JP2014024964A - Cross-linked cycloolefin resin film, laminate, and method for manufacturing laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cross-linked cycloolefin resin film including a cross-linked cycloolefin resin and excellent in terms of adhesiveness with metallic materials.SOLUTION: A cross-linked cycloolefin resin film is obtained by coating a polymerizable composition including (a) 100 pts.mass of a cycloolefin monomer, (b) 0.05-15 pts.mass of an aromatic vinyl polymer, and (c) a polymerization catalyst atop a substrate, subsequently by metathetically polymerizing the composition, and subsequently by peeling the obtained filmy polymer from the substrate.

Description

  The present invention relates to a crosslinked cyclic olefin resin film having excellent adhesion to a metal material, a laminate in which the crosslinked cyclic olefin resin film and a metal foil are bonded, and a method for producing the laminate.

  The cyclic olefin resin obtained by polymerizing a polymerizable monomer containing a cyclic olefin monomer such as a norbornene-based monomer in the presence of a metathesis polymerization catalyst has low water absorption, and its electrical properties, mechanical properties, impact resistance, heat resistance The cyclic olefin resin is used as a raw material for molded articles in a wide range of fields.

  Electrical insulation material that insulates the wiring layer of the printed circuit board formed by using solder, etc., and electrical insulation material that seals the terminal electrodes of electronic components mounted on the printed circuit board are solder heat resistant. Need. Then, the cyclic olefin resin which has the outstanding electrical property and heat resistance is used as electrical insulation materials, such as a printed wiring board and the terminal electrode of an electronic component.

  However, when cyclic olefin resin is used as an insulating material for printed wiring boards, the adhesion between the metal material constituting the printed wiring board and terminal electrodes of electronic components and the cyclic olefin resin is low, and the reliability is insufficient. It was.

  Therefore, it has been studied to improve the adhesion between the cyclic olefin resin and the metal material by previously treating the surface of the metal material to be bonded to the cyclic olefin resin with a predetermined coupling agent (for example, see Patent Document 1). However, the pretreatment of the metal material with the coupling agent complicates the manufacturing process.

JP 2009-255380 A

Recently, a crosslinked cyclic olefin resin film containing a crosslinked cyclic olefin resin obtained by metathesis polymerization of a cyclic olefin monomer and having excellent adhesion to a metal material has been sought, but such a film has not been found. .
The problems to be solved by the present invention include a crosslinked cyclic olefin resin film containing a crosslinked cyclic olefin resin and having excellent adhesion to a metal material, a laminate in which the crosslinked cyclic olefin resin film and a metal foil are bonded, and the It is providing the manufacturing method of a laminated body.

  As a result of intensive studies, the inventor of the present invention applied a polymerizable composition containing (a) a cyclic olefin monomer, (b) an aromatic vinyl polymer, and (c) a polymerization catalyst on a substrate, then metathesis The crosslinked cyclic olefin resin film obtained by polymerizing and then peeling off the obtained film-like polymer from the substrate is found to have excellent adhesion to the metal material, and the crosslinked cyclic olefin resin of the present invention It came to complete the film, the laminated body to which the said crosslinked cyclic olefin resin film and metal foil were adhere | attached, and the manufacturing method of the said laminated body.

  The crosslinked cyclic olefin resin film of the present invention comprises a polymerizable composition containing (a) 100 parts by mass of a cyclic olefin monomer, (b) 0.05 to 15 parts by mass of an aromatic vinyl polymer, and (c) a polymerization catalyst. After coating on a substrate, metathesis polymerization is performed, and then the obtained film-like polymer is peeled off from the substrate. The preferable (a) cyclic olefin monomer is a norbornene monomer. A preferable polymerization catalyst (c) is a ruthenium carbene complex. The cross-linked cyclic olefin resin film of the present invention is preferably corona-treated on one side or both sides.

  In the laminate of the present invention, the crosslinked cyclic olefin resin film and (d) metal foil are bonded. The preferred (d) metal foil is a copper foil. The laminate of the present invention is preferably used for a flexible printed board.

  In the method for producing a laminate of the present invention, the polymerizable composition is coated on a substrate, metathesis polymerized, and then the obtained film-like polymer is peeled from the substrate to form a crosslinked cyclic olefin resin film. And the step of bringing the crosslinked cyclic olefin resin film and the metal foil into contact with each other and then heating them while applying pressure to bond them together.

  The crosslinked cyclic olefin resin film of the present invention has excellent adhesion to a metal material.

One of the raw materials of the crosslinked cyclic olefin resin film of the present invention, (a) the cyclic olefin monomer is a compound having a ring structure formed of carbon atoms and having a carbon-carbon double bond in the ring. . Specific examples thereof include norbornene monomers and monocyclic olefins. The preferred (a) cyclic olefin monomer is a norbornene monomer. The norbornene-based monomer is a monomer containing a norbornene ring. Specific examples of the norbornene monomer include norbornenes, dicyclopentadiene, and tetracyclododecenes. These may contain as substituents hydrocarbon groups such as alkyl groups, alkenyl groups, alkylidene groups, and aryl groups; polar groups such as carboxyl groups and acid anhydride groups.
The norbornene monomer may further have a double bond in addition to the double bond of the norbornene ring. A preferred norbornene-based monomer is a nonpolar monomer, that is, a norbornene-based monomer composed of only carbon atoms and hydrogen atoms.

