WO2023195375A1 - Method for producing fluorine-containing polymer, fluorine-containing polymer, coating material, and substrate equipped with coating film - Google Patents

Method for producing fluorine-containing polymer, fluorine-containing polymer, coating material, and substrate equipped with coating film Download PDF

Info

Publication number
WO2023195375A1
WO2023195375A1 PCT/JP2023/012295 JP2023012295W WO2023195375A1 WO 2023195375 A1 WO2023195375 A1 WO 2023195375A1 JP 2023012295 W JP2023012295 W JP 2023012295W WO 2023195375 A1 WO2023195375 A1 WO 2023195375A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
fluoropolymer
fluorine
monomer
containing polymer
Prior art date
Application number
PCT/JP2023/012295
Other languages
French (fr)
Japanese (ja)
Inventor
祐亮 佐橋
直子 鷲見
修平 尾知
聡 大継
祐二 原
Original Assignee
Ａｇｃ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Publication of WO2023195375A1 publication Critical patent/WO2023195375A1/en

Links

Classifications

    • 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
    • C08F2/00—Processes of polymerisation
    • 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
    • C08F214/00—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 a halogen
    • C08F214/18—Monomers containing fluorine
    • 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

Definitions

  • the present invention relates to a method for producing a fluoropolymer, a fluoropolymer, a paint, and a substrate with a coated film.
  • Patent Document 1 discloses a method of using xylene as a polymerization solvent during the production of a fluoropolymer used in a paint.
  • the present invention was made in view of the above problems, and an object of the present invention is to provide a method for producing a fluoropolymer that can form a coating film with excellent weather resistance, a fluoropolymer, a paint, and a substrate with a coating film.
  • the reactive group is at least one group selected from the group consisting of a hydroxyl group, an amino group, an epoxy group, an oxetanyl group, a hydrolyzable silyl group, a sulfo group, and a carboxy group, [1 ] to [3].
  • a paint characterized by containing the fluoropolymer described in [5].
  • a base material with a coating film comprising a base material and a coating film formed from the coating material according to [6], which is disposed on the base material.
  • the present invention it is possible to provide a method for producing a fluoropolymer that can form a coating film with excellent weather resistance, a fluoropolymer, a paint, and a substrate with a coating film.
  • a numerical range expressed using " ⁇ " means a range that includes the numerical values written before and after " ⁇ " as lower and upper limits.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the value shown in the Examples.
  • one type of substance corresponding to each component may be used alone, or two or more types may be used in combination.
  • the content of the component refers to the total content of the substances used in combination, unless otherwise specified.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • the unit is a general term for an atomic group based on one molecule of the above-mentioned monomer, which is directly formed by polymerization of monomers, and an atomic group obtained by chemically converting a part of the above-mentioned atomic group.
  • the content (mol%) of each unit relative to the total units contained in the polymer is determined by analyzing the polymer by nuclear magnetic resonance spectroscopy, and can also be determined from the amount of ingredients used in the production of the polymer. .
  • (Meth)acrylic is a generic term for "acrylic” and “methacrylic”
  • (meth)acrylate is a generic term for "acrylate” and “methacrylate”.
  • a hydrolyzable silyl group means a group that can undergo a hydrolysis reaction to form a silanol group.
  • the acid value and hydroxyl value are values measured according to the method of JIS K 0070-3 (1992), respectively.
  • Glass transition temperature (Tg) is the midpoint glass transition temperature of a polymer as measured by differential scanning calorimetry (DSC).
  • the number average molecular weight (Mn) is a value measured by size exclusion chromatography (gel permeation chromatography) using polystyrene as a standard substance.
  • the method for producing a fluoropolymer of the present invention uses at least one organic solvent selected from the group consisting of methyl ethyl ketone, acetone, n-butyl acetate, and tetrahydrofuran.
  • the fluoropolymer obtained by this production method can form a coating film with excellent weather resistance.
  • a solvent hereinafter also referred to as a polymerization solvent
  • ultraviolet rays originating from the polymerization solvent may be absorbed.
  • a structure that is easy to use is introduced into a fluoropolymer.
  • xylene is used as a polymerization solvent
  • a trace amount of benzene rings or the like may be introduced into the fluoropolymer.
  • a specific organic solvent is used as a polymerization solvent, so that structures that are derived from the polymerization solvent and that reduce weather resistance are difficult to be introduced into the fluoropolymer. It is presumed that this improved the weather resistance of the coating film obtained using the fluoropolymer.
  • the specific organic solvent is used as a polymerization solvent in this production method.
  • the specific organic solvent is at least one organic solvent selected from the group consisting of methyl ethyl ketone, acetone, n-butyl acetate, and tetrahydrofuran, and from the viewpoint that the effects of the present invention are more excellent, methyl ethyl ketone, acetone, and acetic acid are preferred.
  • it is at least one organic solvent selected from the group consisting of n-butyl.
  • Two or more specific organic solvents may be used in combination.
  • the amount of the specific organic solvent used is preferably 1 to 60 parts by weight, more preferably 30 to 50 parts by weight, based on 100 parts by weight of the total amount of monomers used for producing the fluoropolymer.
  • organic solvents other than the specific organic solvents may be used, but in view of the superior effects of the present invention, other organic solvents are not substantially used. It is preferable. "Substantially no other organic solvents are used” means that the amount of other organic solvents used is 1 part by mass or less per 100 parts by mass of the total mass of monomers used in the production of the fluoropolymer. means. Specific examples of other organic solvents include xylene, toluene, and ethylbenzene.
  • the polymerization of each monomer in this production method is carried out in the absence of vinyl ester. Therefore, the fluoropolymer obtained by this production method does not have units based on vinyl ester.
  • vinyl esters include vinyl acetate, vinyl pivalate, vinyl neononanoate (HEXION brand name: Beova 9), vinyl neodecanoate (HEXION brand name: Beova 10), vinyl versatate, vinyl benzoate, tert-butyl Examples include vinyl benzoate.
  • the amount of monomer a11 to be charged is preferably 20 to 70 mol%, and 30 to 60 mol%, based on the total amount of monomers used for producing the fluoropolymer, in order to obtain better effects of the present invention. % is more preferable, and 45 to 55 mol% is even more preferable.
  • Vinyl ether (hereinafter also referred to as monomer a12) that does not have a fluorine atom or a reactive group is used as a monomer for producing a fluoropolymer.
  • monomer a12 include ethyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, and cyclohexylmethyl vinyl ether.
  • the amount of monomer a12 to be charged is preferably 5 to 60 mol%, and 10 to 50 mol%, based on the total amount of monomers used for producing the fluoropolymer, in order to obtain better effects of the present invention. % is more preferable.
  • a monomer having a reactive group (hereinafter also referred to as monomer a13) is used as a monomer for producing a fluoropolymer.
  • the reactive group examples include at least one group selected from the group consisting of a hydroxyl group, an amino group, an epoxy group, an oxetanyl group, a hydrolyzable silyl group, a sulfo group, and a carboxy group.
  • the sulfo group and the carboxy group may be ionized to become -SO 3 - or -COO - , or may be chlorinated to become -SO 3 - Na + or -COO - Na + or the like.
  • the monomer a13 preferably has a hydroxyl group or a carboxy group as a reactive group, and more preferably has a hydroxyl group, since the strength of the coating film obtained using the fluoropolymer is more excellent.
  • Examples of the monomer a13 having a hydroxyl group include vinyl ether, allyl ether, allyl ester, (meth)acrylic acid ester, allyl alcohol, etc. each having a hydroxyl group.
  • As the monomer a13 having a hydroxyl group hydroxy vinyl ether or hydroxy allyl ether is preferable.
  • a monomer represented by the formula X 1 -Z 1 is preferable.
  • Z 1 is a monovalent organic group having 2 to 42 carbon atoms and having a hydroxyl group.
  • the organic group may be linear or branched. Further, the organic group may have a ring structure or may include a ring structure.
  • the organic group is preferably an alkyl group having 2 to 6 carbon atoms having a hydroxyl group, an alkyl group having a cycloalkylene group having 6 to 8 carbon atoms having a hydroxyl group, or a polyoxyalkylene group having a hydroxyl group.
  • _ _ Note that "-cycloC 6 H 10 -" represents a cyclohexylene group, and the bonding site of "-cycloC 6 H 10 -" is usually 1,4-.
  • Examples of the monomer a13 having a carboxy group include unsaturated carboxylic acids, (meth)acrylic acid, and monomers obtained by reacting the hydroxyl group of the above-mentioned hydroxyl group-containing monomer with a carboxylic acid anhydride. .
  • the amount of monomer a13 to be charged is preferably 0.1 to 45 mol%, and 1 to 45 mol%, based on the total amount of monomers used for producing the fluoropolymer, in order to obtain better effects of the present invention. It is more preferably 30 mol%, and even more preferably 5 to 20 mol%.
  • monomers other than monomer a11, monomer a12, and monomer a13 may be used, but the effects of the present invention may be In terms of superiority, it is preferable to use only monomer a11, monomer a12, and monomer a13.
  • each monomer may be set as appropriate. Each monomer may be added all at once or divided into parts and added continuously.
  • radical polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobiscyclohexane carbonate nitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), , 2'-azobis(2-methylbutyronitrile); ketone peroxides (e.g. cyclohexanone peroxide), hydroperoxides (e.g. tert-butyl hydroperoxide), diacyl peroxides (e.g. , benzoyl peroxide), dialkyl peroxides (e.g.
  • di-tert-butyl peroxide di-tert-butyl peroxide
  • peroxyketals e.g. 2,2-di-(tert-butylperoxy)butane
  • alkyl peroxy esters e.g. Examples include peroxide-based initiators such as tert-butyl peroxypivalate).
  • conventionally known components used in the production of fluoropolymer may be used.
  • other components include chain transfer agents, polymerization inhibitors (hydroquinone monomethyl ether, etc.), stabilizers (bis(1,2,2,6,6-pentamethyl-4-piperidyl) sepacate, methyl 1,2 , 2,6,6-pentamethyl-4-piperidyl sepacate, etc.), and acid acceptors (potassium carbonate, hydrotalcite, etc.).
  • the polymerization form of the fluoropolymer in this production method is preferably solution polymerization in which each monomer is dissolved in a specific organic solvent.
  • the polymerization conditions may be set as appropriate; for example, the polymerization temperature is usually 50 to 90°C, and the polymerization time is usually 3 to 50 hours.
  • the fluoropolymer obtained by this production method does not have a unit based on vinyl ester, but has a unit based on monomer a11, a unit based on monomer a12, and a unit based on monomer a13. It is a polymer and is preferably a copolymer consisting of a unit based on monomer a11, a unit based on monomer a12, and a unit based on monomer a13, since the effects of the present invention are more excellent. .
  • the fluorine-containing polymer of the present invention (hereinafter also referred to as the present fluorine-containing polymer) has a fluorine-containing unit based on the above-mentioned monomer a11 (hereinafter also referred to as unit A11), and a fluorine-containing unit based on the above-mentioned monomer a12. (hereinafter also referred to as unit A12) and a unit based on the above-mentioned monomer a13 (hereinafter also referred to as unit A13), and does not have a vinyl ester-based unit. It is a polymer.
  • the light transmittance of the film obtained using the present fluoropolymer in the wavelength range of 260 nm to 300 nm is 50% or more when the film thickness is 40 ⁇ m.
  • the present fluorine-containing polymer is preferably a fluorine-containing polymer obtained by the present production method described above, since it is easy to obtain a fluorine-containing polymer that satisfies the above-mentioned light transmittance when formed into a film. .
  • This fluoropolymer can form a coating film with excellent weather resistance. Although the details of this reason are not necessarily clear, it is thought to be as follows.
  • a film obtained using the present fluoropolymer has high light transmittance in a specific wavelength range (wavelength range of 260 nm to 300 nm). As a result, the film obtained using the fluoropolymer becomes less susceptible to the effects of light in a specific wavelength range, so it is presumed that the weather resistance of the film itself obtained using the fluoropolymer is improved.
  • the unit A11 is a fluorine-based unit based on the monomer a11.
  • Monomer a11 is the same as monomer a11 in the above-mentioned method for producing a fluoropolymer, so its explanation will be omitted. Two or more types of monomer a11 may be used in combination.
  • the content of unit A11 is preferably 20 to 70 mol%, based on the total units contained in the fluoropolymer, and 30 to 70% by mole, since the weather resistance of the film obtained using the fluoropolymer is better. More preferably 60 mol%, and even more preferably 45 to 55 mol%.
  • the unit A12 is a non-fluorine unit based on the monomer a12.
  • Monomer a12 is the same as monomer a12 in the above-mentioned method for producing a fluoropolymer, so its explanation will be omitted. Two or more types of monomer a12 may be used in combination.
  • the content of the unit A12 is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, based on the total units contained in the present fluoropolymer.
  • Unit A13 is a unit based on monomer a13.
  • Monomer a13 is the same as monomer a13 in the above-mentioned method for producing a fluoropolymer, so its explanation will be omitted. Two or more types of monomer a13 may be used in combination.
  • the content of the unit A13 is preferably 0.1 to 45 mol%, more preferably 1 to 30 mol%, and even more preferably 5 to 20 mol%, based on the total units contained in the present fluoropolymer.
  • This fluoropolymer does not have units based on vinyl ester.
  • Specific examples of the vinyl ester are the same as those mentioned in the above-mentioned method for producing a fluoropolymer, so the explanation thereof will be omitted.
  • the present fluoropolymer is preferably composed of units A11, A12, and A13 from the viewpoint of forming a coating film with better weather resistance.
  • the Tg of the present fluoropolymer is preferably 0 to 120°C, more preferably 10 to 70°C, from the viewpoint of scratch resistance.
  • the Mn of the present fluoropolymer is preferably 3,000 to 50,000, more preferably 5,000 to 30,000, and even more preferably 10,000 to 20,000 from the viewpoint of film formability and weather resistance.
  • the hydroxyl value of the specific fluoropolymer is preferably 1 to 200 mgKOH/g, more preferably 5 to 100 mgKOH/g, and more preferably 40 to 60 mgKOH/g. More preferred.
  • the acid value of the specific fluoropolymer is preferably 1 to 30 mgKOH/g, more preferably 1 to 10 mgKOH/g.
  • the light transmittance of the film obtained using the present fluoropolymer in the wavelength range of 260 nm to 300 nm is 50% or more when the film thickness is 40 ⁇ m.
  • the upper limit of the above light transmittance is usually 100%.
  • the value of the light transmittance being X% or more means that when the transmittance is calculated every 0.5 nm in the wavelength range of 260 nm to 300 nm, the transmittance at each wavelength is also means that it is X% or more.
  • the detailed method for measuring the light transmittance is as described in the Examples section below.
  • the paint of the present invention (hereinafter also referred to as the present paint) contains the above-mentioned present fluoropolymer.
  • the content of the present fluoropolymer is preferably 5 to 100% by mass, more preferably 30 to 100% by mass, and even more preferably 40 to 100% by mass, based on the total mass of the coating material.
  • the paint may contain components other than the fluoropolymer.
  • additives include curing agents, curing catalysts, non-fluorinated polymers ((meth)acrylic resins, urethane resins, epoxy resins, polyester resins, silicone resins, etc.), colorants (dyes, organic pigments, inorganic pigments, metals, or mica). bright pigments, etc.), ultraviolet absorbers, light stabilizers, matting agents, leveling agents, surface conditioners, degassing agents, fillers, heat stabilizers, thickeners, dispersants, surfactants, electrostatic charges
  • Examples include inhibitors, rust preventives, silane coupling agents, antifouling agents, antifouling agents, plasticizers, adhesives, and the like.
  • the paint preferably contains a curing agent from the viewpoint of the durability (water resistance, chemical resistance, weather resistance, etc.) of the coating film.
  • the curing agent preferably has two or more, more preferably 2 to 30, reactive groups in one molecule that can react with the reactive groups contained in the present fluoropolymer.
  • the fluoropolymer has a reactive group
  • the reactive group of the curing agent and the reactive group of the fluoropolymer react, the fluoropolymer is crosslinked by the curing agent, resulting in crosslinking. A fluoropolymer is formed.
  • reactive groups possessed by the curing agent include isocyanate groups, blocked isocyanate groups, epoxy groups, oxazoline groups, and ⁇ -hydroxyalkylamide groups.
  • the reactive group of the fluoropolymer is a hydroxy group
  • the reactive group of the curing agent is preferably an isocyanate group or a blocked isocyanate group.
  • the curing agent is preferably a polyisocyanate having two or more isocyanate groups or blocked isocyanate groups in one molecule.
  • polyisocyanate polyisocyanate monomers and polyisocyanate derivatives are preferred.
  • polyisocyanate monomer alicyclic polyisocyanates, aliphatic polyisocyanates, and aromatic polyisocyanates are preferred.
  • the polyisocyanate derivative is preferably a multimer or modified polyisocyanate monomer (adduct, allophanate, biuret, isocyanurate, etc.).
  • aliphatic polyisocyanates include aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-diisocyanatohexane, lysine diisocyanate, and lysine triisocyanate. , 4-isocyanatomethyl-1,8-octamethylene diisocyanate, and bis(2-isocyanatoethyl) 2-isocyanatoglutarate.
  • aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-diisocyanatohexane, lysine diisocyanate, and lysine triisocyanate.
  • alicyclic polyisocyanates include alicyclic diisocyanates such as isophorone diisocyanate, 1,3-bis(isocyanatomethyl)-cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, norbornene diisocyanate, and hydrogenated xylylene diisocyanate.
  • aromatic polyisocyanates include aromatic diisocyanates such as xylylene diisocyanate.
  • the polyisocyanate may be a compound in which two or more isocyanate groups of the above-mentioned polyisocyanate monomer or polyisocyanate derivative are blocked with a blocking agent.
  • the blocking agent is a compound having active hydrogen, and specific examples include alcohol, phenol, active methylene, amine, imine, acid amide, lactam, oxime, pyrazole, imidazole, imidazoline, pyrimidine, and guanidine.
  • a curing agent having two or more groups in one molecule that can react with a carboxyl group epoxy group, carbodiimide group, oxazoline group, ⁇ -hydroxyalkylamide group, etc.
  • a carboxyl group epoxy group, carbodiimide group, oxazoline group, ⁇ -hydroxyalkylamide group, etc.
  • the content of the curing agent in the paint is preferably 1 to 80 parts by weight, more preferably 15 to 75 parts by weight, based on 100 parts by weight of the fluoropolymer in the paint.
  • the present paint may be a paint in which the present fluoropolymer is dissolved or dispersed in a liquid medium, or may be a paint (such as a powder paint) that does not substantially contain a liquid medium.
  • Liquid media include organic solvents and water
  • paints dissolved or dispersed in liquid media include paints dissolved in organic solvents (solvent-based paints, etc.) and paints dispersed in water. (water-based paints, etc.).
  • the present paint is preferably a solvent-based paint in view of the excellent weather resistance of the paint film.
  • the fact that the present paint does not substantially contain a liquid medium means that the content of the liquid medium is 0.1% by mass or less based on the total mass of the present paint.
  • Examples of the organic solvent include ketone solvents, ester solvents, hydrocarbon solvents, alcohol solvents, glycol ether solvents, and glycol ester solvents.
  • Specific examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and diacetone alcohol.
  • Specific examples of ester solvents include ethyl acetate and butyl acetate.
  • Specific examples of hydrocarbon solvents include hexane, heptane, cyclohexane, and xylene.
  • a specific example of the alcohol solvent is butyl alcohol.
  • glycol ether solvents include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol monopropyl ether.
  • glycol ester solvent is 1-methoxypropyl-2-acetate.
  • the content of the liquid medium is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, based on the total mass of the present paint.
  • the present paint can be produced, for example, by mixing the present fluoropolymer and optional components.
  • the liquid medium may be a polymerization solvent (for example, the above-mentioned specific organic solvent) when producing the present fluoropolymer.
  • the base material with a coated film of the present invention (hereinafter also referred to as the base material with the present coated film) is a coated film formed from a base material and the present composition placed on the base material (hereinafter referred to as the present coated film). ).
  • the material of the base material include inorganic materials, organic materials, and organic-inorganic composite materials.
  • inorganic materials include concrete, natural stone, glass, and metals (iron, stainless steel, aluminum, aluminum alloy, copper, brass, titanium, etc.).
  • organic substances include plastics, rubber, adhesives, and wood.
  • organic-inorganic composite materials include fiber-reinforced plastic, resin-reinforced concrete, and fiber-reinforced concrete.
  • the base material may be subjected to a known surface treatment (chemical conversion treatment, etc.). Further, the surface of the base material may previously have a resin layer (polyester resin layer, acrylic resin layer, silicone resin layer, etc.) formed by applying a primer or the like.
  • the shape, size, etc. of the base material are not particularly limited.
  • Specific examples of base materials include structures (e.g., road structures such as bridges, piers, tunnels, etc.), buildings, aircraft, ships, vehicles (e.g., railway cars, automobiles), traffic signs, traffic lights, power transmission lines, etc. can be mentioned.
  • the thickness of the present coating film is preferably 1 to 200 ⁇ m, more preferably 10 to 100 ⁇ m, and even more preferably 20 to 60 ⁇ m, from the viewpoint of better weather resistance of the base material with this coated film.
  • the method for producing the base material with the present coating film is a method of applying the present paint onto the base material to form the present coated film.
  • the present coating film may be formed by applying the present coating material onto a base material, drying as necessary, and curing by heating.
  • the paint may be applied directly to the surface of the base material, or may be applied after the surface of the base material has been subjected to a known surface treatment (base treatment, etc.).
  • base treatment base treatment, etc.
  • the present coating material may be applied to an article having the above-mentioned base material.
  • the application methods include spray coating, squeegee coating, flow coating, bar coating, spin coating, dip coating, screen printing, gravure printing, Examples include a die coating method, an inkjet method, a curtain coating method, and a method using a brush or spatula.
  • the coating methods include electrostatic coating, electrostatic spraying, electrostatic dipping, spraying, fluidized dipping, spraying, spraying, thermal spraying, plasma spraying, etc. can be mentioned.
  • the paint contains a liquid medium, it is preferable to dry it after application to remove the solvent.
  • the drying temperature is usually 0 to 50°C, and the drying time is usually 1 minute to 2 weeks.
  • the present coating material contains a curing agent, it is preferable to heat and cure it after application.
  • the heat curing temperature is usually 50°C to 300°C, and the heat curing time is usually 1 minute to 24 hours.
  • Examples 1 to 5 are examples, and examples 6 and 7 are comparative examples. However, the present invention is not limited to these examples.
  • Mn of the fluoropolymer was determined by size exclusion chromatography. Tetrahydrofuran was used as a developing solvent, and a polystyrene specimen with a known molecular weight was used as a standard material for molecular weight conversion.
  • Example 1 In a 400 ml stainless steel pressure-resistant reactor equipped with a stirrer, 217 g of butyl acetate, 10 g of ethyl vinyl ether, 6 g of 4-hydroxybutyl vinyl ether, 10 g of cyclohexyl vinyl ether, and bis(1,2,2 , 6,6-pentamethyl-4-piperidyl) separate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl separate (mass ratio 3:1) (manufactured by BASF, product name: TINUVIN292) 0.45 g and 0.26 g of tert-butyl peroxypivalate as a polymerization initiator were charged, and dissolved oxygen in the liquid was removed by degassing with nitrogen.
  • Example 2 In a 400 ml stainless steel pressure-resistant reactor equipped with a stirrer, 99 g of methyl ethyl ketone, 33 g of ethyl vinyl ether, 21 g of 4-hydroxybutyl vinyl ether, 34 g of cyclohexyl vinyl ether, and bis(1,2,2, Mixture of 6,6-pentamethyl-4-piperidyl) sepacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sepacate (mass ratio 3:1) (manufactured by BASF, trade name: TINUVIN292) 1 0.5 g of tert-butyl peroxypivalate, which is a polymerization initiator, were charged, and dissolved oxygen in the liquid was removed by degassing with nitrogen.
  • Example 3 In a 400 ml stainless steel pressure-resistant reactor equipped with a stirrer, 102 g of acetone, 32 g of ethyl vinyl ether, 20 g of 4-hydroxybutyl vinyl ether, 32 g of cyclohexyl vinyl ether, and bis(1,2,2,6, 1.4 g of a mixture of 6-pentamethyl-4-piperidyl) sepacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sepacate (mass ratio 3:1) (manufactured by BASF, trade name: TINUVIN292) , 0.26 g of tert-butyl peroxypivalate as a polymerization initiator was charged, and dissolved oxygen in the liquid was removed by degassing with nitrogen.
  • Example 4 In a 400 ml stainless steel pressure-resistant reactor equipped with a stirrer, 102 g of tetrahydrofuran, 35 g of ethyl vinyl ether, 22 g of 4-hydroxybutyl vinyl ether, 35 g of cyclohexyl vinyl ether, and bis(1,2,2,6,6- 1.5 g of a mixture of pentamethyl-4-piperidyl) sepacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sepacate (mass ratio 3:1) (manufactured by BASF, trade name: TINUVIN292), polymerized 0.26 g of tert-butyl peroxypivalate as an initiator was charged, and dissolved oxygen in the liquid was removed by degassing with nitrogen.
  • Example 5 In a stainless steel pressure-resistant reactor with an internal volume of 2500 ml equipped with a stirrer, 865 g of butyl acetate, 57 g of 4-hydroxybutyl vinyl ether, 220 g of cyclohexyl vinyl ether, and bis(1,2,2,6,6-pentamethyl-4) were added as a stabilizer.
  • the total amount of tert-butylperoxypivalate 20% butyl acetate solution added intermittently into the reactor was 12 ml. After 16 hours, the reactor was cooled with water to stop the reaction. After cooling the reaction solution to room temperature, unreacted monomers are purged, insoluble components of the obtained reaction solution are removed by filtration, the concentration of the obtained reaction solution is adjusted, and fluorine-containing A base solution containing Copolymer 5 and having a solid content concentration of 60.5% by mass was obtained. Mn of fluoropolymer 5 was 13,500.
  • Example 6 In a stainless steel pressure-resistant reactor with an internal volume of 2500 ml equipped with a stirrer, 850 g of xylene, 196 g of ethyl vinyl ether, 123 g of 4-hydroxybutyl vinyl ether, 198 g of cyclohexyl vinyl ether, and bis(1,2,2,6 , 6-pentamethyl-4-piperidyl) sepacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sepacate (mass ratio 3:1) (manufactured by BASF, trade name: TINUVIN292)1. 5 g was charged, and dissolved oxygen in the liquid was removed by degassing with nitrogen.
  • Example 7 Zeffle GK-570 manufactured by Daikin Industries, Ltd. (butyl acetate solution of copolymer of tetrafluoroethylene and vinyl monomer, solid content concentration 65% by mass) was used as the solution of fluoropolymer 7.
  • a base solution containing each of the fluoropolymers of Examples 1 to 7 was applied to a polypropylene plate without any surface treatment using an applicator so that the dry film thickness was approximately 40 ⁇ m or 60 ⁇ m, and the mixture was heated at 60°C for 60 minutes. It was heated and dried to form a coating film. These coatings were peeled off from the polypropylene plate to form a film, and the film was used as a sample to measure wavelengths of 200 nm to 800 nm using an ultraviolet/visible spectrophotometer (manufactured by Shimadzu Corporation, UV-3600 MPC-3100).
  • the absorbance A in the wavelength range was measured, and the transmittance T (%) in the wavelength range of 260 nm to 300 nm was calculated using the following formula (1).
  • Table 1 shows the lowest value among the transmittances determined every 0.5 nm in the wavelength range of 260 nm to 300 nm.
  • the film thickness L ( ⁇ m) shown in Table 1 and Table 1 can be calculated using the following formula (2) created from the relationship of Lambert-Beer's law that the absorbance of an absorbing substance is proportional to the optical path length (film thickness). Using the value of the shown transmittance T, the transmittance T' (%) when the film thickness of the film was corrected to 40 ⁇ m was calculated. Table 1 shows the values of transmittance T'.
  • the film thickness L of the film is measured using a caliper and is the arithmetic mean value at nine arbitrary locations on the film.
  • Weather resistance was evaluated based on the above light transmittance value.
  • the evaluation criteria are as follows, and the evaluation results are shown in Table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Provided are a method for producing a fluorine-containing polymer capable of forming a coating film having exceptional weather resistance, a fluorine-containing polymer, a coating material, and a substrate equipped with a coating film.　A method for producing a fluorine-containing polymer according to the present invention includes polymerizing at least one fluorine monomer selected from the group consisting of CF2=CF2, CF2=CFCl, CF2=CHF, and CH2=CF2, a vinyl ether free of fluorine atoms and reactive groups, and a monomer having a reactive group in the presence of at least one organic solvent selected from the group consisting of methyl ethyl ketone, acetone, n-butyl acetate, and tetrahydrofuran and in the absence of vinyl esters to obtain a fluorine-containing polymer.

