JP2012197392A - Polymerizable composition, resin molded item and laminated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable composition that affords a crosslinked resin molded item and a laminated product, each having a low dielectric loss and being well-balancedly excellent in mechanical strength, heat resistance and peel strength, a crosslinkable resin molded item, and a crosslinked resin molded item and a laminated product obtained by using the polymerizable composition and the crosslinkable resin molded item.SOLUTION: The polymerizable composition comprises a cycloolefin monomer, a metathesis polymerization catalyst, a radical generating agent and a chain transfer agent, represented by general formula (1): Q-A-CH=CH-B-Q. In the formula, Qand Qare each independently a methacryloxy group, an acryloxy group or an ethynyl group; and A and B are each independently a bivalent organic group containing no vinyl or vinylene group in the chemical structure.

Description

  The present invention relates to a polymerizable composition, a crosslinkable resin molded article, a crosslinked resin molded article, and a laminate suitably used as a material for electronic equipment.

  With recent miniaturization of electronic devices and higher communication speed, electronic circuit boards are also required to be smaller and more multifunctional. Since such a circuit board is often used in a high-frequency region and requires excellent high-frequency characteristics, the material used for the insulating layer of the board is required to have a low dielectric loss.

  As such a low dielectric loss resin material, a cycloolefin polymer obtained by bulk polymerization of a cycloolefin monomer has attracted attention.

For example, Patent Document 1 includes a norbornene-based monomer, a metathesis polymerization catalyst, a chain transfer agent, and a crosslinking agent. As the chain transfer agent, CH ₂ = CH-Q (Q is a methacryloyl group, an acryloyl group, a vinylsilyl group, an epoxy group. And a polymerizable composition comprising a compound represented by (a group having at least one group selected from amino groups).

Patent Document 2, cycloolefin monomers, a metathesis polymerization catalyst, cross-linking agents, chain transfer agents, and includes a specific diene rubber as a chain transfer _{agent, CH 2 = CH-Y-} OCO-CR = CH 2 A polymerizable composition using a compound represented by (Y is an alkylene group, R is a hydrogen atom or a methyl group) is disclosed.

Japanese Patent Laid-Open No. 2004-244609 JP 2008-133417 A

As a result of investigation by the present inventors, a molded product obtained by bulk polymerization and crosslinking of the polymerizable compositions described in Patent Document 1 and Patent Document 2 has low dielectric loss, mechanical strength, heat resistance, and peel. Although the strength is generally good, there is room for further improvement in these characteristics in view of further increase in speed and frequency of information transmission.
An object of the present invention is a polymerizable composition and a crosslinkable resin molded body that provide a crosslinked resin molded body and a laminate with excellent balance in mechanical strength, heat resistance, and peel strength with low dielectric loss, and It is providing the crosslinked resin molding and laminated body which are obtained using these.

  As a result of diligent research to achieve the above object, the present inventors have found a cycloolefin monomer, a metathesis polymerization catalyst, a radical generator, and a chain transfer agent having a methacryloxy group, an acryloxy group, or an ethynyl group at both ends. In order to complete the present invention, it is found that a molded product obtained using the polymerizable composition contained therein has a low dielectric loss and excellent mechanical strength, heat resistance and peel strength in a well-balanced manner. It came.

That is, according to the present invention,
[1] A polymerizable composition comprising a cycloolefin monomer, a metathesis polymerization catalyst, a radical generator, and a chain transfer agent represented by the following general formula (1):
Q ¹ -A-CH = CH-BQ ² (1)
(In the general formula (1), Q ¹ and Q ² are each independently a methacryloxy group, an acryloxy group, or an ethynyl group, and A and B each independently contain a vinyl group and a vinylene group in the chemical structure. There are no divalent organic groups.)
[2] The polymerizable composition according to [1], wherein the divalent organic group is a C 1-10 divalent hydrocarbon group which may contain a hetero atom,
[3] The polymerizable composition according to [1] or [2], wherein the cycloolefin monomer has a crosslinkable carbon-carbon unsaturated bond,
[4] A crosslinkable resin molded article obtained by bulk polymerization of the polymerizable composition according to any one of [1] to [3],
[5] A crosslinked resin molded article obtained by bulk polymerization of the polymerizable composition according to any one of the above [1] to [3] and crosslinking, and
[6] At least a cross-linked resin molded product according to [4], or a laminate comprising a layer made of the cross-linked resin molded product according to [5],
Is provided.

  According to the present invention, a polymerizable composition and a crosslinkable resin molded article that give a crosslinked resin molded article and a laminate having a low dielectric loss and excellent mechanical strength, heat resistance and peel strength in a well-balanced manner, and A crosslinked resin molded article and a laminate obtained using the same can be provided. The laminate of the present invention can be suitably used particularly for the production of a high-frequency multilayer circuit board.

  Hereinafter, the present invention will be described in detail. In the following, the crosslinkable resin molded body and the crosslinked resin molded body may be collectively referred to as a resin molded body.

(Polymerizable composition)
The polymerizable composition of the present invention contains a cycloolefin monomer, a metathesis polymerization catalyst, a radical generator, and a chain transfer agent represented by the general formula (1) described later.

