CN102574158B - Method for producing coated article, and coated article - Google Patents

Method for producing coated article, and coated article Download PDF

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Publication number
CN102574158B
CN102574158B CN201080046538.6A CN201080046538A CN102574158B CN 102574158 B CN102574158 B CN 102574158B CN 201080046538 A CN201080046538 A CN 201080046538A CN 102574158 B CN102574158 B CN 102574158B
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fluorine
resin
fluoropolymer
layer
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CN102574158A (en
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山口诚太郎
鸟居宽
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Daikin Industries Ltd
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Daikin Industries Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2506/00—Halogenated polymers
    • B05D2506/10—Fluorinated polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones

Abstract

Disclosed is a method for producing a coated article, which comprises: a step (1) in which a primer coating layer (Ap) is formed by applying a primer coating composition (i), which is composed of a fluorine-containing polymer (a) and a heat-resistant resin, over a base; a step (2) in which a fluorine-containing powder coating layer (Bp) is formed by applying a fluorine-containing powder (ii), which is composed of a melt-processable fluorine-containing polymer (b) and a filler, over the primer coating layer (Ap); a step (3) in which a fluorine-containing powder coating layer (Cp) is formed by applying a fluorine-containing powder (iii), which is composed of a melt-processable fluorine-containing polymer (c), over the fluorine-containing powder coating layer (Bp); and a step (4) in which a coated article that is composed of the base, a primer layer (A), a fluorine-containing layer (B) and a fluorine-containing layer (C) is formed by firing a coating film laminate that is composed of the primer coating layer (Ap), the fluorine-containing powder coating layer (Bp) and the fluorine-containing powder coating layer (Cp).

Description

Covered article manufacture method and covered article
Technical field
The present invention relates to covered article manufacture method and covered article.
Background technology
The fluoropolymers such as tetrafluoroethylene/perfluoro (alkyl vinyl ether) copolymer [PFA] have low-friction coefficient, and the excellents such as non-adhesive, chemical proofing, heat resistance, are therefore widely used in the Surface Machining of the household supplies such as kitchen appliance, flatiron such as food industry articles for use, frying pan or pot, electrical industry articles for use, mechanical industry articles for use etc.
Surface Machining is undertaken by forming the layer formed by fluoropolymer on base material, the fluoropolymer used is if the fluoropolymer of the melt processables such as PFA, then easily obtain thicker layer by common industrial process, the surface of the article obtained easily plays the various characteristics that fluoropolymer has.
But fluoropolymer lacks the adaptation with base material because of its non-adhesive.In order to improve this adaptation, propose the laminate of the layer that there is priming coat and formed by fluoropolymer, wherein, the subbing that obtains using the resin glues such as mixture heat-resistant resin and fluoropolymer of priming coat is applied in advance on base material as primer (under be coated with り) and obtains.
In order to give aesthetic appearance, improve intensity etc., such laminate adds packing material when being formed sometimes, such as, when aesthetic appearance requires light sense, adds bright property packing material.
As the laminate with light sense, have a kind of laminate with double-layer structure, this is two-layer is with the addition of as the priming coat of the mica of bright property packing material and the top coat that formed thereon by PFA respectively.But due to the easy sedimentation in priming coat of mica powder, glass dust, therefore there is the insufficient problem of light sense in this laminate.
In order to solve this problem, someone proposition aluminium powder replaces mica powder as bright property packing material, but aluminium powder sedimentation easier than mica, when producing in a large number, the light sense of not only obtained laminate is unstable, but also can bring harmful effect to corrosion resistance.
As having stable light sense and the laminate of excellent corrosion resistance, someone proposes a kind of laminate of 3-tier architecture (such as, see patent document 1 and 2.), it, using the layer be made up of polytetrafluoroethylene (PTFE) [PTFE] and mica as intermediate layer, is provided with the priming coat be made up of resin glue and fluoropolymer below this layer, and uses the powder coating be made up of PFA to form top coat.Even if the light sense when a large amount of production of this laminate is also stablized.But the article be made up of this laminate and base material are when for kitchen appliances such as pots, water-fast vapor permeability insufficient, likely produce bubble because of steam.
Add when being formed in the laminate of packing material, as the laminate of resistance to marring excellence, there is following laminate: it uses aluminium oxide on base material, to form priming coat as packing material, this priming coat forms the intermediate layer be made up of melt processable fluoropolymer, PTFE and aluminium oxide such as PFA, the top coat that is made up of PTFE is formed again (such as, see patent document 3 on this intermediate layer.)。But due to aluminium oxide possibility sedimentation in priming coat, therefore this laminate brings harmful effect to the corrosion resistance of base material, in addition, because top coat is made up of PTFE, therefore not easily obtain thick layer by general industrial process, there is the problem of the poor durability such as abrasion performance.
In addition, as the laminate adding packing material when being formed, document is also had to disclose a kind of fluorine-containing laminate, it has priming coat (A) containing fluoropolymer (a) and heat-resistant resin, the fluorine-containing layer (B) containing melt processable fluoropolymer (b) and packing material and the fluorine-containing layer (C) containing melt processable fluoropolymer (c) (such as, see patent document 4.)。
Prior art document
Patent document
Patent document 1: Japanese Unexamined Patent Publication 7-111946 publication
Patent document 2: Japan Patent No. 2593043 description
Patent document 3: Japan Patent No. 2644380 description
Patent document 4: International Publication No. 2004/041537 pamphlet
Summary of the invention
But, in fluorine-containing laminate disclosed in patent document 4, fluorine-containing layer (B) containing melt processable fluoropolymer (b) and packing material is formed by coating liquid coating, in this situation, according to the difference of use, corrosion resistance, water-fast vapor permeability possibility are insufficient, there is the space of improving.In addition, fluorine-containing layer (B) is when liquid coating, and need drying process and refrigerating work procedure before coating fluorine-containing layer (C), manufacture method is numerous and diverse.
In view of above-mentioned present situation, the object of the present invention is to provide corrosion resistance, water-fast vapor permeability and excellent wear resistance, manufacturing process simple and also can stablize when a large amount of production manifest light sense (Guang Hui sense) etc. the covered article manufacture method of packing material characteristic and covered article.
The present invention relates to a kind of covered article manufacture method, it is characterized in that, comprise following operation: by coating on base material containing subbing coating composition (i) of fluoropolymer (a) with heat-resistant resin, thus form the operation (1) of subbing coating layer (Ap); In the upper coating of above-mentioned subbing coating layer (Ap) containing the fluorine-containing powder (ii) of melt processable fluoropolymer (b) with packing material, thus form the operation (2) of fluorine-containing powder coating layer (Bp); At the fluorine-containing powder (iii) of the upper coating of above-mentioned fluorine-containing powder coating layer (Bp) containing melt processable fluoropolymer (c), thus form the operation (3) of fluorine-containing powder coating layer (Cp); And the laminate comprising base material, above-mentioned subbing coating layer (Ap), above-mentioned fluorine-containing powder coating layer (Bp) and above-mentioned fluorine-containing powder coating layer (Cp) is fired, thus form the covered article operation (4) comprising base material, priming coat (A), fluorine-containing layer (B) and fluorine-containing layer (C).
In addition, the invention still further relates to by above-mentioned manufacture method obtain covered article.What obtained by manufacture method of the present invention is covered articlely manufactured by fluorine-containing powder (ii) due to fluorine-containing layer (B), thus has more excellent corrosion resistance and water-fast vapor permeability.Such as, when on priming coat, the fluorine-containing layer of lamination is formed by liquid coating, corrosion resistance, water-fast vapor permeability difference sometimes.
Below, the present invention is described in detail.
Covered article manufacture method of the present invention comprises operation (1): by coating on base material containing subbing coating composition (i) of fluoropolymer (a) with heat-resistant resin, thus form subbing coating layer (Ap).
As above-mentioned base material, be not particularly limited, such as, the metal such as the metal simple-substances such as iron, aluminium, copper and their alloy type can be enumerated; The non-metal inorganic materials etc. such as enamel, glass, pottery.As above-mentioned alloy type, stainless steel etc. can be enumerated.As above-mentioned base material, preferable alloy, more preferably aluminium or stainless steel.
If desired, above-mentioned base material can carry out the surface treatment such as ungrease treatment, roughening process.As the method for above-mentioned roughening process, be not particularly limited, such as, the chemical etching, anodic oxidation (alumite process), sandblasting etc. that utilize acid or alkali can be enumerated.Be coated with equably from repulsion (Ha ジ キ) can not be produced above-mentioned subbing coating composition (i) aspect and from considerations such as the aspects that the adaptation of base material and subbing coating layer (Ap) improves, above-mentioned surface treatment is suitably selected according to the kind of base material, subbing coating composition (i) etc., such as, preferred sandblasting.
