JP2014205792A - Crosslinked cyclic olefin resin composition, crosslinked cyclic olefin resin film and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crosslinked cyclic olefin resin composition for providing a film having sufficient releasability from resin used for sealing material, prepreg, adhesive or the like.SOLUTION: A crosslinked cyclic olefin resin composition is obtained by metathesis polymerization of a polymerizable composition comprising (a) cyclic olefin monomer 100 pts.mass, (b) cyclized conjugated diene polymer 0.3-25 pts.mass and (c) 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 conducted a metathesis polymerization of a polymerizable composition containing (a) a cyclic olefin monomer, (b) a conjugated diene polymer cyclized product and (c) a metathesis polymerization catalyst. The crosslinked cyclic olefin resin composition of the present invention is found to provide a film having sufficient releasability from the resin used for the sealing material, prepreg, adhesive and the like. The present inventors have completed a crosslinked cyclic olefin resin film comprising the resin composition and a method for producing the same.

  The crosslinked cyclic olefin resin composition of the present invention comprises (a) 100 parts by mass of a cyclic olefin monomer, (b) 0.3 to 25 parts by mass of a conjugated diene polymer cyclized product, and (c) a metathesis polymerization catalyst. The product is obtained by metathesis polymerization. The polymerizable composition preferably further contains (d) an organic peroxide having a half-temperature of 160 to 200 ° C. for 1 minute. 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 the present invention comprises a 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 manufacturing method of the crosslinked cyclic olefin resin composition of this invention contains (a) 100 mass parts of cyclic olefin monomers, (b) 0.3-25 mass parts of conjugated diene polymer cyclized products, and (c) a metathesis polymerization catalyst. A step of subjecting the polymerizable composition to metathesis polymerization. The polymerizable composition preferably further contains (d) an organic peroxide having a half-temperature of 160 to 200 ° C. for 1 minute. 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 according to the present invention comprises (a) 100 parts by mass of a cyclic olefin monomer, (b) 0.3-25 parts by mass of a conjugated diene polymer cyclized product, and (c) a polymerization containing a metathesis polymerization catalyst. The process which apply | coats an adhesive composition on a base material, and performs metathesis polymerization on the said base material is included. The polymerizable composition preferably further contains (d) an organic peroxide having a half-temperature of 160 to 200 ° C. for 1 minute. 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) 0.3 to 25 parts by mass of a conjugated diene polymer cyclized product, and (c) a metathesis polymerization catalyst. The product is obtained by metathesis polymerization.

(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 ] non-polar 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 ] dodeca-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, acetic acid 5-norbornene-2 -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 polymerizable composition containing (a) a cyclic olefin monomer, (b) a conjugated diene polymer cyclized product, and (c) a metathesis polymerization catalyst is metathesized. To do. (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 catalytic activity during bulk polymerization, a crosslinked cyclic olefin polymer with little residual unreacted monomer can be obtained with high productivity.

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

In the formulas (1) and (2), R ¹ and R ² each independently include a hydrogen atom; a halogen atom; or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. A cyclic or chain-like hydrocarbon group having 1 to 20 carbon atoms; X ¹ and X ² each independently represent 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 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. , 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 above 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 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. Further, 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 at the time of bulk 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 involves metathesis polymerization of a polymerizable composition containing (a) a cyclic olefin monomer, (b) a conjugated diene polymer cyclized product, and (c) a metathesis polymerization catalyst in the presence of an additive used as necessary. It is used suitably in the process to do.
(A) The cyclic olefin monomer is metathesized to obtain a cyclic olefin polymer, and the cyclic olefin polymer is crosslinked after the metathesis polymerization or simultaneously with the metathesis polymerization to obtain a crosslinked cyclic olefin polymer. Conceivable.

