Oxygen barrier cycloolefin resin cured product

Abstract

Provided is a cycloolefin resin cured product having oxygen barrier properties, the cycloolefin resin cured product being obtained by bulk polymerization of a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst. The cycloolefin monomer contains a norbornene-based monomer (a). The antioxidant content of the polymerizable composition is 0.3 mass% or less. The oxygen permeability at 23°C is less than 50 mL / m2･day･atm (100 μm).

Description

[Technical Field]

[0001] The present invention relates to a cured product of a cycloolefin resin with oxygen barrier properties, and more particularly to a cured product of a cycloolefin resin with oxygen barrier properties that can maintain high oxygen barrier properties for a long period of time. [Background technology]

[0002] Cycloolefin resins are known to have excellent mechanical strength, heat resistance, low moisture absorption, dielectric properties, and the like, and are used in a variety of applications.

[0003] For example, Patent Document 1 considers using such cycloolefin resins for sealing semiconductor elements. The technology of Patent Document 1 utilizes the properties of cycloolefin resins, specifically, the low viscosity of the monomer liquid, which allows for a high degree of freedom in molding, and allows for application and curing in a short period of time, to use the cycloolefin resin for sealing semiconductor elements.

[0004] On the other hand, it is known that the oxygen barrier properties of semiconductor device encapsulation may be insufficient, and oxygen in the air can cause deterioration and corrosion of internal elements, reducing long-term reliability and durability. Patent Document 2, for example, describes a technique for improving the oxygen barrier properties of polyolefin resins, in which an oxidation catalyst is used to promote oxidation of the polyolefin resin and trap oxygen, thereby reducing oxygen permeability. However, while the technique in Patent Document 2 can reduce oxygen permeability to a certain extent, it does not ensure sufficient oxygen barrier properties required of encapsulants. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-48295 [Patent Document 2] Japanese Patent Application Publication No. 8-143767 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention has been made in view of the above circumstances, and aims to provide an oxygen-barrier cycloolefin-based resin cured product that can maintain high oxygen-barrier properties for a long period of time, an oxygen-barrier film obtained by molding such a cured product, and a polymerizable composition that is suitably used for forming such a cured product. [Means for solving the problem]

[0007] The present inventors have conducted studies to achieve the above object, and have found that the above object can be achieved by using a norbornene-based monomer (a) as a cycloolefin monomer contained in a polymerizable composition for forming a cycloolefin-based resin cured product, and by controlling the content of an antioxidant in the polymerizable composition to a specific amount or less, thereby completing the present invention.

[0008] That is, according to the present invention, there is provided a cured cycloolefin resin having oxygen barrier properties obtained by bulk polymerization of a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst, the cycloolefin monomer contains a norbornene-based monomer (a), the content of the antioxidant in the polymerizable composition is 0.3% by mass or less, Oxygen permeability at 23°C is 50mL / m 2 The present invention provides a cured product of a cycloolefin resin having an oxygen barrier property of less than 100 μm / day atm (100 μm).

[0009] The oxygen barrier cured cycloolefin resin of the present invention has an oxygen permeability of 15 mL / m at 23°C. 2 ·day·atm (100 μm) or less is preferable. In the oxygen-barrier cycloolefin resin cured product of the present invention, the cycloolefin monomer preferably further contains a monocyclic cycloolefin. In the oxygen-barrier cycloolefin resin cured product of the present invention, the polymerizable composition preferably contains a filler. In the oxygen-barrier cycloolefin resin cured product of the present invention, the filler is preferably a plate-like filler. The cured product of the oxygen-barrier cycloolefin resin of the present invention preferably has an oxide film on at least a part of its surface.

[0010] The present invention also provides an oxygen barrier film obtained by molding any one of the above-mentioned oxygen barrier cycloolefin resin cured products. The oxygen barrier film of the present invention preferably has an oxide film on at least a part of at least one surface. Alternatively, the present invention provides a laminate comprising a layer made of any one of the above cured cycloolefin resins with oxygen barrier properties, and a layer made of another resin or a metal layer.

[0011] Further, according to the present invention, there is provided a polymerizable composition comprising a cycloolefin monomer and a metathesis polymerization catalyst, the cycloolefin monomer is a norbornene-based monomer (a), and the content of the antioxidant in the polymerizable composition is 0.3 mass% or less; There is provided a polymerizable composition for forming a cured product of the above oxygen-barrier cycloolefin resin. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide an oxygen-barrier cycloolefin-based resin cured product that can maintain high oxygen-barrier properties for a long period of time, an oxygen-barrier film obtained by molding such a cured product, and a polymerizable composition that is suitably used for forming such a cured product. DETAILED DESCRIPTION OF THE INVENTION

[0013] The cured cycloolefin resin having oxygen barrier properties of the present invention is obtained by bulk polymerization of a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst, the cycloolefin monomer contains a norbornene-based monomer (a), the content of the antioxidant in the polymerizable composition is 0.3% by mass or less, Oxygen permeability at 23°C is 50mL / m 2 The cured product is a cycloolefin resin with oxygen barrier properties of less than 100μm / day atm.

[0014] <Polymerizable composition> First, the polymerizable composition used to produce the cured product of the oxygen-barrier cycloolefin resin of the present invention will be described. The polymerizable composition used to produce the cured product of the oxygen-barrier cycloolefin resin of the present invention contains a cycloolefin monomer and a metathesis polymerization catalyst.

[0015] A cycloolefin monomer is a compound that has a ring structure formed by carbon atoms and has a carbon-carbon double bond in the ring. In the present invention, at least a norbornene-based monomer (a) is used as the cycloolefin monomer.

[0016] The norbornene-based monomer (a) may be any compound having a norbornene ring structure, and is not particularly limited. Examples of the norbornene-based monomer (a) include bicyclic compounds such as norbornene, norbornadiene, vinylnorbornene, and ethylidenenorbornene; tricyclic compounds such as dicyclopentadiene and dihydrodicyclopentadiene; tetracyclic compounds such as tetracyclododecene and ethylidenetetracyclododecene; pentacyclic compounds such as tricyclopentadiene; and heptacyclic compounds such as tetracyclopentadiene; and derivatives thereof having an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkylidene group having 1 to 10 carbon atoms, an epoxy group, or a (meth)acrylic group (e.g., an ethylidene group). The norbornene-based monomer (a) may be used alone or in combination of two or more. From the viewpoint of further enhancing the effects of the present invention, the tricyclic compounds are preferred as the norbornene-based monomer (a), and dicyclopentadiene is particularly preferred. The norbornene-based monomer (a) used preferably contains the tricyclic ring, particularly dicyclopentadiene, in an amount of 50% by mass or more, more preferably 80 to 95% by mass. When the tricyclic ring is used, it can be suitably combined with a derivative other than the tricyclic ring having an ethylidene group, such as ethylidene norbornene, or a pentacyclic ring, such as tricyclopentadiene, and the content thereof is preferably 5 to 20% by mass.