Specific examples of the nonpolar norbornene-based monomer include noncyclopentadiene, methyldicyclopentadiene, and dihydrodicyclopentadiene (also referred to as tricyclo [5.2.1.0 ^2,6 ] dec-8-ene). Polar dicyclopentadiene;

Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyclohexyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyclopentyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-vinyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-propenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyclohexenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyclopentenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-phenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] nonpolar tetracyclododecenes such as dodec-4-ene;

2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-cyclohexyl-2- Norbornene, 5-cyclopentyl-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-cyclohexenyl-2-norbornene, 5-cyclopentenyl-2- norbornene, 5-phenyl-2-norbornene, tetracyclo [9.2.1.0 ^2,10. 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), tetracyclo [10.2.1.0. ^2,11 . Non-polar norbornenes such as 0 ^4,9 ] pentadeca-4,6,8,13-tetraene (also referred to as 1,4-methano-1,4,4a, 9,9a, 10-hexahydroanthracene);

Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-4,10-diene, pentacyclo [9.2.1.1 ^4,7. 0 ^2,10 . 0 ^3,8 ] pentadeca-5,12-diene, hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-non-polar cyclic olefins or pentacyclic body such as ene; and the like.

  From the viewpoint of easy availability and improved heat resistance of the film, preferred nonpolar norbornene monomers are nonpolar dicyclopentadienes and nonpolar tetracyclododecenes, and more preferred nonpolar norbornene monomers are nonpolar dicyclones. Cyclopentadiene.

Specific examples of the norbornene-based monomer containing a polar group include tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] methyl dodeca-9-ene-4-carboxylate, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-methanol, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic acid, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic anhydride, methyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate, 5-norbornene-2 acetate -Yl, 5-norbornene-2-methanol, 5-norbornene-2-ol, 5-norbornene-2-carbonitrile, 2-acetyl-5-norbornene, 7-oxa-2-norbornene and the like.

  Specific examples of the monocyclic olefin include cyclobutene, cyclopentene, cyclohexene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, and derivatives thereof having a substituent.

  These (a) cyclic olefin monomers are used singly or in combination of two or more. The addition amount of the monocyclic olefin is preferably 40% by mass or less, more preferably 20% by mass or less, based on the total amount of the (a) cyclic olefin monomer. If the amount of monocyclic olefin added is too large, the heat resistance of the film may be insufficient.

  When obtaining the crosslinked cyclic olefin resin film of the present invention, a polymerizable composition containing at least (a) a cyclic olefin monomer, (b) an aromatic vinyl polymer, and (c) a polymerization catalyst is applied onto a substrate. Then, metathesis polymerization is performed. (C) The polymerization catalyst metatheses (a) the cyclic olefin monomer. The (c) polymerization catalyst is not limited to a specific catalyst.

  A complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds around a transition metal atom is used as the (c) polymerization catalyst. Atoms of Group 5, Group 6, and Group 8 (long-period periodic table, the same applies hereinafter) are used as transition metal atoms. The atoms of each group are not particularly limited, but the preferred Group 5 atom is tantalum, the preferred Group 6 atom is molybdenum and tungsten, and the preferred Group 8 atom is ruthenium and osmium.

  A preferred (c) polymerization catalyst is a group 8 ruthenium or osmium complex, and a particularly preferred (c) polymerization catalyst is a ruthenium carbene complex. Since the ruthenium carbene complex is excellent in catalytic activity during bulk polymerization, a crosslinked cyclic olefin polymer with little residual unreacted monomer can be obtained with high productivity.

  Specific examples of the ruthenium carbene complex are complexes represented by the following formula (1) or (2) from the viewpoint of catalytic activity.

In the formulas (1) and (2), R ¹ and R ² each independently include a hydrogen atom; a halogen atom; or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. It represents a good cyclic or chain hydrocarbon group having 1 to 20 carbon atoms. X ¹ and X ² each independently represents an arbitrary anionic ligand. L ¹ and L ² each independently represents a neutral electron donating compound. R ¹ and R ² may be bonded to each other to form an aliphatic ring or an aromatic ring that may contain a hetero atom. Furthermore, R ¹ , R ² , X ¹ , X ² , L ¹ and L ² may be bonded together in any combination to form a multidentate chelating ligand.

  The heteroatom in the present invention is an atom of Groups 15 and 16 of the periodic table. Specific examples of the hetero atom include a nitrogen atom (N), an oxygen atom (O), a phosphorus atom (P), a sulfur atom (S), an arsenic atom (As), and a selenium atom (Se). From the viewpoint of the stability of the carbene compound, preferred heteroatoms are N, O, P, and S, and particularly preferred heteroatoms are N.

  Neutral electron donating compounds are roughly classified into hetero atom-containing carbene compounds and other neutral electron donating compounds. (C) From the viewpoint of the activity of the polymerization catalyst, preferred neutral electron donating compounds are heteroatom-containing carbene compounds. A heteroatom-containing carbene compound in which heteroatoms are adjacently bonded to both sides of the carbene carbon is preferable, and a heteroatom-containing carbene compound in which a heterocycle is formed including the carbene carbon atom and heteroatoms on both sides thereof is more preferable. preferable. The heteroatom adjacent to the carbene carbon preferably has a bulky substituent.