The crosslinked cyclic olefin resin composition of the present invention contains, as one of the raw materials, 0.3 to 25 parts by mass of (b) conjugated diene polymer cyclized product with respect to 100 parts by mass of (a) cyclic olefin monomer. (B) A conjugated diene polymer cyclized product can be obtained by cyclizing a conjugated diene polymer in the presence of an acid catalyst or the like.
As the conjugated diene polymer, a homopolymer of a conjugated diene monomer and a copolymer of a conjugated diene monomer and other monomers copolymerizable therewith can be used.
The conjugated diene monomer is not particularly limited, and specific examples thereof include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1, Examples include 3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene. Among these, 1,3-butadiene and isoprene are preferable, and isoprene is more preferable.
These monomers may be used alone or in combination of two or more.

Examples of other monomers copolymerizable with the conjugated diene monomer include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, and p-tert. Fragrances such as butyl styrene, α-methyl styrene, α-methyl-p-methyl styrene, o-chloro styrene, m-chloro styrene, p-chloro styrene, p-bromo styrene, 2,4-dibromo styrene and vinyl naphthalene Chain vinyl olefin monomers such as ethylene, propylene and 1-butene; cyclic olefin monomers such as cyclopentene and 2-norbornene; 1,5-hexadiene, 1,6-heptadiene, 1,7 Non-conjugated diene monomers such as octadiene, dicyclopentadiene and 5-ethylidene-2-norbornene; (Meth) acrylic acid esters such as methyl (meth) acrylate and ethyl (meth) acrylate; other (meth) acrylic acid derivatives such as (meth) acrylonitrile and (meth) acrylamide; Of these, aromatic vinyl monomers are preferred, and styrene is more preferred.
These monomers may be used alone or in combination of two or more.

The content of the conjugated diene monomer unit in the conjugated diene polymer is appropriately selected within a range not impairing the effects of the present invention, but is preferably 40 mol% or more, more preferably 60 mol% or more, and still more preferably 80. More than mol%. Especially, what consists only of a conjugated diene monomer unit is especially preferable. When the content of the conjugated diene monomer unit is not less than the above lower limit, it is possible to obtain an unsaturated bond reduction rate in an appropriate range.
The polymerization method of the conjugated diene polymer may be in accordance with a conventional method. Performed by polymerization.

  Specific examples of the conjugated diene polymer include natural rubber (NR), styrene-butadiene rubber (SBR), polyisoprene rubber (IR), polybutadiene rubber (BR), isoprene-isobutylene copolymer rubber (IIR), ethylene- Examples thereof include propylene-diene copolymer rubber (EPDM), butadiene-isoprene copolymer rubber (BIR), and aromatic vinyl-conjugated diene block copolymer. Among these, polyisoprene rubber, polybutadiene rubber and styrene-isoprene block copolymer are preferable, and polyisoprene rubber is more preferable.

The (b) conjugated diene polymer cyclized product used in the present invention can be obtained by cyclizing the conjugated diene polymer in the presence of an acid catalyst or the like.
A well-known thing can be used as an acid catalyst used suitably for cyclization reaction. Specific examples thereof include sulfuric acid; fluoromethanesulfonic acid, difluoromethanesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, alkylbenzenesulfonic acid having an alkyl group having 2 to 18 carbon atoms, and anhydrides and alkyls thereof. Organic sulfonic acid compounds such as esters; boron trifluoride, boron trichloride, tin tetrachloride, titanium tetrachloride, aluminum chloride, diethylaluminum monochloride, ethylammonium chloride, aluminum bromide, antimony pentachloride, tungsten hexachloride and chloride Lewis acids such as iron; and the like. These acid catalysts may be used alone or in combination of two or more. Among these, organic sulfonic acid compounds are preferable, p-toluenesulfonic acid and xylenesulfonic acid are more preferable, and p-toluenesulfonic acid is more preferable.
The amount of the acid catalyst used is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.3 to 2 parts by mass with respect to 100 parts by mass of the conjugated diene polymer. is there.