[0017] The derivative preferably has an epoxy group in order to improve the adhesion of the resulting cured product to the substrate (for example, to the semiconductor element when used as an encapsulating material for the semiconductor element). For example, 4,5-epoxytricyclo[5.2.1.0 2,6 ]deca-8-ene [also called dicyclopentadiene monoepoxide (2,3-DCPME). In this specification, it may be referred to simply 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-trifluoromethyltricyclo[5.2.1.0 2,6]dec-8-ene, etc., and among these, DCPME is preferred. The content of the derivative having an epoxy group in the polymerizable composition used in the present invention is preferably 0.1 to 20 mass %, more preferably 0.5 to 10 mass %, and even more preferably 1 to 5 mass %.

[0018] The content of the norbornene-based monomer (a) in the cycloolefin monomer used in the present invention is not particularly limited, but is preferably 1 to 100 mass%, more preferably 30 to 100 mass%, and even more preferably 50 to 100 mass%, relative to 100 mass% of the total cycloolefin monomer.

[0019] In the present invention, a monocyclic cycloolefin may be further used as a cycloolefin monomer constituting the polymerizable composition. By using a monocyclic cycloolefin, the cured cycloolefin resin can be made to have even better crack resistance, stretchability, and high-temperature durability. The monocyclic cycloolefin is not particularly limited, but includes cyclobutene, cyclopentene, cyclohexene, cyclooctene, cyclododecene, cyclopentadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, and derivatives thereof having an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkylidene group having 1 to 10 carbon atoms, an epoxy group, or a (meth)acrylic group (for example, an ethylidene group). From the viewpoint of further enhancing the effects of use, the monocyclic cycloolefin is preferably a monocyclic cycloolefin having one or more unsaturated bonds exhibiting metathesis reactivity in the molecule, and examples of such monocyclic cycloolefins include 1,5-cyclooctadiene and its derivatives. The monocyclic cycloolefins can be used alone or in combination of two or more.

[0020] The content of monocyclic cycloolefin in the cycloolefin monomer used in the present invention is preferably 5 to 99 mass%, more preferably 10 to 70 mass%, and even more preferably 20 to 50 mass%, based on 100 mass% of the total cycloolefin monomer. By setting the content of monocyclic cycloolefin within the above range, the cycloolefin-based resin cured product can be made to have better crack resistance and stretchability, and therefore, when used as an encapsulating material for semiconductor devices, etc., the temperature cycle reliability and durability can be further improved.

[0021] The polymerizable composition used in the present invention may contain other cycloolefin monomers in addition to the norbornene-based monomer (a) and the monocyclic cycloolefin used as needed.

[0022] The content of other cycloolefin monomers in the cycloolefin monomers used in the present invention is preferably 50% by mass or less, more preferably 30% by mass or less, based on 100% by mass of the total cycloolefin monomers.

[0023] The metathesis polymerization catalyst used in the present invention is not particularly limited as long as it can ring-opening polymerize a cycloolefin monomer, and known metathesis polymerization catalysts can be used.

[0024] The metathesis polymerization catalyst used in the present invention is a complex formed by bonding a plurality of ions, atoms, polyatomic ions, and / or compounds to a transition metal atom as a central atom. The transition metal atom is an atom of Groups 5, 6, and 8 (long-form periodic table, the same applies hereinafter). The atom of each group is not particularly limited, but an example of a Group 5 atom is tantalum, an example of a Group 6 atom is molybdenum or tungsten, and an example of a Group 8 atom is ruthenium or osmium. Among these transition metal atoms, ruthenium and osmium of Group 8 are preferred. That is, the metathesis polymerization catalyst used in the present invention is preferably a complex having ruthenium or osmium as a central atom, and more preferably a complex having ruthenium as a central atom. A ruthenium-carbene complex in which a carbene compound is coordinated to ruthenium is preferred as a complex having ruthenium as a central atom. Here, "carbene compound" is a general term for compounds containing a methylene free radical, 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, resulting in polymers with little odor from unreacted monomers, enabling high-quality polymers to be obtained with good productivity. Furthermore, they are relatively stable against oxygen and moisture in the air and are not easily deactivated, making them suitable for use in the atmosphere. Metathesis polymerization catalysts may be used alone or in combination.

[0025] Examples of the ruthenium carbene complex include those represented by the following general formula (1) or (2). [ka]

[0026] In the above general formulas (1) and (2), R 1 and R 2are each 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; and these groups may have a substituent, and may be bonded to each other to form a ring. 1 and R 2 Examples of groups bonded to each other to form a ring include an indenylidene group which may have a substituent, such as a phenylindenylidene group.

[0027] 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, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an alkyl group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an alkyl group having 2 to 20 ...2 to 20 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an alkyl group having 2 to 20 carbon atoms, an alkyl group having 2 to Examples of the organic group include an alkylthio group, a carbonyloxy group, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, an alkylsulfinyl group having 1 to 20 carbon atoms, an alkylsulfonic acid group having 1 to 20 carbon atoms, an arylsulfonic acid group having 6 to 20 carbon atoms, a phosphonic acid group, an arylphosphonic acid group having 6 to 20 carbon atoms, an alkylammonium group having 1 to 20 carbon atoms, and an arylammonium group having 6 to 20 carbon atoms. These organic groups having 1 to 20 carbon atoms, which may contain a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, or silicon atom, may have a substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

[0028] X 1 and X 2 each independently represents an anionic ligand. The anionic ligand is a ligand that has 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 alkoxyl group, an aryloxy group, and a carboxyl group.

[0029] L 1 and L 2 represents a heteroatom-containing carbene compound or a neutral electron donor compound other than a heteroatom-containing carbene compound. Heteroatom-containing carbene compounds and neutral electron donor compounds other than a heteroatom-containing carbene compound are compounds that have a neutral charge when separated from a central metal. From the viewpoint of improving catalytic activity, heteroatom-containing carbene compounds are preferred. The heteroatom refers to an atom of Groups 15 and 16 of the periodic table, and specific examples include a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, an arsenic atom, and a selenium atom. Among these, from the viewpoint of obtaining a stable carbene compound, a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom are preferred, and a nitrogen atom is more preferred.

[0030] The heteroatom-containing carbene compound is preferably a compound represented by the following general formula (3) or (4), and from the viewpoint of improving catalytic activity, a compound represented by the following general formula (3) is more preferred. [ka]

[0031] 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, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, or silicon atom. Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, or silicon atom are the same as those in the general formulae (1) and (2) above. Also, R 3 , R 4 , R 5 and R 6 may be bonded to each other in any combination to form a ring.

