WO2022054762A1 - Composition for coating, and coated article - Google Patents

Composition for coating, and coated article Download PDF

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Publication number
WO2022054762A1
WO2022054762A1 PCT/JP2021/032685 JP2021032685W WO2022054762A1 WO 2022054762 A1 WO2022054762 A1 WO 2022054762A1 JP 2021032685 W JP2021032685 W JP 2021032685W WO 2022054762 A1 WO2022054762 A1 WO 2022054762A1
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Prior art keywords
coating composition
coating
acetylene diol
mass
composition according
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PCT/JP2021/032685
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French (fr)
Japanese (ja)
Inventor
誠太郎 山口
安利 中谷
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ダイキン工業株式会社
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Priority to CN202180058947.6A priority Critical patent/CN116137866A/en
Publication of WO2022054762A1 publication Critical patent/WO2022054762A1/en

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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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • 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
    • C09D127/20—Homopolymers or copolymers of hexafluoropropene
    • 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
    • C09D129/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/04—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • 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
    • C09D7/20—Diluents or solvents
    • 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
    • C09D7/45—Anti-settling agents
    • 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
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the present disclosure relates to a coating composition and a coated article.
  • Fluororesin is excellent in heat resistance, chemical resistance, water repellency, oil repellency, mold release property, slidability and the like. For this reason, fluororesin is used in the fields of mold release materials, office automation [OA] equipment rolls, household products such as irons, kitchen appliances such as frying pans and hot plates, food industry, electrical industry, machine industry, etc. It is used as a covering material.
  • Patent Document 1 discloses a fluororesin-containing aqueous dispersion composition obtained by blending a tetrafluoroethylene polymer with an aliphatic polyoxyalkylene ether dispersant having a 50% decomposition temperature of 250 ° C. or higher. ..
  • Patent Document 2 describes an aqueous fluoropolymer dispersion containing a melt-processable fluoropolymer and a fluorinated surfactant having a molecular weight of 1000 g / mol or less in an amount of less than 10 ppm based on the weight of the fluoropolymer solid content. It has been disclosed.
  • Patent Document 3 describes a fluororesin that can be melt-processed, a nonionic surfactant, and a specific polyhydric alcohol, and is used for an aqueous coating having a low concentration of a fluorine-containing surfactant and excellent film-forming property and storage stability.
  • the composition is disclosed.
  • Patent Document 4 discloses an aqueous dispersion of a fluororesin containing an acetylene diol-based surfactant without containing a fluorine-based surfactant.
  • the present disclosure relates to a fluorine-containing polymer (a) having a 98% integrated particle size of 0.4 ⁇ m or more and less than 1.0 ⁇ m, a non-alkylphenol type nonionic surfactant (b), and an acetylene diol-based surfactant (c).
  • a fluorine-containing polymer having a 98% integrated particle size of 0.4 ⁇ m or more and less than 1.0 ⁇ m
  • a non-alkylphenol type nonionic surfactant b
  • an acetylene diol-based surfactant c
  • the acetylene diol-based surfactant (c) is a coating composition characterized by having a residual amount of 3.0% by mass or more at 300 ° C. by thermogravimetric analysis.
  • the non-alkylphenol type nonionic surfactant (b) is represented by the formula (I) :.
  • ROAH (I) (In the formula, R is a linear or branched saturated or unsaturated acyclic aliphatic hydrocarbon group having 8 to 19 carbon atoms or a saturated cyclic aliphatic hydrocarbon group having 8 to 19 carbon atoms.
  • A is a non-alkylphenol type nonionic surfactant represented by a polyoxyalkylene chain having 3 to 25 oxyethylene units and 0 to 5 oxypropylene units).
  • the acetylene diol-based surfactant (c) is preferably an ethylene oxide adduct of acetylene diol.
  • the acetylene diol-based surfactant (c) preferably has an HLB of more than 4.
  • the coating composition of the present disclosure further preferably contains a water-soluble polyhydric alcohol (d) having a boiling point of 100 ° C. or higher and having two or more hydroxyl groups.
  • the water-soluble polyhydric alcohol (d) having a boiling point of 100 ° C. or higher and having two or more hydroxyl groups is preferably ethylene glycol.
  • the fluorine-containing polymer (a) is composed of a group consisting of a tetrafluoroethylene [TFE] / hexafluoropropylene [HFP] copolymer [FEP] and a TFE / perfluoro (alkyl vinyl ether) [PAVE] copolymer [PFA]. It is preferably at least one selected.
  • the present disclosure is also a coated article obtained by coating the above-mentioned coating composition.
  • the coating composition of the present disclosure comprises a fluoropolymer (a) having a 98% integrated particle size of 0.4 ⁇ m or more and less than 1.0 ⁇ m, a non-alkylphenol type nonionic surfactant (b), and an acetylene diol-based surfactant.
  • the coating composition of the present disclosure has excellent mechanical stability and film formation by using a non-alkylphenol type nonionic surfactant (b) in combination with a specific acetylene diol-based surfactant (c). It is a coating composition that realizes the properties.
  • the above-mentioned mechanical stability is a property that it is difficult to form non-redispersable aggregates even when a strong stirring or shearing force is applied by a homogenizer or the like during liquid feeding or redispersion.
  • Fluororesin tends to have a large surface tension, and when a fluororesin aqueous dispersion is coated on various substrates, repelling occurs and the coating film cannot be formed cleanly, or the storage stability of the fluororesin aqueous dispersion can be improved. Problems with mechanical stability are likely to occur.
  • the coating film property is good and cracks do not occur after the coating film. Further, the dispersed state of the fluororesin in the coating composition is stable.
  • the use of the surfactant (b) in the coating composition containing the fluororesin improves the mechanical stability of the coating composition.
  • the mechanical stability of the coating composition can be improved, and the film-forming property and the smoothness of the coating film can be improved.
  • the acetylene diol-based surfactant (c) is a surfactant having a carbon-carbon triple bond in the molecule.
  • examples of the acetylene diol-based surfactant (c) include acetylene diol (which has an acetylene bond and two hydroxyl groups in the same molecule at the same time) and a surfactant in which an alkylene oxide unit is added to acetylene diol. Be done.
  • Specific examples of such an acetylene diol-based surfactant include a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2).
  • R 1 and R 2 each independently represent an alkyl group having 3 to 9 carbon atoms
  • R 3 and R 4 each independently represent an alkylene group having 1 to 4 carbon atoms.
  • M and n are integers, and the sum of m and n represents 2 to 50.
  • the remaining amount of the acetylene diol-based surfactant (c) at 300 ° C. is 3.0% by mass or more by thermogravimetric analysis.
  • the acetylene diol-based surfactant (c) having a residual amount of 3.0% by mass or more at 300 ° C. in the thermogravimetric analysis the acetylene diol-based interface is heated even when heated at a high temperature during thermal melting.
  • the activator (c) remains in the coating film, which is preferable in that various functions can be exhibited.
  • the residual mass ratio at 300 ° C. is a temperature increase rate of 10 ° C./ It is the mass ratio at which the temperature is raised from room temperature in minutes and the sample remains at 300 ° C.
  • the acetylene diol-based surfactant (c) is preferably an ethylene oxide adduct of acetylene diol represented by the above general formula (2).
  • the ethylene oxide adduct of acetylene diol can easily satisfy the remaining amount at 300 ° C. of 3.0% by mass or more in the above thermogravimetric analysis, which is good even at the time of heat curing at high temperature. It is preferable in that an effect can be obtained.
  • acetylene diol-based surfactant a commercially available product may be used.
  • Surfinol® 440, 465, 485, SE, 2502, Orfin® PD-002W, EXP. 4200, E1004, E1010 (all manufactured by Nisshin Kagaku Kogyo Co., Ltd.), acetylenol (registered trademark) E00, acetylenol E13T, acetylenol E40, acetylenol E60, acerenol E100, acetylenol E200 (all manufactured by Kawaken Fine Chemical Co., Ltd.), etc. Will be.
  • the acetylene diol-based surfactant (c) preferably has an HLB of more than 4, more preferably 5 or more. 6 or more is more preferable, and 8 or more is most preferable.
  • An acetylene diol-based surfactant having a high HLB has excellent heat resistance. By using an acetylene diol-based surfactant having a high HLB, the film-forming property of the coating composition is improved. Further, the acetylene diol-based surfactant having a high HLB has excellent solubility in an aqueous medium, and the mechanical stability of the coating composition becomes more excellent.
  • the coating composition of the present disclosure preferably contains the acetylene diol-based surfactant (c) in an amount of 0.05 to 5.0% by mass with respect to the fluorine-containing polymer (a).
  • the lower limit of the content of the acetylene diol-based surfactant (c) is more preferably 0.1% by mass, further preferably 0.5% by mass.
  • the upper limit of the acetylene diol-based surfactant (c) is more preferably 3.0% by mass, further preferably 2.0% by mass.
  • the fluorine-containing polymer (a) has a 98% integrated particle size of 0.4 ⁇ m or more and less than 1.0 ⁇ m.
  • the 98% integrated particle diameter means a particle diameter at a point where the integrated value from the minimum point of the volume converted from the particle diameter is 98%. Since the 98% integrated particle size is 0.4 ⁇ m or more and less than 1.0 ⁇ m, it is possible to produce a film having good mechanical stability and excellent surface smoothness of the coating composition.
  • the preferred lower limit is 0.5 ⁇ m and the preferred upper limit is 0.9 ⁇ m.
  • Such a fluorine-containing polymer (a) is preferably produced by an emulsion polymerization method.
  • a fluorine-containing polymer (a) having a 98% integrated particle size of 0.4 ⁇ m or more and less than 1.0 ⁇ m can be easily obtained.
  • the fluorine-containing polymer (a) is preferably particles having a 98% integrated particle diameter of 0.4 ⁇ m or more and less than 1.0 ⁇ m and an average particle diameter of 0.01 or more and less than 1.0 ⁇ m. If the average particle size is less than 0.01 ⁇ m, the mechanical stability of the particles made of the fluororesin (a) is poor, and the mechanical stability and storage stability of the coating composition may be poor. When the average particle size is 1.0 ⁇ m or more, the uniform dispersibility of the particles made of the fluorine-containing polymer (a) is lacking, and when coating with the coating composition, a coating film having a smooth surface cannot be obtained. , The physical properties of the coating film may be inferior. A more preferable lower limit is 0.05 ⁇ m, and a more preferable upper limit is 0.8 ⁇ m.
  • the 98% integrated particle diameter and the average particle diameter are measured by a particle size distribution measuring device (Microtrac MT-3000EXII type manufactured by Microtrac Bell) by laser diffraction. With this device, the average particle size and the 98% integrated particle size are automatically calculated.
  • the average particle diameter is a 50% integrated particle diameter automatically calculated by the apparatus.
  • the fluorine-containing polymer (a) is not particularly limited, but is polytetrafluoroethylene [PTFE], tetrafluoroethylene [TFE] / hexafluoropropylene [HFP] copolymer [FEP], TFE / perfluoroalkyl vinyl ether [ PAVE] copolymer [PFA] and the like can be mentioned.
  • PTFE polytetrafluoroethylene
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • PAVE] copolymer [PFA] and the like can be mentioned.
  • it is preferably composed of at least one copolymer selected from the group of TFE / HFP copolymer [FEP] and TFE / PAVE copolymer [PFA], which are fluororesins that can be melt-processed. ..
  • the FEP has an HFP unit of more than 2% by mass, preferably 20% by mass or less, and more preferably 10 to 15% by mass.
  • the PAVE in the PFA preferably has an alkyl group having 1 to 6 carbon atoms, and more preferably perfluoromethyl vinyl ether, perfluoroethyl vinyl ether or perfluoropropyl vinyl ether.
