WO2001019913A1 - Composition de fluororesine susceptible de former un film a basse temperature - Google Patents

Composition de fluororesine susceptible de former un film a basse temperature Download PDF

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Publication number
WO2001019913A1
WO2001019913A1 PCT/JP2000/005781 JP0005781W WO0119913A1 WO 2001019913 A1 WO2001019913 A1 WO 2001019913A1 JP 0005781 W JP0005781 W JP 0005781W WO 0119913 A1 WO0119913 A1 WO 0119913A1
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Prior art keywords
film
organic solvent
fluororesin
organic
soluble
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PCT/JP2000/005781
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English (en)
Japanese (ja)
Inventor
Akira Chida
Kayoko Honda
Yasushi Yonei
Katsuhiko Imoto
Masaru Nagato
Haruhiko Mori
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Daikin Industries, Ltd.
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Publication of WO2001019913A1 publication Critical patent/WO2001019913A1/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
    • C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/16—Homopolymers or copolymers of vinylidene fluoride

Definitions

  • the present invention relates to a fluororesin composition which is capable of forming a film at a low temperature, and whose surface can be easily lyophilic.
  • a fluororesin composition is a film such as a coating film of each molded product, a casting file, a knocking sheet, or the like. It is suitable as a material such as a marking film, and it is easy to remove contaminants, and can also prevent sticking. It is something. Background technology
  • Heat-meltable fluororesins such as ETFE, FEP and PFA make use of their excellent workability and properties to make durable covering materials and film materials. Used. As a characteristic of the reinforced fluororesin, its high water-phobicity makes it easy for lipophilic soiled components to adhere outside the building, resulting in a loss of appearance. There is a problem that is easy to read.
  • these general-purpose fluoroplastics basically have a high melting point, so processing at high temperatures is essential, and therefore, surface modification for antifouling treatment is required. It is difficult to mix chemicals and other additives, and it is not expected that such additives will improve the adhesion of contamination.
  • a paint composition which can form an outstandingly excellent coating film, and an antifouling agent for incorporation into the composition.
  • a is an integer of 0 or 1 to 6
  • b is an integer of 0 or 1 to 5
  • c is an integer of 0 or 1 to 6 (where a + b + c ⁇ 3 and a and c do not become 0 at the same time)
  • X ' is the same or different and is an oxygen atom or a nitrogen atom.
  • a fluorine atom and a monovalent organic or hydrogen atom having 1 to 500,000 carbon atoms which may contain a Z atom or a chlorine atom, and M is a small number.
  • a metal atom having at least a trivalent atomic valence, R 1 ′ is the same or different, and is an oxygen atom, a nitrogen atom, a fluorine atom or the like.
  • R 2 is also acid shift have Ri Do different was or whether the same as Organic compounds having 1 to 20 carbon atoms capable of chelating iodine which may contain atoms, nitrogen atoms, fluorine atoms or chlorine atoms.
  • a known antifouling agent is known (WO97 / 111130 pan fret).
  • the film-forming components described in WO977Z11130 non-fret are resin resins for paints, which contain fluorine. Because of its small weight, its performance as a film or covering material (for example, heat resistance, mechanical strength, elongation, etc.) cannot be said to be sufficient.
  • the present invention relates to a film or a film which can be formed at a low temperature (below 270 ° C, preferably below 180 ° C) and can be obtained.
  • An object of the present invention is to provide a fluororesin composition capable of easily hydrophilizing the surface of a film. Disclosure of the invention
  • the present invention has the following properties:
  • At least one, and preferably at least two, one of Kaffuidani vinyl or vinylidene fluoride Soluble or dispersible in organic solvents consisting of polymers or copolymers containing vinyl fluoride or vinylidene fluoride -Temperature film-forming fluororesin composition containing a natural fluororesin, an organic metal compound having a water-decomposable group, and an organic solvent About.
  • the present invention discloses that the fluorine content S 5 weight%, preferably 35 weight% or more, is soluble or soluble in an organic solvent.
  • a low-temperature film-forming fluororesin composition containing a dispersible fluororesin, an organic metal compound having a water-decomposable group, and an organic solvent.
  • an organic resin having a refractive index of less than 1.40 and soluble or dispersible in an organic solvent and an organic solvent having a water-soluble decomposable group is provided.
  • the present invention relates to a low-temperature film-forming fluororesin composition containing a metal compound and an organic solvent.
  • the present invention relates to a low-temperature film-forming fluororesin composition containing an organic metal compound and an organic solvent.
  • a fluorine resin which is amorphous and has a glass transition point of 70 to 250 V, and which can be dissolved or dispersed in an organic solvent.
  • the present invention relates to a low-temperature film-forming fluororesin composition containing an organic metal compound having a water-decomposable group and an organic solvent.
  • the present invention relates to a low-temperature film-forming fluororesin composition containing an organic metal compound having a water-decomposable group and an organic solvent.
  • fluorine resin examples include tetrafluoroethylene 10 to 50 mol%, and hexafluoropropylene 0 to 50 mol%. % And vinylidene fluoride from 90 to 10 mol%, especially those with a fluorine content of 60% by weight or more. It is better.
  • organic solvent for dissolving or dispersing the fluorine resin a fluorine-based organic solvent is preferred.
  • a silicate compound particularly a fluorosilicate compound, is preferred.
  • the low-temperature film-forming resin composition of the present invention is applied to a substrate, and heated at a room temperature of 7270 t, particularly at a room temperature of ° 180 ° C.
  • a coating film whose surface is lyophilic can be obtained, and the film should be formed at room temperature to 270 ° C, especially room temperature to 180 ° C.
  • the fluororesin used in the invention must be soluble or dispersible in organic solvents.
  • Solvent-soluble fluororesin has been known for some time, but it is similar to heat-meltable fluororesin that is insoluble in solvents such as ETF ⁇ and F ⁇ . They are highly hydrophobic and have similar problems in terms of anti-fouling properties.
  • the reason for using an organic solvent-soluble fluororesin in the present invention is not only to enable low-temperature processing in the solution state but also to be an organic. Due to the presence of the solvent, the organic metal compound containing a water-decomposable group is collected on the surface during film formation, and the effect of making the surface lyophilic is enhanced. It is a car that is. Also, the resin solid content in the preparation of the resin composition for coating can be increased, the viscosity of the coating bath can be reduced, and the fluidity is good. For reasons of becoming a fluorocarbon resin that can be dispersed in an organic solvent, it may be used.
  • a solvent-soluble or solvent-dispersible fluorine resin that can be used in the present invention
  • a conventionally known organic solvent can be dissolved or dispersed.
  • Fluorine content 5% by weight or more, preferably 35% by weight or more, more preferably 40 to 75% by weight, especially 60% by weight. ⁇ 75% by weight force
  • the refractive index is less than 1.40, preferably from 1.39 to 1.25,
  • the fluororesin is a homopolymer of vinyl fluoride or vinylidene fluoride, or a vinyl polymer or a mixture of vinylidene fluoride and vinylidene fluoride.
  • (A) Fluorine resin having a ring structure of the above formula (I) (USP 3, 865, 845, the specification, USP 3, 978, 030, the specification) , USP 4, 5, 33, 741, etc.)
  • Other monomers include fluoropolymers and hydrogenated hydrocarbons having radical polymerization.
  • Other monomers can be used, specifically, TFE, Perfluorovinyl ether, Vinylidene olive , Vinyl full-olide, and chlorotrifluoroethylene.
