JP4165498B2 - Laminated body - Google Patents

Description

  The present invention relates to a fluorine-containing adhesive that can be firmly bonded to a substrate made of various inorganic materials and organic materials, and further relates to an adhesive film and a laminate using the same.

  Conventionally, fluorine-containing polymers have been used in various applications because they are excellent in heat resistance, chemical resistance, weather resistance, surface characteristics (such as low friction) and electrical insulation.

  On the other hand, fluoropolymers generally have insufficient mechanical strength and dimensional stability and are expensive in price.

  Therefore, in order to make the best use of the advantages of the fluorine-containing polymer and minimize the disadvantages, various studies have been made on adhesion between the fluorine-containing polymer and other inorganic materials, adhesion with organic materials, and lamination.

  However, fluoropolymers inherently have low adhesive strength, and it is difficult to directly bond fluoropolymers to other materials (base materials). Adhesive strength is insufficient even when bonding is attempted by heat fusion or the like. Even if there is a certain level of adhesive strength, the adhesive strength tends to vary depending on the type of substrate, and the reliability of adhesiveness is often insufficient.

As a method of bonding the fluoropolymer and other materials,
1. A method of physically roughing the surface of the base material by sand fraster treatment,
2. A method for surface treatment of fluorine-containing polymer such as sodium etching, plasma treatment, photochemical treatment,
3. A method of bonding using an adhesive or the like is mainly studied. However, the processing steps 1 and 2 are necessary, and the process is complicated and productivity is poor. Moreover, the kind and shape of a base material are limited. In the first place, the adhesive strength is insufficient, and problems (coloring and scratches) on the appearance of the obtained laminate are likely to occur.

  3 above. Various studies on adhesives have been conducted. General hydrocarbon adhesives have inadequate adhesion and inadequate heat resistance, and can withstand the adhesive conditions of fluoropolymers that generally require molding and processing at high temperatures. It causes peeling and coloring due to decomposition. Since the laminate using the adhesive also has insufficient heat resistance, chemical resistance, and water resistance of the adhesive layer, the adhesive force cannot be maintained due to temperature change or environmental change, and lacks reliability.

  On the other hand, studies on adhesion using an adhesive and an adhesive composition using a fluorine-containing polymer having a functional group have been conducted.

  For example, a fluorine-containing polymer obtained by graft polymerization of a hydrocarbon-based monomer having a carboxyl group, carboxylic anhydride residue, epoxy group, or hydrolyzable silyl group represented by maleic anhydride or vinyltrimethoxysilane. Reports of using polymers as adhesives (for example, Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5, Patent Document 6) and hydrocarbon-based monomers containing functional groups such as hydroxyl alkyl vinyl ether The adhesive composition of a fluorine-containing copolymer copolymerized with tetrafluoroethylene or chlorotrifluoroethylene and an isocyanate curing agent is cured, and used as an adhesive between PVC and ETFE treated with corona discharge. Has been reported (for example, Patent Document 7).

  These adhesives or adhesive compositions using a fluorine-containing polymer obtained by graft polymerization or copolymerization of a hydrocarbon-based functional group monomer have insufficient heat resistance and are processed at a high temperature with a fluororesin. During use, decomposition, foaming, etc. occur, reducing the adhesive strength, peeling off, or coloring. In the adhesive composition described in Patent Document 7, the fluororesin requires corona discharge treatment.

  Also reported are adhesives and adhesive compositions that use a fluorinated polymer having a functional group obtained by copolymerizing a sulfonic acid or a derivative thereof or a perfluorovinyl ether compound containing a carboxylic acid or a derivative thereof with a fluorine-containing monomer. Has been. Patent Document 8 describes a laminate in which a fluoropolymer having a functional group introduced by copolymerizing perfluorovinyl ether having a sulfonic acid group, a carboxylic acid group, or a derivative thereof with tetrafluoroethylene or the like is used as an adhesive. Has been. This is a laminate using a metal surface treated with an epoxy resin or the like when laminated with an inorganic material such as metal.

  Further, Patent Document 9 describes adhesion between a terpolymer having a sulfonic acid group, a terpolymer of tetrafluoroethylene and perfluoro (alkyl vinyl ether), and a metal. Adhesives made of fluorine-containing polymers with these sulfonic acid groups or carboxylic acid groups introduced have insufficient adhesion to metals, and the functional groups are strongly acidic, which corrodes the metal on the adhesive surface. There is a problem.

  In addition, carboxylic acids are generally easily decomposed at high temperatures, and are liable to cause adhesion failure, foaming, coloring, peeling, etc. during processing and use at high temperatures.

  In addition, when these laminates using adhesives are used for electrical materials, these functional groups are introduced into the fluoropolymer, so that there is a problem that the electrical insulation is greatly reduced because of the ionic nature. is there.

  Furthermore, these polymers generally have high water absorption, and the water resistance of the adhesive strength of laminates obtained using these polymers as adhesives is poor. In addition, because of its high water absorption, it is not suitable for electrical and electronic applications where fluorine-containing polymers are often used.

JP-A-7-18035 Japanese Patent Application Laid-Open No. 7-259592 Japanese Patent Laid-Open No. 7-25594 JP 7-173230 A JP-A-7-173446 JP-A-7-173447 Japanese Unexamined Patent Publication No. 7-228848 US Pat. No. 4,916,020 JP 7-145362 A

  The object of the present invention is to solve the above-mentioned conventional problems, and while maintaining the excellent heat resistance, chemical resistance, weather resistance, electrical insulation properties, etc. possessed by the fluoropolymer, further, a substrate such as metal or glass It is an object of the present invention to provide a fluorine-containing adhesive capable of directly providing strong adhesiveness, and an adhesive film and a laminate using the same.

The present invention relates to (a) 0.05 to 30 mol% of at least one monomer among fluorine-containing ethylenic monomers having a hydroxyl group, and (b) hydroxyl group copolymerizable with the component (a). 70 to 99.95 mol% of at least one monomer among fluorine-containing ethylenic monomers having no group
The present invention relates to a fluorine-containing adhesive (form 1) comprising a fluorine-containing ethylenic polymer having a hydroxyl group obtained by copolymerization of

In the present invention, the fluorine-containing ethylenic monomer (a) having a hydroxyl group is represented by the formula (1):
^{_{CX 2 = CX 1 -R f -CH}} 2 OH (1)
(In the formula, X and X ¹ are the same or different and both are hydrogen atoms or fluorine atoms, R _f is a divalent alkylene group having 1 to 40 carbon atoms, fluorine-containing oxyalkylene group having 1 to 40 carbon atoms, carbon number A fluorine-containing alkylene group containing 1 to 40 ether bonds or a fluorine-containing oxyalkylene group containing 1 to 40 carbon atoms ether bonds)
It is preferable that it is at least one monomer represented by (Form 2).

In the present invention, the fluorine-containing ethylenic monomer (a) having a hydroxyl group is represented by the formula (2):
^{_{CH 2 = CFCF 2 -R f 1}} -CH 2 OH (2)
[Wherein, R _f ¹ is a divalent fluorine-containing alkylene group having ¹ to 39 carbon atoms, or —OR _f ² (R _f ² is a divalent fluorine-containing alkylene group having 1 to 39 carbon atoms, or 1 to 39 carbon atoms. A divalent fluorine-containing alkylene group having an ether bond of
(Form 3) is preferable.

In the present invention, the fluorine-containing ethylenic monomer (b) having no hydroxyl group is preferably tetrafluoroethylene (Form 4).
Further, in the present invention, the fluorine-containing ethylenic monomer (b) having no hydroxyl group contains 85 to 99.7 mol% of tetrafluoroethylene and the formula (3):
CF ₂ = CF-R _f ³ (3)
[Wherein R _f ³ represents —CF ₃ or —OR _f ⁴ (R _f ⁴ represents a perfluoroalkyl group having 1 to 5 carbon atoms)]
It is preferable that it is a monomer mixture with 0.3-15 mol% of monomer shown by (form 5).

  In the present invention, the monomer mixture composed of the fluorine-containing ethylenic monomer (b) having no hydroxyl group is composed of 40 to 80 mol% tetrafluoroethylene or chlorotrifluoroethylene and 20 to 60 mol% ethylene. And a monomer mixture of 0 to 15 mol% of other monomers copolymerizable with these monomers (form 6).

In the present invention, the fluorine-containing ethylenic monomer (b) having no hydroxyl group is preferably vinylidene fluoride (Form 7).
In the present invention, the monomer mixture comprising the fluorine-containing ethylenic monomer (b) having no hydroxyl group is a simple mixture of 70 to 99 mol% vinylidene fluoride and 1 to 30 mol% tetrafluoroethylene. Monomer mixture of 50-99 mol% vinylidene fluoride, 0-30 mol% tetrafluoroethylene and 1-20 mol% chlorotrifluoroethylene or 60-99 mol% vinylidene fluoride and tetrafluoroethylene It is preferably a monomer mixture of 0 to 30 mol% and 1 to 10 mol% hexafluoropropylene (Form 8).

  Furthermore, the present invention relates to a fluorine-containing adhesive film (form 9) obtained by molding a fluorine-containing adhesive comprising the fluorine-containing ethylenic polymer having any of the above hydroxyl groups.

  Furthermore, the present invention is preferably a fluorine-containing adhesive film obtained by melt-molding any one of the above-mentioned fluorine-containing adhesives (Form 10).

Furthermore, the present invention relates to (A-1) a layer comprising an adhesive comprising a fluorine-containing ethylenic polymer having any one of the above hydroxyl groups, and (B-1) a fluorine-containing polymer having no functional group in the side chain. It is preferable that a layer composed of the above layers is laminated (Form 11).

  Further, in the present invention, the fluoropolymer (B-1) having no functional group in the side chain is a polytetrafluoroethylene, tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene-hexa. It is preferably at least one selected from the group consisting of a fluoropropylene copolymer, an ethylene-tetrafluoroethylene copolymer, a polyvinylidene fluoride, and a vinylidene fluoride copolymer.

