WO2023171777A1 - Composition de revêtement, film de revêtement, film de revêtement stratifié et article revêtu - Google Patents

Composition de revêtement, film de revêtement, film de revêtement stratifié et article revêtu Download PDF

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Publication number
WO2023171777A1
WO2023171777A1 PCT/JP2023/009181 JP2023009181W WO2023171777A1 WO 2023171777 A1 WO2023171777 A1 WO 2023171777A1 JP 2023009181 W JP2023009181 W JP 2023009181W WO 2023171777 A1 WO2023171777 A1 WO 2023171777A1
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Prior art keywords
mass
fluorine
coating composition
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ptfe
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PCT/JP2023/009181
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English (en)
Japanese (ja)
Inventor
ツォン祺 呉
宝云 饒
琢哉 木下
智洋 城丸
啓 西村
安利 中谷
丈人 加藤
絵美 山本
拓也 山部
拓 山中
Original Assignee
ダイキン フルオロ コーティングズ （シャンハイ） カンパニー リミテッド
ダイキン工業株式会社
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Priority to JP2024506413A priority Critical patent/JPWO2023171777A1/ja
Publication of WO2023171777A1 publication Critical patent/WO2023171777A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular

Definitions

  • the present disclosure relates to coating compositions, coatings, laminate coatings, and coated articles.
  • An object of the present disclosure is to provide a coating composition that can provide a coating film with excellent abrasion resistance, as well as coatings, laminated coatings, and coated articles using the coating composition.
  • the present disclosure relates to a coating composition containing a fluorine-containing ethylenic polymer, a filler, and water,
  • the content of the fluorine-containing ethylenic polymer is 1 to 50% by mass based on the coating composition
  • the above filler is (i) 0.1 to 80% by mass of a filler having a new Mohs hardness of 9 or more based on the fluorine-containing ethylenic polymer; (ii) a filler having a new Mohs hardness of 5 or more and less than 9, which is 0.1 to 120% by mass based on the fluorine-containing ethylenic polymer; (iii) Provide a coating composition comprising at least one filler selected from the group consisting of fillers having a new Mohs hardness of less than 5 and 1 to 150% by mass based on the fluorine-containing ethylenic polymer.
  • the filler is (i-1) 0.1 to 15% by mass of a filler having a new Mohs hardness of 9 or more based on the fluorine-containing ethylenic polymer, and (ii-1) At least one filler selected from the group consisting of fillers having a new Mohs hardness of 5 or more and less than 9, which is 0.1 to 20% by mass based on the fluorine-containing ethylenic polymer.
  • the coating composition preferably does not contain a heat-resistant resin (excluding the fluorine-containing ethylenic polymer).
  • the content of the fluorine-containing ethylenic polymer is preferably 15% by mass or more based on the coating composition. In the above embodiment, the content of the fluorine-containing ethylenic polymer is preferably 49% by mass or less based on the coating composition. In the above aspect, the coating composition preferably has a viscosity at 25° C. of 10 mPa ⁇ s or more and 1000 mPa ⁇ s or less.
  • the coating composition preferably contains a heat-resistant resin (excluding the fluorine-containing ethylenic polymer).
  • the content of the fluorine-containing ethylenic polymer is preferably 1 to 30% by mass based on the coating composition.
  • the coating composition preferably has a viscosity at 25° C. of 50 mPa ⁇ s or more and 1500 mPa ⁇ s or less.
  • the fluorine-containing ethylenic polymer contains polytetrafluoroethylene.
  • the content of the polytetrafluoroethylene is 50% by mass or more based on the fluorine-containing ethylenic polymer.
  • the coating composition preferably has a gelation time of 4 hours or more in a stirring stability test.
  • the coating composition can be coated 100 times or more before white spots occur in a continuous spray coating test.
  • the present disclosure also provides coatings formed from the coating compositions described above.
  • the present disclosure also provides laminated coatings that include the coatings described above.
  • a coating composition that can provide a coating film with excellent abrasion resistance, as well as coatings, laminated coatings, and coated articles using the coating composition.
  • the present disclosure provides a coating composition containing a fluorine-containing ethylenic polymer, a filler, and water, wherein the content of the fluorine-containing ethylenic polymer is 1 to 50% by mass with respect to the coating composition,
  • the above-mentioned filler is (i) a filler having a new Mohs hardness of 9 or more in an amount of 0.1 to 80% by mass based on the above-mentioned fluorine-containing ethylenic polymer, (ii) based on the above-mentioned fluorine-containing ethylenic polymer.
  • a coating composition comprising at least one filler selected from the group consisting of hard fillers.
  • the coating composition of the present disclosure can provide a coating film with excellent wear resistance. Furthermore, the coating composition of the present disclosure is less likely to clog a coating gun or cause white spots on the coating film during coating.
  • the coating composition of the present disclosure also has excellent stirring stability (does not readily gel).
  • fluorine-containing ethylenic polymer examples include polytetrafluoroethylene (PTFE) and melt-processable fluororesin, and one or more of them can be used.
  • PTFE polytetrafluoroethylene
  • melt-processable fluororesin examples include melt-processable fluororesin, and one or more of them can be used.
  • the above-mentioned PTFE may be a homopolymer of tetrafluoroethylene (TFE), or may be a modified PTFE containing a polymerized unit based on TFE (TFE unit) and a polymerized unit based on a modified monomer (modified monomer unit). It's okay.
  • the modified PTFE may contain 99.0% by mass or more of polymerized units based on TFE and 1.0% by mass or less of polymerized units based on a modifying monomer.
  • the above-mentioned modified PTFE may consist only of TFE units and modified monomer units. Modified PTFE is preferred because the resulting coating film has an excellent appearance.
  • the modified PTFE preferably has a modified monomer unit content in the range of 0.00001 to 1.0% by mass.
  • the lower limit of the content of the modified monomer unit is more preferably 0.0001% by mass, even more preferably 0.001% by mass, even more preferably 0.005% by mass, even more preferably 0.010% by mass, and even more preferably 0.001% by mass.
  • 0.030 wt% is even more preferred, 0.050 wt% is even more preferred, 0.070 wt% is even more preferred, 0.10 wt% is even more preferred, 0.15 wt% is even more preferred, 0. .20% by weight is particularly preferred, and 0.25% by weight is most preferred.
  • the upper limit of the content of modified monomer units is preferably 0.90% by mass, more preferably 0.50% by mass, even more preferably 0.45% by mass, even more preferably 0.40% by mass, and 0.35% by mass. Particularly preferred is 0.30% by weight, most preferably 0.30% by weight.
  • the modified monomer unit means a part of the molecular structure of PTFE that is derived from a modified monomer.
  • each monomer constituting PTFE can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.
  • the above-mentioned modified monomer is not particularly limited as long as it can be copolymerized with TFE; for example, perfluoroolefins such as hexafluoropropylene [HFP]; hydrogen such as trifluoroethylene, vinylidene fluoride [VDF], etc. Containing fluoroolefins; perhaloolefins such as chlorotrifluoroethylene; perfluorovinyl ether: perfluoroallyl ether; (perfluoroalkyl)ethylene, ethylene, and the like.
  • the number of modified monomers used may be one or more than one.
  • perfluoro organic group means an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms.
  • the perfluoro organic group may have an ether oxygen.
  • perfluorovinyl ether examples include perfluoro(alkyl vinyl ether) [PAVE] in the general formula (A) above, in which Rf is a perfluoroalkyl group having 1 to 10 carbon atoms.
  • the perfluoroalkyl group preferably has 1 to 5 carbon atoms.
  • Examples of the perfluoroalkyl group in PAVE include perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, and the like.
  • perfluorovinyl ether further includes those in the above general formula (A) in which Rf is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, and Rf is the following formula:
  • Rf is a group represented by the following formula:
  • n an integer of 1 to 4.
  • PFAE Perfluoroalkylethylene
  • examples thereof include (perfluorobutyl)ethylene (PFBE) and (perfluorohexyl)ethylene.
  • Rf 11 is preferably a perfluoroalkyl group having 1 to 10 carbon atoms or a perfluoroalkoxyalkyl group having 1 to 10 carbon atoms.
  • the modified monomers include cyclic monomers.
  • cyclic monomer the following general formula (ii): ( In the formula , X 2 and , an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms) is preferred.
  • vinyl heterocyclic body represented by the above general formula (ii) for example, it is preferable that X 2 and X 3 are fluorine atoms, and R 1 and R 2 are fluoroalkyl groups having 1 to 6 carbon atoms. Something is preferable.
  • perfluoro- 2,2 - dimethyl- 1,3- Dioxole [PDD] is preferred.
  • the modified monomer is preferably at least one selected from the group consisting of PAVE, PFAE, and the cyclic monomers described above.
  • modified monomer (3) modified monomers having a monomer reactivity ratio of 0.1 to 8 (hereinafter referred to as "modified monomer (3)").
  • modified monomer (3) By allowing the modifying monomer (3) to exist, PTFE particles with a small particle size can be obtained, and an aqueous dispersion with high dispersion stability can be obtained.
  • the monomer reactivity ratio in copolymerization with TFE refers to the rate constant when the growing radical reacts with TFE when the growing radical is less than the repeating unit based on TFE, and the rate constant when the growing radical reacts with the modified monomer. This is the value divided by the rate constant when reacting with The lower this value is, the more reactive the modified monomer is with TFE.
  • the monomer reactivity ratio can be calculated from the Feynman-Ross equation by copolymerizing TFE and a modified monomer and determining the composition of the resulting polymer immediately after initiation.
  • the above copolymerization was carried out in a stainless steel autoclave with an internal volume of 6.0 L using 3600 g of deionized degassed water, 1000 ppm of ammonium perfluorooctanoate relative to the water, and 100 g of paraffin wax, under a pressure of 0.78 MPa. It is carried out at a temperature of 70°C. Add 0.05 g, 0.1 g, 0.2 g, 0.5 g, and 1.0 g of modified monomers to the reactor, add 0.072 g of ammonium persulfate (20 ppm to water), and raise the polymerization pressure to 0.78 MPa. For maintenance, TFE is continuously supplied.
  • the modified monomer (3) having a monomer reactivity ratio of 0.1 to 8 is preferably at least one selected from the group consisting of modified monomers represented by formulas (3a) to (3d).
  • CH 2 CH-Rf 1 (3a) (In the formula, Rf 1 is a perfluoroalkyl group having 1 to 10 carbon atoms.)
  • CF 2 CF-O-Rf 2 (3b) (In the formula, Rf 2 is a perfluoroalkyl group having 1 to 2 carbon atoms.)
  • X 3 and X 4 are F, Cl or a methoxy group, and Y is the formula Y1 or Y2.
  • Z and Z' are F or a fluorinated alkyl group having 1 to 3 carbon atoms.
  • the content of the modifying monomer (3) is preferably in the range of 0.00001 to 1.0% by mass based on PTFE.
  • the lower limit is more preferably 0.0001% by mass, even more preferably 0.001% by mass, even more preferably 0.005% by mass, even more preferably 0.010% by mass, and even more preferably 0.030% by mass.
  • 0.050 wt.% is even more preferred
  • 0.070 wt.% is even more preferred
  • 0.10 wt.% is even more preferred
  • 0.15 wt.% is particularly preferred
  • 0.20 wt.% is most preferred.
  • the upper limit is preferably 0.90% by mass, more preferably 0.50% by mass, even more preferably 0.45% by mass, even more preferably 0.40% by mass, particularly preferably 0.35% by mass, and .30% by weight is most preferred.
  • the above-mentioned modified monomers have low viscosity at high temperatures and excellent mechanical stability at high temperatures. It is preferable to contain at least one selected from the group consisting of ethylene, ethylene, and modified monomers having a functional group and a hydrophilic group that can react with radical polymerization.
  • the modified monomer preferably contains at least one selected from the group consisting of hexafluoropropylene, perfluoro(alkyl vinyl ether), and (perfluoroalkyl)ethylene, and preferably perfluoro(alkyl vinyl ether). More preferred is perfluoro(propyl vinyl ether) (hereinafter also referred to as PPVE).
  • the total amount of the hexafluoropropylene unit, perfluoro(alkyl vinyl ether) unit, and (perfluoroalkyl)ethylene unit is preferably in the range of 0.00001 to 1.0% by mass based on PTFE.
  • the lower limit of the total amount is more preferably 0.0001% by mass, still more preferably 0.001% by mass, even more preferably 0.005% by mass, even more preferably 0.010% by mass, and even more preferably 0.030% by mass.
  • % is even more preferred, 0.050% by mass is even more preferred, 0.070% by mass is even more preferred, 0.10% by mass is even more preferred, 0.15% by mass is particularly preferred, 0.20% by mass is most preferred.
  • the upper limit is preferably 0.90% by mass, more preferably 0.50% by mass, even more preferably 0.45% by mass, even more preferably 0.40% by mass, particularly preferably 0.35% by mass, 0. .30% by weight is most preferred.
  • the total amount of the above units, particularly the amount of perfluoro(alkyl vinyl ether) units is within the above range, the appearance of the resulting coating film can be made even more excellent.
  • modified monomer (4) a modified monomer having a functional group and a hydrophilic group capable of reacting with radical polymerization
  • modified monomer (4) a modified monomer having a functional group and a hydrophilic group capable of reacting with radical polymerization
  • the amount of the modified monomer (4) is preferably an amount exceeding 0.1 ppm of the aqueous medium, more preferably 5 ppm or more, and 10 ppm or more. is even more preferable. If the amount of the modifying monomer (4) is too small, the particle size of the resulting PTFE may become large.
  • the amount of the modifying monomer (4) may be within the above range, but the upper limit can be set to 5000 ppm, for example.
  • a modifying monomer (4) may be added to the system during the reaction in order to improve the stability of the aqueous dispersion during or after the reaction.
  • modified monomer (4) Since the above-mentioned modified monomer (4) is highly water-soluble, even if unreacted modified monomer (4) remains in the aqueous dispersion, it cannot be removed in the concentration step or the coagulation/washing step as described below. It's easy as a compound.
  • the modified monomer (4) is incorporated into the resulting polymer during the polymerization process, but the concentration of the modified monomer (4) itself in the polymerization system is low, and the amount incorporated into the polymer is small, resulting in a decrease in the heat resistance of PTFE. There is no problem with coloring or coloring after firing.
  • the modified monomer (4) has a functional group capable of reacting with radical polymerization and a hydrophilic group.
  • the hydrophilic group in the modified monomer (4) include -NH 2 , -PO 3 M, -OPO 3 M, -SO 3 M, -OSO 3 M, -COOM (in each formula, M is H, metal atom, NR 7 4 , imidazolium which may have a substituent, pyridinium which may have a substituent or phosphonium which may have a substituent, R 7 is H or an organic group; and may be the same or different. Any two may be bonded to each other to form a ring).
  • -SO 3 M and -COOM are preferred.
  • the metal atom is preferably an alkali metal, and examples of the alkali metal include Na, K, and the like.
  • Examples of the "functional group capable of reacting in radical polymerization" in the modified monomer (4) include groups having an unsaturated bond such as a vinyl group and an allyl group.
  • the modified monomer (4) has a functional group that can react in radical polymerization, so when used in the polymerization, it reacts with the fluorine-containing monomer at the initial stage of the polymerization reaction, and the modified monomer (4) has a hydrophilic group derived from the modified monomer (4). It is assumed that particles with high stability are formed. For this reason, it is thought that when polymerization is carried out in the presence of the modified monomer (4), the number of emulsified particles increases.
  • one type of the modified monomer (4) may be present, or two or more types thereof may be present.
  • a compound having an unsaturated bond can be used as the modified monomer (4).
  • hydrophilic groups examples include -NH 2 , -PO 3 M, -OPO 3 M, -SO 3 M, -OSO 3 M, -COOM (in each formula, M is H, a metal atom, NR 7 4 , imidazolium which may have a substituent, pyridinium which may have a substituent or phosphonium which may have a substituent, R 7 is H or an organic group, and may be the same or different. Any two may be bonded to each other to form a ring.).
  • -SO 3 M or -COOM is preferred.
  • R 7 is preferably H or a C 1-10 organic group, more preferably H or a C 1-4 organic group, and even more preferably H or a C 1-4 alkyl group.
  • the metal atoms include monovalent or divalent metal atoms, such as alkali metals (Group 1) and alkaline earth metals (Group 2), with Na, K or Li being preferred.
  • linking group refers to a divalent linking group.
  • the linking group may be a single bond and preferably contains at least one carbon atom, and the number of carbon atoms may be 2 or more, 4 or more, or 8 or more. , may be 10 or more, or may be 20 or more. The upper limit is not limited, but may be, for example, 100 or less, or 50 or less.
