JP2015003962A - Crosslinked cyclic olefin resin composition, crosslinked cyclic olefin resin film, and production method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crosslinked cyclic olefin resin composition that gives a film having sufficient releasing property against a resin used for sealing materials, prepreg, adhesives or the like.SOLUTION: The crosslinked cyclic olefin resin composition is obtained by metathesis polymerization of a polymerizable composition comprising 100 parts by mass of (a) a cyclic olefin monomer, 2 to 40 parts by mass of (b) an aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and/or an aromatic vinyl compound-isobutylene diblock copolymer, and (c) a metathesis polymerization catalyst.

Description

  The present invention is a cross-linked ring that contributes to improving the yield of mounting processes such as a semiconductor sealing process for IC chips, LEDs, etc., a laminated heat pressing process for manufacturing a multilayer printed wiring board, and a coverlay attaching process for manufacturing a flexible printed wiring board. The present invention relates to a crosslinked cyclic olefin resin composition that gives an olefin resin film, the film, and a method for producing them.

  The downsizing and thinning of semiconductor elements such as IC chips and LEDs are progressing along with the downsizing and thinning of mobile devices such as mobile phones. The shape of the sealing chip that seals these elements has also changed. Recently, a chip with a shape in which a lead frame is arranged so as to extend from a sealing chip as seen in a conventional surface mounting element is not mainstream, and a chip size that is a shape in which terminals are arranged directly on the element. Mounting sealing chips in the form of packages (CSP), ball grid arrays (BGA), quad flat now lead packages (QFN) and the like are becoming mainstream. These shapes have the advantage of a small mounting area and contribute to the downsizing of the equipment. Furthermore, the sealing chip for mounting in these shapes is thin, which contributes to the thinning of the sealing film.

  However, cracking of the product and protrusion of the sealing material from the terminal portion are likely to occur in the manufacturing process of the mounting sealing chip having these shapes, resulting in a decrease in manufacturing yield. A sealing method using assist molding with a release film has been studied to improve yield (for example, see Patent Documents 1 and 2). Polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene copolymer (ETFE), and polyimide, which are release film materials used in the sealing method, are expensive, and the release film is incinerated when discarded. Can not.

  On the other hand, a crosslinked resin film obtained by polymerizing a liquid containing a metathesis polymerization catalyst and a cycloolefin capable of metathesis polymerization on a carrier has been studied as a release film (see, for example, Patent Document 3). However, the film does not have sufficient releasability from resins used for sealing materials, prepregs, adhesives, and the like.

Japanese Patent Laid-Open No. 2000-167841 JP 2001-250838 A JP 2001-253934 A

Recently, there has been a demand for a film including a crosslinked cyclic olefin resin obtained by metathesis polymerization of a cyclic olefin monomer and having sufficient releasability with a resin used for a sealing material, a prepreg, an adhesive, and the like. Such a film has not been found.
The problem to be solved by the present invention includes a crosslinked cyclic olefin resin obtained by metathesis polymerization of a cyclic olefin monomer, and has sufficient releasability from resins used for sealing materials, prepregs, adhesives, and the like. It is provision of the crosslinked cyclic olefin resin composition which gives a film, the said film, and those manufacturing methods.

  As a result of intensive studies, the inventors of the present invention have found that (a) a cyclic olefin monomer, a specific amount of (b) an aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or an aromatic vinyl compound. -A crosslinked cyclic olefin resin composition obtained by metathesis polymerizing a polymerizable composition containing an isobutylene diblock copolymer and (c) a metathesis polymerization catalyst is used as a sealing material, a prepreg, an adhesive and the like The present inventors have found that a film having sufficient releasability can be obtained, and have completed the crosslinked cyclic olefin resin composition of the present invention, the crosslinked cyclic olefin resin film comprising the resin composition, and the production method thereof.

  The crosslinked cyclic olefin resin composition of the present invention comprises (a) 100 parts by mass of a cyclic olefin monomer, (b) an aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or an aromatic vinyl compound-isobutylene. It is obtained by subjecting a polymerizable composition containing 2 to 40 parts by mass of a block copolymer and (c) a metathesis polymerization catalyst to metathesis polymerization. The preferred (a) cyclic olefin monomer is a norbornene monomer. A preferred (c) metathesis polymerization catalyst is a ruthenium carbene complex.

