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WO2013035499A1 - Film de résine d'oléfine cyclique réticulé thermodurcissable et son procédé de fabrication - Google Patents

Film de résine d'oléfine cyclique réticulé thermodurcissable et son procédé de fabrication Download PDF

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Publication number
WO2013035499A1
WO2013035499A1 PCT/JP2012/070625 JP2012070625W WO2013035499A1 WO 2013035499 A1 WO2013035499 A1 WO 2013035499A1 JP 2012070625 W JP2012070625 W JP 2012070625W WO 2013035499 A1 WO2013035499 A1 WO 2013035499A1
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cyclic olefin
mass
resin film
olefin resin
parts
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Japanese (ja)
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智 岩渕
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Zeon Corp
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Zeon Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • 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
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3321—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from cyclopentene
    • 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
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3323—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other monocyclic systems
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention is a thermosetting that contributes to improving the yield of mounting processes such as a semiconductor sealing process such as an IC chip and LED, a laminated heat pressing process when manufacturing a multilayer printed wiring board, and a coverlay attaching process when manufacturing a flexible printed wiring board.
  • the present invention relates to a crosslinkable cyclic olefin resin film and a method for producing the same.
  • the downsizing and thinning of semiconductor elements such as IC chips and LEDs are progressing along with the downsizing and thinning of mobile devices such as mobile phones.
  • the shape of the sealing chip that seals these elements has also changed. Recently, a chip with a shape in which a lead frame is arranged so as to extend from a sealing chip as seen in a conventional surface mounting element is not mainstream, and a chip size that is a shape in which terminals are arranged directly on the element.
  • Mounting sealing chips in the form of packages (CSP), ball grid arrays (BGA), quad flat now lead packages (QFN) and the like are becoming mainstream. These shapes have the advantage of a small mounting area and contribute to the downsizing of the equipment. Furthermore, the sealing chip for mounting in these shapes is thin, which contributes to the thinning of the sealing film.
  • 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 was 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 (see, for example, 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”
  • thermosetting crosslinked cyclic olefin resin obtained by ring-opening metathesis polymerization of a cyclic olefin monomer
  • a resin used for a sealing material prepreg, adhesive, tensile elongation at break
  • a film having mechanical strength such as tensile strength at break and high-temperature discoloration resistance has been sought, but such a film has not been found.
  • the problem to be solved by the present invention includes a thermosetting crosslinked cyclic olefin resin obtained by ring-opening metathesis polymerization of a cyclic olefin monomer, and sufficient separation from a resin used for a sealing material, a prepreg, and an adhesive.
  • the present invention provides a film having moldability, mechanical strength such as tensile breaking elongation and tensile breaking strength, and high-temperature discoloration resistance, and a method for producing the film.
  • the inventors of the present invention have (a) a cyclic olefin monomer, (b) a specific polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms, and (c) phenol.
  • Thermosetting crosslinked cyclic olefin resin film obtained by ring-opening metathesis polymerization of a polymerizable composition containing an anti-aging agent and (d) a hindered amine light stabilizer is used for a sealing material, a prepreg, and an adhesive.
  • the present invention has been found to have sufficient releasability from the resin, high mechanical strength and high-temperature discoloration resistance, and has completed the thermosetting crosslinked cyclic olefin resin film of the present invention and its production method.
  • thermosetting crosslinked cyclic olefin resin film of the present invention comprises (a) 100 parts by mass of a cyclic olefin monomer, (b) 100 to 20% by mass of a (meth) acrylic acid alkyl ester having an alkyl group having 3 or more carbon atoms, an aromatic (Co) polymers having an aromatic vinyl compound or (meth) acrylic acid alkyl ester having 0 to 80% by mass of an alkyl group having 2 or less carbon atoms, and having a weight average molecular weight of 1,000 to 2,000,000 (co) polymer Ring opening a polymerizable composition containing 0.5 to 8 parts by mass, (c) 0.5 to 10 parts by mass of a phenolic anti-aging agent, and (d) 0.5 to 10 parts by mass of a hindered amine light stabilizer Obtained by metathesis polymerization.
