KR20140013941A - Coated article - Google Patents

Abstract

A coated article with improved abrasion resistance is provided. The coated article has a base and a layer made of PFA with a melting viscosity of 4.0×103 to 100.0×103 Pa·s at 372 deg. C.

Description

Cloth article {COATED ARTICLE}

The present invention relates to a coated article. More specifically, it relates to a coated article having a layer comprising a fluorine-containing polymer.

Fluorine-containing polymers such as tetrafluoroethylene / perfluoro (alkylvinyl ether) copolymers [PFA] have low friction coefficients and are excellent in non-tackiness, chemical resistance, heat resistance, and the like. It is widely used for surface processing of kitchen appliances, such as a pot, household goods, such as an iron, an electric industrial goods, and a mechanical industrial goods.

Although surface processing is performed by forming the layer which consists of a fluorine-containing polymer on a base material, if a fluorine-containing polymer to be used has melt processability, such as PFA, it is easy to obtain a thick layer by a general industrial production method. And the surface of the article obtained can easily exhibit the various characteristics which a fluoropolymer has.

However, the fluorine-containing polymer lacks adhesiveness with the substrate due to its non-adhesiveness. For the purpose of improving the adhesiveness, a laminate having a primer layer obtained by applying a primer containing a binder resin such as a heat resistant resin and a fluorine-containing polymer in advance on a substrate as a basic coating, and a layer comprising a fluorine-containing polymer Proposed.

For example, a laminate having excellent phosphorus resistance (scratch resistance), which forms a primer layer containing aluminum oxide as a filler on a substrate, and melt-processable fluorine-containing polymer such as PFA, PTFE and aluminum oxide on the primer layer. Forming the intermediate | middle layer which consists of and forming the top coat layer which consists of PTFE on this intermediate | middle layer is disclosed (for example, refer patent document 1).

Moreover, the fluororesin coating film which has a primer layer, an intermediate coat layer containing PFA formed on a base material, fillers, such as diamond powder and glass flakes, and a top coat layer containing PFA is disclosed (for example, a patent document 2).

In addition, a primer layer comprising a fluorine-containing polymer (a) and a heat resistant resin, a fluorine-containing layer (B) comprising a melt-processable fluorine-containing polymer (b) and a filler, and a melt-processable fluorine-containing polymer (c) The coated article which laminated | stacked the fluorine-containing layer (C) which consists of this order is disclosed (for example, refer patent document 3). In order to form this fluorine-containing layer (B), the aqueous dispersion (aqueous paint) containing PFA and a filler is used.

Moreover, it consists of the primer layer which consists of a fluoropolymer (a) and a heat resistant resin, the fluorine-containing layer (B) which consists of a melt-processable fluoropolymer (b), and a filler, and a melt-processable fluoropolymer (c). A coating article in which a fluorine-containing layer (C) is laminated in this order is disclosed (see Patent Document 4, for example). In order to form this fluorine-containing layer (B), PFA powder coating material is used. Patent Document 4 discloses that the drying step at the time of intermediate layer formation becomes unnecessary due to such a configuration, and the manufacturing process can be simplified.

Further, for the purpose of providing a food heating processing apparatus having excellent antifouling property, fluorine having a fluororesin as a tetrafluoroethylene copolymer having a melt viscosity of 10 ⁷ poise or less at 372 ° C while all unstable end groups are fluorinated. The food heating processing mechanism which heat-melts a resin film to the base material surface is proposed (for example, refer patent document 5). In the Example of patent document 5, the coating material which formed the primer layer on the aluminum plate as a base material, and heat-melted-bonded the fluororesin film on it is described.

Japanese Patent No. 2644380 Japanese Patent Laid-Open No. 2006-297685 International Publication No. 2004/041537 Pamphlet International Publication No. 2011/048965 Pamphlet Japanese Patent Laid-Open No. 11-290215

However, since the top coat layer consists of PTFE in the laminated body of patent document 1, it is not easy to obtain a thick layer by the general industrial production method, and there existed a problem that abrasion resistance was inferior. In addition, the articles described in Patent Documents 2 to 5 also had room to further improve wear resistance.

An object of the present invention is to provide a coated article excellent in wear resistance in view of the present situation.

The inventors have found that coated articles having a layer formed of tetrafluoroethylene [TFE] / perfluoro (alkylvinylether) [PAVE] copolymer [PFA] whose melt viscosity is controlled to a specific range are particularly excellent in wear resistance. It has been found that the present invention has been achieved.

That is, this invention is a coating article which has a base material and the layer formed from PFA whose melt viscosity in 372 degreeC is 4.0 * 10 <^3> -100.0 * 10 <^3> Pa * s.

It is preferable that the said layer formed from PFA whose melt viscosity in 372 degreeC is 4.0 * 10 <^3> -100.0 * 10 <^3> Pa * s contains a filler.

The present invention is also a coated article having a substrate, a layer (A) formed of PFA, and a layer (B) formed of PFA, and comprising either or both PFAs constituting the layer (A) and the layer (B). It is also a coated article characterized by a melt viscosity at 372 ° C. of 4.0 × 10 ³ to 100.0 × 10 ³ Pa · s.

It is preferable that either or both of said layer (A) and said layer (B) contains a filler.

The filler is preferably at least one member selected from the group consisting of silicon carbide, silicon nitride, alumina, diamond and fluorinated diamond.

It is preferable that the coating article of this invention has a primer layer further.

It is preferable that the said primer layer consists of a fluoropolymer (a) and heat resistant resin.

The heat resistant resin is at least one member selected from the group consisting of polyamideimide resin, polyimide resin, polyethersulfone resin, polyetherimide resin, polyetheretherketone resin, aromatic polyester resin and polyarylene sulfide resin It is preferable.

The heat resistant resin comprises a polyether sulfone resin and at least one resin selected from the group consisting of polyamideimide resins and polyimide resins,

It is preferable that the said polyether sulfone resin is 65-85 mass% of the total amount of a polyether sulfone resin and at least 1 sort (s) of resin chosen from the group which consists of a polyamideimide resin and a polyimide resin.

It is preferable that the said heat resistant resin is 15-50 mass% of solid content total amount of the said heat resistant resin and a fluoropolymer (a).

The fluorine-containing polymer (a) is a tetrafluoroethylene homopolymer, modified polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer and tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer It is preferable that it is at least 1 sort (s) chosen from the group which contains.

It is preferable that the thickness of the said primer layer is 5-30 micrometers, the thickness of the said layer (A) is 1-90 micrometers, and the thickness of the said layer (B) is 1-90 micrometers.

The coating article of this invention is especially excellent in abrasion resistance by having the structure mentioned above. The coated article of the present invention can be used particularly suitably for cooking utensils and kitchen utensils.

Hereinafter, the present invention will be described in detail.

It does not specifically limit as a base material which comprises the coating article of this invention, For example, metals, such as iron, aluminum, copper, metals, such as these alloys; Nonmetallic inorganic materials, such as enamel, glass, and ceramics, etc. are mentioned. Stainless steel etc. are mentioned as said alloys. As said base material, a metal is preferable and aluminum or stainless steel is more preferable.

The said base material may perform surface treatment, such as a degreasing process and a roughening process, as needed. It does not specifically limit as said roughening process method, For example, chemical etching by an acid or an alkali, anodizing (anodizing), sand blast, etc. are mentioned. The said surface treatment can be used for a base material and a primer from the point which can apply | coat uniformly the coating composition for primers for forming the primer layer mentioned later, without generating a crater, and the adhesiveness of a base material and a primer coating film improve, etc. Although what is necessary is just to select suitably according to the kind of coating composition, etc., For example, it is preferable that it is sand blast.

