KR102385601B1 - Coating Compositions and Coating Articles - Google Patents

Abstract

A coating composition for imparting a coating film having excellent corrosion resistance is provided. A coating composition comprising a polyethersulfone resin, at least one polyimide-based resin selected from the group consisting of polyamideimide resins and polyimide resins, a non-melt-processable fluorine-containing polymer, and a melt-processable fluorine-containing polymer.

Description

Coating Compositions and Coating Articles

The present disclosure relates to coating compositions and coated articles.

Fluorine resins, such as polytetrafluoroethylene, tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer, and tetrafluoroethylene/hexafluoropropylene copolymer, have a low coefficient of friction, non-tackiness, heat resistance, etc. Because of its excellent properties, it is widely used for surface processing of food industry products, cooking utensils such as frying pans and pots, or kitchenware, household products such as irons, electrical industry products, and machine industry products.

Patent Document 1 describes a dispersion containing polyethersulfone, polyamideimide and polytetrafluoroethylene in a predetermined ratio.

Patent Document 2 describes a composition containing polyethersulfone, polyamideimide, and a tetrafluoroethylene/hexafluoropropylene copolymer in a predetermined ratio.

Japanese Patent Laid-Open No. 11-349887 Japanese Patent Laid-Open No. 6-264000

An object of this indication is to provide the coating composition which provides the coating film excellent in corrosion resistance. Another object of the present disclosure is to provide a coated article having excellent corrosion resistance.

The present disclosure provides a polyethersulfone resin, at least one polyimide-based resin selected from the group consisting of polyamideimide resins and polyimide resins, a non-melt-processable fluorine-containing polymer, and a melt-processable fluorine-containing polymer. It relates to a coating composition.

It is preferable that the mass ratio of the said polyethersulfone resin with respect to the said polyimide-type resin is 85/15-65/35.

It is preferable that the mass ratio of the total amount of the polyethersulfone resin and the polyimide-based resin to the total amount of the non-melt-processable fluorine-containing polymer and the melt-processable fluorine-containing polymer is 15/85 to 35/65.

The mass ratio of the non-melt-processable fluorine-containing polymer to the melt-processable fluorine-containing polymer is preferably 5/95 to 95/5.

It is preferable that the said coating composition also contains water.

It is preferable that the average particle diameter of the said polyether sulfone resin and the said polyimide-type resin is 0.1-10 micrometers.

The non-melt-processable fluorine-containing polymer is preferably at least one selected from the group consisting of tetrafluoroethylene homopolymer and modified polytetrafluoroethylene.

The melt processable fluorine-containing polymer is preferably at least one selected from the group consisting of a tetrafluoroethylene/hexafluoropropylene copolymer and a tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer.

The coating composition is preferably applied directly onto a substrate comprising a metallic or non-metallic inorganic material, or applied on a layer comprising a heat-resistant resin.

It is preferable that the said coating composition further contains an organic solvent.

The organic solvent is N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, 3-alkoxy-N,N-dimethylpropanamide, γ-butyrolactone, dimethyl sulfoxide, 1,3 -Dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, dimethylacetamide, dimethylformamide, N-formylmorpholine, N-acetylmorpholine, dimethylpropyleneurea, anisole, diethyl It is preferable that it is at least 1 sort(s) selected from the group which consists of ether, ethylene glycol, acetophenone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, xylene, toluene, ethanol, and 2-propanol.

The present disclosure also relates to a coated article having a substrate, a primer layer (A1) formed of the coating composition, and a fluorine-containing layer (C1) comprising a fluorine-containing polymer (a).

The present disclosure includes a base material, a primer layer (A2) comprising a heat-resistant resin (a), an intermediate layer (B1) formed of the coating composition, and a fluorine-containing layer (C2) comprising a fluorine-containing polymer (a); It is also about clothing items.

ADVANTAGE OF THE INVENTION According to this indication, the coating composition which provides the coating film excellent in corrosion resistance can be provided. According to the present disclosure, a coated article excellent in corrosion resistance can also be provided.

Hereinafter, the present disclosure will be specifically described.

The present disclosure provides a polyethersulfone resin, at least one polyimide-based resin selected from the group consisting of polyamideimide resins and polyimide resins, a non-melt-processable fluorine-containing polymer, and a melt-processable fluorine-containing polymer. It relates to a coating composition.

The coating composition of this indication can provide the coating film excellent in corrosion resistance.

The coating composition of the present disclosure includes a polyethersulfone resin (PES). PES is of the general formula:

It is a resin comprising a polymer having a repeating unit represented by . It does not specifically limit as PES, For example, resin etc. containing the polymer obtained by polycondensation of dichlorodiphenylsulfone and bisphenol are mentioned.

The coating composition of the present disclosure further contains at least one polyimide-based resin selected from the group consisting of polyamideimide resin (PAI) and polyimide resin (PI). As said polyimide-type resin, PAI is preferable.

PAI is a resin containing a polymer having an amide bond and an imide bond in a molecular structure. It does not specifically limit as said PAI, For example, Reaction of aromatic diamine which has an amide bond in a molecule|numerator, and aromatic tetravalent carboxylic acid, such as pyromellitic acid; Reaction of aromatic trivalent carboxylic acids, such as trimellitic anhydride, diamine, such as 4, 4- diaminophenyl ether, and diisocyanate, such as diphenylmethane diisocyanate; Resin containing a high molecular weight polymer obtained by each reaction, such as reaction of diamine and the dibasic acid which has an aromatic imide ring in a molecule|numerator, etc. are mentioned. From the viewpoint of excellent heat resistance, the PAI preferably contains a polymer having an aromatic ring in the main chain.

PI is a resin containing a polymer having an imide bond in its molecular structure. It does not specifically limit as said PI, For example, resin etc. containing the high molecular weight polymer obtained by reaction of aromatic tetravalent carboxylic acid anhydrides, such as pyromellitic anhydride, etc. are mentioned. From the viewpoint of excellent heat resistance, the PI preferably contains a polymer having an aromatic ring in the main chain.

It is preferable that the mass ratio of the said PES with respect to the said polyimide-type resin is 85/15-65/35 at the point from which the coating film which was further excellent in corrosion resistance is obtained. It is more preferable that it is 80/20 or less, and, as for the said mass ratio, it is more preferable that it is 70/30 or more.

It is preferable that the said PES and the said polyimide-type resin have an average particle diameter of 0.1-10 micrometers from a viewpoint of the dispersion stability in the said coating composition and the surface smoothness of the coating film obtained. As for the said average particle diameter, it is more preferable that it is 0.2 micrometer or more, It is more preferable that it is 8 micrometers or less, It is still more preferable that it is 5 micrometers or less.

The said average particle diameter can be measured by the laser-beam scattering method.

The coating composition of the present disclosure also includes a non-melt processable fluorine-containing polymer. "Non-melt processability" means a property in which the melt flow rate cannot be measured at a temperature higher than the crystallization melting point according to ASTM D-1238 and D-2116.

The non-melt-processable fluorine-containing polymer is preferably non-melt-processable polytetrafluoroethylene (PTFE).

It is preferable that the said non-melt-processable PTFE has fibrillation property. The said fibrillation property refers to the characteristic which fibrous easily and forms fibrils. The presence or absence of fibrillation can be judged by "paste extrusion", which is a representative method of molding "high molecular weight PTFE powder", which is a powder made from a polymer of TFE. Usually, paste extrusion is possible because high molecular weight PTFE has fibrillation property. If the green molded article obtained by paste extrusion has no substantial strength or elongation, for example, it is likely to break when elongation is 0%, it can be regarded as having no fibrillability.

The non-melt-workable PTFE preferably has a standard specific gravity (SSG) of 2.130 to 2.230. It is more preferable that it is 2.130-2.190, and, as for the said SSG, it is still more preferable that it is 2.140-2.170. When the SSG of the non-melt-workable PTFE is within the above range, a coating film having further excellent corrosion resistance can be formed. SSG is a value measured based on ASTM D 4895.

The non-melt workable PTFE has a peak top at 333 to 347° C. in the heat of fusion curve obtained at a temperature increase rate of 10° C./min by differential scanning calorimetry with respect to the non-melt workable PTFE without a history of heating to a temperature of 300° C. or higher. (DSC melting point) is preferred. More preferably, it has a peak top at 333-345 degreeC, More preferably, it has a peak top at 340-345 degreeC. When the peak top (DSC melting point) is within the above range, a coating film having further excellent corrosion resistance can be formed.

More specifically, for example, the differential scanning thermometry (DSC) uses RDC220 (manufactured by SII Nanotechnology Co., Ltd.) temperature-corrected using indium and lead as a standard sample in advance, and about 3 mg of PTFE powder It is put into an aluminum pan (crimp container), and the temperature range of 250-380 degreeC is heated up at 10 degreeC/min under an air stream of 200 ml/min, and it carries out. In addition, as a standard sample, the calorific value is calibrated using indium, lead, and tin, and the said empty aluminum pan is sealed and used as a measurement reference. The obtained heat of fusion curve uses Muse standard analysis software (manufactured by SII Nanotechnology Co., Ltd.), and makes the temperature showing the peak top of the amount of heat of fusion the DSC melting point.