  • This solvent-soluble fluororesin has a fluorine content of 60% by weight or more, a refractive index of 1.39 to: L.27, and is non-fluorinated. It is crystalline and has a glass transition point of 70 to 250 ° C.
  • Commercial products include the Teflon AF series (manufactured by Dupont).
  • fluorine-based, hydrocarbon-based, and other monomers having radical polymerization can be used, and specifically, for example, TFE, perfluorinated vinyl, VdF, vinyl fluoride, black mouth trifluoroethylene, etc. It is.
  • This solvent-soluble fluororesin has a fluorine content of 60% by weight or more, a refractive index of 1.39 to 1.27, and is amorphous. It is a glass with a glass transition point of 70 to 250 ° C.
  • As a marketed product there is a site manufactured by Asahi Glass Co., Ltd.
  • fluorine-based, hydrocarbon-based, and other monomers having radical polymerization can be used.
  • TFE perfluorovinyl ether, vinylidenefluoride, vinylfluoride, chlorotrifluoride
  • This solvent-soluble fluororesin has a fluorine content of 60% by weight or more, a refractive index of 1.39 to L.27, and a non-limiting degree. It is crystalline and has a glass transition point of 70 to 250 ° C.
  • As a marketed product there is a site manufactured by Asahi Glass Co., Ltd.
  • composition ratio of the monomers is as described above, and TFE is 10 to 50 mol%, HFP is 0 to 50 mol%, and VdF is 90 to 10 mol%. Furthermore, the TFEZHFPZV d F is in the range of 10 to 30Z 3 to 40/77 to 40.
  • This copolymer may be modified with an isocyanate compound or the like.
  • This solvent-soluble fluorine resin has a fluorine content of 60% by weight or more, a refractive index of 1.39 to 1.27, and a refractive index of 1.27 to 1.27. It has a crystal melting point of 100 to 180 ° C. Examples of marketed products include the THV series (manufactured by Sumitomo Sleep Co., Ltd.).
  • a vinyl fluoride As a polymer of vinyl fluoride, a vinyl fluoride of 100 to 10 mol% and another copolymerizable monomer can be used. A polymer consisting of up to 90 mol% is obtained.
  • Other co-polymerizable monomers include, for example, tetrafluoroethylene, hexafluoropropylene, vinylidene, and the like.
  • fluoromonomer such as fluorofluoride and perfluoro (alkyl vinyl ether)
  • vinyl chloride vinyl chloride Vinyl compounds such as Nilidene, Ethylene, Propylene, Isobutylene are exposed.
  • Commercially available products such as Dupont Tedlar series can be used.
  • vinylidene fluoride-based polymer vinylidene fluoride is 100 to 10 mol% and other copolymerizable polymers. Nomer 0-90 mol% power, such as the polymer power.
  • copolymerizable monomers include, for example, tetrafluoroethylene, hexafluoropropylene, and vinylolfene.
  • fluoromonomer such as Fluoride, Perfluoro (alkyl vinyl ether), vinyl chloride, vinyl chloride, etc.
  • Vinyl compounds such as styrene, ethylene, propylene, and isobutylene are exposed.
  • you can use Elfat Chem's power-in series 500-in, power-in SL, etc.). You may use a mixture of acrylic resin and the like.
  • an organic solvent-soluble fluorocarbon resin (hereinafter, unless otherwise specified, includes a fluorocarbon resin dispersible in a solvent). "Organic solvent-soluble fluororesin”), and the organic solvent other than the specific organic solvent and soluble fluororesin specified above. It is also possible to use a non-fluororesin which is soluble in fluorocarbon resin and Z or an organic solvent.
  • Solvent-soluble fluorinated resins that can be used together include, for example, a hydroxyl- and / or carboxyl group that is soluble in the solvent. Fluoroolefin copolymers that are present are required. Specific examples include, for example, Japanese Patent Publication No. 60-21686, Japanese Patent Laid-Open No. 3-1211, Japanese Patent Laid-Open No. Some of the materials described in each gazette, such as JP-A-Hei 4-28707, and JP-A-Hei 2 232 221 are disclosed.
  • the number average molecular weight (according to GPC) of the copolymer is 100 000 to: 100 000, preferably 150 000 to 300 000. . If the molecular weight is less than 100, the curability and weather resistance tend to be unsatisfactory, and if the molecular weight exceeds 100, the workability and paint will not be sufficient. There is a tendency for problems to arise in the wearability.
  • the hydroxyl value of the copolymer is from 0 to 200 (mg KOH / g), and preferably from 0 to 150 (mg KOHZ g). No. When the number of hydroxyl groups is reduced, the degree of hardening tends to be poor, and when it exceeds 200 (mg KOHZ g), there is a problem in the flexibility of the coating film. Tend to change.
  • the acid value of the copolymer is 0 to 200 (mg KOHZ g), and more preferably 0 to 100 (mg KOHZ g). No. If the acid value is too low, the hardening tends to be poor, and if it exceeds 200 (mg KOH / g), there is a problem in the flexibility of the coating film. Tend to occur.
  • tetrafluoroethylene is used in terms of antifouling property, decontamination property, and protection property. Polymers can also be used.
  • Examples of the above-mentioned copolymers include Zefle manufactured by Daikin Industries, Ltd., Riremi Fron, and Central Glass manufactured by Asahi Glass Co., Ltd. Market sales of Cephalcoat Co., Ltd., Ink Chemicals Industry Co., Ltd., Flounett Co., Ltd., and Toa Kasei Co., Ltd., Zeflon Co., Ltd. The product is obscured.
  • the non-fluorine-based solvent-soluble resin includes thermoplastic acrylic resin, acrylic polyol resin, acrylic silicone resin, fluorine resin, and the like. Silicone resin, inorganic material, etc. are required, but thermoplastic thermoplastic resin and acrylic resin are preferred from the point of actual use. It is better.
  • Thermoplastic acrylic resins include, for example, methyl methacrylate, ethyl methacrylate, and propylmethacrylate.
  • Acrylate esters such as butyral methacrylate, etc. ⁇ methyl acrylate, ethyl acrylate, pill pill
  • a single polymer of acrylate esters such as acrylate, butyryl acrylate, etc., a copolymer thereof, or a copolymer thereof. Copolymers with monomer that can be polymerized are exposed.
  • Monomers that can be copolymerized include, for example, aromatic vinyl compounds such as styrene, acrylonitrile, and various vinyl ethers. , Aryl ethers, vinyl compounds such as various vinyl esters, carboxyl groups, amino groups, epoxy groups, etc. Unsaturated monomers that have public functional groups are required.
  • acrylic resin examples include (a) hydroxyl-containing (meta) acrylic acid esters and hydroxyvinyl resins. Hydroxyl-containing ethylenically unsaturated monomers such as cellulose and aryl alcohol, and (b) a hydroxyl-free unsaturated monomer. , Vinyl ether, aryl ether, vinyl ester, pronyl ester, (meta) acrylic acid ester , Vinyl aromatic compounds, (meth) acrylonitrile, unsaturated monomers containing carboxy groups, unsaturated monomers containing epoxy groups
  • the polymer examples include a polymer with a hydroxyl-free unsaturated monomer such as an isomer or an amino-containing unsaturated monomer.
  • the acrylic polyol resin may have a hydroxyl group, a carboxyl group, an epoxy group, or an amino group.
