KR100674521B1 - Method of Forming Layered Fluororesin Product and Coated Article - Google Patents

Abstract

The present invention provides a fluorine-containing laminate, a method for forming the same, and a coated article, which are excellent in corrosion resistance, water vapor resistance, and abrasion resistance, and can stably express filler characteristics such as brilliance even in mass production. The fluorine-containing laminate includes a primer layer (A) containing a fluorine-containing polymer (a) and a heat resistant resin, a fluorine-containing layer (B) containing a melt-processable fluorine-containing polymer (b) and a filler, and a melt-processable fluorine-containing polymer ( A fluorine-containing laminate having a fluorine-containing layer (C) containing c), wherein the primer layer (A), the fluorine-containing layer (B) and the fluorine-containing layer (C) are laminated in this order.

Fluorine-containing laminate, filler, primer layer, heat resistant resin, coated article, water vapor resistance, corrosion resistance

Description

Method of Forming Fluorine-Containing Laminates, and Coated Articles {Method of Forming Layered Fluororesin Product, and Coated Article}

The present invention relates to a fluorine-containing laminate, a method of forming a fluorine-containing laminate, and a coated article.

Fluorine-containing polymers such as tetrafluoroethylene / perfluoro (alkylvinylether) 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.

Surface processing is performed by forming the layer containing a fluorine-containing polymer on a base material, but if the fluorine-containing polymer to be used is 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 Various characteristics which a fluoropolymer has can be exhibited easily.

However, the fluorine-containing polymer lacks adhesion with the substrate due to its non-adhesiveness. For the purpose of this adhesiveness improvement, the laminated body which has the primer layer obtained by apply | coating the primer which mix | blended binder resin, such as heat resistant resin, and a fluorine-containing polymer previously on a base material as an undercoat, and the layer containing a fluorine-containing polymer is proposed.

Such a laminated body may add the filler at the time of formation for the purpose of providing designability, strength improvement, etc., For example, when the brightness is required as designability, the brightness filler is added.

As a laminated body which has a bright feeling, there exists a laminated body of the 2-layered structure of the primer layer which added mica as a bright filler, and the uppermost coating layer containing PFA formed on it. However, the above laminate had a problem that mica was likely to settle in the primer layer, and the brightness was insufficient.

In order to solve this problem, it has been proposed to use aluminum powder instead of mica as the bright filler, but aluminum powder is more likely to settle than mica, and not only the brightness of the laminate obtained when mass produced is unstable, but also adversely affects corrosion resistance. There was a problem of going crazy.

As a laminate having stable brilliance and excellent corrosion resistance, a layer containing polytetrafluoroethylene [PTFE] and mica is used as an intermediate layer, and a primer layer containing a binder resin and a fluorine-containing polymer is provided thereunder, and PFA is included. There is a laminate having a three-layer structure in which an uppermost coating layer is formed using a powder coating material (for example, Japanese Patent Laid-Open No. 7-111946 (pages 1 to 3) and Japanese Patent No. 2593043 (1 to 3). Page).

Brightness is stabilized even when this laminated body is mass-produced. However, when the article containing this laminated body and a base material is used for kitchen appliances, such as a pot, water vapor resistance is inadequate and there exists a possibility that blister may generate | occur | produce by water vapor.

Among the laminates to which the filler is added during formation, a primer layer using aluminum oxide as a filler is formed on the substrate as having excellent scratch resistance, and a melt-processing fluorine-containing polymer such as PFA, PTFE and aluminum oxide are formed on the primer layer. The intermediate | middle layer containing these is formed, and the uppermost coating layer containing PTFE is formed on this intermediate | middle layer (for example, refer the Unexamined-Japanese-Patent No. 2644380 specification (p. 1-4)).

However, since the laminate has a possibility of precipitation of aluminum oxide in the primer layer, adversely affects the corrosion resistance of the substrate, and since the uppermost coating layer contains PTFE, it is not easy to obtain a thick layer by a general industrial production method. There existed a problem that durability, such as abrasion resistance, fell.

SUMMARY OF THE INVENTION In view of the above-mentioned phenomenon, an object of the present invention is to provide a fluorine-containing laminate, a method for forming the same, and a coated article, which are excellent in corrosion resistance, water vapor resistance, and abrasion resistance, and can stably express properties of fillers such as brightness even during mass production. To provide.

The present invention provides a primer layer (A) containing a fluorine-containing polymer (a) and a heat resistant resin, a fluorine-containing layer (B) containing a melt-processable fluorine-containing polymer (b) and a filler, and a melt-processable fluorine-containing polymer (c). A fluorine-containing laminate having a fluorine-containing layer (C) to be included, wherein the primer layer (A), the fluorine-containing layer (B) and the fluorine-containing layer (C) are laminated in this order.

The present invention provides a method for forming a fluorine-containing laminate for forming the fluorine-containing laminate, comprising: (1) applying a coating composition for a primer containing a fluorine-containing polymer (a) and a heat resistant resin onto a substrate; (2) forming a fluorine-containing coating film (Bp) by applying a filler-containing liquid composition containing a melt-processable fluorine-containing polymer (b) and a filler onto the primer coating film (Ap). (3) forming a fluorine-containing film (Cp) by applying a fluorine-containing powder containing a melt-processing fluorine-containing polymer (c) on the fluorine-containing coating film (Bp), and (4) the primer coating film (Ap), a step of forming the fluorine-containing laminate by firing a coating film laminate comprising the fluorine-containing coating film (Bp) and the fluorine-containing film (Cp). Formation method.

The present invention will be described in detail below.

The fluorine-containing laminate of the present invention includes a primer layer (A) containing a fluorine-containing polymer (a) and a heat resistant resin, a fluorine-containing layer (B) containing a melt-processable fluorine-containing polymer (b) and a filler, and melt-processable fluorine. Having a fluorine-containing layer (C) containing a containing polymer (c), the said primer layer (A), a fluorine-containing layer (B), and a fluorine-containing layer (C) are laminated | stacked in this order.

The fluorine-containing laminated body of this invention does not contain the base material mentioned later.

It is preferable to form the said primer layer (A) in the fluorine-containing laminated body of this invention on a base material. The said primer layer (A) is obtained by apply | coating on the base material the coating composition for primers mentioned later containing a fluoropolymer (a) and heat resistant resin, drying as needed, and then baking. Since the primer layer (A) has a difference in surface tension between the fluorine-containing polymer (a) and the heat-resistant resin, the fluorine-containing polymer (a) floats during firing, and the fluorine-containing polymer (a) is mainly used on the surface side which is far from the substrate. A containing polymer (a) is arrange | positioned and the said heat resistant resin is arrange | positioned mainly in a base material side.

The said primer layer (A) is excellent in adhesiveness with respect to a base material because the said heat resistant resin has adhesiveness with a base material. Moreover, since the said primer layer (A) has affinity with the melt-processable fluorine-containing polymer (b) which the said fluorine-containing polymer (a) mentions later, it is excellent in adhesiveness with the fluorine-containing layer (B) mentioned later. Thus, the said primer layer (A) has the outstanding adhesiveness with respect to both a base material and a fluorine-containing layer (B).

The said primer layer (A) contains a fluoropolymer (a) and heat resistant resin.

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

The said fluoropolymer (a) is obtained by superposing | polymerizing a fluorine-containing monoethylenically unsaturated hydrocarbon (I).

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

In the unsaturated hydrocarbon (I), some 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. It may have been done. However, the said unsaturated hydrocarbon (I) excludes trifluoroethylene mentioned 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., These can use 1 type (s) or 2 or more types.

The fluorine-containing polymer (a) may be a homopolymer of the 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.