  • the method for producing a thermosetting crosslinked cyclic olefin resin film of the present invention includes a step of ring-opening metathesis polymerization of the polymerizable composition in the presence of a polymerization catalyst.
  • thermosetting crosslinked cyclic olefin resin film of the present invention has sufficient releasability from the resin used for the sealing material, prepreg, and adhesive, mechanical strength such as tensile elongation at break and tensile strength at break, and high temperature resistance. Has discoloration.
  • the cyclic olefin monomer has a ring structure formed of carbon atoms, and has a carbon-carbon double bond in the ring.
  • 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 hydrocarbon groups such as alkyl groups, alkenyl groups, alkylidene groups, and aryl groups; polar groups such as carboxyl groups and acid anhydride groups as substituents.
  • the norbornene-based monomer may further have a double bond in addition to the double bond of the norbornene ring.
  • preferred norbornene monomers are nonpolar monomers, that is, norbornene monomers 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.
  • 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.
  • the addition amount of the monocyclic olefin is 40% by mass or less, the heat resistance of the film is improved.
  • A a cyclic olefin monomer
  • a specific polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms (c) a phenolic antioxidant and (d) a hindered amine light stabilizer.
  • the polymerizable composition containing the agent is subjected to ring-opening metathesis polymerization in the presence of a polymerization catalyst.
  • the polymerization catalyst (a) causes ring-opening metathesis polymerization of a cyclic olefin monomer.
  • the 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 a 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 metathesis polymerization catalyst is a complex of Group 8 ruthenium and osmium, and a particularly preferred metathesis polymerization catalyst is a ruthenium carbene complex. Since the ruthenium carbene complex is excellent in catalytic activity during bulk polymerization, a crosslinked cyclic olefin polymer with little residual unreacted monomer can be obtained with high productivity.
  • 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 represents an arbitrary anionic ligand.
  • L 1 and L 2 each independently represents a neutral electron donating compound.
  • R 1 and R 2 may be bonded to each other to contain a hetero atom, and may form an aliphatic ring or an aromatic ring.
  • R 1 , R 2 , X 1 , X 2 , L 1 and L 2 may be bonded together in any combination to form a multidentate chelating ligand.
  • the heteroatom in the present invention is an atom of Groups 15 and 16 of the periodic table.
  • Specific examples of the hetero atom include a nitrogen atom (N), an oxygen atom (O), a phosphorus atom (P), a sulfur atom (S), an arsenic atom (As), and a selenium atom (Se).
  • 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.
  • preferred neutral electron donating compounds are heteroatom-containing carbene compounds.
  • a heteroatom-containing carbene compound in which heteroatoms are adjacently bonded to both sides of the carbene carbon is preferable, and a heteroatom-containing carbene compound in which a heterocycle is formed including the carbene carbon atom and heteroatoms on both sides thereof is more preferable.
  • 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, 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.
  • 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.
  • the most preferable complex compound has one compound represented by the formula (1) and represented by the formula (3) or (4) as a ligand.
  • the amount of the polymerization catalyst used is, for example, 1: 2,000 to 1: 2,000,000, preferably 1: 5,000 to the molar ratio of (metal atom in the polymerization catalyst: (a) cyclic olefin monomer).
  • the range is from 1: 1,000,000, more preferably from 1: 10,000 to 1: 500,000.
  • the amount of the polymerization catalyst is (1: 2,000,000) or more, residual monomer in the polymer due to a decrease in the polymerization reaction rate and a decrease in the degree of crosslinking of the crosslinked polymer can be suppressed. The heat resistance of the resulting film can be improved.
  • the amount of the polymerization catalyst is (1: 2,000) or less, 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 is easy. Can be done.