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”). It is preferably a species.

The modified PTFE is a modified PTFE containing tetrafluoroethylene (TFE) and a monomer other than TFE (hereinafter also referred to as a “modified monomer”).

The modified monomer is not particularly limited as long as it can be copolymerized with TFE, and examples thereof include perfluoroolefins such as hexafluoropropylene (HFP); chlorofluoroolefins such as chlorotrifluoroethylene (CTFE); hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride (VDF); perfluorovinyl ether; Multiple types may be sufficient.

It does not specifically limit as said perfluorovinyl ether, For example, following General formula (1)

CF ₂ =CF-ORf ¹ (1)

(in formula, Rf ¹ represents a perfluoro organic group.) The perfluoro unsaturated compound etc. are mentioned. In the present specification, the "perfluoroorganic group" means an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms. The said perfluoro organic group may have ether oxygen.

Examples of the perfluorovinyl ether include perfluoro(alkylvinyl ether) (PAVE) in which Rf ¹ is a perfluoroalkyl group having 1 to 10 carbon atoms in the general formula (1). Carbon number of the said perfluoroalkyl group becomes like this. Preferably it is 1-5.

As the perfluoroalkyl group in the PAVE, for example, perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, etc. However, it is preferable that the perfluoroalkyl group is a perfluoropropyl group. That is, the PAVE is preferably perfluoropropyl vinyl alcohol (PPVE).

As the perfluorovinyl ether, in the general formula (1), Rf ¹ is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, and Rf ¹ is a formula:

(wherein, m represents 0 or an integer of 1 to 4), Rf ¹ is the following formula:

(in formula, n represents the integer of 1-4.) group represented by, etc. are mentioned.

It does not specifically limit as perfluoroalkylethylene (PFAE), For example, perfluorobutylethylene (PFBE), perfluorohexylethylene, etc. are mentioned.

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. More preferably, it is PAVE, More preferably, it is PPVE.

The homo PTFE contains substantially only TFE units, for example, it is preferably obtained without using a modified monomer.

It is preferable that it is 0.001-2 mol% of modified monomer units, and, as for the said modified PTFE, it is more preferable that it is 0.001-1 mol%.

The content of each monomer unit of the non-melt-processable fluorine-containing polymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescence X-ray analysis according to the type of the monomer.

The coating composition of the present disclosure also includes a melt processable fluorine-containing polymer. The "melt workability" means that it is possible to melt and process a polymer using conventional processing equipment, such as an extruder and an injection molding machine. Therefore, the melt flow rate (MFR) of the melt processable fluorine-containing polymer is usually 0.01 to 100 g/10 min.

In the present specification, the MFR is, in accordance with ASTM D 1238, using a melt indexer (manufactured by Yasuda Seki Seisakusho), and a measurement temperature determined according to the type of fluoropolymer (eg, PFA or FEP). 372 ° C in the case of , 297 ° C in the case of ETFE), load (for example, 5 kg in the case of PFA, FEP and ETFE) It is a value obtained as mass (g/10min).

It is preferable that melting|fusing point of the said melt processable fluorine-containing polymer is 100-333 degreeC, It is more preferable that it is 140 degreeC or more, It is still more preferable that it is 160 degreeC or more, It is especially preferable that it is 180 degreeC or more. Moreover, it is more preferable that it is 332 degrees C or less, It is still more preferable that it is less than 322 degreeC, It is especially preferable that it is 320 degrees C or less.

In the present specification, the melting point of the melt-processable fluorine-containing polymer is a temperature corresponding to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10° C./min using a differential scanning calorimeter [DSC].

Examples of the melt processable fluorine-containing polymer include low molecular weight PTFE, TFE/PAVE copolymer (PFA), TFE/HFP copolymer (FEP), ethylene (Et)/TFE copolymer (ETFE), Et/TFE/HFP copolymer, and at least one selected from the group consisting of polychlorotrifluoroethylene (PCTFE), CTFE/TFE copolymer, Et/CTFE copolymer, and polyvinylidene fluoride (PVDF).

The melt-processable fluorine-containing polymer is preferably at least one selected from the group consisting of FEP and PFA, more preferably FEP, from the viewpoint of obtaining a coating film having further excellent corrosion resistance.

Although it does not specifically limit as said FEP, The copolymer whose molar ratio (TFE unit/HFP unit) of a TFE unit and an HFP unit is 70/30 or more and less than 99/1 is preferable. More preferable molar ratios are 70/30 or more and 98.9/1.1 or less, and still more preferable molar ratios are 80/20 or more and 98.9/1.1 or less. When the TFE unit is too small, the mechanical properties tend to decrease, and when the TFE unit is too large, the melting point becomes too high and the moldability tends to decrease. It is also preferable that the said FEP is a copolymer whose monomeric unit derived from the monomer copolymerizable with TFE and HFP is 0.1-10 mol%, and TFE unit and HFP unit are 90-99.9 mol% in total. As a monomer copolymerizable with TFE and HFP, PAVE, CF ₂ =CF-OCH ₂ -Rf ² (wherein Rf ² represents a perfluoroalkyl group having 1 to 5 carbon atoms) Alkyl perfluorovinyl ether derivatives and the like.

It is preferable that melting|fusing point is less than 150-322 degreeC, as for the said FEP, it is more preferable that it is 200-320 degreeC, It is more preferable that it is 240-320 degreeC.

The FEP preferably has an MFR of 1 to 100 g/10 min.

It is preferable that the said FEP has a thermal decomposition initiation temperature of 360 degreeC or more. As for the said thermal decomposition start temperature, it is more preferable that it is 380 degreeC or more, and it is still more preferable that it is 390 degreeC or more.

In the present specification, the thermal decomposition initiation temperature is determined using a differential thermal/thermogravimetry apparatus [TG-DTA] (trade name: TG/DTA6200, manufactured by Seiko Denshi Corporation), and 10 mg of the sample is heated from room temperature at a temperature increase rate of 10°C/min. It is the temperature at which the temperature was raised and the sample decreased by 1% by mass.

Although it does not specifically limit as said PFA, The copolymer whose molar ratio (TFE unit/PAVE unit) of a TFE unit and a PAVE unit is 70/30 or more and less than 99/1 is preferable. More preferable molar ratios are 70/30 or more and 98.9/1.1 or less, and still more preferable molar ratios are 80/20 or more and 98.9/1.1 or less. When the TFE unit is too small, the mechanical properties tend to decrease, and when the TFE unit is too large, the melting point becomes too high and the moldability tends to decrease. It is also preferable that the said PFA is a copolymer whose monomer unit derived from TFE and a monomer copolymerizable with PAVE is 0.1-10 mol%, and TFE unit and PAVE unit are 90-99.9 mol% in total. As a monomer copolymerizable with TFE and PAVE, HFP, CZ ¹ Z ² =CZ ³ (CF ₂ ) _n Z ⁴ (wherein, Z ¹ , Z ² and Z ³ are the same or different, and a hydrogen atom or a fluorine atom is and Z ⁴ represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 2 to 10.) a vinyl monomer, and CF ₂ =CF-OCH ₂ -Rf ² (wherein, Rf ² represents a perfluoroalkyl group having 1 to 5 carbon atoms).

It is preferable that melting|fusing point of the said PFA is less than 180-322 degreeC, It is more preferable that it is 230-320 degreeC, It is more preferable that it is 280-320 degreeC.

The PFA preferably has a melt flow rate (MFR) of 1 to 100 g/10 min.

It is preferable that the said PFA has a thermal decomposition initiation temperature of 380 degreeC or more. As for the said thermal decomposition start temperature, it is more preferable that it is 400 degreeC or more, and it is still more preferable that it is 410 degreeC or more.

The content of each monomer unit of the melt-processable fluorine-containing polymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescence X-ray analysis according to the type of the monomer.

From the viewpoints of dispersion stability in the coating composition and surface smoothness of the resulting coating film, the non-melt-processable fluorine-containing polymer and the melt-processable fluorine-containing polymer preferably have an average particle diameter of 0.01 to 40 µm. As for the said average particle diameter, it is more preferable that it is 0.05 micrometer or more, It is more preferable that it is 20 micrometers or less, It is still more preferable that it is 10 micrometers or less, It is especially preferable that it is 5 micrometers or less.

The said average particle diameter can be measured by the laser-beam scattering method.

From the viewpoint of obtaining a coating film having further excellent corrosion resistance, the mass ratio of the total amount of the PES and the polyimide-based resin to the total amount of the non-melt-processable fluorine-containing polymer and the melt-processable fluorine-containing polymer is 15/85 to 35/65 desirable. It is more preferable that it is 20/80 or more, and, as for the said mass ratio, it is more preferable that it is 30/70 or less.

