CN103889719B - Fluorine-containing laminate and manufacture method thereof - Google Patents

Fluorine-containing laminate and manufacture method thereof Download PDF

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Publication number
CN103889719B
CN103889719B CN201280050999.XA CN201280050999A CN103889719B CN 103889719 B CN103889719 B CN 103889719B CN 201280050999 A CN201280050999 A CN 201280050999A CN 103889719 B CN103889719 B CN 103889719B
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mentioned
fluorine
layer
resin
fluoropolymer
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CN103889719A (en
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山口诚太郎
荻田耕郎
荻田耕一郎
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Daikin Industries Ltd
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Daikin Industries Ltd
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    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
    • A47J36/00—Parts, details or accessories of cooking-vessels
    • A47J36/02—Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay
    • A47J36/025—Vessels with non-stick features, e.g. coatings
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • 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

Abstract

The present invention provides a kind of and there is not paint film defect, the fluorine-containing laminate of excellent corrosion resistance and manufacture method thereof.The present invention relates to a kind of fluorine-containing laminate, described fluorine-containing laminate has base material, priming coat (A), the powder coating (ii) containing melt processable fluoropolymer (b) layer (B) formed and the layer (C) formed by the liquid coating (iii) comprising the particle being made up of melt processable fluoropolymer (c), the average grain diameter of described powder coating (ii) is 5 μm～30 μm, further, the average grain diameter of the particle being made up of melt processable fluoropolymer (c) is 0.01 μm～1.0 μm.

Description

Fluorine-containing laminate and manufacture method thereof
Technical field
The present invention relates to fluorine-containing laminate and manufacture method thereof.
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 food industry articles for use, frying pan or pot etc. In the Surface Machining of the household supplies such as kitchen appliance, flatiron, electrical industry articles for use, mechanical industry articles for use etc..
Surface Machining is to carry out by forming the layer being made up of fluoropolymer on base material, and used is fluorine-containing poly- Compound if the fluoropolymer of the melt processables such as PFA, then easily obtains thicker layer by common industrial process, The surface of obtained article easily plays the various characteristics that fluoropolymer is had.
But, fluoropolymer lacks the adaptation with base material because of its non-adhesive.In order to improve this adaptation, propose Having priming coat and the laminate of layer being made up of fluoropolymer, wherein, priming coat is viscous with mixture heat-resistant resin etc. The priming paint tying agent resin and fluoropolymer and obtain is coated with in advance as primary coat (lower り) and installs to obtain on base material.
Such as, as the laminate of 3-tier architecture (wherein except base material), disclose following laminate, this laminate be Layer that on the metal base material of pot for cooking rice, lamination fluororesin priming coat, the powder coating that is made up of PFA are formed successively and by PTFE structure Become aqueous dispersion coating formed layer (for example, referring to patent document 1.).Patent document 1 describe have such Release property and initial stage release property during the Long-Time Service of the pot for cooking rice of laminate are excellent.
Prior art literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 11-342072 publication
Summary of the invention
The problem that invention is to be solved
When manufacturing the laminate with priming coat and the layer that is made up of fluoropolymer, in order to improve wearability, intensity Deng, and making film is thick film, usually melt processable fluoropolymer is carried out electrostatic powder body coating for this.If utilizing electrostatic powder Body application, it is possible to be the thickness about 40 μm after being fired with an application.
But, in electrostatic powder body coating, sometimes because of the Coulomb repulsion each other of melt processable fluoropolymer particles And producing paint film defect (pin hole), this paint film defect also remains in film after firing, therefore has and makes corrosion resistance reduce Problem.
On the other hand, the laminate disclosed in patent document 1 has top layer, and described top layer is by being coated with by PFA powder It is coated with aqueous dispersion coating on the intermediate layer that material is formed and is formed.This top layer is PTFE film, and therefore release property is excellent, but The PTFE constituting top layer is significantly different with the thermal coefficient of expansion of the PFA constituting intermediate layer and melt viscosity, and therefore PTFE film holds Being easily generated crackle and paint film defect, corrosion resistance is the most insufficient.
So, prior art there is also the leeway of the research for improving corrosion resistance.
In view of above-mentioned present situation, it is an object of the invention to provide and a kind of there is not paint film defect, the containing of excellent corrosion resistance Fluorine laminate and manufacture method thereof.
For solving the scheme of problem
The inventors discovered that, priming coat is formed the laminate of the layer being made up of melt processable fluoropolymer In, if making this layer being made up of melt processable fluoropolymer be made up of following layer, then the corrosion resistance of this laminate shows Write and improve: the layer that (1) is formed by the powder coating with specific average grain diameter comprising melt processable fluoropolymer；With (2) by the liquid coating institute shape comprising the particle with other specific average grain diameter being made up of melt processable fluoropolymer The layer become.Its reason is considered as, above-mentioned powder coating the paint film defect produced in the film formed is by above-mentioned liquid coating Coating made up.Further, the present inventors have additionally discovered that there is the laminate of such composition as cooking appliance and kitchen articles Covering material in Deng is exceedingly useful, this completes the present invention.
That is, the present invention relates to a kind of fluorine-containing laminate, it is characterised in that described fluorine-containing laminate has base material, priming coat (A) layer (B) that, formed by the powder coating (ii) comprising melt processable fluoropolymer (b) and by comprising by melt-processed The layer (C) that the liquid coating (iii) of the particle that property fluoropolymer (c) is constituted is formed, the average particle of above-mentioned powder coating (ii) Footpath is 5 μm～30 μm, and, the average grain diameter of the particle being made up of melt processable fluoropolymer (c) is 0.01 μm～1.0 μm。
It addition, the invention still further relates to the manufacture method of a kind of fluorine-containing laminate, it is characterised in that described fluorine-containing laminate Manufacture method includes following operation: operation (1), primer coating coating composition (i) on base material, is consequently formed priming paint coating Film (Ap)；Operation (2), the powder comprising melt processable fluoropolymer (b) in the upper coating of above-mentioned priming paint coated film (Ap) is coated with Material (ii), is consequently formed coated film (Bp)；Operation (3), comprises by melt processable fluorine-containing in the upper coating of above-mentioned coated film (Bp) The liquid coating (iii) of the particle that polymer (c) is constituted, is consequently formed coated film (Cl)；And operation (4), to by the above-mentioned end The coated film laminate that paint coated film (Ap), above-mentioned coated film (Bp) and above-mentioned coated film (Cl) are constituted is fired, thus shape Become the fluorine-containing laminate being made up of base material, priming coat (A), layer (B) and layer (C)；The average grain diameter of above-mentioned powder coating (ii) is 5 μm～30 μm, and, the average grain diameter of the particle being made up of above-mentioned melt processable fluoropolymer (c) is 0.01 μm～1.0 μ m。
Below, the present invention is described in detail.
The layer (B) of the fluorine-containing laminate constituting the present invention is by the average particle comprising melt processable fluoropolymer (b) Footpath is that the powder coating (ii) of 5 μm～30 μm is formed.
Above-mentioned melt processable fluoropolymer (b) is to have and constitute main chain or the carbon atom Direct Bonding of side chain There is among the polymer of fluorine atom the material of melt processable.And, comprise the powder of this melt processable fluoropolymer (b) The average grain diameter of body coating (ii) is 5 μm～30 μm.So, the coating being used for being formed layer (B) has specific average grain diameter Powder, it is possible to easily obtain the coated film of thickness with less application number of times.Its result, at obtained fluorine-containing laminate In, more excellent corrosion resistance can be played.
If the average grain diameter of powder coating (ii) is too small, then the carried charge of powder increases, thus likely easily because of electrostatic Repelling and produce pin hole, if average grain diameter is excessive, then film the most easily produces space.
As the average grain diameter of above-mentioned powder coating (ii), preferably 10 μm～25 μm, more preferably 15 μm～25 μm.On The average grain diameter stating powder coating (ii) is equal with following values, and this value is to utilize laser diffraction formula particle size distribution device (day This electronics society manufactures), do not use cascade, under conditions of pressure 0.1MPa, minute 3 seconds mensuration size distribution, with gained The value corresponding to 50% that the size distribution arrived is accumulative.
The layer (C) of the fluorine-containing laminate constituting the present invention is made up of melt processable fluoropolymer (c) by comprising Average grain diameter is that the liquid coating (iii) of the particle of 0.01 μm～1.0 μm is formed.In this specification, " liquid " refers to 20 There is under normal temperature about DEG C the state of mobility.
Above-mentioned melt processable fluoropolymer (c) is to have and constitute main chain or the carbon atom Direct Bonding of side chain There is among the polymer of fluorine atom the material of melt processable.And, constitute being melted by above-mentioned of above-mentioned liquid coating (iii) The average grain diameter of the particle that processability fluoropolymer (c) is constituted is 0.01 μm～1.0 μm.Such fluorine-containing by melt processable The particle that particle diameter that polymer (c) is constituted is little can fill up the painting formed by the powder coating (ii) that average grain diameter is 5 μm～30 μm The paint film defect of film, therefore obtains the laminate that barrier is higher, corrosion resistance is good.
If the average grain diameter of the particle being made up of above-mentioned melt processable fluoropolymer (c) is too small, then particle easily coagulates Poly-, it is possible to the mechanical stability of infringement liquid coating, if average grain diameter is excessive, it is likely that be difficult to penetrate into by powder coating (ii) the paint film defect part of the film formed.
As the average grain diameter of above-mentioned particle, preferably 0.1 μm～0.7 μm, more preferably 0.1 μm～0.5 μm.By above-mentioned The average grain diameter of the particle that melt processable fluoropolymer (c) is constituted can utilize transmission electron microscope to observe and survey Fixed.