  • the linking group may be a chain or branched, cyclic or acyclic structure, saturated or unsaturated, substituted or unsubstituted, and optionally contains one or more members selected from the group consisting of sulfur, oxygen, and nitrogen.
  • the linking group does not contain a carbon atom and may be a catenary heteroatom such as oxygen, sulfur or nitrogen.
  • R a is preferably a catenary heteroatom such as oxygen, sulfur, or nitrogen, or a divalent organic group.
  • R a is a divalent organic group
  • the hydrogen atom bonded to the carbon atom may be replaced with a halogen other than fluorine, such as chlorine, and may or may not contain a double bond.
  • R a may be either chain or branched, and may be cyclic or acyclic.
  • R a may include a functional group (eg, ester, ether, ketone, amine, halide, etc.).
  • R a may also be a non-fluorine divalent organic group or a partially fluorinated or perfluorinated divalent organic group.
  • the modified monomer (4) is preferably at least one selected from the group consisting of compounds represented by the following formulas (4a) to (4e).
  • CF 2 CF-(CF 2 ) n1 -Y 3 (4a)
  • n1 represents an integer from 1 to 10
  • Y 3 represents -SO 3 M 1 or -COOM 1
  • M 1 represents H, NH 4 or an alkali metal.
  • CF 2 CF-(CF 2 C(CF 3 )F) n2 -Y 3 (4b)
  • n2 represents an integer from 1 to 5, and Y3 is the same as defined above.
  • CF 2 CF-O-(CFX 1 ) n3 -Y 3 (4c)
  • X 1 represents F or CF 3
  • n3 represents an integer from 1 to 10
  • Y 3 is the same as defined above.
  • CF 2 CF-O-(CF 2 CFX 1 O) n4 -CF 2 CF 2 -Y 3 (4d) (
  • the above n1 is preferably an integer of 5 or less, more preferably an integer of 2 or less.
  • the above Y 3 is preferably -COOM 1 because it can obtain appropriate water solubility and surface activity, and M 1 is preferably -COOM 1 because it does not easily remain as an impurity and improves the heat resistance of the obtained molded product.
  • M 1 is preferably -COOM 1 because it does not easily remain as an impurity and improves the heat resistance of the obtained molded product.
  • it is H or NH4 .
  • the above n2 is preferably an integer of 3 or less in terms of emulsifying ability, and Y3 is -COOM 1 in terms of obtaining appropriate water solubility and surface activity.
  • M 1 is preferably H or NH 4 because it is less likely to remain as an impurity and the heat resistance of the obtained molded product is improved.
  • the above n3 is preferably an integer of 5 or less from the viewpoint of water solubility, and the above Y 3 is -COOM 1 , from the viewpoint of obtaining appropriate water solubility and surface activity.
  • the above M 1 is preferably H or NH 4 from the viewpoint of improving dispersion stability.
  • the above X 1 is preferably -CF 3 from the viewpoint of surfactant ability
  • the above n4 is preferably an integer of 5 or less from the viewpoint of water solubility
  • the above Y 3 is preferably -COOM 1 from the viewpoint of obtaining appropriate water solubility and surface activity
  • the above M 1 is preferably H or NH 4 .
  • CF 2 CFOCF 2 CF (CF 3 )OCF 2 CF 2 COOM 1 (wherein, M 1 represents H, NH 4 or an alkali metal).
  • the above n5 is preferably 0 or an integer from 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1.
  • the above Y 3 is preferably -COOM 1 because it provides appropriate water solubility and surface activity
  • the above M 1 is preferably -COOM 1 because it does not easily remain as an impurity and improves the heat resistance of the obtained molded product. , H or NH4 .
  • the PTFE preferably has a core-shell structure. Thereby, clogging of the coating gun and white spots on the coating film can be further suppressed, and stirring stability can be further improved.
  • fluoropolymers having a core-shell structure include modified PTFE, which includes a core of high molecular weight PTFE and a lower molecular weight PTFE or modified PTFE shell in the particles. Examples of such modified PTFE include PTFE described in Japanese Patent Publication No. 2005-527652.
  • the core-shell structure may have the following structure.
  • Core TFE homopolymer Shell: TFE homopolymer Core: Modified PTFE Shell: TFE homopolymer Core: Modified PTFE Shell: Modified PTFE Core: TFE homopolymer Shell: Modified PTFE
  • Each of the above structures can take on high and low molecular weight embodiments.
  • the structure of a high molecular weight TFE homopolymer core and a low molecular weight TFE homopolymer shell the structure of a high molecular weight modified PTFE core and a low molecular weight TFE homopolymer shell, and the structure of a high molecular weight modified PTFE core and a low molecular weight TFE homopolymer shell;
  • the PTFE preferably has a core-shell structure having a shell of low molecular weight PTFE, and particularly preferably has a core-shell structure having a core of modified PTFE and a shell of low molecular weight PTFE.
  • the shell can be made of low molecular weight PTFE by polymerizing a monomer composition containing TFE in the presence of a chain transfer agent.
  • the above monomer composition containing TFE may contain only TFE, or may contain TFE and a modified monomer.
  • the modified monomer of the modified PTFE constituting the core is preferably at least one selected from the group consisting of PAVE, PFAE, and the above-mentioned cyclic monomer.
  • PAVE include PPVE, PEVE, PMVE, etc., with PPVE being preferred.
  • PFAE include PFBE and (perfluorohexyl)ethylene, with PFBE being preferred.
  • cyclic monomer include vinyl heterocycles represented by the above-mentioned general formula (ii), and perfluoro-2,2-dimethyl-1,3-dioxole [PDD] is preferred.
  • the content of polymerized units based on the modifying monomer is preferably in the range of 0.00001 to 1.0% by mass based on the PTFE.
  • the lower limit is more preferably 0.0001% by mass, even more preferably 0.001% by mass, even more preferably 0.005% by mass, even more preferably 0.010% by mass, and even more preferably 0.030% by mass.
  • 0.050 wt.% is even more preferred
  • 0.070 wt.% is even more preferred
  • 0.10 wt.% is even more preferred
  • 0.15 wt.% is particularly preferred
  • 0.20 wt.% is most preferred.
  • the upper limit is preferably 0.90% by mass, more preferably 0.50% by mass, even more preferably 0.45% by mass, even more preferably 0.40% by mass, particularly preferably 0.35% by mass, and .30% by weight is most preferred.
  • the low molecular weight PTFE in the shell can be obtained by polymerizing a monomer composition containing TFE in the presence of a chain transfer agent.
  • the chain transfer agent is not particularly limited as long as it reduces the molecular weight of PTFE constituting the shell, and examples thereof include non-peroxide organic compounds such as water-soluble alcohols, hydrocarbons, and fluorinated hydrocarbons; Examples include water-soluble organic peroxides such as oxide [DSP]; persulfates such as ammonium persulfate [APS] and potassium persulfate [KPS].
  • each of the non-peroxide organic compound, the water-soluble organic peroxide and the persulfate can be used singly or in combination of two or more.
  • water-soluble alcohols having 1 to 4 carbon atoms, hydrocarbons having 1 to 4 carbon atoms, and hydrocarbons having 1 to 4 carbon atoms are used, since they have good dispersibility and uniformity in the reaction system.
  • it consists of at least one selected from the group consisting of fluorinated hydrocarbons, and more preferably, it consists of at least one selected from the group consisting of methane, ethane, n-butane, isobutane, methanol, and isopropanol. More preferably, it is at least one selected from the group consisting of methanol and isobutane.
  • the above polymerization is usually carried out in an aqueous medium.
  • the amount of the chain transfer agent is preferably 0.001 to 10,000 ppm based on the aqueous medium.
  • the amount of the chain transfer agent is more preferably 0.01 ppm or more, even more preferably 0.05 ppm or more, particularly preferably 0.1 ppm or more based on the aqueous medium. Further, the amount is more preferably 1000 ppm or less, even more preferably 750 ppm or less, and particularly preferably 500 ppm or less relative to the aqueous medium.
  • the upper limit of the core ratio is preferably 99.5% by mass, more preferably 99.0% by mass, even more preferably 98.0% by mass, and even more preferably 97.0% by mass. , particularly preferably 95.0% by weight, most preferably 90.0% by weight.
  • the lower limit of the shell ratio is preferably 0.5% by mass, more preferably 1.0% by mass, even more preferably 2.0% by mass, and even more preferably 3.0% by mass. , particularly preferably 5.0% by weight, most preferably 10.0% by weight.
  • the core or the shell may have a structure of two or more layers.
  • it may have a three-layer structure including a core center portion of modified PTFE, a core outer layer portion of TFE homopolymer, and a shell of low molecular weight PTFE.
  • the extrusion pressure of the above core-shell structure PTFE at a reduction ratio of 1500 is preferably 80 MPa or less, more preferably 70 MPa or less, and even more preferably 60 MPa or less.
  • An extrusion pressure within the above range at a reduction ratio of 1500 can be achieved in the manufacturing method described below.
  • the above-mentioned "extrusion pressure at a reduction ratio of 1500" is measured according to the following procedure.
  • the aqueous PTFE dispersion is coagulated with methanol, and the resulting wet PTFE powder is further subjected to Soxhlet extraction with methanol to remove additives containing nonionic surfactants.
  • the removed wet PTFE powder is dried at 150° C. for 18 hours to obtain PTFE powder.
  • the PTFE aqueous dispersion after polymerization that is, before adding the nonionic surfactant, is diluted with deionized water so that the PTFE concentration is 10 to 15% by mass, and then mechanical shearing is applied to form the wet PTFE. Get the powder.
  • This wet PTFE powder is dried at 150°C for 18 hours to obtain a PTFE powder.
  • 20.5 parts by mass (12.3 g) of hydrocarbon oil (trade name: Isopar G, manufactured by Exxon Chemical Co., Ltd.) was added as an extrusion aid, and the mixture was heated at room temperature (25 g).
  • the paste was extruded using an extrusion die with a cylinder having an inner diameter of 25.4 mm (reduction ratio: 1500).
  • the value obtained by dividing the pressure at a portion where the pressure reaches an equilibrium state by the cross-sectional area of the cylinder is defined as the extrusion pressure at a reduction ratio of 1500.
  • the average primary particle diameter of the PTFE is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 350 nm or less.
  • the lower limit of the average primary particle diameter is not particularly limited, it may be, for example, 100 nm.
  • From the viewpoint of molecular weight for example, in the case of high molecular weight PTFE, it is preferably 150 nm or more, and more preferably 200 nm or more.
  • the above average primary particle diameter was determined by measuring the transmittance of 550 nm projected light with respect to the unit length of an aqueous dispersion with a resin solid concentration adjusted to 0.15% by mass, and the diameter in a certain direction in a transmission electron micrograph. It is determined from the above transmittance based on a calibration curve between the determined number standard length and average primary particle diameter.
  • the content of PTFE particles having an aspect ratio of 5 or more is preferably less than 1.5% by mass based on the total content of PTFE particles.
  • the above aspect ratio was determined by observing a PTFE aqueous dispersion diluted to a solid content concentration of approximately 1% by mass using a scanning electron microscope (SEM), and performing image processing on more than 200 randomly selected particles. It is determined from the average ratio of its major axis and minor axis.
  • the standard specific gravity (SSG) of the PTFE is preferably 2.220 or less, more preferably 2.190 or less. Further, it is preferably 2.140 or more, and more preferably 2.150 or more.
  • the above SSG is measured by a water displacement method according to ASTM D-792 using a sample molded according to ASTM D 4895-89.
  • the PTFE typically has extensibility, fibrillation properties, and non-melt fabrication properties.
  • the above-mentioned non-melting secondary processability means the property that the melt flow rate cannot be measured at a temperature higher than the crystallization melting point, that is, the property that it does not flow easily even in the melting temperature range, in accordance with ASTM D-1238 and D-2116. do.
  • melt-processable fluororesin examples include tetrafluoroethylene (TFE)/perfluoro(alkyl vinyl ether) (PAVE) copolymer (PFA), TFE/perfluoroallyl ether (PFAE) copolymer, and TFE/hexafluoropropylene.
  • HFP copolymer FEP
  • Et ethylene
  • TFE Et/TFE copolymer
  • PCTFE polychlorotrifluoroethylene
  • CFE chlorotrifluoroethylene
  • VDF polyvinylidene fluoride
  • melt processability means that the polymer can be melted and processed using conventional processing equipment such as extruders and injection molding machines. Therefore, the melt-processable fluororesin usually has a melt flow rate (MFR) of 0.01 to 100 g/10 minutes.
  • the above MFR is defined as the measurement temperature determined by the type of fluoropolymer (for example, 372°C in the case of PFA or FEP) using a melt indexer (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) in accordance with ASTM D 1238. as the mass (g/10 min) of polymer flowing out per 10 minutes from a nozzle with an inner diameter of 2 mm and a length of 8 mm at a load (e.g. 5 kg for PFA, FEP and ETFE) at 297 °C for ETFE). This is the value obtained.
  • a melt indexer manufactured by Yasuda Seiki Seisakusho Co., Ltd.
  • the melt-processable fluororesin preferably has a melting point of 100 to 333°C, more preferably 140°C or higher, even more preferably 160°C or higher, particularly preferably 180°C or higher, More preferably, the temperature is 332°C or lower.
  • the melting point of the melt-processable fluororesin is a temperature corresponding to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10° C./min using a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the melt-processable fluororesin is preferably at least one selected from the group consisting of PFA and FEP, and more preferably FEP.
  • the above-mentioned PFA is not particularly limited, but a copolymer having a molar ratio of TFE units to PAVE units (TFE units/PAVE units) of 70/30 or more and less than 99/1 is preferable.
  • a more preferable molar ratio is 70/30 or more and 98.9/1.1 or less, and an even more preferable molar ratio is 80/20 or more and 98.9/1.1 or less. If the TFE unit is too small, mechanical properties tend to deteriorate, while if it is too large, the melting point becomes too high and moldability tends to deteriorate.
  • the above PFA has 0.1 to 10 mol% of monomer units derived from monomers copolymerizable with TFE and PAVE, and 90 to 99.9 mol% of TFE units and PAVE units in total.
  • a copolymer is also preferred.
  • Examples include alkyl perfluorovinyl ether derivatives represented by 2 -Rf 7 (wherein Rf 7 represents a perfluoroalkyl group having 1 to 5 carbon atoms).
  • the above PFA preferably has a melting point of 180°C or more and less than 322°C, more preferably 230 to 320°C, and even more preferably 280 to 320°C.
  • the PFA preferably has a melt flow rate (MFR) of 1 to 100 g/10 minutes.
  • the PFA has a thermal decomposition initiation temperature of 380° C. or higher.
  • the thermal decomposition start temperature is more preferably 400°C or higher, and even more preferably 410°C or higher.
  • the thermal decomposition start temperature is determined using a differential thermal/thermogravimetric analyzer [TG-DTA] (product name: TG/DTA6200, manufactured by Seiko Electronics Co., Ltd.) and measuring 10 mg of a sample at a heating rate of 10°C/min. This is the temperature at which the sample decreases by 1% by mass when the temperature is increased from room temperature.
  • TG-DTA differential thermal/thermogravimetric analyzer
  • the above-mentioned FEP is not particularly limited, but a copolymer having a molar ratio of TFE units to HFP units (TFE units/HFP units) of 70/30 or more and less than 99/1 is preferable.
  • a more preferable molar ratio is 70/30 or more and 98.9/1.1 or less, and an even more preferable molar ratio is 80/20 or more and 98.9/1.1 or less. If the TFE unit is too small, mechanical properties tend to deteriorate, while if it is too large, the melting point becomes too high and moldability tends to deteriorate.
  • the above FEP has 0.1 to 10 mol% of monomer units derived from monomers copolymerizable with TFE and HFP, and 90 to 99.9 mol% of TFE units and HFP units in total.
  • a copolymer is also preferred.
  • monomers copolymerizable with TFE and HFP include PAVE, alkyl perfluorovinyl ether derivatives, and the like.
  • the above FEP preferably has a melting point of 150°C or more and less than 322°C, more preferably 200 to 320°C, and even more preferably 240 to 320°C.
  • the above FEP preferably has an MFR of 1 to 100 g/10 minutes.
  • the FEP preferably has a thermal decomposition initiation temperature of 360° C. or higher.
  • the thermal decomposition start temperature is more preferably 380°C or higher, and even more preferably 390°C or higher.
  • the content of each monomer unit in the melt-processable fluororesin can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.
  • the fluorine-containing ethylenic polymer preferably contains PTFE, and may contain PTFE and optionally a melt-processable fluororesin.
  • the melt-processable fluororesin is preferably at least one selected from the group consisting of PFA and FEP.
  • PTFE tends to fiberize and agglomerate due to friction with highly hard fillers, which tends to cause clogging of the paint gun and white spots on the paint film during painting, but the coating composition of the present disclosure, when containing PTFE, However, clogging of the paint gun and white spots on the paint film are less likely to occur.
