Electrodeposition coating composition, coating film, coated article, coated wire, and printed substrate

Abstract

The present invention provides an electrodeposition coating composition containing a neutralized product of a perfluorinated polymer compound X and a methacrylate resin, in which the perfluorinated polymer compound X has a relative dielectric constant of 2.0-2.2, the methacrylate resin has an acid value of 10 mgKOH / g or more, and the perfluorinated polymer compound X has a relative dielectric constant of 2.0-2.2, and the methacrylate resin has an acid value of 10 mgKOH / g or more. The electrodeposition coating composition has a solid content concentration of 10% by mass to 70% by mass.

Description

Technical Field

[0001] The present invention relates to an electrodeposition coating composition, a coating film, a coated article, a coated electric wire, and a printed circuit board. Background Art

[0002] Patent Document 1 describes a method for producing an insulated wire, characterized in that an insulating layer is formed by electrodepositing a water-dispersible resin emulsion prepared by dispersing a polyimide resin, a fluororesin, and a charge-imparting agent in water on a conductor, followed by drying and baking.

[0003] Patent Document 2 describes a method for producing a low-dielectric-constant copper-clad insulating film, characterized in that a liquid obtained by emulsion-polymerizing a vinyl monomer having good thermal decomposition properties in an aqueous dispersion of a fluororesin is used as an electrodeposition coating on a copper foil formed by polymerizing a fibrous base material, an electrodeposition layer is formed by electrodeposition coating, and the vinyl polymer is decomposed and volatilized by heating to form an insulating film.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2002-298674

[0007] Patent Document 2: Japanese Patent Application Laid-Open No. 61-042822 Summary of the Invention

[0008] Problems to be solved by the invention

[0009] An object of the present invention is to provide an electrodeposition coating composition that can be prepared without using a material containing a metal component and that can provide a crack-free coating film.

[0010] Means for solving problems

[0011] According to the present invention, there is provided an electrodeposition coating composition comprising a neutralized product of a perfluoropolymer compound X and a methacrylate resin, wherein the perfluoropolymer compound X has a relative dielectric constant of 2.0 to 2.2, the methacrylate resin has an acid value of 10 mgKOH / g or greater, and the electrodeposition coating composition has a solid content concentration of 10% to 70% by mass.

[0012] Effects of the Invention

[0013] According to the present invention, it is possible to provide an electrodeposition coating composition that can be prepared without using a material containing a metal component and that can provide a crack-free coating film. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 These are a front view and a top view of a covered electric wire having a bent portion according to one embodiment.

[0015] Figure 2 This is a cross-sectional view of a covered electric wire having a bent portion according to one embodiment. DETAILED DESCRIPTION

[0016] Hereinafter, specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0017] The first electrodeposition coating composition of the present invention is an electrodeposition coating composition comprising a neutralized product of a perfluoropolymer compound X and a methacrylate resin. In the first electrodeposition coating composition, the perfluoropolymer compound X has a dielectric constant of 2.0 to 2.2, the methacrylate resin has an acid value of 10 mgKOH / g or greater, and the solids concentration of the electrodeposition coating composition is 10% to 70% by mass.

[0018] Conventionally, as an electrodeposition coating composition, a water-dispersible resin emulsion obtained by dispersing a polyimide resin, a fluororesin, and a charge-imparting agent in water is known, as described in Patent Document 1. Patent Document 1 discloses that the use of such a water-dispersible resin emulsion enables the realization of a flat insulated wire having an insulation layer with sufficient insulation performance, a minimized thickness on the long sides, and excellent heat resistance.

[0019] Patent Document 2 describes a technique that, while not intended to form a coating film on a covered electric wire, uses a liquid obtained by emulsion-polymerizing a vinyl monomer with good thermal decomposition properties in an aqueous dispersion of a fluororesin as an electrodeposition coating. When emulsion-polymerizing the vinyl monomer in the aqueous dispersion of the fluororesin, a surfactant, such as a nonionic, anionic, or cationic surfactant, is used. Examples of such surfactants include sodium lauryl sulfate.

[0020] However, the metal components contained in the surfactant remain in the final film, degrading the electrical properties of the film. Therefore, there is a need for an electrodeposition coating composition that can be prepared without using materials containing metal components and can produce a crack-free film.

[0021] The first electrodeposition coating composition of the present invention contains a perfluoropolymer compound having a low relative dielectric constant and a neutralized methacrylate resin obtained by neutralizing a methacrylate resin having a high acid value. It has been discovered that such an electrodeposition coating composition can be prepared without using materials containing metal components, and that by electrodeposition coating such an electrodeposition coating composition on a substrate, a crack-free coating can be obtained on the substrate. Furthermore, the resulting coating has low surface roughness, strongly adheres to the substrate, and has a low relative dielectric constant.

[0022] The second electrodeposition coating composition of the present invention is an electrodeposition coating composition comprising a neutralized product of a perfluoropolymer compound X and a methacrylate resin. In the second electrodeposition coating composition, the perfluoropolymer compound X is a tetrafluoroethylene / fluoroalkyl vinyl ether copolymer, the methacrylate resin has an acid value of 10 mgKOH / g or greater, and the solids concentration of the electrodeposition coating composition is 10% to 70% by mass.

[0023] The second electrodeposition coating composition of the present invention contains a tetrafluoroethylene / fluoroalkyl vinyl ether copolymer as a perfluoropolymer and a neutralized methacrylate resin obtained by neutralizing a methacrylate resin having a high acid value. It has been discovered that such an electrodeposition coating composition can be prepared without using materials containing metal components, and that by electrodeposition coating such an electrodeposition coating composition on a substrate, a crack-free coating can be obtained on the substrate. Furthermore, the resulting coating has low surface roughness, strongly adheres to the substrate, and has a low relative dielectric constant.

[0024] Hereinafter, each component contained in the electrodeposition coating composition of the present invention will be described in detail.

[0025] (Perfluorinated polymer compound X)

[0026] The electrodeposition coating composition of the present invention contains a perfluoropolymer compound X. In the present invention, the perfluoropolymer compound refers to a polymer compound in which the content of perfluoromonomer units is 90 mol % or more based on all polymerized units constituting the polymer compound.

[0027] In the present invention, a perfluorinated monomer refers to a monomer that does not contain a carbon-hydrogen bond in its molecule. A perfluorinated monomer may also be a monomer in which, in addition to carbon atoms and fluorine atoms, some of the fluorine atoms bonded to carbon atoms are replaced by chlorine atoms. A perfluorinated monomer may also contain nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus atoms, boron atoms, or silicon atoms in addition to carbon atoms. Preferred perfluorinated monomers are those in which all hydrogen atoms are replaced by fluorine atoms.

[0028] From the perspective of obtaining a film having a lower relative dielectric constant, the relative dielectric constant of the perfluoropolymer compound X is preferably 2.0 to 2.2. The relative dielectric constant of the perfluoropolymer compound X can be measured in accordance with JIS-C-2138 at 23°C ± 2°C, 50% relative humidity, and 1 kHz frequency.

[0029] As the perfluorinated polymer compound X, a perfluorinated fluororesin is preferred. In the present invention, a fluororesin refers to a partially crystalline fluorinated polymer, which is a fluoroplastic. A fluororesin has a melting point and thermoplastic properties, and can be either melt-processable or non-melt-processable.

[0030] The perfluoropolymer compound X is preferably at least one selected from the group consisting of polytetrafluoroethylene, tetrafluoroethylene (TFE) / fluoroalkyl vinyl ether (FAVE) copolymer, tetrafluoroethylene (TFE) / hexafluoropropylene (HFP) copolymer, and TFE / FAVE / HFP copolymer.

[0031] Polytetrafluoroethylene (PTFE) may be either non-melt-processable or melt-processable, but non-melt-processable PTFE is preferred. In one embodiment, as the perfluoropolymer compound X, PTFE having a relative dielectric constant of 2.0 to 2.2 can be used.

[0032] Non-melt-processable PTFE generally exhibits stretchability, fibrillation properties, and non-melt-processability. Non-melt-processability refers to the property that the melt flow rate cannot be measured at temperatures above the crystallization melting point, according to ASTM D 1238 and D 2116, meaning that it does not readily flow even in the melting temperature range.

[0033] PTFE can be tetrafluoroethylene (TFE) homopolymer, or it can be modified PTFE containing TFE unit and modified monomer unit. In the present invention, " modified PTFE " refers to a material obtained by copolymerizing a small amount of comonomer and TFE that will not give melt processability to the copolymer obtained. As comonomer, there is no particular limitation, and examples thereof include hexafluoropropylene [HFP], chlorotrifluoroethylene [CTFE], perfluoro (alkyl vinyl ether) [PAVE], etc. The ratio of comonomer addition to modified PTFE is different according to its type, for example, relative to the total mass of TFE and a small amount of comonomer, preferably 0.001% by mass to 1% by mass. In the present invention, the content of each monomer unit constituting PTFE can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis according to the type of monomer.

[0034] The standard specific gravity (SSG) of PTFE is preferably 2.280 or less, more preferably 2.210 or less, further preferably 2.200 or less, and preferably 2.130 or more. SSG can be measured by the water displacement method according to ASTM D 792 using a sample molded according to ASTM D 4895-89.

[0035] The peak temperature of PTFE is preferably within the range of 333°C to 347°C. More preferably, it is 335°C or higher and 345°C or lower. The peak temperature is the temperature corresponding to the maximum value in the heat of fusion curve of PTFE that has not been heated to a temperature of 300°C or higher, when the temperature is increased at a rate of 10°C / minute using a differential scanning calorimeter (DSC).

[0036] As the perfluoropolymer compound X, a melt-processable perfluoropolymer compound can also be used. In the present invention, melt-processability means that the polymer can be melted and processed using existing processing equipment such as an extruder and an injection molding machine. Therefore, the melt flow rate of the melt-processable perfluoropolymer compound is generally 0.01 g / 10 min to 500 g / 10 min. In one embodiment, as the perfluoropolymer compound X, a melt-processable perfluoropolymer compound having a relative dielectric constant of 2.0 to 2.2 can be used.

[0037] The melt flow rate of the perfluoropolymer compound X is preferably 0.1 g / 10 min to 100 g / 10 min, more preferably 80 g / 10 min or less, further preferably 70 g / 10 min or less, and preferably 5 g / 10 min or more, more preferably 10 g / 10 min or more.

[0038] The melt flow rate of the perfluoropolymer compound X is a value obtained as the mass (g / 10 minutes) of the polymer flowing out from a nozzle having an inner diameter of 2.1 mm and a length of 8 mm at 372°C and a load of 5 kg using a melt flow indexer (manufactured by Yasuda Seiki Co., Ltd.) in accordance with ASTM D1238.

[0039] The melting point of the perfluoropolymer compound X is preferably 200° C. to 322° C., more preferably 230° C. or higher, further preferably 250° C. or higher, and more preferably 320° C. or lower.

[0040] The melting point can be measured using a differential scanning calorimeter [DSC].

[0041] As the melt-processable perfluoropolymer compound X, at least one selected from the group consisting of TFE / FAVE copolymers, TFE / HFP copolymers, and TFE / FAVE / HFP copolymers is preferred.

[0042] TFE / FAVE copolymer is a copolymer containing tetrafluoroethylene (TFE) units and fluoroalkyl vinyl ether (FAVE) units. In one embodiment, as the perfluoropolymer compound X, a TFE / FAVE copolymer having a relative dielectric constant of 2.0 to 2.2 can be used.

[0043] Examples of FAVE constituting the FAVE unit include those selected from the group consisting of the following general formula (1):

[0044] CF2=CFO(CF2CFY 1 O) p -(CF2CF2CF2O) q -Rf (1)

[0045] (Where Y 1 represents F or CF3, Rf represents a perfluoroalkyl group having 1 to 5 carbon atoms, p represents an integer from 0 to 5, and q represents an integer from 0 to 5. ) and the general formula (2):

[0046] CFX=CXOCF2OR 1 (2)

[0047] (wherein, X is the same or different and represents H, F or CF3, R 1 At least one of the group consisting of monomers represented by a linear or branched fluoroalkyl group having 1 to 6 carbon atoms which may contain 1 to 2 atoms of at least one type selected from the group consisting of H, Cl, Br and I, or a cyclic fluoroalkyl group having 5 or 6 carbon atoms which may contain 1 to 2 atoms of at least one type selected from the group consisting of H, Cl, Br and I.

[0048] As FAVE, the monomer represented by the general formula (1) is preferred, more preferably at least one selected from the group consisting of perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether) (PEVE) and perfluoro(propyl vinyl ether) (PPVE), further preferably at least one selected from the group consisting of PEVE and PPVE, and particularly preferably PPVE.

[0049] The content of the FAVE unit of the TFE / FAVE copolymer is preferably 1.0 mol% to 30.0 mol% relative to all monomer units, more preferably 1.2 mol% or more, further preferably 1.4 mol% or more, further preferably 1.6 mol% or more, particularly preferably 1.8 mol% or more, more preferably 3.5 mol% or less, further preferably 3.2 mol% or less, further preferably 2.9 mol% or less, and particularly preferably 2.6 mol% or less.

[0050] The content of the TFE unit in the TFE / FAVE copolymer is preferably 99.0 mol% to 70.0 mol% relative to all monomer units, more preferably 96.5 mol% or more, further preferably 96.8 mol% or more, further preferably 97.1 mol% or more, particularly preferably 97.4 mol% or more, more preferably 98.8 mol% or less, further preferably 98.6 mol% or less, further preferably 98.4 mol% or less, and particularly preferably 98.2 mol% or less.

[0051] In the present invention, the content of each monomer unit in the copolymer is determined by 19 Determined by F-NMR method.

[0052] The TFE / FAVE copolymer may also contain monomer units derived from monomers copolymerizable with TFE and FAVE. In this case, the content of the monomers copolymerizable with TFE and FAVE is preferably 0 to 29.0 mol%, more preferably 0.1 to 5.0 mol%, and even more preferably 0.1 to 1.0 mol%, relative to all monomer units of the TFE / FAVE copolymer.

[0053] Examples of monomers copolymerizable with TFE and FAVE include HFP, CZ 1 Z 2 =CZ 3 (CF2) n Z 4 (Where Z 1 , Z 2 and Z 3 Same or different, means H or F, Z 4 represents H, F or Cl, n represents an integer of 2 to 10) and a vinyl monomer represented by CF2=CF-OCH2-Rf 1 (Where Rf 1 represents a perfluoroalkyl group having 1 to 5 carbon atoms), an alkyl perfluorovinyl ether derivative represented by (represents a perfluoroalkyl group having 1 to 5 carbon atoms), a monomer having a functional group, etc. Among them, HFP is preferred.

[0054] The TFE / FAVE copolymer is preferably at least one selected from the group consisting of copolymers consisting solely of TFE units and FAVE units and the aforementioned TFE / HFP / FAVE copolymers, and more preferably a copolymer consisting solely of TFE units and FAVE units.

[0055] The melting point of the TFE / FAVE copolymer is preferably 280° C. to 322° C., more preferably 285° C. or higher, more preferably 320° C. or lower, and further preferably 315° C. or lower. The melting point can be measured using a differential scanning calorimeter (DSC).

[0056] The glass transition temperature (Tg) of the TFE / FAVE copolymer is preferably 70° C. to 110° C., more preferably 80° C. or higher, and more preferably 100° C. or lower. The glass transition temperature can be measured by dynamic viscoelasticity measurement.

[0057] TFE / HFP copolymer is a copolymer containing tetrafluoroethylene (TFE) units and hexafluoropropylene (HFP) units.

[0058] The content of the HFP unit in the TFE / HFP copolymer is preferably 0.1 to 30.0 mol %, more preferably 0.7 mol % or more, further preferably 1.4 mol % or more, and more preferably 10.0 mol % or less, based on all monomer units.

[0059] The content of the TFE unit in the TFE / HFP copolymer is preferably 70.0 mol% to 99.9 mol%, more preferably 90.0 mol% or more, more preferably 99.3 mol% or less, and even more preferably 98.6 mol%, based on all monomer units.

[0060] The TFE / HFP copolymer may also contain monomer units derived from monomers copolymerizable with TFE and HFP. In this case, the content of the monomers copolymerizable with TFE and HFP is preferably 0 to 29.9 mol %, more preferably 0.1 to 5.0 mol %, and even more preferably 0.1 to 1.0 mol %, relative to the total monomer units of the TFE / HFP copolymer.

[0061] Examples of monomers copolymerizable with TFE and HFP include FAVE, CZ 1 Z 2 =CZ 3 (CF2) n Z 4 (Where Z 1 , Z 2 and Z 3 Same or different, means H or F, Z 4 represents H, F or Cl, n represents an integer of 2 to 10) and a vinyl monomer represented by CF2=CF-OCH2-Rf 1 (Where Rf 1 represents a perfluoroalkyl group having 1 to 5 carbon atoms), an alkyl perfluorovinyl ether derivative represented by (represents a perfluoroalkyl group having 1 to 5 carbon atoms), a monomer having a functional group, etc. Among them, FAVE is preferred.

[0062] The melting point of the TFE / HFP copolymer is preferably 200°C to 322°C, more preferably 210°C or higher, further preferably 220°C or higher, particularly preferably 240°C or higher, more preferably 320°C or lower, further preferably lower than 300°C, particularly preferably 280°C or lower.

[0063] The glass transition temperature (Tg) of the TFE / HFP copolymer is preferably 60° C. to 110° C., more preferably 65° C. or higher, and further preferably 100° C. or lower.

[0064] The fluorine-containing polymer compound may have a functional group.

[0065] The functional group is preferably at least one selected from the group consisting of a carbonyl-containing group, an amino group, a hydroxyl group, a -CF2H group, an olefin group, an epoxy group, and an isocyanate group.

