JP2013151597A - Heat-curable crosslinked cyclic olefin resin film and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film which comprises a heat-curable crosslinked cyclic olefin resin obtained by subjecting a cyclic olefin monomer to ring-opening metathesis polymerization, and has satisfactory mold releasability with respect to resins used for a sealing material, a prepreg and an adhesive and mechanical strength such as tensile break elongation and tensile break strength, and to provide a method for producing the film.SOLUTION: A heat-curable crosslinked cyclic olefin resin film is obtained by subjecting a polymerizable composition comprising 100 pts.mass of (a) a cyclic olefin monomer and 0.3-40 pts.mass of (b) a fatty acid amide to ring-opening metathesis polymerization.

Description

  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.

  However, cracking of the product and protrusion of the sealing material from the terminal portion are likely to occur in the manufacturing process of the mounting sealing chip having these shapes, resulting in a decrease in manufacturing yield. A sealing method using assist molding with a release film has been studied to improve yield (for example, see Patent Documents 1 and 2). Polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene copolymer (ETFE), and polyimide, which are release film materials used in the sealing method, are expensive, and the release film is incinerated when discarded. Can not.

  On the other hand, a crosslinked resin film obtained by polymerizing a liquid containing a metathesis polymerization catalyst and a cycloolefin capable of metathesis polymerization on a carrier has been studied as a release film (see, for example, Patent Document 3). However, the film does not have sufficient releasability from the resin used for the sealing material, prepreg, and adhesive.

  Furthermore, the outer layer contains a 4-methyl-1-pentene polymer resin, the inner layer contains a polyolefin resin, a phenolic oxidation stabilizer, a phosphorus stabilizer or a sulfur stabilizer, and above and below the inner layer, A release film for producing a printed circuit board comprising a multilayer resin layer having an outer layer has been studied (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.

Japanese Patent Laid-Open No. 2000-167841 JP 2001-250838 A JP 2001-253934 A JP 2000-263724 A

Recently, including a thermosetting crosslinked cyclic olefin resin obtained by ring-opening metathesis polymerization of a cyclic olefin monomer, sufficient releasability with 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.

  As a result of intensive studies, the inventors of the present invention have obtained a thermosetting crosslinked cyclic olefin resin film obtained by ring-opening metathesis polymerization of a polymerizable composition containing (a) a cyclic olefin monomer and (b) a fatty acid amide. To find that it has sufficient releasability from the resin used for the sealing material, prepreg, and adhesive and high mechanical strength, and to complete the thermosetting crosslinked cyclic olefin resin film of the present invention and its production method. It came.

  The thermosetting crosslinked cyclic olefin resin film of the present invention is obtained by ring-opening metathesis polymerization of a polymerizable composition containing (a) 100 parts by mass of a cyclic olefin monomer and (b) 0.3 to 40 parts by mass of a fatty acid amide. It is done. Preferred (b) fatty acid amide is at least one selected from the group consisting of stearic acid amide, oleic acid amide, ethylene bis stearic acid amide, and ethylene bishydroxy stearic acid amide. The preferred (a) cyclic olefin monomer is 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.

  The method for producing a thermosetting crosslinked cyclic olefin resin film of the present invention includes a step of subjecting the polymerizable composition to ring-opening metathesis polymerization in the presence of a composition containing a polymerization catalyst. 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.

  The thermosetting crosslinked cyclic olefin resin film of the present invention has sufficient releasability from resins used for sealing materials, prepregs, and adhesives, and mechanical strength such as tensile elongation at break and tensile strength at break.

(A) The cyclic olefin monomer which is one of the raw materials of the thermosetting crosslinked cyclic olefin resin film of the present invention has a ring structure formed of carbon atoms, and has a carbon-carbon double bond in the ring. A compound. Specific examples thereof include norbornene monomers and monocyclic olefins. The preferred (a) cyclic olefin monomer is a norbornene monomer. The norbornene-based monomer is a monomer containing a norbornene ring. Specific examples of the norbornene monomer include norbornenes, dicyclopentadiene, and tetracyclododecenes. These may contain as substituents hydrocarbon groups such as alkyl groups, alkenyl groups, alkylidene groups, and aryl groups; polar groups such as carboxyl groups and acid anhydride groups.
The norbornene monomer may further have a double bond in addition to the double bond of the norbornene ring. From the viewpoint of improving the releasability of the release film, preferred norbornene monomers are nonpolar monomers, that is, norbornene monomers composed only of carbon atoms and hydrogen atoms.

