WO2012063579A1 - Film de résine thermodurcissable de type cyclo-oléfine réticulée et son procédé de fabrication - Google Patents

Film de résine thermodurcissable de type cyclo-oléfine réticulée et son procédé de fabrication Download PDF

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WO2012063579A1
WO2012063579A1 PCT/JP2011/073016 JP2011073016W WO2012063579A1 WO 2012063579 A1 WO2012063579 A1 WO 2012063579A1 JP 2011073016 W JP2011073016 W JP 2011073016W WO 2012063579 A1 WO2012063579 A1 WO 2012063579A1
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cyclic olefin
resin film
group
olefin resin
polymer
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PCT/JP2011/073016
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English (en)
Japanese (ja)
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智 岩渕
耕一郎 前田
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日本ゼオン株式会社
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Priority claimed from JP2010253455A external-priority patent/JP2012102274A/ja
Priority claimed from JP2011053796A external-priority patent/JP5605276B2/ja
Application filed by 日本ゼオン株式会社 filed Critical 日本ゼオン株式会社
Priority to CN2011800540790A priority Critical patent/CN103180387A/zh
Priority to KR1020137011937A priority patent/KR20130065727A/ko
Publication of WO2012063579A1 publication Critical patent/WO2012063579A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
    • 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
    • C08G2261/3324—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 norbornene
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers

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 a reduction in the sealing film thickness.
  • 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.
  • 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 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 elongation at break and tensile strength, and a method for producing the film.
  • Thermosetting crosslinked cyclic olefin resin film obtained by ring-opening metathesis polymerization of the adhesive composition has sufficient releasability from the resin used for the sealing material, prepreg, and adhesive and high mechanical strength
  • the present inventors have 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 and (b) 100 to 20% by mass of a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms, 0.5 to 8 parts by mass of a polymer containing 0 to 80% by mass of an aromatic vinyl compound unit or a (meth) acrylic acid alkyl ester unit having an alkyl group having 2 or less carbon atoms and having a weight average molecular weight of 1,000 to 2,000,000 It is obtained by ring-opening metathesis polymerization of a polymerizable composition containing
  • the method for producing the thermosetting crosslinked cyclic olefin resin film of the present invention comprises (a) 100 parts by mass of a cyclic olefin monomer and (b) 100 to 20 masses of (meth) acrylic acid alkyl ester units having an alkyl group having 3 or more carbon atoms.
  • a step of ring-opening metathesis polymerization of a polymerizable composition containing 8 parts by mass in the presence of a composition containing a polymerization catalyst is included.
  • thermosetting crosslinked cyclic olefin resin film of the present invention has sufficient releasability from the resin used for the sealant, prepreg, and adhesive, and mechanical strength such as tensile elongation at break and tensile strength at break.
  • 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 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.
  • preferred norbornene monomers are nonpolar monomers, that is, norbornene monomers composed only of carbon atoms and hydrogen atoms.
  • nonpolar norbornene-based monomer examples include nonpolar such as dicyclopentadiene, methyldicyclopentadiene, and dihydrodicyclopentadiene (also referred to as tricyclo [5.2.1.02,6] dec-8-ene).
  • pentadeca -4,6,8,13- tetraene (. 1,4-methano -1,4,4a, 9, 9a, also referred to as 10-hexa hydro anthracene) nonpolar norbornene, such as; Pentacyclo [6.5.1.13, 6.02, 7.09, 13] pentadeca-4,10-diene, pentacyclo [9.2.14, 7.02, 10.03,8] pentadeca
  • Non-polar cyclic olefins having five or more rings such as 5,12-diene, hexacyclo [6.6.1.13, 6.110, 13.02, 7.09,14] heptade-4-ene; It is.
  • 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 [6.2.13, 6.02,7] dodec-9-ene-4-carboxylate, tetracyclo [6.2.1.13, 6.02,7] dodec-9-ene-4-methanol, tetracyclo [6.2.13,6.02,7] dodec-9-ene-4-carboxylic acid, tetracyclo [6.2.1 .13,6.02,7] dodec-9-ene-4,5-dicarboxylic acid, tetracyclo [6.2.13,6.02,7] dodec-9-ene-4,5-dicarboxylic acid Anhydride, methyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate, 5-norbornene-2-yl acetate, 5-norbornene-2-methanol, 5-norbornene-2- All, 5-norbol Down 2-carbonitrile
  • 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 polymerizable composition containing a specific polymer containing (a) a cyclic olefin monomer and (b) a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms is present in the composition containing a polymerization catalyst.