  • the hydroxyl value of the acrylic resin is from 0 to 200 (mg KOH / g), and from 0 to 100 (mg KOH / g). And are preferred. When the hydroxyl value is reduced, hardening tends to deteriorate, and when the hydroxyl value exceeds 200 (mg KOH / g), the flexibility of the coating film is reduced. There is a tendency for problems to arise.
  • the acid value of the acrylic polyol resin is 0 to 200 (mg KOHZ g), and 0 to: L 0 0 (mg KOHZ g). More preferred. If the acid value is too low, the curing will be poor and there is a tendency to tilt.If the acid value exceeds 200 (mg KOH / g), the flexibility of the coating film becomes a problem. Tend to occur.
  • acrylic polyol resins examples include, for example, Mitsubishi Rayon Co., Ltd.'s Dianal, and Dainippon Ink Chemicals Co., Ltd. You may use commercially available products such as Credit, Hitachi Steel Co., Ltd. Hydroid, Mitsui Toatsu Chemicals Co., Ltd. it can .
  • the above-mentioned acrylic silicone resin includes, for example, at least one silane group and a radically polymerizable unsaturated group in one molecule.
  • the acrylic silicone monomer having the above It has been copolymerized with the group-containing ethylenically unsaturated monomer (a) and Z or its hydroxyl-containing unsaturated monomer (b). Just do it.
  • the acrylic silicone resin may have a water-decomposable silyl group, a hydroxyl group, or an epoxy group.
  • Acrylic silicone resins include, for example, Zemlack manufactured by Kaneka Kagaku Kagaku Co., Ltd., and Kryama Co., Ltd. manufactured by Sanyo Kagaku Kogyo Co., Ltd. You can use any commercial products.
  • the above-mentioned paint-based resin is a non-fluorinated non-hydrolyzable group-containing metal (Si, Ti, A1, etc.) as a resin for coating.
  • Inorganic materials such as coxide may also be used.
  • the inorganic materials mentioned above include, for example, Eco-Tone, a product released by Gunze Sangyo Co., Ltd., Glass Capsules manufactured by Nippon Kasei Gum Co., Ltd. ) Poserin, Nippon Yushi Yushi Co., Ltd. Belclean, Belhard, Toray Dow Corning Silicon Co., Ltd. SH, SR and DC Series, Shin-Etsu Chemical Co., Ltd. KR Series, Ajinomoto Co., Ltd. Plan, Nihon Soda Co., Ltd. Net, Kawaken Fine Chemical Co., Ltd.
  • Aluminum Alloy and Aluminum Chelate Compounds Bekko Zirconium Alcoxide manufactured by Gakukogyo Co., Ltd., Compound Modified Silicone Oil manufactured by Nihon Nikka Co., Ltd., and MMCA You can use any of the commercial products.
  • fluorine silicone resin examples include those described in the official gazette of Japanese Patent Application Laid-Open No. Hei 4-279696.
  • the combined solvent-soluble resin used in the present invention is 60 weight of the total resin weight, including the specific solvent-soluble fluororesin described in the present invention. % Or less, preferably 50% by weight or less.
  • the low-temperature film-forming fluororesin composition of the present invention contains an organic solvent.
  • the organic solvent may be fluorine-based or non-fluorine-based, but it depends on the solubility of the fluorine resin and the transparency of the resulting film. Is preferably a fluorine-based organic solvent.
  • fluorine-based organic solvent examples include CF 3 CH 2 OH, F (CF 2 ) 2 CH 2 ⁇ H, (CF 3 ) 2 CH ⁇ H, and F (CF 2 ) 3 CH 2 OH, F (CF 2) 4 C 2 H 5 OH, H (CF 2) 2 CH 2 OH, H (CF 2) 3 CH 2 OH, H (CF 2) 4 CH 2 OH , etc.
  • Non-fluorine-based organic solvents include, for example, xylene, toluene, solvess 100, solvess 150, and hexane. Any hydrocarbon solvent; methyl acetate, ethyl acetate, butyrate acetate, ethyl acetate alcohol monomethyl ether, ethyl acetate Dali alcohol monoethyl ether, ethyl alcohol monoethyl ether, diethyl alcohol mono alcohol monomethyl ether Ruthele, Diethylene glycol acetate methyl ether ether, Diethylene glycol acetate monobutyl ether acetate, Acetic acid Ester-based solvents such as ethylene glycol and diethylene glycol acetate; dimethyl ether , Ethyl ether, dibutyl ether, ethyl glycol mono methyl ether, ethyl glycol mono Ethyl ether, ethylene glycol monobutyral ether, ethylene glycol remelt
  • Ketone-based solvents N, N — dimethyl acetate amide, N — methyl acetoamide, aceto amide, N, N — dimethyl phenol Amido-based solvents such as muamide, N, N—methylholmamide and N—methylholmamide; dimethylsulphoxide Ethyl sulfonate solvents such as methanol, ethanol, isopropanol, butyl alcohol, ethylene glycol, etc. 1
  • alcoholic solvents such as soles, polyethylene glycols, polyethylene glycols (weight: 3 to 100), etc. Seed or Is a mixture of two or more solvents.
  • a mixture of a fluorine-based solvent and a non-fluorine-based solvent may be used.
  • the above-mentioned fluorine-based solvents, ketone-based solvents, and ester-based solvents are preferred from the viewpoint of solubility, appearance of the coating film, and storage stability.
  • methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cellosol acetate, butyric acid acetate , Ethyl acetate, perfluorobenzene, Metaxylene hexafluoride, HCFC-225, CFC-113, HFC-134a, HFC-143a, and HFC-12b are preferred. .
  • hydrolyzable group-containing organic metal compound which can be used in the present invention and has a significant hydrophilizing effect
  • a known compound for example, the above-mentioned formula (1):
  • X ' is the same or different Also contains a oxygen atom, a nitrogen atom, a fluorine atom and a monovalent organic group having 1 to 500,000 carbon atoms, which may contain a Z atom or a chlorine atom.
  • the atom, M is a metal atom having at least trivalent valence
  • R 1 ′ is the same or different, and each is an oxygen atom, a nitrogen atom, a fluorine atom or And / or a chlorine atom-containing monovalent organic group having 1 to 100 carbon atoms, a siloxane residue or a hydrogen atom, and R 2 are the same. Or any other chelating ability which may contain oxygen, nitrogen, fluorine, and Z or chlorine atoms.
  • Carbon number Which represents an organic group of from 1 to 20] (comprising from the oligomer or the oligomer comprising two or more kinds of the organometallic compounds). (The same shall apply hereinafter.) (W097 / 111130 Panfret).
  • a represents 0 or 1 to 1 in terms of surface concentrating property, hydrolyzing property, and desorbing property. It is an integer of 6 and preferably an integer of 2 to 4.
  • b is an integer of 0 or 1 to 5, preferably 0 to 1 from the viewpoint of surface concentrating property and hydrophilicity
  • c is a surface. It is an integer of 0 or 1 to 6, and preferably an integer of 0 to 3 from the viewpoints of concentration, water-decomposability, and desorption.
  • the mole ratio of X to R 1 + R 2 be less than or equal to 0.2 (bZ (a + c) ⁇ 0.2).
  • the total amount of a, b, and c is the force determined by the valence of the metal atom M.
