JP2016087799A - Long-sized laminate for high frequency circuit board, and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which is a long-sized laminate formed by bonding a polyimide film and a fluorine resin, can be manufactured by bonding at a low temperature, and is excellent in adhesiveness between the polyimide film and the fluorine resin.SOLUTION: A long-sized laminate is a laminate formed by bonding a polyimide film produced using one or more aromatic diamine components selected from the group consisting of paraphenylene diamine, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether and 3,4'-diaminodiphenyl ether, and one or more aromatic anhydride components selected from the group consisting of 4,4'-oxydiphthalic anhydride, pyromellitic dianhydride and 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, and a fluorine resin. A bond strength of the polyimide film and the fluorine resin is 0.2 N/cm or more.SELECTED DRAWING: None

Description

  The present invention relates to a long laminate for a high-frequency circuit board formed by bonding a polyimide film and a fluororesin, and a method for producing the same.

  Flexible printed circuit boards (hereinafter also referred to as FPCs) and flexible flat cables (hereinafter also referred to as FFCs) are widely used in electronic and electrical devices such as mobile phones, tablets, and hard disks of personal computers.

In general, an FPC is formed by processing a copper clad laminate (CCL) composed of an insulator layer and a copper foil layer to form a non-linear complex electric circuit, and then protecting the circuit portion with an insulating layer. And a cover lay (CL) made of an adhesive layer is made through a process of attaching the adhesive part to the circuit part.
FFC is obtained by using a base material composed of an insulator layer and an adhesive layer and a conductor such as a copper foil formed in a wiring shape, and arranging and bonding a plurality of conductors between the adhesive parts of the base material. It is a linear electric circuit.
Accordingly, the coverlay in the FPC and the base material in the FFC are structurally the same.

Among FPCs and FFCs, in recent years, with the increase in the amount of information to be transmitted, the demand for circuit boards for high frequency applications is increasing.
A laminate of a polyimide film and a fluororesin has been developed as a coverlay for a high-frequency circuit board or a base material for FFC (Patent Document 1 and Patent Document 2).
However, the coverlay or FFC base material described in Patent Document 1 and Patent Document 2 is only manufactured on a lab scale, and a method for manufacturing a long laminate for a high-frequency circuit board is required. ing.

Patent Document 3 describes a method of laminating a fluororesin on a polyimide film that has been subjected to a discharge treatment. In Patent Document 3, after laminating the polyimide film and the fluorine film subjected to the discharge treatment, pressurizing and laminating at a temperature of about 80 to 200 ° C. while applying pressure using a press roller, As after-cure, a method is described in which annealing is performed by applying heat treatment without applying pressure at a temperature of about 300 to 400 ° C.
However, since such a method requires a heat treatment at high temperature (annealing), a laminate of a polyimide film and a fluororesin that can be produced by a heat treatment at a lower temperature is required to improve productivity. Yes.

  Moreover, in the laminated body of a polyimide film and a fluororesin, it is also required that the adhesiveness between a polyimide film and a fluororesin is excellent.

Japanese Patent Application No. 2013-072570 Japanese Patent Application No. 2014-050759 No. 5-59828

  In view of the above situation, the present invention is a long laminate formed by bonding a polyimide film and a fluororesin, and can be manufactured by bonding at a low temperature, and adhesion between the polyimide film and the fluororesin It aims at providing the laminated body which is excellent in property.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that p-phenylenediamine, 1,3-bis (4-aminophenoxy) benzene, 4,4′-diaminodiphenyl ether and 3,4′- One or more aromatic diamine components selected from the group consisting of diaminodiphenyl ether, 4,4′-oxydiphthalic anhydride, pyromellitic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride A polyimide film manufactured using one or more aromatic acid anhydride components selected from the group consisting of a product and a fluororesin are bonded together by applying a load of 1 to 15 kN with a roll heated to 150 to 230 ° C. By laminating and laminating the laminate and subjecting the laminate to an annealing treatment at a temperature equal to or higher than the melting point of the fluororesin, polyimide film and fluorine Found that elongate laminate fat is obtained.
In addition to the above, the present inventors have obtained various new findings as will be described below, and have made further studies and completed the present invention.

The present invention relates to the following inventions.
[1] one or more aromatic diamine components selected from the group consisting of paraphenylenediamine, 1,3-bis (4-aminophenoxy) benzene, 4,4′-diaminodiphenyl ether and 3,4′-diaminodiphenyl ether; One or more aromatic acid anhydride components selected from the group consisting of 4,4'-oxydiphthalic anhydride, pyromellitic dianhydride and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride; A laminate formed by laminating a polyimide film and a fluororesin produced by using an adhesive, wherein the adhesive strength between the polyimide film and the fluororesin is 0.2 N / cm or more. body.
[2] The laminate according to [1], wherein the adhesive strength between the polyimide film and the fluororesin is 0.5 N / cm or more.
[3] The laminate according to [1] or [2], wherein the polyimide film constituting the laminate has an average thickness of 2.5 to 175 μm, and the fluororesin has an average thickness of 12.5 to 100 μm. A laminate characterized by the above.
[4] The laminate according to any one of [1] to [3], wherein the fluororesin has a melting point of 200 ° C. or lower.
[5] The fluorine resin is a fluorine-containing ethylenic polymer, and the fluorine-containing ethylenic polymer contains a carbonyl group, according to any one of the above [1] to [4] Laminated body.
[6] The laminate according to [5], wherein the carbonyl group content of the fluorine-containing ethylenic polymer is 3 to 1000 in total with respect to 1 × 10 ⁶ main chain carbon atoms. .
[7] Fluorine-containing fluorine-containing resin having at least one selected from the group consisting of a carbonate group, a carboxylic acid halide group, and a carboxylic acid group with respect to 1 × 10 ⁶ main chain carbon atoms in total 3 to 1000 It consists of an ethylenic polymer, The laminated body of any one of said [1]-[4] characterized by the above-mentioned.
[8] The fluororesin is tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, vinyl fluoride, hexafluoropropylene, hexafluoroisobutene, the following formula (X):
CH ₂ = CR ¹ (CF ₂ ) _n R ² (X)
(In the formula, R ¹ represents H or F, R ² represents H, F or Cl, and n represents a positive integer of 1 to 10.)
1 or more types of fluorine-containing ethylenic monomers selected from the group consisting of monomers represented by formula (2) and perfluoro (alkyl vinyl ethers) having 2 to 10 carbon atoms, or the fluorine-containing ethylenic monomers and carbon The laminate according to any one of [1] to [4], which is a fluorine-containing ethylenic polymer obtained by polymerizing an ethylenic monomer having a number of 5 or less.
[9] The laminate according to any one of [1] to [4], wherein the fluororesin is a copolymer obtained by polymerizing at least the following (a), (b), and (c).
(A) Tetrafluoroethylene 20-90 mol%
(B) 10-80 mol% ethylene
(C) Formula CF ₂ = CFR ³ (Y)
(In the formula, R ³ represents CF ₃ or OR ⁴ , and R ⁴ represents a perfluoroalkyl group having 1 to 5 carbon atoms.)
1 to 70 mol% of a compound represented by
[10] one or more aromatic diamine components selected from the group consisting of paraphenylenediamine, 1,3-bis (4-aminophenoxy) benzene, 4,4′-diaminodiphenyl ether and 3,4′-diaminodiphenyl ether; One or more aromatic acid anhydride components selected from the group consisting of 4,4'-oxydiphthalic anhydride, pyromellitic dianhydride and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride; A polyimide film and a fluororesin produced by using a roll are laminated by applying a load of 1 to 15 kN with a roll heated to 150 to 230 ° C., and after laminating, the laminated body is equal to or higher than the melting point of the fluororesin. The manufacturing method of a elongate laminated body characterized by attaching | subjecting annealing treatment at the temperature of.
[11] The manufacturing method according to [10], wherein the annealing process is performed by bringing the laminated body immediately after bonding into contact with a roll heated to 200 to 290 ° C.
[12] The method according to [10], wherein the annealing treatment is performed by continuously heating the laminated body immediately after bonding in an oven heated to 200 to 290 ° C.
[13] one or more aromatic diamine components selected from the group consisting of paraphenylenediamine, 1,3-bis (4-aminophenoxy) benzene, 4,4′-diaminodiphenyl ether, and 3,4′-diaminodiphenyl ether; One or more aromatic acid anhydride components selected from the group consisting of 4,4'-oxydiphthalic anhydride, pyromellitic dianhydride and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride; A polyimide film and a fluororesin produced by using a roll are laminated together by applying a load of 1 to 15 kN with a roll heated to 150 to 230 ° C., and the laminated body is wound into a roll. A method for producing a long laminate, which is later heated in an oven heated to 150 to 290 ° C.
[14] An FPC (flexible printed circuit board) using the laminate according to any one of [1] to [9].
[15] An FFC (flexible flat cable) using the laminate according to any one of [1] to [9].