  • the 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 cocatalyst
  • Specific examples of the 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, for example, 1: 0.05 to 1: 100, preferably 1: 0.2 to 1:20, more preferably (molar ratio of the metal atom in the polymerization catalyst). The range is 1: 0.5 to 1:10.
  • the 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 for the purpose of controlling the polymerization activity and adjusting the polymerization reaction rate.
  • the polymerization regulator include triphenylphosphine, tricyclohexylphosphine, tributylphosphine, 1,1-bis (diphenylphosphino) methane, 1,4-bis (diphenylphosphino) butane, 1,5-bis (diphenyl).
  • Phosphino) phosphorus compounds such as pentane
  • Lewis bases such as ethers, esters and nitriles.
  • the amount of these used is, for example, 0.01 to 50 mol, preferably 0.05 to 10 mol, relative to 1 mol of the polymerization catalyst.
  • the method for producing the thermosetting crosslinked cyclic olefin resin film of the present invention may be either a solution polymerization method or a bulk polymerization method, but does not require a solvent removal step, and a resin composition molded into a film shape simultaneously with polymerization. From the viewpoint of being obtained, the bulk polymerization method is preferred.
  • the bulk polymerization method includes (a) a cyclic olefin monomer, (b) a specific polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms, (c) a phenolic antioxidant and (d ) Including a step of ring-opening metathesis polymerization of a polymerizable composition containing a hindered amine light stabilizer in the presence of a polymerization catalyst and, if necessary, an additive to form a film shape.
  • the cyclic olefin monomer is subjected to ring-opening metathesis polymerization to obtain a cyclic olefin polymer, and the cyclic olefin polymer is crosslinked after the ring-opening metathesis polymerization or simultaneously with the ring-opening metathesis polymerization. It is believed that a polymer is obtained.
  • thermosetting crosslinked cyclic olefin resin film of the present invention comprises (b) 100 to 20% by mass of (meth) acrylic acid alkyl ester having an alkyl group having 3 or more carbon atoms, an aromatic vinyl compound or an alkyl having 2 or less carbon atoms.
  • (B) a polymer having an alkyl group having 3 or more carbon atoms is a (co) polymer of 0 to 80% by mass of an acrylic acid alkyl ester and having a weight average molecular weight of 1,000 to 2,000,000. It may be referred to as “a specific polymer containing an alkyl acrylate unit” or simply “(b) polymer”.
  • the polymer preferably has (meth) acrylic acid alkyl ester having 80 to 20% by mass of an alkyl group having 3 or more carbon atoms and an aromatic vinyl compound or an alkyl group having 2 or less carbon atoms (meth). It is a (co) polymer with 20 to 80% by mass of an acrylic acid alkyl ester and has a weight average molecular weight of 1,000 to 2,000,000.
  • the monomer constituting the (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms include n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, and n-butyl.
  • a (meth) acrylic acid alkyl ester having one or two or
  • monomers constituting the aromatic vinyl compound unit include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, divinylbenzene, N, N— Dimethyl-p-aminoethylstyrene, 2,4-dimethylstyrene, N, N-diethyl-p-aminoethylstyrene, 2,4-diethylstyrene, vinylnaphthalene, vinylanthracene and the like.
  • styrene and ⁇ -methylstyrene are particularly preferred, and styrene is the most preferred aromatic vinyl compound.
  • One or more aromatic vinyl compounds are used.
  • monomers constituting the (meth) acrylic acid alkyl ester unit having an alkyl group having 2 or less carbon atoms are methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.
  • a (meth) acrylic acid alkyl ester having one or two or more alkyl groups having 2 or less carbon atoms is used.
  • the weight average molecular weight of the specific polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms is, for example, 1,000 to 2,000,000, preferably 5,000 to 1.6 million. More preferably, it is 10,000 to 1,200,000, and still more preferably 50,000 to 800,000. If the said weight average molecular weight is more than the said minimum, the mold release property and mechanical strength of a thermosetting crosslinked cyclic olefin resin film will improve.
