EP0646196A1 - Compositions hydrophobes et oleophobes utilisant efficacement le fluor. - Google Patents
Compositions hydrophobes et oleophobes utilisant efficacement le fluor.Info
- Publication number
- EP0646196A1 EP0646196A1 EP92909526A EP92909526A EP0646196A1 EP 0646196 A1 EP0646196 A1 EP 0646196A1 EP 92909526 A EP92909526 A EP 92909526A EP 92909526 A EP92909526 A EP 92909526A EP 0646196 A1 EP0646196 A1 EP 0646196A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- extender
- substrate
- composition according
- amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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.
- CR ⁇ R 2 CR 2 COOR4 wherein R-,, R 2 and R 3 represents hydrogen atoms or methyl groups, and R 4 represents a C 8 alkyl group; and monomer units having the formula:
- This invention provides fluorine-efficient oil- and water-repellent compositions comprising:
- CR,R 2 CR 3 R 4 (V) wherein each of R l f R 2 , R 3 and . ⁇ independently represents hydrogen, halogen, or an organic group such as alkyl, carboxyl, or acyloxyalkyl (i.e., -C0 2 alkyl) ; and
- R 5 represents a hydrogen atom or a methyl group
- X represents a moiety comprising a functional group that can interact with a fibrous substrate
- 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 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 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 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 ethacrylic acid, 2-hydroxyethyl acrylate
- 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
- Rj, R 2 , R 3 , and R 4 independently represents hydrogen, halogen, or an organic group; and (ii) polymerized units derived from a monomer of Formula VII:
- CH 2 CR 5 X (VII) wherein R 5 is hydrogen or methyl and X is a moiety comprising a functional group that can interact with a fibrous substrate.
- 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-l,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, oi- ethylstyrene, ⁇ -cyanomethylstyrene, divinylbenene, N-vinylcarbazole; vinyl esters such as vinyl acetate, vinyl
- a particularly preferred class of monomers of Formula V is acrylate monomers of Formula IX
- R ⁇ , R 7 , and R 8 independently represent a hydrogen atom or a methyl group, and Rg represents a C 8 alkyl group.
- R ⁇ , R 7 , and R 8 independently represent a hydrogen atom or a methyl group
- Rg represents a C 8 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 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
- AMPS 2-acrylamido-2-methylpropanesulfonic acid
- vinyl azlactones vinyl azlactones
- glycidyl acrylate and methacrylate vinyl azlactones
- allyl glycidyl ether vinyl azlactones
- acrolein 2-acrylamido-2-methylpropanesulfonic acid
- N,N-dimethylaminoethyl acrylate and methacrylate N-tert-butylaminoethyl methacrylate; allyl methacrylate; diallyl maleate; vinyltriethoxysilane; vinyltrichlorosilane; and the like.
- Preferred functionalized monomers of Formula VII include those of Formula XI:
- R 5 represents a hydrogen atom or a methyl group. Copolymers comprising such monomers are described in U.S.
- Component (C) in a composition of this invention is a blocked isocyanate. Suitable isocyanates for use
- 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'-diisoc ' yanatodibenzyl, 3,3,-dimethoxy-4,4,-diisocyanatodiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenyl, 2,2,-dichloro-5,5,-dimethoxy-4,4'-diisocyanatodipheny
- 2,2,4-trimethyl-l,6-hexamethylenediisocyanate, and 1,2-ethylenediisocyanate 2,2,4-trimethyl-l,6-hexamethylenediisocyanate, and 1,2-ethylenediisocyanate; aliphatic triisocyanates such as 1,3,6-hexamethylenetriisocyanate; aromatic polyiisocyanates such as polymethylenepolyphenylisocyanate (PAPI) ; and cyclic diisocyanates such as isophorone diisocyanate (IPDI) .
- PAPI polymethylenepolyphenylisocyanate
- IPDI 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-l,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-l,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,
- 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) acetone oxime, butanone oxime
- arylthiols e.g., thiophenol
- organic active hydrogen compounds e.g.; diethyl malonate, acetylacetone, ethyl acetoacetate, ethyl cyanoacetate, e-caprolactam
- sodium bisulfite and hydroxylamine.
- Particularly preferred blocked isocyanates include those blocked with C 2 to C 8 alkanone oxi es, 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.
- the 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 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, 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 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 diethylenetria ine) and their epichlorohydrin adduct ⁇ .
