CN116057135A - Coating composition and coated article - Google Patents
Coating composition and coated article Download PDFInfo
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- CN116057135A CN116057135A CN202180061645.4A CN202180061645A CN116057135A CN 116057135 A CN116057135 A CN 116057135A CN 202180061645 A CN202180061645 A CN 202180061645A CN 116057135 A CN116057135 A CN 116057135A
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- 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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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Abstract
The present invention provides a coating composition and the like which can obtain a coating film with excellent non-adhesiveness and persistence. A coating composition comprising a heat-resistant binder resin, a heat-fusible fluororesin and an organic solvent, wherein the heat-fusible fluororesin is a powder having an average particle diameter of 1.0 [ mu ] m or less, has a melting point of 270 ℃ or more, and has a melt flow rate of 15 to 45g/10 minutes, and the heat-fusible fluororesin is 10 to 200 parts by mass relative to 100 parts by mass of the heat-resistant binder resin.
Description
Technical Field
The present disclosure relates to coating compositions and coated articles.
Background
Heat resistance and non-adhesion are required for frying pans, top plates of gas cookers, inner wall materials of microwave ovens, and the like.
Patent document 1 describes a coating composition containing a polyethersulfone resin, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer having a specific melting point and average particle diameter, and a specific organic solvent in a specific ratio.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2000-026786
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present disclosure is to provide a coating composition that can provide a coating film that has excellent non-adhesion durability, and a coated article that has excellent non-adhesion durability.
Means for solving the problems
The present disclosure relates to a coating composition comprising a heat-resistant binder resin, a heat-fusible fluororesin, and an organic solvent, wherein the heat-fusible fluororesin is a powder having an average particle diameter of 1.0 [ mu ] m or less, a melting point of 270 ℃ or more, and a melt flow rate of 15 to 45g/10 minutes, and the heat-fusible fluororesin is 10 to 200 parts by mass relative to 100 parts by mass of the heat-resistant binder resin.
The present disclosure also relates to a coated article comprising a substrate and a coating film provided on the substrate and formed from the coating composition.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present disclosure, a coating composition that can provide a coating film excellent in non-adhesion durability and a coated article excellent in non-adhesion durability can be provided.
Detailed Description
The present disclosure is specifically described below.
The present disclosure relates to a coating composition comprising a heat-resistant binder resin, a heat-fusible fluororesin, and an organic solvent, wherein the heat-fusible fluororesin is a powder having an average particle diameter of 1.0 [ mu ] m or less, a melting point of 270 ℃ or more, and a melt flow rate of 15 to 45g/10 minutes, and the heat-fusible fluororesin is 10 to 200 parts by mass relative to 100 parts by mass of the heat-resistant binder resin.
The coating composition of the present disclosure can provide a coating film excellent in non-adhesion durability.
The coating composition of the present disclosure can also provide a coating film excellent in surface smoothness.
The coating composition of the present disclosure comprises a heat resistant binder resin.
The heat-resistant binder resin may be any resin that is generally considered to have heat resistance, but does not include a fluoropolymer. In the present specification, "heat resistance" means a property that can be used continuously at a temperature of 150 ℃ or higher.
Examples of the heat-resistant binder resin include polyamide imide resin (PAI), polyimide resin (PI), polyether sulfone resin (PES), polyether imide resin (PEI), aromatic polyether ketone resin, aromatic polyester resin, and polyarylene sulfide resin, and the like, and 1 kind or 2 or more kinds may be used singly or in combination.
PAI is a resin composed of a polymer having an amide bond and an imide bond in a molecular structure. The PAI is not particularly limited, and examples thereof include resins composed of high molecular weight polymers obtained by the following reactions: reaction of an aromatic diamine having an amide bond in the molecule with an aromatic tetracarboxylic acid such as pyromellitic acid; reaction of aromatic tricarboxylic acid such as trimellitic anhydride with diamine such as 4, 4-diaminophenyl ether or diisocyanate such as diphenylmethane diisocyanate; a reaction of a dibasic acid having an aromatic imide ring in the molecule with a diamine; etc. The PAI is preferably composed of a polymer having an aromatic ring in the main chain, because of excellent heat resistance.