  • OR 1 or R 2 In either case, a and c become 0 at the same time because they are necessary for antifouling adhesion, surface thickening, and hydrolytic decomposition. Nevertheless, the total amount of a, b and c is at least 3.
  • X is a hydrogen atom, or an oxygen atom, a nitrogen atom, a fluorine atom, and a hydrogen atom, such as those described in (i) to (iii) below. It is a monovalent organic group having 1 to 500,000 carbon atoms which may contain a chlorine atom.
  • Examples of these are, for example, CH 3 , CH 3 CH 2 , CH 3 CH 2 CH 2 , (CH 3 ) 2 CH, CF 3 CH 2 , CF 3 CF 2 CH 2 , (CF 3 ) 2 CH, F (CF 2 ) 4 CH 2 CH 2 , F (CF 2 ) 8 CH 2 CH 2 , H (CF 2 ) 4 CH 2 etc., but the surface density, CF 3 CF 2 CH 2 , (CF 3 ) in terms of water decomposition and desorption. CH power S preferred.
  • organic group X was example, if NH 2, secondary A Mi amino group, tertiary ⁇ Mi amino group, OH NCO C0 2 H C0 2 Na C0 2 K S0 3 H S0 2 Na S 0 3 K, organic groups having functional groups such as epoxy group and oxyethylene group (CH 2 CH 2 O) are produced. Examples of these are, for example, H 2 N (CH 2 ) 3 OCN (CH 2 ) 3 CH 3 0 (CH 2 CH 2 0) (CH 2 ) 3 CH 3 0 (CH 2 CH 2 0) "CH 2 ) 3 CH 3 O (CH 2 CH 2 O) I 0 (CH 2 ) 3
  • the organic group X may include, for example, an oxygen atom, a nitrogen atom, a fluorine atom, a chlorine atom, a silicon atom, and the like.
  • the polymerizable organic group is exposed.
  • a compound represented by the formula (1) having such a polymerizable organic group is polymerized or co-polymerized.
  • the present invention also includes a polymer or a copolymer having an obtained molecular weight of 200,000, preferably 500,000.
  • the aforementioned R 1 may contain the same or different oxygen atoms, nitrogen atoms, fluorine atoms, and Z or chlorine atoms. , Surface concentration, water-decomposability, desorption It is a monovalent organic group having 1 to 100 carbon atoms or a hydrogen atom, and preferably 1 to 100 carbon atoms. It is even more preferred that the force be between 1 and 16. However, at least one of R 1 is CF 3 CHFCF 2 CH 2 , CF 3 CHF CF 2 CHCH 3 or CF 3 CHFCF 2 C (CH 3 ) 2 .
  • R 1 may be an organic high molecular chain having up to 100,000 carbon atoms.
  • the above R 2 may be the same or different and has excellent chelation properties even if it contains a fluorine atom and Z or a chlorine atom. It has the ability to increase the number of carbon atoms from the viewpoints of surface concentration, hydrolytic decomposition, and desorption. -20, with 2-10 being a preferred organic radical.
  • the use of an antifouling antifouling agent to which an organic substrate having such a cleansing ability is bound is used.
  • the result is superior storage stability, reactivity, solubility, and compatibility.
  • Compounds that may be capable of chelating such organic compounds include, for example, 2,4—pentyl, 2 , 4 — heptane dione, etc. / 3 — ketones such as diketones, methyl acetate acetate, ethyl acetate acetate, butyl acetate acetate, etc.
  • Esters lactate, methyl lactate, ethyl lactate, ammonium lactate, salicylic acid, methyl salicylate, salicylic acid Hydroxycarboxylic acids such as ethyl, linoleic acid, linoleic acid, tartaric acid, and tartaric acid, or esters and salts thereof , 4-Hydroxy 1-4-Methyl-2-Non-hydrating, 4-Hydroxy 2-Pen--Non-hydrating, 4-Hyd opening-2-F Pu no , 4 — hydroxy 41-methyl 1 2 — heptaquinone and other ketoalcohols, mono-no-norre amide, diethanol , ⁇ , —, ⁇ , ,, —, —, —, —, —, —, —, —, —, —, —, —, —, —, —, — N methyl ethanol amine, N, N —
  • the metal atom M is, for example, B, A 1, G a, In, ⁇ 1, S c, Y, L a A c, S i, G e, S n, P b,
  • the organic metal compound represented by the formula (1) may be, for example, an organic metal compound such as a sponge or an organic metal compound obtained therefrom. Rigomers or cool ligomers can be empowered.
  • CH 2 C (CH 3) C0 2 (CH 2) 3 Si (OCOCF 3) 2 (OCH 3),
  • CH 2 C (CH 3) C0 2 (CH 2) 3 Si ( OC_ ⁇ _C 2 F 5) 2 (OCH 3 ),
  • CH 2 C (CH 3) C0 2 (CH 2) 3 Si (OCOC s F 17) 2 (OCH 3)
  • oligomers or core oligomers include those having a straight chain, a branched chain, a ring, a three-dimensional structure, and the like. Oligomers are exposed.
  • the weight of the oligo or oligo sesame is preferably from 2 to 100, more preferably from 4 to 100. Shire.
  • the weight of the oligomer and the oligomer is determined by the molarity of the water to be reacted and, for example, the organic metal compound represented by the formula (1). It can be controlled by the ratio. For example, react [H 2 O] Z [organic metal compound represented by the formula (1)] with a mole ratio in the range of 0.4 to 0.95. Thus, an oligomer or a cool oligomer having a weight of about 2 to 20 is obtained. In addition, by setting the mole ratio in the range of 0.94 to 2.0, the oligomer or the core having a weight greater than 20 can be obtained. The sesame is obtained.
  • kool ligomer a kool ligomer obtained by using two kinds of organic metal compounds represented by the formula (1) is constituted. It is preferable that the composition ratio (molar ratio) of the runit is from 1Z9 to 9Z1.
  • GPC molecular weight of oligomer or oligomer (value converted to polystyrene using tetrahydrofuran as eluent) Is preferably from 500 to 100,000, more preferably from 100,000 to 500,000 in weight average molecular weight. .
  • the effect of hydrophilization decreases, and when the molecular weight exceeds 100000, gelation occurs during synthesis and during storage. There is a tendency.
  • the organic metal compound represented by the above formula (1) can highly lyophilize the surface of the coating film due to the function of the water-decomposable group. It provides a paint composition with excellent antifouling, adhesion, low static electricity and anti-fog properties.
  • CF 3 CHFCF 2 CH 2 , CF 3 CHFCF 2 CHCH 3 or CF 3 CHFCF 2 C (CH 3 ) 2 for example, has excellent surface enrichment, reproducibility of surface hydrophilization, An effect called kingability is obtained.
  • the content of fluorine atoms in the organic metal compound represented by the formula (1) is at least 5% by weight, preferably 15 to 60%. Due to the weight%, effects such as excellent surface concentration and reproducibility of surface hydrophilization can be obtained.
  • a is 4 and b and c are 0, and M is Si and an organic metal compound having a fluorine atom.
  • M is Si and an organic metal compound having a fluorine atom.
  • the present invention provides a low-temperature film-forming fluororesin composition comprising the above-mentioned specific solvent-soluble fluororesin, a hydrolyzable group-containing organic metal compound, and an organic solvent. Basically.
  • the amount of the organic metal compound is 0.1 to 50 parts by weight, and preferably 1 to 30 parts by weight with respect to the parts by weight. When the amount is less than 0.1 parts by weight, the surface lyophilicity is reduced, and when the amount exceeds 50 parts by weight, the appearance of the coating film is poor and the resin is compatible with the resin. The property is reduced.