(Cycloolefin monomer)
The cycloolefin monomer used in the present invention is a compound having an alicyclic structure formed of carbon atoms and having a polymerizable carbon-carbon double bond in the alicyclic structure. As used herein, “polymerizable carbon-carbon double bond” refers to a carbon-carbon double bond involved in chain polymerization (metathesis ring-opening polymerization).

  Examples of the alicyclic structure of the cycloolefin monomer include monocycles, polycycles, condensed polycycles, bridged rings, and combination polycycles thereof. The cycloolefin monomer used in the present invention is preferably a polycyclic cycloolefin monomer from the viewpoint of improving the mechanical strength of the obtained resin molded product. Although there is no limitation in particular in the carbon atom number which comprises each ring structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces. The cycloolefin monomer may have a hydrocarbon group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkylidene group, and an aryl group, or a polar group such as a carboxyl group or an acid anhydride group as a substituent. Good.

  In the present invention, as the cycloolefin monomer, those having at least one crosslinkable carbon-carbon unsaturated bond are preferably used from the viewpoint of improving the mechanical strength of the obtained resin molded body and laminate. As used herein, “crosslinkable carbon-carbon unsaturated bond” refers to a carbon-carbon unsaturated bond that does not participate in metathesis ring-opening polymerization but participates in a crosslinking reaction. “Crosslinking reaction” refers to a reaction that forms a bridge structure. The “crosslinking reaction” usually means a radical crosslinking reaction or a metathesis crosslinking reaction, particularly a radical crosslinking reaction.

Examples of the crosslinkable carbon-carbon unsaturated bond include carbon-carbon unsaturated bonds other than aromatic carbon-carbon unsaturated bonds, that is, aliphatic carbon-carbon double bonds or triple bonds. Usually refers to an aliphatic carbon-carbon double bond. In the cycloolefin monomer having a crosslinkable carbon-carbon unsaturated bond, the position of the unsaturated bond is not particularly limited, and other than the alicyclic structure other than the alicyclic structure formed by carbon atoms. For example, at the end or inside of the side chain. For example, the aliphatic carbon-carbon double bond may be present as a vinyl group (CH ₂ ═CH—), a vinylidene group (CH ₂ ═C <), or a vinylene group (—CH═CH—). In view of good radical cross-linking properties, it is preferably present as a vinyl group and / or vinylidene group, and more preferably as a vinylidene group.

  As the cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond, a norbornene monomer having at least one crosslinkable carbon-carbon unsaturated bond is particularly preferable. The “norbornene monomer” refers to a cycloolefin monomer having a norbornene ring structure in the molecule. Examples include norbornenes, dicyclopentadiene, and tetracyclododecene.

  Examples of the cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond include 3-vinylcyclohexene, 4-vinylcyclohexene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4- Monocyclic cycloolefin monomers such as cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene; 5-ethylidene-2-norbornene, 5-methylidene Norbornene monomers such as 2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylnorbornene, 5-allylnorbornene, 5,6-diethylidene-2-norbornene, dicyclopentadiene, 2,5-norbornadiene; Can be mentioned. Among these, norbornene monomers having at least one crosslinkable carbon-carbon unsaturated bond are preferable.

  In the present invention, as the cycloolefin monomer, in addition to the cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond, a cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond is used.

  Examples of the cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond include cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, Monocyclic cycloolefin monomers such as cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene; norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, tetracyclododecene, 1, , 5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a , 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl -1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3 , 4,4a, 5,8,8a-octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2, -Fluoro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octa Dronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5 , 8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a , 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydro Dicyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene And norbornene monomers such as 5,6-dicarboxyl norbornene anhydrate, 5-dimethylamino norbornene and 5-cyanonorbornene. Among these, norbornene-based monomers having no crosslinkable carbon-carbon unsaturated bond are preferable.

  The above cycloolefin monomers can be used alone or in combination of two or more. For example, a mixture of a cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond and a cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond is used as the cycloolefin monomer.

  In the cycloolefin monomer used in the polymerizable composition of the present invention, the blending ratio of the cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond and the cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond is The weight ratio (cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond / cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond) is usually 5 / The range is 95-100 / 0, preferably 10 / 90-95 / 10, more preferably 15 / 85-90 / 15. By setting these blending ratios in such a range, the heat resistance and mechanical strength are improved in a well-balanced manner in the obtained resin molded body and laminate, which is preferable.

  The polymerizable composition of the present invention may contain any monomer copolymerizable with the above-described cycloolefin monomer as long as the expression of the effect of the present invention is not inhibited.

(Metathesis polymerization catalyst)
The metathesis polymerization catalyst used in the present invention is not particularly limited as long as the above-described cycloolefin monomer can be subjected to metathesis ring-opening polymerization.

  Examples of the metathesis polymerization catalyst include a complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds around a transition metal atom. As transition metal atoms, atoms of Group 5, Group 6, and Group 8 (long-period periodic table, the same shall apply hereinafter) are used. Although the atoms of each group are not particularly limited, the group 5 atom is preferably tantalum, the group 6 atom is preferably molybdenum and tungsten, and the group 8 atom is preferably May include ruthenium and osmium.

  Among these, a group 8 ruthenium or osmium complex is preferable, and a ruthenium carbene complex is particularly preferable. Since the ruthenium carbene complex is excellent in catalytic activity at the time of bulk polymerization, it is possible to efficiently produce a resin molded body with less odor derived from residual unreacted monomers. Moreover, since the group 8 ruthenium and osmium complexes are relatively stable to oxygen and moisture in the air and are not easily deactivated, a resin molded body can be produced even in the atmosphere.

