WO2008041750A1 - Polymère fluoré, son procédé de production et composition hydrofuge et oléofuge - Google Patents

Polymère fluoré, son procédé de production et composition hydrofuge et oléofuge Download PDF

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WO2008041750A1
WO2008041750A1 PCT/JP2007/069488 JP2007069488W WO2008041750A1 WO 2008041750 A1 WO2008041750 A1 WO 2008041750A1 JP 2007069488 W JP2007069488 W JP 2007069488W WO 2008041750 A1 WO2008041750 A1 WO 2008041750A1
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monomer
fluorine
atom
water
mol
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PCT/JP2007/069488
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English (en)
Japanese (ja)
Inventor
Nobuyuki Otozawa
Fumiko Nakayama
Toyomichi Shimada
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Asahi Glass Company, Limited
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Publication of WO2008041750A1 publication Critical patent/WO2008041750A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/10—Homopolymers or copolymers of unsaturated ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/125—Monomers containing two or more unsaturated aliphatic radicals, e.g. trimethylolpropane triallyl ether or pentaerythritol triallyl ether
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1408—Monomers containing halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
    • C09D123/28—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C09D123/283—Halogenated homo- or copolymers of iso-olefines

Definitions

  • Fluoropolymer, production method thereof, and water / oil repellent composition Fluoropolymer, production method thereof, and water / oil repellent composition
  • the present invention relates to a fluoropolymer, a method for producing the same, a water / oil repellent composition containing the fluoropolymer, and a product having a water / oil repellent film comprising the water / oil repellent composition.
  • water and oil repellency is imparted by coating a water and oil repellent agent on a necessary part of the component surface to form a water and oil repellent film.
  • the water / oil repellent film include a display antifouling film, a clothing waterproof film, an ink jet nozzle ink repellent film, a wood waterproof film, a water repellent filter for a precision machine such as a mobile phone and an information terminal.
  • a fluorine-containing compound As the main component of the water / oil repellent, a fluorine-containing compound is often used. This is because the fluorine atom has a low intermolecular cohesive energy and therefore a relatively low surface energy in the coating film of the fluorine-containing compound.
  • a fluorine-containing polymer using a (meth) acrylate containing a perfluoroalkyl group as a monomer is known (see Patent Document 1 below).
  • Patent Document 2 does not relate to a water / oil repellent film, but discloses a fluorine-containing polymer having a cyclic structure in the main chain.
  • Patent Documents 3 and 4 below do not relate to a water / oil repellent film, but describe a copolymer of perfluoroallyl butyl ether and perfluoropropyl butyl ether.
  • Patent Document 1 Japanese Patent Laid-Open No. 06-248256
  • Patent Document 2 JP-A 63-260932
  • Patent Document 3 Japanese Patent No. 2526641
  • Patent Document 4 Japanese Patent No. 2581182
  • the film made of the fluoropolymer described in Patent Document 1 has good water and oil repellency, it has insufficient hardness and heat resistance.
  • the film made of a fluoropolymer described in Patent Document 2 has good hardness and heat resistance, it does not have sufficient water and oil repellency, as it was not developed as a water and oil repellent.
  • the present invention has been made in view of the above circumstances, and includes a fluoropolymer capable of forming a water / oil repellent film having excellent water / oil repellency and excellent hardness and heat resistance, and its production. It aims to provide a method. Another object of the present invention is to provide a water / oil repellent composition containing the fluoropolymer and an article having a water / oil repellent film comprising the water / oil repellent composition.
  • the fluoropolymer of the present invention comprises 30 to 90 mol% of the structural unit (I) derived from the monomer (a) and the monomer (b). Induced structural unit and monomer (c) force One or more structural units (II) selected from the group consisting of induced structural units (II)
  • the method for producing a fluoropolymer of the present invention comprises 30 to 90 mol% of the monomer (a), and at least one selected from the monomer (b) and the monomer (c). It is characterized by having a process of polymerizing 10 to 70 mol% of the above.