  Specific examples of preferred heteroatom-containing carbene compounds are compounds represented by the following formula (3) or formula (4).

In Formula (3) and Formula (4), R ^{3 to} R ⁶ may each independently contain a hydrogen atom; a halogen atom; or a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, or silicon atom. Represents a cyclic or chain hydrocarbon group having 1 to 20 carbon atoms. R ^{3 to} R ⁶ may be bonded to each other in any combination to form a ring.

  Specific examples of the compound represented by the formula (3) or the formula (4) include 1,3-dimesitylimidazolidin-2-ylidene and 1,3-di (1-adamantyl) imidazolidin-2-ylidene. 1-cyclohexyl-3-mesitylimidazolidine-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3- And di (1-phenylethyl) -4-imidazoline-2-ylidene and 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene.

  In addition to the compound represented by the formula (3) or (4), 1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5-ylidene 1,3-dicyclohexylhexahydropyrimidin-2-ylidene, N, N, N ′, N′-tetraisopropylformamidinylidene, 1,3,4-triphenyl-4,5-dihydro-1H-1, Heteroatom-containing carbene compounds such as 2,4-triazole-5-ylidene and 3- (2,6-diisopropylphenyl) -2,3-dihydrothiazol-2-ylidene can be used.

  Neutral electron donating compounds other than heteroatom-containing carbene compounds are ligands that have a neutral charge when pulled away from the central metal. Specific examples of the neutral electron donating compound include carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, thiocyanates, and the like. is there. Preferred neutral electron donating compounds are phosphines, ethers and pyridines, and a more preferred neutral electron donating compound is trialkylphosphine.

In the formulas (1) and (2), the anionic (anionic) ligands X ¹ and X ² are ligands having a negative charge when separated from the central metal atom. Examples are halogen atoms such as fluorine atom (F), chlorine atom (Cl), bromine atom (Br), iodine atom (I), diketonate group, substituted cyclopentadienyl group, alkoxy group, aryloxy group, carboxyl group Etc. A preferred anionic ligand is a halogen atom, and a more preferred ligand is a chlorine atom.

In the above formula (1), an example of a ruthenium carbene complex in which X ² and L ² are bonded to each other to form a multidentate chelating ligand is a Schiff base coordination complex represented by the following formula (5) It is.

In the formula (5), Z represents an oxygen atom, a sulfur atom, a selenium atom, NR ¹² , PR ¹² or AsR ¹² , and R ¹² is the same as those exemplified for R ¹ and R ² .

In Formula (5), R ^{7 to} R ⁹ each independently represent a monovalent organic group that may contain a hydrogen atom, a halogen atom, or a hetero atom. Specific examples of the monovalent organic group that may contain a hetero atom include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group, and a carbon number. An alkoxyl group having 1 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, an aryloxy group, an alkylthio group having 1 to 8 carbon atoms, a carbonyloxy group having 1 to 20 carbon atoms, C1-C20 alkoxycarbonyl group, C1-C20 alkylsulfonyl group, C1-C20 alkylsulfinyl group, C1-C20 alkyl sulfonic acid group, aryl sulfonic acid group, C1-C1 20 phosphonic acid groups, arylphosphonic acid groups, alkylammonium groups having 1 to 20 carbon atoms, arylammonium groups, and the like.
The monovalent organic group which may contain these heteroatoms may have a substituent and may be bonded to each other to form a ring. Examples of the substituent are an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, and an aryl group. When the monovalent organic group forms a ring, the ring may be an aromatic ring, an alicyclic ring, or a heterocyclic ring.

In formula (5), R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a heteroaryl group, and these groups are May have a substituent and may be bonded to each other to form a ring. Examples of the substituent are an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, and an aryl group. When R ¹⁰ and R ¹¹ form a ring, the ring may be an aromatic ring, an alicyclic ring, or a heterocyclic ring.

  Specific examples of the complex compound represented by the formula (1) include benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-4). , 5-Dibromo-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4-imidazoline-2-ylidene) (3-phenyl-1H-indene-1-ylidene) ( Tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4-imidazolidin-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3- Dimesityl-octahydrobenzimida 2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3 -Dimesityl-2,3-dihydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H -1,2,4-triazole-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene 1,3-dimesityl-4-imidazolidin-2-ylidene) pyridine ruthenium dichloride, (1,3-dimesityl-4-imidazolidin-2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride, 1,3-Dimesityl-4-imidazoline-2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) [ (Phenylthio) methylene] (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) (2-pyrrolidone-1-ylmethylene) (tricyclohexylphosphine) ruthenium dichloride Lori A ruthenium complex compound in which one hetero atom-containing carbene compound and one neutral electron donating compound are bonded, such as

  A ruthenium complex compound in which two neutral electron-donating compounds are bonded, such as benzylidenebis (tricyclohexylphosphine) ruthenium dichloride, (3-methyl-2-buten-1-ylidene) bis (tricyclopentylphosphine) ruthenium dichloride;

  Two heteroatom-containing carbene compounds such as benzylidenebis (1,3-dicyclohexyl-4-imidazolidin-2-ylidene) ruthenium dichloride and benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride Ruthenium complex compound in which is bonded;

A ruthenium carbene complex represented by formula (6) in which X ² and L ² are bonded to each other to form a multidentate chelating ligand;

In the formula (6), Mes represents a mesityl group. R ⁷ and R ⁸ are each a hydrogen atom or a methyl group, and at least one of them is a methyl group. R ¹³ and R ¹⁴ each independently represents a monovalent organic group that may contain a hydrogen atom, a halogen atom, or a hetero atom. The “monovalent organic group” is the same as R ^{7 to} R ⁹ described above in the description of the formula (5).