  • the PAVE unit is preferably more than 2.0% by mass, preferably 5.0% by mass or less, and more preferably 2.5 to 4.0% by mass.
  • the FEP and PFA may be obtained by further polymerizing other monomers as long as they have the above-mentioned compositions.
  • the other monomer include PAVE in the case of FEP and HFP in the case of PFA.
  • the above-mentioned other monomers one kind or two or more kinds can be used.
  • the above-mentioned other monomers vary depending on the type, but are usually preferably 1% by mass or less based on the mass of the fluororesin. A more preferable upper limit is 0.5% by mass, and a more preferable upper limit is 0.3% by mass.
  • the non-alkylphenol type nonionic surfactant (b) is a nonionic surfactant which does not contain a benzene ring in its structure.
  • a nonionic surfactant made from a polyoxyethylene alkyl ether-based natural alcohol can be mentioned.
  • the above-mentioned acetylene diol-based surfactant is not included in the non-alkylphenol type nonionic surfactant (b).
  • the non-alkylphenol type nonionic surfactant (b) has the following general formula (I): ROAH (I) (In the formula, R is a linear or branched saturated or unsaturated acyclic aliphatic hydrocarbon group having 8 to 19 carbon atoms, or a saturated cyclic aliphatic hydrocarbon group having 8 to 19 carbon atoms.
  • A is a polyoxyalkylene chain having 3 to 25 oxyethylene units and 0 to 5 oxypropylene units), and is preferably a nonionic surfactant.
  • the nonionic surfactant represented by the above general formula (I) includes the following general formula (II): C x H 2x + 1 CH (C y H 2y + 1 ) C z H 2z O (C 2 H 4 O) n H (II) (In the formula, x is an integer of 1 or more, y is an integer of 1 or more, z is 0 or 1, where x + y + z is an integer of 8 to 18, and n is an integer of 4 to 20).
  • the non-alkylphenol type nonionic surfactant (b) preferably has an HLB of 10 to 15. A more preferred HLB range is 12-14. Within this range, a coating composition having excellent storage stability can be obtained.
  • the content of the non-alkylphenol type nonionic surfactant (b) may be an amount that stabilizes the dispersed state of the coating composition of the present disclosure, for example, with respect to the fluorine-containing polymer (a). An amount of 3 to 15% by mass, more preferably 5 to 12% by mass may be present.
  • the storage stability is generally insufficient when the content of the fluorine-containing surfactant is reduced, but the coating composition of the present disclosure exhibits excellent storage stability. .. Although the reason for this is not clear, it is considered that excellent storage stability can be obtained by adsorbing the non-alkylphenol type nonionic surfactant (b) to the fluororesin.
  • the coating composition of the present disclosure preferably does not contain a silicone-based surfactant. This is because the inclusion of a silicone-based surfactant is disadvantageous in that repellents and pinholes may be generated during painting.
  • the coating composition of the present disclosure further preferably contains the water-soluble polyhydric alcohol (d) having a boiling point of 100 ° C. or higher and having two or more hydroxyl groups.
  • the polyhydric alcohol (d) remains in the coating film even after the water evaporates when the object to be coated is applied and dried, and cracks caused by shrinkage of the coating film due to evaporation of the solvent or water. Shows the action of preventing (so-called mudcrack). Therefore, the coating composition of the present disclosure contains the above-mentioned polyhydric alcohol (d), so that mudcrack is less likely to occur at the time of painting. Further, since the polyhydric alcohol (d) is gradually decomposed at the time of firing, it does not cause coloring of the coating film.
  • the polyhydric alcohol (d) preferably has a boiling point of 100 ° C. or higher. If the boiling point is less than 100 ° C., it evaporates faster than water during drying and cannot remain in the coating film after drying, which makes it difficult to contribute to the improvement of film forming property.
  • the boiling point is preferably a drying temperature or higher, more preferably 150 ° C. or higher, and even more preferably 180 ° C. or higher.
  • the polyhydric alcohol (d) is preferably a water-soluble alcohol having two or more hydroxyl groups.
  • a compound having one or zero hydroxyl groups and having a boiling point of 100 ° C. or higher is inferior in hydrophilicity, and therefore tends to be difficult to uniformly mix.
  • the polyhydric alcohol (d) is preferably liquid at room temperature and has a high effect of preventing mudcrack, and thus preferably has two or three hydroxyl groups.
  • the polyhydric alcohol (d) is finally evaporated or decomposed and volatilized by heating during firing. Therefore, it is preferable that the boiling point or the thermal decomposition temperature is equal to or lower than the melting temperature of the fluororesin, preferably 340 ° C. or lower.
  • polyhydric alcohol (d) examples include 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-butane-1,4-diol (235 ° C).
  • ethylene glycol is preferable because it has excellent film-forming properties.
  • the blending amount of the polyhydric alcohol (d) is preferably 5 to 18 parts by mass, more preferably 7 to 15 parts by mass, and particularly preferably 7 to 7 to 100 parts by mass with respect to 100 parts by mass of the fluorine-containing polymer (a). It is 12 parts by mass. If it is less than 5 parts by mass, the effect of preventing the occurrence of mudcrack may be weakened, and if it exceeds 18 parts by mass, the coating film may become cloudy.
  • the coating composition of the present disclosure comprises an aqueous medium.
  • aqueous medium water may be used alone, or it may be an aqueous mixed solvent in which water and a water-soluble compound are used in combination.
  • the coating composition of the present disclosure may contain other resins, if necessary, as long as the characteristics of the present disclosure are not impaired.
  • the other resins are not particularly limited, and for example, polyethylene oxide (dispersion stabilizer), phenol resin, urea resin, epoxy resin, melamine resin, polyester resin, polyether resin, acrylic silicone resin, silicone resin, silicone polyester resin. And so on.
  • the coating composition of the present disclosure may contain additives used in a more general coating composition for the purpose of improving the coatability and the properties of the obtained coating film.
  • the additive is not particularly limited and can be selected depending on the use of the obtained coated article.
  • a leveling agent, a solid lubricant, wood powder, quartz sand, carbon black, diamond, tourmaline, germanium and alumina can be selected.
  • Viscosity adjuster Viscosity adjuster, anti-gelling agent, UV absorber, light stabilizer, plasticizer, anti-color separation agent, anti-skin agent, anti-scratch agent, anti-mold agent, anti-bacterial agent, antioxidant, anti-static agent , Silane coupling agent, antifoaming agent, desiccant, anti-repellent agent.
  • the bright material examples include mica, metal powder, glass beads, glass bubbles, glass flakes, glass fibers and the like.
  • the content of the bright material is preferably 0.1 to 10.0% by mass with respect to the solid content of the coating composition.
  • the metal powder is not particularly limited, and examples thereof include powders of single metals such as aluminum, iron, tin, zinc, gold, silver, and copper; and powders of alloys such as aluminum alloys and stainless steel.
  • the shape of the metal powder is not particularly limited, and examples thereof include a particle shape and a flake shape.
  • the coating composition of the present disclosure may be a clear paint that does not contain these coloring components.
  • viscosity adjusting agent examples include methyl cellulose, alumina sol, polyvinyl alcohol, and carboxylated vinyl polymer.
  • defoaming agent examples include toluene, xylene, non-polar solvents such as hydrocarbons having 9 to 11 carbon atoms, silicone oil and the like.
  • Examples of the desiccant include cobalt oxide and the like.
  • the coating composition of the present disclosure contains a fluorine-containing polymer (a) and, if necessary, a solid content such as an inorganic material, and the solid content content thereof is 20 to 80% by mass, particularly 30 to 70. It is preferably by mass%. If the solid content concentration is less than 20% by mass, it may be difficult to obtain a thick film by one coating, and if it exceeds 80% by mass, the viscosity becomes high and spray coating may be difficult.
  • the coating composition of the present disclosure can be prepared by a conventional method.
  • a nonionic surfactant (b), an acetylenediol-based surfactant (c), other additives, etc. are added to the fluororesin aqueous dispersion in which the fluororesin-containing polymer (a) is dispersed in an aqueous medium. It can be prepared by adding and mixing under stirring and stirring and mixing at 5 to 30 ° C. for 10 to 40 minutes. Further, an aqueous medium may be added to adjust the solid content concentration.
  • the coating composition of the present disclosure can be suitably used as a coating material, can be used as a top coating material, and can also be used as an intermediate coating material. It can also be used as a paint for lining.
  • various coating methods similar to the conventional ones can be adopted, and examples thereof include a dipping method, a spray method, a roll coating method, a doctor blade method, a spin flow coating, and a curtain flow coating method.
  • the coating composition of the present disclosure may be directly coated on a substrate, but it is desirable to provide a primer layer and coat the coating composition in order to improve adhesion.
  • the base material is not particularly limited, but for example, various metals, enamel, glass, and various ceramics can be used, and it is preferable to roughen the surface by a sandblasting method or the like in order to improve the adhesion.
  • the coating composition applied to the substrate is then dried.
  • the coating composition of the present disclosure is characterized in that mudcrack does not occur during this drying stage. Drying may be carried out under normal conditions and varies depending on the boiling point of the polyhydric alcohol (d) used, but if it is carried out at room temperature to 150 ° C., more preferably 80 to 150 ° C. for 5 to 20 minutes, it reaches dryness to the touch. ..
  • the dried coating film is fired (processed).
  • the firing (processing) temperature and time will vary depending on the type of fluororesin, melting temperature, etc., but for example, the calcination is performed at 340 to 415 ° C. for 5 to 30 minutes, which is equal to or higher than the melting temperature of the fluororesin.
  • the coating composition of the present disclosure may be applied, dried and fired after the primer is applied, dried and fired (2-coat 2-baking method), or the primer is applied and dried before the present invention.
  • the disclosed coating composition may be applied and dried, and both may be fired at the same time (2-coat, 1-bak method), or the primer may be applied and dried, and then the bright material, which is the coating composition of the present disclosure, is contained.
  • It is a method (3 coat 1 bake method) in which a primer paint is applied and dried, and then a top coat paint which is a clear paint other than the coating composition of the present disclosure is applied and dried, and these are simultaneously fired. You may.
  • the coating composition may be sequentially coated with the intermediate coating paint containing a brilliant agent and the top coating coating which is a clear paint, which are the coating compositions of the present disclosure.
  • a thick coating film having a thickness of 30 ⁇ m or more can be obtained by one coating.
  • a coated article characterized by being obtained by painting the coating composition of the present disclosure is also one of the present disclosures.
  • the covered articles of the present disclosure include, for example, frying pans, grill pans, pressure pans, various other pans, rice cookers, rice cake making machines, ovens, hot plates, pan-baking molds, kitchen utensils, gas tables and other cooking utensils; electric pots, Food and beverage containers such as ice trays; Food industry parts such as kneading rolls, rolling rolls, conveyors, and hoppers; Rolls for office automation equipment [OA], belts for OA, separation claws for OA, paper making rolls, calendar rolls for film manufacturing Industrial supplies such as; Molds for foam styrol molding, molds, molding molds such as molds for manufacturing plywood and decorative boards; Kitchen supplies such as range hoods; Frozen food manufacturing equipment such as conveyor belts; Saw, Tools such as razors, dies, and cutters; Household products such as irons, shears, and kitchenettes;
  • the solid content concentration of PFA was 64.0%
  • the amount of nonionic surfactant was equivalent to 3.0% of PFA
  • the integrated particle size of 98% of PFA was 0.
  • a PFA aqueous dispersion having a diameter of .55 ⁇ m and an average particle size of 0.35 ⁇ m was obtained.
  • thermogravimetric analysis of the acetylene diol-based activator (Surfinol 440 (HLB8) manufactured by Nisshin Kagaku Kogyo Co., Ltd.) showed that the residual amount at 300 ° C. was 6% by mass.