[0032] In addition, since the effect of the present invention becomes more remarkable, R 5 and R 6 is preferably a hydrogen atom. 3 and R 4 is preferably an aryl group which may have a substituent, more preferably a phenyl group having an alkyl group of 1 to 10 carbon atoms as a substituent, and even more preferably a mesityl group.

[0033] Examples of the neutral electron donor compound include oxygen atoms, water, carbonyls, ethers, nitriles, esters, phosphines, phosphinites, phosphites, sulfoxides, thioethers, amides, imines, aromatic compounds, cyclic diolefins, olefins, isocyanides, and thiocyanates.

[0034] In the above general formulas (1) and (2), R 1 , R 2 , X 1 , X 2 , L 1 and L 2 may be linked together alone and / or in any combination to form multidentate chelating ligands.

[0035] Furthermore, as the ruthenium carbene complex used in the present invention, among the compounds represented by the above general formula (1) or (2), the compound represented by the above general formula (1) is preferred because the effects of the present invention are more pronounced, and among these, the compound represented by the following general formula (5) or general formula (6) is more preferred.

[0036] General formula (5) is shown below. [ka]

[0037] In the general formula (5), Z is an oxygen atom, a sulfur atom, a selenium atom, or NR 12 , PR 12 or AsR 12 and R 12represents 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; however, an oxygen atom is preferred as Z, as this makes the effects of the present invention more pronounced.

[0038] In addition, R 1 , R 2 , X 1 and L 1 are the same as those in the above general formulas (1) and (2), and may be used alone or / and may be bonded to each other in any combination to form a multidentate chelating ligand, but X 1 and L 1 does not form a multidentate chelating ligand, and R 1 and R 2 are preferably bonded to each other to form a ring, are more preferably an indenylidene group which may have a substituent, and are further preferably a phenylindenylidene group. Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom or silicon atom are the same as those in the general formulae (1) and (2) above.

[0039] In the above general formula (5), R 7 and R 8 are each independently 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, and these groups may have a substituent or may be bonded to each other to form a ring. Examples of the substituent 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, and when a ring is formed, the ring may be any of an aromatic ring, an alicyclic ring, and a heterocyclic ring, but it is preferable to form an aromatic ring, more preferably an aromatic ring having 6 to 20 carbon atoms, and even more preferably an aromatic ring having 6 to 10 carbon atoms.

[0040] In the above general formula (5), R 9 , R 10 and R 11are each 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, and these groups may have a substituent or may be bonded to each other to form a ring. 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 general formulas (1) and (2) above.

[0041] R 9 , R 10 and R 11 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.

[0042] Specific examples of the compound represented by the general formula (5) and the method for producing the same include those described in International Publication No. 03 / 062253 (JP 2005-515260).

[0043] General formula (6) is shown below. [ka]

[0044] In the above general formula (6), m is 0 or 1. m is preferably 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, and preferably a methylene group.

[0045] In the above general formula (6), [ka] is a single bond or a double bond, preferably a single bond.

[0046] R 1 , X 1 , X 2 and L 1are the same as those in the above general formulas (1) and (2), and may be bonded to each other alone or in any combination to form a multidentate chelating ligand, but X 1 , X 2 and L 1 does not form a multidentate chelating ligand, and R 1 is preferably a hydrogen atom.

[0047] 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 and may be bonded to each other to form a ring. 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 general formulas (1) and (2).

[0048] R 13 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and R 14 ~R 17 is preferably a hydrogen atom, and R 18 ~R 21 is preferably a hydrogen atom or a halogen atom.

[0049] Specific examples of the compound represented by the general formula (6) and the method for producing the same include those described in International Publication No. 11 / 079799 (JP 2013-516392 A).

[0050] The content of the metathesis polymerization catalyst is preferably 0.005 mmol or more, more preferably 0.01 to 50 mmol, and even more preferably 0.015 to 20 mmol, per mole of all cycloolefin monomers used in the reaction.

[0051] Furthermore, the polymerizable composition used in the present invention has an antioxidant (generally also called an antidegradant or antiaging agent) content of 0.3 mass % or less. The present inventors have conducted extensive research to achieve high oxygen barrier properties in order to suitably use a cycloolefin-based resin cured product as an encapsulating material for semiconductors and the like. As a result, they have focused on antioxidants that are typically used to form cycloolefin-based resin cured products, and instead of increasing the amount of antioxidant used, they have reduced the amount to a specific amount or less so that the cured product is more susceptible to oxidation. As a result, an oxide film is formed by oxidation, and unexpectedly, oxygen permeability can be significantly reduced, and it has been found that this makes it possible to achieve high oxygen barrier properties over a long period of time.

[0052] The content of the antioxidant in the polymerizable composition used in the present invention is 0.3% by mass or less, preferably 0.2% by mass or less, more preferably 0.1% by mass or less, when the entire polymerizable composition is taken as 100% by mass. It is particularly preferred that the polymerizable composition is substantially free of antioxidant (for example, 0.03% by mass or less).

[0053] In the present invention, the antioxidant may be any known compound used as an antioxidant for plastics and rubber, such as various antioxidants such as phenolic, phosphorus-based, sulfur-containing compounds, and amine-based antioxidants.

[0054] 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, if necessary.

[0055] The radical generator generates radicals when heated, which induces a crosslinking reaction in the cycloolefin polymer formed by bulk polymerization. The sites where the radical generator induces the crosslinking reaction are mainly the carbon-carbon double bonds of the cycloolefin monomer, but crosslinking can also occur at saturated bonds.

[0056] The radical generator includes organic peroxides, diazo compounds and non-polar radical generators. Examples of organic peroxides include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, and cumene hydroperoxide; dialkyl peroxides such as di-t-butyl peroxide, dicumyl peroxide, and t-butylcumyl peroxide; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; peroxyketals such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, and 1,3-di(t-butylperoxyisopropyl)benzene; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; peroxycarbonates such as t-butylperoxyisopropylcarbonate and di(isopropylperoxy)dicarbonate; and alkylsilyl peroxamides such as t-butyltrimethylsilyl peroxide. Among these, dialkyl peroxides are preferred because they cause less interference with the metathesis polymerization reaction in bulk polymerization.

[0057] Examples of diazo compounds include 4,4'-bisazidobenzal(4-methyl)cyclohexanone, 4,4'-diazidochalcone, 2,6-bis(4'-azidobenzal)cyclohexanone, 2,6-bis(4'-azidobenzal)-4-methylcyclohexanone, 4,4'-diazidodiphenylsulfone, 4,4'-diazidodiphenylmethane, and 2,2'-diazidostilbene.

[0058] Examples of non-polar radical generators 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-propene, 1,1,1-triphenyl-4-pentene, and 1,1,1-triphenyl-2-phenylethane.

[0059] 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.