  • the content of PTFE is preferably 50% by mass or more, more preferably 60% by mass or more, based on the fluorine-containing ethylenic polymer, It is more preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more.
  • the content of the fluorine-containing ethylenic polymer is 1 to 50% by mass based on the coating composition.
  • the content is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and even more preferably 20% by mass or more based on the coating composition. It is particularly preferred that the content is 49% by mass or less, and more preferably 45% by mass or less.
  • the coating composition of the present disclosure includes (i) a filler having a new Mohs hardness of 9 or more, which is 0.1 to 80% by mass based on the fluorine-containing ethylenic polymer; (ii) the fluorine-containing ethylenic polymer 0.1 to 120% by mass of a filler having a new Mohs hardness of 5 or more and less than 9 based on the aggregate, and (iii) 1 to 150% by mass of less than 5 based on the fluorine-containing ethylenic polymer. at least one filler selected from the group consisting of fillers having a new Mohs hardness of .
  • the coating composition of the present disclosure contains the filler described above, clogging of the coating gun and white spots on the coating film are less likely to occur.
  • the coating composition of the present disclosure preferably contains at least one selected from the group consisting of the filler (i) and the filler (ii).
  • the filler (i) has a new Mohs hardness of 9 or more.
  • the new Mohs hardness of the filler (i) is preferably 10 or more, more preferably 11 or more, and even more preferably 12 or more.
  • Examples of the filler (i) include diamond, fluorinated diamond, corundum, boron nitride, boron carbide, silicon carbide, chrysoberyl, topaz, garnet, fused zirconia, tantalum carbide, titanium carbide, alumina, tungsten carbide, zirconium carbide, etc.
  • One type or two or more types can be used. Among these, at least one selected from the group consisting of silicon carbide, diamond, and alumina is preferred, and silicon carbide is more preferred. Note that even fillers of the same type (name) may have different new Mohs hardnesses due to differences in crystal structure and other factors.
  • the filler exemplified as the filler (i) has a new Mohs hardness of 9 or more and is of the type described above.
  • the coating composition of the present disclosure contains the filler (i), its content is 0.1 to 80% by mass based on the fluorine-containing ethylenic polymer.
  • the content is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and 70% by mass or more based on the fluorine-containing ethylenic polymer. It is preferably at most 60% by mass, more preferably at most 50% by mass.
  • the filler (ii) has a new Mohs hardness of 5 or more and less than 9.
  • the filler (ii) include iron oxide, ultramarine blue, titanium oxide, jade, germanium, silica, silica, quartz, beryl, tourmaline, etc., and one or more of them can be used. Among these, at least one selected from the group consisting of titanium oxide and iron oxide is preferred, and titanium oxide is more preferred.
  • the filler exemplified as the filler (ii) has a new Mohs hardness of 5 or more and less than 9, and is of the type described above.
  • the coating composition of the present disclosure contains the filler (ii), its content is 0.1 to 120% by mass based on the fluorine-containing ethylenic polymer.
  • the content is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and 8% by mass based on the fluorine-containing ethylenic polymer. It is even more preferable that the amount is above, particularly preferably 10% by weight or more, further preferably 100% by weight or less, more preferably 90% by weight or less, and 80% by weight or less. It is still more preferably 70% by mass or less, even more preferably 60% by mass or less, and most preferably 50% by mass or less.
  • the filler (iii) has a new Mohs hardness of less than 5.
  • the new Mohs hardness of the filler (iii) may be 1 or more, preferably 2 or more, and more preferably 3 or more.
  • Examples of the filler (iii) include clay, talc, mica, barium sulfate, etc., and one type or two or more types can be used. Among these, at least one selected from the group consisting of barium sulfate and talc is preferred, and barium sulfate is more preferred.
  • the filler exemplified as the filler (iii) has a new Mohs hardness of less than 5 and is of the type described above.
  • the coating composition of the present disclosure contains the filler (iii), its content is 1 to 150% by mass based on the fluorine-containing ethylenic polymer.
  • the content is preferably 2% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and 8% by mass based on the fluorine-containing ethylenic polymer. It is even more preferably at least 10% by mass, even more preferably at least 12% by mass, most preferably at least 15% by mass, and at most 130% by mass. It is preferably at most 110% by mass, more preferably at most 90% by mass, even more preferably at most 80% by mass, even more preferably at most 70% by mass. , is particularly preferably 60% by mass or less, and most preferably 50% by mass or less.
  • the coating composition of the present disclosure includes water.
  • the coating composition of the present disclosure may be a water-based coating composition.
  • the coating composition of the present disclosure preferably has particles of the fluorine-containing ethylenic polymer and the filler dispersed in water.
  • the coating composition of the present disclosure may contain, in addition to water, an organic solvent such as a fluorine-free organic solvent such as alcohol, ether, or ketone, or a fluorine-containing organic solvent having a boiling point of 40° C. or less.
  • an organic solvent such as a fluorine-free organic solvent such as alcohol, ether, or ketone, or a fluorine-containing organic solvent having a boiling point of 40° C. or less.
  • water is preferably 90% by mass or more, more preferably 95% by mass or more, based on the total amount of water and organic solvent.
  • the coating composition of the present disclosure further includes a nonionic surfactant.
  • a nonionic surfactant e.g., sodium bicarbonate
  • the nonionic surfactant is preferably a nonionic surfactant that does not contain fluorine.
  • R 3 is a linear or branched primary or secondary alkyl group having 8 to 18 carbon atoms, and A 1 is a polyoxyalkylene chain.
  • the number of carbon atoms in R 3 is preferably 8 to 16, more preferably 10 to 14.
  • affinity with the fluorine-containing ethylenic polymer in the coating composition is high, and excellent mechanical stability can be achieved. Further, clogging of the coating gun and white spots on the coating film can be further suppressed, and stirring stability can be further improved.
  • R 3 is represented by the following general formula (i-1) CHR 31 R 32 - (i-1) (In the formula, R 31 represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, R 32 represents an alkyl group having 1 to 17 carbon atoms, and the total number of carbon atoms of R 31 and R 32 is 7 to 17 ) is preferably an alkyl group represented by the following.
  • the above R 31 is more preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, even more preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and even more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. preferable.
  • R 32 is more preferably an alkyl group having 1 to 15 carbon atoms, even more preferably an alkyl group having 1 to 14 carbon atoms, and even more preferably an alkyl group having 1 to 13 carbon atoms.
  • the above R 3 is preferably an alkyl group having 8 to 18 carbon atoms and having an average number of methyl groups of 2.0 or more.
  • the average number of methyl groups in R 3 is more preferably 2.5 or more, still more preferably 3.0 or more, even more preferably 3.5 or more, and particularly preferably 4.0 or more.
  • the average number of methyl groups in R 3 is also preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less.
  • the above R3 has an average number of methyl groups per molecule of 4.0 in that it can further suppress clogging of the paint gun and white spots on the paint film, and further improve stirring stability. It is preferably at least 4.3, even more preferably at least 4.7, and most preferably at least 5.0.
  • the above R3 is preferably a trimethylnonyl group, and particularly preferably 2 ,6,8-trimethyl-4-nonyl group.
  • the average number of methyl groups is a value determined by adding methanol to a sample, performing Soxhlet extraction, and then measuring the extract using 1 H-NMR.
  • nonionic surfactants examples include the Neugen TDS series, including Genapol (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Reocol TD series (manufactured by Lion Corporation) including Reocol TD-90 (trade name), Lionol (registered trademark) TD series (manufactured by Lion Corporation), T-Det A138 (trade name) ), T-Det A series (manufactured by Harcros Chemicals), Tergitol (registered trademark) 15S series (manufactured by Dow Corporation), and Dispanol TOC (trade name, manufactured by NOF Corporation).
  • Genapol manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
  • Reocol TD series manufactured by Lion Corporation
  • Reocol TD-90 trade name
  • Lionol registered trademark
  • T-Det A138 trade name
  • T-Det A series manufactured by Harcros Chemicals
  • Tergitol registered trademark
  • the nonionic surfactant may be a mixture of two different types of nonionic surfactants, and is a mixture of compounds represented by formula (i) having different average numbers of oxyethylene units in A1 . is preferred.
  • a 1 of the above general formula (i) is a polyoxyalkylene chain having an average number of oxyethylene units of 10.0 to 12.0.
  • a compound in which the average number of oxyethylene units of A 1 in the above general formula (i) is 7.0 or more and less than 10.0
  • a compound in which the average number of oxyethylene units in A 1 in the above general formula (i) is 7.0 or more and less than 10.0
  • It may also be a mixture with a compound having a polyoxyalkylene chain of 10.0 or more and 12.0 or less.
  • nonionic surfactant examples include poly(oxyethylene) 2,6,8-trimethyl-4-nonyl ether having an average number of oxyethylene units of 4.0 to 18.0; More preferably, it is poly(oxyethylene) 2,6,8-trimethyl-4-nonyl ether having a molecular weight of 0 to 12.0, or a mixture thereof.
  • Nonionic surfactants of this type are also commercially available, for example, as TERGITOL TMN-6, TERGITOL TMN-10, and TERGITOL TMN-100X (all product names manufactured by The Dow Chemical Company).
  • the average number of oxyalkylene units of A 1 in the above formula (i) is preferably 5.0 to 20.0, more preferably 7.0 to 15.0, and still more preferably 8.0 to 15.0. It is preferably 8.0 to 12.0, even more preferably 10.0 to 12.0.
  • the average number of oxyethylene units is preferably 7.0 or more, more preferably 8.0 or more, even more preferably 10.1 or more, and even more preferably 10.2 or more. preferably 14.0 or less, more preferably 13.0 or less, even more preferably 12.0 or less, even more preferably 10.8 or less, even more preferably 10.7 or less, particularly preferably 10.6 or less , 10.5 or less is most preferable.
  • the average number of oxyalkylene units is a value determined by adding methanol to a sample, performing Soxhlet extraction, and then measuring the extract by 1 H-NMR.
  • a 1 in the above formula (i) may consist of an oxyethylene unit and an oxypropylene unit.
  • it may be a polyoxyalkylene chain having an average number of oxyethylene units of 5.0 to 20.0 and an average number of oxypropylene units of 0.0 to 2.0.
  • the number of oxyethylene units can include either the broad or narrow unimodal distribution normally provided, or the broader or bimodal distribution obtained by blending.
  • the average number of oxypropylene units is more than 0.0, the oxyethylene units and oxypropylene units in the polyoxyalkylene chain may be arranged in blocks or randomly.
  • polyoxyalkylene chains composed of an average number of oxyethylene units of 7.0 to 12.0 and an average number of oxypropylene units of 0.0 to 2.0 are preferred.
  • a 1 has an average number of propylene units of 0.5 to 1.5 since low foaming properties are good.
  • the nonionic surfactant preferably has an HLB of 13.00 or more, more preferably 13.20 or more, even more preferably 14.00 or more, and 14.05 or more. is even more preferable, and particularly preferably 14.10 or more. Further, it is preferably 15.00 or less, more preferably 14.90 or less, and particularly preferably 14.80 or less.
  • HLB 20 (1-S/N)/5 (wherein, S is the saponification value of the ester; N is the neutralization value of the fatty acid constituting the ester) value)].
  • S is the saponification value of the ester
  • N is the neutralization value of the fatty acid constituting the ester) value
  • the coating composition of the present disclosure uses a nonionic surfactant with an HLB of 13.00 or more and less than 14.10, and a nonionic surfactant with an HLB of 14.10 or more. 15.00 or less of a nonionic surfactant.
  • the coating composition of the present disclosure includes a nonionic surfactant with an HLB of 13.00 or more and less than 13.50, and a nonionic surfactant with an HLB of 13.50 or more and 15.00 or less (preferably 14.50 or less, more 14.00 or less).
  • the cloud point of a nonionic surfactant is a measure of the surfactant's solubility in water.
  • the surfactant used in the coating composition of the present disclosure has a cloud point of 30-90°C, preferably 35-85°C, more preferably 40-80°C, even more preferably 45-75°C.
  • the coating composition of the present disclosure preferably contains a nonionic surfactant with a cloud point of 30°C or more and 60°C or less, and a nonionic surfactant with a cloud point of more than 60°C and 90°C or less. , a nonionic surfactant having a cloud point of 35 to 60°C, and a nonionic surfactant having a cloud point of 65 to 80°C.
  • Mechanical stability can be improved by using nonionic surfactants with high cloud points.
  • the coating composition of the present disclosure may include a nonionic surfactant with a cloud point of 30°C or more and 60°C or less, and a nonionic surfactant with a cloud point of more than 60°C and 90°C or less. is preferred, and more preferably contains a nonionic surfactant with a cloud point of 35 to 60°C and a nonionic surfactant with a cloud point of 65 to 80°C.
  • the nonionic surfactant preferably has an HLB of 14.05 to 14.35 and an average number of oxyalkylene units of 10.2 to 10.9. More specifically, in the nonionic surfactant, R 3 in formula (i) is a 2,6,8-trimethyl-4-nonyl group, and A 1 has an average number of oxyethylene units of 7.0. ⁇ 9.0 polyoxyethylene chain (first component), R 3 in formula (i) is a 2,6,8-trimethyl-4-nonyl group, and A 1 is the average number of oxyethylene units.
  • the nonionic surfactant preferably contains the first component at 10% by mass or more, more preferably 15% by mass or less, and more preferably contains the second component at 85% by mass or more, 90% by mass. It is more preferable to include the following.
  • the nonionic surfactant has an HLB of 13.00 to 13.50 and an average number of oxyalkylene units of 7.0 to 12.0. More specifically, the nonionic surfactant is a compound (first component) in which A 1 in formula (i) is a polyoxyethylene chain having an average number of oxyethylene units of 7.0 to 9.5. , a mixture with a compound (second component) in which A 1 of formula (i) is a polyoxyethylene chain having an average number of oxyethylene units of 10.0 to 12.0, and the first component is 40% by mass or more and 70% by mass % or less, preferably the second component is 30% by mass or more and 60% by mass or less.
  • the nonionic surfactant preferably contains the first component at 45% by mass or more, more preferably 65% by mass or less, and more preferably contains the second component at 35% by mass or more, 55% by mass. It is more preferable to include the following.
  • the content of the nonionic surfactant is preferably 4% by mass or more, more preferably 4.5% by mass or more, even more preferably 5% by mass or more, based on the fluorine-containing ethylenic polymer. It is even more preferably 5.5% by mass or more, preferably 12% by mass or less, more preferably 10% by mass or less, even more preferably 8% by mass or less, and particularly preferably 7% by mass or less. If the amount of nonionic surfactant is too large, the viscosity may become too high, and if it is too small, the storage stability and mechanical stability may become low.
  • the content of the fluorine-containing surfactant in the coating composition is preferably 1000 mass ppb or less.
  • the coating composition of the present disclosure does not substantially contain a fluorine-containing surfactant, it can further suppress clogging of a coating gun and white spots on a coating film, and further improve stirring stability. be able to.
  • the viscosity at high temperatures can be lowered and mechanical stability at high temperatures can be improved.
  • the content of the fluorine-containing surfactant is preferably 700 mass ppb or less, more preferably 600 mass ppb or less, and still more preferably 500 mass ppb or less.
  • the content of the fluorine-containing surfactant may be greater than or equal to the lower detection limit, may be greater than or equal to the lower limit of quantification, and may be greater than or equal to 100 mass ppb.
  • the content of the fluorine-containing surfactant is a value measured using liquid chromatography mass spectrometry, as described in the Examples below. Specifically, it can be measured by the following method. [Method for measuring the content of fluorine-containing surfactant] The solid content of the aqueous dispersion is measured, and an amount of the aqueous dispersion corresponding to 1.5 g of PTFE solid content is weighed into a 100 mL screw tube.
  • a nonionic surfactant is added to the aqueous dispersion of the fluorine-containing ethylenic polymer after polymerization.
  • the amount of the fluorine-containing surfactant can be controlled within the above range by, for example, concentration.
  • fluorine-containing surfactant examples include fluorine-containing anionic surfactants.
  • the fluorine-containing anionic surfactant may be, for example, a surfactant containing a fluorine atom having a total carbon number of 20 or less in the portion of the general formula (N 0 ) below excluding the anionic group Y 0 .
  • the fluorine-containing surfactant may also be a fluorine-containing surfactant whose anion moiety has a molecular weight of 1000 or less.
  • anion moiety means the moiety of the above-mentioned fluorine-containing surfactant excluding the cation.
  • F(CF 2 ) n1 COOM expressed by formula (I) described later, it is the part "F(CF 2 ) n1 COO”.