Further, the present invention provides (A-1) a layer comprising any one of the above-mentioned fluorine-containing adhesives, (B-1) a polytetrafluoroethylene, a tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer, and a tetrafluoroethylene- It is preferable that at least one layer selected from the group consisting of hexafluoropropylene copolymers is laminated.

Further, in the present invention, (A-1) a layer made of the fluorine-containing adhesive and (B-1) a layer made of ethylene-tetrafluoroethylene copolymer or ethylene-chlorotrifluoroethylene copolymer are laminated. It is preferable to become.

Furthermore, in the present invention, it is preferable that (A-1) a layer made of the fluorine-containing adhesive and (B-1) a layer made of polyvinylidene fluoride or a vinylidene fluoride copolymer are laminated.

Furthermore, the present invention relates to a laminate in which (A-2) a layer made of any one of the above fluorine-containing adhesives and (C-1) a layer made of an inorganic material are directly bonded.

Furthermore, the present invention is a laminate in which (A-3) a layer made of any one of the above fluorine-containing adhesives and (D-1) a layer made of an organic material excluding the fluorine-containing polymer are directly bonded. preferable.

  Furthermore, in the present invention, the inorganic material (C-1) is preferably a metal material.

  Furthermore, in the present invention, it is preferable that the metal material is an aluminum metal material.

  Furthermore, in the present invention, it is preferable that the fluorine-containing adhesive (A-2) is any one of the fluorine-containing adhesives.

  Furthermore, in the present invention, the metal material is preferably an iron metal material.

  Furthermore, in the present invention, it is preferable that the fluorine-containing adhesive (A-2) is any one of the fluorine-containing adhesives.

  Furthermore, in the present invention, it is preferable that the metal material is a copper metal material.

  Furthermore, in the present invention, it is preferable that the fluorine-containing adhesive (A-2) is any one of the fluorine-containing adhesives.

  Furthermore, in the present invention, it is preferable that the inorganic material (C-1) is a silicon-based material.

  Furthermore, in the present invention, the inorganic material (C-1) is preferably a glass material.

  Furthermore, in the present invention, it is preferable that the fluorine-containing adhesive (A-2) is any one of the fluorine-containing adhesives.

  Furthermore, in the present invention, the organic material (D-1) is preferably a non-fluorine polymer.

Furthermore, the present invention includes (A-4) a layer made of any one of the above-mentioned fluorine-containing adhesives, (B-2) a layer made of a fluorine-containing ethylenic polymer having no functional group in the side chain, and (C -2) A laminate comprising three layers of the inorganic material, wherein the layer (A-4) comprising a fluorine-containing adhesive is a layer comprising a fluorine-containing ethylenic polymer having no functional group (B -2) and the layer (C-2) made of an inorganic material, preferably an adhesive layer is formed.

  The fluorine-containing adhesive of the present invention maintains heat resistance, chemical resistance, weather resistance, and electrical insulation, and particularly exhibits strong adhesion directly to a substrate such as metal or glass. It can be suitably used for a laminate.

The fluorine-containing ethylenic polymer used in the fluorine-containing adhesive of the present invention is a fluorine-containing ethylenic polymer having a hydroxyl group. Specifically, (a) of the fluorine-containing ethylenic monomers having a hydroxyl group, At least one monomer of 0.05 to 30 mol% of at least one monomer and (b) a fluorine-containing ethylenic monomer having no functional group copolymerizable with the component (a) It is a fluorine-containing ethylenic polymer obtained by copolymerizing 70 to 99.95 mol% of the product.

  The inventors of the present invention are surprised by the fact that the fluorine-containing ethylenic polymer having a hydroxyl group does not undergo surface treatment or the like that is often performed when a fluororesin is used. It has been found that it has strong adhesion.

  It is important that the fluorine-containing adhesive of the present invention is copolymerized using the above-mentioned fluorine-containing ethylenic monomer having a hydroxyl group (a) to introduce a hydroxyl group into the fluorine-containing polymer. An excellent adhesive force can be directly applied to various materials that are insufficiently or impossible to be bonded without surface treatment. In other words, compared with fluorine-containing polymers containing other functional groups such as carboxyl groups, non-fluorinated monomers having hydroxyl groups were copolymerized even with fluorine-containing ethylenic polymers having hydroxyl groups. It is superior in heat resistance, and even if it requires processing at a high temperature, decomposition during processing is suppressed to a small extent, and a large adhesive force can be obtained. Moreover, the laminated body without coloring or foaming can be obtained.

  In addition, the fluorine-containing ethylenic polymer having a hydroxyl group used in the fluorine-containing adhesive of the present invention is not only heat resistant itself, but also heat resistance, chemical resistance, weather resistance, water resistance of the fluorine-containing polymer. It is possible to maintain excellent characteristics such as property and electrical insulation, and to impart such excellent characteristics of the fluorine-containing polymer to the laminated body after bonding without deteriorating.

Specifically, the fluorine-containing ethylenic polymer having a hydroxyl group used in the adhesive of the present invention is (a) the formula (1):
^{_{CX 2 = CX 1 -R f -CH}} 2 OH (1)
(X and X ¹ are the same or different and both are hydrogen atoms or fluorine atoms, R _f is a divalent alkylene group having 1 to 40 carbon atoms, a fluorine-containing oxyalkylene group having 1 to 40 carbon atoms, or 1 to 40 carbon atoms. 0.05 to 30 mol% of at least one monomer represented by (b) a fluorine-containing alkylene group containing an ether bond or a fluorine-containing oxyalkylene group containing an ether bond having 1 to 40 carbon atoms; (A) at least one of fluorine-containing ethylenic monomers copolymerizable with component 70 to 99.95 mol%
And a fluorine-containing ethylenic polymer having a hydroxyl group obtained by copolymerization.

More specifically, the fluorine-containing ethylenic monomer (a) having a hydroxyl group is represented by the formula (4):
^{_{CF 2 = CF-R f 5}} -CH 2 OH (4)
[Wherein, R _f ⁵ represents a divalent fluorinated alkylene group having 1 to 40 carbon atoms or —OR _f ⁶ (R _f ⁶ represents a divalent fluorinated alkylene group having 1 to 40 carbon atoms or 1 to 40 carbon atoms. A divalent fluorine-containing alkylene group containing an ether bond of the following formula:], formula (5):
^{_{CF 2 = CFCF 2 -OR f 7}} -CH 2 OH (5)
Wherein, -R _f ⁷ is a divalent fluorine-containing alkylene group containing an ether bond of the divalent fluorine-containing alkylene group or 1 to 39 carbon atoms to 39 carbon atoms, the formula (2):
^{_{CH 2 = CFCF 2 -R f 1}} -CH 2 OH (2)
Wherein, -R _f ¹ is a divalent fluorine-containing alkylene group having 1 to 39 carbon atoms or -OR _f ² (R _f ² is 1 Number divalent fluorine-containing alkylene group or a carbon of 1 to 39 carbon atoms, A divalent fluorine-containing alkylene group having an ether bond of .about.39)] or formula (6):
^{_{CH 2 = CH-R f 8}} -CH 2 OH (6)
[Wherein, R _f ⁸ is a divalent fluorine-containing alkylene group having 1 to 40 carbon atoms].

  The fluorine-containing ethylenic monomer having the functional groups of the formulas (2) and (4) to (6) has a relatively good copolymerizability with the fluorine-containing ethylenic monomer (b-1). In view of this, it is preferable because the heat resistance of the polymer obtained by copolymerization is not significantly reduced.

  Of these, the compounds of formula (4) and formula (2) are preferred from the viewpoint of copolymerization with other fluorine-containing ethylenic monomers and the heat resistance of the obtained polymer. ) Is preferred.

  The fluorine-containing ethylenic monomer having the functional group represented by the formula (4) is more specifically described.

Etc. are exemplified. As the fluorine-containing ethylenic monomer having a functional group represented by the formula (5),

Etc. are exemplified. As the fluorine-containing ethylenic monomer having a functional group represented by the formula (2),

Etc. are exemplified. As the fluorine-containing ethylenic monomer having a functional group represented by the formula (6),

Etc. are exemplified.

  Other

Etc.

  In the fluorine-containing polymer used in the adhesive of the present invention, the fluorine-containing ethylenic monomer (a) having a hydroxyl group is a fluorine-containing ethylenic monomer having no hydroxyl group copolymerizable with (a). Copolymerized with the body (b).

  Thereby, the adhesive itself of the present invention can have excellent heat resistance, chemical resistance, weather resistance, water resistance, and electrical insulation characteristic of the fluorine-containing polymer. The same excellent characteristics can be given.

  Furthermore, the adhesiveness with a general fluorine-containing polymer not containing a functional group can be improved.

  The fluorine-containing ethylenic monomer (b) is a fluorine-containing ethylenic monomer having essentially no hydroxyl group, such as tetrafluoroethylene, chlorotrifluoroethylene, vinyl fluoride, vinylidene fluoride, hexa Fluoropropylene, hexafluoroisobutene,

(Wherein, X is a hydrogen atom, chlorine atom or fluorine atom, and n is an integer of 1 to 5), perfluoro (alkyl vinyl ether) s and the like.

  The adhesive of the present invention comprises, as essential components, a fluorine-containing ethylenic monomer (a) having a hydroxyl group and a fluorine-containing ethylenic monomer (b) having no hydroxyl group, and further having no fluorine. A copolymer obtained by copolymerizing a polymerizable monomer as an optional component can be used.

  The ethylenic monomer having no fluorine is preferably selected from ethylenic monomers having 5 or less carbon atoms in order not to reduce heat resistance, chemical resistance, etc., specifically, ethylene, propylene 1-butene, 2-butene, vinyl chloride, vinylidene chloride and the like.

  The hydroxyl group content in the fluorine-containing ethylenic polymer having a hydroxyl group used in the fluorine-containing adhesive of the present invention is 0.05 to 30 mol% of the total amount of monomers in the polymer.