[0066] The carbonyl-containing group is a group containing a carbonyl group (-C(=O)-) in its structure. Examples of the carbonyl-containing group include:

[0067] Carbonate group [-OC(=O)-OR 3 (Where R 3 is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms containing an ethereal oxygen atom)],

[0068] Acyl [-C(=O)-R 3 (Where R 3 is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms containing an ethereal oxygen atom)],

[0069] Haloformyl[-C(=O)X 5 、X 5 is a halogen atom],

[0070] Formyl [-C(=O)H],

[0071] Formula: -R 4 -C(=O)-R 5 (Where R 4 is a divalent organic group having 1 to 20 carbon atoms, R 5 is a monovalent organic group having 1 to 20 carbon atoms),

[0072] Formula: -OC(=O)-R 6 (Where R 6 is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms containing an ethereal oxygen atom),

[0073] Carboxyl [-C(=O)OH],

[0074] Alkoxycarbonyl [-C(=O)OR 7 (Where R 7 is a monovalent organic group having 1 to 20 carbon atoms)], carbamoyl [-C(=O)NR 8 R 9(Where R 8 and R 9 may be the same or different and are a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms)],

[0075] anhydride bond [—C(═O)—OC(═O)—] and the like.

[0076] As R 3 Specific examples of R include methyl, ethyl, propyl, isopropyl, and butyl. 4 Specific examples include methylene, -CF2-, -C6H4-, etc., as R 5 Specific examples of R include methyl, ethyl, propyl, isopropyl, and butyl. 7 Specific examples of R include methyl, ethyl, propyl, isopropyl, and butyl. 8 and R 9 Specific examples of include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a phenyl group.

[0077] The hydroxyl group is a group represented by -OH or a group containing a group represented by -OH. In the present invention, -OH constituting a carboxyl group is not included in the hydroxyl group. Examples of the hydroxyl group include -OH, hydroxymethyl, and hydroxyethyl.

[0078] An olefin group is a group having a carbon-carbon double bond. Examples of olefin groups include the following:

[0079] -CR 10 =CR 11 R 12

[0080] (Where R 10 、R 11 and R 12 The functional group may be the same or different and is a hydrogen atom, a fluorine atom or a monovalent organic group having 1 to 20 carbon atoms, preferably at least one selected from the group consisting of -CF=CF2, -CH=CF2, -CF=CHF, -CF=CH2 and -CH=CH2.

[0081] The isocyanate group is a group represented by -N=C=O.

[0082] In addition, examples of the functional group include non-fluorinated alkyl groups or partially fluorinated alkyl groups such as a -CH3 group and a -CFH2 group.

[0083] From the viewpoint of forming a film that is more firmly bonded to the substrate, the number of functional groups of the perfluoropolymer compound X is 6The number of carbon atoms is preferably 5 to 2000. 6 The number of functional groups is more preferably 50 or more, further preferably 100 or more, particularly preferably 200 or more, more preferably 1000 or less, further preferably 800 or less, particularly preferably 700 or less, and most preferably 500 or less.

[0084] In addition, from the viewpoint of forming a film with excellent electrical properties, the number of functional groups of the perfluoropolymer compound X is preferably 6 The number of carbon atoms may be less than 5, or may be 0 to 4.

[0085] The functional groups are functional groups present at the main chain terminal or side chain terminal of the perfluoropolymer compound X, as well as functional groups present in the main chain or side chain, preferably present at the main chain terminal. Examples of the functional groups include -CF=CF2, -CF2H, -COF, -COOH, -COOCH3, -CONH2, -OH, -CH2OH, etc., preferably at least one selected from the group consisting of -CF2H, -COF, -COOH, -COOCH3 and -CH2OH. -COOH includes a dicarboxylic anhydride group (-CO-O-CO-) formed by two -COOH groups bonded together.

[0086] The identification of the types of the functional groups and the measurement of the number of the functional groups can be performed using infrared spectroscopy.

[0087] Regarding the number of functional groups, specifically, the following method is used for determination. First, the copolymer is melted at 330°C to 340°C for 30 minutes and compression molded to produce a film with a thickness of 0.20mm to 0.25mm. The film is analyzed by Fourier transform infrared spectroscopy to obtain an infrared absorption spectrum of the copolymer, and a differential spectrum is obtained from the background spectrum in which no functional groups are present due to complete fluorination. According to the following formula (A), the number of functional groups per 1×10 6 The number of functional groups N per carbon atom.

[0088] N=I×K / t(A)

[0089] I: absorbance

[0090] K: Correction coefficient

[0091] t: film thickness (mm)

[0092] For reference, the absorption frequency, molar absorptivity, and correction coefficient of the functional groups in the present invention are shown in Table 1. The molar absorptivity was determined from FT-IR measurement data of a low-molecular-weight model compound.

[0093] [Table 1]

[0094]

[0095] It should be noted that the absorption frequencies of -CH2CF2H, -CH2COF, -CH2COOH, -CH2COOCH3, and -CH2CONH2 are several tens of kaisekas (cm-1) lower than the absorption frequencies of -CF2H, -COF, free -COOH, and bonded -COOH, -COOCH3, and -CONH2 shown in the table, respectively. 1 ).

[0096] Thus, for example, the functional group number of -COF refers to the absorption frequency 1883 cm-1 due to -CF2COF. 1 The number of functional groups was determined from the absorption peak at 1840 cm-1 due to the absorption frequency of -CH2COF. -1 The total number of functional groups found from the absorption peak at .

[0097] The above-mentioned number of functional groups can be the total number of -CF=CF2, -CF2H, -COF, -COOH, -COOCH3, -CONH2 and -CH2OH, or the total number of -CF2H, -COF, -COOH, -COOCH3 and -CH2OH.

[0098] The above functional groups are introduced into the perfluoropolymer compound X, for example, by a chain transfer agent or polymerization initiator used when producing the perfluoropolymer compound X. For example, when an alcohol is used as a chain transfer agent or a peroxide having a -CH2OH structure is used as a polymerization initiator, -CH2OH is introduced to the main chain terminal of the perfluoropolymer compound X. Alternatively, by polymerizing a monomer having a functional group, the above functional groups are introduced to the side chain terminal of the perfluoropolymer compound X. The perfluoropolymer compound X may contain units derived from a monomer having a functional group.

[0099] Examples of monomers having a functional group include cyclic hydrocarbon monomers having a dicarboxylic anhydride group ((-CO-O-CO-) and a polymerizable unsaturated group in the ring as described in Japanese Patent Application Laid-Open No. 2006-152234, and monomers having a functional group (f) as described in International Publication No. 2017 / 122743. Examples of monomers having a functional group include monomers having a carboxyl group (maleic acid, itaconic acid, citraconic acid, undecylenic acid, etc.); monomers having an acid anhydride group (itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, maleic anhydride, etc.); and monomers having a hydroxyl group or epoxy group (hydroxybutyl vinyl ether, glycidyl vinyl ether, etc.).

[0100] The perfluoropolymer compound X can be produced, for example, by appropriately mixing monomers that will serve as structural units and additives such as a polymerization initiator and performing conventionally known methods such as emulsion polymerization and suspension polymerization.

[0101] (Neutralized product of methacrylate resin)

[0102] The electrodeposition coating composition of the present invention contains a neutralized methacrylate resin. The methacrylate resin is preferably a depolymerizable methacrylate resin. In the present invention, depolymerization means that the polymer forming the resin is decomposed into monomers by heating.

[0103] The neutralized methacrylate resin in the electrodeposition coating composition exhibits emulsifying ability by forming ions in water. This allows it to form emulsified particles with the perfluoropolymer compound X and stably disperse in water, even without the use of surfactants, thereby preparing the electrodeposition coating composition. Furthermore, the neutralized methacrylate resin imparts anionic properties to the perfluoropolymer compound X, facilitating smooth electrodeposition of the perfluoropolymer compound X. Furthermore, when a depolymerizable methacrylate resin is used as the methacrylate resin, the neutralized depolymerizable methacrylate resin slowly depolymerizes upon heating during film formation, contributing to the formation of a crack-free film. After film formation is complete, the majority of the depolymerizable methacrylate resin depolymerizes, leaving only a portion of the depolymerizable methacrylate resin remaining in the film. Compared to neutralized non-depolymerizable methacrylate resins, the neutralized depolymerizable methacrylate resin is less likely to remain in the film, resulting in smooth, crack-free film formation without significantly reducing the relative dielectric constant of the film. When a neutralized product of a non-depolymerizable methacrylate resin is used, it may be difficult to obtain a crack-free film.

[0104] Furthermore, in the present invention, a methacrylate resin having an acid value of 10 mgKOH / g or greater is used. The acid value of the methacrylate resin is preferably 15 mgKOH / g or greater, more preferably 20 mgKOH / g or greater, even more preferably 25 mgKOH / g or greater, and particularly preferably 30 mgKOH / g or greater. The upper limit of the acid value of the methacrylate resin is, for example, 150 mgKOH / g or less. By using a methacrylate resin having an acid value within the above range, an electrodeposition coating composition can be easily prepared without using materials such as surfactants containing metal components, anionic properties can be imparted to the perfluoropolymer compound X, and a crack-free coating can be obtained.

[0105] The acid value of a methacrylate resin is the acid value of the methacrylate resin before neutralization. The acid value of a methacrylate resin can be measured using potentiometric titration in accordance with JIS K5601. For example, the methacrylate resin can be dissolved in a mixed solvent of xylene and isopropyl alcohol and titrated using a 0.1 mol / L potassium hydroxide / ethanol solution using potentiometric titration. The inflection point on the titration curve is defined as the endpoint, and the acid value is calculated from the titration amount of the potassium hydroxide solution up to the endpoint. The acid value of a methacrylate resin can also be calculated based on the monomer composition of the methacrylate resin.

[0106] In one embodiment of the neutralized methacrylate resin, the neutralized product has acid groups in a number sufficient to impart the above-mentioned acid value to the methacrylate resin, and the acid groups are neutralized by a basic compound. The acid groups are, for example, carboxyl groups, and the basic compound is, for example, an amine compound.

[0107] The methacrylate resin may contain, for example, a (meth)acrylate unit, a hydroxyl group-containing (meth)acrylate unit, an unsaturated carboxylic acid unit, etc. In the present invention, "(meth)acrylic acid" means acrylic acid or methacrylic acid.

[0108] In one embodiment of the methacrylate resin, the resin contains (meth)acrylate units and unsaturated carboxylic acid units. In another embodiment of the methacrylate resin, the resin contains (meth)acrylate units, hydroxyl group-containing (meth)acrylate units, and unsaturated carboxylic acid units.

[0109] Examples of the (meth)acrylate include alkyl (meth)acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, methyl methacrylate, n-propyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate. Among these, the (meth)acrylate is preferably at least one selected from the group consisting of methyl methacrylate, n-butyl methacrylate, and n-butyl acrylate.

[0110] Examples of the hydroxyl group-containing (meth)acrylate include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, and 6-hydroxyhexyl methacrylate. Among these, the hydroxyl group-containing (meth)acrylate is preferably at least one selected from the group consisting of 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate.

[0111] The (meth)acrylate units and hydroxyl-containing (meth)acrylate units adjust the glass transition temperature of the neutralized methacrylate resin and impart appropriate film-forming properties to the electrodeposition coating composition. The content of the (meth)acrylate units and hydroxyl-containing (meth)acrylate units is adjusted, for example, to impart appropriate film-forming properties required for the electrodeposition coating composition.

[0112] Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, 3-(2-allyloxyethoxycarbonyl)propionic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, maleic anhydride, fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitate, and undecylenic acid. Among these, the unsaturated carboxylic acid is preferably at least one selected from the group consisting of acrylic acid and methacrylic acid.

[0113] The unsaturated carboxylic acid unit imparts an appropriate acid value to the methacrylate resin. The content of the unsaturated carboxylic acid unit is adjusted, for example, so as to impart an acid value within the above-mentioned range to the methacrylate resin.

[0114] In one embodiment, the methacrylate resin has a carboxyl group and preferably contains an unsaturated carboxylic acid unit. When the methacrylate resin has a carboxyl group, the neutralized methacrylate resin is preferably obtained by neutralizing the carboxyl-containing methacrylate resin with an amine compound. If the neutralized methacrylate resin is obtained by neutralizing the carboxyl-containing methacrylate resin with an amine compound, it is easier to prepare an electrodeposition coating composition without using materials such as surfactants containing metal components, and it is easier to obtain a crack-free coating. Furthermore, since the emulsification ability of the neutralized methacrylate resin is also improved, when the electrodeposition coating composition is prepared by phase inversion emulsification, as described below, the perfluoropolymer compound X can be extremely stably dispersed in the aqueous dispersion, making it easier to prepare the electrodeposition coating composition without using materials such as surfactants containing metal components.

[0115] The amine compound used to neutralize the methacrylate resin having a carboxyl group may be any of primary, secondary, and tertiary amines, with tertiary amines being preferred. Furthermore, the amine compound is preferably an aliphatic amine, preferably at least one selected from the group consisting of ethylamine, diethylamine, diethylpropylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, and diethylethanolamine. Among these amine compounds, triethylamine is preferred.

[0116] The amount of amine compound used is determined by the desired degree of neutralization of the neutralized methacrylate resin. The degree of neutralization of the neutralized methacrylate resin is preferably 50% or higher, more preferably 60% or higher, and even more preferably 70% or higher, and preferably 95% or lower, and even more preferably 90% or lower. If the degree of neutralization of the neutralized methacrylate resin falls within the above range, the electrodeposition coating composition can be prepared more easily without using materials such as surfactants containing metal components, and a crack-free coating can be obtained more easily. Furthermore, since the emulsification ability of the neutralized methacrylate resin is also improved, when the electrodeposition coating composition is prepared by phase inversion emulsification, as described below, the perfluoropolymer compound X can be extremely stably dispersed in the aqueous dispersion, making it easier to prepare the electrodeposition coating composition without using materials such as surfactants containing metal components.

[0117] The degree of neutralization of a neutralized methacrylate resin can be determined by dividing the amine value, measured by potentiometric titration, by the acid value. For example, tetrahydrofuran can be added to the methacrylate resin and titrated to the equivalence point using a 0.1 mol / L hydrochloric acid solution by potentiometric titration. The inflection point on the titration curve is taken as the amine value, and the degree of neutralization is calculated by dividing the amine value by the acid value. The degree of neutralization of a neutralized methacrylate resin can also be determined by calculation based on the monomer composition of the methacrylate resin and the amount of a neutralizing compound, such as an amine compound, used.

[0118] The neutralized product of the methacrylate resin is preferably obtained by neutralizing a methacrylate resin containing an unsaturated carboxylic acid unit in such a content as to provide an acid value within the above range, using an amine compound in such an amount as to provide a degree of neutralization within the above range.

[0119] (Electrodeposition coating composition)

[0120] The electrodeposition coating composition of the present invention can be produced by a production method comprising adding an aqueous dispersion containing a perfluoropolymer compound X and water to a solution containing a neutralized methacrylate resin and an organic solvent, followed by phase inversion emulsification. By using the electrodeposition coating composition obtained by this production method, a crack-free coating can be more easily obtained.

[0121] The organic solvent for the solution containing the neutralized methacrylate resin is preferably an organic solvent capable of dissolving the neutralized methacrylate resin. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, and n-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diethyl ketone; ethers such as dibutyl ether, tetrahydrofuran, and dioxane; and acetates such as ethyl acetate and isopropyl acetate.

[0122] Phase inversion emulsification can be performed, for example, by adding the aqueous dispersion composition to the solution while stirring the solution. The temperature of the solution and the aqueous dispersion composition can be room temperature (eg, 10° C. to 40° C.).

[0123] The electrodeposition coating composition contains a neutralized product of the perfluoropolymer compound X and a methacrylate resin, and preferably further contains water.

[0124] The electrodeposition coating composition contains a neutralized product of a perfluoropolymer compound X and a methacrylate resin, and preferably further contains an organic solvent. Examples of the organic solvent include the organic solvents described above as organic solvents for solutions containing the neutralized product of the methacrylate resin.

[0125] From the viewpoint of efficiently forming a coating by electrodeposition coating, the solid content concentration of the electrodeposition coating composition is preferably 10% to 70% by mass, more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0126] The mass ratio of the neutralized product of the perfluoropolymer X and the methacrylate resin in the electrodeposition coating composition is preferably 10 / 90 to 90 / 10, more preferably 20 / 80 or more, further preferably 25 / 75 or more, more preferably 80 / 20 or less, further preferably 75 / 25 or less.

[0127] The alkali metal content in the electrodeposition coating composition is preferably less than 1 ppm by mass. The electrodeposition coating composition of the present invention can be prepared without using a material containing a metal component, and thus can have a lower alkali metal content than conventional electrodeposition coating compositions.

[0128] The alkali metal content in the electrodeposition coating composition can be determined by inductively coupled plasma mass spectrometry.

[0129] The electrodeposition coating composition of the present invention may contain additives for the purpose of improving coating properties, properties of the resulting film, and the like.

[0130] The electrodeposition coating composition of the present invention can be suitably used as an anionic electrodeposition coating composition.

[0131] (Fluorine-containing compound having a hydrophilic group)

[0132] In one embodiment, an electrodeposition coating composition can be used in which the content of a fluorinated compound having a hydrophilic group is reduced. By reducing the content of the fluorinated compound having a hydrophilic group in the electrodeposition coating composition, a film having a large contact angle and a low coefficient of friction can be obtained. The reason for this is unclear, but it is speculated that if the content of the fluorinated compound having a hydrophilic group in the electrodeposition coating composition is reduced, the dispersion stability of the perfluoropolymer compound X in the electrodeposition coating composition is moderately reduced. Therefore, when the film is formed, the perfluoropolymer compound X is more likely to float on the surface of the film than other components, resulting in a higher content of the perfluoropolymer compound X on the film surface.