  • Monomer (b) a fluorine-containing molecule having two or more groups selected from the group consisting of a group represented by the following formula (B1) and a group represented by the following formula (B2) in the molecule Monomer. [0008] [Chemical 1] ⁇ ⁇ 3
  • Yi Y 3 are each independently a hydrogen atom, a fluorine atom, a chlorine atom or a CF
  • Y i to Y 3 is a fluorine atom.
  • Y 4 to Y 6 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom or CF.
  • one or more of the ⁇ 4 ⁇ 6 is a fluorine atom
  • a Zeta 1 and Zeta 2 are each a hydrogen atom, full Tsu atom, a chlorine atom or CF.
  • the present invention provides a water / oil repellent composition comprising the fluoropolymer of the present invention and a solvent.
  • the present invention also provides an article having a water / oil repellent film comprising the water / oil repellent composition of the present invention.
  • a fluorinated polymer capable of forming a water- and oil-repellent film excellent in water and oil repellency and excellent in hardness and heat resistance.
  • a film using the water / oil repellent composition of the present invention a water / oil repellent film having excellent water and oil repellency and excellent hardness and heat resistance can be obtained.
  • the fluorine-containing polymer of the present invention has one polymerizable double bond, has a perfluoroalkyl group having 1 or more carbon atoms, and has no cyclic structure! /, Monomer It has a structural unit (I) derived from (a).
  • the structural unit (I) is a structural unit formed by cleavage of the polymerizable double bond of the monomer (a).
  • the perfluoroalkyl group in the monomer ( a ) is a group in which all hydrogen atoms bonded to carbon atoms of a linear or branched alkyl group are substituted with fluorine atoms.
  • the alkyl group has 1 or more carbon atoms, preferably! To 6 and more preferably 3 to 6.
  • the monomer ( a ) preferably has a group represented by the following formula (A1)! /.
  • xi to X 5 are each independently a hydrogen atom (H), a fluorine atom (F) or a chlorine atom (C 1), and n is 0 or 1).
  • the monomer ( a ) is preferably a compound represented by the following formula (A2)! /.
  • xi to X 5 are each independently a hydrogen atom (H), a fluorine atom (F) or a chlorine atom (C 1); R 1 may have an etheric oxygen atom, carbon A straight-chain or branched divalent hydrocarbon group of the number;! To 6, wherein some or all of the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group are substituted with fluorine atoms.
  • M is an integer from 0 to 3; R is a perfluoroalkyl group.
  • f is a perfluoroalkyl group.
  • (al): Perfluoroalkyl butyl ether represented by CF CFOR. The compound (a)
  • R is preferably a perfluoroalkyl group having 1 to 6 carbon atoms.
  • the compound (al), in which an isopropyl group is preferred is perfluoro (propyl butyl ether).
  • A is an alkyloxyalkyl group having 1 to 12 carbon atoms having an ether bond of 1 or more, and a part or all of hydrogen atoms bonded to the carbon atom of the alkyloxyalkyl group! / It may be substituted with a fluorine atom. It is preferable that all of the hydrogen atoms are substituted with fluorine atoms.
  • A is particularly preferably a perfluoronorole 2-propoxypropyl group.
  • the compound (a2) is represented by the following formula (A3).
  • a in the formula is synonymous with A in the compound (a2), including preferred embodiments thereof.
  • Ruether A in the formula has the same meaning as A in the compound (a2), including preferred embodiments thereof.
  • the structural unit (I) may be one kind or a combination of two or more kinds.
  • the proportion of the structural unit (I) in all the structural units constituting the fluoropolymer is 30 mol% or more, and more preferably 40 mol% or more.
  • the structural unit (I) When the structural unit (I) is 30 mol% or more, the surface energy is sufficiently low in the film made of the fluoropolymer, and excellent water and oil repellency can be obtained.
  • the upper limit of the proportion of the structural unit (I) is preferably 90 mol% or less from the viewpoint of balance with other structural units. Ku, more preferably 80 mol 0/0 or less.
  • the fluoropolymer of the present invention has an aliphatic ring containing an ether-bonded oxygen atom, and a structural unit (II) in which a fluorine atom is bonded to at least a part of the carbon atoms constituting the ring.
