JP2014136350A - Laminate and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate obtained by adhering, to a metallic foil, a crosslinked cycloolefin resin film including a crosslinked cycloolefin resin and having an excellent adhesiveness to a metallic material.SOLUTION: The provided laminate is obtained by coating, atop a substrate, a polymerizable composition including (a) 100 parts.mass of a cycloolefin monomer, (b) 0.3-20 parts.mass of a (meth)acrylic acid ester monomer, and (c) a ring-opening metathesis polymerization catalyst and, following the metathesis polymerization of the latter, by laminating, onto a metallic foil, a crosslinked cycloolefin resin film obtained by releasing, from the substrate, the resulting filmy polymer.

Description

  The present invention relates to a laminate in which a cross-linked cyclic olefin resin film having excellent adhesion to a metal material and a metal foil are adhered, 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 has become.

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

JP 2009-255380 A

Recently, there has been a demand for a laminate comprising a cross-linked cyclic olefin resin obtained by metathesis polymerization of a cyclic olefin monomer and having a cross-linked cyclic olefin resin film having excellent adhesion to a metal material and a metal foil adhered thereto. No such laminate has been found.
The problem to be solved by the present invention is to provide a laminate in which a crosslinked cyclic olefin resin film containing a crosslinked cyclic olefin resin and excellent in adhesion to a metal material is bonded to a metal foil, and a method for producing the laminate. is there.

  As a result of intensive studies, the inventor of the present invention has found on the substrate a polymerizable composition containing (a) a cyclic olefin monomer, (b) a (meth) acrylic acid ester monomer, and (c) a ring-opening metathesis polymerization catalyst. After coating, metathesis polymerization is performed, and then the obtained film-like polymer is peeled off from the substrate, and the crosslinked cyclic olefin resin film obtained is found to have excellent adhesion to a metal material. It came to complete the laminated body to which the crosslinked cyclic olefin resin film of this and metal foil were adhere | attached, and the manufacturing method of the said laminated body.

  The laminate of the present invention has a polymerizable composition containing (a) 100 parts by mass of a cyclic olefin monomer, (b) 0.3 to 20 parts by mass of a (meth) acrylic acid ester monomer, and (c) a ring-opening metathesis polymerization catalyst. After the product is coated on the substrate, metathesis polymerization is performed, and then the obtained film-like polymer is peeled from the substrate, and the crosslinked cyclic olefin resin film and (d) metal foil are bonded.

  The preferable (a) cyclic olefin monomer is a norbornene monomer. The preferred (c) ring-opening metathesis polymerization catalyst is a ruthenium carbene complex.

  The preferred (d) metal foil is a copper foil. The laminate of the present invention is preferably used for a flexible printed board.

  The manufacturing method of the laminated body of this invention contains (a) 100 mass parts of cyclic olefin monomers, (b) (meth) acrylic acid ester monomer 0.3-20 mass parts, and (c) ring-opening metathesis polymerization catalyst. 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 to obtain a crosslinked cyclic olefin resin film, and the crosslinked cyclic olefin resin. The film and (d) the metal foil are brought into contact with each other, and thereafter, a step of heating the film while applying pressure to bond them together is performed.

  The preferable (a) cyclic olefin monomer is a norbornene monomer. The preferred (c) ring-opening metathesis polymerization catalyst is a ruthenium carbene complex. The preferred (d) metal foil is a copper foil.

  In the laminate of the present invention, a crosslinked cyclic olefin resin film having excellent adhesion to a metal material and a metal foil are bonded.