  • the ratio of the solvent-soluble fluorine resin to 100 parts by weight is as follows: 2,000 parts by weight, and 100 to 150 parts by weight from the viewpoints of coating properties, film forming properties, hardening properties, and appearance of the coating film. More preferred.
  • an alcohol-based solvent is used as an organic solvent, and a hardening agent described later is a cold-hardening type iso- ganate, for example.
  • the alcohol-based solvent is preferably present in an amount of 1 to 15 parts by weight, and the alcohol-based solvent is preferably used in an alcohol-based solvent.
  • the type of the solvent is also preferably a secondary or tertiary alcohol.
  • Additives include, for example, surface conditioners, hydrophilization accelerators (hydrolysis catalysts), pigments, pigment dispersants, thickeners, repelling agents, defoamers, Coating aids, UV absorbers, HALS, killing agents, fillers, colloidal silicas, antifungal agents, silane coupling agents, skin tension Anti-oxidant, anti-oxidant, flame retardant, anti-dripping agent, antistatic agent, anti-oxidant, water-soluble resin (Polyvinyl alcohol, Polyethylene) Oxide, etc.)
  • the surface conditioner not only prevents slippage after painting, improves the leveling properties, but also separates the colors of the coloring paint and prevents color floating. Donate. Addition is optional and, if necessary, known ones may be used.
  • the hydration promoting agent promotes the hydration and decomposition of the water-decomposable organic metal compound, and functions to promote the appearance of surface lyophilicity.
  • Specific examples include metal chelates such as aluminum chelates, titanium chelates, zirconium chelates, and the like.
  • organic soot compounds, organic phosphoric acid esters, organic titanium oxide compounds, and acid phosphoric acid esters Products produced by reacting with amines, saturated or unsaturated polyvalent carboxylic acids or anhydrides thereof, and organic sulfonic acids are produced.
  • Suitable antifoaming agents include, for example, Zeffle GH-200 (manufactured by Daikin Industries, Ltd.) long-chain fluoroalkyl group-modifying resin.
  • Siloxane-based antifoaming agents such as LOXAN, and Fluorocarbons such as FA-600 and FS-126265 (both manufactured by Shin-Etsu Chemical Co., Ltd.) Silicone antifoam, silicone compound antifoam, silicone antifoam, acrylic antifoam, etc. It is.
  • the low-temperature film-forming fluororesin composition of the present invention may be used for forming a coating film as a composition for a paint, or may be used in a casting method or the like. It may be formed into a film by law.
  • Various painting methods are used, such as spraying, brush painting, rollers, curtains, rolls, and dips. .
  • the temperature should be between room temperature and 270 ° C, preferably at room temperature. Drying at a temperature of 180 ° C is especially preferred for coatings or films whose surface has hydrophilic properties. can get .
  • Coatings or films formed from the composition of the present invention readily have a high degree of hydrophilization on the surface, and are capable of adhering lipophilic stains. As a result, antifouling adhesion can be achieved. It also has a high degree of weather resistance, chemical resistance and optical properties (such as transparency), mechanical properties (strength and elongation), adhesion to base materials, heat resistance, It excels in heat resistance and yellowing.
  • the composition may be used in the same manner as ordinary hardening compositions, such as building materials, interior materials, etc., for indoor or building materials, vehicles, airplanes, ships, For outdoor paints such as electric cars, metal, concrete, plastics, etc. are directly connected to or used as a paint primer. It can be applied over primer paints such as stop paints, epoxy resins, acrylic resin paints, and polyester resin paints. Furthermore, it can be used as a screening agent.
  • coating composition various forms such as clearer, solid, filler (filler) combination and the like can be adopted.
  • composition of the present invention can be applied to various kinds of base materials, and the base material to be coated is, for example, a metal base, a cement base, Plastic base materials, etc. are required.
  • metal-based material examples include iron and its chemical conversion products or plating materials, aluminum and its chemical conversion products, stainless steel, and the like. The steel and its chemical conversion products are required.
  • cement-based material examples include cements, limes, cements, concrete, cement mortar, stones, and the like. Cotton slates, plaster boards, etc. are required.
  • plastic base material examples include poly (vinyl chloride), poly (ester), poly (carbonate), and acrylic resin.
  • plastic base material examples include poly (vinyl chloride), poly (ester), poly (carbonate), and acrylic resin.
  • Polyolefins, polystyrenes, polyurenes examples include tans, polyamides, nylons, natural rubbers, urethane rubbers, and ABS resins.
  • the coating composition of the present invention is applied after the undercoating paint and the intermediate coating paint, such as, for example, are applied. It is preferable to apply an object from the viewpoint of corrosion protection and adhesion between phases.
  • zinc paint is preferred as the primer.
  • undercoating and intermediate coatings are preferably epoxy resins (including tar-modified and urethane-modified), and vinyl. Resin (including tar modification, acrylic resin), rubber chloride, polyurethane resin, and at least one selected from phenolic resin.
  • One type of synthetic resin is mixed with commonly used pigmented pigments, extenders, sedimentation inhibitors, dispersants, hardeners, hardening accelerators, diluents, solvents, etc. This is the paint obtained.
  • the film thickness is suitably 1 to 100 Um, preferably 5 to 40 m.
  • the base material is a plastic base material
  • the undercoat paint and the intermediate paint used for the metal base material, cement base material, and the like are used. After the coating, the coating composition of the present invention can be coated.
  • the painting method is, for example, a glass coating material. Singing method, doctor blade method, roll coating method, reverse rolling method, Jay-Nifek method, etc. .
  • the coating film thickness is 1 to 25 ⁇ m, preferably 1 to 1 ⁇ m, from the viewpoint of coating film appearance and coatability.
  • Articles coated with the composition of the present invention may be used, for example, for waterproof sheets for construction, waterproof sheets for tunnels, and agriculture.
  • the film when the film is in the form of, for example, solar battery power films, displays for electrical and electronic equipment, etc. Power rolls, rolls of various types, mold release films, agricultural eight-hour filems, electrets, etc. .
  • the film thickness is from 5 to 300 m, preferably from 5 to 150 m.
  • the organic solvent soluble fluororesin (a) may be TFEZHFP / VdF copolymer (THV-200P manufactured by Sumitomo Corporation, Ltd. Fluorine content: 69% by weight, refractive index: 1.36, crystal melting point: 124 ° C, glass transition point: 144 ° (:, melt-in-one index) (MFI. 2 65 ° C, 5 kgf cm 2 layers): 15 to 25) Replace 100 parts with methyl ethyl ketone (MEK) and metal Fluoride (m XH 1
  • an organic metal compound containing a caro water-decomposable group is represented by the following formula (2):
  • test painted plate is installed on the roof of a three-story building under Osaka Prefecture so that it has an angle of 30 degrees on the horizontal and south sides. Measure the contact angle with water after 14 days
  • test painted plate was fixed on a vertical wall on the 3rd floor rooftop of a building in Osaka Prefecture, and after exposure for 12 power months, the three properties of the bridge were examined. .
  • the exposed coated plate is visually observed and evaluated according to the following criteria. ⁇ : Rain streaks are almost non-contaminated, and no contaminants are spreading. ⁇ : Rain streaks are found in only a small part, but the dirt is not diffused.
