WO2014045712A1 - Composition de résine d'oléfine cyclique réticulée, film de résine d'oléfine cyclique réticulée et son procédé de fabrication - Google Patents

Composition de résine d'oléfine cyclique réticulée, film de résine d'oléfine cyclique réticulée et son procédé de fabrication Download PDF

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WO2014045712A1
WO2014045712A1 PCT/JP2013/070236 JP2013070236W WO2014045712A1 WO 2014045712 A1 WO2014045712 A1 WO 2014045712A1 JP 2013070236 W JP2013070236 W JP 2013070236W WO 2014045712 A1 WO2014045712 A1 WO 2014045712A1
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cyclic olefin
olefin resin
parts
crosslinked cyclic
mass
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Japanese (ja)
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智 岩渕
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日本ゼオン株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/14—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers obtained by ring-opening polymerisation of carbocyclic compounds having one or more carbon-to-carbon double bonds in the carbocyclic ring, i.e. polyalkeneamers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/13—Morphological aspects
    • C08G2261/135—Cross-linked structures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/59—Stability
    • C08G2261/594—Stability against light, i.e. electromagnetic radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/59—Stability
    • C08G2261/596—Stability against oxidation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/76—Post-treatment crosslinking

Definitions

  • 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.
  • 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).
  • the film does not have sufficient releasability from the resin used for the sealing material, prepreg, and adhesive.
  • 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.
  • 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”
  • 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.
  • 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.
  • 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. ,as well as This has led to the completion of the those of the manufacturing method.
  • 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.
  • the crosslinked cyclic olefin resin film of the present invention is composed of 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 method for producing a 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, (c) 0.1 to 10 parts by weight of an organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C.
  • 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 mass of an organic peroxide thermal polymerization initiator having a half-half-temperature of 160 to 200 ° C., (d) 2 to 8 parts by mass of a phenolic antioxidant, (e) 2 to 2 hindered amine light stabilizers 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 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.
  • the cyclic olefin monomer is a compound having a ring structure formed of carbon atoms and having a carbon-carbon double bond in the ring. 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-based 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.
  • nonpolar norbornene-based monomer examples include noncyclopentadiene, methyldicyclopentadiene, 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 .
  • 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 .
  • Nonpolar 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.
  • 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 .
  • nonpolar norbornene monomers are nonpolar dicyclopentadienes and nonpolar tetracyclododecenes, and more preferred nonpolar norbornene monomers are nonpolar dicyclones. Cyclopentadiene.
  • norbornene-based monomer containing a polar group examples include tetracyclo [6.2.1.1 3,6 . 0 2,7 ] methyl dodeca-9-ene-4-carboxylate, tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene-4-methanol, tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene-4-carboxylic acid, tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene-4,5-dicarboxylic acid, tetracyclo [6.2.1.1 3,6 .
  • dodec-9-ene-4,5-dicarboxylic anhydride methyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate, 5-norbornene-2 acetate -Yl, 5-norbornene-2-methanol, 5-norbornene-2-ol, 5-norbornene-2-carbonitrile, 2-acetyl-5-norbornene, 7-oxa-2-norbornene and the like.
  • monocyclic olefin examples include cyclobutene, cyclopentene, cyclohexene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, and derivatives thereof having a substituent.
  • (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.
  • 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, (c) a half-temperature of 160 to 160 minutes per minute. 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.
  • 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 preferred (g) ring-opening metathesis polymerization catalyst is a group 8 ruthenium or osmium complex, and a particularly preferred (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.
  • a specific example of the ruthenium carbene complex is a complex represented by the following formula (1) or (2) from the viewpoint of catalytic activity.
  • 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.
  • 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).
  • preferred heteroatoms are N, O, P, and S, and particularly preferred heteroatoms are N.
  • Neutral electron donating compounds are roughly classified into heteroatom-containing carbene compounds and other neutral electron donating compounds.
  • 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.
  • the heteroatom adjacent to the carbene carbon preferably has a bulky substituent.
  • preferable heteroatom-containing carbene compounds are compounds represented by the following formula (3) or formula (4).
  • R 3 to R 6 may each independently contain 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. 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.
  • the neutral electron donating compound other than the heteroatom-containing carbene compound is a ligand having 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.
  • the anionic (anionic) ligands X 1 and X 2 are ligands having a negative charge when separated from the central metal atom.
  • 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.
  • 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 .
  • R 7 to R 9 each independently represents a monovalent organic group which may contain a hydrogen atom, a halogen atom, or a hetero atom.
  • the monovalent organic group which 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, 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, An alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, an alkylsulfinyl group having 1 to 20 carbon atoms
  • the monovalent organic group that may contain these heteroatoms may have a substituent and may be bonded to each other to form a ring.
  • substituents are an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, and an aryl group.
  • the ring may be an aromatic ring, an alicyclic ring, or a heterocyclic ring.
  • R 10 and R 11 each independently represents 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.
  • substituents are an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, and an aryl group.
  • the ring may be an aromatic ring, an alicyclic ring, or a heterocyclic ring.
  • complex compound represented by the formula (1) examples include benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-4).
  • 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).
  • the complex compound represented by the formula (2) include (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 above formula (1) and having one compound represented by the above formula (3) or (4) as a ligand.
  • 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.
  • 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.
  • 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.
  • an activator include aluminum, scandium, tin, silicon alkylates, halides, alkoxylates and aryloxylates.
  • 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 trialk
  • the amount of the activator used is preferably a molar ratio of ((g) metal atom in the 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.
  • 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.
  • a 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.
  • 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.
  • 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 above-mentioned 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.