[0060] Examples of diisocyanate compounds 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, tolylene diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, and 4,4'-diisocyanate dibenzidine. Examples of suitable diisocyanate compounds include aromatic diisocyanate compounds such as benzoyl; 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; and polyurethane prepolymers obtained by reacting these diisocyanate compounds with low-molecular-weight polyols or polyamines to form isocyanate groups at the terminals. Furthermore, conventionally known compounds having polyfunctional isocyanate groups, such as isocyanurates, biurets, adducts, or polymers, can be used without particular limitation. Examples of such compounds include a dimer of 2,4-toluylene diisocyanate, triphenylmethane triisocyanate, tris-(p-isocyanatophenyl)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, and polyisocyanate prepolymers.Among these, polyfunctional unblocked isocyanate compounds, such as aromatic diisocyanate compounds, aliphatic diisocyanate compounds, and alicyclic diisocyanate compounds, are preferably used because of their easy availability and ease of handling. These compounds can be used either alone or in combination of two or more.

[0061] A polyfunctional blocked isocyanate compound is one in which at least two isocyanate groups in the molecule are reacted with an active hydrogen-containing compound, rendering the compound inactive at room temperature. The isocyanate compound generally has a structure in which the isocyanate groups are masked with a blocking agent such as alcohols, phenols, ε-caprolactam, oximes, and active methylene compounds. Polyfunctional blocked isocyanate compounds generally do not react at room temperature, and therefore have excellent storage stability. However, heating at temperatures typically between 140 and 200°C regenerates the isocyanate groups, enabling them to exhibit excellent reactivity.

[0062] When a 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 a hydroxyl group present in the polyfunctional (meth)acrylate compound, and as a result, it is thought to play a role in improving the adhesion between the cycloolefin monomer and the substrate (for example, the semiconductor element when used as an encapsulating material for a semiconductor element).

[0063] The diisocyanate compounds may 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 even more preferably 2 to 10 parts by mass, relative to 100 parts by mass of all cycloolefin monomers. This range is preferable because it can improve the strength and heat resistance of the resulting cycloolefin-based resin cured product while also improving the adhesion of the cycloolefin-based resin cured product.

[0064] A polyfunctional (meth)acrylate compound may be used to further enhance adhesion to a substrate (for example, a semiconductor element when used as an encapsulating material for a semiconductor element). It is presumed that the use of such a compound together with a diisocyanate compound synergistically enhances the function of the diisocyanate compound as an adhesion improver or adhesion imparter. Preferred examples of the polyfunctional (meth)acrylate compound include ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and neopentyl glycol dimethacrylate.

[0065] The polyfunctional (meth)acrylate compounds may be used alone or in combination of two or more. The amount of the polyfunctional (meth)acrylate compound is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 10 parts by mass, relative to 100 parts by mass of all cycloolefin monomers used. This range is preferable because it synergistically enhances the function of the diisocyanate compound as an adhesion improver or adhesion imparter, thereby further improving the adhesion of the cycloolefin resin cured product.

[0066] Other optional components include an activator, an activity regulator, an elastomer, and the like.

[0067] The activator is a compound that acts as a cocatalyst for the metathesis polymerization catalyst described above and improves the polymerization activity of the catalyst. Examples of activators that can be used include alkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride; alkoxyalkylaluminum halides in which some of the alkyl groups in these alkylaluminum halides are substituted with alkoxy groups; and organotin compounds. The amount of activator used is not particularly limited, but is preferably 0.1 to 100 mol, more preferably 1 to 10 mol, per mol of the total metathesis polymerization catalysts used in the polymerizable composition.

[0068] The activity regulator is used to prevent polymerization from starting during the injection process when a polymerizable composition is prepared by mixing two or more reaction stock solutions as described below and then injected into a mold to initiate polymerization.

[0069] When a compound of a transition metal of Group 5 or 6 of the periodic table is used as the metathesis polymerization catalyst, examples of the activity modifier include compounds that have the effect of reducing the metathesis polymerization catalyst, such as alcohols, haloalcohols, esters, ethers, nitriles, etc. Among these, alcohols and haloalcohols are preferred, and haloalcohols are more preferred.

[0070] Specific examples of alcohols include n-propanol, n-butanol, n-hexanol, 2-butanol, isobutyl alcohol, isopropyl alcohol, t-butyl alcohol, etc. Specific examples of haloalcohols include 1,3-dichloro-2-propanol, 2-chloroethanol, 1-chlorobutanol, etc.

[0071] Examples of activity regulators, particularly when using a ruthenium carbene complex as a metathesis polymerization catalyst, include Lewis base compounds. Examples of Lewis base compounds include phosphorus-containing Lewis base compounds such as tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, triphenylphosphite, and n-butylphosphine; and nitrogen-containing Lewis base compounds such as n-butylamine, pyridine, 4-vinylpyridine, acetonitrile, ethylenediamine, N-benzylidenemethylamine, pyrazine, piperidine, and imidazole. Furthermore, norbornenes substituted with alkenyl groups, such as vinylnorbornene, propenylnorbornene, and isopropenylnorbornene, function not only as cycloolefin monomers but also as activity regulators. The amount of these activity regulators used can be adjusted appropriately depending on the compound used.

[0072] Examples of elastomers include 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 hydrogenated versions of these. Dissolving an elastomer in the polymerizable composition allows for adjustment of its viscosity. Adding an elastomer also improves the impact resistance of the resulting composite molded article. The amount of elastomer used is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass, per 100 parts by mass of all cycloolefin monomers in the polymerizable composition.

[0073] The polymerizable composition used in the present invention may contain a filler as an optional component. Various fillers can be used as the filler, and although there are no particular limitations, it is preferable to use a particulate inorganic filler.

[0074] The particulate inorganic filler preferably has an aspect ratio of 1 to 2, more preferably 1 to 1.5. The 50% cumulative volume diameter of the particulate 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% cumulative volume diameter. The average major axis diameter is the number-average major axis diameter calculated as the arithmetic mean value of the major axis diameters of 100 fillers randomly selected from an optical microscope photograph. The 50% cumulative volume diameter is a value determined by measuring the particle size distribution using an X-ray transmission method.

[0075] Specific examples of particulate inorganic fillers include calcium carbonate, calcium hydroxide, calcium silicate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, titanium oxide, zinc oxide, barium titanate, silica, alumina, carbon black, graphite, antimony oxide, red phosphorus, various metal powders, clay, various ferrites, SmFeN-based rare earth magnetic powder, NdFeB-based rare earth magnetic powder, SmCo-based rare earth magnetic powder, hydrotalcite, etc. Among these, magnesium hydroxide, aluminum hydroxide, silica, and alumina are preferred, and aluminum hydroxide and silica are particularly preferred.

