JPWO2014045712A1 - Cross-linked cyclic olefin resin composition, cross-linked cyclic olefin resin film, and production method thereof - Google Patents

Abstract

The crosslinked cyclic olefin resin composition is prepared by: (a) 100 parts by mass of a cyclic olefin monomer; (b) 0.2 to 40 parts by mass of a crosslinking agent having two or more polymerizable unsaturated bonds; 0.1 to 10 parts by mass of an organic peroxide thermal polymerization initiator at ˜200 ° C., (d) 2 to 8 parts by mass of a phenolic antioxidant, (e) 2 to 8 parts by mass of a hindered amine light stabilizer, f) A polymerizable composition containing 2 to 8 parts by mass of a phosphorus-based antioxidant and (g) a ring-opening metathesis polymerization catalyst is obtained by ring-opening metathesis polymerization.

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 a reduction in the sealing film thickness.

  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 cross-linked 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 the resin used for the sealing material, prepreg, and adhesive.

  Furthermore, the outer layer contains a 4-methyl-1-pentene polymer resin, the inner layer contains a polyolefin resin, a phenolic oxidation stabilizer, a phosphorus stabilizer or a sulfur stabilizer, and above and below the inner layer, A release film for producing a printed circuit board comprising a multilayer resin layer having an outer layer has been studied (for example, see Patent Document 4). However, if the film continues to be exposed to high temperatures during the production of printed circuit boards, the color changes.

Japanese Patent Publication “JP 2000-167841 A” Japanese Patent Publication “JP 2001-250838 A” Japanese Patent Publication “JP 2001-253934 A” Japanese Patent Publication “JP 2000-263724 A”

  Recently, including a crosslinked cyclic olefin resin obtained by ring-opening metathesis polymerization of cyclic olefin monomers, sufficient release properties before and after heating with resins used for sealing materials, prepregs, and adhesives, and high glass transition temperature There has been a demand for a film having low odor during heating, mechanical strength such as tensile elongation at break and tensile strength at break, and high-temperature discoloration resistance, but no such film has been found.

  The problem to be solved by the present invention includes a crosslinked cyclic olefin resin obtained by ring-opening metathesis polymerization of a cyclic olefin monomer, and sufficient separation before and after heating with a resin used for a sealing material, a prepreg, and an adhesive. Cross-linked cyclic olefin resin composition that provides a film having moldability, high glass transition temperature, low odor property during heating, mechanical strength such as tensile elongation at break, tensile strength at break, and high-temperature discoloration resistance, the film And the production method thereof.

  As a result of intensive studies, the inventor of the present invention has found that (a) a cyclic olefin monomer, (b) a crosslinking agent having two or more polymerizable unsaturated bonds, (c) an organic solvent having a half-temperature of 160 to 200 ° C. for 1 minute. Polymeric composition containing oxide thermal polymerization initiator, (d) phenolic antioxidant, (e) hindered amine light stabilizer, (f) phosphorus antioxidant and (g) ring-opening metathesis polymerization catalyst The crosslinked cyclic olefin resin composition obtained by ring-opening metathesis polymerization is sufficiently releasable before and after heating with a resin used for a sealing material, prepreg, adhesive, high glass transition temperature, The present invention provides a film having low odor, mechanical strength such as tensile breaking elongation and tensile breaking strength, and high temperature discoloration resistance, and a film comprising the crosslinked cyclic olefin resin composition of the present invention and the resin composition. And This has led to the completion of the manufacturing method of the et al.

  The crosslinked cyclic olefin resin composition of the present invention comprises (a) 100 parts by mass of a cyclic olefin monomer, (b) 0.2 to 40 parts by mass of a crosslinking agent having two or more polymerizable unsaturated bonds, and (c) halved for 1 minute. 0.1 to 10 parts by mass of an organic peroxide thermal polymerization initiator having a temperature of 160 to 200 ° C., (d) 2 to 8 parts by mass of a phenolic anti-aging agent, and (e) 2 to 8 parts by mass of a hindered amine light stabilizer. Part (f) 2 to 8 parts by mass of a phosphorus-based antioxidant and (g) a ring-opening metathesis polymerization catalyst.

  The crosslinked cyclic olefin resin film of the present invention comprises the above polymerizable composition. A preferable application of the crosslinked cyclic olefin resin film is a release film used in a semiconductor sealing process or a printed board manufacturing process.

  The production method of the crosslinked cyclic olefin resin composition of the present invention includes (a) 100 parts by mass of a cyclic olefin monomer, (b) 0.2 to 40 parts by mass of a crosslinking agent having two or more polymerizable unsaturated bonds, (c) 0.1 to 10 parts by mass of an organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C. for 1 minute, (d) 2 to 8 parts by mass of a phenolic antioxidant, (e) a hindered amine light stabilizer 2 A step of ring-opening metathesis polymerization of a polymerizable composition containing ˜8 parts by mass, (f) 2 to 8 parts by mass of a phosphorus-based antioxidant, and (g) a ring-opening metathesis polymerization catalyst.

  The method for producing a crosslinked cyclic olefin resin film of the present invention comprises (a) 100 parts by mass of a cyclic olefin monomer, (b) 0.2 to 40 parts by mass of a crosslinking agent having two or more polymerizable unsaturated bonds, (c) 1 0.1 to 10 parts by weight of an organic peroxide thermal polymerization initiator having a half-life temperature of 160 to 200 ° C., (d) 2 to 8 parts by weight of a phenolic antioxidant, (e) 2 to 2 hindered amine light stabilizers 8 parts by mass, (f) a polymerizable composition containing 2 to 8 parts by mass of a phosphorus-based antioxidant and (g) a ring-opening metathesis polymerization catalyst is applied onto the support, and the ring-opening metathesis polymerization is performed on the support. The process performed by is implemented.