  Specific examples of the complex compound represented by the formula (2) are (1,3-dimesityl-4-imidazolidin-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butylvinylidene). (1,3-diisopropyl-4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylidene ruthenium dichloride, and the like.

  Particularly preferred complex compounds are those represented by the formula (1) and having one compound represented by the formula (3) or (4) as a ligand.

  These ruthenium carbene complexes are described in (a) Org. Lett. 1999, Vol. 1, page 953, (b) Tetrahedron. Lett. 1999, 40, 2247, (c) International Publication No. 2003/062253 pamphlet and the like.

  The amount of the (c) polymerization catalyst used is usually a molar ratio of ((c) metal atom in the polymerization catalyst: (a) cyclic olefin monomer) and is usually from 1: 2,000 to 1: 2,000,000, preferably The range is from 1: 5,000 to 1: 1,000,000, more preferably from 1: 10,000 to 1: 500,000. (C) If the amount of the polymerization catalyst is too small, the polymerization reaction rate decreases and monomers remain in the polymer, or the crosslinking degree of the crosslinked polymer decreases and the heat resistance of the resulting film decreases. There is a risk. (C) If the amount of the polymerization catalyst is too large, the production cost increases, and the reaction rate becomes too fast, which may make it difficult to form a film during bulk polymerization, which will be described later.

(C) The polymerization catalyst can be used in combination with an activator (cocatalyst) for the purpose of controlling the polymerization activity and improving the polymerization reaction rate. Specific examples of the activator include aluminum, scandium, tin, silicon alkylates, halides, alkoxylates and aryloxylates. Further specific examples of activators include aluminum compounds such as trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride; trialkoxy Scandium compounds such as scandium; titanium compounds such as tetraalkoxy titanium; tin compounds such as tetraalkyls and tetraalkoxytin; zirconium compounds such as tetraalkoxyzirconium; dimethylmonochlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, tetrachlorosilane, bicyclo Heptenylmethyldichlorosilane, phenylmethyldichlorosilane, Hexyl dichlorosilane, phenyl trichlorosilane, silane compounds such as methyltrichlorosilane, and the like.
The use amount of the activator is usually 1: 0.05 to 1: 100, preferably 1: 0.2 to 1:20, in a molar ratio of ((c) metal atom in the polymerization catalyst: activator). More preferably, it is in the range of 1: 0.5 to 1:10.

  (C) The polymerization catalyst can be used in combination with a polymerization regulator for the purpose of controlling the polymerization activity and adjusting the polymerization reaction rate. Specific examples of the polymerization regulator include triphenylphosphine, tricyclohexylphosphine, tributylphosphine, 1,1-bis (diphenylphosphino) methane, 1,4-bis (diphenylphosphino) butane, 1,5-bis (diphenyl). Phosphino) phosphorus compounds such as pentane; Lewis bases such as ethers, esters and nitriles. The amount of these used is usually 0.01 to 50 mol, preferably 0.05 to 10 mol, relative to 1 mol of the polymerization catalyst (c).

  In the production of the crosslinked cyclic olefin resin film of the present invention, the polymerization method may be either a solution polymerization method or a bulk polymerization method, but a solvent removal step is not required, and a resin composition molded into a film shape at the same time as polymerization is used. From the viewpoint of being obtained, the bulk polymerization method is preferred.

The bulk polymerization method involves metathesis polymerization of a polymerizable composition containing (a) a cyclic olefin monomer, (b) an aromatic vinyl polymer, and (c) a polymerization catalyst in the presence of an additive used as necessary. A step of forming into a film shape.
(A) The cyclic olefin monomer is metathesized to obtain a cyclic olefin polymer, and the cyclic olefin polymer is crosslinked after the metathesis polymerization or simultaneously with the metathesis polymerization to obtain a crosslinked cyclic olefin polymer. Conceivable.

The crosslinked cyclic olefin resin film of the present invention contains (b) an aromatic vinyl polymer.
(B) Specific examples of the aromatic vinyl compound constituting the aromatic vinyl polymer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, divinylbenzene, 2,4-dimethylstyrene, 2,4-diethylstyrene, vinylnaphthalene, vinylanthracene and the like. Of these, styrene and α-methylstyrene are particularly preferred aromatic vinyl compounds. One or more aromatic vinyl compounds are used.

  (B) The aromatic vinyl polymer may be modified with a polar group, but an unmodified one is particularly preferred. Specific examples of the polar group-modified aromatic vinyl polymer include acrylic-modified aromatic vinyl polymer, methacryl-modified aromatic vinyl polymer, halogen-modified aromatic vinyl polymer, hydroxyl group-modified aromatic vinyl polymer, carboxylic acid-modified aromatic polymer. Examples thereof include vinyl polymers, amine-modified aromatic vinyl polymers, and epoxy-modified aromatic vinyl polymers.