  • a 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 polymerization catalyst is a group 8 ruthenium or osmium complex, and a particularly preferred 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 represent an arbitrary anionic ligand.
  • L 1 and L 2 each independently represents a neutral electron donating compound.
  • R 1 and R 2 may be bonded to each other, may 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, 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.
  • 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 usually in the range of 1: 2,000 to 1: 2,000,000 in terms of a molar ratio of (metal atom in the polymerization catalyst: (a) cyclic olefin monomer), preferably 1: 5,000 to 1: 1,000,000, more preferably 1: 10,000 to 1: 500,000.
  • the amount of the polymerization catalyst is 1: 2,000,000 or more, a good polymerization reaction rate can be realized, and the monomer can be prevented from remaining in the polymer, or the crosslinking degree of the good crosslinked polymer can be reduced. And 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 is suppressed, and the reaction rate is prevented from being excessively high, so that the film formation at the time of bulk polymerization described later is favorably performed. be able to.
  • 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 use amount of the activator is usually 1: 0.05 to 1: 100, preferably 1: 0.2 to 1:20, more preferably, in a molar ratio of (metal atom in the polymerization catalyst: activator).
  • 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 usually 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 polymerization composition containing a specific polymer containing (a) a cyclic olefin monomer and (b) a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms, a polymerization catalyst, A step of ring-opening metathesis polymerization in the presence of an additive used as necessary 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.
  • the three-dimensional crosslinked structure of the cyclic olefin polymer is confirmed by the solubility in 1,2-dichlorobenzene.
  • the degree of crosslinking expressed by insoluble matter is preferably 70% by mass or more. More preferably, it is 80 mass% or more, More preferably, it is 85 mass% or more.
  • the degree of crosslinking is 70% by mass or more, better heat resistance and mechanical strength can be obtained, and contamination of a substrate, a mold, a press apparatus, etc. due to uncrosslinked components can be suppressed.
  • thermosetting crosslinked cyclic olefin resin film of the present invention comprises (b) 100 to 20% by mass of (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms, an aromatic vinyl compound unit or 2 or less carbon atoms.
  • a polymer containing 0 to 80% by mass of (meth) acrylic acid alkyl ester units having an alkyl group and having a weight average molecular weight of 1,000 to 2,000,000 is contained.
  • (b) 100 to 20% by mass of (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms and an aromatic vinyl compound unit or an alkyl group having 2 or less carbon atoms is referred to as "a polymer containing 0 to 80% by mass of a meth) acrylic acid alkyl ester unit and having a weight average molecular weight of 1,000 to 2,000,000”. It may be referred to as “a specific polymer containing units” or simply “(b) polymer”.
  • the molecular chain terminal of the polymer may be modified with at least one functional group selected from the group consisting of a hydroxyl group, a silyl group, a carboxyl group, and a methacryloyl group.
  • 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
  • the monomer constituting the aromatic vinyl compound unit examples include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-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 1,000 to 2,000,000, preferably 2,000 to 2,000,000. In this range, one preferred range is 1100 to 10,000, more preferably 1200 to 5000, and still more preferably 1300 to 4000. Further, one of the preferable ranges is 50,000 to 1,500,000, more preferably 200,000 to 1,200,000, and still more preferably 400,000 to 1,000,000. When the said weight average molecular weight is too small, the mold release property and mechanical strength of a thermosetting crosslinked cyclic olefin resin film will become small.
  • 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 too low, the releasability and mechanical strength of the thermosetting crosslinked cyclic olefin resin film Decreases.
  • thermosetting crosslinked cyclic olefin resin film becomes brittle.
  • 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.
  • the molecular chain terminal of a specific polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms may be modified with a hydroxyl group. Further, the molecular chain terminal may be modified with at least one functional group selected from the group consisting of a silyl group, a carboxyl group, and a methacryloyl group.
