JP2014162841A - Crosslinked cycloolefin resin composition, crosslinked cycloolefin resin film, laminate, and methods for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crosslinked cyclic olefin resin composition which contains a crosslinked cyclic olefin resin, and provides a crosslinked cyclic olefin resin film having excellent adhesiveness to a metallic material.SOLUTION: The crosslinked cyclic olefin resin composition is obtained by ring-opening metathesis polymerization of a polymerizable composition containing (a) 100 mass parts of a cyclic olefin monomer, (b) 0.01 to 2 mass parts of an aliphatic carboxylic acid of 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule, (c) 1 to 45 mass parts of an inorganic filler, and (d) a catalyst for ring-opening metathesis polymerization.

Description

  The present invention provides a crosslinked cyclic olefin resin composition that gives a crosslinked cyclic olefin resin film having excellent adhesion to a metal material, the crosslinked cyclic olefin resin film, a laminate in which the crosslinked cyclic olefin resin film and a metal foil are bonded, And a manufacturing method thereof.

  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

  When using a laminate obtained by bonding a film made of a cyclic olefin resin and a metal foil for a printed circuit board, etc., the metal foil on the surface of the laminate is etched with an etching solution in order to make the metal part into a complicated shape. Etching is usually performed, but the amount of warpage may increase in the laminated body after the etching.

Recently, there is a need for a crosslinked cyclic olefin resin film containing a crosslinked cyclic olefin resin obtained by metathesis polymerization of a cyclic olefin monomer, having excellent adhesion to a metal material, and having a small warpage after etching treatment in a laminate with a metal foil. However, no such film has been found.
The problem to be solved by the present invention is a crosslinked cyclic olefin resin containing a crosslinked cyclic olefin resin, having excellent adhesion to a metal material and having a small amount of warpage after etching in a laminate with a metal foil. It is provision of the olefin resin composition, the said crosslinked cyclic olefin resin film, the laminated body to which the said crosslinked cyclic olefin resin film and metal foil are adhere | attached, and those manufacturing methods.

  As a result of intensive studies, the inventor of the present invention has (a) a cyclic olefin monomer, (b) an aliphatic carboxylic acid having 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule, (c A crosslinked cyclic olefin resin film comprising a crosslinked cyclic olefin resin composition obtained by ring-opening metathesis polymerization of a polymerizable composition containing an inorganic filler and (d) a ring-opening metathesis polymerization catalyst is adhesive to a metal material. The cross-linked olefin resin composition of the present invention, the cross-linked cyclic olefin resin film, the cross-linked cyclic olefin resin film and the metal foil are bonded to each other. As a result, the laminated body and the manufacturing method thereof have been completed.

  The crosslinked cyclic olefin resin composition of the present invention comprises (a) 100 parts by mass of a cyclic olefin monomer and (b) an aliphatic carboxylic acid having 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule. It is obtained by ring-opening metathesis polymerization of a polymerizable composition containing 0.01 to 2 parts by mass, (c) 1 to 45 parts by mass of an inorganic filler, and (d) a ring-opening metathesis polymerization catalyst.

  The preferred (b) aliphatic carboxylic acid having 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule is 10-undecenoic acid. Preferred (c) inorganic filler is at least selected from the group consisting of calcium carbonate, wollastonite / calcium carbonate hybrid filler, magnesium carbonate, talc, potassium titanate, aluminum oxide, glass, aluminum hydroxide oxide, and mica. One type. The preferable (a) cyclic olefin monomer is a norbornene monomer. A preferable (d) ring-opening metathesis polymerization catalyst is a ruthenium carbene complex.

  The crosslinked cyclic olefin resin film of the present invention comprises a crosslinked cyclic olefin resin composition.

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

  The method for producing a crosslinked cyclic olefin resin composition of the present invention comprises (a) 100 parts by mass of a cyclic olefin monomer and (b) an aliphatic having 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule. A step of ring-opening metathesis polymerization of a polymerizable composition containing 0.01 to 2 parts by weight of a carboxylic acid, (c) 1 to 45 parts by weight of an inorganic filler, and (d) a ring-opening metathesis polymerization catalyst.