[0076] The particulate inorganic filler may have its surface hydrophobized. Using a hydrophobized particulate inorganic filler can prevent aggregation and sedimentation of the particulate inorganic filler in the polymerizable composition and can ensure uniform dispersion of the particulate inorganic filler in the resulting cured cycloolefin resin. As a result, the elasticity of the cured cycloolefin resin can be improved. Examples of treating agents used for the hydrophobization include silane coupling agents such as vinyl silane, titanate coupling agents, aluminum coupling agents, fatty acids such as stearic acid, oils and fats, surfactants, waxes, etc. The treating agent can also be simply blended with the filler in the polymerizable composition.

[0077] The treating agent is preferably a silane coupling agent having at least one hydrocarbon group with a norbornene structure, because even when a filler is blended into the polymerizable composition, the viscosity is low, thixotropy (viscosity at rest) is not likely to increase, and adhesion to the substrate (e.g., the semiconductor element when used as an encapsulating material for a semiconductor element) can be improved. While the silane coupling agent can also function as a monomer, it is treated as a silane coupling agent in the present invention. Specific examples of such silane coupling agents include bicycloheptenyltrimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenylethyltrimethoxysilane, bicycloheptenylethyltriethoxysilane, bicycloheptenylhexyltrimethoxysilane, and bicycloheptenylhexyltriethoxysilane, with bicycloheptenylethyltrimethoxysilane and bicycloheptenylhexyltriethoxysilane being preferred. The content of the silane coupling agent having at least one hydrocarbon group with a norbornene structure in the polymerizable composition used in the present invention is preferably 0.1 to 5 mass %, more preferably 0.3 to 2 mass %, and even more preferably 0.5 to 1 mass %.

[0078] 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.

[0079] Furthermore, the polymerizable composition used in the present invention may contain a fibrous inorganic filler in addition to the particulate inorganic filler. The fibrous inorganic filler preferably has an aspect ratio of 5 to 100, more preferably 10 to 50. The 50% cumulative volume diameter of the fibrous inorganic filler is preferably 0.1 to 50 μm, more preferably 1 to 30 μm.

[0080] Specific examples of fibrous inorganic fillers include glass fiber, wollastonite, potassium titanate, zonolite, basic magnesium sulfate, aluminum borate, tetrapod-type zinc oxide, gypsum fiber, phosphate fiber, alumina fiber, whisker-like calcium carbonate, and whisker-like boehmite. Among these, wollastonite and whisker-like calcium carbonate are preferred. Furthermore, the fibrous inorganic filler may have its surface hydrophobized, similar to the particulate inorganic filler described above.

[0081] Furthermore, it is also suitable to use a plate-like filler as the filler to be blended into the polymerizable composition used in the present invention. The plate-like filler is a filler with an aspect ratio of 30 to 2,000, and has a plate-like or flat shape. By blending a plate-like filler, the oxygen-barrier cycloolefin resin cured product can be made to have excellent water vapor barrier properties in addition to high oxygen barrier properties. From the viewpoint of further improving water vapor barrier properties, the aspect ratio of the plate-like filler is preferably 35 to 1,500, more preferably 40 to 1,000, and particularly preferably 45 to 800.

[0082] By blending such a plate-like filler, the water vapor permeability of the cured product of the oxygen-barrier cycloolefin resin, measured at a temperature of 40°C and a humidity of 90% RH according to JIS K7129 B (1992), can be increased to preferably 10 g / m 2 In other words, when the oxygen-barrier cured cycloolefin resin product is converted into a 100 μm thick product, the water vapor permeability measured under conditions of a temperature of 40°C and a humidity of 90% RH is preferably 10 g / m 2 24 hours or less, preferably 7g / m 2 24 hours or less, preferably 5 g / m 2 The water vapor transmission rate can be measured using a commercially available water vapor transmission rate measuring device under conditions of a temperature of 40°C and a humidity of 90% RH.

[0083] The aspect ratio of a plate-like filler can be calculated by determining the ratio of the planar average diameter to the average thickness of the primary particles of the plate-like filler. Here, the planar average diameter and average thickness are number-average values ​​calculated as the arithmetic mean of the diameters and thicknesses of 100 randomly selected plate-like fillers measured in the planar direction using an atomic force microscope.

[0084] The plate-like filler may be either inorganic or organic, but inorganic fillers are preferred. They may be naturally occurring, naturally occurring products that have been refined, or synthetic. Specific examples of plate-like fillers include kaolinites such as kaolinite and halloysite; smectites such as montmorillonite, beidellite, nontronite, saponite, hectorite, stevensite, and mica; vermiculites; chlorites; talc; and glass flakes, which are amorphous plate-like particles such as E-glass or C-glass. Among these, smectites and glass flakes are preferred, with montmorillonite, mica, and saponite being particularly preferred. These fillers can be used alone or in combination. Furthermore, fillers obtained by subjecting montmorillonite, mica, or saponite to aqueous dispersion treatment to separate the individual layers that make up the multilayered compounds montmorillonite, mica, and saponite can also be used. Of the above, montmorillonite is contained as a main component in bentonite, and therefore, montmorillonite obtained by purifying bentonite can be used.

[0085] The amount of the plate-like filler in the polymerizable composition used in the present invention is preferably 20 to 50 parts by mass, more preferably 30 to 40 parts by mass, per 100 parts by mass of the cycloolefin monomer. By setting the amount of the plate-like filler in this range, it is possible to achieve excellent water vapor barrier properties while maintaining high oxygen barrier properties.

[0086] The polymerizable composition used in the present invention is prepared by appropriately mixing the above-mentioned components according to a known method. The polymerizable composition used in the present invention may also be prepared by preparing two or more premixed liquids and mixing the two or more premixed liquids using a mixing device or the like immediately before forming a cycloolefin resin cured product. Although one premixed liquid alone will not undergo bulk polymerization, the above-mentioned components are prepared by dividing them into two or more liquids so that mixing all the liquids will result in a polymerizable composition containing each component in a predetermined ratio. Such combinations of two or more reaction stock liquids include the following two types (a) and (b), depending on the type of metathesis polymerization catalyst used.

[0087] (a): The metathesis polymerization catalyst may be one that does not have polymerization activity by itself but exhibits polymerization activity when used in combination with an activator. In this case, a premixed liquid (Liquid A) containing a cycloolefin monomer and an activator and a premixed liquid (Liquid B) containing a cycloolefin monomer and a metathesis polymerization catalyst are used and mixed to obtain a polymerizable composition. Furthermore, a premixed liquid (Liquid C) containing a cycloolefin monomer but not a metathesis polymerization catalyst or an activator may also be used in combination.

[0088] (b): When a metathesis polymerization catalyst having polymerization activity by itself is used, a polymerizable composition can be obtained by mixing a premix (i) containing a cycloolefin monomer with a premix (ii) containing a metathesis polymerization catalyst. In this case, the premix (ii) is typically prepared by dissolving or dispersing the metathesis polymerization catalyst in a small amount of an inert solvent. Examples of such solvents include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and trimethylbenzene; 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, and ethyl acetate. Among these, aromatic hydrocarbons are preferred, and toluene is more preferred.

