CN116254022A - Fluororesin solvent-based primer composition, coating film, fluororesin laminate, and article - Google Patents
Fluororesin solvent-based primer composition, coating film, fluororesin laminate, and article Download PDFInfo
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- CN116254022A CN116254022A CN202211569506.5A CN202211569506A CN116254022A CN 116254022 A CN116254022 A CN 116254022A CN 202211569506 A CN202211569506 A CN 202211569506A CN 116254022 A CN116254022 A CN 116254022A
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- fluororesin
- coating film
- primer composition
- mass
- liquid medium
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Classifications
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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
- C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
- C09D181/06—Polysulfones; Polyethersulfones
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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
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
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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
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The present invention provides a fluororesin solvent-based primer composition, a coating film, a fluororesin laminate and an article, wherein the fluororesin solvent-based primer composition comprises a tetrafluoroethylene [ TFE ]/perfluoro (alkyl vinyl ether) [ PAVE ] copolymer [ PFA ] having a Melt Flow Rate (MFR) of 10 to 30 (g/10 min) and a tetrafluoroethylene [ TFE ]/hexafluoropropylene [ HFP ] copolymer [ FEP ], [ PFA ]/[ FEP ] having a mass ratio of 10/90 to 90/10, a binder resin comprising a polyamide imide [ PAI ] and a polyether sulfone [ PES ], [ PAI ]/[ PES ] having a mass ratio of 1/99 to 60/40, a liquid medium (A) having a Melt Flow Rate (MFR) of 10 to 30 (g/10 min) and having a Melt Flow Rate (MFR) of less than 100 ℃ and a liquid medium (B) having a boiling point of 100 ℃ of 1 to 30 mass% in the composition.
Description
Technical Field
The present invention relates to a fluororesin solvent-based primer composition, a coating film, a fluororesin laminate, and an article.
Background
Fluororesin has a wide range of uses in the following aspects: the coating composition is prepared and applied to a substrate of an object such as a bread mold or a rice cooker, which requires corrosion resistance, non-tackiness, heat resistance, etc., to form a fluororesin layer. However, the fluororesin has a problem of lacking adhesiveness to a base material made of metal, ceramic, or the like due to its non-adhesiveness.
Therefore, in general, when a fluororesin is coated on a surface of a substrate such as a metal, ceramic, or glass, the following method is widely performed: after physical irregularities are formed on the surfaces of these substrates by sand blasting, etching, or the like, an undercoat layer is formed by applying an adhesive primer composition to the surfaces of the substrates, and the substrates are bonded to a fluororesin as a top coat layer by the undercoat layer. In this method, the following anchoring effect (anchoring effect) is used for adhesion of the substrate surface to the undercoat layer: the surface roughness of the substrate increases the adhesion area between the primer layer and the substrate surface, thereby improving the adhesion.
In addition, the primer layer must be bonded to the surface of a substrate such as metal, ceramic, or glass, and must also be bonded to a fluororesin as a top coat layer, and therefore the following method is used for forming the primer layer: the resulting primer composition is applied to the surface of a substrate by uniformly dispersing a fluororesin powder of the same material as the top coat layer and a substance having adhesiveness called a binder resin in a liquid medium. As the fluororesin powder used in the primer composition, a fluororesin fine powder having an average particle diameter of less than 1 μm has been widely used in the past from the viewpoints of dispersibility, adhesion to a fluororesin powder of a top coat, and the like.
Patent document 1 discloses an article having a fluororesin coating film comprising an undercoat layer formed on a substrate and a top coat layer formed on the undercoat layer, wherein the undercoat layer comprises a fluororesin coating film formed from a primer composition comprising at least one fluororesin powder (a) having an average particle diameter of not less than the film thickness and at least one fluororesin powder (B) having an average particle diameter smaller than the film thickness, wherein the ratio of the weight of (a) to the weight of (B) is 10 to 100:90 to 0, and wherein at least one of the fluororesin powders (a) and (B) is preferably polytetrafluoroethylene, tetrafluoroethylene/perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/ethylene copolymer, polyvinylidene fluoride, polytetrafluoroethylene, or a mixture thereof.
