Cycloolefin resin cured product

Abstract

The present invention provides a cycloolefin resin cured product, which is obtained by bulk polymerization of a polymerizable composition comprising a cycloolefin monomer and a metathesis polymerization catalyst, wherein the cycloolefin monomer contains a norbornene monomer (a1) and a monocyclic cycloolefin (a2), and the cycloolefin resin cured product has an elongation at break of 30% or more at 23°C.

Description

Technical Field

[0001] The present invention relates to a cycloolefin resin cured product, and more particularly to a cycloolefin resin cured product having excellent crack resistance, stretchability and high-temperature durability. Background Art

[0002] Cycloolefin resins are known to be excellent in mechanical strength, heat resistance, low hygroscopicity, dielectric properties, etc., and are used in various applications.

[0003] For example, the use of such cycloolefin resins for sealing semiconductor elements is studied in Patent Document 1. In the technology of Patent Document 1, the cycloolefin resins are used for sealing semiconductor elements by utilizing the characteristics of the cycloolefin resins, specifically, the characteristics that the monomer liquid has a low viscosity and thus has a high degree of freedom in molding, and can be applied and cured in a short time.

[0004] On the other hand, it has been confirmed that molded products with complex structures, fillers, and metal components will crack and break due to the concentration of internal stress even in low-temperature, high-temperature environments or room-temperature environments. In complex molding with high functionality and low viscosity brought about by compounding with other materials, resin materials with excellent durability at room temperature, temperature cycle reliability in low-temperature and high-temperature environments, and durability for long-term use are required.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2013-48295. Summary of the invention

[0008] Problem that the invention aims to solve

[0009] The present inventors have studied the use of cycloolefin resins as resin materials that utilize the properties of cycloolefin resins, namely, the properties that the monomer liquid has a low viscosity and thus has a high degree of freedom in molding, and can be applied and cured in a short time. As a result, it was found that the cured product obtained using the cycloolefin resins would break during molding or in the environment during use, and there were problems of poor reliability and durability. This problem is particularly prominent when the cycloolefin resin contains a filler.

[0010] The present invention has been made in view of such actual circumstances, and an object of the present invention is to provide a cycloolefin resin cured product having excellent crack resistance, stretchability and high-temperature durability, and a polymerizable composition that can be preferably used to form the cured product.

[0011] Solutions for solving problems

[0012] The present inventors have conducted studies to achieve the above-mentioned purpose and have found that the above-mentioned purpose can be achieved by using a norbornene monomer (a1) and a monocyclic cycloolefin (a2) as cycloolefin monomers for forming a cycloolefin resin cured product and making the elongation at break of the cycloolefin resin cured product at room temperature 30% or more, thereby completing the present invention.

[0013] That is, according to the present invention, there is provided a cycloolefin resin cured product obtained by bulk polymerization of a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst.

[0014] The cycloolefin monomer contains a norbornene-based monomer (a1) and a monocyclic cycloolefin (a2).

[0015] The cycloolefin-based resin cured product has an elongation at break at 23° C. of 30% or more.

[0016] In the cycloolefin-based resin cured product of the present invention, the content of the monocyclic cycloolefin (a2) in the cycloolefin monomer is preferably 30 to 99% by mass.

[0017] In the cycloolefin resin cured product of the present invention, the monocyclic cycloolefin (a2) is preferably 1,5-cyclooctadiene, cyclooctene, cyclohexene, 1,4-cyclohexadiene, or 1,4-cyclohexene. Diene.

[0018] In the cycloolefin-based resin cured product of the present invention, the polymerizable composition preferably contains a filler.

[0019] Furthermore, according to the present invention, there can be provided a polymerizable composition comprising a cycloolefin monomer and a metathesis polymerization catalyst.

[0020] The cycloolefin monomer contains a norbornene-based monomer (a1) and a monocyclic cycloolefin (a2).

[0021] This polymerizable composition is used to form the above-mentioned cycloolefin resin cured product.

[0022] The polymerizable composition of the present invention is preferably formed from two or more pre-formulated solutions that do not undergo polymerization reaction independently, and the polymerizable composition can be formed by mixing the pre-formulated solutions.

[0023] Effects of the Invention

[0024] According to the present invention, a cycloolefin resin cured product having excellent crack resistance, stretchability and high-temperature durability can be provided. DETAILED DESCRIPTION

[0025] The cycloolefin resin cured product of the present invention is obtained by bulk polymerization of a polymerizable composition comprising a cycloolefin monomer and a metathesis polymerization catalyst, wherein the cycloolefin monomer contains a norbornene monomer (a1) and a monocyclic cycloolefin (a2), and the cycloolefin resin cured product has an elongation at break of 30% or more at 23°C.

[0026] <Polymerizable composition>

[0027] First, the polymerizable composition for producing the cycloolefin-based resin cured product of the present invention will be described.

[0028] The polymerizable composition for producing the cycloolefin-based resin cured product of the present invention contains a cycloolefin monomer and a metathesis polymerization catalyst.

[0029] The cycloolefin monomer is a compound having a ring structure formed of carbon atoms and having a carbon-carbon double bond in the ring.

[0030] In the present invention, as the cycloolefin monomer, at least a norbornene-based monomer (a1) and a monocyclic cycloolefin (a2) are used.

[0031] As a norbornene monomer (a1), as long as it is a compound having a norbornene ring structure, it is not particularly limited, and examples include: bicyclic bodies such as norbornene, norbornadiene, and vinyl norbornene; tricyclic bodies such as dicyclopentadiene and dihydrodicyclopentadiene; tetracyclic bodies such as tetracyclododecene and ethylenetetracyclododecene; pentacyclic bodies such as tricyclopentadiene; heptacyclic bodies such as tetracyclopentadiene; and derivatives thereof having alkenyl, alkynyl, alkylene, epoxy, (meth) acrylic acid substituents (for example, ethylene substituents), etc. Norbornene monomers (a1) can be used alone or in combination of two or more. As a norbornene monomer (a1), from the viewpoint of being able to further improve the effect of the present invention, tricyclic bodies are preferred, and dicyclopentadiene is particularly preferred. In addition, from the viewpoint of being able to further improve the effect of the present invention, it is also preferred to use tricyclic bodies and pentacyclic bodies in combination, and as a pentacyclic body, tricyclopentadiene is preferred. When a tricyclic form and a pentacyclic form are used in combination, the ratio of the tricyclic form to the pentacyclic form in the norbornene monomer (a1) is preferably 50:50 to 98:2, more preferably 65:35 to 95:5, and even more preferably 80:20 to 93:7.