Above-mentioned fluoropolymer (a) being has the polymer with the fluorine atom of the carbon atom Direct Bonding forming main chain or side chain.Above-mentioned fluoropolymer (a) can be non melt processable, also can be melt processable.
Above-mentioned fluoropolymer (a) obtains preferably by by fluorine-containing single ethene system unsaturated hydrocarbons (I) polymerization.
It is above-mentioned that " fluorine-containing single ethene system unsaturated hydrocarbons (I) is (hereinafter referred to as " unsaturated hydrocarbons (I) ".) " referring in molecule the unsaturated hydrocarbons with 1 vinyl, the part or all of hydrogen atom of this unsaturated hydrocarbons is replaced by fluorine atoms.
In above-mentioned unsaturated hydrocarbons (I), the hydrogen atom be not partly or entirely replaced by fluorine atoms can be replaced by fluoro-alkyls such as the halogen atom beyond the fluorine atoms such as chlorine atom and/or trifluoromethyls.Just, above-mentioned unsaturated hydrocarbons (I) does not comprise trifluoro-ethylene described later.
As above-mentioned unsaturated hydrocarbons (I), be not particularly limited, such as, can enumerate tetrafluoroethene [TFE], hexafluoropropene [HFP], CTFE [CTFE], vinylidene fluoride [VdF], ethylene fluoride [VF] etc., what can use in them is one kind or two or more.
Above-mentioned fluoropolymer (a) can be the homopolymers of above-mentioned unsaturated hydrocarbons (I).As the homopolymers of above-mentioned unsaturated hydrocarbons (I), such as, proplast [TFE homopolymers], polytrifluorochloroethylene [PCTFE], polyvinylidene fluoride [PVdF], poly-ethylene fluoride [PVF] etc. can be enumerated.
In addition, above-mentioned fluoropolymer (a) also can be the above-mentioned unsaturated hydrocarbons of at least one (I) and can with the copolymer of the unsaturated compound (II) of above-mentioned unsaturated hydrocarbons (I) copolymerization.
Only be polymerized by one kind or two or more unsaturated compound (II) polymer obtained and can not be used as above-mentioned fluoropolymer (a), and be only polymerized by one kind or two or more above-mentioned unsaturated hydrocarbons (I) polymer obtained and can be used as above-mentioned fluoropolymer (a), consider from this point, above-mentioned unsaturated compound (II) is different materials from above-mentioned unsaturated hydrocarbons (I).
As above-mentioned unsaturated compound (II), be not particularly limited, such as, trifluoro-ethylene [3FH] can be enumerated; Single ethene system such as ethene [Et], propylene [Pr] unsaturated hydrocarbons etc.What can use in them is one kind or two or more.
In addition, above-mentioned fluoropolymer (a) can be the copolymer of above-mentioned unsaturated hydrocarbons (I) of more than two kinds.As the copolymer of the copolymer of above-mentioned above-mentioned unsaturated hydrocarbons (I) of more than two kinds, the above-mentioned unsaturated hydrocarbons of above-mentioned at least one (I) and unsaturated compound (II), be not particularly limited, such as, bipolymer, terpolymer etc. can be enumerated.
As above-mentioned bipolymer, be not particularly limited, such as, VdF/HFP copolymer, Et/CTFE copolymer [ECTFE], Et/HFP copolymer etc. can be enumerated.
In addition, above-mentioned bipolymer can be the TFE based copolymers such as TFE/HFP copolymer [FEP], TFE/CTFE copolymer, TFE/VdF copolymer, TFE/3FH copolymer, Et/TFE copolymer [ETFE], TFE/Pr copolymer.In this description, above-mentioned " TFE based copolymer " refers to product TFE and one kind or two or more other monomer copolymerizations except TFE obtained.In above-mentioned TFE based copolymer, the ratio of other monomers except TFE except of addition in above-mentioned TFE based copolymer is usually preferably greater than 1 quality % of the gross mass of above-mentioned TFE and other monomers above-mentioned.
As above-mentioned terpolymer, VdF/TFE/HFP copolymer etc. can be enumerated.
As other monomers except above-mentioned TFE in above-mentioned TFE based copolymer, can be following can with other monomers (III) of TFE copolymerization.Above-mentioned other monomers (III) are preferably selected from by following general formula
X(CF 2) mO nCF＝CF 2
(in formula, X represents-H ,-Cl or-F, and m represents the integer of 1 ~ 6, and n represents the integer of 0 or 1.) compound that represents is (wherein except HFP.), following general formula
C 3F 7O[CF(CF 3)CF 2O] p-CF＝CF 2
(in formula, p represents the integer of 1 or 2.) compound that represents or following general formula
X(CF 2) qCY＝CH 2
(in formula, X is same as described above, and Y represents-H or-F, and q represents the integer of 1 ~ 6.) represent compound composition group at least one monomer.What can use in them is one kind or two or more.As such TFE based copolymer, such as, can enumerate TFE/ perfluor (alkyl vinyl ether) [PAVE] copolymer [PFA] etc.
In addition, above-mentioned fluoropolymer (a) can be modified Teflon [modified ptfe].In this description, above-mentioned " modified ptfe " refers to a small amount of comonomer and TFE copolymerization and the material formed, and the amount of this small amount of comonomer arrives less does not give obtained copolymer melt processable.As above-mentioned a small amount of comonomer, be not particularly limited, such as, HFP, the CTFE etc. in above-mentioned unsaturated hydrocarbons (I) can be enumerated, the 3FH etc. in above-mentioned unsaturated compound (II) can be enumerated, the PAVE in above-mentioned other monomers (III), perfluor (alkoxy vinyl ethers), (perfluoroalkyl) ethene etc. can be enumerated.The one kind or two or more of above-mentioned a small amount of comonomer can be used.
The ratio adding to the above-mentioned a small amount of comonomer in above-mentioned modified ptfe is different because of the difference of its kind, such as, when using PAVE, perfluor (alkoxy vinyl ethers) etc., this ratio is preferably 0.001 quality % ~ 1 quality % of the gross mass of above-mentioned TFE and above-mentioned a small amount of comonomer usually.
As above-mentioned fluoropolymer (a), it can be the mixture of one kind or two or more polymer, also can be the mixture of a kind of above-mentioned unsaturated hydrocarbons (I) homopolymers and one kind or two or more above-mentioned unsaturated hydrocarbons (I) copolymer, or the mixture of two or more above-mentioned unsaturated hydrocarbons (I) copolymer.
As said mixture, such as, the mixture of TFE homopolymers and above-mentioned TFE based copolymer can be enumerated, belong to the mixture etc. of the two or more copolymers of above-mentioned TFE based copolymer, as such mixture, such as, the mixture of TFE homopolymers and PFA can be enumerated; The mixture of TFE homopolymers and FEP; The mixture of TFE homopolymers, PFA and FEP; The mixture etc. of PFA and FEP.
In addition, above-mentioned fluoropolymer (a) can be by have perfluoroalkyl containing perfluoroalkyl ethylenically unsaturated monomers (IV) (hereinafter referred to as " unsaturated monomer (IV) ".) be polymerized the material obtained.Above-mentioned unsaturated monomer (IV) is the material represented with following general formula.
Rf(CH 2) rOCOCR 3＝CH 2、
Rf(CH 2) sCOOCH＝CH 2、
RfCH＝CH(CH 2) rOCOCR 3＝CH 2
(in formula, Rf represents that carbon number is the perfluoroalkyl of 4 ~ 20, R 1represent that-H or carbon number are the alkyl of 1 ~ 10, R 2represent that carbon number is the alkylidene of 1 ~ 10, R 3represent-H or methyl, R 4represent that carbon number is the alkyl of 1 ~ 17, r represents the integer of 1 ~ 10, and s represents the integer of 0 ~ 10.)
Above-mentioned fluoropolymer (a) can be the homopolymers of above-mentioned unsaturated monomer (IV), in addition, also can be above-mentioned unsaturated monomer (IV) and can with the copolymer of the monomer (V) of above-mentioned unsaturated monomer (IV) copolymerization.
As above-mentioned monomer (V), be not particularly limited, such as, can enumerate (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, two (methyl) polyalkylene glycol acrylate ester, N-hydroxymethyl-propane acrylamide, (methyl) acrylamide, alkyl carbon number be (methyl) acrylic acid derivatives such as (methyl) acrylic acid Arrcostab of 1 ~ 20; The substituted or non-substituted ethene such as ethene, vinyl chloride, PVF, styrene, AMS, p-methylstyrene; The carbon number of alkyl is the alkyl vinyl ether of 1 ~ 20, the carbon number of alkyl is the vinyl ethers such as the halogenated alkyl vinyl ethers of 1 ~ 20; The carbon number of alkyl is the vinyl ketones such as the vinyl alkyl ketone of 1 ~ 20; The unsaturated polybasic carboxylic acid of the aliphatic such as maleic anhydride and derivative thereof; The polyenoid etc. such as butadiene, isoprene, chlorobutadiene.