  • the fluorine-containing surfactant mentioned above also includes a fluorine-containing surfactant having a LogPOW of 3.5 or less, preferably 3.4 or less.
  • the above LogPOW is the partition coefficient between 1-octanol and water, and the LogP [where P is in octanol when the octanol/water (1:1) mixture containing a fluorine-containing surfactant undergoes phase separation. is represented by the ratio of fluorine-containing surfactant concentration/fluorine-containing surfactant concentration in water].
  • fluorine-containing 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, and U.S. Patent Application Publication No. 2007/0015866, Published Application No. 2007/0276103, US Patent Application No. 2007/0117914, US Patent Application No. 2007/142541, US Patent Application No. 2008/0015319, US Patent No. 3250808 specification, US Patent No. 3271341, JP 2003-119204, WO 2005/042593, WO 2008/060461, WO 2007/046377, WO 2007/119526 No., International Publication No. 2007/046482, International Publication No. 2007/046345, US Patent Application Publication No. 2014/0228531, International Publication No. 2013/189824, International Publication No. 2013/189826, etc. Can be mentioned.
  • the fluorine-containing anionic surfactant has the following general formula (N 0 ): X n0 - Rf n0 - Y 0 (N 0 ) (In the formula, X n0 is H, Cl , or is an alkylene group, the alkylene group may contain one or more ether bonds, and some H may be substituted with Cl. Y 0 is an anion group). Can be mentioned.
  • the anionic group of Y 0 may be -COOM, -SO 2 M, or -SO 3 M, and may be -COOM or -SO 3 M.
  • M is H, a metal atom, NR 7 4 , imidazolium which may have a substituent, pyridinium which may have a substituent, or phosphonium which may have a substituent, and R 7 is H or an organic group.
  • the metal atoms include alkali metals (Group 1), alkaline earth metals (Group 2), and examples thereof include Na, K, and Li.
  • R 7 may be H or a C 1-10 organic group, H or a C 1-4 organic group, or H or a C 1-4 alkyl group.
  • M may be H, a metal atom or NR74 , and may be H, an alkali metal (group 1), an alkaline earth metal (group 2) or NR74 , H , Na, K, Li or It may be NH4 .
  • Rf n0 50% or more of H may be substituted with fluorine.
  • N 1a X n0 - (CF 2 ) m1 - Y 0 (N 1a )
  • X n0 is H, Cl and F
  • m1 is an integer from 3 to 15, and Y 0 is as defined above.
  • Rf n1 is a perfluoroalkyl group having 1 to 5 carbon atoms
  • m2 is an integer of 0 to 3
  • X n1 is F or CF 3
  • Y 0 is as defined above.
  • N 3 a compound represented by the following general formula (N 3 ): Rf n2 - (CH 2 ) m3 - (Rf n3 ) q - Y 0 (N 3 )
  • Rf n2 is a partially or fully fluorinated alkyl group having 1 to 13 carbon atoms and may contain an ether bond
  • m3 is an integer of 1 to 3
  • Rf n3 is a linear or a branched perfluoroalkylene group having 1 to 3 carbon atoms
  • q 0 or 1
  • Y 0 is as defined above
  • N 4 a compound represented by the following general formula (N 4 ) : Rf m4 -OL 4 -Y 0 (N 4 )
  • Rf m4 is a linear or branched moiety or a fully fluorinated aliphatic group that may contain an ether linkage and/or chlorine
  • L4 is a partially or fully fluorinated Represents a
  • Rf n5 is a linear or branched moiety having 1 to 3 carbon atoms that may contain an ether bond or a fully fluorinated alkylene group, and L is a linking group.
  • Y 0 are as defined above. However, the total carbon number of X n2 , X n3 , X n4 and Rf n5 is 18 or less.
  • the compound represented by the above general formula (N 0 ) includes perfluorocarboxylic acid (I) represented by the following general formula (I), ⁇ -H represented by the following general formula (II) Perfluorocarboxylic acid (II), perfluoropolyether carboxylic acid (III) represented by the following general formula (III), perfluoroalkylalkylene carboxylic acid (IV) represented by the following general formula (IV), the following general Perfluoroalkoxyfluorocarboxylic acid (V) represented by formula (V), perfluoroalkylsulfonic acid (VI) represented by the following general formula (VI), ⁇ -H represented by the following general formula (VII) Perfluorosulfonic acid (VII), perfluoroalkylalkylene sulfonic acid (VIII) represented by the following general formula (VIII), alkylalkylenecarboxylic acid (IX) represented by the following general formula (IX), the following general formula ( Examples include fluoro
  • the above perfluorocarboxylic acid (I) has the following general formula (I) F (CF 2 ) n1 COOM (I) (In the formula, n1 is an integer of 3 to 14, M is H, a metal atom, NR 7 4 , imidazolium which may have a substituent, pyridinium which may have a substituent, or It is a phosphonium which may have a substituent, and R 7 is H or an organic group.
  • ⁇ -H perfluorocarboxylic acid has the following general formula (II) H(CF 2 ) n2 COOM (II) (In the formula, n2 is an integer from 4 to 15, and M is as defined above.)
  • the above perfluoropolyether carboxylic acid (III) has the following general formula (III) Rf 1 -O-(CF(CF 3 )CF 2 O) n3 CF(CF 3 )COOM (III) (In the formula, Rf 1 is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer of 0 to 3, and M is as defined above.) .
  • the perfluoropolyether carboxylic acid (III) is preferably a perfluoropolyether carboxylic acid having a total carbon number of 7 or less and a LogPOW of 3.5 or less. The total number of carbon atoms is particularly preferably 5 to 7. Further, the above LogPOW is more preferably 3.4 or less.
  • the above perfluoroalkylalkylenecarboxylic acid (IV) has the following general formula (IV) Rf 2 (CH 2 ) n4 Rf 3 COOM (IV) (In the formula, 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, and n4 is a perfluoroalkyl group having 1 to 3 carbon atoms. is an integer, and M is defined above.).
  • the above alkoxyfluorocarboxylic acid (V) has the following general formula (V) Rf 4 -O-CY 1 Y 2 CF 2 -COOM (V) (In the formula, Rf 4 is a linear or branched moiety or a fully fluorinated alkyl group that may contain an ether bond and/or chlorine having 1 to 12 carbon atoms, and Y 1 and Y 2 are , the same or different, are H or F, and M is as defined above.
  • the above perfluoroalkyl sulfonic acid has the following general formula (VI) F(CF 2 ) n5 SO 3 M (VI) (In the formula, n5 is an integer from 3 to 14, and M is as defined above.)
  • ⁇ -H perfluorosulfonic acid has the following general formula (VII) H(CF 2 ) n6 SO 3 M (VII) (In the formula, n6 is an integer from 4 to 14, and M is as defined above.)
  • the above perfluoroalkylalkylene sulfonic acid (VIII) has the following general formula (VIII): Rf5 ( CH2 ) n7SO3M ( VIII) (In the formula, Rf 5 is a perfluoroalkyl group having 1 to 13 carbon atoms, n7 is an integer of 1 to 3, and M is as defined above.) .
  • the above alkyl alkylene carboxylic acid (IX) has the following general formula (IX) Rf 6 (CH 2 ) n8 COOM (IX) (wherein Rf 6 is a linear or branched moiety or a fully fluorinated alkyl group having 1 to 13 carbon atoms that may contain an ether bond, and n8 is an integer of 1 to 3; M is defined above.).
  • the above fluorocarboxylic acid (X) has the following general formula (X) Rf 7 -O-Rf 8 -O-CF 2 -COOM (X) (In the formula, Rf 7 is a linear or branched moiety or a fully fluorinated alkyl group having 1 to 6 carbon atoms that may contain an ether bond and/or chlorine, and Rf 8 is a fully fluorinated alkyl group having 1 to 6 carbon atoms. 1 to 6 linear or branched moieties or fully fluorinated alkyl groups, where M is as defined above.
  • the above alkoxyfluorosulfonic acid (XI) has the following general formula (XI) Rf 9 -O-CY 1 Y 2 CF 2 -SO 3 M (XI) (wherein Rf 9 is a linear or branched alkyl group having 1 to 12 carbon atoms, which may contain an ether bond, and which may contain chlorine, and which is partially or fully fluorinated, and Y 1 and Y2 are the same or different and are H or F, and M is as defined above.
  • the above compound (XII) has the following general formula (XII): (In the formula, X 1 , X 2 and Rf 10 is a perfluoroalkylene group having 1 to 3 carbon atoms, L is a linking group, and Y 0 is an anion group. Y 0 may be -COOM, -SO 2 M, or -SO 3 M, and may be -SO 3 M or COOM, where M is as defined above. Examples of L include a single bond, a moiety containing an ether bond having 1 to 10 carbon atoms, or a fully fluorinated alkylene group.
  • examples of the fluorine-containing anionic surfactant include carboxylic acid surfactants, sulfonic acid surfactants, and the like.
  • the number of carbon atoms of Rf m in the formula (N 1 ) is preferably an integer of 3 to 6.
  • m1 in formula (N 1a ) is preferably an integer of 3 to 6.
  • n1 in general formula (I) is preferably an integer of 3 to 6.
  • the above-mentioned fluorine-containing anionic surfactant is particularly a group consisting of fluorine-containing carboxylic acids and salts thereof having 4 to 9 carbon atoms, preferably 4 to 7 carbon atoms, and which may have ether oxygen and/or chlorine. Compounds selected from are preferred.
  • the number of carbon atoms means the total number of carbon atoms in one molecule. Two or more of the above fluorine-containing anionic surfactants may be used in combination.
  • the above-mentioned fluorine-containing anionic surfactant is preferably a compound selected from the group consisting of fluorine-containing carboxylic acids and salts thereof having 4 to 9 carbon atoms, preferably 4 to 7 carbon atoms, and having etheric oxygen and/or chlorine.
  • the fluorine-containing carboxylic acid having etheric oxygen is a compound having 4 to 9 carbon atoms, preferably 4 to 7 carbon atoms, having etheric oxygen in the middle of the main carbon chain, and having -COOH at the end.
  • the terminal --COOH may form a salt.
  • the number of ether oxygens present in the middle of the main chain is one or more, preferably 1 to 4, and more preferably 1 or 2.
  • the number of carbon atoms is preferably 5 to 7.
  • the above-mentioned fluorine-containing anionic surfactant has a main chain having 6 to 7 carbon atoms, 1 to 4 ether oxygen atoms in the main chain, and has a linear, branched, or cyclic main chain. and is preferably a partially or fully fluorinated carboxylic acid or a salt thereof.
  • the "main chain” means a continuous chain having the maximum number of carbon atoms.
  • fluorine-containing surfactant examples include F(CF 2 ) 7 COOM, F(CF 2 ) 5 COOM, H(CF 2 ) 6 COOM, H(CF 2 ) 7 COOM, CF 3 O(CF 2 ) 3 OCHFCF.
  • the coating composition of the present disclosure preferably contains an anionic surfactant for the purpose of adjusting viscosity or improving the miscibility of pigments, fillers, and the like.
  • Anionic surfactants can be added as appropriate to the extent that there are no problems from an economical or environmental standpoint.
  • anionic surfactants examples include fluorine-free anionic surfactants that do not contain fluorine and fluorine-containing anionic surfactants. agent) is preferred.
  • the type is not particularly limited as long as it is a known anionic surfactant, but for example, fluorine-free anionic surfactants described in International Publication No. 2013/146950 and International Publication No. 2013/146947 Activators can be used.
  • examples include those having a saturated or unsaturated aliphatic chain having 6 to 40 carbon atoms, preferably 8 to 20 carbon atoms, and more preferably 9 to 13 carbon atoms.
  • the saturated or unsaturated aliphatic chain may be linear or branched, and may have a cyclic structure.
  • the above-mentioned hydrocarbon may be aromatic or may have an aromatic group.
  • the above-mentioned hydrocarbon may have a heteroatom such as oxygen, nitrogen, or sulfur.
  • the above-mentioned fluorine-free anionic surfactants include alkyl sulfonates, alkyl sulfates, alkylaryl sulfates and their salts; fatty acids (aliphatic carboxylic acids) and their salts; phosphoric acid alkyl esters, phosphoric acid alkylaryl esters or their salts; ; among others, alkyl sulfonates, alkyl sulfates, aliphatic carboxylic acids, or salts thereof are preferred.
  • alkyl sulfate or its salt ammonium lauryl sulfate, sodium lauryl sulfate, etc. are preferable.
  • fatty acid (aliphatic carboxylic acid) or its salt succinic acid, decanoic acid, undecanoic acid, undecenoic acid, lauric acid, hydrododecanoic acid, or a salt thereof is preferable.
  • the fluorine-free anionic surfactant is preferably at least one selected from the group consisting of alkyl sulfates and salts thereof, and fatty acids and salts thereof.
  • the content of the fluorine-free anionic surfactant is 10 ppm to 5000 ppm based on the solid mass of the fluorine-containing ethylenic polymer, although it depends on the type of the fluorine-free anionic surfactant and other compounding agents. is preferred.
  • the lower limit of the amount of the fluorine-free anionic surfactant added is more preferably 50 ppm, and even more preferably 100 ppm. If the amount added is too small, the viscosity adjusting effect will be poor.
  • the upper limit of the amount of the fluorine-free anionic surfactant added is more preferably 4000 ppm, and even more preferably 3000 ppm. If the amount added is too large, the viscosity may increase, particularly at high temperatures. In addition, there is a possibility that foaming may increase.
  • the viscosity of the coating composition of the present disclosure in addition to the fluorine-free anionic surfactant, for example, methyl cellulose, alumina sol, polyvinyl alcohol, carboxylated vinyl polymer, acrylic polymer, etc. can also be blended.
  • a pH adjuster such as aqueous ammonia may be added.
  • the coating composition of the present disclosure preferably has a pH of 8 to 13. More preferably 9 to 12, still more preferably 9 to 11. The above pH is a value measured at 25°C in accordance with JIS K6893.
  • the coating composition of the present disclosure may contain other water-soluble polymer compounds, if necessary, to the extent that the characteristics of the coating composition are not impaired.
  • the other water-soluble polymer compounds mentioned above are not particularly limited, and include, for example, polyethylene oxide (dispersion stabilizer), polyethylene glycol (dispersion stabilizer), polyvinylpyrrolidone (dispersion stabilizer), phenol resin, urea resin, epoxy resin, Examples include melamine resin, polyester resin, polyether resin, acrylic silicone resin, silicone resin, silicone polyester resin, and polyurethane resin.
  • preservatives such as isothiazolone type, azole type, pronopol, chlorothalonil, methylsulfonyltetrachloropyrodine, carventazim, fluorophorbet, sodium diacetate, and diiodomethylparatolylsulfone.
  • the coating composition of the present disclosure may also include an antifoaming agent.
  • Antifoaming agents can be added as appropriate to the extent that there are no problems from an economical or environmental standpoint.
  • Various aqueous antifoaming agents can be used, including lower alcohols such as methanol, ethanol, butanol, etc.; higher alcohols such as amyl alcohol, polypropylene glycol and derivatives thereof; oleic acid, tall oil, and mineral oil.
  • oils and fats such as soap; surfactants such as sorbitan fatty acid ester, polyethylene glycol fatty acid ester, Pluronic (registered trademark) type nonionic surfactants; silicone surfactants such as siloxane, silicone resin, etc.; Alternatively, they are used in combination.
  • Typical commercially available antifoaming agents include B-series (manufactured by Asahi Denka Kogyo Co., Ltd.) such as Adekanate B and Adekanate B1068; SN deformers such as Formaster DL, Nopco NXZ, and SN Deformer 113, 325, 308, and 368.
  • the content of the antifoaming agent is preferably 0.01 to 10% by weight, particularly preferably 0.05 to 5% by weight, based on the coating composition.
  • the coating composition of the present disclosure may contain an antifoaming agent, but preferably does not. Not including an antifoaming agent is advantageous in terms of cost. Further, if an antifoaming agent is included, there is a risk that the coating composition will be colored when formed into a film.
  • the coating compositions of the present disclosure may also include other additives, such as coating materials.
  • paint raw materials include pigments (extender pigments, scaly pigments, etc.), pigment dispersants, thickeners, leveling agents, film forming aids, solid lubricants, anti-settling agents, moisture absorbers, surface conditioners, Thixotropic agent, viscosity modifier, anti-gelling agent, ultraviolet absorber, HALS (light stabilizer), matting agent, plasticizer, color separation inhibitor, anti-skinning agent, anti-scratch agent, rust preventive agent , antifungal agents, antibacterial agents, antioxidants, flame retardants, anti-sagging agents, antistatic agents, silane coupling agents, carbon black, various reinforcing materials, various extenders, conductive fillers, colloidal silica, gold, silver, Common additives for paints include metal powders such as copper, platinum, and stainless steel. More preferably, the coating composition of the present disclosure does not contain colloidal silica.