The cyclization reaction can be performed, for example, by dissolving a conjugated diene polymer in a hydrocarbon solvent.
The hydrocarbon solvent is not particularly limited as long as it does not inhibit the cyclization reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; n-pentane, n-hexane, n-heptane and n -Chain aliphatic hydrocarbons such as octane; Alicyclic hydrocarbons such as cyclopentane and cyclohexane; The boiling point of these hydrocarbon solvents is preferably 70 ° C. or higher.
The solvent used for the polymerization reaction of the conjugated diene polymer and the solvent used for the cyclization reaction may be of the same type. In this case, an acid catalyst for cyclization reaction can be added to the polymerization reaction solution after completion of the polymerization reaction, and the cyclization reaction can be carried out following the polymerization reaction.
The amount of the hydrocarbon solvent used is such that the solid content concentration of the conjugated diene polymer is, for example, 5 to 60% by weight, preferably 20 to 40% by weight.

The cyclization reaction can be performed under pressure, reduced pressure, or atmospheric pressure, but is preferably performed under atmospheric pressure from the viewpoint of simplicity of operation. Further, it is preferable to perform the cyclization reaction in a dry air flow, particularly in an atmosphere of dry nitrogen or dry argon, because side reactions caused by moisture can be suppressed.
The reaction temperature and reaction time in the cyclization reaction are not particularly limited. The reaction temperature is preferably 50 to 150 ° C., more preferably 70 to 110 ° C., and the reaction time is preferably 0.5 to 10 hours, more preferably 2 to 5 hours.
After carrying out the cyclization reaction, the acid catalyst is deactivated by a conventional method, the acid catalyst residue is removed, and then the hydrocarbon solvent is removed to obtain a solid (b) conjugated diene polymer cyclized product. Can do.

(B) The unsaturated bond reduction rate of the conjugated diene polymer cyclized product is preferably 10% or more, more preferably 25 to 75%, and still more preferably 45 to 70%. When the unsaturated bond reduction rate is at least the above lower limit, the mechanical strength of the obtained crosslinked cyclic olefin resin composition of the present invention can be increased. When the unsaturated bond reduction rate is less than or equal to the above upper limit, the production becomes easy.
Here, the unsaturated bond reduction rate is an index representing the degree to which the unsaturated bond is reduced by the cyclization reaction in the conjugated diene monomer unit portion in the conjugated diene polymer, and is obtained as follows. It is a numerical value. That is, by proton NMR analysis, in the conjugated diene monomer unit portion in the conjugated diene polymer, the ratio of the peak area of the proton directly bonded to the double bond to the peak area of all protons is measured before and after the cyclization reaction, respectively. Calculate the reduction rate.
In the conjugated diene monomer unit in the conjugated diene polymer, the total proton peak area before the cyclization reaction is SBT, the peak area of the proton directly bonded to the double bond is SBU, and the total proton peak after the cyclization reaction When the area is SAT and the peak area of protons directly bonded to a double bond is SAU,
The peak area ratio (SB) of the proton directly bonded to the double bond before the cyclization reaction is
SB = SBU / SBT
The peak area ratio (SA) of the proton directly bonded to the double bond after the cyclization reaction is
SA = SAU / SAT
Therefore, the unsaturated bond reduction rate is obtained by the following equation.
Unsaturated bond reduction rate (%) = 100 × (SB−SA) / SB
(B) The unsaturated bond reduction rate of the conjugated diene polymer cyclized product can be adjusted by appropriately selecting the amount of the acid catalyst, the reaction temperature, the reaction time, and the like during the cyclization reaction.

(B) The weight average molecular weight of the conjugated diene polymer cyclized product is a standard polystyrene conversion value measured by gel permeation chromatography, preferably 1,000 to 1,000,000, more preferably 10,000 to. 700,000, more preferably 30,000 to 500,000.
(B) When the weight average molecular weight of the conjugated diene polymer cyclized product is not less than the above lower limit, the mechanical strength of the obtained crosslinked cyclic olefin resin composition of the present invention can be increased. (B) When the weight average molecular weight of the conjugated diene polymer cyclized product is not more than the above upper limit, the viscosity of the reaction solution at the time of the cyclization reaction does not increase, and the handling becomes easy.
(B) The weight average molecular weight of the conjugated diene polymer cyclized product can be adjusted by appropriately selecting the weight average molecular weight of the conjugated diene polymer used as a raw material.

