WO2013024886A1

WO2013024886A1 - Fluorocopolymer composition, coating composition, article having film, and molded article

Info

Publication number: WO2013024886A1
Application number: PCT/JP2012/070800
Authority: WO
Inventors: 中野　貴志; 岡野　邦子
Original assignee: 旭硝子株式会社
Priority date: 2011-08-17
Filing date: 2012-08-16
Publication date: 2013-02-21

Abstract

Provided are: a fluorocopolymer capable of being formed into an article and film having excellent adhesion, excoriation resistance, heat resistance, and other properties even after being baked at a relatively low temperature; a coating composition containing the fluorocopolymer; an article having a film with excellent adhesion, excoriation resistance, heat resistance, and other properties while retaining the characteristics of a fluorocopolymer; and a molded article. Used is a fluorocopolymer composition comprising: a fluorocopolymer (A) having a repeating unit based on ethylene and a repeating unit based on tetrafluoroethylene; a compound (B) having at least one reactive functional group selected from the group consisting of a group having a cyclic ether having ring-opening reactivity and a group having a carbon-carbon double bond having addition reactivity (where the fluorocopolymer (A) is not included); and a medium (C) in which the fluorocopolymer (A) can be dissolved or dispersed, and in which the compound (B) can be dissolved or dispersed.

Description

Fluorine-containing copolymer composition, coating composition, article having coating film, and molded article

The present invention relates to a fluorine-containing copolymer composition, a coating composition containing the fluorine-containing copolymer composition, an article having a coating film formed using the coating composition, and a fluorine-containing copolymer. The present invention relates to a molded product obtained by molding a composition.

Fluoropolymers are used in various applications that cannot be handled by general-purpose plastics because they are excellent in solvent resistance, low dielectric properties, low surface energy, non-adhesiveness, weather resistance, and the like. Among fluororesins, a fluorine-containing copolymer (hereinafter also referred to as ETFE) having a repeating unit based on ethylene and a repeating unit based on tetrafluoroethylene is low in heat resistance, flame resistance, chemical resistance, weather resistance, Because of its excellent frictional properties, low dielectric properties, transparency, etc., it is used in a wide range of fields such as heat-resistant wire coating materials, chemical plant corrosion-resistant piping materials, agricultural vinyl house materials, and mold release films. .

Incidentally, since ETFE is insoluble in organic solvents, it has been considered that a coating composition containing ETFE cannot be prepared. However, recently, ETFE can be dissolved in a specific organic solvent (a fluorine-containing aromatic compound or a chain hydrocarbon compound having a carbonyl group) under heating below the melting point of ETFE. It has been clarified that an ETFE dispersion can be obtained by cooling the ETFE solution dissolved in the aromatic compound (see Patent Documents 1 and 2).

International Publication No. 2010/044421 International Publication No. 2010/044445

However, since the coating film formed by applying the ETFE dispersion on the surface of the substrate and drying it has many voids and insufficient denseness, adhesion, scratch resistance, etc. are insufficient, The substrate cannot be sufficiently protected. If the coating film is baked at a melting point of ETFE or higher, a dense coating film can be obtained, but the characteristics of ETFE are likely to deteriorate due to exposure to high temperatures. Further, when the substrate does not have sufficient heat resistance, firing at a temperature equal to or higher than the melting point cannot be applied.

The present invention is a fluorine-containing copolymer capable of forming a coating film and a molded article excellent in adhesion, scratch resistance, base material protection performance, heat resistance, etc. even when fired at a relatively low temperature; fired at a relatively low temperature However, the coating composition capable of forming a coating film and a molded article excellent in adhesion, scratch resistance, substrate protective performance, heat resistance, etc .; while maintaining the properties of the fluorinated copolymer, To provide an article having a coating film excellent in scratch resistance, substrate protective performance, heat resistance, etc .; and a molded article excellent in scratch resistance, heat resistance, etc. while maintaining the properties of the fluorinated copolymer. With the goal.

The fluorine-containing copolymer composition of the present invention comprises a fluorine-containing copolymer (A) having a repeating unit based on ethylene and a repeating unit based on tetrafluoroethylene, a group having a cyclic ether having ring-opening reactivity, and an addition A compound (B) having at least one reactive functional group selected from the group consisting of a group having a reactive carbon-carbon double bond (excluding the fluorine-containing copolymer (A)); And a medium (C) capable of dissolving or dispersing the fluorine-containing copolymer (A) and capable of dissolving or dispersing the compound (B).
The mixing ratio of the fluorinated copolymer (A) and the compound (B) is preferably 98/2 to 2/98 by mass ratio, and the content ratio of the medium (C) is fluorinated copolymer composition. 10 to 99% by mass is preferable with respect to (100% by mass).
The melting point of the fluorine-containing copolymer (A) is preferably in the range of 150 to 260 ° C.
Furthermore, the melting point of the medium (C) is preferably in the range of 25 ° C. or lower, and the boiling point is preferably in the range of 230 ° C. or lower at normal pressure.

The fluorine-containing copolymer composition of the present invention comprises a reaction of the compound (D1) having a reactive functional group capable of reacting with the reactive functional group of the compound (B) and the reactive functional group of the compound (B). It is preferable to further include at least one compound (D) selected from the group consisting of the compound (D2) that can be promoted (however, excluding the following compound (E)).

The fluorine-containing copolymer composition of the present invention may further contain a compound (E) that can promote dissolution or dispersion of the fluorine-containing copolymer (A) or the compound (B) in the medium (C). preferable.
The compound (E) comprises at least one group selected from the group consisting of a primary amino group, a secondary amino group, and a nitrogen-containing heterocyclic group having a nitrogen-hydrogen bond, and an alkyl group having 1 to 20 carbon atoms. It is preferable that it is a compound (E1) which has.

The medium (C) is preferably a solvent having a solubility index (R) represented by the following formula (1) of less than 49.
R = 4 × (δd−15.7) ² + (δp−5.7) ² + (δh−4.3) ² (1).
However, δd, δp, and δh are a dispersion term, a polar term, and a hydrogen bond term [(MPa) ^1/2 ] in the Hansen solubility parameter of the solvent, respectively.

The coating composition of the present invention includes the fluorine-containing copolymer composition of the present invention.
The article having the coating film of the present invention has a coating film formed using the coating composition of the present invention.
The molded article of the present invention is formed by molding the fluorine-containing copolymer composition of the present invention.

According to the fluorine-containing copolymer composition of the present invention, a coating film and a molded article excellent in adhesion, scratch resistance, heat resistance and the like can be formed even when fired at a relatively low temperature.
According to the coating composition of the present invention, a coating film having excellent adhesion, scratch resistance, heat resistance and the like can be formed even when fired at a relatively low temperature.
The article having the coating film of the present invention has a coating film excellent in adhesion, scratch resistance, heat resistance and the like while maintaining the characteristics of the fluorinated copolymer.
The molded article of the present invention is excellent in scratch resistance, heat resistance and the like while maintaining the characteristics of the fluorine-containing copolymer.

The “repeating unit” in the present specification means a unit derived from the monomer formed by polymerization of the monomer. The repeating unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by treating the polymer.
Further, the “monomer” in the present specification means a compound having a polymerization-reactive carbon-carbon double bond.

Further, in this specification, the “solution state” in which the fluorine-containing copolymer (A) and / or the compound (B) is dissolved in the medium (C) means the fluorine-containing copolymer (A) and / or the compound (B ) And the medium (C) sufficiently mixed to mean that the insoluble matter is not confirmed by visual inspection.

In addition, “melting temperature” in this specification refers to a temperature measured by the following method.
A total of 0.10 g of the fluorinated copolymer (A) and / or the compound (B) is added to 4.90 g of the medium (C), and the mixture is heated with a stirring means or the like while always maintaining a sufficiently mixed state. Whether the polymer (A) and / or the compound (B) is dissolved is visually observed. First, the temperature at which the mixture is found to be in a uniform solution state and completely dissolved is confirmed. Subsequently, the temperature at which the solution becomes turbid is confirmed by gradually cooling, and the temperature at which the solution is reheated and becomes a uniform solution again is defined as the dissolution temperature.

<Fluorine-containing copolymer composition>
The fluorine-containing copolymer composition of the present invention is in a solution state or a dispersion state containing the fluorine-containing copolymer (A), the compound (B), and the medium (C). The fluorine-containing copolymer composition of the present invention may contain a compound (D), a compound (E), another resin (F) or the like as necessary.

(Fluorine-containing copolymer (A))
The fluorine-containing copolymer (A) is a copolymer having a repeating unit based on ethylene and a repeating unit based on tetrafluoroethylene (hereinafter referred to as TFE).

The molar ratio of the repeating unit based on TFE and the repeating unit based on ethylene (TFE / ethylene) is preferably 70/30 to 30/70, more preferably 65/35 to 40/60, and 60/40 to 40/60. Is more preferable. If the molar ratio is within the above range, it is derived from repeating units based on TFE such as heat resistance, weather resistance, chemical resistance and the like, and repeating units based on ethylene such as mechanical strength and melt moldability. Good balance with characteristics.

The fluorine-containing copolymer (A) has repeating units based on monomers other than ethylene and TFE (hereinafter referred to as other monomers) from the viewpoint that various functions can be imparted to the obtained copolymer. Is preferred.
Examples of other monomers include the following compounds.

Fluoroethylenes: CF ₂ = CFCl, CF ₂ = CH ₂ etc. (excluding TFE),
Hexafluoropropylene _{_{_{_{such: CF 2 = CFCF 3, CF}}}} 2 = CHCF 3, CH 2 = CHCF 3 and the like,
Fluoroisobutylenes: (CF ₃ ) ₂ C═CH ₂ etc.
Polyfluoroalkylethylenes having a fluoroalkyl group having 2 to 12 carbon atoms: CF ₃ CF ₂ CH═CH ₂ , CF ₃ CF ₂ CF ₂ CF ₂ CH═CH ₂ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ _{_{_{_{CF 2 CH = CH 2, CF}}}} 3 CF 2 CF 2 CF 2 CF = CH 2, CF 2 HCF 2 CF 2 CF = CH 2 and the like,
Polyfluorodienes having a fluoroalkylene group having 5 to 12 carbon atoms: CH ₂ ═CH (CF ₂ ) ₄ CH═CH ₂ etc.
Perfluorovinyl ^{_{_{ethers: R f (OCFXCF 2) m}}} OCF = CF 2 ( where the ^{R f} is a perfluoroalkyl group having 1 to 6 carbon atoms, X is a fluorine atom or a trifluoromethyl group, m, An integer of 0 to 5), etc.
Perfluorovinyl ethers having groups easily convertible to carboxylic acid groups or sulfonic acid groups; CH ₃ OC (═O) CF ₂ CF ₂ CF ₂ OCF═CF ₂ , FSO ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF = CF ₂ etc.
Olefins: olefins having 3 carbon atoms (propylene, etc.), olefins having 4 carbon atoms (butylene, isobutylene, etc.), 4-methyl-1-pentene, cyclohexene, styrene, α-methylstyrene, etc. (excluding ethylene) ),
Vinyl esters: vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pivalate, vinyl benzoate, etc.
Allyl esters: allyl acetate, etc.
Vinyl ethers: methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, polyoxyethylene vinyl ether, etc.
Allyl ethers: allyl methyl ether, allyl ethyl ether, allyl butyl ether, allyl glycidyl ether, etc.
(Meth) acrylic acid esters: methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid 4-hydroxybutyl, glycidyl (meth) acrylate, etc.
(Meth) acrylamides: (Meth) acrylamide, N-methyl (meth) acrylamide, N-isopropylacrylamide, N, N-dimethyl (meth) acrylamide, etc.
Cyano group-containing monomers: acrylonitrile, etc.
Diene: isoprene, 1,3-butadiene, etc.
Chloroolefins: Vinyl chloride, vinylidene chloride, etc.
Compound containing carboxylic anhydride and unsaturated bond: maleic anhydride, itaconic anhydride, citraconic anhydride and the like.