PI is a resin composed of a polymer having an imide bond in a molecular structure. The PI is not particularly limited, and examples thereof include resins composed of high molecular weight polymers obtained by reaction of aromatic tetracarboxylic acid anhydride such as pyromellitic dianhydride, and the like. The PI is preferably composed of a polymer having an aromatic ring in the main chain, because of excellent heat resistance.
PES is represented by the general formula:
[ chemical 1]
The resin composed of the polymer of the repeating unit represented. The PES is not particularly limited, and examples thereof include resins composed of polymers obtained by polycondensation of dichlorodiphenyl sulfone and bisphenol.
The aromatic polyether ketone resin is a resin containing a repeating unit composed of an arylene group, an ether group [ -O- ] and a carbonyl group [ -C (=O) - ]. Examples of the aromatic polyether ketone resin include polyether ketone resin (PEK), polyether ether ketone resin (PEEK), polyether ether ketone resin (PEEKK), polyether ketone ester resin, and the like. The aromatic polyether ketone resin may be used alone or in combination of 1 or more than 2.
The aromatic polyether ketone resin is preferably at least one selected from the group consisting of PEK, PEEK, PEEKK and polyether ketone ester resins, and more preferably PEEK.
The heat-resistant binder resin preferably contains at least one selected from the group consisting of PAI, PI, PEI and PES. Thus, a coating film having more excellent non-adhesion durability and surface smoothness can be obtained. In addition, the adhesion to the substrate is excellent, and the heat resistance is sufficient even at the temperature at which firing is performed at the time of forming the coating film, and the obtained coating film is excellent in corrosion resistance and water vapor resistance.
In addition to the above effects, PES is more preferably contained in the heat-resistant binder resin from the viewpoints of the degree of freedom in coloring and workability.
The coating composition of the present disclosure comprises a hot melt fluororesin.
The Melt Flow Rate (MFR) of the hot-melt fluororesin is 15 to 45g/10 min. If the MFR is too low, the non-adhesiveness may deteriorate in durability and surface smoothness; if the MFR is too high, the non-adhesiveness may deteriorate in duration.
The MFR is preferably 20g/10 min or more, more preferably 25g/10 min or more. Further, it is preferably 40g/10 minutes or less, more preferably 35g/10 minutes or less.
The MFR is a value obtained as follows: according to ASTM D1238, the mass (g/10 min) of the polymer flowing out of a nozzle having an inner diameter of 2mm and a length of 8mm every 10 minutes was measured under a load (e.g., 5kg in the case of PFA, FEP, and ETFE) at a measurement temperature (e.g., 372℃in the case of PFA, FEP, 297℃in the case of ETFE) determined according to the type of the fluoropolymer using a melt flow index meter (manufactured by An Tian refiner, co., ltd.).
The melting point of the heat-fusible fluorine resin is 270 ℃ or higher. The melting point is preferably 270 to 330℃in view of heat resistance and stain resistance. In addition, from the viewpoints of heat resistance and film forming property of the heat-fusible fluororesin during processing, the melting point is more preferably 280 to 320 ℃.
The above melting point is the peak temperature of an endothermic curve obtained by performing a thermal measurement using a differential scanning calorimeter at a temperature rising rate of 10 ℃/min according to ASTM D-4591.
The heat-fusible fluorine resin may be at least one selected from the group consisting of Tetrafluoroethylene (TFE)/perfluoro (alkyl vinyl ether) (PAVE) copolymer (PFA), TFE/Hexafluoropropylene (HFP) copolymer (FEP), ethylene (Et)/TFE copolymer (ETFE), et/TFE/HFP copolymer, polytrifluoroethylene (PCTFE), CTFE/TFE copolymer, et/CTFE copolymer, and polyvinylidene fluoride (PVDF).