  • a polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms modified at the molecular chain end with a hydroxyl group or a functional group thereof is commercially available. Specific examples of the commercial products are Actflow (registered trademark) UT-1001, AS-301, CB-3060, and BGV-12 manufactured by Soken Kagaku Co., Ltd.
  • additives can 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 antioxidants, fillers, antifoaming agents, foaming agents, colorants, UV absorbers, light stabilizers, flame retardants, wetting agents, dispersants, mold release lubricants, plasticizers.
  • an antioxidant is contained in order to improve the durability and storage stability of the crosslinked cyclic olefin polymer.
  • antioxidants include quinones such as parabenzoquinone, tolquinone and naphthoquinone; hydroquinones such as hydroquinone, para-t-butylcatechol and 2,5-di-t-butylhydroquinone; di-t-butyl para Phenols such as cresol, hydroquinone monomethyl ether and pyrogallol; copper salts such as copper naphthenate and copper octenoate; quaternary ammonium salts such as trimethylbenzylammonium chloride, trimethylbenzylammonium maleate and phenyltrimethylammonium chloride; quinonedioxime And oximes such as methyl ethyl ketoxime; amine hydrochlorides such as triethylamine hydrochloride and dibutylamine hydrochloride.
  • antioxidants are appropriately selected depending on conditions such as mechanical properties at high temperature, film forming workability, and storage stability of the crosslinked cyclic olefin polymer. Phenols are preferred because they have high compatibility with the crosslinked cyclic olefin polymer, are uniformly dispersed, and improve the durability and storage stability of the film.
  • One or more antioxidants are used in combination. The amount of the antioxidant used is usually 0.001 to 10 parts by mass with respect to 100 parts by mass of the (a) cyclic olefin monomer.
  • the filler include inorganic fillers such as silica, silica sand, glass powder, calcium carbonate, aluminum hydroxide, magnesium hydroxide, and clay; organic fillers such as wood powder, polyester beads, and polystyrene beads.
  • 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 5 to 400 parts by mass, more preferably 10 to 300 parts by mass with respect 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 0.1 to 200 parts by mass with respect to 100 parts by mass of (a) the cyclic olefin monomer.
  • the ring-opening metathesis polymerization is carried out in the presence of an additive used depending on the case.
  • 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.
  • a composition containing 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 an additive used as necessary.
  • the viscosity of the product at room temperature is usually 3 to 30,000 Pa ⁇ s, preferably 5 to 500 Pa ⁇ s, although it depends on the desired film thickness.
  • the viscosity of the above composition is a kind of a specific polymer containing a polar group-modified halogenated hydrocarbon, (a) a cyclic olefin monomer, and (b) a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms. It is adjusted according to the amount used.
  • Specific examples of the method for bulk polymerization of the composition into a film shape are a method of pouring or coating the composition on a support and bulk polymerization, and a method of bulk polymerization of the composition in a mold. .
  • the method of pouring or coating the composition on a support and subjecting it to bulk polymerization is more preferable because a thin and uniform film can be continuously produced.
  • Specific known materials such as resin, glass and metal are selected as the support.
  • the resin include polyesters such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, and polyarylate; 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 method for applying the composition to the support is not particularly limited. Specific examples of the method include spray coating, dip coating, roll coating, curtain coating, die coating, and slit coating.
  • 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 usually 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, but is usually 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 subjected to a crosslinking reaction 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 usually 100 to 250 ° C., preferably 150 to 200 ° C.
  • the time for crosslinking is not particularly limited, but is usually 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 ) 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 method for obtaining a film by solution polymerization is as follows. First, (a) a cyclic olefin monomer and a polymerization catalyst are polymerized by a known solution polymerization method to obtain a cyclic olefin polymer. Next, this cyclic olefin polymer, (b) a specific polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms, a crosslinking agent and additives used as necessary are mixed, The film is formed by the following forming method.
  • the cyclic olefin polymer is crosslinked to form a crosslinked cyclic olefin polymer, and the thermosetting crosslinked cyclic olefin resin film of the present invention is obtained.
  • the kind and amount of the thermoplastic cyclic olefin polymer, additive and cross-linking agent used, and the cross-linking method are the same as those in the bulk polymerization method.