  The crosslinked cyclic olefin resin film of this invention contains the said crosslinked cyclic olefin resin composition. A preferable use of the crosslinked cyclic olefin resin film is a release film used for a semiconductor sealing process or a release film for producing a printed circuit board.

  The method for producing the crosslinked cyclic olefin resin composition of the present invention comprises (a) 100 parts by mass of a cyclic olefin monomer, (b) an aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or styrene-isobutylene. 2 to 40 parts by mass of a block copolymer and (c) a step of metathesis polymerizing a polymerizable composition containing a metathesis polymerization catalyst. A preferable (a) cyclic olefin monomer contained in the polymerizable composition is a norbornene monomer. A preferred (c) metathesis polymerization catalyst contained in the polymerizable composition is a ruthenium carbene complex.

  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; (b) aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or aromatic vinyl compound- It includes a step of applying a polymerizable composition containing 2 to 40 parts by mass of an isobutylene diblock copolymer and (c) a metathesis polymerization catalyst on a base material, and performing metathesis polymerization on the base material. A preferable (a) cyclic olefin monomer contained in the polymerizable composition is a norbornene monomer. A preferred (c) metathesis polymerization catalyst contained in the polymerizable composition is a ruthenium carbene complex.

  The crosslinked cyclic olefin resin composition of the present invention provides a film having sufficient releasability from resins used for encapsulants, prepregs, adhesives, and the like.

The crosslinked cyclic olefin resin composition of the present invention comprises (a) 100 parts by mass of a cyclic olefin monomer, (b) an aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or an aromatic vinyl compound-isobutylene. It is obtained by subjecting a polymerizable composition containing 2 to 40 parts by mass of a block copolymer and (c) a metathesis polymerization catalyst to metathesis polymerization.
The crosslinked cyclic olefin resin film of this invention contains the said crosslinked cyclic olefin resin composition.
The crosslinked cyclic olefin resin film of the present invention may contain a material other than the above-mentioned crosslinked cyclic olefin resin composition, but is preferably composed only of the above-mentioned crosslinked cyclic olefin resin composition.

(A) The cyclic olefin monomer which is one of the raw materials of the crosslinked cyclic olefin resin composition of the present invention is a compound having a ring structure formed of carbon atoms and having a carbon-carbon double bond in the ring. is there. 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 tetracyclododecene. 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. From the viewpoint of improving the releasability of the release film, the norbornene monomer is preferably nonpolar, that is, a norbornene 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 and 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) and 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);

Tricyclopentadiene, 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 and 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 improvement in heat resistance of the film, preferred nonpolar norbornene monomers are nonpolar dicyclopentadiene and nonpolar tetracyclododecene, and more preferred nonpolar norbornene monomers are 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-norbornen-2-ol, 5-norbornene-2-carbonitrile, 2-acetyl-5-norbornene and 7-oxa-2-norbornene.

  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. When the addition amount of the monocyclic olefin is not more than the above upper limit, the heat resistance of the film can be sufficiently obtained.

  When obtaining the crosslinked cyclic olefin resin composition of the present invention, at least (a) a cyclic olefin monomer, (b) an aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or an aromatic vinyl compound. -Metathesis polymerizing a polymerizable composition containing an isobutylene diblock copolymer and (c) a metathesis polymerization catalyst. (C) A metathesis polymerization catalyst metatheses (a) a cyclic olefin monomer. The (c) 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) 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 atoms are molybdenum and tungsten, and the preferred Group 8 atoms are ruthenium and osmium.

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

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

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

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

  Neutral electron donating compounds are roughly classified into hetero atom-containing carbene compounds and other neutral electron donating compounds. (C) From the viewpoint of the activity of the metathesis polymerization catalyst, a preferable neutral electron donating compound is a heteroatom-containing carbene compound. 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 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. Or 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 and thiocyanates. 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) and iodine atom (I); diketonate group; substituted cyclopentadienyl group; alkoxy group; aryloxy group; carboxyl group And so on. 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 and arylammonium groups.
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 and (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) (2-pyrrolidone-1-ylmethylene) (tricyclohexylphosphine) ruthenium dichloride A ruthenium complex compound in which one hetero atom-containing carbene compound and one neutral electron donating compound are bonded, such as Lido;

  A ruthenium complex compound in which two neutral electron-donating compounds are bound, such as benzylidenebis (tricyclohexylphosphine) ruthenium dichloride and (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 and bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylidene ruthenium dichloride.