Moreover, it is preferable that the mass ratio of the said non-melt-processable fluoropolymer with respect to the said melt-processable fluorine-containing polymer is 5/95-95/5 at the point from which the coating film which is further excellent in corrosion resistance is obtained. The mass ratio is more preferably 20/80 or more, still more preferably 30/70 or more, still more preferably 40/60 or more, particularly preferably 50/50 or more, and more preferably 90/10 or less. and more preferably 80/20 or less, and particularly preferably 70/30 or less.

Although liquid may be sufficient as the coating composition of this indication, and powder form may be sufficient as it, it is preferable that it is liquid.

It is preferable that the coating composition of this indication contains water. It is preferable that the said coating composition is an aqueous coating composition. It is also preferable that the PES, the polyimide-based resin, the non-melt-processable fluorine-containing polymer and the melt-processable fluorine-containing polymer are dispersed in water.

The coating composition of this indication may also contain an organic solvent. The said organic solvent is an organic compound, and it is preferable that it is a liquid at normal temperature of about 20 degreeC.

Examples of the organic solvent include N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, 3-alkoxy-N,N-dimethylpropanamide, γ-Butyrolactone, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, 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, cyclopentanone, xylene, toluene, ethanol, 2-propanol, etc. and one or two or more types may be used.

The organic solvent is N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, 3-alkoxy-N,N-dimethylpropanamide, γ-butyrolactone, dimethyl sulfoxide, 1,3 -Dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, dimethylacetamide, dimethylformamide, N-formylmorpholine, N-acetylmorpholine, dimethylpropyleneurea, anisole, diethyl It is preferably at least one selected from the group consisting of ether, ethylene glycol, acetophenone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, xylene, toluene, ethanol and 2-propanol, and N-ethyl -2-pyrrolidone, N-butyl-2-pyrrolidone, 3-alkoxy-N,N-dimethylpropanamide, γ-butyrolactone, dimethyl sulfoxide, 1,3-dimethyl-2-imidazoli It is more preferably at least one selected from the group consisting of dione, 3-methyl-2-oxazolidinone, dimethylacetamide, dimethylformamide, N-formylmorpholine, N-acetylmorpholine and dimethylpropyleneurea, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, 3-alkoxy-N,N-dimethylpropanamide, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2 - It is more preferable that it is at least 1 sort(s) selected from the group which consists of -oxazolidinone, N-formylmorpholine, N-acetylmorpholine, and dimethylpropylene urea.

The 3-alkoxy-N,N-dimethylpropanamide is represented by N(CH ₃ ) ₂ COCH ₂ CH ₂ OR ¹¹ (R ¹¹ is an alkyl group). Although the alkoxy group (R ¹¹ O group) is not particularly limited, it 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. . The 3-alkoxy-N,N-dimethylpropanamide is particularly preferably 3-methoxy-N,N-dimethylpropanamide (N(CH ₃ ) ₂ COCH ₂ CH ₂ OCH ₃ ).

The organic solvent preferably has a boiling point of 150°C or higher, more preferably 170°C or higher, and still more preferably 210°C or higher. Thereby, the drying rate at the time of coating can be delayed and the surface smoothness of a coating film can be improved.

The said boiling point is a value measured in 1 atmosphere (atm).

It is also preferred that the coating composition comprises water and optionally an organic solvent.

When the said coating composition contains water and an organic solvent, it is preferable that content of an organic solvent is 1-50 mass % with respect to the total amount of water and an organic solvent. As for the said content, it is more preferable that it is 5 mass % or more, It is still more preferable that it is 10 mass % or more, It is more preferable that it is 40 mass % or less, It is more preferable that it is 30 mass % or less.

Preferably, the coating composition is substantially free of N-methyl-2-pyrrolidone (NMP). That NMP is not included substantially means that content of NMP is 1.0 mass % or less with respect to the said coating composition. It is more preferable that it is 0.01 mass % or less with respect to the said coating composition, and, as for content of NMP, it is still more preferable that it is 0.001 mass % or less.

It is especially preferable that the said coating composition does not contain NMP.

It is preferable that the solid content concentration of the said coating composition is 5-70 mass %, It is more preferable that it is 10 mass % or more, It is more preferable that it is 60 mass % or less, It is more preferable that it is 50 mass % or less, It is especially 40 mass % or less desirable.

The coating composition of this indication may further contain various additives. The additive is not particularly limited and includes, for example, a filler, a leveling agent, a solid lubricant, an anti-settling agent, a water absorbent, a surfactant, a surface modifier, a thixotropic imparting agent, a viscosity modifier, an anti-gelling agent, an ultraviolet absorber, a light stabilizer, plasticizers, color separation inhibitors, film formation inhibitors, abrasive damage inhibitors, mold inhibitors, antibacterial agents, antioxidants, antistatic agents, silane coupling agents, colorants (iron oxide, titanium dioxide, etc.), etc. are mentioned.

The coating composition of the present disclosure may contain a filler as the additive for the purpose of imparting properties to the coated article to be obtained, improving physical properties, increasing the amount, and the like. As said characteristic and physical property, intensity|strength, durability, weather resistance, a flame retardance, designability, etc. are mentioned.

The filler is not particularly limited and includes, for example, wood powder, 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, flaky pigment, glass, glass powder, mica powder, metal powder (gold, silver, copper, platinum, stainless steel, aluminum, etc.), various reinforcing materials, various extenders, conductive fillers, and the like.

It is also preferable that the said coating composition contains surfactant. Although a conventionally well-known thing can be used as said surfactant, a nonionic surfactant and anionic surfactant are preferable, and a polyether type nonionic surfactant is more preferable.

0.01-10.0 mass % is preferable with respect to the said coating composition, and, as for content of the said additive, 0.1-5.0 mass % is more preferable.

The coating composition of the present disclosure is preferably applied directly on a substrate containing a metal or non-metallic inorganic material, or on a layer containing a heat-resistant resin (hereinafter also referred to as a heat-resistant layer), and is preferably a metal or non-metallic inorganic material. More preferably, it is applied directly onto the substrate comprising the material.

Examples of the metal include simple metals such as iron, aluminum, and copper, and alloys thereof. As said alloys, stainless steel etc. are mentioned.

Examples of the non-metallic inorganic material include enamel, glass, and ceramics.

The said base material may contain other materials together with a metal or a non-metallic inorganic material.

As said base material, it is preferable that a metal is included, and it is more preferable that aluminum or stainless steel is included.

The said base material may surface-treated, such as a degreasing process and a roughening process, as needed. It does not specifically limit as a method of the said roughening process, Chemical etching by acid or alkali, anodization (anodizing process), sandblasting, etc. are mentioned. Although the said surface treatment may be suitably selected according to the kind of the said base material, the said coating composition, etc., it is preferable that it is sandblasting, for example.

The substrate may be subjected to a degreasing treatment in which impurities such as oil are removed by thermal decomposition by preheating at 380°C. Moreover, you may use the aluminum base material which roughened using the alumina grinding|polishing material after surface treatment.

It does not specifically limit as heat-resistant resin in the said heat-resistant layer, Usually, although resin recognized as having heat resistance may be sufficient, a fluorine-containing polymer shall be excluded. In this specification, "heat resistance" means the property in which continuous use in the temperature of 150 degreeC or more is possible.

Examples of the heat-resistant resin include polyamideimide resin (PAI), polyimide resin (PI), polyethersulfone resin (PES), polyetherimide resin, aromatic polyetherketone resin, aromatic polyester resin, polyarylene sulfide resin, and the like. These are mentioned, and can be used individually by 1 type or in combination of 2 or more type.

As PAI, PI, and PES, the thing mentioned above is mentioned.

The aromatic polyether ketone resin is a resin including a repeating unit composed of an arylene group, an ether group [-O-], and a carbonyl group [-C(=O)-]. As said aromatic polyether ketone resin, polyether ketone resin (PEK), polyether ether ketone resin (PEEK), polyether ether ketone ketone resin (PEEKK), polyether ketone ester resin, etc. can be illustrated. The said aromatic polyether ketone resin can be used individually by 1 type or in combination of 2 or more type.

As said aromatic polyether ketone resin, at least 1 sort(s) chosen from the group which consists of PEK, PEEK, PEEKK, and polyether ketone ester resin is preferable, and PEEK is more preferable.

The heat-resistant resin in the said heat-resistant layer may be the same as or different from the PES or polyimide-type resin contained in the coating composition of this indication.

Although the said heat-resistant layer may further contain components other than the said heat resistant resin, it is preferable not to contain a fluorine-containing polymer.

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, dip (immersion) coating, impregnation coating, Spin flow coating, curtain flow coating, etc. are mentioned, Especially, spray coating is preferable. When the said coating composition is a powder form, an electrostatic coating, a fluid immersion method, the furnace lining method, etc. are mentioned, Especially, electrostatic coating is preferable.