Patent document 2 discloses a coating composition comprising a fluorine-containing polymer, a heat-resistant resin and a water-soluble inorganic salt, wherein the fluorine-containing polymer is at least one selected from the group consisting of polytetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene copolymer and tetrafluoroethylene/perfluoro (alkyl vinyl ether) copolymer, and has an average particle diameter of 0.01 to 5 μm, the heat-resistant resin has an average particle diameter of 0.1 to 10.0 μm, the mass ratio of the heat-resistant resin to the solid content of the fluorine-containing polymer is 15:85 to 50:50, and the water-soluble inorganic salt is 0.0001 to 10 mass% based on the total solid content of the fluorine-containing polymer and the heat-resistant resin.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2001-219122
Patent document 2: japanese patent laid-open No. 2009-242711
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a fluororesin solvent-based primer composition which is suitable as a primer for a fluororesin layer and which can achieve high adhesion to a substrate and a fluororesin layer. More specifically, a fluororesin laminate excellent in adhesion is provided by providing an undercoat layer having sufficient adhesion to a fluororesin layer.
Means for solving the problems
The present invention relates to a fluororesin solvent-type primer composition comprising a fluororesin and a binder resin dispersed in a liquid medium, characterized in that,
the fluororesin comprises a tetrafluoroethylene [ TFE ]/perfluoro (alkyl vinyl ether) [ PAVE ] copolymer [ PFA ] having a Melt Flow Rate (MFR) of 10 to 30 (g/10 min) and a tetrafluoroethylene [ TFE ]/hexafluoropropylene [ HFP ] copolymer [ FEP ] having a Melt Flow Rate (MFR) of 10 to 30 (g/10 min),
the mass ratio of [ PFA ]/[ FEP ] is in the range of 10/90 to 90/10,
the binder resin contains polyamide imide [ PAI ] and polyether sulfone [ PES ], [ PAI ]/[ PES ] in a mass ratio of 1/99 to 60/40,
further, the composition contains 1 to 30% by mass of a liquid medium (A) having a boiling point of less than 100 ℃, and the composition contains 1 to 30% by mass of a liquid medium (B) having a boiling point of 100 to 150 ℃.
The above fluororesin solvent-based primer composition may have a content of N-methyl-2-pyrrolidone in the composition of less than 1 mass%.
The invention also relates to a coating film formed from the above fluororesin solvent-based primer composition.
The present invention also relates to a fluororesin laminate comprising a coated object, the coating film, and a fluororesin layer containing PFA, wherein the coated object, the coating film, and the fluororesin layer are laminated in this order.
The present invention also relates to an article comprising the above fluororesin laminate.
ADVANTAGEOUS EFFECTS OF INVENTION
The fluororesin solvent-based primer composition of the present invention can form a primer layer excellent in adhesion to a metal substrate and adhesion to a fluororesin layer.
Detailed Description
The present invention will be described in detail below.
The present invention relates to a fluororesin solvent-type primer composition comprising a fluororesin and a binder resin dispersed in a liquid medium, characterized in that,
the fluororesin comprises a tetrafluoroethylene [ TFE ]/perfluoro (alkyl vinyl ether) [ PAVE ] copolymer [ PFA ] having a Melt Flow Rate (MFR) of 10 to 30 (g/10 min) and a tetrafluoroethylene [ TFE ]/hexafluoropropylene [ HFP ] copolymer [ FEP ] having a Melt Flow Rate (MFR) of 10 to 30 (g/10 min),
the mass ratio of [ PFA ]/[ FEP ] is in the range of 10/90 to 90/10,
the binder resin contains polyamide imide [ PAI ] and polyether sulfone [ PES ], [ PAI ]/[ PES ] in a mass ratio of 1/99 to 60/40,
the composition contains a liquid medium (A) having a boiling point of less than 100 ℃ in a range of 1 to 30% by mass, and further contains a liquid medium (B) having a boiling point of 100 to 150 ℃ in a range of 1 to 30% by mass.
The fluorine-containing solvent type primer composition of the present invention (hereinafter referred to as primer composition) contains PFA and FEP having MFR in a specific range in a specific mass ratio range, PAI and PES as binder resins in a specific mass ratio range, and further, a specific amount of a liquid medium (a) having a boiling point of less than 100 ℃ and a liquid medium (B) having a boiling point of 100 to 150 ℃ are mixed, whereby a coating film excellent in adhesion to a coating object and improved in adhesion to a fluororesin layer can be formed.
When a primer composition containing a fluororesin and a binder resin is applied, the fluororesin floats up during firing because of a difference in surface tension between the fluororesin and the binder resin, and a coating film in which the fluororesin is mainly disposed on the surface side of the coating film and the binder resin is mainly disposed on the side of the object to be coated is formed. In the conventional primer composition, since the fluororesin oriented on the surface side of the coating film shows affinity with the fluororesin in the overcoating film as described above, the property of showing excellent adhesion with the overcoating film is utilized.