ADVANTAGE OF THE INVENTION According to this invention, the elongate laminated body of a polyimide film and a fluororesin excellent in the adhesiveness between a polyimide film and a fluororesin can be obtained.
In addition, according to the present invention, since the polyimide film and the fluororesin can be bonded together at a lower temperature than conventional, a long laminate of the polyimide film and the fluororesin can be produced industrially advantageously. .
Moreover, the high frequency circuit board which has the outstanding effect can be obtained using the laminated body of this invention.

It is sectional drawing of the example of the laminated body of this invention formed by bonding a polyimide film and a fluororesin. It is a flowchart which shows the manufacturing method in the case of performing the annealing process using the heated roll in this invention. It is a flowchart which shows the manufacturing method in the case of performing the annealing process using the oven in this invention. It is sectional drawing of the example of the laminated body of this invention formed by bonding a polyimide film to the polyimide film side of the laminated body of this invention shown in FIG. It is sectional drawing of the example of the laminated body of this invention formed by bonding a slightly adhesive pet film to the polyimide film side of the laminated body of this invention shown in FIG.

Hereinafter, the present invention will be described in more detail.
The laminate of the present invention has at least one aromatic selected from the group consisting of paraphenylenediamine, 1,3-bis (4-aminophenoxy) benzene, 4,4′-diaminodiphenyl ether and 3,4′-diaminodiphenyl ether. One or more aromatic acids selected from the group consisting of a diamine component and 4,4′-oxydiphthalic anhydride, pyromellitic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride A laminate obtained by laminating a polyimide film and a fluororesin manufactured using an anhydride component, wherein the adhesive strength between the polyimide film and the fluororesin is 0.2 N / cm or more, It is a long laminate.

<Polyimide film>
First, the polyimide film used in the present invention will be described below.
In producing the polyimide film used for the laminate of the present invention, first, an aromatic diamine component and an aromatic acid anhydride component are polymerized in an organic solvent to obtain a polyamic acid solution.

In the present invention, the aromatic diamine component is usually a group consisting of paraphenylenediamine, 1,3-bis (4-aminophenoxy) benzene, 4,4′-diaminodiphenyl ether and 3,4′-diaminodiphenyl ether. It is 1 or more chosen from these, However, Other aromatic diamine components other than these components may be included.
Specific examples of the aromatic diamine component that may be included in addition to the above include metaphenylenediamine, benzidine, paraxylylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 3,3 ′. -Dimethyl-4,4'-diaminodiphenylmethane, 1,5-diaminonaphthalene, 3,3'-dimethoxybenzidine, 1,4-bis (3methyl-5aminophenyl) benzene, 3,3'-dimethyl-4 , 4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 9,9′-bis (4-aminophenyl) fluorene, 1,4-bis (4-aminophenoxy) be Zen, 1,3-bis (3-aminophenoxy) benzene, 4,4′-bis (aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 2,2′-bis (4- Aminophenoxyphenyl) propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] Examples include hexafluoropropane and 3,3′-dihydroxy-4,4′-diaminobiphenyl. These may be used singly or in combination of two or more.
The aromatic diamine component that may be contained in addition to the above is preferably 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4′-bis ( Aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 2,2′-bis (4-aminophenoxyphenyl) propane, and the like, more preferably 2,2′-bis (4- Aminophenoxyphenyl) propane and the like.

In the present invention, the aromatic acid anhydride component is usually 4,4′-oxydiphthalic anhydride, pyromellitic dianhydride, and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride. Although it is 1 or more chosen from the group which consists of a thing, aromatic acid anhydride ingredients other than these ingredients may be contained in addition.
Specific examples of the aromatic acid anhydride component that may be included in addition to the above include 2,3 ′, 3,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 2,3,6,7-naphthalenedicarboxylic acid, oxydiphthalic acid, 3,4,3 ′, 4′-biphenylsulfonetetracarboxylic acid, 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic acid, meta (Para) -phenyl-3,4,3,4'-tetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) ether, pyridine-2,3,5,6-tetracarboxylic acid and these And acid anhydrides such as amide-forming derivatives. These may be used singly or in combination of two or more.
The aromatic acid anhydride component which may be contained in addition to the above is preferably 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic And acid dianhydrides.

  In the present invention, examples of the organic solvent used for forming the polyamic acid solution include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and formamide such as N, N-dimethylform and N, N-diethylformamide. Solvents, acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- , Or a phenolic solvent such as p-cresol, xylenol, halogenated phenol, and catechol, or an aprotic polar solvent such as hexamethylphosphoramide and γ-butyrolactone. These may be used alone or in combination of two or more. Is preferably used as a mixture. Emissions, also aromatic hydrocarbons such as toluene can be used.

  The polymerization method is not particularly limited and may be carried out by any known method. For example, (1) First, the whole amount of the aromatic diamine component is put in a solvent, and then the aromatic acid anhydride component is converted into the aromatic diamine component. A method in which the total amount is equal to the amount of polymerization.

  (2) A method in which the total amount of the aromatic acid anhydride component is first put in a solvent, and then the aromatic diamine component is added so as to be equivalent to the aromatic acid anhydride component for polymerization.

  (3) After putting one aromatic diamine component (a1) in a solvent, it is necessary for the reaction at a ratio such that one aromatic acid anhydride component (b1) is 95 to 105 mol% with respect to the reaction component. After mixing for a period of time, the other aromatic diamine component (a2) is added, and then the other aromatic acid anhydride component (b2) is mixed with a wholly aromatic diamine component and a wholly aromatic acid anhydride component. A method of adding and polymerizing so as to be approximately equivalent.

  (4) After putting one aromatic acid anhydride component (b1) in a solvent, it is necessary for the reaction at a ratio such that one aromatic diamine component (a1) is 95 to 105 mol% with respect to the reaction component. After mixing for a period of time, the other aromatic acid anhydride component (b2) is added, and then the other aromatic diamine component (a2) is substantially divided into a wholly aromatic diamine component and a wholly aromatic acid anhydride component. A method of adding and polymerizing to an equivalent amount.

  (5) A polyamic acid solution (A) is prepared by reacting one aromatic diamine component and an aromatic acid anhydride component in a solvent so that either one becomes excessive, and the other aromatic diamine component in another solvent. The polyamic acid solution (B) is prepared by reacting either the diamine component or the aromatic acid anhydride component in excess, and the resulting polyamic acid solutions (A) and (B) are mixed to complete the polymerization. The method of doing is mentioned. In the method of (5), when the aromatic diamine component is excessive in preparing the polyamic acid solution (A), the polyamic acid solution (B) contains excessive aromatic acid anhydride components, and the polyamic acid solution (A ), When the aromatic acid anhydride component is excessive, the polyamic acid solution (B) makes the aromatic diamine component excessive, and the polyamic acid solutions (A) and (B) are mixed and used in these reactions. The diamine component and the aromatic acid anhydride component are adjusted to be approximately equivalent.

  The polymerization method is not limited to these, and other known methods may be used.

  The polyamic acid solution thus obtained usually contains 5 to 40% by weight of solid content, and preferably contains 10 to 30% by weight of solid content. The viscosity is usually 10 to 10000 Pa · s as measured by a Brookfield viscometer, and preferably 300 to 5000 Pa · s for stable liquid feeding. Moreover, the polyamic acid in the organic solvent solution may be partially imidized.

  Next, the manufacturing method of the polyimide film of this invention using the said polyamic acid solution is demonstrated.

  As a method for forming a polyimide film, a polyamic acid solution is cast into a film and thermally decyclized and desolvated to obtain a polyimide film, and a polyamic acid solution is mixed with a cyclization catalyst and a dehydrating agent. A method of obtaining a polyimide film by producing a gel film by thermally decyclizing and desolvating it by heating is mentioned.

  The polyamic acid solution may contain a cyclization catalyst (imidization catalyst), a dehydrating agent, a gelation retarder, and the like.

  Specific examples of the cyclization catalyst used in the present invention include aliphatic tertiary amines such as trimethylamine and triethylenediamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic rings such as isoquinoline, pyridine and betapicoline. Although a tertiary amine etc. are mentioned, a heterocyclic tertiary amine is preferable. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  Specific examples of the dehydrating agent used in the present invention include aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride, and aromatic carboxylic acid anhydrides such as benzoic anhydride. Acetic anhydride and / or benzoic anhydride are preferred.

  As a method for producing a polyimide film from a polyamic acid solution, a polyamic acid solution containing the cyclization catalyst and the dehydrating agent is cast from a slit-attached base onto a support, and is molded into a film. Examples of the method include a method in which imidization is partially advanced to form a gel film having self-supporting property, and then peeled from the support, heat-dried / imidized, and heat-treated.