  The hydroxyl group content is appropriately selected depending on the type of substrate to be bonded, shape, purpose of bonding, application, required adhesive strength, adhesive form and bonding method, and the like, but preferably 0. 0.05 to 20 mol%, particularly preferably 0.1 to 10 mol%.

  When the hydroxyl group content is less than 0.05 mol%, it is difficult to obtain sufficient adhesion to other substrates, and peeling due to chemical penetration or temperature change is likely to occur. On the other hand, if it exceeds 30 mol%, the heat resistance is lowered, and peeling, coloring, foaming, elution, etc. are liable to occur due to poor adhesion, coloring or foaming during processing at high temperatures, and decomposition during use at high temperatures.

  The fluorine-containing adhesive of the present invention can be either resinous or elastomeric by selecting the type, combination, composition ratio, etc. of the fluorine-containing ethylenic monomer (b). The properties of the adhesive can be appropriately selected according to the purpose and use of the adhesive and the purpose and use of the laminate.

In the fluorine-containing adhesive of the present invention, as a preferred specific example of the fluorine-containing ethylenic polymer having a hydroxyl group used, the fluorine-containing ethylenic monomer (a) having a hydroxyl group is 0.05 to 30 mol%. A copolymer of 70 to 99.95 mol% of tetrafluoroethylene (so-called polytetrafluoroethylene having a hydroxyl group (PTFE having a hydroxyl group)) is mentioned, and it contains a hydroxyl group with respect to the total amount of monomers. The fluoroethylenic monomer (a) is contained in an amount of 0.05 to 30 mol%, and tetrafluoroethylene 85 to 99.7 mol% and the above formula (3) with respect to the total amount of the monomers excluding the (a). )
CF ₂ = CF-R _f ³ (3)
[R _f ² represents —CF ₃ or OR _f ⁴ (R _f ⁴ represents a perfluoroalkyl group having 1 to 5 carbon atoms)]
Copolymer of 0.3 to 15 mol% of a monomer represented by (tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer having hydroxyl group (PFA having hydroxyl group) or tetrafluoro having hydroxyl group) An ethylene-hexafluoropropylene copolymer (FEP having a hydroxyl group)) and a fluorine-containing ethylenic monomer (a) having a hydroxyl group in an amount of 0.05 to 30 mol% based on the total amount of the monomers; Tetrafluoroethylene or chlorotrifluoroethylene 40 to 80 mol%, ethylene 20 to 60 mol%, other copolymerizable monomers 0 to 15 with respect to the total amount of monomers excluding the monomer (a) Copolymer with mol% (ethylene-tetrafluoroethylene copolymer having hydroxyl groups (hydroxyl Chloro copolymer (ECTFE having a hydroxyl group)) and the like - ethylene with ETFE) or functional group having a.

  The other copolymerizable monomers used in the ethylene-tetrofluoroethylene copolymer and the ethylene-chlorotrifluoroethylene copolymer having a hydroxyl group include hexafluoropropylene, hexafluoroisobutene,

(Wherein X represents H, Cl or F, and n represents an integer of 1 to 5), perfluoro (alkyl vinyl ether) s and the like.

  These exemplified fluorine-containing ethylenic polymers having a hydroxyl group are particularly preferred in that they are excellent in heat resistance, chemical resistance, weather resistance, electrical insulation (especially high frequency characteristics) and non-adhesiveness. In addition, the above-mentioned fluorine-containing polymers not containing hydroxyl groups (PTFE, PFA, FEP, E (C) TFE) have the same excellent characteristics as described above, but are the lowest in terms of adhesion to other materials. These are also preferable from the viewpoint of improvement in adhesion and lamination with other materials.

  In addition, the fluorine-containing adhesive of the present invention is a copolymer (so-called hydroxyl group) of a fluorine-containing ethylenic monomer (a) having a hydroxyl group of 0.05 to 30 mol% and vinylidene fluoride of 70 to 99.95 mol%. Polyvinylidene fluoride having a group (PVDF having a hydroxyl group)), containing 0.05 to 30 mol% of (a) with respect to the total amount of monomers, and further to the total amount of monomers excluding (a) On the other hand, it contains 0.05 to 30 mol% of (a) with respect to the total amount of monomers and copolymers of vinylidene fluoride 50 to 99 mol% and tetrafluoroethylene 1 to 30 mol%, Copolymer and monomer of vinylidene fluoride 60 to 99 mol%, tetrafluoroethylene 0 to 30 mol%, and chlorotrifluoroethylene 1 to 20 mol% with respect to the total amount of monomers excluding (a) Against the total amount of In addition, 0.05 to 30 mol% of the (a), and 60 to 99 mol% of vinylidene fluoride, 0 to 30 mol% of tetrafluoroethylene, and the total amount of the monomers excluding the (a) A copolymer with 1 to 10 mol% of hexafluoropropylene is also a preferred specific example.

  These fluoropolymers mainly composed of vinylidene fluoride have excellent weather resistance, and can be molded and processed at low temperatures and are soluble in solvents, so they have a very high heat resistance. Therefore, it can be laminated with an organic material that is not used, and is a preferable object.

  In addition, as a specific example of the elastomeric fluorine-containing adhesive of the present invention, the fluorine-containing ethylenic monomer (a) having a hydroxyl group is 0.05 to 30 mol% based on the total amount of the monomers, (A) Copolymer having 40 to 90 mol% of vinylidene fluoride, 0 to 30 mol% of tetrafluoroethylene, and 10 to 50 mol% of hexafluoropropene with respect to the monomer excluding component, component (a) Is 0.05 to 30 mol% with respect to the total number of moles of all monomers, tetrafluoroethylene is 40 to 70 mol% with respect to the total number of moles of monomers excluding the component (a), and propylene 30 to 60 mol% %, Copolymerizable with these components (for example, vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, perfluorovinyl ethers, etc.) 0-20 mol% , A polymer comprising tetrafluoroethylene and perfluorovinyl ethers, wherein the component (a) is 0.05 to 30 mol% with respect to the total number of moles of all monomers, and the unit excluding the component (a) Examples of the polymer include tetrafluoroethylene of 40 to 85 mol% and perfluorovinyl ethers of 15 to 60 mol% with respect to the monomer.

  The fluorine-containing adhesive of the present invention comprises the above-mentioned fluorine-containing ethylenic monomer (a) having a hydroxyl group and the fluorine-containing ethylenic monomer (b) having no hydroxyl group by a known polymerization method. It can be obtained by polymerization. Among them, the method by radical copolymerization is mainly used. That is, the means for starting the polymerization is not limited as long as it proceeds radically, but for example, it is started by organic, inorganic radical polymerization initiator, heat, light, ionizing radiation or the like. As the kind of polymerization, solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization and the like can be used. The molecular weight is controlled by the concentration of the monomer used for the polymerization, the concentration of the polymerization initiator, the concentration of the chain transfer agent, and the temperature. The composition of the copolymer produced can be controlled by the composition of the charged monomers.

  The fluorine-containing adhesive of the present invention is preferably used alone for adhesion because it does not impair the adhesiveness, heat resistance, chemical resistance, etc. of the present invention, but does not impair the performance depending on the purpose and application. Thus, various fillers such as inorganic powder, glass fiber, carbon fiber, metal oxide, or carbon can be blended. In addition to the filler, a pigment, an ultraviolet absorber, and other optional additives can be mixed. In addition to the additives, other fluororesins, thermoplastic resins, thermosetting resins and other resins, synthetic rubbers, and the like can also be blended.

  The fluorine-containing adhesive of the present invention can be used in various forms such as powders and pellets, preformed films and sheets, molded articles, aqueous dispersions, organic solvent solubles, and organic solvent dispersions.

  By bringing the fluorine-containing adhesives processed into these various shapes into contact with other base materials, and performing operations such as keeping them in a heated / pressurized state, a good adhesive state between the two base materials is formed. .

  The resinous fluorine-containing adhesive of the present invention, particularly the adhesive that can be melt-molded, uses itself as a molding material, and uses injection molding, extrusion molding, coextrusion molding, inflation molding, coating, molds, and the like. A molded product can be produced by a conventionally known molding method such as insert molding. Moreover, a laminated body can also be manufactured by coextrusion molding. Moreover, a film and a sheet | seat can be manufactured and this film | membrane and sheet | seat can be laminated | stacked with another base material, and a laminated body can be manufactured.

  In the case of the elastomeric fluorine-containing adhesive of the present invention, a vulcanizing agent can be mixed and vulcanized and bonded. As the vulcanization method, organic peroxide vulcanization, polyol vulcanization, and amine vulcanization, which are ordinary fluororubber vulcanization methods, can be employed.

  For example, in the case of organic peroxide vulcanization, a monomer containing bromine or iodine may be copolymerized with fluororubber for the purpose of introducing a vulcanization site, or a chain transfer agent containing iodine may be used in the polymerization. Moreover, even if bromine or iodine is not used as a vulcanization site, organic onium compounds such as organic quaternary ammonium salts and organic quaternary phosphonium salts, nitrogen-containing organic compounds such as amines and imines, phosphines, phosphites, etc. An organic base such as an organic phosphorus compound may be used as a vulcanization accelerator. When bromine or iodine is introduced as a vulcanization site, an unsaturated polyfunctional compound is used as a vulcanization aid. When an organic base is used as a vulcanization accelerator, a divalent metal oxide or hydroxide is used as an acid acceptor.

  Organic peroxides include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3, 1,4-bis (tert-butylperoxide). Oxyisopropyl) benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert -Butylperoxy) hexane, tert-butyl perbenzoate, tert-butyl perphenyl acetate and the like are used. As the unsaturated polyfunctional compound, triallyl isocyanurate, triallyl cyanurate, trimethylolpropane trimethacrylate, polybutadiene or the like is used.