[0133] The fluorine-containing compound having a hydrophilic group includes a fluorine-containing surfactant added during polymerization and a fluorine-containing compound having a hydrophilic group produced by polymerization of a fluorine-containing monomer.

[0134] As the hydrophilic group possessed by the fluorine-containing compound, anionic groups such as acid groups are preferred, for example, -NH2, -PO3M, -OPO3M, -SO3M, -OSO3M, -COOM (wherein M represents a cation) can be mentioned. As the above-mentioned hydrophilic group, -SO3M or -COOM is preferred, and -COOM is more preferred.

[0135] The content of the fluorine-containing compound having a hydrophilic group in the electrodeposition coating composition is preferably 50 ppb by mass or less, more preferably 45 ppb by mass or less, and preferably exceeds 0 ppb by mass, based on the perfluoropolymer compound X.

[0136] The content of the fluorine-containing compound having a hydrophilic group in the electrodeposition coating composition can be quantified by a known method, for example, by LC / MS analysis.

[0137] First, methanol is added to the electrodeposition coating composition for extraction, and the resulting extract is analyzed by LC / MS. To further improve extraction efficiency, Soxhlet extraction, ultrasonic treatment, or other methods can be used. The resulting extract is then concentrated using a nitrogen purge, and the fluorinated compounds in the concentrated extract are analyzed by LC / MS.

[0138] Molecular weight information was extracted from the obtained LC / MS spectrum, and it was confirmed that the molecular weight matched the structural formula of a candidate fluorine-containing compound having a hydrophilic group.

[0139] Then, aqueous solutions of the confirmed fluorinated compound having a hydrophilic group at five or more levels were prepared, and the aqueous solutions at each level were analyzed by LC / MS. The relationship between the content and the area relative to the content was plotted to create a calibration curve.

[0140] Then, using the calibration curve, the area of the LC / MS chromatogram of the fluorine-containing compound having a hydrophilic group in the extract can be converted into the content of the fluorine-containing compound having a hydrophilic group.

[0141] Note that the obtained extract can be concentrated by purging with nitrogen, thereby lowering the lower limit of quantification of the measurement method.

[0142] In one embodiment of the electrodeposition coating composition, the fluorinated compound having a hydrophilic group includes at least a fluorinated surfactant. The fluorinated surfactant may be a fluorinated surfactant commonly used in the polymerization of fluorinated monomers. Typical fluorinated surfactants have a molecular weight of 1000 g / mol or less, preferably 800 g / mol or less.

[0143] The fluorinated surfactant is not particularly limited as long as it contains at least one fluorine atom, and a conventionally known fluorinated surfactant can be used.

[0144] Examples of the fluorinated surfactant include anionic fluorinated surfactants, etc. The anionic fluorinated surfactant may be, for example, a surfactant containing fluorine atoms and having a total carbon number of 20 or less in the moiety excluding the anionic group.

[0145] Furthermore, the fluorine-containing surfactant may be a surfactant containing fluorine whose anionic portion has a molecular weight of 1000 or less.

[0146] It should be noted that the above-mentioned "anionic part" refers to the part other than the cation of the above-mentioned fluorinated surfactant. For example, in the F(CF2) shown in the formula (I) described later n1 In the case of COOM, it is "F(CF2) n1 COO” part.

[0147] Examples of the fluorinated surfactant include those having a LogPOW of 3.5 or less. The LogPOW is the partition coefficient between 1-octanol and water and is represented by LogP [where P represents the ratio of the fluorinated surfactant concentration in octanol to the fluorinated surfactant concentration in water when a 1:1 octanol / water mixture containing the fluorinated surfactant undergoes phase separation].

[0148] The above LogPOW is calculated as follows: On column: TOSOH ODS-120T column ( HPLC was performed on standard substances with known octanol / water partition coefficients (heptanoic acid, octanoic acid, nonanoic acid, and decanoic acid) under the following conditions: (a) a column having a 1:1 ratio of 1:1 and a column temperature of 40°C; (b) a column having a 1:1 ratio of 1:1 and a column temperature of 40°C; (c) a column having a 1:1 ratio of 1:1 and a column temperature of 40°C; (d) a column having a 1:1 ratio of 1:1 and a column temperature of 40°C; (e) a column having a 1:1 ratio of 1:1 and a column temperature of 40°C; (e) a column having a 1:1 ratio of 1:1 and a column temperature of 50°C; (f) a column having a 1:1 ratio of 1:1 and a column temperature of 50°C; (f) a column having a 1:1 ratio of 1:1 and a column temperature of 50°C; (g) a column having a 1:1 ratio of 1:1 and a column temperature of 50°C; (h ...

[0149] Specific examples of the fluorinated surfactants include U.S. Patent Application Publication No. 2007 / 0015864, U.S. Patent Application Publication No. 2007 / 0015865, U.S. Patent Application Publication No. 2007 / 0015866, U.S. Patent Application Publication No. 2007 / 0276103, U.S. Patent Application Publication No. 2007 / 0117914, U.S. Patent Application Publication No. 2007 / 142541, U.S. Patent Application Publication No. 2008 / 0015319, and U.S. Patent No. 3,250,808. 3271341, Japanese Patent Application Publication No. 2003-119204, International Publication No. 2005 / 042593, International Publication No. 2008 / 060461, International Publication No. 2007 / 046377, Japanese Patent Application Publication No. 2007-119526, International Publication No. 2007 / 046482, International Publication No. 2007 / 046345, U.S. Patent Application Publication No. 2014 / 0228531, International Publication No. 2013 / 189824, and International Publication No. 2013 / 189826.

[0150] Examples of the anionic fluorinated surfactant include the following general formula (N 0 ):

[0151] X n0 -Rf n0 -Y 0 (N 0 )

[0152] (Where, X n0 For H, Cl or and F. Rf n0 It is a linear, branched or cyclic alkylene group having 3 to 20 carbon atoms, in which a part or all of the H groups are replaced by F groups. The alkylene group may contain one or more ether bonds, and a part of the H groups may be replaced by Cl groups. 0 is an anionic group).

[0153] Y 0The anionic group may be -COOM, -SO2M or -SO3M, or may be -COOM or -SO3M.

[0154] M is H, metal atom, NR 7 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 7 is H or an organic group.

[0155] Examples of the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), such as Na, K, and Li.

[0156] As R 7 , which can be H or C 1-10 The organic group can also be H or C 1-4 The organic group can also be H or C 1-4 of alkyl.

[0157] M can be H, metal atom or NR 7 4, can also be H, alkali metal (Group 1), alkaline earth metal (Group 2) or NR 7 4, can also be H, Na, K, Li or NH4.

[0158] The above Rf n0 In the present invention, more than 50% of the H can be replaced by fluorine.

[0159] As the above general formula (N 0 ), more specifically, the compounds represented by the following general formula (I), perfluorocarboxylic acid (I) represented by the following general formula (II), perfluoroether carboxylic acid (III) represented by the following general formula (III), perfluoroalkylalkylene carboxylic acid (IV) represented by the following general formula (IV), perfluoroalkoxyfluorocarboxylic acid (V) represented by the following general formula (V), perfluoroalkylsulfonic acid (VI) represented by the following general formula (VI), ω-H perfluorosulfonic acid (VII) represented by the following general formula (VII), perfluoroalkylalkylenesulfonic acid (VIII) represented by the following general formula (VIII), alkylalkylene carboxylic acid (IX) represented by the following general formula (IX), fluorocarboxylic acid (X) represented by the following general formula (X), alkoxyfluorosulfonic acid (XI) represented by the following general formula (XI), compound (XII) represented by the following general formula (XII), compound (XIII) represented by the following general formula (XIII), etc.

[0160] The above-mentioned perfluorocarboxylic acid (I) is represented by the following general formula (I):

[0161] F(CF2) n1 COOM (I)

[0162] (where n1 is an integer from 3 to 13, M is H, metal atom, NR 7 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 7 is H or an organic group).

[0163] The above-mentioned ω-H perfluorocarboxylic acid (II) is represented by the following general formula (II):

[0164] H(CF2) n2 COOM(II)

[0165] (wherein n2 is an integer of 4 to 15, and M is the substance defined above).

[0166] The above-mentioned perfluoroether carboxylic acid (III) is represented by the following general formula (III):

[0167] Rf 1 -O-(CF(CF3)CF2O) n3 CF(CF3)COOM(III)

[0168] (Where Rf 1 is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer of 0 to 3, and M is the substance defined above).

[0169] The above-mentioned perfluoroalkyl alkylene carboxylic acid (IV) is represented by the following general formula (IV):

[0170] Rf 2 (CH2) n4 Rf 3 COOM(IV)

[0171] (Where Rf 2 is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf 3 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, n4 is an integer of 1 to 3, and M is the substance defined above).

[0172] The above-mentioned alkoxy fluorocarboxylic acid (V) is represented by the following general formula (V):

[0173] Rf 4 -O-CY 1 Y 2 CF2-COOM(V)

[0174] (Where Rf 4 is a linear or branched partially or fully fluorinated alkyl group having 1 to 12 carbon atoms which may contain an ether bond and / or a chlorine atom, 1 and Y 2are the same or different, are H or F, and M is the substance defined above).

[0175] The above-mentioned perfluoroalkylsulfonic acid (VI) is represented by the following general formula (VI):

[0176] F(CF2) n5 SO3M(VI)

[0177] (wherein n5 is an integer of 3 to 14, and M is the substance defined above).

[0178] The above-mentioned ω-H perfluorosulfonic acid (VII) is represented by the following general formula (VII):

[0179] H(CF2) n6 SO3M(VII)

[0180] (wherein n6 is an integer of 4 to 14, and M is the substance defined above).

[0181] The above-mentioned perfluoroalkyl alkylene sulfonic acid (VIII) is represented by the following general formula (VIII):

[0182] Rf 5 (CH2) n7 SO3M(VIII)

[0183] (Where Rf 5 is a perfluoroalkyl group having 1 to 13 carbon atoms, n7 is an integer of 1 to 3, and M is the substance defined above).

[0184] The above-mentioned alkyl alkylene carboxylic acid (IX) is represented by the following general formula (IX):

[0185] Rf 6 (CH2) n8 COOM(IX)

[0186] (Where Rf 6 is a linear or branched partially or fully fluorinated alkyl group having 1 to 13 carbon atoms which may contain an ether bond, n8 is an integer of 1 to 3, and M is the substance defined above).

[0187] The above-mentioned fluorocarboxylic acid (X) is represented by the following general formula (X):

[0188] Rf 7 -O-Rf 8 -O-CF2-COOM(X)

[0189] (Where Rf 7 is a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms which may contain an ether bond and / or a chlorine atom, Rf 8is a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms, and M is defined as above).

[0190] The above-mentioned alkoxy fluorosulfonic acid (XI) is represented by the following general formula (XI):

[0191] Rf 9 -O-CY 1 Y 2 CF2-SO3M(XI)

[0192] (Where Rf 9 is a linear or branched, partially or fully fluorinated alkyl group having 1 to 12 carbon atoms, which may contain an ether bond and may contain chlorine, 1 and Y 2 are the same or different, are H or F, and M is the substance defined above).

[0193] The above compound (XII) is represented by the following general formula (XII):

[0194] [Chemistry 1]

[0195]

[0196] (Where, X 1 、X 2 and X 3 Rf may be the same or different and is H, F and a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms which may contain an ether bond. 10 is a perfluoroalkylene group having 1 to 3 carbon atoms, L is a connecting group, Y 0 is an anionic group).

[0197] Y 0 It can be -COOM, -SO2M or -SO3M, or it can be -SO3M or COOM (wherein M is the substance defined above).

[0198] Examples of L include a single bond and a partially or fully fluorinated alkylene group having 1 to 10 carbon atoms which may include an ether bond.

[0199] The above compound (XIII) is represented by the following general formula (XIII):

[0200] Rf 11 -O-(CF2CF(CF3)O) n9 (CF2O) n10 CF2COOM(XIII)

[0201] (Where Rf 11is a fluorinated alkyl group having 1 to 5 carbon atoms and containing chlorine, n9 is an integer from 0 to 3, n10 is an integer from 0 to 3, and M is a substance as defined above). Examples of compound (XIII) include CF2ClO(CF2CF(CF3)O) n9 (CF2O) n10 CF2COONH4 (a mixture having an average molecular weight of 750, wherein n9 and n10 are the numbers defined above).

[0202] As described above, examples of the anionic fluorinated surfactant include carboxylic acid surfactants and sulfonic acid surfactants.

[0203] The fluorinated surfactant may be a single type of fluorinated surfactant or a mixture of two or more types of fluorinated surfactants.

[0204] The fluorinated surfactant preferably has no methylene group (—CH 2 ), more preferably has no CH bond.

[0205] The number of H atoms in the hydrophobic group of the fluorinated surfactant is preferably 0 or 1, more preferably 0. The number of carbon atoms in the hydrophobic group of the fluorinated surfactant having a hydrophobic group and a hydrophilic group is preferably 1 to 50, more preferably 3 to 20, and even more preferably 6 to 12. The hydrophobic group usually constitutes the above-mentioned "part other than the anionic group" in the molecular structure of the fluorinated surfactant. Examples of the hydrophilic group include Y 0 The fluorine-containing surfactant may be a saturated fluorinated surfactant in which all carbon atoms bonded to the hydrophobic group are substituted with fluorine atoms.

[0206] As the fluorinated surfactant, among the above-mentioned anionic fluorinated surfactants, there can be mentioned the general formula (N 1 ) represented by the compound of the general formula (N 2 ) represented by the compound of the general formula (N 4 ):

[0207] Rf n4 -O-(CY n1 F) p CF2-Y 0 (N 4 )

[0208] (Where Rf n4 is a linear or branched partially or fully fluorinated alkyl group having 1 to 12 carbon atoms which may contain an ether bond (excluding alkyl groups having -CH2-), n1 is H or F, p is 0 or 1, Y 0 As defined above), and the compound represented by the general formula (N 5):

[0209] [Chemistry 2]

[0210]

[0211] (Where, X n2 、X n3 and X n4 may be the same or different and are H, F, or a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms and which may contain an ether bond (excluding an alkyl group having -CH2-), wherein X n3 and X n4 Neither is H. Rf n5 is a linear or branched partially or fully fluorinated alkylene group having 1 to 3 carbon atoms and which may contain an ether bond (excluding alkylene groups having -CH2-), L is a connecting group, and Y 0 As defined above. Where X n2 、X n3 、X n4 and Rf n5 The total number of carbon atoms is 18 or less).

[0212] As the fluorinated surfactant, among the above-mentioned anionic fluorinated surfactants, more preferably at least one selected from the group consisting of the following substances: a perfluorocarboxylic acid (I) represented by the general formula (I), an ω-H perfluorocarboxylic acid (II) represented by the general formula (II), a perfluoroether carboxylic acid (III) represented by the general formula (III), a perfluoroalkyl alkylene carboxylic acid (IV) represented by the general formula (IV), a perfluoroalkoxy fluorocarboxylic acid (V) represented by the general formula (V), a perfluoroalkylsulfonic acid (VI) represented by the general formula (VI), an ω-H perfluorosulfonic acid (VII) represented by the general formula (VII), a perfluoroalkyl alkylenesulfonic acid (VIII) represented by the general formula (VIII), and a general formula (X): Rf 7 -O-Rf 8 -O-CF2-COOM

[0213] (Where Rf 7 is a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms (excluding an alkyl group having -CH2-), which may contain an ether bond and / or a chlorine atom, 8 is a fluorinated carboxylic acid (X) represented by a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms (excluding an alkyl group having -CH2-), M being as defined above), and the general formula (XI): Rf 9 -O-CY 1 FCF2-SO3M

[0214] (Where Rf9 is a linear or branched, partially or fully fluorinated alkyl group having 1 to 12 carbon atoms, which may contain an ether bond and may contain chlorine (excluding an alkyl group having -CH2-), 1 is H or F, M is as defined above) represented by an alkoxy fluorosulfonic acid (XI), general formula (XII):

[0215] [Chemistry 3]

[0216]

[0217] (Where, X 1 、X 2 and X 3 may be the same or different and are H, F and a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms and which may contain an ether bond (excluding an alkyl group having -CH2-), wherein X 2 and X 3 Neither of them is H, Rf 10 is a perfluoroalkylene group having 1 to 3 carbon atoms, L is a connecting group, Y 0 is an anionic group. ) represented by compound (XII), and general formula (XIII):

[0218] Rf 11 -O-(CF2CF(CF3)O) n9 (CF2O) n10 CF2COOM

[0219] (Where Rf 11 Compound (XIII) is a fluorinated alkyl group having 1 to 5 carbon atoms (excluding fluorinated alkyl groups having -CH2-) containing chlorine, n9 is an integer of 0 to 3, n10 is an integer of 0 to 3, and M is as defined above.

[0220] When the electrodeposition coating composition contains at least a fluorinated surfactant as the fluorinated compound having a hydrophilic group, the content of the fluorinated surfactant in the electrodeposition coating composition is preferably 50 ppb by mass or less, more preferably 45 ppb by mass or less, and preferably exceeds 0 ppb by mass, relative to the perfluoropolymer compound X.

[0221] In one embodiment of the electrodeposition coating composition, a perfluoroether carboxylic acid is contained as a fluorine-containing compound having a hydrophilic group. As the perfluoroether carboxylic acid, a compound (III) represented by the following general formula (III) is preferred.

