WO2023013545A1 - 被覆用組成物及び被覆物品 - Google Patents
被覆用組成物及び被覆物品 Download PDFInfo
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- WO2023013545A1 WO2023013545A1 PCT/JP2022/029271 JP2022029271W WO2023013545A1 WO 2023013545 A1 WO2023013545 A1 WO 2023013545A1 JP 2022029271 W JP2022029271 W JP 2022029271W WO 2023013545 A1 WO2023013545 A1 WO 2023013545A1
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- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229940028444 muse Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005008 perfluoropentyl group Chemical group FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- GMVPRGQOIOIIMI-DWKJAMRDSA-N prostaglandin E1 Chemical compound CCCCC[C@H](O)\C=C\[C@H]1[C@H](O)CC(=O)[C@@H]1CCCCCCC(O)=O GMVPRGQOIOIIMI-DWKJAMRDSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000011031 topaz Substances 0.000 description 1
- 229910052853 topaz Inorganic materials 0.000 description 1
- 239000011032 tourmaline Substances 0.000 description 1
- 229910052613 tourmaline Inorganic materials 0.000 description 1
- 229940070527 tourmaline Drugs 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
-
- 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
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
- C09D181/06—Polysulfones; Polyethersulfones
-
- 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
-
- 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
-
- 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
- C09D5/002—Priming paints
-
- 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
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Definitions
- the present disclosure relates to coating compositions and coated articles.
- Fluoropolymers such as polytetrafluoroethylene, tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer, and tetrafluoroethylene/hexafluoropropylene copolymer have a low coefficient of friction and are non-adhesive and heat resistant. Due to its excellent properties, it is widely used for surface finishing of food industry products, cooking utensils such as frying pans and pots, kitchen utensils, household products such as irons, electrical industrial products, mechanical industrial products, and the like.
- Patent Document 1 discloses a coating composition containing a polyethersulfone resin, a polyimide resin, a non-melt-processable fluoropolymer, and a melt-processable fluoropolymer.
- Patent Document 2 discloses a coating composition containing a fluororesin, a heat resistant binder and a heat stabilizer.
- An object of the present disclosure is to provide a coating composition and a coated article capable of suppressing foaming in the composition and thereby forming a coating having good physical properties.
- a heat-resistant resin (A), a non-melt-processable fluoropolymer (B), and a melt-processable fluoropolymer (C) are dispersed in an aqueous medium,
- the coating composition is characterized in that the resin particles (A) to (C) have an average particle size of 0.1 to 10 ⁇ m and are substantially free of methyl cellulose.
- the heat-resistant resin (A) is preferably polyamideimide and/or polyimide (A-1).
- the heat-resistant resin (A) is preferably polyamideimide and/or polyimide (A-1) and polyethersulfone (A-2).
- the heat-resistant resin (A) has a mass ratio ((A-1):(A-2)) of polyamideimide and/or polyimide (A-1) and polyethersulfone (A-2) of 85: 15-65:35,
- the mass ratio (( A):(B)+(C)) is preferably 15:85 to 35:65.
- the non-melt-processable fluoropolymer (B) is preferably polytetrafluoroethylene and/or modified polytetrafluoroethylene.
- the melt-processable fluororesin polymer (C) may be a tetrafluoroethylene-hexafluoropropylene copolymer (FEP) and/or a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA). preferable.
- the coating composition preferably further contains a nonionic surfactant having an HLB of 10 or less.
- the coating composition is preferably applied directly onto a substrate made of a metallic or non-metallic inorganic material, or applied onto a layer made of a heat-resistant resin.
- the present disclosure also provides a coated article comprising a substrate, a primer layer formed by directly applying the coating composition to the substrate, and a topcoat layer containing a fluoropolymer.
- the coated article may further have an intermediate coat layer between the primer layer and the top coat layer.
- a coating having good physical properties can be formed.
- a heat-resistant resin (A), a non-melt-processable fluoropolymer (B), and a melt-processable fluoropolymer (C) are dispersed in an aqueous medium,
- the average particle diameter of the resin particles (A) to (C) is 0.1 to 10 ⁇ m
- the coating composition is substantially free of methyl cellulose.
- a coating composition containing the above components (A) to (C) generally contains methyl cellulose as a thickening agent in order to ensure coatability.
- such a coating composition containing methyl cellulose causes foaming in the spray coating process, which sometimes adversely affects coating performance.
- the present disclosure is characterized in that it does not substantially contain methyl cellulose.
- Methyl cellulose dissolves in the medium to increase the viscosity of the medium and stabilize the generated foam. It is also preferable in that it does not cause problems such as deterioration of coating film properties caused by foaming. Specifically, when the amount of foaming is small, the voids in the coating film are reduced, thereby improving the corrosion resistance of the coating film.
- substantially free of methyl cellulose means that the amount of methyl cellulose is less than 0.050% by mass with respect to the total amount of the paint. More preferably, the amount of methyl cellulose is 0.025% by mass or less. Moreover, it may be one that does not contain methyl cellulose.
- the coating composition of the present disclosure is substantially free of methyl cellulose as described above, but if this reduces the viscosity too much, coating becomes difficult. For this reason, it is preferable to contain a nonionic surfactant having an HLB of 10 or less for the purpose of adjusting the viscosity.
- a nonionic surfactant having an HLB of 10 or less for the purpose of adjusting the viscosity.
- the use of such a lipophilic nonionic surfactant is preferable in that the viscosity of the coating composition is increased, thereby improving the paintability. Furthermore, it also has the effect of improving the mechanical stability of the fluorine-containing polymer and the heat-resistant resin dispersed in water and improving the wettability of the metal substrate during coating.
- the chemical structure of the nonionic surfactant is not particularly limited, but specific examples include non-alkylphenol-type nonionic surfactants.
- a non-alkylphenol type nonionic surfactant is a nonionic surfactant that does not contain a benzene ring in its structure. Examples thereof include nonionic surfactants made from polyoxyethylene alkyl ether-based natural alcohols.
- the non-alkylphenol-type nonionic surfactant (b) has the following general formula (I): ROAH (I) (Wherein, 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 represents a polyoxyalkylene chain having 3 to 25 oxyethylene units and 0 to 5 oxypropylene units.).
- nonionic surfactant represented by the general formula (I) represented by the general formula (I), the following general formula (II): CxH2x +1CH ( CyH2y +1 ) CzH2zO ( C2H4O ) nH (II) (Wherein, 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.
- Polyoxy represented by Ethylene alkyl ether surfactant or The following general formula (III): C x H 2x+1 -OA-H (III) (Wherein, 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.