The coated article of the present invention is a layer formed of PFA (hereinafter, also referred to as "specific PFA") having a melt viscosity of 4.0x10 ³ to 100.0x10 ³ Pa · s at 372 ° C (hereinafter referred to as "specific PFA layer"). Also called). As a result, the coated article of the present invention has excellent wear resistance.

5.0 * 10 <^3> Pa * s is preferable and, as for the minimum of melt viscosity at 372 degreeC of the said specific PFA, 6.0 * 10 <^3> Pa * s is more preferable. Moreover, 10.0x10 <^3> Pa * s is preferable and, as for an upper limit, 8.0x10 <^3> Pa * s is more preferable.

The melt viscosity was measured by applying a load of 5 kg at 372 ° C. using a melt indexer manufactured by Dynesko Co., Ltd., Japan, and measuring MFR (melt flow rate) through an orifice having an internal diameter of 2.1 mm, according to ASTM D-1238. I got it.

The said specific PFA has a polymer unit based on tetrafluoroethylene [TFE], and a polymer unit based on perfluoro (alkyl vinyl ether) [PAVE].

As the PAVE,

CF ₂ = CF-ORf ¹

(Wherein Rf ¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms).

Specifically as said PAVE, perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], perfluoro (butyl vinyl ether) These etc. can be mentioned, One or two or more of these can be used. Especially, it is preferable to use PPVE.

In the said specific PFA, it is preferable that the polymer unit based on the said PAVE is 0.1-20 mass% with respect to all the polymer units. The polymerization unit based on the said PAVE becomes like this. Preferably it is 1.0-10 mass%, More preferably, it is 2.0-7.0 mass%.

Content of the polymer unit based on PAVE in the said specific PFA can be measured by ¹⁹ F-NMR method.

The said specific PFA may further contain the polymer unit based on the monomer copolymerizable with TFE and PAVE other than the polymer unit based on TFE and the polymer unit based on PAVE. Examples of the monomer include ethylene, vinylidene fluoride [VdF], hexafluoropropylene [HFP], and CX ¹ X ² = CX ³ (CF ₂ ) _n X ⁴ ( _wherein X ¹ and X ² And X ^{3, which} is the same or different, represents a hydrogen atom or a fluorine atom, X ⁴ represents a hydrogen atom, a fluorine atom or a chlorine atom, n represents an integer of 1 to 10), and a CF monomer, and CF Alkyl perfluoro vinyl ether derivatives represented by ₂ = CF-OCH ₂ -Rf ² (wherein Rf ² represents a perfluoroalkyl group having 1 to 5 carbon atoms); and among these, HFP is preferred. Do.

As the vinyl ether derivative in the alkyl perfluoroalkyl, Rf ² is preferably a perfluoroalkyl group having 1 to 3 carbon atoms, _{and, CF 2 = CF-OCH 2} -CF 2 CF 3 is more preferable.

When the said specific PFA contains the polymer unit based on the monomer copolymerizable with TFE and PAVE, it is preferable that the content is 0.1-10 mass% with respect to all the polymer units. More preferably, it is 1.0-5.0 mass%. The particular PFA preferably does not contain polymerized units based on monomers copolymerizable with TFE and PAVE. That is, it is preferable that the specific PFA includes only the TFE and the PAVE.

It is preferable that melting | fusing point of the said specific PFA is 280-330 degreeC. More preferably, it is 290-320 degreeC.

The said melting point is calculated | required as temperature corresponding to the maximum value in the heat of fusion curve when it heated up at the speed | rate of 10 degree-C / min using a DSC apparatus (made by Shimadzu Corporation).

The said specific PFA can be obtained by a conventionally well-known polymerization method, such as suspension polymerization, solution polymerization, emulsion polymerization, and bulk polymerization. In the said polymerization, each condition, such as temperature and a pressure, a polymerization initiator and other additives can be suitably set according to the composition and quantity of a desired polymer.

The specific PFA may be fluorinated by the method described in International Publication No. 2002/088227 Pamphlet.

The said specific PFA layer may further contain the fluorine-containing polymer (henceforth another fluorine-containing polymer) other than the said specific PFA. As another fluorine-containing polymer, polytetrafluoroethylene (PTFE) etc. are mentioned, for example. It is preferable to make content of another fluoropolymer into 1.0-10 mass% with respect to the said specific PFA. More preferably, the specific PFA layer does not contain a fluorine-containing copolymer other than the specific PFA.

The said specific PFA layer may contain a filler for the purpose of providing the characteristic, the physical property improvement, the increase, etc. with respect to the coating article obtained. Examples of the properties and physical properties include strength, durability, weather resistance, flame retardancy, and designability. When using what has brightness as a filler, the coating article of this invention has favorable brightness.

The filler is not particularly limited, and for example, silicon carbide, silicon nitride, alumina, diamond, fluorinated diamond, wood powder, quartz sand, carbon black, clay, talc, corundum, silica, boron nitride, boron carbide, tourmaline, jade, germanium, Silica powder, chrysoberyl, beryl, garnet, garnet, zirconium oxide, zirconium carbide, tantalum carbide, titanium carbide, tungsten carbide, sieving pigment, bright flat pigment, scaly pigment, glass, various reinforcing materials, various extenders, A conductive filler etc. can be mentioned, 1 type or 2 or more types can be used, respectively.

The fluorinated diamond is obtained by fluorination of diamond. The fluorination of diamond can be performed by the well-known method disclosed, for example by "The 26th collection of fluorine chemical debate summary", November 14, 2002, p24-25. That is, diamond may be enclosed in a reactor containing a material having corrosion resistance to fluorine, such as nickel or an alloy containing nickel, and fluorinated by introducing fluorine gas.

It does not specifically limit as what is classified into the said bright flat pigment and scaly pigment, For example, a mica powder (including thing coated with titanium oxide), a metal powder, etc. are mentioned. It does not specifically limit as said metal powder, For example, Powder of metal single bodies, such as aluminum, iron, tin, zinc, gold, silver, copper, platinum; Alloy powders, such as an aluminum alloy and stainless steel, etc. are mentioned. It does not specifically limit as a shape of the said metal powder, For example, although a particle shape, a flake shape, etc. are mentioned, A flake shape is preferable at the point which is excellent in brightness. For example, as a shape of aluminum powder, a flake shape is preferable.

The glass is not particularly limited, and examples thereof include glass beads, glass bubbles, glass flakes and glass fractions such as glass fibers. Moreover, the glass powder coated with metals, such as gold, silver, and nickel, the glass powder coated with titanium oxide, iron oxide, etc. can also be used.

The filler is preferably at least one selected from the group consisting of silicon carbide, silicon nitride, alumina, diamond and fluorinated diamond, and at least one selected from the group consisting of silicon carbide, silicon nitride, alumina and diamond. It is more preferable that it is 1 type.

When the primer layer mentioned later is black, when the said specific PFA layer contains silicon carbide or silicon nitride, this specific PFA layer will look gray, but if it contains alumina, it can be made black same as a primer layer. Therefore, it is preferable to use alumina from a viewpoint of designability.

It is preferable that the said filler is 0.01 mass% or more and 40 mass% or less with respect to the total amount of the said specific PFA and filler. More preferably, they are 0.05 mass% or more and 30 mass% or less, More preferably, they are 0.1 mass% or more and 10 mass% or less.

It is preferable that the said specific PFA layer is 1-90 micrometers in thickness. If the thickness is too thin, the wear resistance of the coated article may be lowered. If the thickness is too thick, when the coated article is in the presence of water vapor, water vapor tends to remain in the coated article, resulting in poor water vapor resistance. The minimum with said more preferable thickness is 3 micrometers, a more preferable minimum is 5 micrometers, and a more preferable upper limit is 80 micrometers.