  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) metathesis polymerization catalyst used is a molar ratio of ((c) metal atom in the metathesis polymerization catalyst: (a) cyclic olefin monomer) (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). (C) When the amount of the 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 and obtained. The heat resistance of the film can be improved. In addition, when the amount of the 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 during polymerization described later can be easily performed.

(C) The metathesis polymerization catalyst may 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, and silicon alkylates, halides, alkoxylates, and aryloxylates. Further specific examples of activators are aluminum compounds such as trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride and dialkylaluminum chloride; trialkoxy Scandium compounds such as scandium; titanium compounds such as tetraalkoxytitanium; tin compounds such as tetraalkyls and tetraalkoxytin; zirconium compounds such as tetraalkoxyzirconium; dimethylmonochlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, tetrachlorosilane, bicyclo Heptenylmethyldichlorosilane, phenylmethyldichlorosila , Dihexyl dichlorosilane, silane compounds such as phenyl trichlorosilane and methyl trichlorosilane; and the like.
The amount of the activator used is, for example, (1: 0.05) to (1: 100), preferably (1: 0. 0) in a molar ratio of ((c) metal atom in the metathesis polymerization catalyst: activator). 2) to (1:20), more preferably in the range of (1: 0.5) to (1:10).

  (C) The metathesis polymerization catalyst may 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 and 1,5-bis (diphenyl). Phosphorous compounds such as phosphino) pentane; Lewis bases such as ethers, esters and nitriles; These usage-amounts are 0.01-50 mol with respect to 1 mol of (c) metathesis polymerization catalysts, Preferably it is 0.05-10 mol.

  In the production of the crosslinked cyclic olefin resin composition of the present invention, the polymerization method may be either a solution polymerization method or a bulk polymerization method, but the bulk polymerization method is preferred from the viewpoint that a solvent removal step is unnecessary. Further, in the production of the crosslinked cyclic olefin resin film of the present invention, the bulk polymerization method is preferable from the viewpoint that it can be formed into a film shape simultaneously with the polymerization.

The bulk polymerization method includes (a) a cyclic olefin monomer, (b) an aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or an aromatic vinyl compound-isobutylene diblock copolymer, and (c) metathesis. The polymerizable composition containing a polymerization catalyst is suitably used in a process of metathesis polymerization in the presence of an additive used as necessary.
(A) The cyclic olefin monomer is metathesized to obtain a cyclic olefin polymer, and the cyclic olefin polymer is crosslinked after the metathesis polymerization or simultaneously with the metathesis polymerization to obtain a crosslinked cyclic olefin polymer. Conceivable.

  The polymerizable composition which is a precursor of the crosslinked cyclic olefin resin composition of the present invention comprises (a) 100 parts by mass of the cyclic olefin monomer, and (b) an aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer. 2-40 mass parts of a polymer and / or an aromatic vinyl compound-isobutylene diblock copolymer are contained.

  (B) The method for producing the aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or the aromatic vinyl compound-isobutylene diblock copolymer is not particularly limited, but for example, JP-A-3-174403 In the presence of an initiator system composed of a Lewis acid and an organic compound (hereinafter referred to as an initiator compound) that forms a cationic polymerization active species in combination with a Lewis acid according to the method described in 1. A method in which an aromatic vinyl compound and isobutylene are polymerized in an inert solvent such as hexane or methylene chloride by adding a third component such as aldehyde is employed.

  The initiator compound is an organic compound having a functional group such as an alkoxy group, an acyloxy group, or a halogen. Specific examples of the initiator compound include bis (2-methoxy-2-propyl) benzene, bis (2-acetoxy-2-propyl) benzene, bis (2-chloro-2-propyl) benzene and the like. Specific examples of Lewis acids are titanium tetrachloride and the like, and specific examples of amines are triethylamine and the like.

  (B) A preferred specific example of the method for producing an aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer uses the above-described initiator compound and Lewis acid as an initiator system, and substantially uses an aromatic vinyl compound. In this method, isobutylene is introduced into the system after the polymerization is completed, and then the aromatic vinyl compound is polymerized again after the substantial polymerization reaction of isobutylene is completed.