  The polar group-modified aromatic vinyl polymer is a monomer having an acrylic group, a methacryl group, a halogen atom, a hydroxyl group, a carboxyl group, an amino group or an epoxy group together with an aromatic vinyl compound such as styrene or α-methylstyrene. It can be obtained by polymerization, or (b) adding the above-mentioned polar group to an aromatic vinyl polymer.

  In a preferred polar group-modified aromatic vinyl polymer, (b) the aromatic vinyl polymer is modified with a carboxylic acid or a compound having an epoxy group. The (b) aromatic vinyl polymer modified with carboxylic acid includes (b) an aromatic vinyl polymer modified with carboxylic anhydride.

  Polar group-modified aromatic vinyl polymers are commercially available, and specific examples thereof include NOVA Chemicals Japan Ltd. DYLARK D232, NOF Corporation Modiper (registered trademark) A4100, and the like.

  Unmodified aromatic vinyl polymers are commercially available, and specific examples thereof include PS Japan PSJ-polystyrene GPPS HF77.

  (B) The weight average molecular weight of the aromatic vinyl polymer is preferably in the range of 5,000 to 1,000,000, more preferably 10,000 to 500,000.

  (B) Content of aromatic vinyl polymer is 0.05-15 mass parts with respect to 100 mass parts of (a) cyclic olefin monomer, Preferably it is 0.3-10 mass parts, More preferably, 0.3- 5 parts by mass. (B) When there is too little content of an aromatic vinyl polymer, there exists a possibility that the adhesive improvement effect with respect to a metal material may not be acquired. On the other hand, when the content of (b) the aromatic vinyl polymer is too large, (a) a portion that does not dissolve in the cyclic olefin monomer occurs, or the polymerization composition is solidified before polymerization, resulting in a crosslinked cyclic olefin resin. A film cannot be obtained.

  Various additives may be incorporated into the crosslinked cyclic olefin resin film of the present invention for the purpose of improving film characteristics, imparting functions, improving molding workability, etc. according to various applications and purposes. Specific examples of such additives include polymerization inhibitors, fillers, antifoaming agents, foaming agents, colorants, ultraviolet absorbers, stabilizers, flame retardants, wetting agents, dispersing agents, release lubricants, plasticizers, and the like. It is. Preferably, a stabilizer is contained in order to improve the durability and storage stability of the crosslinked cyclic olefin polymer.

  Specific examples of polymerization inhibitors include quinones such as parabenzoquinone, tolquinone and naphthoquinone; hydroquinones such as hydroquinone, para-t-butylcatechol and 2,5-di-t-butylhydroquinone; copper naphthenate and copper octenoate Quaternary ammonium salts such as trimethylbenzylammonium chloride, trimethylbenzylammonium maleate, phenyltrimethylammonium chloride; oximes such as quinonedioxime and methylethylketoxime; amines such as triethylamine hydrochloride and dibutylamine hydrochloride Hydrochlorides; and the like. One or more of these are used in combination.

Specific examples of fillers include inorganic fillers such as carbon black, natural graphite, silica, silica sand, glass powder, calcium carbonate, aluminum hydroxide, magnesium hydroxide, and clay; organic fillers such as wood powder, polyester beads, and polystyrene beads Material; etc. One or more of these are used in combination. The filler improves physical properties such as shrinkage rate, elastic modulus, thermal conductivity, and conductivity of the crosslinked cyclic olefin polymer.
Grades such as the particle size, shape, aspect ratio, and quality of the filler are appropriately determined depending on the physical properties of the crosslinked cyclic olefin polymer. The amount of these fillers to be used is preferably 400 parts by mass or less, more preferably 300 parts by mass or less, relative to 100 parts by mass of (a) the cyclic olefin monomer.

  Specific examples of the release lubricant include silicone oil and zinc stearate. One or more of these are used in combination.

  Preferred stabilizers are phenolic stabilizers, phosphorus stabilizers and hindered amine light stabilizers. Specific examples of the phenol-based stabilizer include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-tert-butyl-4 -Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5 · 5] undecane, 2,6-di-tert-butyl- 4-methylphenol and the like. One or more of these are used in combination.

  Specific examples of phosphorus stabilizers include 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methyl. Phenyl] ethyl ester phosphite, bis- (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, distearyl [(3 , 5-Di-tert-butyl-4-hydroxyphenyl) methyl] phosphonate, diethyl {[(3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) methyl] phosphonate}, 6- [3 -(3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert-butyldiben [D, f] [1,3,2] - a dioxaphosphepine, bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite and the like. One or more of these are used in combination.