  The method for producing a crosslinked cyclic olefin resin film of the present invention comprises (a) 100 parts by mass of a cyclic olefin monomer and (b) an aliphatic carboxylic acid having 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule. A polymerizable composition containing 0.01 to 2 parts by mass of an acid, (c) 1 to 45 parts by mass of an inorganic filler, and (d) a ring-opening metathesis polymerization catalyst is applied onto a support, and the ring-opening metathesis polymerization is performed as described above. A step of performing on a support.

  The method for producing a laminate of the present invention comprises: (a) 100 parts by mass of a cyclic olefin monomer; (b) an aliphatic carboxylic acid having 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule; After coating a polymerizable composition containing 01 to 2 parts by mass, (c) 1 to 45 parts by mass of an inorganic filler, and (d) a ring-opening metathesis polymerization catalyst, metathesis polymerization is performed, and then obtained. The film-like polymer is peeled from the substrate to obtain a crosslinked cyclic olefin resin film, and the crosslinked cyclic olefin resin film and (e) the metal foil are brought into contact with each other. A step of bonding.

  The crosslinked cyclic olefin resin film of the present invention has excellent adhesion to a metal material. The layered product of the present invention has a small amount of warpage after the etching treatment with an etching solution.

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 crosslinked cyclic olefin resin composition, preferred nonpolar norbornene monomers are nonpolar dicyclopentadienes and nonpolar tetracyclododecenes, and more preferred nonpolar norbornene monomers. Is a nonpolar dicyclopentadiene.

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 the monocyclic olefin added is too large, the heat resistance of the crosslinked cyclic olefin resin composition or the crosslinked cyclic olefin resin film may be insufficient.

  The method for producing a crosslinked cyclic olefin resin composition of the present invention comprises (a) 100 parts by mass of a cyclic olefin monomer and (b) an aliphatic having 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule. A step of ring-opening metathesis polymerization of a polymerizable composition containing 0.01 to 2 parts by weight of a carboxylic acid, (c) 1 to 45 parts by weight of an inorganic filler, and (d) a ring-opening metathesis polymerization catalyst.

  When obtaining the crosslinked cyclic olefin resin composition of the present invention, at least (a) 100 parts by mass of a cyclic olefin monomer and (b) 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule. The polymerizable composition containing 0.01 to 2 parts by mass of the aliphatic carboxylic acid, (c) 1 to 45 parts by mass of the inorganic filler, and (d) a ring-opening metathesis polymerization catalyst is subjected to metathesis polymerization. (D) The ring-opening metathesis polymerization catalyst metatheses (a) a cyclic olefin monomer. The (d) 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 (d) a 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 preferable (d) ring-opening metathesis polymerization catalyst is a group 8 ruthenium or osmium complex, and a particularly preferable (d) 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. (D) From the viewpoint of the activity of the ring-opening metathesis 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, C1-C20 alkyl ammonium groups, aryl ammonium 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 (d) ring-opening metathesis polymerization catalyst used is a molar ratio of ((d) 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. (D) 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 the decrease in the polymerization reaction rate, and the decrease in the crosslinking degree of the crosslinked polymer can be suppressed, The heat resistance of the obtained crosslinked cyclic olefin resin composition can be improved. (D) Since 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. Can be easily formed.

(D) 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 amount of the activator used is usually (1: 0.05) to (1: 100), preferably (1: 1, in a molar ratio of (d) metal atom in ring-opening metathesis polymerization catalyst: activator). 0.2) to (1:20), more preferably (1: 0.5) to (1:10).

  (D) 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 (d) the ring-opening metathesis polymerization catalyst.

  In the production of the above-mentioned crosslinked cyclic olefin resin composition, 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 it can be formed into a film shape simultaneously with polymerization. A bulk polymerization method is preferred.

The bulk polymerization method includes (a) 100 parts by mass of a cyclic olefin monomer and (b) 0.01 to 2 parts by mass of an aliphatic carboxylic acid having 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule. And (c) a step of ring-opening metathesis polymerization of a polymerizable composition containing 1 to 45 parts by mass of an inorganic filler and (d) a ring-opening metathesis polymerization catalyst in the presence of an additive used as necessary.
(A) The cyclic olefin monomer is subjected to ring-opening metathesis polymerization to obtain a cyclic olefin polymer, and the cyclic olefin polymer is crosslinked after the ring-opening metathesis polymerization or simultaneously with the ring-opening metathesis polymerization. It is believed that a polymer is obtained.