- the amount of the nonionic surfactant having an HLB of 10 or less is preferably 2.0 to 10.0% by mass based on the total amount of the coating composition.
- the above lower limit is preferably 2.5% by mass, more preferably 3.0% by mass.
- the upper limit is preferably 9.0% by mass, more preferably 8.0% by mass.
- the amount of the nonionic surfactant having an HLB of 11 or more is not particularly limited, and is preferably 1.0 to 5.0% by mass based on the total amount of the coating composition.
- the coating composition of the present disclosure is in a state in which the heat-resistant resin (A), the non-melt-processable fluoropolymer (B), and the melt-processable fluoropolymer (C) are dispersed in an aqueous medium. be.
- the average particle diameter of these resin particles (A) to (C) is 0.1 to 10 ⁇ m. Within this range, good dispersibility can be obtained, the stability of the composition can be obtained, and the physical properties of the coating film can be improved.
- a specific method for making the average particle size of the resin particles (A) to (C) 0.1 to 10 ⁇ m is not particularly limited, and each component (A) to (C) used as raw materials , each having a thickness of 0.1 to 10 ⁇ m and a combination thereof.
- the average particle size of the resin particles was measured with a particle size distribution measuring device (Microtrac MT-3000EXII, manufactured by Microtrac Bell) using laser diffraction.
- the average particle size (50% cumulative particle size) is automatically calculated by this device.
- the heat-resistant resin (A) means a resin that can be used continuously under conditions of 150° C. or higher. Examples of such resins include those other than fluorine-containing resins. In addition, the fluorine-containing resin corresponding to (B) and (C) does not correspond to the heat-resistant resin (A).
- fragrances such as polyetheretherketone resin, polyphenylene sulfide resin, polyaryletherketone (PAEK), polyetherketoneketone (PEKK), polyetherketone (PEK) and polyetheretherketoneketone (PEEKK) group polyetherketone resin, polyethersulfone (PES), liquid crystal polymer (LCP), polysulfone (PSF), amorphous polyarylate (PAR), polyethernitrile (PEN), thermoplastic polyimide (TPI), polyimide ( PI), polyetherimide (PEI), polyamideimide (PAI), and the like.
- PES polyethersulfone
- LCP liquid crystal polymer
- PSF polysulfone
- PAR amorphous polyarylate
- PEN polyethernitrile
- thermoplastic polyimide TPI
- PI polyimide
- PEI polyamideimide
- PAI polyamideimide
- A-1 are particularly preferred because of their excellent adhesion to metals.
- the heat-resistant resin (A) may be a combination of polyamideimide and/or polyimide (A-1) and polyethersulfone (A-2). Combined use of these resins is preferable in that both corrosion resistance and steam resistance of the coating can be achieved.
- the mass ratio of polyamideimide and/or polyimide (A-1) to polyethersulfone (A-2) ((A-1):(A-2)) is 85:15 to 65:35.
- the corrosion resistance and steam resistance of the coating are favorable, which is preferable. More preferably, the range is from 80:20 to 70:30.
- the polyamideimide (PAI) is a resin composed of a polymer having amide bonds and imide bonds in its molecular structure.
- the above PAI is not particularly limited, and examples include the reaction of an aromatic diamine having an amide bond in the molecule with an aromatic tetravalent carboxylic acid such as pyromellitic acid; 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. Resin etc. are mentioned. From the viewpoint of excellent heat resistance, the PAI is preferably composed of a polymer having an aromatic ring in the main chain.
- the polyimide (PI) is a resin composed of a polymer having an imide bond in its molecular structure.
- the PI is not particularly limited, and examples thereof include resins composed of high-molecular-weight polymers obtained by reaction of aromatic tetrahydric carboxylic acid anhydrides such as pyromellitic anhydride. From the viewpoint of excellent heat resistance, the above PI preferably comprises a polymer having an aromatic ring in its main chain.
- the polyether sulfone resin has the following general formula:
- PES is not particularly limited, and examples thereof include a resin made of a polymer obtained by polycondensation of dichlorodiphenylsulfone and bisphenol.
- the aromatic polyether ketone resin include polyether ketone resin (PEK), polyether ether ketone resin (PEEK), polyether ether ketone ketone resin (PEEKK), polyether ketone ester resin, and the like.
- the above aromatic polyether ketone resins can be used singly or in combination of two or more.
- the aromatic polyether ketone resin is preferably at least one selected from the group consisting of PEK, PEEK, PEEKK and polyether ketone ester resins, more preferably PEEK.
- the coating composition of the present disclosure further contains a non-melt-processible fluoropolymer (B).
- B non-melt-processible fluoropolymer
- the non-melt-processable fluoropolymer (B) is preferably non-melt-processable polytetrafluoroethylene (PTFE).
- the non-melt-processable PTFE is preferably fibrillatable.
- the fibrillating property refers to the property of being easily fiberized to form fibrils.
- the presence or absence of fibrillating properties can be determined by "paste extrusion", which is a representative method for molding "high molecular weight PTFE powder", which is a powder made from TFE polymer.
- Paste extrusion is usually possible because high molecular weight PTFE has fibrillating properties. If the green molding obtained by paste extrusion does not have substantial strength or elongation, for example if it has an elongation of 0% and breaks when pulled, it can be considered non-fibrillating.
- the non-melt-processable PTFE preferably has a standard specific gravity (SSG) of 2.130 to 2.230.
- SSG standard specific gravity
- the above SSG is more preferably 2.130 to 2.190, even more preferably 2.140 to 2.170.
- SSG is a value measured according to ASTM D4895.
- the non-melt processable PTFE has a heat of fusion curve of 333 to 333 to It preferably has a peak top (DSC melting point) at 347°C. More preferably, it has a peak top at 333 to 345°C, and more preferably at 340 to 345°C. When the peak top (DSC melting point) is within the above range, a coating film with even better corrosion resistance can be formed.
- RDC220 manufactured by SII Nanotechnology Co., Ltd.
- indium, lead, and tin are used to calibrate the calorific value, and as a measurement reference, the above empty aluminum pan is sealed and used.
- Muse standard analysis software manufactured by SII Nanotechnology Co., Ltd.
- the non-melt-processable PTFE is at least one selected from the group consisting of tetrafluoroethylene homopolymer (hereinafter also referred to as "homo PTFE”) and modified polytetrafluoroethylene (hereinafter also referred to as “modified PTFE”). Seeds are preferred.
- the modified PTFE is a modified PTFE composed of tetrafluoroethylene (TFE) and a monomer other than TFE (hereinafter also referred to as "modified monomer").
- TFE tetrafluoroethylene
- modified monomer a monomer other than TFE
- the modified monomer is not particularly limited as long as it can be copolymerized with TFE.