Another monomer may be used individually by 1 type and may be used in combination of 2 or more type.
The proportion of repeating units based on other monomers is preferably from 0.1 to 50 mol%, more preferably from 0.1 to 30 mol%, and more preferably from 0.1 to 20 mol based on the total repeating units (100 mol%). More preferred is mol%. If the ratio of repeating units based on other monomers is within this range, high solubility and repellency can be achieved without impairing the properties of ETFE consisting essentially of repeating units based on ethylene and repeating units based on TFE. Functions such as aqueous properties, oil repellency, adhesion to the substrate, and reactivity with the compound (B) can be imparted.

The fluorinated copolymer (A) has reactivity with the substrate and the compound (B) from the viewpoints of adhesion of the coating film to the substrate, miscibility with the compound (B), compatibility and the like. It preferably has a reactive functional group. The reactive functional group may be present at any of the molecular end, side chain, or main chain of the fluorine-containing copolymer (A). Moreover, only one type of reactive functional group may be present, or two or more types may be present. The kind of the reactive functional group and the content thereof are appropriately selected depending on the kind of the compound (B), the functional group possessed by the compound (B), the required characteristics, the molding method and the like.

The reactive functional group includes a carboxylic acid group, a group obtained by dehydration condensation of two carboxyl groups in one molecule (hereinafter referred to as an acid anhydride group), a hydroxyl group, a sulfonic acid group, an epoxy group, a cyano group, and a carbonate group. And at least one selected from the group consisting of an isocyanate group, an ester group, an amide group, an aldehyde group, an amino group, a hydrolyzable silyl group, a group having a carbon-carbon double bond, and a carboxylic acid halide group.
The carboxylic acid group means a carboxyl group and a salt thereof (—COOM ¹ ). However, M < ¹ > is a metal atom or atomic group which can form a salt with carboxylic acid.
The sulfonic acid group means a sulfo group and a salt thereof (—SO ₃ M ² ). However, M ² is a metal atom or an atomic group capable of forming a salt with sulfonic acid.
The hydrolyzable silyl group is a group in which an alkoxy group, an amino group, a halogen atom, or the like is bonded to a silicon atom, and is a group that can be crosslinked by forming a siloxane bond by hydrolysis. A trialkoxysilyl group, an alkyl dialkoxysilyl group and the like are preferable.

Among reactive functional groups, carboxylic acid groups, acid anhydride groups, hydroxyl groups, epoxy groups, carbonate groups, amino groups, amide groups, hydrolyzable silyl groups, groups having a carbon-carbon double bond, and carboxylic acids Preferably, at least one selected from the group consisting of halide groups, carboxylic acid groups, acid anhydride groups, hydroxyl groups, epoxy groups, amino groups, amide groups, groups having a carbon-carbon double bond, and carboxylic acid halide groups More preferred is at least one selected from the group consisting of

Examples of the method for introducing a reactive functional group into the fluorinated copolymer (A) include the following methods.
(I) A method of copolymerizing a monomer having a reactive functional group as one of the other monomers when polymerizing ethylene, TFE and another monomer.
(Ii) Fluorine-containing copolymer (A) by using a polymerization initiator having a reactive functional group, a chain transfer agent or the like when copolymerizing ethylene, TFE and other monomers as required. A method of introducing a reactive functional group at the molecular end of the polymer.
(Iii) A method of grafting a compound having a reactive functional group and a functional group capable of grafting (such as an unsaturated bond) (grafting compound) onto the fluorine-containing copolymer (A).

Two or more methods (i) to (iii) may be appropriately combined. Among the methods (i) to (iii), the method (i) and / or (ii) is preferable from the viewpoint of durability of the fluorine-containing copolymer (A).
In addition to the reactive functional group, the functional group introduced as necessary to impart various functions to the fluorine-containing copolymer (A) is the same as the method of introducing the reactive functional group. It can introduce | transduce into a fluorine-containing copolymer (A).

The melting point of the fluorinated copolymer (A) is preferably from 130 to 275 ° C., more preferably from 140 to 265 ° C., and even more preferably from 150 to 260 ° C. from the viewpoints of solubility and strength.
The melting point of the fluorinated copolymer (A) is measured by, for example, a differential scanning calorimetry (DSC) apparatus.

Commercially available ETFE may be used as the fluorinated copolymer (A). The following are mentioned as commercially available ETFE.
Asahi Glass Co., Ltd .: Fluon (registered trademark) ETFE Series, Fluon (registered trademark) LM Series,
Daikin Industries, Ltd .: Neoflon (registered trademark),
Dyneon: Dyneon (registered trademark) ETFE,
DuPont: Tefzel (registered trademark), etc.
A fluorine-containing copolymer (A) may be used individually by 1 type, and may be used in combination of 2 or more type.

(Compound (B))
Compound (B) is a curable compound having at least one reactive functional group selected from the group consisting of a group having a cyclic ether having ring-opening reactivity and a group having a carbon-carbon double bond having addition reactivity. Compound (however, excluding the fluorine-containing copolymer (A)).

As the compound (B), in the temperature range in which the fluorinated copolymer (A) and the medium (C) are in a solution state, those that dissolve in the medium (C), those that partially dissolve in the medium (C), Or what does not melt | dissolve at all may be sufficient. The compound (B) is preferably one that is soluble in the medium (C) from the viewpoint of miscibility and compatibility with the fluorinated copolymer (A).

Examples of the group having a cyclic ether having ring-opening reactivity include an epoxy group, a glycidyl group, and an oxetanyl group.
Examples of the group having a carbon-carbon double bond having addition reactivity include a vinyl group, an allyl group, an acryloyloxy group, a methacryloyloxy group, and a styryl group.

Examples of the compound (B1) containing a group having a cyclic ether having ring-opening reactivity include epoxy resins and oxetane resins.
Examples of the compound (B2) containing a group having a carbon-carbon double bond having addition reactivity include an acrylic monofunctional monomer, an acrylic polyfunctional monomer, an acrylic macromonomer, an allyl monofunctional monomer, and an allyl polyfunctional monomer. A functional monomer, an allylic macromonomer, etc. are mentioned.
Examples of the compound (B3) having a group having a cyclic ether having ring-opening reactivity and a group having a carbon-carbon double bond having addition reactivity include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether. .

The compound (B) may be a curable fluorine-containing compound. Examples of the curable fluorine-containing compound include a fluorine-containing epoxy resin, a curable fluorine-containing copolymer described in International Publication No. 2009/096342, a curable fluorine-containing copolymer described in Japanese Patent Application Laid-Open No. 7-228818, and the like. Is mentioned.

As the compound (B), when the fluorine-containing copolymer (A) has a reactive functional group, the fluorine-containing copolymer (A) is preferable from the viewpoint of miscibility or compatibility with the fluorine-containing copolymer (A). What has a reactive functional group which can react with the reactive functional group of a polymer (A) is preferable.

A commercially available curable compound may be used as the compound (B). The following are mentioned as a commercially available curable compound.
Made by ADEKA: Adeka Resin (registered trademark),
Mitsubishi Chemical Corporation: jER (registered trademark)
DIC Corporation: EPICLON (registered trademark),
Daicel Chemical Industries, Ltd .: Celoxide (registered trademark)
Shin-Nakamura Chemical Co., Ltd .: NK Ester (registered trademark)
Maruzen Petrochemical Co., Ltd .: bisallyl nadiimide, etc.
A compound (B) may be used individually by 1 type, and may be used in combination of 2 or more type.
In addition, as a hardening method of a compound (B), various hardening methods, such as thermosetting, photocuring, and radiation curing, are applicable. It is also preferable to cure by using a compound (D) described later in combination.

(Medium (C))
The medium (C) is a medium that can dissolve or disperse the fluorine-containing copolymer (A) and can dissolve or disperse the compound (B).

As the medium (C), a solvent capable of dissolving the fluorinated copolymer (A) at a temperature not higher than the melting point of the fluorinated copolymer (A) is preferable. After the fine particles of the combined body (A) are precipitated and uniformly dispersed, a solvent that functions as a dispersion medium for allowing the fine particles to exist in a dispersed state is more preferable at least at normal temperature and pressure.

The medium (C) may dissolve the compound (B), or may not dissolve the compound (B) partially or at all, and the fluorine-containing copolymer (A) and the compound From the viewpoint of miscibility with (B) or compatibility, those that dissolve the compound (B) are preferred.

Whether or not a certain solvent is a medium (C) capable of dissolving at least the fluorinated copolymer (A) can be determined by whether or not the polarity of the solvent is within a specific range. In the present invention, it is preferable to select a solvent having a certain range of polarities as the medium (C) based on Hansen solubility parameters (Hansen solubility parameters).

The Hansen solubility parameter is a three-dimensional space where the solubility parameter introduced by Hildebrand is divided by Hansen into three components: a dispersion term δd, a polar term δp, and a hydrogen bond term δh. It is. The dispersion term δd indicates the effect due to the dispersion force, the polar term δp indicates the effect due to the dipole force, and the hydrogen bond term δh indicates the effect due to the hydrogen bond force. The closer the coordinates of a specific resin X in a three-dimensional space are to the coordinates of a certain solvent, the easier the resin X dissolves in the solvent.

The definition and calculation method of the Hansen solubility parameter is described in the following document.
Charles M. Hansen, “Hansen Solubility Parameters: A Users Handbook”, CRC Press, 2007.

For solvents whose literature values are not known, Hansen solubility parameters can be easily estimated from their chemical structures by using computer software (Hansen Solubility Parameters in Practice (HSPIP)).
In the present invention, HSPiP version 3 is used, and the value is used for the solvent registered in the database, and the estimated value is used for the solvent not registered.