Above-mentioned liquid coating (iii) is as long as comprising the average grain diameter being made up of above-mentioned melt processable fluoropolymer (c) It is 0.01 μm～the particle of 1.0 μm and for liquid, is not particularly limited, generally, by fluorine-containing poly-with above-mentioned melt processable The particle that compound (c) is constituted is constituted with liquid medium.More specifically, above-mentioned liquid coating (iii) is typically by above-mentioned melted The particle that processability fluoropolymer (c) is constituted is scattered in liquid medium.
Below, the present invention will be described in more detail to enumerate concrete example.
As the base material of the fluorine-containing laminate constituting the present invention, it is not particularly limited, for example, it is possible to enumerate iron, aluminium, copper etc. The metals such as metal simple-substance and their alloy type；The non-metal inorganic materials etc. such as enamel, glass, pottery.As above-mentioned alloy Class, can enumerate stainless steel etc..As above-mentioned base material, preferably metal, more preferably aluminium or stainless steel.
Above-mentioned base material can carry out the surface such as ungrease treatment, roughening process as required and process.As above-mentioned roughening The method processed, is not particularly limited, for example, it is possible to enumerate utilization acid or the chemical etching of alkali, anodic oxidation (at alumite Reason), sandblasting etc..Process about above-mentioned surface, from can not produce depression and be coated with equably for forming above-mentioned priming coat (A) The aspect of priming paint coating composition (i) and the aspect etc. that improves of the adaptation of base material and priming paint coated film (Ap) set out, Suitably select according to the kind of base material, priming paint coating composition (i) etc., for example, it is preferable to be sandblasting.
Constitute the priming coat (A) of the fluorine-containing laminate of the present invention as long as the most not limiting with the excellent adhesion of base material, excellent Select and be made up of fluoropolymer (a) and heat-resistant resin.
Above-mentioned fluoropolymer (a) is being polymerized of the fluorine atom of the carbon atom Direct Bonding having with constituting main chain or side chain Thing.Above-mentioned fluoropolymer (a) can be non melt processable, it is also possible to for melt processable.
Above-mentioned fluoropolymer (a) preferably obtains by fluorine-containing single ethene system unsaturated hydrocarbons (I) being polymerized.
It is above-mentioned that " fluorine-containing single ethene system unsaturated hydrocarbons (I) is (hereinafter also referred to as " unsaturated hydrocarbons (I) ".) " refer to that molecule has There is the unsaturated hydrocarbons of a vinyl that be instead of part or all of hydrogen atom by fluorine atom.
Above-mentioned unsaturated hydrocarbons (I) can also be that part or all of the hydrogen atom that is not replaced by fluorine atoms is by chlorine atom etc. The material that the fluoro-alkyl such as halogen atom beyond fluorine atom and/or trifluoromethyl instead of.But, above-mentioned unsaturated hydrocarbons (I) is no Including trifluoro-ethylene described later.
As above-mentioned unsaturated hydrocarbons (I), it is not particularly limited, for example, it is possible to enumerate tetrafluoroethene (TFE), hexafluoropropene (HFP), CTFE (CTFE), vinylidene fluoride (VdF), PVF (VF) etc., these can use one kind or two or more.
Above-mentioned fluoropolymer (a) can be the homopolymers of above-mentioned unsaturated hydrocarbons (I).As above-mentioned unsaturated hydrocarbons (I) Homopolymers, for example, it is possible to enumerate proplast (TFE homopolymers), polytrifluorochloroethylene (PCTFE), poly-inclined difluoro second Alkene (PVdF), polyvinyl fluoride (PVF) etc..
It addition, above-mentioned fluoropolymer (a) can be at least a kind of above-mentioned unsaturated hydrocarbons (I) and can be with above-mentioned unsaturation The copolymer of the unsaturated compound (II) of hydrocarbon (I) copolymerization.
In the present invention, can by the polymer obtained by only one kind or two or more above-mentioned unsaturated hydrocarbons (I) being polymerized Use as above-mentioned fluoropolymer (a), on the other hand, by only one kind or two or more unsaturated compound (II) being polymerized Obtained polymer cannot function as above-mentioned fluoropolymer (a) and uses.In this, above-mentioned unsaturated compound (II) is with upper State unsaturated hydrocarbons (I) different.
As above-mentioned unsaturated compound (II), it is not particularly limited, for example, it is possible to enumerate trifluoro-ethylene (3FH)；Ethene Single ethene system such as (Et), propylene (Pr) unsaturated hydrocarbons etc..These can use one kind or two or more.
It addition, above-mentioned fluoropolymer (a) can be the copolymer of above-mentioned unsaturated hydrocarbons (I) of more than two kinds.As above-mentioned The copolymer of above-mentioned unsaturated hydrocarbons (I) of more than two kinds and above-mentioned at least a kind of above-mentioned unsaturated hydrocarbons (I) and unsaturated compound (II) copolymer, is not particularly limited, for example, it is possible to enumerate 2 membered copolymers, 3 membered copolymers etc..
As above-mentioned 2 membered copolymers, it is not particularly limited, for example, it is possible to enumerate VdF/HFP copolymer, Et/CTFE copolymerization Thing (ECTFE), Et/HFP copolymer etc..
It addition, above-mentioned 2 membered copolymers can be TFE/HFP copolymer (FEP), TFE/CTFE copolymer, TFE/VdF copolymerization The TFE based copolymers such as thing, TFE/3FH copolymer, Et/TFE copolymer (ETFE), TFE/Pr copolymer.In this specification, above-mentioned What " TFE based copolymer " referred in other monomer beyond by TFE and TFE one kind or two or more carries out the copolymerization that copolymerization obtains Thing.For above-mentioned TFE based copolymer, it is usually preferred that other beyond addition TFE in above-mentioned TFE based copolymer The ratio of monomer exceedes 1 mass % of above-mentioned TFE and the gross mass of other monomer above-mentioned.
As above-mentioned 3 membered copolymers, VdF/TFE/HFP copolymer etc. can be enumerated.
As other monomer beyond the above-mentioned TFE in above-mentioned TFE based copolymer, can be following can be with TFE copolymerization Other monomer (III).Above-mentioned other monomer (III) is preferably selected from by following formula
X(CF2)mOnCF=CF2
(in formula, X represents that-H ,-Cl or-F, m represent the integer of 1～6, and n represents the integer of 0 or 1.) compound that represents (wherein except HFP.), following formula
C3F7O[CF(CF3)CF2O]p-CF=CF2
(in formula, p represents the integer of 1 or 2.) compound that represents or following formula
X(CF2)qCY=CH2
(in formula, X is same as described above, and Y represents that-H or-F, q represent the integer of 1～6.) represent compound composition group in At least a kind of monomer.These can use one kind or two or more.As such TFE based copolymer, for example, it is possible to enumerate TFE/ perfluor (alkyl vinyl ether) (PAVE) copolymer (PFA) etc..
It addition, above-mentioned fluoropolymer (a) can be modified Teflon (modified ptfe).In this specification, above-mentioned " modified ptfe " refers to a small amount of comonomer and the TFE of the degree by obtained copolymer does not gives melt processable Carry out the material of copolymerization.As above-mentioned a small amount of comonomer, be not particularly limited, for example, it is possible to enumerate above-mentioned not HFP, CTFE etc. in saturated hydrocarbons (I), can enumerate the 3FH etc. in above-mentioned unsaturated compound (II), can enumerate above-mentioned its PAVE in its monomer (III), perfluor (alkoxyalkyl vinyl ethers), (perfluoroalkyl) ethene etc..Above-mentioned a small amount of copolymerization Can use one kind or two or more with monomer.
Above-mentioned a small amount of comonomer addition ratio in above-mentioned modified ptfe is different because of its kind, such as, makes In the case of PAVE, perfluor (alkoxyalkyl vinyl ethers) etc., generally, it is preferred to be above-mentioned TFE and above-mentioned a small amount of copolymerization By 0.001 mass %～1 mass % of the gross mass of monomer.
As above-mentioned fluoropolymer (a), can be one kind or two or more, can be the homopolymerization of above-mentioned unsaturated hydrocarbons (I) The one kind or two or more mixture of a kind of thing and the copolymer of above-mentioned unsaturated hydrocarbons (I) or above-mentioned unsaturated hydrocarbons (I) The mixture of more than two kinds of copolymer.
As said mixture, for example, it is possible to enumerate TFE homopolymers and the mixture of above-mentioned TFE based copolymer, belong to State the mixture etc. of two or more copolymer of TFE based copolymer, as such mixture, for example, it is possible to enumerate TFE homopolymerization Thing and the mixture of PFA, TFE homopolymers and the mixture of FEP, TFE homopolymers and the mixture of PFA and FEP, PFA Yu FEP Mixture etc..
It addition, above-mentioned fluoropolymer (a) can be by the ethylenic containing perfluoroalkyl by having perfluoroalkyl not Saturated monomer (IV) is (hereinafter also referred to as " unsaturated monomer (IV) ".) carry out being polymerized obtained material.Above-mentioned unsaturated single Body (IV) is following formula
[chemical formula 1]
(in formula, Rf represents the perfluoroalkyl that carbon number is 4～20, R1Represent-H or the alkane that carbon number is 1～10 Base, R2Represent the alkylidene that carbon number is 1～10, R3Represent-H or methyl, R4Represent the alkyl that carbon number is 1～17, r Representing the integer of 1～10, s represents the integer of 0～10.) material that represents.