The specific PFA layer is preferably formed of a coating material formed by a melt viscosity at 372 ℃ including 4.0 × 10 ³ to 100.0 × 10 ³ Pa · s is PFA (PFA particular). Thereby, a specific PFA layer can be formed on the base material of various shapes. The coating material may be a powder coating material or a liquid coating material such as an aqueous coating material. However, it is preferable that the coating material is a powder coating material because a drying process is unnecessary and a thick coating film can be easily obtained with a small number of coating times.

In the coated article of the present invention, the specific PFA layer is preferably fired at a temperature above the melting point of the specific PFA.

It is preferable that the coating article of this invention has a primer layer further. Although the said primer layer will not be limited, if it is excellent in adhesiveness with a base material, It is preferable to comprise a fluoropolymer (a) and heat resistant resin.

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

It is preferable that the said fluoropolymer (a) is obtained by superposing | polymerizing a fluorine-containing monoethylenically unsaturated hydrocarbon (I).

Said "fluorine-containing monoethylenically unsaturated hydrocarbon (I) (henceforth also called" unsaturated hydrocarbon (I) "") is an unsaturated hydrocarbon which has one vinyl group in a molecule in which one part or all of the hydrogen atoms were substituted by the fluorine atom. Means.

The unsaturated hydrocarbon (I) may be one in which part or all of the hydrogen atoms not substituted by fluorine atoms are substituted by halogen atoms other than fluorine atoms such as chlorine atoms and / or fluoroalkyl groups such as trifluoromethyl groups. do. However, the unsaturated hydrocarbon (I) excludes trifluoroethylene which will be described later.

It does not specifically limit as said unsaturated hydrocarbon (I), For example, tetrafluoroethylene [TFE], hexafluoropropylene [HFP], chlorotrifluoroethylene [CTFE], vinylidene fluoride [VdF], vinyl fluoride [VF] etc. can be mentioned, These can use 1 type (s) or 2 or more types.

The said fluoropolymer (a) may be a homopolymer of the said unsaturated hydrocarbon (I). As a homopolymer of the said unsaturated hydrocarbon (I), For example, tetrafluoroethylene homopolymer [TFE homopolymer], polychlorotrifluoroethylene [PCTFE], polyvinylidene fluoride [PVdF], polyvinyl fluoride [PVF] ], And the like. TFE homopolymers are non-melt processable.

The fluorine-containing polymer (a) may also be a copolymer of at least one unsaturated hydrocarbon (I) and an unsaturated compound (II) copolymerizable with the unsaturated hydrocarbon (I).

In the present invention, the polymer obtained by polymerizing only one or two or more kinds of the above unsaturated hydrocarbons (I) can be used as the fluorine-containing polymer (a), whereas only one or two or more kinds of unsaturated compounds (II) are 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).

The unsaturated compound (II) is not particularly limited and includes, for example, trifluoroethylene [3FH]; Monoethylenically unsaturated hydrocarbons, such as ethylene [Et] and propylene [Pr], etc. are mentioned. These can use 1 type (s) or 2 or more types.

The said fluoropolymer (a) may be a copolymer of 2 or more types of said unsaturated hydrocarbons (I) further. It does not specifically limit as a copolymer of the said 2 or more types of said unsaturated hydrocarbon (I), and the said at least 1 type of said unsaturated hydrocarbon (I) and an unsaturated compound (II), For example, a binary copolymer, 3 Raw copolymers; and the like.

It does not specifically limit as said binary copolymer, For example, VdF / HFP copolymer, Et / CTFE copolymer [ECTFE], Et / HFP copolymer, etc. are mentioned.

The binary copolymer may also be a TFE / HFP copolymer [FEP], a TFE / CTFE copolymer, a TFE / VdF copolymer, a TFE / 3FH copolymer, an Et / TFE copolymer [ETFE], a TFE / Pr copolymer, or the like. May be a TFE-based copolymer. In this specification, said "TFE type copolymer" means what is obtained by copolymerizing 1 type, or 2 or more types of TFE and other monomers other than TFE. As for the said TFE type copolymer, it is preferable that the ratio of the other monomers other than TFE normally added in the said TFE type copolymer exceeded 1 mass% of the total mass of the said TFE and the said other monomer.

As said terpolymer, VdF / TFE / HFP copolymer etc. are mentioned.

As other monomers other than the said TFE in the said TFE type copolymer, the other monomer (III) which can be copolymerized with the following TFE may be sufficient. The other monomer (III) is of the 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, n represents an integer of 0 or 1, except HFP, Formula

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

(Wherein p represents an integer of 1 or 2) and the following formula

_{X (CF 2) q CY =} CH 2

Wherein X is the same as described above, Y represents -H or -F, and q represents an integer of 1 to 6, wherein the monomer is at least one monomer selected from the group consisting of desirable. These may be used alone or in combination of two or more. As such a TFE type copolymer, TFE / perfluoro (alkyl vinyl ether) [PAVE] copolymer [PFA] etc. are mentioned, for example.

Modified polytetrafluoroethylene [modified PTFE] may be sufficient as the said fluoropolymer (a). In this specification, the said "modified PTFE" means what is formed by copolymerizing a small amount of comonomer with TFE of the grade which does not provide melt processability to the copolymer obtained. It does not specifically limit as said small amount of comonomer, For example, HFP, CTFE, etc. in the said unsaturated hydrocarbon (I) are mentioned, 3FH etc. are mentioned in the said unsaturated compound (II), The said other monomer (III) PAVE, perfluoro (alkoxy vinyl ether), (perfluoroalkyl) ethylene, etc. are mentioned. The small amount of comonomers may be used alone or in combination of two or more.

The proportion of the small amount of comonomer added to the modified PTFE is different depending on the type thereof. For example, in the case of using PAVE, perfluoro (alkoxyvinylether) or the like, the TFE and the small amount of the copolymer are usually used. It is preferable that it is 0.001-1 mass% of the total mass of a monomer.

As said fluoropolymer (a), 1 type, or 2 or more types may be sufficient, and 1 type, or 2 or more types of mixture of the homopolymer of the said unsaturated hydrocarbon (I) and the copolymer of the said unsaturated hydrocarbon (I), or The mixture of two or more types of the copolymer of the said unsaturated hydrocarbon (I) may be sufficient.

As said mixture, the mixture of a TFE homopolymer, the said TFE type copolymer, the mixture of 2 or more types of copolymers which belong to the said TFE type copolymer, etc. are mentioned, For example, as such a mixture, a TFE homopolymer and A mixture of PFA, a mixture of TFE homopolymer and FEP, a mixture of TFE homopolymer and PFA and FEP, a mixture of PFA and FEP, and the like.

The fluoropolymer (a) may further be obtained by polymerizing a perfluoroalkyl group-containing ethylenically unsaturated monomer (VI) having a perfluoroalkyl group (hereinafter also referred to as "unsaturated monomer (VI)"). The unsaturated monomer (VI) is represented by the 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, and 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 said fluoropolymer (a) may be a homopolymer of the said unsaturated monomer (VI), and may be a copolymer of the said unsaturated monomer (VI) and the monomer (V) copolymerizable with the said unsaturated monomer (VI).