  Examples of the organic base include tetrabutylammonium hydrogen sulfate, tetrabutylammonium bromide, 8-benzyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, p-toluenesulfonic acid 1,8-diazabicyclo. [5.4.0] -7-undecenium, tetrabutylphosphonium chloride, trioctylmethylphosphonium chloride, triphenylbenzylphosphonium chloride, 1,8-diazabicyclo [5.4.0] -7-undecene, pyridine, tributylamine , Triphenylphosphine, tributyl phosphite and the like are used.

  In the case of polyol vulcanization using a polyhydroxy compound as a vulcanizing agent, an organic onium compound is used as a vulcanization accelerator, and a divalent metal oxide or hydroxide is used as an acid acceptor. As the polyhydroxy compound, all known compounds used for polyol vulcanization of fluororubber can be used, and among them, aromatic polyhydroxy compounds such as bisphenol AF, bisphenol A, and hydroquinone are preferably used.

  As the organic onium compound, all known compounds used for polyol rubber vulcanization can be used, and quaternary phosphonium salts such as triphenylbenzylphosphonium chloride and trioctylmethylphosphonium chloride, tetrabutylammonium bromide, sulfuric acid. Quaternary ammonium salts such as tetrabutylammonium hydrogen and 8-benzyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, iminium salts, sulfonium salts and the like are used.

  In the case of amine vulcanization using a polyamine compound as a vulcanizing agent, a divalent metal oxide or hydroxide is used as an acid acceptor. As the polyamine compound, all known compounds used for amine vulcanization of fluoro rubber can be used, and hexamethylene diamine, hexamethylene diamine dicarbamate, dicinnamylidene hexamethylene diamine and the like are used. Further, as the acid acceptor, oxides or hydroxides such as magnesium, calcium, zinc and lead are used.

  The elastomeric fluorine-containing adhesive thus obtained can be bonded or laminated to other organic or inorganic materials by a conventionally known method such as extrusion, coextrusion, insert molding using a calendar, coating, mold, etc. It is. By these methods, for example, a laminated film of two layers of the elastomeric adhesive of the present invention and another polymer, or three or more layers in which another polymer is laminated on both sides using the elastomeric adhesive of the present invention as an adhesive layer Laminate, metal coated with the elastomeric adhesive of the present invention, inorganic materials such as glass and ceramics, metal coated with the elastomeric adhesive of the present invention as an adhesive layer and coated with other polymers, inorganic such as glass and ceramics Materials are obtained.

  The various fluorine-containing adhesives of the present invention described above can also be used as powder surface treatments and paints.

  For example, it is possible to obtain a coating composition by using a powder of the fluorine-containing adhesive of the present invention, an aqueous dispersion, an organic solvent dispersion, or an organic solvent soluble material. It can be used as a primer for fluorine-containing paints by utilizing its adhesiveness to various substrates. Specifically, the adhesive described in Form 4 is an aqueous dispersion, the adhesive described in Form 5 is an aqueous dispersion or an organic solvent dispersion or powder, and the adhesive described in Form 6 is a powder. The adhesives described in Form 7 are organic solvent dispersions or powders, the adhesives described in Form 8 are aqueous dispersions, organic solvent solubles and powders, etc. It can be used as a primer for a fluororesin paint that does not contain the corresponding hydroxyl group.

  The second of the present invention is a fluorine-containing adhesive film formed by using the fluorine-containing adhesive of the present invention.

  Although hot melt adhesives have progressed from the viewpoints of development of composite materials, rationalization and automation of bonding operations, and prevention of pollution, general hot melt adhesives require the use of an applicator. On the other hand, the film-like adhesive can be bonded by being sandwiched on or between the substrates without being required for an applicator, and is advantageous in terms of process.

  In addition, since a uniform adhesive layer is formed on the entire surface of the substrate, a uniform adhesive force with no adhesion unevenness can be obtained, and it is possible to deal with incompatible or poor substrates.

  Further, it can be cut into various shapes for use, has a small work loss, has a good work environment, and is advantageous in terms of cost.

  The fluorine-containing adhesive film of the present invention has the above advantages as well.

The fluorine-containing adhesive film of the present invention comprises (a) 0.05 to 30 mol% of at least one monomer of a fluorine-containing ethylenic monomer having a hydroxyl group, and (b) copolymerized with the component (a). 70 to 99.95 mol% of at least one monomer among possible fluorine-containing ethylenic monomers
Is a fluorine-containing adhesive film formed by molding a fluorine-containing ethylenic polymer having a hydroxyl group obtained by copolymerization with the other various groups without using surface treatment or using a general adhesive. It can be adhered to the material, thereby giving the substrate superior properties of fluoropolymers.

  Among the fluorine-containing adhesives shown above, it is possible to manufacture adhesive films using various adhesives according to the purpose and purpose, film manufacturing process, and bonding method, but the adhesive film itself is heat resistant. It must have chemical resistance, mechanical properties, non-adhesiveness, etc., and can be efficiently formed by film such as melt molding, has good moldability, and can be made thin and uniform. Fluorine-containing molded by using the adhesive described in Form 5, 6, 7 or 8 because it can be melted by various thermocompression bonding methods and can be firmly and cleanly adhered to various substrates. An adhesive film is preferred.

  The thickness of the fluorine-containing adhesive film of the present invention is selected according to the purpose and application and is not particularly limited, but is 10 to 3000 μm, preferably 20 to 500 μm, and particularly preferably 40 to 300 μm.

  Films that are too thin require special manufacturing methods, are difficult to handle when performing bonding operations, are prone to wrinkles, breakage, and poor appearance, and have adhesive strength, mechanical strength, chemical resistance, and weather resistance. In some cases, it may be insufficient. A film that is too thick is disadvantageous in terms of cost and workability when joined and integrated.

Second of the fluorine-containing adhesive film of the present invention,
(A-1) A fluorine-containing adhesive film obtained by laminating the fluorine-containing adhesive according to the first embodiment and (B-1) a fluorine-containing ethylenic polymer having no functional group on the side chain.

  That is, one side has adhesion to other base materials by a layer made of a fluorine-containing ethylenic polymer having a hydroxyl group, and the other side is a layer made of a general fluorine-containing polymer. By bringing the adhesive surface into contact with the substrate and bonding it by operations such as thermocompression bonding, the fluorine-containing polymer has excellent chemical resistance, weather resistance, stain resistance, non-tackiness, low friction, electrical properties ( Excellent properties such as high-frequency electrical insulation) can be imparted to a substrate or a laminate including the substrate.

  In the adhesive film formed by laminating (A-1) and (B-1) of the present invention, the fluorine-containing ethylenic polymer (B-1) having no functional group in the side chain is specifically PTFE, PFA, FEP, ETFE, ECTFE, PVDF, and a vinylidene fluoride copolymer are preferable because the excellent properties of the above-mentioned fluoropolymer can be imparted to the substrate and the laminate including the substrate.

  The fluorine-containing adhesive film comprising the two-layer laminate of the present invention can be variously selected depending on the purpose, application, processing method and the like, but the two layers are preferably a combination having good adhesion and compatibility with each other.

  Specifically, of the two layers, the adhesive layer (A-1) has a hydroxyl group that imparts adhesiveness to the monomer structure and composition equivalent to the layer (B-1) made of the fluoropolymer. It is preferably selected from polymers obtained by copolymerizing the fluorine-containing ethylenic monomer (a).

More specifically,
i) a layer made of (A-1) the adhesive according to Form 4 (so-called hydroxyl group-containing PTFE) or the adhesive according to Form 5 (so-called hydroxyl group-containing PFA or FEP); and (B-1) PTFE, PFA And a fluorine-containing adhesive film obtained by laminating a layer made of at least one polymer selected from the group consisting of FEP and FEP has the highest heat resistance, chemical resistance, non-adhesiveness, low friction, It is preferable at the point which has the outstanding characteristics, such as insulation.

ii) (A-1) A fluorine-containing adhesive film formed by laminating a layer made of the adhesive (so-called ETFE having a hydroxyl group) described in Form 6 and a layer made of (B-1) ETFE has excellent heat resistance. In addition to the property, chemical resistance, mechanical properties, etc., it is preferable in terms of excellent melt molding processability.
iii) a layer composed of at least one selected from (A-1) the adhesive according to Form 7 (so-called PVDF having a hydroxyl group) and the adhesive according to Form 8, and (B-1) PVDF and vinylidene fluoride A fluorine-containing adhesive film obtained by laminating a layer made of at least one polymer selected from the group consisting of polymers is preferred in that it has excellent weather resistance and molding processability.

  The thickness of the two-layer fluorine-containing adhesive film of the present invention is selected depending on the purpose and application and is not particularly limited, but the two layers are 20 to 5000 μm, preferably 40 to 1000 μm, particularly preferably 50 to 500 μm. is there.

  The thickness of each layer can be about 5 to 1000 μm for the adhesive layer (A-1) and about 15 to 4995 μm for the fluoropolymer layer (B-1), preferably 10 to 500 μm for the adhesive layer (A-1), The polymer layer (B-1) is 30 to 990 μm, particularly preferably (A-1) 10 to 200 μm and (B-1) 40 to 490 μm.

  In the present invention, an appropriate reinforcing agent, filler, stabilizer, ultraviolet absorber, pigment and other appropriate additives can be incorporated in the fluorine-containing adhesive film as long as the properties are not impaired. Such additives can improve thermal stability, surface hardness, wear resistance, weather resistance, chargeability, and the like.

  The fluorine-containing adhesive film of the present invention comprises a heat melting method, extrusion method, cutting method, solvent casting, powder, aqueous or organic solvent dispersion, depending on the type of polymer used in the film and the shape of the target film. After coating, a continuous film can be obtained by various production methods such as a method of obtaining a film.

  For example, an adhesive that is difficult to be melt-molded such as described in Form 4 (PTFE having a hydroxyl group) can be formed by compression molding, extrusion molding (ram extrusion, paste extrusion and rolling, etc.), etc. For adhesives that can be melt-molded like the polymers described in 6, 7 or 8, compression molding, extrusion molding, etc. are adopted, and melt extrusion molding is a preferred method especially for reasons of productivity and quality. is there.