  • the test painted plate shall be installed on the roof of a three-story building under Osaka Prefecture so that it has an angle of 30 degrees on the horizontal and south sides. Exposure for 12 months, lightness difference, visual appearance, and contact angle with water are examined in the same manner as in the vertical exposure test.
  • carbon black As a carbon contamination standard material, carbon black (MA-100, manufactured by Mitsubishi Chemical Co., Ltd.) should be 8% concentrated in water. After spraying this standard carbon-stained aqueous dispersion onto the test piece, use an aqueous dispersion dispersed in a hot air dryer at 60 ° C. For 4 hours, and forcibly attach the carbon. After that, it is washed with running brush in running water, and the lightness difference before and after washing and the remaining degree of carbon after washing are examined.
  • MA-100 manufactured by Mitsubishi Chemical Co., Ltd.
  • test specimen is visually evaluated according to the following criteria. ⁇ : Carbon dirt has been almost completely removed just by washing with running water.
  • test piece prepared in the carbon removal test (exposed for 14 days at 30 degrees south and washed with water and air-dried), the surface of the test piece was JISK5400 Apply a red marker (Magic Ink, manufactured by Uchida Yoko Co., Ltd.) on a 3 cm square according to the above method, and leave it at 60 X for 24 hours. After drying, wipe lightly 10 times with a cloth (gauze) soaked with ethanol to remove ink residue. Is visually observed, and the following criteria are used. evaluate .
  • red marker Magnetic Ink, manufactured by Uchida Yoko Co., Ltd.
  • the coating composition of the present invention was prepared in the same manner as in Example 1 except that the components shown in Table 1 were used in the amounts shown in the same table (in all Examples). And 2 PHR of Biosorb 130, manufactured by Kyodo Pharmaceutical Co., Ltd., was used as an ultraviolet absorber.) Then, each of the compositions was applied to a chemically treated aluminum plate (those subjected to the same undercoating treatment as in Example 1) in the same manner as in Example 1 and provided. A test plate was prepared. In the same manner as in Example 1, the test coated plate was subjected to a coating film hydrophilicity test, a stain adhesion prevention property, and a stain removal property. Table 2 shows the results.
  • thermoplastic acrylyl resin (Paraloid B-44 manufactured by Nippon Kayaku & Zose Co., Ltd.) 90 Z10 (solid content) mixed resin of polyethylene acrylate (70 Z30 mol%) copolymer
  • a compound having CH 2 C 2 F 5 and a CH 2 C 2 F 5 / CH 3 ratio of 0.5 A compound having CH 2 C 2 F 5 and a CH 2 C 2 F 5 / CH 3 ratio of 0.5.
  • a compound having CH 2 C 2 F 5 and a CH 2 C 2 F 5 ZCH 3 ratio of 0.7 A compound having CH 2 C 2 F 5 and a CH 2 C 2 F 5 ZCH 3 ratio of 0.7.
  • E A compound in which in Formula (3), p is 4, R force SCH and CH 2 CF 2 CFHCF 3 , and the ratio of CH.CF, CFHCF CH 3 is 05.
  • G a compound in which p is 20 and R is CH in the formula (3).
  • Hydrophilization catalyst Hydrophilization catalyst
  • Arremixate D Aluminate compound manufactured by Kawaken Fine Chemicals Co., Ltd.
  • R is CH 3 and C 2 H 4 (CF 2 ) 7 CF 3 , and C 2 H 4 (CF 2 ) 7 CF A compound having a 3 / CH 3 ratio of 0-5.
  • Example 3 Except that the components shown in Table 3 were used in the amounts shown in the same table, the coated composition of the present invention was prepared in the same manner as in Example 1 (all of the practical applications).
  • Biosorb 130 manufactured by Kyodo Pharmaceutical Co., Ltd. was used as an ultraviolet ray absorbent and 2 PHR was combined).
  • each of the compositions was applied to a chemically treated aluminum plate (which had been subjected to the same undercoat treatment as in Example 1) in the same manner as in Example 1 and provided.
  • a trial coating plate was made.
  • the test coated plate was subjected to a coating film lyophilicity test, a stain-preventing property and a stain-removing property. The results are shown in Table 4.
  • Table 3 Table 3
  • Example 5 Except that the components shown in Table 5 were used in the amounts shown in the same table, the coated compositions of the present invention were prepared in the same manner as in Example 1 (all the examples were used).
  • a UV absorber Kyodo Pharmaceutical Co., Ltd./Diosop 130 was combined with 2 PHR).
  • each of the compositions was applied to a chemically treated aluminum plate (which had been subjected to the same undercoat treatment as in Example 1) in the same manner as in Example 1 and subjected to the test.
  • a painted board was made.
  • the coating film was subjected to the water-philicity test, the contamination-preventing property and the stain-removing property in the same manner as in Example 1. Table 6 shows the results. Table 5
  • Example 7 Except that the components shown in Table 7 were used in the amounts shown in the same table, the coated compositions of the present invention were prepared in the same manner as in Example 1 (all Examples). In this case, 2 PHR was blended with Kyodo Pharmaceutical Co., Ltd.'s noisysosorb 130 as an ultraviolet ray absorbent.) Then, each composition was coated on a chemically treated aluminum plate (the same undercoating treatment as in Example 1) as in Example 1. Then, a test coated plate was prepared. Using this test coated plate, the coating film hydrophilicity test, the anti-staining and anti-staining properties, and the anti-staining property were examined in the same manner as in Example 1. Table 8 shows the results. Table 7
  • the coating composition of the present invention was prepared in the same manner as in Example 1 except that the components shown in Table 9 were used in the amounts shown in the table (all Examples).
  • Noobsorb 130 manufactured by Kyodo Pharmaceutical Co., Ltd. was combined with 2 PHR as an ultraviolet absorber.
  • each of the compositions was applied to a chemically treated aluminum plate (those subjected to the same undercoating treatment as in Example 1) in the same manner as in Example 1 and provided.
  • a trial coating plate was made. Using this test coated plate, the coating film hydrophilicity test, the contamination-preventing property and the stain-removing property were examined in the same manner as in Example 1. The results are shown in Table 10.
  • the coated composition of the present invention was prepared in the same manner as in Example 1 (all the components were used).
  • a UV absorbing agent BioPharm 130 (manufactured by Kyodo Pharmaceutical Co., Ltd.) was combined with 2 PHR).
  • each of the compositions was applied to a chemically treated aluminum plate (which had been subjected to the same undercoating treatment as in Example 1) in the same manner as in Example 1 and provided.
  • a trial coating plate was made.
  • the test coated plate was tested for the coating film hydrophilicity test, the anti-fouling property and the stain removal property. The results are shown in Table 12.
  • Example Coating film hydrophilicity Prevention of contamination adhesion Prevention of contamination No. of contact angle with water (degree) Vertical exposure test 30 degree exposure test on the south side Angle (degrees) Lightness difference visual appearance Lightness difference visual appearance Visual appearance
  • the coating composition of the present invention was prepared in the same manner as in Example 1 except that the components shown in Table 13 were used in the amounts shown in the same table (all the compositions were used).
  • 2 PHR was combined with Noysorb 130 manufactured by Kyodo Yakuhin Co., Ltd. as an ultraviolet absorber.
  • each composition was applied to a chemically treated aluminum plate (those subjected to the same undercoating treatment as in Example 1) in the same manner as in Example 1, and the test coated plate was applied. It was made.