  Specific examples of the ruthenium carbene complex include complexes represented by the following formula (2) or formula (3).

In the above formulas (2) and (3), R ¹ and R ² may each independently contain a hydrogen atom, a halogen atom, or a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom or silicon atom. Represents a cyclic or chain hydrocarbon group having 1 to 20 carbon atoms. X ¹ and X ² each independently represent an arbitrary anionic ligand. L ¹ and L ² each independently represent a hetero atom-containing carbene compound or a neutral electron donating compound other than the hetero atom-containing carbene compound. R ¹ and R ² may be bonded to each other to form an aliphatic ring or an aromatic ring that may contain a hetero atom. Furthermore, R ¹ , R ² , X ¹ , X ² , L ¹ and L ² may be bonded together in any combination to form a multidentate chelating ligand.

  A hetero atom refers to an atom of Groups 15 and 16 of the periodic table. Specific examples of the hetero atom 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 preferable, and a nitrogen atom is particularly preferable.

  The heteroatom-containing carbene compound preferably has a structure in which heteroatoms are adjacently bonded to both sides of the carbene carbon atom, and further has a structure in which a heterocycle is formed including the carbene carbon atom and heteroatoms on both sides thereof. What has is more preferable. Moreover, what has a bulky substituent in the hetero atom adjacent to a carbene carbon atom is preferable.

  Examples of the heteroatom-containing carbene compound include compounds represented by the following formula (4) or formula (5).

In the above formulas (4) and (5), R ^{3 to} R ⁶ may each independently contain a hydrogen atom; a halogen atom; or a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom or silicon atom. Represents a cyclic or chain hydrocarbon group having 1 to 20 carbon atoms. R ^{3 to} R ⁶ may be bonded to each other in any combination to form a ring.

  Specific examples of the compounds represented by the above formulas (4) and (5) include 1,3-dimesitylimidazolidin-2-ylidene and 1,3-di (1-adamantyl) imidazolidin-2-ylidene. 1-cyclohexyl-3-mesitylimidazolidine-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3- Examples include di (1-phenylethyl) -4-imidazoline-2-ylidene and 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene.

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

In the above formulas (2) and (3), the anionic (anionic) ligands X ¹ and X ² are ligands having a negative charge when separated from the central metal atom. A halogen atom such as an atom, a chlorine atom, a bromine atom and an iodine atom, a diketonate group, a substituted cyclopentadienyl group, an alkoxy group, an aryloxy group and a carboxyl group can be exemplified. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

  Further, the neutral electron donating compound may be any ligand as long as it has a neutral charge when pulled away from the central metal. Specific examples thereof include carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, and thiocyanates. Among these, phosphines, ethers and pyridines are preferable, and trialkylphosphine is more preferable.

  Examples of the complex compound represented by the above formula (2) include benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-4,5 -Dibromo-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4-imidazoline-2-ylidene) (3-phenyl-1H-indene-1-ylidene) (tricyclohexyl) Phosphine) ruthenium dichloride, (1,3-dimesityl-4-imidazolidin-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl- Octahydrobenzimidazo Ru-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3- Dimesityl-2,3-dihydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H- 1,2,4-triazole-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene ( , 3-Dimesityl-4-imidazolidin-2-ylidene) pyridine ruthenium dichloride, (1,3-Dimesityl-4-imidazolidin-2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride, (1 , 3-Dimesityl-4-imidazoline-2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) [( Phenylthio) methylene] (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) (2-pyrrolidone-1-ylmethylene) (tricyclohexylphosphine) ruthenium dichloride A ruthenium complex compound in which a hetero atom-containing carbene compound and a neutral electron donating compound other than a hetero atom-containing carbene compound are bonded to each other;

  Two neutral electron donating compounds other than hetero atom-containing carbene compounds such as benzylidenebis (tricyclohexylphosphine) ruthenium dichloride and (3-methyl-2-buten-1-ylidene) bis (tricyclopentylphosphine) ruthenium dichloride Bound ruthenium complex compounds;

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

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

  Among these complex compounds, those having one compound represented by the above formula (2) and represented by the above formula (5) as a ligand are particularly preferable.

  The used amount of the metathesis polymerization catalyst is usually 1: 2,000 to 1: 2,000,000, preferably 1: 5,000 to 1: in a molar ratio of (metal atom in the catalyst: cycloolefin monomer). The range is 1,000,000, more preferably 1: 10,000 to 1: 500,000.

  If desired, the metathesis polymerization catalyst can be used dissolved or suspended in a small amount of an inert solvent. Such solvents include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin and mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane , Cycloaliphatic hydrocarbons such as decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile Oxygen-containing hydrocarbons such as diethyl ether and tetrahydrofuran; Among these, it is preferable to use industrially general-purpose aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons. Further, as long as the activity as a metathesis polymerization catalyst is not lowered, a liquid anti-aging agent, a liquid plasticizer, or a liquid elastomer may be used as a solvent.

  The metathesis polymerization catalyst can be used in combination with an activator (cocatalyst) for the purpose of controlling the polymerization activity and improving the polymerization reaction rate.