  • a structural unit (II) in which a fluorine atom is bonded to at least a part of the carbon atoms constituting the ring.
  • the cyclic structure of the structural unit ( ⁇ ) is present in the main chain of the fluoropolymer. That is, one or more carbon atoms constituting the aliphatic ring in the structural unit (II) are included in the carbon chain constituting the main chain of the fluoropolymer.
  • the structural unit (II) has “two or more groups selected from the group consisting of a group represented by the following formula (B1) and a group represented by the following formula (B2) in one molecule”.
  • Fluorine-containing monomer (b) "or" carbon having an aliphatic ring containing a carbon atom to which a fluorine atom is bonded! /, And an ether-bonded oxygen atom, and constituting the ring "
  • a structural unit derived from a fluorine-containing monomer (c) ”having one polymerizable double bond that bonds atoms or a carbon atom constituting the ring and another carbon atom is preferable.
  • Yi Y 3 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom or CF.
  • ⁇ 4 ⁇ 6 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom or a CF
  • ⁇ 4 to ⁇ 6 is a fluorine atom
  • ⁇ 1 and ⁇ 2 are a hydrogen atom and a fluorine atom, respectively.
  • the structural unit (II) is a structural unit formed by cyclopolymerization of the monomer (b) having two or more double bonds, or the polymerizable property in the monomer (c).
  • a structural unit formed by cleavage of a double bond is preferred.
  • monomer (b) two or more groups selected from the group represented by the group represented by the formula (B1) and the group represented by the formula (B2) are present in one molecule, There are preferably two. These groups present in one molecule may be the same as or different from each other.
  • Monomer (b) preferably has no cyclic structure!
  • Y U to Y 16 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom or CF.
  • Z U to Z 14 each represents a hydrogen atom, a fluorine atom, a chlorine atom or CF.
  • One or more of the to Y 13 is a fluorine atom, and one or more of the ⁇ 14 ⁇ 16 is a fluorine atom.
  • Y to Y 2B each independently represents a hydrogen atom, a fluorine atom, a chlorine atom or CF.
  • Z 21 and Z 22 each represents a hydrogen atom, a fluorine atom, a chlorine atom or CF.
  • One or more of Y 21 to Y 23 are fluorine atoms, and one or more of ⁇ 24 to ⁇ 26 are fluorine atoms.
  • ⁇ 31 ⁇ 36 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom or a CF
  • ⁇ 31 and ⁇ 32 each represents a hydrogen atom, a fluorine atom, a chlorine atom or CF.
  • ⁇ 31 to ⁇ 33 are fluorine atoms, and one or more of ⁇ 34 to ⁇ 36 are fluorine atoms.
  • CF 2 CF0 CF2CF2CF Two CF 2
  • CF2 CF0 CF2CF2CF Two CFCI
  • CF 2 CFO GF2CF Two GF 2
  • CF 2 CFO CFCF Two CF 2
  • CF2 CCIOCF 2 OGCI 2 CF2
  • the monomer (b) is particularly perfluoro (aryl butyl ether) represented by the following formula (B3) or the following formula (B4 ) Perfluro (Buturbuerue) Is preferred.
  • a fluorine atom is bonded to at least a part of the carbon atoms constituting the aliphatic ring. Further, it is preferable that a fluorine-containing group is bonded to at least a part of the carbon atoms constituting the aliphatic ring.
  • the fluorine-containing group is preferably CF.
  • ⁇ 24 ⁇ 25 ⁇ , .26 Represents an atom, fluorine atom, chlorine atom or CF.
  • X 1 and X, and X and X za and X May be linked to each other to form a ring.
  • perfluoro (2,2-dimethylol 1,3-dioxole) represented by the above formula (Cll) is particularly preferable.
  • the structural unit (II) may be one kind or a combination of two or more kinds.
  • the proportion of the structural unit (II) in all the structural units constituting the fluoropolymer of the present invention is 10 mol% or more, and more preferably 20 mol% or more. When it is 10 mol% or more, Good hardness and heat resistance can be obtained in a film made of a fluoropolymer.
  • the upper limit of the proportion of the structural unit (II) is 70 mol% or less, more preferably 60 mol% or less, from the viewpoint of balance with other structural units.