The heat-fusible fluorine resin is preferably at least one selected from the group consisting of PFA and FEP, and is more preferably PFA in view of the effect and heat resistance, from the viewpoint of obtaining a coating film having more excellent non-tackiness and surface smoothness.
As PAVE in the PFA, for example, formula (1) may be mentioned:
CF 2 ＝CF-ORf 1 (1)
(wherein Rf 1 Of these, perfluoro (methyl vinyl ether) [ PMVE ] is preferred, which represents a perfluoroalkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms]Perfluoro (ethyl vinyl ether) [PEVE]Perfluoro (propyl vinyl ether) [ PPVE ]]。
The PFA is not particularly limited, but a copolymer having a molar ratio of TFE unit to PAVE unit (TFE unit/PAVE unit) of 70/30 or more and less than 99/1 is preferable. More preferably, the molar ratio is 70/30 to 98.9/1.1, and still more preferably, the molar ratio is 80/20 to 98.9/1.1. If the TFE unit is too small, the mechanical properties tend to be lowered; if the amount is too large, the melting point tends to be too high, and the moldability tends to be lowered. The PFA is also preferably composed of only TFE units and PAVE units, and is also preferably a copolymer in which the monomer units derived from a monomer copolymerizable with TFE and PAVE are 0.1 to 10 mol% and the TFE units and PAVE units are 90 to 99.9 mol% in total. Examples of monomers copolymerizable with TFE and PAVE include HFP and CZ 1 Z 2 ＝CZ 3 (CF 2 ) n Z 4 (wherein Z is 1 、Z 2 And Z 3 Identical or different, representing hydrogen or fluorine atoms, Z 4 Represents a hydrogen atom, a fluorine atom or a chlorine atom, n represents an integer of 2 to 10), and CF 2 ＝CF-OCH 2 -Rf 2 (wherein Rf 2 Alkyl perfluorovinyl ether derivatives represented by perfluoroalkyl groups having 1 to 5 carbon atoms).
The PFA preferably has a thermal decomposition initiation temperature of 380 ℃ or higher. The thermal decomposition initiation temperature is more preferably 400℃or higher, and still more preferably 410℃or higher.
In the present specification, the thermal decomposition initiation temperature was a temperature at which 10mg of the sample was raised from room temperature at a temperature raising rate of 10℃per minute using a differential thermal gravimetric measuring instrument [ TG-DTA ] (trade name: TG/DTA6200, manufactured by SEIKO electronics Co., ltd.) and the sample was reduced by 1% by mass.
The FEP is not particularly limited, but a copolymer having a molar ratio of TFE unit to HFP unit (TFE unit/HFP unit) of 70/30 or more and less than 99/1 is preferable. More preferably, the molar ratio is 70/30 or more and 98.9/1.1 or less, and still more preferably, the molar ratio is 80/20 or more and 98.9/1.1 or less. If the TFE unit is too small, the mechanical properties tend to be lowered; if the amount is too large, the melting point tends to be too high, and the moldability tends to be lowered. The FEP is preferably onlyIt is also preferable that the copolymer comprises 0.1 to 10 mol% of a monomer unit derived from a monomer copolymerizable with TFE and HFP, and 90 to 99.9 mol% of the total of TFE units and HFP units. As monomers copolymerizable with TFE and HFP, PAVE, CF are mentioned 2 ＝CF-OCH 2 -Rf 2 (wherein Rf 2 Alkyl perfluorovinyl ether derivatives represented by perfluoroalkyl groups having 1 to 5 carbon atoms).
The FEP preferably has a thermal decomposition initiation temperature of 360 ℃ or higher. The thermal decomposition initiation temperature is more preferably 380℃or higher, and still more preferably 390℃or higher.
The content of each monomer unit of the heat-fusible fluorine resin can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis according to the kind of monomer.
The heat-fusible fluorine resin is a powder having an average particle diameter of 1.0 μm or less. This gives good dispersibility to the obtained coating film, and a coating film excellent in heat resistance and non-adhesion can be formed on the surface.