The fluorine-containing polymer (a) may be a copolymer of one or more of the above unsaturated hydrocarbons (I) and an unsaturated compound (II) capable of copolymerizing with the above unsaturated hydrocarbons (I).

The unsaturated compound (II) does not use a polymer obtained by polymerizing only one or two or more unsaturated compounds (II) as the fluorine-containing polymer (a), and the unsaturated hydrocarbon (I) is one or two or more of the above-mentioned compounds. The polymer obtained by polymerizing only unsaturated hydrocarbon (I) can be used as said fluorine-containing polymer (a), and is different from the said unsaturated hydrocarbon (I).

It does not specifically limit as said unsaturated compound (II), For example, trifluoroethylene [3FH]; And monoethylenically unsaturated hydrocarbons having no halogen atoms such as ethylene [Et] and propylene [Pr]. These can use 1 type (s) or 2 or more types.

In addition, the said fluoropolymer (a) may be a copolymer of 2 or more types of said unsaturated hydrocarbons (I). It does not specifically limit as a copolymer of the said 2 or more types of unsaturated hydrocarbon (I), and the said 1 or more types of unsaturated hydrocarbon (I) and an unsaturated compound (II), For example, a binary copolymer and a ternary copolymer Etc. can be mentioned.

It does not specifically limit as said binary copolymer, For example, a VdF / HFP copolymer, an Et / CTFE copolymer [ECTFE], an Et / HFP copolymer, etc. are mentioned. In addition, the binary copolymer may 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 TFE and 1 type, or 2 or more types of 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 exceeds 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 another monomer 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 represented by 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, and n is A compound represented by an integer of 0 or 1, except HFP, wherein the formula C ₃ F ₇ O [CF (CF ₃ ) CF ₂ O] _p -CF = CF ₂ , wherein p is 1 Or a compound represented by an integer of 2, or a chemical formula X (CF ₂ ) _q CY = CH ₂ , wherein X is the same as above, Y represents -H or -F, and q is 1 to 6 Represents an integer of). These can use 1 type (s) or 2 or more types.

As such a TFE type copolymer, TFE / perfluoro (alkyl vinyl ether) [PAVE] copolymer [PFA] etc. are mentioned, for example.

In addition, the said fluoropolymer (a) may be modified polytetrafluoroethylene [modified PTFE]. In this specification, said "modified PTFE" means what is achieved by copolymerizing a small amount of comonomer with TFE so that melt processability is not provided 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, and the like. 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 comonomer are usually It is preferable that it is 0.001-1 mass% of total mass.

The fluorine-containing polymer (a) may be one kind or two or more kinds, a mixture of one kind or two or more kinds of the homopolymer of the unsaturated hydrocarbon (I) and a copolymer of the unsaturated hydrocarbon (I), or A mixture of two or more kinds of copolymers of the above unsaturated hydrocarbons (I) may be used.

As said mixture, the mixture of a TFE homopolymer and the said TFE copolymer, the mixture of 2 or more types of copolymers which belong to the said TFE copolymer, etc. are mentioned, For example, as such a mixture, a TFE homopolymer is mentioned, for example. 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.

In addition, the said fluoropolymer (a) may be obtained by superposing | polymerizing the perfluoroalkyl group containing ethylenically unsaturated monomer (IV) (henceforth "unsaturated monomer (IV)") which has a perfluoroalkyl group. The unsaturated monomer (IV) is represented by the following formula.

In the formula, 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 (IV), and may be a copolymer of the said unsaturated monomer (IV) and the monomer (V) copolymerizable with this.

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, (alpha) -methylstyrene, and p-methylstyrene; 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 and derivatives thereof such as maleic anhydride; 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 fluoropolymer (a), a TFE homopolymer, a modified PTFE, and the said TFE type copolymer are preferable at the point that the fluorine-containing laminated body obtained is excellent in corrosion resistance and water vapor resistance. As said TFE type copolymer, FEP and PFA are preferable.

As said fluoropolymer (a), TFE homopolymer, modified PTFE, FEP, and / or PFA are more preferable.

As said fluoropolymer (a), it is more preferable to contain a TFE type copolymer from the point which is excellent in adhesiveness of the primer layer (A) obtained and the fluorine-containing layer (B) mentioned later. Since the fluorine-containing laminate having excellent adhesion between the primer layer (A) and the fluorine-containing layer (B) described later has excellent water vapor resistance, generation of coating film defects such as blisters can be suppressed even in the presence of water vapor. Examples of the fluorine-containing polymer (a) comprising a TFE copolymer include, for example, PFA alone, a mixture of TFE homopolymers and FEP, a mixture of TFE homopolymers and PFA, a mixture of modified PTFE and FEP, and a mixture of modified PTFE and PFA. Etc. can be mentioned.

As a fluorine-containing polymer (a) in a primer layer (A), the obtained fluorine-containing laminated body is excellent in corrosion resistance and water vapor resistance, and the said primer layer (A) is excellent in adhesiveness to the fluorine-containing layer (B) mentioned later. PFA alone, a mixture of TFE homopolymer and PFA, a mixture of TFE homopolymer and FEP are preferred, and a mixture of TFE homopolymer and FEP is more preferred.

The said primer layer (A) contains heat resistant resin with the fluorine-containing polymer (a) mentioned above.

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

It does not specifically limit as said heat resistant resin, For example, polyamideimide resin, polyimide resin, polyether sulfone resin, polyetherimide resin, polyether ether ketone resin, aromatic polyester resin, polyarylene sulfide resin, etc. are mentioned. Can be. 1 type (s) or 2 or more types can be used as said heat resistant resin.

The polyamideimide resin [PAI] is a resin containing 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 molecule, 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; Resin containing 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, etc. are mentioned. As said PAI, it is preferable to include the polymer which has an aromatic ring in a principal chain from the point which is excellent in heat resistance.

The said polyimide resin [PI] is resin containing the polymer which has an imide bond in molecular structure. It does not specifically limit as said PI, For example, resin containing 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, it is preferable to include the polymer which has an aromatic ring in a principal chain.

The polyether sulfone resin [PES] is a resin containing a polymer having a repeating unit represented by the following formula. It does not specifically limit as said PES, For example, resin containing the polymer obtained by polycondensation of dichlorodiphenyl sulfone and bisphenol is mentioned.

The heat resistant resin is excellent in adhesion to the substrate, and has sufficient heat resistance even under the temperature at the time of firing when forming the fluorine-containing laminate, and the resulting fluorine-containing laminate is excellent in corrosion resistance and water vapor resistance, so that it is PAI, PI. And / or PES is preferred. The term "PAI, PI and / or PES" means PAI alone, PI alone, PES alone, a mixture of PAI and PI, a mixture of PES and PAI, a mixture of PES and PI, and a mixture of PES, PAI and PI. .

PAI, PI and PES may be one or two or more kinds each.

As said heat resistant resin, PAI and / or PI are more preferable at the point which is excellent in adhesiveness with a base material, and heat resistance. Said "PAI and / or PI" means PAI alone, PI alone, or a mixture of PAI and PI.

As said heat resistant resin, PES, PAI, and / or PI are more preferable at the point which is excellent in corrosion resistance and water vapor resistance. "PES and PAI and / or PI" means a mixture of PES and PAI, a mixture of PES and PI, or a mixture of PES and PAI and PI. It is particularly preferable that the heat resistant resin is a mixture of the PES and the PAI.

In the said primer layer (A), it is preferable that the said PES is 65-85 mass% of the total amount of PES and PAI and / or PI.

The said primer layer (A) contains the said fluoropolymer (a) and heat resistant resin, It is preferable that the said heat resistant resin is 15-50 mass% of the total amount of solid content of a heat resistant resin and a fluorine-containing polymer (a).