[0089] Optional components such as a radical generator, a diisocyanate compound, and a polyfunctional (meth)acrylate compound may be contained in any of the pre-mixed liquids, or may be added in the form of a mixed liquid other than the pre-mixed liquid.

[0090] Examples of the mixing device used for mixing the pre-mixed liquid include an impingement mixer that is generally used in reaction injection molding, as well as low-pressure mixers such as a dynamic mixer and a static mixer.

[0091] <Cured cycloolefin resin with oxygen barrier properties> The oxygen-barrier cycloolefin resin cured product of the present invention is obtained by bulk polymerization of the polymerizable composition described above, and has an oxygen permeability of 50 mL / m at 23°C. 2 That is, the cycloolefin resin cured product of the present invention has an oxygen permeability of less than 50 mL / m at 23°C when converted into a product with a thickness of 100 μm. 2 15 mL / m 2 ·day·atm or less, and more preferably 10mL / m 2 ·day·atm or less.

[0092] The oxygen-barrier cycloolefin resin cured product of the present invention may have an oxygen permeability at 23°C within the above range, but from the viewpoint of realizing extremely high oxygen barrier properties over a long period of time, it is preferable that it has an oxide film on at least a portion of its surface. Furthermore, for example, the cycloolefin resin cured product of the present invention is preferably formed into a film-shaped cured product and used as an oxygen-barrier film. In this case, it is preferable that it has an oxide film on at least a portion of at least one surface. It is more preferable that the oxide film covers 1 to 100% of the total area of ​​the surface of the cured product or at least one surface of the film, more preferably 50 to 100%, even more preferably 80 to 100%, and particularly preferably the entire surface (i.e., 100% of the total area).

[0093] The oxygen-barrier cycloolefin resin cured product of the present invention is obtained by bulk polymerization of a polymerizable composition containing 0.3 mass% or less of an antioxidant. Therefore, it is easily oxidized in an oxidizing atmosphere (e.g., air), spontaneously forming an oxide film on its surface. However, heating at a predetermined temperature may promote the formation of the oxide film. In particular, when attempting to achieve oxygen barrier properties by incorporating a significant amount of antioxidant, once the oxygen absorption limit is reached, the oxygen barrier properties cannot be maintained, and therefore high oxygen barrier properties cannot be maintained for a long period of time. In contrast, according to the present invention, the antioxidant content is set to a specific amount or less, thereby forming an oxide film, which realizes oxygen barrier properties. Therefore, high oxygen barrier properties can be achieved for a long period of time. The thickness of the oxide film is not particularly limited, but is preferably 200 μm or less, more preferably 5 to 100 μm, and even more preferably 10 to 50 μm.

[0094] The method for producing the oxygen-barrier cured cycloolefin resin of the present invention is not particularly limited. For example, when the cycloolefin resin cured product of the present invention is cured into a film-like product to form an oxygen-barrier film, a preferred method is to mix two or more of the above-mentioned pre-blended liquids, bulk-polymerize them, and mold them into a film.

[0095] A specific example of a method for mixing two or more of the above-mentioned pre-mixed liquids, bulk polymerizing the mixture, and forming the mixture into a film shape includes a method for mixing two or more of the above-mentioned pre-mixed liquids, applying the resulting mixture (polymerizable composition) onto a substrate, and bulk polymerizing the mixture.

[0096] The substrate is not particularly limited, and examples thereof include commonly known materials such as resin and glass. Specific examples of resin include polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polyarylate; polycarbonate; polyolefins such as polypropylene and polyethylene; polyamides such as nylon; and fluororesins such as polytetrafluoroethylene. Polyesters are preferred because they are readily available. If the substrate is made of resin, the preferred shape is a drum or belt. A preferred substrate is a resin film, which is readily available and inexpensive.

[0097] The mixed solution (polymerizable composition) is then bulk polymerized by heating it, if necessary, to a temperature at which the polymerization catalyst becomes active. The polymerization temperature is preferably 0 to 250°C, more preferably 20 to 200°C. The heating method is not particularly limited, but includes heating on a heating plate, heating under pressure using a press (hot pressing), pressing with a heated roller, and using a heating furnace. The polymerization reaction time is determined appropriately depending on the amount of polymerization catalyst and the heating temperature, but is preferably 1 minute to 24 hours.

[0098] The film-shaped cured product obtained by bulk polymerization on a substrate can be peeled off from the substrate to obtain an oxygen barrier film. The method for peeling the film-shaped cured product from the substrate is not particularly limited, and the cured product may be peeled off manually by an operator or by machine, etc. The oxygen barrier film obtained in this manner can be used, for example, as a sealing film for sealing a semiconductor element.

[0099] Alternatively, when producing the cured product of the oxygen-barrier cycloolefin resin of the present invention, for example, the two or more pre-mixed liquids described above may be introduced separately into a low-pressure mixer, instantaneously mixed using a dynamic mixer or static mixer, and then bulk polymerized in a mold or on a substrate.

[0100] For example, when the cured product of the oxygen-barrier cycloolefin resin of the present invention is used as an encapsulating material for encapsulating a semiconductor element, instead of the method for obtaining a film-shaped cured product described above, the two or more pre-blended liquids described above can be introduced separately into a low-pressure mixer, instantaneously mixed in a dynamic mixer or static mixer, and the mixed liquid can be supplied from the dynamic mixer or static mixer so as to cover the surface of the semiconductor element, thereby encapsulating the semiconductor element with the cured product of the cycloolefin resin of the present invention.

[0101] Furthermore, when the oxygen-barrier cycloolefin resin cured product of the present invention is cured into a film shape to form an oxygen-barrier film, it may have other layers in addition to the layer consisting of the cycloolefin resin cured product of the present invention. Such other layers may be appropriately selected depending on the intended use and required properties, and examples thereof include a sealant layer consisting of a heat-sealable resin, a supporting substrate layer, a deodorizer layer containing a deodorizer, a surface resin layer, and a protective layer.

[0102] Furthermore, the cured product of the oxygen-barrier cycloolefin resin of the present invention may be laminated with a layer of another resin or a metal layer to form a laminate. By forming a laminate of a layer of the cured product of the oxygen-barrier cycloolefin resin of the present invention with a layer of another resin or a metal layer, it is possible to obtain an excellent water vapor barrier property in addition to high oxygen barrier property. In this case, it is preferable to form the cured product of the oxygen-barrier cycloolefin resin of the present invention into a film-shaped product and laminate it with a layer of another resin or a metal layer to form a laminate.