(B) The glass transition temperature (Tg) of the conjugated diene polymer cyclized product is not particularly limited and can be appropriately selected depending on the application, but is preferably -50 to 200 ° C, more preferably 0 to 100 ° C. More preferably, it is 20-90 degreeC, Most preferably, it is the range of 30-70 degreeC. (B) When the Tg of the conjugated diene polymer cyclized product is within the above range, the handleability is improved.
(B) The Tg of the conjugated diene polymer cyclized product can be adjusted by appropriately selecting the composition of the conjugated diene polymer used as a raw material and the unsaturated bond reduction rate.

  (B) The amount of gel of the conjugated diene polymer cyclized product (ratio of toluene-insoluble matter) is preferably 10% by mass or less, more preferably 5% by mass or less, but has substantially no gel. It is more preferable. When the gel amount is not more than the above upper limit, it is possible to prepare a polymerizable composition that is a precursor of the crosslinked cyclic olefin resin composition of the present invention as a substantially uniform solution.

  The content of (b) conjugated diene polymer cyclized product in the polymerizable composition which is a precursor of the crosslinked cyclic olefin resin composition of the present invention is 0.3 to 100 parts by mass of (a) 100 parts by mass of the cyclic olefin monomer. 25 parts by mass, preferably 0.5 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass. (B) By making content of a conjugated diene polymer cyclized product into the said range, the mold release property of the crosslinked cyclic olefin resin film of this invention becomes favorable. 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 (b) conjugated diene polymer cyclized product used in the present invention may contain a stabilizer.
(B) The content of the stabilizer in the conjugated diene polymer cyclized product is preferably 500 ppm or less, more preferably 400 ppm or less, and still more preferably 300 ppm or less. The lower limit of the stabilizer content is preferably 10 ppm or more, more preferably 20 ppm or more. About the kind of stabilizer, it is the same as the stabilizer which can be contained in the polymeric composition mentioned later.

  The polymerizable composition which is a precursor of the crosslinked cyclic olefin resin composition of the present invention includes (d) an organic peroxide having a half-temperature of 160 to 200 ° C. for 1 minute (hereinafter referred to as “(d) organic peroxide”). It is preferable to contain. The (d) organic peroxide functions as a cross-linking agent described later in the present invention. Specific examples of the (d) organic peroxide include bis (t-butyldioxyisopropyl) benzene and di-t-butyl peroxide. These (d) organic peroxides having a half-life temperature of 160 to 200 ° C. for 1 minute are used singly or in combination of two or more.

  (D) In an organic peroxide having a half-life temperature of 160 to 200 ° C. for 1 minute, the preferred half-temperature temperature for 1 minute is 170 to 195 ° C., the more preferred half-temperature for 1 minute is 180 to 195 ° C., and even more preferred 1 minute The half-temperature is 185 to 195 ° C, and the particularly preferred half-hour 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, (d) the content of the organic peroxide having a half-temperature of 160 to 200 ° C. for 1 minute is: (a) the cyclic olefin monomer 100 Preferably it is 0.3-8 mass parts with respect to a mass part, More preferably, it is 0.5-6 mass parts, More preferably, it is 0.5-4 mass parts. (D) The content of the organic peroxide having a half-life temperature of 160 to 200 ° C. for 1 minute is not less than the above lower limit, so that the glass transition temperature of the crosslinked cyclic olefin resin composition of the present invention does not decrease, and the present invention. The release property of the crosslinked cyclic olefin resin film becomes good. (D) It can prevent that the crosslinked cyclic olefin resin composition of this invention becomes weak because content of the organic peroxide whose half-temperature for 1 minute is 160-200 degreeC is below the said upper limit.

  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-butyldiben [D, f] [1,3,2] - a dioxaphosphepine 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 and α-cyano-β-methyl-β- [N − (2,2, , 4-6-tetramethylpiperidin-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) a conjugated diene polymer cyclized product, (c) a metathesis polymerization catalyst and additives used as necessary. Metathesis polymerization of the polymerizable composition is contained. (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.