After application of the coating composition, firing may or may not be performed. In addition, when the said coating composition is liquid, you may dry further after the said application|coating, and it is not necessary to dry.

It is preferable to perform the said drying at the temperature of 70-300 degreeC for 5 to 60 minutes. It is preferable to perform the said baking at the temperature of 260-410 degreeC for 10 to 30 minutes.

When the coating composition is liquid, it is preferable to apply the coating composition on the substrate and then dry it. Moreover, it is preferable not to perform baking.

When the coating composition is in the form of a powder, it is preferable to apply the coating composition to the substrate, followed by firing.

The coating composition of the present disclosure is preferably applied under a layer comprising a fluorine-containing polymer. It is one of suitable embodiments that the coating composition of the present disclosure is used for an undercoat (primer) of a layer comprising a fluorine-containing polymer.

The coating composition of this indication can be used in order to form the primer layer (A1) or intermediate|middle layer (B1) which comprises the 1st and 2nd coating article mentioned later.

The present disclosure relates to a coated article (hereinafter also referred to as a first coated article) having a substrate, a primer layer (A1) formed of the above-described coating composition of the present disclosure, and a fluorine-containing layer (C1) comprising a fluorine-containing polymer (a). ) is also about.

A 1st covering article is excellent in corrosion resistance.

As a material of the said base material which comprises a 1st covering article, Metals, such as a metal single-piece|unit, such as iron, aluminum, and copper, and these alloys; Non-metallic inorganic materials, such as enamel, glass, and a ceramic, etc. are mentioned. As said alloys, stainless steel etc. are mentioned.

The said base material may contain other materials together with a metal or a non-metallic inorganic material.

As said base material, it is preferable that a metal is included, and it is more preferable that aluminum or stainless steel is included.

The primer layer (A1) constituting the first coated article is formed from the coating composition of the present disclosure.

About the coating composition of this indication, it is as above-mentioned.

It is preferable that the film thickness of a primer layer (A1) is 5-90 micrometers. When a film thickness is too thin, it is easy to generate|occur|produce a pinhole, and there exists a possibility that the corrosion resistance of a coating|coated article may fall. When a film thickness is too thick, a crack will become easy to generate|occur|produce, and there exists a possibility that the steam resistance of a coating|coated article may fall. A more preferable upper limit of the film thickness when the primer layer (A1) is formed of a liquid composition is 60 µm, and a more preferred upper limit is 50 µm. A more preferable upper limit of the film thickness when the primer layer (A1) is formed of a powdery composition is 80 µm, and a more preferred upper limit is 70 µm.

The fluorine-containing layer (C1) constituting the first coated article contains the fluorine-containing polymer (a).

The fluorine-containing polymer (a) constituting the fluorine-containing layer (C1) is a polymer having a fluorine atom directly bonded to a carbon atom constituting the main chain or side chain. The fluorine-containing polymer (a) may have non-melt processability or melt processability.

The fluorine-containing polymer (a) is preferably obtained by polymerizing a fluorine-containing monoethylenically unsaturated hydrocarbon (I).

The "fluorine-containing monoethylenically unsaturated hydrocarbon (I) (hereinafter also referred to as "unsaturated hydrocarbon (I)")" refers to a vinyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms in a molecule having one unsaturated hydrocarbons.

The unsaturated hydrocarbon (I) is selected from the group consisting of some or all of the hydrogen atoms not substituted with fluorine atoms, halogen atoms other than fluorine atoms such as chlorine atoms, and fluoroalkyl groups such as trifluoromethyl group What is substituted by at least 1 type may be sufficient. However, the said unsaturated hydrocarbon (I) excludes the trifluoroethylene mentioned later.

The unsaturated hydrocarbon (I) is not particularly limited and includes, for example, tetrafluoroethylene [TFE], hexafluoropropylene [HFP], chlorotrifluoroethylene [CTFE], vinylidene fluoride [VdF], fluoride vinyl [VF] etc. are mentioned, These can use 1 type, or 2 or more types.

The fluorine-containing polymer (a) may be a homopolymer of the unsaturated hydrocarbon (I). As the homopolymer of the unsaturated hydrocarbon (I), for example, tetrafluoroethylene homopolymer [TFE homopolymer], polychlorotrifluoroethylene [PCTFE], polyvinylidene fluoride [PVdF], polyvinyl fluoride [ PVF] and the like.

The fluorine-containing polymer (a) may be a copolymer of the unsaturated hydrocarbon (I). Examples of the copolymer include a copolymer of two or more types of the unsaturated hydrocarbon (I), at least one type of the unsaturated hydrocarbon (I), and an unsaturated compound (II) copolymerizable with the unsaturated hydrocarbon (I) copolymers of

In the present disclosure, the polymer obtained by polymerizing only one or two or more of the unsaturated hydrocarbons (I) can be used as the fluorine-containing polymer (a), whereas only one or two or more unsaturated compounds (II) can be used. The polymer obtained by superposing|polymerizing cannot be used as said fluorine-containing polymer (a). In this respect, the unsaturated compound (II) is different from the unsaturated hydrocarbon (I).

It does not specifically limit as said unsaturated compound (II), For example, trifluoroethylene [3FH]; and monoethylenically unsaturated hydrocarbons such as ethylene [Et] and propylene [Pr]. These can use 1 type or 2 or more types.

Specific examples of the copolymer of the unsaturated hydrocarbon (I) are not particularly limited, and TFE/HFP copolymer [FEP], TFE/CTFE copolymer, TFE/VdF copolymer, TFE/3FH copolymer, Et/TFE copolymer [ ETFE] and TFE-based copolymers such as TFE/Pr copolymer; VdF/HFP copolymer; VdF/TFE/HFP copolymer; Et/CTFE copolymer [ECTFE]; Et/HFP copolymer etc. are mentioned.

In the present specification, the "TFE-based copolymer" means one obtained by copolymerizing TFE and one or two or more types of monomers other than TFE. In the TFE-based copolymer, the ratio of the polymerized units based on other monomers other than TFE in the TFE-based copolymer is usually the total mass of the polymerized units based on TFE and the polymerized units based on the other monomers. It is preferable that it exceeds 1 mass %.

Other monomers other than TFE in the TFE-based copolymer may be other monomers (III) copolymerizable with the following TFE. The other monomers (III) have the following general formula

X(CF ₂ ) _m O _n CF=CF ₂

(wherein, X represents -H, -Cl or -F, m represents an integer of 1 to 6, and n represents an integer of 0 or 1.) excluded), the following general formula

C ₃ F ₇ O[CF(CF ₃ )CF ₂ O] _p -CF=CF ₂

(in formula, p represents the integer of 1 or 2.) A compound represented by, and the following general formula

X(CF ₂ ) _q CY=CH ₂

(wherein, X is the same as above, Y represents -H or -F, and q represents an integer of 1 to 6) At least one monomer selected from the group consisting of compounds represented by It is preferable to be These can use 1 type or 2 or more types.

TFE/perfluoro(alkyl vinyl ether) [PAVE] copolymer [PFA] etc. are mentioned as a TFE-type copolymer using the said other monomer (III). As PFA, PFA fluorinated by the method described in International Publication No. 2002/088227 can also be used.

The fluorine-containing polymer (a) may further be modified polytetrafluoroethylene [modified PTFE]. As said modified PTFE, the thing similar to modified PTFE as a non-melting processable fluorine-containing polymer in the coating composition of this indication can be illustrated, for example.

The fluorine-containing polymer (a) may be one or two or more, and one or a mixture of one or two or more of the homopolymer of the unsaturated hydrocarbon (I) and the copolymer of the unsaturated hydrocarbon (I); A mixture of two or more types of the copolymer of the said unsaturated hydrocarbon (I) may be sufficient.

Examples of the mixture include a mixture of a TFE homopolymer and the TFE-based copolymer, and a mixture of two or more types of copolymers belonging to the TFE-based copolymer. As such a mixture, for example, TFE homopolymer a mixture of polymer and PFA, a mixture of TFE homopolymer and FEP, a mixture of TFE homopolymer and PFA and FEP, and a mixture of PFA and FEP.

The fluorine-containing polymer (a) may further be obtained by polymerizing a perfluoroalkyl group-containing ethylenically unsaturated monomer (IV) having a perfluoroalkyl group (hereinafter, also referred to as “unsaturated monomer (IV)”). The unsaturated monomer (IV) has the following general formula

(Wherein, Rf represents a perfluoroalkyl group having 4 to 20 carbon atoms, R ¹ represents -H or an alkyl group having 1 to 10 carbon atoms, R ² represents an alkylene group having 1 to 10 carbon atoms, R ³ represents -H or a methyl group, R ⁴ represents an alkyl group having 1 to 17 carbon atoms, r represents an integer of 1 to 10, and s represents an integer of 0 to 10). .

The fluorine-containing polymer (a) may be a homopolymer of the unsaturated monomer (IV) or a copolymer of the unsaturated monomer (IV) and a monomer (V) copolymerizable with the unsaturated monomer (IV).