Above-mentioned fluoropolymer (a) can be the homopolymers of above-mentioned unsaturated monomer (IV), alternatively, it is also possible to be above-mentioned not Saturated monomer (IV) and can be with the copolymer of the monomer (V) of above-mentioned unsaturated monomer (IV) copolymerization.
As above-mentioned monomer (V), it is not particularly limited, for example, it is possible to enumerate (methyl) cyclohexyl acrylate, (methyl) third Olefin(e) acid benzyl ester, two (methyl) polyalkylene glycol acrylate ester, N-hydroxymethyl-propane acrylamide, (methyl) acrylamide, alkyl Carbon number is (methyl) acrylic acid derivatives such as (methyl) acrylic acid Arrcostab of 1～20；Ethene, vinyl chloride, PVF, The substituted or non-substituted ethene such as styrene, AMS, p-methylstyrene；The carbon number of alkyl is the alkane of 1～20 Base vinyl ethers, the vinyl ethers such as the halogenated alkyl vinyl ethers that carbon number is 1～20 of alkyl；The carbon number of alkyl It it is the vinyl ketones such as vinyl alkyl ketone of 1～20；Aliphatic unsaturated polyester carboxylic acid and the derivatives thereof such as maleic anhydride；Fourth two The polyenoid etc. such as alkene, isoprene, chlorobutadiene.
Above-mentioned fluoropolymer (a) such as can obtain by using the existing known polymerization such as emulsion polymerization etc. Arrive.
As above-mentioned fluoropolymer (a), from corrosion resistance and the water-fast vapor permeability excellence of obtained fluorine-containing laminate Aspect set out, be preferably selected from least a kind in the group being made up of TFE homopolymers, modified ptfe and above-mentioned TFE based copolymer Polymer.As above-mentioned TFE based copolymer, at least a kind of copolymer being preferably selected from the group being made up of FEP and PFA.
According to foregoing, as above-mentioned fluoropolymer (a), it is preferably selected from by TFE homopolymers, modified ptfe, FEP With at least a kind of polymer in the group of PFA composition.
It addition, as above-mentioned fluoropolymer (a), from priming coat (A) obtained fluorine-containing laminate and layer (B) The aspect of excellent adhesion is set out, and preferably comprises TFE based copolymer.The fluorine-containing layer of the excellent adhesion of priming coat (A) and layer (B) Long-pending body is due to water-fast vapor permeability excellence, even if so also being able to suppress the product of the paint film defects such as bubble in the presence of steam Raw.As comprising the fluoropolymer (a) of TFE based copolymer, for example, it is preferable to PFA one matter, TFE homopolymers and FEP's is mixed The mixture of compound, TFE homopolymers and the mixture of PFA, the mixture of modified ptfe and FEP or modified ptfe and PFA.Separately Outward, excellent with the adaptation of layer (B) from corrosion resistance and water-fast vapor permeability excellence, the priming coat (A) of obtained fluorine-containing laminate Different aspect is set out, and the fluoropolymer (a) in priming coat (A) is preferably the mixing of PFA one matter, TFE homopolymers and PFA The mixture of thing or TFE homopolymers and FEP, the mixture of more preferably TFE homopolymers and FEP.
The heat-resistant resin that can constitute above-mentioned priming coat (A) is the resin being typically considered to have heat resistance, excellent The temperature that choosing can use continuously is the resin of more than 150 DEG C.But, as above-mentioned heat-resistant resin, above-mentioned fluoropolymer Except thing (a).
As above-mentioned heat-resistant resin, it is not particularly limited, for example, it is preferable to for selecting free polyamide-imide resin, gathering Imide resin, polyethersulfone resin, polyetherimide resin, polyether-ether-ketone resin, aromatic polyester resins and polyarylene sulfide At least a kind of resin in the group of resin composition.
Above-mentioned polyamide-imide resin (PAI) is by the polymer structure in molecular structure with amido link and imide bond The resin become.As above-mentioned PAI, it is not particularly limited, for example, it is possible to enumerate by the HMW obtained by following each reaction The resin etc. that polymer is constituted, described reaction is: intramolecular has the fragrance such as aromatic diamine and the Pyromellitic Acid of amido link The reaction of race's quaternary carboxylic acid；Diamines, the diphenyl such as the aromatic series tricarboxylic acids such as trimellitic anhydride and 4,4-diamino-phenyl ether The reaction of the diisocyanate such as methane diisocyanate；Intramolecular has the binary acid of aromatic imides ring and the anti-of diamines Should；Etc..As above-mentioned PAI, from the aspect of excellent heat resistance, it is preferably by the polymer structure in main chain with aromatic rings The material become.
Above-mentioned polyimide resin (PI) is the resin being made up of the polymer in molecular structure with imide bond.As Above-mentioned PI, is not particularly limited, for example, it is possible to enumerate by the reaction etc. by aromatic series quaternary carboxylic acid anhydrides such as pyromellitic dianhydrides The resin etc. that the heavy polymer obtained is constituted.As above-mentioned PI, from the aspect of excellent heat resistance, it is preferably by leading Chain has the material that the polymer of aromatic rings is constituted.
Above-mentioned polyethersulfone resin (PES) is by having following formula
[chemical formula 2]
The resin that the polymer of the repetitive represented is constituted.As above-mentioned PES, it is not particularly limited, for example, it is possible to lift Go out the resin etc. being made up of the polymer obtained by the polycondensation of dichloro diphenylsulfone Yu bis-phenol.
About above-mentioned heat-resistant resin, even if carry out when forming fluorine-containing laminate from the excellent adhesion with base material Also there is at a temperature of when firing sufficient heat resistance, the corrosion resistance of obtained fluorine-containing laminate and water-fast vapor permeability excellence Aspect set out, at least a kind of resin being preferably selected from the group being made up of PAI, PI and PES.PAI, PI and PES are the most permissible It is by the one kind or two or more material constituted.
As above-mentioned heat-resistant resin, from the aspect with the adaptation and excellent heat resistance of base material, more preferably choosing At least a kind of resin in the group of free PAI and PI composition.
As above-mentioned heat-resistant resin, from corrosion resistance and the aspect of water-fast vapor permeability excellence, preferably by PES and choosing At least a kind of resin in the group of free PAI and PI composition is constituted.That is, heat-resistant resin can be PES Yu PAI mixture, The mixture of PES Yu PI or the mixture of PES Yu PAI and PI.Above-mentioned heat-resistant resin is particularly preferably the mixing of PES and PAI Thing.
The situation that above-mentioned heat-resistant resin is made up of with at least a kind of resin in the group selecting free PAI and PI to form PES Under, above-mentioned PES is preferably 65 mass %～85 mass % of the total amount of this PES and PAI and/or PI.More preferably 70 mass %～ 80 mass %.
As the content of above-mentioned heat-resistant resin, it is preferably this heat-resistant resin and the solid of above-mentioned fluoropolymer (a) 10 mass % of composition total amount～50 mass %.More preferably 15 mass %～40 mass %, more preferably 15 mass %～30 matter Amount %.
Above-mentioned priming coat (A) is generally formed on base material.Above-mentioned priming coat (A) is the most obtained as below: will be containing fluorine-containing poly- Priming paint coating composition (i) described later of compound (a) and heat-resistant resin is coated on base material, is dried as required, Then fire, thus obtain above-mentioned priming coat (A).The priming coat (A) so obtained is owing to above-mentioned fluoropolymer (a) is with above-mentioned Heat-resistant resin has difference in surface tension, thus above-mentioned fluoropolymer (a) floats when firing, remote at distance base material Face side be mainly configured with above-mentioned fluoropolymer (a), be mainly configured with above-mentioned heat-resistant resin in substrate side.
In the case of above-mentioned priming coat (A) comprises above-mentioned fluoropolymer (a) and above-mentioned heat-resistant resin, due to above-mentioned resistance to Thermal resin has a cementability with base material, thus the excellent adhesion to base material.Further, since above-mentioned fluoropolymer (a) With melt processable fluoropolymer (b) there is compatibility, thus the excellent adhesion of above-mentioned priming coat (A) and layer (B).This Sample, in the case of above-mentioned priming coat (A) comprises above-mentioned fluoropolymer (a) and above-mentioned heat-resistant resin, to base material and layer (B) Both have the adaptation of excellence.
Above-mentioned priming coat (A) is preferably made up of component of polymer and additive described later.Preferably, above-mentioned priming coat (A) component of polymer is fluoropolymer (a) and heat-resistant resin.In this specification, the above-mentioned " polymer of priming coat (A) Composition is fluoropolymer (a) and heat-resistant resin " refer to that the polymer in priming coat (A) is only fluoropolymer (a) with resistance to Thermal resin.Above-mentioned priming coat (A) is fluoropolymer (a) and heat-resistant resin by its component of polymer, can be effectively Have base material and both excellent adaptations of layer described later (B).
From can effectively play base material and the aspect of both excellent adaptations of layer (B), above-mentioned priming coat (A) Preferred polymers composition is fluoropolymer (a) and heat-resistant resin, from improving the corrosion-resistant of fluorine-containing laminate further Property and water-fast vapor permeability aspect set out, can be made up of fluoropolymer (a) and heat-resistant resin and then other resin.Make For other resin, resin described later can be enumerated.
Above-mentioned priming coat (A) preferably thickness is 5 μm～30 μm.If thickness is the thinnest, the most easily produce pin hole, fluorine-containing laminate Corrosion resistance be likely to decrease.If thickness is blocked up, the most easily cracking, the water-fast vapor permeability of fluorine-containing laminate likely drops Low.The preferred upper limit of the thickness of above-mentioned priming coat (A) is 20 μm.