  The crosslinked cyclic olefin resin composition of the present invention comprises (a) 100 parts by mass of a cyclic olefin monomer and (b) an aliphatic carboxylic acid having 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule. It is obtained by ring-opening metathesis polymerization of a polymerizable composition containing 0.01 to 2 parts by mass, (c) 1 to 45 parts by mass of an inorganic filler, and (d) a ring-opening metathesis polymerization catalyst. That is, the crosslinked cyclic olefin resin composition of the present invention contains (b) an aliphatic carboxylic acid having 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule.

  (B) Specific examples of an aliphatic carboxylic acid having 8 to 20 carbon atoms (hereinafter sometimes referred to as “(b) aliphatic carboxylic acid”) having at least one carbon-carbon double bond in one molecule. 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, 13-tetradecenoic acid, 14-pentadecenoic acid, 15-hexadecenoic acid, 16-heptadecene C8-C20 aliphatic carboxylic acid having a carbon-carbon double bond at the molecular end, such as acid, 17-octadecenoic acid, 18-nonadecenoic acid; myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid , Gadoleic acid, eicosenoic acid, linoleic acid, eicosadienoic acid, linolenic acid, pinolenic acid, eleostearic acid, mead acid, eicosatrienoic acid, etc. Carbon addition molecular end - aliphatic carboxylic acid having 8 to 20 carbon atoms and having a carbon double bond; 1,3 diallyl monocarboxylic isocyanuric acid, such as isocyanuric acid and 1,3-carboxy monoallyl isocyanuric acid.

  (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, and more preferred (b) aliphatic carboxylic acid is carbon- It is an aliphatic carboxylic acid having 8 to 16 carbon atoms having a carbon double bond, and more preferable (b) aliphatic carboxylic acid is an aliphatic carboxylic acid having 8 to 12 carbon atoms having a carbon-carbon double bond at the molecular end. Particularly preferred (b) aliphatic carboxylic acid is an aliphatic carboxylic acid having 8 to 12 carbon atoms having a carbon-carbon double bond only at the molecular end, and most preferred (b) aliphatic carboxylic acid is 10-undecenoic acid.

  (B) The amount of the aliphatic carboxylic acid is 0.01 to 2 parts by mass, preferably 0.1 to 1 part by mass, more preferably 0.1 to 100 parts by mass of the (a) cyclic olefin monomer. -0.5 mass part. (B) When there are too few compounding quantities of aliphatic carboxylic acid, there exists a possibility that the adhesive improvement effect with respect to a metal material may not be acquired. On the other hand, if the amount of (b) aliphatic carboxylic acid is too large, the polymerization reaction may be inhibited.

The crosslinked cyclic olefin resin composition of the present invention contains (c) an inorganic filler.
(C) Specific examples of the inorganic filler include calcium carbonate, wollastonite / calcium carbonate hybrid filler, magnesium carbonate, magnesium hydroxide, potassium titanate, aluminum oxide, glass, aluminum hydroxide oxide, mica, silica, silica sand, water Aluminum oxide, talc, clay, carbon black, natural graphite and the like. One or more of these are used in combination.

  (C) The shape of the inorganic filler is not limited to a specific shape. Preferred (c) inorganic filler shapes are needle-like, plate-like and scaly, more preferred (c) inorganic filler shapes are needle-like and plate-like, and particularly preferred (c) inorganic filler shape is plate-like. Is. (C) The inorganic filler may be surface-treated with a surface treatment agent such as fatty acid, ethylene glycol, aminosilane.

  (A) The addition amount of (c) inorganic filler is 1 to 45 parts by mass with respect to 100 parts by mass of the cyclic olefin monomer, the preferable addition amount is 2 to 35 parts by mass, and the more preferable addition amount is 5 to 30 parts by mass. The more preferable addition amount is 5 to 25 parts by mass.

  (C) When there is too little addition amount of an inorganic filler, the curvature amount after the etching process of a laminated body will become large. On the other hand, when the amount of (c) inorganic filler added is too large, the polymerizable composition is solidified and a crosslinked cyclic olefin resin composition cannot be obtained.