  • the obtained coating composition was evaluated for mechanical stability and film-forming property. The results are shown in Table 1.
  • Example 2 The coating composition was prepared in the same manner as in Example 1 except that the raw material composition ratio of the coating composition was adjusted as shown in Table 1, and various performances of the obtained coating composition were evaluated. The results are shown in Table 1.
  • Example 1 A coating film formed from the obtained coating composition was prepared in the same manner as in Example 1 except that an acetylene diol-based activator (Surfinol 440 (HLB8) manufactured by Nisshin Chemical Industry Co., Ltd.) was not blended. Various performances of the membrane were evaluated. The results are shown in Table 4.
  • an acetylene diol-based activator Sudfinol 440 (HLB8) manufactured by Nisshin Chemical Industry Co., Ltd.
  • Example 2 A coating film formed from the obtained coating composition prepared in the same manner as in Example 1 except that an acetylene diol-based activator (Surfinol 104A (HLB4) manufactured by Nisshin Chemical Industry Co., Ltd.) was blended. Various performances were evaluated. The results are shown in Table 4. In the thermogravimetric analysis of the acetylene diol-based activator (Surfinol 104A (HLB4) manufactured by Nissin Chemical Industry Co., Ltd.), the residual amount at 300 ° C. was 0% by mass.
  • Example 3 A coating film formed from the obtained coating composition prepared in the same manner as in Example 1 except that an acetylene diol-based activator (Surfinol 420 (HLB4) manufactured by Nisshin Chemical Industry Co., Ltd.) was blended. Various performances were evaluated. The results are shown in Table 4. In the thermogravimetric analysis of the acetylene diol-based activator (Surfinol 420 (HLB4) manufactured by Nissin Chemical Industry Co., Ltd.), the residual amount at 300 ° C. was 0% by mass.
  • the coating composition of the present disclosure has the above-mentioned structure, it is possible to achieve both mechanical stability and film-forming property, and it is suitable as a coating material for surface coating of cooking utensils and the like.

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Abstract

Provided are: a composition for coating, the composition having good mechanical stability and excellent film-forming properties; and a coated article formed by coating the composition. The composition for coating is an aqueous dispersion composition containing: a fluorine-containing polymer (a) having a 98% cumulative particle diameter of 0.4-1.0 μm (exclusive of 1.0); a non-alkyl phenol-type nonionic surfactant (b); and an acetylene diol-based surfactant (c), the acetylene diol-based surfactant (c) being characterized by having a residual amount of at least 3.0 mass% at 300 °C in a thermogravimetric analysis.

Description

被覆用組成物及び被覆物品Coating composition and coating article
本開示は、被覆用組成物及び被覆物品に関する。 The present disclosure relates to a coating composition and a coated article.
フッ素樹脂は、耐熱性、耐薬品性、撥水撥油性、離型性、摺動性等に優れている。このことから、フッ素樹脂は、成形金型離型材、オフィスオートメーション［ＯＡ］機器用ロール、アイロン等の家庭用品、フライパンやホットプレート等の厨房器具、食品工業、電気工業、機械工業等の分野で被覆材として用いられている。 Fluororesin is excellent in heat resistance, chemical resistance, water repellency, oil repellency, mold release property, slidability and the like. For this reason, fluororesin is used in the fields of mold release materials, office automation [OA] equipment rolls, household products such as irons, kitchen appliances such as frying pans and hot plates, food industry, electrical industry, machine industry, etc. It is used as a covering material.
特許文献１には、テトラフルオロエチレン重合体に、５０％分解温度が２５０℃以上である脂肪族系ポリオキシアルキレンエーテル分散剤を配合してなる含フッ素樹脂水性分散体組成物が開示されている。 Patent Document 1 discloses a fluororesin-containing aqueous dispersion composition obtained by blending a tetrafluoroethylene polymer with an aliphatic polyoxyalkylene ether dispersant having a 50% decomposition temperature of 250 ° C. or higher. ..
特許文献２には、溶融加工可能なフルオロポリマーと、フルオロポリマー固形分の重量を基準にして１０ｐｐｍ未満の量の、分子量が１０００ｇ／ｍｏｌ以下のフッ素化界面活性剤を含む水性フルオロポリマー分散体が開示されている。 Patent Document 2 describes an aqueous fluoropolymer dispersion containing a melt-processable fluoropolymer and a fluorinated surfactant having a molecular weight of 1000 g / mol or less in an amount of less than 10 ppm based on the weight of the fluoropolymer solid content. It has been disclosed.
特許文献３には、溶融加工可能なフッ素樹脂、ノニオン系界面活性剤及び特定の多価アルコールからなり、含フッ素界面活性剤の濃度が低く、造膜性と貯蔵安定性に優れた水性被覆用組成物が開示されている。 Patent Document 3 describes a fluororesin that can be melt-processed, a nonionic surfactant, and a specific polyhydric alcohol, and is used for an aqueous coating having a low concentration of a fluorine-containing surfactant and excellent film-forming property and storage stability. The composition is disclosed.
特許文献４には、フッ素系界面活性剤を含有することなく、アセチレンジオール系界面活性剤を含有するフッ素樹脂水性分散体が開示されている。 Patent Document 4 discloses an aqueous dispersion of a fluororesin containing an acetylene diol-based surfactant without containing a fluorine-based surfactant.
国際公開第２００３／１０６５５６号International Publication No. 2003/106556 特表２００６／５２２８３６号公報Special Table 2006/522836 Gazette 国際公開第２００９／０２８３８５号International Publication No. 2009/0288385 特開２００９－１６１６１６号公報Japanese Unexamined Patent Publication No. 2009-161616
本開示は、機械的安定性が良好で、造膜性に優れた被覆用組成物及びそれを被覆してなる被覆物品を提供することを目的とする。 It is an object of the present disclosure to provide a coating composition having good mechanical stability and excellent film-forming property, and a covering article obtained by coating the composition.
本開示は、９８％積算粒子径が０．４μｍ以上１．０μｍ未満の含フッ素重合体（ａ）と、非アルキルフェノール型ノニオン界面活性剤（ｂ）と、アセチレンジオール系界面活性剤（ｃ）とを含有する水性分散体組成物であり、
前記アセチレンジオール系界面活性剤（ｃ）は熱重量分析で３００℃における残量が３．０質量％以上であることを特徴とする被覆用組成物である。 The present disclosure relates to a fluorine-containing polymer (a) having a 98% integrated particle size of 0.4 μm or more and less than 1.0 μm, a non-alkylphenol type nonionic surfactant (b), and an acetylene diol-based surfactant (c). Is an aqueous dispersion composition containing
The acetylene diol-based surfactant (c) is a coating composition characterized by having a residual amount of 3.0% by mass or more at 300 ° C. by thermogravimetric analysis.
上記非アルキルフェノール型ノニオン界面活性剤（ｂ）は、式（Ｉ）：
Ｒ－Ｏ－Ａ－Ｈ　　（Ｉ）
（式中、Ｒは直鎖状または分岐鎖状の炭素数８～１９の飽和又は不飽和の非環式脂肪族炭化水素基あるいは、炭素数８～１９の飽和環式脂肪族炭化水素基を表す。Ａはオキシエチレンユニットを３～２５個およびオキシプロピレンユニットを０～５個有するポリオキシアルキレン鎖）で示される非アルキルフェノール型ノニオン界面活性剤であることが好ましい。 The non-alkylphenol type nonionic surfactant (b) is represented by the formula (I) :.
ROAH (I)
(In the formula, R is a linear or branched saturated or unsaturated acyclic aliphatic hydrocarbon group having 8 to 19 carbon atoms or a saturated cyclic aliphatic hydrocarbon group having 8 to 19 carbon atoms. A is a non-alkylphenol type nonionic surfactant represented by a polyoxyalkylene chain having 3 to 25 oxyethylene units and 0 to 5 oxypropylene units).
上記アセチレンジオール系界面活性剤（ｃ）は、アセチレンジオールのエチレンオキサイド付加物であることが好ましい。
上記アセチレンジオール系界面活性剤（ｃ）は、ＨＬＢが４を超えるものであることが好ましい。 The acetylene diol-based surfactant (c) is preferably an ethylene oxide adduct of acetylene diol.
The acetylene diol-based surfactant (c) preferably has an HLB of more than 4.
本開示の被覆用組成物は、更に、沸点が１００℃以上でかつ水酸基を２個以上有する水溶性の多価アルコール（ｄ）を含有することが好ましい。
上記沸点が１００℃以上でかつ水酸基を２個以上有する水溶性の多価アルコール（ｄ）は、エチレングリコールであることが好ましい。 The coating composition of the present disclosure further preferably contains a water-soluble polyhydric alcohol (d) having a boiling point of 100 ° C. or higher and having two or more hydroxyl groups.
The water-soluble polyhydric alcohol (d) having a boiling point of 100 ° C. or higher and having two or more hydroxyl groups is preferably ethylene glycol.
含フッ素重合体（ａ）は、テトラフルオロエチレン〔ＴＦＥ〕／ヘキサフルオロプロピレン〔ＨＦＰ〕共重合体〔ＦＥＰ〕及びＴＦＥ／パーフルオロ（アルキルビニルエーテル）〔ＰＡＶＥ〕共重合体〔ＰＦＡ〕よりなる群から選択される少なくとも１種であることが好ましい。
本開示は、上記被覆用組成物を塗装することにより得られた被覆物品でもある。 The fluorine-containing polymer (a) is composed of a group consisting of a tetrafluoroethylene [TFE] / hexafluoropropylene [HFP] copolymer [FEP] and a TFE / perfluoro (alkyl vinyl ether) [PAVE] copolymer [PFA]. It is preferably at least one selected.
The present disclosure is also a coated article obtained by coating the above-mentioned coating composition.
本開示により、機械的安定性が良好で、造膜性に優れた被覆用組成物及びそれを被覆してなる被覆物品を提供することができる。 INDUSTRIAL APPLICABILITY According to the present disclosure, it is possible to provide a coating composition having good mechanical stability and excellent film-forming property, and a covering article obtained by coating the composition.
以下、本開示を詳細に説明する。
本開示の被覆用組成物は、９８％積算粒子径が０．４μｍ以上１．０μｍ未満の含フッ素重合体（ａ）と、非アルキルフェノール型ノニオン界面活性剤（ｂ）と、アセチレンジオール系界面活性剤（ｃ）とを含有する水性分散体組成物であり、前記アセチレンジオール系界面活性剤（ｃ）は熱重量分析で３００℃における残量が３．０質量％以上であるものである。本開示の被覆用組成物は、非アルキルフェノール型ノニオン界面活性剤（ｂ）と、特定のアセチレンジオール系界面活性剤（ｃ）とを組み合わせて用いたことによって、優れた機械的安定性と造膜性を実現した被覆用組成物である。 Hereinafter, the present disclosure will be described in detail.
The coating composition of the present disclosure comprises a fluoropolymer (a) having a 98% integrated particle size of 0.4 μm or more and less than 1.0 μm, a non-alkylphenol type nonionic surfactant (b), and an acetylene diol-based surfactant. An aqueous dispersion composition containing the agent (c), wherein the acetylene diol-based surfactant (c) has a remaining amount of 3.0% by mass or more at 300 ° C. by thermogravimetric analysis. The coating composition of the present disclosure has excellent mechanical stability and film formation by using a non-alkylphenol type nonionic surfactant (b) in combination with a specific acetylene diol-based surfactant (c). It is a coating composition that realizes the properties.
上記機械的安定性とは、送液や再分散の際、ホモジナイザー等による強い攪拌や剪断力を与えても、再分散不可能な凝集体を生成しにくい性質のことである。 The above-mentioned mechanical stability is a property that it is difficult to form non-redispersable aggregates even when a strong stirring or shearing force is applied by a homogenizer or the like during liquid feeding or redispersion.