As melt processable fluoropolymer (b) constituting above-mentioned powder coating (ii), it is possible to use above-mentioned fluorine-containing poly- There is among compound (a) material of melt processable.From obtained layer (B) and above-mentioned priming coat (A) and the adaptation of layer (C) The corrosion resistance of excellent, obtained fluorine-containing laminate and the aspect of water-fast vapor permeability excellence are set out, and above-mentioned melt processable contains Fluoropolymer (b) preferably has 150 DEG C～the fusing point of 350 DEG C, and the melt viscosity at a temperature of than fusing point high 50 DEG C is preferably 106(pascal second) below, the most above-mentioned TFE based copolymer.Above-mentioned melt processable fluoropolymer (b) can be One kind or two or more.In the group of above-mentioned melt processable fluoropolymer (b) more preferably choosing free PFA and FEP composition extremely Few a kind of fluoropolymer.Above-mentioned melt processable fluoropolymer (b) can be the most individually material of PFA or FEP, it is possible to To be their mixture.From the aspect of excellent heat resistance, above-mentioned melt processable fluoropolymer (b) is further preferred For PFA.Above-mentioned fusing point can be obtained as following temperature, and this temperature measures (DSC) device with 10 with using means of differential scanning calorimetry DEG C/min speed heat of fusion curve when heating up in maximum corresponding.
Above-mentioned melt viscosity calculates as follows: use fluidity testing instrument CFT-500C (Shimadzu Seisakusho Ltd.'s manufacture), molten at ratio And extrude, extruded velocity time thus by the aperture of diameter 2.1mm × length 8mm with load 7kgf at a temperature of high 50 DEG C of point Calculate this melt viscosity.
In order to make spherocrystal miniaturization, above-mentioned powder coating (ii) can comprise melt processable fluoropolymer (b) and A small amount of PTFE (TFE homopolymers and/or modified ptfe).In the case of Gai, the content of PTFE be fluorine-containing relative to melt processable poly- Compound (b) is preferably 0.01 mass %～10.0 mass %.
Above-mentioned layer (B) preferably lamination is on above-mentioned priming coat (A).Additionally, it is preferred that be laminated with described later on above-mentioned layer (B) Layer (C).
The component of polymer of the most above-mentioned powder coating (ii) is melt processable fluoropolymer (b).In this specification, Above-mentioned " component of polymer of powder coating (ii) is melt processable fluoropolymer (b) " refers to gathering in powder coating (ii) Compound is only melt processable fluoropolymer (b).By making the component of polymer of above-mentioned powder coating (ii) be melt-processed The average grain diameter of property fluoropolymer (b) and above-mentioned powder coating (ii) is 5 μm～30 μm, and obtained layer (B) can be effective Ground plays above-mentioned priming coat (A) and both excellent adaptations of layer described later (C).
Above-mentioned layer (B) preferably thickness is 10 μm～90 μm.If thickness is the thinnest, then obtained by fluorine-containing laminate corrosion-resistant Property is the most insufficient.If thickness is blocked up, then the moisture passed through is difficult to pass from layer (B), and the water-fast vapor permeability of fluorine-containing laminate has May reduce.The preferred lower limit of the thickness of above-mentioned layer (B) is 20 μm, and the preferred upper limit is 80 μm.
As melt processable fluoropolymer (c) constituting above-mentioned liquid coating (iii), it is possible to use above-mentioned fluorine-containing poly- There is among compound (a) material of melt processable.
Above-mentioned melt processable fluoropolymer (c) is the thing among above-mentioned fluoropolymer (a) with melt processable Matter, in this respect, above-mentioned melt processable fluoropolymer (c) and above-mentioned melt processable fluoropolymer (b) they are common, But, above-mentioned melt processable fluoropolymer (c) is the material in liquid coating (iii), and this liquid coating (iii) comprises flat All particle diameters are the particle being made up of melt processable fluoropolymer (c) of 0.01 μm～1.0 μm, in this aspect, above-mentioned melted Processability fluoropolymer (c) with above-mentioned melt processable fluoropolymer (b) as the material in powder coating (ii) is Different.
As above-mentioned melt processable fluoropolymer (c), from film forming excellent in terms of, obtained layer (C) is with upper The aspect of the excellent adhesion of the layer (B) stated and the corrosion resistance of obtained fluorine-containing laminate and water-fast vapor permeability excellence Aspect set out, be preferably identical type with above-mentioned melt processable fluoropolymer (b).Additionally, it is preferred that have 150 DEG C～ The fusing point of 350 DEG C, the melt viscosity at a temperature of than fusing point high 50 DEG C is preferably 106(pascal second) below.As this Melt processable fluoropolymer (c) of sample, can enumerate TFE based copolymer.As above-mentioned melt processable fluoropolymer C (), from the aspect that heat resistance, non-adhesive and film forming are excellent, is preferably selected from the group being made up of PFA and FEP At least a kind of polymer.Above-mentioned melt processable fluoropolymer (c) can be PFA one matter, FEP one matter or PFA Mixture with FEP.As above-mentioned melt processable fluoropolymer (c), from the aspect that heat resistance is more excellent, more preferably For PFA.
As it has been described above, above-mentioned liquid coating (iii) be typically be made up of above-mentioned melt processable fluoropolymer (c) Grain is dispersion in liquid medium.
Above-mentioned liquid medium is generally made up of water and/or organic liquid.In this specification, " organic liquid " refers to as organic Compound and be liquid under the normal temperature of about 20 DEG C.
In the case of liquid medium in above-mentioned liquid coating (iii) is mainly made up of organic liquid, organic as this Liquid, is not particularly limited, for example, it is possible to enumerate METHYLPYRROLIDONE, 2-Pyrrolidone, DMA Etc. nitrogenous organic liquid；The aromatic hydrocarbon series solvents such as toluene, dimethylbenzene, trimethylbenzene, ethyl methyl benzene, propyl benzene, butylbenzene；Carbon atom Number is the saturated hydrocarbons series solvent of 6～12；The lactone such as gamma-butyrolacton；The non-annularity esters such as butyl acetate；Methyl iso-butyl ketone (MIBK), The ketones such as methyl ethyl ketone；The glycols such as ethylene glycol, triethylene glycol, propane diols；The glycol ethers such as butyl cellosolve；N-butyl alcohol, The unary alcohols such as DAA；Etc..
As above-mentioned aromatic hydrocarbon series solvent, it is possible to use as the Solvesso100 of commercially available product, Solvesso150, Solvesso200 (be trade name, Exxon Mobil society manufactures) etc..As above-mentioned saturated hydrocarbons series solvent, it is possible to use as The Mineral spirits (Japanese Industrial Standards, industrial gasoline No. 4 numbers) etc. of commercially available product.
Above-mentioned organic liquid can be used alone, it is also possible to share two or more.
From the aspect of environmental problem, above-mentioned liquid medium is preferably mainly made up of water.
In the case of above-mentioned liquid medium is mainly made up of water, generally, in order to make to be made up of fluoropolymer (c) Grain decentralized stabilization, above-mentioned liquid coating (iii) comprises surfactant and forms.
As above-mentioned surfactant, it is not particularly limited, for example, it is possible to enumerate fluorine-containing system nonionic surface active agent Deng nonionic surface active agent；The anionic surfactant such as fluorine-containing series anion type surfactant；Fluorine-containing system sun from The cationic surface active agents such as subtype surfactant；Etc..In above-mentioned liquid coating (iii), in order to make by fluorine-containing poly- The particle decentralized stabilization that compound (c) is constituted, additionally it is possible to share above-mentioned organic liquid together with above-mentioned surfactant.
The viscosity of above-mentioned liquid coating (iii) is preferably 0.1mPa s～50000mPa s.If viscosity is too low, then it is being coated with Easily producing sagging etc. during cloth, be sometimes difficult to obtain target film thickness, if viscosity is too high, then painting operation is deteriorated sometimes, has Time obtained layer (C) thickness become uneven, surface smoothness equal difference.Preferred lower limit is 1mPa s, preferred The upper limit is 30000mPa s.
Above-mentioned viscosity can utilize Brookfield viscometer TVB-10 shape (Toki Sangyo Co., Ltd.'s manufacture) to measure.
In order to obtained fluorine-containing laminate giving characteristic, improving physical property, increment etc., above-mentioned liquid coating (iii) can To comprise packing material.As above-mentioned characteristic, physical property, intensity, durability, weatherability, anti-flammability, aesthetic appearance etc. can be enumerated. As packing material, when using the material with light sense, the fluorine-containing laminate of the present invention has good light sense.
As above-mentioned packing material, it is not particularly limited, for example, it is possible to enumerate wood powder, quartz sand, carbon black, clay, cunning Stone, diamond, corundum, silica, boron nitride, boron carbide, carborundum, aloxite (AI2O3), tourmaline, emerald, germanium, extender pigment, The flat pigment of bright property, flakey pigment, glass, various reinforcing material, various inserts, electroconductive stuffing etc..As above-mentioned Packing material, in the case of the fluorine-containing laminate requiring the present invention has light sense, preferably bright property packing material.Above-mentioned " bright property packing material " is the packing material that can give obtained fluorine-containing laminate light sense.
As above-mentioned packing material, can enumerate and be categorized as the flat pigment of bright property, the packing material of flakey pigment, glass Glass etc., they can use one kind or two or more.As the filling material being categorized as the flat pigment of above-mentioned bright property, flakey pigment Material, is not particularly limited, for example, it is possible to enumerate mica powder (including with the material of coated by titanium dioxide), metal dust etc..As Above-mentioned glass, is not particularly limited, for example, it is possible to enumerate the glass dust such as bead, glass envelope, sheet glass, glass fibre.Separately Outward, additionally it is possible to use the glass dust utilizing the metallic cover such as gold, silver, nickel, the glass utilizing titanium dioxide, iron oxide etc. to be coated with Powder.As being classified as the flat pigment of above-mentioned bright property, the packing material of flakey face and glass, it is able to use a kind or 2 More than Zhong.