[0222] General formula (III): Rf 1 -O-(CF(CF3)CF2O) n3 CF(CF3)COOM

[0223] (Where Rf 1 is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer from 0 to 3, M is H, a metal atom, NR 7 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 7 is H or an organic group. )

[0224] When the electrodeposition coating composition contains at least a perfluoroether carboxylic acid as a fluorine-containing compound having a hydrophilic group, the content of the perfluoroether carboxylic acid in the electrodeposition coating composition is preferably 50 ppb by mass or less, more preferably 45 ppb by mass or less, and preferably exceeds 0 ppb by mass, relative to the perfluoropolymer compound X.

[0225] In one embodiment of the electrodeposition coating composition, the electrodeposition coating composition contains a compound represented by the following general formula (H1) as the fluorine-containing compound having a hydrophilic group.

[0226] General formula (H1): [X-Rf-A - ] i M i+

[0227] (wherein, X represents H, Cl, Br, F or I, Rf represents a linear or branched partially fluorinated or fully fluorinated aliphatic group, or a linear or branched partially fluorinated or fully fluorinated aliphatic group interrupted by at least one oxygen atom, A - Represents acid group, M i+ represents a cation having a valence number i, where i represents an integer from 1 to 3)

[0228] In one embodiment of the electrodeposition coating composition, the electrodeposition coating composition contains a compound represented by the following general formula (H2) as the fluorine-containing compound having a hydrophilic group.

[0229] General formula (H2): [C n-1 F 2n-1 COO - ]M +

[0230] (where n represents an integer from 4 to 14, M + represents a cation.)

[0231] It is known that when perfluoroalkyl vinyl ether or the like is used as a modifying monomer, a compound represented by general formula (H2) (perfluoroalkanoic acid) is formed during polymerization (see International Publication No. 2019 / 161153).

[0232] When the electrodeposition coating composition contains at least a compound represented by the general formula (H2) as the fluorine-containing compound having a hydrophilic group, the content of the compound represented by the general formula (H2) in the electrodeposition coating composition is preferably 50 ppb by mass or less, more preferably 45 ppb by mass or less, and preferably exceeds 0 ppb by mass, relative to the perfluoropolymer compound X.

[0233] In one embodiment of the electrodeposition coating composition, the electrodeposition coating composition contains a compound represented by the following general formula (H3) as the fluorine-containing compound having a hydrophilic group.

[0234] General formula (H3): [R 1 -OL-CO2 - ]M +

[0235] (Where R 1 represents a linear or branched partially fluorinated or fully fluorinated aliphatic group, or a linear or branched partially fluorinated or fully fluorinated aliphatic group interrupted by at least one oxygen atom, L represents a linear or branched non-fluorinated, partially fluorinated or fully fluorinated alkylene group, M + represents a cation.)

[0236] When the electrodeposition coating composition contains at least a compound represented by the general formula (H3) as the fluorine-containing compound having a hydrophilic group, the content of the compound represented by the general formula (H3) in the electrodeposition coating composition is preferably 50 ppb by mass or less, more preferably 45 ppb by mass or less, and preferably exceeds 0 ppb by mass, relative to the perfluoropolymer compound X.

[0237] In one embodiment of the electrodeposition coating composition, the compound represented by the general formula (H4) is contained as the fluorine-containing compound having a hydrophilic group.

[0238] General formula (H4): H-Rf n0 -Y 0

[0239] (Where Rf n0 It is an alkylene group having 3 to 20 carbon atoms, which is linear, branched or cyclic, and in which a part or all of the H groups are substituted by F. The alkylene group may contain one or more ether bonds, and a part of the H groups may be substituted by Cl. 0 is an anionic group.)

[0240] Examples of the compound represented by the general formula (H4) include compounds represented by any of the following general formulae.

[0241] General formula: [H-(CF2) m CO2 - ]M +

[0242] (wherein, m represents an integer from 3 to 19, M + represents a cation.)

[0243] General formula: [H-(CF2) m2 -(CF(CF3)) m3 -CO2 - ]M +

[0244] (wherein, m2 represents an integer of 1 to 17, m3 represents an integer of 1 to 9, and M + represents a cation, wherein m2 and m3 are selected so as to satisfy 3≤(m2+2×m3)≤19, and the order of existence of each repeating unit in the formula is arbitrary.

[0245] When the electrodeposition coating composition contains at least a compound represented by the general formula (H4) as the fluorine-containing compound having a hydrophilic group, the content of the compound represented by the general formula (H4) in the electrodeposition coating composition is preferably 50 ppb by mass or less, more preferably 45 ppb by mass or less, and preferably exceeds 0 ppb by mass, relative to the perfluoropolymer compound X.

[0246] The electrodeposition coating composition with a reduced content of a fluorine-containing compound having a hydrophilic group can be prepared by preparing a water-dispersed composition containing the perfluoropolymer X and water and having a reduced content of a fluorine-containing compound having a hydrophilic group, and using the composition as a raw material for the electrodeposition coating composition.

[0247] The content of the fluorinated compound having a hydrophilic group in the aqueous dispersion composition can be adjusted, for example, by polymerizing a fluorinated monomer in the presence of a fluorinated surfactant, a polymerization initiator, and an aqueous medium to prepare an aqueous dispersion containing the perfluoropolymer compound X and water, adding a relatively large amount of a free radical generator to the aqueous dispersion, and then heat-treating the dispersion.

[0248] The aqueous dispersion composition having a reduced content of a fluorinated compound having a hydrophilic group can be produced, for example, by the following production method: in a reactor, in the presence of a fluorinated surfactant, a polymerization initiator, and an aqueous medium, a fluorinated monomer is polymerized to produce an aqueous dispersion containing a perfluorinated polymer compound X; after producing the aqueous dispersion, at least one of the following operations is performed: removing the fluorinated monomer remaining in the reactor from the reactor; and recovering the aqueous dispersion in the reactor and storing it in a container different from the reactor; adding a free radical generator in an amount equivalent to 5 times or more the molar amount of the fluorinated surfactant used in the polymerization to the aqueous dispersion; and heat-treating the aqueous dispersion containing the free radical generator.

[0249] (Polymerization of fluorinated monomers)

[0250] In the above production method, first, a fluorinated monomer is polymerized in a reactor in the presence of a fluorinated surfactant, a polymerization initiator, and an aqueous medium to prepare an aqueous dispersion containing the perfluoropolymer compound X.

[0251] The polymerization of fluorinated monomers can be carried out by placing a fluorinated monomer, a fluorinated surfactant, a polymerization initiator, an aqueous medium, and other additives as needed into a reactor, stirring the contents of the reactor, and then maintaining the reactor at a specified polymerization temperature. A specified amount of polymerization initiator is then added to initiate the polymerization reaction. After the polymerization reaction begins, additional fluorinated monomers, polymerization initiators, fluorinated surfactants, chain transfer agents, etc. may be added depending on the intended purpose. The polymerization method for the fluorinated monomer is not particularly limited, but emulsion polymerization is preferred.

[0252] (Fluorinated surfactant)

[0253] Examples of the fluorinated surfactant used for the polymerization of the fluorinated monomer include the fluorinated surfactants that may be contained in the electrodeposition coating composition of the present invention, and the same fluorinated surfactants are preferably used.

[0254] The amount of the fluorinated surfactant added is preferably 10 to 10 mass ppm, more preferably 100 mass ppm or more, further preferably 300 mass ppm or more, and more preferably 5 mass % or less, further preferably 1 mass % or less, relative to the aqueous medium.

[0255] (Polymerization initiator)

[0256] The polymerization initiator used in the polymerization of the fluorinated monomer is not particularly limited as long as it can generate free radicals within the polymerization temperature range, and known oil-soluble and / or water-soluble polymerization initiators can be used. Furthermore, the polymerization can be initiated in a redox manner in combination with a reducing agent or the like. The concentration of the polymerization initiator is appropriately determined based on the type of monomer, the molecular weight of the target perfluoropolymer compound X, and the reaction rate.

[0257] As the polymerization initiator, an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator can be used.

[0258] The oil-soluble free radical polymerization initiator may be a known oil-soluble peroxide, and examples thereof include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate; peroxyesters such as tert-butyl peroxyisobutyrate and tert-butyl peroxypivalate; and dialkyl peroxides such as di-tert-butyl peroxide.

[0259] The water-soluble free radical polymerization initiator may be a known water-soluble peroxide, for example, ammonium, potassium, or sodium salts of persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, or percarbonic acid, organic peroxides such as disuccinic acid peroxide and diglutaric acid peroxide, t-butyl peroxymaleate, and t-butyl hydroperoxide. A reducing agent such as a sulfite may also be included, and its amount may be 0.1 to 20 times that of the peroxide.

[0260] (Aqueous medium)

[0261] The aqueous medium used in the polymerization of fluorinated monomers is the reaction medium that allows the polymerization to proceed, and is a liquid containing water. The aqueous medium is not particularly limited as long as it contains water and may contain water and a non-fluorinated organic solvent such as an alcohol, ether, or ketone and / or a fluorinated organic solvent with a boiling point of 40°C or less.

[0262] As the aqueous medium, from the perspective of being able to smoothly carry out the polymerization of the fluorinated monomer and also being able to suppress the reduction in the removal efficiency of the fluorinated compound having a hydrophilic group, an aqueous medium containing only water, or an aqueous medium containing only water and a non-fluorinated organic solvent is preferred, and an aqueous medium containing only water is more preferred.

[0263] From the perspective of being able to smoothly carry out the polymerization of the fluorinated monomer and also being able to suppress the reduction in the removal efficiency of the fluorinated compound having a hydrophilic group, the mass of the aqueous medium is preferably 90% or more, more preferably 95% or more, further preferably 99.0% or more, further preferably 99.5% or more, particularly preferably 99.9% or more, and can also be 100%.

[0264] (Chain transfer agent)

[0265] In the above-mentioned production method, the fluorinated monomer can be polymerized in the presence of a chain transfer agent. The use of a chain transfer agent can adjust the polymerization rate and molecular weight. Examples of chain transfer agents include esters such as dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, butyl acetate, and dimethyl succinate; and examples thereof include isopentane, methane, ethane, propane, methanol, isopropanol, acetone, various mercaptans, various halogenated hydrocarbons such as carbon tetrachloride, and cyclohexane.

[0266] The amount of chain transfer agent used is generally 1 to 50,000 ppm by mass, preferably 1 to 20,000 ppm by mass, relative to the total amount of fluorinated monomer supplied. The amount of chain transfer agent used is preferably an amount that is completely consumed during the polymerization of the fluorinated monomer and does not remain in the aqueous dispersion containing the perfluoropolymer compound X, so as to minimize reduction in the efficiency of removing the fluorinated compound having a hydrophilic group. Therefore, the amount of chain transfer agent used is more preferably 10,000 ppm by mass or less, further preferably 5,000 ppm by mass or less, even more preferably 1,000 ppm by mass or less, particularly preferably 500 ppm by mass or less, and most preferably 200 ppm by mass or less, relative to the total amount of fluorinated monomer supplied.

[0267] The chain transfer agent may be added to the reaction vessel all at once before the start of polymerization, may be added all at once after the start of polymerization, may be added in several portions during polymerization, or may be added continuously during polymerization.

[0268] (Other additives)

[0269] In the polymerization of fluorinated monomers, additives such as buffers, pH adjusters, stabilizing agents, and dispersion stabilizers may be used. Furthermore, free radical scavengers and decomposers may be added to adjust the polymerization rate and molecular weight. Furthermore, non-fluorinated anionic surfactants, non-fluorinated nonionic surfactants, and non-fluorinated cationic surfactants may also be used in the polymerization of fluorinated monomers.

[0270] Preferred stabilizing agents include paraffin wax, fluorinated oil, fluorinated solvent, and silicone oil. One stabilizing agent may be used alone or in combination of two or more. Paraffin wax is more preferred. Paraffin wax may be liquid, semisolid, or solid at room temperature, but is preferably a saturated hydrocarbon with 12 or more carbon atoms. The melting point of paraffin wax is generally preferably 40°C to 65°C, more preferably 50°C to 65°C.

[0271] The amount of the stabilizing agent used is preferably 0.1% to 12% by mass, more preferably 0.1% to 8% by mass, based on the mass of the aqueous medium used. The stabilizing agent is preferably sufficiently hydrophobic to be completely separated and removed from the aqueous dispersion after polymerization and not to become a contaminating component.

[0272] (Polymerization Conditions)

[0273] The polymerization of the fluorinated monomer can be carried out under conventional pressure and temperature. Typically, the polymerization temperature is 5°C to 120°C, and the polymerization pressure is 0.05 MPaG to 10 MPaG. The polymerization temperature and pressure are appropriately determined based on the type of monomer, the molecular weight of the target perfluoropolymer compound X, the reaction rate, and other factors.

[0274] (Aqueous dispersion obtained by polymerization)

[0275] By polymerizing the fluorinated monomer, an aqueous dispersion containing the perfluoropolymer compound X is obtained. The content of the perfluoropolymer compound X in the aqueous dispersion after polymerization is usually 8% to 50% by mass based on the aqueous dispersion.

[0276] The aqueous dispersion obtained by polymerizing a fluorinated monomer generally contains, in addition to the perfluoropolymer X, a fluorinated surfactant used in polymerizing the fluorinated monomer as a fluorinated compound having a hydrophilic group. Furthermore, the aqueous dispersion obtained by polymerizing a fluorinated monomer may also contain, in addition to the perfluoropolymer X, a fluorinated compound having a hydrophilic group generated by polymerizing the fluorinated monomer.

[0277] The fluorinated compound having a hydrophilic group in the aqueous dispersion obtained by polymerization is typically a fluorinated compound having a hydrophilic group having a molecular weight of 1000 g / mol or less. The above-mentioned production method ultimately produces an aqueous dispersion composition having a reduced content of the fluorinated compound having a hydrophilic group having a molecular weight of 1000 g / mol or less.

[0278] In one embodiment of the aqueous dispersion obtained by polymerization, the fluorinated compound having a hydrophilic group contains a fluorinated surfactant added during polymerization. The fluorinated surfactant added during polymerization is the same as that used in the polymerization of the fluorinated monomer as described above.

[0279] The content of the fluorine-containing compound having a hydrophilic group in the aqueous dispersion obtained by polymerization may be 200 ppb by mass or more, 300 ppb by mass or more, or 400 ppb by mass or more, and may be 10% by mass or less, 1% by mass or less, or 0.5% by mass or less, relative to the aqueous dispersion.

[0280] The content of the fluorinated surfactant used when polymerizing the fluorinated monomer in the aqueous dispersion obtained by polymerization may be 200 ppb by mass or more, 300 ppb by mass or more, or 400 ppb by mass or more, and may be 10% by mass or less, 1% by mass or less, or 0.5% by mass or less, relative to the aqueous dispersion.

[0281] In one embodiment of the aqueous dispersion obtained by polymerization, a perfluoroether carboxylic acid is contained as a fluorine-containing compound having a hydrophilic group. As the perfluoroether carboxylic acid, a compound (III) represented by the following general formula (III) is preferred.

[0282] General formula (III): Rf1 -O-(CF(CF3)CF2O) n3 CF(CF3)COOM

[0283] (Where Rf 1 is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer from 0 to 3, M is H, a metal atom, NR 7 4. an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent, R 7 is H or an organic group. )

[0284] When the aqueous dispersion obtained by polymerization contains at least a perfluoroether carboxylic acid as the fluorine-containing compound having a hydrophilic group, the content of the perfluoroether carboxylic acid in the aqueous dispersion obtained by polymerization may be 200 ppb by mass or more, 300 ppb by mass or more, or 400 ppb by mass or more, and may be 10% by mass or less, 1% by mass or less, or 0.5% by mass or less, relative to the aqueous dispersion.

[0285] In one embodiment of the aqueous dispersion obtained by polymerization, the compound represented by the following general formula (H1) is contained as the fluorine-containing compound having a hydrophilic group.

[0286] General formula (H1): [X-Rf-A - ] i M i+

[0287] (wherein, X represents H, Cl, Br, F or I, Rf represents a linear or branched partially fluorinated or fully fluorinated aliphatic group, or a linear or branched partially fluorinated or fully fluorinated aliphatic group interrupted by at least one oxygen atom, A - Represents acid group, M i+ represents a cation having a valence number i, where i represents an integer from 1 to 3)

[0288] In one embodiment of the aqueous dispersion obtained by polymerization, the compound represented by the following general formula (H2) is contained as the fluorine-containing compound having a hydrophilic group.

[0289] General formula (H2): [C n-1 F 2n-1 COO - ]M +

[0290] (where n represents an integer from 4 to 14, M + represents a cation.)

[0291] It is known that the compound represented by general formula (2) (perfluoroalkanoic acid) is formed during polymerization when perfluoro(alkyl vinyl ether) or the like is used as a fluorine-containing monomer (see International Publication No. 2019 / 161153).

[0292] In one embodiment of the aqueous dispersion obtained by polymerization, the fluorine-containing compound having a hydrophilic group contains a compound represented by the following general formula (H3).

[0293] General formula (H3): [R 1 -OL-CO2 - ]M +

[0294] (Where R 1 represents a linear or branched partially fluorinated or fully fluorinated aliphatic group, or a linear or branched partially fluorinated or fully fluorinated aliphatic group interrupted by at least one oxygen atom, L represents a linear or branched non-fluorinated, partially fluorinated or fully fluorinated alkylene group, M + represents a cation.)

[0295] In one embodiment of the aqueous dispersion obtained by polymerization, the compound represented by the following general formula (H4) is contained as the fluorine-containing compound having a hydrophilic group.