The said primer layer (A) mainly contains a polymer component and the additives mentioned later. It is preferable that a polymer component of the said primer layer (A) is a fluorine-containing polymer (a) and heat resistant resin. In the present specification, the "primer layer (A) is a polymer component is a fluorine-containing polymer (a) and a heat resistant resin '' means that the polymer in the primer layer (A) is only a fluorine-containing polymer (a) and a heat resistant resin. it means. Since the said polymer component is a fluorine-containing polymer (a) and heat resistant resin, the said primer layer (A) efficiently has the adhesiveness outstanding with respect to both a base material and the fluorine-containing layer (B) mentioned later.

The primer layer (A) is preferably a fluorine-containing polymer (a) and a heat resistant resin in view of efficiently having excellent adhesion to both the substrate and the fluorine-containing layer (B) described later. It is also possible to further include other resin together with the fluorine-containing polymer (a) and the heat resistant resin in that the corrosion resistance and water vapor resistance of the resin can be further improved.

It does not specifically limit as said other resin, For example, 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. can be mentioned. As said other resin, since it is obtained by baking the fluorine-containing laminated body of this invention, it is preferable that it is heat resistant.

The fluorine-containing laminate of the present invention has a fluorine-containing layer (B) containing a melt processable fluorine-containing polymer (b) and a filler.

In the fluorine-containing laminate of the present invention, the fluorine-containing layer (B) is formed on the primer layer (A). In the said fluorine-containing layer (B), the fluorine-containing layer (C) mentioned later is laminated | stacked on it.

The said melt processable fluoropolymer (b) has melt processability in the polymer which has a fluorine atom directly bonded to the carbon atom which comprises a main chain or a side chain.

As said melt processable fluoropolymer (b), the thing which has melt processability in the above-mentioned fluoropolymer (a) can be used. The said melt-processable fluoropolymer (b) is excellent in adhesiveness of the said fluorine-containing layer (B) with the primer layer (A) mentioned above, and the fluorine-containing layer (C) mentioned later, and the fluorine-containing laminated body obtained has corrosion resistance and water vapor resistance. It is preferable that it has melting | fusing point of 150-350 degreeC from the point which is excellent, and melt viscosity at temperature 50 degreeC higher than melting | fusing point is 10 ⁶ (Pa * sec) or less, and it is preferable that it is the above-mentioned TFE type copolymer. The melt-processable fluorine-containing polymer (b) may be one kind or two or more kinds. As for the said melt processable fluoropolymer (b), it is more preferable that it is PFA and / or FEP. Said "PFA and / or FEP" means that PFA or FEP may be individual, or a mixture thereof may be sufficient as it. The melt-processable fluorine-containing polymer (b) is more preferably PFA in terms of excellent heat resistance.

The said fluorine-containing layer (B) contains a filler with the said melt-processable fluoropolymer (b).

In this specification, said "filler" is used for the purpose of providing the characteristic, the physical property improvement, the increase, etc. with respect to the fluorine-containing laminated body obtained, and means that it does not melt | dissolve in the liquid medium in the filler containing composition mentioned later. Examples of the above properties and physical properties include strength, durability, weather resistance, flame retardancy, and the like.

It does not specifically limit as said filler, For example, wood powder, quartz sand, carbon black, clay, talc, a sieving pigment, a bright flat pigment, a scaly pigment, glass, various reinforcing materials, various extenders, a conductive filler, etc. are mentioned. . As the filler, when the fluorine-containing laminate of the present invention is required to have brightness, a brightness filler is preferable. Said "bright filler" is a filler which can give a bright feeling to the fluorine-containing laminated body obtained.

As said bright filler, what is classified as a bright flat pigment, a scaly pigment, glass, etc. are mentioned, These can be used 1 type (s) or 2 or more types. It does not specifically limit as what is classified into the said bright flat pigment and scale-like pigment, For example, a mica, a metal powder, etc. are mentioned. It does not specifically limit as said glass, For example, glass beads, glass bubbles, glass flakes, glass fiber, etc. are mentioned. 1 type (s) or 2 or more types can be used for the thing classified into the said brightness | luminance flat pigment, a scaly pigment, and glass, respectively.

As the filler, a bright filler containing mica, metal powder and / or glass beads is more preferable. Such bright fillers may include mica, metal powder and / or glass beads, and may be mica, metal powder and / or glass beads only, and mica, metal powder and / or glass beads and fluorine-containing laminates. It may be another filler that can impart a sense of brightness to the film. The term "mica, metal powder and / or glass beads" means mica alone, metal powder alone, glass beads alone, a mixture of mica and metal powder, a mixture of mica and glass beads, or a mixture of metal powder and glass beads. it means.

In general, although mica, metal powder and glass may not be able to impart brightness to the resulting fluorine-containing laminate, mica in the `` bright filler comprising mica, metal powder and / or glass beads '', Metal powder and / or glass beads can give a brightness.

It does not specifically limit as said metal powder, For example, powder of metal single bodies, such as aluminum, iron, coal, zinc, copper; Alloy powders, such as an aluminum alloy and stainless steel, etc. are mentioned. The shape of the metal powder is not particularly limited, and examples thereof include particulate, flaky, and the like, but flaky is preferable because of its excellent brightness.

The filler is more preferably a bright filler containing mica and / or aluminum powder in that it is excellent in brightness and economy. Examples of such bright fillers include mica alone, aluminum powder alone, or a mixture of mica and aluminum powder. As a shape of the said aluminum powder, flaky shape is preferable. It is particularly preferable that the filler is a bright filler containing mica in that the resulting fluorine-containing laminate has excellent corrosion resistance.

In the said fluorine-containing layer (B), it is preferable that the said filler is 0.001-10 mass% with respect to solid content of a melt-processable fluoropolymer (b). If it is less than 0.001 mass%, when the said fluorine-containing layer (B) contains the filler which can give a glossiness, the brightness of the obtained fluorine-containing laminated body will be inadequate, and if it exceeds 10 mass%, corrosion resistance and water vapor resistance will be There is a risk of deterioration. The minimum with preferable is 0.01 mass%, and a preferable upper limit is 5 mass%.

The said fluorine-containing layer (B) mainly contains a polymer component, a filler, and the additives mentioned later. It is preferable that a polymer component of the said fluorine-containing layer (B) is a melt-processable fluoropolymer (b). In the present specification, the "fluorine-containing layer (B)" means that the polymer component is a melt-processable fluorine-containing polymer (b), that the polymer in the fluorine-containing layer (B) is only a melt-processable fluorine-containing polymer (b). Since the said polymer component is a melt processable fluorine-containing polymer (b), the said fluorine-containing layer (B) has the adhesiveness excellent in both the said primer layer (A) and the fluorine-containing layer (C) mentioned later efficiently.

The fluorine-containing laminate of the present invention has a fluorine-containing layer (C) containing a melt processable fluorine-containing polymer (c).

In the fluorine-containing laminate of the present invention, the fluorine-containing layer (C) is formed on the above-described fluorine-containing layer (B). The fluorine-containing layer (C) may be a coating film formed on the fluorine-containing layer (B), or may be a molded article such as a film or a sheet. In any case, the temperature is higher than the melting point of the melt-processable fluorine-containing polymer (c). It is fired by. It is preferable that the said fluorine-containing layer (C) is a coating film formed on the fluorine-containing layer (B) from the point which is excellent in adhesiveness with a fluorine-containing layer (B).

The said melt processable fluoropolymer (c) has melt processability in the polymer which has a fluorine atom directly bonded to the carbon atom which comprises a main chain or a side chain.