The primer composition of the present invention further controls the fluidity of the fluororesin by limiting the MFR of the fluororesin to a specific range. Since the fluororesin having the MFR in the above range can float up rapidly during firing, a coating film in which the fluororesin is disposed on the surface of the coating film can be efficiently formed.
The primer composition of the present invention contains a liquid medium having a low boiling point of 150 ℃ or lower. Conventionally, primer compositions blended with a liquid medium having a relatively low boiling point have been studied, but liquid media having a boiling point of about 160 to 180 ℃ have been mainly studied, and liquid media having a boiling point of 150 ℃ or less have not been studied. The present invention can form a coating film having more excellent adhesion by combining a liquid medium (A) having a boiling point of less than 100 ℃ with a liquid medium (B) having a boiling point of 100 to 150 ℃. This effect is thought to be due to: when the coating film is fired, the two liquid mediums are sequentially transferred to the surface of the coating film, so that the fluororesin can also rise to the surface of the coating film more rapidly.
(fluororesin)
The primer composition of the present invention contains PFA having a Melt Flow Rate (MFR) of 10 to 30 (g/10 min) and FEP having a Melt Flow Rate (MFR) of 10 to 30 (g/10 min) as a fluororesin.
In the above FEP, the HFP unit in the copolymer exceeds 2% by mass, preferably 20% by mass or less, and more preferably 10% by mass to 15% by mass.
PAVE in the PFA is preferably an alkyl group having 1 to 6 carbon atoms, more preferably perfluoro (methyl vinyl ether) [ PMVE ], perfluoro (ethyl vinyl ether) [ PEVE ] or perfluoro (propyl vinyl ether) [ PPVE ]. In the PFA, the PAVE unit in the copolymer exceeds 2% by mass, preferably 5% by mass or less, and more preferably 2.5% by mass to 4.0% by mass.
In the present specification, the "monomer unit" such as the HFP unit refers to a portion derived from the corresponding monomer as a part of the molecular structure of the fluororesin.
The PFA and FEP may have the above compositions, and other monomers may be further polymerized. As the other monomer, for example, PAVE is further included in the case of FEP, and HFP is further included in the case of PFA. The other monomer may be used in an amount of 1 or 2 or more.
The other monomer varies depending on the kind thereof, but is generally preferably 1 mass% or less of the mass of the fluororesin. The upper limit is more preferably 0.5 mass%, and the upper limit is still more preferably 0.3 mass%.
The MFR of the PFA and FEP are each in the range of 10 to 30 (g/10 min). If the MFR is less than 10 (g/10 min), the transfer to the surface of the coating film may be insufficient. When the MFR exceeds 30 (g/10 min), the molecular weight is low, and the coating film strength is lowered, which is not preferable.
In the present specification, the MFR is a value measured according to ASTM D3307 and D2116 at 372℃under a load of 5.0 kg.
The MFR is more preferably 15 to 28 (g/10 min).
The average particle diameters of the PFA and FEP are preferably 0.01 μm to 5. Mu.m. If the particle size is less than 0.01. Mu.m, the mechanical stability of the particles made of the fluororesin may be poor, and the mechanical stability and storage stability of the resulting primer composition may be poor. If the particle size exceeds 5. Mu.m, the particles composed of the fluororesin may lack uniform dispersibility, and when the primer composition obtained is used for coating, a coating film having a smooth surface may not be obtained, and the coating film may have poor physical properties. The more preferable upper limit is 0.5 μm, and the more preferable lower limit is 0.05 μm.
The above mechanical stability refers to the following properties: in the case of liquid transportation/redispersion, it is difficult to generate aggregates which cannot be redispersed even if strong stirring or shearing force is provided by a homogenizer or the like.
In the present specification, the average particle diameter of the fluororesin is measured by observation with a transmission electron microscope.
The total content of PFA and FEP is preferably in the range of 10 to 40% by mass of the composition. If the total content is less than 10% by mass, the adhesion between the primer layer and the topcoat layer may be reduced. If the total content exceeds 40 mass%, the strength of the primer layer tends to be low, and the adhesion to the substrate may be low. The total content of PFA and FEP is more preferably in the range of 15 to 35% by mass of the composition.
The mass ratio of [ PFA ]/[ FEP ] is in the range of 10/90 to 90/10.
The mass ratio is more preferably in the range of 20/80 to 80/20.
The primer coating composition of the present invention may contain other fluororesin such as polytetrafluoroethylene [ PTFE ] within a range that does not impair the effects of the present application. In addition, PFA and FEP having MFR outside the above ranges may be contained within a range that does not impair the effects of the present application.