  • the coating composition of the present disclosure also preferably includes a preservative.
  • a preservative examples include hydrogen peroxide, organic bromine compounds, organic nitrogen sulfur compounds, organic iodine compounds, organic sulfur compounds, and triazine compounds.
  • a compound or an organic nitrogen sulfur compound is preferable.
  • Specific examples of organic iodine compounds and organic nitrogen sulfur compounds include Deltop series manufactured by Osaka Gas Chemical Co., Ltd., and the like.
  • the amount of the preservative added is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the coating composition.
  • the gelation time in the stirring stability test is preferably 4 hours or more, more preferably 6 hours or more, and even more preferably 8 hours or more.
  • the upper limit is not particularly limited, but may be, for example, 24 hours.
  • the above gelation time is a value measured by the following method. A 250 ml container containing 200 ml of the paint composition was immersed in a water tank kept at 40°C, and a stirring blade (propeller type 4 blades) was rotated at 300 rpm until aggregates were generated or solidified in the paint composition. The time is measured as the gelation time.
  • the coating composition of the present disclosure may be coated 70 times or more, preferably 100 times or more, and more preferably 120 times or more, until gun clogging occurs in a continuous spray coating test. , more preferably 150 times or more.
  • the upper limit is not particularly limited, but may be, for example, 200 times.
  • the number of times of coating until gun clogging occurs is a value measured by the following method. Iwata spray gun W88 (nozzle diameter 1.5 mm) was set at 9.8 N (1 kgf), the application amount valve was returned one turn, and the pattern valve was fully closed, and the trigger was opened and closed intermittently, and paint came out from the gun. Count the number of times it disappears.
  • the coating composition of the present disclosure may be coated 45 times or more, preferably 100 times or more, and more preferably 120 times or more, until white spots occur in a continuous spray coating test. It is more preferably 140 times or more, particularly preferably 150 times or more, and most preferably 200 times or more.
  • the upper limit is not particularly limited, but may be, for example, 250 times.
  • the number of times of coating until the above white spots occur is a value measured by the following method. Iwata Spray Gun W88 (nozzle diameter 1.5 mm) with 9.8 N (1 kgf), application amount valve back one turn, pattern valve fully closed, trigger opening and closing intermittently on 10 sheets of 20 cm x 60 cm black kraft paper. Paint and visually count the number of shots where white spots occur.
  • the coating composition of the present disclosure can be suitably used as a top coat or a primer.
  • a coating composition suitable for a top coat also referred to as a first coating composition
  • a coating composition suitable for an undercoat also referred to as a second coating composition
  • the filler is (i-1) a filler having a new Mohs hardness of 9 or more, which is 0.1 to 15% by mass based on the fluorine-containing ethylenic polymer; , (ii-1) At least one filler selected from the group consisting of fillers having a new Mohs hardness of 5 or more and less than 9, in an amount of 0.1 to 20% by mass based on the fluorine-containing ethylenic polymer. is preferred.
  • a filler having such a high new Mohs hardness a coating film with even better wear resistance can be provided.
  • the first coating composition is less likely to clog a coating gun or cause white spots on the coating film during coating.
  • Examples of the filler (i-1) include those similar to the filler (i) described above.
  • the first coating composition contains the filler (i-1), its content is 0.1 to 15% by mass based on the fluorine-containing ethylenic polymer, but not less than 1% by mass. It is preferably at least 3% by mass, even more preferably at least 5% by mass, further preferably at most 12% by mass, and more preferably at most 10% by mass.
  • Examples of the filler (ii-1) include those similar to the filler (ii) described above.
  • the first coating composition contains the filler (ii-1), its content is 0.1 to 20% by mass based on the fluorine-containing ethylenic polymer, but not less than 1% by mass. It is preferably at least 3% by mass, more preferably at least 5% by mass, even more preferably at least 8% by mass, particularly preferably at least 10% by mass, Moreover, it is preferably 18% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less.
  • the first coating composition preferably does not contain a heat-resistant resin (excluding the fluorine-containing ethylenic polymer).
  • a heat-resistant resin include heat-resistant resins that can be used in the second coating composition described below.
  • the content of the fluorine-containing ethylenic polymer is 1 to 50% by mass based on the coating composition, preferably 5% by mass or more, and preferably 10% by mass or more. It is more preferably 15% by mass or more, even more preferably 20% by mass or more, and preferably 49% by mass or less, more preferably 45% by mass or less. preferable.
  • the first coating composition preferably has a viscosity at 25° C. of 10 mPa ⁇ s or more and 1000 mPa ⁇ s or less in terms of excellent sprayability in spray coating.
  • the viscosity is more preferably 100 mPa ⁇ s or more, still more preferably 150 mPa ⁇ s or more, more preferably 600 mPa ⁇ s or less, even more preferably 500 mPa ⁇ s or less.
  • the above viscosity is measured at 25° C. using a B-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd., rotor No. 2) at a rotation speed of 60 rpm and a measurement time of 120 seconds.
  • the first coating composition further includes depolymerizable acrylic resin particles.
  • the depolymerizable acrylic resin particles gradually decompose while maintaining the binder effect on the fluorine-containing ethylenic polymer particles when the first coating composition is applied and dried, thereby preventing the occurrence of shrinkage cracks. To prevent. Therefore, the depolymerizable acrylic resin particles are melted below the melting temperature of the fluorine-containing ethylenic polymer and depolymerization has started, and at least a portion remains at the melting temperature of the fluorine-containing ethylenic polymer particles. , it is necessary that most of it decomposes and volatilizes at the firing temperature.
  • the remaining nonionic surfactant begins to evaporate or decompose and volatilize, and the depolymerizable acrylic resin particles begin to thermally melt.
  • the nonionic surfactant must remain at least until the thermal melting of the depolymerizable acrylic resin particles is completed.
  • the remaining nonionic surfactant completes evaporation or decomposition, and the thermally melted depolymerizable acrylic resin begins to depolymerize.
  • Depolymerization of such depolymerizable acrylic resin gradually begins at a temperature below the melting temperature of the fluorine-containing ethylenic polymer, but is not yet completed at the temperature at which the fluorine-containing ethylenic polymer particles begin to thermally melt (melting temperature). Furthermore, the firing is completed when the temperature reaches a temperature exceeding the melting temperature of the fluorine-containing ethylenic polymer. By doing so, it is possible to avoid a large amount of the depolymerizable acrylic resin remaining in the resulting fluorine-containing ethylenic polymer coating film.
  • This depolymerizable acrylic resin has viscosity when it is heated and depolymerization progresses gradually, so when the fluorine-containing ethylenic polymer particles melt and fuse together, there is no sudden contraction, and heat shrinkage occurs. The generation of cracks can be suppressed.
  • the depolymerizable acrylic resin particles remain until the temperature at which the fluorine-containing ethylenic polymer particles begin to melt (melting temperature), and are fired (processed).
  • a temperature of For example, at least 5% or more, preferably 10% or more, more preferably 20% or more, particularly preferably 50% or more remains at the melting temperature of the fluorine-containing ethylenic polymer, and the fluorine-containing ethylenic polymer It is preferable that only 10% or less, especially 5% or less, remains at a temperature exceeding the melting temperature of the coalescence and up to 415°C, preferably 360 to 400°C, and that substantially no residue remains at the completion of firing.
  • the depolymerization (decomposition) temperature of the depolymerizable acrylic resin particles should be approximately 200°C or higher and lower than the firing (processing) temperature of the fluorine-containing ethylenic polymer, especially lower than the melting temperature of the fluorine-containing ethylenic polymer. It is desirable that there be.
  • coating defects such as pinholes are likely to occur in the resulting coating film.
  • depolymerizable acrylic resin which remains approximately 25 to 50% in the temperature range of 300 to 320°C and approximately 20 to 10% in the temperature range of 330 to 345°C, prevents shrinkage cracks regardless of the type of resin. It is suitable from the viewpoint of the balance between the action and the action of preventing coloration, and any depolymerizable acrylic resin particles that satisfy this condition can be used.
  • Preferred examples of the methacrylate monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, dimethylpropyl methacrylate, butyl methacrylate, and pentyl methacrylate.
  • a depolymerizable acrylic resin containing butyl methacrylate as a monomer is preferred because it has a low glass transition temperature and good depolymerizability (degradability).
  • a stable emulsion can be formed using a homopolymer, but from the viewpoint of stabilizing the emulsion, a monomer having a carboxyl group or a hydroxyl group may be used as a comonomer as appropriate.
  • the depolymerizable acrylic resin particles for example, fine particles (depolymerizable acrylic resin emulsion) produced by a method such as emulsion polymerization can be used as they are, and the average particle diameter thereof is 0.1 to 100 ⁇ m, particularly 0.2 ⁇ m.
  • the thickness is preferably 1 ⁇ m. If the average particle size is less than 0.1 ⁇ m, mud cracks tend to occur, and if it exceeds 100 ⁇ m, coating tends to become difficult.
  • the amount of the depolymerizable acrylic resin particles is 5 to 25 parts, preferably 7 to 20 parts, particularly preferably 10 to 15 parts, based on 100 parts of the fluorine-containing ethylenic polymer (solid content).
  • the amount is less than 5 parts, it becomes difficult to form a film of the fluorine-containing ethylenic polymer, and when it exceeds 25 parts, the coating film may be colored.
  • the depolymerizable acrylic resin particles are preferably mixed with other components in the form of an emulsion.
  • the first coating composition may contain other liquid organic compounds having hydrophilic groups in order to have an affinity with water and to improve the dispersion stability of the coating composition.
  • a hydrophilic group-containing organic compound a high boiling point polyhydric alcohol is preferable.
  • polyhydric alcohols that do not contain nitrogen atoms are preferred because they are less likely to cause coloring due to thermal decomposition during baking.
  • the preferred number of hydroxyl groups is 2 to 3. Those with 4 or more hydroxyl groups are often solid at room temperature.
  • Suitable polyhydric alcohols include, for example, ethylene glycol (boiling point: 198°C), 1,2-propanediol (188°C), 1,3-propanediol (214°C), and 1,2-butanediol (190°C). , 1,3-butanediol (208°C), 1,4-butanediol (229°C), 1,5-pentanediol (242°C), 2-butene-1,4-diol (235°C), glycerin ( 290°C), 2-ethyl-2-hydroxymethyl-1,3-propanediol (295°C), and 1,2,6-hexanetriol (178°C/5mmHg).
  • an organic solvent other than the high-boiling polyhydric alcohol may be used in combination within a range that does not impair the effects of the present disclosure.
  • organic solvents include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents having 9 to 11 carbon atoms.
  • the blending amount of the polyhydric alcohol is 5 to 18 parts, preferably 7 to 15 parts, particularly preferably 7 to 12 parts, based on 100 parts of the fluorine-containing ethylenic polymer (solid content). If the amount is less than 5 parts, the effect of preventing the occurrence of mud cracks will be weakened, and if it exceeds 18 parts, the coating may become cloudy.
  • the second coating composition preferably contains a heat-resistant resin (excluding the fluorine-containing ethylenic polymer).
  • the above-mentioned heat-resistant resin may be any resin that is generally recognized to have heat resistance, but excludes the above-mentioned fluorine-containing ethylenic polymer.
  • heat resistance means a property that allows continuous use at temperatures of 150° C. or higher.
  • heat-resistant resins examples include polyamide-imide resin (PAI), polyimide resin (PI), polyethersulfone resin (PES), polyetherimide resin, aromatic polyetherketone resin (PAEK), aromatic polyester resin, and polyamide resin.
  • PAI polyamide-imide resin
  • PI polyimide resin
  • PES polyethersulfone resin
  • PAEK aromatic polyetherketone resin
  • PAS rensulfide resin
  • PAS rensulfide resin
  • one type can be used alone or two or more types can be used in combination.
  • PAI is a resin made of a polymer having amide bonds and imide bonds in its molecular structure.
  • the above-mentioned PAI is not particularly limited, and includes, for example, the reaction between an aromatic diamine having an amide bond in its molecule and an aromatic tetravalent carboxylic acid such as pyromellitic acid; Consists of high molecular weight polymers obtained by various reactions such as reaction with diamines such as 4,4-diaminophenyl ether and diisocyanates such as diphenylmethane diisocyanate; reaction with diamines and dibasic acids having an aromatic imide ring in the molecule. Examples include resin. From the viewpoint of excellent heat resistance, the above-mentioned PAI is preferably made of a polymer having an aromatic ring in the main chain.
  • PI is a resin made of a polymer having imide bonds in its molecular structure.
  • the above-mentioned PI is not particularly limited, and examples thereof include resins made of high molecular weight polymers obtained by reaction of aromatic tetravalent carboxylic acid anhydrides such as pyromellitic anhydride. From the viewpoint of excellent heat resistance, the above-mentioned PI is preferably made of a polymer having an aromatic ring in the main chain.
  • PES has the following general formula:
  • PES polymer having a repeating unit represented by: PES is not particularly limited, and examples include resins made of polymers obtained by polycondensation of dichlorodiphenylsulfone and bisphenol.
  • Examples of the aromatic polyetherketone resin include polyetherketone resin (PEK), polyetheretherketone resin (PEEK), polyetherketoneketone resin (PEKK), polyetheretherketoneketone resin (PEEKK), and polyetherketone ester. Examples include resin.
  • the above-mentioned aromatic polyetherketone resins can be used alone or in combination of two or more.
  • the aromatic polyetherketone resin is preferably at least one selected from the group consisting of PEK, PEEK, PEKK, PEEKK, and polyetherketone ester resin, and at least one selected from the group consisting of PEEK and PEKK. More preferred is PEEK.
  • PAS is the general formula below
  • Ar represents an arylene group.
  • PAS polyphenylene sulfide
  • the heat-resistant resin is preferably at least one selected from the group consisting of PAI, PI, PES, aromatic polyetherketone resin, and PAS, and preferably selected from the group consisting of PAI, PI, PES, PEEK, PEKK, and PPS. At least one selected from the group consisting of PAI, PI and PES is more preferable, and PAI is particularly preferable.
  • the mass ratio of the fluorine-containing ethylenic polymer and the heat-resistant resin is preferably 10/90 to 90/10, and is 20/80 or more. is more preferable, more preferably 30/70 or more, even more preferably 40/60 or more, particularly preferably 50/50 or more, most preferably 55/45 or more, and , more preferably 80/20 or less, and still more preferably 70/30 or less.
  • the content of the fluorine-containing ethylenic polymer is preferably 1 to 30% by mass based on the coating composition.
  • the content is more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 15% by mass or more, and 25% by mass based on the coating composition. It is more preferably at most 20% by mass, even more preferably at most 20% by mass.
  • the second coating composition contains the filler (i)
  • its content is 0.1 to 80% by mass, but not less than 1% by mass, based on the fluorine-containing ethylenic polymer. is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, particularly preferably 10% by mass or more, and 12% by mass or more. % or more, more preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
  • the content thereof is 0.1 to 120% by mass, but not less than 1% by mass, based on the fluorine-containing ethylenic polymer. is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, particularly preferably 10% by mass or more, and 12% by mass or more. % or more, more preferably 100% by mass or less, more preferably 90% by mass or less, even more preferably 80% by mass or less, and even more preferably 70% by mass or less. is even more preferred, particularly preferably 60% by mass or less, and most preferably 50% by mass or less.
  • the second coating composition contains the filler (iii)
  • its content is 1 to 150% by mass based on the fluorine-containing ethylenic polymer, but preferably 2% by mass or more. , more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 8% by mass or more, even more preferably 10% by mass or more, and even more preferably 12% by mass. It is particularly preferably at least 15% by mass, most preferably at least 130% by mass, more preferably at most 110% by mass, and preferably at most 90% by mass. It is still more preferably 80% by mass or less, even more preferably 70% by mass or less, particularly preferably 60% by mass or less, and most preferably 50% by mass or less.
  • the second coating composition preferably contains at least one selected from the group consisting of the filler (i) and the filler (ii).
  • the second coating composition preferably has a viscosity at 25° C. of 50 mPa ⁇ s or more and 1500 mPa ⁇ s or less in terms of excellent sprayability in spray coating.
  • the viscosity is more preferably 100 mPa ⁇ s or more, still more preferably 150 mPa ⁇ s or more, more preferably 700 mPa ⁇ s or less, and still more preferably 500 mPa ⁇ s or less.
  • the above viscosity is measured at 25° C. using a B-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd., rotor No. 2) at a rotation speed of 60 rpm and a measurement time of 120 seconds.
  • the coating composition of the present disclosure and the first and second coating compositions can be prepared, for example, by mixing necessary components into the aqueous dispersion of the fluorine-containing ethylenic polymer, and then concentrating or diluting the mixture as necessary. It can be manufactured by performing the following steps.