  The support is a metal rotating drum or endless belt, and its temperature is controlled by a liquid or gaseous heat medium and / or by radiant heat from an electric heater or the like.

  The gel film is usually heated to 30 to 200 ° C., preferably 40 to 150 ° C. by receiving heat from the support and / or receiving heat from a heat source such as hot air or an electric heater, and a ring-closing reaction is performed. By drying the volatile matter, it becomes self-supporting and is peeled off from the support.

  The gel film peeled off from the support may be stretched in the traveling direction while regulating the traveling speed with a rotating roll, if necessary. The draw ratio (MDX) in the machine conveyance direction and the draw ratio (TDX) in the direction perpendicular to the machine conveyance direction are usually 1.01 to 3.0 times, preferably 1.05 to 2.0 times. Is done.

  The film dried in the drying zone is usually heated for 15 seconds to 10 minutes with hot air, an infrared heater or the like. Next, heat treatment is usually performed at a temperature of 250 to 500 ° C. for 15 seconds to 20 minutes with hot air and / or an electric heater.

  Moreover, although the travel speed is adjusted to adjust the thickness of the polyimide film, the average thickness of the polyimide film is usually about 2 to 250 μm, preferably about 2.5 to 250 μm, and more preferably about 5 to 75 μm. If it is thinner or thicker than this, the film-forming property of the film is remarkably deteriorated.

  A commercially available product may be used as the polyimide film used in the present invention. Although it does not specifically limit as a commercial item, For example, EN type (For example, 50EN-S (brand name, the Toray DuPont company make), 100EN (brand name, the Toray DuPont company make) etc.) etc. of Kapton, Kapton H type (for example, Kapton 100H (trade name, manufactured by Toray DuPont), etc.), Kapton KJ type (for example, Kapton 100KJ (trade name, manufactured by DuPont, USA)), Kapton JP type (for example, Kapton) 100JP (trade name, manufactured by DuPont, USA) and the like. Among such polyimide films, polyimide films manufactured using 4,4′-diaminodiphenyl ether and pyromellitic dianhydride, paraphenylenediamine, 4,4′-diaminodiphenyl ether, and pyromellitic dianhydride Polyimide film manufactured using, or paraphenylenediamine, 4,4'-diaminodiphenyl ether, pyromellitic dianhydride and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride The polyimide film manufactured by manufacturing is preferable.

  The polyimide film in the present invention may contain a plasticizer, other resin and the like as long as the object of the present invention is not impaired.

  The plasticizer is not particularly limited, and examples thereof include bisphenol compounds such as hexylene glycol, glycerin, β-naphthol, dibenzylphenol, octylcresol, bisphenol A, octyl p-hydroxybenzoate, p-hydroxybenzoic acid- 2-ethylhexyl, p-hydroxy p-hydroxybenzoate, ethylene oxide and / or propylene oxide adducts of p-hydroxybenzoic acid, ε-caprolactone, phosphate compounds of phenols, N-methylbenzenesulfonamide, N-ethylbenzenesulfone Examples include amide, N-butylbenzenesulfonamide, toluenesulfonamide, N-ethyltoluenesulfonamide, N-cyclohexyltoluenesulfonamide, and the like.

  As said other resin mix | blended with a polyimide, what is excellent in compatibility is preferable, for example, ester and / or carboxylic acid modified olefin resin, acrylic resin (especially acrylic resin which has a glutarimide group), ionomer resin, polyester resin , Phenoxy resin, ethylene-propylene-diene copolymer, polyphenylene oxide and the like.

  The polyimide film in the present invention may contain a colorant, various additives and the like as long as the object of the present invention is not impaired. Examples of the additive include an antistatic agent, a flame retardant, a heat stabilizer, an ultraviolet absorber, a lubricant, a mold release agent, a crystal nucleating agent, and a reinforcing agent (filler). The polyimide film surface may be coated with ink or the like.

<Fluorine resin>
Although the fluororesin used for the laminated body of this invention is not specifically limited, A fluorine-containing ethylenic polymer is preferable. The fluorinated ethylenic polymer in the present invention is one in which a carbonyl group or a carbonyl group-containing functional group is bonded to a fluorinated ethylenic polymer chain.

  The “carbonyl group” refers to a functional group having —C (═O) — that can basically react with an imide group or an amino group in a polyimide film. Specific examples include carbonates, carboxylic acid halides, aldehydes, ketones, carboxylic acids, esters, acid anhydrides, and isocyanate groups. The carbonyl group is not particularly limited, but a carbonate group, a carboxylic acid halide group, a carboxylic acid group, an ester group, and an acid anhydride group are preferable because they can be easily introduced and have high reactivity with a polyamide-based resin. More preferred are carbonate groups and carboxylic acid halide groups.

The number of carbonyl groups in the fluorine-containing ethylenic polymer in the present invention is the type, shape, purpose of adhesion, use, required adhesive strength of the laminated material, the form of the polymer and the adhesion method, etc. Although it may be appropriately selected depending on the difference, the number of carbonyl groups is preferably 3 to 1000 in total with respect to 1 × 10 ⁶ main chain carbon atoms. If the number of carbonyl groups is less than 3 with respect to 1 × 10 ⁶ main chain carbon atoms, sufficient adhesive strength may not be exhibited. On the other hand, when the number exceeds 1,000, the adhesive force may be lowered due to a chemical change of the carbonyl group in accordance with the bonding operation. The number is more preferably 3 to 500, still more preferably 3 to 300, and particularly preferably 5 to 150. In addition, content of the carbonyl group in a fluorine-containing ethylenic polymer can be measured by infrared absorption spectrum analysis.

Therefore, when the fluorine-containing ethylenic polymer of the present invention has, for example, a carbonate group and / or a carboxylic acid halide group, and has a carbonate group, the number of carbonate groups is 1 × 10 ⁶ carbon atoms in the main chain. The number is preferably 3 to 1000. Moreover, when the fluorine-containing ethylenic polymer of this invention has a carboxylic acid halide group, it is preferable that the number of the carboxylic acid halide group is 3-1000 with respect to 1 * 10 < ⁶ > main chain carbon number. When the fluorine-containing ethylenic polymer of the present invention has both carbonate groups and carboxylic acid halide groups, the total number of carbonate groups and carboxylic acid halide groups is 3 to 1000 with respect to 1 × 10 ⁶ main chain carbon atoms. Are preferred. If the number of carbonate groups and / or carboxylic acid halide groups is less than 3 with respect to 1 × 10 ⁶ main chain carbon atoms, sufficient adhesive strength may not be exhibited. On the other hand, when the number exceeds 1,000, the generation of gas that appears at the bonding interface due to the chemical change of the carbonate group or the carboxylic acid halide group may be adversely affected and the adhesive force may be reduced. From the viewpoint of heat resistance and chemical resistance, the number is more preferably 3 to 500, still more preferably 3 to 300, and particularly preferably 5 to 150. In addition, 10 or more, more preferably 20 or more carboxylic acid halide groups having excellent reactivity with the polyamide-based resin are present in the fluorine-containing ethylenic polymer with respect to 1 × 10 ⁶ main chain carbon atoms. If this is the case, even if the total carbonyl group content is less than 150 with respect to 1 × 10 ⁶ carbon atoms in the main chain, excellent adhesion to the polyamide resin layer (A) can be exhibited. Can do.

The carbonate group in the fluorine-containing ethylenic polymer in the present invention is generally a group having a bond of —OC (═O) O—, specifically, a —OC (═O) O—R group [R the organic group _(e.g., C 1 _{-C 20} alkyl group (preferably _C 1 _{-C 10} alkyl group), _C 2 _{-C 20} alkyl group having an ether bond) or VII group element. ] Of the structure. The carbonate group, for _{example, -OC (= O) OCH 3} , -OC (= O) OC 3 H 7, -OC (= O) OC 8 H 17, -OC (= O) OCH 2 CH 2 CH 2 Preferred examples include OCH ₂ CH _{3 and the} like.

  The carboxylic acid halide group in the fluorine-containing ethylenic polymer in the present invention specifically has a structure of —COY [Y is a halogen element], and examples thereof include —COF and —COCl.

  The fluorine-containing ethylenic polymer having these carbonyl groups can maintain the excellent characteristics of the fluorine-containing resin itself, reducing the excellent characteristics of the fluorine-containing resin in the laminate after molding. Can be given without.