  • the fluorine-containing polymer of the present invention may be one in which part or all of the terminals have been modified.
  • the terminal when the terminal is COF, it is preferably modified to COOH, Si (OC H), or the like from the viewpoint of more expressing water and oil repellency.
  • the mass average molecular weight Mw (in terms of polystyrene by gel permeation chromatography (GPC), the same shall apply hereinafter) of the fluoropolymer of the present invention is not particularly limited, but is preferably 1000 to 1000000. ⁇ , More than 5000-200000! If it is below the upper limit of the above Mw range, it is easy to form a uniform coating film if it is above the lower limit that facilitates uniform dissolution in the solvent.
  • the fluorine-containing polymer of the present invention is obtained by polymerizing the monomer (a) and the monomer (b) and / or (c).
  • polymerization method an ordinary radical polymerization method is used.
  • initiator an azo polymerization initiator, a peroxide polymerization initiator or the like is preferable.
  • Solution polymerization, suspension polymerization, emulsion polymerization and the like can be used.
  • a structural unit represented by the following formula (B41) and / or a structural unit represented by the following formula (B42) is derived from perfluoro (butyr ether) represented by the above formula (B4).
  • the proportion of the monomer (a) in the total monomers constituting the fluoropolymer of the present invention is 30 mol% or more, and more preferably 40 mol% or more.
  • the surface energy is sufficiently low because of the film made of the fluoropolymer, and excellent water and oil repellency can be obtained.
  • the total of the monomers (b) and (c) is preferably 10 mol% or more, more preferably 20 mol% or more.
  • the upper limit of the total ratio of the monomers (b) and (c) is 70 mol% or less, more preferably 60 mol% or less, from the viewpoint of balance with the other monomers.
  • monomer constituting the fluoropolymer either or both of monomer (b) and monomer (c) may be used, or both may be used in combination. It is preferable to use either one. When both are used together, the ratio of the amount of monomer (b) to monomer (c) used is arbitrary.
  • the proportion of the other monomers is preferably 20 mol% or less, preferably 10 mol% or less, and may be zero.
  • the water / oil repellent composition of the present invention contains the fluoropolymer of the present invention and a solvent.
  • Repellent In the water / oil repellent composition the fluorine-containing polymer may be completely dissolved in the solvent, or a part or all of it may be dispersed without dissolving. That is, the water / oil repellent composition of the present invention may be in the form of a solution or a dispersed liquid.
  • the solvent in the present invention includes a dispersion medium in the dispersion liquid.
  • the solvent is preferably a fluorinated solvent, water, alcohol (not containing fluorine), or a hydrocarbon solvent.
  • a fluorinated solvent water, alcohol (not containing fluorine), or a hydrocarbon solvent.
  • water, an alcohol, or a hydrocarbon solvent is used when the fluoropolymer is dispersed in a preferred solvent to form a dispersed liquid. preferable.
  • a fluorine-containing solvent you may use together a fluorine-containing alcohol.
  • a fluorine-containing alcohol is used in combination, the solubility of a polar solute is improved.
  • solvents such as fluorocarbon, hydrated fluorocarbon, hydrated fluoroether, and hydrated fluorocarbon are preferred from the viewpoint of solubility.
  • Fluorocarbons such as perfluorobenzene, hexafluorometaxylene, etc .; polyfluorinated mouthmatic compounds; perfluorotributylamine, perfluorinated tributylamine, etc .; Polyfluoroalkane compounds such as hexane, perfluorooctane, (perfluoro-n-octinole) ethane, perfluoro (2, 3, 5-trimethylhexane); perfluorocyclohexane, perfluorodecalin, etc. Polyfluorocycloalkane compounds; polyfluorocyclic ether compounds such as perfluoro (2-butyltetrahydrofuran)
  • hyde mouth fluoroether examples include a separated type hyde mouth fluoro ether and a non-separable type hyde mouth fluoro ether.
  • the separated-type hyde mouth fluoroether is a compound in which a perfluoroalkyl group or a perfluoroalkylene group, and an alkyl group or an alkylene group are bonded via an etheric oxygen atom.