  The crosslinked cyclic olefin resin composition of the present invention has sufficient release properties before and after heating with a resin used for a sealing material, a prepreg, and an adhesive, a high glass transition temperature, and a low odor property during heating, A film having mechanical strength such as tensile elongation at break and tensile strength at break and high-temperature discoloration resistance is provided.

  (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 tetracyclododecenes. These may contain as substituents hydrocarbon groups such as alkyl groups, alkenyl groups, alkylidene groups, and aryl groups; polar groups such as carboxyl groups and acid anhydride groups.

  The norbornene monomer may further have a double bond in addition to the double bond of the norbornene ring. A preferred norbornene-based monomer is a non-polar monomer, that is, a norbornene-based monomer composed only of carbon atoms and hydrogen atoms.

Specific examples of the nonpolar norbornene-based monomer include noncyclopentadiene, methyldicyclopentadiene, and dihydrodicyclopentadiene (also referred to as tricyclo [5.2.1.0 ^2,6 ] dec-8-ene). Polar dicyclopentadiene;
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyclohexyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyclopentyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-vinyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-propenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyclohexenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyclopentenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-phenyltetracyclo [6.2.1.1 ^3,6 . Non-polar tetracyclododecenes such as 0 ^2,7 ] dodec-4-ene;
2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-cyclohexyl-2- Norbornene, 5-cyclopentyl-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-cyclohexenyl-2-norbornene, 5-cyclopentenyl-2- norbornene, 5-phenyl-2-norbornene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), tetracyclo [10.2.1.0. ^2,11 . Non-polar norbornenes such as 0 ^4,9 ] pentadeca-4,6,8,13-tetraene (also referred to as 1,4-methano-1,4,4a, 9,9a, 10-hexahydroanthracene);
Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-4,10-diene, pentacyclo [9.2.1.1 ^4,7. 0 ^2,10 . 0 ^3,8 ] pentadeca-5,12-diene, hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-non-polar cyclic olefins or pentacyclic body such as ene; and the like.

  From the viewpoint of availability and improvement in heat resistance of the film, preferred nonpolar norbornene monomers are nonpolar dicyclopentadienes and nonpolar tetracyclododecenes, and more preferred nonpolar norbornene monomers are nonpolar dicyclones. Cyclopentadiene.

Specific examples of the norbornene-based monomer containing a polar group include tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] methyl dodeca-9-ene-4-carboxylate, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-methanol, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] 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-norbornene-2-ol, 5-norbornene-2-carbonitrile, 2-acetyl-5-norbornene, 7-oxa-2-norbornene and the like.

  Specific examples of the monocyclic olefin include cyclobutene, cyclopentene, cyclohexene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, and derivatives thereof having a substituent.

  These (a) cyclic olefin monomers are used singly or in combination of two or more. The addition amount of the monocyclic olefin is preferably 40% by mass or less, more preferably 20% by mass or less, based on the total amount of the (a) cyclic olefin monomer. If the amount of monocyclic olefin added is too large, the heat resistance of the film may be insufficient.

  When obtaining the crosslinked cyclic olefin resin composition of the present invention, at least (a) a cyclic olefin monomer, (b) a crosslinking agent having two or more polymerizable unsaturated bonds, and (c) a half-minute temperature of 160 to 160 minutes. Contains an organic peroxide thermal polymerization initiator at 200 ° C., (d) a phenolic antioxidant, (e) a hindered amine light stabilizer, (f) a phosphorus antioxidant, and (g) a ring-opening metathesis polymerization catalyst. The polymerizable composition is subjected to metathesis polymerization. (G) The ring-opening metathesis polymerization catalyst metatheses (a) a cyclic olefin monomer. The (g) ring-opening metathesis polymerization catalyst is not limited to a specific catalyst.

  A complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds around a transition metal atom is used as the (g) ring-opening metathesis polymerization catalyst. Atoms of Group 5, Group 6, and Group 8 (long-period periodic table, the same applies hereinafter) are used as transition metal atoms. The atoms of each group are not particularly limited, but the preferred Group 5 atom is tantalum, the preferred Group 6 atom is molybdenum and tungsten, and the preferred Group 8 atom is ruthenium and osmium.

  A preferable (g) ring-opening metathesis polymerization catalyst is a complex of Group 8 ruthenium and osmium, and a particularly preferable (g) ring-opening metathesis polymerization catalyst is a ruthenium carbene complex. Since the ruthenium carbene complex is excellent in catalytic activity during bulk polymerization, there are few residual unreacted monomers, and a crosslinked cyclic olefin polymer can be obtained with high productivity.

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

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

  Heteroatoms in the formulas (1) and (2) are atoms in 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. (G) From the viewpoint of the activity of the polymerization catalyst, a preferred 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. Represents a cyclic or chain hydrocarbon group having 1 to 20 carbon atoms. R ^{3 to} R ⁶ may be bonded to each other in any combination to form a ring.

  Specific examples of the compound represented by the formula (3) or the formula (4) include 1,3-dimesitylimidazolidin-2-ylidene and 1,3-di (1-adamantyl) imidazolidin-2-ylidene. 1-cyclohexyl-3-mesitylimidazolidine-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3- And di (1-phenylethyl) -4-imidazoline-2-ylidene and 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene.

  In addition to the compound represented by the formula (3) or (4), 1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5-ylidene 1,3-dicyclohexylhexahydropyrimidin-2-ylidene, N, N, N ′, N′-tetraisopropylformamidinylidene, 1,3,4-triphenyl-4,5-dihydro-1H-1, Heteroatom-containing carbene compounds such as 2,4-triazole-5-ylidene and 3- (2,6-diisopropylphenyl) -2,3-dihydrothiazol-2-ylidene can be used.