Description

含フッ素重合体の製造方法、含フッ素重合体、塗料及び塗膜付き基材Method for producing fluoropolymer, fluoropolymer, paint, and base material with coating film
　本発明は、含フッ素重合体の製造方法、含フッ素重合体、塗料及び塗膜付き基材に関する。 The present invention relates to a method for producing a fluoropolymer, a fluoropolymer, a paint, and a substrate with a coated film.
　耐候性等に優れた塗膜を形成できる点から、含フッ素重合体を含む塗料が広く用いられている。特許文献１には、塗料に用いる含フッ素重合体の製造時に、重合溶媒としてキシレンを使用する方法が開示されている。 Paints containing fluorine-containing polymers are widely used because they can form coatings with excellent weather resistance. Patent Document 1 discloses a method of using xylene as a polymerization solvent during the production of a fluoropolymer used in a paint.
国際公開第２０１７／０９４８６１号International Publication No. 2017/094861
　近年、含フッ素重合体を含む塗料は多様な環境下で用いられることから、含フッ素重合体を含む塗料を用いて得られた塗膜の耐候性について、更なる向上が求められている。
　本発明者らが、特許文献１に記載されているように重合溶媒としてキシレンを用いて含フッ素重合体を製造したところ、これを用いて得られる塗膜の耐候性に改善の余地があることを知見した。 In recent years, since paints containing fluoropolymers are used in a variety of environments, there has been a demand for further improvement in the weather resistance of coating films obtained using paints containing fluoropolymers.
When the present inventors produced a fluoropolymer using xylene as a polymerization solvent as described in Patent Document 1, there was room for improvement in the weather resistance of the coating film obtained using this. I found out.
　本発明は、上記課題に鑑みてなされ、耐候性に優れた塗膜を形成できる含フッ素重合体の製造方法、含フッ素重合体、塗料及び塗膜付き基材の提供を課題とする。 The present invention was made in view of the above problems, and an object of the present invention is to provide a method for producing a fluoropolymer that can form a coating film with excellent weather resistance, a fluoropolymer, a paint, and a substrate with a coating film.
　本発明者らは、上記課題について鋭意検討した結果、特定の有機溶剤の存在下で、かつ、ビニルエステルの不存在下で、特定の単量体を重合して得られた含フッ素重合体を用いた場合、耐候性に優れた塗膜を形成できることを見出し、本発明に至った。 As a result of intensive study on the above-mentioned problem, the present inventors have discovered that a fluoropolymer obtained by polymerizing a specific monomer in the presence of a specific organic solvent and in the absence of a vinyl ester. It has been discovered that when used, a coating film with excellent weather resistance can be formed, leading to the present invention.
　すなわち、発明者らは、以下の構成により上記課題が解決できることを見出した。
［１］　メチルエチルケトン、アセトン、酢酸ｎ－ブチル、及び、テトラヒドロフランからなる群から選択される少なくとも１種の有機溶剤の存在下で、かつ、ビニルエステルの不存在下で、
　ＣＦ２＝ＣＦ２、ＣＦ２＝ＣＦＣｌ、ＣＦ２＝ＣＨＦ及びＣＨ２＝ＣＦ２からなる群から選択される少なくとも１種のフッ素系単量体と、フッ素原子及び反応性基を有しないビニルエーテルと、反応性基を有する単量体と、を重合して、含フッ素重合体を得ることを特徴とする、含フッ素重合体の製造方法。
［２］　上記有機溶剤が、メチルエチルケトン、アセトン、及び、酢酸ｎ－ブチルからなる群から選択される少なくとも１種の有機溶剤である、［１］に記載の含フッ素重合体の製造方法。
［３］　上記フッ素系単量体が、ＣＦ２＝ＣＦ２及びＣＦ２＝ＣＦＣｌからなる群から選択される少なくとも１種の単量体である、［１］又は［２］に記載の含フッ素重合体の製造方法。
［４］　上記反応性基が、水酸基、アミノ基、エポキシ基、オキセタニル基、加水分解性シリル基、スルホ基、及び、カルボキシ基からなる群から選択される少なくとも１種の基である、［１］～［３］のいずれか１つに記載の含フッ素重合体の製造方法。
［５］　ＣＦ２＝ＣＦ２、ＣＦ２＝ＣＦＣｌ、ＣＦ２＝ＣＨＦ及びＣＨ２＝ＣＦ２からなる群から選択される少なくとも１種のフッ素系単量体に基づくフッ素系単位と、
　フッ素原子及び反応性基を有しない、ビニルエーテルに基づく非フッ素系単位と、
　反応性基を有する単量体に基づく単位と、を有し、ビニルエステルに基づく単位を有しない含フッ素重合体であって、
　上記含フッ素重合体を用いて得られた膜の波長２６０ｎｍ～３００ｎｍの波長域における光線透過率が、上記膜の厚さを４０μｍとした際に、５０％以上であることを特徴とする、含フッ素重合体。
［６］　［５］に記載の含フッ素重合体を含むことを特徴とする、塗料。
［７］　基材と、上記基材上に配置された［６］に記載の塗料から形成された塗膜と、を有することを特徴とする、塗膜付き基材。 That is, the inventors have found that the above problem can be solved by the following configuration.
[1] In the presence of at least one organic solvent selected from the group consisting of methyl ethyl ketone, acetone, n-butyl acetate, and tetrahydrofuran, and in the absence of vinyl ester,
At least one fluorine-based monomer selected from the group consisting of CF2 = CF2 , CF2 =CFCl, CF2 =CHF and CH2 = CF2 , and a vinyl ether having no fluorine atom or reactive group. , and a monomer having a reactive group to obtain a fluoropolymer.
[2] The method for producing a fluoropolymer according to [1], wherein the organic solvent is at least one organic solvent selected from the group consisting of methyl ethyl ketone, acetone, and n-butyl acetate.
[3] The fluorine-containing monomer according to [1] or [2], wherein the fluorine-based monomer is at least one monomer selected from the group consisting of CF 2 =CF 2 and CF 2 =CFCl. Method for producing polymers.
[4] The reactive group is at least one group selected from the group consisting of a hydroxyl group, an amino group, an epoxy group, an oxetanyl group, a hydrolyzable silyl group, a sulfo group, and a carboxy group, [1 ] to [3]. The method for producing a fluoropolymer according to any one of [3].
[5] A fluorine-based unit based on at least one fluorine - based monomer selected from the group consisting of CF2= CF2 , CF2 =CFCl, CF2 =CHF, and CH2 = CF2 ;
a non-fluorinated unit based on vinyl ether, which does not have a fluorine atom and a reactive group;
A fluoropolymer having a unit based on a monomer having a reactive group and not having a unit based on a vinyl ester,
The light transmittance of the film obtained using the fluorine-containing polymer in the wavelength range of 260 nm to 300 nm is 50% or more when the thickness of the film is 40 μm. Fluoropolymers.
[6] A paint characterized by containing the fluoropolymer described in [5].
[7] A base material with a coating film, comprising a base material and a coating film formed from the coating material according to [6], which is disposed on the base material.
　本発明によれば、耐候性に優れた塗膜を形成できる含フッ素重合体の製造方法、含フッ素重合体、塗料及び塗膜付き基材を提供できる。 According to the present invention, it is possible to provide a method for producing a fluoropolymer that can form a coating film with excellent weather resistance, a fluoropolymer, a paint, and a substrate with a coating film.
　本発明における用語を以下に説明する。
　「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。本明細書に段階的に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、実施例に示されている値に置き換えてもよい。
　本明細書において、各成分は、各成分に該当する物質を１種単独でも用いても、２種以上を併用してもよい。ここで、各成分について２種以上の物質を併用する場合、その成分についての含有量とは、特段の断りが無い限り、併用した物質の合計の含有量を指す。
　本明細書において、２以上の好ましい態様の組み合わせは、より好ましい態様である。
　単位とは、単量体の重合により直接形成された、上記単量体１分子に基づく原子団と、上記原子団の一部を化学変換して得られる原子団との総称である。重合体が含む全単位に対する、それぞれの単位の含有量（モル％）は、重合体を核磁気共鳴スペクトル法により分析して求められ、重合体の製造に際して使用する成分の仕込み量からも決定できる。
　「（メタ）アクリル」とは「アクリル」と「メタクリル」の総称であり、「（メタ）アクリレート」とは「アクリレート」と「メタクリレート」の総称である。
　加水分解性シリル基とは、加水分解反応してシラノール基を形成し得る基を意味する。
　酸価及び水酸基価は、それぞれ、ＪＩＳ　Ｋ　００７０－３（１９９２）の方法に準じて測定される値である。
　ガラス転移温度（Ｔｇ）は、示差走査熱量測定（ＤＳＣ）法で測定される、重合体の中間点ガラス転移温度である。
　数平均分子量（Ｍｎ）は、ポリスチレンを標準物質としてサイズ排除クロマトグラフィー（ゲルパーミエーションクロマトグラフィー）で測定される値である。 Terms used in the present invention will be explained below.
A numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as lower and upper limits. In the numerical ranges described stepwise in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise. Moreover, in the numerical ranges described in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the value shown in the Examples.
In this specification, for each component, one type of substance corresponding to each component may be used alone, or two or more types may be used in combination. Here, when two or more types of substances are used together for each component, the content of the component refers to the total content of the substances used in combination, unless otherwise specified.
In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.
The unit is a general term for an atomic group based on one molecule of the above-mentioned monomer, which is directly formed by polymerization of monomers, and an atomic group obtained by chemically converting a part of the above-mentioned atomic group. The content (mol%) of each unit relative to the total units contained in the polymer is determined by analyzing the polymer by nuclear magnetic resonance spectroscopy, and can also be determined from the amount of ingredients used in the production of the polymer. .
"(Meth)acrylic" is a generic term for "acrylic" and "methacrylic", and "(meth)acrylate" is a generic term for "acrylate" and "methacrylate".
A hydrolyzable silyl group means a group that can undergo a hydrolysis reaction to form a silanol group.
The acid value and hydroxyl value are values measured according to the method of JIS K 0070-3 (1992), respectively.
Glass transition temperature (Tg) is the midpoint glass transition temperature of a polymer as measured by differential scanning calorimetry (DSC).
The number average molecular weight (Mn) is a value measured by size exclusion chromatography (gel permeation chromatography) using polystyrene as a standard substance.
　本発明の含フッ素重合体の製造方法（以下、本製造方法ともいう。）は、メチルエチルケトン、アセトン、酢酸ｎ－ブチル、及び、テトラヒドロフランからなる群から選択される少なくとも１種の有機溶剤（以下、特定有機溶剤ともいう。）の存在下で、かつ、ビニルエステルの不存在下で、ＣＦ２＝ＣＦ２、ＣＦ２＝ＣＦＣｌ、ＣＦ２＝ＣＨＦ及びＣＨ２＝ＣＦ２からなる群から選択される少なくとも１種のフッ素系単量体と、フッ素原子及び反応性基を有しないビニルエーテルと、反応性基を有する単量体と、を重合して、含フッ素重合体を得る方法である。 The method for producing a fluoropolymer of the present invention (hereinafter also referred to as the present production method) uses at least one organic solvent selected from the group consisting of methyl ethyl ketone, acetone, n-butyl acetate, and tetrahydrofuran. (also referred to as a specific organic solvent) and in the absence of a vinyl ester, selected from the group consisting of CF 2 =CF 2 , CF 2 =CFCl, CF 2 =CHF and CH 2 =CF 2 This is a method of obtaining a fluoropolymer by polymerizing at least one fluorine-based monomer, a vinyl ether having no fluorine atom or reactive group, and a monomer having a reactive group.
　本製造方法によって得られた含フッ素重合体は、耐候性に優れた塗膜を形成できる。この理由は必ずしも明らかではないが、以下のように考えられている。
　含フッ素重合体の製造時に用いる単量体を重合する際に用いる溶媒（以下、重合溶媒ともいう。）として特定有機溶剤以外の有機溶剤を用いた場合、重合溶媒を由来とする紫外線を吸収しやすいような構造が含フッ素重合体に導入される場合がある。例えば、重合溶媒としてキシレンを用いた場合には、含フッ素重合体にベンゼン環等が微量に導入されることがある。このような問題に対して、本製造方法では重合溶媒として特定有機溶剤を用いるので、重合溶媒に由来する耐候性を低下させるような構造が含フッ素重合体に導入されにくくなる。これにより、含フッ素重合体を用いて得られる塗膜の耐候性が向上したと推測される。 The fluoropolymer obtained by this production method can form a coating film with excellent weather resistance. Although the reason for this is not necessarily clear, it is thought to be as follows.
When an organic solvent other than a specified organic solvent is used as a solvent (hereinafter also referred to as a polymerization solvent) when polymerizing monomers used in the production of a fluoropolymer, ultraviolet rays originating from the polymerization solvent may be absorbed. In some cases, a structure that is easy to use is introduced into a fluoropolymer. For example, when xylene is used as a polymerization solvent, a trace amount of benzene rings or the like may be introduced into the fluoropolymer. In order to solve such problems, in this production method, a specific organic solvent is used as a polymerization solvent, so that structures that are derived from the polymerization solvent and that reduce weather resistance are difficult to be introduced into the fluoropolymer. It is presumed that this improved the weather resistance of the coating film obtained using the fluoropolymer.
　特定有機溶剤は、本製造方法において重合溶媒として用いられる。
　特定有機溶剤は、メチルエチルケトン、アセトン、酢酸ｎ－ブチル、及び、テトラヒドロフランからなる群から選択される少なくとも１種の有機溶剤であり、本発明の効果がより優れる点から、メチルエチルケトン、アセトン、及び、酢酸ｎ－ブチルからなる群から選択される少なくとも１種の有機溶剤であるのが好ましい。 The specific organic solvent is used as a polymerization solvent in this production method.
The specific organic solvent is at least one organic solvent selected from the group consisting of methyl ethyl ketone, acetone, n-butyl acetate, and tetrahydrofuran, and from the viewpoint that the effects of the present invention are more excellent, methyl ethyl ketone, acetone, and acetic acid are preferred. Preferably, it is at least one organic solvent selected from the group consisting of n-butyl.
　特定有機溶剤は、２種以上を併用してもよい。
　特定有機溶剤の使用量は、含フッ素重合体の製造に用いる単量体の全仕込み量１００質量部に対して、１～６０質量部が好ましく、３０～５０質量部がより好ましい。 Two or more specific organic solvents may be used in combination.
The amount of the specific organic solvent used is preferably 1 to 60 parts by weight, more preferably 30 to 50 parts by weight, based on 100 parts by weight of the total amount of monomers used for producing the fluoropolymer.
　本製造方法では、特定有機溶剤以外の有機溶剤（以下、他の有機溶剤ともいう。）を用いてもよいが、本発明の効果がより優れる点から、他の有機溶剤を実質的に使用しないことが好ましい。
　他の有機溶剤を実質的に使用しないとは、他の有機溶剤の使用量が、含フッ素重合体の製造に用いる単量体の全質量１００質量部に対して、１質量部以下であること意味する。