[0103] The other resin for forming the layer made of the other resin is not particularly limited, but examples thereof include acrylic resin, urethane resin, silicone resin, epoxy resin, polyimide resin, etc. Among these, epoxy resin is preferred because it can further enhance the water vapor barrier property. The thickness of the layer made of the other resin is not particularly limited, but is preferably 0.5 to 100 μm, more preferably 1 to 50 μm.

[0104] The layer made of other resin may contain, as necessary, a curing agent, a curing aid, a filler such as calcium carbonate or titanium oxide, a plasticizer, a surfactant (leveling agent), an ultraviolet absorber, a light stabilizer, an antioxidant, a dehydrating agent, an adhesion imparting agent, a pot life extender (acetylacetone, methanol, methyl orthoacetate, etc.), a repelling improver, etc.

[0105] Examples of metals for forming the metal layer include copper, gold, silver, stainless steel, aluminum, nickel, chromium, and alloys thereof. Among these, copper is preferred because it can further enhance the water vapor barrier property. The thickness of the metal layer is not particularly limited, but is preferably 1 to 35 μm, and more preferably 3 to 18 μm.

[0106] There are no particular limitations on the method for producing a laminate of the cured product of the oxygen-barrier cycloolefin resin of the present invention with a layer of another resin or a metal layer. When a laminate with a layer of another resin is to be produced, the laminate can be produced by a method in which a solution in which a resin or the like for forming the layer of another resin is dissolved in a solvent is applied to the surface of the cured product of the oxygen-barrier cycloolefin resin of the present invention, the solvent is removed by drying or the like, and then a curing reaction or the like is carried out as necessary to form the layer of another resin.

[0107] Alternatively, a laminate of a cured cycloolefin resin with oxygen barrier properties and a layer made of another resin or a metal layer can be produced by placing a film of another resin or a metal in a mold in advance, instantaneously mixing the two or more pre-mixed liquids (two or more mixed liquids for forming a cured cycloolefin resin) using the method described above, and then bulk polymerizing the mixture in the mold.

[0108] According to the present invention, the above-mentioned norbornene-based monomer (a) is used as the cycloolefin monomer constituting the polymerizable composition, the content of the antioxidant in the polymerizable composition is 0.3 mass% or less, and by using such a polymerizable composition, it is possible to obtain a polymerizable composition having an oxygen permeability of 50 mL / m or less at 23°C when converted into a thickness of 100 μm. 2The present invention provides a cured cycloolefin resin having a viscosity of less than 1000 ppm / day. Therefore, according to the present invention, high oxygen barrier properties can be achieved. In particular, by setting the antioxidant content to 0.3 mass % or less, an oxide film is formed on at least a portion of the surface, thereby achieving oxygen barrier properties, thereby achieving high oxygen barrier properties over a long period of time. Therefore, the cured cycloolefin resin with oxygen barrier properties of the present invention can be suitably used as a sealing material for electrical and electronic components or a coating material for electrical and electronic components. Specifically, the cured cycloolefin resin with oxygen barrier properties of the present invention can be suitably used as a sealing material for various resin-encapsulated semiconductor devices, a sealing / coating material for capacitors, a sealing / coating material for power modules, a sealing / coating material for coils, etc., and by using it in these applications, oxygen-induced deterioration and corrosion of electrical and electronic components can be effectively prevented. Furthermore, from the viewpoint of effectively preventing deterioration and corrosion due to oxygen, the cured product of the oxygen-barrier cycloolefin resin of the present invention can also be suitably used for the following applications: coating materials for pump casings, bearings, etc.; packaging applications for liquid beverages such as milk, juice, sake, whiskey, shochu, coffee, tea, jelly drinks, and health drinks; packaging applications for condiments such as liquid seasonings, sauces, soy sauce, dressings, liquid soup stock, mayonnaise, miso, and grated spices; packaging applications for paste-like foods such as jam, cream, chocolate paste, yogurt, and jelly; packaging applications for liquid processed foods such as liquid soups, simmered dishes, pickles, and stews; packaging applications for solid and liquid chemicals such as pesticides and insecticides; packaging applications for liquid and paste-like pharmaceuticals; and packaging applications for cosmetic products such as lotions, cosmetic creams, cosmetic emulsions, hair styling products, and hair dyes. [Example]

[0109] The present invention will be described below based on examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" and "%" are by mass. Tests and evaluations were performed according to the following methods.

[0110] <Oxygen permeability (initial)> The film-shaped cycloolefin resin cured product was measured by the differential pressure method in accordance with JIS K7126-2 using an oxygen permeability measuring device (MOCON oxygen permeability measuring device OX-TRAN2 / 21, manufactured by Hitachi High-Tech Science Corporation) under the conditions of a temperature of 23°C, a relative humidity of 0%, and 1 atmosphere, with the shape of the permeable surface being a circle with a diameter of 4.4 cm. The measurement results were converted to a thickness of 100 μm to obtain the oxygen permeability (unit: mL / m 2 The oxygen permeability was calculated according to the following formula: Oxygen permeability [mL / m 2 ·day·atm(100μm)] = {Measurement value by oxygen permeability measuring device [mL / m 2 ·day·atm]×measurement sample thickness [μm]}÷100

[0111] <Oxygen permeability (after heating)> The film-shaped cured cycloolefin resin was heated at 170°C for 190 hours, and the oxygen permeability (unit: mL / m) of the film-shaped cured cycloolefin resin after heating was measured in the same manner as above. 2 ·day·atm(100μm)" was measured.

[0112] <Water vapor permeability (initial)> The film-shaped cycloolefin resin cured product was measured in accordance with JIS K 7129-2008 Method A using a water vapor transmission rate measuring device (product name "Lyssy L80-5000", manufactured by SYSTECH) under conditions of a temperature of 40°C, humidity of 90% RH, and 1 atmosphere, with the transmission surface shape being a circle with a diameter of 4.4 cm. The measurement results were converted to a thickness of 100 μm to obtain the water vapor transmission rate (unit: g / m 2 The water vapor permeability was calculated according to the following formula: Water vapor permeability [g / m 2 ·24h(100μm)] = {Measurement value by water vapor permeability measuring device [g / m 2 24h × thickness of measurement sample [μm] ÷ 100

[0113] Example 1 100 parts of RIM monomer (manufactured by Zeon Corporation) containing 90 parts of dicyclopentadiene and 10 parts of tricyclopentadiene as norbornene-based monomers was used as a preliminary blend liquid (i).

[0114] As a metathesis polymerization catalyst, 0.4 parts of a ruthenium catalyst (Zhan1N) represented by formula (7) and 43.0 parts of triphenylphosphine were dissolved in 56.6 parts of cyclopentanone to obtain a premixed solution (ii). Note that in this example, neither premixed solution (i) nor premixed solution (ii) contained an antioxidant, and therefore, premixed solution (i), premixed solution (ii), and the polymerizable composition obtained by mixing these solutions were substantially free of antioxidant (0.03 mass% or less) (the same applies to Examples 2 and 3 described below). [ka] (In the formula, Mes represents a mesityl group.)