  Specific examples of the nonpolar norbornene monomer include nonpolar such as dicyclopentadiene, methyldicyclopentadiene, and dihydrodicyclopentadiene (also referred to as tricyclo [5.2.1.02,6] dec-8-ene). Of dicyclopentadiene;

  Tetracyclo [6.2.13,6.02,7] dodec-4-ene, 9-methyltetracyclo [6.2.13,6.02,7] dodec-4-ene, 9- Ethyltetracyclo [6.2.13,6.02,7] dodec-4-ene, 9-cyclohexyltetracyclo [6.2.1.13,6.02,7] dodec-4-ene, 9-cyclopentyltetracyclo [6.2.13,6.02,7] dodec-4-ene, 9-methylenetetracyclo [6.2.13,6.02,7] dodec-4- Ene, 9-ethylidenetetracyclo [6.2.13,6.02,7] dodec-4-ene, 9-vinyltetracyclo [6.2.13,6.02,7] dodeca 4-ene, 9-propenyltetracyclo [6.2.13, 6.02,7] dodec-4-e 9-cyclohexenyltetracyclo [6.2.13, 6.02,7] dodec-4-ene, 9-cyclopentenyltetracyclo [6.2.1.13,6.02,7] dodeca Non-polar tetracyclododecenes such as -4-ene, 9-phenyltetracyclo [6.2.1.13, 6.02,7] 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 [9.2.1.02,10.03,8] tetradeca-3,5,7,12-tetraene (1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene.), Tetracyclo [10.2.1.02, 11. 4,9] 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 pentacycles such as 5,12-diene, hexacyclo [6.6.1.13, 6.110, 13.02, 7.09,14] heptade-4-ene; It is.

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

  Specific examples of the norbornene-based monomer containing a polar group include tetracyclo [6.2.13, 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-norbornene 2-carbonitrile, 2-acetyl-5-norbornene, and the like 7-oxa-2-norbornene.

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

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

 The polymerizable composition containing (a) a cyclic olefin monomer and (b) a fatty acid amide is subjected to ring-opening metathesis polymerization in the presence of a composition containing 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.

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

In the formulas (1) and (2), R ¹ and R ² each independently include a hydrogen atom; a halogen atom; or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. It represents a good cyclic or chain hydrocarbon group having 1 to 20 carbon atoms. X ¹ and X ² each independently 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. Furthermore, R ¹ , R ² , X ¹ , X ² , L ¹ and L ² may be bonded together in any combination to form a multidentate chelating ligand.

  The heteroatom in the present invention is an atom of Groups 15 and 16 of the periodic table. Specific examples of the hetero atom include a nitrogen atom (N), an oxygen atom (O), a phosphorus atom (P), a sulfur atom (S), an arsenic atom (As), and a selenium atom (Se). From the viewpoint of the stability of the carbene compound, preferred heteroatoms are N, O, P, and S, and particularly preferred heteroatoms are N.

  Neutral electron donating compounds are roughly classified into hetero atom-containing carbene compounds and other neutral electron donating compounds. From the viewpoint of the activity of the polymerization catalyst, 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. preferable. The heteroatom adjacent to the carbene carbon preferably has a bulky substituent.

  Specific examples of preferred heteroatom-containing carbene compounds are compounds represented by the following formula (3) or formula (4).

In Formula (3) and Formula (4), R ^{3 to} R ⁶ may each independently contain a hydrogen atom; a halogen atom; or a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, or silicon atom. Represents a cyclic or chain hydrocarbon group having 1 to 20 carbon atoms. R ^{3 to} R ⁶ may be bonded to each other in any combination to form a ring.

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

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

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

In the formulas (1) and (2), the anionic (anionic) ligands X ¹ and X ² are ligands having a negative charge when separated from the central metal atom. Examples are halogen atoms such as fluorine atom (F), chlorine atom (Cl), bromine atom (Br), iodine atom (I), diketonate group, substituted cyclopentadienyl group, alkoxy group, aryloxy group, carboxyl group Etc. A preferred anionic ligand is a halogen atom, and a more preferred ligand is a chlorine atom.