  In the present invention, the adhesive film composed of the two layers (A-1) and (B-1) is joined and compressed by superposing the respective molded films (A-1) and (B-1). A method of coating the other on one molded film, a method of achieving joint integration at the same time as film formation by a multilayer coextrusion molding method, etc. In particular, multilayer coextrusion in terms of productivity and quality A molding method is preferred.

  Adhesion of the fluorine-containing adhesive film of the present invention with another substrate is achieved by thermal activation by heating or the like, and further, hot melt adhesion is preferable. Typical bonding methods are the hot roll method and the hot press method, as well as the high frequency heating method, the micro method, the vacuum pressure bonding method (vacuum press, etc.) and the pneumatic method. It can be selected as appropriate depending on the state and type.

  The fluorine-containing adhesive film of the present invention is composed of various shapes, sizes, thicknesses, and the like as described above, and has a wide range of properties due to excellent adhesiveness to various substrates and excellent properties of the fluorine-containing polymer. Can be used for applications. For example, a tube, a flat plate, a bent plate, a curved plate, or the like, such as a metal tube or rod exterior or interior protective coating, is appropriate. Specific examples of applications include anticorrosion tape wrapped around chemical plant piping, anticorrosion tape wrapped around the bottom of the enclosure, tape for anticorrosion of piping such as ship decks, other anticorrosion tape for piping, signage, agriculture It is also suitable for other applications such as roofs or side walls of greenhouses, exterior materials, solar cell surfaces, and other interior materials with excellent contamination resistance. Furthermore, it can be used for applications requiring chemical resistance such as food packaging and chemical packaging.

  In addition, fixing rolls and pressure rolls such as copiers and printers, food processing equipment, cooking appliances and other non-adhesive / low friction applications, printed circuit boards and other applications requiring electrical properties, water repellency It can be used for applications that require water repellency such as glass, liquid crystal related materials such as liquid crystal displays, and automotive related materials.

  3rd of this invention is related with the laminated body formed by adhere | attaching the fluorine-containing adhesive of this invention, and a base material directly.

  The adhesive made of a fluoropolymer having a hydroxyl group of the present invention has a good adhesiveness directly to various inorganic materials and organic materials, without subjecting the substrate to surface treatment. A laminate can be formed.

The first of the laminates of the present invention is:
(A-2) A laminate comprising an adhesive composed of a fluoropolymer having a hydroxyl group as described in Form 1 and (C-1) an inorganic material.

  Specific examples of the inorganic material (C-1) include metal materials, silicon materials, other ceramics, boron materials, and carbon materials.

  Metallic materials also include metals and alloys of two or more metals, metal salts such as metal oxides, metal hydroxides, carbonates and sulfates.

  Of these, metals, metal oxides, and alloys are more preferable in terms of adhesion.

  In the laminate of the present invention, the type of metal material (C-1) used is aluminum, iron, nickel, titanium, molybdenum, magnesium, manganese, copper, silver, lead, tin, chromium, beryllium, tungsten, cobalt Examples thereof include metals, metal compounds, and alloys composed of two or more of these, and can be selected according to the purpose and application.

  Specific examples of alloys include carbon steel, Ni steel, Cr steel, Ni-Cr steel, Cr-Mo steel, stainless steel, silicon steel, alloy steel such as permalloy, Al-Cl, Al-Mg, Al-Si, Aluminum alloys such as Al-Cu-Ni-Mg, Al-Si-Cu-Ni-Mg, brass, bronze, silicon bronze, silicon brass, white, nickel bronze and other copper alloys, nickel manganese (D nickel) ), Nickel-aluminum (Z nickel), nickel-silicon, monel metal, constantan, nichrome inconel, nickel alloy such as hastelloy, and the like.

  In addition, for the purpose of preventing metal corrosion, the metal surface is coated with other metals by electroplating, hot dipping, chromizing, siliconizing, calorizing, shell dying, spraying, etc. A phosphate film may be formed, a metal oxide may be formed by anodic oxidation or heat oxidation, or electrochemical corrosion protection may be performed.

  Furthermore, for the purpose of further improving the adhesion, the metal surface is subjected to chemical conversion treatment with phosphate, sulfuric acid, chromic acid, oxalic acid, etc., sand blast, shot blast, grit blast, honing, paper scratch, wire scratch Further, surface roughening treatment such as hairline treatment may be performed, and for the purpose of design properties, coloring, printing, etching, or the like may be performed on the metal surface.

  Note that aluminum-based metal materials, iron-based metal materials, and copper-based metal materials are preferred as those that have better adhesion and are required to have an excellent function by laminating a fluorine-containing polymer.

  Examples of silicon-based materials include glass-based materials, single crystal silicon, polycrystalline silicon, amorphous silicon, clays, cement, etc. Among them, glass-based materials have good adhesiveness and are laminated with a fluoropolymer. It is preferable in that it is required to provide a more excellent function.

Specific examples of preferred combinations in the laminate comprising the fluorine-containing adhesive (A-2) and the inorganic material (C-1) of the present invention are as follows:
i) (A-2) A laminate comprising the fluorine-containing adhesive according to Embodiment 4, 5, 6, 7 or 8 and (C-1) an aluminum-based metal material. Examples of the aluminum-based metal material include pure aluminum, aluminum oxide, Al-Cu-based, Al-Si-based, Al-Mg-based, Al-Cu-Ni-Mg-based, and Al-Si-Cu-Ni-Mg-based alloys. Further, an aluminum alloy for casting or spreading such as a high-strength aluminum alloy or a corrosion-resistant aluminum alloy can be used. In addition, anodized with caustic soda, oxalic acid, sulfuric acid, chromic acid to form an oxide film on the surface of the aluminum or aluminum alloy for the purpose of anticorrosion, surface hardening, and adhesion improvement (anodized) ), And those subjected to the above-described surface treatment can also be used.

ii) (A-2) A laminate comprising the fluorine-containing adhesive according to Embodiments 4, 5, 6, 7, and 8 and (C-1) an iron-based metal material. Ferrous metal materials include pure iron, iron oxide, carbon steel, Ni steel, Cr steel, Ni-Cr steel, Cr-Mo steel, Ni-Cr-Mo steel, stainless steel, silicon steel, permalloy, and dead magnetic steel Magnetic steel, cast iron, etc. can be used.

  Further, in the same manner as described above, the other metal plated on the surface, for example, hot dip galvanized steel sheet, alloyed hot dip galvanized steel sheet, aluminum plated steel sheet, zinc nickel plated steel sheet, zinc aluminum steel sheet, etc. A metal-coated film, a chromic acid-based or phosphoric acid-based chemical conversion treatment or a heat treatment, an oxide coating formed thereon, an anti-corrosion method (for example, a carbonic steel plate), or the like can be used.

i) and ii) can give corrosion resistance, rust prevention, chemical resistance, weather resistance, non-adhesiveness, and slidability to aluminum materials and iron materials, respectively, as building materials, chemical plants, food processing, This is preferable in that it can be used for various applications such as cooking equipment, housing equipment, home appliance-related parts, automobile-related parts, and OA-related parts. And even more
iii) (A-2) The laminate comprising the fluorine-containing adhesive according to embodiments 4 and 5 and (C-1) a copper-based metal material has low water absorption, and the copper-based material has excellent electrical properties (particularly It is a preferable object because it can be applied to electrical and electronic related products such as high-frequency printed circuit boards and electrical and electronic parts.

iv) (A-2) A laminate comprising the fluorine-containing adhesive according to Form 5, 6, 7 or 8 and (C-1) a glass-based material has transparency, and further has a water repellency on the glass surface. It provides oil repellency, antireflection properties, low refractive index, etc., and can be used for optical related parts, liquid crystal related parts, glass for building materials, glass cooking equipment, glass for automobiles, and the like. Moreover, it plays a role of preventing breakage of glass and can be used for lighting-related equipment and the like, which is a preferable object.

  Moreover, the laminated body which consists of a fluorine-containing adhesive (A-2) and inorganic material (C) of this invention can further laminate | stack the fluorine-containing polymer which does not have a functional group in a side chain on the adhesive agent side. .

That is, a laminate comprising (A-4) Form 1 fluorine-containing adhesive, (B-2) a fluorine-containing polymer having no functional group in the side chain, and (C-2) an inorganic material,
(A-4) is a laminate in which an adhesive layer is formed between (B-2) and (C-2), and more effectively gives the excellent properties of the fluoropolymer to the inorganic material. be able to.

In this case, the fluorine-containing adhesive (A-4) used for the adhesive layer of the laminate composed of these three layers is a polymer similar to the fluorine-containing polymer (B-2) of the outer layer and containing a hydroxyl group. Is preferable from the viewpoint of mutual adhesiveness. For example, i) (A-4) is an adhesive according to Form 4 or 5,
A polymer in which (B-2) is selected from PTFE, PFA, and FEP;
A laminate in which (C-2) is an inorganic material;
ii) The adhesive according to (6), wherein (A-4) is
(B-2) is ETFE.
A laminate in which (C-2) is an inorganic material;
iii) (A-4) is an adhesive according to Form 7 or 8,
A polymer in which (B-2) is selected from PVDF or VDF copolymers,
A laminate in which (C-3) is an inorganic material is a preferred example.

  In the laminate with the inorganic material (C-1) of the present invention, adhesion to the fluorine-containing adhesive layer (A-2) and the fluorine-containing polymer layer (B-2) and other properties of the fluorine-containing polymer are not impaired. An appropriate reinforcing agent, filler, stabilizer, ultraviolet absorber, pigment, and other appropriate additives may be included in the range. Such additives can also improve thermal stability, surface hardness, wear resistance, weather resistance, chargeability, and other properties.

The second of the laminates of the present invention is:
(A-3) Adhesive comprising the hydroxyl group-containing fluoropolymer described in Form 1 (D-1) A laminate comprising an organic material excluding the fluoropolymer.