[0296] General formula (H4): H-Rf n0 -Y 0

[0297] (Where Rf n0 It is an alkylene group having 3 to 20 carbon atoms, which is linear, branched or cyclic, and in which a part or all of the H groups are substituted by F. The alkylene group may contain one or more ether bonds, and a part of the H groups may be substituted by Cl. 0 is an anionic group.)

[0298] Examples of the compound represented by the general formula (H4) include compounds represented by any of the following general formulae.

[0299] General formula: [H-(CF2) m CO2 - ]M +

[0300] (wherein, m represents an integer from 3 to 19, M + represents a cation.)

[0301] General formula: [H-(CF2) m2 -(CF(CF3)) m3 -CO2 - ]M +

[0302] (wherein, m2 represents an integer of 1 to 17, m3 represents an integer of 1 to 9, and M + represents a cation, wherein m2 and m3 are selected so as to satisfy 3≤(m2+2×m3)≤19, and the order of existence of each repeating unit in the formula is arbitrary.

[0303] (Removal of fluorinated monomers or recovery of aqueous dispersions)

[0304] In the above production method, after the aqueous dispersion is prepared by polymerization and before the free radical generator is added to the aqueous dispersion, at least one of (a) removing the fluorinated monomer remaining in the reactor from the reactor and (b) recovering the aqueous dispersion in the reactor and storing it in a container separate from the reactor can be performed. In particular, using the method of removing the fluorinated monomer in the reactor is preferred because subsequent steps can be performed in the same reactor used for polymerization, thereby improving the productivity of the aqueous dispersion composition.

[0305] After the aqueous dispersion is prepared, it is preferred to stop stirring the contents of the reactor and then remove the fluorinated monomer or recover the aqueous dispersion because subsequent operations become easier and the polymerization of the fluorinated monomer can be stopped smoothly.

[0306] The method for removing the fluorinated monomer from the reactor is not particularly limited. After the aqueous dispersion is prepared, the stirring of the contents of the reactor can be stopped as needed, and the exhaust gas can be exhausted until the pressure in the reactor reaches normal pressure, thereby removing the fluorinated monomer from the reactor. The pressure in the reactor can also be reduced to less than 0.0 MPaG, thereby removing the fluorinated monomer from the reactor. An inert gas can also be supplied to the reactor, thereby replacing the fluorinated monomer in the reactor with an inert gas such as nitrogen. In addition, the entire amount of the fluorinated monomer in the reactor can be reacted to convert it into a perfluorinated polymer compound X, and as a result, the fluorinated monomer is removed from the reactor. As long as the fluorinated monomer remaining in the reactor can be removed from the reactor to the extent that the polymerization reaction of the fluorinated monomer is fully stopped, a small amount of fluorinated monomer can also remain in the reactor. The removed fluorinated monomer can be recovered by known means. The recovered fluorinated monomer can also be reused in the manufacture of fluorinated polymers.

[0307] A preferred method for removing the fluorinated monomer from the reactor is to, after preparing the aqueous dispersion, stop stirring the contents of the reactor as needed, reduce the pressure in the reactor to less than 0.0 MPaG, and then supply an inert gas into the reactor. This depressurization and supply of inert gas into the reactor may be repeated multiple times.

[0308] When polymerizing fluorinated monomers at temperatures exceeding room temperature, the reactor may be cooled before or after the fluorinated monomers are removed from the reactor. When the fluorinated monomers are removed from the reactor by venting, nitrogen substitution, or other means, unreacted fluorinated monomers, particularly liquid fluorinated monomers, may remain in the reactor. However, cooling the reactor can effectively suppress the reaction of the unreacted fluorinated monomers.

[0309] The method for recovering the aqueous dispersion in the reactor and storing it in a container different from the reactor used for polymerization is not particularly limited. For example, after preparing the aqueous dispersion, stirring of the contents of the reactor may be stopped as needed, the reactor may be opened, and the aqueous dispersion in the reactor may be poured into another container. Alternatively, after preparing the aqueous dispersion, stirring of the contents of the reactor may be stopped as needed, and the aqueous dispersion may be supplied from the reactor to the other container via a pipe connecting the reactor and the other container.

[0310] In order to stop the polymerization reaction of the fluorinated monomer, a polymerization inhibitor (radical scavenger) may be added.

[0311] As polymerization inhibitors, compounds that add to free radicals in the polymerization system or do not have the ability to reinitiate after chain transfer are used. Specifically, compounds with the following functions are used: they easily undergo chain transfer reactions with primary free radicals or growing free radicals, and then generate stable free radicals that do not react with monomers, or they easily undergo addition reactions with primary free radicals or growing free radicals to generate stable free radicals. The activity of substances generally referred to as chain transfer agents is characterized by the chain transfer constant and reinitiation efficiency. Among chain transfer agents, substances with a reinitiation efficiency of basically 0% are called polymerization inhibitors. As polymerization inhibitors, it is preferred that at least one of the group consisting of aromatic hydroxyl compounds, aromatic amines, N,N-diethylhydroxylamine, quinone compounds, terpenes, thiocyanates and copper chloride (CuCl2) is selected. As aromatic hydroxyl compounds, unsubstituted phenols, polyphenols, salicylic acid, m-salicylic acid or p-salicylic acid, gallic acid, naphthol, etc. can be mentioned. Examples of the above-mentioned unsubstituted phenols include o-nitrophenol, m-nitrophenol or p-nitrophenol, o-aminophenol, m-aminophenol or p-aminophenol, and p-nitrosophenol. Examples of the polyphenols include catechol, resorcinol, hydroquinone, pyrogallol, pyrogallol, and naphthol resorcinol. Examples of the aromatic amines include o-phenylenediamine, m-phenylenediamine or p-phenylenediamine, and benzidine. Examples of the above-mentioned quinone compounds include hydroquinone, o-benzoquinone, m-benzoquinone or p-benzoquinone, 1,4-naphthoquinone, and alizarin. Examples of thiocyanates include ammonium thiocyanate (NH4SCN), potassium thiocyanate (KSCN), and sodium thiocyanate (NaSCN). Among the above-mentioned polymerization inhibitors, quinone compounds are preferred, and hydroquinone is more preferred.

[0312] (Free radical generator)

[0313] In the above production method, after performing at least one of steps (a) and (b), and before heat-treating the aqueous dispersion, a free radical generator is added to the aqueous dispersion in an amount equivalent to at least 5 molar times the molar amount of the fluorinated surfactant used in the polymerization. By adding a relatively large amount of the free radical generator, the content of the fluorinated compound having a hydrophilic group can be sufficiently reduced.

[0314] The aqueous dispersion to which the radical generator is added may be the aqueous dispersion remaining in the reactor, or may be the aqueous dispersion recovered from the reactor and contained in another container.

[0315] The radical generator is not particularly limited as long as it is a compound that can decompose at the temperature during heat treatment to generate radicals. As the radical generator, a water-soluble radical generator is preferred because it can easily diffuse the radicals into the aqueous dispersion.

[0316] Examples of the radical generator include organic peroxides, inorganic peroxides, organic azo compounds, and combinations of oxidizing agents and reducing agents. Preferably, the radical generator is at least one selected from the group consisting of inorganic peroxides, organic peroxides, and combinations of oxidizing agents and reducing agents.

[0317] As the inorganic peroxide, a water-soluble inorganic peroxide is preferred. Examples of the inorganic peroxide include hydrogen peroxide, perchlorates, perborates, perphosphates, percarbonates, and persulfates, with persulfates being preferred. As the persulfate, at least one selected from the group consisting of ammonium persulfate, sodium persulfate, and potassium persulfate is preferred, with ammonium persulfate being more preferred.

[0318] As the organic peroxide, a water-soluble organic peroxide is preferred. Examples of the organic peroxide include peroxydicarbonates such as disuccinic acid peroxide and diglutaric acid peroxide.

[0319] As the free radical generator, an oxidizing agent and a reducing agent may be used in combination. By using the oxidizing agent and the reducing agent in combination, free radicals can be generated from the free radical generator by a redox reaction between the oxidizing agent and the reducing agent, thereby lowering the temperature during the heat treatment.

[0320] Examples of oxidizing agents include persulfates, organic peroxides, potassium permanganate, manganese triacetate, and cerium ammonium nitrate. Examples of reducing agents include sulfites, bisulfites, bromates, diimides, and oxalic acid. Examples of persulfates include ammonium persulfate and potassium persulfate. Examples of sulfites include sodium sulfite and ammonium sulfite. In order to increase the decomposition rate of the oxidizing agent, it is also preferable to add copper salts or iron salts. Examples of copper salts include copper (II) sulfate, and examples of iron salts include iron (II) sulfate.

[0321] Examples of combinations of oxidizing agents and reducing agents include potassium permanganate / oxalic acid, ammonium persulfate / bisulfite / ferric sulfate, manganese triacetate / oxalic acid, ceric ammonium nitrate / oxalic acid, and bromate / bisulfite, with potassium permanganate / oxalic acid being preferred. When using a combination of an oxidizing agent and a reducing agent, either the oxidizing agent or the reducing agent may be pre-added to the aqueous dispersion, followed by the addition of the other agent continuously or intermittently.

[0322] From the perspective of being able to further improve the removal efficiency of the fluorinated compound having a hydrophilic group, the amount of the free radical generator added is preferably 5 mole times or more, more preferably 10 mole times or more, preferably 1000 mole times or less, more preferably 500 mole times or less, and further preferably 100 mole times or less, relative to the molar amount of the fluorinated surfactant used in the polymerization.

[0323] The method for adding the free radical generator is not particularly limited. The free radical generator may be added directly to the aqueous dispersion, or a solution containing the free radical generator may be prepared and added to the aqueous dispersion. Furthermore, the free radical generator may be added while stirring the aqueous dispersion, or the aqueous dispersion may be stirred after the free radical generator is added.

[0324] The temperature of the aqueous dispersion to which the free radical generator is added is not particularly limited and may be the temperature of the aqueous dispersion after polymerization of the fluorinated monomer, the temperature reached by cooling the aqueous dispersion after polymerization of the fluorinated monomer, or the temperature of the heat treatment. Specifically, the aqueous dispersion may be heated for heat treatment after the free radical generator is added, or the free radical generator may be added after the aqueous dispersion is heated to a temperature suitable for heat treatment.

[0325] (Heat Treatment)

[0326] In the above-mentioned production method, the aqueous dispersion to which the free radical generator is added (the aqueous dispersion containing the free radical generator) is heat-treated. By heat-treating the aqueous dispersion containing a relatively large amount of the free radical generator, the content of the fluorinated compound having a hydrophilic group in the aqueous dispersion can be surprisingly reduced.

[0327] Before heat treatment, the content of the perfluoropolymer compound X in the aqueous dispersion may be adjusted. The content of the perfluoropolymer compound X may be adjusted by a known method such as concentration or dilution.

[0328] From the perspective of being able to produce an aqueous dispersion containing a perfluoropolymer compound X with high productivity without compromising the removal efficiency of the fluorinated compound having a hydrophilic group, the content of the perfluoropolymer compound X in the aqueous dispersion subjected to the heat treatment is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the mass of the aqueous dispersion. The upper limit of the content of the perfluoropolymer compound X is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less.

[0329] The content of the fluorinated surfactant added during polymerization in the aqueous dispersion subjected to heat treatment is preferably 500 mass ppm or more, more preferably 1000 mass ppm or more, and is preferably 10 mass % or less, more preferably 5 mass % or less, and even more preferably 1 mass % or less, relative to the mass of the perfluoropolymer compound X in the aqueous dispersion.

[0330] The content of the fluorinated compound having a hydrophilic group produced by polymerization of the fluorinated monomer in the aqueous dispersion subjected to the heat treatment is preferably 500 ppb by mass or more, more preferably 1000 ppb by mass or more, and is preferably 1.0% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less, relative to the mass of the perfluoropolymer compound X in the aqueous dispersion.

[0331] The content of the fluorinated compound having a hydrophilic group in the aqueous dispersion subjected to the heat treatment (the total amount of the fluorinated surfactant added during polymerization and the fluorinated compound having a hydrophilic group generated by polymerization of the fluorinated monomer) is preferably 500 mass ppm or more, more preferably 1000 mass ppm or more, and is preferably 10 mass % or less, more preferably 5 mass % or less, and even more preferably 1 mass % or less, relative to the perfluoropolymer compound X in the aqueous dispersion.

[0332] From the perspective of further improving the removal efficiency of the fluorinated compound having a hydrophilic group, the heat treatment temperature is preferably 35°C or higher, more preferably 40°C or higher, even more preferably 45°C or higher, particularly preferably 50°C or higher, and is preferably 120°C or lower, more preferably 110°C or lower, even more preferably 100°C or lower, and particularly preferably 90°C or lower. When heat-treating an aqueous dispersion to which a free radical generator has been added, the heat treatment temperature is preferably at least the temperature at which the free radical generator decomposes to generate free radicals (decomposition temperature).

[0333] In the heat treatment of the aqueous dispersion, it is not necessary to heat the aqueous dispersion as long as the aqueous dispersion can be maintained at a temperature above the desired temperature. For example, when the temperature for polymerizing the fluorinated monomer is sufficiently high and the temperature of the resulting aqueous dispersion is also sufficiently high, the heat treatment can be started before the resulting aqueous dispersion is cooled. However, from the perspective of facilitating the control of the temperature of the heat treatment, it is preferred to cool the aqueous dispersion before and after removing the fluorinated monomer from the reactor or recovering the aqueous dispersion in the reactor, heat the aqueous dispersion to the above-mentioned temperature range, and maintain the temperature for a certain period of time. The temperature of the aqueous dispersion to be heat treated can be, for example, 30°C or less.

[0334] The heating means for heat-treating the aqueous dispersion while heating the aqueous dispersion is not particularly limited. For example, the container containing the aqueous dispersion may be placed in a thermostatic bath for heating, or the aqueous dispersion may be placed in a container equipped with a heater and heated by the heater.

[0335] The heat treatment pressure is not particularly limited and may be normal pressure. For example, when the heat treatment temperature is relatively high and boiling of the aqueous dispersion needs to be suppressed, the heat treatment pressure may be higher than normal pressure.

[0336] From the perspective of being able to further improve the removal efficiency of fluorine-containing compounds having hydrophilic groups, the heat treatment time is preferably 15 minutes or more, more preferably 30 minutes or more, further preferably 60 minutes or more, preferably 1200 minutes or less, more preferably 900 minutes or less, further preferably 600 minutes or less.

[0337] The heat treatment may be performed while stirring the aqueous dispersion.

[0338] (Films and covered articles)

[0339] The electrodeposition coating composition of the present invention can be used to form a coating film. The coating film formed from the electrodeposition coating composition of the present invention has no cracks, low surface roughness, and a low relative dielectric constant.

[0340] A coating formed from an electrodeposition coating composition can be formed, for example, on a substrate. In a coated article comprising a substrate and a coating formed from the electrodeposition coating composition of the present invention, the coating exhibits no cracks, low surface roughness, and a low relative dielectric constant, and furthermore, the substrate and the coating are firmly bonded.

[0341] As the material forming the substrate, metals such as iron, aluminum, copper and alloys thereof can be cited. Examples of the alloys include stainless steel, etc. The substrate may also include other materials together with the metal material.

[0342] In addition, the substrate can be made of materials such as copper, copper alloy, aluminum, aluminum alloy, iron, silver, nickel, etc., and is preferably made of copper, copper alloy, aluminum or aluminum alloy.

[0343] The film thickness of the coating is preferably 2 μm to 100 μm, more preferably 5 μm or more, more preferably 70 μm or less, and even more preferably 30 μm or less.

[0344] The relative dielectric constant of the film is preferably 2.0 to 2.4, more preferably 2.3 or less.

[0345] Examples of the articles to be covered include: cooking utensils such as frying pans, pressure cookers, pots, grill pans, rice cookers, ovens, hot plates, bread baking molds, kitchen knives, and gas stoves; kitchen appliances such as electric kettles, ice trays, molds, and range hoods; food industry parts such as mixing rollers, calendar rollers, conveyors, and hoppers; industrial products such as rollers for office automation (OA) equipment, OA belts, OA separation claws, papermaking rollers, and calendar rollers for film manufacturing; molds and castings for foamed polystyrene molding; mold release for molding molds such as release plates for plywood and decorative board manufacturing; industrial containers (especially for the semiconductor industry); tools such as saws and files; household items such as irons, scissors, and kitchen knives; metal foil; coated electric wires; printed circuit boards; sliding bearings for food processing machines, packaging machines, and textile machinery; sliding parts for cameras and clocks; automobile parts such as pipes, valves, and bearings; snow shovels; hoes; chutes, etc.

[0346] Among them, the covered article is preferably a covered electric wire or a printed circuit board.

[0347] (Covered wire)

[0348] The electrodeposition coating composition of the present invention can be used to form a coating for a coated electric wire. A coated electric wire, for example, comprises a wire substrate and a coating formed on the outer periphery of a flat wire substrate. A coated electric wire having a coating formed from the electrodeposition coating composition of the present invention exhibits no cracks, low surface roughness, and a low relative dielectric constant, and furthermore, the substrate and the coating are firmly bonded.

[0349] In one embodiment, a covered electric wire includes a rectangular electric wire base material and a coating film formed on the outer periphery of the rectangular electric wire base material and made of an electrodeposition coating composition.

[0350] The shape of the flat wire substrate is not particularly limited, as long as it is a flat wire with a substantially rectangular cross-section. The corners of the flat wire substrate's cross-section may be right angles or rounded. Furthermore, the flat wire substrate may be a single wire, a bundle of wires, or a stranded wire, as long as the overall cross-section is substantially rectangular. A single wire is preferred.