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

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

In Formula (5), R ^{7 to} R ⁹ each independently represent a monovalent organic group that may contain a hydrogen atom, a halogen atom, or a hetero atom. Specific examples of the monovalent organic group that may contain a hetero atom include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group, and a carbon number. An alkoxyl group having 1 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, an aryloxy group, an alkylthio group having 1 to 8 carbon atoms, a carbonyloxy group having 1 to 20 carbon atoms, C1-C20 alkoxycarbonyl group, C1-C20 alkylsulfonyl group, C1-C20 alkylsulfinyl group, C1-C20 alkyl sulfonic acid group, aryl sulfonic acid group, C1-C1 20 phosphonic acid groups, arylphosphonic acid groups, alkylammonium groups having 1 to 20 carbon atoms, arylammonium groups, and the like.
The monovalent organic group which may contain these heteroatoms may have a substituent and may be bonded to each other to form a ring. Examples of the substituent are an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, and an aryl group. When the monovalent organic group forms a ring, the ring may be an aromatic ring, an alicyclic ring, or a heterocyclic ring.

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

  Specific examples of the complex compound represented by the formula (1) include benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-4). , 5-Dibromo-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4-imidazoline-2-ylidene) (3-phenyl-1H-indene-1-ylidene) ( Tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4-imidazolidin-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3- Dimesityl-octahydrobenzimida 2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3 -Dimesityl-2,3-dihydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H -1,2,4-triazole-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene 1,3-dimesityl-4-imidazolidin-2-ylidene) pyridine ruthenium dichloride, (1,3-dimesityl-4-imidazolidin-2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride, 1,3-Dimesityl-4-imidazoline-2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) [ (Phenylthio) methylene] (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) (2-pyrrolidone-1-ylmethylene) (tricyclohexylphosphine) ruthenium dichloride Lori A ruthenium complex compound in which one hetero atom-containing carbene compound and one neutral electron donating compound are bonded, such as

  A ruthenium complex compound in which two neutral electron-donating compounds are bonded, such as benzylidenebis (tricyclohexylphosphine) ruthenium dichloride, (3-methyl-2-buten-1-ylidene) bis (tricyclopentylphosphine) ruthenium dichloride;

  Two heteroatom-containing carbene compounds such as benzylidenebis (1,3-dicyclohexyl-4-imidazolidin-2-ylidene) ruthenium dichloride and benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride Ruthenium complex compound in which is bonded;

A ruthenium carbene complex represented by formula (6) in which X ² and L ² are bonded to each other to form a multidentate chelating ligand;

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

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

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

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

  The amount of the polymerization catalyst used is a molar ratio of (metal atom in the polymerization catalyst: (a) cyclic olefin monomer) and is usually 1: 2,000 to 1: 2,000,000, preferably 1: 5,000 to The range is from 1: 1,000,000, more preferably from 1: 10,000 to 1: 500,000. If the amount of the polymerization catalyst is too small, the polymerization reaction rate may decrease and monomers may remain in the polymer, or the crosslinking degree of the crosslinked polymer may decrease and the heat resistance of the resulting film may decrease. is there. If the amount of the polymerization catalyst is too large, the production cost increases, and the reaction rate becomes too fast, which may make it difficult to form a film during bulk polymerization, which will be described later.

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. Specific examples of the activator include aluminum, scandium, tin, silicon alkylates, halides, alkoxylates and aryloxylates. Further specific examples of activators include aluminum compounds such as trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride; trialkoxy Scandium compounds such as scandium; titanium compounds such as tetraalkoxy titanium; tin compounds such as tetraalkyls and tetraalkoxytin; zirconium compounds such as tetraalkoxyzirconium; dimethylmonochlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, tetrachlorosilane, bicyclo Heptenylmethyldichlorosilane, phenylmethyldichlorosilane, Hexyl dichlorosilane, phenyl trichlorosilane, silane compounds such as methyltrichlorosilane, and the like.
The 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. Specific examples of the polymerization regulator include triphenylphosphine, tricyclohexylphosphine, tributylphosphine, 1,1-bis (diphenylphosphino) methane, 1,4-bis (diphenylphosphino) butane, 1,5-bis (diphenyl). Phosphino) phosphorus compounds such as pentane; Lewis bases such as ethers, esters and nitriles. The amount 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.