- examples include perfluoroolefins such as hexafluoropropylene (HFP); chlorofluoroolefins such as chlorotrifluoroethylene (CTFE); Hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride (VDF); perfluorovinyl ether; perfluoroalkylethylene, ethylene and the like.
- HFP hexafluoropropylene
- CTFE chlorofluoroolefins
- VDF Hydrogen-containing fluoroolefins
- perfluorovinyl ether perfluoroalkylethylene, ethylene and the like.
- one type of modifying monomer may be used, or a plurality of types thereof may be used.
- Rf 1 represents a perfluoro organic group.
- 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 which Rf 1 is a perfluoroalkyl group having 1 to 10 carbon atoms in the general formula (1).
- the perfluoroalkyl group preferably has 1 to 5 carbon atoms.
- perfluoroalkyl group in PAVE examples include perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, and perfluorohexyl group.
- the group is a perfluoropropyl group. That is, the PAVE is preferably perfluoropropyl vinyl ether (PPVE).
- Rf 1 is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, and Rf 1 is the following formula:
- Rf 1 is a group represented by the following formula:
- n an integer of 1 to 4.
- Perfluoroalkylethylene is not particularly limited, and examples thereof include perfluorobutylethylene (PFBE), perfluorohexylethylene, and the like.
- the modified monomer in the modified PTFE is preferably at least one selected from the group consisting of HFP, CTFE, VDF, PAVE, PFAE and ethylene. PAVE is more preferred, and PPVE is even more preferred.
- the homo-PTFE consists essentially of TFE units, and is preferably obtained without using modified monomers, for example.
- the modified PTFE preferably has a modified monomer unit content of 0.001 to 2 mol %, more preferably 0.001 to 1 mol %.
- the content of each monomer unit in the non-melt-processable fluoropolymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.
- the coating composition of the present disclosure further contains a melt-processable fluoropolymer (C).
- C melt-processable fluoropolymer
- melt processable means that the polymer can be melt processed using conventional processing equipment such as extruders and injection molding machines. Therefore, the melt-processable fluoropolymer generally has a melt flow rate (MFR) of 0.01 to 100 g/10 minutes.
- the MFR is defined by the type of fluoropolymer measured using a melt indexer (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) according to ASTM D 1238 (for example, 372 in the case of PFA and FEP). °C, 297 °C for ETFE), as the mass of polymer (g/10 min) flowing out per 10 min from a nozzle with an inner diameter of 2 mm and a length of 8 mm under load (e.g., 5 kg for PFA, FEP and ETFE). is the value obtained.
- the melt-processable fluoropolymer (C) preferably has a melting point of 100 to 333° C., more preferably 140° C. or higher, even more preferably 160° C. or higher, and 180° C. or higher. is particularly preferred. Also, it is more preferably 332° C. or lower, still more preferably lower than 322° C., and particularly preferably 320° C. or lower.
- the melting point of the melt-processable fluoropolymer (C) corresponds 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]. is the temperature at which
- melt-processable fluoropolymer (C) examples include low-molecular-weight PTFE, TFE/PAVE copolymer (PFA), TFE/HFP copolymer (FEP), and ethylene (Et)/TFE copolymer (ETFE). , Et/TFE/HFP copolymer, polychlorotrifluoroethylene (PCTFE), CTFE/TFE copolymer, Et/CTFE copolymer and at least one selected from the group consisting of polyvinylidene fluoride (PVDF) mentioned.
- the melt-processable fluoropolymer (C) is preferably at least one selected from the group consisting of FEP and PFA, more preferably FEP, in that a coating film with even better corrosion resistance can be obtained. preferable.
- the FEP is not particularly limited, 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 a still more preferable molar ratio is 80/20 or more and 98.9/1.1 or less. If the TFE unit content is too small, the mechanical properties tend to deteriorate.
- the FEP contains 0.1 to 10 mol% of monomer units derived from monomers copolymerizable with TFE and HFP, and the total amount of TFE units and HFP units is 90 to 99.9 mol%.
- a copolymer is also preferred.
- the FEP preferably has a melting point of 150 to less than 322.degree. C., more preferably 200 to 320.degree. C., even more preferably 240 to 320.degree.
- the 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 initiation temperature is more preferably 380° C. or higher, even more preferably 390° C. or higher.
- the thermal decomposition initiation temperature is measured using a differential thermal/thermogravimetry device [TG-DTA] (trade name: TG/DTA6200, manufactured by Seiko Electronics Co., Ltd.), and 10 mg of a sample is heated at a rate of 10 ° C./min. It is the temperature at which the sample is reduced by 1% by mass when the temperature is raised from room temperature.
- TG-DTA differential thermal/thermogravimetry device
- the above PFA is not particularly limited, but is preferably 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.
- a more preferable molar ratio is 70/30 or more and 98.9/1.1 or less, and a still more preferable molar ratio is 80/20 or more and 98.9/1.1 or less. If the TFE unit content is too small, the mechanical properties tend to deteriorate.
- the PFA contains 0.1 to 10 mol% of monomer units derived from monomers copolymerizable with TFE and PAVE, and the total amount of TFE units and PAVE units is 90 to 99.9 mol%.
- a copolymer is also preferred.
- the PFA preferably has a melting point of 180 to less than 322°C, more preferably 230 to 320°C, even more preferably 280 to 320°C.
- the PFA preferably has a melt flow rate (MFR) of 1 to 100 g/10 minutes.
- the above PFA preferably has a thermal decomposition initiation temperature of 380° C. or higher.
- the thermal decomposition initiation temperature is more preferably 400° C. or higher, even more preferably 410° C. or higher.
- the content of each monomer unit in the melt-processable fluoropolymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.
- the non-melt-processable fluoropolymer and the melt-processable fluoropolymer have an average particle size of 0. It is preferably between 0.01 and 40 ⁇ m.
- the average particle size is more preferably 0.05 ⁇ m or more, more preferably 20 ⁇ m or less, even more preferably 10 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
- the average particle size can be measured by a laser light scattering method.
- the weight ratio of the total amount of the PES and the polyimide resin to the total amount of the non-melt-processable fluoropolymer and the melt-processable fluoropolymer is 15 in order to obtain a coating film with even better corrosion resistance. /85 to 35/65 is preferred.
- the mass ratio is more preferably 20/80 or more, and more preferably 30/70 or less.
- the weight ratio of the non-melt-processable fluoropolymer to the melt-processable fluoropolymer is preferably from 5/95 to 95/5 in order to obtain a coating film with even better corrosion resistance.