[0351] The rectangular wire substrate is not particularly limited as long as it is made of a conductive material. It can be made of copper, copper alloys, aluminum, aluminum alloys, iron, silver, nickel, and other materials, preferably copper, copper alloys, aluminum, or aluminum alloys. Alternatively, a rectangular wire substrate plated with silver or nickel plating may be used. Copper can be oxygen-free copper, low-oxygen copper, or copper alloys.

[0352] The cross-sectional width of the flat wire substrate can be 1 mm to 75 mm, and the cross-sectional thickness of the flat wire substrate can be 0.1 mm to 30 mm. The outer diameter of the flat wire substrate can be 6.5 mm or greater and 200 mm or less. Furthermore, the ratio of width to thickness can be greater than 1 and less than 30.

[0353] From the perspective of stronger adhesion between the rectangular wire substrate and the coating, the surface roughness Sz of the rectangular wire substrate is preferably 0.2 μm to 12 μm, more preferably 1 μm or more, further preferably 5 μm or more, and more preferably 10 μm or less.

[0354] The surface roughness of the flat wire substrate can be adjusted by surface treatment of the flat wire substrate using surface treatment methods such as etching, sandblasting, and laser treatment. Furthermore, surface treatment can also be used to provide unevenness on the surface of the flat wire substrate. The smaller the distance between the unevenness and the convexity from the convexity to the convexity, the better, for example, 5 μm or less. Regarding the size of the unevenness, for example, the area of each concave portion when the convexity is cut relative to the unprocessed surface is 1 μm. 2 The concave-convex shape may be a single concave-convex shape like a crater, or may be branched like an ant's nest.

[0355] A coating on a substrate such as a flat wire substrate can be formed by electrodeposition coating the substrate with an electrodeposition coating composition. Electrodeposition coating can be performed, for example, by immersing the substrate in the electrodeposition coating composition and applying electricity to the substrate as an anode. Electrodeposition coating conditions are appropriately selected depending on the type of substrate, etc. For example, the temperature of the electrodeposition coating composition can be set to 10°C to 40°C, the voltage to 50V to 500V, and the duration of the electricity application to 1 to 10 minutes.

[0356] After electrodeposition coating, the film deposited on the substrate can be washed with water. After electrodeposition coating, the film deposited on the substrate is baked and dried. Drying can be performed once or multiple times. For example, pre-drying can be performed at a low temperature, followed by baking and drying at a high temperature.

[0357] The electrodeposition coating composition of the present invention contains a neutralized methacrylate resin. Therefore, it is preferable to select drying conditions that allow the coating to be baked onto the substrate, with only a portion of the neutralized methacrylate resin in the electrodeposition coating composition remaining in the coating. Selecting such conditions results in a coating that is crack-free, has low surface roughness, adheres firmly to the substrate, and has a low relative dielectric constant.

[0358] The drying temperature is preferably 300°C or higher, more preferably 350°C or higher. From the perspective of suppressing oxidation of the substrate and degradation of the film, the upper limit of the drying temperature may be 400°C or lower. The drying time is preferably 5 minutes or longer, more preferably 10 minutes or longer. From the perspective of suppressing oxidation of the substrate and degradation of the film, the upper limit of the drying time may be 60 minutes or shorter.

[0359] Drying in the absence of oxygen can suppress oxidation of the substrate. Drying a film formed on a substrate in the absence of oxygen may damage the substrate. Drying can be performed, for example, in an inert gas containing up to 1% by mass of oxygen. Nitrogen, for example, can be used as the inert gas.

[0360] (Coating layer of covered electric wire)

[0361] The covered electric wire of the present invention may further include a covering layer formed on the outer periphery of the covering film. The covering layer may be a coating formed from a coating composition or an extrudate formed from an extrusion molding composition. The covering layer may be a single layer or may be two or more layers.

[0362] The coating composition may be a liquid coating composition or a powder coating composition, but a powder coating composition is preferred because a thick coating layer can be easily formed.

[0363] As the powder coating composition, a powder coating composition containing a powder of the fluorinated polymer compound Y can be used. In the present invention, the term "powder coating composition" is used even when the powder coating composition contains only a powder of the fluorinated polymer compound Y, that is, when the powder coating composition does not contain multiple components.

[0364] The layer formed of the coating composition can be formed by applying the coating composition to the outer periphery of the film.

[0365] The method for forming a layer by applying the powder coating composition is not particularly limited, and examples thereof include electrostatic coating, flow dip coating, and the like.

[0366] Alternatively, after applying the powder coating composition, the resulting coating film may be calcined to form a layer. Calcination can be performed by conventionally known methods, preferably at a temperature above the melting point or curing temperature of the fluorinated polymer compound Y for 5 to 60 minutes. Calcination may be performed each time the coating composition is applied, or after multiple applications to form multiple layers (coating films).

[0367] The extrusion molding composition may contain a fluorinated polymer compound Z. In the present invention, the term "extrusion molding composition" is used even when the extrusion molding composition contains only the fluorinated polymer compound Z, that is, when the extrusion molding composition does not contain multiple components.

[0368] As a method for forming a layer by extruding the fluorinated polymer compound Z (extrusion molding composition), an extrusion molding method is used. For example, an extruder can be used to heat the fluorinated polymer compound to melt it, and the fluorinated polymer compound in a molten state is extruded onto a film to form a layer.

[0369] There is no particular limitation on the type of the extruder, and there is no particular limitation on the shape of the screw of the extruder. L / D24, the screw is a full-stroke screw, the compression ratio is 2.8, and the extrusion temperature conditions are: C1 under the hopper, adjust the temperature of C2, C3, C4 and the barrel in sequence, and adjust the temperature of each part of the head, die, and mold. The die shape is a right-angle head, which is inserted vertically with respect to the extrusion to coat the fluorine-containing polymer compound. Regarding the die / blade, a die / blade adjusted according to the desired shape of the flat wire substrate and the coating thickness is used. Tube die, pressure die, etc. can also be used separately. The cooling of the resin after extrusion coating can be controlled by considering air cooling, water cooling, insulation cooling, and the desired physical properties of the fluorine-containing polymer compound and the physical properties of the wire.

[0370] The coated wire may also be heat treated. This heat treatment can be performed after the coating layer has been formed, either before or after cooling. The heat treatment temperature is generally above the glass transition temperature of the fluorinated polymer compound, and preferably 10°C to 15°C lower than the melting point of the fluorinated polymer compound.

[0371] In one embodiment, the coating layer is an extrudate formed from an extrusion molding composition by an extrusion molding method. The extrudate can easily form a layer having a thickness greater than that of a coating film formed by the coating composition. For example, the thickness of the extrudate (the thickness of the layer formed by the extrusion molding composition) can be 90 μm or more, and the thickness of the coating film (the thickness of the layer formed by the coating composition) can be less than 90 μm.

[0372] The thickness of the coating film formed from the coating composition containing the fluorinated polymer compound Y is preferably 5 μm to 100 μm, more preferably 50 μm or more, further preferably 75 μm or more, and more preferably less than 90 μm.

[0373] The thickness of the layer formed by extrusion molding of the extrusion molding composition containing the fluorinated polymer compound Z is preferably 25 μm to 400 μm, more preferably 50 μm or more, further preferably 75 μm or more, further preferably 90 μm or more, more preferably 290 μm or less, further preferably 240 μm or less.

[0374] The relative dielectric constant of the coating layer is preferably 2.0 to 2.4, more preferably 2.3 or less.

[0375] Examples of the fluorinated polymer Y contained in the powder coating composition include polytetrafluoroethylene, TFE / FAVE copolymers, TFE / HFP copolymers, TFE / FAVE / HFP copolymers, TFE / ethylene copolymers [ETFE], TFE / ethylene / HFP copolymers, ethylene / chlorotrifluoroethylene (CTFE) copolymers [ECTFE], polychlorotrifluoroethylene [PCTFE], CTFE / TFE copolymers, polyvinylidene fluoride [PVdF], TFE / vinylidene fluoride (VdF) copolymers [VT], polyvinyl fluoride [PVF], TFE / VdF / CTFE copolymers [VTC], and TFE / HFP / VdF copolymers.

[0376] As the fluorinated polymer compound Y contained in the powder coating composition, a perfluorinated polymer compound is preferred. As the perfluorinated polymer compound, the polymers described as the perfluorinated polymer compound X can be used. As the fluorinated polymer compound Y, a melt-processable perfluorinated polymer compound is preferred, and more preferably at least one selected from the group consisting of a TFE / FAVE copolymer, a TFE / HFP copolymer, and a TFE / FAVE / HFP copolymer.

[0377] Examples of the fluorinated polymer Z contained in the extrusion molding composition include polytetrafluoroethylene, TFE / FAVE copolymers, TFE / HFP copolymers, TFE / FAVE / HFP copolymers, TFE / ethylene copolymers [ETFE], TFE / ethylene / HFP copolymers, ethylene / chlorotrifluoroethylene (CTFE) copolymers [ECTFE], polychlorotrifluoroethylene [PCTFE], CTFE / TFE copolymers, polyvinylidene fluoride [PVdF], TFE / vinylidene fluoride (VdF) copolymers [VT], polyvinyl fluoride [PVF], TFE / VdF / CTFE copolymers [VTC], and TFE / HFP / VdF copolymers.

[0378] As the fluorinated polymer compound Z contained in the extrusion molding composition, a perfluorinated polymer compound is preferred. As the perfluorinated polymer compound, the polymer described as the perfluorinated polymer compound X can be used. As the fluorinated polymer compound Z, a melt-processable perfluorinated polymer compound is preferred, and more preferably at least one selected from the group consisting of a TFE / FAVE copolymer, a TFE / HFP copolymer, and a TFE / FAVE / HFP copolymer.

[0379] The coating composition, the extrusion molding composition, and the coating layer may contain other components as needed. Other components include crosslinking agents, antistatic agents, heat stabilizers, foaming agents, foam nucleating agents, antioxidants, surfactants, photopolymerization initiators, antiwear agents, surface modifiers, various organic / inorganic pigments, copper poison inhibitors, bubble preventers, adhesion imparting agents, lubricants, processing aids, colorants, phosphorus stabilizers, lubricants, release agents, sliding materials, ultraviolet absorbers, dyes and pigments, reinforcing materials, anti-drip agents, fillers, curing agents, ultraviolet curing agents, flame retardants and other additives.

[0380] The covered electric wire of the present invention can be suitably used for, for example, LAN cables, USB cables, Lightning cables, HDMI cables, QSFP cables, aerospace wires, underground power transmission cables, submarine power cables, high-voltage cables, superconducting cables, packaged wires, automotive wires, wiring harnesses for electrical equipment, wires for robots and FA equipment, wires for office automation equipment, wires for information equipment (optical fiber cables, LAN cables, HDMI cables, Lightning cables, audio cables, etc.), internal wiring for communication base stations, high-current internal wiring (inverters, power conditioners, battery systems, etc.), internal wiring for electronic equipment, wiring for small electronic equipment and mobile devices, wiring for movable parts, internal wiring for electrical equipment, internal wiring for measuring equipment, power cables (for construction, wind power / solar power generation, etc.), cables for control and measurement wiring, and cables for motors.

[0381] The covered electric wire of the present invention can be wound and used as a coil. The covered electric wire and coil of the present invention can be suitably used in electrical or electronic equipment such as motors, generators, and inductors. Furthermore, the covered electric wire and coil of the present invention can be suitably used in in-vehicle electrical or electronic equipment such as in-vehicle motors, in-vehicle generators, and in-vehicle inductors.

[0382] The covered wire can be long or short, or Figure 1 The covered electric wire shown has a bent portion.

[0383] A coated electric wire with a curved portion, according to one embodiment, comprises: a flat electric wire base having one or more curved portions curved along its edge; and a coating formed on the outer periphery of the flat electric wire base. The coated electric wire with a curved portion is suitable for use as a segment coil inserted into slots formed in a stator core or a rotor core. For example, a segment coil can be formed by inserting the coated electric wire with a curved portion into the slots and joining the ends of the coated electric wires.

[0384] Figure 1 These are a front view and a top view of a covered electric wire body having a bent portion according to one embodiment. Figure 2 This is a cross-sectional view of a covered electric wire having a bent portion according to one embodiment. Figure 1 The coated electric wire 100 with a bent portion shown is a resin coated conductor (segment coil) that is inserted into each slot of the iron core of a rotating electric machine to form a coil. The resin coated conductor 100 is formed by bending a resin coated conductor of a predetermined length into a U-shape along a planar direction. Figure 2 As shown, the resin-coated conductor 100 includes a rectangular electric wire base 21 and a coating 22 formed on the outer periphery of the rectangular electric wire base 21 .

[0385] like Figure 1 As shown, resin-coated conductor 100 has a substantially U-shaped structure, consisting of a bent portion 11 and slot insertion portions 12 extending from both ends of bent portion 11. Shoulders 13a and 13b are formed at the portion connecting bent portion 11 and slot insertion portion 12, formed by bending a rectangular wire base material in the edge direction. Furthermore, bent portion 11 is formed with a convex portion 14 formed by bending the rectangular wire base material in the edge direction, and a cranked portion 15 formed by bending the rectangular wire base material in the planar direction.

[0386] While the embodiments have been described above, it will be understood that various changes can be made to the aspects and details without departing from the spirit and scope of the claims.

[0387] <1> According to a first aspect of the present invention, there is provided an electrodeposition coating composition comprising a neutralized product of a perfluoropolymer compound X and a methacrylate resin, wherein:

[0388] The relative dielectric constant of the perfluoropolymer compound X is 2.0 to 2.2.

[0389] The acid value of the methacrylate resin is 10 mgKOH / g or more.

[0390] The solid content concentration of the electrodeposition coating composition is 10% by mass to 70% by mass.

[0391] <2> According to a second aspect of the present invention, there is provided an electrodeposition coating composition comprising a neutralized product of a perfluoropolymer compound X and a methacrylate resin, wherein:

[0392] The perfluorinated polymer compound X is a tetrafluoroethylene / fluoroalkyl vinyl ether copolymer.

[0393] The acid value of the methacrylate resin is 10 mgKOH / g or more.

[0394] The solid content concentration of the electrodeposition coating composition is 10% by mass to 70% by mass.

[0395] <3> According to a third aspect of the present invention, there is provided the electrodeposition coating composition according to the first or second aspect, wherein the content of the fluorine-containing compound having a hydrophilic group relative to the perfluoropolymer compound X is 50 ppb by mass or less.

[0396] <4> According to a fourth aspect of the present invention, there is provided the electrodeposition coating composition according to any one of the first to third aspects, further comprising water.

[0397] <5> According to a fifth aspect of the present invention, there is provided an electrodeposition coating composition according to any one of the first to fourth aspects, which is obtained by a production method comprising adding an aqueous dispersion containing the perfluoropolymer compound X and water to a solution containing a neutralized product of the methacrylate resin and an organic solvent, followed by phase inversion emulsification.

[0398] <6> According to a sixth aspect of the present invention, there is provided an electrodeposition coating composition according to any one of the first to fifth aspects, wherein the methacrylate resin has a carboxyl group, and the neutralized product of the methacrylate resin is a neutralized product obtained by neutralizing the methacrylate resin having a carboxyl group with an amine compound.

[0399] <7> According to a seventh aspect of the present invention, there is provided the electrodeposition coating composition according to any one of the first to sixth aspects, wherein the neutralization degree of the neutralized product of the methacrylate resin is 50% or more.

[0400] <8> According to an eighth aspect of the present invention, there is provided an electrodeposition coating composition according to any one of the first to seventh aspects, wherein the perfluoropolymer compound X has a functional group, and the number of functional groups of the perfluoropolymer compound X is 10 6 The number of carbon atoms ranges from 5 to 2000.

[0401] <9> According to a ninth aspect of the present invention, there is provided the electrodeposition coating composition according to any one of the first to eighth aspects, wherein the alkali metal content is less than 1 mass ppm.

[0402] <10> According to a tenth aspect of the present invention, there is provided the electrodeposition coating composition according to any one of the first to ninth aspects, wherein the mass ratio of the neutralized product of the perfluoropolymer compound X to the methacrylate resin is 10 / 90 to 90 / 10.

[0403] <11> According to an eleventh aspect of the present invention, there is provided a coating film formed from the electrodeposition coating composition according to any one of the first to tenth aspects.

[0404] <12> According to a twelfth aspect of the present invention, there is provided a coated article comprising a substrate and a coating covering the substrate, wherein the coating is formed from the electrodeposition coating composition according to any one of the first to tenth aspects.

[0405] <13> According to a 13th aspect of the present invention, there is provided the coated article according to the 12th aspect, wherein the material forming the substrate is at least one selected from the group consisting of copper, copper alloys, aluminum, and aluminum alloys.

[0406] <14> According to a fourteenth aspect of the present invention, there is provided a covered electric wire comprising a rectangular electric wire substrate and a coating formed on the outer periphery of the rectangular electric wire substrate, wherein the coating is formed from the electrodeposition coating composition according to any one of the first to tenth aspects.

[0407] <15> According to a fifteenth aspect of the present invention, there is provided the covered electric wire according to the fourteenth aspect, wherein the rectangular electric wire base is formed of at least one material selected from the group consisting of copper, copper alloys, aluminum, and aluminum alloys.

[0408] <16> According to a sixteenth aspect of the present invention, there is provided the covered electric wire according to the fourteenth aspect or the fifteenth aspect, which has a bent portion.

[0409] <17> According to a seventeenth aspect of the present invention, there is provided the covered electric wire according to the fourteenth aspect or the fifteenth aspect, which is a long electric wire.