  • the aqueous dispersion of the fluorine-containing ethylenic polymer can be prepared by, for example, adding a nonionic surfactant to the aqueous dispersion of the fluorine-containing ethylenic polymer after polymerization, or by concentrating, diluting, etc. It can be obtained by adjusting the solid content concentration of the polymer.
  • the PTFE aqueous dispersion is, for example, a method for producing a PTFE aqueous dispersion, comprising: Step A of emulsion polymerizing TFE in the presence of a fluorine-containing anionic surfactant to obtain a dispersion containing PTFE; Step B of adding a nonionic surfactant (1) to the dispersion obtained in Step A; A step of removing the fluorine-containing anionic surfactant from the dispersion obtained in Step B and further concentrating, or concentrating the dispersion obtained in Step B and further removing the fluorine-containing anionic surfactant.
  • Step C which is a step
  • Step D which adds a nonionic surfactant (2) and a fluorine-free anionic surfactant to the dispersion obtained in Step C.
  • Step C which is a step
  • Step D which adds a nonionic surfactant (2) and a fluorine-free anionic surfactant to the dispersion obtained in Step C.
  • the above emulsion polymerization can be carried out, for example, by charging an aqueous medium, a fluorine-containing anionic surfactant, a monomer, and other additives as necessary into a reaction apparatus, stirring the contents of the reaction apparatus, and then turning the reaction apparatus into a predetermined polymerization state. This can be carried out by maintaining the temperature and then adding a predetermined amount of a polymerization initiator to initiate the polymerization reaction. After the start of the polymerization reaction, monomers, polymerization initiators, chain transfer agents, the above-mentioned surfactants, etc. may be additionally added depending on the purpose. The surfactant may be added after the polymerization reaction has started.
  • the polymerization temperature and polymerization pressure in the emulsion polymerization are appropriately determined depending on the type of monomer used, the target molecular weight of PTFE, and the reaction rate.
  • the polymerization temperature is 10 to 150°C.
  • the polymerization temperature is more preferably 30°C or higher, and even more preferably 50°C or higher.
  • the temperature is more preferably 120°C or lower, and even more preferably 100°C or lower.
  • the polymerization pressure is 0.05 to 10 MPa.
  • the polymerization pressure is more preferably 0.3 MPa or higher, and even more preferably 0.5 MPa or higher.
  • 5.0 MPa or less is more preferable, and 3.0 MPa or less is still more preferable.
  • the polymerization initiator is not particularly limited as long as it can generate radicals within the polymerization temperature range, and any known oil-soluble and/or water-soluble polymerization initiators can be used. Furthermore, polymerization can also be initiated as redox in combination with a reducing agent or the like. The concentration of the polymerization initiator is appropriately determined depending on the type of monomer, the target molecular weight of PTFE, and the reaction rate.
  • an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator can be used as the polymerization initiator.
  • the oil-soluble radical polymerization initiator may be a known oil-soluble peroxide, such as dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate, disec-butylperoxydicarbonate, t-butylperoxycarbonate, etc.
  • Peroxy esters such as isobutyrate, t-butylperoxypivalate, dialkyl peroxides such as di-t-butyl peroxide, etc.
  • the water-soluble radical polymerization initiator may be a known water-soluble peroxide, such as ammonium salts, potassium salts, and sodium salts such as persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, and percarbonate. , t-butyl permaleate, t-butyl hydroperoxide, and the like. Reducing agents such as sulfites and sulfites may also be included, and the amount used may be 0.1 to 20 times that of peroxide.
  • a redox initiator that combines an oxidizing agent and a reducing agent as the polymerization initiator.
  • the oxidizing agent include persulfates, organic peroxides, potassium permanganate, manganese triacetate, cerium ammonium nitrate, and bromates.
  • the reducing agent include sulfites, bisulfites, bromates, diimines, oxalic acid, and the like.
  • persulfates include ammonium persulfate and potassium persulfate.
  • sulfites include sodium sulfite and ammonium sulfite.
  • a copper salt or an iron salt to the redox initiator combination.
  • the copper salt include copper(II) sulfate
  • the iron salt include iron(II) sulfate.
  • Examples of the redox initiator include potassium permanganate/oxalic acid, ammonium persulfate/bisulfite/iron(II) sulfate, ammonium persulfate/sulfite/iron(II) sulfate, ammonium persulfate/sulfite, and ammonium persulfate.
  • Potassium permanganate/oxalic acid ammonium persulfate/ Sulfites/iron(II) sulfate are preferred.
  • a redox initiator either an oxidizing agent or a reducing agent may be charged into a polymerization tank in advance, and then the other may be added continuously or intermittently to initiate polymerization.
  • potassium permanganate/oxalic acid it is preferable to charge the oxalic acid into a polymerization tank and continuously add potassium permanganate thereto.
  • the amount of the polymerization initiator added is not particularly limited, but it may be added in an amount that does not significantly reduce the polymerization rate (for example, several ppm to water concentration) or more at the beginning of the polymerization, either all at once, sequentially, or continuously. Just add it.
  • the upper limit is a range in which the reaction temperature can be raised while removing heat from the polymerization reaction from the device surface, and a more preferable upper limit is a range in which the polymerization reaction heat can be removed from the device surface.
  • a radical polymerization initiator can also be used as the polymerization initiator.
  • peroxide is preferred.
  • examples of the radical polymerization initiator include the above-mentioned oil-soluble radical polymerization initiators, water-soluble radical polymerization initiators, and the like, but the above-mentioned water-soluble radical polymerization initiators are preferred.
  • the water-soluble radical polymerization initiator is more preferably a peroxide, and even more preferably a persulfate, an organic peroxide, or a mixture thereof.
  • persulfates include ammonium persulfate, potassium persulfate, and the like.
  • the water-soluble radical polymerization initiator is preferably used in an amount of 500 ppm or less relative to the aqueous medium, the amount is more preferably 400 ppm or less, even more preferably 300 ppm or less, particularly preferably 200 ppm or less, Further, it is preferably 5 ppm or more, more preferably 10 ppm or more, and even more preferably 20 ppm or more.
  • the water-soluble radical polymerization initiator is preferably 0.1 ppm or more, more preferably 1.0 ppm or more, even more preferably 1.5 ppm or more, even more preferably 2.0 ppm or more, based on the aqueous medium.
  • ammonium persulfate of 2.5 ppm or more.
  • ammonium sulfate is preferably used in an amount of preferably 50 ppm or less, more preferably 40 ppm or less, even more preferably 30 ppm or less, based on the aqueous medium.
  • the water-soluble radical polymerization initiator is preferably 10 ppm or more, more preferably 30 ppm or more, still more preferably 50 ppm or more of disuccinic acid peroxide, based on the aqueous medium.
  • disuccinic acid peroxide is preferably used in an amount of 500 ppm or less, more preferably 300 ppm or less, and even more preferably 200 ppm or less, based on the aqueous medium.
  • ammonium persulfate and disuccinic acid peroxide in combination, and when used together, the amounts of ammonium persulfate and disuccinic acid peroxide are the same as the above amounts of ammonium persulfate and disuccinic acid peroxide. It can be used as In the above emulsion polymerization, a radical polymerization initiator may be added continuously or intermittently after starting the polymerization.
  • chain transfer agent examples include esters such as dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, butyl acetate, and dimethyl succinate, as well as isopentane, methane, ethane, propane, isobutane, methanol, ethanol, and isopropanol. , acetone, various mercaptans, various halogenated hydrocarbons such as carbon tetrachloride, and cyclohexane.
  • esters such as dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, butyl acetate, and dimethyl succinate, as well as isopentane, methane, ethane, propane, isobutane, methanol, ethanol, and isopropanol.
  • acetone various mercaptans
  • various halogenated hydrocarbons such as carbon tetrachloride,
  • At least one selected from the group consisting of alkanes and alcohols is preferred from the standpoint of polymerization reactivity, crosslinking reactivity, ease of availability, and the like.
  • the number of carbon atoms in the alkane is preferably 1 to 6, more preferably 1 to 5.
  • the alcohol preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms.
  • the chain transfer agent is particularly preferably at least one selected from the group consisting of methane, ethane, propane, isobutane, methanol, ethanol, and isopropanol.
  • the amount of the chain transfer agent is preferably 0.001 to 10,000 ppm based on the aqueous medium.
  • the amount of the chain transfer agent is more preferably 0.01 ppm or more, even more preferably 0.05 ppm or more, particularly preferably 0.1 ppm or more based on the aqueous medium. Further, the amount is more preferably 1000 ppm or less, and even more preferably 500 ppm or less, based on the aqueous medium.
  • the chain transfer agent mentioned above may be added all at once into the reaction apparatus before the start of polymerization, may be added all at once after the start of polymerization, or may be added in multiple portions during polymerization. Alternatively, it may be added continuously during the polymerization.
  • step (A) is a step of polymerizing TFE and a monomer copolymerizable with TFE.
  • monomers copolymerizable with the TFE include the above-mentioned modified monomers, and at least one monomer selected from the group consisting of PAVE, PFAE, perfluoroallyl ether, and cyclic monomers is particularly preferred. , PAVE are more preferred.
  • PAVE examples include perfluoro(alkyl vinyl ether), such as perfluoro(methyl vinyl ether) [PMVE], perfluoro(ethyl vinyl ether) [PEVE], perfluoro(propyl vinyl ether) [PPVE], and perfluoro( butyl vinyl ether) [PBVE], at least one selected from the group consisting of PMVE, PEVE and PPVE is preferred, and PPVE is more preferred.
  • PFAE perfluorobutyl)ethylene [PFBE], (perfluorohexyl)ethylene, and the like.
  • Rf 12 is preferably a perfluoroalkyl group having 1 to 10 carbon atoms or a perfluoroalkoxyalkyl group having 1 to 10 carbon atoms.
  • the cyclic monomer has general formula (ii): ( In the formula , X 2 and , an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms) is preferred.
  • X 2 and X 3 are fluorine atoms
  • R 1 and R 2 are fluoroalkyl groups having 1 to 6 carbon atoms.
  • PDD perfluoro- 2,2 - dimethyl- 1,3- Dioxole
  • the fluorine-containing anionic surfactant includes the fluorine-containing anionic surfactant described in the coating composition of the present disclosure, for example, a fluorine-containing anionic surfactant having a LogPOW of 3.5 or less, preferably a fluorine-containing anionic surfactant.
  • a fluorine-containing anionic surfactant having a LogPOW of 3.4 or less may be used.
  • step A is preferably a step of obtaining a dispersion of PTFE having a core-shell structure.
  • TFE and optionally modified monomers are first polymerized to produce a core (PTFE or modified PTFE), and then TFE and optionally modified monomers are polymerized to produce a shell (PTFE or modified PTFE).
  • step A is a step of obtaining a dispersion of modified polytetrafluoroethylene having a core-shell structure, in which TFE is selected from the group consisting of perfluoro(alkyl vinyl ether), (perfluoroalkyl)ethylene, and a cyclic type monomer.
  • the shell may be obtained by copolymerizing a modified monomer that is copolymerizable with TFE, or by adding a chain transfer agent during polymerization. , or both of these may be performed.
  • the chain transfer agent used in the production of the shell is not particularly limited as long as it reduces the molecular weight of the PTFE constituting the shell.
  • examples include compounds, water-soluble organic peroxides such as disuccinic acid peroxide [DSP], and/or persulfates such as ammonium persulfate [APS] and potassium persulfate [KPS].
  • the chain transfer agent may be one containing at least one of a non-peroxide organic compound, a water-soluble organic peroxide, and a persulfate. In the above chain transfer agent, each of the non-peroxide organic compound, the water-soluble organic peroxide, and the persulfate can be used alone or in combination of two or more.
  • the above chain transfer agents include water-soluble alcohols having 1 to 4 carbon atoms, hydrocarbons having 1 to 4 carbon atoms, and fluorinated alcohols having 1 to 4 carbon atoms, since they have good dispersibility and uniformity in the reaction system. It is preferably made of at least one selected from the group consisting of hydrocarbons, etc., and at least one selected from the group consisting of methane, ethane, n-butane, isobutane, methanol, isopropanol, DSP, APS, and KPS. More preferably, it consists of methanol and/or isobutane.
  • the modified monomer used for producing the shell is preferably a fluoroolefin represented by the general formula (iv).
  • the fluoroolefins include perfluoroolefins having 2 to 4 carbon atoms and hydrogen-containing fluoroolefins having 2 to 4 carbon atoms.
  • perfluoroolefins are preferred, and hexafluoropropylene [HFP] is particularly preferred.
  • the modifier unit derived from the modifying monomer is 0.001 to 0.5% by mass of the entire primary particles constituting PTFE, depending on the type of modifying monomer used, but from the viewpoint of stability of the PTFE dispersion. It is preferable that the lower limit is 0.005% by mass, the more preferable upper limit is 0.2% by mass, and the most preferable upper limit is 0.10% by mass.
  • HFP is used as a modified monomer in the shell, it is preferably 0.001 to 0.3% by mass of the entire primary particles constituting the PTFE, the lower limit is more preferably 0.005% by mass, and the upper limit is more preferably 0.005% by mass. It is 15% by mass.
  • the shell may be obtained either by using a chain transfer agent or by copolymerizing a modifier, or by both copolymerizing a modifying monomer and using a chain transfer agent. It may also be obtained by When the above-mentioned PTFE uses fluoro(alkyl vinyl ether) represented by the above general formula (iii) as a modified monomer in the PTFE constituting the core, especially PPVE, methanol, isobutane, DSP and/or APS is used as a chain transfer agent. or copolymerizing HFP and/or PPVE as a modifier, and more preferably using methanol or HFP.
  • Step A is a step of polymerizing TFE and a modified monomer to produce a core, and then polymerizing a monomer composition containing TFE in the presence of a chain transfer agent to produce a shell.
  • the modified monomer and chain transfer agent the modified monomer and/or chain transfer agent described for the above-mentioned core-shell structure PTFE can be used.
  • the core-shell structure examples include the structures described above, and the core-shell structure has a core of modified PTFE and a shell of low molecular weight PTFE obtained by polymerizing a monomer composition containing TFE in the presence of a chain transfer agent. It is particularly preferable.
  • a low molecular weight PTFE shell can be obtained by polymerizing a monomer composition comprising TFE in the presence of a chain transfer agent.
  • the modified PTFE contains polymerized units (modified monomer units) based on a modified monomer of 0.050% by mass or more and 1.00% by mass or less.
  • the modified PTFE preferably contains 99.00% by mass or more and 99.95% by mass of TFE-based polymer units.
  • the modified PTFE may consist only of polymerized units based on TFE and polymerized units based on modified monomers.
  • the lower limit of the content of the modified monomer unit is more preferably 0.070% by mass, even more preferably 0.10% by mass, even more preferably 0.15% by mass, particularly preferably 0.20% by mass, 0. .25% by weight is particularly preferred.
  • the upper limit of the content of modified monomer units is preferably 0.90% by mass, more preferably 0.50% by mass, even more preferably 0.45% by mass, even more preferably 0.40% by mass, and 0.35% by mass. % by weight is particularly preferred.
  • step A deionized water, a fluorine-containing anionic surfactant (excluding PFOA or its salt), and a stabilizing agent are charged into a reaction apparatus, oxygen is removed, TFE is added, and a polymerization initiator is added. It is preferable to include step 1 of adding, step 2 of adding a monomer copolymerizable with TFE, step 3 of adding a chain transfer agent, and step 4 of cooling and removing the stabilizing aid after completion of polymerization. .
  • the fluorine-containing anionic surfactant (excluding PFOA or its salt) may be any fluorine-containing anionic surfactant other than PFOA or its salt among the above-mentioned fluorine-containing surfactants, such as , a fluorine-containing anionic surfactant having a LogPOW of less than 3.5 is preferred, and a fluorine-containing anionic surfactant having a LogPOW of 3.4 or less is preferred.
  • compounds represented by the above general formula (N 1 ) (excluding PFOA or its salts), compounds represented by the above general formula (N 2 ), and compounds represented by the above general formula (N 3 ) at least one compound selected from the group consisting of a compound represented by the above general formula (N 4 ), and a compound represented by the above general formula (N 5 ) (provided that PFOA or a salt thereof is ).
  • perfluorocarboxylic acid (I) represented by the above general formula (I) (excluding PFOA or its salt), ⁇ -H perfluorocarboxylic acid represented by the above general formula (II) (II), perfluoropolyether carboxylic acid (III) represented by the above general formula (III), perfluoroalkylalkylenecarboxylic acid (IV) represented by the above general formula (IV), above general formula (V) perfluoroalkoxyfluorocarboxylic acid (V) represented by, perfluoroalkylsulfonic acid (VI) represented by the above general formula (VI), ⁇ -H perfluorosulfonic acid represented by the above general formula (VII) (VII), perfluoroalkylalkylene sulfonic acid (VIII) represented by the above general formula (VIII), alkylalkylenecarboxylic acid (IX) represented by the above general formula (IX), fluorocarboxylic acid (X), an alkyl
  • At least one type is mentioned.