Above-mentioned fluoropolymer (a) such as can obtain by using the existing known polymerizations etc. such as emulsion polymerisation.
As above-mentioned fluoropolymer (a), from the viewpoint of obtained covered article corrosion resistance and water-fast vapor permeability excellence, be preferably selected from least one polymer in the group be made up of TFE homopolymers, modified ptfe and above-mentioned TFE based copolymer.In addition, as above-mentioned TFE based copolymer, be also preferably selected from least one copolymer in the group be made up of FEP and PFA.
Thus, as above-mentioned fluoropolymer (a), be preferably selected from least one polymer in the group be made up of TFE homopolymers, modified ptfe, FEP and PFA.
In addition, as above-mentioned fluoropolymer (a), from the viewpoint of the excellent adhesion in obtained covered article middle priming coat (A) and fluorine-containing layer (B), preferably comprise TFE based copolymer.Therefore the covered article water-fast vapor permeability excellence of the excellent adhesion of priming coat (A) and fluorine-containing layer (B), even if also can suppress the generation of the paint film defects such as bubble in the presence of steam.As the fluoropolymer (a) comprising TFE based copolymer, such as, the mixture of the mixture of preferred PFA one matter, TFE homopolymers and FEP, TFE homopolymers and PFA, modified ptfe and the mixture of FEP or the mixture of modified ptfe and PFA.In addition, as the fluoropolymer (a) in priming coat (A), from the viewpoint of the excellent adhesion of obtained covered article corrosion resistance and water-fast vapor permeability excellence, priming coat (A) and fluorine-containing layer (B), preferred PFA one matter, the mixture between TFE homopolymers and PFA or the mixture between TFE homopolymers and FEP, the mixture more preferably between TFE homopolymers and FEP.
As long as above-mentioned heat-resistant resin is considered to have the resin of heat resistance usually, the temperature that preferably can use continuously is the resin of more than 150 DEG C.Just, as above-mentioned heat-resistant resin, above-mentioned fluoropolymer (a) is not comprised.
As above-mentioned heat-resistant resin, be not particularly limited, such as, at least one resin in the group be made up of polyamide-imide resin, polyimide resin, polyethersulfone resin, polyetherimide resin, polyether-ether-ketone resin, aromatic polyester resins and polyarylene sulfide resin is preferably selected from.As above-mentioned heat-resistant resin, one kind or two or more above-mentioned resin can be used.
Above-mentioned polyamide-imide resin [PAI] is the resin formed by the polymer in molecular structure with amido link and imide bond.As above-mentioned PAI, be not particularly limited, such as, can enumerate the resin etc. formed by the heavy polymer be respectively obtained by reacting as follows: the reaction in molecule with aromatic series quaternary carboxylic acids such as the aromatic diamine of amido link and PMAs; The reaction of the vulcabond such as diamines or methyl diphenylene diisocyanate such as the aromatic series tricarboxylic acids such as trimellitic anhydride and 4,4-diamino-phenyl ethers; There is in molecule the binary acid of aromatic imides ring and the reaction of diamines; Etc..As above-mentioned PAI, from the viewpoint of excellent heat resistance, preferably formed by the polymer in main chain with aromatic rings.
Above-mentioned polyimide resin [PI] is the resin formed by the polymer in molecular structure with imide bond.As above-mentioned PI, be not particularly limited, such as, can enumerate the resin etc. that the heavy polymer that obtained by the reaction etc. of the aromatic series quaternary carboxylic acid anhydrides such as pyromellitic acid dianhydride is formed.As above-mentioned PI, from the viewpoint of excellent heat resistance, preferably formed by the polymer in main chain with aromatic rings.
Above-mentioned polyethersulfone resin [PES] is the resin formed by the polymer of the repetitive with following chemical formulation.
As above-mentioned PES, be not particularly limited, such as, the resin etc. that the polymer that obtained by the polycondensation of dichloro diphenylsulfone and bis-phenol is formed can be enumerated.
Even if from the excellent adhesion with base material carry out when being formed covered article fire time temperature also have sufficient heat resistance and the covered article corrosion resistance obtained and water-fast vapor permeability excellence in consider, above-mentioned heat-resistant resin is preferably selected from least one resin in the group be made up of PAI, PI and PES.PAI, PI and PES comprise one kind or two or more respectively.
As above-mentioned heat-resistant resin, from the viewpoint of the adaptation and excellent heat resistance with base material, be more preferably at least one resin in the group being selected from and being made up of PAI and PI.
As above-mentioned heat-resistant resin, from the viewpoint of corrosion resistance and water-fast vapor permeability excellence, at least one resin in preferably including PES and being selected from the group that is made up of PAI and PI.That is, heat-resistant resin can be the mixture of the mixture of PES and PAI, the mixture of PES and PI or PES, PAI and PI.Above-mentioned heat-resistant resin is particularly preferably the mixture of PES and PAI.
In above-mentioned operation (1), above-mentioned subbing coating composition (i) comprises fluoropolymer (a) and heat-resistant resin.Above-mentioned subbing coating composition (i) can be liquid, also can be powder.When above-mentioned subbing coating composition (i) is liquid, it also comprises liquid medium while comprising fluoropolymer (a) and heat-resistant resin.Above-mentioned liquid medium generally includes water and/or organic liquid.In this description, above-mentioned " organic liquid " refers to the organic compound for liquid under the normal temperature of about 20 DEG C.
When the liquid medium of above-mentioned subbing coating composition (i) is formed primarily of organic liquid, above-mentioned heat-resistant resin and fluoropolymer (a) are scattered in above-mentioned liquid medium in the form of granules and/or are dissolved in above-mentioned liquid medium.As above-mentioned organic liquid, be not particularly limited, such as, the nitrogenous organic liquids such as METHYLPYRROLIDONE, 2-Pyrrolidone, DMA can be enumerated; The aromatic hydrocarbon solvents such as toluene, dimethylbenzene, trimethylbenzene, methyl-ethyl benzene, propylbenzene, butyl benzene; Carbon number is the saturated hydrocarbons solvent of 6 ~ 12; The lactone such as gamma-butyrolacton; The non-annularity ester classes such as butyl acetate; The ketone such as methyl iso-butyl ketone (MIBK), methyl ethyl ketone; The glycols such as ethylene glycol, triethylene glycol, propane diols; The glycol ethers such as butyl cellosolve; The unary alcohol such as n-butyl alcohol, diacetone alcohol etc.
As above-mentioned aromatic hydrocarbon solvent, the Solvesso 100 of commercially available product, Solvesso 150, Solvesso 200 (be trade name, Exxon Chemical society manufactures) etc. can be used as.As above-mentioned saturated hydrocarbons solvent, commercially available mineral spirits (No. 4, Japanese Industrial Standards, industrial gasoline) etc. can be used.
Above-mentioned organic liquid can be used alone, and also can share two or more.
When the liquid medium of above-mentioned subbing coating composition (i) is formed primarily of water, above-mentioned heat-resistant resin is scattered in above-mentioned liquid medium in the form of granules or is dissolved in above-mentioned liquid medium, and fluoropolymer (a) is scattered in above-mentioned liquid medium in the form of granules.
During above-mentioned liquid medium primary aqueous, generally for the particle stabilized dispersion making to be formed by fluoropolymer (a), forming above-mentioned subbing coating composition (i) by adding surfactant.As above-mentioned surfactant, be not particularly limited, such as, can the nonionic surface active agent such as fluorine-containing nonionic surface active agent be enumerated; The anionic surfactant such as fluo anion type surfactant; The cationic surface active agents such as fluorine-containing cationic type surfactant; Etc..In order to make the particle stabilized dispersion be made up of fluoropolymer (a), above-mentioned subbing coating composition (i) can also also share above-mentioned organic liquid while share above-mentioned surfactant.
In addition, above-mentioned subbing coating composition (i) can also be the organosol obtained by the method etc. that Japanese Patent Publication 49-17017 publication is recorded, the method is add as turning the organic solvent of layer liquid and turning layer agent in the water-borne dispersions that forms primarily of water of the particle that is made up of above-mentioned fluoropolymer (a) and the particle be made up of heat-resistant resin, dispersant in dispersate, makes the above-mentioned particle be made up of fluoropolymer (a) and the particle be made up of heat-resistant resin turn layer in above-mentioned organic solvent.