  Preferred (c) inorganic fillers are calcium carbonate, wollastonite / calcium carbonate hybrid filler, magnesium carbonate, talc, potassium titanate, aluminum oxide, glass, aluminum hydroxide oxide and mica. More preferable (c) inorganic fillers are acicular calcium carbonate, acicular potassium octatitanate surface-treated with aminosilane, plate-like glass surface-treated with aminosilane, and plate-like boehmite (main component is aluminum hydroxide oxide). . Particularly preferred (c) inorganic filler is plate boehmite from the viewpoint of handleability. One or more of these are used in combination.

The potassium titanate is represented by the general formula K ₂ O · nTiO ₂ (n is an integer of 1 to 8), among which n is preferably 1, 2, 4, 6, or 8, and n = 8, i.e., potassium octatitanate is particularly preferred.

Boehmite is mainly composed of aluminum hydroxide oxide. Aluminum oxide hydroxide of the general formula AlO (OH), or represented by _{Al 2 O 3 · H 2 O} .

  Various additives are used as precursors for the crosslinked cyclic olefin resin composition of the present invention for the purpose of improving the properties of the crosslinked cyclic olefin resin composition according to various uses and purposes, imparting functions, and improving molding workability. It is made to contain in the said polymeric composition which is. Specific examples of such additives include polymerization inhibitors, antifoaming agents, foaming agents, colorants, ultraviolet absorbers, stabilizers, flame retardants, wetting agents, dispersing agents, release lubricants, plasticizers, and the like. Preferably, a stabilizer is contained in order to improve durability and storage stability of the crosslinked cyclic olefin resin composition.

  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 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 types and blending amounts 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 resin composition. 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 composition of the present invention, at least (a) 100 parts by mass of a cyclic olefin monomer and (b) 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule. A polymerizable composition comprising 0.01 to 2 parts by weight of an aliphatic carboxylic acid, (c) 1 to 45 parts by weight of an inorganic filler, and (d) a ring-opening metathesis polymerization catalyst, and additives used as necessary. Ring-opening metathesis polymerization. (D) 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. (D) 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 crosslinked cyclic olefin resin film of the present invention comprises the crosslinked cyclic olefin resin composition of the present invention.

  The method for producing a crosslinked cyclic olefin resin film of the present invention comprises (a) 100 parts by mass of a cyclic olefin monomer and (b) an aliphatic carboxylic acid having 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule. A polymerizable composition containing 0.01 to 2 parts by mass of an acid, (c) 1 to 45 parts by mass of an inorganic filler, and (d) a ring-opening metathesis polymerization catalyst is applied onto a support, and the ring-opening metathesis polymerization is performed as described above. A step of performing on a support.

  (A) 100 parts by mass of a cyclic olefin monomer, (b) 0.01 to 2 parts by mass of an aliphatic carboxylic acid having 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule, (c) inorganic The viscosity at room temperature of the polymerizable composition containing 1 to 45 parts by mass of filler, (d) a ring-opening metathesis polymerization catalyst, and an additive used as necessary depends on the thickness of the desired film. ˜500 mPa · s is preferred. It becomes easy to form in a film shape because a viscosity exists in said preferable range. The viscosity of the polymerizable composition is (a) a cyclic olefin monomer, (b) an aliphatic carboxylic acid having 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule, and (c) an inorganic filler. And (d) It adjusts with the kind and usage-amount of a ring-opening metathesis polymerization catalyst.

  A specific example of a method for forming the polymerizable composition into a film shape by ring-opening metathesis polymerization is a method in which the polymerizable composition is coated on a support and the ring-opening metathesis polymerization is performed on the support. . Bulk polymerization is preferred as a polymerization method for carrying out ring-opening metathesis polymerization.

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

  If necessary, the polymerizable composition is heated to a temperature at which (d) 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 (d) 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 performed simultaneously with the polymerization is more preferable because the crosslinked cyclic olefin resin composition of the present invention can be obtained industrially advantageously in 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 preferred from the viewpoint of easy control of physical properties and economical efficiency of the crosslinked cyclic olefin resin composition.

  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 crosslinking density varies depending on the use of the crosslinked cyclic olefin resin composition. 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.

  Bulk polymerization and crosslinking in the present invention are preferably carried out 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 polymerizable 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 crosslinked cyclic olefin resin composition is not oxidized.