As above-mentioned packing material, in the group that more preferably the free mica powder of choosing, metal dust and glass dust form extremely Few a kind of packing material.Such packing material can simply be mica powder, metal dust or glass dust, it is also possible to is mica powder, gold Belong to powder or glass dust and other packing material that fluorine-containing laminate light sense can be given.Above-mentioned packing material can be mica Powder one matter, metal dust one matter, glass dust one matter, mica powder and the mixture of metal dust, mica powder with The mixture of the mixture of glass dust or metal dust and glass dust.
Relative to melt processable fluoropolymer (c) 100 mass parts, packing material be preferably more than 0.01 mass parts and Below 5 mass parts.
As above-mentioned metal dust, it is not particularly limited, for example, it is possible to enumerate the metals such as aluminium, iron, tin, zinc, gold, silver, copper The powder of simple substance；The powder of the alloy such as aluminium alloy, stainless steel；Etc..As the shape of above-mentioned metal dust, limit the most especially Fixed, for example, it is possible to enumerate graininess, sheet etc., from the aspect that light sense is excellent, preferably sheet.Such as, as aluminium powder The shape at end, preferably sheet.
From the aspect of the excellent corrosion resistance of obtained fluorine-containing laminate, the particularly preferably choosing of above-mentioned packing material At least a kind of packing material in the group of free mica powder and glass dust composition.Above-mentioned mica powder and glass dust are preferably bright property Packing material.
From the aspect that light sense and economy are excellent, above-mentioned packing material is for selecting free mica powder and aluminium powder composition Group at least a kind of packing material be also one of preferred mode.More preferably mica powder and aluminium powder is that bright property fills material Material.As such packing material, mica powder one matter, aluminium powder one matter or mica powder and aluminium powder can be enumerated Mixture.
It addition, in order to by spherocrystal miniaturization, above-mentioned liquid coating (iii) can with by melt processable fluoropolymer C particle that () is constituted comprises a small amount of PTFE (TFE homopolymers and/or modified ptfe) together.In the case of Gai, the content phase of PTFE 0.01 mass %～10.0 mass % are preferably for melt processable fluoropolymer (c).
It addition, above-mentioned liquid coating (iii) does not preferably contain coloring pigment.Coloring pigment be typically considered make corrosion-resistant Property deteriorate reason, therefore, if above-mentioned liquid coating (iii) does not contains coloring pigment, then obtained by fluorine-containing laminate have More excellent corrosion resistance.
Above-mentioned liquid coating (iii) is further preferably made up of component of polymer and additive.It is further preferred, that above-mentioned liquid The component of polymer of state coating (iii) is melt processable fluoropolymer (c).In this specification, above-mentioned " liquid coating (iii) component of polymer is melt processable fluoropolymer (c) " refer to that the polymer in liquid coating (iii) is only molten Melt processability fluoropolymer (c).By making the component of polymer of above-mentioned liquid coating (iii) be melt processable fluoropolymer Thing (c), obtained layer (C) has the adaptation of excellence for above-mentioned layer (B).
In the fluorine-containing laminate of the present invention, above-mentioned layer (C) is preferably formed on above-mentioned layer (B), preferably at melt processable Fire at a temperature of more than the fusing point of fluoropolymer (c).
Above-mentioned layer (C) preferably thickness is 1 μm～30 μm.If thickness is the thinnest, then the film that cannot fill up layer (B) fully lacks Falling into, the corrosion resistance of fluorine-containing laminate is likely to decrease.If thickness is blocked up, then layer (C) easily cracks, and corrosion resistance is sometimes Difference.The preferred lower limit of the thickness of above-mentioned layer (C) is 5 μm, and the preferred upper limit is 20 μm.
The thickness of above-mentioned priming coat (A) be the thickness of 5 μm～30 μm, above-mentioned layer (B) be 10 μm～90 μm and layer (C) Thickness is 1 μm～30 μm are one of the preferred embodiment of the present invention.
The laminated order of each layer of the fluorine-containing laminate constituting the present invention is not particularly limited, the most above-mentioned base material, on State priming coat (A), above-mentioned layer (B) and above-mentioned layer (C) with this sequential laminating.Thereby, it is possible to significantly more play above-mentioned layer (B) and Corrosion resistance produced by above-mentioned layer (C) improves effect.
It is particularly preferred that above-mentioned base material, above-mentioned priming coat (A), above-mentioned layer (B) and above-mentioned layer (C) are with this sequential laminating, And according to above-mentioned layer (C) the mode lamination adjacent with above-mentioned layer (B).
Generally, the fluorine-containing laminate of the present invention does not exists at each interlayer of base material, priming coat (A), layer (B) and layer (C) Other layer, but such as, as required, it is also possible to the interlayer at the interlayer of priming coat (A) and layer (B) or layer (B) with layer (C) is deposited At other layer.
It addition, as it has been described above, the fluorine-containing laminate of the present invention has above-mentioned priming coat (A), above-mentioned layer (B) and above-mentioned layer (C), it is also possible to layer is set on above-mentioned layer (C) further, but preferred above-mentioned layer (C) is outermost layer.By at outermost Layer configuration layer (C), it is possible to more effectively improve the corrosion resistance of fluorine-containing laminate.
In the case of above-mentioned base material, above-mentioned priming coat (A), above-mentioned layer (B) and above-mentioned layer (C) are with this sequential laminating, this The fluorine-containing laminate of invention can be on above-mentioned priming coat (A) and/or the above enforcement word of above-mentioned layer (B), picture etc. Printing.
It addition, the invention still further relates to the manufacture method of fluorine-containing laminate.Manufacture method according to the following stated, it is possible to easily Ground manufactures the fluorine-containing laminate that there is not paint film defect, excellent corrosion resistance as described above.
The manufacture method of the fluorine-containing laminate of the present invention includes operation (1): primer coating coating composition on base material I (), is consequently formed priming paint coated film (Ap).
In above-mentioned operation (1), above-mentioned priming paint coating composition (i) preferably comprises fluoropolymer (a) and heat resistance tree Fat.About fluoropolymer (a) and heat-resistant resin, as above to described in priming coat (A).Above-mentioned priming paint wraps Covering composition (i) can be liquid, it is also possible to for powder.In the case of above-mentioned priming paint coating composition (i) is liquid, by Fluoropolymer (a) and heat-resistant resin and liquid medium are constituted.Above-mentioned liquid medium is generally by water and/or organic liquid structure Become.In this specification, above-mentioned " organic liquid " refers to as organic compound and is liquid under the normal temperature of about 20 DEG C.
In the case of the liquid medium of above-mentioned priming paint coating composition (i) is mainly made up of organic liquid, above-mentioned resistance to Thermal resin and fluoropolymer (a) are the materials being scattered in the form of granules in above-mentioned liquid medium and/or are dissolved in Material in above-mentioned liquid medium.As above-mentioned organic liquid, it is not particularly limited, for example, it is possible to enumerate N-methyl-2-pyrroles The nitrogenous organic liquids such as alkanone, 2-Pyrrolidone, DMAC N,N' dimethyl acetamide；Toluene, dimethylbenzene, trimethylbenzene, ethyl methyl benzene, The aromatic hydrocarbon series solvent such as propyl benzene, butylbenzene；Carbon number is the saturated hydrocarbons series solvent of 6～12；The lactone such as gamma-butyrolacton；Second The non-annularity esters such as acid butyl ester；The ketone such as methyl iso-butyl ketone (MIBK), methyl ethyl ketone；The glycol such as ethylene glycol, triethylene glycol, propane diols Class；The glycol ethers such as butyl cellosolve；The unary alcohol such as n-butyl alcohol, diacetone alcohol；Etc..
As above-mentioned aromatic hydrocarbon series solvent, it is possible to use as the Solvesso100 of commercially available product, Solvesso150, Solvesso200 (be trade name, Exxon Mobil society manufactures) etc..As above-mentioned saturated hydrocarbons series solvent, it is possible to use as The Mineral spirits (Japanese Industrial Standards, industrial gasoline No. 4 numbers) etc. of commercially available product.
Above-mentioned organic liquid can be used alone, it is also possible to share two or more.
In the case of the liquid medium of above-mentioned priming paint coating composition (i) is mainly made up of water, above-mentioned heat resistance tree Fat is the material being scattered in the form of granules in above-mentioned liquid medium or is dissolved in the material in above-mentioned liquid medium, fluorine-containing Polymer (a) is the material being scattered in above-mentioned liquid medium in the form of granules.
In the case of above-mentioned liquid medium is mainly made up of water, generally, in order to make to be made up of fluoropolymer (a) Grain decentralized stabilization, above-mentioned priming paint coating composition (i) can be added surfactant and be formed.As above-mentioned surface-active Agent, is not particularly limited, for example, it is possible to enumerate the nonionic surface active agent such as fluorine-containing system nonionic surface active agent；Contain The anionic surfactant such as fluorine series anion type surfactant；The cationics such as fluorine-containing cation type surfactant Surfactant etc..In order to make the particle decentralized stabilization being made up of fluoropolymer (a), above-mentioned priming paint coating composition I () can also share above-mentioned organic liquid together with above-mentioned surfactant.