From the viewpoint of the excellent adhesion with base material, above-mentioned subbing coating composition (i) is preferably liquid, and from the viewpoint of reducing environmental pressure, more preferably above-mentioned liquid medium is formed primarily of water.
When above-mentioned subbing coating composition (i) is liquid, the viscosity of above-mentioned subbing coating composition (i) is preferably 0.1mPas ~ 50000mPas.If viscosity is lower than 0.1mPas, easily sagging etc. is produced when being then coated with on base material, sometimes be difficult to obtain target film thickness, if viscosity is more than 50000mPas, then coating operations is deteriorated sometimes, the membrane thickness unevenness of not only obtained subbing coating layer (Ap), and surface smoothness equal difference sometimes.Preferred lower limit is 1mPas, and the preferred upper limit is 30000mPas.
In above-mentioned subbing coating composition (i), the average grain diameter of above-mentioned fluoropolymer (a) is preferably 0.01 μm ~ 5 μm.Above-mentioned heat-resistant resin is when being scattered in the form of granules in above-mentioned subbing coating composition (i), and its average grain diameter is preferably 0.2 μm ~ 8 μm.
In above-mentioned subbing coating composition (i), at least one resin during heat-resistant resin comprises polyethersulfone resin and is selected from the group that is made up of polyamide-imide resin and polyimide resin, polyethersulfone resin is preferably 65 quality % ~ 90 quality % of the total amount of at least one resin in the group be made up of above-mentioned polyamide-imide resin and polyimide resin this polyethersulfone resin and being selected from.If lower than 65 quality %, then obtained covered article water-fast vapor permeabilityly may to reduce, if more than 90 quality %, then corrosion resistance may reduce.The preferred upper limit is 85 quality %.Above-mentioned heat-resistant resin usually formed covered article time carry out fire in also can not decompose, therefore the ratio of the ratio of above-mentioned PES in fact with it in priming coat (A) is identical.It should be noted that, when only comprising any one in PAI and PI, " total amount of PES and PAI and PI " refers to the total amount of any one and PES in PAI and PI contained in subbing coating composition (i).
In above-mentioned subbing coating composition (i), above-mentioned heat-resistant resin is preferably 15 quality % ~ 50 quality % of the total amount of above-mentioned heat-resistant resin and fluoropolymer (a).If above-mentioned heat-resistant resin is lower than 15 quality % of the total amount of above-mentioned heat-resistant resin and fluoropolymer (a), then obtained covered article in priming coat (A) sometimes insufficient with the closing force of base material.If more than 50 quality %, then obtained covered article in priming coat (A) sometimes insufficient with the adaptation of fluorine-containing layer (B).Preferred lower limit is 20 quality %, and the preferred upper limit is 40 quality %.
The total amount of above-mentioned heat-resistant resin and fluoropolymer (a) can be the total amount of the solid constituent of heat-resistant resin and fluoropolymer (a), in this description, is the material of solid when above-mentioned " solid constituent " refers to 20 DEG C.In this description, above-mentioned " the solid constituent total amount of above-mentioned heat-resistant resin and fluoropolymer (a) " refers to subbing coating composition (i) to coat after on base material and carries out drying in the temperature of 80 DEG C ~ 100 DEG C, then the gross mass of the above-mentioned heat-resistant resin fired at 380 DEG C ~ 400 DEG C after 45 minutes in residue and fluoropolymer (a).
In order to improve coating operations and the covered article corrosion resistance that obtains and water-fast vapor permeability further, above-mentioned subbing coating composition (i) while comprising above-mentioned fluoropolymer (a) and heat-resistant resin, can comprise the additive except packing material in fluorine-containing layer described later (B) further.
As above-mentioned additive, be not particularly limited, such as, levelling agent can be enumerated, kollag, sagging inhibitor, moisture absorber, surface conditioner, thixotropy conferring agents, viscosity modifier, anti-gel agent, ultra-violet absorber, light stabilizer, plasticizer, anti-agent of growing dim, anti skinning agent, scratching agent, mould inhibitor, antiseptic, antioxidant, antistatic additive, silane coupling agent, wood powder, quartz sand, carbon black, clay, talcum, diamond, tourmaline, emerald, germanium, extender pigment, the flat pigment of the bright properties such as aluminum slice, flakey pigment, glass, various reinforcing material, various inserts, electroconductive stuffing, gold, silver, the metal dusts etc. such as copper.
From the viewpoint of to obtained covered article base material and fluorine-containing layer (B), both have excellent adaptation, above-mentioned subbing coating composition (i) preferred polymers composition is fluoropolymer (a) and heat-resistant resin, from the viewpoint of improving further covered article corrosion resistance and water-fast vapor permeability, preferably while comprising fluoropolymer (a) and heat-resistant resin, also comprise other resins.
As other resins above-mentioned, be not particularly limited, such as, phenolic resins, carbamide resin, epoxy resin, carbamate resins, melmac, mylar, polyether resin, acrylic resin, acrylic compounds silicone resin, silicone resin, silicone mylar etc. can be enumerated.Covered articlely to obtain by firing, so other resins above-mentioned are preferably the resin of heat resistance due to of the present invention.
Above-mentioned operation (1) is following operation: on base material, coating is containing subbing coating composition (i) of fluoropolymer (a) with heat-resistant resin, thus forms subbing coating layer (Ap).
As the method for above-mentioned coating, be not particularly limited, when above-mentioned subbing coating composition (i) is liquid, such as, spraying, roller coat, scraper for coating, dip-coating, dip coated, eddy flow coating, curtain flow coat cloth etc. can be enumerated, wherein preferably spray.When above-mentioned subbing coating composition (i) is for powder, electrostatic applications, slipper dip method, rotational forming (ロ ト ラ イ ニ Application グ) method etc. can be enumerated, wherein preferred electrostatic applications.
Above-mentioned operation (1) as long as by being coated with above-mentioned subbing coating composition (i) thus forming above-mentioned subbing coating layer (Ap) on base material, can fire carry out operation (2) after above-mentioned coating before, also can not fire, in addition, when above-mentioned subbing coating composition (i) is liquid, drying can also be carried out after above-mentioned coating, also can not carry out drying.
In above-mentioned operation (1), above-mentioned drying preferably carries out 5 minutes ~ 60 minutes with the temperature of 70 DEG C ~ 300 DEG C.Above-mentioned firing preferably carries out 10 minutes ~ 30 minutes with the temperature of 260 DEG C ~ 410 DEG C.
When above-mentioned subbing coating composition (i) is liquid, above-mentioned operation (1) preferably carries out drying coating after on base material.In addition, owing to carrying out firing of laminate in aftermentioned operation (4), so preferably do not fire herein.
When above-mentioned subbing coating composition (i) is for powder, above-mentioned operation (1) is preferably fired coating after on base material.
Above-mentioned subbing coating layer (Ap) is formed by being coated with above-mentioned subbing coating composition (i) on base material.Above-mentioned subbing coating layer (Ap) can be formed by means of only above-mentioned coating in above-mentioned operation (1), also can be formed by dry afterwards in above-mentioned coating, can also be carry out drying as required after above-mentioned coating, then carry out firing being formed.Above-mentioned subbing coating layer (Ap) obtained covered article in become priming coat (A).
Covered article manufacture method of the present invention comprises following operation (2): in the upper coating of subbing coating layer (Ap) containing the fluorine-containing powder (ii) of melt processable fluoropolymer (b) with packing material, thus form fluorine-containing powder coating layer (Bp).
There is among the polymer that above-mentioned melt processable fluoropolymer (b) being has a fluorine atom be bonded directly on the carbon atom forming main chain or side chain the polymer of melt processable.
As above-mentioned melt processable fluoropolymer (b), the polymer among above-mentioned fluoropolymer (a) with melt processable can be used.From the viewpoint of fluorine-containing layer (B) and above-mentioned priming coat (A) and the excellent adhesion of fluorine-containing layer (C), the covered article corrosion resistance obtained and water-fast vapor permeability excellence, above-mentioned melt processable fluoropolymer (b) preferably has the fusing point of 150 DEG C ~ 350 DEG C and the melt viscosity at the temperature higher than fusing point 50 DEG C is 10 6(handkerchief second) polymer below, preferred above-mentioned TFE based copolymer.Above-mentioned melt processable fluoropolymer (b) can comprise one kind or two or more fluoropolymer.Above-mentioned melt processable fluoropolymer (b) being more preferably is selected from least one fluoropolymer in the group be made up of PFA and FEP.Above-mentioned melt processable fluoropolymer (b) can be PFA or FEP one matter separately, also can be their mixture.From the viewpoint of excellent heat resistance, above-mentioned melt processable fluoropolymer (b) more preferably PFA.In this description, above-mentioned " packing material " is to use for the purpose of obtained covered article imparting characteristic, raising physical property, increment etc.As above-mentioned characteristic and physical property, intensity, durability, weatherability, anti-flammability etc. can be enumerated.