  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.

The above-mentioned crosslinked cyclic olefin resin composition is formed using a known surface treatment technique such as gas phase reaction, coating, vacuum deposition, ion plating, sputtering, CVD, electroless plating, etc. Or on the surface of a crosslinked cyclic olefin resin film. 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 composition and a crosslinked cyclic olefin resin film is 135 degreeC or more from a viewpoint of heat resistance, sealing performance, and shape followability.

  The said crosslinked cyclic olefin resin film and (e) metal foil are made to contact, Then, it heats, pressurizing, and both are adhere | attached, and the laminated body of this invention is manufactured. The crosslinked cyclic olefin resin film and (e) 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 above (e) metal foil 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, when (e) metal foil is copper foil, copper foil with resin (Resin Coated Copper (RCC)) is obtained. (E) The preferred 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 1-24 and Comparative Examples 1-2
10 masses of 10-undecenoic acid, inorganic filler, phenol stabilizer, phosphorus stabilizer, hindered amine light stabilizer, and triphenylphosphine in the masses shown in Tables 1 and 2 were mixed with 90 parts of dicyclopentadiene and tricyclopentadiene 10 A reaction stock solution was obtained by dissolving or dispersing in a norbornene-based monomer mixture consisting of parts. Next, a polymerizable composition obtained by adding a ruthenium catalyst having a structure of the formula (7) and triphenylphosphine having a mass shown in Tables 1 and 2 to the reaction stock solution and mixing them with a line mixer, 25 The coating was carried out on a carrier film made of polyethylene terephthalate having a thickness of 0.075 mm at a temperature of C, and casted, and then immediately the same carrier film prepared separately from the top of the coating layer was laminated. Then, after heating at 200 degreeC for 3 minutes 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 (however, in Comparative Example 2, the crosslinked cyclic olefin resin film was obtained). Was not possible).

  Using two sheets of 300 mm x 300 mm cross-linked cyclic olefin resin film of the same size electrolytic copper foil (Furukawa Electric Co., Ltd., surface GTS treatment, thickness 0.018 mm), the roughened surface is applied to the film. It was sandwiched from above and below so as to touch. The obtained copper foil / resin film / copper foil laminate was inserted into a vacuum press, heated while pressing at a surface pressure of 9.0 MPa at 180 ° C. for 60 minutes, and then cooled to 20 ° C. to obtain a sample obtained. It took out from the vacuum press and obtained the laminated body by which the copper foil, 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 foil, 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 test piece has a 180 ° adhesive strength to the copper foil of the crosslinked cyclic olefin resin film in JIS. Measured according to K 6854-2. 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.

  Moreover, the said laminated body was cut out to the magnitude | size of 60 mm x 60 mm, and it was set as the test piece, and the line | wire was drawn on the single side | surface of the said test piece at intervals of 10 mm from the edge with the oil-based magic pen. Further, lines were drawn on the other surface with an oil-based magic pen in a grid pattern every 5 mm from the end. Thereafter, the test piece was immersed in an etching solution (35% aqueous solution of ferric chloride) heated to 55 ° C. for 15 minutes, and copper other than the portion drawn with an oil-based magic pen was dissolved. Remove the etched test piece and place it on a horizontal surface with a line drawn with an oil-based magic pen in a grid pattern every 10 mm, and place the test piece in the center with a diameter of 10 mm, a height of 10 mm, and a weight of 10 g. A weight was placed, the height at which the four corners of the test piece floated from the horizontal plane was measured with a ruler, and the average value thereof was taken as the amount of warpage. 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) Shin-Nakamura Chemical Co., Ltd. Escalon # 2300
5) Sankyo Seiko Co., Ltd. AHW-75
6) MSS manufactured by Kamijima Chemical Co., Ltd.
7) Hitron A manufactured by Takehara Chemical Industry Co., Ltd.
8) Whiscal A manufactured by Maruo Calcium Co., Ltd.
9) Tismo D manufactured by Otsuka Chemical Co., Ltd.
10) Tismo D101 manufactured by Otsuka Chemical Co., Ltd.
11) Seraph YFA10030 manufactured by Kinsei Tech Co., Ltd.
12) Nihon Sheet Glass Co., Ltd. micro glass glass flake REF-015
13) Nippon Sheet Glass Co., Ltd. micro glass glass flake REF-015A
14) Kamijima Chemical Co., Ltd. 15) Otsuka Chemical Co., Ltd. Terrases TF-S
16) Sericite manufactured by Kinsei Matech Co., Ltd. 17) VC843 manufactured by RIMTEC Co., Ltd. (cyclopentanone solution containing 1.8% ruthenium catalyst)