  Specific examples of the hindered amine light stabilizer include 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl- 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1- (4-t-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy -2,2,6,6-tetramethylpiperidine, 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6 Pentamethylpiperidine, 1,2,2,6,6-pentamethylpiperidin-4-yl-β (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, Zir-2,2,6,6-tetramethyl-4-piperidinyl maleate, (di-2,2,6,6-tetramethylpiperidin-4-yl) -adipate, (di-2 , 2,6,6-tetramethylpiperidin-4-yl) -sebacate, (di-1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) -sebacate, (di- 1-allyl-2,2,6,6-tetramethyl-piperidin-4-yl) -phthalate, 1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-acetate, trimellitic acid- Tri- (2,2,6,6-tetramethylpiperidin-4-yl) ester, 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine, dibutyl-malonic acid-di- ( 1,2,2,6,6-pentamethyl-piperidin-4-yl) -ester, dibenzyl-malonic acid-di- (1,2,3,6-tetramethyl-2,6-diethyl-piperidine-4- Yl) -ester, dimethyl-bis- (2,2,6,6-tetramethylpiperidine-4-oxy) -silane, tris- (1-propyl-2,2,6,6-tetramethylpiperidine-4- Yl) -phosphite, tris- (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) -phosphate, N, N′-bis- (2,2,6,6-tetramethyl) Piperidin-4-yl) -hexamethylene-1,6-diamine, N, N′-bis- (2,2,6,6-tetramethylpiperidin-4-yl) -hexamethylene-1,6-diacetamide 1-acetyl- -(N-cyclohexylacetamide) -2,2,6,6-tetramethyl-piperidine, 4-benzylamino-2,2,6,6-tetramethylpiperidine, N, N'-bis- (2,2, 6,6-tetramethylpiperidin-4-yl) -N, N′-dibutyl-adipamide, N, N′-bis- (2,2,6,6-tetramethylpiperidin-4-yl) -N, N '-Dicyclohexyl- (2-hydroxypropylene), N, N'-bis- (2,2,6,6-tetramethylpiperidin-4-yl) -p-xylylene-diamine, 4- (bis-2-hydroxy Ethyl) -amino-1,2,2,6,6-pentamethylpiperidine, 4-methacrylamide-1,2,2,6,6-pentamethylpiperidine, α-cyano-β-methyl-β- [N -(2,2,6 4-6-tetramethylpiperidin-4-yl)] - amino - methyl acrylate and the like. One or more of these are used in combination.

  The kind and amount of these stabilizers are appropriately selected depending on conditions such as mechanical properties at high temperature, film forming workability, and storage stability of the crosslinked cyclic olefin polymer. The usage-amount of a stabilizer is 20 mass parts or less normally with respect to 100 mass parts of (a) cyclic olefin monomers.

  In obtaining the crosslinked cyclic olefin resin film of the present invention, at least a polymerization comprising (a) a cyclic olefin monomer, (b) an aromatic vinyl polymer, (c) a polymerization catalyst, and additives used as necessary. The composition is metathesis polymerized. (C) The polymerization catalyst is used after being dissolved or suspended in a small amount of an inert solvent, if necessary. Specific examples of the solvent include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin, and mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, Alicyclic hydrocarbons such as diethylcyclohexane, decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; and alicyclic rings such as indene and tetrahydronaphthalene Hydrocarbons having an aromatic ring; Nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; Oxygen-containing hydrocarbons such as diethyl ether, tetrahydrofuran, cyclopentanone and cyclohexanone And the like. Preferred solvents are oxygen-containing hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and hydrocarbons having an alicyclic ring and an aromatic ring. (C) A liquid anti-aging agent or plasticizer that does not decrease the activity as a polymerization catalyst may be used as a solvent.

  The viscosity at room temperature of the polymerizable composition containing (a) a cyclic olefin monomer, (b) an aromatic vinyl polymer, (c) a polymerization catalyst, and an additive used as necessary is also the desired film thickness. However, 0.4 to 500 mPa · s is preferable. It becomes easy to form in a film shape because a viscosity exists in said preferable range. The viscosity of the polymerizable composition is adjusted by the type and amount of (a) cyclic olefin monomer and (b) polymer.

  A specific example of the method for bulk polymerization of the polymerizable composition to form into a film shape is a method of coating the polymerizable composition on a support and bulk polymerization.

  General known materials such as resin and glass are selected as the support. Specific examples of the resin include polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polyarylate; polycarbonates; polyolefins such as polypropylene and polyethylene; polyamides such as nylon; fluororesins such as polytetrafluoroethylene; Is preferred. A preferable shape of the support is a drum or a belt if the material is a resin. A preferred support is a resin film that is easily available and inexpensive.

  If necessary, the polymerizable composition is heated to a temperature at which (c) the polymerization catalyst exhibits activity, and bulk polymerization is performed. The polymerization temperature is usually 0 to 250 ° C, preferably 20 to 200 ° C. The method for heating the polymerizable composition is not particularly limited. Specific examples of the heating method include a method of heating on a heating plate, a method of heating (hot pressing) while applying pressure using a press, a method of pressing with a heated roller, and a method of using a heating furnace. The polymerization reaction time is appropriately determined depending on the amount of (c) the polymerization catalyst and the heating temperature, but is usually 1 minute to 24 hours.

 The cyclic olefin polymer is crosslinked. Crosslinking is performed after polymerization or simultaneously with polymerization. Crosslinking carried out simultaneously with the polymerization is more preferable because the crosslinked cyclic olefin resin film of the present invention can be obtained industrially advantageously with fewer steps.

  Specific examples of the crosslinking method include: (A) (a) a method in which a crosslinkable monomer is used as at least a part of the cyclic olefin monomer and polymerized to obtain a polymer having a three-dimensional crosslinked structure; (B) the above composition A bulk polymerization is carried out by adding a crosslinking agent to the polymer, and a crosslinking reaction is carried out by carrying out a crosslinking reaction simultaneously with or after the polymerization; (C) a cyclic olefin polymer is irradiated with light or an electron beam and subjected to a crosslinking reaction after the polymerization. Cross-linking method; One of these methods may be used, or two or more methods may be used in combination. The method (A) is preferable from the viewpoint of easy control of physical properties of the film and economical efficiency.

