WO1992017636A1 - Compositions hydrophobes et oleophobes utilisant efficacement le fluor - Google Patents

Compositions hydrophobes et oleophobes utilisant efficacement le fluor Download PDF

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Publication number
WO1992017636A1
WO1992017636A1 PCT/US1992/000592 US9200592W WO9217636A1 WO 1992017636 A1 WO1992017636 A1 WO 1992017636A1 US 9200592 W US9200592 W US 9200592W WO 9217636 A1 WO9217636 A1 WO 9217636A1
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Prior art keywords
weight
extender
substrate
composition according
amount
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PCT/US1992/000592
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English (en)
Inventor
Rudolf J. Dams
Johan E. De Witte
Christoffel C. Maes
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Minnesota Mining And Manufacturing Company
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Application filed by Minnesota Mining And Manufacturing Company filed Critical Minnesota Mining And Manufacturing Company
Priority to JP50874192A priority Critical patent/JP3294266B2/ja
Priority to KR1019930702857A priority patent/KR100214319B1/ko
Priority to BR9205831A priority patent/BR9205831A/pt
Priority to DE69212505T priority patent/DE69212505T2/de
Priority to EP92909526A priority patent/EP0646196B1/fr
Publication of WO1992017636A1 publication Critical patent/WO1992017636A1/fr