[0032] In addition, as the above-mentioned derivatives, from the viewpoint of improving the adhesion between the obtained cured product and the substrate (for example, the semiconductor element when used as a sealing material for a semiconductor element), derivatives having an epoxy group are preferred. For example, 4,5-epoxytricyclo[5.2.1.0 2,6] dec-8-ene〔also known as dicyclopentadiene monoepoxide (2,3-DCPME). In this specification, it may be simply referred to as DCPME〕, 4,5-epoxy-8-chlorotricyclo[5.2.1.0 2,6 ]dec-8-ene, 4,5-epoxy-8-methyltricyclo[5.2.1.0 2,6 ]dec-8-ene, 4,5-epoxy-8-trifluoromethyl tricyclo[5.2.1.0 2,6 ] dec-8-ene, etc., among which DCPME is preferred. The content of the above derivative having an epoxy group in the polymerizable composition used in the present invention is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and further preferably 1 to 5% by mass.

[0033] The monocyclic cycloolefin (a2) is not particularly limited, and examples thereof include cyclobutene, cyclopentene, cyclohexene, cyclooctene, cyclododecene, cyclopentadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, and derivatives thereof having alkyl, alkenyl, alkynyl, alkylene, epoxy, (meth)acrylic acid substitution (e.g., ethylene substitution). For example, as a derivative of 1,4-cyclohexadiene, 1,4-cyclohexadiene can be preferably used. Diene. As the monocyclic cycloolefin (a2), from the viewpoint of being able to further improve the effect of the present invention, a monocyclic cycloolefin having one or more unsaturated bonds showing metathesis reactivity in the molecule is preferred, and examples of such monocyclic cycloolefins include 1,5-cyclooctadiene and the above-mentioned derivatives thereof. The monocyclic cycloolefin (a2) can be used alone or in combination of two or more.

[0034] The content of the monocyclic cycloolefin (a2) in the cycloolefin monomer used in the present invention is preferably 30 to 99% by mass, more preferably 30 to 80% by mass, further preferably 30 to 60% by mass, and further preferably 40 to 50% by mass in 100% by mass of the cycloolefin monomer as a whole. By making the content of the monocyclic cycloolefin (a2) within the above range, the crack resistance and expansion and contraction properties of the cycloolefin-based resin cured product can be made more excellent, thereby, for example, when used as a sealing material for a semiconductor device, the temperature cycle reliability and durability can be further improved.

[0035] In addition, the content of the norbornene monomer (a1) in the cycloolefin monomer used in the present invention is preferably 1 to 70% by mass, more preferably 20 to 70% by mass, further preferably 40 to 70% by mass, and further preferably 50 to 60% by mass in 100% by mass of the total cycloolefin monomer. By making the content of the norbornene monomer (a1) within the above range, the crack resistance and expansion and contraction properties of the cycloolefin resin cured product can be made more excellent, thereby, for example, when used as a sealing material for a semiconductor device, the temperature cycle reliability and durability can be further improved.

[0036] Furthermore, the polymerizable composition used in the present invention may contain other cycloolefin monomers (a3) ​​in addition to the norbornene-based monomer (a1) and the monocyclic cycloolefin (a2).

[0037] The content of the other cycloolefin monomer (a3) ​​in the cycloolefin monomer used in the present invention is preferably 70% by mass or less, more preferably 50% by mass or less, based on 100% by mass of the entire cycloolefin monomer.

[0038] The metathesis polymerization catalyst used in the present invention is not particularly limited as long as it can ring-opening polymerize the cycloolefin monomer, and a known metathesis polymerization catalyst can be used.

[0039] Metathesis polymerization catalyst used in the present invention is a complex formed by combining a transition metal atom as a central atom, a plurality of ions, atoms, polyatomic ions and / or compounds. As a transition metal atom, an atom of the 5th, 6th and 8th families (long period type periodic table, the same below) is used. The atom of each family is not particularly limited, and as an atom of the 5th family, for example tantalum can be mentioned, as an atom of the 6th family, for example molybdenum and tungsten can be mentioned, and as an atom of the 8th family, for example ruthenium and osmium can be mentioned. Among these transition metal atoms, ruthenium and osmium of the 8th family are preferred. That is, as a metathesis polymerization catalyst used in the present invention, a complex preferably having ruthenium or osmium as a central atom, more preferably a complex having ruthenium as a central atom. As a complex having ruthenium as a central atom, a ruthenium carbene complex formed by the coordination of a preferred carbene compound and ruthenium. Here, "carbene compound" refers to a general term for compounds having a methylene free group, and refers to a compound having an uncharged divalent carbon atom (carbene carbon) represented by (>C:). Ruthenium carbene complexes have excellent catalytic activity during bulk ring-opening polymerization, so the resulting polymer has less odor from unreacted monomers, and the polymer can be obtained with good productivity. In addition, it is relatively stable to oxygen and moisture in the air and is not easily deactivated, so it can also be used in the atmosphere. Metathesis polymerization catalysts can be used alone or in combination of multiple catalysts.

[0040] Examples of the ruthenium carbene complex include ruthenium carbene complexes represented by the following general formula (1) or (2).

[0041] [Chemical formula 1]

[0042]

[0043] In the above general formulas (1) and (2), R 1 and R 2 Each is independently a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom; these groups may have a substituent and may be combined with each other to form a ring. 1 and R 2 Examples of groups that are bonded to form a ring include indenylidene groups which may have a substituent, such as phenylindenylidene.

[0044] Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon 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 having 6 to 20 carbon atoms, an alkoxy 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, and a 6 to 20 carbon atom group. The organic groups may include alkyl groups having 1 to 20 carbon atoms, alkylthio groups having 1 to 8 carbon atoms, carbonyloxy groups, alkoxycarbonyl groups having 1 to 20 carbon atoms, alkylsulfonyl groups having 1 to 20 carbon atoms, alkylsulfinyl groups having 1 to 20 carbon atoms, alkylsulfonic acid groups having 1 to 20 carbon atoms, arylsulfonic acid groups having 6 to 20 carbon atoms, phosphonic acid groups, arylphosphonic acid groups having 6 to 20 carbon atoms, alkylammonium groups having 1 to 20 carbon atoms, and arylammonium groups having 6 to 20 carbon atoms. These organic groups having 1 to 20 carbon atoms which may contain halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, or silicon atoms may have a substituent. Examples of the substituent include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and aryl groups having 6 to 10 carbon atoms.