  • the non-separated type hyde mouth fluoroether is a hyde mouth fluoro ether containing a partially fluorinated alkyl group or an alkylene group.
  • fluorinated alcohols examples include trifluoroethanol, 2, 2, 3, 3, 3 pentafluoroleolol 1 propanol, 2- (pentafluorobutyl) ethanol, 2- (pentoexoxysil) ethanol, 2- ( Perfluorinated hexyl) ethanol, 2- (Penorooctyl) ethanol, 2- (Perfluorodecyl) ethanol, 2- (Perfluoro-3-methylbutynole) ethanol, 1H, 1H, 3H Tetrafluoro-1 propanol, 1H, 1H , 5H octafluoro 1-heptanol, 1H, 1H, 9H hexade force fluor 1-nonanol, 2H hexafluoro-2-propanol, 1H, 1H, 3H oxafluoro-2-butanol, etc.
  • two or more solvents may be used as long as they are compatible with one or more solvents.
  • the content of the solvent in the water / oil repellent composition is preferably 80 99.9% by mass, more preferably 90 99.9% by mass.
  • the content of the fluorinated polymer in the water / oil repellent composition is preferably 0. 20% by mass in terms of solid content, more preferably 10% by mass.
  • a dye such as a dye or pigment may be mixed in the water / oil repellent composition of the present invention.
  • a dye When a dye is mixed, the presence or absence of the film becomes easy to see when the film is formed using the water / oil repellent composition, and the visibility is excellent.
  • a silane coupling agent, a primer, etc. may be added to the water / oil repellent composition so as not to impair the oil repellency and the storage stability of the solution! /.
  • the water / oil repellent composition of the present invention can be formed on a substrate by applying it on a substrate and drying to remove the solvent.
  • Preferable coating methods include spraying, dipping, brushing, potting, and spin methods.
  • the temperature of the heat treatment is preferably 40 ° C to 300 ° C, more preferably 50 ° C to 250 ° C.
  • the heat treatment time is preferably 1 minute to 500 minutes, more preferably 5 minutes to 100 minutes.
  • the substrate is not particularly limited! /.
  • fiber fabrics such as single fibers, composite fibers, fabrics, and carpets; leather products such as fur; paper; wood; plastics; glass; metals; metal oxides; asbestos: ceramic products such as bricks and cements; It is done.
  • additives can be added to the base material for the purpose of imparting special characteristics or as a processing aid.
  • UV stabilizers, colorants, plasticizers, antistatic agents, antibacterial agents, and the like can be added within a range that does not adversely affect the final product.
  • pretreatment may be performed before applying the water / oil repellent composition to the substrate.
  • Specific examples include plasma treatment, UV ozone treatment, EB treatment, and adhesion layer coating.
  • the article of the present invention has a water / oil repellent film comprising the water / oil repellent composition of the present invention.
  • Article The entire surface in the case of a shape having an inner surface, including the inner surface in addition to the outer surface) may be covered with the water / oil repellent film, or may be partially covered. .
  • Optical components such as microscope lenses, mirrors, display screens, exposure masks, photomasks, spectacle lenses, camera lenses, and window materials.
  • Breathable filters such as filters for differential pressure adjustment of cameras and mobile phones, air filter media for vacuum cleaners, and in-vehicle breathable filters.
  • Rotating parts such as roll belts, printer rolls, rotating rollers and fan motors.
  • Devices such as microreactor channels, sliding bubble devices, molds, etc.
  • Kitchen accessories such as a range hood, gas stove, and gas range oil splash prevention sheet.
  • Exhaust gas filters, lead wires, bearings, gears, coating head nozzles, writing instrument parts, carpets, filaments, clothing show windows, inkjet paper, cosmetics, ink jet nozzles, metal plates, food packaging seals Materials, indicators, separation membranes for fuel cells, insulation spacers, film gloves, fuel tanks, tombstones, stones such as stone monuments, wall materials, building materials, wood, tiles, etc.