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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. Description of the Related Art
  • R 1 , R 2 and R 3 represents hydrogen atoms or methyl groups, and R 4 represents a C 1-18 alkyl group; and monomer units having the formula:
  • R 5 represents a hydrogen atom or a methyl group.
  • This invention provides fluorine-efficient oil- and water-repellent compositions comprising:
  • CH 2 CR 5 X (VII) wherein R 5 represents a hydrogen atom or a methyl group, and X represents a moiety comprising a functional group that can interact with a fibrous substrate; and
  • 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
  • Component (A) in a composition of the invention is a fluorochemical oil- and water-repellent agent
  • R f R f ) groups.
  • agents 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
  • 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.,
  • 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 aerylate 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-methylolacrylamide,
  • 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.),
  • Component (B) in a composition of the invention is a copolymer extender comprising
  • CR 1 R 2 CR 3 R 4 (V) wherein each of R 1 , R 2 , R 3 , and R 4 independently represents hydrogen, halogen, or an organic group;
  • Examples of monomers of Formula V include general classes of ethylenic compounds capable of
  • 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
  • vinyl esters such as vinyl acetate, vinyl propionate, vinyl isobutyrate, vinyl succinate, vinyl stearate,
  • divinylcarbonate allyl esters such as allyl acetate and allyl heptanoate
  • alkylvinyl or alkylallyl ethers such as cetyl vinyl ether, dodecyl vinyl ether, isobutyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, tetrallyloxyethane
  • vinyl alkyl ketones such as vinyl methyl ketone
  • unsaturated acids such as acrylic, ⁇ -chloro acrylic, ⁇ -fluoro acrylic, crotonic, maleic, fumaric, itaconic, and citraconic acids, and anhydrides and esters thereof such as dimethyl maleate, ethyl crotonate, acid methyl maleate, acid butyl itaconate, and vinyl, allyl, methyl, ethyl, butyl, isobutyl, hexyl, 2-ethylhexyl, chlorohe
  • trimethoxysilane trimethoxysilane
  • nitriles such as acrylonitrile
  • dimethacrylate isobornyl acrylate and methacrylate, trimethylopropane triacrylate, allyl methacrylate; acrylamides and methacrylamides; mono or di (meth) acrylates of glycols or polyalkylene glycols such as ethylene glycol dimethacrylate, triethylene glycol acrylate, mono, di, and polyacrylates and methacrylates of methoxypolyethylene glycols and polyethylene glycols of various molecular weights (available as CARBOWAXTM), block copolymers of ethylene oxide and propylene oxide endcapped by hydroxy groups (available as PLURONICTM), tetramethyleneoxide glycols (available as TERATHANETM), amino or diamino-terminated polyethers (available as JEFFAMINETM); mono, di, and polyacrylates and methacrylates of siloxane mono-, di-, or polyols such as 1,3-bis(4-hydroxybutyl)tetra
  • siloxane diol (Wacker - Germany); Q4-3667 siloxane diol (Dow Corning); Q4-3557 siloxane diol (Dow Corning);
  • acrylamides and methacrylamides of siloxane mono, di, or polyamines such as 1,3-bis(y-aminopropyl) tetramethyl disiloxane (Petrarch Systems); DC-531 siloxane polyamine (Dow Corning); DC-536 siloxane polyamine (Dow Corning); and others described in U.S. Pat. No. 4,728,571 (Clemens et al.), the disclosure of which is incorporated herein by reference.
  • a particularly preferred class of monomers of Formula V is acrylate monomers of Formula IX
  • CR 6 R 7 CR 8 COOR 9 (IX) wherein R 6 , R 7 , and R 8 independently represent a hydrogen atom or a methyl group, and R 9 represents a C 1-18 alkyl group.
  • 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
  • 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 composition of the invention.
  • Representative groups suitable for interacting with a substrate include
  • hydrosilation reaction epoxy, amino, hydroxy, halo, haloformyl, aziridino, acid groups such as carboxy, sulfo, sulfino, sulfeno, dihydroxyphosphinyl, and
  • 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 and styrene p-sulfonic acids and their metal salts; monoallylamine;
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • vinyl azlactones vinyl azlactones
  • glycidyl acrylate 2-acrylamido-2-methylpropanesulfonic acid
  • N,N-dimethylaminoethyl acrylate and methacrylate N-tert-butylaminoethyl methacrylate; allyl methacrylate; diallyl maleate; vinyltriethoxysilane;
  • Preferred functionalized monomers of Formula VII include those of Formula XI:
  • Component (C) in a composition of this invention is a blocked isocyanate. Suitable isocyanates for use
  • aromatic diisocyanates such as 4,4'-methylenediphenylenediisocyanate
  • aliphatic diisocyanates such as methylenediisocyanate, 1,6-hexamethylenediisocyanate,
  • 1,2-ethylenediisocyanate 1,2-ethylenediisocyanate
  • aliphatic triisocyanates such as 1,3,6-hexamethylenetriisocyanate
  • aromatic polyiisocyanates such as polymethylenepolyphenylisocyanate (PAPI)
  • PAPI polymethylenepolyphenylisocyanate
  • cyclic diisocyanates such as isophorone diisocyanate
  • 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.
  • Suitable low molecular weight polyols include trimethylolpropane, 1,3,5-hexanetriol, glycerol, pentaerythritol, propylene glycol, hexylene glycol and diethylene glycol.
  • other low molecular weight polyhydroxy compounds such as triethanolamine.
  • These low molecular weight polyurethanes can be prepared by reacting a polyol with an excess of
  • 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
  • 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
  • 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
  • Each extender is preferably present in an amount such that the improvement in fluorine
  • 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 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.
  • 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 composition of the invention When a composition of the invention is applied as a treatment to a fibrous substrate, e.g., a fabric intended for use in a garment, it is preferred that a treated substrate comprise 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 in an amount of abut 0.1% to about 0.6% by weight based on the weight of the untreated substrate. Further, it is
  • 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
  • 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.
  • auxilliary extenders can be used, either alone or in combination with each other. Suitable
  • auxilliary extenders include paraffin; compositions
  • alkylketenes or derivatives thereof 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
  • auxilliary products such as polyglycols, colloids such as starch, dextrin, casein, sizing agents, fixing or retaining agents,
  • 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 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
  • 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
  • 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
  • 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
  • methyldiethanolamine (6 g, 0.05 mol) were added. The reaction was continued at 90°C for 4 hours. A clear, brown solution was obtained. To 200 g of the solution, 101 g butyl acetate, 3.5 g acetic acid and 87 g ethylene glycol were added. The resulting organic solution was warmed to 75°C.
  • 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
  • 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
  • a polymethylhydrogensiloxane 12 g, 0.2 equivalents
  • BAYSILONE- ⁇ LTM MH15 silicone Bayer
  • 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.
  • MeFOSEA octadecyl methacrylate
  • polydimethylsiloxane monomethacrylate molecular weight of about 2000
  • 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) were mixed and heated at 90°C.
  • 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. After cooling to about 80°C, hexafluoroxylene solvent was added to make a 40% solids solution (in total, 348 g hexafluoroxylene was used).
  • a dispersion was
  • 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
  • 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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (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.
PCT/US1992/000592 1991-04-02 1992-01-24 Compositions hydrophobes et oleophobes utilisant efficacement le fluor WO1992017636A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP50874192A JP3294266B2 (ja) 1991-04-02 1992-01-24 フッ素効果の油−及び水−反発性組成物
KR1019930702857A KR100214319B1 (ko) 1991-04-02 1992-01-24 불소-효율이 우수한 발유 및 발수 조성물
BR9205831A BR9205831A (pt) 1991-04-02 1992-01-24 Composição flúor-eficiente repelente ao óleo e à água, substrato com propriedade repelentes ao óleo e à água, disperso aquosa, processo para proporcionar a um material subtrato fibroso propriedades de repelência ao óleo e à água, e, processo para melhorar a flúor-eficiência de um agente fluoroquimico
DE69212505T DE69212505T2 (de) 1991-04-02 1992-01-24 Fluorhaltige Oel- und Wasserabweisende Zusammensetzungen
EP92909526A EP0646196B1 (fr) 1991-04-02 1992-01-24 Compositions hydrophobes et oleophobes utilisant efficacement le fluor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US67955891A 1991-04-02 1991-04-02
US679,558 1991-04-02