The average particle diameter is preferably 0.5 μm or less. The average particle diameter is preferably 0.1 μm or more, more preferably 0.3 μm or more. Within these ranges, the film forming property and the melting property of the fluororesin during firing are excellent.
The average particle diameter was measured at a dispersion pressure of 1.0bar without using cascade, using "CAPA-700" manufactured by horiba, inc., and the particle diameter corresponding to 50% of the particle size distribution accumulation was equal to the average particle diameter.
The heat-fusible fluororesin can be obtained by, for example, the method described in JP-A-1-25506. More specifically, the resin is obtained by allowing a monomer to coexist in an aqueous medium to perform emulsion polymerization, and precipitating and drying the resulting dispersion without adding a surfactant.
Thus, the average particle diameter can be made 1.0 μm or less.
Further, by appropriately using a chain transfer agent, the MFR of the hot-melt fluororesin can be controlled within the above range.
The chain transfer agent is preferably at least one selected from the group consisting of saturated hydrocarbons having 1 to 6 carbon atoms, alcohols having 1 to 4 carbon atoms, carboxylic acid ester compounds having 4 to 8 carbon atoms, chlorine-substituted hydrocarbons having 1 to 2 carbon atoms, ketones having 3 to 5 carbon atoms, and thiols having 10 to 12 carbon atoms.
The chain transfer agent is more preferably at least one selected from the group consisting of ethane, isopentane, methanol, isopropanol, acetone, and ethyl acetate from the viewpoints of dispersibility in a polymerization medium, chain transfer property, and removability from a target product.
The hot-melt fluororesin is preferably produced without using a fluorinated surfactant which is a perfluorocarboxylic acid having 8 to 14 carbon atoms or less and a salt thereof, and more preferably is produced without using a fluorinated surfactant. Thus, a heat-fusible fluororesin which does not contain a fluorosurfactant, particularly a perfluorocarboxylic acid having 8 to 14 carbon atoms and a salt thereof can be obtained.
The fluorosurfactant includes the following general formula (N) 1 )：
X n0 -(CF 2 ) m1 -Y 0 (N 1 )
(wherein X is n0 H, cl and F, m1 is an integer of 3 to 15, Y 0 is-SO 3 M、-SO 4 M、-SO 3 R、-SO 4 R、-COOM、-PO 3 M 2 、-PO 4 M 2 (M represents H, NH) 4 Or an alkali metal, R represents an alkyl group having 1 to 12 carbon atoms), and a compound represented by the following general formula (N) 2 )：
Rf n1 -O-(CF(CF 3 )CF 2 O) m2 CFX n1 -Y 0 (N 2 )
(wherein Rf n1 Is a perfluoroalkyl group having 1 to 5 carbon atoms, m2 is an integer of 0 to 3, X n1 Is F or CF 3 ，Y 0 A group as defined above).
In the coating composition of the present disclosure, the content of the hot-melt fluororesin is 10 to 200 parts by mass relative to 100 parts by mass of the heat-resistant binder resin. If the amount of the heat-fusible fluororesin is too small, the non-tackiness may be deteriorated in durability; if it is too large, the adhesion of the resulting coating composition to a substrate may be lowered. The content of the heat-fusible fluorine resin is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, and preferably 150 parts by mass or less, more preferably 120 parts by mass or less, relative to 100 parts by mass of the heat-resistant adhesive resin, from the viewpoint of further improving non-tackiness and adhesiveness.
The coating compositions of the present disclosure comprise an organic solvent. The coating composition of the present disclosure may be a solvent-based coating composition.
The organic solvent is preferably an organic compound and is liquid at a room temperature of about 20 ℃.
The organic solvent may be a solvent that dissolves the heat-resistant binder resin, or may be a solvent that disperses the heat-fusible fluororesin.