[0045] X 1 and X 2 Each independently represents an arbitrary anionic ligand. The anionic ligand is a ligand having a negative charge when separated from the central metal atom, and examples thereof include a halogen atom, a diketonate group, a substituted cyclopentadienyl group, an alkoxy group, an aryloxy group, and a carboxyl group.

[0046] L 1 and L 2Represents a heteroatom carbene compound or a neutral electron-donating compound other than a heteroatom carbene compound. Heteroatom carbene compounds and neutral electron-donating compounds other than heteroatom carbene compounds are compounds having a neutral charge when separated from a central metal. From the viewpoint of improving the activity of the catalyst, heteroatom carbene compounds are preferred. Heteroatoms refer to atoms of the 15th and 16th groups of the periodic table, and specifically, nitrogen atoms, oxygen atoms, phosphorus atoms, sulfur atoms, arsenic atoms, and selenium atoms can be cited. Among these, from the viewpoint of obtaining a stable carbene compound, nitrogen atoms, oxygen atoms, phosphorus atoms, and sulfur atoms are preferred, and nitrogen atoms are more preferred.

[0047] As the heteroatom-containing carbene compound, a compound represented by the following general formula (3) or (4) is preferred. From the viewpoint of improving the catalyst activity, a compound represented by the following general formula (3) is more preferred.

[0048] [Chemical formula 2]

[0049]

[0050] In the above general formulas (3) and (4), R 3 , R 4 , R 5 and R 6 Each independently represents a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom. Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom are the same as those in the above-mentioned general formulae (1) and (2).

[0051] In addition, R 3 , R 4 , R 5 and R 6 They can be combined with each other in any combination to form a ring.

[0052] In addition, from the viewpoint of making the effect of the present invention more remarkable, it is preferred that R 5 and R 6 is a hydrogen atom. In addition, R 3 and R 4 An aryl group which may have a substituent is preferred, a phenyl group having an alkyl group having 1 to 10 carbon atoms as a substituent is more preferred, and a mesityl group is further preferred.

[0053] Examples of the neutral electron-donating compound include oxygen atoms, water, carbonyl groups, ethers, nitriles, esters, phosphines, phosphites, phosphites, sulfoxides, thioethers, amides, imines, aromatics, cyclic dienes, olefins, isocyanides, and isothiocyanates.

[0054] In the above general formulas (1) and (2), R 1 , R 2 , X 1 , X 2 , L 1 and L 2 They can be combined individually and / or in any combination to form a multidentate chelating ligand.

[0055] In addition, as the ruthenium carbene complex used in the present invention, among the compounds represented by the above-mentioned general formula (1) or (2), from the perspective of making the effect of the present invention more significant, the compound represented by the above-mentioned general formula (1) is preferred, among which the compound represented by the following general formula (5) or general formula (6) is more preferred.

[0056] The general formula (5) is shown below.

[0057] [Chemical formula 3]

[0058]

[0059] In the above general formula (5), Z is an oxygen atom, a sulfur atom, a selenium atom, NR 12 , PR 12 AsR 12 , R 12 is a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom; from the perspective of making the effect of the present invention more significant, Z is preferably an oxygen atom.

[0060] In addition, R 1 , R 2 , X 1 and L 1 As in the case of the above general formulas (1) and (2), each can be combined alone and / or in any combination to form a multidentate chelate ligand, preferably X 1 and L 1 No multidentate chelating ligand is formed and R 1 and R 2 They are bonded to each other to form a ring, and an indenylene group which may have a substituent is more preferred, and a phenylindenylene group is further preferred.

[0061] Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom are the same as those in the above-mentioned general formulae (1) and (2).

[0062] In the above general formula (5), R 7 and R 8 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 having 6 to 20 carbon atoms. These groups may have a substituent and may be combined with each other to form a ring. Examples of substituents include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. When a ring is formed, the ring may be any of an aromatic ring, an alicyclic ring, and a heterocyclic ring. Preferably, an aromatic ring is formed, more preferably, an aromatic ring having 6 to 20 carbon atoms is formed, and further preferably, an aromatic ring having 6 to 10 carbon atoms is formed.

[0063] In the above general formula (5), R 9 , R 10 and R 11 Each is independently a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom; these groups may have a substituent or may be combined with each other to form a ring. In addition, specific examples of organic groups having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom are the same as those in the above-mentioned general formulas (1) and (2).

[0064] R 9 , R 10 and R 11 It is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0065] Specific examples of the compound represented by the general formula (5) and a method for producing the compound include compounds and methods for producing the compound described in International Publication No. 03 / 062253 (Japanese Patent Publication No. 2005-515260).

[0066] The general formula (6) is shown below.

[0067] [Chemical formula 4]

[0068]

[0069] In the above general formula (6), m is 0 or 1. Preferably, m is 1, in which case, Q is an oxygen atom, a nitrogen atom, a sulfur atom, a methylene group, an ethylene group or a carbonyl group, preferably a methylene group.

[0070] In the above general formula (6),

[0071] [Chemical formula 5]

[0072]

[0073] It is a single bond or a double bond, preferably a single bond.

[0074] R 1 , X 1 , X 2 and L 1 As in the case of the above general formulas (1) and (2), each can be combined alone and / or in any combination to form a multidentate chelate ligand, preferably X 1 , X 2 and L 1 No multidentate chelating ligand is formed and R 1 A hydrogen atom.

[0075] R 13 ~R 21 is a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom; these groups may have a substituent or may be combined with each other to form a ring. In addition, specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom are the same as those in the above-mentioned general formulas (1) and (2).

[0076] R 13 It is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. 14 ~R 17 Preferably, a hydrogen atom, R 18 ~R 21 Preferred is a hydrogen atom or a halogen atom.

[0077] Specific examples of the compound represented by the general formula (6) and a production method thereof include compounds and production methods described in International Publication No. 2011 / 079799 (Japanese Patent Publication No. 2013-516392).

[0078] The content of the metathesis polymerization catalyst is preferably 0.005 mmol or more, more preferably 0.01 to 50 mmol, and further preferably 0.015 to 20 mmol, based on 1 mol of all cycloolefin monomers used in the reaction.

[0079] Furthermore, the polymerizable composition used in the present invention may contain a radical generator, a diisocyanate compound, a polyfunctional (meth)acrylate compound, and other optional components as necessary.