It does not specifically limit as said monomer (V), (meth)acrylic acid cyclohexyl, (meth)acrylic acid benzyl ester, di(meth)acrylic acid polyethyleneglycol, N-methylol propane acrylamide, (meth)acrylic acid amide, carbon number of an alkyl group (meth)acrylic acid derivatives such as alkyl esters of (meth)acrylic acid having a value of 1 to 20; substituted or unsubstituted ethylene such as ethylene, vinyl chloride, vinyl fluoride, styrene, α-methylstyrene, and p-methylstyrene; vinyl ethers such as alkyl vinyl ethers having 1 to 20 carbon atoms in the alkyl group and halogenated alkyl vinyl ethers having 1 to 20 carbon atoms in the alkyl group; vinyl ketones such as vinyl alkyl ketones having 1 to 20 carbon atoms in the alkyl group; Aliphatic unsaturated polycarboxylic acids, such as maleic anhydride, and its derivative(s); Polyenes, such as a butadiene, an isoprene, and a chloroprene, etc. are mentioned.

The said fluorine-containing polymer (a) can be obtained by using conventionally well-known polymerization methods, such as emulsion polymerization, etc., for example.

As the fluorine-containing polymer (a), at least one polymer selected from the group consisting of TFE homopolymer, modified PTFE, and the TFE-based copolymer is preferable from the viewpoint that the obtained coating film is excellent in corrosion resistance and water vapor resistance. As the TFE-based copolymer, at least one copolymer selected from the group consisting of PFA and FEP is preferable.

From the above, the fluorine-containing polymer (a) is preferably at least one selected from the group consisting of TFE homopolymer, modified PTFE, PFA and FEP, and is selected from the group consisting of TFE homopolymer, modified PTFE and PFA. At least 1 type is more preferable, and PFA is still more preferable.

The fluorine-containing layer (C1) may contain additives other than the fluorine-containing polymer (a). It does not specifically limit as said additive, For example, the additive illustrated in the coating composition of this indication can be used.

0.01-30 mass % is preferable with respect to the total mass of a fluorine-containing layer (C1), and, as for content of the said additive, 0.1-20 mass % is more preferable.

The fluorine-containing layer (C1) may contain a filler as the additive for the purpose of imparting properties to the obtained coated article, improving physical properties, increasing the amount, and the like. As said characteristic and physical property, intensity|strength, durability, weather resistance, a flame retardance, designability, etc. are mentioned. When what has a brilliance feeling is used as a filler, the coated article of this indication has a favorable brilliance feeling.

The filler is not particularly limited and includes, for example, wood powder, 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, flaky pigment, glass, glass powder, mica powder, metal powder (gold, silver, copper, platinum, stainless steel, etc.) ), various reinforcing materials, various extenders, conductive fillers, and the like. As said filler, when it is calculated|required that the fluorine-containing laminated body of this invention should have a luminous feeling, a luminous filler is preferable. The said "bright filler" is a filler which can provide a luminous feeling to the fluorine-containing laminated body obtained.

It is preferable that the said filler is 0.01-40 mass % with respect to the total mass of a fluorine-containing layer (C1), It is more preferable that it is 0.05-30 mass %, It is still more preferable that it is 0.1-10 mass %.

The fluorine-containing layer (C1) preferably has a film thickness of 5 to 90 µm. When a film thickness is too thin, there exists a possibility that the corrosion resistance of a coating|coated article may fall. When 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, and the water vapor resistance may be poor. A more preferable upper limit of the film thickness when the fluorine-containing layer (C1) is formed of a liquid composition is 60 µm, a more preferable upper limit is 50 µm, and a particularly preferable upper limit is 40 µm. A more preferable upper limit of the film thickness when the fluorine-containing layer (C1) is formed of a powdery composition is 80 μm, a more preferable upper limit is 75 μm, and a particularly preferable upper limit is 70 μm.

1st coating article WHEREIN: It is one of suitable aspects that the film thickness of a primer layer (A1) is 5-90 micrometers and the film thickness of a fluorine-containing layer (C1) is 5-90 micrometers.

In the first coated article, it is preferable that the base material, the primer layer (A1) and the fluorine-containing layer (C1) are laminated in this order.

In other words, it is preferable that the primer layer (A1) is provided on the base material and the fluorine layer (C1) is provided on the primer layer (A1).

It is preferable that the primer layer (A1) is in direct contact with the base material.

Although the fluorine-containing layer (C1) may be in direct contact with the primer layer (A1) or may be in contact with another layer, it is preferable that the fluorine-containing layer (C1) is in direct contact.

Although a layer may be further provided on the fluorine-containing layer (C1), it is preferable that the fluorine-containing layer (C1) is the outermost layer.

Characters, drawings, etc. may be printed on the upper surface of the primer layer (A1).

The present disclosure provides a base material, a primer layer (A2) comprising a heat-resistant resin (a), an intermediate layer (B1) formed of the coating composition of the present disclosure described above, and a fluorine-containing layer comprising a fluorine-containing polymer (a) ( It also relates to a coated article (hereinafter also referred to as a second coated article) having C2).

A 2nd coating article is excellent in corrosion resistance.

As said base material which comprises a 2nd coated article, the thing similar to the base material which can be used for the 1st coated article mentioned above can be illustrated, and a preferable example is also the same.

The primer layer (A2) constituting the second coated article contains the heat-resistant resin (a).

As the heat-resistant resin (a) constituting the primer layer (A2), polyamideimide resin (PAI), polyimide resin (PI), polyethersulfone resin (PES), polyetherimide resin, aromatic polyetherketone resin, aromatic A polyester resin, polyarylene sulfide resin, etc. are mentioned, 1 type can be used individually or in combination of 2 or more type. In addition, the heat resistant resin (a) shall exclude a fluorine-containing polymer.

As PAI, PI, PES, and aromatic polyether ketone resin, the thing mentioned above is mentioned.

It is preferable that heat resistant resin (a) is at least 1 sort(s) chosen from the group which consists of PAI, PI, and PES. Thereby, it is excellent in adhesiveness with a base material, has sufficient heat resistance even under the temperature at the time of the baking performed when forming a coating film, and the coating film obtained is excellent in corrosion resistance and water vapor resistance.

PAI, PI, and PES should just contain 1 type, or 2 or more types, respectively.

It is preferable that the heat resistant resin (a) contains at least 1 sort(s) selected from the group which consists of PES, PAI, and PI at the point which is especially excellent in the corrosion resistance of a coating film. It is particularly preferable that the heat-resistant resin (a) comprises PES and PAI.

When the heat resistant resin (a) contains PES and at least one selected from the group consisting of PAI and PI, PES is 65 to the total amount of PES and at least one selected from the group consisting of PAI and PI It is preferable that it is 85 mass %. More preferably, it is 70-80 mass %.

It is preferable that the primer layer (A2) does not contain a fluorine-containing polymer.

The primer layer (A2) may further contain an additive other than the heat resistant resin (a). As said additive, the additive which can be used for the coating composition of this indication mentioned above can be illustrated.

0.01-10.0 mass % is preferable with respect to the total mass of a primer layer (A2), and, as for content of the said additive, 0.1-5.0 mass % is more preferable.

It is preferable that the film thickness of a primer layer (A2) is 5-90 micrometers. When a film thickness is too thin, it is easy to generate|occur|produce a pinhole, and there exists a possibility that the corrosion resistance of a coating|coated article may fall. When a film thickness is too thick, a crack will become easy to generate|occur|produce, and there exists a possibility that the steam resistance of a coating|coated article may fall. A more preferable upper limit of the film thickness when the primer layer (A2) is formed of a liquid composition is 60 µm, and a more preferred upper limit is 50 µm. A more preferable upper limit of the film thickness when the primer layer (A2) is formed of a powdery composition is 80 µm, and a more preferred upper limit is 70 µm.

The intermediate layer (B1) constituting the second coated article is formed of the coating composition of the present disclosure.

About the coating composition of this indication, it is as above-mentioned.

It is preferable that the film thickness of an intermediate|middle layer (B1) is 5-90 micrometers. When the film thickness is too thin, the abrasion resistance of the coated article obtained may not be sufficient. When the film thickness is too thick, it becomes difficult for the water|moisture content which permeate|transmitted from the intermediate|middle layer (B1) to escape, and there exists a possibility that the water vapor resistance of a coating|coated article may fall. The more preferable upper limit of the film thickness of an intermediate|middle layer (B1) is 60 micrometers, and a more preferable upper limit is 50 micrometers.

The fluorine-containing layer (C2) constituting the second coated article contains the fluorine-containing polymer (a).

Examples of the fluorine-containing polymer (a) constituting the fluorine-containing layer (C2) include those similar to those of the fluorine-containing polymer (a) that can be used for the fluorine-containing layer (C1) of the first coated article, and preferred examples are also the same. am.

The fluorine-containing layer (C2) may contain additives other than the fluorine-containing polymer (a). It does not specifically limit as said additive, For example, the additive illustrated in the coating composition of this indication can be used.