  Neutral electron donating compounds other than heteroatom-containing carbene compounds are ligands that have a neutral charge when pulled away from the central metal. Specific examples of the neutral electron donating compound include carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, thiocyanates, and the like. is there. Preferred neutral electron donating compounds are phosphines, ethers and pyridines, and a more preferred neutral electron donating compound is trialkylphosphine.

In the 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), iodine atom (I), diketonate group, substituted cyclopentadienyl group, alkoxy group, aryloxy group, carboxyl group Etc. A preferred anionic ligand is a halogen atom, and a more preferred ligand is a chlorine atom.

In the above formula (1), an example of a ruthenium carbene complex in which X ² and L ² are bonded to each other to form a multidentate chelating ligand is a Schiff base coordination represented by the following formula (5) It is a complex.

In the formula (5), Z represents an oxygen atom, a sulfur atom, a selenium atom, NR ¹² , PR ¹² or AsR ¹² , and R ¹² is the same as those exemplified for R ¹ and R ² .

In Formula (5), R ^{7 to} R ⁹ each independently represent a monovalent organic group that may contain a hydrogen atom, a halogen atom, or a hetero atom. Specific examples of the monovalent organic group that may contain a hetero atom include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group, and a carbon number. An alkoxyl group having 1 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, an aryloxy group, an alkylthio group having 1 to 8 carbon atoms, a carbonyloxy group having 1 to 20 carbon atoms, C1-C20 alkoxycarbonyl group, C1-C20 alkylsulfonyl group, C1-C20 alkylsulfinyl group, C1-C20 alkyl sulfonic acid group, aryl sulfonic acid group, C1-C1 20 phosphonic acid groups, arylphosphonic acid groups, alkylammonium groups having 1 to 20 carbon atoms, arylammonium groups, and the like.

  The monovalent organic group which may contain these heteroatoms may have a substituent and may be bonded to each other to form a ring. Examples of the substituent are an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, and an aryl group. When the monovalent organic group forms a ring, the ring may be an aromatic ring, an alicyclic ring, or a heterocyclic ring.

In Formula (5), R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a heteroaryl group, and these groups are May have a substituent and may be bonded to each other to form a ring. Examples of the substituent are an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, and an aryl group. When R ¹⁰ and R ¹¹ form a ring, the ring may be an aromatic ring, an alicyclic ring, or a heterocyclic ring.

Specific examples of the complex compound represented by the formula (1) include benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-4). , 5-Dibromo-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4-imidazoline-2-ylidene) (3-phenyl-1H-indene-1-ylidene) ( Tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4-imidazolidin-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3- Dimesityl-octahydrobenzimida 2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3 -Dimesityl-2,3-dihydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H -1,2,4-triazole-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene 1,3-dimesityl-4-imidazolidin-2-ylidene) pyridine ruthenium dichloride, (1,3-dimesityl-4-imidazolidin-2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride, 1,3-Dimesityl-4-imidazoline-2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) [ (Phenylthio) methylene] (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) (2-pyrrolidone-1-ylmethylene) (tricyclohexylphosphine) ruthenium dichloride Lori A ruthenium complex compound in which one hetero atom-containing carbene compound and one neutral electron donating compound are bonded, such as
A ruthenium complex compound in which two neutral electron-donating compounds are bonded, such as benzylidenebis (tricyclohexylphosphine) ruthenium dichloride, (3-methyl-2-buten-1-ylidene) bis (tricyclopentylphosphine) ruthenium dichloride;
Two heteroatom-containing carbene compounds such as benzylidenebis (1,3-dicyclohexyl-4-imidazolidin-2-ylidene) ruthenium dichloride and benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride Ruthenium complex compound in which is bonded;
A ruthenium carbene complex represented by formula (6) in which X ² and L ² are bonded to each other to form a multidentate chelating ligand;

In the formula (6), Mes represents a mesityl group. R ⁷ and R ⁸ are each a hydrogen atom or a methyl group, and at least one of them is a methyl group. R ¹³ and R ¹⁴ each independently represents a monovalent organic group that may contain a hydrogen atom, a halogen atom, or a hetero atom. The “monovalent organic group” is the same as R ^{7 to} R ⁹ described above in the description of the formula (5).

  Specific examples of the complex compound represented by the formula (2) are (1,3-dimesityl-4-imidazolidin-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butylvinylidene). (1,3-diisopropyl-4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylidene ruthenium dichloride, and the like.

  Particularly preferred complex compounds are those represented by the formula (1) and having one compound represented by the formula (3) or (4) as a ligand.

  These ruthenium carbene complexes are described in (a) Org. Lett. 1999, Vol. 1, page 953, (b) Tetrahedron. Lett. 1999, 40, 2247, (c) International Publication No. 2003/062253 pamphlet and the like.

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

  (G) The ring-opening metathesis polymerization catalyst can be used in combination with an activator (cocatalyst) for the purpose of controlling the polymerization activity and improving the polymerization reaction rate. Specific examples of the activator include aluminum, scandium, tin, silicon alkylates, halides, alkoxylates and aryloxylates. Further specific examples of activators include aluminum compounds such as trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride; trialkoxy Scandium compounds such as scandium; titanium compounds such as tetraalkoxy titanium; tin compounds such as tetraalkyls and tetraalkoxytin; zirconium compounds such as tetraalkoxyzirconium; dimethylmonochlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, tetrachlorosilane, bicyclo Heptenylmethyldichlorosilane, phenylmethyldichlorosilane, Hexyl dichlorosilane, phenyl trichlorosilane, silane compounds such as methyltrichlorosilane, and the like.