[0080] The free radical generator generates free radicals by heating, thereby initiating a crosslinking reaction in the cycloolefin polymer formed by bulk polymerization. The free radical generator initiates the crosslinking reaction mainly at the carbon-carbon double bond of the cycloolefin monomer, but sometimes crosslinking also occurs at the saturated bond portion.

[0081] Examples of free radical generators include organic peroxides, diazo compounds and non-polar free radical generators. Examples of organic peroxides include tert-butyl hydroperoxide, Hydroperoxides such as alkane hydroperoxide and cumene hydroperoxide; dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide, and tert-butylcumyl peroxide; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; peroxyketals such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, and 1,3-di(tert-butylperoxyisopropyl)benzene; peroxyesters such as tert-butyl peroxyacetate and tert-butyl peroxybenzoate; peroxycarbonates such as tert-butyl peroxyisopropylcarbonate and di(isopropylperoxy)dicarbonate; alkylsilyl peroxides such as tert-butyltrimethylsilyl peroxide, etc. Among them, dialkyl peroxides are preferred from the viewpoint of having little influence on metathesis polymerization reaction in bulk polymerization.

[0082] Examples of the diazo compound include 4,4'-bisazidobenzylidene(4-methyl)cyclohexanone, 4,4'-diazidechalcone, 2,6-bis(4'-azidobenzylidene)cyclohexanone, 2,6-bis(4'-azidobenzylidene)-4-methylcyclohexanone, 4,4'-diazidediphenylsulfone, 4,4'-diazidediphenylmethane, and 2,2'-diazidestilbene.

[0083] Examples of the nonpolar radical generator include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diphenylbutane, 1,4-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1,1,2,2-tetraphenylethane, 2,2,3,3-tetraphenylbutane, 3,3,4,4-tetraphenylhexane, 1,1,2-triphenylpropane, 1,1,2-triphenylethane, triphenylmethane, 1,1,1-triphenylethane, 1,1,1-triphenylpropane, 1,1,1-triphenylbutane, 1,1,1-triphenylpentane, 1,1,1-triphenyl-2-propylene, 1,1,1-triphenyl-4-pentene, and 1,1,1-triphenyl-2-phenylethane.

[0084] The amount of the radical generator in the polymerizable composition used in the present invention is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of all cycloolefin monomers used.

[0085] Examples of the diisocyanate compound include 4,4′-methylenediphenyl diisocyanate (MDI), toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 1,4-phenylene diisocyanate, toluene diisocyanate, xylyl diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, and 4,4′- Aromatic diisocyanate compounds such as dibenzyl diisocyanate; aliphatic diisocyanate compounds such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate; alicyclic diisocyanate compounds such as 4-cyclohexylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, and hydrogenated XDI, etc., polyurethane prepolymers obtained by reacting these diisocyanate compounds with low molecular weight polyols and polyamines so that the ends become isocyanates, etc. In addition, the compounds having a multifunctional isocyanate group that have been used and are known to be made into isocyanurate bodies, biuret bodies, adducts, or polymers of these compounds can be used without particular limitation. Examples of such compounds include dimers of 2,4-toluene diisocyanate, triphenylmethane triisocyanate, tris(p-isocyanatephenyl)thiophosphite, polyfunctional aromatic isocyanate compounds, polyfunctional aromatic aliphatic isocyanate compounds, polyfunctional aliphatic isocyanate compounds, fatty acid-modified polyfunctional aliphatic isocyanate compounds, polyfunctional blocked isocyanate compounds such as blocked polyfunctional aliphatic isocyanate compounds, polyisocyanate prepolymers, etc. Among these, aromatic diisocyanate compounds, aliphatic diisocyanate compounds, and alicyclic diisocyanate compounds, which are polyfunctional non-blocked isocyanate compounds, are preferably used from the perspective of being easy to obtain and easy to handle.

[0086] These compounds can be used alone or in combination of two or more.

[0087] In addition, a multifunctional blocked isocyanate compound refers to a compound that is inactive at room temperature by reacting at least two isocyanate groups in the molecule with an active hydrogen-containing compound. The isocyanate compound generally has a structure in which the isocyanate group is masked by a blocking agent such as alcohols, phenols, ε-caprolactam, oximes, and active methylene compounds. The multifunctional blocked isocyanate compound generally does not react at room temperature, so it has excellent storage stability, and generally regenerates the isocyanate group by heating at 140 to 200°C, which can show excellent reactivity.

[0088] It is believed that when the diisocyanate compound is used in combination with a polyfunctional (meth)acrylate compound, the active hydrogen-reactive group in the molecule forms a chemical bond with the hydroxyl group present in the polyfunctional (meth)acrylate compound, thereby playing a role in improving the adhesion between the cycloolefin monomer and the substrate (for example, a semiconductor element when used as a sealing material for a semiconductor element).

[0089] The diisocyanate compound can be used alone or in combination of two or more. The amount of the diisocyanate compound in the polymerizable composition used in the present invention is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and further preferably 2 to 10 parts by mass relative to 100 parts by mass of all cycloolefin monomers. If it is within this range, the strength and heat resistance of the obtained cycloolefin resin cured product can be good, and the adhesion of the cycloolefin resin cured product can be improved, so it is preferred.

[0090] From the viewpoint of further improving the adhesion to the substrate (for example, the semiconductor element when used as a sealing material of the semiconductor element), a multifunctional (meth)acrylate compound can be used. It is speculated that by using the compound together with the diisocyanate compound, the function of the diisocyanate compound as an adhesion improver or adhesion imparting agent can be synergistically improved. As the multifunctional (meth)acrylate compound, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and neopentyl glycol dimethacrylate can be cited as preferred examples.

[0091] The multifunctional (meth) acrylate compound can be used alone or in combination of two or more. As the amount of the multifunctional (meth) acrylate compound, it is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and further preferably 2 to 10 parts by mass relative to 100 parts by mass of all cycloolefin monomers used. If it is within this range, the function of the diisocyanate compound as an adhesion enhancer or adhesion imparting agent can be synergistically improved, and the adhesion of the cycloolefin resin cured product can be further improved, so it is preferred.

[0092] Examples of other optional components include active agents, activity regulators, elastomers, antioxidants, and the like.