　他の有機溶剤の具体例としては、キシレン、トルエン、エチルベンゼン等が挙げられる。 In this manufacturing method, organic solvents other than the specific organic solvents (hereinafter also referred to as other organic solvents) may be used, but in view of the superior effects of the present invention, other organic solvents are not substantially used. It is preferable.
"Substantially no other organic solvents are used" means that the amount of other organic solvents used is 1 part by mass or less per 100 parts by mass of the total mass of monomers used in the production of the fluoropolymer. means.
Specific examples of other organic solvents include xylene, toluene, and ethylbenzene.
　本製造方法における各単量体の重合は、ビニルエステルの不存在下で実施される。そのため、本製造方法によって得られる含フッ素重合体は、ビニルエステルに基づく単位を有しない。
　ビニルエステルの具体例としては、酢酸ビニル、ピバル酸ビニル、ネオノナン酸ビニル（ＨＥＸＩＯＮ社商品名　ベオバ９）、ネオデカン酸ビニル（ＨＥＸＩＯＮ社商品名　ベオバ１０）、バーサチック酸ビニル、安息香酸ビニル、ｔｅｒｔ－ブチル安息香酸ビニルが挙げられる。 The polymerization of each monomer in this production method is carried out in the absence of vinyl ester. Therefore, the fluoropolymer obtained by this production method does not have units based on vinyl ester.
Specific examples of vinyl esters include vinyl acetate, vinyl pivalate, vinyl neononanoate (HEXION brand name: Beova 9), vinyl neodecanoate (HEXION brand name: Beova 10), vinyl versatate, vinyl benzoate, tert-butyl Examples include vinyl benzoate.
　フッ素系単量体は、ＣＦ２＝ＣＦ２、ＣＦ２＝ＣＦＣｌ、ＣＦ２＝ＣＨＦ及びＣＨ２＝ＣＦ２からなる群から選択される少なくとも１種の単量体（以下、単量体ａ１１ともいう）であり、含フッ素重合体を製造するための単量体として用いられる。
　単量体ａ１１は、本発明の効果がより優れる点、及び、単量体ａ１１以外の単量体との重合性の点から、ＣＦ２＝ＣＦ２及びＣＦ２＝ＣＦＣｌからなる群から選択される少なくとも１種が好ましく、ＣＦ２＝ＣＦＣｌがより好ましい。 The fluoromonomer is at least one monomer selected from the group consisting of CF 2 =CF 2 , CF 2 =CFCl, CF 2 =CHF, and CH 2 =CF 2 (hereinafter also referred to as monomer a11). ) and is used as a monomer for producing fluoropolymers.
Monomer a11 is selected from the group consisting of CF 2 =CF 2 and CF 2 =CFCl from the viewpoint of superior effects of the present invention and polymerizability with monomers other than monomer a11. At least one type is preferable, and CF 2 =CFCl is more preferable.
　単量体ａ１１は、２種以上を併用してもよい。
　単量体ａ１１の仕込み量は、本発明の効果がより優れる点から、含フッ素重合体の製造に用いる単量体の全仕込み量に対して、２０～７０モル％が好ましく、３０～６０モル％がより好ましく、４５～５５モル％が更に好ましい。 Two or more types of monomer a11 may be used in combination.
The amount of monomer a11 to be charged is preferably 20 to 70 mol%, and 30 to 60 mol%, based on the total amount of monomers used for producing the fluoropolymer, in order to obtain better effects of the present invention. % is more preferable, and 45 to 55 mol% is even more preferable.
　フッ素原子及び反応性基を有しないビニルエーテル（以下、単量体ａ１２ともいう。）は、含フッ素重合体を製造するための単量体として用いられる。
　単量体ａ１２の具体例としては、エチルビニルエーテル、ｔｅｒｔ－ブチルビニルエーテル、２－エチルヘキシルビニルエーテル、シクロヘキシルビニルエーテル、シクロヘキシルメチルビニルエーテルが挙げられる。 Vinyl ether (hereinafter also referred to as monomer a12) that does not have a fluorine atom or a reactive group is used as a monomer for producing a fluoropolymer.
Specific examples of monomer a12 include ethyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, and cyclohexylmethyl vinyl ether.
　単量体ａ１２は、２種以上を併用してもよい。
　単量体ａ１２の仕込み量は、本発明の効果がより優れる点から、含フッ素重合体の製造に用いる単量体の全仕込み量に対して、５～６０モル％が好ましく、１０～５０モル％がより好ましい。 Two or more types of monomer a12 may be used in combination.
The amount of monomer a12 to be charged is preferably 5 to 60 mol%, and 10 to 50 mol%, based on the total amount of monomers used for producing the fluoropolymer, in order to obtain better effects of the present invention. % is more preferable.
　反応性基を有する単量体（以下、単量体ａ１３ともいう。）、は、含フッ素重合体を製造するための単量体として用いられる。単量体ａ１３は、ビニルエステル構造（ＣＨ２＝ＣＨＯＣ（Ｏ）－）を有しない。
　単量体ａ１３は、フッ素原子を有しないことが好ましい。 A monomer having a reactive group (hereinafter also referred to as monomer a13) is used as a monomer for producing a fluoropolymer. Monomer a13 does not have a vinyl ester structure (CH 2 =CHOC(O)-).
It is preferable that monomer a13 does not have a fluorine atom.
　反応性基としては、水酸基、アミノ基、エポキシ基、オキセタニル基、加水分解性シリル基、スルホ基、カルボキシ基からなる群から選択される少なくとも１種の基が挙げられる。なお、スルホ基及びカルボキシ基は、イオン化して－ＳＯ３ －又は－ＣＯＯ－となっていてもよく、塩化して－ＳＯ３ －Ｎａ＋又は－ＣＯＯ－Ｎａ＋等になっていてもよい。
　単量体ａ１３は、含フッ素重合体を用いて得られた塗膜の強度がより優れる点から、反応性基として水酸基又はカルボキシ基を有することが好ましく、水酸基を有することがより好ましい。
　水酸基を有する単量体ａ１３としては、水酸基を有する、ビニルエーテル、アリルエーテル、アリルエステル若しくは（メタ）アクリル酸エステル、又はアリルアルコール等が挙げられる。水酸基を有する単量体ａ１３としては、ヒドロキシビニルエーテル又はヒドロキシアリルエーテルが好ましい。 Examples of the reactive group include at least one group selected from the group consisting of a hydroxyl group, an amino group, an epoxy group, an oxetanyl group, a hydrolyzable silyl group, a sulfo group, and a carboxy group. Note that the sulfo group and the carboxy group may be ionized to become -SO 3 - or -COO - , or may be chlorinated to become -SO 3 - Na + or -COO - Na + or the like.
The monomer a13 preferably has a hydroxyl group or a carboxy group as a reactive group, and more preferably has a hydroxyl group, since the strength of the coating film obtained using the fluoropolymer is more excellent.
Examples of the monomer a13 having a hydroxyl group include vinyl ether, allyl ether, allyl ester, (meth)acrylic acid ester, allyl alcohol, etc. each having a hydroxyl group. As the monomer a13 having a hydroxyl group, hydroxy vinyl ether or hydroxy allyl ether is preferable.
　水酸基を有する単量体ａ１３としては、式Ｘ１－Ｚ１で表される単量体が好ましい。
　Ｘ１は、ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－、ＣＨ２＝ＣＨＣＨ２ＯＣ（Ｏ）－、ＣＨ２＝ＣＨＯ－又はＣＨ２＝ＣＨＣＨ２Ｏ－であり、ＣＨ２＝ＣＨＯ－又はＣＨ２＝ＣＨＣＨ２Ｏ－であることが好ましい。
　Ｚ１は、水酸基を有する炭素数２～４２の１価の有機基である。有機基は、直鎖状でもよく、分岐状でもよい。また、有機基は、環構造からなっていてもよく、環構造を含んでいてもよい。
　上記有機基としては、水酸基を有する炭素数２～６のアルキル基、水酸基を有する炭素数６～８のシクロアルキレン基を有するアルキル基、又は水酸基を有するポリオキシアルキレン基が好ましい。 As the monomer a13 having a hydroxyl group, a monomer represented by the formula X 1 -Z 1 is preferable.
X 1 is CH 2 =CHC(O)O-, CH 2 =C(CH 3 )C(O)O-, CH 2 =CHCH 2 OC(O)-, CH 2 =CHO- or CH 2 =CHCH 2 O-, preferably CH 2 =CHO- or CH 2 =CHCH 2 O-.
Z 1 is a monovalent organic group having 2 to 42 carbon atoms and having a hydroxyl group. The organic group may be linear or branched. Further, the organic group may have a ring structure or may include a ring structure.
The organic group is preferably an alkyl group having 2 to 6 carbon atoms having a hydroxyl group, an alkyl group having a cycloalkylene group having 6 to 8 carbon atoms having a hydroxyl group, or a polyoxyalkylene group having a hydroxyl group.
　水酸基を有する単量体ａ１３の具体例としては、ＣＨ２＝ＣＨＯ－ＣＨ２－ｃｙｃｌｏＣ６Ｈ１０－ＣＨ２ＯＨ、ＣＨ２＝ＣＨＣＨ２Ｏ－ＣＨ２－ｃｙｃｌｏＣ６Ｈ１０－ＣＨ２ＯＨ、ＣＨ２＝ＣＨＯ－ＣＨ２－ｃｙｃｌｏＣ６Ｈ１０－ＣＨ２－（ＯＣＨ２ＣＨ２）１５ＯＨ、ＣＨ２＝ＣＨＯＣＨ２ＣＨ２ＯＨ、ＣＨ２＝ＣＨＣＨ２ＯＣＨ２ＣＨ２ＯＨ、ＣＨ２＝ＣＨＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＨ、及びＣＨ２＝ＣＨＣＨ２ＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＨが挙げられる。
　なお、「－ｃｙｃｌｏＣ６Ｈ１０－」はシクロへキシレン基を表し、「－ｃｙｃｌｏＣ６Ｈ１０－」の結合部位は、通常１，４－である。 Specific examples of the monomer a13 having a hydroxyl group include CH 2 =CHO-CH 2 -cycloC 6 H 10 -CH 2 OH, CH 2 =CHCH 2 O-CH 2 -cycloC 6 H 10 -CH 2 OH, CH 2 = CHO-CH 2 -cycloC 6 H 10 -CH 2 -(OCH 2 CH 2 ) 15 OH, CH 2 = CHOCH 2 CH 2 OH, CH 2 = CHCH 2 OCH 2 CH 2 OH, CH 2 = CHOCH 2 CH 2CH2CH2OH , and CH2 = CHCH2OCH2CH2CH2CH2OH . _ _
Note that "-cycloC 6 H 10 -" represents a cyclohexylene group, and the bonding site of "-cycloC 6 H 10 -" is usually 1,4-.
　カルボキシ基を有する単量体ａ１３としては、不飽和カルボン酸、（メタ）アクリル酸、上述の水酸基を有する単量体の水酸基にカルボン酸無水物を反応させて得られる単量体等が挙げられる。
　カルボキシ基を有する単量体ａ１３の具体例としては、ＣＨ２＝ＣＨＣＯＯＨ、ＣＨ（ＣＨ３）＝ＣＨＣＯＯＨ、ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＨ、ＨＯＯＣＣＨ＝ＣＨＣＯＯＨ、ＣＨ２＝ＣＨ（ＣＨ２）ｎ１１ＣＯＯＨで表される単量体（ただし、ｎ１１は１～１０の整数を示す。）、ＣＨ２＝ＣＨＯ（ＣＨ２）ｎ１２ＯＣ（Ｏ）ＣＨ２ＣＨ２ＣＯＯＨで表される単量体（ただし、ｎ１２は１～１０の整数を示す。）が挙げられる。 Examples of the monomer a13 having a carboxy group include unsaturated carboxylic acids, (meth)acrylic acid, and monomers obtained by reacting the hydroxyl group of the above-mentioned hydroxyl group-containing monomer with a carboxylic acid anhydride. .
Specific examples of the monomer a13 having a carboxyl group include CH2 =CHCOOH, CH( CH3 )=CHCOOH, CH2 =C( CH3 )COOH, HOOCCH=CHCOOH, CH2 =CH( CH2 ) n11 Monomers represented by COOH (however, n11 represents an integer from 1 to 10), CH 2 =CHO(CH 2 ) n12 OC(O) CH 2 CH 2 Monomers represented by COOH (however, , n12 represents an integer from 1 to 10).
　単量体ａ１３は、２種以上を併用してもよい。
　単量体ａ１３の仕込み量は、本発明の効果がより優れる点から、含フッ素重合体の製造に用いる単量体の全仕込み量に対して、０．１～４５モル％が好ましく、１～３０モル％がより好ましく、５～２０モル％が更に好ましい。 Two or more types of monomer a13 may be used in combination.
The amount of monomer a13 to be charged is preferably 0.1 to 45 mol%, and 1 to 45 mol%, based on the total amount of monomers used for producing the fluoropolymer, in order to obtain better effects of the present invention. It is more preferably 30 mol%, and even more preferably 5 to 20 mol%.
　本製造方法では、単量体ａ１１、単量体ａ１２及び単量体ａ１３以外の単量体（ただし、ビニルエーテル構造を有する単量体を除く。）を用いてもよいが、本発明の効果がより優れる点から、単量体ａ１１、単量体ａ１２及び単量体ａ１３のみを用いることが好ましい。 In this production method, monomers other than monomer a11, monomer a12, and monomer a13 (excluding monomers having a vinyl ether structure) may be used, but the effects of the present invention may be In terms of superiority, it is preferable to use only monomer a11, monomer a12, and monomer a13.
　各単量体の添加順序は、適宜設定すればよい。各単量体は、一括して添加してもよく、分割して連続的に添加してもよい。 The order of addition of each monomer may be set as appropriate. Each monomer may be added all at once or divided into parts and added continuously.
　本製造方法は、ラジカル重合開始剤の存在下で行われるのが好ましい。
　ラジカル重合開始剤の具体例としては、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビスシクロヘキサンカーボネートニトリル、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２－メチルブチロニトリル）等のアゾ系開始剤；ケトンパーオキサイド（例えば、シクロヘキサノンパーオキサイド）、ハイドロパーオキサイド（例えば、ｔｅｒｔ－ブチルハイドロパーオキサイド）、ジアシルパーオキサイド（例えば、ベンゾイルパーオキサイド）、ジアルキルパーオキサイド（例えば、ジ－ｔｅｒｔ－ブチルパーオキサイド）、パーオキシケタール（例えば、２，２－ジ－（ｔｅｒｔ－ブチルパーオキシ）ブタン）、アルキルパーオキシエステル（例えば、ｔｅｒｔ－ブチルパーオキシピバレート）等の過酸化物系開始剤が挙げられる。 This production method is preferably carried out in the presence of a radical polymerization initiator.
Specific examples of radical polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobiscyclohexane carbonate nitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), , 2'-azobis(2-methylbutyronitrile); ketone peroxides (e.g. cyclohexanone peroxide), hydroperoxides (e.g. tert-butyl hydroperoxide), diacyl peroxides (e.g. , benzoyl peroxide), dialkyl peroxides (e.g. di-tert-butyl peroxide), peroxyketals (e.g. 2,2-di-(tert-butylperoxy)butane), alkyl peroxy esters (e.g. Examples include peroxide-based initiators such as tert-butyl peroxypivalate).
　本製造方法では、含フッ素重合体の製造に用いる従来公知の成分（以下、他の成分ともいう。）を用いてもよい。
　他の成分の具体例としては、連鎖移動剤、重合禁止剤（ハイドロキノンモノメチルエーテル等）、安定剤（ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）セパケート、メチル１，２，２，６，６－ペンタメチル－４－ピペリジルセパケート等）、受酸剤（炭酸カリウム、ハイドロタルサイト等）が挙げられる。 In this production method, conventionally known components (hereinafter also referred to as other components) used in the production of fluoropolymer may be used.
Specific examples of other components include chain transfer agents, polymerization inhibitors (hydroquinone monomethyl ether, etc.), stabilizers (bis(1,2,2,6,6-pentamethyl-4-piperidyl) sepacate, methyl 1,2 , 2,6,6-pentamethyl-4-piperidyl sepacate, etc.), and acid acceptors (potassium carbonate, hydrotalcite, etc.).
　本製造方法における含フッ素重合体の重合形態は、重合安定性の点から、特定有機溶剤中に各単量体が溶解した状態で行う溶液重合が好ましい。 In terms of polymerization stability, the polymerization form of the fluoropolymer in this production method is preferably solution polymerization in which each monomer is dissolved in a specific organic solvent.
　本製造方法において重合条件は適宜設定すればよく、例えば、重合温度は通常５０～９０℃であり、重合時間は通常３～５０時間である。 In this production method, the polymerization conditions may be set as appropriate; for example, the polymerization temperature is usually 50 to 90°C, and the polymerization time is usually 3 to 50 hours.
　本製造方法によって得られる含フッ素重合体は、ビニルエステルに基づく単位を有しないで、単量体ａ１１に基づく単位、単量体ａ１２に基づく単位、及び、単量体ａ１３に基づく単位を有する共重合体であり、本発明の効果がより優れる点から、単量体ａ１１に基づく単位、単量体ａ１２に基づく単位、及び、単量体ａ１３に基づく単位からなる共重合体であるのが好ましい。 The fluoropolymer obtained by this production method does not have a unit based on vinyl ester, but has a unit based on monomer a11, a unit based on monomer a12, and a unit based on monomer a13. It is a polymer and is preferably a copolymer consisting of a unit based on monomer a11, a unit based on monomer a12, and a unit based on monomer a13, since the effects of the present invention are more excellent. .