  (B) A preferred specific example of the method for producing an aromatic vinyl compound-isobutylene diblock copolymer uses the above initiator compound together with a Lewis acid, and after isobutylene is polymerized until the reaction is substantially completed, In this method, an aromatic vinyl compound is introduced into the system to continue the polymerization reaction.

  Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, divinylbenzene, diisopropenylstyrene, 1,1-diphenylstyrene, and the like. These monomers are used alone or in combination of two or more. A preferred aromatic vinyl compound is styrene.

  (B) A preferred specific example of the aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or the aromatic vinyl compound-isobutylene diblock copolymer is a styrene-isobutylene-styrene triblock copolymer. (SIBS), styrene-isobutylene diblock copolymer (SIB), a mixture of styrene-isobutylene-styrene triblock copolymer (SIBS) and styrene-isobutylene diblock copolymer (SIB), and the like. A more specific example is a styrene-isobutylene-styrene triblock copolymer (SIBS).

  (B) The content of the aromatic vinyl compound in the aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or the aromatic vinyl compound-isobutylene diblock copolymer is preferably 10 to 40 mass. %, More preferably 10 to 35% by mass. When the content of the aromatic vinyl compound is excessively small, (a) the solubility in the cyclic olefin monomer is lowered, and (b) an aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or aromatic. A polymerizable composition in which an aromatic vinyl compound-isobutylene diblock copolymer is dissolved often becomes a cloudy or heterogeneous phase, and the physical properties of the crosslinked cyclic olefin resin composition vary. If the content of the aromatic vinyl compound is excessively large, the crosslinked cyclic olefin resin film becomes brittle.

  (B) The number average molecular weight of the aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or aromatic vinyl compound-isobutylene diblock copolymer is preferably 30,000 to 500,000. Preferably it is 50,000-400,000. When the number average molecular weight is excessively small, the crosslinked cyclic olefin resin film becomes brittle. When the number average molecular weight is excessively large, the solubility in (a) the cyclic olefin monomer is lowered, and the viscosity at the time of dissolution is increased, so that it is difficult to obtain a crosslinked cyclic olefin resin composition.

  (B) Aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or aromatic vinyl compound-isobutylene diblock in the polymerizable composition which is a precursor of the crosslinked cyclic olefin resin composition of the present invention The content of the copolymer is 2 to 40 parts by weight, preferably 2 to 20 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the (a) cyclic olefin monomer. Preferably it is 3-5 mass parts. (B) By setting the content of the aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or the aromatic vinyl compound-isobutylene diblock copolymer in the above range, the crosslinked cyclic olefin of the present invention is used. The releasability of the resin film is improved. Moreover, by setting it as the said upper limit or less, it can prevent that a polymeric composition solidifies before performing metathesis polymerization, and can obtain the crosslinked cyclic olefin resin composition of this invention suitably.

  The polymerizable composition which is a precursor of the crosslinked cyclic olefin resin composition of the present invention has an organic peroxide having a half-life temperature of 160 to 200 ° C. for 1 minute (hereinafter sometimes referred to as “organic peroxide”). May be contained. The organic peroxide acts as a crosslinking agent in the present invention. Preferred specific examples of the organic peroxide include bis (t-butyldioxyisopropyl) benzene and di-t-butyl peroxide. These organic peroxides having a half-minute temperature of 160 to 200 ° C. are used singly or in combination of two or more.

  In an organic peroxide having a 1 minute half temperature of 160 to 200 ° C, the preferred 1 minute half temperature is 170 to 195 ° C, the more preferred 1 minute half temperature is 180 to 195 ° C, and the more preferred 1 minute half temperature is It is 185 to 195 ° C, and a particularly preferable half-temperature for 1 minute is 185 to 192 ° C. When the half-life temperature for 1 minute is not less than the above lower limit, the glass transition temperature of the crosslinked cyclic olefin resin composition of the present invention does not decrease, and the releasability of the crosslinked cyclic olefin resin film of the present invention is improved.