The Hansen solubility parameter of a specific resin X is usually determined by conducting a solubility test in which the resin X is dissolved in a number of different solvents for which the Hansen solubility parameter has been determined and the solubility is measured. Specifically, when the coordinates of the Hansen solubility parameters of all the solvents used in the solubility test are shown in a three-dimensional space, the coordinates of the solvent in which the resin X is dissolved are all contained inside the sphere and the solvent is not dissolved. A sphere (solubility sphere) that is outside the sphere is found, and the center coordinates of the solubility sphere are used as the Hansen solubility parameter of the resin X.
Further, when the coordinates of the Hansen solubility parameter of a certain solvent not used in the solubility test are (δd, δp, and δh), if the coordinates are included inside the solubility sphere, the solvent contains the resin X. It is thought to dissolve. On the other hand, if the coordinates are outside the solubility sphere, it is considered that the solvent cannot dissolve the resin X.

In the present invention, the most suitable solvent for dissolving at least the fluorinated copolymer (A) at a temperature below its melting point and dispersing it as fine particles without agglomerating the fluorinated copolymer (A) at room temperature. It is assumed that diisopropyl ketone is a substance having a property closest to the fluorine-containing copolymer (A) as a Hansen solubility parameter. Then, with diisopropyl ketone as the reference (the center of the solubility sphere), the solvent at a certain distance (ie, inside the solubility sphere) from the coordinates (15.7, 5.7, and 4.3) of the Hansen solubility parameter of diisopropyl ketone. Groups can be used as medium (C).

Specifically, an expression well known as an expression for obtaining the distance Ra between two points in the three-dimensional space of the Hansen solubility parameter,
Based on (Ra) ² = 4 × (δd2−δd1) ² + (δp2−δp1) ² + (δh2−δh1) ² , the coordinates of diisopropyl ketone and the coordinates and distance of a solvent are estimated by the following formula (1) And R represented by the following formula (1) is used as a solubility index for the fluorinated copolymer (A).
R = 4 × (δd−15.7) ² + (δp−5.7) ² + (δh−4.3) ² (1).
However, δd, δp, and δh are a dispersion term, a polar term, and a hydrogen bond term [(MPa) ^1/2 ] in the Hansen solubility parameter of the solvent, respectively.

The medium (C) preferably has a solubility index (R) of less than 49, more preferably less than 36. The medium (C) having the solubility index (R) within this range has high affinity with the fluorinated copolymer (A), and the solubility and dispersibility of the fluorinated copolymer (A) are increased.
Even when the medium (C) is a mixed solvent in which two or more solvents are combined, the solubility index (R) can be used as a solubility index for the fluorinated copolymer (A). For example, an average Hansen solubility parameter is obtained from the mixing ratio (volume ratio) of the mixed solvent, and the dissolution index (R) is calculated from the average value.

Examples of the solvent that can be used as the medium (C) include ketones having 3 to 10 carbon atoms, esters, carbonates, ethers, or nitriles, fluorine-containing aromatic compounds having at least two fluorine atoms, or heterocyclic rings. Compounds (fluorinated benzonitrile, fluorine-containing benzoic acid or ester, fluorine-containing nitrobenzene, fluorine-containing phenyl alkyl alcohol, fluorine-containing phenol ester, fluorine-containing aromatic ketone, fluorine-containing aromatic ether, fluorine-containing pyridine compound, Fluoroaromatic carbonate, perfluoroalkyl-substituted benzene, perfluorobenzene, polyfluoroalkyl ester of benzoic acid, polyfluoroalkyl ester of phthalic acid, etc.), hydrofluorocarbons, hydrofluoroethers, hydrofluoroa Call, and the like can be mentioned. Preferred are ketones or esters having 3 to 10 carbon atoms and fluorine-containing aromatic compounds.

Specific examples of the medium (C) having a dissolution index (R) of less than 49 include the following solvents.

As the medium (C), the following solvents are preferable from the viewpoint of high affinity with the fluorinated copolymer (A) and sufficiently high solubility and dispersibility of the fluorinated copolymer (A).
Methyl ethyl ketone, 2-pentanone, methyl isopropyl ketone, 2-hexanone, methyl isobutyl ketone, pinacholine, 2-heptanone, 4-heptanone, diisopyrrole ketone, isoamyl methyl ketone, 2-octanone, 2-nonanone, diisobutyl ketone, cyclohexanone 2-methylcyclohexanone, 3-methylcyclohexanone, 4-ethylcyclohexanone, 2,6-dimethylcyclohexanone, 3,3,5-trimethylcyclohexanone, cycloheptanone, isophorone, (-)-fencon, propyl formate, isopropyl formate, Butyl formate, isobutyl formate, sec-butyl formate, amyl formate, isoamyl formate, hexyl formate, heptyl formate, octyl formate, 2-ethylhexyl formate, ethyl acetate, propyl acetate Isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, cyclohexyl acetate, heptyl acetate, 2,2,2-trifluoroethyl acetate, 2,2,3,3-tetraacetate Fluoropropyl, 2,2,3,3,3-pentafluoropropyl acetate, 1,1,1,3,3,3-hexafluoro-2-propyl acetate, 2,2-bis (trifluoromethyl) propyl acetate 2,2,3,3,4,4,4-heptafluorobutyl acetate, 2,2,3,4,4,4-hexafluorobutyl acetate, 2,2,3,3,4,4, acetic acid 5,5,5-nonafluoropentyl, acetic acid 2,2,3,3,4,4,5,5-octafluoropentyl, acetic acid 3,3,4,4,5,5,6,6,6- Nonafluorohexyl, Acid 4,4,5,5,6,6,7,7,7-nonafluoroheptyl, acetic acid 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro Heptyl, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, sec-butyl propionate, t-butyl propionate, amyl propionate, isoamyl propionate, hexyl propionate, Cyclohexyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, sec-butyl butyrate, t-butyl butyrate, amyl butyrate, isoamyl butyrate, methyl isobutyrate, ethyl isobutyrate, propyl isobutyrate, Isopropyl isobutyrate, butyl isobutyrate, isobutyrate isobutyrate , Sec-butyl isobutyrate, t-butyl isobutyrate, amyl isobutyrate, isoamyl isobutyrate, methyl valerate, ethyl valerate, propyl valerate, isopropyl valerate, butyl valerate, isobutyl valerate, sec-valerate Butyl, t-butyl valerate, methyl isovalerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, sec-butyl isovalerate, t-isovalerate Butyl, methyl hexanoate, ethyl hexanoate, propyl hexanoate, isopropyl hexanoate, methyl heptanoate, ethyl heptanoate, methyl octoate, methyl cyclohexanecarboxylate, ethyl cyclohexanecarboxylate, cyclohexanecarboxylic acid 2,2,2-tri Fluoroethyl, bis succinate (2,2,2 Trifluoroethyl), bis (2,2,2-trifluoroethyl) glutarate, ethyl trifluoroacetate, propyl trifluoroacetate, isopropyl trifluoroacetate, butyl trifluoroacetate, isobutyl trifluoroacetate, sec-trifluoroacetic acid sec- Butyl, t-butyl trifluoroacetate, amyl trifluoroacetate, isoamyl trifluoroacetate, hexyl trifluoroacetate, cyclohexyl trifluoroacetate, heptyl trifluoroacetate, ethyl difluoroacetate, ethyl perfluoropropionate, methyl perfluorobutanoate, perfluorobutane Ethyl acetate, methyl perfluoropentanoate, ethyl perfluoropentanoate, methyl 2,2,3,3,4,4,5,5-octafluoropentanoate, 2,2,3,3,4,4,5,5 Ethyl octafluoropentanoate, methyl perfluoroheptanoate, ethyl perfluoroheptanoate, methyl 2,2,3,3,4,5,5,6,6,7,7-dodecafluoroheptanoate, 2,2, 3,3,4,4,5,5,6,6,7,7-ethyl dodecafluoroheptanoate, methyl 2-trifluoromethyl-3,3,3-trifluoropropionate, 2-trifluoromethyl- Ethyl 3,3,3-trifluoropropionate, 2-propoxyethyl acetate, 2-butoxyethyl acetate, 2-pentyloxyethyl acetate, 1-methoxy-2-acetoxypropane, 1-ethoxy-2-acetoxypropane, 1 -Propoxy-2-acetoxypropane, 1-butoxy-2-acetoxypropane, 3-methoxybutyl acetate, 3-ethoxybutylacetate , 3-propoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, 3-ethoxy-3-methylbutyl acetate, 4-methoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, diethyl carbonate, dipropyl carbonate, Dibutyl carbonate, bis (2,2,2-trifluoroethyl) carbonate, bis (2,2,3,3-tetrafluoropropyl) carbonate, tetrahydrofuran, butyronitrile, isobutyronitrile, valeronitrile, isovaleronitrile, capronitrile , Isocapronitrile, heptanenitrile, octanenitrile, nonanenitrile, 3- (trifluoromethyl) benzonitrile, methyl pentafluorobenzoate, ethyl pentafluorobenzoate, methyl 3- (trifluoromethyl) benzoate, 4- (bird Fluoromethyl) methyl benzoate, methyl 3,5-bis (trifluoromethyl) benzoate, 1- (pentafluorophenyl) ethanol, pentafluorophenyl formate, pentafluorophenyl acetate, pentafluorophenyl propanoate, pentafluorophenyl butanoate Pentafluorophenyl pentanoate, 2 ′, 3 ′, 4 ′, 5 ′, 6′-pentafluoroacetophenone, 3 ′, 5′-bis (trifluoromethyl) acetophenone, 3 ′-(trifluoromethyl) acetophenone, Pentafluoroanisole, 3,5-bis (trifluoromethyl) anisole, pentafluoropyridine, 4-chlorobenzotrifluoride, 1,3-bis (trifluoromethyl) benzene, 2,2,2-trifluoroethyl benzoate Benzoic acid 2,2,3,3-teto Lafluoropropyl, benzoic acid 2,2,3,3,3-pentafluoropropyl, benzoic acid 1,1,1,3,3,3-hexafluoro-2-propyl, benzoic acid 2,2-bis (tri Fluoromethyl) propyl, benzoic acid 2,2,3,3,4,4,4-heptafluorobutyl, benzoic acid 2,2,3,4,4,4-hexafluorobutyl, benzoic acid 2,2,3 , 3,4,4,5,5,5-nonafluoropentyl, benzoic acid 2,2,3,3,4,4,5,5-octafluoropentyl, bis (2,2,2-triphthalate) Fluoroethyl), 5- (perfluorobutyl) bicyclo [2.2.1] -2-heptene, 5- (perfluorobutyl) bicyclo [2.2.1] heptane, 1,1,2,2,3,3 , 4-Heptafluorocyclopentane, 1,1,1 2,3,3-hexafluoro-4- (1,1,2,3,3,3-hexafluoropropoxy) pentane, 2,2,3,4,4,4-hexafluoro-1-butanol, 2 , 2,3,3,4,4,5,5-octafluoro-1-pentanol, 2,2-bis (trifluoromethyl) -1-propanol, 3,3,4,4,5,5 6,6,6-nonafluoro-1-hexanol, 2,3,3,3-tetrafluoro-2- (perfluoropropyloxy) -1-propanol, 4,4,5,5,6,6,7,7 , 7-nonafluoro-1-heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1-heptanol, 3,3,4,4,5 5,6,6,7,7,8,8,8-tridecafluoro-1-octanol, 7 7,8,8,8-pentafluoro-1-octanol, 4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-1-nonanol, 7 , 8,8,8-Tetrafluoro-7- (trifluoromethyl) -1-octanol.