  The viscosity at room temperature (20 ° C.) of the polymerizable composition containing (a) a cyclic olefin monomer, (b) a conjugated diene polymer cyclized product, (c) a metathesis polymerization catalyst and an additive used as necessary is as desired. Although depending on the thickness of the film, 0.4 to 500 mPa · s is preferable. 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 adjusted by the type and amount of (a) cyclic olefin monomer, (b) conjugated diene polymer cyclized product, (c) metathesis polymerization catalyst and additives used as necessary. .

  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.

  If necessary, the polymerizable composition is heated to a temperature at which (c) the metathesis polymerization catalyst exhibits activity, and bulk polymerization is performed. The polymerization temperature is, for example, 0 to 250 ° C, preferably 20 to 200 ° C. The method for heating the polymerizable composition is not particularly limited. Specific examples of the heating method include a method of heating on a heating plate, a method of heating (hot pressing) while applying pressure using a press, a method of pressing with a heated roller, and a method of using a heating furnace. The polymerization reaction time is appropriately determined depending on the amount of (c) metathesis polymerization catalyst and the heating temperature, and is, for example, 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 these, (d) organic peroxides described above are particularly preferable. The amount of the crosslinking agent used is preferably 0.3 to 8 parts by mass, more preferably 0.5 to 6 parts by mass with respect to 100 parts by mass of (a) the cyclic olefin monomer. The temperature at which crosslinking is performed when a thermal crosslinking agent is used is, for example, 100 to 250 ° C, preferably 150 to 200 ° C. The time for crosslinking is not particularly limited, and is, for example, 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. For example, the thickness is 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 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, 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 film of the present invention is 135 ° C. or higher from the viewpoint 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.

Various physical properties were measured as follows.
(1) (b) Weight average molecular weight of conjugated diene polymer cyclized product The above weight average molecular weight was determined in terms of standard polystyrene in GPC (gel permeation chromatography) method under the following conditions.
Solvent; tetrahydrofuran column temperature: 40 ° C
Flow rate: 0.3 ml / min
Guard column: Plgel MiniMix-A GUARD 20 μm, 4.6 mm I.D. D. × 5cm (manufactured by Polymer Laboratories)
Analytical column: Plgel MiniMix-A 20 μm, 4.6 mm I.D. D. × 25cm × 3 (manufactured by Polymer Laboratories)
Detector: RI detector / Waters 2414 (manufactured by Waters)

(2) Pre-preg peeling force for crosslinked cyclic olefin resin film 300 mm × 300 mm printed board lamination prepreg (FR-4 R-1661 (G) GB type, thickness 0.2 mm, manufactured by Panasonic Electric Works Co., Ltd.) Both surfaces are sandwiched between the release films of each Example or Comparative Example and inserted into a vacuum press, heat cured at 1.0 MPa and 180 ° C. for 70 minutes, then cooled to 40 ° C., and the resulting sample is vacuumed Removed from the press. A test piece of 25 mm × 150 mm was cut out from the sample, and a 180 ° peeling force (peeling speed 200 mm / min) was measured according to JIS K 6854-2. The said peeling force was made into the prepreg peeling force. The smaller the prepreg peel force is, the higher the releasability is.