  • 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.
  • 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.
  • the polymerizable composition as 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.
  • 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.
  • An organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C. for 1 minute has a preferable half-temperature of 1 minute of 170 to 195 ° C., more preferably a half-temperature of 1 minute of 180 to 195 ° C., and more preferably 1 minute.
  • the half-temperature is 185 to 195 ° C.
  • the particularly preferred one-minute half-temperature is 185 to 192 ° C.
  • the content of the organic peroxide thermal polymerization initiator having a half-life temperature of 160 to 200 ° C. for 1 minute is 0.1 to 10 parts by mass, preferably 0 with respect to 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) If the content of the organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C. for 1 minute is too small, the glass transition temperature of the crosslinked cyclic olefin resin film and the releasability before and after heating are lowered.
  • the polymerizable composition that 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.
  • phenolic antioxidant examples include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis ⁇ 2- [3- (3-tert -Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl ⁇ -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,6-di-tert -Butyl-4-methylphenol and the like. One or more of these are used in combination.
  • hindered amine light stabilizers include 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, -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- ⁇ (3,5-di-t-butyl-4-hydroxyphenyl) -propionate 1-benzyl-2,2,6,6-tetramethyl-4-piperidinyl maleate, (di-2,2,6,6,6-te
  • 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
  • the contents of (d) phenolic antioxidant, (e) hindered amine light stabilizer and (f) phosphorus antioxidant are 2-8 parts by mass with respect to 100 parts by mass of (a) cyclic olefin monomer, respectively. It is.
  • 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. .
  • additives 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.
  • additives include polymerization inhibitors, fillers, antifoaming agents, foaming agents, colorants, ultraviolet absorbers, flame retardants, wetting agents, dispersing agents, release lubricants, plasticizers, and the like.
  • 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 Copper salts such as trimethylbenzylammonium chloride, trimethylbenzylammonium maleate, quaternary ammonium salts such as phenyltrimethylammonium chloride; Oximes such as quinone dioxime and methyl ethyl ketoxime; Amines such as triethylamine hydrochloride and dibutylamine hydrochloride Hydrochlorides; and the like. One or more of these are used in combination.
  • 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 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.
  • release lubricant examples include silicone oil and zinc stearate. One or more of these are used in combination.
  • 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, (c) a half-temperature of 160 to 160 minutes per minute.
  • 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.
  • the ring-opening metathesis polymerization catalyst is used, if necessary, dissolved or suspended in a small amount of an inert solvent.
  • the solvent include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin, mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, Alicyclic hydrocarbons such as diethylcyclohexane, decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; and alicyclic rings such as indene and tetrahydronaphthalene Hydrocarbons having an aromatic ring; Nitro
  • Preferred solvents are oxygen-containing hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and hydrocarbons having an alicyclic ring and an aromatic ring.
  • 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.
  • the polymerizable composition has a viscosity of (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.
  • Specific known materials such as resin and glass are selected as the support.
  • 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.
  • 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.
  • 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.
  • a cyclic olefin monomer having two or more carbon-carbon double bonds is used as a 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.
  • a preferred use amount of the crosslinkable monomer is 0.1 to 100 mol% as a ratio of the crosslinkable monomer in the total amount of the (a) cyclic olefin monomer.
  • thermal crosslinking agents and photocrosslinking agents are used as the thermal crosslinking agent and the 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 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 thermal crosslinking agent is used, the crosslinking temperature 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 carried out in the absence of oxygen and water.
  • Specific examples of the bulk polymerization and crosslinking method include (1) a method of bulk polymerization and crosslinking in an inert gas atmosphere such as nitrogen gas and argon gas, and (2) a method of bulk polymerization and crosslinking under vacuum, (3 ) A method of performing bulk polymerization and crosslinking in a state where the polymerizable composition coated on the support is covered with a resin film and sealed.
  • Specific examples of the resin film are those exemplified as the support.
  • the thickness of the crosslinked cyclic olefin resin film of the present invention varies depending on the application and is not particularly limited, but is preferably 0.5 to 5,000 ⁇ m, and is more preferable from the viewpoint of handling properties.
  • the thickness is 5 to 500 ⁇ m.
  • 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.
  • 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.
  • 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.
  • the crosslinked cyclic olefin resin film of the present invention the releasability is improved without fluorination.
  • the preferred 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.
  • 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 ) 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.
  • the method for producing a 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 weight of an organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C.
  • 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.
  • the preferable (a) cyclic olefin monomer is a norbornene monomer.
  • the preferred (g) ring-opening metathesis polymerization catalyst is a ruthenium carbene complex.
  • the sample taken out from the vacuum press was stored in an oven at 90 ° C. for 3 days, a 25 mm ⁇ 150 mm test piece 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.
  • Examples 1 to 12 and Comparative Examples 1 to 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.
  • the 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.
  • 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 and the mold release before and after heating are too small in the content of the organic peroxide thermal polymerization initiator having a half-temperature of 160 to 200 ° C. for 1 minute. 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 was 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 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) 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.
  • 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 circuit board and at the time of a coverlay application process of a flexible printed circuit board.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine d'oléfine cyclique réticulée qui est obtenue par réalisation d'une polymérisation par métathèse par ouverture de cycle sur une composition polymérisable qui comprend (a) 100 parties en masse d'un monomère d'oléfine cyclique, (b) 0,2-40 parties en masse d'un agent de réticulation ayant au moins deux liaisons insaturées polymérisables, (c) 0,1-10 parties en masse d'un amorceur de polymérisation thermique de type peroxyde organique ayant une température de demi-vie d'une minute de 160-200°, (d) 2-8 parties en masse d'un antioxydant phénolique, (e) 2-8 parties en masse d'un photostabilisant amine encombrée, (f) 2-8 parties en masse d'un antioxydant phosphorique et (g) un catalyseur de polymérisation par métathèse par ouverture de cycle.
PCT/JP2013/070236 2012-09-21 2013-07-25 Composition de résine d'oléfine cyclique réticulée, film de résine d'oléfine cyclique réticulée et son procédé de fabrication WO2014045712A1 (fr)