A medium (C) may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, as long as it can be used as a medium (C) after mixing, you may use the mixed solvent which mixed another solvent with the medium (C). Furthermore, as long as it can be used as the medium (C) after mixing, a mixed solvent obtained by mixing two or more other solvents may be used.
Specific examples of the mixed solvent that can be used as the medium (C) include the following combinations.

As the medium (C), it is preferable to use a solvent having a temperature range of 230 ° C. or less that exhibits a solution state with the fluorine-containing copolymer (A). If the temperature range is 230 ° C. or less, the fluorine-containing copolymer (A) and the compound (B) described later can be mixed at a temperature sufficiently lower than the melting point of the fluorine-containing copolymer (A). It is possible and the deterioration of the characteristics of the fluorine-containing copolymer (A) and the compound (B) can be suppressed.

The following solvent is mentioned as a medium (C) whose temperature range which exhibits a solution state with a fluorine-containing copolymer (A) is 230 degrees C or less, ie, a melting temperature is 230 degrees C or less.
Diisopropyl ketone (melting temperature: 175 ° C.),
2-hexanone (melting temperature: 175 ° C.),
Cyclohexanone (dissolution temperature: 170 ° C.),
3 ′, 5′-bis (trifluoromethyl) acetophenone (melting temperature: 160 ° C.),
2 ′, 3 ′, 4 ′, 5 ′, 6′-pentafluoroacetophenone (melting temperature: 155 ° C.),
Benzotrifluoride (melting temperature: 170 ° C.),
Isobutyl acetate (melting temperature: 175 ° C.).
However, the dissolution temperature in parentheses is the dissolution temperature when the fluorine-containing copolymer (A) is the fluorine-containing copolymer (A-1) in Examples described later.

As the medium (C), a solid content comprising a mixture of the fluorine-containing copolymer (A) and the compound (B) is separated from the fluorine-containing copolymer composition by reprecipitation or the like, or the fluorine-containing copolymer composition From the point of using as a coating composition, a solvent that is liquid at room temperature (25 ° C.) is preferable. Further, the melting point of the medium (C) is preferably 20 ° C. or lower for the same reason. Furthermore, the boiling point (normal pressure) of the medium (C) is preferably 230 ° C. or less from the viewpoint of the handleability of the medium (C) and the solvent removability when the solid content is separated from the fluorine-containing copolymer composition, 200 degrees C or less is more preferable.

(Compound (D))
The compound (D) is obtained from the compound (D1) having a reactive functional group capable of reacting with the reactive functional group of the compound (B) and the compound (D2) capable of promoting the reaction of the reactive functional group of the compound (B). And at least one compound selected from the group (excluding compound (E)).
The compound (D) may be any of those that dissolve in the medium (C), those that partially dissolve in the medium (C), or those that do not dissolve at all, but the fluorine-containing copolymer (A), the compound (B), Those that are soluble in the medium (C) are preferred from the viewpoint of miscibility or compatibility, and those that are soluble in the medium (C) at a temperature below the melting point of the fluorinated copolymer (A) are more preferred.

Compound (D1) reacts with the reactive functional group of fluorine-containing copolymer (A) or compound (B) to form a three-dimensional network structure, and has a function of curing the fluorine-containing copolymer composition. It is an agent.
The compound (D2) has a function of reacting the reactive functional groups of the fluorine-containing copolymer (A) and the compound (B) to form a three-dimensional network structure and curing the fluorine-containing copolymer composition. Catalyst or initiator.

In the case where the compound (B) is a compound containing a group having a cyclic ether having ring-opening reactivity, examples of the compound (D1) include acid anhydrides, polyamines, polyphenols, polythiols, and the like (D2). A tertiary amine compound, an imidazole compound, etc. are mentioned.

When the compound (B) is a compound containing a group having a carbon-carbon double bond having addition reactivity, examples of the compound (D1) include primary amines, secondary amines, and thiols. ) Include known thermal polymerization initiators, photopolymerization initiators, and the like.

As the compound (D), commercially available curing agents, catalysts, initiators and the like may be used. The following are mentioned as a commercially available hardening | curing agent, a catalyst, and an initiator.
Made by ADEKA: Adeka Hardener (registered trademark), Adekaoptomer (registered trademark),
DIC Corporation: EPICLON (registered trademark), LUCKAMIDE (registered trademark), PHENOLITE (registered trademark),
BASF Corporation: IRGACURE (registered trademark), etc.

(Compound (E))
The compound (E) is a dissolution accelerator or a dispersant that can promote dissolution or dispersion of the fluorine-containing copolymer (A) or the compound (B) in the medium (C).
The compound (E) is preferably soluble in the medium (C) from the viewpoint of the solubility or dispersibility of the fluorine-containing copolymer (A) or the compound (B) in the medium (C). What melt | dissolves in a medium (C) at the temperature below the melting | fusing point of a copolymer (A) is preferable.

Compound (E) includes surfactants, dispersants, viscosity modifiers and the like.

The compound (E) has a primary amino group, a secondary amino group, and a nitrogen-hydrogen bond because it also serves as a catalyst for promoting the reaction of a group having a cyclic ether having ring-opening reactivity. A compound (E1) having at least one group selected from the group consisting of nitrogen-containing heterocyclic groups and an alkyl group having 1 to 20 carbon atoms is preferable, and has an imidazolyl group and an alkyl group having 4 to 20 carbon atoms. Compounds are more preferred.

The fluorine-containing copolymer composition of the present invention contains at least one selected from the group consisting of the compound (D) and the compound (E1) from the viewpoints of coating film adhesion, scratch resistance, heat resistance, and the like. Is preferable, and it is more preferable that the compound (D) and the compound (E1) are included.

(Other resin (F))
The other resin (F) is a thermoplastic resin or a thermosetting resin other than the fluorine-containing copolymer (A) and the compounds (B) to (E).
The other resin (F) is one that dissolves in the medium (C) or partly dissolves in the medium (C) in a temperature range in which the fluorine-containing copolymer (A) and the medium (C) are in a solution state. However, from the viewpoint of miscibility or compatibility between the fluorinated copolymer (A) and the other resin (F), those that are soluble in the medium (C) are preferable.

Examples of the thermoplastic resin include fluorine resins and hydrocarbon resins other than the fluorine-containing copolymer (A).
Examples of the fluorine resin include polytetrafluoroethylene, ethylene-chlorotrifluoroethylene copolymer, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, chlorotrifluoroethylene-vinyl ether copolymer, poly (2,2 , 3,3,3-pentafluoropropyl methacrylate), poly (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl methacrylate) and the like. It is done.

Examples of hydrocarbon resins include polyethylene, polypropylene, poly (4-methyl-1-pentene), poly (1-butene), polystyrene, polyvinyl chloride, polyvinylidene chloride, polymethyl methacrylate, polyethyl methacrylate, and polybutyl methacrylate. , Polyisobutyl methacrylate, polyhexyl methacrylate, polyvinyl alcohol, methyl methacrylate-styrene copolymer, maleic anhydride-styrene copolymer, acrylonitrile-styrene copolymer, polyoxymethylene, polyvinyl acetal, polyvinyl formal, polyvinyl butyral, poly Vinyl acetate, acrylonitrile-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-maleic anhydride copolymer , Vinylidene chloride-vinyl chloride copolymer, poly (2,6-dimethyl-1,4-phenylene oxide), polyamide 6, polyamide 66, polyamide 9T, polyamide 11, polyamide 12, polyethylene terephthalate, polytrimethylene terephthalate, Examples include polybutylene terephthalate, polysulfone, polyethersulfone, polycarbonate, polyetheretherketone, polyphenylene sulfide, thermoplastic polyimide, polyamideimide, polyetherimide, polyarylate, cycloolefin polymer, and polylactic acid.

Thermosetting resins include phenolic resin, urea resin, melamine resin, guanamine resin, aniline resin, benzoxazine resin, cyanate ester resin, isocyanate resin, alkyd resin, phthalic acid resin, polyurethane, thiourethane resin, thermosetting Examples include polyimide, xylene resin, ketone resin, furan resin, COPNA resin, silicone resin, polyazomethine and the like.

(Method for preparing fluorine-containing copolymer composition)
The fluorinated copolymer composition of the present invention comprises a fluorinated copolymer (A) and a compound (B) in the medium (C), and if necessary, a compound (D), a compound (E), and other resins. It can be prepared by a method of mixing (F) and the like.

(Mixture of fluorine-containing copolymer (A) and compound (B))
Mixing of the fluorinated copolymer (A) and the compound (B) is carried out in the medium (C) under a temperature condition not higher than the melting point of the fluorinated copolymer (A).

Mixing should just be a dispersion liquid state which a fluorine-containing copolymer (A) obtains through a solution state or a solution state.
At the time of mixing, the compound (B) may be in a solution state or a dispersion state, and the miscibility or compatibility between the fluorine-containing copolymer (A) and the compound (B). Therefore, a solution state is preferable.

Examples of the mixing method include the following methods (α) to (ε).
(Α) After the fluorine-containing copolymer (A) and, if necessary, the compound (E) are dissolved in the medium (C), the fluorine-containing copolymer (A) is precipitated and dispersed as necessary. The compound (B) and, if necessary, the compound (D) are added thereto and dissolved or dispersed, followed by mixing.
(Β) The fluorine-containing copolymer (A) and the compound (D), and if necessary, the compound (E) is dissolved in the medium (C), and the fluorine-containing copolymer (A) is precipitated if necessary. The compound (B) and, if necessary, the compound (D) are added thereto and dissolved or dispersed, and then mixed.
(Γ) The fluorine-containing copolymer (A) and the compound (B), and if necessary, the compound (E) is dissolved in the medium (C), and the fluorine-containing copolymer (A) is precipitated as necessary. The compound (D) is added and dissolved or dispersed, and then mixed.
(Δ) A method in which the fluorine-containing copolymer (A) and the compound (B) and, if necessary, the compound (D), the compound (E) and the like are dissolved or dispersed in the medium (C) and mixed.
(Ε) A part of the fluorine-containing copolymer (A) and the compound (B), and if necessary, the compound (E) is dissolved in the medium (C), and the fluorine-containing copolymer (A) if necessary. Is precipitated and dispersed, and then the remainder of the compound (B) and, if necessary, the compound (D) are added to dissolve or disperse and mix.

In a solution or dispersion obtained by dissolving the fluorine-containing copolymer (A) in the medium (C), the compound (B), and if necessary, the compound (D), the compound (E), other resin (F) In the case of adding a compound (B), a compound (D), a compound (E), another resin (F), or the like, a solution previously dissolved in a part of the medium (C) may be added.