[0093] The activator is a compound that functions as a co-catalyst of the metathesis polymerization catalyst and improves the polymerization activity of the catalyst. As the activator, alkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride can be used; alkoxyalkylaluminum chlorides in which a part of the alkyl groups of these alkylaluminum halides are substituted with alkoxy groups; organic tin compounds, etc. The amount of the activator used is not particularly limited, but is preferably 0.1 to 100 moles, more preferably 1 to 10 moles, relative to 1 mole of the total metathesis polymerization catalyst used in the polymerizable composition.

[0094] The activity regulator is used to prevent polymerization from initiating during injection when two or more reaction stock solutions are mixed to prepare a polymerizable composition and injected into a mold to initiate polymerization as described later.

[0095] When a compound of a transition metal of Group 5 or Group 6 of the periodic table is used as a metathesis polymerization catalyst, an activity regulator may include a compound having a function of reducing the metathesis polymerization catalyst, and alcohols, halogenated alcohols, esters, ethers, nitriles, etc. can be used. Among them, alcohols and halogenated alcohols are preferred, and halogenated alcohols are more preferred.

[0096] Specific examples of alcohols include n-propanol, n-butanol, n-hexanol, 2-butanol, isobutanol, isopropanol, tert-butanol, etc. Specific examples of halogenated alcohols include 1,3-dichloro-2-propanol, 2-chloroethanol, 1-chlorobutanol, etc.

[0097] In particular, when a ruthenium carbene complex is used as a metathesis polymerization catalyst, a Lewis base compound can be cited as an activity regulator. As a Lewis base compound, tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, triphenyl phosphite, n-butylphosphine and other Lewis base compounds containing phosphorus atoms can be cited; n-butylamine, pyridine, 4-vinylpyridine, acetonitrile, ethylenediamine, N-benzylidenemethylamine, pyrazine, piperidine, imidazole and other Lewis base compounds containing nitrogen atoms, etc. In addition, while vinyl norbornene, propenyl norbornene and isopropenyl norbornene are the above-mentioned cycloolefin monomers, they can also be used as activity regulators. The amount of these activity regulators used can be appropriately adjusted according to the compound used.

[0098] As elastomers, for example, natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), ethylene-propylene-diene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA) and their hydrogenated products can be cited. By dissolving the elastomer in the polymerizable composition and using it, its viscosity can be adjusted. In addition, by adding an elastomer, the impact resistance of the obtained composite molded body can be improved. The amount of the elastomer used is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass, relative to 100 parts by mass of all cycloolefin monomers in the polymerizable composition.

[0099] Examples of the antioxidant include various antioxidants for plastics and rubber, such as phenol-based, phosphorus-based, and amine-based antioxidants.

[0100] In addition, a filler may be blended as an optional component in the polymerizable composition used in the present invention. As the filler, various fillers can be used without particular limitation, but a granular inorganic filler is preferably used.

[0101] The granular inorganic filler preferably has an aspect ratio of 1 to 2, and more preferably has an aspect ratio of 1 to 1.5. In addition, the 50% volume cumulative diameter of the granular inorganic filler is preferably 0.1 to 50 μm, more preferably 1 to 30 μm, and particularly preferably 1 to 10 μm. Here, the aspect ratio refers to the ratio of the average major axis diameter of the filler to the 50% volume cumulative diameter. The average major axis diameter is the number average major axis diameter calculated as the arithmetic mean of the major axis diameters of 100 randomly selected fillers measured on an optical microscope photograph. In addition, the 50% volume cumulative diameter is a value obtained by measuring the particle size distribution using an X-ray transmission method.

[0102] Specific examples of granular inorganic fillers include calcium carbonate, calcium hydroxide, calcium silicate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, titanium oxide, zinc oxide, barium titanate, silicon dioxide, aluminum oxide, carbon black, graphite, antimony oxide, red phosphorus, various metal powders, clay, various ferrites, hydrotalcite, etc. Among these, magnesium hydroxide, aluminum hydroxide, silicon dioxide, and aluminum oxide are preferred, and aluminum hydroxide and silicon dioxide are particularly preferred.

[0103] The granular inorganic filler can be an inorganic filler whose surface has been subjected to hydrophobic treatment. By using the granular inorganic filler subjected to hydrophobic treatment, it is possible to prevent the condensation and sedimentation of the granular inorganic filler in the polymerizable composition, and in addition, it is possible to make the dispersion of the granular inorganic filler in the obtained cycloolefin resin cured product uniform. And, as a result, it is possible to improve the elasticity of the cycloolefin resin cured product. As the treating agent for hydrophobic treatment, fatty acids, greases, surfactants, waxes, etc. such as silane coupling agents, titanate coupling agents, aluminum coupling agents, stearic acid, etc., such as vinyl silane, can be cited.

[0104] As the above-mentioned treating agent, from the viewpoint that the viscosity is low even when the filler is added to the polymerizable composition, the thixotropy (viscosity at rest) is not easy to improve, and the adhesion with the substrate (for example, when used as a sealing material for a semiconductor element, it is a semiconductor element) can be improved, it is preferred to use a silane coupling agent having at least one hydrocarbon group with a norbornene structure. Although the silane coupling agent can also function as a monomer, it is regarded as a silane coupling agent in the present invention. As specific examples of the silane coupling agent, for example, dicycloheptenylethyltrimethoxysilane, dicycloheptenylethyltriethoxysilane, dicycloheptenylhexyltrimethoxysilane, dicycloheptenylhexyltriethoxysilane, etc. can be cited, preferably dicycloheptenylethyltriethoxysilane and dicycloheptenylhexyltrimethoxysilane.

[0105] The content of the silane coupling agent having at least one norbornene structure in the polymerizable composition used in the present invention is preferably 0.1 to 5% by mass, more preferably 0.3 to 2% by mass, and even more preferably 0.5 to 1% by mass.

[0106] The amount of the particulate inorganic filler in the polymerizable composition used in the present invention is preferably 10 to 1000 parts by mass, more preferably 100 to 500 parts by mass, based on 100 parts by mass of the cycloolefin monomer.

[0107] In addition, the polymerizable composition used in the present invention may contain a fibrous inorganic filler in addition to a granular inorganic filler. As the fibrous inorganic filler, a fibrous inorganic filler having an aspect ratio of 5 to 100 is preferred, and a fibrous inorganic filler having an aspect ratio of 10 to 50 is more preferred. In addition, the 50% volume cumulative diameter of the fibrous inorganic filler is preferably 0.1 to 50 μm, and more preferably 1 to 30 μm.