In the bulk polymerization method, a polymerizable composition containing (a) a cyclic olefin monomer and (b) a fatty acid amide is formed into a film by ring-opening metathesis polymerization in the presence of a polymerization catalyst and additives used as necessary. The process of carrying out is included.
(A) 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 thermosetting crosslinked cyclic olefin resin film of the present invention contains (b) a fatty acid amide. Specific examples of the fatty acid amide include saturated fatty acid monoamides such as lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxy stearic acid amide; methylene bis stearic acid amide, ethylene bishydroxy stearic acid amide, ethylene biscaprin Acid amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bis isostearic acid amide, ethylene bis behenic acid amide, hexamethylene bis stearic acid amide, hexamethylene bis behenic acid amide, hexamethylene bis hydroxy stearic acid amide, N Saturated fatty acid bisamides such as N, N′-distearyl adipic acid amide and N, N′-distearyl sebacic acid amide; oleic acid amide, erucic acid amide, ricinoleic acid amide and the like Unsaturated fatty acid monoamides; Unsaturation such as ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide Fatty acid bisamides; substituted amides such as N-stearyl stearic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, N-oleyl palmic acid amide; Methylolamides such as methylol stearamide and methylolbehenamide; and the like. A particularly preferred fatty acid amide is ethylene bis stearic acid amide.

  The polymerizable composition is used in an amount of 0.3 to 40 parts by weight, preferably 0.3 to 20 parts by weight, and more preferably 0.3 to 5 parts by weight (100 parts by weight of (a) the cyclic olefin monomer. b) Contains a fatty acid amide. (B) When there is too little content of fatty acid amide, the mold release property of a thermosetting crosslinked cyclic olefin resin film will fall. On the other hand, when there is too much content of (b) fatty acid amide, there exists a possibility that it may become difficult to obtain the film of a uniform composition.

  Various additives are contained in the thermosetting crosslinked cyclic olefin resin film of the present invention for the purpose of improving the properties of the film according to various uses and purposes, imparting functions, and improving molding workability. Specific examples of such additives include polymerization inhibitors, fillers, antifoaming agents, foaming agents, colorants, ultraviolet absorbers, stabilizers, flame retardants, wetting agents, dispersing agents, release lubricants, plasticizers, and the like. It is. Preferably, a stabilizer is contained in order to improve the durability and storage stability of the crosslinked cyclic olefin polymer.

  Specific examples of polymerization inhibitors include quinones such as parabenzoquinone, tolquinone and naphthoquinone; hydroquinones such as hydroquinone, para-t-butylcatechol and 2,5-di-t-butylhydroquinone; copper naphthenate and copper octenoate Quaternary ammonium salts such as trimethylbenzylammonium chloride, trimethylbenzylammonium maleate, phenyltrimethylammonium chloride; oximes such as quinonedioxime and methylethylketoxime; amines such as triethylamine hydrochloride and dibutylamine hydrochloride Hydrochlorides; and the like. One or more of these are used in combination.

Specific examples of fillers include inorganic fillers such as carbon black, natural graphite, silica, silica sand, glass powder, calcium carbonate, aluminum hydroxide, magnesium hydroxide, and clay; organic fillers such as wood powder, polyester beads, and polystyrene beads Material; etc. One or more of these are used in combination. The filler improves physical properties such as shrinkage rate, elastic modulus, thermal conductivity, and conductivity of the crosslinked cyclic olefin polymer.
Grades such as the particle size, shape, aspect ratio, and quality of the filler are appropriately determined depending on the physical properties of the 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.

  Specific examples of the release lubricant other than the fatty acid amide include silicone oil and zinc stearate. One or more of these are used in combination. Mold release lubricants other than fatty acid amides improve the moldability, mold release and handling properties of the film and impart functions such as lubricant properties to the film. The amount of the release lubricant other than the fatty acid amide is preferably 200 parts by mass or less with respect to 100 parts by mass of the (a) cyclic olefin monomer.

  Preferred stabilizers are phenolic stabilizers, phosphorus stabilizers and hindered amine light stabilizers. Specific examples of the phenol-based stabilizer include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4). -Hydroxyphenyl) propionate, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-tert-butyl-4 -Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,6-di-tert-butyl- 4-methylphenol and the like. One or more of these are used in combination.