  The (a) cyclic olefin monomer having two or more carbon-carbon double bonds is used as the crosslinkable monomer used in the method (A). Specific examples of the cyclic olefin monomer include dicyclopentadiene and tricyclopentadiene. The crosslinking density can be controlled by the amount of the crosslinking monomer used and the heating temperature during polymerization. The amount of the crosslinkable monomer used is not particularly limited because appropriate crosslink density varies depending on the use of the film. A preferable use amount of the crosslinkable monomer is 0.1 to 100 mol% in a ratio of the crosslinkable monomer in the total amount of the cyclic olefin monomer.

  A known thermal crosslinking agent and photocrosslinking agent are used as the crosslinking agent used in the method (B). Preferred thermal crosslinking agents are radical generators such as organic peroxides, diazo compounds, and nonpolar radical generators. The amount of the crosslinking agent to be used is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of (a) the cyclic olefin monomer. The temperature at which crosslinking is performed when a thermal crosslinking agent is used is usually 100 to 250 ° C, preferably 150 to 200 ° C. The time for crosslinking is not particularly limited, but is usually from several minutes to several hours.

  The bulk polymerization and crosslinking in the present invention are preferably performed in the absence of oxygen and water. Specific examples of the bulk polymerization and crosslinking method include (1) a method of bulk polymerization and crosslinking in an inert gas atmosphere such as nitrogen gas and argon gas, and (2) a method of bulk polymerization and crosslinking under vacuum, (3 ) A method of performing bulk polymerization and crosslinking in a state where the composition coated on the support is covered with a resin film and sealed. Specific examples of the resin film are those exemplified as the support. When bulk polymerization and crosslinking are performed in the presence of oxygen or water, the surface of the resulting film may be oxidized, making it difficult to exhibit desired flexibility.

  The thickness of the crosslinked cyclic olefin resin film of the present invention has various appropriate values depending on the application and is not particularly limited, but is usually 0.5 to 5,000 μm, which is preferable from the viewpoint of handling properties. The thickness is 5 to 500 μm. The surface of the crosslinked cyclic olefin resin film of the present invention may be smooth, but by embossing, processing by being sandwiched by a substrate such as a polyethylene terephthalate film having unevenness, and processing to give the surface an uneven shape, etc. An uneven shape may be formed.

In the laminate of the present invention, the crosslinked cyclic olefin resin film and (d) metal foil are bonded.
The cross-linked cyclic olefin resin film and (d) the metal foil are brought into contact with the cross-linked cyclic olefin resin film, and then heated and pressurized to bond both to produce the laminate of the present invention. The crosslinked cyclic olefin resin film and (d) metal foil may be hot pressed together with other materials such as metal plates and metal parts. The hot press pressure is usually 0.5 to 20 MPa, preferably 1 to 10 MPa. The hot pressing may be performed under vacuum or under reduced pressure. The hot pressing can be performed by a known press having a press frame mold for flat plate molding, a sheet molding compound (SMC), a bulk mold compound (BMC) or the like.

Specific examples of the metal foil (d) are copper foil, gold foil, silver foil, stainless steel foil, aluminum foil, nickel foil, chrome foil, and the like. Among these, copper foil is preferable.
The other materials are not limited to specific ones. Specific examples of the other materials include resins such as polyethylene, polypropylene, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, polyarylate, and nylon; iron, stainless steel, copper, aluminum, nickel, 42 alloy, chromium, gold, silver, and the like. Metal. Another preferred material is a metal. The shape of other materials is not limited. Preferred shapes of other materials are metal plates, metal parts, metal frames and the like. In addition, (d) When metal foil is copper foil, copper foil with resin (Resin Coated Copper (RCC)) is obtained. (D) The preferable thickness of the metal foil is usually 1 to 150 μm, preferably 2 to 100 μm, more preferably 3 to 75 μm from the viewpoint of workability and the like. The metal plate and the metal frame which are preferable as other materials are made of copper subjected to nickel-palladium-gold plating or the like (copper plated in the order of nickel, palladium and gold from the outermost layer). The copper plate and copper frame are excellent in heat resistance and corrosion resistance. The thicknesses of the metal plate and the metal frame are appropriately set.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. Unless otherwise indicated, the part and% in an Example and a comparative example are a mass reference | standard.

Examples 1-19 and Comparative Examples 1-2
An aromatic vinyl polymer, a phenol-based stabilizer, a phosphorus-based stabilizer, and a hindered amine-based light stabilizer shown in Tables 1 to 3 are mixed into a norbornene-based monomer mixture solution including 90 parts of dicyclopentadiene and 10 parts of tricyclopentadiene. Dissolved to obtain a reaction stock solution. Next, a ruthenium catalyst having the structure of the mass (7) shown in Tables 1 to 3 is added to the reaction stock solution, mixed with a line mixer, and a polyethylene terephthalate carrier having a thickness of 0.075 mm at 25 ° C. The film was coated on the film and cast to form a film, and then immediately the same carrier film prepared separately from above the coating layer was laminated. Then, after heating for 3 minutes at 200 degreeC and cooling to 20 degreeC after that, the upper and lower carrier films were peeled off, respectively, and the crosslinked cyclic olefin resin film was obtained.