  That is, the fluorine-containing adhesive (A-3) of the present invention gives good adhesion even in organic materials other than the fluorine-containing polymer due to the effect of the hydroxyl group contained therein.

  The organic material in the laminate of the present invention is a synthetic polymer, synthetic rubber, synthetic fiber, synthetic polymer material such as synthetic leather, natural rubber, natural fiber, natural organic matter such as wood, paper, leather, or These are composites.

  Among them, the non-fluorinated polymer material is laminated with the fluorine-containing polymer, so that the disadvantages of each other can be compensated for and used in various applications.

  Non-fluorinated polymers include, for example, polyester, polyamide, polyphenylene sulfide, acrylic, vinyl acetate, polyolefin, vinyl chloride, polycarbonate, styrene, polyurethane, ABS, polyimide, polyamideimide, PEEK, PES, polysulfone, PPO, polyaramid, Examples include polyacetal, polyether imide, silicone resin, epoxy resin, phenol resin, amino resin, unsaturated polyester, cellophane and the like.

  Among them, a polymer material having a functional group or a polar group in the molecule is preferable in terms of adhesion to the adhesive of the present invention, and a polymer material having higher heat resistance can withstand the high molding temperature of a fluororesin, and a laminate. This is preferable in that the overall heat resistance is maintained, and a laminate having the excellent characteristics of the fluorine-containing polymer and the characteristics of other polymer materials can be obtained.

  Specifically, polyamide, polyester, polyphenylene sulfide, polycarbonate, polyimide, polyamideimide, PEEK, PES, polysulfone, PPO, polyetherimide, polyacetal, etc. are preferable, and among them, melt moldability is good, and the polymer itself is mechanical. Excellent properties, and by laminating with fluororesin, they are given excellent chemical resistance, solvent resistance, solvent impermeability, weather resistance, antifouling properties, and optical properties (low refractive index). It is requested to do. Polyamide, polyester, polycarbonate and the like are particularly preferred examples.

  In the laminate composed of the fluorine-containing adhesive (A-3) and the organic material (D-1) of the present invention, an appropriate reinforcing agent and filling to the extent that adhesion and other properties of the fluorine-containing polymer are not impaired in each layer. Agents, stabilizers, ultraviolet absorbers, pigments, and other appropriate additives can also be included. Such additives can improve thermal stability, surface hardness, wear resistance, weather resistance, chargeability, and the like.

  The manufacturing method of the laminated body of this invention is suitably selected by the kind form of a fluorine-containing adhesive, the kind and shape of an inorganic material, and the kind and shape of an organic material.

  For example, a method of making a fluorine-containing adhesive film as described in the form 9 or 11 using a fluorine-containing adhesive, and laminating with an inorganic or organic material and laminating by heat activation as described above, In addition, a method of applying a fluorine-containing adhesive in the form of an aqueous or organic solvent dispersion, organic solvent-soluble material, powder, etc. on an inorganic material or an organic material and applying heat activation by heating, etc. When the adhesive can be melt-molded, an insert molding method can be used, and when a fluorine-containing adhesive that can be melt-molded and a thermoplastic polymer are laminated, a co-extrusion method or the like can be employed.

  By these methods, the laminate of the present invention can be formed into shapes such as hoses, pipes, tubes, sheets, seals, gaskets, packings, films, tanks, rollers, bottles and containers.

  Next, the present invention will be described based on reference examples and examples, but the present invention is not limited to these examples. In the following examples, Examples 1 to 7 and 9 are examples that fall within the scope of the present invention.

Synthesis example 1
(Synthesis of PFA having hydroxyl group)
A 6-liter glass-lined autoclave equipped with a stirrer, valve, pressure gauge, and thermometer was charged with 1500 ml of pure water, sufficiently purged with nitrogen gas, evacuated, and 1,2-dichloro-1,1,2, 1500 g of 2-tetrafluoroethane (R-114) was charged.

  Next, perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol) (formula 7)

Of nitrogen, 180 g of perfluoro (propyl vinyl ether) (PPVE) and 180 g of methanol were injected using nitrogen gas, and the temperature in the system was kept at 35 ° C.

While stirring, tetrafluoroethylene gas (TFE) was injected so that the internal pressure was 8.0 kgf / cm ² G. Next, 0.5 g of a 50% methanol solution of di-n-propyl peroxydicarbonate was injected using nitrogen to initiate the reaction.

Since the pressure lowered with the progress of the polymerization reaction, 7.5 kgf / cm ² again pressurized at the time when lowered to G with tetrafluoroethylene gas to 8.0 kgf / cm ^2, the step-down was repeated boosting.

  Every time about 60 g of tetrafluoroethylene gas is consumed from the start of polymerization while continuing to supply tetrafluoroethylene, the fluorine-containing ethylenic monomer having a hydroxy group (the compound represented by the formula (7)) The polymerization was continued by injecting 2.5 g in total 9 times (22.5 g in total), and when about 600 g of tetrafluoroethylene was consumed from the start of the polymerization, the supply was stopped and the autoclave was cooled. Was released.

The obtained copolymer was washed with water and methanol, and then vacuum dried to obtain 710 g of a white solid. The composition of the obtained copolymer was TFE / PPVE / (fluorinated ethylenic monomer having a hydroxy group represented by formula (7)) = 97.0 / 2.0 by ¹⁹ F-NMR analysis and IR analysis. /1.0 mol%. In the infrared spectrum, characteristic absorption of -OH was observed at 3620 to 3400 cm- ¹ . It was Tm = 305 ° C. by DSC analysis, and the decomposition start point was 365 ° C. and 1% thermal decomposition temperature Td = 375 ° C. by DTGA analysis. Using a Koka flow tester and a nozzle having a diameter of 2 mm and a length of 8 mm, the melt flow rate was measured at 372 ° C. for 5 minutes with a load of 7 kgf / cm ² and found to be 32 g / 10 min.

  The obtained white powder was extruded at 350 to 370 ° C. with a twin-screw extruder (Toyo Seiki Co., Ltd., Labo Plast Mill) to produce pellets.

Synthesis example 2
(Synthesis of PFA having hydroxyl group)
A 6-liter glass-lined autoclave equipped with a stirrer, valve, pressure gauge, and thermometer was charged with 1500 ml of pure water, sufficiently purged with nitrogen gas, evacuated, and 1,2-dichloro-1,1,2, 1500 g of 2-tetrafluoroethane (R-114) was charged.

  Then, 2.5 g of perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol) (formula (7)), perfluoro (propyl Vinyl ether) (PPVE) 132 g and methanol 230 g were injected using nitrogen gas, and the temperature in the system was maintained at 35 ° C.

While stirring, tetrafluoroethylene gas (TFE) was injected so that the internal pressure was 8.0 kgf / cm ² G. Next, 0.5 g of a 50% methanol solution of di-n-propyl peroxydicarbonate was injected using nitrogen to initiate the reaction.

Since the pressure lowered with the progress of the polymerization reaction, 7.5 kgf / cm ² again pressurized at the time when lowered to G with tetrafluoroethylene gas to 8.0 kgf / cm ^2, the step-down was repeated boosting.

  Every time about 60 g of tetrafluoroethylene gas is consumed from the start of polymerization while continuing to supply tetrafluoroethylene, the fluorine-containing ethylenic monomer having a hydroxy group (the compound represented by the formula (7)) The polymerization was continued by injecting 1.23 g in total 9 times (total of 11.10 g), and when about 600 g of tetrafluoroethylene was consumed from the start of the polymerization, the supply was stopped and the autoclave was cooled, and the unreacted monomer and R-114 Was released.

The obtained copolymer was washed with water and methanol, and then vacuum-dried to obtain 680 g of a white solid. The composition of the obtained copolymer was TFE / PPVE / (fluorinated ethylenic monomer having a hydroxy group represented by the formula (7)) = 97.6 / 2.0 by ¹⁹ F-NMR analysis and IR analysis. /0.4 mol%. In the infrared spectrum, characteristic absorption of -OH was observed at 3620 to 3400 cm- ¹ . The DSC analysis showed Tm = 310 ° C., and the DTGA analysis showed decomposition start temperature 368 ° C. and 1% thermal decomposition temperature Td = 375 ° C. Using a Koka flow tester and a nozzle having a diameter of 2 mm and a length of 8 mm, the melt flow rate was measured at 372 ° C. for 5 minutes with a load of 7 kgf / cm ² and found to be 42 g / 10 min.

  The obtained white powder was extruded at 350 to 370 ° C. with a twin-screw extruder (Toyo Seiki Co., Ltd., Labo Plast Mill) to produce pellets.

Synthesis example 3
(Synthesis of PFA containing no functional group)
In Reference Example 1, perfluoro (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol) (a compound represented by the formula (7)) is not used. In addition, synthesis was carried out in the same manner as in Reference Example 1 except that 240 g of methanol was used, and 597 g of PFA containing no functional group was obtained.

The obtained PFA was analyzed in the same manner as in Reference Example 1. TFE / PPVE = 98.2 / 1.8 mol%
Tm = 310 ° C
Td = 469 ° C. (1% weight loss)
Melt flow rate = 24 g / 10 min
Met.

  The obtained white powder was extruded in the same manner as in Synthesis Example 1 to produce pellets.

Synthesis example 4
(Synthesis of PFA having a methyl ester group)
A 6-liter glass-lined autoclave equipped with a stirrer, valve, pressure gauge, and thermometer was charged with 1500 ml of pure water, sufficiently purged with nitrogen gas, evacuated, and 1,2-dichloro-1,1,2, 1500 g of 2-tetrafluoroethane (R-114) was charged.

  Then perfluoro- (9,9-dihydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenoic acid) methyl (formula 8)

2.7 g, perfluoro (propyl vinyl ether) (PPVE) 130 g, and methanol 220 g were injected using nitrogen gas, and the temperature inside the system was maintained at 35 ° C.