- the mass ratio is more preferably 20/80 or more, further preferably 30/70 or more, even more preferably 40/60 or more, and particularly preferably 50/50 or more, Further, it is more preferably 90/10 or less, still more preferably 80/20 or less, and particularly preferably 70/30 or less.
- the coating composition of the present disclosure is in the form of the resin particles dispersed in an aqueous medium.
- the coating compositions of the present disclosure may contain organic solvents.
- the organic solvent is preferably an organic compound and is liquid at room temperature of about 20°C.
- organic solvent examples include N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, 3-alkoxy-N,N-dimethylpropanamide, ⁇ -butyrolactone, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, dimethylacetamide, dimethylformamide, N-formylmorpholine, N-acetylmorpholine, dimethylpropyleneurea, anisole, diethyl ether, ethylene glycol, Acetophenone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, xylene, toluene, ethanol, 2-propanol, etc., may be used alone or in combination of two or more.
- NMP N-methyl-2-pyrrolidone
- the above organic solvents include N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, 3-alkoxy-N,N-dimethylpropanamide, ⁇ -butyrolactone, dimethylsulfoxide, 1,3-dimethyl-2-imidazolide non, 3-methyl-2-oxazolidinone, dimethylacetamide, dimethylformamide, N-formylmorpholine, N-acetylmorpholine, dimethylpropylene urea, anisole, diethyl ether, ethylene glycol, acetophenone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopenta It is preferably at least one selected from the group consisting of non, xylene, toluene, ethanol and 2-propanol, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, 3-alkoxy-
- the above 3-alkoxy-N,N-dimethylpropanamide is represented by N(CH 3 ) 2 COCH 2 CH 2 OR 11 (R 11 is an alkyl group).
- the alkoxy group (R 11 O group) is not particularly limited, but is preferably an alkoxy group containing a lower alkyl group having about 1 to 6 carbon atoms, and may be a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. is more preferred.
- 3-alkoxy-N,N-dimethylpropanamide 3-methoxy-N,N-dimethylpropanamide (N(CH 3 ) 2 COCH 2 CH 2 OCH 3 ) is particularly preferred.
- the organic solvent preferably has a boiling point of 150° C. or higher, more preferably 170° C. or higher, and even more preferably 210° C. or higher. This makes it possible to retard the drying speed during coating and improve the surface smoothness of the coating film.
- the above boiling point is a value measured at 1 atmosphere (atm).
- the solid content concentration of the coating composition is preferably 5 to 70% by mass, more preferably 10% by mass or more, more preferably 60% by mass or less, and 50% by mass or less. is more preferable, and 40% by mass or less is particularly preferable.
- the coating compositions of the present disclosure may further include various additives.
- the above additives are not particularly limited, and examples include fillers, leveling agents, solid lubricants, anti-settling agents, water absorbents, surfactants, surface modifiers, thixotropic agents, viscosity modifiers, and anti-gelling agents.
- agent UV absorber, light stabilizer, plasticizer, anti-color separation agent, anti-skinning agent, anti-scratch agent, anti-mold agent, antibacterial agent, antioxidant, antistatic agent, silane coupling agent, colorant (iron oxide, titanium dioxide, etc.) and the like.
- the coating composition of the present disclosure may contain a filler as the above additive for the purpose of imparting characteristics to the coated article to be obtained, improving physical properties, increasing the amount, and the like.
- the characteristics and physical properties mentioned above include strength, durability, weather resistance, flame retardancy, and designability.
- the filler is not particularly limited, and examples thereof include wood flour, quartz sand, carbon black, clay, talc, diamond, fluorinated diamond, corundum, silica stone, boron nitride, boron carbide, silicon carbide, fused alumina, tourmaline, Jade, germanium, zirconium oxide, zirconium carbide, chrysoberyl, topaz, beryl, garnet, extender pigment, bright flat pigment, scale pigment, glass, glass powder, mica powder, metal powder (gold, silver, copper, platinum, stainless steel) , aluminum, etc.), various reinforcing materials, various bulking materials, conductive fillers, and the like.
- the content of the additive is preferably 0.01 to 10.0% by mass, more preferably 0.1 to 5.0% by mass, relative to the coating composition.
- the coating composition of the present disclosure has a viscosity of 100 to 300 cP at 25°C when applied.
- the object of the present disclosure can be particularly suitably achieved by setting the viscosity within such a range without substantially containing methyl cellulose.
- the coating composition of the present disclosure can be used as a coating composition for forming a primer layer in a coating method in which a primer layer is formed on a substrate and then a topcoat layer containing a fluoropolymer is formed. can be done.
- a coated article may hereinafter be referred to as a first coated article.
- the first coated article may further have an intermediate coat layer between the primer layer and the top coat layer.
- the intermediate coating layer is not particularly limited, and can be formed by a known intermediate coating.
- the coating composition of the present disclosure is a coating composition for forming an intermediate coating layer of a multilayer coating film further comprising a primer layer containing a heat-resistant resin, an intermediate coating layer, and a top coating layer containing a fluoropolymer.
- a coated article may hereinafter be referred to as a second coated article.
- Such a method of use is the same as in JP-A-2020-176216 filed by the present applicant, and the method of use can be the same as the method of use described in the prior art.
- the base material for example, a metal or a non-metallic inorganic material can be used, but a metal is preferable, and aluminum or stainless steel is more preferable.
- Examples of the metals include simple metals such as iron, aluminum, and copper, and alloys thereof. Stainless steel etc. are mentioned as said alloys.
- Examples of the nonmetallic inorganic materials include enamel, glass, and ceramics.
- the substrate may include other materials as well as metallic or non-metallic inorganic materials.
- the base material may be subjected to surface treatment such as degreasing treatment or surface roughening treatment, if necessary.
- the roughening treatment method is not particularly limited, and includes chemical etching with an acid or alkali, anodizing (alumite treatment), sandblasting, and the like.
- the surface treatment may be appropriately selected according to the types of the base material, the coating composition, and the like, and is preferably sandblasting, for example.
- the base material may be subjected to a degreasing treatment in which impurities such as oil are thermally decomposed and removed by air baking at 380°C.
- a degreasing treatment in which impurities such as oil are thermally decomposed and removed by air baking at 380°C.
- an aluminum base material may be used which has been roughened with an alumina abrasive after surface treatment.
- the method of applying the coating composition on the substrate or the heat-resistant layer is not particularly limited, and when the coating composition is liquid, spray coating, roll coating, coating with a doctor blade, dipping ( Immersion) coating, impregnation coating, spin flow coating, curtain flow coating and the like can be mentioned, among which spray coating is preferred.