  As the activator, aluminum, scandium, tin alkylates, halides, alkoxylates, aryloxylates, and the like can be used. Specific examples thereof include trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium, tetra Examples thereof include alkoxy tin and tetraalkoxy zirconium.

  The use amount of the activator is usually 1: 0.05 to 1: 100, preferably 1: 0.2 to 1:20, more preferably 1 in terms of a molar ratio of (metal atom in the catalyst: activator). : It is the range of 0.5-1: 10.

  In addition, when using a complex of transition metal atoms of Group 5 and Group 6 as the metathesis polymerization catalyst, it is preferable that both the metathesis polymerization catalyst and the activator are used by dissolving them in the monomer. As long as it is essentially not damaged, it can be suspended or dissolved in a small amount of solvent.

(Radical generator)
The radical generator used in the present invention is used for the purpose of inducing a crosslinking reaction in a crosslinkable resin obtained by generating radicals by heating and thereby bulk polymerizing the polymerizable composition of the present invention. Therefore, the crosslinkable resin obtained by bulk polymerization of the polymerizable composition of the present invention can be a postcrosslinkable thermoplastic resin. Examples of the radical generator include organic peroxides, diazo compounds, and nonpolar radical generators.

  Examples of the organic peroxide include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide; dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis (t- Butylperoxy-m-isopropyl) benzene, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2,5-di ( dialkyl peroxides such as t-butylperoxy) hexane; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; 2,2-di (t-butylperoxy) butane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -2-methyl Peroxyketals such as chlorocyclohexane and 1,1-di (t-butylperoxy) cyclohexane; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; t-butylperoxyisopropylcarbonate, di (isopropylperoxy) ) Peroxycarbonates such as dicarbonate; alkylsilyl peroxides such as t-butyltrimethylsilyl peroxide; and the like. Among these, dialkyl peroxides and peroxyketals are preferable in that there are few obstacles to the metathesis polymerization reaction.

  Examples of the diazo compound include 4,4′-bisazidobenzal (4-methyl) cyclohexanone, 4,4′-diazidochalcone, 2,6-bis (4′-azidobenzal) cyclohexanone, and 2,6-bis. (4′-azidobenzal) -4-methylcyclohexanone, 4,4′-diazidodiphenylsulfone, 4,4′-diazidodiphenylmethane, 2,2′-diazidostilbene and the like.

  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, Examples include 1,1-triphenyl-2-propene, 1,1,1-triphenyl-4-pentene, 1,1,1-triphenyl-2-phenylethane, and the like.

  These radical generators can be used alone or in combination of two or more. It is possible to arbitrarily control the glass transition temperature and the molten state of the resulting resin molded article by using two or more kinds of radical generators in combination and adjusting the amount ratio. The 1-minute half-life temperature of the radical generator is not particularly limited, but is usually in the range of 150 to 300 ° C, preferably 180 to 250 ° C. Here, the 1-minute half-life temperature is a temperature at which half of the radical generator decomposes in 1 minute. The 1-minute half-life temperature of the radical generator may be referred to, for example, a catalog or homepage of each radical generator manufacturer (for example, Nippon Oil & Fats Co., Ltd.).

  The usage-amount of a radical generator is 0.1-10 weight part normally with respect to 100 weight part of cycloolefin monomers, Preferably it is 0.5-5 weight part. If the usage-amount of a radical generating agent exists in this range, since the crosslinked resin molding obtained has sufficient crosslinking density and the laminated body which has a desired physical property is obtained efficiently, it is suitable.

(Chain transfer agent)
The chain transfer agent has an effect of improving the followability of the resin to the surface of the laminate on the surface of the crosslinkable resin obtained by bulk polymerization of the polymerizable composition of the present invention when heated and melted. . Therefore, by blending a chain transfer agent, the adhesion between the layers in the case of a laminate can be improved, and thereby the peel strength can be improved. The chain transfer agent used in the present invention is a compound represented by the following general formula (1).
Q ¹ -A-CH = CH-BQ ² (1)

In the general formula (1), Q ¹ and Q ² are each independently a methacryloxy group, an acryloxy group, or an ethynyl group, preferably a methacryloxy group or an acryloxy group, more preferably a methacryloxy group. It is particularly preferred that both Q ¹ and Q ² are methacryloxy groups.

Moreover, in the said General formula (1), A and B are bivalent organic groups which do not contain a vinyl group and vinylene group in a chemical structure each independently. That is, A and B are composed of a divalent organic group that does not include a vinyl group (CH ₂ ═CH—) and a vinylene group (—CH═CH—) in its chemical structure. Although it does not specifically limit as a bivalent organic group which comprises A and B, The C1-C10 bivalent hydrocarbon group which may contain the hetero atom is preferable, and even if it contains the hetero atom A good divalent hydrocarbon group having 4 to 10 carbon atoms is more preferred.

  Examples of such a divalent hydrocarbon group include an aliphatic hydrocarbon group that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or such an aliphatic carbon group. Examples thereof include a chain hydrocarbon group having a hydrogen group and / or an aromatic hydrocarbon group as a repeating unit.

  The aliphatic hydrocarbon group which may have a substituent may be a saturated group or an unsaturated group. Further, the structure may be any of linear, branched, or cyclic, and may be a combination of these structures. Examples of the aliphatic hydrocarbon group which may have such a substituent include an alkylene group which may have a substituent.