It does not specifically limit as said monomer (V), For example, (meth) acrylic-acid cyclohexyl, (meth) acrylic-acid benzyl ester, di (meth) acrylic-acid polyethyleneglycol, N-methylol propane acrylamide, (meth) acrylic acid amide (Meth) acrylic acid derivatives such as alkyl esters of (meth) acrylic acid having 1 to 20 carbon atoms of an alkyl group; Substituted or unsubstituted ethylene such as ethylene, vinyl chloride, vinyl fluoride, styrene, α-methylstyrene, p-methylstyrene and the like; Vinyl ethers such as alkyl vinyl ethers having 1 to 20 carbon atoms of alkyl groups and halogenated alkyl vinyl ethers having 1 to 20 carbon atoms of alkyl groups; Vinyl ketones such as vinyl alkyl ketone having 1 to 20 carbon atoms of an alkyl group; Aliphatic unsaturated polycarboxylic acids such as maleic anhydride and derivatives thereof; And polyenes such as butadiene, isoprene and chloroprene.

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

As said fluorine-containing polymer (a), at least 1 sort (s) of polymer chosen from the group which consists of a TFE homopolymer, a modified PTFE, and the said TFE type copolymer is preferable at the point which the coated article obtained is excellent in corrosion resistance and water vapor resistance. Do. As said TFE type copolymer, at least 1 sort (s) of copolymer chosen from the group which consists of FEP and PFA is preferable.

As mentioned above, as said fluorine-containing polymer (a), at least 1 sort (s) of polymer chosen from the group which consists of TFE homopolymer, modified PTFE, FEP, and PFA is preferable.

As said fluoropolymer (a), in the coating article obtained further, it is preferable to contain a TFE type copolymer from the point which is excellent in the adhesiveness of a primer layer and a PFA layer. Since the coated article excellent in the adhesiveness between the primer layer and the PFA layer is excellent in water vapor resistance, it is possible to suppress the occurrence of coating film defects such as blisters even in the presence of water vapor. Examples of the fluorine-containing polymer (a) comprising a TFE copolymer include, for example, TFE homopolymer alone, PFA alone, a mixture of TFE homopolymer and FEP, a mixture of TFE homopolymer and PFA, a mixture of modified PTFE and FEP, or Mixtures of modified PTFE and PFA are preferred. In addition, the fluorine-containing polymer (a) in the primer layer is excellent in corrosion resistance and water vapor resistance, and excellent in adhesion between the primer layer and the PFA layer. Thus, the TFE homopolymer alone, the PFA alone, and the TFE homopolymer are used. It is preferable that it is a mixture of PFA or a mixture of TFE homopolymer and FEP, and it is more preferable that it is a TFE homopolymer alone or a mixture of TFE homopolymer and FEP.

The heat resistant resin which can comprise the said primer layer should just be resin recognized as having heat resistance normally, and resin whose continuous usable temperature is 150 degreeC or more is preferable. However, as said heat resistant resin, the above-mentioned fluoropolymer (a) is excluded.

Although it does not specifically limit as said heat resistant resin, For example, including polyamideimide resin, polyimide resin, polyether sulfone resin, polyetherimide resin, polyether ether ketone resin, aromatic polyester resin, and polyarylene sulfide resin It is preferable that it is at least 1 sort (s) of resin chosen from the group which consists of.

The polyamideimide resin [PAI] is a resin comprising a polymer having an amide bond and an imide bond in its 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 a pyromellitic acid; Reaction of aromatic trivalent carboxylic acids such as trimellitic anhydride with diisocyanates such as diamines such as 4,4-diaminophenyl ether and diphenylmethane diisocyanate; The resin etc. which contain the high molecular weight polymer obtained by each reaction, such as reaction of the dibasic acid and diamine which have an aromatic imide ring in a molecule | numerator, are mentioned. As said PAI, in the point which is excellent in heat resistance, what consists of the polymer which has an aromatic ring in a principal chain is preferable.

The said polyimide resin [PI] is resin which contains the polymer which has an imide bond in molecular structure. It does not specifically limit as said PI, For example, resin etc. which contain the high molecular weight polymer obtained by reaction of aromatic tetravalent carboxylic anhydride, such as pyromellitic anhydride, etc. are mentioned. As said PI, since it is excellent in heat resistance, what consists of the polymer which has an aromatic ring in a principal chain is preferable.

The polyether sulfone resin [PES] is represented by the following formula

It is resin containing the polymer which has a repeating unit represented by the following. It does not specifically limit as said PES, For example, resin etc. which contain the polymer obtained by polycondensation of dichlorodiphenyl sulfone and bisphenol are mentioned.

The heat resistant resin is excellent in adhesion to the substrate, has sufficient heat resistance even under the temperature at the time of firing when forming the coated article, and the coated article obtained has excellent corrosion resistance and water vapor resistance, so that PAI, PI, and PES It is preferable that it is at least 1 sort (s) of resin chosen from the group which consists of including. Each of PAI, PI, and PES may include one kind or two or more kinds.

As said heat resistant resin, it is more preferable that it is at least 1 sort (s) of resin chosen from the group which consists of PAI and PI from the point which is excellent in adhesiveness with a base material, and heat resistance.

As said heat resistant resin, what consists of PES and at least 1 sort (s) of resin chosen from the group which consists of PAI and PI from the point which is excellent in corrosion resistance and water vapor resistance is preferable. That is, the heat resistant resin may be a mixture of PES and PAI, a mixture of PES and PI, or a mixture of PES, PAI and PI. It is particularly preferable that the heat resistant resin is a mixture of PES and PAI.

When the said heat resistant resin consists of PES and at least 1 sort (s) of resin chosen from the group which consists of PAI and PI, the said PES is selected from the group which consists of PES, PAI, and PI. It is preferable that it is 65-85 mass% of the total amount with at least 1 sort (s) of resin. More preferably, it is 70-80 mass%.

As content of the said heat resistant resin, it is preferable that it is 10-50 mass% of the total amount of solid content of the said heat resistant resin and the said fluoropolymer (a), and it is more preferable that it is 15-50 mass%. More preferably, it is 10-40 mass%, Especially preferably, it is 15-30 mass%. In this specification, said "solid content" means a solid at 20 degreeC. In this specification, said "the total amount of solid content of the said heat resistant resin and a fluorine-containing polymer (a)" means after apply | coating a coating composition for primers on a base material, drying at the temperature of 80-100 degreeC, and 45 minutes at 380-400 degreeC The total mass of the said heat resistant resin and a fluoropolymer (a) in the residue after baking is meant.

The said primer layer is normally formed on a base material. The said primer layer is obtained by apply | coating the coating composition for primers which consists of a fluoropolymer (a) and heat resistant resin, for example on a base material, drying as needed, and continuing baking. The primer layer obtained in this way has a difference in surface tension between the fluoropolymer (a) and the heat resistant resin, so that the fluoropolymer (a) floats during firing, and the surface side is far from the substrate. The said fluorine-containing polymer (a) is arrange | positioned at the mainly, and the said heat resistant resin is arrange | positioned mainly at the base material side.

When the said primer layer contains the said fluoropolymer (a) and the said heat resistant resin, since the said heat resistant resin has adhesiveness with a base material, it is excellent in adhesiveness with respect to a base material. Since the said fluoropolymer (a) has affinity with PFA, the said primer layer is excellent in adhesiveness with a PFA layer. Thus, when the said primer layer consists of the said fluoropolymer (a) and the said heat resistant resin, it has the outstanding adhesiveness with respect to both a base material and a PFA layer.