- the coating composition is in the form of powder, electrostatic coating, fluidization dipping method, rotolining method and the like can be used, and among them, electrostatic coating is preferred.
- the present disclosure aims to suppress foaming by substantially not containing methyl cellulose. This is particularly noticeable in the case of spray painting using. Therefore, the effect can be particularly favorably exhibited when performing coating by spraying using a low-pressure atomization gun.
- drying may be performed.
- the drying is preferably carried out at a temperature of 70-300° C. for 5-60 minutes.
- the thickness of the primer layer is preferably 5 to 90 ⁇ m. If the film thickness is too thin, pinholes are likely to occur and the corrosion resistance of the coated article may deteriorate. If the film thickness is too thick, cracks are likely to occur and the water vapor resistance of the coated article may decrease.
- the upper limit of the film thickness is more preferably 60 ⁇ m, and the more preferable upper limit is 50 ⁇ m.
- the upper limit of the film thickness is more preferably 80 ⁇ m, and the upper limit is more preferably 70 ⁇ m.
- the first coated article has such a primer layer and a topcoat layer containing a fluoropolymer.
- the topcoat layer may be the same as the fluorine-containing layer described in detail in JP-A-2020-176216 filed by the present applicant.
- the fluorine-containing layer preferably has a film thickness of 5 to 90 ⁇ m. If the film thickness is too thin, the corrosion resistance of the coated article may deteriorate. If the film thickness is too thick, when the coated article is in the presence of water vapor, the water vapor tends to remain in the coated article, which may result in poor water vapor resistance.
- the upper limit of the film thickness is more preferably 60 ⁇ m, more preferably 50 ⁇ m, and particularly preferably 40 ⁇ m.
- the upper limit of the film thickness is preferably 80 ⁇ m, more preferably 75 ⁇ m, and particularly preferably 70 ⁇ m.
- the primer layer is preferably in direct contact with the substrate.
- the fluorine-containing layer may be in direct contact with the primer layer or may be in contact via another layer, but is preferably in direct contact.
- the coating composition of the present disclosure can provide coatings with excellent corrosion resistance, and the first and second coated articles have excellent corrosion resistance. Therefore, the coating composition and the first and second coated articles of the present disclosure can be suitably used in all fields where corrosion resistance is required.
- Applicable uses are not particularly limited, and include uses that make use of the non-adhesiveness, heat resistance, slipperiness, etc. of the fluoropolymer.
- non-adhesive cooking utensils such as frying pans, pressure cookers, pots, grill pans, rice cookers, ovens, hot plates, bread baking molds, kitchen knives, gas stoves; electric pots, ice trays, molds, Kitchen supplies such as range hoods; food industry parts such as kneading rolls, rolling rolls, conveyors and hoppers; office automation (OA) rolls, OA belts, OA separation claws, paper rolls, calendar rolls for film production, etc.
- OA office automation
- the coating composition of the present disclosure and the first and second coated articles are preferably used in cooking utensils or kitchen utensils, more preferably in cooking utensils, and more preferably in rice cookers. preferable.
- the first and second coated articles are also preferably cooking utensils, kitchen utensils or components thereof, more preferably cooking utensils or components thereof, and even more preferably rice cookers or components thereof. .
- parts and “%” represent “mass parts” and “mass%”, respectively, unless otherwise specified.
- the average particle size is measured by a particle size distribution analyzer (Microtrac MT-3000EXII, manufactured by Microtrac Bell) using laser diffraction.
- the film thickness was measured using a high-frequency film thickness meter (trade name: LZ-300C, manufactured by Kett Science Laboratory).
- PAI Polyamideimide resin [PAI] varnish (containing 71% N-methyl-2-pyrrolidone (hereinafter referred to as NMP)) having a solid content of 29% was put into water. to precipitate PAI. This was pulverized in a ball mill for 48 hours to obtain a PAI aqueous dispersion (average particle size 2 ⁇ m). The solids content of the resulting PAI aqueous dispersion was 20%.
- NMP N-methyl-2-pyrrolidone
- Production Example 3 Coating composition of the present disclosure: Example 1 To the PAI aqueous dispersion obtained in Production Example 1, a tetrafluoroethylene homopolymer [TFE homopolymer, hereinafter referred to as PTFE] aqueous dispersion (average particle size 0.28 ⁇ m, solid content 60%, non-alkylphenol type poly containing 6% ether-based nonionic surfactant with respect to PTFE) and tetrafluoroethylene-hexafluoropropylene copolymer (hereinafter referred to as FEP) aqueous dispersion (average particle size 0.20 ⁇ m, solid content 60%, non-alkylphenol type polyether nonionic surfactant as a dispersing agent 5% with respect to FEP), so that FEP is 8.4% of PTFE in mass ratio of solid content and added so that PAI is 25% of the total solid content of PAI, PTFE and FEP, and a non-alkylphenol-type polyether-based non
- Production Example 4 (coating composition of the present disclosure: Examples 2, 3, 5)
- the PES aqueous dispersion obtained in Production Example 2 and the PAI aqueous dispersion obtained in Production Example 1 were mixed so that PES was 75% of the total solid content of PES and PAI.
- Tetrafluoroethylene homopolymer [TFE homopolymer, hereinafter referred to as PTFE] aqueous dispersion (average particle size 0.28 ⁇ m, solid content 60%, non-alkylphenol type polyether nonionic surfactant as a dispersant for PTFE and tetrafluoroethylene-hexafluoropropylene copolymer (hereinafter referred to as FEP) aqueous dispersion (average particle size 0.20 ⁇ m, solid content 60%, polyether nonionic as a dispersant containing 5% of the surfactant to FEP), FEP is 50% of PTFE in terms of solid content mass ratio, and PES and PAI are the total solid content of PES, PAI, PTFE and FEP In addition to 25% of the solid content of the polymer, a non-alkylphenol type polyether nonionic surfactant (HLB value 9.5) is added as a thickener at 11% relative to the solid content of the polymer. A 3
- Production Example 5 (Coating composition of the present disclosure: Example 4) A coating composition for undercoat (3) having a polymer solid content of 36% was obtained in the same manner as in Production Example 4 except that 0.068% of methyl cellulose was added to the solid content of the polymer.
- Comparative production example 1 In the same manner as in Production Example 3, except that the thickener was changed to a non-alkylphenol-type polyether-based nonionic surfactant (HLB value 9.5) and 0.61% of methyl cellulose was added to the solid content of the polymer. , with a polymer solids content of 33% (4).
- HLB value 9.5 non-alkylphenol-type polyether-based nonionic surfactant
- Comparative production example 2 In the same manner as in Production Example 4, except that the thickener was changed to a non-alkylphenol-type polyether-based nonionic surfactant (HLB value 9.5) and 0.61% of methyl cellulose was added to the solid content of the polymer. , with a polymer solids content of 33% (5).