フッ素樹脂は、表面張力が大きくなる傾向にあり、フッ素樹脂水性分散液を各種の基材にコーティングすると、はじきが生じて塗膜がきれいに形成できなかったり、フッ素樹脂水性分散液の貯蔵安定性や機械的安定性に問題が生じたりしやすい。 Fluororesin tends to have a large surface tension, and when a fluororesin aqueous dispersion is coated on various substrates, repelling occurs and the coating film cannot be formed cleanly, or the storage stability of the fluororesin aqueous dispersion can be improved. Problems with mechanical stability are likely to occur.
本開示においては、非アルキルフェノール型ノニオン界面活性剤（ｂ）と、特定のアセチレンジオール系界面活性剤（ｃ）とを用いることにより、塗膜性が良好で、塗膜後のクラック発生がなく、また、被覆用組成物中のフッ素樹脂の分散状態が安定するものである。 In the present disclosure, by using the non-alkylphenol type nonionic surfactant (b) and the specific acetylene diol-based surfactant (c), the coating film property is good and cracks do not occur after the coating film. Further, the dispersed state of the fluororesin in the coating composition is stable.
フッ素樹脂を含有する被覆用組成物において界面活性剤（ｂ）を使用すると、被覆用組成物の機械的安定性が向上する。界面活性剤（ｃ）を使用すると、被覆用組成物の機械的安定性を向上させ、かつ造膜性と塗膜の平滑性を向上させることができる。 The use of the surfactant (b) in the coating composition containing the fluororesin improves the mechanical stability of the coating composition. When the surfactant (c) is used, the mechanical stability of the coating composition can be improved, and the film-forming property and the smoothness of the coating film can be improved.
上記アセチレンジオール系界面活性剤（ｃ）は、分子中に炭素－炭素三重結合を有する界面活性剤である。上記アセチレンジオール系界面活性剤（ｃ）としては、例えば、アセチレンジオール（同一分子内にアセチレン結合と２つの水酸基を同時に有する）界面活性剤、アセチレンジオールにアルキレンオキサイドユニットが付加した界面活性剤が挙げられる。
このようなアセチレンジオール系界面活性剤として具体的には例えば、下記一般式（１）で表される化合物、及び／又は下記一般式（２）で表される化合物を挙げることができる。 The acetylene diol-based surfactant (c) is a surfactant having a carbon-carbon triple bond in the molecule. Examples of the acetylene diol-based surfactant (c) include acetylene diol (which has an acetylene bond and two hydroxyl groups in the same molecule at the same time) and a surfactant in which an alkylene oxide unit is added to acetylene diol. Be done.
Specific examples of such an acetylene diol-based surfactant include a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
 （式中、Ｒ１およびＲ２は、各々、独立して、炭素数３～９のアルキル基を表し、Ｒ３およびＲ４は、各々独立して、炭素数１～４のアルキレン基を表し、ｍおよびｎは整数であり、ｍとｎの合計は２～５０を表す。）
Figure JPOXMLDOC01-appb-C000002
 (In the formula, R 1 and R 2 each independently represent an alkyl group having 3 to 9 carbon atoms, and R 3 and R 4 each independently represent an alkylene group having 1 to 4 carbon atoms. , M and n are integers, and the sum of m and n represents 2 to 50.)
上記アセチレンジオール系界面活性剤（ｃ）は、熱重量分析で３００℃における残量が３．０質量％以上である。熱重量分析で３００℃における残量が３．０質量％以上であるアセチレンジオール系界面活性剤（ｃ）を使用することで、熱溶融時に高温での加熱を行った場合でも、アセチレンジオール系界面活性剤（ｃ）が塗膜中に残存し、これによって、各種機能を発揮することができる点で好ましい。 The remaining amount of the acetylene diol-based surfactant (c) at 300 ° C. is 3.0% by mass or more by thermogravimetric analysis. By using the acetylene diol-based surfactant (c) having a residual amount of 3.0% by mass or more at 300 ° C. in the thermogravimetric analysis, the acetylene diol-based interface is heated even when heated at a high temperature during thermal melting. The activator (c) remains in the coating film, which is preferable in that various functions can be exhibited.
本開示において、３００℃における残質量割合は、示差熱・熱重量測定装置〔ＴＧ－ＤＴＡ〕（商品名：ＴＧ／ＤＴＡ７２００、日立ハイテクサイエンス社製）を用い、試料１０ｍｇを昇温速度１０℃／分で室温から昇温し、３００℃で試料が残存した質量割合である。 In the present disclosure, the residual mass ratio at 300 ° C. is a temperature increase rate of 10 ° C./ It is the mass ratio at which the temperature is raised from room temperature in minutes and the sample remains at 300 ° C.
本開示において、アセチレンジオール系界面活性剤（ｃ）は、上記一般式（２）で表されるアセチレンジオールのエチレンオキサイド付加物が好ましい。アセチレンジオールのエチレンオキサイド付加物は、上記熱重量分析で３００℃における残量が３．０質量％以上を満たすものとすることが容易であり、これによって、高温での加熱硬化時時にも良好な効果が得られる点で好ましい。 In the present disclosure, the acetylene diol-based surfactant (c) is preferably an ethylene oxide adduct of acetylene diol represented by the above general formula (2). The ethylene oxide adduct of acetylene diol can easily satisfy the remaining amount at 300 ° C. of 3.0% by mass or more in the above thermogravimetric analysis, which is good even at the time of heat curing at high temperature. It is preferable in that an effect can be obtained.
上記アセチレンジオール系界面活性剤は、市販品を使用してもよい。例えば、サーフィノール（登録商標）４４０、４６５、４８５、ＳＥ、２５０２、オルフィン（登録商標）ＰＤ－００２Ｗ、ＥＸＰ．４２００、Ｅ１００４、Ｅ１０１０（いずれも日信化学工業社製）、アセチレノール（登録商標）Ｅ００、アセチレノールＥ１３Ｔ、アセチレノールＥ４０、アセチレノールＥ６０、アセレノールＥ１００、アセチレノールＥ２００（以上、川研ファインケミカル株式会社製）などが挙げられる。 As the acetylene diol-based surfactant, a commercially available product may be used. For example, Surfinol® 440, 465, 485, SE, 2502, Orfin® PD-002W, EXP. 4200, E1004, E1010 (all manufactured by Nisshin Kagaku Kogyo Co., Ltd.), acetylenol (registered trademark) E00, acetylenol E13T, acetylenol E40, acetylenol E60, acerenol E100, acetylenol E200 (all manufactured by Kawaken Fine Chemical Co., Ltd.), etc. Will be.
上記アセチレンジオール系界面活性剤（ｃ）は、ＨＬＢが４を超えることが好ましく、５以上であることがより好ましい。６以上が更に好ましく、８以上が最も好ましい。
ＨＬＢが高いアセチレンジオール系界面活性剤は、耐熱性に優れる。ＨＬＢが高いアセチレンジオール系界面活性剤を使用することで、被覆用組成物の造膜性が向上する。また、ＨＬＢが高いアセチレンジオール系界面活性剤は、水性媒体に対して溶解性に優れるものであり、被覆用組成物の機械的安定性がより優れるものとなる。
なお、本開示において、ＨＬＢは、グリフィン法により、次の算出式で定義される値である。
ＨＬＢ値＝２０×［親水部の化学式量の総和］／分子量 The acetylene diol-based surfactant (c) preferably has an HLB of more than 4, more preferably 5 or more. 6 or more is more preferable, and 8 or more is most preferable.
An acetylene diol-based surfactant having a high HLB has excellent heat resistance. By using an acetylene diol-based surfactant having a high HLB, the film-forming property of the coating composition is improved. Further, the acetylene diol-based surfactant having a high HLB has excellent solubility in an aqueous medium, and the mechanical stability of the coating composition becomes more excellent.
In the present disclosure, HLB is a value defined by the following calculation formula by the Griffin method.
HLB value = 20 x [sum of chemical formulas of hydrophilic part] / molecular weight
本開示の被覆用組成物は、アセチレンジオール系界面活性剤（ｃ）の含有量が、含フッ素重合体（ａ）に対して０．０５～５．０質量％であることが好ましい。上記アセチレンジオール系界面活性剤（ｃ）の含有量の下限は０．１質量％であることがより好ましく、０．５質量％であることが更に好ましい。上記アセチレンジオール系界面活性剤（ｃ）の上限は、３．０質量％であることがより好ましく、２．０質量％であることが更に好ましい。アセチレンジオール系界面活性剤（ｃ）の含有量がこの範囲であれば、被覆用組成物の造膜性と機械的安定性が良好である。 The coating composition of the present disclosure preferably contains the acetylene diol-based surfactant (c) in an amount of 0.05 to 5.0% by mass with respect to the fluorine-containing polymer (a). The lower limit of the content of the acetylene diol-based surfactant (c) is more preferably 0.1% by mass, further preferably 0.5% by mass. The upper limit of the acetylene diol-based surfactant (c) is more preferably 3.0% by mass, further preferably 2.0% by mass. When the content of the acetylene diol-based surfactant (c) is in this range, the film-forming property and mechanical stability of the coating composition are good.
上記含フッ素重合体（ａ）は、９８％積算粒子径が０．４μｍ以上１．０μｍ未満である。上記９８％積算粒子径とは、粒子径から換算した体積の最小点からの積算値が９８％の点の粒子径をいう。
９８％積算粒子径が０．４μｍ以上１．０μｍ未満であることから、被覆用組成物の機械的安定性が良好で、表面平滑性に優れた被膜を作製することができる。好ましい下限は０．５μｍであり、好ましい上限は０．９μｍである。 The fluorine-containing polymer (a) has a 98% integrated particle size of 0.4 μm or more and less than 1.0 μm. The 98% integrated particle diameter means a particle diameter at a point where the integrated value from the minimum point of the volume converted from the particle diameter is 98%.
Since the 98% integrated particle size is 0.4 μm or more and less than 1.0 μm, it is possible to produce a film having good mechanical stability and excellent surface smoothness of the coating composition. The preferred lower limit is 0.5 μm and the preferred upper limit is 0.9 μm.
このような含フッ素重合体（ａ）は、乳化重合法で作製することが好ましい。
乳化重合法で作製することによって、容易に、９８％積算粒子径が０．４μｍ以上１．０μｍ未満の含フッ素重合体（ａ）を得ることができる。 Such a fluorine-containing polymer (a) is preferably produced by an emulsion polymerization method.
By producing by the emulsification polymerization method, a fluorine-containing polymer (a) having a 98% integrated particle size of 0.4 μm or more and less than 1.0 μm can be easily obtained.
上記含フッ素重合体（ａ）は、９８％積算粒子径が０．４μｍ以上１．０μｍ未満であり、かつ、平均粒子径が０．０１以上１．０μｍ未満の粒子であることが好ましい。平均粒子径が０．０１μｍ未満であると、フッ素樹脂（ａ）からなる粒子の機械的安定性が悪く、被覆用組成物の機械的安定性及び貯蔵安定性が劣るおそれがある。平均粒子径が１．０μｍ以上であると、含フッ素重合体（ａ）からなる粒子の均一分散性に欠け、被覆用組成物を用いて塗装する際、表面が平滑な塗膜が得られず、塗膜物性が劣るおそれがある。より好ましい下限は０．０５μｍであり、より好ましい上限は０．８μｍである。 The fluorine-containing polymer (a) is preferably particles having a 98% integrated particle diameter of 0.4 μm or more and less than 1.0 μm and an average particle diameter of 0.01 or more and less than 1.0 μm. If the average particle size is less than 0.01 μm, the mechanical stability of the particles made of the fluororesin (a) is poor, and the mechanical stability and storage stability of the coating composition may be poor. When the average particle size is 1.0 μm or more, the uniform dispersibility of the particles made of the fluorine-containing polymer (a) is lacking, and when coating with the coating composition, a coating film having a smooth surface cannot be obtained. , The physical properties of the coating film may be inferior. A more preferable lower limit is 0.05 μm, and a more preferable upper limit is 0.8 μm.