  • the thickness of the thermosetting crosslinked cyclic olefin resin film of the present invention varies depending on the application and is not particularly limited, but is usually 0.5 to 5,000 ⁇ m, from the viewpoint of handling properties, The thickness is preferably 5 to 500 ⁇ m.
  • the surface of the thermosetting crosslinked cyclic olefin resin film of the present invention may be smooth, but may have an uneven shape formed by embossing.
  • the layer of a heterogeneous material such as an organic substance, an inorganic substance, or a metal is subjected to the thermosetting property of the present invention by using a known surface treatment technique such as gas phase reaction, coating, vacuum deposition, ion plating, sputtering, CVD, and electroless plating.
  • a known surface treatment technique such as gas phase reaction, coating, vacuum deposition, ion plating, sputtering, CVD, and electroless plating.
  • the film surface can be fluorinated by providing a film surface layer with a thin film made of a material that improves releasability such as SiO 2 , MgF 2 , or a fluororesin, or by performing a surface treatment with fluorine gas or a CF-based precursor.
  • the polymer (b) preferably has a weight average molecular weight of 2,000 to 2,000,000.
  • the molecular chain terminal of the polymer (b) can be modified with a hydroxyl group.
  • the molecular chain terminal of the (b) polymer may be modified with at least one functional group selected from the group consisting of a silyl group, a carboxyl group, and a methacryloyl group.
  • the preferable (a) cyclic olefin monomer is a norbornene monomer.
  • the preferable use of the said thermosetting crosslinked cyclic olefin resin film is a release film used for a semiconductor sealing process or a printed circuit board manufacturing process.
  • the weight average molecular weight of the preferred (b) polymer is 20 to 2 million.
  • the molecular chain terminal of the polymer (b) can be modified with a hydroxyl group.
  • the molecular chain terminal of the (b) polymer may be modified with at least one functional group selected from the group consisting of a silyl group, a carboxyl group, and a methacryloyl group.
  • the preferred (a) cyclic olefin monomer is a norbornene monomer
  • the preferred polymerization catalyst is a ruthenium carbene complex.
  • 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.
  • the solubility of a specific polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms in a cyclic olefin monomer was visually evaluated according to the following criteria.
  • B A specific polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms did not dissolve in the cyclic olefin monomer.
  • thermosetting crosslinked cyclic olefin resin film The tensile breaking elongation and tensile breaking 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.
  • Examples 1 to 9 and Comparative Examples 1 to 4 Polymers shown in Table 1 were prepared.
  • a specific polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms in the mass shown in Tables 2 and 3 was dissolved in dicyclopentadiene to obtain a reaction stock solution.
  • a ruthenium catalyst having the structure of mass (7) shown in Tables 2 and 3 is added to the reaction stock solution, mixed with a line mixer, and a cast film is made of a polyethylene terephthalate carrier film having a thickness of 50 ⁇ m. Performed at 25 ° C above. Thereafter, heating was performed at 200 ° C. for 5 minutes in a nitrogen atmosphere to obtain a release film.
  • the results are shown in Tables 2 and 3.
  • Polymer 1 Actflow (registered trademark) UT-1001 manufactured by Soken Kagaku Co., Ltd., the terminal is modified with a hydroxyl group, and the hydroxyl value is 57 ⁇ 2.
  • Polymer 6 Zefiac (registered trademark) F340M manufactured by Ganz Kasei Co., Ltd.
  • Production Example 1 A monomer mixture consisting of 65% 2-ethylhexyl acrylate and 35% styrene and 0.03 parts 2,2′-azobisisobutyronitrile were dissolved in 700 parts ethyl acetate in the reactor. After nitrogen substitution, the polymerization reaction was performed at 80 ° C. for 6 hours. The polymerization conversion rate was 95%. The obtained copolymer was dried under reduced pressure to evaporate ethyl acetate to obtain a viscous solid copolymer. The copolymer had a weight average molecular weight of 400,000 and a weight average molecular weight / number average molecular weight of 3.1.
  • Production Example 2 A monomer mixture consisting of 25% n-butyl acrylate and 75% styrene and 0.03 parts 2,2′-azobisisobutyronitrile were dissolved in 700 parts ethyl acetate in the reactor. After nitrogen substitution, the polymerization reaction was performed at 80 ° C. for 6 hours. The polymerization conversion rate was 95%. The obtained copolymer was dried under reduced pressure to evaporate ethyl acetate to obtain a viscous solid copolymer. The weight average molecular weight of the copolymer was 40,000.