　本発明の含フッ素重合体（以下、本含フッ素重合体ともいう。）は、上述の単量体ａ１１に基づくフッ素系単位（以下、単位Ａ１１ともいう。）と、上述の単量体ａ１２に基づく非フッ素系単位（以下、単位Ａ１２ともいう。）と、上述の単量体ａ１３に基づく単位（以下、単位Ａ１３ともいう。）と、を有し、ビニルエステルに基づく単位を有しない含フッ素重合体である。また、本含フッ素重合体を用いて得られた膜の波長２６０ｎｍ～３００ｎｍの波長域における光線透過率は、膜の厚さを４０μｍとした際に５０％以上である。
　本含フッ素重合体は、膜にした際に上記光線透過率を満たすような含フッ素重合体が容易に得られる点から、上述の本製造方法によって得られた含フッ素重合体であるのが好ましい。 The fluorine-containing polymer of the present invention (hereinafter also referred to as the present fluorine-containing polymer) has a fluorine-containing unit based on the above-mentioned monomer a11 (hereinafter also referred to as unit A11), and a fluorine-containing unit based on the above-mentioned monomer a12. (hereinafter also referred to as unit A12) and a unit based on the above-mentioned monomer a13 (hereinafter also referred to as unit A13), and does not have a vinyl ester-based unit. It is a polymer. Furthermore, the light transmittance of the film obtained using the present fluoropolymer in the wavelength range of 260 nm to 300 nm is 50% or more when the film thickness is 40 μm.
The present fluorine-containing polymer is preferably a fluorine-containing polymer obtained by the present production method described above, since it is easy to obtain a fluorine-containing polymer that satisfies the above-mentioned light transmittance when formed into a film. .
　本含フッ素重合体は、耐候性に優れた塗膜を形成できる。この理由の詳細は必ずしも明らかではないが、以下のように考えられている。
　本含フッ素重合体を用いて得られる膜は、特定波長領域（波長２６０ｎｍ～３００ｎｍの波長域）における光線透過率が高い。これにより、含フッ素重合体を用いて得られる膜が特定波長領域の光線による影響を受けにくくなるので、含フッ素重合体を用いて得られる膜自体の耐候性が向上したと推測される。 This fluoropolymer can form a coating film with excellent weather resistance. Although the details of this reason are not necessarily clear, it is thought to be as follows.
A film obtained using the present fluoropolymer has high light transmittance in a specific wavelength range (wavelength range of 260 nm to 300 nm). As a result, the film obtained using the fluoropolymer becomes less susceptible to the effects of light in a specific wavelength range, so it is presumed that the weather resistance of the film itself obtained using the fluoropolymer is improved.
　単位Ａ１１は、単量体ａ１１に基づくフッ素系単位である。単量体ａ１１は、上述の含フッ素重合体の製造方法における単量体ａ１１と同様であるので、その説明を省略する。単量体ａ１１は、２種以上を併用してもよい。
　単位Ａ１１の含有量は、本含フッ素重合体を用いて得られる膜の耐候性がより優れる点から、本含フッ素重合体が含む全単位に対して、２０～７０モル％が好ましく、３０～６０モル％がより好ましく、４５～５５モル％が更に好ましい。 The unit A11 is a fluorine-based unit based on the monomer a11. Monomer a11 is the same as monomer a11 in the above-mentioned method for producing a fluoropolymer, so its explanation will be omitted. Two or more types of monomer a11 may be used in combination.
The content of unit A11 is preferably 20 to 70 mol%, based on the total units contained in the fluoropolymer, and 30 to 70% by mole, since the weather resistance of the film obtained using the fluoropolymer is better. More preferably 60 mol%, and even more preferably 45 to 55 mol%.
　単位Ａ１２は、単量体ａ１２に基づく非フッ素系単位である。単量体ａ１２は、上述の含フッ素重合体の製造方法における単量体ａ１２と同様であるので、その説明を省略する。単量体ａ１２は、２種以上を併用してもよい。
　単位Ａ１２の含有量は、本含フッ素重合体が含む全単位に対して、５～６０モル％が好ましく、１０～５０モル％がより好ましい。 The unit A12 is a non-fluorine unit based on the monomer a12. Monomer a12 is the same as monomer a12 in the above-mentioned method for producing a fluoropolymer, so its explanation will be omitted. Two or more types of monomer a12 may be used in combination.
The content of the unit A12 is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, based on the total units contained in the present fluoropolymer.
　単位Ａ１３は、単量体ａ１３に基づく単位である。単量体ａ１３は、上述の含フッ素重合体の製造方法における単量体ａ１３と同様であるので、その説明を省略する。単量体ａ１３は、２種以上を併用してもよい。
　単位Ａ１３の含有量は、本含フッ素重合体が含む全単位に対して、０．１～４５モル％が好ましく、１～３０モル％がより好ましく、５～２０モル％が更に好ましい。 Unit A13 is a unit based on monomer a13. Monomer a13 is the same as monomer a13 in the above-mentioned method for producing a fluoropolymer, so its explanation will be omitted. Two or more types of monomer a13 may be used in combination.
The content of the unit A13 is preferably 0.1 to 45 mol%, more preferably 1 to 30 mol%, and even more preferably 5 to 20 mol%, based on the total units contained in the present fluoropolymer.
　本含フッ素重合体は、ビニルエステルに基づく単位を有しない。ビニルエステルの具体例としては、上述の含フッ素重合体の製造方法で挙げた通りであるので、その説明を省略する。 This fluoropolymer does not have units based on vinyl ester. Specific examples of the vinyl ester are the same as those mentioned in the above-mentioned method for producing a fluoropolymer, so the explanation thereof will be omitted.
　本含フッ素重合体は、耐候性により優れた塗膜を形成できる点から、単位Ａ１１、単位Ａ１２及び単位Ａ１３からなるのが好ましい。 The present fluoropolymer is preferably composed of units A11, A12, and A13 from the viewpoint of forming a coating film with better weather resistance.
　本含フッ素重合体のＴｇは、耐傷性の点から、０～１２０℃が好ましく、１０～７０℃がより好ましい。 The Tg of the present fluoropolymer is preferably 0 to 120°C, more preferably 10 to 70°C, from the viewpoint of scratch resistance.
　本含フッ素重合体のＭｎは、成膜性、耐候性の点から、３０００～５００００が好ましく、５０００～３００００がより好ましく、１００００～２００００が更に好ましい。 The Mn of the present fluoropolymer is preferably 3,000 to 50,000, more preferably 5,000 to 30,000, and even more preferably 10,000 to 20,000 from the viewpoint of film formability and weather resistance.
　本含フッ素重合体が水酸基価を有する場合、耐水性の点から、特定含フッ素重合体の水酸基価は、１～２００ｍｇＫＯＨ／ｇが好ましく、５～１００ｍｇＫＯＨ／ｇがより好ましく４０～６０ｍｇＫＯＨ／ｇが更に好ましい。
　本含フッ素重合体が酸価を有する場合、顔料分散性の点から、特定含フッ素重合体の酸価は、１～３０ｍｇＫＯＨ／ｇが好ましく、１～１０ｍｇＫＯＨ／ｇがより好ましい。 When the present fluoropolymer has a hydroxyl value, from the viewpoint of water resistance, the hydroxyl value of the specific fluoropolymer is preferably 1 to 200 mgKOH/g, more preferably 5 to 100 mgKOH/g, and more preferably 40 to 60 mgKOH/g. More preferred.
When the present fluoropolymer has an acid value, from the viewpoint of pigment dispersibility, the acid value of the specific fluoropolymer is preferably 1 to 30 mgKOH/g, more preferably 1 to 10 mgKOH/g.
　本含フッ素重合体を用いて得られた膜の波長２６０ｎｍ～３００ｎｍの波長域における光線透過率は、膜の厚さを４０μｍとした際に、５０％以上である。上記光線透過率の上限は、通常１００％である。
　ここで、本発明において、上記光線透過率の値がＸ％以上であるとは、波長２６０ｎｍ～３００ｎｍの波長域で０．５ｎｍ毎に透過率を求めた際に、各波長における透過率がいずれもＸ％以上であることを意味する。
　上記光線透過率の詳細な測定方法は、後述する実施例欄に記載の通りである。 The light transmittance of the film obtained using the present fluoropolymer in the wavelength range of 260 nm to 300 nm is 50% or more when the film thickness is 40 μm. The upper limit of the above light transmittance is usually 100%.
Here, in the present invention, the value of the light transmittance being X% or more means that when the transmittance is calculated every 0.5 nm in the wavelength range of 260 nm to 300 nm, the transmittance at each wavelength is also means that it is X% or more.
The detailed method for measuring the light transmittance is as described in the Examples section below.
　本発明の塗料（以下、本塗料ともいう。）は、上述の本含フッ素重合体を含む。
　本含フッ素重合体の含有量は、本塗料の全質量に対して、５～１００質量％が好ましく、３０～１００質量％がより好ましく、４０～１００質量％が更に好ましい。 The paint of the present invention (hereinafter also referred to as the present paint) contains the above-mentioned present fluoropolymer.
The content of the present fluoropolymer is preferably 5 to 100% by mass, more preferably 30 to 100% by mass, and even more preferably 40 to 100% by mass, based on the total mass of the coating material.
　本塗料は、本含フッ素重合体以外の成分を含んでいてもよい。該成分としては、添加剤が挙げられる。
　添加剤としては、硬化剤、硬化触媒、非フッ素重合体（（メタ）アクリル樹脂、ウレタン樹脂、エポキシ樹脂、ポリエステル樹脂、シリコーン樹脂等）、着色剤（染料、有機顔料、無機顔料、金属又はマイカ等を用いた光輝顔料等）、紫外線吸収剤、光安定剤、つや消し剤、レベリング剤、表面調整剤、脱ガス剤、充填剤、熱安定剤、増粘剤、分散剤、界面活性剤、帯電防止剤、防錆剤、シランカップリング剤、防汚剤、低汚染化処理剤、可塑剤、接着剤等が挙げられる。 The paint may contain components other than the fluoropolymer. Such components include additives.
Additives include curing agents, curing catalysts, non-fluorinated polymers ((meth)acrylic resins, urethane resins, epoxy resins, polyester resins, silicone resins, etc.), colorants (dyes, organic pigments, inorganic pigments, metals, or mica). bright pigments, etc.), ultraviolet absorbers, light stabilizers, matting agents, leveling agents, surface conditioners, degassing agents, fillers, heat stabilizers, thickeners, dispersants, surfactants, electrostatic charges Examples include inhibitors, rust preventives, silane coupling agents, antifouling agents, antifouling agents, plasticizers, adhesives, and the like.
　本塗料は、上述した添加剤の中でも、塗膜の耐久性（耐水性、耐薬品性、耐候性等）の点から、硬化剤を含むのが好ましい。硬化剤は、本含フッ素重合体が含む反応性基と反応し得る反応性基を１分子中に２個以上有することが好ましく、２～３０個有することがより好ましい。
　本含フッ素重合体が反応性基を有する場合、硬化剤が有する反応性基と、含フッ素重合体が有する反応性基とが反応すると、本含フッ素重合体が硬化剤によって架橋し、架橋した含フッ素重合体が形成される。 Among the above-mentioned additives, the paint preferably contains a curing agent from the viewpoint of the durability (water resistance, chemical resistance, weather resistance, etc.) of the coating film. The curing agent preferably has two or more, more preferably 2 to 30, reactive groups in one molecule that can react with the reactive groups contained in the present fluoropolymer.
When the fluoropolymer has a reactive group, when the reactive group of the curing agent and the reactive group of the fluoropolymer react, the fluoropolymer is crosslinked by the curing agent, resulting in crosslinking. A fluoropolymer is formed.
　硬化剤が有する反応性基の具体例としては、イソシアネート基、ブロック化イソシアネート基、エポキシ基、オキサゾリン基、β－ヒドロキシアルキルアミド基が挙げられる。
　特に、含フッ素重合体が有する反応性基がヒドロキシ基である場合、硬化剤が有する反応性基としては、イソシアネート基、ブロック化イソシアネート基が好ましい。この場合、硬化剤としては、イソシアネート基又はブロック化イソシアネート基を１分子中に２以上有する硬化剤であるポリイソシアネートが好ましい。
　ポリイソシアネートとしては、ポリイソシアネート単量体、ポリイソシアネート誘導体が好ましい。
　ポリイソシアネート単量体としては、脂環族ポリイソシアネート、脂肪族ポリイソシアネート、芳香族ポリイソシアネートが好ましい。ポリイソシアネート誘導体としては、ポリイソシアネート単量体の多量体又は変性体（アダクト体、アロファネート体、ビウレット体、イソシアヌレート体等）が好ましい。 Specific examples of reactive groups possessed by the curing agent include isocyanate groups, blocked isocyanate groups, epoxy groups, oxazoline groups, and β-hydroxyalkylamide groups.
In particular, when the reactive group of the fluoropolymer is a hydroxy group, the reactive group of the curing agent is preferably an isocyanate group or a blocked isocyanate group. In this case, the curing agent is preferably a polyisocyanate having two or more isocyanate groups or blocked isocyanate groups in one molecule.
As the polyisocyanate, polyisocyanate monomers and polyisocyanate derivatives are preferred.
As the polyisocyanate monomer, alicyclic polyisocyanates, aliphatic polyisocyanates, and aromatic polyisocyanates are preferred. The polyisocyanate derivative is preferably a multimer or modified polyisocyanate monomer (adduct, allophanate, biuret, isocyanurate, etc.).
　脂肪族ポリイソシアネートの具体例としては、テトラメチレンジイソシアネート、ペンタメチレンジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４－トリメチル－１，６－ジイソシアナトヘキサン、リジンジイソシアネート等の脂肪族ジイソシアネート、リジントリイソシアネート、４－イソシアナトメチル－１，８－オクタメチレンジイソシアネート、ビス（２－イソシアナトエチル）２－イソシアナトグルタレートが挙げられる。
　脂環族ポリイソシアネートの具体例としては、イソホロンジイソシアネート、１，３－ビス（イソシアナトメチル）－シクロヘキサン、４，４’－ジシクロヘキシルメタンジイソシアネート、ノルボルネンジイソシアネート、水添キシリレンジイソシアネート等の脂環族ジイソシアネートが挙げられる。
　芳香族ポリイソシアネートの具体例としては、キシリレンジイソシアネート等の芳香族ジイソシアネートが挙げられる。 Specific examples of aliphatic polyisocyanates include aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-diisocyanatohexane, lysine diisocyanate, and lysine triisocyanate. , 4-isocyanatomethyl-1,8-octamethylene diisocyanate, and bis(2-isocyanatoethyl) 2-isocyanatoglutarate.
Specific examples of alicyclic polyisocyanates include alicyclic diisocyanates such as isophorone diisocyanate, 1,3-bis(isocyanatomethyl)-cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, norbornene diisocyanate, and hydrogenated xylylene diisocyanate. can be mentioned.
Specific examples of aromatic polyisocyanates include aromatic diisocyanates such as xylylene diisocyanate.
　ポリイソシアネートは、上述したポリイソシアネート単量体又はポリイソシアネート誘導体が有する２以上のイソシアネート基が、ブロック化剤によってブロックされている化合物であってもよい。
　ブロック化剤は、活性水素を有する化合物であり、具体例としては、アルコール、フェノール、活性メチレン、アミン、イミン、酸アミド、ラクタム、オキシム、ピラゾール、イミダゾール、イミダゾリン、ピリミジン、グアニジンが挙げられる。 The polyisocyanate may be a compound in which two or more isocyanate groups of the above-mentioned polyisocyanate monomer or polyisocyanate derivative are blocked with a blocking agent.
The blocking agent is a compound having active hydrogen, and specific examples include alcohol, phenol, active methylene, amine, imine, acid amide, lactam, oxime, pyrazole, imidazole, imidazoline, pyrimidine, and guanidine.