  • the number of carbon atoms in Rf m in formula (N 1 ) is preferably an integer of 3 to 6.
  • m1 in formula (N 1a ) is preferably an integer of 3 to 6.
  • n1 in general formula (I) is preferably an integer of 3 to 6.
  • fluorine-containing anionic surfactant compounds selected from the group consisting of fluorine-containing carboxylic acids and salts thereof having 4 to 7 carbon atoms and optionally having ether oxygen are particularly preferred.
  • the number of carbon atoms means the total number of carbon atoms in one molecule. Two or more of the above fluorine-containing anionic surfactants may be used in combination.
  • the fluorine-containing anionic surfactant is preferably a compound selected from the group consisting of fluorine-containing carboxylic acids and salts thereof having 4 to 7 carbon atoms and ether oxygen.
  • the fluorine-containing carboxylic acid having etheric oxygen is a compound having 4 to 7 carbon atoms, etheric oxygen in the middle of the main carbon chain, and -COOH at the end.
  • the terminal --COOH may form a salt.
  • the number of ether oxygens present in the middle of the main chain is one or more, preferably 1 to 4, and more preferably 1 or 2.
  • the number of carbon atoms is preferably 5 to 7.
  • the above-mentioned fluorine-containing anionic surfactant has a main chain having 6 to 7 carbon atoms, 1 to 4 ether oxygen atoms in the main chain, and has a linear, branched, or cyclic main chain. and is preferably a partially or fully fluorinated carboxylic acid or a salt thereof.
  • the "main chain” means a continuous chain having the maximum number of carbon atoms.
  • fluorine-containing surfactant examples include F(CF 2 ) 7 COOM, F(CF 2 ) 5 COOM, H(CF 2 ) 6 COOM, H(CF 2 ) 7 COOM, CF 3 O(CF 2 ) 3 OCHFCF.
  • the stabilizing aids include those mentioned above, and paraffin wax is particularly preferred.
  • the paraffin wax may be liquid, semi-solid, or solid at room temperature, but saturated hydrocarbons having 12 or more carbon atoms are preferred.
  • the melting point of paraffin wax is usually preferably 40 to 65°C, more preferably 50 to 65°C.
  • step 1 the polymerization initiator described in step A can be used, and the amount added is not particularly limited.
  • the above-mentioned modified monomers can be used as the monomer copolymerizable with TFE, and for example, at least one monomer selected from the group consisting of PAVE, PFAE, and cyclic monomers is preferable.
  • PAVE is preferably at least one selected from the group consisting of PMVE, PEVE, and PPVE.
  • cyclic monomer a vinyl heterocyclic body represented by the above general formula (II) is preferable.
  • the PFAE include (perfluorobutyl)ethylene (PFBE), (perfluorohexyl)ethylene, and the like.
  • the monomer copolymerizable with TFE is preferably added before the start of polymerization or after the start of polymerization, when the solid content concentration of PTFE is less than 5% by mass. Thereby, a PTFE dispersion having a modified PTFE core can be obtained.
  • step 2 the method for removing oxygen is not particularly limited, and conventionally known methods can be used.
  • step 3 above the amount of chain transfer agent added may be the same as described for step A above.
  • p1/p2 is 0.60 or more.
  • p1/p2 is more preferably 0.70 or more, still more preferably 0.80 or more, even more preferably 0.90 or more, and particularly preferably 0.95 or more.
  • the upper limit of p1/p2 is not particularly limited, but may be, for example, 0.98.
  • the above p1/p2 indicates the proportion of the core in the entire PTFE, and is the ratio of the amount of TFE charged when a modifying monomer or chain transfer agent is charged during polymerization to the total amount of TFE charged in the polymerization of PTFE. It shows.
  • the above p1 is the amount of TFE to be charged when the shell is charged, and p2 is the total amount of TFE to be charged.
  • the method for removing the cooling and stabilizing aid is not particularly limited, and conventionally known methods can be used.
  • additives can be used to stabilize each compound.
  • the additives include buffers, pH adjusters, stabilizing agents, and dispersion stabilizers.
  • Preferred stabilizing aids include paraffin wax, fluorine oil, fluorine solvent, silicone oil, and the like.
  • the stabilizing aids may be used alone or in combination of two or more.
  • paraffin wax is more preferred.
  • the paraffin wax may be liquid, semi-solid, or solid at room temperature, but saturated hydrocarbons having 12 or more carbon atoms are preferred.
  • the melting point of paraffin wax is usually preferably 40 to 65°C, more preferably 50 to 65°C.
  • the amount of the stabilizing aid used is preferably 0.1 to 12% by weight, more preferably 0.1 to 8% by weight, based on the weight of the aqueous medium (eg, deionized water) used. It is desirable that the stabilizing aid be sufficiently hydrophobic so that it can be completely separated from the PTFE aqueous emulsion after TFE emulsion polymerization and not become a contaminating component.
  • the aqueous medium eg, deionized water
  • the aqueous medium is a reaction medium for polymerization, and means a liquid containing water.
  • the aqueous medium is not particularly limited as long as it contains water, and includes water and a non-fluorine-containing organic solvent such as alcohol, ether, ketone, etc., and/or a fluorine-containing organic solvent with a boiling point of 40°C or less. It may also include.
  • the nonionic surfactant (1) added in step B the nonionic surfactant represented by the above-mentioned formula (i) can be used.
  • the nonionic surfactant (1) The following formula (1): R 4 -O-A 2 -H (1) (In the formula, R 4 is a linear or branched primary or secondary alkyl group having 8 to 18 carbon atoms and has an average number of methyl groups per molecule of 2.0 or more, and A 2 is It is preferably a compound represented by a polyoxyalkylene chain having an average number of oxyethylene units of 7.0 to 12.0 and an average number of oxypropylene units of 0.0 to 2.0.
  • R 4 is represented by the following general formula (1-1): CHR 41 R 42 - (1-1) (In the formula, R 41 represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, R 42 represents an alkyl group having 1 to 17 carbon atoms, and the total number of carbon atoms of R 41 and R 42 is 7 to 17 ) is preferably an alkyl group represented by the following.
  • the above R 41 is more preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, even more preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and even more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. preferable.
  • R 42 is more preferably an alkyl group having 1 to 15 carbon atoms, even more preferably an alkyl group having 1 to 14 carbon atoms, and even more preferably an alkyl group having 1 to 13 carbon atoms.
  • the above R 4 is preferably an alkyl group having 8 to 18 carbon atoms and having an average number of methyl groups of 2.5 or more.
  • the average number of methyl groups in R 4 is more preferably 3.0 or more, still more preferably 3.5 or more, and even more preferably 4.0 or more.
  • the average number of methyl groups in R 4 is also preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less.
  • R 4 is preferably a trimethylnonyl group, more preferably a 2,6,8-trimethyl-4-nonyl group.
  • the average number of oxyethylene units is preferably 10.0 to 10.5. In this case, the average number of oxypropylene units is 0.0.
  • the removal of the fluorine-containing anionic surfactant in Step C is preferably carried out by bringing the aqueous dispersion into contact with an anion exchange resin.
  • the anion exchange resin in Step C is not particularly limited, but any known one can be used. Furthermore, a known method can be used for contacting with the anion exchange resin.
  • the anion exchange resin include strong basic anion exchange resins having three -N + X - (CH 3 ) groups (X represents Cl or OH) as functional groups, -N + X -
  • Known resins include strongly basic anion exchange resins having a (CH 3 ) 3 (C 2 H 4 OH) group (X is the same as above). Specifically, those described in International Publication No. 99/62858, International Publication No. 03/020836, International Publication No. 2004/078836, International Publication No. 2013/027850, International Publication No. 2014/084399, etc. can be mentioned.
  • the above-mentioned cation exchange resin is not particularly limited, and examples thereof include a strongly acidic cation exchange resin having a -SO 3 - group as a functional group, a weakly acidic cation exchange resin having a -COO - group as a functional group, and the like. Among them, from the viewpoint of removal efficiency, strongly acidic cation exchange resins are preferred, and H + type strongly acidic cation exchange resins are more preferred.
  • the above-mentioned "mixed bed consisting of a cation exchange resin and an anion exchange resin” is not particularly limited, and if both are packed in the same column, if both are packed in different columns, This includes cases where it is dispersed in an aqueous dispersion.
  • the fluorine-containing anionic surfactant in Step C may be removed by concentration. As described in International Publication No. 2005/042593, the concentration step may be performed twice or more. Therefore, step C may involve concentrating the dispersion obtained in step B two or more times. Moreover, it is preferable that Step C is carried out by bringing the aqueous dispersion into contact with an anion exchange resin.
  • a known method is employed as the concentration method in step C above. Specifically, those described in International Publication No. 2007/046482 and International Publication No. 2014/084399 can be mentioned. Examples include phase separation, centrifugal sedimentation, cloud point concentration, electroconcentration, electrophoresis, filtration treatment using ultrafiltration, filtration treatment using reverse osmosis membrane (RO membrane), nanofiltration treatment, and the like.
  • the PTFE concentration can be concentrated to 50 to 70% by mass depending on the application. Since concentration may impair the stability of the dispersion, a nonionic surfactant may be further added in step C.
  • the nonionic surfactant in Step C is the same as in the coating composition of the present disclosure.
  • a dispersion stabilizer other than the nonionic surfactant may be used as necessary.
  • the total amount of the dispersion stabilizer is in a concentration of 0.5 to 20% by weight based on the solid content of PTFE. If it is less than 0.5% by mass, the dispersion stability may be poor, and if it exceeds 20% by mass, there will be no dispersion effect commensurate with the amount present, making it impractical.
  • a more preferable lower limit of the dispersion stabilizer is 2% by mass, and a more preferable upper limit is 12% by mass.
  • the above concentration is preferably cloud point concentration.
  • Cloud point concentration is preferably carried out, for example, by heating at a temperature that is 5° C. lower than the cloud point of the nonionic surfactant. More specifically, it is preferable that the mixture be heated at a temperature 5° C. lower than the cloud point of the nonionic surfactant or higher and then allowed to stand to separate into a supernatant phase and a concentrated phase.
  • the above concentration may be performed only once or twice or more.
  • Step D is a step of adding a nonionic surfactant (2) and a fluorine-free anionic surfactant to the dispersion obtained in Step C.
  • the order of adding the nonionic surfactant (2) and the fluorine-free anionic surfactant is not limited, and the fluorine-free anionic surfactant is added after the nonionic surfactant (2) is added.
  • the nonionic surfactant (2) may be added after adding the fluorine-free anionic surfactant, or the fluorine-free anionic surfactant and the nonionic surfactant may be added at the same time. May be added.
  • addition of the nonionic surfactant (2) and the fluorine-free anionic surfactant may each be performed multiple times, and the addition of the nonionic surfactant (2) and the fluorine-free anionic surfactant may be performed multiple times. The addition may be carried out alternately several times.
  • nonionic surfactant (2) added in step D a nonionic surfactant represented by the above-mentioned formula (i) can be used.
  • the nonionic surfactant (2) has the following formula (2): R 5 -O-A 3 -H (2) (In the formula, R 5 is a linear or branched primary or secondary alkyl group having 8 to 18 carbon atoms and has an average number of methyl groups per molecule of 2.0 or more, and A 3 is It is preferably a compound represented by a polyoxyalkylene chain having an average number of oxyethylene units of 10.0 to 12.0.
  • R 5 is the following general formula (2-1): CHR 51 R 52 - (2-1) (In the formula, R 51 represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, R 52 represents an alkyl group having 1 to 17 carbon atoms, and the total number of carbon atoms of R 51 and R 52 is 7 to 17 ) is preferably an alkyl group represented by the following.
  • the above R 51 is more preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, even more preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and even more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. preferable.
  • R 52 is more preferably an alkyl group having 1 to 15 carbon atoms, even more preferably an alkyl group having 1 to 14 carbon atoms, and even more preferably an alkyl group having 1 to 13 carbon atoms.
  • the above R 5 is preferably an alkyl group having 8 to 18 carbon atoms and having an average number of methyl groups of 2.5 or more.
  • the average number of methyl groups in R 5 is more preferably 3.0 or more, still more preferably 3.5 or more, and even more preferably 4.0 or more.
  • the upper limit of the average number of methyl groups in R 5 is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less.
  • R 5 is preferably a trimethylnonyl group, more preferably a 2,6,8-trimethyl-4-nonyl group.
  • the average number of oxyethylene units is preferably 10.1 to 11.0. In this case, the average number of oxypropylene units is 0.0.
  • the above step D is a step of adding the nonionic surfactant (2) so that the concentration of the nonionic surfactant in the dispersion is 4 to 12% by mass based on polytetrafluoroethylene. is preferred. More preferably, it is added in an amount of 5% by mass or more, more preferably it is added in an amount of 10% by mass or less, and even more preferably it is added in an amount of 8% by mass or less. It is to be.
  • the fluorine-free anionic surfactants added in step D include alkyl sulfonates, alkyl sulfates, alkylaryl sulfates and their salts; fatty acids (aliphatic carboxylic acids) and salts thereof; alkyl phosphates, alkylaryl phosphates; esters or salts thereof; among these, alkyl sulfonates, alkyl sulfates, aliphatic carboxylic acids, or salts thereof are preferred. Among these, at least one selected from the group consisting of alkyl sulfates and their salts, and fatty acids and their salts is more preferred.
  • alkyl sulfate and its salt ammonium lauryl sulfate, sodium lauryl sulfate, etc. are preferable.
  • Preferred fatty acids and salts thereof are succinic acid, decanoic acid, undecanoic acid, undecenoic acid, lauric acid, hydrododecanoic acid, or salts thereof.
  • the content of the fluorine-free anionic surfactant is preferably 50 to 5000 ppm based on PTFE.
  • the lower limit of the amount of the fluorine-free anionic surfactant added is more preferably 50 ppm, even more preferably 100 ppm, and even more preferably 200 ppm. If the amount added is too small, the viscosity adjusting effect will be poor.
  • the upper limit of the amount of the fluorine-free anionic surfactant added is more preferably 4000 ppm, still more preferably 3000 ppm, even more preferably 2000 ppm, and particularly preferably 1000 ppm. If the amount added is too large, the viscosity may increase, particularly at high temperatures. In addition, there is a possibility that foaming may increase.
  • the above manufacturing method further includes the step of adding a preservative to the aqueous dispersion.
  • Preservatives include those described in the coating composition of the present disclosure.
  • the above manufacturing method further includes a step of adding a paint raw material.
  • paint raw materials include additives that can be added to paints. Specifically, pigments (extender pigments, scaly pigments, etc.), pigment dispersants, thickeners, leveling agents, film forming aids, solid lubricants, anti-settling agents, moisture absorbers, surface conditioners, thixotropes. Additives, viscosity modifiers, anti-gelling agents, ultraviolet absorbers, HALS (light stabilizers), matting agents, plasticizers, anti-color separation agents, anti-skinning agents, anti-scratch agents, anti-rust agents, anti-corrosion agents.
  • additives that can be added to paints. Specifically, pigments (extender pigments, scaly pigments, etc.), pigment dispersants, thickeners, leveling agents, film forming aids, solid lubricants, anti-settling agents, moisture absorbers, surface conditioners, thixotropes. Additives, viscosity modifier
  • Mold agents antibacterial agents, antioxidants, flame retardants, anti-sag agents, antistatic agents, silane coupling agents, carbon black, various reinforcing materials, various extenders, conductive fillers, colloidal silica, gold, silver, copper,
  • Common additives for paints include metal powders such as platinum and stainless steel.
  • the above additive may be an additive other than colloidal silica.
  • the content of the paint raw material is not particularly limited, and may be appropriately set depending on the application.
  • the above manufacturing method may also include a step of recovering the PTFE aqueous dispersion obtained by polymerization.
  • the aqueous dispersion when the fluoroethylenic polymer is a melt-processable fluororesin can be produced by a known production method such as emulsion polymerization.
  • a film can be formed by applying the coating composition of the present disclosure or the first or second coating composition.
  • the present disclosure also provides a coating formed from the coating composition of the present disclosure or a first or second coating composition.
  • the coating of the present disclosure can be obtained, for example, by applying the coating composition of the present disclosure or a first or second coating composition, preferably the coating composition of the present disclosure or a second coating composition to a substrate. It can be formed by
  • the material for the base material is not particularly limited, and includes, for example, metals such as iron, aluminum, stainless steel, copper, and alloys thereof; non-metallic inorganic materials such as enamel, glass, and ceramics. Examples of the above alloys include aluminum alloys and stainless steel.