As above-mentioned packing material, be not particularly limited, such as, can enumerate wood powder, quartz sand, carbon black, clay, talcum, diamond, tourmaline, emerald, germanium, extender pigment, the flat pigment of bright property, flakey pigment, glass, various reinforcing material, various inserts, electroconductive stuffing etc.When require of the present invention covered article have light sense, as above-mentioned packing material, preferred bright property packing material.Above-mentioned " bright property packing material " is the packing material can giving obtained covered article light sense.
As above-mentioned packing material, can enumerate the material, glass etc. that are classified as the flat pigment of bright property or flakey pigment, what can use in them is one kind or two or more.As the material being categorized as the flat pigment of above-mentioned bright property or flakey pigment, be not particularly limited, such as, can enumerate mica powder (comprising the mica powder of the coated processing such as the mica powder be coated to titanium dioxide), metal dust etc.As above-mentioned glass, be not particularly limited, such as, can enumerate the glass dust such as bead, glass marble, glass flake, glass fibre.In addition, can also use with the glass dust of the coating metal such as gold, silver, nickel; With the glass dust that titanium dioxide, iron oxide etc. are coating.As the above-mentioned material and the glass that are categorized as the flat pigment of bright property or flakey pigment, can use one kind or two or more respectively.
As above-mentioned packing material, be more preferably selected from least one packing material in the group be made up of mica powder, metal dust and glass dust.Such packing material can be only mica powder, metal dust or glass dust, also for mica powder, metal dust or glass dust and can give other packing materials that covered article light feels.Above-mentioned packing material can be the mixture of mica powder one matter, metal dust one matter, glass dust one matter, mica powder and metal dust, mica powder and the mixture of glass dust or the mixture of metal dust and glass dust.
Relative to melt processable fluoropolymer (b) 100 mass parts, packing material is preferably more than 0.001 mass parts and below 10 mass parts, is more preferably more than 0.01 mass parts and below 5 mass parts.
As above-mentioned metal dust, be not particularly limited, such as, can enumerate the powder of the metal simple-substances such as aluminium, iron, tin, zinc, gold, silver, copper; The powder etc. of the alloy such as aluminium alloy, stainless steel.As the shape of above-mentioned metal dust, be not particularly limited, such as, can enumerate graininess, flake etc., from the viewpoint of light sense excellence, preferably flake.Such as, the shape of aluminium powder is preferably laminar.
From the viewpoint of obtained covered article excellent corrosion resistance, above-mentioned packing material is particularly preferably at least one packing material in the group being selected from and being made up of mica powder and glass dust.Above-mentioned mica powder and glass dust are preferably bright property packing material.
From the viewpoint of light sense and economy excellence, above-mentioned packing material is at least one packing material be selected from the group that is made up of mica powder and aluminium powder is also one of preferred form.Mica powder and aluminium powder are more preferably bright property packing material.As such packing material, the mixture of mica powder one matter, aluminium powder one matter or mica powder and aluminium powder can be enumerated.
Fluorine-containing powder (ii) comprises melt processable fluoropolymer (b) and packing material.Above-mentioned fluorine-containing powder (ii), owing to being powder, therefore easily obtains thicker coating layer with less application frequency.
In above-mentioned fluorine-containing powder (ii), the above-mentioned average grain diameter comprising the particle of melt processable fluoropolymer (b) is preferably 0.1 μm ~ 50 μm, is more preferably 5 μm ~ 50 μm.The average grain diameter of above-mentioned packing material is preferably 0.1 μm ~ 600 μm.Be more preferably 1 μm ~ 600 μm, more preferably 5 μm ~ 200 μm.
It should be noted that, the average grain diameter of above-mentioned fluoropolymer (a), melt processable fluoropolymer (b) and (c) and packing material can be passed through laser scattering method (Nikkiso Company Limited's manufacture, microscratch Particle Size Analyzer, MODEL 9320-HRA type) and measure.
In order to improve coating operations and the covered article corrosion resistance that obtains and water-fast vapor permeability and medium in order to make above-mentioned packing material be scattered in fluorine-containing layer (B) equably further, above-mentioned fluorine-containing powder (ii) while comprising melt processable fluoropolymer (b) and packing material, also can comprise additive.The additive same with the additive that can be used in above-mentioned subbing coating composition (i) can be used.In order to make the above-mentioned packing material stable dispersion such as the flat pigment of bright property, above-mentioned fluorine-containing powder (ii) preferably comprises pigment dispersing agent.
Above-mentioned operation (2) by being coated with fluorine-containing powder (ii) and forming fluorine-containing powder coating layer (Bp) on above-mentioned subbing coating layer (Ap).As above-mentioned coating process, be not particularly limited, such as can enumerate with above-mentioned subbing coating composition (i) is the identical method etc. of coating process during powder, wherein preferred electrostatic applications.
In above-mentioned operation (2), after base material is coated with fluorine-containing powder (ii), can fire.The preferred temperature with 260 DEG C ~ 410 DEG C in the same manner as firing in above-mentioned operation (1) of firing in above-mentioned operation (2) carries out 10 minutes ~ 30 minutes.
Above-mentioned fluorine-containing powder (ii), owing to carrying out firing of laminate in operation described later (4), therefore coating after on above-mentioned subbing coating layer (Ap), is not preferably fired usually.
Fluorine-containing powder coating layer (Bp) is by being formed above-mentioned subbing coating layer (Ap) the above-mentioned fluorine-containing powder of upper coating (ii).Above-mentioned fluorine-containing powder coating layer (Bp) can be formed by means of only above-mentioned coating in above-mentioned operation (2), also can carry out as required firing and being formed after above-mentioned coating.Above-mentioned fluorine-containing powder coating layer (Bp) obtained covered article among become fluorine-containing layer (B).
Covered article manufacture method of the present invention is due to the good dispersion of packing material in fluorine-containing powder (ii), therefore in obtained covered article fluorine-containing layer (B), packing material disperses equably, and the characteristics such as the light sense that packing material has can stably show.
Manufacture method of the present invention comprises following operation (3): at the fluorine-containing powder (iii) of the upper coating of above-mentioned fluorine-containing powder coating layer (Bp) containing melt processable fluoropolymer (c), thus form fluorine-containing powder coating layer (Cp).
There is among the polymer that above-mentioned melt processable fluoropolymer (c) being has a fluorine atom be bonded directly on the carbon atom forming main chain or side chain the polymer of melt processable.
As above-mentioned melt processable fluoropolymer (c), the polymer among above-mentioned fluoropolymer (a) with melt processable can be used.Above-mentioned melt processable fluoropolymer (c) is for having the polymer of melt processable in above-mentioned fluoropolymer (a), identical with above-mentioned melt processable fluoropolymer (b) in this, but be in the polymer this point in fluorine-containing layer (C) at it, above-mentioned melt processable fluoropolymer (c) is from the polymer in fluorine-containing layer (B)---above-mentioned melt processable fluoropolymer (b) is different.
As above-mentioned melt processable fluoropolymer (c),, fluorine-containing layer (C) excellent from the viewpoint of film forming to the excellent adhesion of above-mentioned fluorine-containing layer (B) and the covered article corrosion resistance obtained and water-fast vapor permeability excellence, preferably identical with above-mentioned melt processable fluoropolymer (b) polymer.In addition, preferably there is the fusing point of 150 DEG C ~ 350 DEG C and the melt viscosity at the temperature higher than fusing point 50 DEG C is 10 6(handkerchief second) polymer below.As such melt processable fluoropolymer (c), TFE based copolymer can be enumerated.As above-mentioned melt processable fluoropolymer (c), from the viewpoint of heat resistance, non-adhesive and film forming excellence, be preferably selected from least one polymer in the group be made up of PFA and FEP.Above-mentioned melt processable fluoropolymer (c) can be the mixture of PFA one matter, FEP one matter or PFA and FEP.As above-mentioned melt processable fluoropolymer (c), more excellent from the viewpoint of heat resistance, more preferably PFA.
Above-mentioned operation (3) is following operation: at the fluorine-containing powder (iii) of the upper coating of fluorine-containing powder layer (Bp) containing melt processable fluoropolymer (c), thus form fluorine-containing powder coating layer (Cp).By containing the fluorine-containing powder (iii) of melt processable fluoropolymer (c) in the upper use of fluorine-containing powder layer (Bp), thus easily obtain thicker coating layer with less application frequency.In addition, due to above-mentioned fluorine-containing layer (C) can be made to form thicker layer, therefore, it is possible to form the covered article of excellent wear resistance.