　本含フッ素重合体が酸価を有する場合等に、カルボキシ基と反応し得る基（エポキシ基、カルボジイミド基、オキサゾリン基、β－ヒドロキシアルキルアミド基等）を１分子中に２以上有する硬化剤を使用してもよい。 When the present fluoropolymer has an acid value, a curing agent having two or more groups in one molecule that can react with a carboxyl group (epoxy group, carbodiimide group, oxazoline group, β-hydroxyalkylamide group, etc.) is used. May be used.
　硬化剤は、２種以上を併用してもよい。
　本塗料における硬化剤の含有量は、本塗料中の本含フッ素重合体の含有量１００質量部に対して、１～８０質量部が好ましく、１５～７５質量部がより好ましい。 Two or more types of curing agents may be used in combination.
The content of the curing agent in the paint is preferably 1 to 80 parts by weight, more preferably 15 to 75 parts by weight, based on 100 parts by weight of the fluoropolymer in the paint.
　本塗料は、本含フッ素重合体及が液状媒体に溶解又は分散している塗料であってもよく、液状媒体を実質的に含まない塗料（粉体塗料等）であってもよい。
　液状媒体としては有機溶剤及び水が挙げられ、液状媒体に溶解又は分散している塗料としては、有機溶剤等に溶解している塗料（溶剤型塗料等）、及び、水に分散している塗料（水系塗料等）が挙げられる。本塗料は、塗膜の耐候性に優れる点から溶剤型塗料であることが好ましい。
　本塗料が液状媒体を実質的に含まないとは、液状媒体の含有量が、本塗料の全質量に対して、０．１質量％以下であることを意味する。 The present paint may be a paint in which the present fluoropolymer is dissolved or dispersed in a liquid medium, or may be a paint (such as a powder paint) that does not substantially contain a liquid medium.
Liquid media include organic solvents and water, and paints dissolved or dispersed in liquid media include paints dissolved in organic solvents (solvent-based paints, etc.) and paints dispersed in water. (water-based paints, etc.). The present paint is preferably a solvent-based paint in view of the excellent weather resistance of the paint film.
The fact that the present paint does not substantially contain a liquid medium means that the content of the liquid medium is 0.1% by mass or less based on the total mass of the present paint.
　有機溶剤としては、ケトン系溶剤、エステル系溶剤、炭化水素系溶剤、アルコール系溶剤、グリコールエーテル系溶剤、グリコールエステル系溶剤が挙げられる。
　ケトン系溶剤の具体例としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン、ジアセトンアルコールが挙げられる。
　エステル系溶剤の具体例としては、酢酸エチル、酢酸ブチルが挙げられる。
　炭化水素系溶剤の具体例としては、ヘキサン、へプタン、シクロヘキサン、キシレンが挙げられる。
　アルコール系溶剤の具体例としては、ブチルアルコールが挙げられる。
　グリコールエーテル系溶剤の具体例としては、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノプロピルエーテルが挙げられる。
　グリコールエステル系溶剤の具体例としては、１－メトキシプロピル－２－アセテートが挙げられる。 Examples of the organic solvent include ketone solvents, ester solvents, hydrocarbon solvents, alcohol solvents, glycol ether solvents, and glycol ester solvents.
Specific examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and diacetone alcohol.
Specific examples of ester solvents include ethyl acetate and butyl acetate.
Specific examples of hydrocarbon solvents include hexane, heptane, cyclohexane, and xylene.
A specific example of the alcohol solvent is butyl alcohol.
Specific examples of glycol ether solvents include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol monopropyl ether.
A specific example of the glycol ester solvent is 1-methoxypropyl-2-acetate.
　本塗料が液状媒体を含む場合、液状媒体の含有量は、本塗料の全質量に対して、１０～９５質量％が好ましく、２０～９０質量％がより好ましい。 When the present paint contains a liquid medium, the content of the liquid medium is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, based on the total mass of the present paint.
　本塗料は、例えば、本含フッ素重合体及び任意成分を混合して製造できる。液状媒体は、本含フッ素重合体を製造する際の重合溶媒（例えば、上述の特定有機溶剤）であってもよい。 The present paint can be produced, for example, by mixing the present fluoropolymer and optional components. The liquid medium may be a polymerization solvent (for example, the above-mentioned specific organic solvent) when producing the present fluoropolymer.
　本発明の塗膜付き基材（以下、本塗膜付き基材ともいう。）は、基材と、上記基材上に配置された本組成物から形成された塗膜（以下、本塗膜ともいう。）と、を有する。 The base material with a coated film of the present invention (hereinafter also referred to as the base material with the present coated film) is a coated film formed from a base material and the present composition placed on the base material (hereinafter referred to as the present coated film). ).
　基材の材質の具体例としては、無機物、有機物、有機無機複合材が挙げられる。
　無機物の具体例としては、コンクリート、自然石、ガラス、金属（鉄、ステンレス、アルミニウム、アルミニウム合金、銅、真鍮、チタン等）が挙げられる。
　有機物の具体例としては、プラスチック、ゴム、接着剤、木材が挙げられる。
　有機無機複合材の具体例としては、繊維強化プラスチック、樹脂強化コンクリート、繊維強化コンクリートが挙げられる。
　また、基材は、公知の表面処理（化成処理等）が施されていてもよい。また、基材の表面には、プライマー等を塗布して形成される樹脂層（ポリエステル樹脂層、アクリル樹脂層、シリコーン樹脂層等）等をあらかじめ有していてもよい。 Specific examples of the material of the base material include inorganic materials, organic materials, and organic-inorganic composite materials.
Specific examples of inorganic materials include concrete, natural stone, glass, and metals (iron, stainless steel, aluminum, aluminum alloy, copper, brass, titanium, etc.).
Specific examples of organic substances include plastics, rubber, adhesives, and wood.
Specific examples of organic-inorganic composite materials include fiber-reinforced plastic, resin-reinforced concrete, and fiber-reinforced concrete.
Further, the base material may be subjected to a known surface treatment (chemical conversion treatment, etc.). Further, the surface of the base material may previously have a resin layer (polyester resin layer, acrylic resin layer, silicone resin layer, etc.) formed by applying a primer or the like.
　基材の形状、サイズ等は、特に限定されない。
　基材の具体例としては、構造物（例えば、橋梁、橋脚、トンネル等の道路構造物）、建築物、航空機、船舶、車両（例えば、鉄道車両、自動車）、交通標識、信号機、送電線等が挙げられる。 The shape, size, etc. of the base material are not particularly limited.
Specific examples of base materials include structures (e.g., road structures such as bridges, piers, tunnels, etc.), buildings, aircraft, ships, vehicles (e.g., railway cars, automobiles), traffic signs, traffic lights, power transmission lines, etc. can be mentioned.
　本塗膜の膜厚は、本塗膜付き基材の耐候性がより優れる点から、１～２００μｍが好ましく、１０～１００μｍがより好ましく、２０～６０μｍが更に好ましい。 The thickness of the present coating film is preferably 1 to 200 μm, more preferably 10 to 100 μm, and even more preferably 20 to 60 μm, from the viewpoint of better weather resistance of the base material with this coated film.
　本塗膜付き基材の製造方法は、基材上に本塗料を塗布して本塗膜を形成する方法である。本塗膜は、基材上に本塗料を塗布し、必要に応じて乾燥し、加熱硬化して形成すればよい。
　本塗料は、基材の表面に直接塗布してもよく、基材の表面に公知の表面処理（下地処理等）を施した上に塗布してもよい。更に、基材に下塗り層を形成した後、この下塗り層上に塗布してもよい。また、本塗料は、上記基材を有する物品に塗布してもよい。 The method for producing the base material with the present coating film is a method of applying the present paint onto the base material to form the present coated film. The present coating film may be formed by applying the present coating material onto a base material, drying as necessary, and curing by heating.
The paint may be applied directly to the surface of the base material, or may be applied after the surface of the base material has been subjected to a known surface treatment (base treatment, etc.). Furthermore, after forming an undercoat layer on the base material, it may be applied onto this undercoat layer. Further, the present coating material may be applied to an article having the above-mentioned base material.
　本塗料が水系塗料又は溶剤型塗料である場合、塗布方法としては、スプレーコート法、スキージコート法、フローコート法、バーコート法、スピンコート法、ディップコート法、スクリーン印刷法、グラビア印刷法、ダイコート法、インクジェット法、カーテンコート法、はけやへらを用いる方法等が挙げられる。
　本塗料が粉体塗料である場合、塗装方法としては、静電塗装法、静電吹付法、静電浸漬法、噴霧法、流動浸漬法、吹付法、スプレー法、溶射法、プラズマ溶射法等が挙げられる。
　本塗料が液状媒体を含む場合、塗布後に乾燥させて溶媒を除去することが好ましい。乾燥温度は、通常、０～５０℃であり、乾燥時間は、通常、１分～２週間である。
　本塗料が硬化剤を含む場合、塗布後に加熱硬化させることが好ましい。加熱硬化温度は、通常５０℃～３００℃であり、加熱硬化時間は、通常１分～２４時間である。 When the paint is a water-based paint or a solvent-based paint, the application methods include spray coating, squeegee coating, flow coating, bar coating, spin coating, dip coating, screen printing, gravure printing, Examples include a die coating method, an inkjet method, a curtain coating method, and a method using a brush or spatula.
If the paint is a powder coating, the coating methods include electrostatic coating, electrostatic spraying, electrostatic dipping, spraying, fluidized dipping, spraying, spraying, thermal spraying, plasma spraying, etc. can be mentioned.
When the paint contains a liquid medium, it is preferable to dry it after application to remove the solvent. The drying temperature is usually 0 to 50°C, and the drying time is usually 1 minute to 2 weeks.
When the present coating material contains a curing agent, it is preferable to heat and cure it after application. The heat curing temperature is usually 50°C to 300°C, and the heat curing time is usually 1 minute to 24 hours.
　以下、例を挙げて本発明を詳細に説明する。例１～５は実施例であり、例６及び例７は比較例である。ただし本発明はこれらの例に限定されない。 Hereinafter, the present invention will be explained in detail by giving examples. Examples 1 to 5 are examples, and examples 6 and 7 are comparative examples. However, the present invention is not limited to these examples.
＜数平均分子量（Ｍｎ）＞
　含フッ素重合体のＭｎを、サイズ排除クロマトグラフィーにより求めた。展開溶媒としてテトラヒドロフラン、分子量換算用の標準物質として分子量が既知のポリスチレン標品を用いた。 <Number average molecular weight (Mn)>
Mn of the fluoropolymer was determined by size exclusion chromatography. Tetrahydrofuran was used as a developing solvent, and a polystyrene specimen with a known molecular weight was used as a standard material for molecular weight conversion.
＜例１＞ 
　攪拌機が装着された内容積４００ｍｌのステンレス鋼製耐圧反応器に、酢酸ブチルの２１７ｇ、エチルビニルエーテルの１０ｇ、４－ヒドロキシブチルビニルエーテルの６ｇ、シクロヘキシルビニルエーテルの１０ｇ、安定剤としてビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）セパケートとメチル１，２，２，６，６－ペンタメチル－４－ピペリジルセパケートの混合物（質量比３：１）（ＢＡＳＦ社製、商品名；ＴＩＮＵＶＩＮ２９２）０．４５ｇ、重合開始剤であるｔｅｒｔ－ブチルパーオキシピバレートの０．２６ｇを仕込み、窒素による脱気により液中の溶存酸素を除去した。反応器に、クロロトリフルオロエチレンの３３ｇを導入して徐々に６５℃に昇温し、重合を進行させた。
　重合開始剤の添加開始から２０時間後、反応器を水冷して反応を停止した。反応液を室温まで冷却した後、未反応単量体をパージし、得られた反応液の濃度を調節して、含フッ素重合体１を含む固形分濃度６０．６質量％のベース溶液を得た。含フッ素重合体１のＭｎは、１６８００であった。 <Example 1>
In a 400 ml stainless steel pressure-resistant reactor equipped with a stirrer, 217 g of butyl acetate, 10 g of ethyl vinyl ether, 6 g of 4-hydroxybutyl vinyl ether, 10 g of cyclohexyl vinyl ether, and bis(1,2,2 , 6,6-pentamethyl-4-piperidyl) separate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl separate (mass ratio 3:1) (manufactured by BASF, product name: TINUVIN292) 0.45 g and 0.26 g of tert-butyl peroxypivalate as a polymerization initiator were charged, and dissolved oxygen in the liquid was removed by degassing with nitrogen. 33 g of chlorotrifluoroethylene was introduced into the reactor, and the temperature was gradually raised to 65° C. to advance polymerization.
Twenty hours after the start of addition of the polymerization initiator, the reactor was cooled with water to stop the reaction. After cooling the reaction solution to room temperature, unreacted monomers were purged and the concentration of the obtained reaction solution was adjusted to obtain a base solution containing fluoropolymer 1 with a solid content concentration of 60.6% by mass. Ta. Mn of fluoropolymer 1 was 16,800.
＜例２＞　
　攪拌機が装着された内容積４００ｍｌのステンレス鋼製耐圧反応器に、メチルエチルケトンの９９ｇ、エチルビニルエーテルの３３ｇ、４－ヒドロキシブチルビニルエーテルの２１ｇ、シクロヘキシルビニルエーテルの３４ｇ、安定剤としてビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）セパケートとメチル１，２，２，６，６－ペンタメチル－４－ピペリジルセパケートの混合物（質量比３：１）（ＢＡＳＦ社製、商品名；ＴＩＮＵＶＩＮ２９２）１．５ｇ、重合開始剤であるｔｅｒｔ－ブチルパーオキシピバレートの０．２６ｇを仕込み、窒素による脱気により液中の溶存酸素を除去した。反応器に、クロロトリフルオロエチレンの１０７ｇを導入して徐々に６５℃に昇温し、重合を進行させた。
　重合開始剤の添加開始から２０時間後、反応器を水冷して反応を停止した。反応液を室温まで冷却した後、未反応単量体をパージし、得られた反応液の濃度を調節して、含フッ素重合体２を含む固形分濃度６０．８質量％のベース溶液を得た。含フッ素重合体２のＭｎは、２４７００であった。 <Example 2>
In a 400 ml stainless steel pressure-resistant reactor equipped with a stirrer, 99 g of methyl ethyl ketone, 33 g of ethyl vinyl ether, 21 g of 4-hydroxybutyl vinyl ether, 34 g of cyclohexyl vinyl ether, and bis(1,2,2, Mixture of 6,6-pentamethyl-4-piperidyl) sepacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sepacate (mass ratio 3:1) (manufactured by BASF, trade name: TINUVIN292) 1 0.5 g of tert-butyl peroxypivalate, which is a polymerization initiator, were charged, and dissolved oxygen in the liquid was removed by degassing with nitrogen. 107 g of chlorotrifluoroethylene was introduced into the reactor, and the temperature was gradually raised to 65° C. to proceed with polymerization.
Twenty hours after the start of addition of the polymerization initiator, the reactor was cooled with water to stop the reaction. After cooling the reaction solution to room temperature, unreacted monomers were purged, and the concentration of the obtained reaction solution was adjusted to obtain a base solution containing fluoropolymer 2 with a solid content concentration of 60.8% by mass. Ta. Mn of fluoropolymer 2 was 24,700.
＜例３＞　