  The adhesive strength to copper foil of the crosslinked cyclic olefin resin films of Examples 1 to 24 was high. The amount of warpage after the etching treatment with the etching solution of the laminate obtained from these crosslinked cyclic olefin resin films was small.

  The adhesive strength to copper foil of the crosslinked cyclic olefin resin film of Comparative Example 1 containing no inorganic filler was low. The amount of warpage after the etching treatment with the etchant of the laminate obtained from the crosslinked cyclic olefin resin film was large. The polymerizable composition of Comparative Example 2 in which the added amount of the inorganic filler was too large solidified, and no film was obtained.

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 (12)

  (A) 100 parts by mass of a cyclic olefin monomer, (b) 0.01 to 2 parts by mass of an aliphatic carboxylic acid having 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule, (c) inorganic A crosslinked cyclic olefin resin composition obtained by ring-opening metathesis polymerization of a polymerizable composition containing 1 to 45 parts by mass of filler and (d) a ring-opening metathesis polymerization catalyst.   The crosslinked cyclic olefin resin composition according to claim 1, wherein (b) the aliphatic carboxylic acid having 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule is 10-undecenoic acid. object.   The inorganic filler (c) is at least one selected from the group consisting of calcium carbonate, wollastonite / calcium carbonate hybrid filler, magnesium carbonate, talc, potassium titanate, aluminum oxide, glass, aluminum hydroxide oxide, and mica. The crosslinked cyclic olefin resin composition according to claim 1 or 2, which is a seed.   The crosslinked cyclic olefin resin composition according to any one of claims 1 to 3, wherein the (a) cyclic olefin monomer is a norbornene-based monomer.   The crosslinked cyclic olefin resin composition according to any one of claims 1 to 4, wherein the (d) ring-opening metathesis polymerization catalyst is a ruthenium carbene complex.   The crosslinked cyclic olefin resin film which consists of a crosslinked cyclic olefin resin composition as described in any one of Claims 1-5.    The laminated body by which the crosslinked cyclic olefin resin film described in Claim 6 and (e) metal foil were adhere | attached.    The laminate according to claim 7, wherein the metal foil (e) is a copper foil.   The laminate according to claim 8, which is for a flexible printed board.   (A) 100 parts by mass of a cyclic olefin monomer, (b) 0.01 to 2 parts by mass of an aliphatic carboxylic acid having 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule, (c) inorganic The method for producing a crosslinked cyclic olefin resin composition according to claim 1, comprising a step of ring-opening metathesis polymerization of a polymerizable composition containing 1 to 45 parts by mass of filler and (d) a ring-opening metathesis polymerization catalyst. .   (A) 100 parts by mass of a cyclic olefin monomer, (b) 0.01 to 2 parts by mass of an aliphatic carboxylic acid having 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule, (c) inorganic The method comprises applying a polymerizable composition containing 1 to 45 parts by mass of filler and (d) a ring-opening metathesis polymerization catalyst on a support, and performing ring-opening metathesis polymerization on the support. A method for producing the described crosslinked cyclic olefin resin film. (A) 100 parts by mass of a cyclic olefin monomer, (b) 0.01 to 2 parts by mass of an aliphatic carboxylic acid having 8 to 20 carbon atoms having at least one carbon-carbon double bond in one molecule, (c) inorganic After coating a polymerizable composition containing 1 to 45 parts by mass of filler and (d) a ring-opening metathesis polymerization catalyst on a substrate, metathesis polymerization is performed, and then the obtained film-like polymer is removed from the substrate. Peeling to obtain a crosslinked cyclic olefin resin film, and
The manufacturing method of the laminated body described in Claim 7 including the process which the said bridge | crosslinking cyclic olefin resin film and (e) metal foil are made to contact, and after that, heating and pressurizing are made to adhere | attach both.