Examples of the organic solvent include N-ethyl-2-pyrrolidone, 3-alkoxy-N, N-dimethylpropionamide, γ -butyrolactone, dimethylsulfoxide, 1, 3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, N-formylmorpholine, N-acetylmorpholine, dimethylacrylurea, anisole, diethyl ether, ethylene glycol, acetophenone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, xylene, toluene, ethanol, and 2-propanol, and 1 or 2 or more thereof may be used.
The above-mentioned organic solvent is preferably at least one selected from the group consisting of N-ethyl-2-pyrrolidone, 3-alkoxy-N, N-dimethylpropionamide, γ -butyrolactone, dimethylsulfoxide, 1, 3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, N-formylmorpholine, N-acetylmorpholine, dimethylacrylurea, anisole, diethyl ether, ethylene glycol, acetophenone, methylethylketone, methylisobutylketone, cyclohexanone, cyclopentanone, xylene, toluene, ethanol and 2-propanol, more preferably at least one selected from the group consisting of N-ethyl-2-pyrrolidone, 3-alkoxy-N, N-dimethylpropionamide, γ -butyrolactone, dimethylsulfoxide, 1, 3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, N-formylmorpholine, N-acetylmorpholine and dimethylacrylurea, further preferably at least one selected from the group consisting of N-ethyl-2-pyrrolidone, 3-alkoxy-N, 3-dimethylpropionamide, 1, 3-dimethyl-2-imidazolidinone and dimethylacrylamide.
The 3-alkoxy-N, N-dimethylpropionamide is prepared from N (CH) 3 ) 2 COCH 2 CH 2 OR 11 (R 11 Alkyl). Alkoxy (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, more preferably a methoxy group, an ethoxy group, a propoxy group or a butoxy group. As the above-mentioned 3-alkoxy-N, N-dimethylpropionamide, 3-methoxy-N, N-dimethylpropionamide (N (CH) 3 ) 2 COCH 2 CH 2 OCH 3 )。
The mixing amount of the organic solvent may be selected in a range that imparts film formability to the obtained coating composition and imparts a coating viscosity suitable for the coating method.
The total amount of N-methyl-2-pyrrolidone, N-dimethylacetamide and N, N-dimethylformamide in the coating composition of the present disclosure is preferably less than 0.1 mass% relative to the above coating composition. The total amount is more preferably less than 0.01 mass%, and still more preferably less than 0.001 mass%.
The total amount is a value measured by liquid chromatography.
The coating compositions of the present disclosure also preferably do not include any of N-methyl-2-pyrrolidone, N-dimethylacetamide, and N, N-dimethylformamide.
The content of water in the coating composition of the present disclosure is preferably less than 1% by mass with respect to the above-mentioned coating composition.
The water content can be determined by the karl fischer method.
The content of the perfluorocarboxylic acid having 8 to 14 carbon atoms and the salt thereof in the coating composition of the present disclosure is preferably less than 25 ppb by mass relative to the coating composition. The content is more preferably 20 ppb by mass or less, still more preferably 15 ppb by mass or less, still more preferably 10 ppb by mass or less, particularly preferably 5 ppb by mass or less, and most preferably less than 5 ppb by mass.
The content of the perfluorocarboxylic acid and its salt can be measured by liquid chromatography.
The fluorosurfactant content in the coating composition of the present disclosure is preferably less than 25 ppb by mass relative to the above-described coating composition. The content is more preferably 20 ppb by mass or less, still more preferably 15 ppb by mass or less, still more preferably 10 ppb by mass or less, particularly preferably 5 ppb by mass or less, and most preferably less than 5 ppb by mass.
The content of the above fluorosurfactant can be measured by liquid chromatography.
The coating composition of the present disclosure may further contain, as other components, conventionally used additives such as pigments, brighteners, antibacterial agents, fillers, and the like, within a range that does not impair the effects of the coating composition of the present disclosure.
The total amount of the components other than the surfactant may be in a range of not more than 50% by mass based on the total amount of the heat-resistant adhesive and the heat-fusible fluororesin, from the viewpoint of not reducing non-tackiness of the coating film composed of the obtained coating composition.