[0410] <18> According to an 18th aspect of the present invention, there is provided a covered electric wire according to any one of the 14th to 17th aspects, wherein the covered electric wire further comprises a covering layer formed on the periphery of the coating, the covering layer being a layer formed of a powder coating composition containing a fluorinated polymer compound Y.

[0411] <19> According to a 19th aspect of the present invention, there is provided a covered electric wire according to any one of the 14th to 17th aspects, wherein the covered electric wire further comprises a covering layer formed on the periphery of the coating, the covering layer being a layer formed by extrusion molding of the fluorinated polymer compound Z.

[0412] <20> According to a 20th aspect of the present invention, there is provided the covered electric wire according to the 18th aspect, wherein:

[0413] The fluorine-containing polymer compound Y is a perfluorinated polymer compound.

[0414] The relative dielectric constant of the fluorine-containing polymer compound Y is 2.0 to 2.2.

[0415] The melting point of the fluorine-containing polymer compound Y is 250°C to 320°C.

[0416] <21> According to a 21st aspect of the present invention, there is provided the covered electric wire according to the 18th aspect, wherein the fluorinated polymer compound Y has a melt flow rate of 0.1 g / 10 min to 100 g / 10 min.

[0417] <22> According to a 22nd aspect of the present invention, there is provided the covered electric wire according to the 18th aspect, wherein the fluorinated polymer compound Y has functional groups, and the number of the functional groups is 10 6 The number of carbon atoms is 5 to 1000.

[0418] <23> According to a 23rd aspect of the present invention, there is provided the covered electric wire according to the 18th aspect, wherein the fluorinated polymer compound Y has functional groups, and the number of the functional groups is 10 6 The number of carbon atoms is 0 to 4.

[0419] <24> According to a 24th aspect of the present invention, there is provided a printed circuit board comprising a substrate and a film covering the substrate, wherein the film is formed from the electrodeposition coating composition according to any one of the first to tenth aspects.

[0420] <25> According to a 25th aspect of the present invention, there is provided the printed circuit board according to the 24th aspect, wherein the base material is made of at least one material selected from the group consisting of copper, copper alloys, aluminum, and aluminum alloys.

[0421] Example

[0422] Next, embodiments of the present invention will be described with reference to examples, but the present invention is not limited to these examples.

[0423] The properties shown in the examples were measured by the following methods.

[0424] (Number of functional groups of perfluorinated polymer compound X, fluorinated polymer compound Y, and fluorinated polymer compound Z)

[0425] The polymer compound was melted at 330°C to 340°C for 30 minutes and compression molded to produce a film with a thickness of 0.20mm to 0.25mm. The film was scanned 40 times using a Fourier transform infrared spectrometer [FT-IR (trade name: 1760X, manufactured by PerkinElmer)] and analyzed to obtain an infrared absorption spectrum. The difference spectrum from the background spectrum in which the functional groups are completely fluorinated and do not exist was obtained. According to the following formula (A), the absorption peak of the specific functional group appearing in the differential spectrum was used to calculate the relative amount of functional groups in the polymer compound per 10 6 The number of functional groups N per carbon atom.

[0426] N=I×K / t(A)

[0427] I: absorbance

[0428] K: Correction coefficient

[0429] t: film thickness (mm)

[0430] For reference, the absorption frequency, molar absorptivity, and correction factor of the functional groups in the present invention are shown in the table. The molar absorptivity was determined from FT-IR measurement data of low-molecular-weight model compounds.

[0431] [Table 2]

[0432]

[0433] (resin acid value)

[0434] The depolymerizable methacrylate resin was dissolved in a mixed solvent of xylene and isopropyl alcohol and titrated with a 0.1 mol / L potassium hydroxide ethanol solution by potentiometric titration. The inflection point on the titration curve was used as the endpoint, and the titration amount of the potassium hydroxide solution up to the endpoint was calculated.

[0435] (Degree of Neutralization of Depolymerizable Methacrylate Resin)

[0436] After adding tetrahydrofuran to the depolymerizable methacrylate resin, titrate with 0.1 mol / L hydrochloric acid solution by potentiometric titration to the equivalence point. The inflection point on the titration curve is taken as the amine value. The degree of neutralization is calculated by dividing this amine value by the acid value.

[0437] (Relative dielectric constant of polymer compounds)

[0438] The measurement was conducted in accordance with JIS-C-2138 at 23°C ± 2°C, a relative humidity of 50%, and a frequency of 1 kHz.

[0439] (Melt Flow Rate (MFR))

[0440] According to ASTM D1238, the mass (g / 10 min) of the copolymer flowing out from a nozzle having an inner diameter of 2.1 mm and a length of 8 mm at 372°C and a load of 5 kg was determined using a melt flow indexer (manufactured by Yasuda Seiki Co., Ltd.).

[0441] (Alkali Metal Content in Electrodeposition Coating Composition)

[0442] The alkali metal content in the electrodeposition coating composition was determined by inductively coupled plasma mass spectrometry.

[0443] (film thickness of film)

[0444] The film thickness was measured using a film thickness meter LZ-373 manufactured by Kett Scientific Laboratory Co., Ltd. If cracks were visually observed in the film, the film thickness was not measured and the film was recorded as "cracked".

[0445] (Surface roughness of the film)

[0446] The surface roughness Ra of the film was measured using a surface roughness measuring instrument Surtronic DUOII manufactured by Taylor Hobson Co. If cracks were visually observed in the film, the film thickness was not measured and the film was recorded as "cracked".

[0447] (Adhesion strength between film and substrate)

[0448] Use AGS-JAutograph (50N) (made by Shimadzu Corporation) to measure the adhesion strength between the film and the substrate. Cut two strips of 50mm approximately parallel in the long axis direction, cut the film into right angles at both ends along the short axis direction, peel off 10cm of the end, and clamp it on the upper chuck. The conductor is fixed to the bottom in a way that the long face direction becomes horizontal. When moving the device in the tensile direction, use a clamp that moves in a linked manner in the transverse direction according to its longitudinal movement distance, and adjust the angle so that the peeled film is always perpendicular to the conductor in the long face direction. Measure the tensile stress when it is stretched to 30mm at 100mm / min, and use the maximum point stress as the adhesion strength. In the case where cracks are found in the film by visual inspection, the adhesion strength is not evaluated and is recorded as "cracked".

[0449] (Relative dielectric constant of the film)

[0450] The capacitance was measured using LCR HiTESTER 3522-50 manufactured by Hioki Co., Ltd., and the relative dielectric constant was calculated from the following formula: If cracks were observed in the film by visual inspection, the relative dielectric constant was not evaluated and the film was recorded as "cracked".

[0451] C=Ca+Cb

[0452] (Where C is the electrostatic charge per unit length of the coating (pf / m), which is the sum of the electrostatic capacitance Ca of the flat portion and the electrostatic capacitance Cb of the corner portion.)

[0453] Ca=(ε / ε0)×2×(L1+L2) / T

[0454] Cb=(ε / ε0)×2πε0 / Log{(r+T) / r} / r

[0455] (Where ε0 is the dielectric constant of a vacuum, L1 is the long side of the copper plate, L2 is the short side, and T is the thickness of the film.)

[0456] Preparation of Depolymerizable Methacrylate Resin A:

[0457] Under a nitrogen atmosphere, methyl methacrylate (1.44 g), butyl n-methacrylate (123.13 g), 2-hydroxyethyl methacrylate (13.92 g), methacrylic acid (11.51 g), and azobisisobutyronitrile (1.5 g) as a polymerization initiator were added dropwise to a stirred isopropyl alcohol (335 g) over 3 hours while maintaining the liquid temperature at 70°C. After the addition, stirring was continued for 2 hours while maintaining the liquid temperature at 70°C. This yielded a solution of depolymerizable methacrylate resin A having a resin acid value of 50 mgKOH / g and a solids content of 30% by mass.

[0458] Preparation of depolymerizable methacrylate resin B:

[0459] Under a nitrogen atmosphere, while maintaining the liquid temperature at 70°C, methyl methacrylate (7.03g), butyl n-methacrylate (122.15g), 2-hydroxyethyl methacrylate (13.92g), methacrylic acid (6.9g), and azobisisobutyronitrile (1.5g) as a polymerization initiator were added dropwise to a stirred isopropyl alcohol (335g) over 3 hours. After the addition was complete, stirring was continued for 2 hours while maintaining the liquid temperature at 70°C. This yielded a solution of a depolymerizable methacrylate resin B having a resin acid value of 30 mgKOH / g and a solids content of 30% by mass.

[0460] Preparation of Depolymerizable Methacrylate Resin C:

[0461] Under a nitrogen atmosphere, methyl methacrylate (13.67 g), butyl n-methacrylate (104 g), 2-hydroxyethyl methacrylate (13.92 g), methacrylic acid (18.41 g), and azobisisobutyronitrile (1.5 g) as a polymerization initiator were added dropwise to a stirred isopropyl alcohol (335 g) over 3 hours while maintaining the liquid temperature at 70°C. After the addition, stirring was continued for 2 hours while maintaining the liquid temperature at 70°C. This yielded a solution of depolymerizable methacrylate resin C having a resin acid value of 80 mgKOH / g and a solids content of 30% by mass.

[0462] Preparation of electrodeposition coating composition A:

[0463] Triethylamine was added to the solution of the depolymerizable methacrylate resin A so as to obtain a neutralized solution of the depolymerizable methacrylate resin A at a degree of neutralization of 80%. PTFE (relative dielectric constant: 2.2, number of functional groups: 100% per 100%) was further added while stirring to obtain a solution of the depolymerizable methacrylate resin A at a ratio of 50 / 50 (mass %) of perfluoropolymer compound / methacrylate resin. 6 An aqueous dispersion composition (solid content: 30% by mass) of PTFE particles (having 18 carbon atoms) and pure water were mixed and phase inversion emulsification was performed to obtain an electrodeposition coating composition A having a solid content of 15% by mass, in which PTFE particles and neutralized particles of a depolymerizable methacrylate resin A were emulsified.

[0464] Preparation of Electrodeposition Coating Composition B:

[0465] Triethylamine was added to the solution of the depolymerizable methacrylate resin A to obtain a neutralized solution of the depolymerizable methacrylate resin A at a degree of neutralization of 80%. PFA (relative dielectric constant: 2.2, number of functional groups: 100% per 100%) was further added while stirring to obtain a ratio of perfluoropolymer compound / methacrylate resin of 50 / 50 (mass %). 6 An aqueous dispersion composition (solid content: 30% by mass) of PFA particles (having 220 carbon atoms) and pure water were mixed and subjected to phase inversion emulsification to obtain an electrodeposition coating composition B having a solid content of 15% by mass and in which PFA particles and neutralized particles of a depolymerizable methacrylate resin A were emulsified.

[0466] Preparation of Electrodeposition Coating Composition C:

[0467] Triethylamine was added to the solution of the depolymerizable methacrylate resin A so as to obtain a neutralized solution of the depolymerizable methacrylate resin A at a degree of neutralization of 80%. FEP (relative dielectric constant: 2.2, number of functional groups: 100% per 100%) was further added while stirring to obtain a solution of the depolymerizable methacrylate resin A at a ratio of 50 / 50 (mass %) of perfluoropolymer compound / methacrylate resin.6 An aqueous dispersion composition (solid content: 20% by mass) of FEP particles (containing 625 carbon atoms) and pure water were mixed and phase inversion emulsification was performed to obtain an electrodeposition coating composition C having a solid content of 15% by mass and in which FEP particles and neutralized particles of a depolymerizable methacrylate resin A were emulsified.

[0468] Preparation of Electrodeposition Coating Composition D:

[0469] Triethylamine was added to the solution of the depolymerizable methacrylate resin A so as to obtain a neutralized solution of the depolymerizable methacrylate resin A at a degree of neutralization of 80%. PFA (relative dielectric constant: 2.2, number of functional groups: 100% per 100%) was further added while stirring to obtain a ratio of perfluoropolymer compound / methacrylate resin of 30 / 70 (mass %). 6 An aqueous dispersion composition (solid content: 30% by mass) of PFA particles (having 220 carbon atoms) and pure water were mixed and subjected to phase inversion emulsification to obtain an electrodeposition coating composition D having a solid content of 15% by mass, in which PFA particles and neutralized particles of a depolymerizable methacrylate resin A were emulsified.

[0470] Preparation of Electrodeposition Coating Composition E:

[0471] Triethylamine was added to the solution of the depolymerizable methacrylate resin A so as to obtain a neutralized solution of the depolymerizable methacrylate resin A at a degree of neutralization of 80%. PFA (relative dielectric constant: 2.2, number of functional groups: 100% per 100%) was further added while stirring to obtain a ratio of perfluoropolymer compound / methacrylate resin of 70 / 30 (mass %). 6 An aqueous dispersion composition (solid content: 30% by mass) of PFA particles (having 220 carbon atoms) and pure water were mixed and subjected to phase inversion emulsification to obtain an electrodeposition coating composition E having a solid content of 15% by mass and in which PFA particles and neutralized particles of a depolymerizable methacrylate resin A were emulsified.

[0472] Preparation of Electrodeposition Coating Composition F:

[0473] Triethylamine was added to the solution of the depolymerizable methacrylate resin B so that the neutralization degree was 80%, thereby obtaining a neutralized solution of the depolymerizable methacrylate resin B. PFA (relative dielectric constant: 2.2, number of functional groups: 100% per 100%) was further added while stirring so that the perfluoropolymer compound / methacrylate resin = 50 / 50 (mass %). 6An aqueous dispersion composition (solid content: 30% by mass) of PFA particles (having 220 carbon atoms) and pure water were mixed and subjected to phase inversion emulsification to obtain an electrodeposition coating composition F having a solid content of 15% by mass and in which PFA particles and neutralized particles of a depolymerizable methacrylate resin B were emulsified.

[0474] Preparation of Electrodeposition Coating Composition G:

[0475] Triethylamine was added to the solution of the depolymerizable methacrylate resin C to obtain a neutralized solution of the depolymerizable methacrylate resin C at a degree of neutralization of 80%. PFA (relative dielectric constant: 2.2, number of functional groups: 100% per 100%) was further added while stirring to obtain a ratio of perfluoropolymer compound / methacrylate resin of 50 / 50 (mass %). 6 An aqueous dispersion composition (solid content: 30% by mass) of PFA particles (having 220 carbon atoms) and pure water were mixed and subjected to phase inversion emulsification to obtain an electrodeposition coating composition F having a solid content of 15% by mass and in which PFA particles and neutralized particles of a depolymerizable methacrylate resin C were emulsified.

[0476] Preparation of Electrodeposition Coating Composition H:

[0477] Triethylamine was added to a solution of a non-depolymerizable acrylic resin (Almatex WA911 manufactured by Mitsui Chemicals, Inc., resin acid value 48 mgKOH / g) to a neutralization degree of 80% to obtain a neutralized solution of a non-depolymerizable acrylic resin. Furthermore, PFA (relative dielectric constant: 2.2, number of functional groups: 100% per 100%) was added while stirring to obtain a ratio of perfluoropolymer compound / acrylic resin of 50 / 50 (mass %). 6 The aqueous dispersion composition (solid content: 30% by mass) of PFA particles (containing 220 carbon atoms) and pure water were subjected to phase inversion emulsification to obtain an electrodeposition coating composition H having a solid content of 15% by mass and in which PFA particles and neutralized particles of a non-depolymerizable acrylic resin were emulsified.

[0478] Preparation of Electrodeposition Coating Composition J:

[0479] PTFE (relative dielectric constant: 2.2, number of functional groups: 0.000 / 0.000 / 0.000) was mixed with an aqueous dispersion of depolymerizable methacrylate resin particles (ACRYSETTF-300 manufactured by Nippon Shokubai Co., Ltd., solid content: 40% by mass, resin acid value: 0.5 mgKOH / g) at a ratio of perfluoropolymer compound / methacrylate resin = 50 / 50 (mass %). 6 An aqueous dispersion composition (solid content: 60% by mass) of particles having 18 carbon atoms and pure water was mixed to obtain an electrodeposition coating composition J having a solid content of 15% by mass.

[0480] Preparation of Electrodeposition Coating Composition K:

[0481] Add PTFE (relative dielectric constant: 2.2, number of functional groups: per 10 6 20 kg of an aqueous dispersion composition (solids content: 60% by mass) of particles of a depolymerizable methacrylate resin (having 18 carbon atoms per unit area), 10 kg of ion-exchanged water, and 6 g of sodium lauryl sulfate were stirred under a nitrogen atmosphere for 30 minutes. The mixture was heated to 70°C, and a solution of 6 g of ammonium persulfate and 2 g of sodium bisulfite dissolved in 20 g of pure water was added. Immediately thereafter, 600 g of methyl methacrylate was added dropwise over 30 minutes. After the addition was completed, the mixture was maintained at 70°C and stirred for 2 hours to obtain an aqueous dispersion composition of particles of a depolymerizable methacrylate resin D (resin acid value: 0.4 mgKOH / g). Subsequently, pure water was added to obtain an electrodeposition coating composition K having a solids content of 20% by mass and composed of a mixture of PTFE particles and particles of the depolymerizable methacrylate resin D.

[0482] Examples 1 to 7, Comparative Examples 1 to 3

[0483] Electrodeposition coating compositions A to H, J, and K were applied to copper plates at a liquid temperature of 25°C and an applied voltage of 150 V for 120 seconds. The coatings were pre-dried at 100°C for 20 minutes and then heated at 380°C for 20 minutes in a drying oven purged with nitrogen and free of oxygen to produce films. The properties of these films were evaluated.