In order to improve coating operations and the covered article corrosion resistance that obtains and water-fast vapor permeability further, above-mentioned fluorine-containing powder (iii) can while comprising melt processable fluoropolymer (c), also comprise additive, this additive is identical with the additive that can be used in above-mentioned subbing coating composition (i).
The average grain diameter of above-mentioned melt processable fluoropolymer (c) is preferably 5 μm ~ 50 μm.The preferred lower limit of the average grain diameter of the particle containing above-mentioned melt processable fluoropolymer (c) is 10 μm, and the preferred upper limit is 30 μm.
Above-mentioned operation (3) utilizes above-mentioned melt processable fluoro-containing composition above-mentioned fluorine-containing powder coating layer (Bp) the fluorine-containing coating layer of upper formation (Cp).
The method forming above-mentioned fluorine-containing layer (Cp) is at the above-mentioned melt processable fluoro-containing composition of the upper coating of above-mentioned fluorine-containing powder coating layer (Bp).As above-mentioned coating process, be not particularly limited, such as can enumerate with above-mentioned subbing coating composition (i) is the identical method etc. of coating process during powder, wherein preferred electrostatic applications.
Above-mentioned fluorine-containing layer (Cp) is by being formed at above-mentioned fluorine-containing powder coating layer (Bp) the above-mentioned melt processable fluoro-containing composition of upper use.Above-mentioned fluorine-containing layer (Cp) also can carry out as required firing and being formed after above-mentioned coating, above-mentioned fluorine-containing layer (Cp) become obtained covered article in fluorine-containing layer (C).
Manufacture method of the present invention comprises following operation (4): by firing the laminate comprising base material, above-mentioned subbing coating layer (Ap), above-mentioned fluorine-containing powder coating layer (Bp) and above-mentioned fluorine-containing powder coating layer (Cp), thus formation comprises the covered article of base material, priming coat (A), fluorine-containing layer (B) and fluorine-containing layer (C).
Above-mentioned in operation (4) is fired the preferred temperature with 260 DEG C ~ 410 DEG C in the same manner as firing in above-mentioned operation (1) ~ (3) and carries out 10 minutes ~ 30 minutes.
Covered article manufacture method of the present invention also can have the operation of printing word, picture etc. after the operation (1) forming above-mentioned subbing coating layer (Ap) or after the operation (2) of the above-mentioned fluorine-containing powder coating layer (Bp) of formation.Such as when covered article be pot for cooking rice, above-mentioned word, picture etc. are represent the word of the water yield and line etc.
As above-mentioned printing process, be not particularly limited, such as, can enumerate trans-printing (パ Star De translocation writes printing).As the printing-ink for above-mentioned printing, be not particularly limited, such as, can enumerate the composition be made up of PES, TFE homopolymers and titanium dioxide.
The invention still further relates to by above-mentioned manufacture method obtain covered article.Above-mentionedly covered articlely be laminated with base material, priming coat (A), fluorine-containing layer (B) and fluorine-containing layer (C) successively.Usually, covered article each interlayer in base material, priming coat (A), fluorine-containing layer (B) and fluorine-containing layer (C) of the present invention is not mingled with other layers, but, as required such as also can at the interlayer of priming coat (A) with fluorine-containing layer (B) or other layers of intercalation of fluorine-containing layer (B) and fluorine-containing layer (C).
Above-mentioned priming coat (A) comprises fluoropolymer (a) and heat-resistant resin.
Above-mentioned priming coat (A) is formed on base material usually.Above-mentioned priming coat (A) obtains in the following way: on base material, coating comprises aftermentioned subbing coating composition (i) of fluoropolymer (a) and heat-resistant resin, and carry out drying as required, then fire and obtain above-mentioned priming coat (A).In above-mentioned priming coat (A), because above-mentioned fluoropolymer (a) is different with the surface tension of above-mentioned heat-resistant resin, when firing, above-mentioned fluoropolymer (a) can be floated, therefore above-mentioned fluoropolymer (a) is mainly configured at the face side away from base material, and above-mentioned heat-resistant resin is mainly configured at substrate side.
Because above-mentioned heat-resistant resin and base material have cementability, the therefore excellent adhesion of above-mentioned priming coat (A) and base material.In addition, because above-mentioned fluoropolymer (a) and melt processable fluoropolymer (b) have compatibility, the therefore excellent adhesion of above-mentioned priming coat (A) and fluorine-containing layer (B).Like this, above-mentioned priming coat (A) all has excellent adaptation for both base material and fluorine-containing layer (B).
In above-mentioned priming coat (A), above-mentioned PES is preferably PES and 65 quality % ~ 90 quality % of the total amount of at least one resin be selected from the group that is made up of PAI and PI, is more preferably 65 quality % ~ 85 quality %.
Above-mentioned priming coat (A) comprises above-mentioned fluoropolymer (a) and above-mentioned heat-resistant resin, and above-mentioned heat-resistant resin is preferably 15 quality % ~ 50 quality % of the total amount of above-mentioned heat-resistant resin and fluoropolymer (a).
Above-mentioned priming coat (A) preferably comprises component of polymer and above-mentioned additive.The component of polymer of preferred above-mentioned priming coat (A) is fluoropolymer (a) and heat-resistant resin.In this description, above-mentioned " component of polymer of priming coat (A) is fluoropolymer (a) and heat-resistant resin " refers to that the polymer in priming coat (A) is only fluoropolymer (a) and heat-resistant resin.Above-mentioned priming coat (A) is fluoropolymer (a) and heat-resistant resin by making its component of polymer, thus all has excellent adaptation for both base material and fluorine-containing layer described later (B).
From the viewpoint of for base material and fluorine-containing layer (B), both all have excellent adaptation, above-mentioned priming coat (A) preferred polymers composition is fluoropolymer (a) and heat-resistant resin, but from the viewpoint of improving further covered article corrosion resistance and water-fast vapor permeability, while comprising fluoropolymer (a) and heat-resistant resin, can also comprise other resins.As other resins, above-mentioned resin can be enumerated.
Above-mentioned priming coat (A) preferably thickness is 5 μm ~ 30 μm.If thickness lower than 5 μm, then easily produces pin hole, covered article corrosion resistance likely reduces.If thickness more than 30 μm, then easily cracks, covered article water-fast vapor permeabilityly likely to reduce.The preferred upper limit of the thickness of above-mentioned priming coat (A) is 20 μm.
Of the present invention covered articlely have the fluorine-containing layer (B) comprising melt processable fluoropolymer (b) and packing material.
Of the present inventionly covered articlely on above-mentioned priming coat (A), be laminated with above-mentioned fluorine-containing layer (B).Above-mentioned fluorine-containing layer (B) is laminated with fluorine-containing layer described later (C) thereon.
In above-mentioned fluorine-containing layer (B), above-mentioned packing material is preferably 0.001 quality % ~ 10 quality % relative to melt processable fluoropolymer (b).When above-mentioned fluorine-containing layer (B) comprises the packing material can giving light sense, if this packing material is lower than 0.001 quality %, then obtained covered article light sense is insufficient, if more than 10 quality %, then and corrosion resistance and water-fastly vapor permeabilityly likely to reduce.The preferred lower limit of above-mentioned packing material is 0.01 quality %, and preferred upper limit is 5 quality %.
Above-mentioned fluorine-containing layer (B) preferably comprises component of polymer, packing material and above-mentioned additive.In addition, the component of polymer of preferred above-mentioned fluorine-containing layer (B) is melt processable fluoropolymer (b).In this description, above-mentioned " component of polymer of fluorine-containing layer (B) is melt processable fluoropolymer (b) " refers to that the polymer in fluorine-containing layer (B) is only melt processable fluoropolymer (b).Above-mentioned fluorine-containing layer (B) is melt processable fluoropolymer (b) by making its component of polymer, thus all has excellent adaptation for both above-mentioned priming coat (A) and fluorine-containing layer described later (C).
Above-mentioned fluorine-containing layer (B) preferably thickness is 0.1 μm ~ 30 μm.When using the packing material with light sense to feel to give covered article light, if thickness is lower than 0.1 μm, then obtained covered article light sense is sometimes insufficient.If thickness is more than 30 μm, then fluorine-containing layer (B) easily cracks, and covered article water-fast vapor permeabilityly likely to reduce.The preferred lower limit of the thickness of above-mentioned fluorine-containing layer (B) is 1 μm, and the preferred upper limit is 25 μm.