It is preferable that the said primer layer contains a polymer component and an additive. It does not specifically limit as said additive, For example, a leveling agent, a solid lubricant, a sedimentation inhibitor, a water absorbent, a surface regulator, a thixotropic imparting agent, a viscosity modifier, an antigelling agent, a ultraviolet absorber, a light stabilizer, a plasticizer, a color separation inhibitor, Anti-foaming agent, anti-abrasion, anti-fungal, antibacterial, antioxidant, antistatic, silane coupling agent, wood powder, quartz, carbon black, clay, talc, diamond, fluorinated diamond, tourmaline, jade, germanium, sieving pigment, corundum , Silica, boron nitride, boron carbide, silicon carbide, silicon nitride, alumina, silica powder, chrysoberyl, topaz, beryl, garnet, quartz, garnet, zirconium oxide, zirconium carbide, tantalum carbide, titanium carbide, tungsten carbide, mica, Bright flat pigments such as aluminum flakes, scaly pigments, glass, various reinforcing materials, various extenders, conductive fillers, gold, , Copper, and the like of metal powder such as Pt.

It is preferable that a polymer component of the said primer layer is a fluorine-containing polymer (a) and heat resistant resin. In this specification, the said "primer layer is a fluorine-containing polymer (a) and heat resistant resin" means that the polymer in a primer layer is only a fluorine-containing polymer (a) and heat resistant resin. Since the said polymer component is a fluorine-containing polymer (a) and heat resistant resin, the said primer layer has the outstanding adhesiveness with respect to both a base material and a PFA layer efficiently.

Since the said primer layer exhibits the outstanding adhesiveness with respect to both a base material and a PFA layer efficiently, it is preferable that a polymer component is a fluorine-containing polymer (a) and heat resistant resin, but the corrosion resistance and water vapor resistance of a coating article are more In the point which can be improved, it may consist of another resin together with a fluoropolymer (a) and heat resistant resin. As other resin, a phenol resin, a urea resin, an epoxy resin, a urethane resin, a melamine resin, a polyester resin, a polyether resin, an acrylic resin, an acrylic silicone resin, a silicone resin, a silicone polyester resin etc. are mentioned, for example. .

It is preferable that the said primer layer is 5-30 micrometers in thickness. If the thickness is too thin, pinholes are likely to occur, and the corrosion resistance of the coated article may be lowered. If the thickness is too thick, cracks tend to occur and there is a fear that the water vapor resistance of the coated article is lowered. The upper limit with more preferable thickness of the said primer layer is 20 micrometers.

It is one of preferable embodiment of this invention that the thickness of the said primer layer is 5-30 micrometers, and the thickness of the said specific PFA layer is 1-90 micrometers.

When the coated article of the present invention has a substrate, a primer layer and the specific PFA layer, it is preferable that the substrate, the primer layer and the specific PFA layer are laminated in this order. Moreover, it is preferable that the said specific PFA layer is outermost layer. By arranging the specific PFA layer which greatly contributes to the wear resistance in the outermost layer where wear resistance is particularly required under the use environment, the effect according to the wear resistance of the present invention can be further remarkably exhibited.

When the base material, the primer layer, and the specific PFA layer are laminated | stacked in this order, the coating | coated article of this invention may be the one which prints letters, drawings, etc. on the upper surface of a primer layer.

Usually, the coating article of this invention does not interpose another layer between each layer of a base material, a primer layer, and a specific PFA layer, For example, it is a thing where another layer is interposed between the layer of a primer layer and a specific PFA layer as needed. You can do it.

The coated article of the present invention may have two or more layers formed of the specific PFA. Moreover, you may further have a layer formed from PFA other than the said specific PFA.

A coated article having a substrate, a layer (A) formed of PFA, and a layer (B) formed of PFA, and at 372 ° C. of either or both of the PFAs constituting the layer (A) and the layer (B). A coated article characterized by having a melt viscosity of 4.0 × 10 ³ to 100.0 × 10 ³ Pa · s is also one of the present invention. The coated article having the above structure is preferable because of its excellent barrier property and good corrosion resistance. In this coating article, either or both of the layer (A) and the layer (B) is the specific PFA layer described above.

When layer (A) or layer (B) is said particular PFA layer, the material for forming said layer is as described above.

If the layer (A) or layer (B) formed of a PFA other than the particular PFA, the Examples of PFA, a melt viscosity at 372 ℃ less than 4.0 × 10 ³ Pa · s or 100.0 × 10 ³ Pa · s It will not specifically limit, if it is larger PFA. About materials other than PFA, it is the same as that of the said specific PFA layer.

Although the lamination order of a base material, a layer (A), and a layer (B) is not specifically limited, It is preferable that a base material, a layer (A), and a layer (B) are laminated | stacked in this order. Hereinafter, embodiment in which the base material, the layer (A) and the layer (B) are laminated in this order will be described.

In the coated article of the present invention, at least one of the layer (A) and the layer (B) may be the specific PFA layer, but from the viewpoint of providing a coated article excellent in wear resistance, the layer (B) located on the surface side of the coated article Is preferably the specific PFA layer. Moreover, it is more preferable that both are the said specific PFA layer, ie, melt viscosity in 372 degreeC of both PFA which comprises layer (A) and layer (B) is 4.0 * 10 <^3> -100.0 * 10 <^3> Pa * s. Do.

It is preferable that either or both of a layer (A) and a layer (B) contains a filler. From the point that the wear resistance of the coated article can be improved, it is more preferable that the layer (A) includes a filler, and more preferably both of the layer (A) and the layer (B) contain a filler.

As said filler, what was mentioned above is mentioned.

When layer (A) contains a filler, it is preferable that the content is 0.01 mass% or more and 40 mass% or less with respect to the total amount of PFA and filler which comprise layer (A). More preferably, they are 0.05 mass% or more and 30 mass% or less, More preferably, they are 0.1 mass% or more and 10 mass% or less.

When layer (B) contains a filler, it is preferable that the content is 0 mass% or more and 40 mass% or less with respect to the total amount of PFA and filler which comprise a layer (B). That is, it is preferable not to contain a filler or to contain the quantity more than 0 mass% and 40 mass% or less. More preferably, they are 0.05 mass% or more and 30 mass% or less, More preferably, they are 0.1 mass% or more and 10 mass% or less.

It is preferable that the said layer (A) is 1-90 micrometers in thickness. If the thickness is too thin, the corrosion resistance of the coated article obtained may not be sufficient. If the thickness is too thick, the moisture permeated from the layer (A) is less likely to fall out, which may lower the water vapor resistance of the coated article. The minimum with more preferable thickness of the said layer (A) is 5 micrometers, and a more preferable upper limit is 60 micrometers.

It is preferable that the said layer (B) is 1-90 micrometers in thickness. If the thickness is too thin, the wear resistance of the coated article may be lowered. If the thickness is too thick, when the coated article is in the presence of water vapor, the water vapor may easily remain in the coated article and the water vapor resistance may be inferior. The minimum with more preferable thickness of the said layer (B) is 3 micrometers, a more preferable minimum is 5 micrometers, and a more preferable upper limit is 80 micrometers.

It is preferable that the said layer (A) and the layer (B) are formed with the coating material containing PFA (specific PFA or other PFA). Thereby, a PFA layer can be formed on the base material of various shapes. The coating material may be a powder coating material or a liquid coating material such as an aqueous coating material. However, it is preferable that the coating material is a powder coating material because a drying process is unnecessary and a thick coating film can be easily obtained with a small number of coating times.

In the coated article of the present invention, the layer (B) is preferably baked at a temperature equal to or higher than the melting point of the PFA constituting the layer (B).

It is preferable that the coating article of this invention has a primer layer other than a base material, a layer (A), and a layer (B) further. About the material and thickness which comprise a primer layer, it is as above-mentioned.

The thickness of the said primer layer is 5-30 micrometers, and it is one of preferable embodiment of this invention that the thickness of the said layer (B) is 1-90 micrometers.