  The fluorine-containing ethylenic polymer in the present invention contains a carbonyl group in the polymer chain, but the embodiment in which the carbonyl group is contained in the polymer chain is not particularly limited, for example, a carbonyl group or a functional group containing a carbonyl group May be bonded to the polymer chain end or side chain. Among them, those having a carbonyl group at the end of the polymer chain are preferable because they do not significantly reduce heat resistance, mechanical properties and chemical resistance, or are advantageous in terms of productivity and cost. Among these, a method of introducing a carbonyl group at the end of a polymer chain using a polymerization initiator containing a carbonyl group such as peroxycarbonate or peroxyester or having a functional group that can be converted into a carbonyl group is introduced. This is a preferred embodiment because it is very easy and the amount of introduction can be easily controlled. In the present invention, the carbonyl group derived from peroxide refers to a carbonyl group derived directly or indirectly from a functional group contained in the peroxide.

In addition, in the fluorine-containing ethylenic polymer in the present invention, even if a fluorine-containing ethylenic polymer not containing a carbonyl group is present, the total amount of the polymer as described above is 1 × 10 ⁶ main chain carbons. It is sufficient that the number of carbonyl groups is within the range.

  In the present invention, the type and structure of the fluorine-containing ethylenic polymer can be appropriately selected depending on the purpose, application, and method of use, and the melting point is preferably 160 to 270 ° C. Such a polymer is advantageous, especially when laminating by heating and melt-bonding, since it can sufficiently exert the adhesiveness between the carbonyl group and the counterpart material, and can give a strong adhesive force directly to the counterpart material. is there. The melting point is more preferably 250 ° C. or less, further preferably 230 ° C. or less, and particularly preferably 200 ° C. or less in that lamination with an organic material having relatively low heat resistance is possible. The melting point was recorded as the melting peak when the temperature was raised at a rate of 10 ° C./min using a Seiko DSC apparatus (manufactured by Seiko Denshi), and the temperature corresponding to the maximum value was defined as the melting point (Tm).

  Regarding the molecular weight of the fluorinated ethylenic polymer in the present invention, the polymer can be molded at a temperature lower than the thermal decomposition temperature, and the obtained molded product can express the original excellent mechanical properties and the like of the fluorinated ethylenic polymer. It is preferable that it is a range. Specifically, with the melt flow rate (MFR) as the molecular weight index, the MFR at an arbitrary temperature in the range of about 230 to 350 ° C., which is a general molding temperature range of fluororesin, is 0.5 to 100 g / 10 min. It is preferable. MFR uses a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the weight of the polymer flowing out in a unit time (10 minutes) from a nozzle having a diameter of 2 mm and a length of 8 mm under various temperatures and 5 kg load (g) Was measured.

  The structure of the fluorine-containing ethylenic polymer chain is generally a homopolymer chain or a copolymer chain having a repeating unit derived from at least one fluorine-containing ethylenic monomer, and only the fluorine-containing ethylenic monomer, Alternatively, it may be a polymer chain obtained by polymerizing a fluorine-containing ethylenic monomer and an ethylenic monomer having no fluorine atom.

The fluorine-containing ethylenic monomer is an olefinically unsaturated monomer having a fluorine atom, specifically, tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, vinyl fluoride, hexafluoropropylene, Hexafluoroisobutene, formula (X):
CH ₂ = CR ¹ (CF ₂ ) _n R ² (X)
(In the formula, R ¹ represents H or F, R ² represents H, F or Cl, and n represents a positive integer of 1 to 10.)
And perfluoro (alkyl vinyl ether) s having 2 to 10 carbon atoms.

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

  When a fluorine-containing ethylenic monomer and an ethylenic monomer having no fluorine atom are used, the monomer composition is 10 mol% or more and less than 100 mol% (for example, 30 mol%). The molar ratio may be greater than 0 mol% and less than 90 mol% (for example, greater than 0 mol% and less than 70 mol%).

  In the fluorine-containing ethylenic polymer in the present invention, the melting point or glass transition of the polymer can be selected by selecting the type, combination, composition ratio, etc. of the fluorine-containing ethylenic monomer and the ethylenic monomer having no fluorine atom. The point can be adjusted.

  As the fluorine-containing ethylenic polymer in the present invention, in terms of heat resistance and chemical resistance, a carbonyl group-containing fluorine-containing ethylenic polymer having a tetrafluoroethylene unit as an essential component is preferable, and in terms of molding processability. Then, a carbonyl group-containing fluorine-containing ethylenic copolymer having a vinylidene fluoride unit as an essential component is preferable.

Preferable specific examples of the fluorine-containing ethylenic polymer in the present invention include a carbonyl group-containing fluorine-containing ethylenic copolymer (I), which is obtained by essentially polymerizing the following monomers. (V) and the like can be mentioned:
(I) a copolymer obtained by polymerizing at least tetrafluoroethylene and ethylene,
(II) At least tetrafluoroethylene and the following formula (Y):
CF ₂ = CFR ³ (Y)
(In the formula, R ³ represents CF ₃ or OR ⁴ , and R ⁴ represents a perfluoroalkyl group having 1 to 5 carbon atoms.)
A copolymer obtained by polymerizing a compound represented by
(III) a copolymer obtained by polymerizing at least vinylidene fluoride,
(IV) a copolymer obtained by polymerizing at least the following (a), (b) and (c):
(A) Tetrafluoroethylene 20-90 mol%
(B) 10-80 mol% ethylene
(C) CF ₂ = CFR ³ (Y)
(Wherein R ³ represents the same meaning as described above.)
1 to 70 mol% of the compound represented by:
(V) A copolymer obtained by polymerizing at least the following (d), (e) and (f).
(D) 15-60 mol% vinylidene fluoride
(E) Tetrafluoroethylene 35-80 mol%
(F) 5-30 mol% hexafluoropropylene
In these specific examples, other known monomers may be added as long as they contain the aforementioned monomers and do not impair the effects of the present invention.

  All of these exemplified carbonyl group-containing fluorine-containing ethylenic polymers are particularly preferable in terms of excellent heat resistance.

  As said copolymer (I), tetrafluoroethylene unit 20-90 mol% with respect to the whole monomer except the monomer which has a carbonyl group (when it has a carbonyl group containing functional group in a side chain), for example (For example, 20 to 60 mol%), 10 to 80 mol% (for example, 20 to 60 mol%) of ethylene units, and 0 to 70 mol% of other monomer units copolymerizable therewith. And a containing copolymer.

Examples of the other copolymerizable monomer include hexafluoropropylene, chlorotrifluoroethylene, and formula (X):
CH ₂ = CR ¹ (CF ₂ ) _n R ² (X)
(In the formula, R ¹ represents H or F, R ² represents H, F or Cl, and n represents a positive integer of 1 to 10.)
, C2-C10 perfluoro (alkyl vinyl ether) s, propylene, and the like, and usually one or more of these are used.

Further, as the copolymer (I), for example, the following can maintain the excellent performance of the tetrafluoroethylene / ethylene copolymer, can have a relatively low melting point, and can adhere to other materials. It is preferably mentioned in that it can exhibit the maximum properties.
(I-1) a carbonyl group-containing copolymer of a polymer chain comprising 62 to 80 mol% of tetrafluoroethylene units, 20 to 38 mol% of ethylene units, and 0 to 10 mol% of other monomer units,
(I-2) Polymer chain carbonyl comprising 20 to 80 mol% tetrafluoroethylene units, 10 to 80 mol% ethylene units, 0 to 30 mol% hexafluoropropylene units, and 0 to 10 mol% other monomer units Group-containing copolymer.

As said copolymer (II), the following are mentioned suitably, for example.
(II-1) containing a carbonyl group in a polymer chain composed of 65 to 95 mol% (preferably 75 to 95 mol%) tetrafluoroethylene units and 5 to 35 mol% (preferably 5 to 25 mol%) hexafluoropropylene units Copolymer,
(II-2) tetrafluoroethylene units 70 to 97 ^{_{mol%, CF 2 = CFOR 4 (}} R 4 is a perfluoroalkyl group having 1 to 5 carbon atoms) copolymer containing carbonyl groups in the polymer chain of 3 to 30 mole percent Polymer,
(II-3) a copolymer having a carbonyl group of a polymer chain comprising a tetrafluoroethylene unit, a hexafluoropropylene unit, and a CF ₂ ═CFOR ⁴ (R ⁴ is the same as above) unit, A copolymer in which the total of CF ₂ = CFOR ⁴ units is 5 to 30 mol%.

  Said (II-1)-(II-3) is also a perfluoro-type copolymer, and is the most excellent in heat resistance, electrical insulation, etc. among a fluorine-containing polymer.