上記９８％積算粒子径及び平均粒子径は、レーザー回折による粒度分布測定装置（マイクロトラック・ベル社製マイクロトラックＭＴ－３０００ＥＸＩＩ型）により測定したものである。
この装置により、平均粒子径と９８％積算粒子径は自動計算される。
なお、本開示において、上記平均粒子径は、上記装置により自動計算された５０％積算粒子径である。 The 98% integrated particle diameter and the average particle diameter are measured by a particle size distribution measuring device (Microtrac MT-3000EXII type manufactured by Microtrac Bell) by laser diffraction.
With this device, the average particle size and the 98% integrated particle size are automatically calculated.
In the present disclosure, the average particle diameter is a 50% integrated particle diameter automatically calculated by the apparatus.
上記含フッ素重合体（ａ）は、特に限定されないが、ポリテトラフルオロエチレン〔ＰＴＦＥ〕、テトラフルオロエチレン〔ＴＦＥ〕／ヘキサフルオロプロピレン〔ＨＦＰ〕共重合体〔ＦＥＰ〕、ＴＦＥ／パーフルオロアルキルビニルエーテル〔ＰＡＶＥ〕共重合体〔ＰＦＡ〕等が挙げられる。 特に、溶融加工可能なフッ素樹脂である、ＴＦＥ／ＨＦＰ共重合体〔ＦＥＰ〕、ＴＦＥ／ＰＡＶＥ共重合体〔ＰＦＡ〕なる群から選択される少なくとも一種の共重合体からなるものであることが好ましい。 The fluorine-containing polymer (a) is not particularly limited, but is polytetrafluoroethylene [PTFE], tetrafluoroethylene [TFE] / hexafluoropropylene [HFP] copolymer [FEP], TFE / perfluoroalkyl vinyl ether [ PAVE] copolymer [PFA] and the like can be mentioned. In particular, it is preferably composed of at least one copolymer selected from the group of TFE / HFP copolymer [FEP] and TFE / PAVE copolymer [PFA], which are fluororesins that can be melt-processed. ..
上記ＦＥＰは、ＨＦＰ単位が２質量％を超え、２０質量％以下であることが好ましく、１０～１５質量％であることがより好ましい。 The FEP has an HFP unit of more than 2% by mass, preferably 20% by mass or less, and more preferably 10 to 15% by mass.
上記ＰＦＡにおけるＰＡＶＥとしては、炭素数１～６のアルキル基を有するものが好ましく、パーフルオロメチルビニルエーテル、パーフルオロエチルビニルエーテル又はパーフルオロプロピルビニルエーテルがより好ましい。 The PAVE in the PFA preferably has an alkyl group having 1 to 6 carbon atoms, and more preferably perfluoromethyl vinyl ether, perfluoroethyl vinyl ether or perfluoropropyl vinyl ether.
上記ＰＦＡは、ＰＡＶＥ単位が２．０質量％を超え、５．０質量％以下であることが好ましく、２．５～４．０質量％であることがより好ましい。 The PAVE unit is preferably more than 2.0% by mass, preferably 5.0% by mass or less, and more preferably 2.5 to 4.0% by mass.
上記ＦＥＰ、ＰＦＡは、それぞれ上述の組成を有するものであれば、更に、その他の単量体を重合させたものであってよい。上記その他の単量体としては、例えば、上記ＦＥＰである場合ＰＡＶＥが挙げられ、上記ＰＦＡである場合ＨＦＰが挙げられる。上記その他の単量体は、１種又は２種以上を用いることができる。 The FEP and PFA may be obtained by further polymerizing other monomers as long as they have the above-mentioned compositions. Examples of the other monomer include PAVE in the case of FEP and HFP in the case of PFA. As the above-mentioned other monomers, one kind or two or more kinds can be used.
上記その他の単量体は、その種類によって異なるが、通常、フッ素樹脂の質量の１質量％以下であることが好ましい。より好ましい上限は０．５質量％であり、更に好ましい上限は０．３質量％である。 The above-mentioned other monomers vary depending on the type, but are usually preferably 1% by mass or less based on the mass of the fluororesin. A more preferable upper limit is 0.5% by mass, and a more preferable upper limit is 0.3% by mass.
上記非アルキルフェノール型ノニオン界面活性剤（ｂ）は、構造中に、ベンゼン環を含んでいないノニオン界面活性剤である。例えば、ポリオキシエチレンアルキルエーテル系の天然アルコールを原料としたノニオン界面活性剤等が挙げられる。 なお、上記アセチレンジオール系界面活性剤は、非アルキルフェノール型ノニオン界面活性剤（ｂ）に包含されないものである。 The non-alkylphenol type nonionic surfactant (b) is a nonionic surfactant which does not contain a benzene ring in its structure. For example, a nonionic surfactant made from a polyoxyethylene alkyl ether-based natural alcohol can be mentioned. The above-mentioned acetylene diol-based surfactant is not included in the non-alkylphenol type nonionic surfactant (b).
非アルキルフェノール型ノニオン界面活性剤（ｂ）は、下記一般式（Ｉ）：
Ｒ－Ｏ－Ａ－Ｈ　　　　　（Ｉ）
（式中、Ｒは直鎖状又は分岐鎖状の炭素数８～１９の飽和又は不飽和の非環式脂肪族炭化水素基、あるいは、炭素数８～１９の飽和環式脂肪族炭化水素基を表す。Ａはオキシエチレンユニットを３～２５個及びオキシプロピレンユニットを０～５個有するポリオキシアルキレン鎖を表す。）で表されるノニオン界面活性剤であることが好ましい。 The non-alkylphenol type nonionic surfactant (b) has the following general formula (I):
ROAH (I)
(In the formula, R is a linear or branched saturated or unsaturated acyclic aliphatic hydrocarbon group having 8 to 19 carbon atoms, or a saturated cyclic aliphatic hydrocarbon group having 8 to 19 carbon atoms. A is a polyoxyalkylene chain having 3 to 25 oxyethylene units and 0 to 5 oxypropylene units), and is preferably a nonionic surfactant.
上記一般式（Ｉ）で表されるノニオン界面活性剤としては、下記一般式（ＩＩ）：
ＣｘＨ２ｘ＋１ＣＨ（ＣｙＨ２ｙ＋１）ＣｚＨ２ｚＯ（Ｃ２Ｈ４Ｏ）ｎＨ　　　　（ＩＩ）
（式中、ｘは１以上の整数、ｙは１以上の整数、ｚは０又は１、但しｘ＋ｙ＋ｚは８～１８の整数、ｎは４～２０の整数を表す。）で表されるポリオキシエチレンアルキルエーテル系界面活性剤、又は、 The nonionic surfactant represented by the above general formula (I) includes the following general formula (II):
C x H 2x + 1 CH (C y H 2y + 1 ) C z H 2z O (C 2 H 4 O) n H (II)
(In the formula, x is an integer of 1 or more, y is an integer of 1 or more, z is 0 or 1, where x + y + z is an integer of 8 to 18, and n is an integer of 4 to 20). Ethylene alkyl ether-based surfactant or
下記一般式（ＩＩＩ）：
ＣｘＨ２ｘ＋１－Ｏ－Ａ－Ｈ　　　　（ＩＩＩ）
（式中、ｘは８～１８の整数、Ａはオキシエチレンユニットを５～２０個及びオキシプロピレンユニットを１又は２個有するポリオキシアルキレン鎖を表す。）で表されるポリオキシエチレンアルキルエーテル系界面活性剤が好ましい。 The following general formula (III):
C x H 2x + 1 -OA-H (III)
(In the formula, x is an integer of 8 to 18, A represents a polyoxyalkylene chain having 5 to 20 oxyethylene units and 1 or 2 oxypropylene units.) Polyoxyethylene alkyl ether system represented by Surfactants are preferred.
上記非アルキルフェノール型ノニオン界面活性剤（ｂ）は、ＨＬＢが１０～１５であることが好ましい。より好ましいＨＬＢ範囲は、１２～１４である。この範囲にあれば、貯蔵安定性に優れた被覆用組成物が得られる。 The non-alkylphenol type nonionic surfactant (b) preferably has an HLB of 10 to 15. A more preferred HLB range is 12-14. Within this range, a coating composition having excellent storage stability can be obtained.
上記非アルキルフェノール型ノニオン界面活性剤（ｂ）の含有量は、本開示の被覆用組成物の分散状態を安定にさせる量であればよく、例えば、上記含フッ素重合体（ａ）に対して、好ましくは３～１５質量％、より好ましくは５～１２質量％の量を存在させればよい。 The content of the non-alkylphenol type nonionic surfactant (b) may be an amount that stabilizes the dispersed state of the coating composition of the present disclosure, for example, with respect to the fluorine-containing polymer (a). An amount of 3 to 15% by mass, more preferably 5 to 12% by mass may be present.
従来のフッ素樹脂の分散液においては、一般的に、含フッ素界面活性剤の含有量が低減すると貯蔵安定性が不十分であるが、本開示の被覆用組成物は優れた貯蔵安定性を示す。この理由は明確でないが、非アルキルフェノール型ノニオン界面活性剤（ｂ）のフッ素樹脂への吸着により、優れた貯蔵安定性を得ることができるものと考えられる。 In the conventional fluororesin dispersion, the storage stability is generally insufficient when the content of the fluorine-containing surfactant is reduced, but the coating composition of the present disclosure exhibits excellent storage stability. .. Although the reason for this is not clear, it is considered that excellent storage stability can be obtained by adsorbing the non-alkylphenol type nonionic surfactant (b) to the fluororesin.
本開示の被覆用組成物は、シリコーン系界面活性剤を含有しないものであることが好ましい。シリコーン系界面活性剤を含有すると、塗装時にハジキ、ピンホールを発生させることがあるという点で不利となるためである。 The coating composition of the present disclosure preferably does not contain a silicone-based surfactant. This is because the inclusion of a silicone-based surfactant is disadvantageous in that repellents and pinholes may be generated during painting.
本開示の被覆用組成物は、更に、上記沸点が１００℃以上でかつ水酸基を２個以上有する水溶性の多価アルコール（ｄ）を含むことが好ましい。
上記多価アルコール（ｄ）は、被塗装物を塗布して乾燥させる場合に、水が蒸発した後にも塗膜中に残存して、溶剤や水の蒸散に伴う塗膜の収縮に起因するクラック（いわゆるマッドクラック）を防止する作用を示す。従って、本開示の被覆用組成物は、上記多価アルコール（ｄ）を含有することにより、塗装の際に、よりマッドクラックが生じにくい。また、上記多価アルコール（ｄ）は、焼成時に徐々に分解されるため、塗膜の着色の原因とならない。 The coating composition of the present disclosure further preferably contains the water-soluble polyhydric alcohol (d) having a boiling point of 100 ° C. or higher and having two or more hydroxyl groups.
The polyhydric alcohol (d) remains in the coating film even after the water evaporates when the object to be coated is applied and dried, and cracks caused by shrinkage of the coating film due to evaporation of the solvent or water. Shows the action of preventing (so-called mudcrack). Therefore, the coating composition of the present disclosure contains the above-mentioned polyhydric alcohol (d), so that mudcrack is less likely to occur at the time of painting. Further, since the polyhydric alcohol (d) is gradually decomposed at the time of firing, it does not cause coloring of the coating film.