  Specific examples of the alkylene group which may have a substituent include a methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, butylene group, 2-methylpropylene group, pentamethylene group, pentylene group, 2 -Methyltetramethylene group, 2,2-dimethyltrimethylene group, 2-ethyltrimethylene group, hexamethylene group, hexylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, heptamethylene group, heptylene group, Octamethylene group, octylene group, 2-ethylhexylene group, nonamethylene group, nonylene group, decamethylene group, decylene group, cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group , Cyclononylene group, cyclodecylene group, Tylcyclobutylene group, methylcyclopentylene group, methylcyclohexylene group, methylcycloheptylene group, methylcyclooctylene group, ethylcyclobutylene group, ethylcyclopentylene group, ethylcyclohexylene group, ethylcycloheptylene group Group, ethylcyclooctylene group, dimethylcyclobutylene group, dimethylcyclopentylene group, dimethylcyclohexylene group, dimethylcycloheptylene group, dimethylcyclooctylene group, trimethylcyclobutylene group, trimethylcyclopentylene group, trimethylcyclohexene group Silene group, trimethylcycloheptylene group, trimethylcyclooctylene group, propylcyclobutylene group, propylcyclopentylene group, propylcyclohexylene group, propylcycloheptylene group, propylcycle An octylene group, a butylcyclobutylene group, a butylcyclopentylene group, a butylcyclohexylene group, a butylcycloheptylene group, a butylcyclooctylene group, and the like. These groups include a methoxy group, a hydroxy group, a chlorine atom, It may be substituted with a bromine atom, a fluorine atom or the like.

  Moreover, the aromatic hydrocarbon group which may have a substituent may have any ring structure of a monocyclic ring, a polycyclic ring, a condensed polycyclic ring, a bridged ring, or a combination polycyclic ring thereof. Examples of the aromatic hydrocarbon group which may have such a substituent include an arylene group which may have a substituent.

  Specific examples of the arylene group which may have a substituent include a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, a pyrenylene group, a naphthacenylene group, a fluorenylene group, and the like. A group, a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom or the like may be substituted.

  Among the divalent hydrocarbon groups described above, an aliphatic hydrocarbon group which may have a substituent is preferable, an alkylene group which may have a substituent is more preferable, and an unsubstituted alkylene group is more preferable. Particularly preferred.

  Specific examples of the chain transfer agent used in the present invention include 9-trans-eicosenyl-1,20-dimethacrylate and 4-cis-octenyl-1,8-dimethacrylate.

In the present invention, in the crosslinkable resin obtained by bulk polymerization of the polymerizable composition of the present invention by containing the chain transfer agent represented by the general formula (1), the cyclohexane constituting the resin is included. The -AQ ¹ group or -BQ ² group may be bonded to both ends of the olefin polymer. That is, a methacryloxy group, an acryloxy group, or an ethynyl group resulting from Q ¹ and Q ² in the general formula (1) is introduced at both ends of the cycloolefin polymer. And the methacryloxy group, the acryloxy group, or the ethynyl group introduced into both ends of the cycloolefin polymer constituting such a crosslinkable resin acts as a crosslinking point when the crosslinkable resin is crosslinked. Thereby, the action of the radical generator can increase the number of cross-linking points when the cross-linking reaction is performed, thereby improving the cross-linking density of the cross-linked resin molded product obtained by the cross-linking reaction. In addition to the effect of improving peel strength, the mechanical strength and heat resistance can be improved in a well-balanced manner.

The amount of the chain transfer agent used is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the cycloolefin monomer. If the amount of the chain transfer agent used is too small, it is difficult to obtain the effect of improving the crosslinking density. On the other hand, if the amount is too large, the molecular weight of the crosslinkable resin obtained by bulk polymerization may be reduced, and the mechanical strength may be reduced. There is.
In addition, as long as expression of the desired effect of this invention is not inhibited, you may use together well-known chain transfer agents other than the compound represented by General formula (1).

(Other ingredients)
In addition to the cycloolefin monomer, the metathesis polymerization catalyst, the radical generator and the chain transfer agent, the polymerizable composition of the present invention may optionally include a filler, a polymerization regulator, a polymerization reaction retarder, a reactive fluidizing agent. Other compounding agents such as a crosslinking aid, a flame retardant, an antioxidant, and a colorant can be added.

  The filler is not particularly limited as long as it is generally used industrially, and any of inorganic fillers and organic fillers can be used, but inorganic fillers are preferred. By mix | blending a filler with the polymeric composition of this invention, the mechanical strength and heat resistance of the resin molding which are obtained and a laminated body can be improved more.

  Examples of the inorganic filler include metal particles such as iron, copper, nickel, gold, silver, aluminum, lead, and tungsten; carbon particles such as carbon black, graphite, activated carbon, and carbon balloon; silica, silica balloon, alumina, Inorganic oxide particles such as titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, beryllium oxide, barium ferrite, strontium ferrite; inorganic carbonate particles such as calcium carbonate, magnesium carbonate, sodium hydrogen carbonate; calcium sulfate, etc. Inorganic sulfate particles; inorganic silicate particles such as talc, clay, mica, kaolin, fly ash, montmorillonite, calcium silicate, glass, glass balloon; titanate particles such as calcium titanate and lead zirconate titanate; Aluminum nitride, silicon carbide particles Whiskers, and the like. Examples of the organic filler include compound particles such as wood powder, starch, organic pigments, polystyrene, nylon, polyolefins such as polyethylene and polypropylene, vinyl chloride, and waste plastics. These fillers can be used alone or in combination of two or more.