Examples of the copolymer (III) include vinylidene fluoride units of 15 to 99 mol with respect to the whole monomer excluding the monomer having a carbonyl group (when the side chain has a carbonyl group-containing functional group). %, A carbonyl group-containing copolymer of a polymer chain composed of 0 to 30 mol% of tetrafluoroethylene units and 0 to 30 mol% of one or more units of hexafluoropropylene or chlorotrifluoroethylene.
Specific examples of the copolymer (III) include the following.
(III-1) a carbonyl group-containing copolymer of a polymer chain comprising 30 to 99 mol% of vinylidene fluoride units and 1 to 70 mol% of tetrafluoroethylene units,
(III-2) a carbonyl group-containing copolymer of a polymer chain comprising vinylidene fluoride units 60 to 90 mol%, tetrafluoroethylene units 0 to 30 mol%, chlorotrifluoroethylene units 1 to 20 mol%,
(III-3) a carbonyl group-containing copolymer of a polymer chain comprising 60 to 99 mol% of vinylidene fluoride units, 0 to 30 mol% of tetrafluoroethylene units, and 5 to 30 mol% of hexafluoropropylene units,
(III-4) A carbonyl group-containing copolymer of a polymer chain comprising 15 to 60 mol% of vinylidene fluoride units, 35 to 80 mol% of tetrafluoroethylene units, and 5 to 30 mol% of hexafluoropropylene units.

  It does not specifically limit as a manufacturing method of the fluorine-containing ethylenic polymer in this invention. The fluorine-containing ethylenic polymer of the present invention is obtained by copolymerizing an ethylenic monomer having a carbonyl group with a fluorine-containing and / or ethylenic monomer of a type and blended with the target fluorine-containing polymer. Can be manufactured. The ethylenic monomer having a carbonyl group is preferably perfluoroacrylic acid (fluoride), 1-fluoroacrylic acid (fluoride), acrylic acid fluoride, 1-trifluoromethacrylic acid (fluoride), perfluoro. Fluorine-containing monomers such as butenoic acid; monomers not containing fluorine, such as acrylic acid, methacrylic acid, acrylic acid chloride, vinylene carbonate, itaconic acid, citraconic acid, and the like.

  On the other hand, in order to obtain a fluorine-containing ethylenic polymer having a carbonyl group at the polymer molecule end, various methods can be employed, but peroxides, particularly peroxycarbonates and peroxyesters are used as polymerization initiators. The method can be preferably employed in terms of quality such as economy, heat resistance and chemical resistance. According to this method, a carbonyl group derived from peroxide (for example, a carbonate group derived from peroxycarbonate; an ester group derived from peroxyester; or a carboxylic acid halide group obtained by converting these functional groups Alternatively, carboxylic acid groups) can be introduced at the polymer chain ends. Among these polymerization initiators, when peroxycarbonate is used, the polymerization temperature can be lowered, and it is more preferable because no side reaction is involved in the initiation reaction.

Examples of the peroxycarbonate include the following formulas (1) to (4):
(1)
(2)
(3)
(4)
[Wherein, R and R ^a are linear or branched monovalent saturated hydrocarbon groups having 1 to 15 carbon atoms, or linear or branched groups having 1 to 15 carbon atoms containing an alkoxy group at the terminal. R ^b represents a linear or branched divalent saturated hydrocarbon group having 1 to 15 carbon atoms, or a straight chain having 1 to 15 carbon atoms containing an alkoxy group at the terminal. Represents a branched or branched divalent saturated hydrocarbon group. ]
The compound etc. which are represented by these are mentioned suitably. In particular, diisopropyl peroxycarbonate, di-n-propyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, etc. preferable.

  The amount of initiator used such as peroxycarbonate and peroxyester varies depending on the type of polymer (composition, etc.), the molecular weight, the polymerization conditions, and the type of initiator used. It is 0.05-20 weight part normally with respect to a weight part, and it is especially preferable that it is 0.1-10 weight part.

As the polymerization method, suspension polymerization in an aqueous medium using a fluorine-based solvent industrially and using peroxycarbonate or the like as a polymerization initiator is preferable, but other polymerization methods such as solution polymerization and emulsion polymerization are preferable. Also, bulk polymerization and the like can be employed. In suspension polymerization, a fluorinated solvent may be used in addition to water. Examples of the fluorine-based solvent used for suspension polymerization include hydrochlorofluoroalkanes (for example, CH ₃ CClF ₂ , CH ₃ CCl ₂ F, CF ₃ CF ₂ CCl ₂ H, CF ₂ ClCF ₂ CFHCl), and chlorofluoroalkanes. class _{(e.g., CF 2 ClCFClCF 2 CF 3,} CF 3 CFClCFClCF 3), perfluoroalkanes (e.g., _{perfluorocyclobutane, CF 3 CF 2 CF 2 CF} 3, CF 3 CF 2 CF 2 CF 2 CF 3, CF 3 CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ ) can be used, and perfluoroalkanes are preferred. The amount of the fluorine solvent to be used is not particularly limited, but in the case of suspension polymerization, it is preferably 10 to 100% by weight with respect to the aqueous medium from the viewpoint of suspension and economy.

  The polymerization temperature is not particularly limited, and may be 0 to 100 ° C. The polymerization pressure is appropriately determined according to other polymerization conditions such as the type, amount and vapor pressure of the solvent used, and the polymerization temperature, but may be 0 to 9.8 MPaG.

  A known chain transfer agent can be used for adjusting the molecular weight. Examples of the chain transfer agent include hydrocarbons such as isopentane, n-pentane, n-hexane, and cyclohexane; alcohols such as methanol and ethanol; halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, and methyl chloride. be able to. The content of the terminal carbonate group or ester group can be controlled by adjusting the polymerization conditions, and can be controlled by the amount of peroxycarbonate or peroxyester used, the amount of chain transfer agent used, the polymerization temperature, or the like.

  In order to obtain a fluorinated ethylenic polymer having a carboxylic acid halide group or a carboxylic acid group at the polymer molecule end, various methods can be employed. For example, the fluorinated ethylenic polymer having the above-mentioned carbonate group or ester group at the end can be adopted. The coalescence can be obtained by heating and pyrolysis (decarboxylation). The heating temperature varies depending on the type of carbonate group or ester group and the type of fluorine-containing ethylenic polymer, but is usually 270 ° C or higher, preferably 280 ° C or higher, and particularly preferably 300 ° C or higher. Moreover, it is preferable to make heating temperature below the thermal decomposition temperature of parts other than the carbonate group or ester group of a fluorine-containing ethylenic polymer, specifically 400 degrees C or less is preferable, and 350 degrees C or less is more preferable.

<Method for measuring the number of carbonate groups>
The obtained white powder of the fluorinated ethylenic polymer or a cut piece of the melt-extruded pellet was compression molded at room temperature to produce a uniform film having an average thickness of 0.05 to 0.2 mm. According to infrared absorption spectrum analysis of this film, a peak derived from a carbonyl group of a carbonate group (—OC (═O) O—) appears at an absorption wavelength of 1809 cm ⁻¹ (ν _C═O ), and its ν _C═O The absorbance of the peak was measured. The number (N) of carbonate groups per 10 ⁶ main chain carbon atoms was calculated by the following formula (5).
N = 500 AW / εdf (5)
A: Absorbance of ν _{C = O} peak of carbonate group (—OC (═O) O—) ε: Molar absorbance coefficient of ν _{C = O} peak of carbonate group (—OC (═O) O—) [l · cm ⁻¹ · mol ⁻¹ ]. Ε = 170 from the model compound.
W: Average molecular weight of monomer calculated from monomer composition d: Film density [g / cm ³ ]
f: Average thickness of the film [mm]
The infrared absorption spectrum analysis was performed by scanning 40 times using a Perkin-Elmer FTIR spectrometer 1760X (manufactured by PerkinElmer). The obtained IR spectrum was analyzed using Perkin-Elmer Spectrum for Windows (registered trademark) Ver. The baseline was automatically determined at 1.4 C, and the absorbance of the peak at 1809 cm ⁻¹ was measured. Moreover, the average thickness of the film was measured with a micrometer.

<Method for measuring the number of carboxylic acid fluoride groups>
A peak derived from the carbonyl group of the carboxylic acid fluoride group (—C (═O) F) was found to be 1880 cm ⁻¹ (ν) by infrared spectrum analysis of the film obtained in the same manner as in the above method for measuring the number of carbonate groups. The absorbance at the ν _C═O peak appears at the absorption wavelength of _{C═O 2} ). Except that the molar absorbance coefficient [l · cm ⁻¹ · mol ⁻¹ ] of the ν _C═O peak of the carboxylic acid fluoride group was set to ε = 600 by the model compound, The number of carboxylic acid fluoride groups was measured in the same manner as the number measurement method.

<Measurement method of the number of other carbonyl groups>
Functional groups such as amide groups and amino groups in polyamide-based resins such as carboxylic acid groups, ester groups, and acid anhydride groups by infrared spectrum analysis of the film obtained in the same manner as the method for measuring the number of carbonate groups. The number of other carbonyl groups that can basically react with can also be measured. However, except that the molar absorbance coefficient [l · cm ⁻¹ · mol ⁻¹ ] of the ν _C═O peak derived from these carbonyl groups is ε = 530, the above carbonate group is obtained using the above formula (5). The number of other carbonyl groups was measured in the same manner as the method for measuring the number of carbonyl groups.