Moreover, the thickness of the said primer layer is 5-30 micrometers, the thickness of a layer (A) is 1-90 micrometers, and the thickness of the said layer (B) is 1-90 micrometers is one of the preferable embodiment of this invention. .

When the coating article of this invention has a base material, a primer layer, a layer (A), and a layer (B), the lamination order of each layer is not specifically limited, A base material, a primer layer, a layer (A), and a layer (B) are the same. It is preferable to stack in order. In addition, since wear resistance of a coated article is exhibited more remarkably, it is preferable that layer (B) is an outermost layer. By arrange | positioning the layer (B) which contributes greatly to the wear resistance improvement in the outermost layer which especially requires abrasion resistance in a use environment, the effect according to the abrasion resistance of this invention can be exhibited more remarkably.

In the coated article of the present invention, when the base material, the primer layer, the layer (A) and the layer (B) are laminated in this order, printing of letters, drawings, etc. is performed on the upper surface of the primer layer and / or the upper surface of the layer (A). It may be implemented.

Typically, the coated article of the present invention does not interpose another layer between each of the substrate, the primer layer, the layer (A) and the layer (B), but for example, if necessary, between the primer layer and the layer (A), Alternatively, another layer may be interposed between the layers (A) and (B).

The coating article of this invention can be manufactured, for example by the following manufacturing methods, when it has a base material, a primer layer, a layer (A), and a layer (B).

That is, the process (1) of forming a primer coating film by apply | coating the coating composition (i) for primers on a base material, and the process of forming a coating film (Ap) by apply | coating the coating material (ii) containing PFA on a primer coating film. (2) Process (3) of forming coating film Bp by apply | coating the coating material which consists of PFA on coating film Ap, primer coating film, coating film Ap, and coating film Bp In the method comprising the step (4) of forming a coated article comprising a base material, a primer layer, a layer (A) and a layer (B) by firing a coating film laminate comprising a coating material (ii). ) And the PFA constituting the coating material, the coating article of the present invention is produced by using either or both of the PFAs constituting the paint as PFA having a melt viscosity of 4.0 × 10 ³ to 100.0 × 10 ³ Pa · s at 372 ° C. can do.

The said process (1) is a process of forming a primer coating film by apply | coating the coating composition (i) for primers on a base material.

In the said process (1), it is preferable that the said coating composition (i) for primers consists of a fluoropolymer (a) and heat resistant resin. The fluorine-containing polymer (a) and the heat resistant resin are as described above. The coating composition (i) for the primer may be a liquid or powder. The said coating composition for primers (iii) consists of a liquid medium with a fluoropolymer (a) and a heat resistant resin, when liquid. The liquid medium usually contains water and / or an organic liquid. In this specification, said "organic liquid" is an organic compound, and means a liquid at normal temperature about 20 degreeC.

When the liquid medium of the coating composition for primers (iii) mainly comprises an organic liquid, the heat resistant resin and the fluorine-containing polymer (a) are dispersed as particles in the liquid medium and / or in the liquid medium. It is dissolved. As said organic liquid, you may use a conventionally well-known organic solvent etc., may be used independently, and may use 2 or more types together.

When the liquid medium of the said coating composition for primers (iii) consists mainly of water, the said heat resistant resin is disperse | distributed as particle | grains in the said liquid medium, and a fluoropolymer (a) is a particle | grain in the said liquid medium. It is distributed.

When the said liquid medium mainly consists of water, the said coating composition for primers (a) is normally formed by adding surfactant, for the purpose of dispersion-stabilizing the particle | grains which contain a fluorine-containing polymer (a). will be. As said surfactant, you may use a conventionally well-known thing. In the said coating composition for primers (iii), you may use together the said organic liquid with the said surfactant for the purpose of dispersion-stabilizing the particle | grains containing a fluorine-containing polymer (a).

The coating composition (i) for the primer may further be an organosol obtained by the method described in JP-A-49-17017.

It is preferable that the said coating composition (i) for primers is liquid in the point which is excellent in adhesiveness with a base material, and it is more preferable that the said liquid medium mainly contains water from a viewpoint of an environmental problem.

The coating composition (i) for the primer further contains the above-mentioned additive for the purpose of further improving the coating workability and the corrosion resistance and water vapor resistance of the coated article obtained together with the fluorine-containing polymer (a) and the heat resistant resin. It may be achieved by.

Since the coating composition (i) for primers can further improve the corrosion resistance and water vapor resistance of a coating | coated article, it may be what further contains other resin mentioned above with a fluoropolymer (a) and heat resistant resin.

It does not specifically limit as a method of apply | coating a coating composition (i) for primers on a base material, When the said coating composition (i) for primers is a liquid, it is spray coating, roll coating, coating by a doctor blade, dip (immersion), for example. ) Coating, impregnation coating, spin flow coating, curtain flow coating, etc. are mentioned, and spray coating is especially preferable. When the said coating composition for primers (i) is powder, electrostatic coating, the fluid immersion method, the low-triining method, etc. are mentioned, Especially, electrostatic coating is preferable.

After application | coating of the coating composition (i) for primers in the said process (1), you may bake before performing process (2), and you may not bake. In addition, when the said coating composition (i) for primers is a liquid, you may dry further after the said application | coating and does not need to dry.

In the said process (1), it is preferable to perform the said drying for 5 to 60 minutes at the temperature of 70-300 degreeC. The firing is preferably performed at a temperature of 260 to 410 DEG C for 10 to 30 minutes.

When the said coating composition (i) for primers is a liquid, it is preferable to carry out drying after apply | coating on a base material in the said process (1). In addition, in order to bake a coating film laminated body in the process (4) mentioned later, it is preferable not to bake.

When the said coating composition for primers (i) is powder, it is preferable to bake after apply | coating on a base material in the said process (1).

The said primer coating film is formed by drying or baking as needed after apply | coating the said coating composition for primers on a base material. The said primer coating film becomes a primer layer in the coating article obtained.

The said process (2) is a process of forming a coating film Ap by apply | coating the coating material (ii) which consists of PFA on a primer coating film.

The coating material (ii) in the step (2) may be a powder coating material containing particles containing PFA, or may be a liquid coating material such as an aqueous coating material. It is preferable that it is a powder coating material from the point which a drying process is unnecessary and it is easy to obtain a thick coating film with few coating times. In the case where the paint (ii) is a liquid paint, it is preferable that the particles made of PFA are dispersed in a liquid medium, and the particles made of PFA are an aqueous paint made by being dispersed in an aqueous medium mainly containing water. It is more preferable.

It is preferable that the average particle diameter of the particle | grains which contain PFA in coating material (ii) is 0.01-40 micrometers when it is a liquid paint, and 1.0-50 micrometers when it is a powder paint.

The coating material (ii) may contain a filler for the purpose of imparting properties, improving physical properties, increasing the amount of the coated article to be obtained. Examples of the properties and physical properties include strength, durability, weather resistance, flame retardancy, and designability. The above-mentioned thing can be mentioned as said filler.

The said coating material (ii) may also contain a small amount of PTFE (TFE homopolymer, modified PTFE) with PFA for the purpose of refine | purifying a spherical crystal. In this case, it is preferable to make content of PTFE into 0.01-10.0 mass% with respect to PFA.

It does not specifically limit as a method of apply | coating coating material (ii) on the said primer coating film, For example, the method similar to the coating method of the coating composition (i) for said primers, etc. are mentioned. In the case where the coating material (ii) is a powder coating material, electrostatic coating is preferable.

In the said process (2), after apply | coating coating material (ii) on a base material, you may dry or bake. It is preferable to perform drying or baking in the said process (2) on the conditions similar to drying or baking in the said process (1).