It addition, above-mentioned priming paint coating composition (i) can also is that with the record of Japanese Patent Publication 49-17017 publication The organosol that method etc. obtain, the method is to be the particle being made up of above-mentioned fluoropolymer (a) and by heat-resisting in dispersate Property resin constitute particle, the water-borne dispersions that is mainly made up of water of dispersant adds as turn layer liquid organic solvent and turn Layer agent, makes the above-mentioned particle being made up of fluoropolymer (a) and the particle being made up of heat-resistant resin turn layer to above-mentioned organic molten In agent.
From the aspect with the excellent adhesion of base material, above-mentioned priming paint coating composition (i) is preferably liquid, from ring The aspect of border problem is set out, and the most above-mentioned liquid medium is mainly made up of water.
When above-mentioned priming paint coating composition (i) is liquid, the viscosity of above-mentioned priming paint coating composition (i) is preferably 0.1mPa s～50000mPa s.If viscosity is too low, then on base material, easily produces sagging etc. when coating, be sometimes difficult to obtain Target film thickness, if viscosity is too high, painting operation is deteriorated the most sometimes, the membrane thickness unevenness of obtained priming paint coated film (Ap), Sometimes surface smoothness equal difference.Preferred lower limit is 1mPa s, and the preferred upper limit is 30000mPa s.
Above-mentioned viscosity can utilize Brookfield viscometer TVB-10 type (Toki Sangyo Co., Ltd.'s manufacture) to measure.
In above-mentioned priming paint coating composition (i), above-mentioned fluoropolymer (a) preferably average grain diameter is 0.01 μm～5 μ m.Above-mentioned heat-resistant resin is in the case of being scattered in the form of granules in above-mentioned priming paint coating composition (i), and it is average Particle diameter is preferably 0.2 μm～8 μm.
In above-mentioned priming paint coating composition (i), heat-resistant resin is by polyethersulfone resin (PES) and the free polyamide acyl of choosing At least a kind of resin in the group that imide resin (PAI) and polyimide resin (PI) form is constituted, and polyethersulfone resin is preferably should At least a kind of resin in the group of polyethersulfone resin and choosing freely described polyamide-imide resin and polyimide resin composition 65 mass % of total amount～90 mass %.If polyethersulfone resin is very few, then obtained by fluorine-containing laminate water-fast vapor permeability have can Can reduce, if polyethersulfone resin is too much, then corrosion resistance is likely to decrease.The preferred upper limit is 85 mass %.Above-mentioned heat resistance Resin generally formed fluorine-containing laminate time carry out fire in also will not decompose, the ratio of the most above-mentioned PES substantially with its Ratio in priming coat (A) is identical.It should be noted that when only comprising any one in PAI and PI, " PES and The total amount of PAI and PI " it is the total amount with PES of any one in PAI and PI contained in priming paint coating composition (i).
In above-mentioned priming paint coating composition (i), above-mentioned heat-resistant resin is preferably above-mentioned heat-resistant resin and fluorine-containing poly- 10 mass % of the solid constituent total amount of compound (a)～50 mass %.In this specification, above-mentioned " solid constituent " refer at 20 DEG C be The composition of solid.In this specification, above-mentioned " the solid constituent total amount of above-mentioned heat-resistant resin and fluoropolymer (a) " refer to by Priming paint coating composition (i) is dried, then at 380 DEG C～400 DEG C in the temperature of 80 DEG C～100 DEG C after coating on base material Above-mentioned heat-resistant resin in residue and the gross mass of fluoropolymer (a) after firing 45 minutes.
If the amount of above-mentioned heat-resistant resin is very few, then the obtained priming coat (A) in fluorine-containing laminate is close with base material Make a concerted effort the most insufficient.If the amount of above-mentioned heat-resistant resin is too much, then obtained by fluorine-containing laminate in priming coat (A) with The adaptation of layer (B) is the most insufficient.Preferred lower limit is 15 mass %, and the preferred upper limit is 40 mass %.
In order to improve painting operation and the corrosion resistance of obtained fluorine-containing laminate and water-fast vapor permeability further, on State priming paint coating composition (i) to comprise further while comprising above-mentioned fluoropolymer (a) and heat-resistant resin Additive.
As above-mentioned additive, be not particularly limited, for example, it is possible to enumerate levelling agent, kollag, sagging inhibitor, Moisture absorber, surface conditioner, thixotropy conferring agents, viscosity modifier, anti-gel agent, ultra-violet absorber, light are stable Agent, plasticizer, anti-agent of growing dim, anti skinning agent, scratching agent, mould inhibitor, antiseptic, antioxidant, antistatic additive, silane coupled The bright properties such as agent, wood powder, quartz sand, carbon black, clay, talcum, diamond, tourmaline, emerald, germanium, extender pigment, aluminum slice are flat The metal dusts such as flat pigment, flakey pigment, glass, various reinforcing material, various inserts, electroconductive stuffing, gold, silver, copper Deng.
From obtained priming coat (A) can effectively to base material and layer (B) both play excellent adaptation in terms of Setting out, above-mentioned priming paint coating composition (i) preferred polymers composition is fluoropolymer (a) and heat-resistant resin, from can The corrosion resistance and the water-fast vapor permeability aspect that improve fluorine-containing laminate further are set out, and can comprise fluoropolymer (a) With also comprise other resin while heat-resistant resin.
As other resin above-mentioned, be not particularly limited, for example, it is possible to enumerate phenolic resin, carbamide resin, epoxy resin, Carbamate resins, melmac, polyester resin, polyether resin, acrylic resin, acrylic compounds silicone resin, Silicone resin, silicone polyester resin etc..Owing to the fluorine-containing laminate of the present invention obtains by firing, so other tree above-mentioned Fat preferably has heat resistance.
Above-mentioned operation (1) is following operation: primer coating coating composition (i) on base material, is consequently formed priming paint and is coated with Cloth film (Ap).
As the method for above-mentioned coating, it is not particularly limited, when above-mentioned priming paint coating composition (i) is liquid, example As, spraying, roller coat, scraper for coating, dip-coating, infiltration coating, eddy flow coating, curtain flow coat cloth etc. can be enumerated, the most preferably spray. When above-mentioned priming paint coating composition (i) is powder, electrostatic applications, slipper dip method can be enumerated, rotate liner (ロ ト ラ イ ニ Application グ) method etc., wherein preferred electrostatic applications.
Above-mentioned operation (1) is as long as forming above-mentioned priming paint by being coated with above-mentioned priming paint coating composition (i) on base material Coated film (Ap), can be fired before carrying out operation (2), it is also possible to be not fired after above-mentioned coating, it addition, When above-mentioned priming paint coating composition (i) is liquid, can be dried further after above-mentioned coating, it is also possible to do not carry out It is dried.
In above-mentioned operation (1), above-mentioned being dried preferably carries out 5 minutes～60 minutes with the temperature of 70 DEG C～300 DEG C.Above-mentioned burning System preferably carries out 10 minutes～30 minutes with the temperature of 260 DEG C～410 DEG C.
When above-mentioned priming paint coating composition (i) is liquid, above-mentioned operation (1) is preferably done after coating on base material Dry.Further, since aftermentioned operation (4) is coated firing of film laminate, so not being fired.
When above-mentioned priming paint coating composition (i) is powder, above-mentioned operation (1) is preferably burnt after coating on base material System.
Above-mentioned priming paint coated film (Ap) is formed by being coated with above-mentioned priming paint coating composition (i) on base material. Above-mentioned priming paint coated film (Ap) can only be formed by above-mentioned coating in above-mentioned operation (1), it is also possible to is in above-mentioned painting By being dried formation after cloth, it is also possible to be to be dried as required after above-mentioned coating, be then fired and formed. Above-mentioned priming paint coated film (Ap) becomes priming coat (A) in obtained fluorine-containing laminate.
The manufacture method of the fluorine-containing laminate of the present invention includes following operation (2): the upper coating of priming paint coated film (Ap) by The powder coating (ii) that melt processable fluoropolymer (b) is constituted, is consequently formed coated film (Bp).
Powder coating (ii) is made up of melt processable fluoropolymer (b), and average grain diameter is 5 μm～30 μm.By making Above-mentioned powder coating (ii) is powder, it is possible to easily obtain thicker coated film with less application number of times.
Above-mentioned operation (2) forms coated film by being coated with powder coating (ii) on above-mentioned priming paint coated film (Ap) (Bp).As the method for above-mentioned coating, it is not particularly limited, for example, it is possible to enumerate with above-mentioned priming paint coating composition (i) is The method etc. that coating process during powder is identical, wherein, preferably electrostatic applications.
Coated film (Bp) is by being formed above-mentioned priming paint coated film (Ap) the above-mentioned powder coating of upper coating (ii).On State coated film (Bp) in obtained fluorine-containing laminate, become layer (B).
In the manufacture method of the fluorine-containing laminate of the present invention, after forming coated film (Bp) in above-mentioned operation (2), Ke Yishe Put the operation that obtained coated film laminate is fired.That is, above-mentioned manufacture method can include being coated with by above-mentioned priming paint The operation (2 ') that the coated film laminate that cloth film (Ap) and above-mentioned coated film (Bp) are constituted is fired.In operation (2 '), priming paint Coated film (Ap) can not be burned, it is also possible to is burned (before coated film (Bp) is formed).
After having carried out above-mentioned operation (2 '), by being coated the operation (3) of aftermentioned liquid coating (iii), for Because paint film defect produced by the application of powder coating (ii) the most still remains in the painting in film even across ablating work procedure Film defect, it is also possible to utilize the coating of liquid coating (iii) positively to fill up, the film of therefore obtained fluorine-containing laminate Defect is less, and corrosion resistance is more excellent.