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

  (G) The ring-opening metathesis polymerization catalyst can be used in combination with a polymerization regulator for the purpose of controlling the polymerization activity and adjusting the polymerization reaction rate. Specific examples of the polymerization regulator include triphenylphosphine, tricyclohexylphosphine, tributylphosphine, 1,1-bis (diphenylphosphino) methane, 1,4-bis (diphenylphosphino) butane, 1,5-bis (diphenyl). Phosphino) phosphorus compounds such as pentane; Lewis bases such as ethers, esters and nitriles. The amount to be used is preferably 0.01 to 50 mol, more preferably 0.05 to 10 mol, per 1 mol of (g) the ring-opening metathesis polymerization catalyst.

  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 does not require a solvent removal step, and is a resin composition molded into a film shape simultaneously with polymerization. From the viewpoint of obtaining a polymer, a bulk polymerization method is preferred.

  The bulk polymerization method includes (a) a cyclic olefin monomer, (b) a crosslinking agent having two or more polymerizable unsaturated bonds, and (c) an organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C. for 1 minute. , (D) a phenolic antioxidant, (e) a hindered amine light stabilizer, (f) a phosphorus antioxidant, and (g) a polymerizable composition containing a ring-opening metathesis polymerization catalyst is used as needed. A step of metathesis polymerization in the presence of an additive.

  (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 contains (b) a crosslinking agent having two or more polymerizable unsaturated bonds. Specific examples of the crosslinking agent include pentaerythritol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, and 1,12-dodecanediol di (meth). Acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane Examples include tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. A polyfunctional (meth) acrylate having 2 or more polymerizable unsaturated bonds is preferred, a polyfunctional (meth) acrylate having 2 to 4 polymerizable unsaturated bonds is more preferred, and trimethylolpropane tri (meth) acrylate is further preferred. preferable.

  Moreover, the crosslinking agent which has 1 type, or 2 or more types and (b) 2 or more polymerizable unsaturated bonds is used.

  (B) The content of the crosslinking agent having two or more polymerizable unsaturated bonds is 0.2 to 40 parts by mass, preferably 1 to 30 parts by mass, more preferably 100 parts by mass of the cyclic olefin monomer (a). Is 2 to 20 parts by mass, more preferably 4 to 10 parts by mass. (B) If the content of two or more polymerizable unsaturated bonds is too small, the releasability of the crosslinked cyclic olefin resin film before and after heating, the low odor and high temperature discoloration resistance during heating are lowered. On the other hand, if the content of (b) two or more polymerizable unsaturated bonds is too large, the crosslinked cyclic olefin resin film becomes brittle and impractical.

  The polymerizable composition which is a raw material of the crosslinked cyclic olefin resin composition of the present invention contains (c) an organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C. for 1 minute. Specific examples of the thermal polymerization initiator include bis (t-butyldioxyisopropyl) benzene and di-t-butyl peroxide.

  One type or two or more types of (c) organic peroxide thermal polymerization initiators having a one-minute half-temperature of 160 to 200 ° C. are used.

  (C) An organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C. for 1 minute is preferably 170 to 195 ° C., more preferably a half-temperature of 180 to 195 ° C., more preferably 1 minute. The half-temperature is 185 to 195 ° C, and the particularly preferred half-temperature for 1 minute is 185 to 192 ° C.

  (C) The content of the organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C. for 1 minute is 0.1 to 10 parts by mass, preferably 0, per 100 parts by mass of the (a) cyclic olefin monomer. .3 to 8 parts by mass, more preferably 0.5 to 5 parts by mass. (C) When there is too little content of the organic peroxide type | system | group thermal-polymerization initiator whose half-temperature is 160-200 degreeC for 1 minute, the glass transition temperature of a crosslinked cyclic olefin resin film and the mold release property before and behind heating will fall. On the other hand, if the content of the organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C. for 1 minute is too large, the crosslinked cyclic olefin resin film becomes brittle and impractical.

  The polymerizable composition which is a raw material of the crosslinked cyclic olefin resin composition of the present invention contains (d) a phenol-based antioxidant, (e) a hindered amine light stabilizer, and (f) a phosphorus-based antioxidant. (D) Specific examples of the phenol-based antioxidant are pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-tert -Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,6-di-tert -Butyl-4-methylphenol and the like. One or more of these are used in combination.

  Specific examples of (e) hindered amine light stabilizers 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-tert-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, -Benzyl-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) -Tetramethylpiperidin-4-yl) -hexamethylene-1,6-diamine, N, N'-bis- (2,2,6,6-tetramethylpiperidin-4-yl) -hexamethylene-1,6 -Diacetamide, 1-acetate 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, α-cyano-β-methyl-β -[N- (2, , 6,6-tetramethyl-piperidin-4-yl)] - amino - methyl acrylate and the like. One or more of these are used in combination.

  (F) Specific examples of phosphorus antioxidants include 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphite, bis- (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, di Stearyl [(3,5-di-tert-butyl-4-hydroxyphenyl) methyl] phosphonate, diethyl {[(3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) methyl] phosphonate}, 6- [3- (3-tert-Butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert-butyl Dibenz [d, f] [1,3,2] - a dioxaphosphepine, bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite and the like. One or more of these are used in combination.

