JP2014024963A - 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) a cycloolefin monomer and (c) a polymerization catalyst atop a substrate, subsequently by metathetically polymerizing the composition, subsequently by peeling the obtained filmy polymer from the substrate, and by irradiating the film surface with ultraviolet rays.

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 inventors of the present invention applied a polymerizable composition containing (a) a cyclic olefin monomer and (c) a polymerization catalyst on a substrate, followed by metathesis polymerization, and then obtained. It was found that the crosslinked cyclic olefin resin film obtained by peeling the film-like polymer from the substrate and irradiating the surface with ultraviolet rays has 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 is obtained by applying a polymerizable composition containing (a) a cyclic olefin monomer and (c) a polymerization catalyst onto a substrate, followed by metathesis polymerization, and then the obtained film-like weight. It is obtained by peeling the coalesced from the substrate and irradiating the surface with ultraviolet rays. The polymerizable composition preferably further comprises (a) 0.01 to 2 parts by mass of (b) a carbon-carbon double bond in one molecule with respect to 100 parts by mass of the cyclic olefin monomer. An aliphatic carboxylic acid having 8 to 20 carbon atoms or an aliphatic carboxylic acid having 6 to 14 carbon atoms having no carbon-carbon double bond and two or more carboxyl groups in one molecule (hereinafter referred to as “(b) fat”. Group carboxylic acid "). The preferable (a) cyclic olefin monomer is a norbornene monomer. Preferred (b) aliphatic carboxylic acid is an aliphatic carboxylic acid having 8 to 20 carbon atoms having a carbon-carbon double bond at the molecular end. A preferable polymerization catalyst (c) is a ruthenium carbene complex.

  In the laminate of the present invention, the crosslinked cyclic olefin resin film and the metal foil (d) are bonded to each other on the surface of the crosslinked cyclic olefin resin film irradiated with ultraviolet rays. 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, after the polymerizable composition is applied on a substrate, metathesis polymerization is performed, and then the obtained film-like polymer is peeled from the substrate, and ultraviolet light is applied to the surface. Irradiation to obtain a crosslinked cyclic olefin resin film, and the crosslinked cyclic olefin resin film and (d) the metal foil are brought into contact with the surface of the crosslinked cyclic olefin resin film irradiated with ultraviolet rays, and then pressurized. A step of heating and bonding the two is performed.

  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 the crosslinked cyclic olefin resin film of the present invention is obtained, at least a polymerizable composition containing (a) a cyclic olefin monomer and (c) a polymerization catalyst is applied on a substrate, and then metathesis polymerized to form a film. It is necessary to obtain a polymer. (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 includes a step of metathesis-polymerizing a polymerizable composition containing (a) a cyclic olefin monomer and (c) a polymerization catalyst into a film shape in the presence of an additive used as necessary.
(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 has, as necessary, (b) an aliphatic carboxylic acid having 8 to 20 carbon atoms or a carbon-carbon double bond having at least one carbon-carbon double bond in one molecule. It contains C6-C14 aliphatic carboxylic acid which has 2 or more carboxyl groups in 1 molecule.

  Specific examples of the aliphatic carboxylic acid having 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule include 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid ( Undecylenic acid), 11-dodecenoic acid, 12-tridecenoic acid, 13-tetradecenoic acid, 14-pentadecenoic acid, 15-hexadecenoic acid, 16-heptadecenoic acid, 17-octadecenoic acid, 18-nonadecenoic acid, etc. C8-20 aliphatic carboxylic acid having a carbon double bond; myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, linoleic acid, eicosadienoic acid, linolenic acid, pinolenic acid , Carbon having carbon-carbon double bonds in addition to molecular ends, such as eleostearic acid, mead acid, eicosatrienoic acid Aliphatic carboxylic acid having 8 to 20; 1,3 diallyl monocarboxylic isocyanuric acid, isocyanuric acids such as 1,3-carboxyl monoallyl isocyanuric acid, an the like.

Specific examples of the aliphatic carboxylic acid having 6 to 14 carbon atoms having no carbon-carbon double bond and two or more carboxyl groups in one molecule are adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid Etc.
(B) One or more aliphatic carboxylic acids can be used. Preferred (b) aliphatic carboxylic acid is an aliphatic carboxylic acid having 8 to 20 carbon atoms having a carbon-carbon double bond at the molecular end.

  (B) The amount of the aliphatic carboxylic acid is preferably 0.01-2 parts by mass, more preferably 0.2-2 parts by mass, and still more preferably 100 parts by mass of the (a) cyclic olefin monomer. 0.3 to 2 parts by mass, particularly preferably 0.5 to 2 parts by mass. (B) When the compounding quantity of aliphatic carboxylic acid exists in said range, the adhesive improvement effect with respect to a metal material is acquired, and there is also no possibility that a polymerization reaction may be inhibited.