(adhesive resin)
The primer composition of the present invention can provide a coating film having excellent adhesion to a coating object, and further having excellent corrosion resistance and water vapor resistance by containing a binder resin.
The binder resin exhibits heat resistance at a temperature of 150 ℃ or higher. The binder resin generally has a molecular structure or a functional group that exhibits adhesiveness to a coating object, such as an amide bond and an imide bond, and therefore exhibits adhesiveness to a coating object.
The primer composition of the present invention must contain polyamideimide [ PAI ] and polyethersulfone [ PES ] as binder resins.
The 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 a reaction between an aromatic diamine having an amide bond in the molecule and 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; and resins comprising high molecular weight polymers obtained by respective reactions such as the reaction of dibasic acids having aromatic imide rings in the molecule with diamines. The PAI is preferably composed of a polymer having an aromatic ring in the main chain, because of excellent heat resistance.
The PES is represented by the following formula:
[ chemical formula 1 ]
The polymers of the repeating units shown constitute resins.
The PES is not particularly limited, and examples thereof include resins composed of polymers obtained by polycondensation of dichlorodiphenyl sulfone and bisphenol.
The total content of PAI and PES is preferably 10 to 40% by mass, more preferably 15 to 35% by mass of the composition.
The PAI/PES mass ratio is 1/99 to 60/40. If the mass ratio is less than 1/99, the adhesion of the coating film obtained from the primer composition to the substrate may be reduced; if the mass ratio exceeds 60/40, the adhesion between the coating film and the top coat layer may be reduced.
The average particle diameter of the binder resin is preferably 0.1 μm to 10. Mu.m. When the average particle diameter of the binder resin is within the above range, the resulting coating film has good corrosion resistance. The average particle diameter of the binder resin is more preferably 0.2 μm to 8. Mu.m.
In the present specification, the average particle diameter of the binder resin is measured using an ultracentrifuge automatic particle size distribution measuring apparatus CAPA-700 manufactured by horiba, inc.
The primer composition of the present invention may also contain other binder resins. Examples of the other binder resin include polyarylene sulfide resins represented by polyimide resins [ PI ], polyetherimide resins, polyetheretherketone resins, aromatic polyester resins, and polyphenylene sulfide [ PPS ].
In the primer composition of the present invention, the mass ratio of the solid content of the fluororesin to the binder resin is preferably from 15:85 to 85:15. If the binder resin is less than 15 mass% of the total solid content of the fluororesin and the binder resin, the binder resin is small, and thus the adhesion between the obtained coating film and the object to be coated is insufficient. If the amount exceeds 50% by mass, the amount of the fluororesin is small, and thus the adhesion between the coating film and the overcoating film is insufficient.
The above-mentioned solid content mass ratio is more preferably a binder resin of fluororesin=25:75 to 75:25, and still more preferably a binder resin of fluororesin=35:65 to 65:35.
The solid content mass ratio is calculated from the amount of the fluororesin and the binder resin mixed at the time of preparation.
(liquid Medium (A))
The liquid medium (A) has a boiling point of less than 100 ℃. The liquid medium (a) is not particularly limited as long as it has wettability to a fluororesin.
Specific examples of the liquid medium (a) include methyl ethyl ketone, ethanol, acetone, benzene, etc., and 1 or 2 or more kinds of the liquid medium (a) may be used.
The content of the liquid medium (a) in the composition is 1 to 30% by mass. If the content is less than 1 mass%, the transfer of the fluororesin may be insufficient. If the content exceeds 30 mass%, the transfer of the fluororesin is excessive, and coagulation failure in the primer layer tends to occur, which is not preferable. The content of the liquid medium (a) in the composition is more preferably 3 to 25% by mass.
(liquid Medium (B))
The liquid medium (B) has a boiling point of 100 to 150 ℃. The liquid medium (B) is not particularly limited as long as it has wettability to a fluororesin similar to the liquid medium (a).
Specific examples of the liquid medium (B) include 1-butanol, methyl isobutyl ketone, butyl acetate, toluene, xylene, etc., and 1 or 2 or more kinds thereof may be used.
The content of the liquid medium (B) is 1 to 30% by mass based on the composition. If the content is less than 1 mass%, the transfer of the fluororesin may be insufficient. If the content exceeds 30 mass%, the transfer of the fluororesin is excessive, and coagulation failure in the primer layer tends to occur, which is not preferable. The content of the liquid medium (B) in the composition is more preferably 3 to 25% by mass.