  The contents of (d) phenolic anti-aging agent, (e) hindered amine light stabilizer and (f) phosphorus anti-aging agent are 2-8 parts by mass with respect to 100 parts by mass of (a) cyclic olefin monomer, respectively. It is. When the content of (d) a phenolic antioxidant, (e) a hindered amine light stabilizer and (f) a phosphorus antioxidant is too low, the high temperature discoloration resistance after heating of the crosslinked cyclic olefin resin film is lowered. . On the other hand, when the content of (d) phenolic anti-aging agent, (e) hindered amine light stabilizer and (f) phosphorus anti-aging agent is too large, the glass transition temperature and mechanical strength of the crosslinked cyclic olefin resin film are Or the crosslinked cyclic olefin resin film is too soft to be peeled off from the support (base material).

  Various additives, the above-mentioned polymerizability, which is a precursor of the crosslinked cyclic olefin resin composition of the present invention, for the purpose of improving the properties of the film according to various uses and purposes, imparting functions, and improving the workability of molding. It is contained in the composition. Specific examples of such additives include polymerization inhibitors, fillers, antifoaming agents, foaming agents, colorants, ultraviolet absorbers, flame retardants, wetting agents, dispersing agents, release lubricants, plasticizers, and the like.

  Specific examples of polymerization inhibitors include quinones such as parabenzoquinone, tolquinone and naphthoquinone; hydroquinones such as hydroquinone, para-t-butylcatechol and 2,5-di-t-butylhydroquinone; copper naphthenate and copper octenoate Quaternary ammonium salts such as trimethylbenzylammonium chloride, trimethylbenzylammonium maleate 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 fillers include inorganic fillers such as carbon black, natural graphite, silica, silica sand, glass powder, calcium carbonate, aluminum hydroxide, magnesium hydroxide, and clay; organic fillers such as wood powder, polyester beads, and polystyrene beads Material; etc. One or more of these are used in combination. The filler improves physical properties such as shrinkage rate, elastic modulus, thermal conductivity, and conductivity of the crosslinked cyclic olefin polymer.

  Grades such as the particle size, shape, aspect ratio, and quality of the filler are appropriately determined depending on the physical properties of the crosslinked cyclic olefin polymer. The amount of these fillers to be used is preferably 400 parts by mass or less, more preferably 300 parts by mass or less, relative to 100 parts by mass of (a) the cyclic olefin monomer.

  Specific examples of the release lubricant include silicone oil and zinc stearate. One or more of these are used in combination.

  When obtaining the crosslinked cyclic olefin resin composition of the present invention, at least (a) a cyclic olefin monomer, (b) a crosslinking agent having two or more polymerizable unsaturated bonds, and (c) a half-minute temperature of 160 to 160 minutes. An organic peroxide thermal polymerization initiator at 200 ° C., (d) a phenolic antioxidant, (e) a hindered amine light stabilizer, (f) a phosphorus antioxidant, (g) a ring-opening metathesis polymerization catalyst, and Metathesis polymerization is performed on the polymerizable composition containing the additives used as necessary. (G) The ring-opening metathesis polymerization catalyst is used, if necessary, dissolved or suspended in a small amount of an inert solvent. Specific examples of the solvent include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin, and mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, Alicyclic hydrocarbons such as diethylcyclohexane, decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; and alicyclic rings such as indene and tetrahydronaphthalene Hydrocarbons having an aromatic ring; Nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; Oxygen-containing hydrocarbons such as diethyl ether, tetrahydrofuran, cyclopentanone and cyclohexanone And the like. Preferred solvents are oxygen-containing hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and hydrocarbons having an alicyclic ring and an aromatic ring. (G) A liquid anti-aging agent or plasticizer that does not decrease the activity as a ring-opening metathesis polymerization catalyst may be used as a solvent.

  (A) a cyclic olefin monomer, (b) a crosslinking agent having two or more polymerizable unsaturated bonds, (c) an organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C. for 1 minute, (d) phenol A polymerizable composition comprising an anti-aging agent, (e) a hindered amine-based light stabilizer, (f) a phosphorus-based anti-aging agent, (g) a ring-opening metathesis polymerization catalyst, and an additive used as necessary at room temperature The viscosity is preferably 0.4 to 500 mPa · s, although it depends on the desired film thickness. It becomes easy to form in a film shape because a viscosity exists in said preferable range. The polymerizable composition has the following viscosity: (a) a cyclic olefin monomer, (b) a crosslinking agent having two or more polymerizable unsaturated bonds, and (c) an organic peroxide system having a half-temperature of 160 to 200 ° C. for 1 minute. It is adjusted according to the type and amount of use of a thermal polymerization initiator, (d) a phenolic antioxidant, (e) a hindered amine light stabilizer, and (f) a phosphorus antioxidant.

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

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

  If necessary, the polymerizable composition is heated to a temperature at which (g) the ring-opening metathesis polymerization catalyst exhibits activity, and bulk polymerization is performed. 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 (g) the ring-opening metathesis polymerization catalyst and the heating temperature, and is preferably 1 minute to 24 hours.

  The cyclic olefin polymer is crosslinked. Crosslinking is performed after polymerization or simultaneously with polymerization. Crosslinking carried out simultaneously with the polymerization is more preferable because the crosslinked cyclic olefin resin film of the present invention can be obtained industrially advantageously with fewer steps.

  Specific examples of the crosslinking method include: (A) (a) a method in which a crosslinkable monomer is used as at least a part of the cyclic olefin monomer and polymerized to obtain a polymer having a three-dimensional crosslinked structure; A method in which at least one of a thermal crosslinking agent and a photocrosslinking agent is added to the composition to perform bulk polymerization, and a crosslinking reaction is performed simultaneously with polymerization or after polymerization; (C) a cyclic olefin polymer is subjected to light or electron. A method of irradiating a line and performing a crosslinking reaction after polymerization to carry out crosslinking. One of these methods may be used, or two or more methods may be used in combination. The method (A) is preferable from the viewpoint of easy control of physical properties of the film and economical efficiency.