The temperature at the time of mixing is 0 ° C. or higher and not higher than the melting point of the fluorine-containing copolymer (A). The melting point of the fluorinated copolymer (A) (that is, ETFE) is the highest and is approximately 275 ° C.
The upper limit temperature during mixing is preferably 230 ° C., more preferably 200 ° C., from the viewpoint of suppressing deterioration of the properties of the fluorinated copolymer (A) and the compound (B).
The lower limit temperature at the time of mixing is a temperature at which the fluorine-containing copolymer (A) is dissolved in the medium (C) or the fine particles are uniformly dispersed from the viewpoint of obtaining a sufficiently dissolved state, preferably 0 ° C., 20 ° C is more preferred. It is not always necessary to dissolve the fluorine-containing copolymer (A) and the compound (B) again in the medium (C).
When heating is required, mixing and heating of each component may be performed simultaneously, and after mixing each component, you may heat, stirring as needed.

The pressure during mixing is usually preferably normal pressure or a slight pressure of about 0.5 MPa. When the temperature at the time of mixing is higher than the boiling point of the medium (C), the pressure is at least not more than the spontaneously generated pressure, preferably not more than 3 MPa, more preferably not more than 2 MPa, more preferably not more than 1 MPa, most preferably normal pressure It is the following, and it is preferable to mix in a pressure vessel. Usually, the pressure is preferably about 0.01 to 1 MPa.

The mixing time depends on the mixing ratio of the fluorinated copolymer (A) and the compound (B), the shape of the fluorinated copolymer (A) and the compound (B) before being added to the medium (C), and the like. . The shape of the fluorinated copolymer (A) is preferably a powder from the viewpoint of shortening the dissolution time in the medium (C), and a pellet is preferred from the viewpoint of availability. The shape of the compound (B) is preferably liquid or powder from the viewpoint of shortening the dissolution time in the medium (C).

Mixing means include homomixers, high-pressure homogenizers, bead mills, planetary ball mills, Henschel mixers, Banbury mixers, pressure kneaders, ultrasonic stirrers, high-pressure abutting dispersers, thin-film swivel high-speed mixers, and various static mixers and motions A known stirring mixer such as a less mixer may be used.
When mixing under pressure, an apparatus such as an autoclave with a stirrer may be used. Examples of the stirring blade include a marine propeller blade, a paddle blade, an anchor blade, and a turbine blade. When performing on a small scale, a magnetic stirrer or the like may be used as the stirring device.

The mixing ratio of the fluorinated copolymer (A) and the compound (B) may be appropriately determined according to the use of the obtained fluorinated copolymer composition, and is not particularly limited. The mixing ratio ((A) / (B) (mass ratio)) of (A) and compound (B) is preferably 99/1 to 1/99, more preferably 98/2 to 2/98.

The ratio of the medium (C) can be determined by separating the solid content of the mixture of the fluorine-containing copolymer (A) and the compound (B) from the fluorine-containing copolymer composition by reprecipitation or the like. In view of using the product as a coating composition, the content of the fluorinated copolymer composition (100% by mass) is preferably 5 to 99.9% by mass, and more preferably 10 to 99% by mass. When the ratio of the medium (C) is within this range, the medium (C) can be easily removed when the solid content is separated from the fluorine-containing copolymer composition. Moreover, it is excellent in the handleability etc. as a coating composition, and the obtained coating film can be made uniform.

The proportion of the compound (D) is preferably from 0.1 to 20 parts by mass, preferably from 0.5 to 100 parts by mass with respect to 100 parts by mass of the compound (B) from the viewpoints of adhesion, scratch resistance, heat resistance and the like of the coating film. 10 parts by mass is more preferable.
The proportion of the compound (E) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the fluorine-containing copolymer (A) from the viewpoint of solubility or dispersibility of the fluorine-containing copolymer (A). 0.5 to 5 parts by mass is more preferable.

(Precipitation of fine particles)
By placing the obtained fluorinated copolymer solution under conditions where the fluorinated copolymer (A) and / or the compound (B) is precipitated in the medium (C) (usually under normal temperature and normal pressure), The fluorine copolymer (A) and / or compound (B) is precipitated in the medium (C) to obtain a slurry (dispersion).
Further, depending on the types of the fluorinated copolymer (A), the compound (B) and the medium (C), only the fine particles of the fluorinated copolymer (A) are precipitated in the medium (C), and the slurry (dispersion) Liquid). At this time, the compound (B) is in a state of being dissolved or dispersed in the medium (C).
Specifically, when the fluorine-containing copolymer (A) and the compound (B) are mixed with heating, the resulting solution is mixed with the fluorine-containing copolymer (A) and the compound (B), or A mixture of the fluorinated copolymer (A) and the compound (B) or the fine particles of the fluorinated copolymer (A) by cooling to a temperature not higher than the temperature at which only the fluorocopolymer (A) is precipitated (usually normal temperature). Is precipitated in the medium (C). The cooling method may be slow cooling or rapid cooling.

Specific examples of the state of the obtained fluorine-containing copolymer composition near room temperature include the following states (I) to (V).

When the melting temperature of the fluorinated copolymer (A) in the medium (C) is higher than room temperature:
(I) A slurry (dispersion) state in which fine particles of a uniform mixture of the fluorinated copolymer (A) and the compound (B) are precipitated in the medium (C).
(II) A slurry (dispersion) state in which fine particles of the fluorinated copolymer (A) are precipitated in the medium (C) and the compound (B) is dissolved in the medium (C).
(III) A slurry (dispersion) state in which core-shell type fine particles formed by precipitation of the fluorinated copolymer (A) on the surface of the fine particles of the compound (B) are precipitated in the medium (C).

When the melting temperature of the fluorinated copolymer (A) in the medium (C) is lower than room temperature:
(IV) A slurry (dispersion) state in which fine particles of the compound (B) are dispersed in the medium (C) and the fluorinated copolymer (A) is dissolved in the medium (C).
(V) A solution state in which the fluorine-containing copolymer (A) and the compound (B) are dissolved in the medium (C).

(Function and effect)
Since the fluorine-containing copolymer composition of the present invention contains the compound (B) in addition to the fluorine-containing copolymer (A) and the medium (C), the compound (B) Curing can form a coating film and a molded product excellent in adhesion, scratch resistance, heat resistance and the like.

<Coating composition>
The coating composition of the present invention contains various additives as necessary.
The state of the coating composition of the present invention may be any of the above states (I) to (V).
Content of the fluorine-containing copolymer (A) in the coating composition of this invention can be suitably changed according to the thickness of the target coating film. From the viewpoint of the formability of the coating film, the proportion of the fluorinated copolymer (A) is preferably 0.05 to 50% by mass, and preferably 0.1 to 30% by mass in the coating composition (100% by mass). More preferred. When the content is within this range, the handleability is good, the viscosity, the drying speed, the uniformity of the film, etc. are excellent, and a uniform coating film can be formed.
Further, the content of the compound (B) in the coating composition of the present invention is appropriately determined from the mixing ratio with the fluorinated copolymer (A) according to the use of the obtained fluorinated copolymer composition. The Among them, the ratio of the compound (B) is preferably 0.01 to 89% by mass, more preferably 0.02 to 50% by mass in the coating composition (100% by mass). When the content is within this range, the handleability is good, the viscosity, the drying speed, the uniformity of the film, etc. are excellent, and a uniform coating film can be formed.

(Additive)
Examples of the additive include an antioxidant, a light stabilizer, an ultraviolet absorber, a lubricant, a thickener, a filler (filler), a reinforcing agent, a pigment, a dye, a flame retardant, and an antistatic agent.
The total proportion of the additives is preferably 30% by mass or less, more preferably 25% by mass or less in the coating composition (100% by mass).

Since the additive can be added in the process of mixing the fluorine-containing copolymer (A) and the compound (B) in the medium (C), it is abundant and uniform compared to the case of adding in the process of melt kneading. Can be added. Moreover, since the coating film obtained by using the coating composition containing the additive at a high concentration can exhibit a necessary function with a thinner film thickness, the fluorine-containing copolymer (A) and the compound (B) The ratio can be reduced.

(Use)
The following uses are mentioned as a coating composition of this invention.
Optical field: Protective coating agent, antifouling coating agent, low reflection coating agent for various optical films, etc.
Solar cell field: protective cover material, transparent conductive member, protective coating agent such as back sheet, gas barrier layer, thin glass support resin layer, adhesive layer, etc.
Display panel / display field: Protective coating agent, antifouling coating agent, low reflection coating agent for transparent members used in various display panels (liquid crystal display panel, plasma display panel, electrochromic display panel, electroluminescence display panel, touch panel); Thin glass support resin, etc.
Electrical and electronic fields: Optical discs, liquid crystal cells, printed circuit boards, IC cards, photosensitive drums, various sensors, antennas, covered electric wires, motors, protective coating agents for various electrical and electronic parts, water repellent coating agents, low reflection Coating agent; interlayer insulating film in semiconductor element and integrated circuit device, protective film; solder mask, solder resist, IC sealing agent, LED sealing agent, electrically insulating coating material, etc.
Transportation equipment field: Protective coating agent, antifouling coating agent, low-reflective coating agent, etc. for various members (exterior members such as display device surface materials, interior members such as instrument panel surface materials, safety glass laminates, etc.)
Architectural field: Protective coating agents for mirrors, glass windows, resin windows, etc., antifouling coating agents, low-reflective coating agents, etc .; sealants for building components, antifouling coating agents for sealants,
Separation membrane field: Adhesives, antifouling coating agents in membrane module production; functional layers such as reverse osmosis membranes and nanofiltration membranes; functional layers of gas separation membranes that separate carbon dioxide, hydrogen, etc.
Others: Rubber / plastic, wood, stone protective coating agent, weathering / antifouling coating agent; fiber / fabric protective coating agent; anticorrosion paint, resin adhesion inhibitor, ink adhesion inhibitor, laminated steel plate primer, various adhesives Agents, binders, etc.

In particular, if the coating composition of the present invention is used as an interlayer insulating film, protective film, etc. in semiconductor elements and integrated circuit devices, the low water absorption, low dielectric constant, high heat resistance, etc. possessed by the fluorinated copolymer (A) Thus, a semiconductor element and an integrated circuit device having a high response speed and few malfunctions can be obtained.
In addition, the coating composition of the present invention can be used as a protective coating agent or antifouling coating agent for a condensing mirror used in concentrating solar power generation; If used, a highly durable power generation system that does not require maintenance can be obtained due to the properties of the fluorine-containing copolymer (A) such as high heat resistance and low water absorption.

(Function and effect)
The coating composition of the present invention includes a fluorine-containing copolymer composition in which the fluorine-containing copolymer (A) and the compound (B) are uniformly mixed. A coating film having excellent properties, scratch resistance, heat resistance, and the like can be formed.

<Article with coating film>
The article having the coating film of the present invention has a coating film formed using the above-described coating composition on the surface of the substrate. The coating film may be used as a film by separating from the substrate.

(Coating)
The coating film or film formed using the coating composition of the present invention is thinner and more uniform than the ETFE film obtained by melt molding.
What is necessary is just to determine the thickness of a coating film or a film suitably according to a use. If a coating composition with a high solid content concentration is used, a thick coating film is obtained, and if a coating composition with a low solid content concentration is used, a thin coating film is obtained. Moreover, a thicker coating film can also be obtained by repeating application | coating several times.