上記多価アルコール（ｄ）は、沸点が１００℃以上であることが好ましい。沸点が１００℃未満であると、乾燥時に水よりも早く蒸散してしまい、乾燥後に塗膜中に残存させることができず、造膜性の改善に寄与しにくい。上記沸点は、乾燥温度以上であることが好ましく、１５０℃以上であることがより好ましく、１８０℃以上であることが更に好ましい。 The polyhydric alcohol (d) preferably has a boiling point of 100 ° C. or higher. If the boiling point is less than 100 ° C., it evaporates faster than water during drying and cannot remain in the coating film after drying, which makes it difficult to contribute to the improvement of film forming property. The boiling point is preferably a drying temperature or higher, more preferably 150 ° C. or higher, and even more preferably 180 ° C. or higher.
上記多価アルコール（ｄ）は、水酸基を２個以上有する水溶性のものであることが好ましい。水酸基の数が１個又はゼロの化合物であって、沸点が１００℃以上のものは、親水性に劣るため、均一な混合が困難となる傾向にある。上記多価アルコール（ｄ）は、室温で液体でありマッドクラックの防止効果が高い点で、水酸基を２～３個有するものであることが好ましい。 The polyhydric alcohol (d) is preferably a water-soluble alcohol having two or more hydroxyl groups. A compound having one or zero hydroxyl groups and having a boiling point of 100 ° C. or higher is inferior in hydrophilicity, and therefore tends to be difficult to uniformly mix. The polyhydric alcohol (d) is preferably liquid at room temperature and has a high effect of preventing mudcrack, and thus preferably has two or three hydroxyl groups.
上記多価アルコール（ｄ）は、焼成時の加熱により最終的に蒸散し尽くすか分解揮散し尽くすことが好ましい。従って、沸点又は熱分解温度がフッ素樹脂の溶融温度以下、好ましくは３４０℃以下のものが好ましい。 It is preferable that the polyhydric alcohol (d) is finally evaporated or decomposed and volatilized by heating during firing. Therefore, it is preferable that the boiling point or the thermal decomposition temperature is equal to or lower than the melting temperature of the fluororesin, preferably 340 ° C. or lower.
上記多価アルコール（ｄ）としては、例えば、エチレングルコール（沸点：１９８℃）、１，２－プロパンジオール（１８８℃）、１，３－プロパンジオール（２１４℃）、１，２－ブタンジオール（１９０℃）、１，３－ブタンジオール（２０８℃）、１，４－ブタンジオール（２２９℃）、１，５－ペンタンジオール（２４２℃）、２－ブテン－１，４－ジオール（２３５℃）、グリセリン（２９０℃）、２－エチル－２－ヒドロキシメチル－１，３－プロパンジオール（２９５℃）、１，２，６－ヘキサントリオール（１７８℃／５ｍｍＨｇ）、トリエチレングリコール（２８８℃）等が挙げられる。なかでも、造膜性が優れる点でエチレングリコールであることが好ましい。 Examples of the polyhydric alcohol (d) include 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-butane-1,4-diol (235 ° C). ), Glycerin (290 ° C), 2-ethyl-2-hydroxymethyl-1,3-propanediol (295 ° C), 1,2,6-hexanetriol (178 ° C / 5 mmHg), triethylene glycol (288 ° C). And so on. Of these, ethylene glycol is preferable because it has excellent film-forming properties.
多価アルコール（ｄ）の配合量は、上記含フッ素重合体（ａ）１００質量部に対して５～１８質量部であることが好ましく、より好ましくは７～１５質量部、特に好ましくは７～１２質量部である。５質量部未満であると、マッドクラックの発生防止効果が弱くなるおそれがあり、１８質量部を超えると、塗膜が白濁するおそれがある。 The blending amount of the polyhydric alcohol (d) is preferably 5 to 18 parts by mass, more preferably 7 to 15 parts by mass, and particularly preferably 7 to 7 to 100 parts by mass with respect to 100 parts by mass of the fluorine-containing polymer (a). It is 12 parts by mass. If it is less than 5 parts by mass, the effect of preventing the occurrence of mudcrack may be weakened, and if it exceeds 18 parts by mass, the coating film may become cloudy.
本開示の被覆用組成物は、水性媒体を含むものである。上記水性媒体としては、水を単独で使用してもよいし、水と水溶性化合物と併用した水性混合溶媒としてもよい。 The coating composition of the present disclosure comprises an aqueous medium. As the aqueous medium, water may be used alone, or it may be an aqueous mixed solvent in which water and a water-soluble compound are used in combination.
本開示の被覆用組成物は、必要に応じ、本開示の特徴を損なわない範囲でその他の樹脂を含有するものであってもよい。
上記その他の樹脂としては特に限定されず、例えば、ポリエチレンオキサイド（分散安定剤）、フェノール樹脂、尿素樹脂、エポキシ樹脂、メラミン樹脂、ポリエステル樹脂、ポリエーテル樹脂、アクリルシリコーン樹脂、シリコーン樹脂、シリコーンポリエステル樹脂等が挙げられる。 The coating composition of the present disclosure may contain other resins, if necessary, as long as the characteristics of the present disclosure are not impaired.
The other resins are not particularly limited, and for example, polyethylene oxide (dispersion stabilizer), phenol resin, urea resin, epoxy resin, melamine resin, polyester resin, polyether resin, acrylic silicone resin, silicone resin, silicone polyester resin. And so on.
本開示の被覆用組成物は、塗装性、得られる塗膜の性質向上等を目的として、更に一般的な被覆用組成物に用いられる添加剤を含むものであってもよい。
上記添加剤としては特に限定されず、得られる被覆物品の用途に応じて選択することができ、例えば、レベリング剤、固体潤滑剤、木粉、石英砂、カーボンブラック、ダイヤモンド、トルマリン、ゲルマニウム、アルミナ、窒化珪素、蛍石、クレー、タルク、体質顔料、各種増量材、導電性フィラー、光輝材、顔料、充填材、顔料分散剤、沈降防止剤、水分吸収剤、表面調整剤、チキソトロピー性付与剤、粘度調節剤、ゲル化防止剤、紫外線吸収剤、光安定剤、可塑剤、色分かれ防止剤、皮張り防止剤、スリ傷防止剤、防カビ剤、抗菌剤、酸化防止剤、帯電防止剤、シランカップリング剤、消泡剤、乾燥剤、ハジキ防止剤が挙げられる。 The coating composition of the present disclosure may contain additives used in a more general coating composition for the purpose of improving the coatability and the properties of the obtained coating film.
The additive is not particularly limited and can be selected depending on the use of the obtained coated article. For example, a leveling agent, a solid lubricant, wood powder, quartz sand, carbon black, diamond, tourmaline, germanium and alumina can be selected. , Silicon nitride, fluorite, clay, talc, extender pigments, various extenders, conductive fillers, brighteners, pigments, fillers, pigment dispersants, anti-settling agents, moisture absorbers, surface conditioners, thixotropy-imparting agents. , Viscosity adjuster, anti-gelling agent, UV absorber, light stabilizer, plasticizer, anti-color separation agent, anti-skin agent, anti-scratch agent, anti-mold agent, anti-bacterial agent, antioxidant, anti-static agent , Silane coupling agent, antifoaming agent, desiccant, anti-repellent agent.
上記光輝材としては、例えば、マイカ、金属粉末、ガラスビーズ、ガラスバブル、ガラスフレーク、ガラス繊維等が挙げられる。本開示の被覆用組成物は、このような光輝材を含有する場合、優れた外観を有する塗膜を形成することができる。上記光輝材の含有量は、上記被覆用組成物の固形分に対して０．１～１０．０質量％であることが好ましい。 Examples of the bright material include mica, metal powder, glass beads, glass bubbles, glass flakes, glass fibers and the like. When the coating composition of the present disclosure contains such a bright material, it is possible to form a coating film having an excellent appearance. The content of the bright material is preferably 0.1 to 10.0% by mass with respect to the solid content of the coating composition.
上記金属粉末としては特に限定されず、例えば、アルミニウム、鉄、すず、亜鉛、金、銀、銅等の金属単体の粉末；アルミニウム合金、ステンレス等の合金の粉末等が挙げられる。上記金属粉末の形状としては特に限定されず、粒子状、フレーク状等が挙げられる。本開示の被覆用組成物は、これらの着色成分を含まないクリヤー塗料であってもよい。 The metal powder is not particularly limited, and examples thereof include powders of single metals such as aluminum, iron, tin, zinc, gold, silver, and copper; and powders of alloys such as aluminum alloys and stainless steel. The shape of the metal powder is not particularly limited, and examples thereof include a particle shape and a flake shape. The coating composition of the present disclosure may be a clear paint that does not contain these coloring components.
上記粘度調節剤としては、例えば、メチルセルロース、アルミナゾル、ポリビニルアルコール、カルボキシル化ビニルポリマー等が挙げられる。 Examples of the viscosity adjusting agent include methyl cellulose, alumina sol, polyvinyl alcohol, and carboxylated vinyl polymer.
上記消泡剤としては、例えば、トルエン、キシレン、炭素数９～１１の炭化水素系等の非極性溶剤、シリコーンオイル等が挙げられる。 Examples of the defoaming agent include toluene, xylene, non-polar solvents such as hydrocarbons having 9 to 11 carbon atoms, silicone oil and the like.
上記乾燥剤として、例えば、酸化コバルト等が挙げられる。 Examples of the desiccant include cobalt oxide and the like.
本開示の被覆用組成物には、含フッ素重合体（ａ）と、必要に応じて無機材料等の固形分が含まれるが、それらの固形分含量は２０～８０質量％、特に３０～７０質量％であることが好ましい。固形分濃度が２０質量％未満では一回の塗装により厚膜を得ることが困難となるおそれがあり、８０質量％を超えると粘度が高くなり、スプレー塗装が困難になるおそれがある。 The coating composition of the present disclosure contains a fluorine-containing polymer (a) and, if necessary, a solid content such as an inorganic material, and the solid content content thereof is 20 to 80% by mass, particularly 30 to 70. It is preferably by mass%. If the solid content concentration is less than 20% by mass, it may be difficult to obtain a thick film by one coating, and if it exceeds 80% by mass, the viscosity becomes high and spray coating may be difficult.
本開示の被覆用組成物の調製は、通常の方法で行うことができる。例えば、含フッ素重合体（ａ）が水性媒体に分散しているフッ素樹脂水性分散液に、非イオン性界面活性剤（ｂ）、アセチレンジオール系界面活性剤（ｃ）、他の添加剤等を攪拌下に投入混合し、５～３０℃にて１０～４０分間攪拌混合することによって調製できる。更に、水性媒体を追加して固形分濃度を調整してもよい。 The coating composition of the present disclosure can be prepared by a conventional method. For example, a nonionic surfactant (b), an acetylenediol-based surfactant (c), other additives, etc. are added to the fluororesin aqueous dispersion in which the fluororesin-containing polymer (a) is dispersed in an aqueous medium. It can be prepared by adding and mixing under stirring and stirring and mixing at 5 to 30 ° C. for 10 to 40 minutes. Further, an aqueous medium may be added to adjust the solid content concentration.
本開示の被覆用組成物は、塗料として好適に使用でき、上塗り塗料として使用できるし、中塗り塗料としても使用できる。また、ライニング用の塗料としても使用できる。 The coating composition of the present disclosure can be suitably used as a coating material, can be used as a top coating material, and can also be used as an intermediate coating material. It can also be used as a paint for lining.
塗装方法としては従来と同様な各種の塗装方法が採用でき、例えば、ディッピング法、スプレー法、ロールコート法、ドクターブレード法、スピンフローコート、カーテンフローコート法等が挙げられる。 As the coating method, various coating methods similar to the conventional ones can be adopted, and examples thereof include a dipping method, a spray method, a roll coating method, a doctor blade method, a spin flow coating, and a curtain flow coating method.