As said melt-processable fluoropolymer (c), what has melt-processability in the above-mentioned fluoropolymer (a) can be used. The melt-processable fluorine-containing polymer (c) is the same as the melt-processable fluorine-containing polymer (b) in that it has melt processability in the above-described fluorine-containing polymer (a), but in that it is in the fluorine-containing layer (C). It differs from the said melt processable fluorine-containing polymer (b) which is in a fluorine-containing layer (B).

As said melt processable fluoropolymer (c), it is excellent in film formability, the fluorine-containing layer (C) is excellent in adhesiveness to the above-mentioned fluorine-containing layer (B), and the obtained fluorine-containing laminate has corrosion resistance and water vapor resistance. The same thing as the said melt-processable fluoropolymer (b) etc. is mentioned from the point which is excellent, Among these, it has a melting | fusing point of 150-350 degreeC, and melt viscosity in temperature 50 degreeC higher than melting | fusing point is 10 ⁶ (Pa *). It is preferable that it is below), and TFE type copolymer is mentioned as such. As the melt-processable fluorine-containing polymer (c), PFA and / or FEP are preferable in terms of excellent heat resistance, non-tackiness, and film formability. Said "PFA and / or FEP" means PFA alone, FEP alone, and a mixture of PFA and FEP. As the melt processable fluorine-containing polymer (c), PFA is more preferable because it is more excellent in heat resistance.

It is preferable that the said fluorine-containing layer (C) is a transparent layer, when the obtained fluorine-containing laminated body is required to have designability, such as a glossiness. If the said fluorine-containing layer (C) is a transparent layer, since the filler in the said fluorine-containing layer (B) can be confirmed through a fluorine-containing layer (C), when using what has brightness as a filler, the fluorine-containing laminated body of this invention is favorable. It has a bright feeling.

Moreover, if the said fluorine-containing layer (C) is a transparent layer, since the said fluorine-containing layer (C) does not have the coloring pigment normally considered to be a cause of deteriorating corrosion resistance, the obtained fluorine-containing laminated body has more excellent corrosion resistance and water vapor resistance. Have

The said fluorine-containing layer (C) mainly contains a polymer component and the additives mentioned later. It is preferable that a polymer component of the said fluorine-containing layer (C) is a melt processable fluoropolymer (c). In this specification, the said "fluorine-containing layer (C) means that a polymer component is a melt-processable fluorine-containing polymer (c)" means that the polymer in a fluorine-containing layer (C) is only a melt-processable fluorine-containing polymer (c). Since the said polymer component is a melt processable fluoropolymer (c), the said fluorine-containing layer (C) has the adhesiveness outstanding with respect to the said fluorine-containing layer (B).

In the fluorine-containing laminate of the present invention, the primer layer (A) preferably has a thickness of 5 to 30 µm. If it is less than 5 micrometers, a pinhole will generate easily and there exists a possibility that the corrosion resistance of a fluorine-containing laminated body may fall. When it exceeds 30 micrometers, a crack will occur easily and there exists a possibility that the water vapor resistance of a fluorine-containing laminated body may fall. The upper limit with preferable film thickness of the said primer layer (A) is 20 micrometers.

In the fluorine-containing laminate of the present invention, the fluorine-containing layer (B) preferably has a film thickness of 5 to 30 µm. When it is less than 5 micrometers, when the filler which has brightness is used in order to provide brightness to a fluorine-containing laminated body, the brightness of the obtained fluorine-containing laminated body may be inadequate. When it exceeds 30 micrometers, a crack will arise easily in a fluorine-containing layer (B), and there exists a possibility that the water vapor resistance of a fluorine-containing laminated body may fall. The minimum with preferable film thickness of the said fluorine-containing layer (B) is 10 micrometers, and a preferable upper limit is 20 micrometers.

In the fluorine-containing laminate of the present invention, the fluorine-containing layer (C) preferably has a film thickness of 10 to 90 µm. If it is less than 10 micrometers, a pinhole will produce easily and there exists a possibility that the corrosion resistance and abrasion resistance of a fluorine-containing laminated body may fall. When it exceeds 90 micrometers, when a fluorine-containing laminated body exists in water vapor | steam, water vapor may easily remain in a fluorine-containing laminated body, and water vapor resistance may be inferior. The minimum with preferable film thickness of the said fluorine-containing layer (C) is 30 micrometers, and a preferable upper limit is 70 micrometers.

In the fluorine-containing laminate of the present invention, the primer layer (A), the fluorine-containing layer (B), and the fluorine-containing layer (C) are laminated in this order. In the fluorine-containing laminate of the present invention, as long as the primer layer (A), the fluorine-containing layer (B) and the fluorine-containing layer (C) are laminated in this order, the upper surface of the primer layer (A), and / or the fluorine Printing such as letters and drawings may be performed on the upper surface of the containing layer (B).

In addition, the fluorine-containing laminate of the present invention may be one having the primer layer (A), the fluorine-containing layer (B) and the fluorine-containing layer (C) as described above, and further a layer is formed on the fluorine-containing layer (C). It may be installed.

In the fluorine-containing laminate of the present invention, as described above, the fluorine-containing layer (B) formed on the primer layer (A) contains a melt processable fluorine-containing polymer (b) and a filler, and is on the fluorine-containing layer (B). The fluorine-containing layer (C) formed in the layer contains a melt processable fluorine-containing polymer (c).

The fluorine-containing laminate of the present invention is excellent in adhesion between the fluorine-containing layer (B) and the fluorine-containing layer (C) because both the melt-processable fluorine-containing polymer (b) and the melt-processable fluorine-containing polymer (c) are melt-processable. It is excellent in corrosion resistance and water vapor resistance. Although a laminate in which a conventional primer layer, an intermediate layer containing a TFE homopolymer, and a top coating layer containing PFA are laminated in this order has a problem of poor water vapor resistance, this problem is caused by the separation between the primer layer and the intermediate layer. It is considered to be due to the easy. The peeling is due to the difference in thermal expansion rate and thermal shrinkage rate of the TFE homopolymer and PFA, and internal stress (strain) is likely to remain in the intermediate layer and the top coating layer, or pinholes are easily generated. It is thought to occur easily.

As described above, the fluorine-containing laminate of the present invention is excellent in adhesion between the fluorine-containing layer (B) and the fluorine-containing layer (C), and excellent in corrosion resistance and water vapor resistance, and also excellent in wear resistance.

Moreover, since the said filler can be disperse | distributed uniformly in a fluorine-containing layer (B), the fluorine-containing laminated body of this invention is excellent in brightness when using what has brightness as a filler. Moreover, since the filler does not contact a base material, the fluorine-containing laminated body of this invention is excellent in corrosion resistance even when the above-mentioned metal powder is used as a filler.

The formation method of the fluorine-containing laminated body of this invention is for forming the above-mentioned fluorine-containing laminated body, The primer is apply | coated on (i) base material by apply | coating the coating composition for primers containing a fluorine-containing polymer (a) and heat resistant resin. Forming a coating film Ap, (ii) forming a fluorine-containing coating film Bp by applying a filler-containing composition containing a melt-processable fluorine-containing polymer (b) and a filler on the primer coating film Ap. And (iii) forming a fluorine-containing film (Cp) on the fluorine-containing coating film (Bp) using a melt-processing fluorine-containing composition containing a melt-processing fluorine-containing polymer (c) to form a fluorine-containing laminate. It includes the process of forming.

In the said process (i), the said coating composition for primers contains a fluoropolymer (a) and heat resistant resin. The coating composition for primers may be a liquid or powder. When the said coating composition for primers is a liquid, it contains a liquid medium with a fluoropolymer (a) and heat resistant resin. The liquid medium usually contains water and / or an organic liquid. In this specification, said "organic liquid" is an organic compound and means that it is a liquid at normal temperature about 20 degreeC.