　攪拌機が装着された内容積４００ｍｌのステンレス鋼製耐圧反応器に、アセトン１０２ｇ、エチルビニルエーテルの３２ｇ、４－ヒドロキシブチルビニルエーテル２０ｇ、シクロヘキシルビニルエーテルの３２ｇ、安定剤としてビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）セパケートとメチル１，２，２，６，６－ペンタメチル－４－ピペリジルセパケートの混合物（質量比３：１）（ＢＡＳＦ社製、商品名；ＴＩＮＵＶＩＮ２９２）１．４ｇ、重合開始剤であるｔｅｒｔ－ブチルパーオキシピバレートの０．２６ｇを仕込み、窒素による脱気により液中の溶存酸素を除去した。反応器に、クロロトリフルオロエチレンの１０３ｇを導入して徐々に６５℃に昇温し、重合を進行させた。
　重合開始剤の添加開始から２０時間後、反応器を水冷して反応を停止した。反応液を室温まで冷却した後、未反応単量体をパージし、得られた反応液の濃度を調節して、含フッ素重合体３を含む固形分濃度５９．３質量％のベース溶液を得た。含フッ素重合体３のＭｎは、４６７００であった。 <Example 3>
In a 400 ml stainless steel pressure-resistant reactor equipped with a stirrer, 102 g of acetone, 32 g of ethyl vinyl ether, 20 g of 4-hydroxybutyl vinyl ether, 32 g of cyclohexyl vinyl ether, and bis(1,2,2,6, 1.4 g of a mixture of 6-pentamethyl-4-piperidyl) sepacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sepacate (mass ratio 3:1) (manufactured by BASF, trade name: TINUVIN292) , 0.26 g of tert-butyl peroxypivalate as a polymerization initiator was charged, and dissolved oxygen in the liquid was removed by degassing with nitrogen. 103 g of chlorotrifluoroethylene was introduced into the reactor, and the temperature was gradually raised to 65° C. to allow polymerization to proceed.
Twenty hours after the start of addition of the polymerization initiator, the reactor was cooled with water to stop the reaction. After cooling the reaction solution to room temperature, unreacted monomers were purged and the concentration of the obtained reaction solution was adjusted to obtain a base solution containing fluoropolymer 3 with a solid content concentration of 59.3% by mass. Ta. Mn of fluoropolymer 3 was 46,700.
＜例４＞　
　攪拌機が装着された内容積４００ｍｌのステンレス鋼製耐圧反応器に、テトラヒドロフラン１０２ｇ、エチルビニルエーテル３５ｇ、４－ヒドロキシブチルビニルエーテル２２ｇ、シクロヘキシルビニルエーテル３５ｇ、安定剤としてビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）セパケートとメチル１，２，２，６，６－ペンタメチル－４－ピペリジルセパケートの混合物（質量比３：１）（ＢＡＳＦ社製、商品名；ＴＩＮＵＶＩＮ２９２）１．５ｇ、重合開始剤であるｔｅｒｔ－ブチルパーオキシピバレート０．２６ｇを仕込み、窒素による脱気により液中の溶存酸素を除去した。反応器に、クロロトリフルオロエチレン１１１ｇを導入して徐々に６５℃に昇温し、重合を進行させた。
　重合開始剤の添加開始から２０時間後、反応器を水冷して反応を停止した。反応液を室温まで冷却した後、未反応単量体をパージし、得られた反応液の濃度を調節して、含フッ素重合体４を含む固形分濃度６０．１質量％のベース溶液を得た。含フッ素重合体４のＭｎは、５９００であった。 <Example 4>
In a 400 ml stainless steel pressure-resistant reactor equipped with a stirrer, 102 g of tetrahydrofuran, 35 g of ethyl vinyl ether, 22 g of 4-hydroxybutyl vinyl ether, 35 g of cyclohexyl vinyl ether, and bis(1,2,2,6,6- 1.5 g of a mixture of pentamethyl-4-piperidyl) sepacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sepacate (mass ratio 3:1) (manufactured by BASF, trade name: TINUVIN292), polymerized 0.26 g of tert-butyl peroxypivalate as an initiator was charged, and dissolved oxygen in the liquid was removed by degassing with nitrogen. 111 g of chlorotrifluoroethylene was introduced into the reactor, and the temperature was gradually raised to 65° C. to advance polymerization.
Twenty hours after the start of addition of the polymerization initiator, the reactor was cooled with water to stop the reaction. After cooling the reaction solution to room temperature, unreacted monomers were purged, and the concentration of the obtained reaction solution was adjusted to obtain a base solution containing fluoropolymer 4 with a solid content concentration of 60.1% by mass. Ta. Mn of fluoropolymer 4 was 5,900.
＜例５＞
　攪拌機が装着された内容積２５００ｍｌのステンレス鋼製耐圧反応器に、酢酸ブチル８６５ｇ、４－ヒドロキシブチルビニルエーテル５７ｇ、シクロヘキシルビニルエーテル２２０ｇ、安定剤としてビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）セパケートとメチル１，２，２，６，６－ペンタメチル－４－ピペリジルセパケートの混合物（質量比３：１）（ＢＡＳＦ製、商品名：ＴＩＮＵＶＩＮ２９２）１８ｇ、ハイドロタルサイト（協和化学工業社製、商品名「ＫＷ５００」、粒径４５μｍ以下：３８％、４５～７５μｍ：３５％、７５～１０６μｍ：２１％、１０６～５００μｍ：６％）２４ｇを仕込み、窒素による脱気により液中の溶存酸素を除去した。反応器に、クロロトリフルオロエチレン２６１ｇを導入して、反応器内の温度が６５℃に達するまで加温した。その後、重合開始剤であるｔｅｒｔ－ブチルパーオキシピバレート２０％酢酸ブチル溶液６ｍｌを反応器内に添加し、反応を開始させた。
　反応速度を維持しつつ、クロロトリフルオロエチレン１７１ｇ、シクロヘキシルビニルエーテル１４４ｇ及び４－ヒドロキシブチルビニルエーテル３８ｇの追加単量体を連続的に反応器内に加えるとともに、ｔｅｒｔ－ブチルパーオキシピバレート２０％酢酸ブチル溶液を断続的に反応器内に添加して、重合を進行させた。重合開始後、反応器内に断続的に添加されたｔｅｒｔ－ブチルパーオキシピバレート２０％酢酸ブチル溶液の合計添加量は、１２ｍｌであった。１６時間後、反応器を水冷して反応を停止した。反応液を室温まで冷却した後、未反応の単量体をパージし、得られた反応液の不溶解成分を、ろ過により除去して、得られた反応液の濃度を調節して、含フッ素共重合体５を含む固形分濃度６０．５質量％のベース溶液を得た。含フッ素重合体５のＭｎは、１３５００であった。 <Example 5>
In a stainless steel pressure-resistant reactor with an internal volume of 2500 ml equipped with a stirrer, 865 g of butyl acetate, 57 g of 4-hydroxybutyl vinyl ether, 220 g of cyclohexyl vinyl ether, and bis(1,2,2,6,6-pentamethyl-4) were added as a stabilizer. -piperidyl) sepacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sepacate (mass ratio 3:1) (manufactured by BASF, product name: TINUVIN292) 18 g, hydrotalcite (Kyowa Chemical Industry Co., Ltd.) Co., Ltd., product name "KW500", particle size of 45 μm or less: 38%, 45-75 μm: 35%, 75-106 μm: 21%, 106-500 μm: 6%) was charged, and the liquid was degassed with nitrogen. Dissolved oxygen was removed. 261 g of chlorotrifluoroethylene was introduced into the reactor and heated until the temperature inside the reactor reached 65°C. Thereafter, 6 ml of a 20% butyl acetate solution of tert-butyl peroxypivalate, which is a polymerization initiator, was added into the reactor to initiate the reaction.
While maintaining the reaction rate, additional monomers of 171 g of chlorotrifluoroethylene, 144 g of cyclohexyl vinyl ether, and 38 g of 4-hydroxybutyl vinyl ether were continuously added into the reactor, while tert-butyl peroxypivalate 20% butyl acetate was added. The solution was added intermittently into the reactor to allow the polymerization to proceed. After the start of polymerization, the total amount of tert-butylperoxypivalate 20% butyl acetate solution added intermittently into the reactor was 12 ml. After 16 hours, the reactor was cooled with water to stop the reaction. After cooling the reaction solution to room temperature, unreacted monomers are purged, insoluble components of the obtained reaction solution are removed by filtration, the concentration of the obtained reaction solution is adjusted, and fluorine-containing A base solution containing Copolymer 5 and having a solid content concentration of 60.5% by mass was obtained. Mn of fluoropolymer 5 was 13,500.
＜例６＞　
　攪拌機が装着された内容積２５００ｍｌのステンレス鋼製耐圧反応器に、キシレン８５０ｇ、エチルビニルエーテルの１９６ｇ、４－ヒドロキシブチルビニルエーテルの１２３ｇ、シクロヘキシルビニルエーテルの１９８ｇ、安定剤としてビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）セパケートとメチル１，２，２，６，６－ペンタメチル－４－ピペリジルセパケートの混合物（質量比３：１）（ＢＡＳＦ社製、商品名；ＴＩＮＵＶＩＮ２９２）１．５ｇ、を仕込み、窒素による脱気により液中の溶存酸素を除去した。反応器に、クロロトリフルオロエチレンの６２９ｇを導入して徐々に昇温し、温度６５℃に達したところで、重合開始剤であるｔｅｒｔ－ブチルパーオキシピバレート８．８ｇを間欠的に添加することで重合を進行させた。
　重合開始剤の添加開始から２０時間後、反応器を水冷して反応を停止した。反応液を室温まで冷却した後、未反応単量体をパージし、得られた反応液の濃度を調節して、含フッ素重合体６を含む固形分濃度６０．３質量％のベース溶液を得た。含フッ素重合体６のＭｎは、１４６００であった。 <Example 6>
In a stainless steel pressure-resistant reactor with an internal volume of 2500 ml equipped with a stirrer, 850 g of xylene, 196 g of ethyl vinyl ether, 123 g of 4-hydroxybutyl vinyl ether, 198 g of cyclohexyl vinyl ether, and bis(1,2,2,6 , 6-pentamethyl-4-piperidyl) sepacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sepacate (mass ratio 3:1) (manufactured by BASF, trade name: TINUVIN292)1. 5 g was charged, and dissolved oxygen in the liquid was removed by degassing with nitrogen. 629 g of chlorotrifluoroethylene was introduced into the reactor, and the temperature was gradually raised, and when the temperature reached 65 ° C., 8.8 g of tert-butyl peroxypivalate, which was a polymerization initiator, was added intermittently. Polymerization was allowed to proceed.
Twenty hours after the start of addition of the polymerization initiator, the reactor was cooled with water to stop the reaction. After cooling the reaction solution to room temperature, unreacted monomers were purged, and the concentration of the obtained reaction solution was adjusted to obtain a base solution containing fluoropolymer 6 with a solid content concentration of 60.3% by mass. Ta. Mn of fluoropolymer 6 was 14,600.
＜例７＞
　ダイキン工業社製のゼッフルＧＫ－５７０（テトラフルオロエチレンとビニルモノマーとの共重合体の酢酸ブチル溶液、固形分濃度６５質量％）を、含フッ素重合体７の溶液として用いた。 <Example 7>
Zeffle GK-570 manufactured by Daikin Industries, Ltd. (butyl acetate solution of copolymer of tetrafluoroethylene and vinyl monomer, solid content concentration 65% by mass) was used as the solution of fluoropolymer 7.
＜光線透過率＞
　例１～７の各含フッ素重合体を含むベース溶液を、アプリケーターにて乾燥膜厚が４０μｍ程度または６０μｍ程度になるようになんら表面処理を施していないポリプロピレン板に塗布し、６０℃で６０分加熱乾燥させて、塗膜を形成した。これらの塗膜をポリプロピレン板から剥がしてフィルム状とし、該フィルムを試料として紫外・可視分光光度計（島津製作所製、ＵＶ－３６００　ＭＰＣ－３１００）を用いて、該フィルムの波長２００ｎｍ～８００ｎｍの波長域における吸光度Ａを測定し、下記式(１)を用いて、波長２６０ｎｍ～３００ｎｍの波長域における透過率Ｔ（％）を算出した。なお、透過率Ｔ（％）として、波長２６０ｎｍ～３００ｎｍの波長域で０．５ｎｍ毎に求めた透過率のうち、最も低い値を表１に記した。 <Light transmittance>
A base solution containing each of the fluoropolymers of Examples 1 to 7 was applied to a polypropylene plate without any surface treatment using an applicator so that the dry film thickness was approximately 40 μm or 60 μm, and the mixture was heated at 60°C for 60 minutes. It was heated and dried to form a coating film. These coatings were peeled off from the polypropylene plate to form a film, and the film was used as a sample to measure wavelengths of 200 nm to 800 nm using an ultraviolet/visible spectrophotometer (manufactured by Shimadzu Corporation, UV-3600 MPC-3100). The absorbance A in the wavelength range was measured, and the transmittance T (%) in the wavelength range of 260 nm to 300 nm was calculated using the following formula (1). As the transmittance T (%), Table 1 shows the lowest value among the transmittances determined every 0.5 nm in the wavelength range of 260 nm to 300 nm.
Figure JPOXMLDOC01-appb-M000001
 ・・・式（１）
Figure JPOXMLDOC01-appb-M000001
 ...Formula (1)
　吸収物質の吸光度が光路長(膜厚)に比例するというランバルト・ベールの法則の関係性から作成した下記式（２）によって、表１に示したフィルムの膜厚Ｌ（μｍ）と表１に示した透過率Ｔの値を用いて、フィルムの膜厚を４０μｍに補正した際の透過率Ｔ’（％）を算出した。透過率Ｔ’の値を表１に示す。
　なお、フィルムの膜厚Ｌは、ノギスを用いて測定し、フィルムの任意の９箇所における算術平均値である。 The film thickness L (μm) shown in Table 1 and Table 1 can be calculated using the following formula (2) created from the relationship of Lambert-Beer's law that the absorbance of an absorbing substance is proportional to the optical path length (film thickness). Using the value of the shown transmittance T, the transmittance T' (%) when the film thickness of the film was corrected to 40 μm was calculated. Table 1 shows the values of transmittance T'.
The film thickness L of the film is measured using a caliper and is the arithmetic mean value at nine arbitrary locations on the film.
Figure JPOXMLDOC01-appb-M000002
 ・・・式（２）
Figure JPOXMLDOC01-appb-M000002
 ...Formula (2)
＜耐候性＞
　上記光線透過率の値に基づいて耐候性を評価した。評価基準は以下の通りであり、評価結果を表１に示す。
（評価基準）
　Ａ：　波長２６０ｎｍ～３００ｎｍの波長域における光線透過率が、前記膜の厚さを４０μｍとした際に５０％以上で、紫外線吸収による樹脂破壊が抑制されて、耐候性が良好であった。
　Ｂ：　波長２６０ｎｍ～３００ｎｍの波長域における光線透過率が、前記膜の厚さを４０μｍとした際に５０％未満で、紫外線吸収による樹脂破壊が生じ、耐候性が不十分であった。 <Weather resistance>
Weather resistance was evaluated based on the above light transmittance value. The evaluation criteria are as follows, and the evaluation results are shown in Table 1.
(Evaluation criteria)
A: The light transmittance in the wavelength range of 260 nm to 300 nm was 50% or more when the thickness of the film was 40 μm, resin destruction due to ultraviolet absorption was suppressed, and weather resistance was good.
B: The light transmittance in the wavelength range of 260 nm to 300 nm was less than 50% when the thickness of the film was 40 μm, resin destruction occurred due to ultraviolet absorption, and weather resistance was insufficient.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表１に示す通り、特定有機溶剤の存在下で、かつ、ビニルエステルの不存在下で、単量体ａ１１、単量体ａ１２及び単量体ａ１３を重合して得られた含フッ素重合体を用いた場合、耐候性に優れた塗膜を形成できることが確認された。
　なお、２０２２年４月４日に出願された日本特許出願２０２２－０６２３８８号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 As shown in Table 1, a fluoropolymer obtained by polymerizing monomer a11, monomer a12, and monomer a13 in the presence of a specific organic solvent and in the absence of vinyl ester. It was confirmed that when used, a coating film with excellent weather resistance could be formed.
The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2022-062388 filed on April 4, 2022 are cited here and incorporated as disclosure of the specification of the present invention. It is something.