The content of the liquid medium (a) and (B) is the total content when 2 or more kinds are used together.
The primer composition of the present invention preferably uses an organic solvent other than the liquid medium (a) or (B) as a dispersion medium. The organic solvent used as the dispersion medium is preferably a compound having excellent dispersibility of the fluororesin and dispersibility or solubility of the binder resin. The organic solvent is not particularly limited, and specifically, an organic solvent which can dissolve and disperse the binder resin and has a boiling point of 200 ℃ or higher is preferable.
Specifically, examples thereof include: lower alcohols such as diacetone alcohol; ketones; esters; amides such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, and 3-methoxy-N, N-dimethylpropionamide; the aromatic hydrocarbon such as trimethylbenzene, methylethylbenzene, propylbenzene, butylbenzene, etc., may be used in an amount of 1 or 2 or more.
As the dispersion medium, a mixed solvent of water and the organic solvent may be used.
The "organic solvents other than the liquid media (a) and (B)" should be treated as an organic solvent which does not belong to any of the above-mentioned mixed amounts of the liquid media (a) and (B).
The content of the organic solvent other than the liquid medium (a) or (B) is preferably 20 to 50% by mass in the composition. If the content is less than 20 mass%, the dissolution and dispersion of the binder resin may be insufficient. If the content exceeds 50 mass%, the proportion of the fluororesin is decreased, which is not preferable.
The primer composition of the present invention may be substantially free of N-methyl-2-pyrrolidone. In the present specification, substantially free means that the content of N-methyl-2-pyrrolidone is less than 1% by mass of the composition. N-methyl-2-pyrrolidone is a solvent excellent in dissolution ability, but has a problem that it has too high surface tension, insufficient wettability to a substrate, and difficulty in obtaining good adhesion. A primer composition which does not substantially use N-methyl-2-pyrrolidone is preferable in that better adhesion can be obtained.
In addition, since the fluororesin is well impregnated with a solvent having a surface tension lower than that of N-methyl-2-pyrrolidone as a main solvent, such as 3-methoxy-N, N-dimethylpropionamide, aggregation in the paint is prevented, and thus storage stability is improved. When aggregation of the fluororesin occurs, the fluororesin is difficult to transfer to the surface of the coating film during firing, and the peel strength is lowered.
The primer composition of the present invention may contain other resins as needed. By blending the other resins, the film forming property, corrosion resistance, and the like of a coating film obtained from the primer composition can be improved.
The other resin is not particularly limited, and examples thereof include phenol resins, urea resins, epoxy resins, urethane resins, melamine resins, polyester resins, polyether resins, acrylic silicone resins, silicone polyester resins, and the like.
The primer composition of the present invention may be further blended with additives for general coating compositions in a range that does not impair the features of the present invention, for the purpose of improving coatability, the properties of a coating film obtained from the primer composition, and the like.
The additive is not particularly limited and may be selected according to the application of the coated article obtained, and examples thereof include leveling agents, solid lubricants, wood flour, silica sand, carbon black, diamond, tourmaline, germanium, alumina, silicon nitride, fluorite, clay, talc, extender pigments, various fillers, conductive fillers, brightening materials, pigments, fillers, pigment dispersants, anti-settling agents, moisture absorbers, surface regulators, thixotropy imparting agents, viscosity regulators, anti-gelling agents, ultraviolet absorbers, light stabilizers, plasticizers, anti-blooming agents, anti-skinning agents, anti-scratch agents, mold inhibitors, antibacterial agents, antioxidants, antistatic agents, silane coupling agents, and the like.
Examples of the brightening material include mica, metal powder, glass beads, glass bubbles, glass flakes, and glass fibers.
The metal powder is not particularly limited, and examples thereof include powders of elemental metals such as aluminum, iron, tin, zinc, gold, silver, and copper; powder of alloys such as aluminum alloy and stainless steel; etc. The shape of the metal powder is not particularly limited, and examples thereof include particles, flakes, and the like. The primer composition of the present invention can form a coating film having an excellent appearance in the case of containing such a bright material. The content of the brightening material is preferably 0.1 to 10.0% by mass based on the solid content of the primer composition.
Examples of the viscosity modifier include methylcellulose and alumina sol.
The primer composition of the present invention can be obtained, for example, by: (1) After preparing a dispersion composed of a fluororesin, a liquid medium (a), a liquid medium (B) and a dispersion medium, (2) a binder resin, additives as needed, and the like are added to the obtained dispersion. Here, the binder resin is preferably used in a state dissolved in an organic solvent other than the above-mentioned "liquid medium (a) (B)".