  The (a) cyclic olefin monomer having two or more carbon-carbon double bonds is used as the crosslinkable monomer used in the method (A). Specific examples of the cyclic olefin monomer include dicyclopentadiene and tricyclopentadiene. The crosslinking density can be controlled by the amount of the crosslinking monomer used and the heating temperature during polymerization. The amount of the crosslinkable monomer used is not particularly limited because appropriate crosslink density varies depending on the use of the film. The preferable use amount of the crosslinkable monomer is 0.1 to 100 mol% in the ratio of the crosslinkable monomer in the total amount of the (a) cyclic olefin monomer.

  A known thermal crosslinking agent and photocrosslinking agent are used as the thermal crosslinking agent and photocrosslinking agent used in the method (B). Preferred thermal crosslinking agents are radical generators such as organic peroxides, diazo compounds, and nonpolar radical generators. The amount of the thermal crosslinking agent and the photocrosslinking agent used is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the (a) cyclic olefin monomer. The temperature at which crosslinking is performed 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 bulk polymerization and crosslinking in the present invention are preferably performed in the absence of oxygen and water. Specific examples of the bulk polymerization and crosslinking method include (1) a method of bulk polymerization and crosslinking in an inert gas atmosphere such as nitrogen gas and argon gas, and (2) a method of bulk polymerization and crosslinking under vacuum, (3 ) A method of performing bulk polymerization and crosslinking in a state where the polymerizable composition coated on the support is covered with a resin film and sealed. Specific examples of the resin film are those exemplified as the support. By performing bulk polymerization and crosslinking in the absence of oxygen or water, the surface of the resulting film is not oxidized, and desired flexibility can be exhibited.

  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. Although the surface of the crosslinked cyclic olefin resin film of the present invention may be smooth, it is polymerized by embossing or sandwiching a support (substrate) such as a polyethylene terephthalate film having unevenness to give the surface an uneven shape. An uneven shape may be formed by processing or the like.

Using a known surface treatment technique such as gas phase reaction, coating, vacuum deposition, ion plating, sputtering, CVD, electroless plating, a layer made of a different material such as an organic substance, an inorganic substance, or a metal is used. It can form on the surface of a resin composition and a crosslinked cyclic olefin resin film. Preferably, a thin film made of a material that improves releasability such as SiO ₂ , MgF ₂ , or fluororesin is provided on the film surface layer, or the film surface is fluorinated by surface treatment with fluorine gas or a CF-based precursor. Can do. However, in the crosslinked cyclic olefin resin film of the present invention, the releasability is improved without fluorination.

  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.

  The crosslinked cyclic olefin resin film of the present invention described above can be preferably used for a release film used in a semiconductor sealing process and a release film for producing a printed circuit board.

  In addition, the manufacturing method of the crosslinked cyclic olefin resin film of this invention is (a) 100 mass parts of cyclic olefin monomers, (b) 0.2-40 mass parts of crosslinking agents which have a 2 or more polymerizable unsaturated bond, (c ) 0.1 to 10 parts by mass of an organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C for 1 minute, (d) 2 to 8 parts by mass of a phenolic antioxidant, (e) a hindered amine light stabilizer. 2-8 parts by mass, (f) 2-8 parts by mass of a phosphorus-based antioxidant, and (g) a polymerizable composition containing a ring-opening metathesis polymerization catalyst is applied onto a support to support the ring-opening metathesis polymerization as described above. The process performed on the body is performed. Moreover, the manufacturing method of the crosslinked cyclic olefin resin composition of this invention is (a) 100 mass parts of cyclic olefin monomers, (b) 0.2-40 mass parts of crosslinking agents which have 2 or more polymerizable unsaturated bonds, ( c) 0.1 to 10 parts by mass of an organic peroxide-based thermal polymerization initiator having a half-temperature of 160 to 200 ° C. for 1 minute, (d) 2 to 8 parts by mass of a phenol-based antioxidant, (e) a hindered amine-based light stability A step of ring-opening metathesis polymerization of a polymerizable composition containing 2 to 8 parts by weight of the agent, (f) 2 to 8 parts by weight of the phosphorus-based antioxidant, and (g) a ring-opening metathesis polymerization catalyst. About description of each component of a polymerizable composition, metathesis polymerization, and a support body, it applies to the description performed about the crosslinked cyclic olefin resin composition of this invention.

  As described above, in the crosslinked cyclic olefin resin composition of the present invention, the method for producing the crosslinked cyclic olefin resin composition of the present invention, and the method for producing the crosslinked cyclic olefin resin film of the present invention, (b) two or more polymerizations are preferable. The crosslinking agent having a polymerizable unsaturated bond is a polyfunctional (meth) acrylate having two or more polymerizable unsaturated bonds. Preferred (c) organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C. for 1 minute is selected from the group consisting of bis (t-butyldioxyisopropyl) benzene and di-t-butyl peroxide. At least one. The preferable (a) cyclic olefin monomer is a norbornene monomer. The preferred (g) ring-opening metathesis polymerization catalyst is a ruthenium carbene complex.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. Unless otherwise indicated, the part and% in an Example and a comparative example are a mass reference | standard.

Various physical properties were measured as follows.
(1) Glass transition temperature of crosslinked cyclic olefin resin film Using a dynamic viscoelasticity measuring device (DMS6100 manufactured by SII Nano Technology Co., Ltd.), the distance between grips is 20 mm, the heating rate is 5 ° C./min, and the measurement temperature range is 30. The measurement was performed at a temperature of from 250C to 250C and a frequency of 2 Hz, and the peak top temperature of tan? The glass transition temperature should just be 135 degreeC or more.