In the same manner as situation about being fired in above-mentioned operation (1), firing preferably with 260 DEG C in above-mentioned operation (2 ') ～the temperature of 410 DEG C carries out 10 minutes～30 minutes.
The manufacture method of the present invention includes following operation (3): comprises in the upper coating of above-mentioned coated film (Bp) and is added by melted The average grain diameter that work fluoropolymer (c) is constituted is the liquid coating (iii) of the particle of 0.01 μm～1.0 μm, is consequently formed Coated film (Cl).
It is 0.01 μm～1.0 μm that the particle being made up of above-mentioned melt processable fluoropolymer (c) has average grain diameter Small particle, fills up paint film defect therefore, it is possible to penetrate in the paint film defect of above-mentioned coated film (Bp), it is possible to formed resistance to The fluorine-containing laminate that corrosivity is excellent.
As in the upper method being coated with above-mentioned liquid coating (iii) of above-mentioned coated film (Bp), it is not particularly limited, such as, Can enumerate with above-mentioned priming paint coating composition (i) is the method etc. that coating process during liquid is identical, wherein, preferably sprays It is coated with.
Above-mentioned coated film (Cl) can be formed by being fired as required after above-mentioned coating.Above-mentioned coating Film (Cl) becomes the layer (C) in obtained fluorine-containing laminate.
The manufacture method of the present invention includes following operation (4): to by above-mentioned priming paint coated film (Ap), above-mentioned coated film (Bp) The coated film laminate constituted with above-mentioned coated film (Cl) is fired, and is consequently formed by base material, priming coat (A), layer (B) and layer (C) fluorine-containing laminate constituted.
In above-mentioned operation (4), as long as the fluorine-containing laminate finally given by this operation is by base material, priming coat (A), layer (B) Constitute with layer (C), be not necessarily required to priming coat (A), layer (B) and layer (C) and be entirely first formation in this operation (4).
Therefore, for being fed into the above-mentioned priming paint coated film (Ap) of above-mentioned operation (4), above-mentioned coated film (Bp) and above-mentioned For coated film (Cl), these films can not be burned in the operation before this operation (4), it is also possible in these films extremely Few one operation before this operation (4) is burned.
In the same manner as firing in above-mentioned operation (1)～(3), firing preferably with 260 DEG C～410 in above-mentioned operation (4) DEG C temperature carry out 10 minutes～30 minutes.
In the manufacture method of the fluorine-containing laminate of the present invention, owing to can more reliably fill up because of powder coating (ii) Paint film defect produced by application, thus after being preferably included in above-mentioned operation (2) formation coated film (Bp), to obtained painting The operation that cloth film laminate is fired.
That is, one of the preferred embodiment of the present invention is: above-mentioned manufacture method includes following operation: operation (1), at base material Upper primer coating coating composition (i), is consequently formed priming paint coated film (Ap)；Operation (2), above-mentioned priming paint coated film (Ap) The powder coating (ii) that upper coating is made up of melt processable fluoropolymer (b), is consequently formed coated film (Bp)；Operation (2 '), are fired the coated film laminate being made up of above-mentioned priming paint coated film (Ap) and above-mentioned coated film (Bp), thus shape Become the fluorine-containing laminate (P) being made up of base material, priming coat (A) and layer (B)；Operation (3), is coated with bag in above-mentioned coated film (Bp) Containing the liquid coating (iii) of the particle being made up of melt processable fluoropolymer (c), it is consequently formed coated film (Cl)；And Operation (4), to the coated film lamination being made up of above-mentioned priming paint coated film (Ap), above-mentioned coated film (Bp) and above-mentioned coated film (Cl) Body is fired, and is consequently formed the fluorine-containing laminate being made up of base material, priming coat (A), layer (B) and layer (C), above-mentioned powder coating (ii) average grain diameter is 5 μm～30 μm, and, the particle being made up of above-mentioned melt processable fluoropolymer (c) average Particle diameter is 0.01 μm～1.0 μm.
It addition, the manufacture method of the fluorine-containing laminate of the present invention can also be in the operation forming above-mentioned priming paint coated film (Ap) (1) after or there is after forming the operation (2) of above-mentioned coated film (Bp) operation of printing word, picture etc..Such as containing Fluorine laminate is in the case of pot for cooking rice, and above-mentioned word, picture etc. are word and the line etc. representing the water yield.
As above-mentioned printing process, it is not particularly limited, for example, it is possible to enumerate trans-printing (パ ッ De writes printing).Make For the printing-ink for above-mentioned printing, it is not particularly limited, for example, it is possible to enumerate by PES, TFE homopolymers and titanium dioxide The composition constituted.
The fluorine-containing laminate of the present invention can also constitute covering articles with.The excellent corrosion resistance of above-mentioned fluorine-containing laminate, because of This all can suitably use in all spectra require corrosion resistance.As above-mentioned covering articles with, it is not particularly limited, it is possible to In the purposes of the non-adhesive that make use of fluoropolymer to be had, heat resistance, sliding etc., such as, non-as utilizing The covering articles with of cohesive, frying pan can be enumerated, dish is decocted by pressure cooker, pot, striped side, pot for cooking rice, baking oven, heating plate, toaster, The device for cooking such as kitchen knife, gas range；The kitchen articles such as insulating pot, ice-making disc, mould, range hood；Agitating roller, stack, defeated Send the food industry components such as band, loading hopper；Office automation (OA) roller, OA band, OA disengaging pawl, paper bowl processed, film system Make with industrial goods such as pressure rollers；The mould of foamed polystyrene shaping use etc., mold, glued board style strip manufacture stripper plate In the mould demoulding, industrial container (U Application テ Na) (particularly semiconductor industry) etc., as utilizing sliding Covering articles with, can enumerate the instruments such as saw, file；The household supplies such as flatiron, scissors, kitchen knife；Metal forming, electric wire, food processor, The automobile components such as the sliding bearing of packing machine, textile machine etc., the slide unit of camera clock and watch, pipe, valve, bearing, shovel snow Shovel, plough, chute etc..
It addition, such covering articles with above-mentioned fluorine-containing laminate is also one of present invention.
Invention effect
There is not paint film defect by having above-mentioned composition in the fluorine-containing laminate of the present invention, excellent corrosion resistance.So Fluorine-containing laminate can be particularly suitable for cooking appliance and kitchen articles etc..
Detailed description of the invention
Enumerating 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.
Manufacture the preparation of example 1 polyethersulfone resin water-borne dispersions
By the polyethersulfone resin (PES) 60 parts of number-average molecular weight about 24000 and deionized water 60 parts in ceramic ball mill Stir about 10 minutes, until the particle being made up of PES is pulverized completely.It follows that add METHYLPYRROLIDONE (hereafter In be referred to as NMP) 180 parts, pulverize 48 hours further, obtain dispersion.Obtained dispersion is used sand mill powder further Broken 1 hour, obtain PES concentration and be about the PES water-borne dispersions of 20%.The particle being made up of PES in PES water-borne dispersions Average grain diameter is 2 μm.
Manufacture the preparation of example 2 polyamide-imide resin water-borne dispersions
Polyamide-imide resin (PAI) varnish (comprising the NMP of 71%) that solid constituent is 29% is put in water, makes PAI separates out.It is pulverized 48 hours in ball mill, obtains PAI water-borne dispersions.Consolidating of obtained PAI water-borne dispersions Body composition is 20%, and the average grain diameter of the PAI in PAI water-borne dispersions is 2 μm.
Manufacture the example 3 priming paint preparation of coating composition (i)
The PES water-borne dispersions obtained in example 1 will be manufactured and manufacture the PAI water-borne dispersions mixing obtained in example 2, so that PES is the 75% of the solid constituent total amount of PES and PAI, is added thereto to proplast (TFE homopolymers) aqueous dispersion Body (average grain diameter be 0.28 μm, solid constituent be 60%, containing relative to the polyethers system non-ionic surface that TFE homopolymers is 6% Activating agent (polyoxyethylene tridecyl ether) is as dispersant) so that the solid that PES and PAI is PES, PAI and TFE homopolymers The 25% of composition total amount, and add the methylcellulose that solid constituent is 0.7% relative to TFE homopolymers as thickener, Add the nonionic surface active agent that solid constituent is 6% (ethylene nonyl phenyl ether) conduct relative to TFE homopolymers Dispersion stabilizer, obtains the aqueous liquid dispersion that solid constituent is 34% of TFE homopolymers.
Embodiment 1
After the inner surface acetone degreasing of aluminum and canister that inner capacities is 2 liters, carry out sandblasting so that based on JIS The surface roughness Ra value that B1982 measures is 2.0 μm～3.0 μm, makes rough surface.The dust on surface is removed by air blast After, utilize RG-2 type gravity type spray gun (trade name, ANEST IWATA Corporation manufacture, nozzle diameter is 1.0mm) Priming paint coating composition (i) obtained in example 3 is manufactured, so that dry film thickness is about 12 μm with expulsion pressure 0.2MPa spraying. Coated film on obtained aluminium is dried 15 minutes at 80 DEG C～100 DEG C, and is cooled to room temperature.It is coated with at obtained priming paint To apply condition electrostatic applications PFA powder coating (trade name: the NEOFLON that voltage is as 50kV, pressure is as 0.08MPa on cloth film PFA ACX-34, Daikin Industries society manufacture, the average grain diameter of PFA is about 23 μm) so that the thickness after firing is about 45 μm, and 20 minutes are fired at 380 DEG C.After being cooled to room temperature, utilize RG-2 type gravity type spray gun (trade name, ANEST IWATA Corporation manufacture, nozzle diameter be 1.0mm) with expulsion pressure 0.2MPa spray thereon PFA water paint (trade name: NEOFLON PFA AD-2CRER, Daikin Industries society manufacture, the average grain diameter of PFA is 0.3 μm) it is about so that firing rear thickness 10μm.Obtained coated film is dried 15 minutes at 80 DEG C～100 DEG C, fires 20 minutes at 380 DEG C, obtain test application Pot.Inner surface at obtained test application pot defines priming coat, PFA layer (floating coat) and by little on aluminium (base material) The layer (whole coating) that the PFA of particle diameter is constituted.