<Method for measuring composition of fluorine-containing ethylenic polymer>
^It was measured by ¹⁹ F-NMR analysis.

  The fluorine-containing ethylenic polymer in the present invention is preferably used alone because it does not impair the adhesiveness, heat resistance, chemical resistance, etc. of itself, but it does not impair the performance depending on the purpose and application. Thus, various known 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 additives, other fluororesins, thermoplastic resins, thermosetting resins, etc., synthetic rubber, etc. can also be blended, improving mechanical properties, improving weather resistance, imparting design, and preventing static electricity It becomes possible to improve moldability.

In addition, the fluorine-containing ethylenic polymer in the present invention itself has adhesiveness as described above, but for the purpose of further improving the adhesiveness, the fluorine-containing ethylenic polymer and its molded body ( For example, by applying surface treatment such as corona treatment, plasma treatment, electron beam irradiation treatment, sputtering treatment, coating treatment to films, etc., control of surface free energy or introduction of adhesive functional groups, adjustment of surface roughness May be performed. Conventionally known methods can be used for these treatments.
In corona treatment, plasma treatment, and electron beam irradiation treatment, fine irregularities are formed by the etching effect generated on the film surface by passing the film through the discharge atmosphere, thereby improving the adhesion area and the adhesion effect by the anchor effect. . In addition, in these treatments, the surface free energy can be controlled by introducing oxygen and hydrogen into the discharge atmosphere. For example, by using a fluorine-containing ethylenic polymer into which acrylic acid is introduced, a carboxyl group or the like is added to the film surface. Adhesive functional groups can also be formed.
In the sputtering process, the surface roughness is adjusted by the etching effect, and the reaction is activated and the adhesion is improved by cutting the molecular chain.
By forming a resin having adhesiveness dissolved in an organic solvent on the surface of the fluorinated ethylenic polymer by a coating treatment, the adhesiveness can be improved. Adhesive resin can be selected appropriately depending on the adherend, but if the wetness to the fluorine-containing ethylenic polymer surface is insufficiently repelled or peeled off, combine it with the above surface treatment. You can also.

<Method for producing laminate>
The long laminate of the present invention is formed by bonding the polyimide film and the fluororesin described above.
Although it does not specifically limit as an apparatus used for manufacture of the laminated body of this invention, For example, the apparatus normally used for bonding in manufacture of the elongate base material for FPC and FFC can be used.

  In the first aspect of the method for producing a long laminate of the present invention, the polyimide film and the fluororesin are usually heated to 150 to 230 ° C, preferably 170 to 210 ° C (in the present specification, It is characterized by applying a load of 1 to 15 kN with a heat roll) to form a laminate, and after the lamination, the laminate is subjected to an annealing treatment at a temperature equal to or higher than the melting point of the fluororesin.

As the annealing treatment, the laminate immediately after bonding is continuously heated to 200 to 290 ° C., preferably 205 to 270 ° C., more preferably 210 to 245 ° C. (in this specification, heated). It is preferably performed by contacting with a roll).
The time for contacting the heated roll is not particularly limited, but is preferably 5 to 600 seconds, and more preferably 10 to 100 seconds.

FIG. 2 is a flow diagram showing a manufacturing method in the case where the laminated body immediately after bonding is subsequently brought into contact with a heated roll for annealing treatment.
In this case, as shown in FIG. 2, the polyimide film and the fluororesin are laminated by applying a load with a heat roll to form a laminated body, and the laminated body immediately after the bonding is continued as it is, in-line, Contact with heated roll.

As another aspect of the annealing treatment, the laminated body immediately after bonding is continuously heated in an oven usually heated to 200 to 290 ° C., preferably 205 to 270 ° C., more preferably 210 to 245 ° C. It is also preferable that this is performed.
The time for heating in the heated oven is not particularly limited, but is preferably 5 to 600 seconds, more preferably 10 to 300 seconds.

FIG. 3 shows a flow chart showing a manufacturing method in the case where the laminated body immediately after bonding is subsequently heated in a heated oven for annealing treatment.
In this case, as shown in FIG. 3, the polyimide film and the fluororesin are laminated by applying a load with a heat roll to form a laminated body, and the laminated body immediately after the bonding is continued as it is, in-line, Heat in a heated oven.

  In addition, in the manufacturing line which laminates the laminated body, the above-mentioned “continuous lamination immediately after bonding” is processed after the bonding process without taking out the laminated body which has been bonded from the manufacturing line. It means to process inline continuously.

  The second embodiment of the method for producing a long laminate according to the present invention includes paraphenylenediamine, 1,3-bis (4-aminophenoxy) benzene, 4,4′-diaminodiphenyl ether, and 3,4′-diaminodiphenyl ether. One or more aromatic diamine components selected from the group consisting of 4,4'-oxydiphthalic anhydride, pyromellitic dianhydride and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride A polyimide film and a fluororesin produced using one or more aromatic acid anhydride components selected from the group consisting of 1 to 15 kN in a roll heated to usually 150 to 230 ° C., preferably 170 to 210 ° C. After laminating by applying a load to form a laminated body and winding the laminated body into a roll, it is usually 150 to 290 ° C., preferably 160 to 24 ℃ wherein the heating in the heated oven.

  The method of winding the laminated body in a roll shape is not particularly limited, and may be a method usually used in the production of a long laminated body or a film.

  In the second aspect, the heating time in the heated oven is not particularly limited, but is preferably 1 minute or more, more preferably 5 minutes or more, and further preferably 15 minutes or more. The heating time is preferably 12 hours or less, but even if the heating time exceeds 12 hours, a further excellent effect is not achieved.

The oven used in the second aspect is not particularly limited as long as it is an oven that can heat a roll formed by winding a long body.
In the second aspect, heating of the laminated body in the oven does not have to be performed in the same inline as the production line for laminating the laminated body.

<Laminate>
Although the length of the elongate laminated body of this invention is not specifically limited, For example, 10 m or more is preferable.
Moreover, the width | variety of the laminated body of this invention is not specifically limited.

  In the laminate of the present invention, the adhesive strength between the polyimide film and the fluororesin is usually 0.2 N / cm or more, preferably 0.5 N / cm or more.

In the laminate of the present invention, the average thickness of the polyimide film constituting the laminate is not particularly limited, but is usually 2.5 to 175 μm, preferably 5 to 75 μm.
Moreover, in the laminated body of this invention, although the average thickness of a fluororesin is not specifically limited, Usually, it is 12.5-100 micrometers, Preferably it is 12.5-75 micrometers.

  In the laminate of the present invention, a laminate having a two-layer structure in which a polyimide film and a fluororesin are bonded together, and a polyimide film having an average thickness of 35 μm or more is bonded to the polyimide film side of the laminate. It may have a three-layer structure of polyimide film / polyimide film / fluororesin. A cross-sectional view of an example of a laminate having such a three-layer structure is shown in FIG.

  As the polyimide film having an average thickness of 35 μm or more, the polyimide film used in the laminate of the present invention described above can be preferably used.

  In addition, the laminate of the present invention has a two-layer structure in which a polyimide film and a fluororesin are bonded together, and a slightly adhesive pet film having an average thickness of 25 μm or more is attached to the fluororesin side of the laminate. A combined three-layer structure of polyimide film / fluororesin / slightly adhesive pet film may be used.

  In addition, the laminate of the present invention has a two-layer structure in which a polyimide film and a fluororesin are bonded together, and a slightly adhesive pet film having an average thickness of 25 μm or more is attached to the polyimide film side of the laminate. The three-layer structure of the slightly sticky pet film / polyimide film / fluororesin combined may be used. A cross-sectional view of an example of such a three-layer structure is shown in FIG.

  As described above, when the polyimide film and the fluororesin are bonded together by further bonding a polyimide film having an average thickness of 35 μm or more or a slightly adhesive pet film having an average thickness of 25 μm or more to a laminate having a two-layer structure. In addition, wrinkles and curls that are generated when the bonded laminate is heated with a heated roll or oven can be reduced.

  In the description of the above configuration, the symbol “/” indicates that the films or fluororesins on both sides thereof are bonded (heat-sealed).

  Although it does not specifically limit as said slightly adhesive pet film, For example, Panaprotect MK38S by Panac Co., Ltd. can be used.

  In addition, the laminated body of the 3 layer structure mentioned above can be manufactured similarly to the laminated body of a 2 layer structure. In the first or second aspect of the method for producing a long laminate of the present invention described above, the laminate having a three-layer structure is applied with a polyimide film and a fluororesin by applying a load of 1 to 15 kN with a hot roll. When combining, the polyimide film or the slightly sticky PET film to be further bonded as the third layer is processed together, and the three layers are bonded together to form a laminate, and the bonded laminate is heated in a heated roll or oven. It can be manufactured by heating.