  • the release film of Comparative Example 4 obtained by ring-opening metathesis polymerization of a polymerizable composition having too much content of a specific polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms is It was brittle and the physical properties of the release film could not be measured.
  • Examples 10 to 16 and Comparative Examples 5 to 7 Polymers shown in Table 4 were prepared.
  • a specific polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms in the mass shown in Tables 5 and 6 was dissolved in dicyclopentadiene to obtain a reaction stock solution.
  • a ruthenium catalyst having the structure of mass (7) shown in Tables 5 and 6 is added to the reaction stock solution, mixed with a line mixer, and a cast film is a polyethylene terephthalate carrier film having a thickness of 50 ⁇ m. Performed at 25 ° C above. Thereafter, heating was performed at 200 ° C. for 5 minutes in a nitrogen atmosphere to obtain a release film.
  • the results are shown in Tables 5 and 6.
  • Polymer 7 Act Flow (registered trademark) AS-301 manufactured by Soken Kagaku Co., Ltd.
  • Polymer 8 Act Flow (registered trademark) CB-3060 manufactured by Soken Kagaku Co., Ltd.
  • Polymer 9 Actflow (registered trademark) BGV-12 manufactured by Soken Kagaku Co., Ltd.
  • the release films and mechanical strengths of the release films of Examples 10 to 16 were high.
  • the release film of the release film of Comparative Example 5 obtained by ring-opening metathesis polymerization of a polymerizable composition not containing a polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms is low. It was.
  • Release of the release film of Comparative Example 6 obtained by ring-opening metathesis polymerization of a polymerizable composition having too little polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms Sex was low.
  • the release film of Comparative Example 7 obtained by ring-opening metathesis polymerization of a polymerizable composition having too much polymer containing a (meth) acrylic acid alkyl ester unit having an alkyl group having 3 or more carbon atoms is very much. It was brittle and its physical properties could not be measured.
  • thermosetting crosslinked cyclic olefin resin film of the present invention is suitably used for a semiconductor sealing step in the production 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 circuit board and at the time of a coverlay application process of a flexible printed circuit board.

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Abstract

Le film de résine thermodurcissable de type cyclo-oléfine réticulée faisant l'objet de la présente invention peut être obtenu par polymérisation en métathèse par ouverture de cycle d'une composition polymérisable qui comprend (a) 100 parties en poids d'un monomère de cyclo-oléfine et (b) 0,5 à 8 parties en poids d'un polymère qui comprend de 100 à 20 % en poids de motifs (méth)acrylate d'alkyle, l'alkyle ayant trois atomes de carbone ou plus, et 0 à 80 % en poids de motifs vinyle aromatique ou de motifs (méth)acrylate d'alkyle, l'alkyle ayant deux atomes de carbone ou moins, et qui a un poids moléculaire moyen en poids de 1000 à 2 000 000.
PCT/JP2011/073016 2010-11-12 2011-10-05 Film de résine thermodurcissable de type cyclo-oléfine réticulée et son procédé de fabrication WO2012063579A1 (fr)

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WO2013035499A1 (fr) * 2011-09-09 2013-03-14 日本ゼオン株式会社 Film de résine d'oléfine cyclique réticulé thermodurcissable et son procédé de fabrication
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
CN104619743A (zh) * 2012-09-26 2015-05-13 Rimtec株式会社 聚合性组合物及树脂成型体的制造方法

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JPS61188444A (ja) * 1985-02-15 1986-08-22 Nippon Zeon Co Ltd ノルボルネン系ポリマ−組成物
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Publication number Priority date Publication date Assignee Title
WO2013035499A1 (fr) * 2011-09-09 2013-03-14 日本ゼオン株式会社 Film de résine d'oléfine cyclique réticulé thermodurcissable et son procédé de fabrication
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
CN104619743A (zh) * 2012-09-26 2015-05-13 Rimtec株式会社 聚合性组合物及树脂成型体的制造方法
US9777086B2 (en) 2012-09-26 2017-10-03 Rimtec Corporation Polymerizable composition and method of production of resin shaped article

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