  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. The mold release lubricant improves the moldability, mold release and handling properties of the film and imparts functions such as lubricant properties to the film. The amount of the release lubricant used is preferably 200 parts by mass or less with respect to 100 parts by mass of the (a) cyclic olefin monomer.

  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.

  When obtaining the crosslinked cyclic olefin resin film of the present invention, at least a polymerizable composition containing (a) a cyclic olefin monomer, (c) a polymerization catalyst, and an additive used as necessary is metathesized to form a film. It is necessary to obtain a polymer. (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 composition containing (a) a cyclic olefin monomer, (c) a polymerization catalyst, and additives used as necessary depends on the desired film thickness, but is 0.4 to 500 mPa · s. preferable. It becomes easy to form in a film shape because a viscosity exists in said preferable range. The viscosity of the said composition is adjusted with the kind and usage-amount of (a) cyclic olefin monomer.

  A specific example of a method for obtaining a film polymer by bulk polymerization of the above composition is a method in which the above composition is applied on a substrate and subjected to bulk polymerization.

  General known materials such as resin and glass are selected as the substrate. 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 substrate is a drum or a belt if the material is resin. A preferable base material is a resin film that is easily available and inexpensive.

  If necessary, the 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 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. The preferable use amount of the crosslinkable monomer is 0.1 to 100 mol% in the ratio of the crosslinkable monomer in the total amount of the (a) 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 a substrate is covered with a resin film and sealed. Specific examples of the resin film are those exemplified as the substrate. 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 film-like polymer obtained by applying the above composition on a substrate and bulk polymerization is peeled off from the substrate, and one or both surfaces thereof are irradiated with ultraviolet rays, whereby the crosslinked cyclic olefin resin of the present invention. A film is obtained. The conditions for irradiating ultraviolet rays are not limited to a specific range.
The preferable wavelength of the ultraviolet rays applied to the film polymer is 243 nm or less. Specific examples of an ultraviolet light source having a wavelength of 243 nm or less include an Ar excimer laser (126 nm), a Kr excimer laser (146 nm), an Xe excimer laser (172 nm), a KrCl excimer laser (222 nm), an ArF excimer laser (193 nm), and a Kr excimer. A lamp (126 nm), a Xe excimer lamp (172 nm), a KrCl excimer lamp (222 nm), an ArF excimer lamp (193 nm), a low-pressure mercury lamp (185 nm), etc. (in parentheses represent the main wavelengths of the respective light sources). Among these, a lamp light source having a wavelength of 170 to 190 nm is preferable, and an Xe excimer lamp is particularly preferable.

  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 the metal foil (d) are bonded to each other on the surface of the crosslinked cyclic olefin resin film irradiated with ultraviolet rays. The preferred (d) metal foil is a copper foil. The laminate of the present invention is preferably used for a flexible printed board.

  The cross-linked cyclic olefin resin film of the present invention and (d) the metal foil are brought into contact with the surface of the cross-linked cyclic olefin resin film irradiated with ultraviolet rays, and then heated while applying pressure to adhere both to produce a laminate. Is done. The crosslinked cyclic olefin resin film of the present invention and (d) the metal foil may be hot pressed together with other materials such as a metal plate 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 1-9 and Comparative Examples 1-2
Aliphatic carboxylic acid, phenolic stabilizer, phosphorus stabilizer and hindered amine light stabilizer shown in Table 1 and Table 2 are dissolved in a norbornene monomer mixture composed of 90 parts of dicyclopentadiene and 10 parts of tricyclopentadiene. The reaction stock solution was obtained. Next, a ruthenium catalyst having the structure of mass (7) shown in Table 1 and Table 2 is added to the reaction stock solution, mixed with a line mixer, and made of polyethylene terephthalate having a thickness of 0.075 mm at 25 ° C. The coating was carried out on the carrier film to form a cast 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, in Examples 1 to 9, the distance between the surface of the crosslinked cyclic olefin resin film and the excimer lamp L11751 manufactured by Hamamatsu Photonics Co., Ltd. was adjusted to 2 mm, the output was 0.25 kW, the emission wavelength was 172 nm, The cross-linked cyclic olefin resin film irradiated with ultraviolet rays was obtained by irradiating the front and back surfaces of the cross-linked cyclic olefin resin film once each under the conditions of an irradiation time of 30 seconds, an ambient temperature of 23 ° C., and an ambient relative humidity of 55% RH. It was.
In each of Examples 1 to 9 and Comparative Example 1, adhesive strength to copper foil of the finally obtained crosslinked cyclic olefin resin film was measured as follows.