The primer composition of the present invention can form a coating film on an object to be coated by applying the primer composition to the object to be coated. In the present specification, "coating" of the primer composition means a process comprising: the primer composition is applied, dried as necessary, and then fired.
The primer composition of the present invention can form a coating film having excellent adhesion to an overcoated coating film in addition to adhesion to an object to be coated.
As the top coating material applied to the coating film obtained from the primer composition of the present invention, a coating material containing a fluororesin is preferable. In this case, in the above-mentioned coating film, since the fluororesin oriented on the surface side of the coating film shows affinity with the fluororesin in the overcoating film as described above, excellent adhesion with the overcoating film is exhibited.
The coating film obtained from the primer composition of the present invention can be formed as follows: the primer composition is applied to a coating object, dried to obtain a coating film, and then fired as needed.
The object to be coated is not particularly limited, and examples thereof include metals such as elemental metals of iron, aluminum, copper, and the like, and alloys thereof; non-metallic inorganic materials such as enamel, glass, ceramic, etc. The alloy may be stainless steel or the like.
The object to be coated is preferably subjected to a surface treatment such as degreasing treatment or surface roughening treatment in advance, from the viewpoint of being able to uniformly coat the primer composition and from the viewpoint of improving adhesion to a coating film obtained from the primer composition. The surface roughening treatment is not particularly limited, and examples thereof include chemical etching with an acid or an alkali, anodic oxidation (alumite treatment), and sand blasting.
The coating method is not particularly limited, and examples thereof include spray coating, roll coating, coating with a doctor blade, impregnating (dipping) coating, impregnating coating, swirl coating, curtain coating, and the like.
The drying may be performed by a conventionally known method, and is preferably performed at a temperature of 60 to 200℃for 5 to 60 minutes.
The coating film is not usually fired before the application of the topcoat material, but may be fired as needed. In order to simplify the process, reduce energy, labor, time, and the like, it is preferable not to perform firing before applying the above-mentioned topcoat material.
The overcoating film may be formed by, for example, applying a overcoating material to the coating film or the coating film, followed by firing.
The fluororesin in the overcoating material is not particularly limited, and examples thereof include PTFE, PFA, FEP, and from the viewpoint of improving the interlayer adhesion between the coating film and the overcoating film, the same material as the fluororesin in the primer composition of the present invention, and materials having similar properties such as the presence or absence of melt processability are preferable.
Examples of the overcoating material include PTFE-based material containing PTFE as a main component, PFA-based material containing PFA as a main component, FEP-based material containing FEP as a main component, and the like, and PFA-based material is preferable.
The top coat may be further blended with additives similar to those used in the primer composition for the purpose of improving the coatability, the properties of the resulting coating film, and the like.
In the case where PFA or FEP is the main component, the above-mentioned top coating material can be made into a powder coating material.
As a method for applying the top coating, in the case of a powder coating, there are mentioned electrostatic spray coating, flow dip coating, and spin lining.
The firing after the application of the primer composition may be performed under the same conditions as the firing performed after the application and drying of the primer composition.
The film thickness of each of the coating film obtained from the primer composition of the present invention and the overcoating film is not particularly limited, and it is preferable that the film thickness of the coating film is 1 μm to 100 μm and the film thickness of the overcoating film is 10 μm to 200 μm.
The fluorine-containing resin laminate of the present invention comprises a coated object, a coating film and a fluorine-containing resin layer. As described above, the coating film is obtained by coating the primer composition of the present invention, and the fluororesin laminate is obtained by coating the primer composition of the present invention onto the object to be coated. The fluororesin layer is obtained by applying a topcoat material containing the fluororesin. In the fluororesin laminate of the present invention, the object to be coated, the coating film, and the fluororesin layer are laminated in this order.
The use of the fluororesin laminate of the present invention is not particularly limited, and for example, the fluororesin laminate may be used as a product requiring heat resistance, non-tackiness, slidability, etc. on the surface of a substrate.
Examples of such applications include: frying pans, baking trays, pressure cookers, other various pans, electric cookers, rice cake machines, ovens, heating plates, bread baking molds, kitchen knives, gas cookers, and other cooking devices; food containers such as electric kettles and ice making trays; stirring roller, calendaring roller, conveyor, hopper and other food industry components; industrial products such as rolls for office automation equipment [ OA ], OA belts, OA separating claws, paper making rolls, and calender rolls for film production; demolding the mold for molding foamed styrene, the mold for molding plywood and decoration board, and the mold for demolding; kitchen articles such as a range hood; frozen food manufacturing devices such as conveyor belts; saw, file, etc.; household articles such as flatirons, scissors and the like; a metal foil; sliding bearings for food processors, packaging machines, textile equipment, etc.; sliding parts of camera and clock; automobile parts.