When the liquid medium of the coating composition for the primer is mainly an organic liquid, the heat resistant resin and the fluorine-containing polymer (a) are dispersed as particles in the liquid medium and / or dissolved in the liquid medium. will be. It does not specifically limit as said organic liquid, For example, nitrogen-containing organic liquids, such as N-methyl- 2-pyrrolidone, 2-pyrrolidone, N, N- dimethylacetamide; Aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene, methylethylbenzene, propylbenzene and butylbenzene; Saturated hydrocarbon solvents having 6 to 12 carbon atoms; lactones such as γ-butyrolactone; Acyclic esters such as butyl acetate; Ketones such as methyl isobutyl ketone and methyl ethyl ketone; Glycols such as ethylene glycol, triethylene glycol and propylene glycol; Glycol ethers such as butyl cellosolve; Monoalcohols, such as 1-butanol and diacetone alcohol, etc. are mentioned.

As said aromatic hydrocarbon solvent, the commercially available solvose 100, solvose 150, solvose 200 (all are brand names, Exxon Chemical Co., Ltd. product) etc. can also be used. As the saturated hydrocarbon solvent, commercially available mineral spirits (Japanese Industrial Standard, Industrial Gasoline No. 4) and the like can also be used.

The said organic liquid may be used independently and may use 2 or more types together.

When the liquid medium of the coating composition for the primer is mainly water, the heat resistant resin is dispersed as particles in the liquid medium or dissolved in the liquid medium, and the fluorine-containing polymer (a) is the liquid Dispersed as particles in the medium.

When the said liquid medium mainly contains water, the said coating composition for primers consists of adding surfactant for the purpose of dispersion-stabilizing the particle | grains containing a fluorine-containing polymer (a) normally. It does not specifically limit as said surfactant, For example, Nonionic surfactant, such as a fluorine-containing nonionic surfactant; Anionic surfactants such as fluorine-containing anionic surfactants; And cationic surfactants such as fluorine-containing cationic surfactants. The said coating composition for primers can also use together the said organic liquid with the said surfactant for the purpose of dispersion-stabilizing the particle | grains containing a fluoropolymer (a).

In addition, the coating composition for primers is a method described in JP-A-49-17017, that is, a dispersoid is particles containing the fluorine-containing polymer (a) and particles containing a heat resistant resin, and a dispersion medium The organic solvent which is a full-layer liquid, and a whole-layer agent are added to the aqueous dispersion whose water mainly contains water, and the particle | grains containing the said fluoropolymer (a) and the particle | grains containing heat resistant resin are made into the said organic dispersion. It may be an organosol obtained by a method of layering on a solvent.

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

When the coating composition for primers is a liquid, the viscosity of the coating composition for primers is preferably 0.1 to 50000 mPa · s. If it is less than 0.1 mPa · s, sagging or the like is liable to occur during application onto the substrate, and it may be difficult to obtain a target film thickness. If it exceeds 50000 mPa · s, the coating workability may deteriorate. The film thickness of the primer coating film Ap obtained may not become uniform, and surface smoothness etc. may fall. The minimum with more preferable is 1 mPa * s, and a more preferable upper limit is 30000 mPa * s.

In the said coating composition for primers, it is preferable that the said fluoropolymer (a) is 0.01-5 micrometers in average particle diameter. When the said heat resistant resin is disperse | distributed as particle | grains in the said coating composition for primers, it is preferable that the average particle diameter is 0.5-8 micrometers.

In the coating composition for primers, PES, PAI and / or PI are preferable as described above for the primer layer (A) of the fluorine-containing laminate as the heat resistant resin, and PAI and / or PI are more preferred. PES and PAI and / or PI are more preferred.

In the coating composition for primers, the PES is preferably 65 to 85 mass% of the total amount of PES and PAI and / or PI. If it is less than 65 mass%, there exists a possibility that the water vapor resistance of the fluorine-containing laminated body obtained may fall, and when it exceeds 85 mass%, there exists a possibility that corrosion resistance may fall.

The ratio of the PES is substantially the same ratio in the primer layer (A) of the fluorine-containing laminate, because the above-mentioned heat-resistant resin is not decomposed even in the sintering performed during the formation of the fluorine-containing laminate as described later.

In the coating composition for primers, the heat resistant resin is preferably 15 to 50% by mass of the total amount of solids of the heat resistant resin and the fluorine-containing polymer (a).

In this specification, said "solid content" means a solid at 20 degreeC.

In this specification, said "the total amount of solid content of a 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 or less, and 45 to 380-400 degreeC. It means the total mass of the said heat resistant resin and fluoropolymer (a) in the residue after baking for minutes.

When the said heat resistant resin is less than 15 mass% of the total amount of solid content of the said heat resistant resin and a fluorine-containing polymer (a), the adhesive force of the primer layer (A) and a base material in the obtained fluorine-containing laminated body may be inadequate. When it exceeds 50 mass%, the adhesiveness of the primer layer (A) and fluorine-containing layer (B) in the fluorine-containing laminated body obtained may be inadequate. The minimum with more preferable is 20 mass%, and a more preferable upper limit is 40 mass%.

The coating composition for primers is the fluorine-containing layer further described above for the purpose of further improving the coating workability and the corrosion resistance and water vapor resistance of the obtained fluorine-containing laminate together with the fluorine-containing polymer (a) and the heat-resistant resin. It may also contain additives other than the filler in B).

It does not specifically limit as said additives, For example, a leveling agent, a solid lubricant, a sedimentation inhibitor, a moisture absorber, a surface regulator, a thixotropic agent, a viscosity modifier, an antigelling agent, an ultraviolet absorber, a light stabilizer, a plasticizer, a color separation inhibitor, Surface expansion inhibitors, anti-friction scratches, mold inhibitors, antibacterial agents, antioxidants, antistatic agents, silane coupling agents and the like.

The said process (i) forms a primer coating film Ap by apply | coating the coating composition for primers on a base material.

The said base material may be 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 with an acid or an alkali, anodizing (anodizing), sand blast, etc. are mentioned. It is preferable to perform the said surface treatment from the point that the coating composition for primers can be apply | coated uniformly without a cratering, and the adhesiveness of a base material and a primer coating film Ap improves.

It does not specifically limit as said coating method, When the said coating composition for primers is liquid, For example, spray coating, roll coating, coating by a doctor blade, dip (immersion) coating, impregnation coating, spin flow coating, curtain flow coating Etc. are mentioned, and spray coating is especially preferable. When the coating composition for primers is powder, electrostatic coating, flow immersion method, roto lining, etc. are mentioned, Especially, electrostatic coating is preferable.

It is preferable to form the said primer coating film Ap by apply | coating the said coating composition for primers on a base material, and the said process (i) may be what is baked after performing the above-mentioned process (ii), It may not be calcined, and when the coating composition for primers is liquid, it may further be dried after the said application, and may not be dried.

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

When the said coating composition for primers is liquid, it is preferable to apply it on a base material, and to dry normally, and since baking of a coating film laminated body is performed in the process (iii) mentioned later, it is more preferable not to perform baking. .

When the coating composition for primers is powder, it is preferable to carry out baking normally after apply | coating on a base material.

The said primer coating film Ap is formed by apply | coating the said coating composition for primers on a base material. In the said process (i), the said primer coating film Ap may be formed only by the said application | coating, may be formed by drying after the said application, and may be formed by drying after baking and drying as needed after the said application | coating. . The said primer coating film Ap becomes a primer layer (A) in the fluorine-containing laminated body obtained.

Said process (i) is also called "process (1)" below.