[0484] Example 8

[0485] On the film obtained in Example 2, a fluorinated polymer compound Y made of PFA (relative dielectric constant: 2.2, number of functional groups: 10 6 The coating layer was formed from a powder coating composition having a carbon number of 220 and an MFR of 27 g / 10 min. The properties of the film and the coating layer (the film and the coating layer are collectively referred to as "film" in Table 3) were evaluated.

[0486] Example 9

[0487] On the film obtained in Example 2, a fluorinated polymer compound Y made of PFA (relative dielectric constant: 2.2, number of functional groups: 10 6 The coating layer was formed from a powder coating composition having a carbon content of 2, a carbon number of 2, and an MFR of 28 g / 10 min. The properties of the film and the coating layer (the film and the coating layer are collectively referred to as "film" in Table 3) were evaluated.

[0488] Example 10

[0489] PFA (relative dielectric constant: 2.2, number of functional groups: 100) as the fluorinated polymer compound Z was extruded onto the film obtained in Example 2. 6 A coating layer was formed by coating with 55 carbon atoms and MFR of 12 g / 10 min. The properties of the coating and the coating layer (the coating and the coating layer are collectively referred to as "film" in Table 3) were evaluated.

[0490] Experimental Example 1

[0491] Electrodeposition coating composition B was applied to a copper plate at a liquid temperature of 25°C, an applied voltage of 150 V, and a duration of 120 seconds. After preliminary drying at 100°C for 20 minutes, the plate was heated at 380°C for 20 minutes in a drying oven with oxygen introduced from outside air to obtain a coating. However, oxidation of the copper plate progressed, and cracks were observed.

[0492] The above results are shown in Table 3.

[0493]

[0494] In Table 3, "simultaneously emulsified particles" refer to particles of a perfluoropolymer compound and particles of a methacrylate resin (acrylic resin) in an electrodeposition coating composition obtained by a production method in which an aqueous dispersion composition containing a perfluoropolymer compound X and water is added to a solution containing a methacrylate resin (acrylic resin) and an organic solvent, followed by phase inversion emulsification.

[0495] In Table 3, "mixed particles" refer to particles of a perfluoropolymer compound and particles of a methacrylate resin (acrylic resin) in an electrodeposition coating composition obtained by mixing an aqueous dispersion composition containing a methacrylate resin (acrylic resin) and water with an aqueous dispersion composition containing a perfluoropolymer compound X and water.

[0496] Each description in Table 3 represents the following polymers, and the detailed properties of each polymer are as described above.

[0497] Perfluorinated polymer compoundsX

[0498] PTFE: polytetrafluoroethylene, relative dielectric constant: 2.2, number of functional groups: 18 / C10 6 indivual

[0499] PFA (1): Tetrafluoroethylene / perfluoro(propyl vinyl ether) copolymer, relative dielectric constant: 2.2, number of functional groups: 220 / C10 6 indivual

[0500] FEP: tetrafluoroethylene / hexafluoropropylene copolymer, relative dielectric constant: 2.2, number of functional groups: 625 / C106 indivual

[0501] Methacrylate resin (acrylic resin)

[0502] Methacrylate resin A: depolymerizable methacrylate resin, resin acid value: 50 mgKOH / g

[0503] Methacrylate resin B: depolymerizable methacrylate resin, resin acid value: 30 mgKOH / g

[0504] Methacrylate resin C: depolymerizable methacrylate resin, resin acid value: 80 mgKOH / g

[0505] Acrylic resin E: Non-depolymerizable acrylic resin, Almatex WA911 manufactured by Mitsui Chemicals, Inc., resin acid value: 48 mgKOH / g

[0506] Methacrylate resin F: Depolymerizable methacrylate resin, ACRYSETTF-300 manufactured by Nippon Shokubai Co., Ltd., resin acid value: 0.5 mgKOH / g

[0507] Methacrylate resin D: Depolymerizable methacrylate resin, resin acid value: 0.4 mgKOH / g

[0508] Fluorinated polymer compound Y

[0509] PFA (3): tetrafluoroethylene / perfluoro(propyl vinyl ether) copolymer, relative dielectric constant: 2.2, number of functional groups: 10 6 220 carbon atoms, MFR: 27g / 10min

[0510] PFA (4): tetrafluoroethylene / perfluoro(propyl vinyl ether) copolymer, relative dielectric constant: 2.2, number of functional groups: per 10 6 There are 2 carbon atoms, MFR: 28g / 10min

[0511] Fluorine-containing polymer compound Z

[0512] PFA (5): tetrafluoroethylene / perfluoro(propyl vinyl ether) copolymer, relative dielectric constant: 2.2, number of functional groups: per 10 6 55 carbon atoms, MFR: 12g / 10min

[0513] <Measurement of Fluorinated Compounds Having a Hydrophilic Group>

[0514] 0. Extraction of fluorinated compounds with hydrophilic groups from aqueous dispersions or aqueous dispersion compositions

[0515] 5.0 g of the aqueous dispersion was weighed, 10 g of methanol was added, and the mixture was passed through a cylindrical filter paper. Soxhlet extraction was performed with a total amount of 150 g of methanol as the extraction solvent. The volume of the obtained extract was fixed with methanol to 250 ml, thereby obtaining an extract containing a fluorine-containing compound having a hydrophilic group.

[0516] <Determination of Perfluoroether Carboxylic A>

[0517] 1. Calibration curve of perfluoroether carboxylic acid A

[0518] Five methanol standard solutions of perfluoroethercarboxylic acid A at known concentrations were prepared and measured using a liquid chromatography-mass spectrometer (Agilent, Ultivo triple quadrupole LC-MS). Within each concentration range, a calibration curve was constructed using linear approximation based on the methanol standard solution concentrations and peak integration values.

[0519] Measurement equipment structure and LC-MS measurement conditions

[0520] [Table 4]

[0521] Table 4 Measurement equipment structure and LC-MS measurement conditions

[0522]

[0523] MRM assay parameters

[0524] [Table 5]

[0525] Table 5 MRM assay parameters

[0526]

[0527] 2. Content of perfluoroether carboxylic acid A in the aqueous dispersion or aqueous dispersion composition

[0528] Perfluoroether carboxylic acid A was measured using a liquid chromatography-mass spectrometer. The extract was appropriately diluted with methanol to prepare a measurement solution so that the amount of perfluoroether carboxylic acid A in the measurement solution fell within the calibration curve. The peak area of perfluoroether carboxylic acid A in the measurement solution was determined using the MRM method, and the content of perfluoroether carboxylic acid A was determined from the calibration curve.

[0529] <Content of the compound represented by general formula (H2)>

[0530] The content of the compound represented by the general formula (H2) was determined using a calibration curve of linear perfluorocarboxylic acids having the same number of carbon atoms.

[0531] 1. Calibration curve of perfluorocarboxylic acid

[0532] Five methanol standard solutions of perfluorobutyric acid, perfluoropentanoic acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, and perfluorotetradecanoic acid at known concentrations were prepared and measured using a liquid chromatography-mass spectrometer (Agilent Ultivo triple quadrupole LC-MS). Calibration curves were constructed using linear approximation based on the concentrations of the methanol standard solutions and the peak integral values within each concentration range.

[0533] Measurement equipment structure and LC-MS measurement conditions

[0534] [Table 6]

[0535] Table 6 Measurement equipment structure and LC-MS measurement conditions

[0536]

[0537] MRM measurement parameters

[0538] [Table 7]

[0539] Table 7 MRM assay parameters

[0540]

[0541] 3. Content of the compound represented by the general formula (H2) contained in the aqueous dispersion or aqueous dispersion composition

[0542] The content of the compound represented by the general formula (H2) with the number of carbon atoms n in the extract was determined using a liquid chromatography-mass spectrometer based on a calibration curve. The peak area of the fluorinated compound represented by the general formula (H2) having a hydrophilic group was determined for the extract using the MRM method to determine the content of the fluorinated compound represented by the general formula (H2) having a hydrophilic group in the aqueous dispersion or aqueous dispersion composition.

[0543] MRM measurement parameters

[0544] [Table 8]

[0545] Table 8 MRM assay parameters

[0546]

[0547] Synthesis example 1

[0548] By the method described in Synthesis Example 1 of International Publication No. 2021 / 045228, a white solid A of perfluoroether carboxylic acid A having a molecular weight of 1000 or less was obtained.

[0549] Production Example 1

[0550] 3750 g of deionized water and 5.49 g of the white solid A obtained in Synthesis Example 1 as a fluorinated surfactant were added to a SUS reactor with a capacity of 6 L and equipped with a stirrer. Then, the contents of the reactor were heated to 60° C. while being sucked and purged with TFE to remove oxygen from the reactor, and the contents were stirred. After adding 6.9 g of dichloromethane and 27 g of perfluoro(propyl vinyl ether) (PPVE) to the reactor, TFE was added until a pressure of 1.3 MPaG was reached. 990 mg of ammonium persulfate (APS) initiator dissolved in 20 g of deionized water was injected into the reactor. After the initiator was injected, a decrease in pressure occurred, and the start of polymerization was observed. TFE was added to the reactor, and the pressure was kept constant at 1.3 MPaG. After the polymerization started, 4 g of PPVE was added continuously relative to 100 g of TFE. When the TFE consumed in the reaction reached about 1600 g, the supply of TFE was stopped, and the stirring was stopped to terminate the reaction. Then, the reactor was evacuated until the pressure inside reached normal pressure, thereby obtaining an aqueous dispersion of tetrafluoroethylene / perfluoro(propyl vinyl ether) copolymer (PFA).

[0551] Preparation Example 1

[0552] The PFA aqueous dispersion obtained in Preparation Example 1 was placed in a separate reactor, and the contents of the reactor were heated to 80°C. 30.3 g of ammonium persulfate (10 molar times the molar amount of the fluorinated surfactant used in the polymerization) was added as a free radical generator. The temperature was then maintained at 80°C for 3 hours to obtain a heat-treated PFA-containing aqueous dispersion composition.

[0553] Next, embodiments of the electrodeposition coating composition containing the aqueous dispersion obtained in Production Example 1 or the aqueous dispersion composition obtained in Preparation Example 1 will be described with reference to examples.

[0554] Preparation of Electrodeposition Coating Composition B:

[0555] Triethylamine was added to the solution of the depolymerizable methacrylate resin A so as to obtain a neutralized solution of the depolymerizable methacrylate resin A at a degree of neutralization of 80%. The aqueous dispersion obtained in Preparation Example 1 (PFA relative dielectric constant: 2.2, number of functional groups of PFA: 100% per 100%) was further added while stirring to obtain a solution of perfluoropolymer compound / methacrylate resin = 50 / 50 (mass %). 6 A fluorine-containing compound having 220 carbon atoms and a hydrophilic group relative to PFA (content: 42 mass ppb, solid content: 30 mass%) and pure water were subjected to phase inversion emulsification to obtain an electrodeposition coating composition B having a solid content of 15 mass% and emulsified PFA particles and particles of a neutralized product of a depolymerizable methacrylate resin A.

[0556] Preparation of Electrodeposition Coating Composition L:

[0557] Triethylamine was added to the solution of the depolymerizable methacrylate resin A so as to obtain a neutralized solution of the depolymerizable methacrylate resin A at a degree of neutralization of 80%. The aqueous dispersion obtained in Production Example 1 (PFA relative dielectric constant: 2.2, number of functional groups of PFA: 100% per 100%) was further added while stirring to obtain a solution of the perfluoropolymer compound / methacrylate resin of 50 / 50 (mass %). 6 The present invention relates to an electrodeposition coating composition L having a solid content of 15% by mass and containing a fluorine-containing compound having 220 carbon atoms and a hydrophilic group relative to PFA (content: 551 mass ppb, solid content: 30 mass%) and pure water, and phase inversion emulsification is carried out to obtain an electrodeposition coating composition L having a solid content of 15% by mass and emulsified PFA particles and neutralized product particles of a depolymerizable methacrylate resin A.

[0558] Example 11, Experimental Example 2

[0559] Electrodeposition coating was applied to copper plates using Electrodeposition Coating Composition B (Example 11) and Electrodeposition Coating Composition L (Experimental Example 2) at a liquid temperature of 25°C and an applied voltage of 150V for 120 seconds. The coating was pre-dried at 100°C for 20 minutes and then heated at 380°C for 20 minutes in a drying oven purged with nitrogen and free of oxygen to produce a film. The contact angle and coefficient of friction of the films were measured according to the following procedures.

[0560] <Contact Angle>

[0561] The contact angles with respect to water and n-hexadecane were measured using a contact angle meter CA-DT manufactured by Kyowa Interface Science Co., Ltd.

[0562] <Friction Coefficient>

[0563] Using a surface property tester HEIDON Type 38 manufactured by Shinto Scientific Co., Ltd., the static friction coefficient and the dynamic friction coefficient were measured while pressing (ball indenter) with a load (1 kg) and moving at a speed of 600 mm / min.

[0564] The above results are shown in Table 9.

[0565] [Table 9]

[0566] Table 9

[0567] unit Example 11 Experimental Example 2 Contact angle (relative to water) Spend 101 88 Contact angle (relative to n-hexadecane) Spend 34 25 Static friction coefficient － 0.15 0.25 Dynamic friction coefficient － 0.06 0.15

Claims

1. An electrodeposition coating composition comprising a neutralized product of a perfluoropolymer compound X and a methacrylate resin, wherein: The relative dielectric constant of the perfluoropolymer compound X is 2.0 to 2.

2. The acid value of the methacrylate resin is greater than 10 mgKOH / g, The solid content concentration of the electrodeposition coating composition is 10% by mass to 70% by mass.

2. An electrodeposition coating composition comprising a neutralized product of a perfluoropolymer compound X and a methacrylate resin, wherein: The perfluorinated polymer compound X is a tetrafluoroethylene / fluoroalkyl vinyl ether copolymer, The acid value of the methacrylate resin is greater than 10 mgKOH / g, The solid content concentration of the electrodeposition coating composition is 10% by mass to 70% by mass.

3. The electrodeposition coating composition according to claim 1 or 2, wherein The content of the fluorine-containing compound having a hydrophilic group relative to the perfluoropolymer compound X is 50 ppb by mass or less. 4 . The electrodeposition coating composition according to claim 1 , further comprising water.

5. The electrodeposition coating composition according to any one of claims 1 to 4, which is obtained by a production method comprising adding an aqueous dispersion containing the perfluoropolymer compound X and water to a solution containing a neutralized product of the methacrylate resin and an organic solvent, followed by phase inversion emulsification.

6. The electrodeposition coating composition according to any one of claims 1 to 5, wherein The methacrylate resin has a carboxyl group, and the neutralized product of the methacrylate resin is a neutralized product obtained by neutralizing the methacrylate resin having a carboxyl group with an amine compound.

7. The electrodeposition coating composition according to any one of claims 1 to 6, wherein The neutralization degree of the neutralized product of the methacrylate resin is greater than 50%.

8. The electrodeposition coating composition according to any one of claims 1 to 7, wherein The perfluoropolymer compound X has a functional group, and the number of functional groups of the perfluoropolymer compound X is 6 The number of carbon atoms ranges from 5 to 2000.

9. The electrodeposition coating composition according to any one of claims 1 to 8, wherein The alkali metal content is less than 1 mass ppm.

10. The electrodeposition coating composition according to any one of claims 1 to 9, wherein The mass ratio of the perfluoropolymer compound X to the neutralized product of the methacrylate resin is 10 / 90 to 90 / 10. 11 . A coating formed from the electrodeposition coating composition according to claim 1 . 12 . A coated article comprising a substrate and a coating covering the substrate, wherein the coating is formed from the electrodeposition coating composition according to claim 1 .

13. The covered article according to claim 12, wherein The substrate is formed of at least one material selected from the group consisting of copper, copper alloys, aluminum, and aluminum alloys. 14 . A covered electric wire comprising a rectangular electric wire base and a coating formed on the outer periphery of the rectangular electric wire base, wherein the coating is formed from the electrodeposition coating composition according to claim 1 .

15. The covered electric wire according to claim 14, wherein The rectangular electric wire base material is formed of at least one material selected from the group consisting of copper, copper alloys, aluminum, and aluminum alloys.

16. The covered electric wire according to claim 14 or 15, comprising a bent portion.

17. The covered electric wire according to claim 14 or 15, which is a long electric wire.

18. The covered electric wire according to any one of claims 14 to 17, wherein The covered electric wire further includes a covering layer formed on the outer periphery of the coating film, wherein the covering layer is a layer formed of a powder coating composition containing a fluorinated polymer compound Y.

19. The covered electric wire according to any one of claims 14 to 17, wherein The covered electric wire further includes a covering layer formed on the outer periphery of the coating film, wherein the covering layer is formed by extrusion molding of the fluorinated polymer compound Z.

20. The covered electric wire according to claim 18, wherein The fluorine-containing polymer compound Y is a perfluorinated polymer compound. The relative dielectric constant of the fluorine-containing polymer compound Y is 2.0 to 2.

2. The melting point of the fluorine-containing polymer compound Y is 250°C to 320°C.

21. The covered electric wire according to claim 18, wherein The melt flow rate of the fluorinated polymer compound Y is 0.1 g / 10 min to 100 g / 10 min.

22. The covered electric wire according to claim 18, wherein The fluorinated polymer compound Y has functional groups, and the number of functional groups is 6 The number of carbon atoms is 5 to 1000.

23. The covered electric wire according to claim 18, wherein The fluorinated polymer compound Y has functional groups, and the number of functional groups is 6 The number of carbon atoms is 0 to 4. 24 . A printed circuit board comprising a substrate and a film covering the substrate, wherein the film is formed from the electrodeposition coating composition according to claim 1 .

25. The printed circuit board according to claim 24, wherein The substrate is formed of at least one material selected from the group consisting of copper, copper alloys, aluminum, and aluminum alloys.

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