  The blending amount of the filler is usually in the range of 1 to 1,000 parts by weight, preferably 10 to 500 parts by weight, more preferably 100 to 500 parts by weight with respect to 100 parts by weight of the cycloolefin monomer.

  The polymerization regulator is blended for the purpose of controlling the polymerization activity or improving the polymerization reaction rate. Specific examples thereof include trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium, tetra Examples thereof include alkoxy tin and tetraalkoxy zirconium. These polymerization regulators may be used alone or in combination of two or more. The use amount of the polymerization regulator is usually 1: 0.05 to 1: 100, preferably 1: 0.2 to 1:20, in a molar ratio of (metal atom in the metathesis polymerization catalyst: polymerization regulator). More preferably, it is in the range of 1: 0.5 to 1:10.

  When the polymerizable composition of the present invention contains a polymerization reaction retarder, an increase in viscosity is suppressed, which is preferable. Polymerization reaction retarders include phosphine compounds such as triphenylphosphine, tributylphosphine, trimethylphosphine, triethylphosphine, dicyclohexylphosphine, vinyldiphenylphosphine, allyldiphenylphosphine, triallylphosphine, styryldiphenylphosphine; Lewis bases such as aniline and pyridine Etc. can be used.

  The reactive fluidizing agent used in the present invention is an aliphatic carbon-carbon unsaturation that can participate in a ring-opening polymerization reaction such as a polymerizable carbon-carbon double bond or a vinyl group in a cycloolefin monomer. It is a monofunctional compound having one aliphatic carbon-carbon unsaturated bond or one organic group that does not have a bond and can participate in a crosslinking reaction induced by a radical generator and can be bonded to a polymer. As the reactive fluidizing agent, a monofunctional compound having no polymerizable aliphatic carbon-carbon unsaturated bond and having one crosslinkable aliphatic carbon-carbon unsaturated bond is preferable. The crosslinkable aliphatic carbon-carbon unsaturated bond that can be bonded to the polymer by participating in the crosslinking reaction induced by the radical generator includes, for example, a terminal vinylidene group in the compound constituting the reactive fluidizing agent. In particular, it preferably exists as an isopropenyl group or a methacryl group, and more preferably as a methacryl group. Examples of the organic group include an epoxy group, an isocyanate group, and a sulfo group.

  Examples of such reactive fluidizing agents include monofunctional compounds having one methacrylic group such as lauryl methacrylate, benzyl methacrylate, tetrahydrofurfuryl methacrylate, and methoxydiethylene glycol methacrylate; 1 isopropenyl group such as isopropenylbenzene. A monofunctional compound having one methacryl group, and the like. These reactive fluidizing agents can be used alone or in combination of two or more. The blending amount of the reactive fluidizing agent may be appropriately selected as desired, but is usually 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, more preferably 100 parts by weight of the cycloolefin monomer. Is 1-30 parts by weight.

  The crosslinking aid used in the present invention is preferably a compound having two or more crosslinkable carbon-carbon unsaturated bonds that do not participate in ring-opening polymerization and can participate in a crosslinking reaction induced by a radical generator. Such a crosslinkable carbon-carbon unsaturated bond is preferably present as a terminal vinylidene group, particularly as an isopropenyl group or a methacryl group, more preferably as a methacryl group, in the compound constituting the crosslinking aid. preferable.

  Specific examples of the crosslinking aid include polyfunctional compounds having two or more isopropenyl groups, such as p-diisopropenylbenzene, m-diisopropenylbenzene, o-diisopropenylbenzene; ethylene dimethacrylate, 1, 3 -Butylene dimethacrylate, 1,4-butylene dimethacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 2,2 2 or more methacrylic groups such as' -bis (4-methacryloxydiethoxyphenyl) propane, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate Such as a polyfunctional compound having may be mentioned. Especially, as a crosslinking adjuvant, the polyfunctional compound which has 2 or more of methacryl groups is preferable from a viewpoint of improving the heat resistance and crack resistance of the laminated body obtained. Among polyfunctional compounds having two or more methacryl groups, polyfunctional compounds having three methacryl groups such as trimethylolpropane trimethacrylate and pentaerythritol trimethacrylate are more preferable.

  The crosslinking assistants can be used alone or in combination of two or more. As a compounding quantity of the crosslinking adjuvant to the polymeric composition of this invention, it is 0.1-100 weight part normally with respect to 100 weight part of cycloolefin monomers, Preferably it is 0.5-50 weight part, More preferably Is 1-30 parts by weight.

  When both the reactive fluidizing agent and the crosslinking aid are blended, the blending ratio of the two may be appropriately selected as desired, but the weight ratio (reactive fluidizing agent / crosslinking aid) is usually 5 / The range is 95 to 90/10, preferably 10/90 to 70/30, and more preferably 15/85 to 70/30. If the blending ratio is in such a range, the flowability of the resin is improved in the resulting crosslinkable resin molded article, and the laminates are balanced with each of the properties of peel strength, heat resistance and crack resistance. is there.