  • the weight average molecular weight is not more than the above upper limit, a specific polymer containing (b) a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms is dissolved in (a) the cyclic olefin monomer. It becomes easy.
  • the weight average molecular weight can be measured using polystyrene as a standard substance by GPC (gel permeation chromatography) using a solvent such as tetrahydrofuran (THF) or toluene.
  • the polymerizable composition includes 0.5 to 8 parts by mass of (b) a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms with respect to 100 parts by mass of (a) the cyclic olefin monomer. Contains specific polymers. (B) If the content of the specific polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms is not less than the above lower limit, the releasability of the thermosetting crosslinked cyclic olefin resin film and Mechanical strength is improved.
  • thermosetting crosslinked cyclic olefin resin film will become tough.
  • the polymerization method of a specific polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms is not limited to a specific polymerization method.
  • Specific examples of the polymerization method include solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization.
  • a specific polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms is commercially available.
  • a specific example of the commercially available product is Ganz Pearl GBS-40N manufactured by Ganz Kasei Co., Ltd.
  • thermosetting crosslinked cyclic olefin resin film of the present invention contains (c) a phenolic anti-aging agent.
  • a phenolic anti-aging agent 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.
  • the content of the phenolic anti-aging agent is 0.5 to 10 parts by mass, preferably 1 to 5 parts by mass with respect to 100 parts by mass of (a) the cyclic olefin monomer.
  • the thermosetting crosslinked cyclic olefin resin film is hardly discolored at a high temperature.
  • content of a phenol type anti-aging agent is below the said upper limit, it can suppress that an anti-aging agent bleeds from a thermosetting crosslinked cyclic olefin resin film, and the mutual adhesion of films.
  • the thermosetting crosslinked cyclic olefin resin film of the present invention contains (d) a hindered amine light stabilizer.
  • a hindered amine light stabilizer 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) -
  • the content of the hindered amine light stabilizer is, for example, 0.5 to 10 parts by mass, preferably 1 to 5 parts by mass with respect to 100 parts by mass of the (a) cyclic olefin monomer.
  • content of a hindered amine light stabilizer is more than the said minimum, it becomes difficult to discolor a thermosetting crosslinked cyclic olefin resin film at high temperature.
  • content of a hindered amine light stabilizer is below the said upper limit, it can suppress that a light stabilizer bleeds from a thermosetting crosslinked cyclic olefin resin film, and mutual adhesion of films.
  • thermosetting crosslinked cyclic olefin resin film of the present invention may contain (e) a phosphorus-based antioxidant.
  • phosphorus-based 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] phosphon
  • a preferable content of the phosphorus-based anti-aging agent is 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of (a) the cyclic olefin monomer.
  • additives may be incorporated into the thermosetting crosslinked cyclic olefin resin film of the present invention for the purpose of improving the properties of the film according to various applications and purposes, imparting functions, and improving the workability of molding.
  • additives include anti-aging agents other than (c) and (e), fillers, antifoaming agents, foaming agents, colorants, ultraviolet absorbers, light stabilizers other than (d), difficulty Such as a flame retardant, a wetting agent, a dispersant, a release lubricant, and a plasticizer.
  • an antioxidant other than (c) and (e) is contained in order to improve the durability and storage stability of the crosslinked cyclic olefin polymer.
  • anti-aging agent other than (c) and (e) are quinones such as parabenzoquinone, tolquinone and naphthoquinone; hydroquinones such as hydroquinone, para-t-butylcatechol and 2,5-di-t-butylhydroquinone.
  • Copper salts such as copper naphthenate and copper octenoate; quaternary ammonium salts such as trimethylbenzylammonium chloride, trimethylbenzylammonium maleate and phenyltrimethylammonium chloride; oximes such as quinonedioxime and methylethylketoxime; triethylamine hydrochloride Amine hydrochlorides such as salts and dibutylamine hydrochloride.