- HLB value 9.5 non-alkylphenol-type polyether-based nonionic surfactant
- Comparative production example 3 A coating composition for undercoat (6) having a polymer solid content of 36% was obtained in the same manner as in Production Example 4 except that 0.14% of methyl cellulose was added to the solid content of the polymer.
- a water-based PTFE coating (Polyflon PTFE EK-3700C21R, manufactured by Daikin Industries, Ltd.) or a PFA powder coating (Neoflon PFA ACX-34, manufactured by Daikin Industries, Ltd.) was applied onto the resulting coating film.
- the middle coat of Example 5 is ACX-34 mixed with 2.0% by mass of silicon carbide, and the top coat is ACX-34 mixed with 1.5% by mass of glass flakes and 1.0% by mass of diamond powder. I painted what I did.
- RG-2 type gravity spray gun (trade name, Anest Iwata Co., Ltd., nozzle diameter 1.0 mm) is used to spray paint at a spray pressure of 0.2 MPa and bake at 380 ° C. for 20 minutes. After cooling, a PTFE layer having a thickness of about 20 ⁇ m was formed on the overcoat to obtain a coated test panel.
- the obtained test coated plate had an undercoat layer and a PTFE topcoat layer formed on an aluminum plate.
- the top coat is ACX-34
- electrostatic coating is applied under the conditions of an applied voltage of 40 KV and a pressure of 0.08 MPa, baked at 380 ° C. for 20 minutes, and cooled to form a PFA layer with a thickness of about 40 ⁇ m on the top coat.
- the obtained test coated plate had an undercoat layer and a PFA topcoat layer formed on an aluminum plate.
- the intermediate coating is a filler-containing powder coating
- ACX-34 containing silicon carbide is electrostatically coated under the conditions of an applied voltage of 40 KV and a pressure of 0.08 MPa, followed by a top coating of ACX containing glass flakes and diamond powder. -34 was similarly electrostatically coated. Bake at 380° C.
- the resulting coated test plate had an aluminum plate, an undercoat layer, an intermediate coat layer made of PFA and silicon carbide, and an overcoat layer made of PFA, glass flakes and diamond powder.
- a corrosion resistance test was performed on the coated plate obtained above.
- the coating composition of the present disclosure can be suitably used in applications requiring corrosion resistance, and can be particularly suitably used for cooking utensils or kitchen utensils.
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Abstract
Description
特許文献2には、フッ素樹脂、耐熱性バインダー及び熱安定剤を含有する被覆用組成物が開示されている。
(A)~(C)の樹脂粒子の平均粒子径が0.1~10μmであり、かつメチルセルロースを実質的に含まないことを特徴とする被覆用組成物である。
上記耐熱性樹脂(A)は、ポリアミドイミド及び/又はポリイミド(A-1)並びにポリエーテルスルホン(A-2)であることが好ましい。
上記耐熱性樹脂(A)は、ポリアミドイミド及び/又はポリイミド(A-1)と、ポリエーテルスルホン(A-2)との質量比((A-1):(A-2))が85:15~65:35で、
ポリエーテルスルホンとポリアミドイミド及び/又はポリイミド(A)との合計量の非溶融加工性の含フッ素重合体(B)と溶融加工性の含フッ素重合体(C)の合計量に対する質量比((A):(B)+(C))が15:85~35:65であることが好ましい。
上記溶融加工性の含フッ素樹脂重合体(C)は、テトラフルオロエチレン-ヘキサフロオロプロピレン共重合体(FEP)及び/又はテトラフルオロエチレン-パーフルオロアルキルビニルエーテル共重合体(PFA)であることが好ましい。
上記被覆用組成物は、金属又は非金属無機材料からなる基材上に直接塗布されるか、又は、耐熱性樹脂からなる層の上に塗布されることが好ましい。
上記被覆物品は、上記プライマー層と上記上塗り層の間に、さらに中塗り層を有するものであってよい。
本開示は、耐熱性樹脂(A)、非溶融加工性の含フッ素重合体(B)及び溶融加工性の含フッ素重合体(C)が水媒体に分散し、
(A)~(C)の樹脂粒子の平均粒子径が0.1~10μmであり、
かつメチルセルロースを実質的に含まない被覆用組成物である。
上記(A)~(C)の成分を含有する被覆用組成物は、塗装性を確保するために、増粘剤としてメチルセルロースを添加するのが一般的であった。しかし、このようなメチルセルロースを含有する被覆用組成物は、スプレー塗装工程において、発泡を生じてしまい、これが塗膜性能に悪影響を及ぼすことがあった。
HLB=20×[(界面活性剤中に含まれる親水基の分子量)/(界面活性剤の分子量)]
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。
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):