本開示の被覆用組成物は基材に直接塗装してもよいが、密着性を向上させるために、プライマー層を設けてその上に塗装することが望ましい。基材としては特に限定されないが、たとえば各種金属、ホーロー、ガラス、各種セラミックスが採用でき、また密着性を高めるために表面をサンドブラスト法などで粗面化することが好ましい。 The coating composition of the present disclosure may be directly coated on a substrate, but it is desirable to provide a primer layer and coat the coating composition in order to improve adhesion. The base material is not particularly limited, but for example, various metals, enamel, glass, and various ceramics can be used, and it is preferable to roughen the surface by a sandblasting method or the like in order to improve the adhesion.
基材に塗布された被覆用組成物は次いで乾燥される。本開示の被覆用組成物はこの乾燥の段階でマッドクラックを生じない点に特徴がある。乾燥は通常の条件でよく、用いる多価アルコール（ｄ）の沸点によって異なるが、好ましくは室温～１５０℃、より好ましくは８０～１５０℃にて５～２０分間実施すれば、指触乾燥に達する。 The coating composition applied to the substrate is then dried. The coating composition of the present disclosure is characterized in that mudcrack does not occur during this drying stage. Drying may be carried out under normal conditions and varies depending on the boiling point of the polyhydric alcohol (d) used, but if it is carried out at room temperature to 150 ° C., more preferably 80 to 150 ° C. for 5 to 20 minutes, it reaches dryness to the touch. ..
乾燥した塗膜は焼成（加工）される。焼成（加工）温度及び時間はフッ素樹脂の種類や溶融温度などによって異なるが、例えば、フッ素樹脂の溶融温度以上、通常３４０～４１５℃にて５～３０分間行う。 The dried coating film is fired (processed). The firing (processing) temperature and time will vary depending on the type of fluororesin, melting temperature, etc., but for example, the calcination is performed at 340 to 415 ° C. for 5 to 30 minutes, which is equal to or higher than the melting temperature of the fluororesin.
プライマー層を設ける場合は、プライマーを塗布、乾燥、焼成した後に本開示の被覆用組成物を塗布、乾燥、焼成する方法（２コート２ベーク法）でもよいし、プライマーを塗布、乾燥した後に本開示の被覆用組成物を塗布、乾燥し、両者を同時に焼成する方法（２コート１ベーク法）でもよいし、プライマーを塗布、乾燥した後に本開示の被覆用組成物である光輝材を含む中塗り塗料を塗布、乾燥して、更にその上に本開示の被覆用組成物以外のクリヤー塗料である上塗り塗料を塗布、乾燥して、これらを同時に焼成する方法（３コート１ベーク法）であってもよい。また、プライマー塗布後にいずれも本開示の被覆用組成物である、光輝剤を含む中塗り塗料、クリヤー塗料である上塗り塗料による塗装を順次行うものであってもよい。 When the primer layer is provided, the coating composition of the present disclosure may be applied, dried and fired after the primer is applied, dried and fired (2-coat 2-baking method), or the primer is applied and dried before the present invention. The disclosed coating composition may be applied and dried, and both may be fired at the same time (2-coat, 1-bak method), or the primer may be applied and dried, and then the bright material, which is the coating composition of the present disclosure, is contained. It is a method (3 coat 1 bake method) in which a primer paint is applied and dried, and then a top coat paint which is a clear paint other than the coating composition of the present disclosure is applied and dried, and these are simultaneously fired. You may. Further, after the primer is applied, the coating composition may be sequentially coated with the intermediate coating paint containing a brilliant agent and the top coating coating which is a clear paint, which are the coating compositions of the present disclosure.
本開示の被覆用組成物によれば、１回の塗装で溶融塗膜の膜厚が３０μｍ以上の厚膜の塗膜を得ることもできる。 According to the coating composition of the present disclosure, a thick coating film having a thickness of 30 μm or more can be obtained by one coating.
本開示の被覆用組成物を塗装することにより得られたことを特徴とする被覆物品も本開示の一つである。
本開示の被覆物品としては、例えば、フライパン、グリル鍋、圧力鍋、その他の各種鍋、炊飯器、餅つき器、オーブン、ホットプレート、パン焼き型、包丁、ガステーブル等の調理器具；電気ポット、製氷トレー等の飲食用容器；練りロール、圧延ロール、コンベア、ホッパー等の食品工業用部品；オフィスオートメーション機器〔ＯＡ〕用ロール、ＯＡ用ベルト、ＯＡ用分離爪、製紙ロール、フィルム製造用カレンダーロール等の工業用品；発泡スチロール成形用等の金型、鋳型、合板・化粧板製造用離型板等の成形金型離型；レンジフード等の厨房用品；コンベアーベルト等の冷凍食品製造装置；のこぎり、やすり、ダイス、きり等の工具；アイロン、鋏、包丁等の家庭用品；金属箔、電線；食品加工機、包装機、紡繊機械等のすべり軸受；カメラ・時計の摺動部品；パイプ、バルブ、ベアリング等の自動車部品、雪かきシャベル、すき、シュート、船底、ボイラー、工業用コンテナ（特に半導体工業用）、プリント配線基板、燃料電池の部材、絶縁テープ、壁材の裏打ち用、テント、工事用シート、照明カバー等の用途で用いられるガラスクロス、医療用ガイドワイヤー、カテーテル、シース、シースイントロデューサー等が挙げられる。
特に、調理器具、厨房用品、ガラスクロス、医療用ガイドワイヤー、カテーテル、シース、シースイントロデューサー、燃料電池の部材に好適に使用できる。 A coated article characterized by being obtained by painting the coating composition of the present disclosure is also one of the present disclosures.
The covered articles of the present disclosure include, for example, frying pans, grill pans, pressure pans, various other pans, rice cookers, rice cake making machines, ovens, hot plates, pan-baking molds, kitchen utensils, gas tables and other cooking utensils; electric pots, Food and beverage containers such as ice trays; Food industry parts such as kneading rolls, rolling rolls, conveyors, and hoppers; Rolls for office automation equipment [OA], belts for OA, separation claws for OA, paper making rolls, calendar rolls for film manufacturing Industrial supplies such as; Molds for foam styrol molding, molds, molding molds such as molds for manufacturing plywood and decorative boards; Kitchen supplies such as range hoods; Frozen food manufacturing equipment such as conveyor belts; Saw, Tools such as razors, dies, and cutters; Household products such as irons, shears, and kitchenettes; Metal foils, electric wires; Sliding bearings for food processing machines, packaging machines, spinning machines, etc .; Sliding parts for cameras and watches; Pipes, valves , Automotive parts such as bearings, snow shovels, plows, chutes, bottoms, boilers, industrial containers (especially for the semiconductor industry), printed wiring boards, fuel cell components, insulating tape, wall lining, tents, construction Examples thereof include glass cloths used in applications such as sheets and lighting covers, medical guide wires, catheters, sheaths, sheath introducers and the like.
In particular, it can be suitably used for cooking utensils, kitchen utensils, glass cloths, medical guide wires, catheters, sheaths, sheath introducers, and fuel cell members.
以下、本開示を実施例に基づいて具体的に説明する。
以下の実施例においては特に言及しない場合は、「部」「％」はそれぞれ「質量部」「質量％」を表す。 Hereinafter, the present disclosure will be specifically described based on examples.
In the following examples, unless otherwise specified, "parts" and "%" represent "parts by mass" and "% by mass", respectively.
（フッ素樹脂（ａ）の９８％積算粒子径及び平均粒子径）
レーザー回折による粒度分布測定装置（マイクロトラック・ベル社製マイクロトラックＭＴ－３０００ＥＸＩＩ型）により測定した。
平均粒子径（５０％積算粒子径）と９８％積算粒子径は、この装置で自動計算される。 (98% integrated particle size and average particle size of fluororesin (a))
The measurement was performed by a particle size distribution measuring device (Microtrack MT-3000EXII type manufactured by Microtrack Bell Co., Ltd.) by laser diffraction.
The average particle size (50% integrated particle size) and 98% integrated particle size are automatically calculated by this device.
（アセチレンジオール系界面活性剤の３００℃における残質量割合）
示差熱・熱重量測定装置〔ＴＧ－ＤＴＡ〕（商品名：ＴＧ／ＤＴＡ７２００、日立ハイテクサイエンス社製）を用い、試料１０ｍｇを昇温速度１０℃／分で室温から昇温し、３００℃において残存していた試料の質量割合を算出した。 (Ratio of residual mass of acetylene diol-based surfactant at 300 ° C)
Using a differential thermal / thermogravimetric measuring device [TG-DTA] (trade name: TG / DTA7200, manufactured by Hitachi High-Tech Science Co., Ltd.), the temperature of 10 mg of the sample was raised from room temperature at a heating rate of 10 ° C./min, and remained at 300 ° C. The mass ratio of the sample was calculated.
（機械的安定性）
各実施例、比較例で得られた被覆用組成物を、４０℃、３００ｒｐｍで６時間連続攪拌し、固まりができなければ、良好、固まりができた場合を不良とした。 (Mechanical stability)
The coating compositions obtained in each Example and Comparative Example were continuously stirred at 40 ° C. and 300 rpm for 6 hours.
（造膜性）
各実施例、比較例で得られた被覆用組成物を、ノンブラストアルミニウム板に、スプレー法により塗装し、乾燥（１００℃、１５分）、焼成（３８０℃、２０分）後の膜厚が２０μｍ以上でクラックの発生が無ければ、良好、クラックの発生がある場合は不良とした。 (Film formation)
The coating composition obtained in each Example and Comparative Example was coated on a non-blast aluminum plate by a spray method, and the film thickness after drying (100 ° C., 15 minutes) and firing (380 ° C., 20 minutes) was increased. If there was no crack at 20 μm or more, it was considered good, and if there was a crack, it was considered defective.
（実施例１）
公知の乳化重合法でＴＦＥ単位とパーフルオロ（プロピルビニルエーテル）（ＰＰＶＥ）単位とからなるＰＦＡ粒子を含むＰＦＡの固形分濃度が２０．０％のＰＦＡ水性分散液を得た。得られたＰＦＡ水性分散液に、ポリオキシエチレンアルキルエーテル（第一工業製薬株式会社製ノイゲンＴＤＳ－８０Ｃ、ＨＬＢ＝１３）をＰＦＡに対して１０％添加し、公知の相分離濃縮方法により、濃縮を行った。
上澄相を除去し、濃縮相を回収したところ、ＰＦＡの固形分濃度が６４．０％、ノニオン界面活性剤がＰＦＡの３．０％に相当する量、ＰＦＡの９８％積算粒子径が０．５５μｍ、平均粒子径が０．３５μｍであるＰＦＡ水性分散体を得た。
得られたＰＦＡ水性分散体７８．１質量部に、ポリオキシエチレンアルキルエーテル（第一工業製薬株式会社製　ノイゲンＴＤＳ－７０（ＨＬＢ値＝１２））の２０％水溶液１２．０質量部、ポリオキシエチレンアルキルエーテル（第一工業製薬株式会社製　ノイゲンＴＤＳ－５０（ＨＬＢ値＝１０．５））の２０％水溶液３．５質量部、エチレングリコール５．０質量部、アセチレンジオール系活性剤（日信化学工業株式会社製　サーフィノール４４０（ＨＬＢ値＝８））０．５質量部、純水６．４質量部を添加し、被覆用組成物を調製した。
なお、アセチレンジオール系活性剤（日信化学工業株式会社製　サーフィノール４４０（ＨＬＢ８））の熱重量分析で３００℃における残存量は、６質量％であった。
得られた被覆用組成物について、機械的安定性、造膜性の各評価を行った。結果を表１に示す。 (Example 1)
A PFA aqueous dispersion having a solid content concentration of 20.0% containing PFA particles composed of TFE units and perfluoro (propyl vinyl ether) (PPVE) units was obtained by a known emulsion polymerization method. To the obtained PFA aqueous dispersion, 10% of polyoxyethylene alkyl ether (Neugen TDS-80C, HLB = 13 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was added to PFA, and the mixture was concentrated by a known phase-separated concentration method. Was done.