(evaluation method)
For the film of obtained test application pot inner surface, carry out following evaluation.
Thickness
High frequency type film thickness gauge (trade name: LZ-300C, Kett Electric Laboratory manufactures) is used to survey Fixed.
Pinhole test
In order to investigate the presence or absence of the paint film defect of laminate, carry out pinhole test.Test application pot is filled by The mixed liquor that isopropanol/water=1/3 (weight ratio) is constituted, applies the voltage of 125V between test application pot and mixed liquor.Profit The digital insulating-resistance meter MY40 type manufactured with Yokogawa Meters&Instruments Corporation determines resistance Value.Resistance value is the biggest, then judge that paint film defect (pin hole) is the fewest, and corrosion resistance is the best.
For the test application pot obtained in embodiment 1, carry out above-mentioned pinhole test.Result is shown in table 1.Pin hole tries The resistance value tested is infinitely great, and the film of the test application pot inner surface obtained in embodiment 1 does not exist paint film defect.
Embodiment 2
Except replacing PFA water paint (trade name: NEOFLON PFA AD-2CRER, Daikin Industries society manufacture, PFA Average grain diameter 0.3 μm) and use FEP water paint (trade name: NEOFLON FEP ND-110, Daikin Industries society manufacture, FEP Average grain diameter 0.13 μm) beyond, utilize step similarly to Example 1 to obtain test application pot.In obtained test On aluminium (base material), priming coat, PFA layer (floating coat) and the layer being made up of the FEP of small particle is defined with the inner surface of application pot (whole coating).
For obtained test application pot, carry out pinhole test similarly to Example 1.Result is shown in table 1.Pin The resistance value of hole test is infinitely great, and the film of the test application pot inner surface obtained in embodiment 2 does not exist paint film defect.
Comparative example 1
Application PFA powder coating (trade name: NEOFLON PFA ACX-34, Daikin Industries society manufacture), so that after firing Thickness be about 45 μm, not application PFA water paint (trade name: NEOFLON PFA AD-2CRER, Daikin Industries society manufacture), System is tested with the film of application pot inner surface the most similarly to Example 1.At obtained test application pot Inner surface defines priming coat, PFA layer (floating coat) on aluminium (base material).
For obtained test application pot, carry out pinhole test similarly to Example 1.Result is shown in table 1.Pin The resistance value of hole test is 1.2M Ω, and the film of the test application pot inner surface obtained in comparative example 1 exists paint film defect.
Comparative example 2
Not application PFA powder coating (trade name: NEOFLON PFA ACX-34, Daikin Industries society manufacture), application PFA water Property coating (trade name: NEOFLON PFA AD-2CRER, Daikin Industries society manufacture), so that firing rear thickness to be about 15 μm, remove Beyond this, system is tested and uses application pot similarly to Example 1.At obtained test application pot inner surface at aluminium (base Material) on define the PFA layer (whole coating) of priming coat, small particle.
For obtained test application pot, carry out pinhole test similarly to Example 1.Result is shown in table 1.Pin The resistance value of hole test is 0.1M Ω, and the film of the test application pot inner surface obtained in comparative example 2 exists paint film defect.
Comparative example 3
Utilize the operation of embodiment 1 described in Japanese Unexamined Patent Publication 11-342072 publication, make test with in application pot The film on surface.
For obtained test application pot, carry out pinhole test similarly to Example 1.Result is shown in table 1.Pin The resistance value of hole test is 1.2M Ω, and the film of the test application pot inner surface obtained in comparative example 3 exists paint film defect.
[table 1]
Abbreviation in table 1 is as follows.
Manufacture example 3: manufacture priming paint coating composition (i) obtained in example 3
ACX-34: Daikin Industries society manufactures, PFA powder coating
AD-2CRER: Daikin Industries society manufactures, PFA water paint
ND-110: Daikin Industries society manufactures, FEP water paint
EK-1959DGN: Daikin Industries society manufactures, aqueous priming paint
ACX-31: Daikin Industries society manufactures, PFA powder coating
EK-4300CR: Daikin Industries society manufactures, aqueous PTFE dispersion
Industrial applicibility
Owing to having above-mentioned composition, the most there is not paint film defect, excellent corrosion resistance, energy in the fluorine-containing laminate of the present invention Enough it is particularly suitable for the covering articles with such as cooking appliance and kitchen articles.

Claims (10)

1. a fluorine-containing laminate, it is characterised in that described fluorine-containing laminate has base material, priming coat (A), layer (B) and layer (C), described layer (B) is formed and is not contained packing material by powder coating (ii), and described powder coating (ii) comprises melt-processed Property fluoropolymer (b), described layer (C) is formed by liquid coating (iii), and described liquid coating (iii) comprises by melt-processed The particle that property fluoropolymer (c) is constituted,
The average grain diameter of described powder coating (ii) is 5 μm～30 μm, and, it is made up of melt processable fluoropolymer (c) The average grain diameter of particle be 0.01 μm～1.0 μm,
Described fluorine-containing laminate is that described base material, described priming coat (A), described layer (B) and described layer (C) are with this order tegillum Long-pending and according to the adjacent mode of described layer (C) and described layer (B) by lamination,
Described melt processable fluoropolymer (b) is choosing free tetrafluoroethylene/perfluoro (alkyl vinyl ether) copolymer and four In the group of PVF/hexafluoropropylene copolymer composition at least a kind,
Described melt processable fluoropolymer (c) is choosing free tetrafluoroethylene/perfluoro (alkyl vinyl ether) copolymer and four In the group of PVF/hexafluoropropylene copolymer composition at least a kind.
2. fluorine-containing laminate as claimed in claim 1, wherein, described priming coat (A) be thickness be 5 μm～the layer of 30 μm, layer (B) be thickness be 10 μm～the layer of 90 μm, layer (C) be thickness be 1 μm～the layer of 30 μm.
3. fluorine-containing laminate as claimed in claim 1 or 2, wherein, described priming coat (A) comprises fluoropolymer (a) with resistance to Thermal resin.
4. fluorine-containing laminate as claimed in claim 3, wherein, described heat-resistant resin is for selecting free polyamidoimide tree Fat, polyethersulfone resin, polyetherimide resin, polyether-ether-ketone resin, aromatic polyester resins and polyarylene sulfide resin composition Group at least a kind.
5. fluorine-containing laminate as claimed in claim 3, wherein, described heat-resistant resin is for selecting free polyimide resin, gathering In the group of ether sulfone resin, polyether-ether-ketone resin, aromatic polyester resins and polyarylene sulfide resin composition at least a kind.
6. fluorine-containing laminate as claimed in claim 3, wherein, described heat-resistant resin is sub-by polyethersulfone resin and polyamide acyl Polyimide resin is constituted,
Described polyethersulfone resin is 65 mass %～85 matter of the total amount of this polyethersulfone resin and polyamide-imide resin Amount %.
7. fluorine-containing laminate as claimed in claim 3, wherein, described heat-resistant resin is by polyethersulfone resin and polyimides tree Fat is constituted,
Described polyethersulfone resin is 65 mass %～85 mass % of the total amount of this polyethersulfone resin and polyimide resin.
8. fluorine-containing laminate as claimed in claim 3, wherein, described heat-resistant resin is this heat-resistant resin and described fluorine-containing 10 mass % of the solid constituent total amount of polymer (a)～50 mass %.
9. fluorine-containing laminate as claimed in claim 3, wherein, described fluoropolymer (a) is for selecting free tetrafluoroethene homopolymerization Thing, modified Teflon, tetrafluoroethylene/hexafluoropropylene copolymer and tetrafluoroethylene/perfluoro (alkyl vinyl ether) copolymer In the group of composition at least a kind.
10. the manufacture method of a fluorine-containing laminate, it is characterised in that the manufacture method of described fluorine-containing laminate includes following work Sequence:
Operation (1), primer coating coating composition (i) on base material, it is consequently formed priming paint coated film (Ap)；
Operation (2), comprises the powder coating of melt processable fluoropolymer (b) in the upper coating of described priming paint coated film (Ap) (ii), it is consequently formed and does not contains the coated film (Bp) of packing material；
Operation (3), comprises the liquid of the particle being made up of melt processable fluoropolymer (c) in the upper coating of described coated film (Bp) State coating (iii), is consequently formed coated film (Cl)；And
Operation (4), to the coated film being made up of described priming paint coated film (Ap), described coated film (Bp) and described coated film (Cl) Laminate is fired, and is consequently formed the fluorine-containing laminate being made up of base material, priming coat (A), layer (B) and layer (C),
The average grain diameter of described powder coating (ii) is 5 μm～30 μm, and, by described melt processable fluoropolymer (c) The average grain diameter of the particle constituted is 0.01 μm～1.0 μm,
Described melt processable fluoropolymer (b) is choosing free tetrafluoroethylene/perfluoro (alkyl vinyl ether) copolymer and four In the group of PVF/hexafluoropropylene copolymer composition at least a kind,
Described melt processable fluoropolymer (c) is choosing free tetrafluoroethylene/perfluoro (alkyl vinyl ether) copolymer and four In the group of PVF/hexafluoropropylene copolymer composition at least a kind.
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