Claims (7)

  1. 　メチルエチルケトン、アセトン、酢酸ｎ－ブチル、及び、テトラヒドロフランからなる群から選択される少なくとも１種の有機溶剤の存在下で、かつ、ビニルエステルの不存在下で、
    　ＣＦ２＝ＣＦ２、ＣＦ２＝ＣＦＣｌ、ＣＦ２＝ＣＨＦ及びＣＨ２＝ＣＦ２からなる群から選択される少なくとも１種のフッ素系単量体と、フッ素原子及び反応性基を有しないビニルエーテルと、反応性基を有する単量体と、を重合して、含フッ素重合体を得ることを特徴とする、含フッ素重合体の製造方法。     In the presence of at least one organic solvent selected from the group consisting of methyl ethyl ketone, acetone, n-butyl acetate, and tetrahydrofuran, and in the absence of vinyl ester,
    At least one fluorine-based monomer selected from the group consisting of CF2 = CF2 , CF2 =CFCl, CF2 =CHF and CH2 = CF2 , and a vinyl ether having no fluorine atom or reactive group. , and a monomer having a reactive group to obtain a fluoropolymer.
  2. 　前記有機溶剤が、メチルエチルケトン、アセトン、及び、酢酸ｎ－ブチルからなる群から選択される少なくとも１種の有機溶剤である、請求項１に記載の含フッ素重合体の製造方法。 The method for producing a fluoropolymer according to claim 1, wherein the organic solvent is at least one organic solvent selected from the group consisting of methyl ethyl ketone, acetone, and n-butyl acetate.
  3. 　前記フッ素系単量体が、ＣＦ２＝ＣＦ２及びＣＦ２＝ＣＦＣｌからなる群から選択される少なくとも１種の単量体である、請求項１又は２に記載の含フッ素重合体の製造方法。 The method for producing a fluoropolymer according to claim 1 or 2, wherein the fluorine-based monomer is at least one monomer selected from the group consisting of CF 2 =CF 2 and CF 2 =CFCl. .
  4. 　前記反応性基が、水酸基、アミノ基、エポキシ基、オキセタニル基、加水分解性シリル基、スルホ基、及び、カルボキシ基からなる群から選択される少なくとも１種の基である、請求項１又は２に記載の含フッ素重合体の製造方法。 2. The reactive group is at least one group selected from the group consisting of a hydroxyl group, an amino group, an epoxy group, an oxetanyl group, a hydrolyzable silyl group, a sulfo group, and a carboxy group. A method for producing a fluoropolymer according to .
  5. 　ＣＦ２＝ＣＦ２、ＣＦ２＝ＣＦＣｌ、ＣＦ２＝ＣＨＦ及びＣＨ２＝ＣＦ２からなる群から選択される少なくとも１種のフッ素系単量体に基づくフッ素系単位と、
    　フッ素原子及び反応性基を有しない、ビニルエーテルに基づく非フッ素系単位と、
    　反応性基を有する単量体に基づく単位と、を有し、ビニルエステルに基づく単位を有しない含フッ素重合体であって、
    　前記含フッ素重合体を用いて得られた膜の波長２６０ｎｍ～３００ｎｍの波長域における光線透過率が、前記膜の厚さを４０μｍとした際に、５０％以上であることを特徴とする、含フッ素重合体。     a fluorine-based unit based on at least one fluorine-based monomer selected from the group consisting of CF2= CF2 , CF2 =CFCl, CF2 =CHF , and CH2 = CF2 ;
    a non-fluorinated unit based on vinyl ether, which does not have a fluorine atom and a reactive group;
    A fluoropolymer having a unit based on a monomer having a reactive group and not having a unit based on a vinyl ester,
    The light transmittance of the film obtained using the fluorine-containing polymer in the wavelength range of 260 nm to 300 nm is 50% or more when the thickness of the film is 40 μm. Fluoropolymers.
  6. 　請求項５に記載の含フッ素重合体を含むことを特徴とする、塗料。 A paint comprising the fluoropolymer according to claim 5.
  7. 　基材と、前記基材上に配置された請求項６に記載の塗料から形成された塗膜と、を有することを特徴とする、塗膜付き基材。 A base material with a coated film, comprising a base material and a coated film formed from the paint according to claim 6 placed on the base material.
PCT/JP2023/012295 2022-04-04 2023-03-27 Method for producing fluorine-containing polymer, fluorine-containing polymer, coating material, and substrate equipped with coating film WO2023195375A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022062388 2022-04-04
JP2022-062388 2022-04-04