(2) Heated weight reduction rate of crosslinked cyclic olefin resin film Using Thermo Plus TG8120 manufactured by Rigaku Corporation, sample weighing 1 mg, heating rate 20 ° C./min, measurement temperature range 30 ° C. to 250 ° C. under nitrogen atmosphere The weight reduction rate of 50 ° C. to 200 ° C. was defined as the heating weight reduction rate. The smaller the value, the weaker the odor during heating. The heating weight reduction rate may be 3% or less.

(3) Tensile properties of crosslinked cyclic olefin resin film The tensile elongation at break and tensile strength of the crosslinked cyclic olefin resin film were measured according to JIS K6871. The larger the tensile elongation at break of the film, the higher the sealing property of the mold, and the generation of burr of the sealing resin can be suppressed. The greater the tensile strength at break of the film, the more difficult it is to break and the leakage of the sealing resin can be suppressed.

(4) Peeling force against prepreg of crosslinked cyclic olefin resin film Both sides of prepreg for printed circuit board lamination (FR-4 R-1661 (G) GB type manufactured by Panasonic Electric Works Co., Ltd.) punched out to 300 mm x 300 mm were carried out. The film was inserted into a vacuum press with the release film of Example or Comparative Example. Next, the release film was heat-cured at 2.0 MPa and 180 ° C. for 70 minutes, then 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 peel force was defined as initial prepreg peel force.

  The sample taken out from the vacuum press was stored in an oven at 90 ° C. for 3 days, 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 peeling force was defined as a prepreg peeling force after heating. The smaller the prepreg peel force is, the higher the releasability is. The prepreg peel force may be 1 or less.

(5) Discoloration after heating of the crosslinked cyclic olefin resin film The resin film punched out to 50 mm x 150 mm was stored in an oven at 90 ° C for 3 days and taken out, and the color difference ΔE * of the taken out film was determined by Konica Minolta Sensing Co., Ltd. Measurement was performed using a color difference meter CR-400. The smaller the value, the higher the high temperature discoloration resistance. The said value should just be 6 or less.

Examples 1-12 and Comparative Examples 1-9
A crosslinking agent and a stabilizer having two or more polymerizable unsaturated bonds in the masses shown in Tables 1 and 2 are dissolved in a norbornene-based monomer mixture solution comprising 90% by mass of dicyclopentadiene and 10% by mass of tricyclopentadiene. The reaction stock solution was obtained. Next, a ruthenium catalyst having the structure of mass (7) shown in Tables 1 and 2 and an organic peroxide thermal polymerization initiator were added to the reaction stock solution and mixed with a line mixer. The mixture was coated at 25 ° C. on a release treatment surface of a polyethylene terephthalate carrier film having a thickness of 0.075 mm and a silicone release treatment on the surface, to form a cast film. Immediately thereafter, a carrier film similar to the above prepared separately from above the coating layer was laminated. Then, it heated at 200 degreeC for 3 minute (s), and obtained the resin film. The results are shown in Tables 1 and 2.

1) IRGANOX1076 manufactured by BASF Japan
2) Adeka Stub HP-10 manufactured by ADEKA Corporation
3) TINUVIN770 manufactured by BASF Japan
4) Kyoeisha Chemical Co., Ltd. light ester TMP
5) Kayaku Akzo Co., Ltd. Kayalen 6-70 1 minute half-temperature 150 ° C
6) Kayaku Akzo Parka Dox 14R-G 1 minute half temperature 185 ° C
7) Kayaku Co., Ltd. Kayabutyl D 1 minute half-temperature 192 ° C
8) Wako Pure Chemical Industries, Ltd. 9) RIMTEC, Inc. VC843 (cyclopentanone solution containing 1.8% ruthenium catalyst)
Films obtained from the crosslinked cyclic olefin resin compositions of Examples 1 to 12 have sufficient releasability before and after heating, high glass transition temperature, mechanical strength such as tensile elongation at break, tensile strength at break, and high temperature. It had discoloration resistance, and the odor during heating was weak.

  Glass transition temperature of a film obtained from the crosslinked cyclic olefin resin composition of Comparative Example 1 which does not contain an organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C. for 1 minute and releasability before and after heating. Was low. Comparative Examples 2 and 3 containing no organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C. per minute and containing an organic peroxide thermal polymerization initiator having a half-temperature of less than 160 ° C. for 1 minute The glass transition temperature of the film obtained from the crosslinked cyclic olefin resin composition was low, and the odor during heating was strong. The high-temperature discoloration resistance of the film obtained from the crosslinked cyclic olefin resin composition of Comparative Example 4 in which the content of the phenol-based anti-aging agent, hindered amine light stabilizer and phosphorus-based anti-aging agent is too small was low.

  The glass transition temperature of the film obtained from the crosslinked cyclic olefin resin composition of Comparative Example 5 having too little content of the organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C. for 1 minute and the release before and after heating. Sex was low. The film obtained from the crosslinked cyclic olefin resin composition of Comparative Example 6 in which the content of the organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C. for 1 minute is too large was fragile, and its physical properties could not be evaluated. . The film obtained from the crosslinked cyclic olefin resin composition of Comparative Example 7 in which the content of the crosslinking agent having two or more polymerizable unsaturated bonds was too large was brittle, and its physical properties could not be evaluated. The glass transition temperature and the tensile strength at break of the film obtained from the crosslinked cyclic olefin resin composition of Comparative Example 8 in which the content of the phenol-based antioxidant, the hindered amine light stabilizer and the phosphorus-based antioxidant was too large were low. The film obtained from the crosslinked cyclic olefin resin composition of Comparative Example 9 having too much content of phenolic anti-aging agent, hindered amine light stabilizer and phosphorus anti-aging agent is too soft, and the film is made of polyethylene terephthalate carrier. The film could not be peeled off and its physical properties could not be evaluated.