While stirring, tetrafluoroethylene gas (TFE) was injected so that the internal pressure was 8.0 kgf / cm ² G. Next, 0.5 g of a 50% methanol solution of di-n-propyl peroxydicarbonate was injected using nitrogen to initiate the reaction.

Since the pressure lowered with the progress of the polymerization reaction, 7.5 kgf / cm ² again pressurized at the time when lowered to G with tetrafluoroethylene gas to 8.0 kgf / cm ^2, the step-down was repeated boosting.

  Every time about 60 g of tetrafluoroethylene gas is consumed from the start of polymerization while continuing to supply tetrafluoroethylene, the fluorine-containing ethylenic monomer having a hydroxy group (the compound represented by the formula (7)) 2.7 g was injected 9 times in total (24.3 g in total) and the polymerization was continued. When about 600 g of tetrafluoroethylene was consumed from the start of polymerization, the supply was stopped and the autoclave was cooled to remove unreacted monomers and R-114. Was released.

The obtained copolymer was washed with water and methanol, and then vacuum dried to obtain 710 g of a white solid. The composition of the obtained copolymer was TFE / PPVE / (fluorinated ethylenic monomer having a methyl ester group represented by the formula (8)) by ¹⁹ F-NMR analysis and IR analysis = 97.8 / 1. It was 0 / 1.2 mol%. In the infrared spectrum, a characteristic absorption of -COOMe was observed at 1795 cm- ¹ . It was Tm = 308 ° C. by DSC analysis and 1% thermal decomposition temperature Td = 376 ° C. by DTGA analysis. Using a Koka flow tester and a nozzle with a diameter of 2 mm and a length of 8 mm, the melt flow rate was measured at 372 ° C. for 5 minutes with a load of 7 kgf / cm ² and found to be 29 g / 10 min.

Synthesis example 5
(Synthesis of PFA having a carboxyl group)
10 g of white powder of PFA having a methyl ester group obtained in Synthesis Example 4 was added to a solution obtained by dissolving 40 g of NaOH in a mixed solvent of 600 ml of methanol and 200 ml of water, followed by stirring at 70 to 75 ° C. for 5 hours.

  After cooling, 2N-HCl aqueous solution was added until the pH of the solution was 2, followed by stirring for 3 hours.

  The white powder was taken out, washed with water and methanol, and dried at 100 ° C.

Absorption of the carbonyl group of the carboxyl group from IR analysis to 1700 cm ^-1, absorption of OH group were newly observed at 3200~3700cm ^-1.

Synthesis Example 6
(Synthesis of fluoropolymers using functional group-containing monomers not containing fluorine)
In a 1 liter stainless steel autoclave equipped with a stirrer, a valve, a pressure gauge, and a thermometer, 250 g of butyl acetate, 36.4 g of vinyl pivalate (VPi), a hydroxyl group-containing monomer having no fluorine, Charge 32.5 g of hydroxyl butyl vinyl ether (HBVE) and 4.0 g of isopropoxycarbonyl peroxide, cool with ice at 0 ° C., fill and replace with nitrogen gas, and then evacuate. 47.5 g of isobutylene (IB) and tetrafluoroethylene ( (TFE) 142g was charged.

While stirring, the mixture was heated to 40 ° C. and reacted for 30 hours. The reaction was stopped when the pressure in the reaction vessel decreased to 2.0 kg / cm ² or less. When the autoclave was cooled and the unreacted gas monomer was released, a butyl acetate solution of a fluorinated copolymer was obtained. The polymer concentration was 45%.

The fluorinated copolymer was taken out from the butyl acetate solution of the obtained fluorinated copolymer by a reprecipitation method, and isolated by sufficiently drying under reduced pressure. When the fluorine-containing copolymer obtained by 1H-NMR and ¹⁹ F-NMR elemental analysis was analyzed, it was a copolymer comprising TFE / IB / VPi / HBVE = 44/34/15/7 mol.

Reference example 1
(Preparation of PFA film having hydroxyl group)
8.0 g of the pellet obtained in Synthesis Example 1 was put in a 100 mmφ mold and set in a press machine set at 350 ° C., preheated for 30 minutes, and then compression molded at 70 kg / cm ² for 1 minute to obtain a thickness of 0 A 5 mm film was obtained.

Reference example 2
(Preparation of PFA film having hydroxyl group)
A film having a thickness of 0.5 mm was obtained in the same manner as in Reference Example 1 except that the pellets obtained in Synthesis Example 2 were used.

Reference example 3
(Preparation of PFA film containing no functional group)
A film having a thickness of 0.5 mm was obtained in the same manner as in Reference Example 1 except that the pellets obtained in Synthesis Example 3 were used.

Reference example 4
(Production of film by extrusion of PFA having hydroxyl group)
Using the pellets obtained in Synthesis Example 2, extrusion was performed at 360 ° C. to 380 ° C. and a roll temperature of 120 ° C. with a single screw extruder (Toyo Seiki Co., Ltd., Labo Plast Mill), and the width was 10 cm and the thickness was 100 to 150 μm. I got a film.

Reference Example 5
(Production of film by extruding PFA not containing functional group)
A film having a width of 10 cm and a thickness of 100 to 150 μm was obtained in the same manner as in Reference Example 4 except that the pellets obtained in Synthesis Example 3 were used.

Reference Example 6
(Laminated film of PFA and PTFE having a hydroxyl group)
The PFA film having a hydroxyl group obtained in Reference Example 1 and a PTFE film having a thickness of 0.5 mm were overlaid and compression-molded in the same manner as in Reference Example 1.
The two layers were firmly adhered to each other.

Reference Example 7
(Preparation of PFA film having methyl ester group)
Using 8.0 g of the white powder obtained in Synthesis Example 4, a film having a thickness of 0.5 mm was obtained in the same manner as in Reference Example 1.

Examples 1-4
(Adhesion test between hydroxyl group-containing PFA and metal)
Using a defatted chromic acid having a thickness of 0.5 mm, treated aluminum, pure aluminum, and a steel plate as a metal plate, an adhesion test with a PFA film having hydroxyl groups (films of Reference Examples 1 and 2) is as follows. I went to. The results are shown in Table 1.

(Preparation of test specimen for peel test)
As shown in FIG. 1, the fluorine-containing film having a hydroxyl group obtained in the reference example and a spacer (aluminum foil) having a thickness of 0.1 mm are sandwiched between two metal plates and set in a press machine set at 350 ° C., After preheating (20 minutes), pressurization was performed at 50 kg / cm ² for 1 minute.

  The adhesive layers of the obtained laminates were all 0.1 mm. Further, the laminate was cut to a width of 25 mm, and the spacer portion was bent into a T shape as shown in FIG. 1 to obtain a test piece for a peel test.

(Peel test)
Based on the T-type peel test method of JIS K6854-1977, measurement was performed at room temperature and at a cross-head speed of 50 mm / min using a Tensilon universal testing machine manufactured by Orientec Co., Ltd. The measurement showed the maximum peel strength (kgf / 25 mm) and the minimum peel strength (kgf / 25 mm).

Comparative Examples 1-3
(Adhesion test between PFA containing no functional group and metal)
A test piece was prepared and a peel test was conducted in the same manner as in Example 1 except that the PFA film containing no functional group obtained in Reference Example 3 was used instead of the PFA film having a hydroxyl group in Reference Examples 1 and 2. . The results are shown in Table 1.

Examples 6-7 (Example 5 is a missing number)
(Adhesion test between PFA having hydroxyl group and glass)
Using a Pyrex glass of 30 × 20 × 5 mm as a glass plate, an adhesion test with PFA having a hydroxyl group was performed as follows.

  Furthermore, the hot water resistance test and methanol immersion test of the laminated body after adhesion were also performed. The results are shown in Table 2.

(Preparation of specimen for tensile shear test)
As shown in FIG. 2, the PFA film (20 × 10 mm) having a hydroxyl group obtained in the reference example is sandwiched between Pyrex glass plates, a load of 3 kg is placed, and the sample is left in an electric furnace at 350 ° C. for 30 minutes. Yeah. The film thickness of the adhesive layer was adjusted to 0.1 mm with a spacer.

(Adhesive strength)
The adhesive strength was measured by a tensile shear method. A test jig adapted to the sample shape as shown in FIG. 3 was set on a Tensilon universal testing machine manufactured by Orientec Co., Ltd., and a tensile shear test was performed at a crosshead speed of 20 mm / min. The measurement showed the maximum adhesive strength (kgf / cm ² ).

(Hot water resistance test)
Using the test piece prepared by the method described above, it was immersed in warm water at 50 ° C., the adhesiveness after 6 hours was observed, and the adhesive strength (kgf / cm ² ) after 72 hours was measured.

(Methanol immersion test)
The test piece prepared by the method described above was immersed in methanol at room temperature and the adhesion was observed.

Comparative Example 4
(Adhesion test between PFA containing no functional group and glass)
A test piece was prepared and various tests were performed in the same manner as in Example 6 except that the PFA film containing no functional group obtained in Reference Example 3 was used instead of the PFA film having a hydroxyl group of Reference Examples 1 and 2. .

Example 8
(Adhesion between PFA having hydroxyl group and stainless steel)
A laminate test plate was prepared as follows using a degreased SUS304 steel plate having a length of 150 mm, a width of 70 mm, and a thickness of 0.5 mm as a metal plate. The PFA film containing the hydroxyl group obtained in Reference Example 4 and the PFA film containing no functional group obtained in Reference Example 5 were cut into the same size as the SUS plate.

  Furthermore, a polyimide film (DuPont Kapton 200-H) was cut into the same size as a release film.

Next, as shown in FIG. 4, the hydroxyl group-containing PFA film, the PFA film not containing the functional group, and the polyimide film are sandwiched between two SUS plates, set in a press machine set at 350 ° C., and preheated ( 20 minutes) and then pressurized at 50 kg / cm ² for 1 minute.

  After cooling, when the SUS plate in contact with the polyimide film (reference numeral 1 in FIG. 4) was removed, the polyimide film spontaneously peeled off at the interface of the PFA film (reference numeral 4 in FIG. 4) containing no functional group.