0.01-30 mass % is preferable with respect to the total mass of a fluorine-containing layer (C2), and, as for content of the said additive, 0.1-20 mass % is more preferable.

The fluorine-containing layer (C2) may contain the same filler as those exemplified for the fluorine-containing layer (C1) of the first covering article.

It is preferable that the said filler is 0.01-40 mass % with respect to the total mass of a fluorine-containing layer (C2), It is more preferable that it is 0.05-30 mass %, It is more preferable that it is 0.1-10 mass %.

It is preferable that the film thickness of a fluorine-containing layer (C2) is 5-90 micrometers. When a film thickness is too thin, there exists a possibility that the corrosion resistance of a coating|coated article may fall. When 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, and the water vapor resistance may be poor. A more preferable upper limit of the film thickness when the fluorine-containing layer (C2) is formed of a liquid composition is 60 µm, a more preferable upper limit is 50 µm, and a particularly preferable upper limit is 40 µm. A more preferable upper limit of the film thickness when the fluorine-containing layer (C2) is formed of a powdery composition is 80 µm, a more preferable upper limit is 75 µm, and a particularly preferable upper limit is 70 µm.

In the second coated article, the primer layer (A2) has a film thickness of 5-90 µm, the intermediate layer (B1) has a film thickness of 5-90 µm, and the fluorine-containing layer (C2) has a film thickness of 5-90 µm. It is one of suitable aspects.

In the second coated article, it is preferable that the base material, the primer layer (A2), the intermediate layer (B1), and the fluorine-containing layer (C2) are laminated in this order.

In other words, it is preferable that the primer layer (A2) is provided on the substrate, the intermediate layer (B1) is provided on the primer layer (A2), and the fluorine layer (C2) is provided on the intermediate layer (B1).

It is preferable that the primer layer (A2) is in direct contact with the base material.

The intermediate layer (B1) may be in direct contact with the primer layer (A2) or may be in contact with another layer, but it is preferably in direct contact with the primer layer (A2).

Although the fluorine-containing layer (C2) may be in direct contact with the intermediate layer (B1) or may be in contact with another layer, it is preferable that the fluorine-containing layer (C2) is in direct contact.

Although a layer may be further provided on the fluorine-containing layer (C2), it is preferable that the fluorine-containing layer (C2) is the outermost layer.

Characters, drawings, etc. may be printed on the upper surface of the primer layer (A2), the upper surface of the intermediate layer (B1), or both.

The 1st coating article is, for example, the process (A1) of forming a primer coating film (A1p) by apply|coating the coating composition (A1) for primers on a base material,

Step (C1) of forming a coating film (C1p) by applying a fluorine-containing paint (C1) on the primer coating film (A1p);

The step (D1) of forming a first coated article having the base material, the primer layer (A1) and the fluorine-containing layer (C1) by firing the primer coating film (A1p) and the coating film laminate having the coating film (C1p)

It can manufacture by the method (henceforth a 1st manufacturing method) containing.

In a process (A1), the coating composition for primers (A1) should just be the coating composition of this indication mentioned above.

The method of applying the coating composition (A1) for a primer on the substrate is not particularly limited, and when the coating composition (A1) for a primer is liquid, spray coating, roll coating, coating with a doctor blade, dip (immersion) coating , impregnation coating, spin flow coating, curtain flow coating, etc. are mentioned, Especially, spray coating is preferable. When the coating composition for primers (A1) is in the form of a powder, electrostatic coating, a fluid immersion method, the furnace lining method, etc. are mentioned, Especially, electrostatic coating is preferable.

After application|coating of the coating composition (A1) for primers in a process (A1), before performing a process (C1), you may bake and it is not necessary to bake. In addition, when the coating composition (A1) for primers is liquid, you may dry after the said application|coating, and it is not necessary to dry.

In the step (A1), the drying is preferably performed at a temperature of 70 to 300°C for 5 to 60 minutes. It is preferable to perform the said baking at the temperature of 260-410 degreeC for 10 to 30 minutes.

When the coating composition (A1) for primers is liquid, in a process (A1), after apply|coating on the said base material, it is preferable to dry. In addition, in order to bake a coating-film laminated body in the process (D1) mentioned later, it is preferable not to bake.

When the coating composition for primers (A1) is in the form of a powder, in the step (A1), it is preferable to apply it on the base material and then bake.

A primer coating film (A1p) is formed by apply|coating the coating composition for primers (A1) on the said base material, and drying or baking as needed. A primer coating film (A1p) turns into a primer layer (A1) in the coating article obtained.

Step (C1) is a step of forming a coating film (C1p) by applying a fluorine-containing paint (C1) on the primer coating film (A1p).

It is preferable that the fluorine-containing paint (C1) in the step (C1) contains the fluorine-containing polymer (a).

The fluorine-containing paint (C1) may further optionally contain an additive.

About the fluorine-containing polymer (a) and the said additive, it is as above-mentioned.

The fluorine-containing paint (C1) may be a powder paint or a liquid paint such as a water-based paint. A drying process is unnecessary, and it is preferable that it is a powder coating material from the point which it is easy to obtain a thick coating film with a small number of coatings. When the fluorine-containing paint (C1) is a liquid paint, it is preferably a liquid paint in which the particles of the fluorine-containing polymer (a) are dispersed in a liquid medium, and an aqueous medium in which the particles of the fluorine-containing polymer (a) mainly contain water. It is more preferable that it is a water-based paint in which is dispersed.

The average particle diameter of the particles of the fluorine-containing polymer (a) in the fluorine-containing paint (C1) is preferably 0.01 to 40 µm in the case of a liquid paint and 1 to 50 µm in the case of a powder paint.

When the fluorine-containing polymer (a) is melt processable, the fluorine-containing paint (C1) may contain a small amount of PTFE (at least one of a TFE homopolymer and a modified PTFE) for the purpose of refining the spherulite. In this case, it is preferable that content of PTFE shall be 0.01-10.0 mass % with respect to a fluorine-containing polymer (a).

Moreover, it is preferable that a fluorine-containing paint (C1) does not contain a coloring pigment. Since a colored pigment may cause deterioration of corrosion resistance, as long as the fluorine-containing paint (C1) does not contain a color pigment, the obtained coated article will have more excellent corrosion resistance and water vapor resistance.

It does not specifically limit as a method of apply|coating the fluorine-containing paint (C1) on the primer coating film (Ap), The method similar to the method of application|coating of the coating composition (A1) for primers mentioned above, etc. are mentioned. When the fluorine-containing coating material (C1) is a powder coating material, electrostatic coating is preferable.

The coating film (C1p) may be formed by drying or baking as needed after the above application. It is preferable to perform drying or baking in a process (C1) on the conditions similar to the drying or baking in a process (A1). The coating film (C1p) becomes the fluorine-containing layer (C1) in the coated article to be obtained.

Step (D1) is to form a first coated article having the base material, primer layer (A1) and fluorine-containing layer (C) by firing a coating film laminate having a primer coating film (A1p) and a coating film (C1p) it is fair

It is preferable to perform the firing in the step (D1) under the same conditions as the firing in the steps (A1) and (C1).

The 1st manufacturing method may have a process of printing a character, a drawing, etc. after the process (A1) of forming the primer coating film (A1p). The characters, drawings, and the like are, for example, characters and lines indicating the amount of water when the coated article is a rice cooker.

It does not specifically limit as a method of the said printing, For example, putt transfer printing is mentioned. It does not specifically limit as a printing ink used for the said printing, For example, the composition containing PES, a TFE homopolymer, and titanium oxide is mentioned.

The second coating article is, for example, a step (A2) of forming a primer coating film (A2p) by applying the coating composition (A2) for a primer on a substrate;

Step (B1) of forming a coating film (B1p) by applying a fluorine-containing paint (B1) on the primer coating film (A2p);

A step (C2) of forming a coating film (C2p) by applying a fluorine-containing paint (C2) on the coating film (B1p) (C2);

By firing a coating film laminate having a primer coating film (A2p), a coating film (B1p), and a coating film (C2p), the agent having the base material, the primer layer (A2), the intermediate layer (B1) and the fluorine-containing layer (C2) 2 Step (D2) of forming the coated article

It can be manufactured by a method containing.

A process (A2) is a process of forming a primer coating film (A2p) on a base material by apply|coating the coating composition for primers (A2).

In a process (A2), it is preferable that the coating composition for primers (A2) contains a heat resistant resin (a).

The coating composition for primers (A2) may further optionally contain an additive.

About the heat resistant resin (a) and the said additive, it is as above-mentioned.

It is preferable that the coating composition for primers (A2) does not contain a fluorine-containing polymer.