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JP5922292B1 (ja) * 2015-02-16 2016-05-24 住友化学株式会社 硬化性接着剤組成物及びそれを用いた偏光板

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WO2009107844A1 (fr) * 2008-02-29 2009-09-03 日本ゼオン株式会社 Composition de résine durcissable, corps moulé utilisant ladite composition, préimprégné et stratifié
JP2012131957A (ja) * 2010-12-24 2012-07-12 Nippon Zeon Co Ltd 重合性組成物、及び成形体
WO2012132150A1 (fr) * 2011-03-28 2012-10-04 日本ゼオン株式会社 Composition de résine de cyclooléfine, réticulée, thermodurcissable, film de résine de cyclooléfine, réticulée, thermodurcissable, procédé pour la production d'une composition de résine de cyclooléfine, réticulée thermodurcissable et procédé pour la production d'un film de résine de cyclooléfine, réticulée, thermodurcissable

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WO2005017033A1 (fr) * 2003-08-13 2005-02-24 Zeon Corporation Composition de resine reticulable et corps forme en resine realise a partir de cette composition
WO2009107844A1 (fr) * 2008-02-29 2009-09-03 日本ゼオン株式会社 Composition de résine durcissable, corps moulé utilisant ladite composition, préimprégné et stratifié
JP2012131957A (ja) * 2010-12-24 2012-07-12 Nippon Zeon Co Ltd 重合性組成物、及び成形体
WO2012132150A1 (fr) * 2011-03-28 2012-10-04 日本ゼオン株式会社 Composition de résine de cyclooléfine, réticulée, thermodurcissable, film de résine de cyclooléfine, réticulée, thermodurcissable, procédé pour la production d'une composition de résine de cyclooléfine, réticulée thermodurcissable et procédé pour la production d'un film de résine de cyclooléfine, réticulée, thermodurcissable

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017525836A (ja) * 2014-08-07 2017-09-07 テルヌ エスアーエスＴｅｌｅｎｅ Ｓａｓ 硬化性組成物及びその組成物を含む成形品

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