The above-exemplified coated article having the above-mentioned fluororesin laminate is also one of the present invention.
Examples
Hereinafter, the present invention will be specifically described based on examples.
In the following examples, unless otherwise mentioned, "parts" and "%" represent "parts by mass" and "% by mass", respectively.
The fluororesin powder used is as follows.
PFA particles a:
MFR:7 (g/10 min), melting point: 306 ℃, average particle size: 23 μm
PFA particles B:
MFR:28 (g/10 min), melting point: 301 ℃, average particle size: 24 μm
PFA particle C
MFR:37 (g/10 min), melting point: 298 ℃ and average particle diameter: 20 μm
PFA particle D
MFR:29 (g/10 min), melting point: 301 ℃, average particle size: 0.3 μm
FEP particle A
MFR:22 (g/10 min), melting point: 256 ℃, average particle size: 20 μm
FEP particle B
MFR:9 (g/10 min), melting point: 254 ℃ and average particle diameter: 0.3 μm
FEP particle C
MFR:20 (g/10 min), melting point: 258 ℃, average particle size: 0.3 μm
FEP particle D
MFR:35 (g/10 min), melting point: 256 ℃, average particle size: 0.2 μm
Examples 1 to 8 and comparative examples 1 to 13
Any one of PFA particles a to D as a fluororesin, any one of FEP particles a to D, a Polyamideimide (PAI) varnish a (28% solids solution, manufactured by sho-o electric materials, inc.) as a binder resin, and polyether sulfone (PES) powder (24000 number average molecular weight, manufactured by sumitomo chemical company), N-methylpyrrolidone, methyl isobutyl ketone, 1-butanol, methyl ethyl ketone, ethanol, diacetone alcohol were mixed in a predetermined mass ratio as shown in tables 1 to 3 to obtain a fluorine-containing solvent-type primer composition.
An iron plate (SS 400, surface roughness Ra:2 μm to 3 μm) was subjected to sand blast treatment with alumina powder (TOSA Emery #40, manufactured by Yuzhi electrochemical industries Co., ltd.) at a jet pressure of 1.0MPa, and the above-mentioned fluorine-containing solvent type primer composition was spray-coated on the iron plate, and dried at 150℃for 30 minutes. Further, a PFA powder (ACX-34, manufactured by Daiko Co., ltd.) was electrostatically coated on the upper layer, and the resultant was fired at 380℃for 20 minutes to obtain a laminate having a total film thickness of 40. Mu.m.
The boiling point of the solvent used is shown below.
Examples 9 to 10
The PFA particles B and FEP particles C as fluorine resin, polyamideimide (PAI) varnish B (manufactured by ELANTAS corporation, solid content 36%, 3-methoxy-N, N-dimethylpropionamide solution), and polyether sulfone (PES) powder (manufactured by sumitomo chemical corporation, number average molecular weight 24000), 3-methoxy-N, N-dimethylpropionamide, methyl isobutyl ketone, methyl ethyl ketone were mixed in a predetermined mass ratio as shown in table 3 to obtain a fluorine-containing solvent type primer composition.
Thereafter, the same procedure as in example 1 was carried out to obtain a laminate.
(peel Strength)
The peel strength of the laminate obtained above was measured by the following method.
The peel strength was measured at a tensile speed of 50mm/min in a direction of 90℃relative to the test piece using a Tensilon universal tester according to JIS K6854-1.
The portion where peeling occurred is shown below.
A: damage to the topcoat
B: failure of the primer layer
C: stripping between top coat/base coat layers
(peel Strength after paint storage)
The same procedure as in example 1 was also carried out for the fluorine-containing solvent-based primer compositions obtained in examples 5, 6, 9 and 10 after further standing at 50℃for 1 month, and the adhesiveness of the laminate was evaluated.
[ Table 1 ]
[ Table 2 ]
[ Table 3 ]
As shown by the results in tables 1 to 3, the fluororesin laminate obtained in the examples has sufficient peel strength. In contrast to the failure of the top coat layer in the fluororesin laminate obtained in the examples, the failure of the primer layer or peeling between the top coat layer and the primer layer occurred in the comparative examples, and therefore the primer composition of the present invention had sufficient coating film strength and adhesion.