(Base material)
Base materials include metals (iron, stainless steel, aluminum, titanium, copper, silver, etc.), glasses (soda lime glass, silicate glass, synthetic quartz, etc.), silicon, organic materials (polycarbonate, polyethylene terephthalate, polymethyl) Methacrylate, glass fiber reinforced plastic, polyvinyl chloride, etc.), stone, wood, ceramics, cloth, paper and the like.
The shape of the substrate is not particularly limited.

The base material may be pretreated for the purpose of improving the adhesion between the base material and the coating film. Examples of the pretreatment method include a method of applying a silane coupling agent, polyethyleneimine or the like to the substrate, a method of physically treating the surface with sandblasting, a method of treating with corona discharge, or the like.

(Formation method of coating film)
Examples of the method for forming a coating film include a method in which the coating composition of the present invention is applied to a substrate to form a wet film, and the medium (C) is removed from the wet film to form a coating film.
Examples of the application method include gravure coating, dip coating, die coating, electrostatic coating, brush coating, screen printing, roll coating, spin coating and the like.

The state of the coating composition of the present invention when applied to the substrate may be any of the states (I) to (V) described above. Even in the slurry state, each fine particle is in a state of being uniformly dispersed in the medium (C). Therefore, the coating composition in the slurry state is dissolved so that the fluorinated copolymer (A) is dissolved in the medium (C). It can apply | coat to a base material at the application temperature less than temperature, and can remove a medium (C) at a comparatively low drying temperature. By making the coating temperature and the drying temperature relatively low, workability is improved and a dense and flat coating film can be obtained.

The application temperature depends on the composition of the coating composition, but is preferably 0 to 210 ° C, more preferably 0 to 130 ° C, and further preferably 0 to 50 ° C. A coating temperature of 0 ° C. or higher is preferable because the dispersion state of the fluorine-containing copolymer (A) is good. When the coating temperature is 210 ° C. or lower, the medium (C) does not volatilize rapidly, and thus generation of bubbles and the like can be suppressed.

The removal temperature of the medium (C), that is, the drying temperature is preferably 0 ° C. or higher and lower than the melting point of the fluorinated copolymer (A), more preferably 0 to 200 ° C., and further preferably 0 to 150 ° C. A drying temperature of 0 ° C. or higher is preferable because it does not take too much time to remove the solvent. When the drying temperature is lower than the melting point of the fluorinated copolymer (A), the occurrence of coloring, decomposition and the like can be suppressed.

The firing (curing) temperature is preferably 0 ° C. or higher and lower than the melting point of the fluorinated copolymer (A), more preferably 20 to 260 ° C., and further preferably 30 to 210 ° C. A firing (curing) temperature of 0 ° C. or higher is preferable because it does not take too long to cure. If the firing (curing) temperature is lower than the melting point of the fluorine-containing copolymer (A), the occurrence of coloring, decomposition, etc. can be suppressed.

(Use)
The following uses are mentioned as an article | item which has a coating film.
Optical field: optical fiber, lens, optical disk, various optical films, etc.
Solar cell field: condensing mirror, protective cover material made of glass or resin, transparent conductive member, etc.
Display panel / display field: Transparent members (glass substrates and resin substrates) used in various display panels, etc.
Electrical / electronic field: Various electrical / electronic components, semiconductor elements, hybrid ICs, printed circuit boards, IC cards, various sensors, photosensitive drums, film capacitors, electric wires / cables, antennas, motors, power generators, LED sealants, etc.
Transportation equipment field: various components such as trains, buses, trucks, automobiles, ships, aircraft,
Architectural field: mirror, glass window, resin window, outer wall, roofing material, bridge, tunnel, etc.
Medical field: syringe, pipette, thermometer, etc.
Chemical field: Beakers, petri dishes, graduated cylinders, etc.
Separation membrane field: reverse osmosis membrane, nanofiltration membrane, gas separation membrane, etc.

(Function and effect)
Since the article having the coating film of the present invention has a coating film formed by using the coating composition described above, the coating film to be formed adheres while maintaining the characteristics of the fluorinated copolymer. Excellent in resistance, scratch resistance, heat resistance and the like.
Further, by using the coating composition of the present invention, it is not necessary to perform application and drying at a high temperature, so that the base material can be decomposed or decomposed even for materials having low heat resistance such as plastic, paper, and cloth. A coating film can be formed without causing deformation.

<Molded product>
The molded article of the present invention is formed by molding the above-mentioned fluorine-containing copolymer composition.
The molded article is usually produced by molding a solid content composed of a mixture of the fluorine-containing copolymer (A) and the compound (B) separated from the fluorine-containing copolymer composition.

Examples of the solid content separation method include a method of filtering the slurry-containing fluorine-containing copolymer composition. As the filtration method, a known method may be mentioned.
When the fluorine-containing copolymer composition is in a solution state (or a state where a solution state and a slurry state are mixed), a solvent having a low affinity for the fluorine-containing copolymer (A) and the compound (B) (hereinafter, It is preferable to complete precipitation by adding a poor solvent). Examples of the poor solvent include hexane and methanol.

The separated solid content is preferably dried to remove the medium (C) and the poor solvent. Examples of the drying means include a vacuum drying oven.
As the molding method, a known method may be mentioned.
As a use of a molded article, the same use as an article having a coating film can be given.

(Function and effect)
Since the molded article of the present invention is obtained using the above-mentioned fluorine-containing copolymer composition, it is excellent in scratch resistance, heat resistance and the like while maintaining the properties of the fluorine-containing copolymer.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is limited to these Examples and is not interpreted.
Examples 1 to 38 and 41 to 67 are examples, and examples 39, 40 and 68 are comparative examples.

(surface hardness)
The surface hardness was measured according to a pencil scratch test (JIS K5600).

(Pyrolysis temperature)
The thermal decomposition temperature was measured using a differential thermal analyzer (TG-DTA2000SA, manufactured by Bruker AXS). The temperature range of the measurement was room temperature to 600 ° C., about 10 mg of a sample was put in a platinum pan, and the measurement was performed at a temperature increase rate of 10 ° C./min in an air stream with a mixed air flow rate of 100 mL / min. The heat resistance was evaluated at a 10% mass reduction temperature observed by differential thermal analysis.

(Adhesion test)
The adhesion test was measured according to JIS K5600. In other words, the coating film on the substrate is cut with 11 vertical and horizontal cuts at 2 mm intervals using a cutter knife, a 100 square grid is made, and a cellophane adhesive tape is strongly pressure-bonded on the grid, and the tape The film was peeled off instantaneously, and the coating film remaining on the substrate without being peeled was observed. Evaluation was made based on the state of peeling of the coating film after five peeling tests.
The case where 91 squares or more remained was marked as ◯ (excellent), the case where 90 to 51 squares remained was marked as △ (good), and the case where 50 to 0 squares remained was marked as x (bad).

(Hot press molding)
The press film was produced using a heating press (Tester Sangyo Co., Ltd., SA-301).

(Tensile test)
A dumbbell-shaped test piece (length: 45 mm, length of parallel part: 22 mm, width: 5 mm, thickness: about 100 μm) was produced from a press film formed by a heating press. Using Tensilon RTC-1210 manufactured by Orientec Co., Ltd., yield stress and elongation at break were measured under the following conditions.
Distance between grips: 22mm
Tensile speed: 10 mm / min,
Temperature: 25 ° C
Relative humidity: 50%
Other conditions: Conforms to JIS K7113 (plastic tensile test method).

(thickness)
About the coating film obtained by potting, thickness was measured with the stylus type surface shape measuring device (the product made by Sloan, DEKTAK 3ST).
About the thickness of the press film shape | molded with the heating press machine, thickness was measured with the digital micrometer (the Niigata Seiki company make, MCD191-30WD).
About the coating film obtained by methods other than the above, the thickness was measured with a non-contact optical thin film measuring apparatus (Filmtrics F-20, manufactured by Filmetrics).

(Fluorine-containing copolymer (A))
The fluorine-containing copolymers (A-1) and (A-2) were produced by the method described in Japanese Patent No. 3272474 or International Publication No. 2006/134664.
Fluorine-containing copolymer (A-1): ratio of repeating units based on monomer (molar ratio): TFE / ethylene / 3,3,4,4,4-pentafluoro-1-butene / itaconic anhydride = 57.5 / 39.9 / 2.3 / 0.3, melting point: 240 ° C.
Fluorine-containing copolymer (A-2): Ratio of repeating units based on monomer (molar ratio): TFE / ethylene / hexafluoropropylene / 3,3,4,4,5,5,6,6,6 Nonafluoro-1-hexene / itaconic anhydride = 47.7 / 42.5 / 8.4 / 1.2 / 0.2, melting point: 188 ° C.

(Compound (B))
Compound (B1-1): 3,4-epoxycyclohexylmethyl 3 ′, 4′-epoxycyclohexanecarboxylate (manufactured by Wako Chemical Co., catalog number: 326-64072).
Compound (B1-2): 1,4-butanediol diglycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: B0964).
Compound (B1-3): Neopentyl glycol diglycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: N0448).
Compound (B1-4): Trimethylolpropane triglycidyl ether (manufactured by Aldrich, catalog number: 430269).
Compound (B1-5): diglycidyl 1,2-cyclohexanedicarboxylate (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: C1434).
Compound (B1-6): Hydrogenated bisphenol A glycidyl ether (manufactured by Shin Nippon Chemical Co., Ltd., Rica Resin HBE-100).
Compound (B1-7): 2,2-bis (4-glycidyloxyphenyl) propane (bisphenol A type epoxy resin, manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: B1796).
Compound (B1-8): Bisphenol A-epichlorohydrin copolymer (glycidylated product) (manufactured by Aldrich, catalog number: 406721).
Compound (B1-9): Phenyl glycidyl ether-formaldehyde copolymer (phenol novolac epoxy resin, manufactured by Aldrich, catalog number: 406775).
Compound (B1-10): o-cresyl glycidyl ether-formaldehyde copolymer (cresol novolac epoxy resin, manufactured by Aldrich, catalog number: 405515).
Compound (B1-11): 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (manufactured by Mitsubishi Gas Chemical Company, product name: Tetrad-C).
Compound (B3-1): glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: M0590).
Compound (B3-2): allyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: A0221).
Compound (B2-1): trimethylolpropane triacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: T0949).
Compound (B2-2): Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: A-DCP).
Compound (B2-3): Neopentyl glycol diacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: N0790).
Compound (B2-4): 1,6-bis (acryloyloxy) -2,2,3,3,4,4,5,5-octafluorohexane (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: B2340).
Compound (B2-5): Bisallyl nadiimide resin (manufactured by Maruzen Petrochemical Co., Ltd., product name: BANI-M).
Compound (B2-6): Bisallyl nadiimide resin (manufactured by Maruzen Petrochemical Co., Ltd., product name: BANI-X).
Compound (B2-7): Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: M0087).
Compound (B2-8): Isobutyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: M0132).