When the supernatant phase was removed and the concentrated phase was recovered, the solid content concentration of PFA was 64.0%, the amount of nonionic surfactant was equivalent to 3.0% of PFA, and the integrated particle size of 98% of PFA was 0. A PFA aqueous dispersion having a diameter of .55 μm and an average particle size of 0.35 μm was obtained.
78.1 parts by mass of the obtained PFA aqueous dispersion, 12.0 parts by mass of a 20% aqueous solution of polyoxyethylene alkyl ether (Neugen TDS-70 (HLB value = 12) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), polyoxy 3.5 parts by mass of 20% aqueous solution of ethylene alkyl ether (Neugen TDS-50 (HLB value = 10.5) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 5.0 parts by mass of ethylene glycol, acetylene diol-based activator (Nisshin) A coating composition was prepared by adding 0.5 parts by mass of Surfinol 440 (HLB value = 8) manufactured by Chemical Industry Co., Ltd. and 6.4 parts by mass of pure water.
The thermogravimetric analysis of the acetylene diol-based activator (Surfinol 440 (HLB8) manufactured by Nisshin Kagaku Kogyo Co., Ltd.) showed that the residual amount at 300 ° C. was 6% by mass.
The obtained coating composition was evaluated for mechanical stability and film-forming property. The results are shown in Table 1.
（実施例２、３）
被覆用組成物の原料組成比を、表１に示すように調整した以外は実施例１と同様にして被覆用組成物の調製を行い、得られた被覆用組成物について各種性能を評価した。結果を表１に示す。 (Examples 2 and 3)
The coating composition was prepared in the same manner as in Example 1 except that the raw material composition ratio of the coating composition was adjusted as shown in Table 1, and various performances of the obtained coating composition were evaluated. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
（実施例４）
ＰＦＡ水性分散体の代わりに、ＦＥＰ水性分散体（９８％積算粒子径０．５１μｍ、平均粒子径０．２０μｍ、ＦＥＰの固形分濃度が６５．０質量％、レオコールＴＤ－９０Ｄ（ＨＬＢ値＝１３）６．５質量部含有）を用い、被覆用組成物の配合量を、表２に示すように調整した以外は実施例１と同様にして調製を行い、得られた被覆用組成物から形成した塗膜について各種性能を評価した。結果を表２に示す。 (Example 4)
Instead of the PFA aqueous dispersion, the FEP aqueous dispersion (98% integrated particle diameter 0.51 μm, average particle diameter 0.20 μm, FEP solid content concentration 65.0 mass%, Leocol TD-90D (HLB value = 13) ) 6.5 parts by mass) was used to prepare the coating composition in the same manner as in Example 1 except that the blending amount of the coating composition was adjusted as shown in Table 2, and the coating composition was formed from the obtained coating composition. Various performances were evaluated for the coated film. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
（実施例５）
ＰＦＡ水性分散体の代わりに、ＰＴＦＥ水性分散体（ＰＴＦＥ９８％積算粒子径０．８７μｍ、平均粒子径０．２８μｍ、ＰＴＦＥの固形分濃度が６１．０質量％、レオコールＴＤ－９０Ｄ（ＨＬＢ値＝１３）４．０質量部含有）を用い、被覆用組成物の配合量を、表３に示すように調整した以外は実施例１と同様にして調製を行い、得られた被覆用組成物から形成した塗膜について各種性能を評価した。結果を表３に示す。 (Example 5)
Instead of the PFA aqueous dispersion, the PTFE aqueous dispersion (PTFE 98% integrated particle diameter 0.87 μm, average particle diameter 0.28 μm, PTFE solid content concentration 61.0% by mass, Leocol TD-90D (HLB value = 13) ) 4.0 parts by mass) was used to prepare the coating composition in the same manner as in Example 1 except that the blending amount of the coating composition was adjusted as shown in Table 3, and the coating composition was formed from the obtained coating composition. Various performances were evaluated for the coated film. The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
（比較例１）
アセチレンジオール系活性剤（日信化学工業株式会社製　サーフィノール４４０（ＨＬＢ８））を配合しなかったこと以外は実施例１と同様にして調製を行い、得られた被覆用組成物から形成した塗膜について各種性能を評価した。結果を表４に示す。 (Comparative Example 1)
A coating film formed from the obtained coating composition was prepared in the same manner as in Example 1 except that an acetylene diol-based activator (Surfinol 440 (HLB8) manufactured by Nisshin Chemical Industry Co., Ltd.) was not blended. Various performances of the membrane were evaluated. The results are shown in Table 4.
（比較例２）
アセチレンジオール系活性剤（日信化学工業株式会社製　サーフィノール１０４Ａ（ＨＬＢ４））を配合したこと以外は実施例１と同様にして調製を行い、得られた被覆用組成物から形成した塗膜について各種性能を評価した。結果を表４に示す。
なお、アセチレンジオール系活性剤（日信化学工業株式会社製　サーフィノール１０４Ａ（ＨＬＢ４））の熱重量分析で３００℃における残存量は、０質量％であった。 (Comparative Example 2)
A coating film formed from the obtained coating composition prepared in the same manner as in Example 1 except that an acetylene diol-based activator (Surfinol 104A (HLB4) manufactured by Nisshin Chemical Industry Co., Ltd.) was blended. Various performances were evaluated. The results are shown in Table 4.
In the thermogravimetric analysis of the acetylene diol-based activator (Surfinol 104A (HLB4) manufactured by Nissin Chemical Industry Co., Ltd.), the residual amount at 300 ° C. was 0% by mass.
（比較例３）
アセチレンジオール系活性剤（日信化学工業株式会社製　サーフィノール４２０（ＨＬＢ４））を配合したこと以外は実施例１と同様にして調製を行い、得られた被覆用組成物から形成した塗膜について各種性能を評価した。結果を表４に示す。
なお、アセチレンジオール系活性剤（日信化学工業株式会社製　サーフィノール４２０（ＨＬＢ４））の熱重量分析で３００℃における残存量は、０質量％であった。 (Comparative Example 3)
A coating film formed from the obtained coating composition prepared in the same manner as in Example 1 except that an acetylene diol-based activator (Surfinol 420 (HLB4) manufactured by Nisshin Chemical Industry Co., Ltd.) was blended. Various performances were evaluated. The results are shown in Table 4.
In the thermogravimetric analysis of the acetylene diol-based activator (Surfinol 420 (HLB4) manufactured by Nissin Chemical Industry Co., Ltd.), the residual amount at 300 ° C. was 0% by mass.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
本開示の被覆用組成物は、上述の構成を有するので、機械的安定性と造膜性を両立することが可能であり、調理器具等の表面被覆用塗料として好適である。
  Since the coating composition of the present disclosure has the above-mentioned structure, it is possible to achieve both mechanical stability and film-forming property, and it is suitable as a coating material for surface coating of cooking utensils and the like.

Claims (8)

  1. ９８％積算粒子径が０．４μｍ以上１．０μｍ未満の含フッ素重合体（ａ）と、非アルキルフェノール型ノニオン界面活性剤（ｂ）と、アセチレンジオール系界面活性剤（ｃ）とを含有する水性分散体組成物であり、
    前記アセチレンジオール系界面活性剤（ｃ）は熱重量分析で３００℃における残量が３．０質量％以上であることを特徴とする被覆用組成物。     Aqueous solution containing a fluorine-containing polymer (a) having a 98% integrated particle size of 0.4 μm or more and less than 1.0 μm, a non-alkylphenol type nonionic surfactant (b), and an acetylene diol-based surfactant (c). Dispersion composition,
    The coating composition of the acetylene diol-based surfactant (c) is characterized in that the remaining amount at 300 ° C. is 3.0% by mass or more by thermogravimetric analysis.
  2. 非アルキルフェノール型ノニオン界面活性剤（ｂ）は、式（Ｉ）：
    Ｒ－Ｏ－Ａ－Ｈ　　（Ｉ）
    （式中、Ｒは直鎖状または分岐鎖状の炭素数８～１９の飽和又は不飽和の非環式脂肪族炭化水素基あるいは、炭素数８～１９の飽和環式脂肪族炭化水素基を表す。Ａはオキシエチレンユニットを３～２５個およびオキシプロピレンユニットを０～５個有するポリオキシアルキレン鎖）で示される非アルキルフェノール型ノニオン界面活性剤である請求項１に記載の被覆用組成物。     The non-alkylphenol type nonionic surfactant (b) is represented by the formula (I) :.
    ROAH (I)
    (In the formula, R is a linear or branched chain-shaped saturated or unsaturated acyclic aliphatic hydrocarbon group having 8 to 19 carbon atoms or a saturated cyclic aliphatic hydrocarbon group having 8 to 19 carbon atoms. The coating composition according to claim 1, wherein A is a non-alkylphenol type nonionic surfactant represented by a polyoxyalkylene chain having 3 to 25 oxyethylene units and 0 to 5 oxypropylene units.
  3. アセチレンジオール系界面活性剤（ｃ）は、アセチレンジオールのエチレンオキサイド付加物である請求項１又は２記載の被覆用組成物。 The coating composition according to claim 1 or 2, wherein the acetylene diol-based surfactant (c) is an ethylene oxide adduct of acetylene diol.
  4. アセチレンジオール系界面活性剤（ｃ）は、ＨＬＢが４を超えるものである請求項１、２又は３記載の被覆用組成物。 The coating composition according to claim 1, 2 or 3, wherein the acetylene diol-based surfactant (c) has an HLB of more than 4.
  5. 更に、沸点が１００℃以上でかつ水酸基を２個以上有する水溶性の多価アルコール（ｄ）を含有する請求項１、２、３又は４記載の被覆用組成物。 The coating composition according to claim 1, 2, 3 or 4, further comprising a water-soluble polyhydric alcohol (d) having a boiling point of 100 ° C. or higher and having two or more hydroxyl groups.
  6. 沸点が１００℃以上でかつ水酸基を２個以上有する水溶性の多価アルコール（ｄ）は、エチレングリコールである請求項５記載の被覆用組成物。 The coating composition according to claim 5, wherein the water-soluble polyhydric alcohol (d) having a boiling point of 100 ° C. or higher and having two or more hydroxyl groups is ethylene glycol.
  7. 含フッ素重合体（ａ）は、テトラフルオロエチレン〔ＴＦＥ〕／ヘキサフルオロプロピレン〔ＨＦＰ〕共重合体〔ＦＥＰ〕及びＴＦＥ／パーフルオロ（アルキルビニルエーテル）〔ＰＡＶＥ〕共重合体〔ＰＦＡ〕よりなる群から選択される少なくとも１種である請求項１、２、３、４、５又は６記載の被覆用組成物。 The fluoropolymer (a) is composed of a group consisting of a tetrafluoroethylene [TFE] / hexafluoropropylene [HFP] copolymer [FEP] and a TFE / perfluoro (alkyl vinyl ether) [PAVE] copolymer [PFA]. The coating composition according to claim 1, 2, 3, 4, 5 or 6, which is at least one selected.
  8. 請求項１、２、３、４、５、６又は７記載の被覆用組成物を塗装することにより得られたことを特徴とする被覆物品。

          A coated article obtained by painting the coating composition according to claim 1, 2, 3, 4, 5, 6 or 7.
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