(Production Example 1: Production of conjugated diene polymer cyclized product A)
Nipol IR-2200 (manufactured by Nippon Zeon Co., Ltd., cis-1,4-bond unit content 99% or more) was kneaded with a roll to obtain high cis polyisoprene (weight average molecular weight 302,000). 300 parts of high-cis polyisoprene cut into 10 mm square were charged together with 700 parts of toluene into a pressure-resistant reactor equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas introduction pipe. After the inside of the reactor was purged with nitrogen, it was heated to 85 ° C. and the high-cis polyisoprene was completely dissolved in toluene with stirring, and then p-toluenesulfonic acid (in toluene, the water content was adjusted to 150 ppm or less). (Hereinafter referred to as “paratoluenesulfonic anhydride”) was added in an amount of 2.16 parts, and a cyclization reaction was performed at 85 ° C. After reacting for 4 hours, a 25% aqueous sodium carbonate solution containing 0.75 part of sodium carbonate was added to stop the reaction. Washing with 300 parts of ion-exchanged water was repeated 3 times at 85 ° C. to remove catalyst residues in the system. The resulting conjugated diene polymer cyclized product A had an unsaturated bond reduction rate of 61% and a weight average molecular weight of 200,000.
(Production Example 2: Production of conjugated diene polymer cyclized product B)
A conjugated diene polymer cyclized product B was obtained in the same manner as in Production Example 1 except that the reaction time was changed to 3 hours. The resulting conjugated diene polymer cyclized product B had an unsaturated bond reduction rate of 49% and a weight average molecular weight of 200,000.

Example 1
1 part phenolic antioxidant (IRSFANOX1076 manufactured by BASF Japan), 1 part phosphorus antioxidant (ADEKA STAB HP-10 manufactured by ADEKA), hindered amine light stabilizer (TINUVIN770 manufactured by BASF Japan) 1 part, 0.5 part of conjugated diene polymer cyclized product A and 1 part of triphenylphosphine are dissolved in 100 parts of a norbornene-based monomer mixture composed of 90% by mass of dicyclopentadiene and 10% by mass of tricyclopentadiene, and the reaction stock solution. Got. 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.

(Examples 2 to 5)
A crosslinked cyclic olefin resin film was obtained in the same manner as in Example 1 except that the addition amount of the conjugated diene polymer cyclized product A was changed to the amount shown in Table 1. The results are shown in Table 1.
(Example 6)
Along with 1.7 parts of a 1.8% cyclopentanone solution of a ruthenium catalyst having the structure of the formula (7) (RIMTEC Co., Ltd., VC843), an organic peroxide (manufactured by Kayaku Akzo Co., Ltd., Kayabutyl D, A crosslinked cyclic olefin resin film was obtained in the same manner as in Example 3 except that 0.5 part (half-temperature 192 ° C. for 1 minute) was added to the reaction stock solution and mixed with a line mixer. The results are shown in Table 1.
(Examples 7 to 8)
A crosslinked cyclic olefin resin was prepared in the same manner as in Example 6 except that the addition amount of the organic peroxide (manufactured by Kayaku Akzo Co., Ltd., Kayabutyl D, half minute temperature 192 ° C.) was changed to the amount shown in Table 1. A film was obtained. The results are shown in Table 1.
Example 9
A crosslinked cyclic olefin resin film was obtained in the same manner as in Example 1 except that 0.5 part of the conjugated diene polymer cyclized product A was changed to 1 part of the conjugated diene polymer cyclized product B. The results are shown in Table 1.
(Example 10)
A crosslinked cyclic olefin resin film was obtained in the same manner as in Example 9 except that the addition amount of the conjugated diene polymer cyclized product B was changed to the amount shown in Table 1. The results are shown in Table 1.
(Example 11)
A crosslinked cyclic olefin resin film was obtained in the same manner as in Example 7 except that 5 parts of the conjugated diene polymer cyclized product A was changed to 5 parts of the conjugated diene polymer cyclized product B. The results are shown in Table 1.

(Comparative Example 1)
A crosslinked cyclic olefin resin film was obtained in the same manner as in Example 1 except that the conjugated diene polymer cyclized product A was not added. The results are shown in Table 2.
(Comparative Example 2)
A crosslinked cyclic olefin resin film was obtained in the same manner as in Example 1 except that the addition amount of the conjugated diene polymer cyclized product A was changed to 30 parts. The results are shown in Table 2.
(Comparative Example 3)
A polymerizable composition was obtained in the same manner as in Example 1 except that the addition amount of the conjugated diene polymer cyclized product A was changed to 50 parts. However, the polymerizable composition was solidified to obtain a crosslinked cyclic olefin resin film. I couldn't.