  • the test coated plate was subjected to the coating film hydrophilicity test, to prevent contamination and adherence, and to remove the contamination. The results are shown in Table 14.
  • Example Solvent-soluble organometallic compound Hydrophilization catalyst surface conditioner No. Fluororesin Type Amount (PHR) Amount (PHR) Amount (PHR)
  • the coating composition of the present invention was prepared in the same manner as in Example 1 except that the components shown in Table 15 were used in the amounts shown in the same table.
  • 2 PHR was combined with Noysorb 130 manufactured by Kyodo Yakuhin Co., Ltd. as an ultraviolet absorber.
  • each of the compositions was applied to a chemically treated aluminum plate (which had been subjected to the same undercoating treatment as in Example 1) in the same manner as in Example 1.
  • a test coated plate was prepared. In the same manner as in Example 1, the test coating plate was tested for the coating water lyophilicity test, the stain adhesion prevention property, and the stain removal property. The results are shown in Table 16.
  • Example Solvent-soluble organometallic compound Hydrophilic catalyst surface conditioner No. Fluororesin Type Amount (PHR) Amount (PHR) Amount (PHR)
  • the coating composition of the present invention was prepared in the same manner as in Example 1 except that the components shown in Table 17 were used in the amounts shown in the same table (all of the working examples).
  • a UV absorber Kyodo Pharmaceutical Co., Ltd. was combined with 2 PHR of noisysosorb 130).
  • each of the compositions was applied to a chemically treated aluminum plate (which had been subjected to the same undercoating treatment as in Example 1) in the same manner as in Example 1 and provided.
  • a trial coating plate was made. Using this test coated plate, the coating film hydrophilicity test, the anti-staining and anti-staining properties, and the anti-staining property were examined in the same manner as in Example 1. The results are shown in Table 18. Table 17
  • a coating composition for comparison was prepared in the same manner as in Example 1 except that the components shown in Table 19 were used in the amounts shown in the same table. Then, the composition for each comparison was treated with a chemically treated aluminum plate in the same manner as in Example 1 (the same undercoating treatment as in Example 1). ) To produce a test painted board. In the same manner as in Example 1, the test coating plate was subjected to a coating film hydrophilicity test, a stain-preventing property and a stain-removing property. The results are shown in Table 20. Table 19
  • the fluororesin composition obtained above was applied on a glass plate in a 30-mil film applique overnight, and after curing at room temperature for 2 hours. Then, the film was heated and dried at 60 for 5 hours to prepare a cast film (dry film thickness: about 50 m) for testing.
  • This film was tested for its hydrophilicity, anti-contamination adhesion (vertical wall exposure test), and contaminant removal (carbon removal).
  • the light transmittance, mechanical properties (tensile strength and elongation), and heat resistance (color difference) were measured by the following methods. The results are shown in Table 22.
  • the light transmittance (550 nm) of a film with a thickness of 50 n is measured with a spectrophotometer.
  • a tensile tester (Tensilon UCT-500) manufactured by Orientec Co., Ltd. is used.
  • the test speed is 100 mm / min according to JISK540. Check the breaking strength and breaking extension.
  • the compound shown in Table 21 as a water-decomposable group-containing organic metal compound was subjected to 7 PHR addition D and mixed. Then, the fluorine resin composition of the present invention was prepared, and a film was further prepared. In the same manner as in Example 12 1, this film was subjected to a coating film lyophilicity test, anti-contamination adhesion prevention, decontamination removal, light transmission, and mechanical properties. The characteristics and heat resistance were examined. The results are shown in Table 22.
  • Example 14 45 to 15 2 Organic Solvent Soluble Fluorocarbon Resin (e) as Polyvinylidene Fluoride (Elfatochem Co., Ltd.) ) And Thermoplastic Acrylic Resin (Paraloy B-44, manufactured by ROHM & NO., INC.). Dimethyl acetate amide (DMA) of mixed resin of 90 Z10 (solid content) of ethyl acrylate (70 Z30 mol%) copolymer ) Using the solution (concentration 25%), add the compound shown in Table 23 as an organic metal compound containing a water-decomposable group and add 7 PHR to the mixture, and mix.
  • DMA Dimethyl acetate amide
  • Example 12 1 in the same manner as in Example 12 1 (however, in Examples 15 1 and 15 2, the water-splitting catalyst (Kawaken Fineke) was also used. Almikilet D) manufactured by Mikaru Co., Ltd.
  • the PHR-combined fluororesin composition of the present invention was prepared, and the fluororesin composition obtained as described above was prepared on a glass plate by 3%. 0 Apply it overnight to the Milli-Rem appliqué, cure for 2 hours at room temperature, heat and dry at 80 ° C for 3 hours, and use it for testing. A film (dry film thickness about 50 m) was produced. .
  • Example 12-21 In the same manner as in Example 12-21, this film was subjected to a coating film lyophilicity test, contamination adhesion prevention, stain removal, light transmittance, mechanical properties, and mechanical properties.
  • the heat resistance (however, left in a hot air circulating drier at 130 ° C for 2 weeks) was examined, and the results are shown in Table 24.
  • Example Coating film hydrophilicity Stain adhesion preventing property Stain removal property Light transmittance (%) Mechanical property Heat resistance Contact angle to water (degree) (Carbon removal) (550 nm) Tensile strength Elongation (color difference) Contact angle to water (degree) Lightness difference Visual appearance Lightness difference Visual appearance (MPa) (%) ( ⁇ )
  • the organic solvent soluble fluororesin (el) is polyvinylidene fluoride (Kinner 500 manufactured by Elphachem) and Thermoplastic Acrylic Resin (PARAROID B144, manufactured by ROHM & Haas Co., Ltd.) 70/30 mol%) 90/10 (solid content) of copolymer) 45% of resin mixed with isophorone, containing water-decomposable groups
  • the compounds shown in Table 25 were mixed with 7 PHR as the metallurgical compounds except that they were mixed in the same manner as in Example 12 1 (however, in Example 1). In 159 and 160, the hydrolysis catalyst was further combined with 0.7 PHR.)
  • the fluororesin composition of the present invention was prepared.
  • the isophorone solution of the synthetic resin is obtained by dissolving a thermoplastic acrylic resin in isophorone and then removing the polyvinylidene fluoride. In addition, it was prepared by dispersing and dispersing it with a homodisperse (manufactured by Tokushu Kika Kogyo Co., Ltd.).
  • the fluororesin composition obtained above was further subjected to a dissolving force of about 40 with a Fed cup viscosity (Cup No. 4). Diluted to the second.
  • the diluted solution is spray-coated on a glass plate and dried in a hot-air circulating drier at 230 ° C for 3 minutes.
  • a film (dry film thickness of about 50 / m) was prepared.
  • this film was subjected to a coating water-philicity test, a stain-proofing property, a stain removal property, a light transmittance, a mechanical characteristic, and the like. The heat resistance and heat resistance were examined. The results are shown in Table 26. Table 25
  • Example 16 1 to 1668 Organic solvent-soluble fluororesin (f) as vinylidene fluoride / ⁇ F ⁇ copolymer (gel fat) 5 L of Chem Co., Ltd.) was adjusted to a concentration of 30% with a mixed solvent of ⁇ -anone (8/2) to contain a water-decomposable group.