  • metal is preferable, and aluminum alloy, aluminum, or stainless steel is more preferable.
  • various conventional coating methods can be employed. Examples include a dipping method, a spray method, a roll coating method, a doctor blade method, a flow coating method, a spin coating method, and the like.
  • the coating composition applied to the substrate may be dried. Drying may be carried out under normal conditions, for example, at room temperature to 80°C, preferably 80 to 100°C, for 5 minutes to 1 hour.
  • the dried film may be fired.
  • the firing temperature and time vary depending on the type and melting temperature of the fluorine-containing ethylenic polymer, but are preferably at least the melting temperature of the fluorine-containing ethylenic polymer, and in the case of PTFE, usually at 360 to 420°C for 5 to 30 minutes, preferably It is carried out at 360-380°C for 10-30 minutes.
  • the thickness of the film of the present disclosure is preferably 20 ⁇ m or more, and preferably 100 ⁇ m or less.
  • a laminated film can also be obtained by coating.
  • the present disclosure also provides a laminate coating that includes a coating formed from the coating composition of the present disclosure or a first or second coating composition.
  • the laminated film of the present disclosure can be obtained by applying, drying, and baking the other coating composition described above, and then applying, drying, and baking the coating composition of the present disclosure, or the first or second coating composition (two coats).
  • the coating composition of the present disclosure, or the first or second coating composition may be applied after coating and drying the other coating composition described above. It may be manufactured by a method of coating, drying, and baking both at the same time (two-coat one-bake method, three-coat one-bake method, three-coat two-bake method).
  • the present disclosure also provides painted articles having a coating of the present disclosure or a laminate coating of the present disclosure.
  • the above-mentioned coated articles include, for example, frying pans, grill pans, pressure cookers, various other pots, rice cookers, rice cake makers, ovens, hot plates, bread molds, kitchen knives, gas stoves, air fryers, and other cooking utensils; electric kettles.
  • Food and beverage containers such as , mug bottles, and ice trays; Food industry parts such as kneading rolls, rolling rolls, conveyors, and hoppers; Rolls for office automation equipment (OA), OA belts, OA separation claws, paper rolls, and film manufacturing.
  • OA office automation equipment
  • Industrial products such as calendar rolls; Molds and casting molds for polystyrene molding, mold release plates such as release plates for plywood and decorative laminate production; Kitchen supplies such as range hoods; Frozen food production equipment such as conveyor belts ; Tools such as saws, files, dies, and awls; Household items such as irons, scissors, knives, etc.; Metal foils, electric wires; Sliding bearings in food processing machines, packaging machines, spinning machines, etc.; Sliding parts in cameras and watches; Examples include automobile parts such as pipes, valves, and bearings, snow shovels, plows, chutes, ship bottoms, boilers, and industrial containers (especially for the semiconductor industry). Among these, metal cooking utensils are preferred, and frying pans are more preferred.
  • PPVE content is calculated by multiplying the ratio of absorbance at 995 cm -1 / absorbance at 935 cm -1 by 0.14 from the infrared absorbance obtained by creating a thin film disk by press-molding PTFE powder and measuring the thin film disk by FT-IR. I asked.
  • TMN-6:TMN-10 30:70 (weight ratio) Structural formula of TMN-6: C 12 H 25 O(CH 2 CH 2 O) 8 H (average number of methyl groups per molecule: 5.0), HLB 13.10, cloud point 36°C
  • Synthesis example 1 After purging the 1 L autoclave with nitrogen, 16.5 g of dehydrated tetramethylurea and 220 g of diethylene glycol dimethyl ether were charged and cooled. 38.5 g of carbonyl fluoride was charged, and then 100 g of hexafluoropropylene oxide was introduced and stirred. Thereafter, 38.5 g of carbonyl fluoride and 100 g of hexafluoropropylene oxide were additionally charged. Thereafter, carbonyl fluoride and hexafluoropropylene oxide were further charged in equal amounts. After the reaction was completed, the reaction mixture was taken out and separated to obtain a lower layer reaction product.
  • TFE was added so that the pressure was constant at 1.5 MPaG.
  • the amount of TFE consumed in the reaction reached 1466 g, 0.5 g of methanol was injected into the reactor, and the reaction was continued.
  • the amount of TFE consumed in the reaction reached 1543 g, the supply of TFE was stopped, stirring was stopped, and the reaction was completed. Thereafter, the pressure inside the reactor was evacuated to normal pressure, and the contents were taken out from the reactor and cooled. Paraffin wax was removed to obtain modified PTFE aqueous dispersion 1-1.
  • the solid content concentration of the obtained aqueous dispersion 1-1 was 30.0% by mass, and the average primary particle diameter was 272 nm.
  • the obtained PTFE is a modified PTFE having a core-shell structure with a shell of low molecular weight PTFE.
  • the obtained modified PTFE aqueous dispersion 1-1 was diluted with deionized water to a solid content concentration of about 10% by mass, coagulated under high-speed stirring conditions, and the coagulated wet powder was dried at 150° C. for 10 hours to complete the modification.
  • a PTFE powder was obtained.
  • the standard specific gravity of the obtained modified PTFE powder was 2.167, and the PPVE content was 0.28% by mass.
  • an OH type anion exchange resin trade name: Amberjet 4002, manufactured by Rohm and Haas
  • surfactant (a) was added to the aqueous dispersion obtained by passing through the solution in an amount of 16 parts by mass per 100 parts by mass of modified PTFE, and the mixture was kept at 65°C for 3 hours to separate a supernatant phase and a concentrated phase. It was separated into The concentrated phase was collected to obtain modified PTFE aqueous dispersion 1-2.
  • the obtained modified PTFE aqueous dispersion 1-2 had a solid content concentration of 68.3% by mass, a nonionic surfactant content of 2.7% by mass based on the modified PTFE, and a fluorine-containing surfactant concentration. It was 420 ppb relative to the modified PTFE aqueous dispersion.
  • surfactant (b) was added in an amount of 2.3% by mass based on the modified PTFE
  • ammonium lauryl sulfate was added at 500 ppm based on the modified PTFE, and deionized water and Ammonia water was added to obtain PTFE aqueous dispersion A.
  • Table 2 shows the solid content concentration (mass %) of the obtained PTFE aqueous dispersion A and the content (mass %) of each component relative to PTFE.
  • Manufacturing example 2 Modified PTFE aqueous dispersion 2-1 was obtained in the same manner as in Production Example 1, except that methanol was not injected into the reactor when the amount of TFE consumed in the reaction reached 1466 g, and the reaction was continued. .
  • the solid content concentration of the obtained modified PTFE aqueous dispersion 2-1 was 30.0% by mass, and the average primary particle diameter was 270 nm.
  • the obtained PTFE is a modified PTFE that does not have a core-shell structure.
  • a modified PTFE powder was obtained from the obtained modified PTFE aqueous dispersion 2-1 in the same manner as in Production Example 1.
  • the standard specific gravity of the obtained modified PTFE powder was 2.163, and the PPVE content was 0.28% by mass.
  • Modified PTFE aqueous dispersion 2-2 and PTFE aqueous dispersion B were obtained in the same manner as in Production Example 1, except that modified PTFE aqueous dispersion 1-1 was replaced with modified PTFE aqueous dispersion 2-1.
  • Table 2 shows the solid content concentration (mass %) of the obtained PTFE aqueous dispersion B and the content (mass %) of each component relative to PTFE. Further, the fluorine-containing surfactant concentration was 430 mass ppb relative to the PTFE aqueous dispersion B.
  • Manufacturing example 3 3500 g of deionized water, 100 g of paraffin wax, and 5.3 g of a white solid as a fluorine-containing surfactant were placed in a 6 L SUS reactor equipped with stirring blades. Next, the contents of the reactor were heated to 70° C. while being suctioned and simultaneously purged with TFE to remove oxygen in the reactor, and the contents were stirred. TFE was pressurized so that the internal pressure was 0.78 MPaG, and 10 g of a 0.6% by mass ammonium persulfate (APS) aqueous solution was charged to start the reaction.
  • APS ammonium persulfate
  • PTFE powder was obtained in the same manner as in Production Example 1.
  • the standard specific gravity of the obtained PTFE powder was 2.210.
  • PTFE aqueous dispersion 3-2 and PTFE aqueous dispersion C were obtained in the same manner as in Production Example 1, except that modified PTFE aqueous dispersion 1-1 was replaced with PTFE aqueous dispersion 3-1.
  • Table 2 shows the solid content concentration (mass %) of the obtained PTFE aqueous dispersion C and the content (mass %) of each component relative to PTFE.
  • Production example 4 3540 g of deionized water, 94 g of paraffin wax, and 5.4 g of the white solid obtained in Synthesis Example 1 as a fluorine-containing surfactant were placed in a 6 L SUS reactor equipped with a stirrer. Next, the contents of the reactor were heated to 70° C. while being suctioned and simultaneously purged with TFE to remove oxygen in the reactor, and the contents were stirred. 0.78 g of perfluoropropyl vinyl ether (PPVE) was pressurized into the reactor using TFE.
  • PPVE perfluoropropyl vinyl ether
  • DSP disuccinic acid peroxide
  • APS ammonium persulfate
  • the solid content concentration of the obtained aqueous dispersion 4-1 was 30.0% by mass, and the average primary particle diameter was 254 nm.
  • the obtained PTFE is a modified PTFE having a core-shell structure with a shell of low molecular weight PTFE.
  • a modified PTFE powder was obtained from the obtained PTFE aqueous dispersion 4-1 in the same manner as in Production Example 1.
  • the standard specific gravity of the obtained modified PTFE powder was 2.174, and the PPVE content was 0.046% by mass.
  • an OH type anion exchange resin trade name: Amberjet AMJ4002, manufactured by Rohm and Haas
  • a surfactant (c) was added to the aqueous dispersion obtained by passing through the solution in an amount of 20 parts by mass per 100 parts by mass of PTFE, and the mixture was kept at 65°C for 3 hours to separate a supernatant phase and a concentrated phase. separated. The concentrated phase was collected to obtain PTFE aqueous dispersion 4-2.
  • the obtained PTFE aqueous dispersion 4-2 has a solid content concentration of 71.5% by mass, a nonionic surfactant content of 2.7% by mass based on PTFE, and a fluorine-containing surfactant concentration of PTFE aqueous dispersion.
  • the amount was 480 ppb by mass based on the dispersion.
  • PTFE aqueous dispersion 4-2 obtained above, surfactant (c) was added at a concentration of 4.0% by mass based on PTFE, and surfactant (d) was further added to the PTFE aqueous dispersion 4-2.
  • PTFE aqueous dispersion D was obtained by adding 2.0% by mass of ammonium lauryl sulfate at 500 ppm based on PTFE, and further adding deionized water and aqueous ammonia.
  • Table 2 shows the solid content concentration (mass %) of the obtained PTFE aqueous dispersion D and the content (mass %) of each component relative to PTFE.
  • the extract was measured by 1H-NMR, and the average number of oxyalkylene units was 10.4. .
  • Modified PTFE aqueous dispersion 5-1 was obtained in the same manner as in Production Example 4, except that methanol was not injected into the reactor when the amount of TFE consumed in the reaction reached 1380 g, and the reaction was continued. .
  • the solid content concentration of the obtained PTFE aqueous dispersion was 30.0% by mass, and the average primary particle diameter was 252 nm.
  • the obtained PTFE is a modified PTFE that does not have a core-shell structure.
  • a modified PTFE powder was obtained from the obtained modified PTFE aqueous dispersion 5-1 in the same manner as in Production Example 1.
  • the standard specific gravity of the obtained modified PTFE powder was 2.170, and the PPVE content was 0.046% by mass.
  • PTFE aqueous dispersion 5-2 and PTFE aqueous dispersion E were obtained in the same manner as in Production Example 4, except that PTFE aqueous dispersion 5-1 was replaced with PTFE aqueous dispersion 4-1.
  • Table 2 shows the solid content concentration (mass %) of the obtained PTFE aqueous dispersion E and the content (mass %) of each component relative to PTFE.
  • Example 1 The following components were mixed in the order listed.
  • ⁇ Viscosity> The viscosity at 25° C. was measured using a B-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd., rotor No. 2) at a rotation speed of 60 rpm and a measurement time of 120 seconds.
  • ⁇ Stirring stability> A 250 ml container containing 200 ml of the paint composition was immersed in a water tank kept at 40°C, and a stirring blade (propeller type 4 blades) was rotated at 300 rpm until aggregates were generated or solidified in the paint composition. The time was measured as the gelation time.
  • Example 2 to 28 and Comparative Examples 1 to 7 A coating composition was obtained in the same manner as in Example 1, except that the components shown in Tables 3 and 4 were blended in the proportions shown in Tables 3 and 4. The properties of the obtained coating composition were investigated in the same manner as in Example 1. The results are shown in Tables 3 and 4.
  • Nonionic surfactant B in Tables 3 and 4 represents polyoxyethylene tridecyl ether.
  • Example 29 The following components were mixed in the order listed.
  • Nonionic surfactant A polyoxyethylene tridecyl ether, Dispanol TOC (50% aqueous solution) manufactured by NOF Corporation
  • F Organic solvent (N-methyl-2-pyrrolidone) 13.0 parts
  • G Amines (ammonia) 0.1 part
  • H Thickener (methyl cellulose) 0.2 parts
  • I Water 41.9 parts
  • J Filler (SiC, new Mohs hardness: 13) 2.6 parts
  • Table 5 The properties of the obtained coating composition were investigated in the same manner as in Example 1. The results are shown in Table 5.
  • Examples 30 to 48 and Comparative Examples 8 to 9 A coating composition was obtained in the same manner as in Example 29, except that the components shown in Table 5 were blended in the proportions shown in Table 5. The properties of the obtained coating composition were investigated in the same manner as in Example 29. The results are shown in Table 5.

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
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  • Paints Or Removers (AREA)
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Abstract

L'invention concerne une composition de revêtement susceptible de donner des films de revêtement ayant une excellente résistance à l'usure ; et un film de revêtement, un film de revêtement stratifié et un article revêtu, chacun étant obtenu à partir de la composition de revêtement ou par utilisation de cette dernière. La composition de revêtement comprend un polymère de l'éthylène fluoré, une charge et de l'eau, la teneur en polymère d'éthylène fluoré étant de 1 à 50 % en masse par rapport à la composition de revêtement, et la charge étant au moins une charge choisie dans le groupe consistant en (i) une charge ayant une dureté Mohs nouvelle de 9 ou plus, sa quantité étant de 0,1 à 80 % en masse par rapport au polymère de l'éthylène fluoré, (ii) une charge ayant une dureté Mohs nouvelle de 5 ou plus mais inférieure à 9, sa quantité étant de 0,1 à 120 % en masse par rapport au polymère de l'éthylène fluoré, et (iii) une charge ayant une dureté Mohs nouvelle inférieure à 5, sa quantité étant de 1 à 150 % en masse par rapport au polymère de l'éthylène fluoré.
PCT/JP2023/009181 2022-03-09 2023-03-09 Composition de revêtement, film de revêtement, film de revêtement stratifié et article revêtu WO2023171777A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000238205A (ja) * 1999-02-19 2000-09-05 E I Du Pont De Nemours & Co 耐摩耗性被覆剤組成物、それを被覆された基板、およびその被覆方法
JP2004533941A (ja) * 2001-04-02 2004-11-11 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー フルオロポリマーノンスティックコーティング
JP2009519816A (ja) * 2005-12-14 2009-05-21 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ダイヤモンド粒子を含む非付着性被膜組成物および前記組成物が適用された基材
JP2011514184A (ja) * 2008-02-07 2011-05-06 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 不粘着仕上塗料および改善された耐引掻性を有する物品
WO2021045228A1 (fr) * 2019-09-05 2021-03-11 ダイキン工業株式会社 Dispersion aqueuse de polytétrafluoroéthylène

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000238205A (ja) * 1999-02-19 2000-09-05 E I Du Pont De Nemours & Co 耐摩耗性被覆剤組成物、それを被覆された基板、およびその被覆方法
JP2004533941A (ja) * 2001-04-02 2004-11-11 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー フルオロポリマーノンスティックコーティング
JP2009519816A (ja) * 2005-12-14 2009-05-21 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ダイヤモンド粒子を含む非付着性被膜組成物および前記組成物が適用された基材
JP2011514184A (ja) * 2008-02-07 2011-05-06 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 不粘着仕上塗料および改善された耐引掻性を有する物品
WO2021045228A1 (fr) * 2019-09-05 2021-03-11 ダイキン工業株式会社 Dispersion aqueuse de polytétrafluoroéthylène

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