The method for applying the coating composition (A2) for a primer on the substrate is not particularly limited, and when the coating composition (A2) for a primer is liquid, spray coating, roll coating, coating with a doctor blade, dip (immersion) coating , impregnation coating, spin flow coating, curtain flow coating, etc. are mentioned, Especially, spray coating is preferable. When the coating composition for primers (A2) is in the form of a powder, electrostatic coating, a fluid immersion method, the furnace lining method, etc. are mentioned, Especially, electrostatic coating is preferable.

After application|coating of the coating composition (A2) for primers in a process (A2), before performing a process (B1), you may bake and it is not necessary to bake. In addition, when the coating composition (A2) for primers is liquid, you may dry after the said application|coating, and it is not necessary to dry.

In the step (A2), the drying is preferably performed at a temperature of 70 to 300°C for 5 to 60 minutes. It is preferable to perform the said baking at the temperature of 260-410 degreeC for 10 to 30 minutes.

When the coating composition (A2) for primers is liquid, in a process (A2), after apply|coating on the said base material, it is preferable to dry. In addition, in order to bake a coating-film laminated body in the process (D2) mentioned later, it is preferable not to bake.

When the coating composition (A2) for primers is in a powder form, in a process (A2), it is preferable to bake, after apply|coating on the said base material.

A primer coating film (A2p) is formed by apply|coating the coating composition for primers (A2) on the said base material, and drying or baking as needed. A primer coating film (A2p) turns into a primer layer (A2) in the coating|coated article obtained.

Step (B1) is a step of forming a coating film (B1p) by applying a fluorine-containing paint (B1) on the primer coating film (A2p).

The fluorine-containing paint (B1) in the step (B1) may be the coating composition of the present disclosure described above.

It does not specifically limit as a method of apply|coating a fluorine-containing paint (B1) on a primer coating film (A2p), The method similar to the method of application|coating of the coating composition for primers (A2), etc. are mentioned. When the fluorine-containing coating material (B1) is a powder coating material, electrostatic coating is preferable.

In the step (B1), after the fluorine-containing paint (B1) is applied on the primer coating film (A2p), drying or baking may be performed. It is preferable to perform drying or baking in a process (B1) on the conditions similar to the drying or baking in a process (A2).

After the fluorine-containing paint (B1) is applied on the primer coating film (A2p), it is preferable not to perform firing. It is because all the coating films can be baked simultaneously when baking a coating-film laminated body in the process (D2) mentioned later.

The coating film (B1p) is formed by applying the fluorine-containing paint (B1) on the primer coating film (A2p) and then drying or baking as needed. A coating film (B1p) turns into an intermediate|middle layer (B1) in the coating|coated article obtained.

The process (C2) is a process of forming the coating film C2p by apply|coating the fluorine-containing paint (C2) on the coating film B1p.

It is preferable that the fluorine-containing paint (C2) in the step (C2) contains the fluorine-containing polymer (a).

The fluorine-containing paint (C2) may further optionally contain an additive.

About the fluorine-containing polymer (a) and the said additive, it is as above-mentioned.

The fluorine-containing paint (C2) may be a powder paint or a liquid paint such as a water-based paint. A drying process is unnecessary, and it is preferable that it is a powder coating material from the point which it is easy to obtain a thick coating film with a small number of coatings. When the fluorine-containing paint (C2) is a liquid paint, it is preferably a liquid paint in which the particles of the fluorine-containing polymer (a) are dispersed in a liquid medium, and an aqueous medium in which the particles of the fluorine-containing polymer (a) mainly contain water. It is more preferable that it is a water-based paint in which is dispersed.

The average particle diameter of the particles of the fluorine-containing polymer (a) in the fluorine-containing paint (C2) is preferably 0.01 to 40 µm in the case of a liquid paint and 1 to 50 µm in the case of a powder paint.

When the fluorine-containing polymer (a) is melt-processable, the fluorine-containing paint (C2) may contain a small amount of PTFE (at least one of a TFE homopolymer and a modified PTFE) for the purpose of refining the spherulite. In this case, it is preferable that content of PTFE shall be 0.01-10.0 mass % with respect to a fluorine-containing polymer (a).

Moreover, it is preferable that a fluorine-containing paint (C2) does not contain a coloring pigment. Since a colored pigment may cause deterioration of corrosion resistance, if the fluorine-containing paint (C2) does not contain a colored pigment, the obtained coated article will have more excellent corrosion resistance and water vapor resistance.

It does not specifically limit as a method of apply|coating the fluorine-containing paint (C2) on the coating film (B1p), The method similar to the method of application|coating of the coating composition for primers (A2) mentioned above, etc. are mentioned. When the fluorine-containing coating material (C2) is a powder coating material, electrostatic coating is preferable.

The coating film (C2p) may be formed by drying or baking as needed after the above application. It is preferable to perform drying or baking in a process (C2) on the conditions similar to the drying or baking in a process (A2). The coating film (C2p) becomes a fluorine-containing layer (C2) in the coated article to be obtained.

In the step (D2), the base material, the primer layer (A2), the intermediate layer (B1) and the fluorine-containing layer ( It is a process of forming the 2nd coated article which has C2).

It is preferable to perform the firing in the step (D2) under the same conditions as the firing in the steps (A2), (B1) and (C2).

The second manufacturing method is a step of printing characters, drawings, etc., after the step (A2) of forming the primer coating film (A2p), after the step (B1) of forming the coating film (B1p), or on both sides may have The characters, drawings, and the like are, for example, characters and lines indicating the amount of water when the coated article is a rice cooker.

It does not specifically limit as said printing method, For example, the method illustrated in 1st manufacturing method is mentioned.

The coating composition of the present disclosure can provide a coating film excellent in corrosion resistance, and the first and second coating articles are excellent in corrosion resistance. For this reason, the coating composition of this indication, and a 1st and 2nd coating article can be used suitably in all the fields|areas by which corrosion resistance is calculated|required. It does not specifically limit as an applicable use, The use which utilized the non-tackiness, heat resistance, slipperiness, etc. which a fluorine-containing polymer has is mentioned. For example, as a thing using non-adhesiveness, Cooking utensils, such as a frying pan, a pressure pot, a pot, a grill pot, a rice cooker, an oven, a hot plate, a bread baking type, a kitchen knife, a gas range; kitchen appliances such as electric pots, ice trays, molds, and range hoods; parts for the food industry, such as dough rolls, rolling rolls, conveyors, and hoppers; Industrial articles, such as a roll for office automation (OA), an OA belt, an OA separation tank, a paper roll, and the calender roll for film manufacture; Molds, molds, etc. for foaming styrofoam molding; Mold release, such as a release plate for plywood and decorative board manufacture; Industrial containers (especially for semiconductor industry) etc. are mentioned, As a thing using slidability, Tools, such as a saw and a file; household items such as irons, scissors, and kitchen knives; metal foil; wire; plain bearings for food processing machines, packaging machines, and textile machines; sliding parts for cameras and watches; automobile parts such as pipes, valves and bearings; snow shovel; plow; A suit etc. are mentioned.

The coating composition of the present disclosure, and the first and second coated articles, are preferably used in a cooking appliance or kitchen appliance, more preferably used in a cooking appliance, and still more preferably used in a rice cooker.

It is also preferable that they are a cooking utensil, a kitchen appliance, or its structural member, as for a 1st and 2nd covering article, It is more preferable that they are a cooking utensil or its structural member, It is more preferable that it is a rice cooker or its structural member.

Example

Next, although an Example is given and this indication is demonstrated in more detail, this indication is not limited only to these Examples. "%" and "part" represent mass % and a mass part, respectively.

Preparation Example 1 Preparation of Aqueous Polyamideimide Resin Dispersion (1)

A polyamideimide resin [PAI] varnish (N-methyl-2-pyrrolidone (hereinafter also referred to as NMP) (with a boiling point of 202°C) of 71%) having a solid content of 29% was charged into water to precipitate PAI. This was pulverized in a ball mill for 48 hours to obtain an aqueous PAI dispersion (average particle diameter of 2 µm). The solid content of the obtained PAI aqueous dispersion was 20 %.

Preparation Example 2 Preparation of Aqueous Polyethersulfone Resin Dispersion (1)

60 parts of polyethersulfone resin [PES] having a number average molecular weight of about 24000 and 60 parts of deionized water were stirred in a ceramic ball mill for about 10 minutes until particles containing PES were completely pulverized. Subsequently, 180 parts of NMP was added, and it further grind|pulverized for 48 hours, and obtained the dispersion. The obtained dispersion was further pulverized with a sand mill for 1 hour to obtain an aqueous PES dispersion (average particle diameter of 2 µm) having a PES concentration of about 20%.

Production Example 3 Preparation of Aqueous Polyamideimide Resin Dispersion (2)

Polyamideimide resin [PAI] varnish (N-ethyl-2-pyrrolidone (hereinafter also referred to as NEP) (with a boiling point of 218°C) of 71%) having a solid content of 29% was charged into water to precipitate PAI. This was pulverized in a ball mill for 48 hours to obtain an aqueous PAI dispersion (average particle diameter of 2 µm). The solid content of the obtained PAI aqueous dispersion was 20 %.