The coating compositions of the present disclosure can be manufactured by conventional methods. For example, the composition can be produced by stirring and mixing the components by using a stirring and mixing device such as a ball mill, a three-roll mill, a disperser, or the like.
In the coating composition of the present disclosure, the solid content concentration is preferably 10 to 50 mass%, more preferably 15 mass% or more, and still more preferably 35 mass% or less from the viewpoint of coatability.
The present disclosure also relates to a coated article comprising a substrate and a coating film provided on the substrate and formed from the coating composition of the present disclosure.
The non-adhesion of the coated article of the present disclosure is excellent in durability.
In addition, the coated article of the present disclosure is also excellent in surface smoothness.
Examples of the material of the base material include metals such as elemental metals including iron, aluminum, and copper, alloys thereof, and plated steel sheets; non-metallic inorganic materials such as enamels, glasses, ceramics, etc. The alloy may be stainless steel or the like.
If necessary, an undercoat layer such as an anti-rust undercoat layer may be provided on the base material.
Examples of the shape of the substrate include a plate shape, a rod shape, and a sphere shape, and may be a desired final shape of the coated article.
In the case of applying the coating composition to the above substrate, for example, the coating can be carried out by a conventional method using a roll coater, a flow coater, a sprayer, or the like. In addition, from the viewpoint of adhesion to a substrate, it is preferable to treat the surface of the substrate with sand blast, acid, alkali, chromate, or the like and then apply the surface.
Firing may be performed after coating.
When the coating composition of the present disclosure is applied to a substrate, the dry film thickness thereof may be within a range that is not detrimental to heat resistance, and is preferably 5 to 40 μm in view of the persistence of non-adhesion; from the viewpoint of processability, it is more preferably 10 to 20. Mu.m.
The application to which the coating composition of the present disclosure can be applied and the coated article of the present disclosure is not particularly limited, and examples thereof include applications utilizing the properties of corrosion resistance, heat resistance, non-adhesion, sliding properties, and the like, which are possessed by a hot-melt fluororesin. Examples thereof include: frying pans, pressure cookers, pans, bakeware, rice cookers, ovens, heating plates, bread baking molds, kitchen knives, gas burners (e.g., top plates), microwave ovens (e.g., inner wall materials), and the like; kitchen supplies such as electric kettles, oilcan, ice making trays, molds, range hoods and the like; stirring roller, calendaring roller, conveyor, hopper and other food industry components; industrial products such as Office Automation (OA) rolls, OA belts, OA separation claws, paper making rolls, and film production calender rolls; injection mold, mold for molding foamed styrene, etc., and casting mold; demolding a molding die such as a stripper plate for manufacturing plywood and decorative plates; industrial containers (in particular for the semiconductor industry); saw, file, etc.; household articles such as flatirons, scissors, kitchen knives and the like; a metal foil; an electric wire; sliding bearings for food processors, packaging machines, textile machines, etc.; sliding parts of camera and clock; automotive parts such as pipes, valves, bearings, etc.; snow removing shovel; hoe; a chute, etc.
The coating composition of the present disclosure and the coated article of the present disclosure are preferably used for cooking devices or kitchen supplies. The coated article of the present disclosure is also preferably a cooking device, a kitchen appliance, or a component thereof.
The cooking device or the kitchen appliance is preferably a frying pan, a top plate of a gas cooker, or an inner wall material of a microwave oven.
Examples
The present disclosure will be described in more detail with reference to examples, but the present disclosure is not limited to these examples.
The values of the examples were measured by the following methods.
(melting point)
The peak temperature of the obtained endothermic curve was obtained as the melting point by performing a thermal measurement at a temperature rise rate of 10℃per minute using a differential scanning calorimeter in accordance with ASTM D-4591.
(MFR)
The mass (g/10 min) of the polymer flowing out of a nozzle having an inner diameter of 2mm and a length of 8mm at 372℃under a load of 5kg every 10 minutes was measured as MFR using a melt flow index meter (manufactured by An Tian refiner, co.) in accordance with ASTM D1238.