  A 300 mm x 300 mm cross-linked cyclic olefin resin film is placed on a copper plate of the same size with a thickness of 0.1 mm whose surface has been etched, and an electrolytic copper foil of the same size (manufactured by 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 and 2.

1) IRGANOX1076 manufactured by BASF Japan
2) Adeka Stub HP-10 manufactured by ADEKA Corporation
3) TINUVIN770 manufactured by BASF Japan
4) Ito Oil Co., Ltd. 5) Ito Oil Co., Ltd. 6) Wako Pure Chemical Industries, Ltd. 7) Wako Pure Chemical Industries, Ltd. 8) RIMTEC Corporation's VC843 (ruthenium catalyst 1. 8% cyclopentanone solution)

  The adhesive strength to copper foil of the crosslinked cyclic olefin resin films obtained from the polymerizable compositions of Examples 1 to 9 was high.

  The adhesive strength to copper foil of the crosslinked cyclic olefin resin film obtained from the polymerizable composition of Comparative Example 1 which was not irradiated with ultraviolet rays was low. Moreover, the cyclic olefin resin film obtained from the polymerizable composition of Comparative Example 2 was not sufficiently cured, and the upper and lower carrier films could not be peeled cleanly. Therefore, ultraviolet rays were not irradiated and the adhesive strength of the cyclic olefin resin film to 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 (13)

  After applying a polymerizable composition containing (a) a cyclic olefin monomer and (c) a polymerization catalyst onto a substrate, metathesis polymerization is performed, and then the obtained film-like polymer is peeled from the substrate, A crosslinked cyclic olefin resin film obtained by irradiating the surface with ultraviolet rays.   The polymerizable composition further comprises (a) 0.01 to 2 parts by mass of (b) 100 parts by mass of the cyclic olefin monomer, and (b) 8 carbon atoms having at least one carbon-carbon double bond in one molecule. 2 to 20 aliphatic carboxylic acids or 6 to 14 carbon carboxylic acids having 2 or more carboxyl groups in one molecule without carbon-carbon double bonds. Cross-linked cyclic olefin resin film.   The crosslinked cyclic olefin resin film according to claim 1 or 2, wherein the (a) cyclic olefin monomer is a norbornene-based monomer.   The bridge | crosslinking as described in any one of Claims 1-3 whose said (b) aliphatic carboxylic acid is C8-C20 aliphatic carboxylic acid which has a carbon-carbon double bond in the molecular terminal. Cyclic olefin resin film.   The crosslinked cyclic olefin resin film described in any one of claims 1 to 4, wherein the polymerization catalyst (c) is a ruthenium carbene complex.   The laminated body by which the bridge | crosslinking cyclic olefin resin film described in any one of Claims 1-5 and (d) metal foil are adhere | attached on the surface irradiated with the ultraviolet-ray of the said bridge | crosslinking cyclic olefin resin film.   The laminate according to claim 6, wherein the metal foil (d) is a copper foil.   The laminate according to claim 7, which is for a flexible printed board. After applying a polymerizable composition containing (a) a cyclic olefin monomer and (c) a polymerization catalyst onto a substrate, metathesis polymerization is performed, and then the obtained film-like polymer is peeled from the substrate, A first step of obtaining a crosslinked cyclic olefin resin film by irradiating the surface with ultraviolet rays,
A second step is performed in which the crosslinked cyclic olefin resin film and (d) the metal foil are brought into contact with the surface of the crosslinked cyclic olefin resin film irradiated with ultraviolet light, and then heated while being pressed to bond them together. The manufacturing method of a laminated body.   The polymerizable composition further includes (a) 0.01 to 2 parts by mass with respect to 100 parts by mass of the cyclic olefin monomer, and (b) 8 carbon atoms having at least one carbon-carbon double bond in one molecule. The aliphatic carboxylic acid having 6 to 14 carbon atoms having no more than -20 aliphatic carboxylic acids or carbon-carbon double bonds and having two or more carboxyl groups in one molecule. The manufacturing method of the laminated body.   The method for producing a laminate according to claim 9 or 10, wherein the (a) cyclic olefin monomer is a norbornene-based monomer.   The manufacturing method of the laminated body described in any one of Claims 9-11 whose said (c) polymerization catalyst is a ruthenium carbene complex.   The manufacturing method of the laminated body described in any one of Claims 9-12 whose said (d) metal foil is copper foil.