Production Example 4 Preparation of Aqueous Polyethersulfone Resin Dispersion (2)

60 parts of polyethersulfone resin [PES] having a number average molecular weight of about 24000 and 60 parts of deionized water were stirred in a ceramic ball mill for about 10 minutes until particles containing PES were completely pulverized. Next, 180 parts of NEP was added, and it further grind|pulverized for 48 hours, and obtained the dispersion. The obtained dispersion was further pulverized with a sand mill for 1 hour to obtain an aqueous PES dispersion (average particle diameter of 2 µm) having a PES concentration of about 20%.

Production Example 5 Preparation of Aqueous Polyamideimide Resin Dispersion (3)

Polyamideimide resin [PAI] varnish (3-methoxy-N,N-dimethylpropanamide (hereinafter also referred to as NDPA) (boiling point 215°C) containing 71%) having a solid content of 29% was put into water to prepare PAI precipitated. This was pulverized in a ball mill for 48 hours to obtain an aqueous PAI dispersion (average particle diameter of 2 µm). The solid content of the obtained PAI aqueous dispersion was 20 %.

Production Example 6 Preparation of Aqueous Polyethersulfone Resin Dispersion (3)

60 parts of polyethersulfone resin [PES] having a number average molecular weight of about 24000 and 60 parts of deionized water were stirred in a ceramic ball mill for about 10 minutes until particles containing PES were completely pulverized. Subsequently, 180 parts of NDPA was added, and further, it grind|pulverized for 48 hours, and obtained the dispersion. The obtained dispersion was further pulverized with a sand mill for 1 hour to obtain an aqueous PES dispersion (average particle diameter of 2 µm) having a PES concentration of about 20%.

Example 1

The PES aqueous dispersion obtained in Production Example 2 and the PAI aqueous dispersion obtained in Production Example 1 were mixed so that PES became 75% of the total solid content of PES and PAI, and tetrafluoroethylene homopolymer [TFE homopolymer [TFE homopolymer] was mixed thereto. Polymer, hereinafter referred to as PTFE] Aqueous dispersion (average particle diameter 0.28 µm, solid content 60%, and polyether-based nonionic surfactant 6% with respect to PTFE as a dispersant) and tetrafluoroethylene-hexafluoropropylene air The coal (hereinafter also referred to as FEP) aqueous dispersion (average particle diameter of 0.20 µm, solid content 60%, and polyether-based nonionic surfactant as a dispersant 5% with respect to FEP is contained) in the mass ratio of solid content, FEP is 50 of PTFE %, and PES and PAI are added so as to be 25% of the total solid content of PES, PAI, PTFE and FEP, methylcellulose as a thickener is added 0.7% with respect to the solid content of the TFE homopolymer, and polyether as a dispersion stabilizer A nonionic surfactant was added 6% with respect to the solid content of the TFE homopolymer to obtain an aqueous dispersion (coating composition (1) for undercoating) having a polymer solid content of 34%.

Example 2

In the same manner as in Example 1, except that PES was 65% of the total solid content of PES and PAI, and PES and PAI were 20% of the total solid content of PES, PAI and PTFE and FEP, except that the blending amount was changed, A coating composition (2) for undercoating was obtained.

Example 3

Except having made the addition amount of FEP into 100 % by mass ratio of solid content with respect to PTFE, it carried out similarly to Example 1, and obtained the coating composition (3) for undercoating.

Example 4

Instead of FEP aqueous dispersion, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (hereinafter also referred to as PFA) aqueous dispersion (average particle diameter 0.26 µm, solid content 68%, polyether-based nonionic surfactant as a dispersant PFA A coating composition (4) for undercoating was obtained in the same manner as in Example 1 except for adding 3%.

Example 5

The PES aqueous dispersion obtained in Production Example 4 was replaced with the PES aqueous dispersion obtained in Production Example 2, and the PAI aqueous dispersion obtained in Production Example 3 was used instead of the PAI aqueous dispersion obtained in Production Example 1 Similarly, the coating composition for undercoating (5) was obtained.

Example 6

The PES aqueous dispersion obtained in Production Example 6 was replaced with the PES aqueous dispersion obtained in Production Example 2, and the PAI aqueous dispersion obtained in Production Example 5 was used instead of the PAI aqueous dispersion obtained in Production Example 1 Similarly, the coating composition for undercoating (6) was obtained.

Comparative Example 1

Except not adding the FEP aqueous dispersion, it carried out similarly to Example 1, and obtained the coating composition (7) for undercoating.

Comparative Example 2

Except not adding the FEP aqueous dispersion, it carried out similarly to Example 2, and obtained the coating composition (8) for undercoating.

<Production of trial version>

After the surface of the aluminum plate (A-1050P) was degreased with acetone, it sandblasted so that the surface roughness Ra value measured based on JIS B 1982 might be set to 2.5-4.0 micrometers, and the surface was roughened. After removing the dust on the surface by air blowing, the coating composition for undercoating obtained in Examples and Comparative Examples was applied with a RG-2 type gravity spray gun (trade name, manufactured by ANEST IWATA, Nozzle) so that the dry film thickness was about 10 µm. 1.0 mm in diameter) and spray-coated by the injection pressure of 0.2 MPa. The obtained coating film on the aluminum plate was dried at 80-100 degreeC for 15 minutes, and it cooled to room temperature. On the obtained coating film, a PFA powder coating was electrostatically coated under the conditions of an applied voltage of 40 KV and a pressure of 0.08 MPa, calcined at 380 ° C. for 20 minutes, cooled, and a PFA layer having a film thickness of about 40 μm on the top coat By forming, the coating board for a test was obtained. As for the obtained coating plate for a test, the undercoat layer and the top coat layer containing PFA were formed on the aluminum plate.

In addition, the film thickness was measured using the high frequency type film thickness meter (trade name: LZ-300C, the Ket Chemicals company make).

<Evaluation method>

The following evaluation was performed about the coating film of the obtained coating board for a test.

(corrosion test)

A crosscut was put into the surface of the coating film of the obtained coating plate for a test with a cutter knife, and the flaw reaching a base material was put. This test plate was immersed in a solution in which 20 g of oden material (manufactured by S&B Shokuhin Co., Ltd.) was dissolved in 1 liter of water, kept warm at 70°C, and checked every 100 hours whether there was any abnormality such as generation of blisters. Table 1 shows the time for maintaining the coating film without abnormalities such as the occurrence of swelling.

Claims (14)

a polyethersulfone resin, at least one polyimide-based resin selected from the group consisting of polyamideimide resins and polyimide resins, a non-melt-processable fluorine-containing polymer, and a melt-processable fluorine-containing polymer;
A coating composition wherein a mass ratio of the non-melt-processable fluorine-containing polymer to the melt-processable fluorine-containing polymer is 40/60 or more. The coating composition according to claim 1, wherein the mass ratio of the polyethersulfone resin to the polyimide-based resin is 85/15 to 65/35. The mass ratio of the total amount of the polyethersulfone resin and the polyimide-based resin to the total amount of the non-melt-processable fluorine-containing polymer and the melt-processable fluorine-containing polymer is 15/85 to 35. /65 coating composition. The coating composition according to claim 1 or 2, wherein the mass ratio of the non-melt-processable fluorine-containing polymer to the melt-processable fluorine-containing polymer is 40/60 to 95/5. The coating composition according to claim 1 or 2, further comprising water. The coating composition according to claim 1 or 2, wherein the polyethersulfone resin and the polyimide-based resin have an average particle diameter of 0.1 to 10 µm. The coating composition according to claim 1 or 2, wherein the non-melt-processable fluorine-containing polymer is at least one selected from the group consisting of tetrafluoroethylene homopolymer and modified polytetrafluoroethylene. The fluorine-containing polymer according to claim 1 or 2, wherein the melt processable fluorine-containing polymer is selected from the group consisting of a tetrafluoroethylene/hexafluoropropylene copolymer and a tetrafluoroethylene/perfluoro(alkylvinyl ether) copolymer. at least one coating composition. 3. The coating composition according to claim 1 or 2, which is applied directly onto a substrate comprising a metallic or non-metallic inorganic material, or on a layer comprising a heat-resistant resin. The coating composition according to claim 1 or 2, further comprising an organic solvent. 11. The method of claim 10, wherein the organic solvent is N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, 3-alkoxy-N,N-dimethylpropanamide, γ-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 and at least one selected from the group consisting of 2-propanol coating composition. The coating composition according to claim 1 or 2, which is a coating composition for a cook utensil or a kitchen appliance. description and
A primer layer (A1) formed of the coating composition according to claim 1 or 2;
A coated article having a fluorine-containing layer (C1) comprising a fluorine-containing polymer (a). description and
A primer layer (A2) comprising a heat-resistant resin (a), and
An intermediate layer (B1) formed of the coating composition according to claim 1 or 2;
A coated article having a fluorine-containing layer (C2) comprising a fluorine-containing polymer (a).