  Tables 1 and 2 show the measurement results of the prepreg peel strength of the obtained crosslinked cyclic olefin resin film.

1) IRGANOX1076 manufactured by BASF Japan
2) Adeka Stub HP-10 manufactured by ADEKA Corporation
3) TINUVIN770 manufactured by BASF Japan
4) Kayabutyl D manufactured by Kayaku Akzo Co., Ltd.

  The crosslinked cyclic olefin resin films obtained from the polymerizable compositions of Examples 1 to 11 had a small prepreg peeling force and a high releasability.

The crosslinked cyclic olefin resin film obtained from the polymerizable composition of Comparative Example 1 that does not contain a conjugated diene polymer cyclized product had a large prepreg peel force and low releasability as compared with Examples 1-11. .
The crosslinked cyclic olefin resin film obtained from the polymerizable composition of Comparative Example 2 containing more than the specified amount of the conjugated diene polymer cyclized product has a large prepreg peeling force compared to Examples 1 to 11, and the mold release The sex was low. Since the polymerizable composition of Comparative Example 3 containing a larger amount of the conjugated diene polymer cyclized product than the amount used in Comparative Example 2 was solidified and a film was not obtained, evaluation of prepreg peel strength was not performed. It was.

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 (15)

  (A) 100 mass parts of cyclic olefin monomer, (b) 0.3-25 mass parts of conjugated diene polymer cyclized product, and (c) cross-linked cyclic olefin resin obtained by metathesis polymerization of a polymerizable composition containing a metathesis polymerization catalyst Composition.   The crosslinked cyclic olefin resin composition according to claim 1, wherein the polymerizable composition further contains (d) an organic peroxide having a half-temperature of 160 to 200 ° C for 1 minute.   The crosslinked cyclic olefin resin composition according to claim 1 or 2, 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 3, wherein the (c) metathesis polymerization catalyst is a ruthenium carbene complex.   The crosslinked cyclic olefin resin film which consists of a crosslinked cyclic olefin resin composition of any one of Claims 1-4.   The crosslinked cyclic olefin resin film according to claim 5, which is a release film used in a semiconductor sealing process.   The crosslinked cyclic olefin resin film according to claim 5, which is a release film for producing a printed circuit board.   (A) 100 mass parts of cyclic olefin monomer, (b) 0.3-25 mass parts of conjugated diene polymer cyclized product, and (c) cross-linked cyclic comprising a step of metathesis polymerizing a polymerizable composition containing a metathesis polymerization catalyst A method for producing an olefin resin composition.   The method for producing a crosslinked cyclic olefin resin composition according to claim 8, wherein the polymerizable composition further contains (d) an organic peroxide having a half-temperature of 160 to 200 ° C for 1 minute.   The method for producing a crosslinked cyclic olefin resin composition according to claim 8 or 9, wherein the (a) cyclic olefin monomer is a norbornene-based monomer.   The manufacturing method of the crosslinked cyclic olefin resin composition of any one of Claims 8-10 whose said (c) metathesis polymerization catalyst is a ruthenium carbene complex.   (A) 100 parts by mass of a cyclic olefin monomer, (b) 0.3 to 25 parts by mass of a conjugated diene polymer cyclized product, and (c) a polymerizable composition containing a metathesis polymerization catalyst is applied onto a substrate, and metathesis polymerization is performed. The manufacturing method of a crosslinked cyclic olefin resin film including the process of performing on the said base material.   The method for producing a crosslinked cyclic olefin resin film according to claim 12, wherein the polymerizable composition further contains (d) an organic peroxide having a half-temperature of 160 to 200 ° C for 1 minute.   The method for producing a crosslinked cyclic olefin resin film according to claim 12 or 13, wherein the (a) cyclic olefin monomer is a norbornene-based monomer.   The manufacturing method of the crosslinked cyclic olefin resin film of any one of Claims 12-14 whose said (c) metathesis polymerization catalyst is a ruthenium carbene complex.