  A particularly preferred combination of the reactive fluidizing agent and the crosslinking aid in the present invention includes a combination of benzyl methacrylate (reactive fluidizing agent) and trimethylolpropane trimethacrylate (crosslinking aid). If the combination is used, the resin flowability is improved in the resulting crosslinkable resin molded article, and the laminate is highly suitable for the properties of peel strength, heat resistance and crack resistance, which are highly balanced. is there.

  As a blending amount of the combination of the reactive fluidizing agent and the crosslinking aid into the polymerizable composition of the present invention (total blending amount of the reactive fluidizing agent and the crosslinking aid), the cycloolefin monomer is 100 weights. The amount is usually 0.2 to 200 parts by weight, preferably 1 to 100 parts by weight, and more preferably 2 to 60 parts by weight with respect to parts.

  The flame retardant is not particularly limited, and from known flame retardants, for example, halogen flame retardants, phosphorus-nitrogen flame retardants, phosphate ester flame retardants, nitrogen flame retardants, and inorganic flame retardants, It can be appropriately selected and used. What is necessary is just to adjust the compounding quantity suitably so that a desired effect may be acquired.

  By adding at least one antioxidant selected from the group consisting of phenolic antioxidants, amine-based antioxidants, phosphorus-based antioxidants and sulfur-based antioxidants as an antioxidant to the polymerizable composition It is preferable because the heat resistance of the obtained laminate can be improved to a high degree without inhibiting the crosslinking reaction. Among these, a phenolic antioxidant and an amine antioxidant are preferable, and a phenolic antioxidant is particularly preferable. These antioxidants may be used alone or in combination of two or more. The blending amount of the antioxidant is appropriately selected according to the purpose of use, but is usually 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, based on 100 parts by weight of the cycloolefin monomer. Preferably it is the range of 0.01-1 weight part.

  The polymerizable composition of the present invention can be obtained by mixing the above components. As a mixing method, a conventional method may be followed. For example, a liquid (catalyst solution) in which a metathesis polymerization catalyst is dissolved or dispersed in an appropriate solvent is added to each component such as a cycloolefin monomer, a radical generator, a chain transfer agent, And if desired, it can be prepared by adding to a liquid (monomer liquid) containing other compounding agents and stirring.

(Crosslinkable resin molding)
The crosslinkable resin molded article of the present invention can be obtained by bulk polymerization of the above-described polymerizable composition of the present invention. Examples of a method for obtaining a crosslinkable resin molded body by bulk polymerization of the polymerizable composition include, for example, (a) a method in which a polymerizable composition is applied on a support and then bulk polymerization, and (b) a polymerizable composition. Are injected into a mold, and then bulk polymerization is performed, and (c) a fibrous reinforcing material is impregnated with a polymerizable composition and then bulk polymerization is performed.

  Since the polymerizable composition of the present invention has a low viscosity, the application in the method (a) can be carried out smoothly, and in the injection in the method (b), even if it is a space portion having a complicated shape, the foam bite is rapidly formed. The polymerizable composition can be spread without causing it, and in the method (c), the fibrous reinforcing material can be impregnated with the polymerizable composition quickly and uniformly.

  According to the method (a), a crosslinkable resin molded product such as a film or plate can be obtained. The thickness of the molded body is usually 15 mm or less, preferably 5 mm or less, more preferably 0.5 mm or less, and most preferably 0.1 mm or less. Examples of the support include films and plates made of resins such as polyethylene terephthalate, polypropylene, polyethylene, polycarbonate, polyethylene naphthalate, polyarylate, and nylon; iron, stainless steel, copper, aluminum, nickel, chromium, gold, and silver. And films and plates made of metal materials such as Among these, use of a metal foil or a resin film is preferable. The thickness of the metal foil or resin film is usually 1 to 150 μm, preferably 2 to 100 μm, more preferably 3 to 75 μm, from the viewpoint of workability and the like. The metal foil preferably has a smooth surface, and the surface roughness (Rz) is a value measured by an AFM (atomic force microscope), usually 10 μm or less, preferably 5 μm or less, more preferably Is 3 μm or less, more preferably 2 μm or less. The surface of the metal foil is preferably treated with a known coupling agent or adhesive. According to the method (a), for example, when a copper foil is used as the support, a resin-coated copper foil (Resin Coated Copper (RCC)) can be obtained.

  Examples of the method for applying the polymerizable composition of the present invention on the support include known coating methods such as spray coating, dip coating, roll coating, curtain coating, die coating, and slit coating. .

  The polymerizable composition coated on the support is optionally dried and then bulk polymerized. Bulk polymerization is performed by heating the polymerizable composition at a predetermined temperature. The method for heating the polymerizable composition is not particularly limited, and the polymerizable composition applied to the support is heated on a heating plate, and heated (hot press) while being pressed using a press. Examples thereof include a method, a method of pressing with a heated roller, and a method of heating in a heating furnace.

  According to the method (b), a crosslinkable resin molded body having an arbitrary shape can be obtained. Examples of the shape include a sheet shape, a film shape, a column shape, a columnar shape, and a polygonal column shape.