The said process (ii) forms a fluorine-containing coating film Bp by apply | coating a filler containing composition on the said primer coating film Ap.

The filler-containing composition comprises a melt processable fluoropolymer (b) and a filler. It is preferable that the said filler containing composition is a liquid filler containing liquid composition, and it is preferable to contain a melt processable fluoropolymer (b), a filler, and a liquid medium. The liquid medium usually contains water and / or an organic liquid.

When the liquid medium of the filler-containing liquid composition mainly contains an organic liquid, the melt processable fluorine-containing polymer (b) is dispersed as particles in the liquid medium, and / or dissolved in the liquid medium. The filler is dispersed as particles in the liquid medium. It does not specifically limit as said organic liquid, For example, the thing similar to the organic liquid which can be used as a liquid medium of the said coating composition for primers, etc. are mentioned.

When the liquid medium of the filler-containing liquid composition mainly contains water, the melt-processable fluorine-containing polymer (b) and the filler are dispersed as particles in the liquid medium. As said filler containing liquid composition, although the said liquid medium may contain an organic liquid, it is preferable from a viewpoint of an environment that the said liquid medium is a filler containing aqueous dispersion which mainly contains water. In the filler-containing aqueous dispersion, the liquid medium may contain a water-soluble organic liquid such as a low molecular weight alcohol as long as it mainly contains water, but is preferably made of water only.

When the said liquid medium mainly contains water, the said filler containing composition consists of adding surfactant for the purpose of disperse | distributing and stabilizing the particle | grains containing the said melt-processable fluoropolymer (b) normally. It does not specifically limit as said surfactant, For example, the thing similar to surfactant which can be used for the said coating composition for primers, etc. are mentioned.

It is preferable that the viscosity of the said filler containing composition is 0.1-50000 mPa * s similarly to the case where the said coating composition for primers is a liquid. The minimum with more preferable is 1 mPa * s, and a more preferable upper limit is 30000 mPa * s.

In the said filler containing composition, it is preferable that the particle | grains containing the said melt-processable fluoropolymer (b) are 0.01-5 micrometers in average particle diameter. It is preferable that the said filler is 1-100 micrometers in average particle diameter.

The filler-containing composition, together with the melt processable fluorine-containing polymer (b) and the filler, further improves the coating workability and the corrosion resistance and water vapor resistance of the resulting fluorine-containing laminate, and the filler in the fluorine-containing layer (B). In order to disperse | distribute uniformly, etc., you may further contain the same additives as the additives which can be used for the coating composition for primers mentioned above. It is preferable that the said filler containing composition consists of adding a pigment dispersant for the purpose of disperse | distributing and stabilizing said fillers, such as a bright flat pigment.

The said process (ii) forms a fluorine-containing coating film Bp by apply | coating a filler containing composition on the said primer coating film Ap.

It does not specifically limit as said coating method, For example, the method similar to the coating method when the said coating composition for primers is a liquid, etc. are mentioned, Especially, spray coating is preferable.

It is preferable to form the said fluorine-containing coating film Bp by apply | coating the said filler containing composition on the said primer coating film Ap in the said process (ii), and after the said application, performing the process (iii) mentioned above. It may be previously dried, may not be dried, may be further baked, or may not be baked.

It is preferable to perform drying in the said process (ii) for 5 to 60 minutes at the temperature of 70-300 degreeC similarly to the drying in the said process (i).

It is preferable to perform baking in the said process (ii) for 10 to 30 minutes at the temperature of 260-410 degreeC similarly to the baking in the said process (i).

It is preferable to dry normally after apply | coating the said filler containing composition on the said primer coating film Ap, and since baking of a coating film laminated body is performed at the process (iii) mentioned later, it is more preferable not to bake. .

The fluorine-containing coating film Bp is formed by applying the filler-containing composition on the primer coating film Ap. In the said process (ii), the said fluorine-containing coating film Bp may be formed only by the said application | coating, may be formed by drying after the said application, and may be formed by baking after drying as needed after the said application and baking. have. The said fluorine-containing coating film Bp becomes a fluorine-containing layer (B) in the fluorine-containing laminated body obtained.

In the step (ii), the filler-containing composition is preferably a liquid filler-containing liquid composition, and the step (ii) includes the fluorine-containing liquid by applying the filler-containing liquid composition on the primer coating film Ap. It is preferable that it is a process (henceforth "a process (2)") of forming a coating film Bp.

The said process (iii) forms a fluorine-containing laminated body by forming a fluorine-containing film (Cp) using a melt-processing fluorine-containing composition on the said fluorine-containing coating film (Bp).

The melt processable fluorine-containing composition contains a melt processable fluorine-containing polymer (c).

The melt-processable fluorine-containing composition may be a molded article such as a film or a sheet, may be a liquid, or may be a powder. When the melt processable fluorine-containing composition is liquid, the melt processable fluorine-containing composition contains a liquid medium together with the melt processable fluorine-containing polymer (c). The liquid medium usually contains water and / or an organic liquid.

When the liquid medium of the melt processable fluorine-containing composition mainly comprises an organic liquid, the melt processable fluorine-containing polymer (c) is dispersed as particles in the liquid medium, and / or dissolved in the liquid medium. will be. It does not specifically limit as said organic liquid, For example, the thing similar to the organic liquid which can be used as a liquid medium of the said coating composition for primers, etc. are mentioned.

When the liquid medium of the melt processable fluorine-containing composition mainly contains water, the melt processable fluorine-containing polymer (c) is dispersed as particles in the liquid medium. When the said liquid processable fluorine-containing composition is an aqueous dispersion which mainly contains water, normally, surfactant is added for the purpose of dispersion-stabilizing the particle | grains containing the said melt processable fluorine-containing polymer (c), It is done. It does not specifically limit as said surfactant, For example, the thing similar to surfactant which can be used for the coating composition for primers mentioned above, etc. are mentioned.

When melt-processing fluorine-containing polymer (c) is disperse | distributed as the particle | grain in the said liquid medium, it is preferable that average particle diameter is 0.01-5 micrometers, and when said melt-processing fluorine-containing composition is powder, average particle diameter is 5 It is preferable that it is to 50 micrometers. When the said melt processable fluorine-containing composition is powder, the minimum with more preferable average particle diameter of the particle | grains containing the said melt processable fluorine-containing polymer (c) is 10 micrometers, and a more preferable upper limit is 30 micrometers.

The melt-processable fluorine-containing composition is preferably a fluorine-containing powder which is a powder because a thick coating film can be easily obtained with a small number of coatings.

The melt-processable fluorine-containing composition, together with the melt-processable fluorine-containing polymer (c), further has a coating composition for primers described above for the purpose of further improving the corrosion resistance and water vapor resistance of the resulting fluorine-containing laminate. It may be one containing the same additives as the additives that can be used for.

The said process (iii) forms a fluorine-containing laminated body by forming a fluorine-containing film Cp on the said fluorine-containing coating film Bp using the said melt processable fluorine-containing composition.

The method for forming the fluorine-containing film Cp is achieved by applying the melt-processable fluorine-containing composition onto the fluorine-containing coating film Bp when the melt-processable fluorine-containing composition is powder. When the said melt processable fluorine-containing composition is powder, it does not specifically limit as said coating method, For example, the method similar to the coating method when the above-mentioned coating composition for primers is powder, etc. are mentioned, Especially, electrostatic coating is desirable.

The method for forming the fluorine-containing film Cp is achieved by applying the melt-processable fluorine-containing composition onto the fluorine-containing coating film Bp when the melt-processable fluorine-containing composition is a liquid. When the melt-processable fluorine-containing composition is a liquid, the coating method is not particularly limited. For example, the same method as the coating method in the case where the coating composition for primers is a liquid, etc. may be mentioned, and spray coating is preferred. Do.