Of the present invention covered articlely have the fluorine-containing layer (C) formed by melt processable fluoropolymer (c).
Of the present inventionly covered articlely in above-mentioned fluorine-containing layer (B), be formed with fluorine-containing layer (C).Above-mentioned fluorine-containing layer (C), for being formed at the layer in above-mentioned fluorine-containing layer (B), being fired under being preferably the temperature more than the fusing point of melt processable fluoropolymer (c) and is formed.
Require obtained covered article there is the aesthetic appearance such as light sense time, above-mentioned fluorine-containing layer (C) is hyaline layer preferably.If above-mentioned fluorine-containing layer (C) is hyaline layer, then can be seen clearly the packing material in above-mentioned fluorine-containing layer (B) by fluorine-containing layer (C), thus use there is light sense material as packing material time, of the present invention covered articlely have good light sense.
In addition, if above-mentioned fluorine-containing layer (C) is hyaline layer, then because above-mentioned fluorine-containing layer (C) does not comprise the coloring pigment being usually considered to cause corrosion resistance to worsen, thus the obtained covered article more excellent corrosion resistance and water-fast vapor permeability of having.
Above-mentioned fluorine-containing layer (C) is also preferably containing component of polymer and additive.In addition, the component of polymer of preferred above-mentioned fluorine-containing layer (C) is melt processable fluoropolymer (c).In this description, above-mentioned " component of polymer of fluorine-containing layer (C) is melt processable fluoropolymer (c) " refers to that the polymer in fluorine-containing layer (C) is only melt processable fluoropolymer (c).Above-mentioned fluorine-containing layer (C) is melt processable fluoropolymer (c) by making its component of polymer, thus has excellent adaptation for above-mentioned fluorine-containing layer (B).
Above-mentioned fluorine-containing layer (C) preferably thickness is 10 μm ~ 90 μm.If thickness lower than 10 μm, then easily produces pin hole, covered article corrosion resistance and abrasion performance likely reduce.If thickness is more than 90 μm, then covered article when being under the condition that there is steam, steam easily remain in covered article in, water-fast vapor permeabilityly have the time difference.The preferred lower limit of the thickness of above-mentioned fluorine-containing layer (C) is 30 μm, and the preferred upper limit is 70 μm.
It should be noted that, the thickness of above-mentioned each layer can utilize the commercially available film thickness gauges such as high frequency type film thickness gauge to measure.
Covered article lamination successively of the present invention above-mentioned base material, above-mentioned priming coat (A), above-mentioned fluorine-containing layer (B) and above-mentioned fluorine-containing layer (C).As long as covered article lamination successively of the present invention above-mentioned base material, above-mentioned priming coat (A), above-mentioned fluorine-containing layer (B) and above-mentioned fluorine-containing layer (C), then can on above-mentioned priming coat (A) and/or above-mentioned fluorine-containing layer (B) above implement the printing of word, picture etc.
In addition, covered article there is above-mentioned priming coat (A), above-mentioned fluorine-containing layer (B) and above-mentioned fluorine-containing layer (C) as mentioned above as long as of the present invention, in above-mentioned fluorine-containing layer (C), layer can also be set further.
As mentioned above, of the present invention covered article in, the fluorine-containing layer (B) that the priming coat (A) that base material is formed is formed comprises melt processable fluoropolymer (b) and packing material, comprises melt processable fluoropolymer (c) in the upper fluorine-containing layer (C) formed of fluorine-containing layer (B).
Because covered article melt processable fluoropolymer (b) of the present invention and melt processable fluoropolymer (c) all have melt processable, thus the excellent adhesion of fluorine-containing layer (B) and fluorine-containing layer (C), corrosion resistance and water-fast vapor permeability excellence.There is the problem of water-fast vapor permeability difference in the existing priming coat of lamination successively, the intermediate layer formed by TFE homopolymers and the top coat that formed by PFA and the laminate that obtains, this problem is considered to cause owing to easily peeling off between priming coat and intermediate layer.Can think that the reason of this stripping is because the coefficient of thermal expansion of TFE homopolymers and PFA, the shrinkage factor that caused by heat there are differences, intermediate layer and the easy remaining internal stress (strain) of top coat or easily produce pin hole, thus easily between priming coat and intermediate layer, produce this stripping.As mentioned above, the excellent adhesion between covered article fluorine-containing layer (B) of the present invention and fluorine-containing layer (C), corrosion resistance and water-fast vapor permeability excellence, and abrasion performance is also excellent.
In addition, of the present invention covered article due to above-mentioned packing material can be disperseed equably in fluorine-containing layer (B), when thus there is the material of light sense as packing material use, light sense excellence.In addition, of the present invention covered article due to packing material not contact substrate, even if when thus such as using above-mentioned metal dust as packing material, corrosion resistance is also excellent.
As of the present invention covered article, be not particularly limited, can use in the purposes of the non-adhesive utilizing fluoropolymer to have, heat resistance, sliding etc., such as utilizing the covered article of non-adhesive, frying pan can be enumerated, pressure cooker, pot, striped side decoct the device for cooking such as dish, pot for cooking rice, baking oven, heating plate, toaster, kitchen knife, gas range; The kitchen articles etc. such as insulating pot, ice-making disc, metal die, range hood, as utilizing the covered article of sliding, can enumerate the instruments such as saw, file; The household supplies such as flatiron; Metal forming etc.Wherein, preferably require that dish is decocted by corrosion resistance and water-fast vapor permeability pot for cooking rice, pressure cooker and striped side, more preferably require the pot for cooking rice of aesthetic appearance.
Covered article manufacture method of the present invention by having above-mentioned formation, thus can manufacture corrosion resistance, water-fast vapor permeability and excellent wear resistance and also can stablize when a large amount of production and manifest the covered article of the packing material characteristics such as light sense.
Detailed description of the invention
Enumerate embodiment and comparative example below, the present invention will be described in more detail, but the present invention is not limited in these embodiments." % " and " part " represents quality %, mass parts respectively.
The preparation of Production Example 1 polyethersulfone resin water-borne dispersions
Number-average molecular weight is about polyethersulfone resin [PES] 60 parts and deionized water 60 parts stir about 10 minutes in ceramic ball mill of 24000, until the particle formed by PES is pulverized completely.Next, add METHYLPYRROLIDONE (hereinafter referred to as NMP) 180 parts, pulverize 48 hours further, obtain dispersion.Obtained dispersion is pulverized 1 hour with sand mill further, obtains the PES water-borne dispersions that PES concentration is about 20%.The average grain diameter of the particle formed by PES in PES water-borne dispersions is 2 μm.
The preparation of Production Example 2 polyamide-imide resin water-borne dispersions
By solid constituent be 29% polyamide-imide resin [PAI] varnish (NMP containing 71%) drop in water, PAI is separated out.It is pulverized 48 hours in ball mill, obtains PAI water-borne dispersions.The solid constituent of the PAI water-borne dispersions obtained is that the average grain diameter of the PAI in 20%, PAI water-borne dispersions is 2 μm.
The preparation of coating composition (i) of Production Example 3 subbing
By the PAI water-borne dispersions mixing obtained in the PES water-borne dispersions obtained in Production Example 1 and Production Example 2, 85% of the solid constituent total amount being PES and PAI to make PES, (average grain diameter is 0.28 μm to add proplast [TFE homopolymers] water-borne dispersions wherein, solid constituent is 60%, containing relative to TFE homopolymers is that polyethers system nonionic surface active agent (polyoxyethylene tridecyl ether) of 6% is as dispersant), to make PES and PAI for PES, 20% of the solid constituent total amount of PAI and TFE homopolymers, and adding relative to the solid constituent of TFE homopolymers is that the methylcellulose of 0.7% is as thickener, adding relative to the solid constituent of TFE homopolymers is that the nonionic surface active agent (ethylene nonyl phenyl ether) of 6% is as dispersion stabilizer, the solid constituent obtaining TFE homopolymers is the aqueous liquid dispersion of 34%.
The preparation of the powder coating composition of Production Example 4 containing packing material
In tetrafluoroethylene/perfluoro (alkyl vinyl ether) [PFA] powder coating (trade name: ACX-31, Daikin Industries society manufacture, the average grain diameter of PFA be 25 μm), add relative to PFA be 0.5% glass flake (relative density is about 2.5, average grain diameter is 40 μm; Glass flake with titanium dioxide is coated to) mix as packing material, obtain powder coating composition.