(average particle diameter)
The particle size corresponding to 50% of the cumulative particle size distribution was determined as the average particle size by measurement using CAPA-700 manufactured by horiba, inc. under a dispersion pressure of 1.0bar without using cascade connection.
Example 1
10g of polyether sulfone resin (PES 5003P, manufactured by Sumitomo chemical industry Co., ltd.) and 10g of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA 1, melting point 318 ℃, MFR30g/10min, average particle diameter 0.3 μm) were added to a mixed solvent of 50g of N-ethyl-2-pyrrolidone, 15g of methyl isobutyl ketone and 15g of xylene, and the mixture was dissolved and dispersed by a ball mill to obtain a coating composition of the present disclosure. Next, the composition was applied to a 0.5mm stainless steel sheet subjected to a coating type chromate treatment with a bar coater so that the dry film thickness was 10 μm, and baked at 400 ℃ for 90 seconds, to obtain a coated article of the present disclosure.
Example 2
A coating composition and a coated article were obtained in the same manner as in example 1, except that 10g of polyether sulfone resin (PES 5003P, manufactured by Sumitomo chemical Co., ltd.) and 10g of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA 1, melting point 318 ℃, MFR30g/10min, average particle diameter 0.3 μm) were added to 5g of composite oxide pigment (DAIPYROXIDE color #9510, manufactured by Dain Seiki Seisaku-Kogyo Co., ltd.) and dissolved and dispersed in a mixed solvent of 47g of N-ethyl-2-pyrrolidone, 14g of methyl isobutyl ketone and 13g of xylene by a ball mill, and 1g of aluminum flake (HS-2, manufactured by Toyo aluminum Co., ltd.) were further stirred and dispersed.
Example 3
A coating composition and a coated article were obtained in the same manner as in example 1, except that tetrafluoroethylene-perfluoroalkyl vinyl ether-hexafluoropropylene copolymer (FEP 1, melting point 282 ℃, MFR30g/10min, average particle diameter 0.2 μm) was used instead of the above PFA 1.
Example 4
A coating composition and a coated article were obtained in the same manner as in example 1, except that a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA 2, melting point 304 ℃, MFR 31g/10min, average particle diameter 0.15 μm) was used in place of the PFA 1.
Example 5
A coating composition and a coated article were obtained in the same manner as in example 1, except that a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA 3, melting point 316 ℃, MFR 16g/10min, average particle diameter 0.3 μm) was used instead of the PFA 1.
Example 6
A coating composition and a coated article were obtained in the same manner as in example 1, except that a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA 4, melting point 316 ℃, MFR 43g/10min, average particle diameter 0.3 μm) was used instead of the PFA 1.
Example 7
A coating composition and a coated article were obtained in the same manner as in example 1, except that 14g of a polyethersulfone resin (PES 5003P, manufactured by Sumitomo chemical Co., ltd.) and 7g of a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA 1, melting point 318 ℃, MFR30g/10min, average particle diameter 0.3 μm) were used.
Example 8
A coating composition and a coated article were obtained in the same manner as in example 1, except that 8g of a polyethersulfone resin (PES 5003P, manufactured by Sumitomo chemical Co., ltd.) and 12g of a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA 1, melting point 318 ℃, MFR30g/10min, average particle diameter 0.3 μm) were used.
Example 9
A coating composition and a coated article were obtained in the same manner as in example 1, except that 3-methoxy-N, N-dimethylpropionamide was used instead of the N-ethyl-2-pyrrolidone.
Example 10
A coating composition and a coated article were obtained in the same manner as in example 1, except that 1, 3-dimethyl-2-imidazolidinone was used instead of the N-ethyl-2-pyrrolidone.
Example 11
A coating composition and a coated article were obtained in the same manner as in example 1, except that 33g of a polyamideimide resin (HPC-3010, manufactured by Showa electric materials Co., ltd., gamma-butyrolactone dissolved product, solid content concentration: 30%) was added to a mixed solvent of 27g of N-ethyl-2-pyrrolidone, 15g of methyl isobutyl ketone, and 15g of xylene.