[0108] As the specific example of fibrous inorganic filling material, glass fiber, wollastonite, potassium titanate, xonotlite, basic magnesium sulfate, aluminum borate, tetrahedral pyramid type zinc oxide, gypsum fiber, phosphate fiber, alumina fiber, whisker-like calcium carbonate, whisker-like boehmite etc. can be enumerated. Among these, preferably wollastonite and whisker-like calcium carbonate. In addition, fibrous inorganic filling material can also be the fibrous inorganic filling material whose surface has been hydrophobized similarly to the above-mentioned granular inorganic filling material.

[0109] The polymerizable composition used in the present invention can be prepared by appropriately mixing the above-mentioned components according to a known method. The polymerizable composition used in the present invention can be prepared by preparing two or more pre-formulated liquids in advance, and mixing the two or more pre-formulated liquids using a mixing device or the like before making a cycloolefin resin cured product. The pre-formulated liquid is prepared by dividing the above-mentioned components into two or more liquids, and only one liquid does not undergo bulk polymerization. When all the liquids are mixed, a polymerizable composition containing each component in a specified ratio is formed. As a combination of such two or more reaction stock solutions, depending on the type of metathesis polymerization catalyst used, the following two types (a) and (b) can be cited.

[0110] (a): As the above-mentioned metathesis polymerization catalyst, a metathesis polymerization catalyst that does not have polymerization reaction activity alone and exhibits polymerization reaction activity by using an activator in combination can be used. In this case, a pre-formulated liquid (A liquid) containing a cycloolefin monomer and an activator and a pre-formulated liquid (B liquid) containing a cycloolefin monomer and a metathesis polymerization catalyst can be used, and they are mixed to obtain a polymerizable composition. Furthermore, a pre-formulated liquid (C liquid) containing a cycloolefin monomer and not containing any of a metathesis polymerization catalyst and an activator can also be used in combination.

[0111] (b): In addition, when a metathesis polymerization catalyst having polymerization reaction activity alone is used as a metathesis polymerization catalyst, a polymerizable composition can be obtained by mixing a pre-formulated solution (i) containing a cycloolefin monomer and a pre-formulated solution (ii) containing a metathesis polymerization catalyst. At this time, as a pre-formulated solution (ii), a pre-formulated solution in which the metathesis polymerization catalyst is dissolved or dispersed in a small amount of an inactive solvent can generally be used. As such a solvent, aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and trimethylbenzene can be cited; ketones such as methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and 4-hydroxy-4-methyl-2-pentanone; cyclic ethers such as tetrahydrofuran; diethyl ether, dichloromethane, dimethyl sulfoxide, ethyl acetate, etc., preferably aromatic hydrocarbons, more preferably toluene.

[0112] Optional components such as the radical generator, the diisocyanate compound, and the polyfunctional (meth)acrylate compound may be contained in any of the above-mentioned pre-formulated liquids, or may be added in the form of a mixed liquid other than the above-mentioned pre-formulated liquids.

[0113] Examples of a mixing device for mixing the pre-mixed liquid include a collision mixer generally used in the reaction injection molding method and a low-pressure mixer such as a dynamic mixer and a static mixer.

[0114] <Cycloolefin resin cured product>

[0115] The cycloolefin resin cured product of the present invention is obtained by bulk polymerizing the above-mentioned polymerizable composition, and has an elongation at break at 23° C. of 30% or more.

[0116] The method for producing the cycloolefin resin cured product of the present invention includes, for example, introducing the two or more pre-mixed liquids into a collision mixing device, mixing them instantly with a mixing head, and subjecting them to bulk polymerization in a mold or on a substrate.

[0117] For example, when the cycloolefin-based resin cured product of the present invention is used as a sealing material for sealing semiconductor elements such as power semiconductor elements, the above-mentioned two or more pre-prepared liquids are separately introduced into a collision mixing device, instantly mixed with a mixing head, and the mixed liquid is supplied from the mixing head to cover the surface of the semiconductor element, thereby obtaining a semiconductor device in which the semiconductor element is sealed with the cycloolefin-based resin cured product of the present invention.

[0118] In addition, the elongation at break of the cycloolefin resin cured product of the present invention at 23°C is 30% or more, more preferably 50% or more, and further preferably 100% or more. The upper limit of the elongation at break is not particularly limited, and is, for example, 1000% or less. The elongation at break of the cycloolefin resin cured product can be measured as follows: the cycloolefin resin cured product is made into a dumbbell shape based on A1 of JIS K7161, and for the dumbbell-shaped test piece, a tensile test is performed according to JIS K7161 under the conditions of a distance between clamps: 110 mm, a tensile speed: 50 mm / s, a distance between markings: 75 mm, and a temperature: 23°C, and the elongation at break is measured.

[0119] In addition, the elongation at break of the cycloolefin resin cured product of the present invention at 23°C may be within the above range, and the elongation at break at -25°C is preferably 7% or more, more preferably 30% or more, further preferably 50% or more, and further preferably 100% or more. The upper limit of the elongation at break at -25°C is not particularly limited, and is, for example, 1000% or less. The elongation at break at -25°C is measured in the same manner as the elongation at break at 23°C, except that the temperature condition is set to -25°C.

[0120] Furthermore, the elongation at break of the cycloolefin resin cured product of the present invention at 23°C after being stored at 155°C for 1000 hours is preferably 7% or more, more preferably 20% or more, further preferably 28% or more, and further preferably 50% or more, and the upper limit thereof is not particularly limited, and is, for example, 500% or less. The elongation at break at 23°C after being stored at 155°C for 1000 hours can be measured by storing the cycloolefin resin cured product at 155°C for 1000 hours and then measuring the elongation at break at 23°C by the above-mentioned method.

[0121] According to the present invention, by using the above-mentioned norbornene-based monomer (a1) and monocyclic cycloolefin (a2) in combination as cycloolefin monomers, and by making the elongation at break at 23°C within the above-mentioned range, the cycloolefin-based resin cured product can have sufficient crack resistance and excellent elasticity and high-temperature durability, thereby, when the cycloolefin-based resin cured product of the present invention is used for electrical sealing purposes, especially when used as a sealing material for a resin-sealed semiconductor device, the temperature cycle reliability and durability of the semiconductor device obtained using it can be excellent. In particular, the temperature cycle reliability and durability of the semiconductor device obtained by using the cycloolefin-based resin cured product of the present invention as a sealing material are excellent, so even in an environment where a power semiconductor element (for example, a power semiconductor element using a wide bandgap material such as SiC, GaN, Ga2O3, or diamond) is used, sufficient reliability and durability can be achieved, and therefore, as a semiconductor element, it is particularly suitable as a semiconductor device having a power semiconductor element. Furthermore, the cycloolefin resin cured product of the present invention is obtained using a cycloolefin monomer and therefore has the characteristics of a cycloolefin resin, namely, a high degree of freedom in molding due to the low viscosity of the monomer liquid and the characteristics of being applied and cured in a short time.