The relatively preparation of the water-borne dispersions of Production Example 1 containing packing material
In tetrafluoroethylene/perfluoro (alkyl vinyl ether) [PFA] water-borne dispersions (average grain diameter is 0.35 μm, solid constituent is 48%, containing be that the polyethers system nonionic surface active agent of 6% is as dispersant relative to PFA), add relative to the solid constituent of PFA be 0.6% mica powder (relative density is about 3, average grain diameter is 30 μm; Mica with titanium dioxide has been coated to) as packing material, obtain the aqueous liquid dispersion that solid constituent is 48%.
Embodiment
By the surface of aluminium sheet (A-1050P) with after acetone degreasing, carry out sandblasting to make the surface roughness Ra value measured based on JIS B 1982 be 2.0 μm ~ 3.0 μm, make surface roughening.After dust by air blast removing surface, RG-2 type gravity type spray gun (trade name, the manufacture of ア ネ ス ト Yan Tian society, nozzle diameter are 1.0mm) is utilized to spray subbing coating composition (i) obtained in Production Example 3 with expulsion pressure 0.2MPa, to make dry film thickness for about 10 μm.By the coating layer on obtained aluminium sheet at 80 DEG C ~ 100 DEG C dry 15 minutes, and be cooled to room temperature.To apply the powder coating composition containing packing material obtained in voltage is 50kV, pressure is 0.08MPa condition electrostatic applications Production Example 4 on obtained subbing coating layer, to make the thickness after firing for about 25 μm.Thereon to apply the condition electrostatic applications PFA powder coating (average grain diameter of trade name: ACX-31, the manufacture of Daikin Industries society, PFA is 25 μm) that voltage is 50kV, pressure is 0.08MPa, to make to fire rear thickness for about 40 μm, and obtained unfired laminate is fired 20 minutes at 380 DEG C, obtain test coated panel.The layer that the test coated panel obtained is formed with priming coat on aluminium sheet, packing material contains layer and formed by PFA.
(evaluation method)
Film for obtained test coated panel carries out following evaluation.
Thickness
High frequency type film thickness gauge (trade name: LZ-300C, ケ Star ト scientific research is manufactured) is used to measure.
The corrosion resistance test of mixture powder (ぉ In ん element)
With cutter in the film coated surface cross-cut of obtained test coated panel to form the scar of through aluminium sheet.This test coated panel is impregnated into by 20g mixture powder (water-soluble powder flavoring; ヱ ス PVC one food society manufactures) be dissolved in the solution formed in 1 premium on currency, 70 DEG C of insulations, visualization in every 100 hours has the exceptions such as bubble-free generation, and test proceeds to 1000 hours.It is qualified to be designated as when not having bubble generation etc. abnormal, confirm bubble generation etc. abnormal time be designated as defective.
Resistance to water-vapo(u)r test
Obtained test coated panel is placed 8 hours in the steam of 0.6MPa, is taken out after returning normal pressure, then with 200 DEG C of heating 1 minute.In this, as 1 circulation, repeatedly carry out 10 circulations, investigation has bubble-free generation.It is qualified that 10 circulations are designated as when not producing bubble, is designated as defective when producing bubble within 10 circulations.
The test coated panel obtained in embodiment is qualified in the corrosion resistance test of mixture powder, in resistance to water-vapo(u)r test, do not produce bubble to 10 circulations, also qualified.
Comparative example
With subbing with in the same manner as coating composition (i), on the subbing coating layer obtained in an embodiment, the water-borne dispersions containing packing material obtained in Production Example 1 is compared in spraying, to replace the powder coating composition containing packing material obtained in Production Example 4, and dry film thickness is made to be about 25 μm.By the obtained coating layer containing packing material at 80 DEG C ~ 100 DEG C dry 15 minutes, and be cooled to room temperature.To apply the condition electrostatic applications PFA powder coating (average grain diameter of trade name: ACX-31, the manufacture of Daikin Industries society, PFA is 25 μm) that voltage is 50kV, pressure is 0.08MPa on the obtained coating layer containing packing material, and fire 20 minutes with 380 DEG C, form the PFA layer that thickness is about 40 μm, make test coated panel and evaluate.
The test coated panel obtained is qualified in the corrosion resistance test of mixture powder, but produces bubble after 3 circulations in resistance to water-vapo(u)r test, and result is defective.Be visually observed in addition: carried out containing between layer at priming coat and packing material in the part of the generation bubble of the test coated panel after resistance to water-vapo(u)r test creating stripping.
Defining packing material at the PFA powder coating used containing packing material contains in the embodiment of layer, the corrosion resistance of the test coated panel obtained and water-fast both equal excellence vapor permeability; But define packing material contain in the comparative example of layer using the water-borne dispersions that comprises PFA and packing material, although the excellent corrosion resistance of the test coated panel obtained, be positioned in steam and bubble can be caused to produce, water-fast vapor permeability difference.
Industrial applicibility
Covered article manufacture method of the present invention has above-mentioned formation, therefore, it is possible to obtain corrosion resistance and water-fast vapor permeability excellence and also can stablize when a large amount of production manifesting the covered article of the packing material characteristics such as light sense.

Claims (11)

1. a covered article manufacture method, is characterized in that, this manufacture method comprises following operation:
Operation (1), by coating on base material containing the subbing coating composition (i) of fluoropolymer (a) with the liquid state of heat-resistant resin, thus forms subbing coating layer (Ap);
Operation (2), by containing the fluorine-containing powder (ii) of melt processable fluoropolymer (b) and packing material in the upper coating of above-mentioned subbing coating layer (Ap), thus form fluorine-containing powder coating layer (Bp);
Operation (3), by containing the fluorine-containing powder (iii) of melt processable fluoropolymer (c) in the upper coating of above-mentioned fluorine-containing powder coating layer (Bp), thus forms fluorine-containing powder coating layer (Cp); And
Operation (4), by firing the laminate comprising base material, above-mentioned subbing coating layer (Ap), above-mentioned fluorine-containing powder coating layer (Bp) and above-mentioned fluorine-containing powder coating layer (Cp), thus formation comprises the covered article of base material, priming coat (A), fluorine-containing layer (B) and fluorine-containing layer (C).
2. manufacture method covered article as claimed in claim 1, wherein,
The average grain diameter of melt processable fluoropolymer (b) is 5 μm ~ 50 μm,
Relative to melt processable fluoropolymer (b) 100 mass parts, packing material is more than 0.01 mass parts and below 5 mass parts.
3. manufacture method covered article as claimed in claim 1 or 2, wherein, above-mentioned heat-resistant resin is be selected from least one resin in the group that is made up of polyamide-imide resin, polyimide resin, polyethersulfone resin, polyetherimide resin, polyether-ether-ketone resin, aromatic polyester resins and polyarylene sulfide resin.
4. manufacture method covered article as claimed in claim 3, wherein,
Heat-resistant resin comprises polyethersulfone resin and at least one resin be selected from the group that is made up of polyamide-imide resin and polyimide resin,
Polyethersulfone resin is 65 quality % ~ 90 quality % of the total amount of this polyethersulfone resin and the above-mentioned at least one resin be selected from the group be made up of polyamide-imide resin and polyimide resin.
5. manufacture method covered article as claimed in claim 1 or 2, wherein, heat-resistant resin is 15 quality % ~ 50 quality % of the total amount of above-mentioned heat-resistant resin and fluoropolymer (a).
6. manufacture method covered article as claimed in claim 1 or 2, wherein, melt processable fluoropolymer (c) is for being selected from least one copolymer in the group that is made up of tetrafluoroethylene/perfluoro (alkyl vinyl ether) copolymer and tetrafluoroethylene/hexafluoropropylene copolymer.
7. manufacture method covered article as claimed in claim 1 or 2, wherein, fluoropolymer (a) is for being selected from least one polymer in the group that is made up of proplast, modified Teflon, tetrafluoroethylene/hexafluoropropylene copolymer and tetrafluoroethylene/perfluoro (alkyl vinyl ether) copolymer.
8. manufacture method covered article as claimed in claim 1 or 2, wherein, melt processable fluoropolymer (b) is for being selected from least one copolymer in the group that is made up of tetrafluoroethylene/perfluoro (alkyl vinyl ether) copolymer and tetrafluoroethylene/hexafluoropropylene copolymer.
9. manufacture method covered article as claimed in claim 1 or 2, wherein, packing material is be selected from least one packing material in the group that is made up of mica powder and glass dust.
10. manufacture method covered article as claimed in claim 1 or 2, wherein,
The thickness of priming coat (A) is 5 μm ~ 30 μm,
The thickness of fluorine-containing layer (B) is 0.1 μm ~ 30 μm,
The thickness of fluorine-containing layer (C) is 10 μm ~ 90 μm.
11. 1 kinds covered article, it is characterized in that, it is obtained by the manufacture method described in claim 1,2,3,4,5,6,7,8,9 or 10.
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