In the method for forming the fluorine-containing film (Cp), when the melt-processable fluorine-containing composition is a liquid, it is preferable to apply the melt-processable fluorine-containing composition on the fluorine-containing coating film (Bp), and after the coating It may or may not be dry.

It is preferable to perform the said drying for 5 to 60 minutes at the temperature of 70-300 degreeC similarly to the drying in the said process (i) and the process (ii).

The method for forming the fluorine-containing film (Cp) is, when the melt-processing fluorine-containing composition is a molded article such as a film, for example, a molded article such as a film form previously molded by a conventionally known method or the like, the fluorine-containing coating film The conventionally well-known method, such as putting on (Bp) and heat crimping, etc. are mentioned.

The said fluorine-containing film Cp is formed by using the said melt processable fluorine-containing composition on the said fluorine-containing coating film Bp. In the step (iii), the fluorine-containing film Cp may be formed by drying, if necessary, after the coating, if the melt-processable fluorine-containing composition is a liquid, and the melt-processable fluorine-containing composition is a molded article. In this case, it may be formed by heat pressing. The said fluorine-containing film Cp becomes a fluorine-containing layer (C) in the fluorine-containing laminated body obtained.

The said process (iii) forms a fluorine-containing laminated body by forming a fluorine-containing film Cp on the said fluorine-containing coating film Bp.

The method for forming the fluorine-containing laminate includes the fluorine-containing film Cp by applying the melt-processable fluorine-containing composition onto the fluorine-containing coating film Bp when the melt-processing fluorine-containing composition is powder or liquid. After forming the film, a method of baking the coating film laminate including the primer coating film Ap, the fluorine-containing coating film Bp, and the fluorine-containing film Cp may be mentioned.

It is preferable to perform the said baking for 10 to 30 minutes at the temperature of 260-410 degreeC similarly to the baking in the said process (i) and the process (ii).

When the melt-processable fluorine-containing composition is a molded article such as a film, the step (iii) can form the fluorine-containing film (Cp) and at the same time obtain the fluorine-containing laminate.

In the method for forming the fluorine-containing laminate, in the case where the melt-processing fluorine-containing composition is a molded article, the primer coating film Ap and the fluorine-containing coating film Bp are formed by firing before performing the following steps, respectively. It is desirable to be.

In the step (iii), a fluorine-containing powder containing powder is preferably used as the melt-processing fluorine-containing composition, and the fluorine-containing film (Cp) is applied by applying the fluorine-containing powder on the fluorine-containing coating film (Bp). ) By baking the coating film laminate including the step (hereinafter also referred to as "step (3)") and the primer coating film (Ap), the fluorine-containing coating film (Bp) and the fluorine-containing film (Cp). It is preferable that it is a process (henceforth a "process (4)") which forms a fluorine-containing laminated body.

The method for forming the fluorine-containing laminate according to the present invention includes a character, a drawing, and the like after step (i) of forming the primer coating film (Ap) or after step (ii) of forming the fluorine-containing coating film (Bp). It may have a process of printing. The letters, drawings, and the like are letters and lines indicating the amount of water, for example, when the coated article described later is a cooking container.

It does not specifically limit as said printing method, For example, pat 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 formation method of the fluorine-containing laminated body of this invention is for forming the above-mentioned fluorine-containing laminated body, (1) Applying the coating composition for primers containing a fluorine-containing polymer (a) and a heat resistant resin on a base material, and applying a primer Process of forming coating film Ap, (2) Coating fluorine-containing coating film Bp by apply | coating the filler containing liquid composition containing a melt-processable fluorine-containing polymer (b) and a filler on said primer coating film Ap. A step of forming, (3) A step of forming a fluorine-containing film (Cp) by applying a fluorine-containing powder containing a melt-processable fluorine-containing polymer (c) on the fluorine-containing coating film (Bp), and (4) the It is preferable to include the process of forming the said fluorine-containing laminated body by baking the coating film laminated body containing a primer coating film (Ap), a fluorine-containing coating film (Bp), and a fluorine-containing film (Cp).

The method for forming the fluorine-containing laminate according to the present invention includes the above-described fluorine-containing layer (C) in the fluorine-containing laminate with a small number of coatings by applying the fluorine-containing powder containing the melt-processable fluorine-containing polymer (c). You can do it with the same thick membrane. The fluorine-containing laminate obtained by the method for forming a fluorine-containing laminate of the present invention has excellent adhesion between the fluorine-containing layer (B) and the fluorine-containing layer (C) as described above, and is excellent in corrosion resistance and water vapor resistance. Since the fluorine-containing layer (C) is the thick film described above, the wear resistance is particularly excellent.

Moreover, in the formation method of the fluorine-containing laminated body of this invention, since filler dispersion is favorable in a filler containing liquid composition, a filler is disperse | distributed uniformly in the fluorine-containing layer (B) of the fluorine-containing laminated body obtained, and a filler has Properties such as brightness can be stably expressed.

Since the formation method of the fluorine-containing laminated body of this invention includes the structure mentioned above, it is preferable as a method of forming a fluorine-containing laminated body on a base material.

The coating article of this invention contains a base material and the fluorine-containing laminated body mentioned above. It does not specifically limit as said base material, For example, Metals, such as metal single bodies, such as iron, aluminum, copper, and these alloys; Nonmetallic inorganic materials, such as a porcelain, glass, and a ceramic, etc. are mentioned. Stainless steel etc. are mentioned as said alloys. As said base material, a metal is preferable and aluminum and stainless are more preferable.

The coating article of the present invention is not particularly limited, and can be used for applications utilizing the non-tackiness, heat resistance, slip resistance, and the like of the fluorine-containing polymer. For example, a frying pan, a pressure pot, a pot, a grill pot, Cooking utensils such as a cooking vessel, an oven, a hot plate, a baking pan, a kitchen knife, and a gas table; Kitchenware, such as an electric pot, an ice-making tray, a metal mold, a stove hood, etc. are mentioned, A tool, such as a saw and a string, used as slip property; Household items such as irons; Metal foil, and the like. Especially, it is preferable that it is a cooking container, a pressure pot, and a grill pot which require corrosion resistance and water vapor resistance, and it is more preferable that it is a cooking container which requires designability.

Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited only to these Examples. "%" "Part" represents mass% and a mass part, respectively.

Preparation Example 1 Preparation of Polyethersulfone Resin Aqueous Dispersion

60 parts of polyethersulfone resin [PES] and 60 parts of deionized water having a number average molecular weight of about 24000 were stirred for about 10 minutes in the ceramic ball mill until the particles containing PES were completely ground. Subsequently, 180 parts of N-methyl-2-pyrrolidone (hereinafter referred to as "NMP") was added, and the mixture was further ground for 48 hours to obtain a 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 particle diameter of the particles containing PES in the PES aqueous dispersion was 2-3 μm.

Preparation Example 2 Preparation of Aqueous Dispersion of Polyamideimide Resin

Polyamideimide resin [PAI] varnish (containing 71% of NMP) having a solid content of 29% was added to water to precipitate PAI. This was ground in a ball mill for 48 hours to obtain an PAI aqueous 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 for Primer

The PES aqueous dispersion obtained in Preparation Example 1 and the PAI aqueous dispersion obtained in Preparation Example 2 were mixed such that PES became 85% of the total amount of solids of PES and PAI, and tetrafluoroethylene homopolymer [TFE homopolymer] was added thereto. Aqueous dispersions (average particle diameter 0.28 μm, solid content 60%, polyether-based nonionic surfactants as a dispersant containing 6% of the TFE homopolymer) were contained in the total amount of solids of PES, PAI and TFE homopolymers. 20% is added, methyl cellulose is added as a thickener to 0.7% of the solid content of the TFE homopolymer, and polyether-based nonionic surfactant is added to the solid content of the TFE homopolymer as the dispersion stabilizer by 6% to add the TFE homopolymer. An aqueous dispersion having a solid content of 34% was obtained.