Usually, after apply | coating the said coating material (ii) on a primer coating film, it is preferable not to perform baking. It is because all the coating films can be baked simultaneously when baking a coating film laminated body in the process (4) mentioned later.

Coating film Ap is formed by apply | coating coating material (ii) on the said primer coating film, and then drying or baking as needed. The said coating film Ap becomes a layer (A) in the coating article obtained.

The said process (3) is a process of forming a coating film Bp by apply | coating the coating material which consists of PFA on coating film Ap.

The coating material in the step (3) may be a powder coating material containing particles containing PFA, or may be a liquid coating material such as an aqueous coating material, but a drying process is unnecessary and it is easy to obtain a thick coating film with a small number of coatings. In one point, it is preferable that it is powder coating material. In the case where the paint is a liquid paint, the particles comprising PFA are preferably dispersed in a liquid medium, and the particles containing PFA are aqueous coatings which are mainly dispersed in an aqueous medium containing water. It is more preferable.

It is preferable that the average particle diameter of the particle | grains which contain PFA in coating material is 0.01-40 micrometers when it is a liquid paint, and 1.0-50 micrometers when it is powder coating material.

The paint may contain a filler for the purpose of imparting properties, improving physical properties, increasing the amount of the coated article to be obtained. Examples of the properties and physical properties include strength, durability, weather resistance, flame retardancy, and designability. As said filler, what was mentioned above is mentioned.

The said coating material may also contain a small amount of PTFE (TFE homopolymer, modified PTFE) with PFA for the purpose of refine | purifying a spherical crystal. In this case, it is preferable to make content of PTFE into 0.01-10.0 mass% with respect to PFA.

Moreover, it is preferable that the said coating material does not contain a coloring pigment. Since a colored pigment is normally considered to be a cause of worsening corrosion resistance, if the said coating material does not contain a colored pigment, the coating goods obtained will have more excellent corrosion resistance and water vapor resistance.

It does not specifically limit as a method of apply | coating a coating material on the said coating film Ap, For example, the method similar to the method of application | coating of the coating composition (i) for primers mentioned above, etc. are mentioned. In the case where the paint is a powder paint, electrostatic coating is preferable.

The said coating film Bp may be formed by drying or baking as needed after the said application | coating. It is preferable to perform drying or baking in the said process (3) on the conditions similar to drying or baking in the said process (1). The said coating film Bp becomes a layer (B) in the coating article obtained.

The step (4) includes a substrate, a primer layer, a layer (A) and a layer (B) by firing a coating film laminate comprising a primer coating film, a coating film Ap and a coating film Bp. It is a process of forming the coating article which consists of.

It is preferable to perform baking in the said process (4) on the conditions similar to the baking in the said process (1)-(3).

The said manufacturing method may have a process of printing a letter, a drawing, etc. after the process (1) of forming the said primer coating film, or after the process (2) of forming the said coating film Ap. Said letters, figures, etc. are letters, a line, etc. which show the quantity of water, for example, when a coated article is a rice cooker.

It does not specifically limit as said printing method, For example, pad 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 coated article of the present invention can be used for applications utilizing non-tackiness, heat resistance, slipperiness, etc. of the fluorine-containing polymer, and for example, using non-tackiness, a frying pan, pressure pan, pan, grill pan, rice cooker, oven Cooking utensils such as hot plates, baking pans, kitchen knives, and gas tables; Kitchen appliances such as electric pots, ice trays, molds, and range hoods; Food industry components such as kneading rolls, rolling rolls, conveyors, and hoppers; Industrial articles such as rolls for office automation (OA), belts for OA, separation hooks for OA, paper rolls, and calender rolls for film production; Molds such as molds for molding foamed styrol, molds, molds for molds such as molds for producing plywoods and lacquers, industrial containers (especially for semiconductor industries), and tools using saws and saws. Household products such as irons, scissors, and kitchen knives; Sliding bearings such as metal foils, electric wires, food processors, packing machines, and textile machines; sliding parts for cameras and watches; automotive parts such as pipes, valves, and bearings; snow shovels, plows, chutes, and the like. Especially, it can use suitably for cooking utensils and kitchen utensils, and can use suitably for a rice cooker especially.

[Example]

Although an Example and a comparative example are given to the following and this invention is demonstrated to it in more detail, this invention is not limited only to these Examples. "%" And "part" represent the mass% and a mass part, respectively.

Preparation Example 1 Preparation of Polyethersulfone Resin Aqueous Dispersion

60 parts of polyether sulfone resin [PES] and 60 parts of deionized water which have a number average molecular weight of about 24000 were stirred for about 10 minutes, until the particle | grains which consist of PES are completely grind | pulverized in a ceramic ball mill. Subsequently, 180 parts of N-methyl-2-pyrrolidone (henceforth NMP) was added, and also it grind | pulverized for 48 hours and obtained the dispersion. The obtained dispersion was ground for 1 hour with a sand mill to obtain an PES aqueous dispersion having a PES concentration of about 20%. The average particle diameter of the particles including PES in the PES aqueous dispersion was 2 μm.

Preparation Example 2 Preparation of Polyamideimide Resin Aqueous Dispersion

Polyamideimide resin [PAI] varnish (containing 71% of NMP) having a solid content of 29% was added to water to precipitate PAI. This was pulverized for 48 hours in a ball mill to obtain an aqueous PAI dispersion. Solid content of the obtained PAI aqueous dispersion was 20%, and the average particle diameter of PAI in PAI aqueous dispersion was 2 micrometers.

Preparation Example 3 Preparation of Coating Composition (VII) for Primer

The PES aqueous dispersion obtained in Production Example 1 and the PAI aqueous dispersion obtained in Production Example 2 were mixed so that PES became 75% of the total solids content of PES and PAI, and to this tetrafluoroethylene homopolymer [TFE homopolymer] ] PES and PAI contain an aqueous dispersion (average particle diameter of 0.28 µm, solid content of 60%, and a polyether nonionic surfactant (polyoxyethylenetridecylether) 6% of the TFE homopolymer) as a dispersant, It is added so that it may become 25% of the total amount of solid content of PES, PAI, and a TFE homopolymer, methylcellulose is added as a thickener 0.7% with respect to the solid content of a TFE homopolymer, and a nonionic surfactant (polyoxyethylene nonyl phenyl ether) is a dispersion stabilizer. Was added 6% with respect to the solid content of the TFE homopolymer to obtain an aqueous dispersion having a solid content of the TFE homopolymer of 34%.

Example 1

After degreasing the surface of the aluminum plate (A-1050P) with acetone, the surface was roughened by sand blasting so that the surface roughness Ra value measured based on JISB1982 was set to 2.0-3.0 micrometers. After removing the dust of the surface by air blow, the coating composition for primers obtained in Production Example 3 was subjected to an RG-2 type gravity spray gun (trade name, manufactured by Anest Iwata Co., Ltd.) so that the dry film thickness was 10 µm. Spray coating was carried out using an injection pressure of 0.2 MPa using a nozzle diameter of 1.0 mm). The coating film on the obtained aluminum plate was dried for 15 minutes at 80-100 degreeC, and it cooled to room temperature. PFA (trade name: ACX-21, manufactured by Daikin Kogyo Co., Ltd., melt viscosity at 372 ° C at 6.5 × 10 3 Pa · s) and silicon carbide (3% of the total amount of PFA and silicon carbide) as a filler on the obtained primer coating film The powder coating material was electrostatically coated under conditions of an applied voltage of 50 kPa and a pressure of 0.08 MPa so that the film thickness after firing was 40 µm. The obtained coating plate was baked at 380 degreeC for 20 minutes, and the test coating plate was obtained. The obtained coating plate for test was a primer layer and the PFA layer (finish coating layer) formed on the aluminum plate.