C xH 2x+1CH(C yH 2y+1)C zH 2zO(C 2H 4O) 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、
下記一般式(III):
C xH 2x+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。
耐熱性樹脂(A)は、150℃以上の条件で連続使用することができる樹脂を意味する。このような樹脂であって、含フッ素樹脂以外のものを挙げることができる。なお,(B)(C)に該当する含フッ素樹脂は、耐熱性樹脂(A)には該当しない。
より具体的には、ポリエーテルエーテルケトン樹脂、ポリフェニレンサルファイド樹脂、ポリアリールエーテルケトン(PAEK)、ポリエーテルケトンケトン(PEKK)、ポリエーテルケトン(PEK)及びポリエーテルエーテルケトンケトン(PEEKK)等の芳香族ポリエーテルケトン樹脂、ポリエーテルサルフォン(PES)、液晶ポリマー(LCP)、ポリサルフォン(PSF)、非晶性ポリアリレート(PAR)、ポリエーテルニトリル(PEN)、熱可塑ポリイミド(TPI)、ポリイミド(PI)、ポリエーテルイミド(PEI)、ポリアミドイミド(PAI)等を挙げることができる。
なかでも、ポリアミドイミド及び/又はポリイミド(A-1)であることが金属との接着性に優れるという点で特に好ましい。
上記芳香族ポリエーテルケトン樹脂としては、PEK、PEEK、PEEKK及びポリエーテルケトンエステル樹脂からなる群より選択される少なくとも1種が好ましく、PEEKがより好ましい
CF2=CF-ORf1 (1)
(式中、Rf1は、パーフルオロ有機基を表す。)で表されるパーフルオロ不飽和化合物等が挙げられる。本明細書において、上記「パーフルオロ有機基」とは、炭素原子に結合する水素原子が全てフッ素原子に置換されてなる有機基を意味する。上記パーフルオロ有機基は、エーテル酸素を有していてもよい。
上記溶融加工性含フッ素重合体(C)は、耐食性に一層優れる塗膜が得られる点で、FEP及びPFAからなる群より選択される少なくとも1種であることが好ましく、FEPであることがより好ましい。
上記平均粒子径は、レーザー光散乱法により測定することができる。
上記沸点は、1気圧(atm)において測定する値である。
上記第1の被覆物品は、上記プライマー層と上記上塗り層の間に、さらに中塗り層を有するものであってもよい。上記中塗り層としては特に限定されず、公知の中塗り塗料により形成することができる。
上記非金属無機材料としては、ホーロー、ガラス、セラミック等が挙げられる。
上記基材は、金属又は非金属無機材料とともに、他の材料を含んでもよい。
含フッ素層は、プライマー層と直接接していてもよく、他の層を介して接していてもよいが、直接接していることが好ましい。
第1及び第2の被覆物品は、調理器具、厨房用品又はその構成部材であることも好ましく、調理器具又はその構成部材であることがより好ましく、炊飯釜又はその構成部材であることが更に好ましい。
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。
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。膜厚は、高周波式膜厚計(商品名:LZ-300C、ケット科学研究所製)を用いて測定した。
固形分29%のポリアミドイミド樹脂〔PAI〕ワニス(N-メチル-2-ピロリドン(以下、NMPという)を71%含む)を水中に投入してPAIを析出させた。これをボールミル中で48時間粉砕してPAI水性分散体(平均粒子径2μm)を得た。得られたPAI水性分散体の固形分は、20%であった。
数平均分子量約24000のポリエーテルスルホン樹脂〔PES〕60部及び脱イオン水60部を、セラミックボールミル中でPESからなる粒子が完全に粉砕されるまで約10分間攪拌した。次いで、NMP180部を添加し、更に、48時間粉砕し、分散体を得た。得られた分散体を更にサンドミルで1時間粉砕し、PES濃度が約20%のPES水性分散体(平均粒子径2μm)を得た。
製造例1で得られたPAI水性分散体に、テトラフルオロエチレンホモポリマー〔TFEホモポリマー、以下PTFEという〕水性分散体(平均粒子径0.28μm、固形分60%、分散剤として非アルキルフェノール型ポリエーテル系非イオン性界面活性剤をPTFEに対して6%含有している)とテトラフルオロエチレン-ヘキサフロオロプロピレン共重合体(以下、FEPという)水性分散体(平均粒子径0.20μm、固形分60%、分散剤として非アルキルフェノール型ポリエーテル系非イオン性界面活性剤をFEPに対して5%含有している)を、固形分の質量比でFEPがPTFEの8.4%となるように添加し、かつPAIが、PAI、PTFE及びFEPの固形分合計量の25%となるように加え、増粘剤として非アルキルフェノール型ポリエーテル系非イオン性界面活性剤(HLB値9.5)をポリマーの固形分に対して11%添加して、ポリマーの固形分37%の水性分散液(下塗り用被覆組成物(1))を得た。
製造例2で得られたPES水性分散体、及び、製造例1で得られたPAI水性分散体を、PESが、PESとPAIとの固形分合計量の75%となるように混合し、これにテトラフルオロエチレンホモポリマー〔TFEホモポリマー、以下PTFEという〕水性分散体(平均粒子径0.28μm、固形分60%、分散剤として非アルキルフェノール型ポリエーテル系非イオン性界面活性剤をPTFEに対して6%含有している)とテトラフルオロエチレン-ヘキサフロオロプロピレン共重合体(以下、FEPという)水性分散体(平均粒子径0.20μm、固形分60%、分散剤としてポリエーテル系非イオン性界面活性剤をFEPに対して5%含有している)を、固形分の質量比でFEPがPTFEの50%となり、かつPES及びPAIが、PES、PAI、PTFE及びFEPの固形分合計量の25%となるように加え、増粘剤として非アルキルフェノール型ポリエーテル系非イオン性界面活性剤(HLB値9.5)をポリマーの固形分に対して11%添加して、ポリマーの固形分37%の水性分散液(下塗り用被覆組成物(2))を得た。
製造例4にメチルセルロースをポリマーの固形分に対して0.068%添加した以外は製造例4と同様にしてポリマーの固形分36%の下塗り用被覆用組成物(3)を得た。
増粘剤を非アルキルフェノール型ポリエーテル系非イオン性界面活性剤(HLB値9.5)に替えてメチルセルロースをポリマーの固形分に対して0.61%添加した以外は製造例3と同様にして、ポリマーの固形分33%の下塗り用被覆用組成物(4)を得た。
増粘剤を非アルキルフェノール型ポリエーテル系非イオン性界面活性剤(HLB値9.5)に替えてメチルセルロースをポリマーの固形分に対して0.61%添加した以外は製造例4と同様にして、ポリマーの固形分33%の下塗り用被覆用組成物(5)を得た。
製造例4にメチルセルロースをポリマーの固形分に対して0.14%添加した以外は製造例4と同様にしてポリマーの固形分36%の下塗り用被覆用組成物(6)を得た。
縦5cm、横10cmに切断した厚みが1.5mmのアルミニウム板(A-1050P)の表面をアセトンで脱脂した後、JIS B 1982に準拠して測定した表面粗度Ra値が2.5~4.0μmとなるようにサンドブラストを行い、表面を粗面化した。エアーブローにより表面のダストを除去した後、製造例及び比較製造例で得られた下塗り用被覆用組成物を、乾燥膜厚が約10μmとなるように、RG-2型重力式スプレーガン(商品名、アネスト岩田社製、ノズル径1.0mm)を用い、吹き付け圧力0.2MPaでスプレー塗装した。得られたアルミニウム板上の塗布膜を80~100℃で15分間乾燥し、室温まで冷却した。
実施例5の中塗りとしては、ACX-34に炭化ケイ素を2.0質量%混合したもの、上塗りとしてはACX-34にガラスフレークを1.5質量%とダイヤモンド粉末を1.0質量%混合したものを塗装した。