  • the type and amount of the anti-aging agent other than (c) and (e) are appropriately selected depending on the conditions such as the mechanical properties at high temperature, the film forming workability, and the storage stability of the crosslinked cyclic olefin polymer.
  • Anti-aging agents other than (c) and (e) are used alone or in combination.
  • the amount of the anti-aging agent other than (c) and (e) is, for example, 10 parts by mass or less with respect to 100 parts by mass of the (a) cyclic olefin monomer.
  • the filler include inorganic fillers such as carbon black, natural graphite, silica, silica sand, glass powder, calcium carbonate, aluminum hydroxide, magnesium hydroxide, and clay; organic filling such as wood powder, polyester beads, and polystyrene beads. Material; 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 thermosetting 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.
  • the release lubricant examples include silicone oil and zinc stearate.
  • the mold release lubricant improves the moldability, mold release and handling properties of the film and imparts functions such as lubricant properties to the film.
  • the amount of the release lubricant used is preferably 200 parts by mass or less with respect to 100 parts by mass of the (a) cyclic olefin monomer.
  • A a cyclic olefin monomer
  • a specific polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms (c) a phenolic antioxidant and (d) a hindered amine light stabilizer.
  • the polymerizable composition containing the agent is subjected to ring-opening metathesis polymerization in the presence of a polymerization catalyst and optionally used additives.
  • the polymerization catalyst is used after being dissolved or suspended in a small amount of an inert solvent, if necessary.
  • the solvent include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin, mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, Alicyclic hydrocarbons such as diethylcyclohexane, decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; and alicyclic rings such as indene and tetrahydronaphthalene Hydrocarbons having an aromatic ring; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, and acetonitrile; oxygen-containing hydrocarbons such as diethyl,
  • Preferred solvents are aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and hydrocarbons having an alicyclic ring and an aromatic ring. You may use the liquid anti-aging agent or plasticizer which does not reduce the activity as a polymerization catalyst as a solvent.
  • composition containing the agent and the additive used as necessary 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 viscosity of the composition is (a) a cyclic olefin monomer, (b) a specific polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms, (c) a phenolic antioxidant and ( d) It is adjusted according to the type and amount of hindered amine light stabilizer.
  • Specific examples of the method of bulk polymerization of the above composition into a film shape include a method of bulk polymerization by sandwiching the above composition between two supports, and bulk polymerization by pouring or applying the above composition onto a support.
  • a method of bulk polymerization of the above composition in a mold The method of bulk polymerization by sandwiching the composition between two supports is more preferable because a thin and uniform film can be produced with high accuracy in thickness. More preferably, the composition is sandwiched between two supports, passed between two rolls having a predetermined gap, and then bulk polymerized.
  • Specific known materials such as resin, glass and metal 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 metal or resin.
  • a preferred support is a resin film that is easily available and inexpensive.
  • the above composition is subjected to bulk polymerization by heating to a temperature at which the polymerization catalyst exhibits activity as necessary.
  • the polymerization temperature is, for example, 0 to 250 ° C., preferably 20 to 200 ° C.
  • the method for heating the composition is not particularly limited. Specific examples of the heating method include a method of heating on a heating plate, a method of heating (hot pressing) while applying pressure using a press, a method of pressing with a heated roller, and a method of using a heating furnace.
  • the polymerization reaction time is appropriately determined depending on the amount of the polymerization catalyst and the heating temperature, and is, for example, 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 thermosetting crosslinked cyclic olefin resin film of the present invention can be obtained industrially advantageously with fewer steps.
  • crosslinking method examples include: (A) (a) a method in which a crosslinkable monomer is used as at least a part of the cyclic olefin monomer and polymerized to obtain a polymer having a three-dimensional crosslinked structure; (B) the above composition A bulk polymerization is carried out by adding a crosslinking agent to the polymer, and a crosslinking reaction is carried out by carrying out a crosslinking reaction simultaneously with or after the polymerization; (C) a cyclic olefin polymer is irradiated with light or an electron beam, and a crosslinking reaction is carried out after the polymerization.