  • the film formed using the water / oil repellent composition containing the fluoropolymer of the present invention has good water / oil repellency and excellent film hardness and heat resistance. Having good water and oil repellency means having both water repellency and oil repellency and good liquid repellency. Specifically, a film having an n-decane contact angular force of 3 ⁇ 40 ° or more, which is an index of liquid repellency, is obtained. The larger the contact angle of n-decane, the higher the liquid repellency.
  • the structural unit (I) contributes to improving the water / oil repellency without decreasing the surface energy of the film and damaging the heat resistance
  • the structural unit (II) is It is considered that the introduction of a fluorine-containing ring structure into the main chain of the fluorine-containing polymer contributes to improving the hardness and heat resistance of the film made of the fluorine-containing polymer.
  • composition of the obtained polymer was analyzed by F-NMR.
  • Example 1 the amount of perfluoro (propyl butyl ether) used as the monomer (a) was changed to 23 g (0.086 monole), and perfluoro (butenyl vinyl ether) as the monomer (b) was used. ) was changed to 10 g (0.037 mol). Otherwise, the polymer was synthesized in the same manner as in Example 1, and the unreacted monomer was recovered. The polymer thus obtained was 15 g.
  • the polymer is composed of 47 mol% of the constituent units.
  • Mw was obtained by GPC, it was 1.0 X 10 3 .
  • Example 1 the monomer (a) was changed to 43 g (0.1 mol) of perfluoro (2-propoxypropyl butyl ether) represented by the above formula (A3). Otherwise A polymer was synthesized in the same manner as in Example 1, and unreacted monomers were recovered. The polymer thus obtained was 19 g.
  • the obtained water / oil repellent composition was dubbed and pulled up to apply the water / oil repellent composition, followed by heating at 150 ° C. for 30 minutes to obtain a coating film.
  • the coating hardness of this coating film was evaluated by pencil hardness.
  • the n-decane contact angle (initial contact angle) of the film immediately after film formation, and the n-decane contact angle (heat contact angle after heating) after the film was heated at 200 ° C for 1000 hours. was measured respectively.
  • a fluoropolymer composed of a (meth) acrylate monomer containing a perfluoroalkyl group was prepared.
  • a perfluorooctyl acrylate homopolymer was prepared, and a coating film was formed on a glass substrate in the same manner as in the test examples.
  • the film hardness, the n-decane contact angle of the film immediately after film formation, and the n-decane contact angle after the heating test were measured in the same manner as in the test examples. The results are shown in Table 1.
  • Example 1 the monomer (a) was not used, and the monomer used as the monomer (b) A homopolymer of olo (buturbu ether) was prepared.
  • a coating film was formed on a glass substrate in the same manner as in the test example.
  • the film hardness, the n-decane contact angle of the film immediately after film formation, and the n-decane contact angle after the heating test were measured in the same manner as in the test example. The results are shown in Table 1.
  • the coating films using the fluoropolymers obtained in Examples 1 to 3 have good hardness and water / oil repellency, and n-decane contact angles before and after the heating test. It has excellent heat resistance. / I understand that.
  • the coating film obtained in Comparative Example 1 had low hardness. It can also be seen that the contact angle of n-decane was greatly reduced after the heating test, indicating poor heat resistance.
  • the coating film obtained in Comparative Example 2 has a good hardness but a small contact angle of n-decane and poor water and oil repellency.

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Abstract

La présente invention concerne un polymère fluoré capable de former un film hydrofuge et oléofuge qui possède des caractères hydrofuge et oléofuge favorables et est également excellent en termes de dureté et de résistance thermique. La présente invention concerne un polymère fluoré caractérisé en ce qu'il comprend : (I) de 30 à 90 % en mole d'un motif structural dérivé d'un monomère (a) portant une liaison double polymérisable et un groupe perfluoroalkyle possédant un ou plusieurs atomes de carbone mais ne possède aucune structure cyclique ; et (II) de 10 à 70 % en mole d'un autre motif structural possédant un groupe alicyclique contenant un atome d'oxygène formant une liaison éther, dans lequel un ou plusieurs atomes de fluor sont attachés à au moins une partie des atomes de carbone constituant le cycle et d'un ou plusieurs atomes de carbone constituant le cycle sont impliqués dans une chaîne d'atomes de carbone constituant la chaîne principale.