[0122] In addition, the cycloolefin resin cured product of the present invention has excellent crack resistance, elasticity and high temperature durability. Therefore, in addition to being used as a sealing material for resin-sealed semiconductor devices, it can also be preferably used for metal composite molding applications, more specifically, for covering components with metal parts on the surface and placed in an environment with large temperature changes, such as the covering application of pipeline field joints (the covering application of the welding fastening part of pipeline field joints), etc. In particular, in the covering application of pipeline field joints, it is hoped that the characteristics of cycloolefin resins can be fully utilized when curing in a short time, that is, the characteristics that can be applied and cured in a short time, so it is preferred. Furthermore, in addition to these uses, the cycloolefin resin cured product of the present invention can also effectively utilize the excellent characteristics of crack resistance, elasticity and high temperature durability, and is suitable for automotive applications such as bumpers and deflectors, construction and industrial machinery applications such as wheel loaders and shovels, leisure applications such as golf carts and game consoles, medical applications such as medical equipment, industrial applications such as large panels and chairs, residential equipment applications such as shower trays and washbasins, etc.

[0123] Example

[0124] Hereinafter, the present invention will be described based on examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, "parts" and "%" are based on mass. In addition, the tests and evaluations are as follows.

[0125] <Elongation at break (normal temperature)>

[0126] A dumbbell-shaped test piece was prepared by punching out a cycloolefin resin cured product into a dumbbell shape of size A1 according to JIS K7161. Then, the obtained dumbbell-shaped test piece was subjected to a tensile test according to JIS K7161 under the conditions of a distance between clamps: 110 mm, a tensile speed: 50 mm / s, a distance between markings: 75 mm, and a temperature: 23° C., and the elongation at break was measured to determine the elongation at break at room temperature.

[0127] <Elongation at break (-25℃)>

[0128] A dumbbell-shaped test piece was prepared by punching out a cycloolefin resin cured product into a dumbbell shape of No. A1 according to JIS K7161. Then, the obtained dumbbell-shaped test piece was subjected to a tensile test according to JIS K7161 under the conditions of a distance between clamps: 110 mm, a tensile speed: 50 mm / s, a distance between markings: 75 mm, and a temperature: -25°C, and the elongation at break was measured to determine the elongation at break at -25°C.

[0129] <High temperature durability>

[0130] A plurality of dumbbell-shaped test pieces were prepared by punching a cycloolefin resin cured product into a dumbbell shape of A1 according to JIS K7161. The dumbbell-shaped test pieces were stored at 125° C. for 1000 hours, 155° C. for 1000 hours, and 175° C. for 1000 hours, and the elongation at break was measured under the same conditions as in the above-mentioned “elongation at break (normal temperature)” for each test piece after storage.

[0131] <Example 1>

[0132] 70 parts of RIM monomer (manufactured by Japan Zeon Co., Ltd.) and 30 parts of 1,5-cyclooctadiene were mixed to obtain a pre-formulated solution (i). The RIM monomer contained 90 parts of dicyclopentadiene and 10 parts of tricyclopentadiene as norbornene-based monomers.

[0133] 0.3 parts of a ruthenium catalyst (Zhan1N) represented by formula (7) as a metathesis polymerization catalyst, 30 parts of 2,6-di-tert-butyl-p-cresol (BHT, an anti-aging agent) and 30 parts of triphenylphosphine were dissolved in 39.7 parts of cyclopentanone to obtain a pre-formulated solution (ii).

[0134] [Chemical formula 6]

[0135]

[0136] (In the formula, Mes represents mesityl.)

[0137] The molding die used was a flat molded product reaction injection molding die consisting of two stainless steel plates with a space of 245 mm long x 210 mm wide x 4 mm thick. The reaction injection molding die had a structure with a reaction liquid injection hole at the bottom of one of the stainless steel plates.

[0138] Then, the pre-prepared solution (i) and the pre-prepared solution (ii) prepared above were mixed in a ratio of (i): (ii) = 100: 3.5 (mass ratio), and after vacuum degassing, they were injected into the reaction injection molding mold from the reaction solution injection hole, and heated in an oven heated to 40°C for 30 minutes, and then heated at 175°C for 60 minutes to obtain a polymerized cycloolefin resin cured product. Then, the obtained cycloolefin resin cured product was measured and evaluated for elongation at break (normal temperature and -25°C) and high temperature durability. The results are shown in Table 1.

[0139] <Example 2>

[0140] A cycloolefin resin cured product was obtained in the same manner as in Example 1 except that the amount of the RIM monomer and the amount of 1,5-cyclooctadiene were changed to 60 parts and 40 parts, respectively, when preparing the pre-formulated solution (i). The results are shown in Table 1.

[0141] <Example 3>

[0142] A cycloolefin resin cured product was obtained in the same manner as in Example 1 except that the amount of the RIM monomer and the amount of 1,5-cyclooctadiene were changed to 50 parts and 50 parts, respectively, when preparing the pre-formulated solution (i). The results are shown in Table 1.

[0143] <Example 4>

[0144] A cycloolefin resin cured product was obtained in the same manner as in Example 1 except that the amount of the RIM monomer and 1,5-cyclooctadiene was changed to 30 parts and 70 parts, respectively, when preparing the pre-formulated solution (i). The results are shown in Table 1.

[0145] <Example 5>

[0146] A cycloolefin resin cured product was obtained in the same manner as in Example 1 except that the amount of the RIM monomer and the amount of 1,5-cyclooctadiene were changed to 10 parts and 90 parts respectively when preparing the pre-formulated solution (i), and was evaluated in the same manner. The results are shown in Table 1.

[0147] <Example 6>

[0148] A cycloolefin resin cured product was obtained in the same manner as in Example 1 except that 1,5-cyclooctadiene was not added when preparing the pre-formulated liquid (i), and the amount of the RIM monomer and cyclooctene was changed to 70 parts and 30 parts, respectively, and the results were evaluated in the same manner. Table 1 shows.