Publications (1)

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JP (1) JP3294266B2 (fr)
KR (1) KR100214319B1 (fr)
BR (1) BR9205831A (fr)
CA (1) CA2105276A1 (fr)
DE (1) DE69212505T2 (fr)
WO (1) WO1992017636A1 (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
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EP0648887A1 (fr) * 1993-10-19 1995-04-19 Minnesota Mining And Manufacturing Company Compositions oléophobes et hydrophobes hautement perfomantes
US5466770A (en) * 1994-05-26 1995-11-14 Minnesota Mining And Manufacturing Company Fluorine-efficient oil- and water-repellent compositions
EP0889157A1 (fr) * 1997-06-30 1999-01-07 Asahi Glass Company Ltd. Composition antisalissure, procédé pour sa préparation et produit avec cette composition
EP0898011A1 (fr) * 1997-07-23 1999-02-24 Asahi Glass Company Ltd. Composition oléofuge et hydrofuge
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
WO1999049124A2 (fr) * 1998-03-24 1999-09-30 Avantgarb, Llc Tissus et autres matieres modifiees, procedes d'obtention
EP0987362A1 (fr) * 1998-08-24 2000-03-22 Asahi Glass Company Ltd. Composition oléofuge et hydrofuge en dispersion aqueuse
US6309752B1 (en) 1991-04-02 2001-10-30 3M Innovative Properties Company Substrate having high initial water repellency and a laundry durable water repellency
US6380336B1 (en) 1998-03-24 2002-04-30 Nano-Tex, Llc Copolymers and oil-and water-repellent compositions containing them
EP0692566B1 (fr) * 1994-05-16 2002-11-13 Asahi Glass Company Ltd. Dispersion aqueuse répulsive aux taches et procédé pour sa production
WO2003100159A1 (fr) * 2002-05-24 2003-12-04 3M Innovative Properties Company Composition fluorochimique contenant un perfluoropolyether et une charge et servant au traitement de substrats fibreux
WO2004059073A1 (fr) * 2001-12-19 2004-07-15 3M Innovative Properties Company Composition aqueuse permettant de rendre impermeables des substrats fibreux
US7094829B2 (en) 2002-05-24 2006-08-22 3M Innovative Properties Company Fluorochemical composition comprising a fluorinated polymer and treatment of a fibrous substrate therewith
US7214736B2 (en) 2002-05-24 2007-05-08 3M Innovative Properties Company Fluorochemical composition for treatment of a fibrous substrate
US7344758B2 (en) 2004-09-07 2008-03-18 E.I. Du Pont De Nemours And Company Hydrocarbon extenders for surface effect compositions
US7425279B2 (en) 2002-05-24 2008-09-16 3M Innovative Properties Company Fluorochemical composition for treatment of a fibrous substrate
US7772290B2 (en) 2005-03-21 2010-08-10 Ho Cheong Poon Method to prepare a nanosized-structure film of multi-phobic effects and its application

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EP1143063B1 (fr) * 2000-03-31 2008-09-17 Dainichiseika Color & Chemicals Mfg. Co. Ltd. Cuir synthétique
US6479605B1 (en) 2001-05-15 2002-11-12 E. I. Du Pont De Nemours And Company High-durability, low-yellowing repellent for textiles
EP1496073A1 (fr) 2003-07-08 2005-01-12 Ciba Spezialitätenchemie Pfersee GmbH Extenseurs pour le traitement de matériaux fibreux

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US4388372A (en) * 1980-05-13 1983-06-14 E. I. Du Pont De Nemours And Company Durable antisoiling coatings for textile filaments
EP0314944A2 (fr) * 1987-11-06 1989-05-10 Minnesota Mining And Manufacturing Company Composition de finissage et procédé de traitement de matériaux fibreux
EP0429983A2 (fr) * 1989-11-29 1991-06-05 Bayer Ag Composition hydro- et oléophobante