  The crosslinked cyclic olefin resin film comprising the crosslinked cyclic olefin resin composition of the present invention provides a film that is suitably used in a semiconductor sealing step 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) Resin sealing with a release film interposed between a lead frame on which a semiconductor chip is mounted and a mold inner surface on one side so as to contact the lead frame substrate. Method (II) The lead frame substrate on which the semiconductor chip is mounted is separated so that the sealing material is filled between the semiconductor chip surface and at least one mold inner surface between the chip and the mold at the time of sealing. In this method, a mold film is interposed for resin sealing, that is, a release 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 (18)

  (A) 100 parts by mass of a cyclic olefin monomer, (b) 0.2 to 40 parts by mass of a crosslinking agent having two or more polymerizable unsaturated bonds, and (c) an organic peroxide having a half-temperature of 160 to 200 ° C. for 1 minute. 0.1 to 10 parts by mass of a thermal polymerization initiator, (d) 2 to 8 parts by mass of a phenolic antioxidant, (e) 2 to 8 parts by mass of a hindered amine light stabilizer, (f) a phosphorus antioxidant 2 A crosslinked cyclic olefin resin composition obtained by ring-opening metathesis polymerization of a polymerizable composition containing -8 parts by mass and (g) a ring-opening metathesis polymerization catalyst.   The crosslinked cyclic olefin resin composition according to claim 1, wherein the crosslinking agent (b) having two or more polymerizable unsaturated bonds is a polyfunctional (meth) acrylate having two or more polymerizable unsaturated bonds. object.   (C) The organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C. for 1 minute is at least selected from the group consisting of bis (t-butyldioxyisopropyl) benzene and di-t-butyl peroxide. The crosslinked cyclic olefin resin composition according to claim 1 or 2, which is one type.   The crosslinked cyclic olefin resin composition according to any one of claims 1 to 3, wherein the (a) cyclic olefin monomer is a norbornene-based monomer.   The crosslinked cyclic olefin resin composition according to any one of claims 1 to 4, wherein the (g) ring-opening metathesis polymerization catalyst is a ruthenium carbene complex.   The crosslinked cyclic olefin resin film which consists of a crosslinked cyclic olefin resin composition as described in any one of Claims 1-5.   The crosslinked cyclic olefin resin film according to claim 6, which is a release film used in a semiconductor sealing process.   The crosslinked cyclic olefin resin film according to claim 6, which is a release film for producing a printed circuit board.   (A) 100 parts by mass of a cyclic olefin monomer, (b) 0.2 to 40 parts by mass of a crosslinking agent having two or more polymerizable unsaturated bonds, and (c) an organic peroxide having a half-temperature of 160 to 200 ° C. for 1 minute. 0.1 to 10 parts by mass of a thermal polymerization initiator, (d) 2 to 8 parts by mass of a phenolic antioxidant, (e) 2 to 8 parts by mass of a hindered amine light stabilizer, (f) a phosphorus antioxidant 2 The manufacturing method of the bridge | crosslinking cyclic olefin resin composition described in Claim 1 including the process of ring-opening metathesis polymerization of -8 mass parts and the polymerizable composition containing (g) ring-opening metathesis polymerization catalyst.   The crosslinked cyclic olefin resin composition according to claim 9, wherein the crosslinking agent (b) having two or more polymerizable unsaturated bonds is a polyfunctional (meth) acrylate having two or more polymerizable unsaturated bonds. Manufacturing method.   (C) The organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C. for 1 minute is at least selected from the group consisting of bis (t-butyldioxyisopropyl) benzene and di-t-butyl peroxide. The manufacturing method of the crosslinked cyclic olefin resin composition described in Claim 9 or 10 which is 1 type.   The manufacturing method of the crosslinked cyclic olefin resin composition described in any one of Claims 9-11 whose said (a) cyclic olefin monomer is a norbornene-type monomer.   The manufacturing method of the crosslinked cyclic olefin resin composition as described in any one of Claims 9-12 whose said (g) ring-opening metathesis polymerization catalyst is a ruthenium carbene complex.   (A) 100 parts by mass of a cyclic olefin monomer, (b) 0.2 to 40 parts by mass of a crosslinking agent having two or more polymerizable unsaturated bonds, and (c) an organic peroxide having a half-temperature of 160 to 200 ° C. for 1 minute. 0.1 to 10 parts by mass of a thermal polymerization initiator, (d) 2 to 8 parts by mass of a phenolic antioxidant, (e) 2 to 8 parts by mass of a hindered amine light stabilizer, (f) a phosphorus antioxidant 2 The step of applying a polymerizable composition containing -8 parts by mass and (g) a ring-opening metathesis polymerization catalyst on a support, and performing ring-opening metathesis polymerization on the support is performed. A method for producing a crosslinked cyclic olefin resin film.   The crosslinked cyclic olefin resin film according to claim 14, wherein the crosslinking agent (b) having two or more polymerizable unsaturated bonds is a polyfunctional (meth) acrylate having two or more polymerizable unsaturated bonds. Manufacturing method.   (C) The organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C. for 1 minute is at least selected from the group consisting of bis (t-butyldioxyisopropyl) benzene and di-t-butyl peroxide. The method for producing a crosslinked cyclic olefin resin film according to claim 14 or 15, which is one type.   The method for producing a crosslinked cyclic olefin resin film according to any one of claims 14 to 16, wherein the (a) cyclic olefin monomer is a norbornene-based monomer.   The method for producing a crosslinked cyclic olefin resin film according to any one of claims 14 to 17, wherein the (g) ring-opening metathesis polymerization catalyst is a ruthenium carbene complex.