  • Cross-linking method 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 are 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 cyclic olefin monomer.
  • thermal crosslinking agents and photocrosslinking agents are used as the crosslinking 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 crosslinking 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 (a) the cyclic olefin monomer.
  • the thermal crosslinking agent is used, the crosslinking temperature is, for example, 100 to 250 ° C., preferably 150 to 200 ° C.
  • the time for crosslinking is not particularly limited, and is, for example, several minutes to several hours.
  • the 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 ) Bulk polymerization and crosslinking in a state where the 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 thermosetting crosslinked cyclic olefin resin film of the present invention has various appropriate values depending on the application and is not particularly limited. For example, it is 0.5 to 5,000 ⁇ m, and from the viewpoint of handling properties, The thickness is preferably 5 to 500 ⁇ m.
  • the surface of the electroconductive thermosetting film of the present invention may be smooth, but it may be embossed, polymerized by sandwiching it with a substrate such as polyethylene terephthalate having irregularities, and processed to give irregularities to the surface. May be formed.
  • the conductive heat of the present invention is applied to a layer made of a different material such as an organic material, an inorganic material, or a metal by using a known surface treatment technology such as gas phase reaction, coating, vacuum deposition, ion plating, sputtering, CVD, electroless plating. You may form in the cured film surface.
  • a thin film made of a material that improves conductivity, such as a conductive inorganic compound or metal can be provided on the film surface layer.
  • the polymerizable composition is preferably further 0.5 to 10 parts by mass with respect to 100 parts by mass of the (a) cyclic olefin monomer.
  • Part (e) of phosphorus-based anti-aging agent is preferably a norbornene monomer.
  • a preferable use of the thermosetting crosslinked cyclic olefin resin film is a release film used in a semiconductor sealing process or a release film for producing a printed circuit board.
  • thermosetting crosslinked cyclic olefin resin film preferably, a composition containing the polymerizable composition and the polymerization catalyst is applied onto a support, and ring-opening metathesis polymerization is performed on the support.
  • a preferred polymerization catalyst is a ruthenium carbene complex.
  • thermosetting crosslinked cyclic olefin resin film The tensile elongation at break and tensile strength of the thermosetting 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.
  • 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.
  • Examples 1 to 4 and Comparative Examples 1 to 9 A norbornene-based monomer mixture solution comprising 90% by mass of dicyclopentadiene and 10% by mass of tricyclopentadiene with the polymers, phenolic antioxidants, hindered amine light stabilizers and phosphorus-based antioxidants shown in Tables 1 and 2 To obtain a reaction stock solution. Next, a ruthenium catalyst having the structure of mass (7) shown in Table 1 and Table 2 is added to the reaction stock solution, mixed with a line mixer, and made of polyethylene terephthalate having a thickness of 0.075 mm at 25 ° C.
  • the coating was carried out on the carrier film to form a cast film, and then immediately the same carrier film prepared separately from above the coating layer was laminated. Then, it heated at 200 degreeC for 3 minute (s), and obtained the resin film.
  • Tables 1 and 2 The results are shown in Tables 1 and 2.
  • the high temperature discoloration resistance of the release films of Comparative Examples 1 and 2 not containing a phenolic anti-aging agent and a hindered amine light stabilizer was low, and these release films after heating did not peel from the prepreg.
  • the polymerization conversion rate of the polymerizable composition of Comparative Example 3 containing no phenolic anti-aging agent was low, and the initial release property and release property after heating of the release film obtained from the polymerizable composition were low.
  • the release film of Comparative Example 4 containing no hindered amine light stabilizer had low initial release properties and high-temperature discoloration resistance, and the release film after heating did not peel from the prepreg.