  In the polymerizable composition which is a precursor of the crosslinked cyclic olefin resin composition of the present invention, the content of the organic peroxide having a half-temperature of 160 to 200 ° C. per minute is (a) 100 parts by mass of the cyclic olefin monomer. On the other hand, it is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass. The glass transition temperature of the crosslinked cyclic olefin resin composition of the present invention does not decrease because the content of the organic peroxide having a half-temperature of 1 minute at 160 to 200 ° C. is not less than the above lower limit. The releasability of the olefin resin film is improved. When the content of the organic peroxide having a half-temperature of 1 minute at 160 to 200 ° C. is below the above upper limit, the crosslinked cyclic olefin resin composition of the present invention can be prevented from becoming brittle.

  Various additives are used for various purposes and purposes in order to improve the properties of the crosslinked cyclic olefin resin composition and crosslinked cyclic olefin resin film of the present invention, imparting functions and improving molding workability, etc. In the polymerizable composition which is a precursor of the crosslinked cyclic olefin resin composition. Specific examples of such additives include polymerization inhibitors, antifoaming agents, foaming agents, colorants, UV absorbers, stabilizers, flame retardants, wetting agents, dispersing agents, release lubricants, plasticizers and fillers, etc. It is. In order to improve the durability and storage stability of the crosslinked cyclic olefin resin composition, it is preferable to contain a stabilizer.

As the stabilizer that can be contained in the polymerizable composition that is a precursor of the crosslinked cyclic olefin resin composition of the present invention, a phenol-based stabilizer, a phosphorus-based stabilizer, and a hindered amine-based light stabilizer are preferable.
Specific examples of the phenol-based stabilizer include N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) acetyl] hydrazine, N, N′-bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) butyronyl] hydrazine, N, N ′ -Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) octylonyl] hydrazine, N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Phenol stabilizers having a hydrazine structure such as stearoyl] hydrazine and N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) benzoyl] hydrazine; N, N′-bis [2- [3- (3 , 5-Di-t-butyl-4-hydroxyphenyl) acetyloxy] ethyl] oxamide, N, N′-bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl Oxy] ethyl] oxamide, N, N′-bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) butyronyloxy] ethyl] oxamide, N, N′-bis [2- [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) octylonyloxy] ethyl] oxamide, N, N′-bis [2- [3- (3,5-di-tert-butyl- Oxami, such as 4-hydroxyphenyl) stearoyloxy] ethyl] oxamide and N, N′-bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) benzoyloxy] ethyl] oxamide Phenol stabilizer having structure; 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 and 2,6-di-tert-butyl-4 -Phenolic stabilizers other than phenolic stabilizers having a hydrazine structure or an oxamide structure, such as methylphenol; is there.

  One or more of the above phenol-based stabilizers are used in combination. Among these, from the viewpoint of high-temperature discoloration resistance, a phenol-based stabilizer other than a phenol-based stabilizer having a hydrazine structure or an oxamide structure is preferable, and octadecyl-3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionate is particularly preferred.

  Specific examples of the phosphorus stabilizer 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} and 6- [3 -(3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [D, f] [1,3,2] -dioxaphosphine 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-4 (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-hydroxyethyl) ) -Amino-1,2,2,6,6-pentamethylpiperidine, 4-methacrylamide-1,2,2,6,6-pentamethylpiperidine and α-cyano-β-methyl-β- [N- (2,2,6,6-te La methylpiperidin-4-yl)] - amino - methyl acrylate and the like. One or more of these are used in combination.

  The kind and content of the stabilizer that can be contained in the polymerizable composition that is the precursor of the crosslinked cyclic olefin resin composition of the present invention are the mechanical properties and film molding workability of the crosslinked cyclic olefin resin composition at high temperatures. It is appropriately selected depending on conditions such as storage stability. The total content of these stabilizers is preferably 20 parts by mass or less, more preferably 1 to 15 parts by mass, and further preferably 1 to 10 parts by mass with respect to (a) 100 parts by mass of the cyclic olefin monomer. Part. By being more than the above lower limit, the high temperature discoloration resistance of the crosslinked cyclic olefin resin composition is excellent. By being below the above upper limit, (a) a cyclic olefin resin film can be obtained satisfactorily without causing an insoluble portion in the cyclic olefin monomer.

  Specific examples of the polymerization inhibitor 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 chloride and 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. The content of these release lubricants is preferably 200 parts by mass or less with respect to 100 parts by mass of (a) the cyclic olefin monomer.