  The three-layer structure laminate is a two-layer laminate formed by laminating a polyimide film and a fluororesin using the first or second aspect of the method for producing a long laminate of the present invention described above. After producing the body, the laminate of the two-layer structure may be manufactured by further bonding with a polyimide film or a slightly adhesive pet film to be bonded as a third layer using a hot roll or a non-heated roll. it can.

<FPC>
The present invention also includes an FPC using the above-described laminate of the present invention.
The FPC can be manufactured by bonding the laminate of the present invention as a coverlay and a copper clad laminate. Examples of the method for producing the copper-clad laminate include a three-layer CCL in which a base film and a copper foil are laminated via an adhesive, and a copper layer using vapor deposition, sputtering, and electroplating on the base film. , A so-called cast type two-layer CCL (COC) formed by casting a polyimide layer on a copper foil, and a base film formed by forming a copper layer using electroless plating.

  Examples of the base film include polyimide films and LCP films for high-frequency circuits. Examples of the adhesive layer include epoxy-based, acrylic-based, polyimide-based adhesive, and fluororesin. A commercially available product can be used as the adhesive. Although it does not specifically limit as a commercial item, LF series (acrylic adhesive) etc. of Pirarax (Pyralux, DuPont Co., Ltd.) etc. are mentioned. Among these, preferred forms are a copper clad laminate using an LCP film, and a copper clad laminate in which a base film and a copper foil are laminated via a fluororesin.

  Examples of the polyimide film used for the copper-clad laminate include the same polyimide films used for the laminate of the present invention, and the composition is the same as the polyimide film for the laminate of the present invention. May be different.

  Although it does not specifically limit as a fluorine resin used for the said copper clad laminated body, A well-known fluorine resin can be used and a commercial item may be used. Examples of the commercially available products include Toyoflon F, FE, FL, FR, and FV (trade names; above, manufactured by Toray Film Processing Co., Ltd.).

  The average thickness of the polyimide layer in the copper-clad laminate (when using a polyimide adhesive, the layer including the adhesive) is not particularly limited, but is 0.01 to 2 of the average thickness of the fluororesin layer. About 0 times is preferable, about 0.05 to 1.0 times is more preferable, and about 0.1 to 0.9 times is more preferable. When the average thickness of the polyimide layer exceeds 2.0 times the average thickness of the fluororesin layer, although the rigidity and dimensional stability as a copper clad laminate are improved, the dielectric constant increases, which is not preferable. Moreover, when it is less than 0.01 times, the rigidity of the polyimide layer decreases and the linear expansion coefficient tends to increase, and the rigidity and dimensional stability as a copper clad laminate decrease.

  The copper clad laminate is etched to obtain a copper clad laminate obtained by wiring. The method for the etching treatment is not particularly limited, and a known method can be used.

  In the manufacture of the high-frequency circuit board, the FPC coverlay is laminated so that the fluororesin side is in contact with the circuit of the copper clad laminate, and the coverlay and the copper clad laminate are temporarily fixed.

  As a temporary fixing process of the copper clad laminate and the cover lay, a known method can be used, and is not particularly limited. For example, the copper clad laminate and the cover lay are aligned and kiss-laminated. Later, if necessary, a method of laminating at a temperature of about 150 to 200 ° C. by quick pressing, a method of aligning the copper clad laminate and the cover lay, and a method of multi-stage pressing can be mentioned. The maximum temperature in the temporary fixing step is not particularly limited as long as it is lower than the melting point of the fluororesin used for the coverlay, but is within the range of 100 to 250 ° C. from the viewpoint that sufficient adhesive strength can be obtained by the subsequent annealing treatment. Is preferable. The processing time of the temporary fixing process is not particularly limited.

  Although it does not specifically limit in manufacture of a high frequency circuit board, It is preferable to perform the process of annealing the copper clad laminated body to which the coverlay was attached following the said temporary fixing process.

  The maximum heating temperature in the annealing process is not particularly limited, but the temperature higher than the maximum temperature in the temporary fixing process within the range of 150 ° C. or higher and 350 ° C. or lower is the adhesive strength of the resulting high-frequency circuit board. The temperature difference is preferably 20 ° C. or more. Moreover, it is preferable that the annealing process is performed with free tension at 150 ° C. or more and 350 ° C. or less. Free tension has the advantage of simplifying the treatment process, and the annealing temperature is more preferably 200 ° C. or higher and 280 ° C. or lower, and further preferably 205 ° C. or higher and 275 ° C. or lower. The annealing time is not particularly limited.

  By the annealing treatment, the adhesive strength is increased based on the adhesive strength of the fluororesin layer, and a high-frequency circuit board having a practical adhesive strength (peel strength) is obtained.

<FFC>
The present invention also includes an FFC using the above-described laminate of the present invention.
The FFC can be manufactured by thermocompression bonding with a conductor sandwiched between the laminates of the present invention as an FFC substrate.
FFC, for example, while heating two laminates of the present invention formed by bonding the polyimide film and the fluororesin in an adhesive state with the conductor in between so that the fluororesin layer faces each other Method of pasting and thermocompression bonding: After heating and pressing the two fluororesin molded bodies while heating so that the molded bodies face each other with the conductor in between, the two polyimide films are bonded together It can manufacture using the method of sticking up and down the molded object of this fluororesin. The method for thermocompression bonding is not particularly limited, and may be according to a method used in the production of a conventionally known FFC, and is similar to the method using a hot roll or a heated roll used in the method for producing a laminate of the present invention described above. This method can be used.

  The conductor is not particularly limited, and examples thereof include a flat foil or round wire of conductive metal, a rectangular conductor having a rectangular cross section, and an organic conductor. Although it does not specifically limit as a conductive metal, Copper, silver, tin, indium, aluminum, molybdenum, these alloys, etc. can be used. The width and thickness of the conductor are not particularly limited, but are, for example, about 20 μm to 0.5 mm.

  A high frequency circuit board can be manufactured by laminating the laminate of the present invention and a copper-clad laminate processed by wiring, or by sandwiching a conductor between the laminate of the present invention.

  EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples at all, and many variations are within the technical idea of the present invention. This is possible by those with ordinary knowledge.

(Adhesive strength measurement)
A laminate of a polyimide film and a fluororesin is cut into a size of 10 mm × 120 mm, and subjected to a 90 ° C. pulling test (tensile speed: 50 mm / min, measurement length: using Shimadzu Universal Tensile Tester Autograph AG-IS). The peel strength (adhesive strength) was measured at 20 mm and measurement range: 5.0-20.0 mm. (Unit of adhesive strength: N / cm).

(Average thickness)
The average thickness of the polyimide film, the fluororesin film and the slightly sticky PET film before bonding, and the average thickness of the polyimide film and the fluororesin in the laminate are microscopic at any five locations of the film or laminate to be measured. It is the average value of the thickness measured with a meter.

(Production Example 1) Production of fluororesin film Using a 65φ short screw extruder with a fluororesin (fluorinated ethylenic polymer) having the monomer composition and physical properties shown in Table 1 and having a set temperature of 230 ° C to 280 ° C. Pelletized, and then formed into a film with a 50φ short-shaft extruder equipped with a T-die having a set temperature of 230 ° C. to 280 ° C. to obtain fluororesin films having an average thickness of 25 and 50 μm.

  In Table 1, TEE represents tetrafluoroethylene, Et represents ethylene, HEP represents hexafluoropropylene, and HF-Pa represents perfluoro (1,1,5-trihydro-1- Pentene).

Below, the Example and comparative example of a laminated body are shown.
The thicknesses of the polyimide film and the fluororesin film do not change both before and after bonding and after being subjected to bonding and annealing. In the following Examples 1-8 and Comparative Examples 1-3, the average thickness of the polyimide film and the average thickness of the fluororesin in each of the obtained laminates are the average of the polyimide film (kapton) before bonding, respectively. It is the same as the thickness and the average thickness of the fluororesin film (the film obtained in Production Example 1).

Example 1
Kapton 100KJ (average thickness 25 μm) and the film obtained in Production Example 1 (average thickness 25 μm) were superposed and bonded with a heat roll heated to 200 ° C. under a load of 10 kN, and subsequently heated to 220 ° C. It was made to contact with a roll for 0.25 minutes, and the laminated body was obtained.

(Example 2)
Kapton 50EN (average thickness 12.5 μm) and the film obtained in Production Example 1 (average thickness 25 μm) were superposed and bonded together with a heat roll heated to 200 ° C. under a load of 10 kN, and subsequently heated to 240 ° C. The laminated roll was contacted for 0.25 minutes to obtain a laminate.