- salts of inorganic or organic acids such as aluminum stearate, zirconium acetate, zirconium oxychloride or Werner complexes such as chromium stearatochloride. If it is desired to improve the softness or
- 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.
- Oil Repellency Test The 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) . Launderinq Procedure
- MARLOWETTM 5401 cationic emulsifier (5.7 g, 10 percent by weight based on total solids, Hiils, 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.
- 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.
- VAZOTM 52 initiator (2,2'-azobis-(2,4-dimethylvaleronitrile) , 5 g, Du Pont)] in 10 g of dichloro ethane was added over a period of 4 hours. The reation was continued for 4 hours at 70°C. A hazy, slightly yellow reaction mixture was formed. Dry ethyl acetate (100 g) and trimethylhexa ethylenediisocyanate (22 g, 0.1 mol, TMDI, Bayer) were added and the reaction mixture was heated to 80°C. Dibutyltin dilaureate catalyst (0.2 g) was added. The reaction was continued for 8 hours at 95°C.
- N-Methylperfluorooctylsulfona idoethyl 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-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-OLTM 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.
- Intermediate M FC-214 a composition containing a blend of a fluorochemical urethane and a fluorochemical copolymer, and commercially available from 3M Company.
- 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
- 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.
Landscapes
- 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)
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 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0646196A1 true EP0646196A1 (fr) | 1995-04-05 |
EP0646196B1 EP0646196B1 (fr) | 1996-07-24 |
Family
ID=24727404
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92909526A Expired - Lifetime EP0646196B1 (fr) | 1991-04-02 | 1992-01-24 | Compositions hydrophobes et oleophobes utilisant efficacement le fluor |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0646196B1 (fr) |
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 (2)
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 |
US6479605B1 (en) | 2001-05-15 | 2002-11-12 | E. I. Du Pont De Nemours And Company | High-durability, low-yellowing repellent for textiles |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69330790T2 (de) * | 1993-10-19 | 2002-05-23 | Minnesota Mining And Mfg. Co., Saint Paul | Hochleistungszusammensetzungen mit wasser- und ölabweisenden Eigenschaften |
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 |
EP1143063B1 (fr) * | 2000-03-31 | 2008-09-17 | Dainichiseika Color & Chemicals Mfg. Co. Ltd. | Cuir synthétique |
KR20040093670A (ko) * | 2001-12-19 | 2004-11-06 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 섬유성 재질을 발수성으로 만드는 수성조성물 |
BR0311207A (pt) | 2002-05-24 | 2005-03-15 | 3M Innovative Properies Compan | Composição fluoroquìmica, composição de revestimento, método de tratamento de um substrato fibroso, e , artigo |
CN100540586C (zh) | 2002-05-24 | 2009-09-16 | 3M创新有限公司 | 含有氟化聚合物的含氟化合物组合物和利用其处理纤维底物 |
EP1507918A1 (fr) * | 2002-05-24 | 2005-02-23 | 3M Innovative Properties Company | Composition fluorochimique contenant un perfluoropolyether et une charge et servant au traitement de substrats fibreux |
US7425279B2 (en) | 2002-05-24 | 2008-09-16 | 3M Innovative Properties Company | Fluorochemical composition for treatment of a fibrous substrate |
EP1496073A1 (fr) | 2003-07-08 | 2005-01-12 | Ciba Spezialitätenchemie Pfersee GmbH | Extenseurs pour le traitement de matériaux fibreux |
US7344758B2 (en) | 2004-09-07 | 2008-03-18 | E.I. Du Pont De Nemours And Company | Hydrocarbon extenders for surface effect compositions |
CN100506927C (zh) | 2005-03-21 | 2009-07-01 | 刘景春 | 多质离散效应纳米结构液膜及其制备方法和应用 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3736177A (en) * | 1971-05-12 | 1973-05-29 | Us Army | Water and oil-resistant,antistatic and abrasion-resistant finish for nylon fabrics |
US3949124A (en) * | 1974-07-12 | 1976-04-06 | Hca-Martin, Inc. | Method for treating textile materials and textile materials treated in such a way, and textile treating compositions |
US4388372A (en) * | 1980-05-13 | 1983-06-14 | E. I. Du Pont De Nemours And Company | Durable antisoiling coatings for textile filaments |
DE3737753A1 (de) * | 1987-11-06 | 1989-06-15 | Pfersee Chem Fab | Waessriges ausruestungsmittel und verfahren zur weichen hydrophob/oleophob-behandlung von fasermaterialien |