PTFE水性塗料の場合、RG-2型重力式スプレーガン(商品名、アネスト岩田社製、ノズル径1.0mm)を用い、吹き付け圧力0.2MPaでスプレー塗装し、380℃で20分間焼成し、冷却して、上塗りに膜厚が約20μmのPTFE層を形成することにより、試験用塗装板を得た。得られた試験用塗装板は、アルミニウム板上に下塗り層、及びPTFEからなる上塗り層が形成されていた。
中塗りが充填材含有粉体塗料の場合、印加電圧40KV、圧力0.08MPaの条件で炭化ケイ素を含有するACX-34を静電塗装し、続いて上塗りのガラスフレークとダイヤモンド粉末を含有するACX-34を同様に静電塗装した。380℃で20分間焼成し、冷却して、中塗りに膜厚が約40μmの充填材含有PFA(PFA98%と炭化ケイ素2%を含む)層、上塗りに約5μmの充填材含有PFA(PFA97.5%、ガラスフレーク1.5%、ダイヤモンド粉末1.0%を含む)層を形成することにより、試験用塗装板を得た。得られた試験用塗装板は、アルミニウム板上に下塗り層、PFAと炭化ケイ素からなる中塗り層、及びPFA、ガラスフレーク、ダイヤモンド粉末からなる上塗り層形成されていた。上記で得られた塗装板で耐食試験を行った。
下記の評価を行った。
(下塗り用被覆組成物の塗装試験)
縦5cm、横10cmに切断した厚みが1.5mmのアルミニウム板(A-1050P)の表面をアセトンで脱脂した後、実施例及び比較例で得られた下塗り用被覆組成物を、乾燥膜厚が約10μmとなるように、W-101型重力式スプレーガン(商品名、アネスト岩田社製、ノズル径1.2mm)を用い、吹き付け圧力0.1MPaでスプレー塗装した。塗装直後の泡の数を調べた。
得られた試験用塗装板の塗膜表面にカッターナイフでクロスカットを入れ、基材に達する傷を入れた。この試験板を、おでんの素(ヱスビー食品株式会社製)20gを水1リットルに溶解した溶液中に浸漬し、70℃に保温して、カッターナイフでクロスカットを入れた試験板を1000時間浸漬し、クロスカット部の膨れの数を数えた。
下記の通り、点数を付与した。
5点 膨れなし
4点 膨れ(3mm以下)が3個以下
3点 膨れが4~6個、又は4mm以上の膨れ
2点 膨れが7~10個、又は10mm以上の膨れ、又は4mm以上の膨れ3個以上
1点 膨れが11個以上
B型粘度計(東機産業株式会社製TVB10型)を使用し、No.2ローター、60rpm、25℃の条件で粘度を測定した。
Claims (10)
- 耐熱性樹脂(A)、非溶融加工性の含フッ素重合体(B)及び溶融加工性の含フッ素重合体(C)が水媒体に分散し、
(A)~(C)の樹脂粒子の平均粒子径が0.1~10μmであり、
かつメチルセルロースを実質的に含まないことを特徴とする被覆用組成物。 - 耐熱性樹脂(A)は、ポリアミドイミド及び/又はポリイミド(A-1)である請求項1記載の被覆用組成物。
- 耐熱性樹脂(A)は、ポリアミドイミド及び/又はポリイミド(A-1)並びにポリエーテルスルホン(A-2)である請求項1記載の被覆用組成物。
- ポリアミドイミド及び/又はポリイミド(A-1)と、ポリエーテルスルホン(A-2)との質量比((A-1):(A-2))が85:15~65:35で、
ポリエーテルスルホンとポリアミドイミド及び/又はポリイミド(A)との合計量の非溶融加工性の含フッ素重合体(B)と溶融加工性の含フッ素重合体(C)の合計量に対する質量比((A):(B)+(C))が15:85~35:65である請求項3記載の被覆用組成物。 - 非溶融加工性の含フッ素重合体(B)は、ポリテトラフルオロエチレン及び/又は変性ポリテトラフルオロエチレンである請求項1~4のいずれかに記載の被覆用組成物。
- 溶融加工性の含フッ素樹脂重合体(C)は、テトラフルオロエチレン-ヘキサフロオロプロピレン共重合体(FEP)及び/又はテトラフルオロエチレン-パーフルオロアルキルビニルエーテル共重合体(PFA)である請求項1~5のいずれかに記載の被覆用組成物。
- さらに、HLBが10以下である非イオン性界面活性剤を含有する請求項1~6のいずれかに記載の被覆用組成物。
- 金属又は非金属無機材料からなる基材上に直接塗布されるか、又は、耐熱性樹脂からなる層の上に塗布される請求項1~7のいずれかに記載の被覆用組成物。
- 基材と、
請求項1~7のいずれかに記載の被覆用組成物を基材に直接塗布し、形成したプライマー層と、
含フッ素重合体を含む上塗り層を有することを特徴とする被覆物品。 - プライマー層と上塗り層の間に、さらに中塗り層を有する請求項9記載の被覆物品。
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JPH0539451A (ja) * | 1990-06-23 | 1993-02-19 | Sumitomo Electric Ind Ltd | 弗素樹脂被覆物 |
JPH11349887A (ja) * | 1998-06-05 | 1999-12-21 | Daikin Ind Ltd | フッ素樹脂被覆用水性プライマー組成物 |
JP2004204073A (ja) * | 2002-12-25 | 2004-07-22 | Daikin Ind Ltd | 被覆用組成物、塗膜及び被覆物品 |
JP2009532247A (ja) * | 2006-04-04 | 2009-09-10 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 非付着性仕上げ塗り |
JP2020176216A (ja) * | 2019-04-19 | 2020-10-29 | ダイキン工業株式会社 | 被覆組成物及び被覆物品 |
CN112480757A (zh) * | 2020-12-15 | 2021-03-12 | 深圳市易珑科技有限公司 | 环境友好型水性高固体份不粘涂层底漆、其制备方法及其应用 |
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JP2003053261A (ja) | 2001-08-10 | 2003-02-25 | Daikin Ind Ltd | フッ素樹脂塗膜製造方法、フッ素樹脂塗膜及び加工物品 |
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Patent Citations (6)
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JPH0539451A (ja) * | 1990-06-23 | 1993-02-19 | Sumitomo Electric Ind Ltd | 弗素樹脂被覆物 |
JPH11349887A (ja) * | 1998-06-05 | 1999-12-21 | Daikin Ind Ltd | フッ素樹脂被覆用水性プライマー組成物 |
JP2004204073A (ja) * | 2002-12-25 | 2004-07-22 | Daikin Ind Ltd | 被覆用組成物、塗膜及び被覆物品 |
JP2009532247A (ja) * | 2006-04-04 | 2009-09-10 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 非付着性仕上げ塗り |
JP2020176216A (ja) * | 2019-04-19 | 2020-10-29 | ダイキン工業株式会社 | 被覆組成物及び被覆物品 |
CN112480757A (zh) * | 2020-12-15 | 2021-03-12 | 深圳市易珑科技有限公司 | 环境友好型水性高固体份不粘涂层底漆、其制备方法及其应用 |
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