(Medium (C))
Medium (C-1): diisopropyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: D0770).
Medium (C-2): 2-hexanone (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: H0114).

(Compound (D))
Compound (D1-1): 1,2-cyclohexanedicarboxylic anhydride (manufactured by Aldrich, catalog number: 123463).
Compound (D1-2): 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: M1192).
Compound (D1-3): phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: P1614).
Compound (D1-4): Isooctadecyl succinic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: I0146).
Compound (D1-5): 1,8-diamino-p-menthane (manufactured by Aldrich, catalog number: D19605).
Compound (D2-1): 2-ethyl-4-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: E0232).
Compound (D2-2): Tetrabutylphosphonium-O, O-diethyl phosphorodithioate (manufactured by Wako Chemical Co., catalog number: 328-33902).
Compound (D2-3): Diphenyliodonium hexafluorophosphate (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: D2238).
Compound (D2-4): 1-hydroxycyclohexyl phenyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: H0617).
Compound (D2-5): 2,2-dimethoxy-1,2-diphenylethane 1-one (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: D1702)

(Compound (E))
Compound (E1-1): tetradecylamine (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: T0090).
Compound (E1-2): N-methyloctadecylamine (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: M0912).
Compound (E1-3): 2-undecylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: U0012).
Compound (E1-4): 2-heptadecylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., catalog number: H0021).

(Other resin (F))
Other resin (F-1): PMMA: Polymethyl methacrylate (manufactured by Aldrich, catalog number: 200036, mass average molecular weight: 15000).
Other resin (F-2): PIBMA: polyisobutyl methacrylate (manufactured by Aldrich, catalog number: 181544, mass average molecular weight: 70000).
Other resin (F-3): PVC: polyvinyl chloride (manufactured by Aldrich, catalog number: 81388).

[Example 1]
In a 30 mL reaction vessel, 640 mg of the fluorinated copolymer (A-1), 7.0 mg of the compound (E1-1), and 15.36 g of the medium (C-1) are placed, and the mixture is stirred while being sealed under 30 ml. Heated to 185 ° C. for minutes to give a uniform and clear solution. Next, the solution was once cooled to room temperature while stirring to obtain a uniform fine particle dispersion without sediment. To the dispersion, 320 mg of a 10% by mass medium (C-1) solution of compound (B1-1), 290 mg of a 10% by mass medium (C-1) solution of compound (D1-1), and compound ( D2-1) 0.5 mg% medium (C-1) solution 320 mg was added and stirred using a planetary ball mill (Sinky Corp., rotation / revolution mixer Awatori Nertaro ARE-310). A fine particle dispersion without sediment was obtained. The dispersion was applied onto a glass substrate by potting at room temperature and air-dried. Then, it dried for 120 minutes at 90 degreeC using the dry oven, and also heated for 60 minutes at 150 degreeC, the coating film was hardened, and the glass substrate with which the coating film was formed in the surface was obtained. Table 10 shows the evaluation results.

[Examples 2 to 13]
A glass substrate having a coating film formed on the surface thereof was obtained in the same manner as in Example 1 except that the formulation shown in Table 9 was changed. Table 10 shows the evaluation results.

[Example 14]
A coating film was formed on the surface in the same manner as in Example 1 except that the compound (D2-1) was not added and the composition of the other components was changed to the composition shown in Table 9 and the curing condition was changed to 200 ° C for 360 minutes. A glass substrate was obtained. Table 10 shows the evaluation results.

[Examples 15 to 22]
A glass substrate having a coating film formed on the surface thereof was obtained in the same manner as in Example 14 except that the formulation shown in Table 9 was changed. Table 10 shows the evaluation results.

[Example 23]
A glass substrate having a coating film formed on the surface thereof was obtained in the same manner as in Example 1 except that the compound (D1-1) was not added and the composition of the other components was changed to the composition shown in Table 9. Table 10 shows the evaluation results.

[Example 24]
A glass substrate having a coating film formed on the surface thereof was obtained in the same manner as in Example 23 except that the formulation shown in Table 9 was changed. Table 10 shows the evaluation results.

[Example 25]
In a 30 mL reaction vessel, 640 mg of the fluorinated copolymer (A-1), 8.9 mg of the compound (E1-3), and 15.36 g of the medium (C-1) are placed. Heated to 185 ° C. for minutes to give a uniform and clear solution. Next, the solution was once cooled to room temperature while stirring to obtain a uniform fine particle dispersion without sediment. To the dispersion, 320 mg of a 10% by mass medium (C-1) solution of the compound (B1-1) and 290 mg of a 10% by mass medium (C-1) solution of the compound (D1-1) were added, The mixture was stirred using a planetary ball mill (manufactured by Shinky Co., Ltd., rotation / revolution mixer Awatori Nertaro ARE-310) to obtain a uniform fine particle dispersion without sediment. The dispersion was applied onto a glass substrate by potting at room temperature and air-dried. Then, it dried for 120 minutes at 90 degreeC using the dry oven, and also heated for 60 minutes at 150 degreeC, the coating film was hardened, and the glass substrate with which the coating film was formed in the surface was obtained. Table 10 shows the evaluation results.

[Examples 26 to 30]
A glass substrate having a coating film formed on the surface thereof was obtained in the same manner as in Example 25 except that the formulation shown in Table 9 was changed. Table 10 shows the evaluation results.

Example 31
A glass substrate having a coating film formed on the surface thereof was obtained in the same manner as in Example 25 except that the compound (D1-1) was not added. Table 10 shows the evaluation results.

[Example 32]
A glass substrate having a coating film formed on the surface thereof was obtained in the same manner as in Example 31 except that the formulation shown in Table 9 was changed. Table 10 shows the evaluation results.

[Example 33]
In a 30 mL reaction vessel, 320 mg of the fluorinated copolymer (A-1), 160 mg of a 10% by mass medium (C-2) solution of the compound (B1-1), and 4.0 mg of the compound (E1-1) And 15.39 g of the medium (C-2) were added and heated to 185 ° C. for 30 minutes with stirring under tight sealing to obtain a uniform and transparent solution. Next, the solution was once cooled to room temperature while stirring to obtain a uniform fine particle dispersion without sediment. In the dispersion, 130 mg of a 10% by mass medium (C-2) solution of the compound (D1-1) and 160 mg of a 0.5% by mass medium (C-2) solution of the compound (D2-1) were added. The mixture was stirred using a planetary ball mill (manufactured by Shinky Corp., rotation / revolution mixer Awatori Nertaro ARE-310) to obtain a uniform fine particle dispersion without sediment. The dispersion was applied onto a glass substrate by potting at room temperature and air-dried. Then, it dried for 120 minutes at 90 degreeC using the dry oven, and also heated for 60 minutes at 150 degreeC, the coating film was hardened, and the glass substrate with which the coating film was formed in the surface was obtained. Table 10 shows the evaluation results.

[Examples 34 to 38]
A glass substrate having a coating film formed on the surface was obtained in the same manner as in Example 33 except that the formulation shown in Table 9 was changed. Table 10 shows the evaluation results.

[Example 39]
A glass substrate having a coating film formed on the surface was obtained in the same manner as in Example 1 except that the compound (B) and the compound (D) were not used and the curing conditions shown in Table 10 were changed. Table 10 shows the evaluation results.

[Example 40]
A glass substrate having a coating film formed on the surface was obtained in the same manner as in Example 39 except that the fluorinated copolymer (A-2) was used instead of the fluorinated copolymer (A-1). Table 10 shows the evaluation results.

In Table 10, “-” indicates that the measurement was not performed or was not measured.

[Example 41]
In a 30 mL reaction vessel, 640 mg of the fluorinated copolymer (A-1), 8.5 mg of the compound (E1-1), and 15.36 g of the medium (C-1) were placed, and the mixture was stirred while being sealed under 30 ml. Heated to 185 ° C. for minutes to give a uniform and clear solution. Next, the solution was once cooled to room temperature while stirring to obtain a uniform fine particle dispersion without sediment. To the dispersion, 320 mg of a 10% by mass medium (C-1) solution of compound (B1-1) and 320 mg of a 0.5% by mass medium (C-1) solution of compound (D2-3) were added. The mixture was stirred using a planetary ball mill (manufactured by Shinky Corp., rotation / revolution mixer Awatori Nertaro ARE-310) to obtain a uniform fine particle dispersion without sediment. The dispersion was applied onto a glass substrate by potting at room temperature and air-dried at room temperature for 20 minutes. Then, it dried for 30 minutes at 90 degreeC using the hotplate, and also the ultraviolet-ray (wavelength of 254 nm) with an illumination intensity of 10 mW / cm < ² > was irradiated for 20 minutes at 100 degreeC, and the coating film was formed on the surface. A glass substrate was obtained. The evaluation results are shown in Table 12.

[Examples 42 to 45]
A glass substrate having a coating film formed on the surface thereof was obtained in the same manner as in Example 41 except that the mixing, drying, and curing conditions shown in Tables 11 and 12 were changed. The evaluation results are shown in Table 12.

[Example 46]
In a 30 mL reaction vessel, 640 mg of the fluorinated copolymer (A-1), 120 mg of a 10% by mass medium (C-1) solution of the compound (B3-1), and 8.5 mg of the compound (E1-1) And 15.25 g of medium (C-1) were added and heated to 185 ° C. for 30 minutes with stirring under tight sealing to obtain a uniform and transparent solution. Next, the solution was once cooled to room temperature while stirring to obtain a uniform fine particle dispersion without sediment. To the dispersion, 320 mg of a 10% by mass medium (C-1) solution of compound (B2-1) and 320 mg of a 0.5% by mass medium (C-1) solution of compound (D2-4) were added. The mixture was stirred using a planetary ball mill (manufactured by Shinky Corp., rotation / revolution mixer Awatori Nertaro ARE-310) to obtain a uniform fine particle dispersion without sediment. The dispersion was applied onto a glass substrate by potting at room temperature and air-dried at room temperature for 20 minutes. Thereafter, while heating to 100 ° C. using a hot plate, ultraviolet rays having an illuminance of 10 mW / cm ² were irradiated for 30 minutes to cure the coating film, thereby obtaining a glass substrate on which the coating film was formed. The evaluation results are shown in Table 12.

[Examples 47 to 59]
A glass substrate having a coating film formed on the surface was obtained in the same manner as in Example 46 except that the formulation, drying, and curing conditions shown in Table 11 and Table 12 were changed. The evaluation results are shown in Table 12.

In Table 12, “-” indicates that drying at 90 ° C. has not been performed.