(A) The cyclic olefin monomer that is one of the raw materials of the crosslinked cyclic olefin resin film provided in the laminate of the present invention has a ring structure formed of carbon atoms, and a carbon-carbon double bond is formed in the ring. It is a compound that has. 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 provided in the laminate of the present invention, polymerization containing at least (a) a cyclic olefin monomer, (b) a (meth) acrylate monomer, and (c) a ring-opening metathesis polymerization catalyst. The composition is metathesis polymerized. (C) The ring-opening metathesis polymerization catalyst metatheses (a) a cyclic olefin monomer. The (c) ring-opening metathesis 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) ring-opening metathesis 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) ring-opening metathesis polymerization catalyst is a group 8 ruthenium or osmium complex, and a particularly preferred (c) ring-opening metathesis polymerization catalyst is a ruthenium carbene complex. Since the ruthenium carbene complex is excellent in catalytic activity during bulk polymerization, there are few residual unreacted monomers, and a crosslinked cyclic olefin polymer 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 (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 (I) Org. Lett. 1999, Vol. 1, p. 953, (II) Tetrahedron. Lett. 1999, Vol. 40, page 2247, (III) International Publication No. 2003/062253 pamphlet and the like.

  The amount of the (c) ring-opening metathesis polymerization catalyst used is usually a molar ratio of ((c) metal atom in the ring-opening metathesis polymerization catalyst: (a) cyclic olefin monomer) and is usually (1: 2,000) to ( 1: 2,000,000), preferably (1: 5,000) to (1: 1,000,000), more preferably (1: 10,000) to (1: 500,000). is there. (C) When the amount of the ring-opening metathesis polymerization catalyst is not less than the above lower limit, the residual monomer in the polymer due to a decrease in the polymerization reaction rate, and the decrease in the degree of crosslinking of the crosslinked polymer can be suppressed, The heat resistance of the obtained film can be improved. (C) When the amount of the ring-opening metathesis polymerization catalyst is not more than the above upper limit, the production cost can be suppressed, and the reaction rate is prevented from becoming too fast, and film formation at the time of bulk polymerization described later is facilitated. It can be carried out.

(C) The ring-opening metathesis 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: 1 :) in a molar ratio of ((c) metal atom in ring-opening metathesis polymerization catalyst: activator). 0.2) to (1:20), more preferably (1: 0.5) to (1:10).

  (C) The ring-opening metathesis 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 (c) ring-opening metathesis polymerization catalyst.

  In the production of the crosslinked cyclic olefin resin film, the polymerization method may be either a solution polymerization method or a bulk polymerization method, but from the viewpoint that a solvent removal step is unnecessary and the film can be formed simultaneously with the polymerization. A polymerization method is preferred.

In the bulk polymerization method, a polymerizable composition containing (a) a cyclic olefin monomer, (b) a (meth) acrylic acid ester monomer, and (c) a ring-opening metathesis polymerization catalyst is used in the presence of an additive used as necessary. A step of metathesis polymerization.
(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 provided in the laminate of the present invention contains (b) (meth) acrylic acid ester monomer.

  (B) Specific examples of (meth) acrylic acid ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n- Butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, cyclohexyl Acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl Methacrylate, n- decyl acrylate, n- decyl methacrylate, n- dodecyl acrylate, n- dodecyl methacrylate, n- tridecyl acrylate, n- tridecyl methacrylate. Among them, (meth) acrylic acid alkyl ester monomers are preferable, (meth) acrylic acid alkyl ester monomers having 2 to 12 carbon atoms are more preferable, and (meth) acrylic acid alkyl ester monomers having 4 to 8 carbon atoms are more preferable. N-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred. One or more (b) (meth) acrylic acid ester monomers are used.

  The said polymerizable composition contains 0.3-20 mass parts (b) (meth) acrylic acid ester monomer with respect to 100 mass parts (a) cyclic olefin monomer. The preferable content of the (b) (meth) acrylic acid ester monomer with respect to 100 parts by mass of the (a) cyclic olefin monomer is 0.5 to 15 parts by mass, and the more preferable content is 5 to 15 parts by mass. (B) When there is too little content of a (meth) acrylic acid ester monomer, the adhesive force with respect to the metal foil of a crosslinked cyclic olefin resin film will fall. On the other hand, when there is too much content of (b) (meth) acrylic acid ester monomer, a crosslinked cyclic olefin resin film will become too soft.