  • the compounds listed in Table 27 as organic metal compounds were added with 7 PHR of calorific value, and the relative concentrations were the same as in Example 12 1 (however, In Examples 1667 and 1688, the additional water-splitting catalyst was
  • the fluorinated resin composition of the present invention was prepared, and the fluorinated resin composition obtained above was prepared on a glass plate. 30 mil film precoat Apply in the evening, cure at room temperature for 2 hours, heat and dry at 80 t: for 3 hours, and use for testing. A just film (dry film thickness of about 50 m) was prepared. . In the same manner as in Example 12-1, the film was subjected to a coating film hydrophilicity test, anti-fouling property, stain removal property, light transmittance, mechanical properties, and mechanical properties. The heat resistance was examined. The results are shown in Table 28. Table 27
  • Example 16 9 to 1776 As an organic solvent and soluble fluororesin (g), polyvinyl fluoride (Tedlar manufactured by Dupont) was used as the organic solvent. Was adjusted to a concentration of 25% with a mixed solvent of DMA / Mexilene and a water-decomposable group. The compounds shown in Table 29 as the metal compounds were mixed with 7 PHR added in the same manner as in Example 12-21 (however, in Example 1). At 75 and 1 76, the hydrolyzation catalyst was further combined with 0.7 PHR.) The fluororesin composition of the present invention was prepared, and the glass plate was prepared.
  • Tedlar manufactured by Dupont polyvinyl fluoride
  • Example Coating film hydrophilicity Stain adhesion prevention Stain removal Light transmittance ⁇ ) Mechanical properties Heat resistance Contact angle to water (degree) (Vertical exposure test) (Carbon removal property) (550 nm) Tensile strength Elongation (Color difference) Water contact angle (degrees) Brightness difference Visual appearance Visual appearance (MPa) (%) ( ⁇ )
  • Examples 1 2 1 using organic solvent and soluble fluororesin (a)) and 129 (using organic solvent and soluble fluororesin) (B) Use) and 133 (use of organic solvent and soluble fluororesin (c)) both contain water-decomposable groups and organic metal compounds.
  • the film was made in the same manner, and the film was subjected to the lyophilicity test and stain adhesion in the same manner as in Example 12-1. The protection, contamination removal, light transmittance, mechanical properties and heat resistance were examined. The results are shown in Table 32.
  • a general-purpose fluorine resin composition 1 (Fluoronet K-170 (Dainippon Ink Chemicals, Ltd.) ) was adjusted to a concentration of 40% with xylene, and as a hardener, colonotone HX (manufactured by Nippon Polyurethane Co., Ltd.) was added in a predetermined amount. ), And the above-mentioned compound G was added as a hydrolyzable group-containing organic metal compound to the PHR by 7 PHR, and further, a hydrophilization catalyst (Alumi-kyle) was added.
  • Example 12-21 a fluororesin composition for comparison was prepared in the same manner as in Example 12 1, and the mixture was further treated with 0.7 PHR. Room made. This film was placed in a thermo-hygrostat (35 ° C x 95% RH) to make the surface hydrophilic.
  • the obtained hydrophilized film was subjected to the coating film hydrophilicity test, antifouling prevention, antifouling removal, light transmission, and mechanical properties in the same manner as in Example 12 1. The properties and heat resistance were examined. The results are shown in Table 32.
  • the fluororesin composition was a general-purpose fluororesin composition 2 (Lumifron LF-200 (Asahi Glass Co., Ltd.) Was adjusted to a concentration of 40% with xylene, and as a hardening agent, Colonet HX (manufactured by Nippon Polyurethane Co., Ltd.) was added in a prescribed amount.
  • a fluororesin composition for comparison was prepared, and a film was made and hydrophilized. .
  • the lyophilic film is treated in the same manner as in Example 12 1 in the same manner as in Example 12 1, for the lyophilicity test of the coating film, the anti-staining property, the removal of the stain, and the light transmission. The ratio, mechanical properties and heat resistance were examined. The results are shown in Table 32.
  • Example 31 there are three types of high water-phobic hydrofluoric resin films that are commercially available:!
  • the coating film was subjected to a hydrophilicity test, anti-fouling property, stain-removing property, light transmittance, and mechanical properties. And heat resistance.
  • the results are shown in Table 32.
  • Highly water-hydrophobic fluororesin film 1 TFEPAVE copolymer (neoplon PFA manufactured by Daikin Industries, Ltd., thickness: 50 ⁇ m). The same hydrophilization treatment as in Comparative Example 8 was performed.
  • TFEZHFP copolymer (Neofluoron FEP manufactured by Daikin Industries, Ltd., thickness 50 / m)
  • Highly hydrophobic fluorine resin film 3 Ethylene ZTFE copolymer (Neoflon ETFE manufactured by Daikin Industries, Ltd., 50 m thick)
  • Examples 14 45 using an organic solvent soluble fluororesin (e)) and 15 3 (organic solvent-soluble fluororesin (e1)) ), 161 (use of organic solvent soluble fluororesin (f)) and 169 (use of organic solvent soluble fluorine)
  • resin (g) the organic metal compound containing a water-decomposable group was not added, as in these examples. Then, a film was produced, and in the same manner as in Example 12-21, the hydrophilicity test of the coating film, anti-adhesion property, stain removal property, light transmittance, mechanical The characteristics and heat resistance were examined. The results are shown in Table 32.
  • a film can be formed at a low temperature (below 270 ° C., preferably 180 ° C. or less), and a film can be obtained. Further, it is possible to provide a fluororesin composition capable of easily making the surface of the film hydrophilic.

Abstract

L'invention se rapporte à une composition de fluororésine susceptible de former un film à basse température. Ladite composition comprend une fluororésine qui est soluble ou dispersible dans des solvants organiques et possède au moins l'une des caractéristiques suivantes: contenir une quantité de fluor supérieure ou égale à 5 % en poids, posséder un indice de réfraction inférieur à 1,4, posséder un point de fusion cristallin compris entre 100 et 180 °C, être un polymère amorphe doté d'un point de transition vitreuse compris entre 70 et 250 °C, posséder une structure cyclique et comporter 10 à 50 % en moles d'unités de tétrafluoroéthylène, 0 à 50 % en moles d'unités d'hexafluoropropylène et 90 à 10 % en moles d'unités de fluorure de vinylidène. Ladite composition comporte également un composé organométallique ayant un groupe hydrolysable et un solvant organique. Cette composition de fluororésine est susceptible de former un film à basses températures (inférieures ou égales à 270 °C, de préférence inférieures ou égales à 180°C), le film ainsi obtenu possédant une surface facilement hydrolysable.
PCT/JP2000/005781 1999-09-13 2000-08-28 Composition de fluororesine susceptible de former un film a basse temperature WO2001019913A1 (fr)

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WO2006077751A1 (fr) * 2005-01-19 2006-07-27 Daikin Industries, Ltd. Composition de revêtement faiblement teintant et film de revêtement faiblement teintant produit à partir de celle-ci

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JP6278599B2 (ja) 2010-12-03 2018-02-14 旭硝子株式会社 電荷保持媒体の製造方法
TW201410451A (zh) * 2012-08-09 2014-03-16 Asahi Glass Co Ltd 玻璃板氟樹脂積層體
KR102500397B1 (ko) * 2014-12-19 2023-02-15 메르크 파텐트 게엠베하 불소 화합물
JP6776508B2 (ja) * 2015-04-23 2020-10-28 ダイキン工業株式会社 コーティング組成物
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