(Example 3)
Kapton 50EN-S (average thickness 12.5 μm) and the film obtained in Production Example 1 (average thickness 50 μm) were superposed and bonded with a hot roll heated to 200 ° C. under a load of 10 kN, and subsequently 270 ° C. The laminate was brought into contact with a heated roll for 1 minute to obtain a laminate.

Example 4
Kapton 100EN (average thickness 25 μm) and the film obtained in Production Example 1 (average thickness 25 μm) were superposed and bonded with a heat roll heated to 210 ° C. under a load of 10 kN, and subsequently heated to 250 ° C. The laminate was brought into contact with the roll for 0.5 minutes to obtain a laminate.

(Example 5)
Kapton 100H (average thickness 25 μm) and the film obtained in Production Example 1 (average thickness 50 μm) were superposed and bonded with a heat roll heated to 200 ° C. under a load of 10 kN, and subsequently heated to 210 ° C. The laminate was obtained by heating in an oven for 3 minutes.

(Example 6)
Kapton 50EN (average thickness 12.5 μm) and the film obtained in Production Example 1 (average thickness 25 μm) were superposed and bonded with a heat roll heated to 210 ° C. under a load of 13 kN, and subsequently heated to 250 ° C. The resulting laminate was heated for 0.5 minutes to obtain a laminate.

(Example 7)
Kapton 50H (average thickness 12.5 μm) and the film obtained in Production Example 1 (average thickness 50 μm) were superposed and bonded with a hot roll heated to 200 ° C. with a load of 10 kN, and the laminate was rolled. After being wound, the laminate was heated in an oven heated to 210 ° C. for 60 minutes to obtain a laminate.

(Example 8)
Kapton 50EN (average thickness of 12.5 μm) and the film obtained in Production Example 1 (average thickness of 25 μm) were superposed and bonded with a heat roll heated to 180 ° C. under a load of 5 kN, and the laminate was rolled. After being wound on, it was heated in an oven heated to 270 ° C. for 40 minutes to obtain a laminate.

(Comparative Example 1)
Kapton 50EN-S (average thickness 12.5 μm) and the film obtained in Production Example 1 (average thickness 25 μm) were superposed and bonded with a heat roll heated to 200 ° C. under a load of 10 kN, and the laminate was laminated. Obtained.

(Comparative Example 2)
Kapton 100KJ (average thickness 25 μm) and the film obtained in Production Example 1 (average thickness 50 μm) were superposed and bonded with a heat roll heated to 200 ° C. under a load of 10 kN, and then continuously increased to 175 ° C. The laminated body was obtained by contacting the heated roll for 0.5 minutes.

(Comparative Example 3)
Kapton 50EN-S (average thickness 12.5 μm) and the film obtained in Production Example 1 (average thickness 25 μm) were superposed and bonded with a heat roll heated to 200 ° C. under a load of 10 kN, and the laminate was laminated. After being wound into a roll, it was heated in an oven heated to 80 ° C. for 10 minutes to obtain a laminate.

  Table 2 shows the results of the adhesive strength of the laminates obtained in Examples 1 to 8 and Comparative Examples 1 to 3.

The laminates of Examples 1 to 8 all had a high adhesive strength of 0.7 N / cm or higher, whereas the laminates of Comparative Examples 1 to 3 were as low as 0.1 N / cm or less.
Moreover, all the laminated bodies of Examples 1-8 were able to be manufactured by the annealing process at the low temperature of 270 degrees C or less.

Since the laminated body of this invention is a long laminated body excellent in the adhesiveness of a polyimide film and a fluororesin, it is suitable as base materials, such as FFC and FPC.
Moreover, in the manufacturing method of this invention, since a polyimide film and a fluororesin can be bonded together at low temperature than before, it is possible to manufacture a long laminate of a polyimide film and a fluororesin in an industrially advantageous manner. it can.

1. Polyimide film Fluorine resin 3. Light-adhesive pet film Polyimide film (35μm or more)
21. Heat roll 22. Heated roll 23. Oven 31. Laminate

Claims (15)

  One or more aromatic diamine components selected from the group consisting of paraphenylenediamine, 1,3-bis (4-aminophenoxy) benzene, 4,4′-diaminodiphenyl ether and 3,4′-diaminodiphenyl ether; One or more aromatic acid anhydride components selected from the group consisting of '-oxydiphthalic anhydride, pyromellitic dianhydride and 3,3', 4,4'-biphenyltetracarboxylic dianhydride are used. A long laminate obtained by laminating a polyimide film and a fluororesin produced together, wherein the adhesive strength between the polyimide film and the fluororesin is 0.2 N / cm or more.   The laminate according to claim 1, wherein the adhesive strength between the polyimide film and the fluororesin is 0.5 N / cm or more.   It is a laminated body of Claim 1 or 2, Comprising: The average thickness of the polyimide film which comprises a laminated body is 2.5-175 micrometers, The average thickness of a fluororesin is 12.5-100 micrometers, It is characterized by the above-mentioned. Laminated body.   The laminate according to any one of claims 1 to 3, wherein the fluororesin has a melting point of 200 ° C or lower.   The laminate according to any one of claims 1 to 4, wherein the fluororesin is a fluorinated ethylenic polymer, and the fluorinated ethylenic polymer contains a carbonyl group. The laminate according to claim 5, wherein the content of carbonyl groups in the fluorine-containing ethylenic polymer is 3 to 1000 in total with respect to 1 × 10 ⁶ main chain carbon atoms. The fluorine-containing ethylenic heavy polymer having at least one selected from the group consisting of a carbonate group, a carboxylic acid halide group and a carboxylic acid group with a total of 3 to 1000 carbon atoms per 1 × 10 ⁶ main chain carbon atoms. The laminate according to any one of claims 1 to 4, wherein the laminate is a combination. The fluororesin is tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, vinyl fluoride, hexafluoropropylene, hexafluoroisobutene, the following formula (X):
CH ₂ = CR ¹ (CF ₂ ) _n R ² (X)
(In the formula, R ¹ represents H or F, R ² represents H, F or Cl, and n represents a positive integer of 1 to 10.)
1 or more types of fluorine-containing ethylenic monomers selected from the group consisting of monomers represented by formula (2) and perfluoro (alkyl vinyl ethers) having 2 to 10 carbon atoms, or the fluorine-containing ethylenic monomers and carbon The laminate according to any one of claims 1 to 4, which is a fluorine-containing ethylenic polymer obtained by polymerizing an ethylenic monomer having a number of 5 or less. The laminate according to any one of claims 1 to 4, wherein the fluororesin is a copolymer obtained by polymerizing at least the following (a), (b) and (c).
(A) Tetrafluoroethylene 20-90 mol%
(B) 10-80 mol% ethylene
(C) Formula CF ₂ = CFR ³ (Y)
(In the formula, R ³ represents CF ₃ or OR ⁴ , and R ⁴ represents a perfluoroalkyl group having 1 to 5 carbon atoms.)
1 to 70 mol% of a compound represented by   One or more aromatic diamine components selected from the group consisting of paraphenylenediamine, 1,3-bis (4-aminophenoxy) benzene, 4,4′-diaminodiphenyl ether and 3,4′-diaminodiphenyl ether; One or more aromatic acid anhydride components selected from the group consisting of '-oxydiphthalic anhydride, pyromellitic dianhydride and 3,3', 4,4'-biphenyltetracarboxylic dianhydride are used. The polyimide film and the fluororesin produced in this manner are laminated by applying a load of 1 to 15 kN with a roll heated to 150 to 230 ° C., and after laminating, the laminate is heated at a temperature equal to or higher than the melting point of the fluororesin. A method for producing a long laminate, which is subjected to an annealing treatment.   The manufacturing method according to claim 10, wherein the annealing treatment is performed by bringing the laminate immediately after bonding into contact with a roll heated to 200 to 290 ° C.   The manufacturing method according to claim 10, wherein the annealing treatment is performed by continuously heating the laminated body immediately after bonding in an oven heated to 200 to 290 ° C.   One or more aromatic diamine components selected from the group consisting of paraphenylenediamine, 1,3-bis (4-aminophenoxy) benzene, 4,4′-diaminodiphenyl ether and 3,4′-diaminodiphenyl ether; One or more aromatic acid anhydride components selected from the group consisting of '-oxydiphthalic anhydride, pyromellitic dianhydride and 3,3', 4,4'-biphenyltetracarboxylic dianhydride are used. The polyimide film and the fluororesin produced in the above are laminated by applying a load of 1 to 15 kN with a roll heated to 150 to 230 ° C., and the laminated body is wound into a roll and then 150 to A method for producing a long laminate, comprising heating in an oven heated to 290 ° C.   An FPC (flexible printed circuit board) using the laminate according to any one of claims 1 to 9.   An FFC (flexible flat cable) using the laminate according to any one of claims 1 to 9.