  As a result, a SUS plate having good transparency (reference numeral 1 in FIG. 5) and a PFA film (reference numeral in FIG. 5) using a PFA film having a hydroxyl group as shown in FIG. 5 (reference numeral 2 in FIG. 5) as an adhesive layer. A three-layer laminate with 3) in 5 was obtained.

  Further, 100 1 mm square bases were made on the obtained PFA laminate plate of FIG. 5 with a cutter knife until reaching the substrate, and the center of the base was pushed out 5 mm by an Eriksen tester. As a result, the film did not peel at all and adhered firmly to the substrate.

  The PFA film showed strong adhesion to the SUS plate.

Comparative Example 5
(Adhesion between PFA film containing no functional group and stainless steel)
Except not using the PFA film which has a hydroxyl group, it carried out similarly to Example 8, and obtained the laminated body of the SUS board shown in FIG. 6, and the PFA film which does not contain a functional group.

  The obtained laminated SUS plate was adhered in appearance but could be easily peeled off.

  Further, an Erichsen test was conducted in the same manner as in Example 8. In 60 of 100 bases, the cuts were peeled off at the center.

Example 9
(Adhesion between PFA film having hydroxyl group and polyimide film)
A PFA film containing a hydroxyl group obtained in Reference Example 4, a PFA film containing no functional group obtained in Reference Example 5 and a polyimide film (same as in Example 8) were cut into the same size as in Example 8, and FIG. And sandwiched between two SUS plates and heated in the same manner as in Example 8. After cooling, the SUS plate (reference numeral 1 in FIG. 7) was peeled off to obtain a laminate as shown in FIG. Furthermore, the laminate was cut into a width of 25 mm.

  A part of the interface between the polyimide film layer (reference numeral 4 in FIG. 8) and the hydroxyl machine-containing PFA film layer (reference numeral 2 in FIG. 8) is peeled off, and in the direction shown in FIG. As a result, an adhesion of 4.0 kgf / 25 mm was shown by an average peel load by the area method.

Comparative Example 6
(Adhesion between PFA film not containing functional group and polyimide film)
A part of the interface between the polyimide film layer (reference numeral 4 in FIG. 8) of the 25 mm wide laminate obtained in Example 9 and the PFA film layer not containing a functional group is peeled off in the direction shown in FIG. A T-type peel test was performed, but the adhesive strength was not shown.

Example 10
(Adhesion between PFA film containing hydroxyl groups and polycrystalline silicon)
A PFA film containing a hydroxyl group cut to the same size on a polycrystalline silicon plate having a length of 100 mm and a width of 50 mm (obtained in Reference Example 4), a PFA film not containing a functional group (obtained in Reference Example 5), A polyimide film (the same as in Example 8) and a glass plate were stacked as shown in FIG. 11, and a load of 1.5 kg was applied on the glass plate and heated at 350 ° C. for 20 minutes.

  After cooling, the glass plate (reference numeral 5 in FIG. 11) is removed, the polyimide film (reference numeral 4 in FIG. 11) is peeled off, and a PFA film containing hydroxyl groups as shown in FIG. 12 (reference numeral 2 in FIG. 12). A three-layer laminate of a polycrystalline silicon plate having good transparency (reference numeral 1 in FIG. 12) and a PFA film (reference numeral 3 in FIG. 12) was obtained.

  The PFA film showed strong adhesion to the polycrystalline silicon plate.

Comparative Example 7
(Adhesiveness between PFA film having methyl ester group and metal)
An adhesion test with a PFA film having a methyl ester group (film of Reference Example 7) was performed in the same manner as in Example 1 using pure aluminum having a thickness of 0.5 mm as a metal plate. In addition, 1.0 (kgf / 25 mm) showed no adhesive force.

Comparative Example 8
(Heat resistance of PFA having carboxyl group)
When the decomposition temperature of the PFA having a carboxyl group obtained in Synthesis Example 5 was measured by TGA analysis, the decomposition start point was 257 ° C. and the 1% thermal decomposition temperature was 335 ° C. It was found that the heat resistance was lower than that of PFA having a hydroxyl group.

  Furthermore, according to DTGA analysis, the melting point was Tm = 308 ° C. That is, it can be seen that under the melt processing conditions above the melting point, thermal decomposition is started and processing is difficult.

Comparative Example 9
(Heat resistance of fluoropolymers using functional group-containing monomers that do not have fluorine)
When the thermal decomposition temperature of the fluorine-containing copolymer obtained in Synthesis Example 6 was measured by TGA analysis, it was 220 ° C. at a 1% thermal decomposition temperature. It was found that the fluorine-containing copolymer using the functional group-containing monomer having no fluorine as obtained in Synthesis Example 6 has low heat resistance.

  Furthermore, the fluorine-containing copolymer obtained in Synthesis Example 6 was dissolved in butyl acetate at a concentration of 10% by weight.

  The aluminum plate subjected to the same pretreatment as in Example 1 was coated with a butyl acetate solution of the fluoropolymer of Synthesis Example 6 by air spraying so as to have a film thickness of about 10 μm, and then infrared dried at 90 ° C. for 10 minutes. .

  On the coated surface, a PFA film not containing the functional group obtained in Reference Example 5, a polyimide film for release (same as Example 8), and an aluminum plate are sequentially stacked (FIG. 13). And heated and pressurized at 350 ° C.

  After cooling, the aluminum plate in contact with the polyimide film and the polyimide film were removed.

  The obtained laminate was colored yellow-brown, and foaming and peeling occurred between the PFA film and the aluminum substrate, and a uniform and transparent laminate plate could not be obtained.

It is a schematic diagram for demonstrating the test piece with which it uses for the adhesiveness test (peeling test) in this invention. It is a schematic diagram for demonstrating the test piece with which it uses for the adhesiveness test (tensile shear test) in this invention. It is a schematic diagram for demonstrating the test apparatus used for the adhesive test (tensile shear test) in this invention. It is a schematic sectional drawing of the laminate test board produced in Example 8 of this invention. It is a schematic sectional drawing of the PFA laminated board obtained in Example 8 of this invention. It is a schematic sectional drawing of the laminated SUS board obtained in the comparative example 5 of this invention. It is a schematic sectional drawing of the test board for producing the laminated body in Example 9 of this invention. It is a schematic sectional drawing of the laminated body obtained in Example 9 of this invention. It is a schematic sectional drawing of the laminated body with which it uses for the T-type peeling test done in Example 9 of this invention. It is a schematic sectional drawing of the laminated body with which it uses for the T-type peeling test done in the comparative example 6 of this invention. It is a schematic sectional drawing explaining preparation of the test board in Example 10 of this invention. It is a schematic sectional drawing of the laminated body obtained in Example 10 of this invention. It is a schematic sectional drawing explaining preparation of the test board in the comparative example 9 of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 SUS board 2 Hydroxyl group containing PFA film 3 PFA film which does not contain a functional group 4 Polyimide film 5 Glass board 6 Polycrystalline silicon board 7 Aluminum board 8 Fluorine-containing copolymer using the functional group containing monomer which does not contain fluorine Coating

Claims (4)

(A-2) (a) 0.05 to 30 mol% of at least one monomer among fluorine-containing ethylenic monomers having a hydroxyl group and (b) copolymerizable with the component (a) 70 to 99.95 mol% of at least one monomer among fluorine-containing ethylenic monomers having no hydroxyl group
A layer made of an adhesive composed of a fluorine-containing ethylenic polymer having a hydroxyl group obtained by copolymerizing with a base material,
The fluorine-containing ethylenic monomer (b) having no hydroxyl group is
(B-1) tetrafluoroethylene,
(B-2) 85 to 99.7 mol% tetrafluoroethylene and formula (3):
CF ₂ = CF-R _f ³ (3)
[Wherein R _f ³ represents —CF ₃ or —OR _f ⁴ (R _f ⁴ represents a perfluoroalkyl group having 1 to 5 carbon atoms)] Monomer mixture, or (b-3) tetrafluoroethylene or chlorotrifluoroethylene 40-80 mol%, ethylene 20-60 mol%, and other monomers 0-15 copolymerizable with these monomers A laminate that is any one of a monomer mixture with mol%. (A-2) (a) 0.05 to 30 mol% of at least one monomer among fluorine-containing ethylenic monomers having a hydroxyl group and (b) copolymerizable with the component (a) 70 to 99.95 mol% of at least one monomer among fluorine-containing ethylenic monomers having no hydroxyl group
A layer made of an adhesive composed of a fluorine-containing ethylenic polymer having a hydroxyl group obtained by copolymerizing with a base material,
In the adhesive, the fluorine-containing ethylenic monomer (a) having a hydroxyl group is 0.05 to 30 mol% based on the total amount of the monomer, and the fluorine-containing ethylenic monomer (a) is free from the monomer excluding the component (a). A copolymer of 40 to 90 mol% of vinylidene chloride, 0 to 30 mol% of tetrafluoroethylene, and 10 to 50 mol% of hexafluoropropene; the component (a) is added to the total number of moles of all monomers; 05-30 mol%, tetrafluoroethylene is 40-70 mol%, propylene 30-60 mol%, vinylidene fluoride, hexafluoropropylene, chlorotrifluoro with respect to the total number of moles of monomers excluding component (a) A copolymer of at least one selected from the group consisting of ethylene and perfluorovinyl ethers and 0-20 mol%; and / or tetrafluoroethylene and perfluoroethylene A polymer comprising a fluorovinyl ether, wherein the component (a) is 0.05 to 30 mol% based on the total number of moles of all monomers, and the monomer excluding the component (a) A laminate which is an elastomeric fluorine-containing adhesive which is a polymer of tetrafluoroethylene 40 to 85 mol% and perfluorovinyl ethers 15 to 60 mol% . The laminate according to claim 1 or 2, wherein the substrate is an inorganic material. The laminate according to claim 1 or 2, wherein the substrate is an organic material.

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