PCT/JP2007/069488 2006-10-05 2007-10-04 Polymère fluoré, son procédé de production et composition hydrofuge et oléofuge WO2008041750A1 (fr)

Applications Claiming Priority (2)

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CN102381000A (zh) * 2010-09-06 2012-03-21 Jsr株式会社 固化性组合物和防反射用层叠体
WO2012086606A1 (fr) * 2010-12-22 2012-06-28 旭硝子株式会社 Filtre perméable à l'air, imperméable à l'eau, oléophobe et son procédé de production
WO2013150780A1 (fr) * 2012-04-06 2013-10-10 日東電工株式会社 Film perméable à l'air doté de propriétés oléofuges
JP2013230459A (ja) * 2012-04-06 2013-11-14 Nitto Denko Corp 撥油性が付与された粘着層付き通気フィルタ
CN105629509A (zh) * 2016-02-25 2016-06-01 侯绪华 一种清洁型防蓝光眼镜片
US9508971B2 (en) 2011-02-28 2016-11-29 Nitto Denko Corporation Gas-permeable filter provided with oil repellency
WO2022172951A1 (fr) * 2021-02-10 2022-08-18 ダイキン工業株式会社 Composé, composition, dispositif électrochimique, batterie secondaire au lithium-ion et module

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Publication number Priority date Publication date Assignee Title
WO2011027782A1 (fr) * 2009-09-01 2011-03-10 旭硝子株式会社 Composition de produit de revêtement pour appareil d’exposition par immersion dans du liquide, stratifié, procédé de formation de stratifié et appareil d’exposition par immersion dans du liquide
US20120156504A1 (en) * 2009-09-01 2012-06-21 Asahi Glass Company, Limited Coating material composition for liquid immersion exposure apparatus, laminate, method for forming laminate, and liquid immersion exposure apparatus
CN102549714A (zh) * 2009-09-01 2012-07-04 旭硝子株式会社 浸液曝光装置用涂布材料组合物、叠层体、叠层体的形成方法以及浸液曝光装置
CN102381000A (zh) * 2010-09-06 2012-03-21 Jsr株式会社 固化性组合物和防反射用层叠体
CN102381000B (zh) * 2010-09-06 2015-11-25 Jsr株式会社 固化性组合物和防反射用层叠体
WO2012086606A1 (fr) * 2010-12-22 2012-06-28 旭硝子株式会社 Filtre perméable à l'air, imperméable à l'eau, oléophobe et son procédé de production
JP2012130885A (ja) * 2010-12-22 2012-07-12 Asahi Glass Co Ltd 撥油防水性通気フィルタおよびその製造方法
US9508971B2 (en) 2011-02-28 2016-11-29 Nitto Denko Corporation Gas-permeable filter provided with oil repellency
US9168472B2 (en) 2012-04-06 2015-10-27 Nitto Denko Corporation Air-permeable film imparted with oil repellency
JP2013230459A (ja) * 2012-04-06 2013-11-14 Nitto Denko Corp 撥油性が付与された粘着層付き通気フィルタ
WO2013150780A1 (fr) * 2012-04-06 2013-10-10 日東電工株式会社 Film perméable à l'air doté de propriétés oléofuges
CN105629509A (zh) * 2016-02-25 2016-06-01 侯绪华 一种清洁型防蓝光眼镜片
CN105629509B (zh) * 2016-02-25 2018-10-12 江苏优立光学眼镜有限公司 一种清洁型防蓝光眼镜片
WO2022172951A1 (fr) * 2021-02-10 2022-08-18 ダイキン工業株式会社 Composé, composition, dispositif électrochimique, batterie secondaire au lithium-ion et module
JP2022122846A (ja) * 2021-02-10 2022-08-23 ダイキン工業株式会社 化合物、組成物、電気化学デバイス、リチウムイオン二次電池及びモジュール
JP7168897B2 (ja) 2021-02-10 2022-11-10 ダイキン工業株式会社 化合物、組成物、電気化学デバイス、リチウムイオン二次電池及びモジュール

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