Specific examples of the filler include inorganic fillers such as carbon black, natural graphite, silica, silica sand, glass powder, calcium carbonate, aluminum hydroxide, magnesium hydroxide and clay; organic filler 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 resin composition.
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 resin composition. The content of these fillers is preferably 400 parts by mass or less, more preferably 300 parts by mass or less with respect to 100 parts by mass of (a) the cyclic olefin monomer.

  When obtaining the crosslinked cyclic olefin resin composition of the present invention, at least (a) a cyclic olefin monomer, (b) an aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or an aromatic vinyl compound. -A metathesis polymerization is performed on a polymerizable composition containing an isobutylene diblock copolymer, (c) a metathesis polymerization catalyst, and additives used as necessary. (C) The 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 and mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, Alicyclic hydrocarbons such as diethylcyclohexane, decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; alicyclics such as indene and tetrahydronaphthalene And hydrocarbons having aromatic rings; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; such as diethyl ether, tetrahydrofuran, cyclopentanone and cyclohexanone Oxygen hydrocarbons; 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. You may use the liquid anti-aging agent or plasticizer which does not reduce the activity as a polymerization catalyst as a solvent.

  (A) cyclic olefin monomer, (b) aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or aromatic vinyl compound-isobutylene diblock copolymer, (c) metathesis polymerization catalyst and as required The viscosity at room temperature (20 ° C.) of the polymerizable composition containing the additive used accordingly depends on the desired film thickness, but is preferably 0.4 to 500 mPa · s. It becomes easy to shape | mold into a film shape because a viscosity exists in the said range. The viscosity of the polymerizable composition is (a) a cyclic olefin monomer, (b) an aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or an aromatic vinyl compound-isobutylene diblock copolymer, (C) It adjusts with the kind and usage-amount of the metathesis polymerization catalyst and the additive used as needed.

  A preferred specific example of a method for obtaining the crosslinked cyclic olefin resin film of the present invention by metathesis polymerization of the polymerizable composition to form a film shape is to apply the polymerizable composition on a substrate and perform metathesis polymerization. This is a method of performing bulk polymerization on the substrate.

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

  The polymerizable composition is subjected to metathesis polymerization by heating to a temperature at which the (c) metathesis polymerization catalyst exhibits activity, if necessary. The polymerization temperature is preferably 0 to 250 ° C, more 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 the (c) metathesis polymerization catalyst and the heating temperature, and is preferably 1 minute to 24 hours.

  (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. Crosslinking carried out simultaneously with the metathesis polymerization is preferred because the crosslinked cyclic olefin resin composition 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; A method of carrying out polymerization by adding a crosslinking agent to the composition, and further carrying out a crosslinking reaction by carrying out a crosslinking reaction simultaneously with or after the polymerization; (C) irradiating the cyclic olefin polymer with light or electron beam, and carrying out a crosslinking reaction after the polymerization. A method of performing cross-linking; One of these methods may be used, or two or more methods may be used in combination. From the viewpoint of economy, the method (A) and / or (B) is preferred.

  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 crosslinkable monomer include dicyclopentadiene and tricyclopentadiene. One or more of these are used in combination. 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 of the present invention. The preferable usage-amount of the said crosslinkable monomer is 0.1-100 mol% in the ratio of the crosslinkable monomer in (a) cyclic olefin monomer whole quantity.

  A well-known thermal crosslinking agent and photocrosslinking agent are mentioned as a crosslinking agent used for the method of (B). As the crosslinking agent, a thermal crosslinking agent is preferable. Among the thermal crosslinking agents, radical generators such as organic peroxides, diazo compounds, and nonpolar radical generators are preferable, and among them, the above-described organic peroxides are particularly preferable. The amount of the crosslinking agent used is preferably 8 parts by mass or less, more preferably 0.5 to 6 parts by mass with respect to 100 parts by mass of the (a) cyclic olefin monomer. The temperature at which crosslinking is performed in the case of using a thermal crosslinking agent is preferably 100 to 250 ° C, more preferably 150 to 200 ° C. The time for crosslinking is not particularly limited, but is preferably from several minutes to several hours.