[0149] <Example 7>

[0150] A cycloolefin resin cured product was obtained in the same manner as in Example 1 except that 1,5-cyclooctadiene was not added when preparing the pre-formulated liquid (i), and the amount of the RIM monomer and the amount of cyclooctene were changed to 50 parts and 50 parts, respectively. The results are shown in Table 1.

[0151] <Example 8>

[0152] A cycloolefin resin cured product was obtained in the same manner as in Example 1 except that 1,5-cyclooctadiene was not added when preparing the pre-formulated liquid (i), and the amount of the RIM monomer and the amount of cyclohexene were changed to 50 parts and 50 parts, respectively, and the results were evaluated in the same manner. Table 1 shows.

[0153] <Example 9>

[0154] When preparing the pre-mixed solution (i), 1,5-cyclooctadiene was not added, and the amount of the RIM monomer was changed to 70 parts and 1,4-cyclooctadiene was added to 70 parts. The same procedure as in Example 1 was carried out except that the amount of the diene added was changed to 30 parts to obtain a cycloolefin-based resin cured product, which was evaluated in the same manner. The results are shown in Table 1.

[0155] <Example 10>

[0156] When preparing the pre-formulated solution (i), the blending amount of the RIM monomer was changed to 14.5 parts, the blending amount of 1,5-cyclooctadiene was changed to 14.5 parts, and 0.6 parts of a dicyclopentadiene monoepoxide (DCPME) solution and 0.4 parts of dicycloheptenylethyltrimethoxysilane were mixed. In addition, the DCPME solution was used in the form of a cyclopentanone solution containing 5,6-DCPME and DCPDE (dicyclopentadiene diepoxide) as by-products (DCPME content: about 40%, by-product content: about 27%). A cycloolefin resin cured product was obtained in the same manner as in Example 1 except that 70 parts of aluminum hydroxide (aspect ratio: 1, 50% volume cumulative diameter: 3 μm) was further added thereto to obtain a pre-prepared liquid (i). The prepared pre-prepared liquid (i) and the pre-prepared liquid (ii) were mixed at a ratio of (i): (ii) = 100: 1.1 (mass ratio). The results were evaluated in the same manner as in Example 1. Table 1 shows the results.

[0157] <Comparative Example 1>

[0158] A cycloolefin resin cured product was obtained in the same manner as in Example 1 except that the amount of the RIM monomer was changed to 100 parts and 1,5-cyclooctadiene was not added when preparing the pre-formulated liquid (i), and was evaluated in the same manner.

[0159] <Comparative Example 2>

[0160] A cycloolefin resin cured product was obtained in the same manner as in Example 1 except that the amount of the RIM monomer and 1,5-cyclooctadiene was changed to 90 parts and 10 parts, respectively, when preparing the pre-formulated solution (i). The results are shown in Table 1.

[0161] <Comparative Example 3>

[0162] A cycloolefin resin cured product was obtained in the same manner as in Example 1 except that the amount of the RIM monomer and the amount of 1,5-cyclooctadiene were changed to 80 parts and 20 parts respectively when preparing the pre-formulated solution (i), and was evaluated in the same manner. The results are shown in Table 1.

[0163] <Comparative Example 4>

[0164] A cycloolefin resin cured product was obtained in the same manner as in Example 10 except that the amount of the RIM monomer was changed to 29 parts and 1,5-cyclooctadiene was not added when preparing the pre-formulated liquid (i), and was evaluated in the same manner.

[0165] [Table 1]

[0166]

[0167] As shown in Table 1, the cycloolefin resin cured product obtained by using a polymerizable composition containing a norbornene monomer (a1) and a monocyclic cycloolefin (a2) as a cycloolefin monomer and having an elongation at break of 30% or more at 23°C (normal temperature) has not only a large elongation at break at normal temperature but also a large elongation at break at -25°C, but also a sufficient elongation at break after high-temperature storage, and is excellent in crack resistance, stretchability, and high-temperature durability. Therefore, it can be said that when used as a sealing material for a semiconductor element, excellent temperature cycle reliability and excellent high-temperature durability can be achieved (Examples 1 to 10).

[0168] On the other hand, as a cycloolefin monomer, whether in the case of using a polymerizable composition not containing a monocyclic cycloolefin (a2) or in the case of using a polymerizable composition containing a monocyclic cycloolefin (a2), when the elongation at break at 23°C (normal temperature) is less than 30%, the elongation at break at -25°C and the elongation at break after high-temperature storage are poor (Comparative Examples 1 to 4).

Claims

1. A cycloolefin resin cured product, which is obtained by bulk polymerization of a polymerizable composition comprising a cycloolefin monomer and a metathesis polymerization catalyst, The cycloolefin monomer contains a norbornene-based monomer (a1) and a monocyclic cycloolefin (a2), The cycloolefin resin cured product has an elongation at break of 30% or more at 23°C. A tricyclic ring and a pentacyclic ring are used as the norbornene monomer (a1), and the ratio of the tricyclic ring to the pentacyclic ring is 65:35 to 95:5 in terms of the mass ratio of the tricyclic ring:the pentacyclic ring.

2. The cycloolefin resin cured product according to claim 1, wherein The content of the monocyclic cycloolefin (a2) in the cycloolefin monomer is 30 to 99% by mass.

3. The cycloolefin resin cured product according to claim 1 or 2, wherein The monocyclic cycloolefin (a2) is selected from 1,5-cyclooctadiene, cyclooctene, cyclohexene, 1,4-cyclohexadiene and 1,4-cyclohexadiene. At least one of the dienes.

4. The cycloolefin resin cured product according to claim 3, wherein The monocyclic cycloolefin (a2) is 1,5-cyclooctadiene.

5. The cycloolefin resin cured product according to claim 1 or 2, wherein The polymerizable composition contains a filler.

6. A polymerizable composition comprising a cycloolefin monomer and a metathesis polymerization catalyst, The cycloolefin monomer contains a norbornene-based monomer (a1) and a monocyclic cycloolefin (a2), The polymerizable composition is used to form the cycloolefin resin cured product according to claim 1. 7 . The polymerizable composition according to claim 6 , which is formed from two or more pre-formulated liquids that do not undergo polymerization reaction independently, and the polymerizable composition can be formed by mixing the pre-formulated liquids.

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