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

  Specific examples of the hindered amine light stabilizer include 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl- 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1- (4-t-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy -2,2,6,6-tetramethylpiperidine, 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6 Pentamethylpiperidine, 1,2,2,6,6-pentamethylpiperidin-4-yl-β (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, Zir-2,2,6,6-tetramethyl-4-piperidinyl maleate, (di-2,2,6,6-tetramethylpiperidin-4-yl) -adipate, (di-2 , 2,6,6-tetramethylpiperidin-4-yl) -sebacate, (di-1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) -sebacate, (di- 1-allyl-2,2,6,6-tetramethyl-piperidin-4-yl) -phthalate, 1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-acetate, trimellitic acid-tri -(2,2,6,6-tetramethylpiperidin-4-yl) ester, 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine, dibutyl-malonic acid-di- (1 , 2,2,6,6-pentamethyl-piperidin-4-yl) -ester, dibenzyl-malonic acid-di- (1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) ) -Ester, dimethyl-bis- (2,2,6,6-tetramethylpiperidin-4-oxy) -silane, tris- (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) ) -Phosphite, tris- (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) -phosphate, N, N′-bis- (2,2,6,6-tetramethylpiperidine -4-yl) -hexamethylene-1,6-diamine, N, N′-bis- (2,2,6,6-tetramethylpiperidin-4-yl) -hexamethylene-1,6-diacetamide, 1-acetyl-4 (N-cyclohexylacetamide) -2,2,6,6-tetramethyl-piperidine, 4-benzylamino-2,2,6,6-tetramethylpiperidine, N, N′-bis- (2,2,6 , 6-Tetramethylpiperidin-4-yl) -N, N′-dibutyl-adipamide, N, N′-bis- (2,2,6,6-tetramethylpiperidin-4-yl) -N, N ′ -Dicyclohexyl- (2-hydroxypropylene), N, N'-bis- (2,2,6,6-tetramethylpiperidin-4-yl) -p-xylylene-diamine, 4- (bis-2-hydroxyethyl) ) -Amino-1,2,2,6,6-pentamethylpiperidine, 4-methacrylamide-1,2,2,6,6-pentamethylpiperidine, α-cyano-β-methyl-β- [N- (2, 2, 6, - tetramethylpiperidine-4-yl)] - amino - methyl acrylate and the like. One or more of these are used in combination.

  The kind and amount of these stabilizers 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. The usage-amount of a stabilizer is 20 mass parts or less normally with respect to 100 mass parts of (a) cyclic olefin monomers.

  The polymerizable composition containing (a) a cyclic olefin monomer and (b) a fatty acid amide is subjected to ring-opening metathesis polymerization in the presence of a composition containing a polymerization catalyst and additives used as necessary. The polymerization catalyst is used after being dissolved or suspended in a small amount of an inert solvent, if necessary. Specific examples of the solvent include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin, and mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, Alicyclic hydrocarbons such as diethylcyclohexane, decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; and alicyclic rings such as indene and tetrahydronaphthalene Hydrocarbons having an aromatic ring; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; oxygen-containing hydrocarbons such as diethyl ether and tetrahydrofuran; 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.

  Although the viscosity at room temperature of the composition containing (a) a cyclic olefin monomer, (b) a fatty acid amide and an additive used as necessary depends on the desired film thickness, it is preferably 3 to 500 Pa · s. It becomes easy to form in a film shape because a viscosity exists in said preferable range. The viscosity of the composition is adjusted by the type and amount of (a) cyclic olefin monomer and (b) fatty acid amide.

  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.

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

  The composition is subjected to bulk polymerization by heating to a temperature at which the polymerization catalyst exhibits activity, if 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.

  Specific examples of the crosslinking method include: (A) (a) a method in which a crosslinkable monomer is used as at least a part of the cyclic olefin monomer and polymerized to obtain a polymer having a three-dimensional crosslinked structure; (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; 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.

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

  A known thermal crosslinking agent and photocrosslinking agent 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 to be 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 temperature at which crosslinking is performed when a thermal crosslinking agent is used 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 performed in the absence of oxygen and water. Specific examples of the bulk polymerization and crosslinking method include (1) a method of bulk polymerization and crosslinking in an inert gas atmosphere such as nitrogen gas and argon gas, and (2) a method of bulk polymerization and crosslinking under vacuum, (3 ) 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. When bulk polymerization and crosslinking are performed in the presence of oxygen or water, the surface of the resulting film may be oxidized, making it difficult to exhibit desired flexibility.

  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 μm, from the viewpoint of handling properties, The thickness is preferably 5 to 500 μm. 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.

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

Various physical properties were measured as follows.
(1) Tensile properties of thermosetting crosslinked cyclic olefin resin film The tensile breaking elongation and tensile breaking strength of the thermosetting crosslinked cyclic olefin resin film were measured at 23 ° C. in accordance with 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.