  Next, using a corona treatment device (high-frequency power source; CT-0212 manufactured by Kasuga Electric Co., Ltd., transmitter body; CT-0212 manufactured by Kasuga Electric Co., Ltd., high-voltage transformer; CT-T022 manufactured by Kasuga Electric Co., Ltd.) Adjusting the distance between the surface of the crosslinked cyclic olefin resin film and the electrode of the corona treatment device to 2 mm, conditions of output 0.15 kW, line speed 0.5 m / min, ambient temperature 23 ° C., ambient relative humidity 55% RH Thus, the front and back surfaces of the crosslinked cyclic olefin resin films of Examples 12 to 19 were each subjected to corona treatment once.

  A cross-linked cyclic olefin resin film of 300 mm × 300 mm that has not been subjected to corona treatment or has been subjected to a corona treatment is placed on a copper plate having the same size and a thickness of 0.1 mm, and an electrolytic copper foil of the same size ( Furukawa Electric Co., Ltd., surface GTS treatment, thickness 0.018 mm) was placed on the film so that the roughened surface of the copper foil was in contact with the film. The obtained copper plate / resin film / copper foil laminate was inserted into a vacuum press, thermocompression bonded at a surface pressure of 9.0 MPa, 180 ° C. for 60 minutes, and then cooled to 20 ° C. to obtain a sample obtained from the vacuum press. It took out and obtained the laminated body by which the copper plate, the bridge | crosslinking cyclic olefin resin film, and the copper foil were adhere | attached and laminated | stacked in this order, respectively. Then, the copper foil adhesive force of the crosslinked cyclic olefin resin film was measured as follows. A laminate of the crosslinked cyclic olefin resin film and the copper foil was cut into a size of 10 mm × 150 mm to obtain a test piece, and the 180 degree adhesive strength of the crosslinked cyclic olefin resin film to the copper foil in the test piece was JIS K 6854- Measured according to 2. The maximum adhesive force obtained by the measurement was defined as the adhesive strength against copper foil. The results are shown in Tables 1-3.

1) IRGANOX1076 manufactured by BASF Japan
2) Adeka Stub HP-10 manufactured by ADEKA Corporation
3) TINUVIN770 manufactured by BASF Japan
4) PS Japan PSJ-polystyrene GPPS HF77
5) DYLARK D232 made by NOVA Chemicals Japan Ltd.
6) NOF Corporation Modiper (registered trademark) A4100
7) VC843 (1.8% cyclopentanone solution of ruthenium catalyst) manufactured by RIMTEC Co., Ltd.

  The adhesive strength to copper foil of the crosslinked cyclic olefin resin films obtained from the polymerizable compositions of Examples 1 to 19 was high.

  The adhesive strength to copper foil of the crosslinked cyclic olefin resin film obtained from the polymerizable composition of Comparative Example 1 containing no aromatic vinyl polymer was low. Since the crosslinked cyclic olefin resin film obtained from the polymerizable composition of Comparative Example 2 having a too high content of the aromatic vinyl polymer was very brittle and the upper and lower carrier films could not be peeled cleanly, The surface could not be corona-treated, and the adhesive strength against copper foil could not be measured.

  The crosslinked cyclic olefin resin film of the present invention is suitably used as various electronic materials, and in particular, is suitably used for sealing materials such as coils, capacitors, and semiconductors, flexible substrates, multilayer circuit boards, LED substrates, and the like.

Claims (11)

  (A) 100 parts by mass of a cyclic olefin monomer, (b) 0.05 to 15 parts by mass of an aromatic vinyl polymer, and (c) a polymerizable composition containing a polymerization catalyst is applied onto a substrate, and then metathesis polymerization. Then, a crosslinked cyclic olefin resin film obtained by peeling the obtained film polymer from the substrate.   The crosslinked cyclic olefin resin film according to claim 1, wherein the (a) cyclic olefin monomer is a norbornene-based monomer.   The crosslinked cyclic olefin resin film according to claim 1 or 2, wherein the polymerization catalyst (c) is a ruthenium carbene complex.   The crosslinked cyclic olefin resin film according to any one of claims 1 to 3, wherein one side or both sides are corona-treated.   The laminated body by which the bridge | crosslinking cyclic olefin resin film described in any one of Claims 1-4 and (d) metal foil were adhere | attached.   The laminate according to claim 5, wherein the (d) metal foil is a copper foil.   The laminate according to claim 6, which is for a flexible printed board. (A) 100 parts by mass of a cyclic olefin monomer, (b) 0.05 to 15 parts by mass of an aromatic vinyl polymer, and (c) a polymerizable composition containing a polymerization catalyst is applied onto a substrate, and then metathesis polymerization. And then peeling the obtained film polymer from the substrate to obtain a crosslinked cyclic olefin resin film, and
The manufacturing method of a laminated body by which the said crosslinked cyclic olefin resin film and (d) metal foil are made to contact, and the process which heats and then adhere | attaches after pressing is implemented.   The method for producing a laminate according to claim 8, wherein the (a) cyclic olefin monomer is a norbornene-based monomer.   The method for producing a laminate according to claim 8 or 9, wherein the polymerization catalyst (c) is a ruthenium carbene complex.   The manufacturing method of the laminated body described in any one of Claims 8-10 whose said (d) metal foil is copper foil.