DE3939341A1 (de) * | 1989-11-29 | 1991-06-06 | Bayer Ag | Hydrophobierungs- und oleophobierungsmittel |
-
1992
- 1992-01-24 BR BR9205831A patent/BR9205831A/pt not_active Application Discontinuation
- 1992-01-24 CA CA 2105276 patent/CA2105276A1/fr not_active Abandoned
- 1992-01-24 JP JP50874192A patent/JP3294266B2/ja not_active Expired - Fee Related
- 1992-01-24 DE DE69212505T patent/DE69212505T2/de not_active Expired - Fee Related
- 1992-01-24 WO PCT/US1992/000592 patent/WO1992017636A1/fr active IP Right Grant
- 1992-01-24 KR KR1019930702857A patent/KR100214319B1/ko not_active IP Right Cessation
- 1992-01-24 EP EP92909526A patent/EP0646196B1/fr not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
See references of WO9217636A1 * |
Cited By (2)
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 |
US6479605B1 (en) | 2001-05-15 | 2002-11-12 | E. I. Du Pont De Nemours And Company | High-durability, low-yellowing repellent for textiles |
Also Published As
Publication number | Publication date |
---|---|
KR100214319B1 (ko) | 1999-08-02 |
EP0646196B1 (fr) | 1996-07-24 |
JP3294266B2 (ja) | 2002-06-24 |
JPH06506966A (ja) | 1994-08-04 |
DE69212505T2 (de) | 1997-02-27 |
BR9205831A (pt) | 1994-08-02 |
DE69212505D1 (de) | 1996-08-29 |
CA2105276A1 (fr) | 1992-10-03 |
WO1992017636A1 (fr) | 1992-10-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0646196B1 (fr) | Compositions hydrophobes et oleophobes utilisant efficacement le fluor | |
JP3242920B2 (ja) | フルオロケミカル表面改質剤、フッ素化化合物、及び水性分散液の安定化方法 | |
US6309752B1 (en) | Substrate having high initial water repellency and a laundry durable water repellency | |
EP0573526B1 (fr) | Composition de traitement hydrofuge et oleoresistant | |
US5019428A (en) | Modified polyurethanes containing perfluoroaliphatic groups and use thereof | |
JP4009749B2 (ja) | 優れた洗濯空気乾燥性能を提供するフルオロケミカルポリウレタン | |
EP0763155B1 (fr) | Compositions oleofuges et hydrofuges contenant du fluor | |
JP4955565B2 (ja) | カルボジイミド化合物および基材撥油・撥水性付与組成物 | |
CA2243772C (fr) | Composition hydrofuge et oleofuge | |
EP0981560B1 (fr) | Composition fluoree comprenant un polyurethanne presentant un oligomere fluore et un segment hydrophile afin de doter un substrat d'une aptitude au detachage | |
JPH11279527A (ja) | 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 | |
EP0981563B1 (fr) | Composition fluoree contenant un produit de condensation d'un polyether fluore et d'un poly-isocyanate pour doter un substrat d'une aptitude au detachage | |
CN111417753A (zh) | 组合物、处理方法和经处理的纤维基底 | |
JP3276958B2 (ja) | フルオロカーバメート防汚剤 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19931028 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE CH DE FR GB IT LI NL |
|
17Q | First examination report despatched |
Effective date: 19950419 |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
ITF | It: translation for a ep patent filed |
Owner name: BARZANO' E ZANARDO ROMA S.P.A. |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE CH DE FR GB IT LI NL |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: E. BLUM & CO. PATENTANWAELTE |
|
REF | Corresponds to: |
Ref document number: 69212505 Country of ref document: DE Date of ref document: 19960829 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PFA Owner name: MINNESOTA MINING AND MANUFACTURING COMPANY Free format text: MINNESOTA MINING AND MANUFACTURING COMPANY#3M CENTER, P.O. BOX 33427#ST. PAUL, MINNESOTA 55133-3427 (US) -TRANSFER TO- MINNESOTA MINING AND MANUFACTURING COMPANY#3M CENTER, P.O. BOX 33427#ST. PAUL, MINNESOTA 55133-3427 (US) |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20080130 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20080129 Year of fee payment: 17 Ref country code: NL Payment date: 20080124 Year of fee payment: 17 Ref country code: IT Payment date: 20080130 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20080117 Year of fee payment: 17 Ref country code: DE Payment date: 20080229 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20080206 Year of fee payment: 17 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20090124 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20090801 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090131 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090801 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090131 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20091030 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090801 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090124 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090202 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090124 |