  The above polymerizable composition, which is a precursor of the crosslinked cyclic olefin resin film of the present invention, for various additives, for the purpose of various properties, film property modification, function addition, and improvement of molding workability according to purposes. It is included in the product. 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 blending 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 compounding quantity of these stabilizers is 20 mass parts or less normally with respect to 100 mass parts of (a) cyclic olefin monomers. (A) The said preferable compounding quantity with respect to 100 mass parts of cyclic olefin monomers is 0.5-5 mass parts, and the said more preferable said compounding quantity is 0.5-3 mass parts.

  When obtaining the crosslinked cyclic olefin resin film provided in the laminate of the present invention, at least (a) a cyclic olefin monomer, (b) a (meth) acrylate monomer, (c) a ring-opening metathesis polymerization catalyst, and The polymerizable composition containing the additive used accordingly is subjected to metathesis polymerization. (C) The ring-opening metathesis polymerization catalyst is used, if necessary, dissolved or suspended in a small amount of an inert solvent. Specific examples of the solvent include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin, 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 ring-opening metathesis polymerization catalyst may be used as a solvent.

  The viscosity at room temperature of the polymerizable composition comprising (a) a cyclic olefin monomer, (b) a (meth) acrylic acid ester monomer, (c) a ring-opening metathesis polymerization catalyst, and an additive used as necessary is a desired value. Although depending on the thickness of the film, 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, (b) (meth) acrylic acid ester monomer, and (c) ring-opening metathesis polymerization catalyst.

  A specific example of a method for bulk polymerization of the polymerizable composition to form a film is a method in which the polymerizable composition is coated on a support and ring-opening metathesis polymerization is performed by bulk polymerization on the support. It is.

  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 ring-opening metathesis 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 ring-opening metathesis polymerization catalyst and the heating temperature, and 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 method of carrying out bulk polymerization by adding a thermal crosslinking agent or a photocrosslinking agent to the polymer, further performing a crosslinking reaction simultaneously with the polymerization or after the polymerization; (C) polymerizing by irradiating the cyclic olefin polymer with light or an electron beam A method of performing a crosslinking reaction later to perform crosslinking; and the like. 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 terms of the ratio of the crosslinkable monomer in the total amount of the (a) cyclic olefin monomer.

  Known thermal crosslinking agents and photocrosslinking agents are used as thermal crosslinking agents and photocrosslinking agents 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 thermal crosslinking agent and the photocrosslinking agent 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 the (a) 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. By performing bulk polymerization and crosslinking in the absence of oxygen or water, the surface of the resulting film is not oxidized, and desired flexibility can be exhibited.

  The thickness of the crosslinked cyclic olefin resin film provided in the laminate of the present invention varies depending on the application and is not particularly limited, but is usually 0.5 to 5,000 μm, from the viewpoint of handling properties. The preferable 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.

The above-mentioned crosslinked cyclic olefin resin film is formed by using a known surface treatment technique such as vapor phase reaction, coating, vacuum deposition, ion plating, sputtering, CVD, electroless plating on a layer made of different materials such as organic, inorganic and metal. It can also be formed on the surface. For example, a film made of a material that improves releasability such as SiO ₂ , MgF ₂ , or fluororesin may be provided on the film surface layer, or surface treatment may be performed with fluorine gas or a CF-based precursor to fluorinate the film surface. it can.
The preferable glass transition temperature of the said crosslinked cyclic olefin resin film is 135 degreeC or more from a viewpoint of heat resistance, sealing performance, and shape followability.