Publications (1)

Publication Number Publication Date
WO2023195375A1 true WO2023195375A1 (en) 2023-10-12

Family

ID=88242857

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/012295 WO2023195375A1 (en) 2022-04-04 2023-03-27 Method for producing fluorine-containing polymer, fluorine-containing polymer, coating material, and substrate equipped with coating film

Country Status (2)

Country Link
TW (1) TW202342561A (en)
WO (1) WO2023195375A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04226111A (en) * 1990-05-29 1992-08-14 Daikin Ind Ltd Fluoropolymer and composition for coating material
JPH04279612A (en) * 1990-06-29 1992-10-05 Daikin Ind Ltd Fluorine-containing copolymer and curable composition using the same
JP2003295442A (en) * 2002-04-03 2003-10-15 Fuji Photo Film Co Ltd Positive resist composition
JP2009013299A (en) * 2007-07-05 2009-01-22 Asahi Glass Co Ltd Aqueous coating material composition, its manufacturing method and two-pack curable aqueous coating material kit
JP2020176208A (en) * 2019-04-18 2020-10-29 Ａｇｃ株式会社 Coating and vehicle exterior member

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04226111A (en) * 1990-05-29 1992-08-14 Daikin Ind Ltd Fluoropolymer and composition for coating material
JPH04279612A (en) * 1990-06-29 1992-10-05 Daikin Ind Ltd Fluorine-containing copolymer and curable composition using the same
JP2003295442A (en) * 2002-04-03 2003-10-15 Fuji Photo Film Co Ltd Positive resist composition
JP2009013299A (en) * 2007-07-05 2009-01-22 Asahi Glass Co Ltd Aqueous coating material composition, its manufacturing method and two-pack curable aqueous coating material kit
JP2020176208A (en) * 2019-04-18 2020-10-29 Ａｇｃ株式会社 Coating and vehicle exterior member

Also Published As

Publication number Publication date
TW202342561A (en) 2023-11-01

Similar Documents

Publication Publication Date Title
US6803426B2 (en) Functional fluoropolymers and thermosetting compositions containing same
JP5438970B2 (en) Two-component fluorine coating composition
CN110536939B (en) Fluorine-based paint, method for producing fluorine-based paint, coated article, and method for producing coated article
EP3219769B1 (en) Composition for powder coating material, powder coating material and coated article
JP6056867B2 (en) Method for producing fluorine-containing copolymer solution and coating composition
WO1991006584A1 (en) Fluorocopolymer and production thereof
JP2004307666A (en) Fluorine-containing copolymer for coating, coating composition and coating
JP5103252B2 (en) Fluorine copolymer solution and method for producing the same
JP5838856B2 (en) Fluorine-based graft copolymer and coating agent
JP2016150996A (en) Coating material composition for release film and release film
WO2023195375A1 (en) Method for producing fluorine-containing polymer, fluorine-containing polymer, coating material, and substrate equipped with coating film
WO2020017563A1 (en) Coating material, coating film-equipped substrate, and method for producing coating film-equipped substrate
JPH0686581B2 (en) Paint composition
JP6789037B2 (en) An acrylic resin composition, an article produced using the acrylic resin composition, and a method for producing the acrylic resin composition.
JP3160869B2 (en) Fluorine-containing copolymer and coating composition containing the copolymer as a main component
WO2023195374A1 (en) Composition and base material with coating film
JP2004277716A (en) Fluorine containing copolymer for paint, composition for paint, and paint
JP2006002034A (en) Fluororesin powder coating composition
JP2007277577A (en) Polymers derived from isobutylene and fluoromonomer
JPH0428707A (en) Vinylidene fluoride copolymer and curable composition containing the same
JPH05163457A (en) Resin composition
JP3861680B2 (en) Active energy ray curable primer composition for polyolefin resin
JP3632783B2 (en) Adhesive composition for fluorine-based film
JPH01247448A (en) Fluorinated copolymer composition
JP2964561B2 (en) Composition for paint

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23784665

Country of ref document: EP

Kind code of ref document: A1