  The metathesis polymerization and crosslinking in the present invention are preferably performed in the absence of oxygen molecules and water. Specific examples of the metathesis polymerization and crosslinking method include (1) a method of performing metathesis polymerization and crosslinking in an inert gas atmosphere such as nitrogen gas and argon gas, and (2) a method of performing metathesis polymerization and crosslinking under vacuum, (3 ) A method of performing metathesis polymerization and crosslinking in a state where the polymerizable composition coated on the substrate is covered with a resin film or the like and sealed. Specific examples of the resin film are the same as those exemplified as the substrate. By performing the metathesis polymerization and crosslinking in the present invention in the absence of oxygen molecules and water, oxidation of the surface of the obtained crosslinked cyclic olefin resin composition and crosslinked cyclic olefin resin film of the present invention is prevented, and desired bending is achieved. It becomes possible to demonstrate the nature.

  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 preferably 0.5 to 5,000 μm, and more preferable from the viewpoint of handling properties. The thickness is 5 to 500 μm. The surface of the cross-linked cyclic olefin resin film of the present invention may be smooth, such as by embossing or polymerizing by sandwiching it with a substrate such as polyethylene terephthalate having irregularities to give the surface an irregular shape. May be formed.

Using a known surface treatment technique such as gas phase reaction, coating, vacuum deposition, ion plating, sputtering, CVD, and electroless plating, a layer made of a different material such as an organic material, an inorganic material, or a metal is used to form the crosslinked cyclic olefin of the present invention. It can also be formed on the surface of a resin film. For example, a thin film made of a material that improves releasability, such as silica (SiO ₂ ), magnesium fluoride (MgF ₂ ), and fluorine resin, is provided on the surface layer of the crosslinked cyclic olefin resin film, or a fluorine gas or carbon fiber precursor. The surface of the crosslinked cyclic olefin resin film can be fluorinated by performing a surface treatment.

  The preferable glass transition temperature of the crosslinked cyclic olefin resin composition of the present invention is 135 ° C. or higher from the viewpoints of heat resistance, sealing properties and shape followability.

  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, parts and% in Examples and Comparative Examples are based on mass.

The prepreg peel strength of the crosslinked cyclic olefin resin film was measured as follows.
Printed circuit board lamination prepreg (FR-4 R-1661 (G) GB type manufactured by Panasonic Electric Works Co., Ltd.) punched out to 300mm x 300mm is sandwiched between the crosslinked cyclic olefin resin films of each Example or Comparative Example The sample was inserted into a vacuum press, cured by heating at 2.0 MPa and 180 ° C. for 70 minutes, cooled to 40 ° C., and the obtained sample was taken out from the vacuum press. A test piece of 25 mm × 150 mm was cut out from the sample, and the 180 ° peeling force was measured according to JIS K 6854-2. The said peeling force was made into initial stage prepreg peeling force (N / 25mm).

(Examples 1-8 and Comparative Examples 1-2)
1 part phenolic antioxidant (IRGANOX1076 made by BASF Japan), 1 part phosphorus antioxidant (ADEKA STAB HP-10 made by ADEKA), hindered amine light stabilizer (TINUVIN770 made by BASF Japan) 1 part of an aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or aromatic vinyl compound-isobutylene diblock copolymer in an amount shown in Table 1 and 1 part of triphenylphosphine are added to dicyclophosphine. A reaction stock solution was obtained by dissolving in 100 parts of a norbornene monomer mixture composed of 90% by mass of pentadiene and 10% by mass of tricyclopentadiene. Next, 1.7 parts of a 1.8% cyclopentanone solution (VC843 manufactured by RIMTEC Co., Ltd.) of a ruthenium catalyst having the structure of the formula (7) is added to the reaction stock solution and mixed with a line mixer to obtain a polymerizable composition. I got a thing. The polymerizable composition was cast on a release treatment surface of a polyethylene terephthalate carrier film having a thickness of 0.075 mm and a silicone release treatment at 25 ° C., and cast film was formed. Was covered with a similar carrier film prepared above. Then, it heated at 200 degreeC for 3 minute (s), and the crosslinked cyclic olefin resin film was obtained. 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) Kaneka Corporation SIBSTAR 102T (styrene-isobutylene-styrene triblock copolymer (SIBS), styrene content 15%)
5) SIBSTAR 103T manufactured by Kaneka Corporation (styrene-isobutylene-styrene triblock copolymer (SIBS), styrene content 30%)
6) SIBSTAR 062M manufactured by Kaneka Corporation (mixture of styrene-isobutylene-styrene triblock copolymer (SIBS) and styrene-isobutylene diblock copolymer (SIB), styrene content 23% in the mixture)
7) VC843 manufactured by RIMTEC Co., Ltd. (cyclopentanone solution containing 1.8% ruthenium catalyst)

  The crosslinked cyclic olefin resin films obtained from the polymerizable compositions of Examples 1 to 8 had a small initial prepreg peeling force and were excellent in releasability.