Example 12
A coating composition and a coated article were obtained in the same manner as in example 1, except that a polyetherimide resin (Ultem 1000, manufactured by SABIC) was used instead of the above polyethersulfone resin.
Comparative example 1
A coating composition and a coated article were obtained in the same manner as in example 1, except that a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA 5, melting point 316 ℃, MFR 11g/10min, average particle diameter 0.3 μm) was used instead of the PFA 1.
Comparative example 2
A coating composition and a coated article were obtained in the same manner as in example 1, except that a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA 6, melting point 317 ℃, MFR 62g/10min, average particle diameter 0.3 μm) was used instead of the PFA 1.
Comparative example 3
A coating composition and a coated article were obtained in the same manner as in example 1, except that tetrafluoroethylene-perfluoroalkyl vinyl ether-hexafluoropropylene copolymer (FEP 2, melting point 241 ℃, MFR29g/10min, average particle diameter 0.2 μm) was used instead of the above PFA 1.
Comparative example 4
A coating composition and a coated article were obtained in the same manner as in example 1, except that a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA 7, melting point 304 ℃, MFR 31g/10min, average particle diameter 5 μm) was used instead of the PFA 1.
Comparative example 5
A coating composition and a coated article were obtained in the same manner as in example 1, except that 10g of a polyethersulfone resin (PES 5003P, manufactured by Sumitomo chemical Co., ltd.) and 0.9g of a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA 1, melting point 318 ℃, MFR30g/10min, average particle diameter 0.3 μm) were used.
Comparative example 6
A coating composition and a coated article were obtained in the same manner as in example 1, except that 6g of a polyethersulfone resin (PES 5003P, manufactured by Sumitomo chemical Co., ltd.) and 15g of a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA 1, melting point 318 ℃, MFR30g/10min, average particle diameter 0.3 μm) were used.
The coated articles obtained in examples and comparative examples were cut to obtain test pieces, and the test pieces were subjected to the following test and evaluation. The results are shown in Table 1.
[ test method ]
(1) Surface roughness (surface smoothness)
The surface roughness (Ra) of the test piece was measured by using Surtronic DuoII (manufactured by TAYLOR HOBSON).
(2) Initial non-adhesion
The contaminated liquid composed of egg/granulated sugar/soy sauce=1/1/1 (mass ratio) was dropped onto a test piece, and after baking at 260 ℃ for 30 minutes, the contamination was removed by fingernails. The case where the contaminant can be removed easily and the coating film has little adhesion is denoted as a, the case where the contaminant can be removed easily but the adhesion has a degree of scraping off with the nail is denoted as B, the case where the contaminant is difficult to remove and the adhesion has a degree of scraping off with the nail is denoted as C, the case where the contaminant is difficult to remove and the adhesion has a degree of scraping off with the nail is denoted as D, and the case where the contaminant is not removed and the coating film is peeled off is denoted as E.
(3) Non-adhesive persistence
The initial non-adhesion test was used as 1 cycle, and the number of cycles until the contaminants could not be removed was examined.
TABLE 1
Claims (2)
1. A coating composition comprising a heat-resistant binder resin, a hot-melt fluororesin and an organic solvent, wherein,
the heat-fusible fluorine resin is a powder having an average particle diameter of 1.0 [ mu ] m or less, a melting point of 270 ℃ or more, and a melt flow rate of 15g/10 min to 45g/10 min,
the hot-melt fluororesin is 10 to 200 parts by mass per 100 parts by mass of the heat-resistant binder resin.
2. A coated article comprising a substrate and a coating film provided on the substrate, wherein the coating film is formed from the coating composition according to claim 1.
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| JP2020151930 | 2020-09-10 | ||
| JP2020-151930 | 2020-09-10 | ||
| PCT/JP2021/033354 WO2022054916A1 (en) | 2020-09-10 | 2021-09-10 | Coating composition and coated article |
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