(Measurement Method of Melt Viscosity of PFA)

Using a melt indexer manufactured by Daishinko Corp., Japan, a load of 5 kg was applied at 372 ° C., and the MFR (melt flow rate) was measured through an orifice having an internal diameter of 2.1 mm, and obtained according to ASTM D-1238.

(Assessment Methods)

The following evaluation was performed about the coating film of the obtained test plate. The evaluation results are shown in Table 1.

Film thickness

It measured using the high frequency film | membrane thickness meter (brand name: LZ-300C, Kette Kakuku Kyusho Co., Ltd. product).

Abrasion Resistance Test (Taver Type Abrasion Test)

The abrasion resistance of the obtained test plate was measured using a rotary abrasion tester manufactured by Toyo Seiki Seisakusho Co., Ltd. under a load of 1 kg and a wear wheel CS-10 under conditions of 500 revolutions.

Examples 2 and 3

A test coating plate was produced in the same manner as in Example 1 except that the types of fillers in the paint forming the PFA layer (finish coating layer) were changed to silicon nitride and alumina, respectively, and the coating film was evaluated. The results are shown in Table 1.

Example 4

A test plate was produced in the same manner as in Example 1 except that no filler was added to the paint forming the PFA layer (finish coating layer), and the coating film was evaluated. The results are shown in Table 1.

Example 5

After degreasing the surface of the aluminum plate (A-1050P) with acetone, the surface was roughened by sand blasting so that the surface roughness Ra value measured based on JISB1982 was set to 2.0-3.0 micrometers. After removing the dust of the surface by air blow, the coating composition for primers obtained in Production Example 3 was subjected to an RG-2 type gravity spray gun (trade name, manufactured by Anest Iwata Co., Ltd.) so that the dry film thickness was 10 µm. Spray coating was carried out at a spray pressure of 0.2 MPa using a nozzle diameter of 1.0 mm). The coating film on the obtained aluminum plate was dried for 15 minutes at 80-100 degreeC, and it cooled to room temperature. PFA (trade name: ACX-21, manufactured by Daikin Kogyo Co., Ltd., melt viscosity at 372 ° C at 6.5 × 10 3 Pa · s) and silicon carbide (3% of the total amount of PFA and silicon carbide) as a filler on the obtained primer coating film The powder coating material was electrostatically coated under conditions of an applied voltage of 50 kPa and a pressure of 0.08 MPa so that the film thickness after firing was 40 µm. Powder coating containing PFA (trade name: ACX-21) and diamond (1% of the total amount of PFA and diamond) as a filler was subjected to an applied voltage of 50 kPa and a pressure of 0.08 MPa so that the film thickness after baking was 5 µm. Electrostatic coating at. The obtained coating plate was baked at 380 degreeC for 20 minutes, and the test coating plate was obtained. As for the obtained test plate, the primer layer, the PFA layer (intermediate coating layer), and the PFA layer (finish coating layer) were formed on the aluminum plate.

The test coating plate obtained in Example 5 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Examples 6 and 7

A test coating plate was produced in the same manner as in Example 5 except that the types of fillers in the paint forming the PFA layer (intermediate coating layer) were changed to silicon nitride and alumina, respectively, and the coating film was evaluated. The results are shown in Table 1.

Example 8

The amount of filler in the paint forming the PFA layer (intermediate coating layer) is changed to 5% of the total amount of PFA and filler, the thickness of the PFA layer (intermediate coating layer) is changed to 10 μm, and the PFA layer ( A test coating plate was produced in the same manner as in Example 5 except that no filler was added to the coating material forming the finishing coating layer) and the thickness of the PFA layer (finishing coating layer) was changed to 40 μm, thereby evaluating the coating film. Was performed. The results are shown in Table 1.

Comparative Example 1

The coating material which forms a PFA layer (intermediate coating layer) is PFA (brand name: ACX-34, Daikin Kogyo Co., Ltd. make, melt viscosity at 372 degreeC 1.8 * 10 <^3> Pa.s), and a glass flake (PFA) as a filler. And the coating film for a test were produced like Example 8 except having changed into the powder coating material containing 1% of the total amount of glass flakes, and the coating film was evaluated. The results are shown in Table 1.

The

PFA powder coating material (brand name: ACX-34, Daikin Kogyo Co., Ltd. make, melt viscosity at 372 degreeC 1.8 * 10 ³ Pa.s) which does not contain filler for paint which forms PFA layer (finish coating layer) Except having changed into, the test coating plate was produced like Example 4, and the coating film was evaluated. The results are shown in Table 1.

Abbreviated-name in Table 1 is as follows.

Production Example 3: The coating composition (i) for the primer obtained in Production Example 3

ACX-21: Daikin Kogyo Co., Ltd. product, PFA powder coating material, melt viscosity at 372 ° C 6.5 × 10 ³ Pa.s

ACX-34: Daikin Kogyo Co., Ltd. product, PFA powder coating material, melt viscosity at 372 ° C 1.8 × 10 ³ Pa · s

Since the coated article of this invention has the structure mentioned above, it is especially excellent in abrasion resistance, and can be used especially suitably for cooking utensils, kitchen utensils, etc.

Claims (12)

Base materials,
A coated article having a layer formed of PFA having a melt viscosity at 372 ° C. of 4.0 × 10 ³ to 100.0 × 10 ³ Pa · s. A substrate,
Layer (A) formed of PFA,
A coated article having a layer (B) formed of PFA,
The coated article characterized by the melt viscosity in 372 degreeC of either or both PFA which comprises a layer (A) and a layer (B) being 4.0 * 10 <^3> -100.0 * 10 <^3> Pa * s. The method of claim 1,
The coated article in which the layer formed from PFA whose melt viscosity in 372 degreeC is 4.0 * 10 <^3> -100.0 * 10 <^3> Pa * s contains a filler. 3. The method of claim 2,
A coated article in which one or both of layers (A) and (B) comprise a filler. The method according to claim 3 or 4,
The filler is at least one member selected from the group consisting of silicon carbide, silicon nitride, alumina, diamond and fluorinated diamond. 5. The method according to any one of claims 1 to 4,
A coated article further having a primer layer. The method according to claim 6,
The primer layer contains a fluoropolymer (a) and heat resistant resin. 8. The method of claim 7,
The heat resistant resin is at least one coating selected from the group consisting of polyamideimide resin, polyimide resin, polyethersulfone resin, polyetherimide resin, polyetheretherketone resin, aromatic polyester resin and polyarylene sulfide resin article. 9. The method of claim 8,
The heat resistant resin comprises a polyether sulfone resin and at least one resin selected from the group consisting of polyamideimide resins and polyimide resins,
The polyether sulfone resin is 65 to 85 mass% of the total amount of polyether sulfone resin and at least 1 sort (s) of resin chosen from the group which consists of a polyamideimide resin and a polyimide resin. 8. The method of claim 7,
The heat resistant resin is 15-50 mass% of solid content total amount of a heat resistant resin and a fluoropolymer (a). 8. The method of claim 7,
Fluorine-containing polymers (a) include tetrafluoroethylene homopolymers, modified polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymers and tetrafluoroethylene / perfluoro (alkylvinylether) copolymers The coated article which is at least 1 sort (s) chosen from the group which consists of the following. The method according to claim 6,
The coated article has a thickness of the primer layer of 5 to 30 µm, a thickness of the layer (A) of 1 to 90 µm, and a thickness of the layer (B) of 1 to 90 µm.