(2) Peeling force against prepreg of thermosetting crosslinked cyclic olefin resin film Printed circuit board lamination prepreg punched to 300 mm x 300 mm (FR-4 R-1661 (G) GB type manufactured by Panasonic Electric Works Co., Ltd.) Thickness 0. 2 mm) was inserted into a vacuum press with the release film of each Example or Comparative Example, cured at 1.0 MPa and 180 ° C. for 70 minutes, and then cooled to 40 ° C. to obtain The sample was removed from the vacuum press. A test piece of 25 mm × 150 mm was cut out from the sample, and the 180 ° peeling force was measured according to JIS K 6854-2. The peel force was defined as initial prepreg peel force. The smaller the prepreg peel force is, the higher the releasability.

Examples 1-7 and Comparative Examples 1-2
Fatty acid amides, phenolic stabilizers, phosphorus stabilizers and hindered amine light stabilizers shown in Table 1 are dissolved in a norbornene monomer mixture consisting of 90% by mass of dicyclopentadiene and 10% by mass of tricyclopentadiene and reacted. A stock solution was obtained. Next, a ruthenium catalyst having the structure of the formula (7) in mass shown in Table 1 and Table 2 is added to the reaction stock solution, mixed with a line mixer, and a polyethylene terephthalate having a thickness of 0.075 mm at 25 ° C. Coating was carried out on a 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. The results are shown in Table 1.

1) IRGANOX1076 manufactured by BASF Japan
2) Adeka Stub HP-10 manufactured by ADEKA Corporation
3) TINUVIN770 manufactured by BASF Japan
4) Kao Wax EB-P manufactured by Kao Corporation
5) Nihon Kasei Co., Ltd. Sripax H
6) Nippon Kasei's Diamond 200
7) Nippon Kasei Co., Ltd. fatty acid ON
8) HF77 manufactured by PS Japan Corporation
9) VC843 manufactured by RIMTEC

  The initial release properties and mechanical strength of the release films obtained from the polymerizable compositions of Examples 1 to 7 were high.

  The initial release property of the release film obtained from the polymerizable composition of Comparative Example 1 containing no fatty acid amide was low. The initial release property of the release film obtained from the polymerizable composition of Comparative Example 2 in which the fatty acid amide content was too low was low. The fatty acid amide contained in the reaction stock solution of Comparative Example 3 containing too much fatty acid amide was not completely dissolved, and no resin film was obtained from the reaction stock solution. The release film obtained from the polymerizable composition of Comparative Example 4 containing polystyrene dissolved in the norbornene-based monomer mixed solution but not containing the rosin resin and the terpene resin could not be peeled from the prepreg.

The thermosetting crosslinked cyclic olefin resin composition of the present invention provides a film that is suitably used in 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. In this method, a mold film is interposed for resin sealing, that is, a release film is interposed on at least one side of the upper mold and the lower mold inner surface.
The 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.

Claims (8)

  A thermosetting crosslinked cyclic olefin resin film obtained by ring-opening metathesis polymerization of a polymerizable composition containing (a) 100 parts by mass of a cyclic olefin monomer and (b) 0.3 to 40 parts by mass of a fatty acid amide.   2. The heat according to claim 1, wherein the (b) fatty acid amide is at least one selected from the group consisting of stearic acid amide, oleic acid amide, ethylenebisstearic acid amide, and ethylenebishydroxystearic acid amide. Curable crosslinked cyclic olefin resin film.   The thermosetting crosslinked cyclic olefin resin film according to claim 1 or 2, wherein the (a) cyclic olefin monomer is a norbornene-based monomer.   The thermosetting crosslinked cyclic olefin resin film described in any one of claims 1 to 3, which is a release film used in a semiconductor sealing process.   The thermosetting crosslinked cyclic olefin resin film described in any one of claims 1 to 3, which is a release film for producing a printed circuit board.   The thermosetting crosslinked cyclic olefin resin film according to any one of claims 1 to 5, comprising a step of ring-opening metathesis polymerization of the polymerizable composition in the presence of a composition containing a polymerization catalyst. Production method.   The thermosetting crosslinked cyclic olefin resin film according to claim 6, wherein 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. Production method.   The method for producing a thermosetting crosslinked cyclic olefin resin film according to claim 6 or 7, wherein the polymerization catalyst is a ruthenium carbene complex.