition selon la revendication 1 efficace pour lui conférer des propriétés oléofuges et hydrofuges.
  16. Substrat selon la revendication 15, dans lequel le substrat est du papier, un non tissé, du coton, un mélange polyester/coton, du nylon ou du cuir.
  17. Substrat selon la revendication 15, dans lequel l'agent chimique fluoré est présent dans une proportion d'environ 0,1% à environ 0,6% en poids, rapportée au poids du substrat non traité.
  18. Substrat selon la revendication 15, dans lequel l'agent chimique fluoré, le diluant copolymère et le diluant isocyanate bloqué sont présents dans une proportion totale combinée d'environ 0,1% à environ 1% en poids, rapportée au poids du substrat non traité.
  19. Dispersion aqueuse comprenant de l'eau, une quantité d'une composition selon la revendication 1, efficace pour procurer des propriétés repoussantes à un substrat traité avec cette dernière, et un émulsifiant dans une proportion efficace pour stabiliser la dispersion.
  20. Dispersion aqueuse selon la revendication 19, dans laquelle l'eau est présente dans une proportion d'environ 70 à environ 900 parties en poids, pour 100 parties en poids de la composition, et l'émulsifiant est présent dans une proportion d'environ 1 à environ 25 parties en poids, pour 100 parties en poids de la composition.
  21. Dispersion aqueuse selon la revendication 19, dans laquelle l'eau est présente dans une proportion d'environ 70 à environ 900 parties en poids, pour 100 parties en poids de la composition, et l'émulsifiant est présent dans une proportion d'environ 5 à environ 10 parties en poids, pour 100 parties en poids de la composition.
  22. Procédé pour conférer des propriétés oléofuges et hydrofuges à une matière de substrat fibreuse, comprenant les étapes consistant à:
    (1) appliquer sur la surface de la matière de substrat fibreuse une quantité d'une composition selon la revendication 1, efficace pour procurer des propriétés oléofuges et hydrofuges au substrat; et
    (2) chauffer le substrat traité de l'étape (1) à une température et pendant une durée suffisantes pour durcir le substrat traité.
  23. Procédé pour améliorer l'efficacité en fluor d'un agent chimique fluoré, comprenant l'étape consistant à formuler l'agent chimique fluoré avec;
    (a) un diluant copolymère comprenant:
    (i) des motifs polymérisés dérivés d'un monomère de formule:

            CR1R2=CR3R4

    dans laquelle chacun des radicaux R1, R2, R3 et R4 représente indépendamment un atome d'hydrogène, un atome d'halogène, ou un groupe organique; et
    (ii) des motifs polymérisés dérivés d'un monomère de formule:

            CH2=CR5X

    dans laquelle R5 représente un atome d'hydrogène ou un groupe méthyle, et X représente un groupement comprenant un groupe fonctionnel pouvant interagir avec un substrat fibreux; et
    (C) un diluant isocyanate bloqué.
EP92909526A 1991-04-02 1992-01-24 Compositions hydrophobes et oleophobes utilisant efficacement le fluor Expired - Lifetime EP0646196B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US67955891A 1991-04-02 1991-04-02
US679558 1991-04-02
PCT/US1992/000592 WO1992017636A1 (fr) 1991-04-02 1992-01-24 Compositions hydrophobes et oleophobes utilisant efficacement le fluor

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EP0646196A1 EP0646196A1 (fr) 1995-04-05
EP0646196B1 true EP0646196B1 (fr) 1996-07-24

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JP (1) JP3294266B2 (fr)
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BR (1) BR9205831A (fr)
CA (1) CA2105276A1 (fr)
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WO (1) WO1992017636A1 (fr)

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JP3629753B2 (ja) * 1994-05-16 2005-03-16 旭硝子株式会社 水分散型防汚加工剤
US5466770A (en) * 1994-05-26 1995-11-14 Minnesota Mining And Manufacturing Company Fluorine-efficient oil- and water-repellent compositions
US5948480A (en) * 1997-03-31 1999-09-07 E.I. Du Pont De Nemours And Company Tandem application of soil and stain resists to carpeting
JPH11279527A (ja) * 1997-06-30 1999-10-12 Asahi Glass Co Ltd 防汚加工剤組成物、その製造方法およびそれを用いた被処理物
CA2243772C (fr) 1997-07-23 2008-04-15 Asahi Glass Company Ltd. Composition hydrofuge et oleofuge
CA2324949A1 (fr) * 1998-03-24 1999-09-30 Avantgarb, Llc Tissu et autres matieres modifiees, procedes d'obtention
US6380336B1 (en) 1998-03-24 2002-04-30 Nano-Tex, Llc Copolymers and oil-and water-repellent compositions containing them
JP2000136377A (ja) * 1998-08-24 2000-05-16 Asahi Glass Co Ltd 水分散型撥水撥油剤組成物
DE60135797D1 (de) * 2000-03-31 2008-10-30 Dainichiseika Color Chem Kunstleder
US6479605B1 (en) 2001-05-15 2002-11-12 E. I. Du Pont De Nemours And Company High-durability, low-yellowing repellent for textiles
EP1483441B1 (fr) * 2001-12-19 2006-11-15 3M Innovative Properties Company Composition aqueuse permettant de rendre impermeables des substrats fibreux
KR20050014834A (ko) * 2002-05-24 2005-02-07 쓰리엠 이노베이티브 프로퍼티즈 컴파니 퍼플루오로폴리에테르 및 연장제를 포함하는 섬유 기질처리용 플루오로화합물 조성물
MXPA04011448A (es) 2002-05-24 2005-03-23 3M Innovative Properties Co Composicion fluoroquimica para el tratamiento de un substrato fibroso.
US7425279B2 (en) 2002-05-24 2008-09-16 3M Innovative Properties Company Fluorochemical composition for treatment of a fibrous substrate
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US7344758B2 (en) 2004-09-07 2008-03-18 E.I. Du Pont De Nemours And Company Hydrocarbon extenders for surface effect compositions
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CA2105276A1 (fr) 1992-10-03
EP0646196A1 (fr) 1995-04-05
BR9205831A (pt) 1994-08-02
DE69212505T2 (de) 1997-02-27
WO1992017636A1 (fr) 1992-10-15
JPH06506966A (ja) 1994-08-04
JP3294266B2 (ja) 2002-06-24
KR100214319B1 (ko) 1999-08-02

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