[0115] The pre-mixed liquids (i) and (ii) prepared above were mixed in a ratio of pre-mixed liquid (i):pre-mixed liquid (ii) = 100:2.5 (mass ratio). The mixture was degassed in a vacuum, applied to a SUS plate as a substrate, and heated in an oven heated to 40°C for 30 minutes, followed by heating at 175°C for 60 minutes to obtain a polymerized and cured film-shaped cycloolefin-based resin cured product with a thickness of 500 μm. After heating, the obtained film-shaped cured cycloolefin-based resin was analyzed by FT-IR and found to have an oxide film formed on one side. Measurement using a Keyence digital microscope revealed that the oxide film was 30 μm thick. The obtained film-shaped cured cycloolefin-based resin was then measured for oxygen permeability (initial and post-heating) and water vapor permeability (initial) according to the methods described above. The results are shown in Table 1.

[0116] <Example 2> A film-shaped cured cycloolefin resin product was obtained and evaluated in the same manner as in Example 1, except that 100 parts of a norbornene-based monomer containing 93 parts of dicyclopentadiene and 7 parts of ethylidene norbornene was used as pre-blended liquid (i) instead of the RIM monomer. The results are shown in Table 1. The thickness of the oxide film on the obtained film-shaped cured cycloolefin resin product after heating was 30 μm.

[0117] <Comparative Example 1> A film-shaped cured cycloolefin resin was obtained in the same manner as in Example 1, except that a solution of 0.4 parts of a ruthenium catalyst (Zhan1N) represented by formula (7), 14 parts of 2,6-di-t-butyl-p-cresol (BHT, antioxidant), and 43 parts of triphenylphosphine dissolved in 42.6 parts of cyclopentanone was used as pre-mixture liquid (ii), and the resulting polymerizable composition was evaluated in the same manner. The results are shown in Table 1. In Comparative Example 1, when pre-mixture liquid (i):pre-mixture liquid (ii) were mixed in a ratio of 100:2.5 (mass ratio), the content of 2,6-di-t-butyl-p-cresol (BHT, antioxidant) in the resulting polymerizable composition was 0.33 mass%.

[0118] <Comparative Example 2> A film-like cured cycloolefin resin was obtained and evaluated in the same manner as in Comparative Example 1, except that 100 parts of a norbornene-based monomer containing 93 parts of dicyclopentadiene and 7 parts of ethylidene norbornene was used as pre-blended liquid (i) instead of the RIM monomer. The results are shown in Table 1.

[0119] [Table 1]

[0120] As shown in Table 1, the polymerizable composition was prepared using a norbornene-based monomer (a) as the cycloolefin monomer and the antioxidant content was 0.3 mass % or less, and the oxygen permeability (initial) at 23°C was 50 mL / m 2The cycloolefin-based resin cured product having a viscosity of less than 100 μm per day atm (100 μm) exhibited low oxygen permeability even after heating at 175°C for 190 hours, and thus exhibited high oxygen barrier properties (Examples 1 and 2). On the other hand, when the polymerizable composition contained more than 0.3% by mass of antioxidant, both the oxygen permeability (initial value and after heating at 175°C for 190 hours) were high, and the oxygen barrier property was poor (Comparative Examples 1 and 2).

[0121] Example 3 A film-like cured cycloolefin resin was obtained in the same manner as in Example 1, except that when preparing the pre-blended liquid (i), glass flakes with an aspect ratio of 20 were blended as the plate-like filler in a ratio of 33 parts per 100 parts of the norbornene-based monomer. The film-like cured cycloolefin resin was evaluated in the same manner, and the oxygen permeability (initial) was 0.5 mL / m 2 ·day·atm (100μm), and the oxygen permeability (after heating at 175℃ for 190 hours) is 0.8mL / m 2 ·day·atm (100μm), and had excellent oxygen barrier properties. Furthermore, the water vapor permeability of the obtained film-like cured cycloolefin resin was measured under conditions of a temperature of 40°C and a humidity of 90% RH, and the water vapor permeability was 1.6 g / m 2 -24h (100μm) and also had excellent water vapor barrier properties.

Claims

1. A cured cycloolefin resin with oxygen barrier properties obtained by bulk polymerization of a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst, the cycloolefin monomer contains a norbornene-based monomer (a), The norbornene-based monomer (a) contains 80 to 95% by mass of tricyclic units and 5 to 20% by mass of pentacyclic units, the content of the antioxidant in the polymerizable composition is 0.3% by mass or less, Oxygen permeability at 23°C is 50 mL / m ２ A cured product of a cycloolefin resin having oxygen barrier properties of less than 100 μm / day.

2. Oxygen permeability at 23°C is 15 mL / m ２ 2. The cured product of claim 1, wherein the oxygen barrier property of the cycloolefin resin is 0.1 day atm (100 μm) or less.

3. The cured product of a cycloolefin resin with oxygen-barrier properties according to claim 1 or 2, wherein the cycloolefin monomer further contains a monocyclic cycloolefin.

4. 4. The cured product of a cycloolefin resin with oxygen barrier properties according to claim 1, wherein the polymerizable composition contains a filler.

5. The cured product of a cycloolefin resin with oxygen barrier properties according to claim 4, wherein the filler is a plate-like filler.

6. 6. The cured product of a cycloolefin resin with oxygen barrier properties according to claim 1, which has an oxide film on at least a portion of its surface.

7. An oxygen barrier film obtained by molding a cured product of the oxygen barrier cycloolefin resin according to any one of claims 1 to 5.

8. 8. The oxygen barrier film according to claim 7, which has an oxide film on at least a portion of at least one surface.

9. A laminate comprising a layer made of the cured product of the cycloolefin resin with oxygen barrier properties according to any one of claims 1 to 5, and a layer made of another resin or a metal layer.

10. 1. A polymerizable composition comprising a cycloolefin monomer and a metathesis polymerization catalyst, the cycloolefin monomer contains a norbornene-based monomer (a), the norbornene-based monomer (a) contains a tricyclic monomer in a proportion of 80 to 95% by mass and a pentacyclic monomer in a proportion of 5 to 20% by mass, and the content of an antioxidant in the polymerizable composition is 0.3% by mass or less; The polymerizable composition for forming a cured product of the cycloolefin resin having oxygen barrier properties according to claim 1 .

11. The polymerizable composition of claim 10, wherein the cycloolefin monomer further comprises a monocyclic cycloolefin.

12. The polymerizable composition according to claim 10 or 11, which comprises two or more pre-mixed liquids that do not undergo a polymerization reaction by themselves, and which can form the polymerizable composition by combining the pre-mixed liquids.

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