In addition, with the primer compositions of examples 5, 6, 9 and 10, the fluorine-containing resin laminate obtained after standing at 50℃for 1 month also had good peel strength, thus indicating that the primer composition of the present invention has excellent storage stability.
Industrial applicability
The primer composition of the present invention is a coating composition capable of forming a coating film having both adhesion to a coating object and adhesion to a fluororesin layer, and can be suitably used as a primer for a fluororesin layer.
Claims (5)
1. A fluororesin solvent-based primer composition comprising a fluororesin and a binder resin dispersed in a liquid medium, characterized in that,
the fluororesin comprises tetrafluoroethylene [ TFE ]/perfluoro (alkyl vinyl ether) [ PAVE ] copolymer [ PFA ] having a melt flow rate MFR of 10g/10min to 30g/10min and tetrafluoroethylene [ TFE ]/hexafluoropropylene [ HFP ] copolymer [ FEP ] having a melt flow rate MFR of 10g/10min to 30g/10min,
the mass ratio of [ PFA ]/[ FEP ] is in the range of 10/90 to 90/10,
the binder resin comprises polyamideimide [ PAI ] and polyethersulfone [ PES ], [ PAI ]/[ PES ] in a mass ratio of 1/99 to 60/40,
further, the composition contains 1 to 30% by mass of a liquid medium (A) having a boiling point of less than 100 ℃, and the composition contains 1 to 30% by mass of a liquid medium (B) having a boiling point of 100 to 150 ℃.
2. The fluororesin solvent type primer composition according to claim 1, wherein the content of N-methyl-2-pyrrolidone in the composition is less than 1% by mass.
3. A coating film formed from the fluororesin solvent-based primer composition according to claim 1 or 2.
4. A fluorine-containing resin laminate comprising a coated object, the coating film of claim 3, and a fluorine resin layer containing PFA, wherein the coated object, the coating film, and the fluorine resin layer are laminated in this order.
5. An article comprising the fluororesin laminate according to claim 4.
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| JP2021200857A JP7428915B2 (en) | 2021-12-10 | 2021-12-10 | Fluorine-containing resin solvent-based primer composition, coating film, fluorine-containing resin laminate, and articles |
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| JP2002172731A (en) * | 2000-12-06 | 2002-06-18 | Daikin Ind Ltd | Laminated body, coating method for article, and coated article |
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| CN103889719A (en) * | 2011-10-18 | 2014-06-25 | 大金工业株式会社 | Fluororesin laminate and method for manufacturing same |
| JP2015134865A (en) * | 2014-01-16 | 2015-07-27 | 旭硝子株式会社 | Primer composition and laminate prepared using the same |
| CN107406719A (en) * | 2015-03-13 | 2017-11-28 | 大金工业株式会社 | Coating composition and covered article |
| CN113710478A (en) * | 2019-04-19 | 2021-11-26 | 大金工业株式会社 | Coating composition and coated article |
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| JP2003053261A (en) | 2001-08-10 | 2003-02-25 | Daikin Ind Ltd | Method for producing fluororesin coating film, fluororesin coating film and processed article |
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| JP2013075498A (en) | 2011-09-30 | 2013-04-25 | Daikin Industries Ltd | Fluorine-containing laminate, and method for manufacturing the same |
| KR102085595B1 (en) | 2019-05-22 | 2020-03-09 | 주식회사 셰프라인 | Manufacturing method for kitchen appliances with thermosetting composite coating layer and kitchen appliances prepared using the same |
| CN110305579B (en) | 2019-06-05 | 2021-07-06 | 浙江鹏孚隆科技股份有限公司 | Wear-resistant scratch-resistant long-service-life non-stick coating and coating method thereof |
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| JP2002172731A (en) * | 2000-12-06 | 2002-06-18 | Daikin Ind Ltd | Laminated body, coating method for article, and coated article |
| JP2003340369A (en) * | 2002-05-27 | 2003-12-02 | Daikin Ind Ltd | Method for forming fluorine-containing resin layer, fluorine-containing resin layer and article |
| JP2006045490A (en) * | 2004-06-30 | 2006-02-16 | Daikin Ind Ltd | Water base paint composition |
| JP2006192356A (en) * | 2005-01-12 | 2006-07-27 | Nippon Futsuso Kogyo Kk | Primer layer and paint composition |
| CN103889719A (en) * | 2011-10-18 | 2014-06-25 | 大金工业株式会社 | Fluororesin laminate and method for manufacturing same |
| JP2015134865A (en) * | 2014-01-16 | 2015-07-27 | 旭硝子株式会社 | Primer composition and laminate prepared using the same |
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