  The crosslinked cyclic olefin resin film obtained from the polymerizable composition of Comparative Example 1 containing neither an aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer nor an aromatic vinyl compound-isobutylene diblock copolymer is Compared with Examples 1 to 8, the initial prepreg peel force was large, and the release property was inferior. In Comparative Example 2, the polymerizable composition having an excessive content of the aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer was solidified, and a film could not be formed from these polymerizable compositions. .

The crosslinked cyclic olefin resin composition of the present invention provides a crosslinked cyclic olefin resin film suitable as a release film used in a semiconductor sealing process in the production of a semiconductor device. The method for carrying out semiconductor sealing using the crosslinked cyclic olefin resin film of the present invention is not particularly limited. Specific examples of the semiconductor sealing method include: (I) a resin encapsulating with a crosslinked cyclic olefin resin film interposed between the lead frame on which the semiconductor chip is mounted and the inner surface of the mold on one side so as to contact the lead frame substrate. And (II) a sealing material is filled between the chip and the mold at the time of sealing between the semiconductor chip surface and at least one mold inner surface of the lead frame substrate on which the semiconductor chip is mounted. In this method, the resin is sealed with a crosslinked cyclic olefin resin film interposed therebetween, that is, a method in which the crosslinked cyclic olefin resin film is interposed on at least one side of the upper mold and the lower mold inner surface.
The crosslinked cyclic olefin resin film of the present invention is suitably used as a release film at the time of manufacturing a printed board and at the time of a cover-laying step for a flexible printed board.

Claims (12)

  (A) 100 parts by mass of a cyclic olefin monomer, (b) 2 to 40 parts by mass of an aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or an aromatic vinyl compound-isobutylene diblock copolymer, and ( c) A crosslinked cyclic olefin resin composition obtained by metathesis polymerization of a polymerizable composition containing a metathesis polymerization catalyst.   The crosslinked cyclic olefin resin composition according to claim 1, wherein the (a) cyclic olefin monomer is a norbornene-based monomer.   The crosslinked cyclic olefin resin composition according to claim 1 or 2, wherein the (c) metathesis polymerization catalyst is a ruthenium carbene complex.   A crosslinked cyclic olefin resin film comprising the crosslinked cyclic olefin resin composition according to claim 1.   The crosslinked cyclic olefin resin film according to claim 4, which is a release film used in a semiconductor sealing process.   The crosslinked cyclic olefin resin film according to claim 4, which is a release film for producing a printed circuit board.   (A) 100 parts by mass of a cyclic olefin monomer, (b) 2 to 40 parts by mass of an aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or an aromatic vinyl compound-isobutylene diblock copolymer, and ( c) A method for producing a crosslinked cyclic olefin resin composition, comprising a step of metathesis polymerizing a polymerizable composition containing a metathesis polymerization catalyst.   The manufacturing method of the crosslinked cyclic olefin resin composition of Claim 7 whose said (a) cyclic olefin monomer is a norbornene-type monomer.   The method for producing a crosslinked cyclic olefin resin composition according to claim 7 or 8, wherein the (c) metathesis polymerization catalyst is a ruthenium carbene complex.   (A) 100 parts by mass of a cyclic olefin monomer, (b) 2 to 40 parts by mass of an aromatic vinyl compound-isobutylene-aromatic vinyl compound triblock copolymer and / or an aromatic vinyl compound-isobutylene diblock copolymer, and ( c) The manufacturing method of a crosslinked cyclic olefin resin film including the process of apply | coating polymeric composition containing a metathesis polymerization catalyst on a base material, and performing metathesis polymerization on the said base material.   The manufacturing method of the crosslinked cyclic olefin resin film of Claim 10 whose said (a) cyclic olefin monomer is a norbornene-type monomer.   The method for producing a crosslinked cyclic olefin resin film according to claim 10 or 11, wherein the (c) metathesis polymerization catalyst is a ruthenium carbene complex.