Preparation Example 4 Preparation of Filler-Containing Aqueous Dispersion

Filler in tetrafluoroethylene / perfluoro (alkylvinylether) [PFA] aqueous dispersion (average particle size 0.35 탆, solid content 48%, polyether-based nonionic surfactant 6% to PFA as dispersant) As a mica (specific gravity about 3, mica coated with titanium dioxide having an average particle diameter of 30 µm), 0.6% was added to the solid content of PFA to obtain an aqueous dispersion having a solid content of 48%.

<Example>

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 according to JIS B 1982 became 2.5-4.0 micrometers. After surface dust was removed by air blowing, 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, nozzle diameter 1.0 mm) so that the dry film thickness was about 10 µm. Spray coating at a spray pressure of 0.2 MPa. The coating film on the obtained aluminum plate was dried at 80-100 degreeC for 15 minutes, and it cooled to room temperature. The filler-containing aqueous dispersion obtained in Production Example 4 was spray-coated on the obtained primer coating film in the same manner as the coating composition for primers so that the dry film thickness was about 15 µm. The obtained filler-containing coating film was dried at 80 to 100 ° C. for 15 minutes and cooled to room temperature. PFA powder coating material (trade name: ACX-31, manufactured by Daikin Kogyo Co., Ltd., 25 µm in average) on the obtained filler-containing coating film was electrostatically coated under conditions of an applied voltage of 50 KV and a pressure of 0.08 MPa. It baked for 1 minute, the PFA layer whose film thickness is about 40 micrometers was formed, and the coating plate for a test was obtained. In the obtained test plate, a layer containing a primer layer, a filler-containing layer, and PFA was formed on the aluminum plate.

(Assessment Methods)

The following evaluation was performed about the coating film of the obtained test coating plate.

Thickness

The measurement was performed using a high frequency film thickness meter (trade name: LZ-300C, manufactured by Kate Chemical Industries, Ltd.).

Corrosion resistance test of fish paste material

Scratches reaching the aluminum plate were placed on the coating film surface of the obtained test plate by cross cutting with a cutter knife. This test paint plate was immersed in a solution in which 20 g of a fish cake material (made by SB Corporation) was dissolved in 1 L of water, and kept warm at 70 ° C to visually check whether there were no blisters or the like every 100 hours, and then tested for 1000 hours. Was performed. When there was no abnormality such as blistering, it was passed. When abnormality such as blistering was confirmed, it was rejected.

Water vapor resistance test

The test paint plate thus obtained was left to stand in water vapor of 0.6 MPa for 8 hours, was taken out at normal pressure, and then heated at 200 ° C for 1 minute. This cycle was repeated up to 10 cycles to check for blisters. When there was no blister, it was passed, and when there was blister, it was rejected.

The test paint plate obtained in the Example passed up to 1000 hours in the fish cake material corrosion resistance test, and also passed up to 10 cycles in the water vapor test.

Comparative Example

A test coating plate was prepared and evaluated in the same manner as in Example, except that the TFE homopolymer was used instead of PFA for the filler-containing aqueous dispersion obtained in Production Example 4.

The obtained coating plate for testing was passed up to 1000 hours in the fish-bowl material corrosion resistance test, but in the water vapor test, blisters occurred in one cycle and failed. In addition, peeling between the primer layer and the filler containing layer was observed in the blister generation | occurrence | production part visually in the test coating plate after performing the water vapor test.

In the embodiment in which the filler-containing layer was formed using the filler-containing aqueous dispersion containing PFA, although the obtained test coating plate was excellent in both corrosion resistance and water vapor resistance, the filler-containing layer was used by using an aqueous dispersion containing a TFE homopolymer. Although the obtained test plate was excellent in corrosion resistance, the comparative example formed was that foam | bubble generate | occur | produced by leaving it in steam and inferior to water vapor resistance.

Since the formation method of the fluorine-containing laminated body and fluorine-containing laminated body of this invention has the above-mentioned structure, it is excellent in corrosion resistance and water vapor resistance, and can fluorine-containing laminated material which can stably express filler characteristics, such as a glossiness, even in mass production. Sieves and coated articles can be obtained.

Claims (17)

delete delete delete delete delete delete delete (1) Process of forming primer coating film (Ap) by apply | coating the coating composition for primers containing a fluoropolymer (a) and a heat resistant resin on a base material, (2) forming a fluorine-containing coating film (Bp) by applying a filler-containing liquid composition containing a melt-processable fluorine-containing polymer (b), a filler, and water on the primer coating film (Ap), (3) forming a fluorine-containing film (Cp) by applying a fluorine-containing powder containing a melt-processing fluorine-containing polymer (c) on the fluorine-containing coating film (Bp), and (4) Process of forming the said fluorine-containing laminated body by baking the coating film laminated body containing the said primer coating film Ap, the fluorine-containing coating film Bp, and the fluorine-containing film Cp. A primer layer (A) containing a fluorine-containing polymer (a) and a heat resistant resin, a fluorine-containing layer (B) containing a melt-processable fluorine-containing polymer (b) and a filler, and a melt-processable fluorine-containing polymer, characterized by having The formation method of the fluorine-containing laminated body for forming the fluorine-containing laminated body which has a fluorine-containing layer (C) containing (c). The heat-resistant resin is a mixture of a polyether sulfone resin, at least one of a polyamideimide resin and a polyimide resin, and the polyether sulfone resin is the polyether sulfone resin and the polyamideimide resin. And a method for forming a fluorine-containing laminate which is 65 to 85% by mass of the total amount of the mixture with at least one of the polyimide resins. The method for forming a fluorine-containing laminate according to claim 8 or 9, wherein the heat resistant resin is 15 to 50% by mass of the total amount of solids of the heat resistant resin and the fluorine-containing polymer (a). A coated article comprising a base material and a fluorine-containing laminate formed by the method for forming a fluorine-containing laminate according to claim 8 or 9. The fluorine-containing laminate according to claim 8, wherein the melt processable fluorine-containing polymer (c) is a tetrafluoroethylene / perfluoro (alkylvinylether) copolymer, a tetrafluoroethylene / hexafluoropropylene copolymer or a mixture thereof. How to form a sieve. 9. The fluorine-containing polymer (a) of claim 8, wherein the fluoropolymer (a) is a tetrafluoroethylene homopolymer, modified polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer and tetrafluoroethylene / perfluoro (alkylvinyl) Ether) A method for forming a fluorine-containing laminate, which is one or a mixture of two or more selected from the group consisting of copolymers. The fluorine-containing laminate according to claim 8, wherein the melt processable fluorine-containing polymer (b) is a tetrafluoroethylene / perfluoro (alkylvinylether) copolymer, a tetrafluoroethylene / hexafluoropropylene copolymer or a mixture thereof. How to form a sieve. The method for forming a fluorine-containing laminate according to claim 8, wherein the filler is one kind or a mixture of two or more kinds selected from bright fillers including mica, metal powder and glass beads. The primer layer (A) has a film thickness of 5 to 30 µm, the fluorine-containing layer (B) has a film thickness of 5 to 30 µm, and the fluorine-containing layer (C) has a film thickness of 10 to 90 µm. Formation method of a fluorine-containing laminated body. The method for forming a fluorine-containing laminate according to claim 8, wherein the step (2) spray-paints the filler-containing liquid composition to form a fluorine-containing coating film (Bp).