  The above-mentioned crosslinked cyclic olefin resin film and (d) metal foil are brought into contact with each other, and then heated and heated to adhere 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; etc. 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 1-6 and Comparative Examples 1-3
A norbornene-based monomer comprising 90 parts of dicyclopentadiene and 10 parts of tricyclopentadiene having an acrylic ester, a phenol-based stabilizer, a phosphorus-based stabilizer, a hindered amine-based light stabilizer, and triphenylphosphine in the mass shown in Table 1. The reaction stock solution was obtained by dissolving in the mixed solution. Next, a polymerizable composition obtained by adding the ruthenium catalyst having the structure of the formula (7) in the mass shown in Table 1 to the reaction stock solution and mixing with a line mixer is obtained at 25 ° C. with a thickness of 0. The film was coated on a 0.075 mm polyethylene terephthalate carrier film to form a cast film, and immediately thereafter, 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.

  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, heated while pressing at a surface pressure of 9.0 MPa and 180 ° C. for 60 minutes, and then cooled to 20 ° C. to obtain a vacuum. It took out from the press and obtained the laminated body by which the copper plate, the bridge | crosslinking cyclic olefin resin film, and the copper foil were each adhere | attached and laminated | stacked in this order. Then, the copper foil adhesive force of the crosslinked cyclic olefin resin film was measured as follows. A laminate of a copper plate, a crosslinked cyclic olefin resin film, and a copper foil is cut into a size of 10 mm × 150 mm to obtain a test piece, and the 180 ° adhesion force of the crosslinked cyclic olefin resin film to the copper foil in the test piece is JIS K. Measured according to 6854-2. The maximum adhesive force obtained by the measurement was defined as the adhesive strength against copper foil. The results are shown in Table 1.

1) IRGANOX1076 manufactured by BASF Japan
2) Adeka Stub HP-10 manufactured by ADEKA Corporation
3) TINUVIN770 manufactured by BASF Japan
4) Wako Pure Chemical Industries, Ltd. 5) Wako Pure Chemical Industries, Ltd. 6) RIMTEC VC843 (cyclopentanone solution containing 1.8% ruthenium catalyst)

  The adhesive strength to copper foil of the crosslinked cyclic olefin resin films included in the laminates of Examples 1 to 6 was high.

  The adhesive strength to copper foil of the crosslinked cyclic olefin resin film provided in the laminate of Comparative Example 1 obtained from the polymerizable composition containing no (meth) acrylate monomer was low. The crosslinked cyclic olefin resin films of Comparative Examples 2 and 3 obtained from the polymerizable composition having too much content of the (meth) acrylic acid ester monomer are too soft to peel from the carrier film, and the adhesive strength to copper foil Could not be measured.

  The laminate of the present invention is suitably used as various electronic materials, and is particularly suitably used for flexible substrates, multilayer circuit boards, LED substrates and the like.

Claims (9)

  A polymerizable composition containing (a) 100 parts by mass of a cyclic olefin monomer, (b) 0.3 to 20 parts by mass of a (meth) acrylic acid ester monomer, and (c) a ring-opening metathesis polymerization catalyst is applied onto a substrate. After that, metathesis polymerization is performed, and then the obtained film-like polymer is peeled from the substrate, and the crosslinked cyclic olefin resin film and (d) a metal foil are bonded to each other.   The laminate according to claim 1, wherein the (a) cyclic olefin monomer is a norbornene-based monomer.   The laminate according to claim 1 or 2, wherein the (c) ring-opening metathesis polymerization catalyst is a ruthenium carbene complex.    The laminated body as described in any one of Claims 1-3 whose said (d) metal foil is copper foil.   The laminate according to claim 4, which is for a flexible printed circuit board. A polymerizable composition containing (a) 100 parts by mass of a cyclic olefin monomer, (b) 0.3 to 20 parts by mass of a (meth) acrylic acid ester monomer, and (c) a ring-opening metathesis 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 6, wherein the (a) cyclic olefin monomer is a norbornene-based monomer.   The method for producing a laminate according to claim 6 or 7, wherein (c) the ring-opening metathesis polymerization catalyst is a ruthenium carbene complex.   The manufacturing method of the laminated body described in any one of Claims 6-8 whose said (d) metal foil is copper foil.