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FR2277927A1 (fr) * 1974-07-12 1976-02-06 Martin Inc H C A Traitement de matieres textiles, notamment traitement antistatique
US4388372A (en) * 1980-05-13 1983-06-14 E. I. Du Pont De Nemours And Company Durable antisoiling coatings for textile filaments
EP0314944A2 (fr) * 1987-11-06 1989-05-10 Minnesota Mining And Manufacturing Company Composition de finissage et procédé de traitement de matériaux fibreux
EP0429983A2 (fr) * 1989-11-29 1991-06-05 Bayer Ag Composition hydro- et oléophobante

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6309752B1 (en) 1991-04-02 2001-10-30 3M Innovative Properties Company Substrate having high initial water repellency and a laundry durable water repellency
EP0648887A1 (fr) * 1993-10-19 1995-04-19 Minnesota Mining And Manufacturing Company Compositions oléophobes et hydrophobes hautement perfomantes
US5516578A (en) * 1993-10-19 1996-05-14 Minnesota Mining And Manufacturing Company Oil and water repellent compositions
EP0692566B1 (fr) * 1994-05-16 2002-11-13 Asahi Glass Company Ltd. Dispersion aqueuse répulsive aux taches et procédé pour sa production
US5466770A (en) * 1994-05-26 1995-11-14 Minnesota Mining And Manufacturing Company Fluorine-efficient oil- and water-repellent compositions
WO1995033093A1 (fr) * 1994-05-26 1995-12-07 Minnesota Mining And Manufacturing Company Compositions oleofuges et hydrofuges contenant du fluor
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
US6207777B1 (en) 1997-06-30 2001-03-27 Asahi Glass Company Ltd. Antifouling composition, method for its production and product treated therewith
EP0889157A1 (fr) * 1997-06-30 1999-01-07 Asahi Glass Company Ltd. Composition antisalissure, procédé pour sa préparation et produit avec cette composition
EP0898011A1 (fr) * 1997-07-23 1999-02-24 Asahi Glass Company Ltd. Composition oléofuge et hydrofuge
US6177531B1 (en) 1997-07-23 2001-01-23 Asahi Glass Company Ltd. Water and oil repellent compositon
US6379753B1 (en) 1998-03-24 2002-04-30 Nano-Tex, Llc Modified textile and other materials and methods for their preparation
US6617267B2 (en) 1998-03-24 2003-09-09 Nano-Tex, Llc Modified textile and other materials and methods for their preparation
WO1999049124A3 (fr) * 1998-03-24 1999-12-09 Avantgarb Llc Tissus 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
WO1999049124A2 (fr) * 1998-03-24 1999-09-30 Avantgarb, Llc Tissus et autres matieres modifiees, procedes d'obtention
US6376592B1 (en) 1998-08-24 2002-04-23 Asahi Glass Company, Ltd. Water dispersion type water and oil repellent composition
EP0987362A1 (fr) * 1998-08-24 2000-03-22 Asahi Glass Company Ltd. Composition oléofuge et hydrofuge en dispersion aqueuse
US6472476B1 (en) 2000-01-18 2002-10-29 Nano-Tex, Llc Oil- and water-repellent finishes for textiles
WO2004059073A1 (fr) * 2001-12-19 2004-07-15 3M Innovative Properties Company Composition aqueuse permettant de rendre impermeables des substrats fibreux
WO2003100159A1 (fr) * 2002-05-24 2003-12-04 3M Innovative Properties Company Composition fluorochimique contenant un perfluoropolyether et une charge et servant au traitement de substrats fibreux
US7094829B2 (en) 2002-05-24 2006-08-22 3M Innovative Properties Company Fluorochemical composition comprising a fluorinated polymer and treatment of a fibrous substrate therewith
US7214736B2 (en) 2002-05-24 2007-05-08 3M Innovative Properties Company Fluorochemical composition for treatment of a fibrous substrate
US7425279B2 (en) 2002-05-24 2008-09-16 3M Innovative Properties Company Fluorochemical composition for treatment of a fibrous substrate
US7344758B2 (en) 2004-09-07 2008-03-18 E.I. Du Pont De Nemours And Company Hydrocarbon extenders for surface effect compositions
US7772290B2 (en) 2005-03-21 2010-08-10 Ho Cheong Poon Method to prepare a nanosized-structure film of multi-phobic effects and its application

Also Published As

Publication number Publication date
DE69212505T2 (de) 1997-02-27
KR100214319B1 (ko) 1999-08-02
JP3294266B2 (ja) 2002-06-24
DE69212505D1 (de) 1996-08-29
EP0646196A1 (fr) 1995-04-05
JPH06506966A (ja) 1994-08-04
BR9205831A (pt) 1994-08-02
CA2105276A1 (fr) 1992-10-03
EP0646196B1 (fr) 1996-07-24

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