  • the high temperature discoloration resistance of the release film of Comparative Example 5 which does not contain a phenolic antioxidant and a hindered amine light stabilizer was low, and the release film after heating did not peel from the prepreg.
  • the polymerization conversion rate of the polymerizable composition of Comparative Example 6 containing no phenolic anti-aging agent was low, and the initial release property and release property after heating of the release film obtained from the polymerizable composition were low.
  • the release film of Comparative Example 7 containing no hindered amine light stabilizer had a low high temperature discoloration resistance.
  • the high temperature discoloration resistance of the release film of Comparative Example 8 containing no phenolic anti-aging agent was low.
  • the high temperature discoloration resistance of the release film of Comparative Example 9 containing no hindered amine light stabilizer was low, and the release film after heating did not peel from the prepreg.
  • thermosetting crosslinked cyclic olefin resin composition of the present invention provides a film that is suitably used for a semiconductor sealing step in the manufacture of a semiconductor device.
  • the method for carrying out semiconductor encapsulation using the thermosetting 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.
  • thermosetting 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 step of applying a coverlay on a flexible printed board.

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Abstract

L'invention concerne un film de résine d'oléfine cyclique réticulé thermodurcissable qui est obtenu par polymérisation par méthatèse à ouverture de cycle d'une composition polymérisable qui contient : (a) 100 parties en masse d'un monomère oléfine cyclique ; (b) 0,5-8 parties en masse d'un (co)polymère qui est un (co)polymère de 100-20 % en masse d'un ester alkylique d'acide (méth)acrylique ayant un groupe alkyle ayant 3 atomes de carbone ou plus et 0-80 % en masse d'un composé vinyl aromatique ou d'un ester alkylique d'acide (méth)acrylique ayant un groupe alkyle présentant 2 atomes de carbone ou moins et qui présente une masse moléculaire moyenne en poids de 1 000-2 000 000 ; (c) 0,5-10 parties en masse d'un agent anti-vieillissement constitué par un phénol ; et (d) 0,5-10 parties en masse d'un stabilisant vis-à-vis de la lumière constitué par une amine encombrée.
PCT/JP2012/070625 2011-09-09 2012-08-13 Film de résine d'oléfine cyclique réticulé thermodurcissable et son procédé de fabrication Ceased WO2013035499A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2013136963A1 (fr) * 2012-03-14 2013-09-19 日本ゼオン株式会社 Film de résine d'oléfine cyclique réticulé thermodurcissable et son procédé de fabrication
JP2015193680A (ja) * 2014-03-31 2015-11-05 三井化学株式会社 環状オレフィン共重合体組成物およびその架橋体
JP2017504504A (ja) * 2014-01-17 2017-02-09 スリーエム イノベイティブ プロパティズ カンパニー 長期間の紫外線安定性を有する連続して剥離可能な共押出ポリマーフィルム
EP4332997A4 (fr) * 2021-04-28 2025-04-16 Kyocera Corporation Corps isolant organique, plaque stratifiée plaquée de métal, et carte de circuit imprimé

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Publication number Priority date Publication date Assignee Title
WO2013136963A1 (fr) * 2012-03-14 2013-09-19 日本ゼオン株式会社 Film de résine d'oléfine cyclique réticulé thermodurcissable et son procédé de fabrication
JP2017504504A (ja) * 2014-01-17 2017-02-09 スリーエム イノベイティブ プロパティズ カンパニー 長期間の紫外線安定性を有する連続して剥離可能な共押出ポリマーフィルム
US10696028B2 (en) 2014-01-17 2020-06-30 3M Innovative Properties Company Successively peelable coextruded polymer film with extended UV stability
JP2015193680A (ja) * 2014-03-31 2015-11-05 三井化学株式会社 環状オレフィン共重合体組成物およびその架橋体
EP4332997A4 (fr) * 2021-04-28 2025-04-16 Kyocera Corporation Corps isolant organique, plaque stratifiée plaquée de métal, et carte de circuit imprimé

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