[Example 60]
In a 30 mL reaction vessel, 640 mg of the fluorinated copolymer (A-1), 120 mg of a 10 mass% medium (C-1) solution of the compound (B3-1), and 8. 8 of the compound (E1-1) are added. 5 mg and 15.25 g of the medium (C-1) were added, and the mixture was heated to 185 ° C. for 30 minutes with stirring under tight sealing to obtain a uniform and transparent solution. Next, the solution was once cooled to room temperature while stirring to obtain a uniform fine particle dispersion without sediment. To the dispersion, 320 mg of a 10% by mass medium (C-1) solution of compound (B2-1), 96 mg of compound (B2-7), 0.5% by mass medium of compound (D2-5) ( C-1) 1280 mg of the solution and 640 mg of a 10% by mass medium (C-1) solution of the other resin (F-1) were put into a planetary ball mill (Sinky Corp., rotation / revolution mixer Nertaro Awatori ARE -310) to obtain a uniform fine particle dispersion without sediment. The dispersion was applied onto a glass substrate by potting at room temperature and air-dried at room temperature for 20 minutes. Thereafter, while heating to 90 ° C. using a hot plate, ultraviolet rays having an illuminance of 10 mW / cm ² were irradiated for 30 minutes to cure the coating film, thereby obtaining a glass substrate on which the coating film was formed. The evaluation results are shown in Table 14.

[Examples 61 to 62]
Except having changed into the mixing | blending shown in Table 13, it carried out similarly to Example 60, and obtained the glass substrate in which the coating film was formed on the surface. The evaluation results are shown in Table 14.

(Adhesion evaluation)
[Example 63]
In a 30 mL reaction vessel, 640 mg of the fluorinated copolymer (A-1), 8.9 mg of the compound (E1-3), and 15.36 g of the medium (C-1) are placed. Heated to 185 ° C. for minutes to give a uniform and clear solution. Next, the solution was once cooled to room temperature while stirring to obtain a uniform fine particle dispersion without sediment. To this dispersion, 320 mg of a 10% by mass medium (C-1) solution of compound (B1-1) and 360 mg of a 10% by mass medium (C-1) solution of compound (D1-2) were added, The mixture was stirred using a planetary ball mill (manufactured by Shinky Co., Ltd., rotation / revolution mixer Awatori Nertaro ARE-310) to obtain a uniform fine particle dispersion without sediment. The dispersion was applied to a silicon substrate (thickness: 200 μm) by bar coating at room temperature, dried at 90 ° C. for 2 hours, and further cured at the temperature shown in Table 13 for 1 hour to form a coating film on the silicon substrate. Formed. In addition, the dispersion obtained in Example 39 as a comparative sample was coated on a silicon substrate by bar coating at room temperature, dried at 90 ° C. for 2 hours, and further heated at the temperature shown in Table 13 for 1 hour to obtain a silicon substrate. A coating was formed on top. The adhesion of the obtained coating film was evaluated before and after a heat and humidity resistance (PCT) test (121 ° C., 100% RH, 48 hours). The evaluation results are shown in Table 15.

In Table 15, “-” indicates that evaluation has not been performed.

[Example 64]
The dispersion obtained in Example 41 was applied to a glass substrate by bar coating at room temperature, dried at 90 ° C. for 30 minutes, and irradiated with ultraviolet rays having an illuminance of 10 mW / cm ² at 100 ° C. for 30 minutes to cure the coating film. And a glass substrate having a coating film formed on the surface was obtained. Similarly, a glass substrate having a coating film formed on the surface thereof was obtained using the dispersion obtained in Example 54. In addition, the dispersion obtained in Example 39 as a comparative sample was coated on a glass substrate by bar coating at room temperature, dried at 90 ° C. for 30 minutes, and further heated at 100 ° C. for 30 minutes, so that the coating film was applied to the surface. A formed glass substrate was obtained. The adhesion of the obtained coating film was evaluated. The evaluation results are shown in Table 16.

In Table 16, “-” indicates that UV irradiation has not been performed.

As shown in Table 15 and Table 16, the adhesion to the silicon substrate and the glass substrate could be improved by coating the fluorine-containing copolymer composition of the present invention.

(Chemical resistant protective coating)
[Example 65]
The dispersion obtained in Example 20 was applied on an aluminum substrate (thickness: 200 μm) by dip coating at room temperature, dried at 90 ° C. for 2 hours, and further cured at 150 ° C. for 1 hour to be applied onto the aluminum substrate. A film was formed. Moreover, the dispersion liquid obtained in Example 39 as a comparative sample was applied on an aluminum substrate (thickness: 200 μm) by dip coating at room temperature, dried at 90 ° C. for 2 hours, and further heated at 150 ° C. for 1 hour, A coating film was formed on an aluminum substrate. The aluminum substrate on which the coating film was formed was immersed in 1N hydrochloric acid, and the change was observed. The evaluation results are shown in Table 17.

As shown in Table 17, the chemical resistance of the aluminum substrate could be remarkably improved by coating the fluorine-containing copolymer composition of the present invention.

[Example 66]
In a 30 mL reaction vessel, 320 mg of the fluorinated copolymer (A-1), 28 mg of a 10% by weight medium (C-1) solution of the compound (B3-1), and 4.3 mg of the compound (E1-1) And 15.68 g of the medium (C-1) were added and heated to 185 ° C. for 30 minutes with stirring under tight sealing to obtain a uniform and transparent solution. Next, the solution was once cooled to room temperature while stirring to obtain a uniform fine particle dispersion without sediment. To the dispersion, 320 mg of 10% by mass medium (C-1) solution of compound (B2-1) and 38 mg of 0.5% by mass medium (C-1) solution of compound (D2-5) were added. The mixture was stirred using a planetary ball mill (manufactured by Shinky Corp., rotation / revolution mixer Awatori Nertaro ARE-310) to obtain a uniform fine particle dispersion without sediment. The dispersion was applied to a polyethylene terephthalate (hereinafter referred to as PET) film (Toyobo Co., Ltd., Cosmo Shine A4300, thickness 100 μm) by bar coating at room temperature, dried at room temperature for 20 minutes, and further at 90 ° C. An ultraviolet ray having an illuminance of 10 mW / cm ² was irradiated for 30 minutes to be cured to form a coating film on the PET film. In addition, the dispersion obtained in Example 39 as a comparative sample was coated on a PET film by bar coating at room temperature, dried at room temperature for 20 minutes, and heated at 90 ° C. for 30 minutes to form a coating film on the PET film. Formed. The adhesion of the obtained coating film was evaluated before and after a chemical resistance test (room temperature, immersed in 1N hydrochloric acid for 1 hour). The evaluation results are shown in Table 18.

As shown in Table 18, the fluorine-containing copolymer composition of the present invention can be coated even on a substrate that does not have sufficient heat resistance such as a PET film. And adhesion could be remarkably improved.

(Molding)
Example 67
In a 30 mL reaction vessel, 640 mg of the fluorinated copolymer (A-2), 32 mg of the compound (B1-8), 21 mg of the compound (D1-1), 8.5 mg of the compound (E1-1), E1-4) (1.6 mg) and medium (C-1) (15.36 g) were added, and the mixture was heated to 185 ° C. for 30 minutes with stirring under tight sealing to obtain a uniform and transparent solution. Next, the solution was once cooled to room temperature while stirring to obtain a uniform fine particle dispersion without sediment. Further, the dispersion was added to 70 g of hexane and stirred for 15 minutes. After filtration, it was dried under reduced pressure at 70 ° C. for 12 hours, and the fluorinated copolymer (A-2), compound (B1-8), compound (D1-1), compound (E1-1) and compound (E1-4) 568 mg of a composition consisting of Then, using a hot press machine, the composition was hot press molded under the conditions of temperature: 200 ° C., pressure: 10 Ma, time: 5 minutes, and a press film was produced. The evaluation results are shown in Table 19.

Example 68
Using only the fluorinated copolymer (A-2), the fluorinated copolymer was subjected to hot press molding under the conditions of temperature: 200 ° C., pressure: 10 Ma, time: 5 minutes using a heat press machine. A press film was prepared. The evaluation results are shown in Table 19.

As shown in Table 19, the fluorine-containing copolymer composition of the present invention was able to improve the surface hardness and heat resistance without affecting the mechanical properties of the molded product.

The coating composition of the present invention includes a fluorine-containing copolymer (ETFE) having a repeating unit based on ethylene and a repeating unit based on TFE, and has good adhesion, scratch resistance, heat resistance, etc. even when baked at a low temperature. Can be easily formed, and is suitable for surface treatments that require heat resistance, flame resistance, chemical resistance, weather resistance, low friction, low dielectric properties, transparency, etc. It is industrially useful.
It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2011-178195 filed on August 17, 2011 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims

A fluorine-containing copolymer (A) having a repeating unit based on ethylene and a repeating unit based on tetrafluoroethylene;
Compound (B) having at least one reactive functional group selected from the group consisting of a group having a cyclic ether having ring-opening reactivity and a group having a carbon-carbon double bond having addition reactivity (provided that Except for the fluorinated copolymer (A)),
A fluorine-containing copolymer composition comprising: a medium (C) capable of dissolving or dispersing the fluorine-containing copolymer (A) and capable of dissolving or dispersing the compound (B).
The fluorine-containing copolymer composition according to claim 1, wherein a mixing ratio of the fluorine-containing copolymer (A) and the compound (B) is 98/2 to 2/98 (mass ratio).
The fluorine-containing copolymer composition according to claim 1 or 2, wherein the content ratio of the medium (C) is 10 to 99% by mass with respect to the fluorine-containing copolymer composition (100% by mass).
The fluorine-containing copolymer composition according to any one of claims 1 to 3, wherein the melting point of the fluorine-containing copolymer (A) is 150 to 260 ° C.
The fluorine-containing copolymer composition according to any one of claims 1 to 4, wherein the medium (C) has a melting point of 25 ° C or lower and a boiling point of 230 ° C or lower at normal pressure.
Selected from the group consisting of the compound (D1) having a reactive functional group capable of reacting with the reactive functional group of the compound (B) and the compound (D2) capable of promoting the reaction of the reactive functional group of the compound (B) At least one compound (D) (excluding the compound (E) that can promote dissolution or dispersion of the fluorine-containing copolymer (A) or the compound (B) in the medium (C)). The fluorine-containing copolymer composition according to any one of claims 1 to 5, further comprising:
The fluorine-containing compound according to any one of claims 1 to 6, further comprising a compound (E) capable of promoting dissolution or dispersion of the fluorine-containing copolymer (A) or the compound (B) in the medium (C). Copolymer composition.
The compound (E) comprises at least one group selected from the group consisting of a primary amino group, a secondary amino group, and a nitrogen-containing heterocyclic group having a nitrogen-hydrogen bond, and an alkyl group having 1 to 20 carbon atoms. The fluorine-containing copolymer composition according to claim 7, which is a compound (E1) having.
The fluorine-containing copolymer composition according to any one of claims 1 to 8, wherein the medium (C) is a solvent having a solubility index (R) represented by the following formula (1) of less than 49.
R = 4 × (δd−15.7) 2 + (δp−5.7) 2 + (δh−4.3) 2 (1).
However, δd, δp, and δh are a dispersion term, a polar term, and a hydrogen bond term [(MPa) 1/2 ] in the Hansen solubility parameter of the solvent, respectively.
A coating composition comprising the fluorine-containing copolymer composition according to any one of claims 1 to 9.
An article having a coating film formed using the coating composition according to claim 10.
A molded product obtained by molding the fluorine-containing copolymer composition according to any one of claims 1 to 9.