  As the mold used here, a conventionally known mold, for example, a split mold structure, that is, a mold having a core mold and a cavity mold, can be used, and a polymerizable composition is formed in these voids (cavities). Is injected to cause bulk polymerization. The core mold and the cavity mold are produced so as to form a gap that matches the shape of the target molded product. The shape, material, size, etc. of the mold are not particularly limited. Furthermore, a plate-shaped mold such as a glass plate or a metal plate and a spacer having a predetermined thickness are prepared, and the polymerizable composition is injected into a space formed by sandwiching the spacer between two plate-shaped molds. By carrying out bulk polymerization, a sheet-like or film-like crosslinkable resin molded article can also be obtained.

  The filling pressure (injection pressure) when filling the polymerizable composition into the cavity of the mold is usually 0.01 to 10 MPa, preferably 0.02 to 5 MPa. If the filling pressure is too low, the transfer surface formed on the inner peripheral surface of the cavity tends not to be transferred well. If the filling pressure is too high, the mold must be rigid and economical. is not. The mold clamping pressure is usually in the range of 0.01 to 10 MPa. Examples of the method for heating the polymerizable composition include a method using a heating means such as an electric heater and steam disposed in the mold, and a method for heating the mold in an electric furnace.

  The method (c) is suitably used for obtaining a sheet-like or film-like crosslinkable resin molded article. For example, the impregnation of the polymerizable composition into the fibrous reinforcing material is performed by using a predetermined amount of the polymerizable composition such as a spray coating method, a dip coating method, a roll coating method, a curtain coating method, a die coating method, and a slit coating method. It can apply by apply | coating to a fibrous reinforcement by a well-known method, stacking a protective film on it as needed, and pressing with a roller etc. from an upper side. After impregnating the polymerizable composition with the fibrous reinforcing material, the impregnated material is heated to a predetermined temperature to cause the polymerizable composition to undergo bulk polymerization to obtain a desired crosslinkable resin molded article.

  As the fibrous reinforcing material, inorganic and / or organic fibers can be used, such as glass fibers, metal fibers, ceramic fibers, carbon fibers, aramid fibers, polyethylene terephthalate fibers, vinylon fibers, polyester fibers, amide fibers, Examples include known liquid crystal fibers such as polyarylate. These can be used individually by 1 type or in combination of 2 or more types. The shape of the fibrous reinforcing material is not particularly limited, and examples thereof include mats, cloths, and nonwoven fabrics.

  Examples of the heating method of the impregnated product obtained by impregnating the fibrous reinforcing material with the polymerizable composition include, for example, a method in which the impregnated product is placed on a support and heated as in the method (a) above, Examples thereof include a method in which a fibrous reinforcing material is placed in the mold, an impregnated product is obtained by impregnating the polymerizable composition in the mold, and heating is performed as in the method (b).

  The thickness of the crosslinkable resin molded product obtained by the method (c) is not particularly limited, but is usually 1 μm to 10 mm. Moreover, what is necessary is just to select suitably content of the fibrous reinforcement in this molded object according to a use purpose, However, Usually, it is 5-50 volume%, Preferably it is the range of 15-40 volume%. If the content of the fibrous reinforcing material is within this range, the obtained laminate is suitable because the mechanical strength and the dielectric properties are highly balanced.

  In any of the methods (a), (b) and (c), the heating temperature for polymerizing the polymerizable composition is usually 30 to 250 ° C, preferably 50 to 200 ° C, more preferably 90. It is in the range of ˜150 ° C. and is usually 1 minute half-life temperature or less of the radical generator, preferably 10 minutes or less of 1-minute half-life temperature, more preferably 20 ° C. or less of 1-minute half-life temperature. . The polymerization time may be appropriately selected, but is usually 1 second to 20 minutes, preferably 10 seconds to 5 minutes. Heating the polymerizable composition under such conditions is preferable because a crosslinkable resin molded article with less unreacted monomer can be obtained.

  The polymer (cycloolefin polymer) constituting the crosslinkable resin molded article obtained as described above has substantially no crosslink structure and is soluble in, for example, toluene. The molecular weight of the polymer is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (eluent: tetrahydrofuran), and is usually 1,000 to 1,000,000, preferably 5,000 to It is in the range of 500,000, more preferably 10,000 to 100,000.

  The crosslinkable resin molded article of the present invention is a post-crosslinkable resin molded article, but a part of the constituent resin may be crosslinked. For example, when the polymerizable composition is bulk-polymerized in the mold, the temperature of a part of the mold may become too high because the polymerization reaction heat hardly diffuses in the central part of the mold. In the high temperature part, a cross-linking reaction occurs, and cross-linking may occur. However, the crosslinkable resin molded article of the present invention can exhibit a desired effect as long as the surface portion that easily dissipates heat is formed of a crosslinkable resin that can be postcrosslinked.

The crosslinkable resin molded article of the present invention is obtained by completing bulk polymerization, and there is no possibility that the polymerization reaction further proceeds during storage. In addition, the crosslinkable resin molded article of the present invention contains a radical generator, but unless it is heated to a temperature higher than that causing a crosslinking reaction, it does not cause problems such as a change in surface hardness and is excellent in storage stability. .
The crosslinkable resin molded article of the present invention is suitably used for the production of the crosslinked resin molded article and laminate of the present invention, for example, as a prepreg.

(Crosslinked resin molding)
The crosslinked resin molded article of the present invention is obtained by bulk polymerization of the above-described polymerizable composition of the present invention and crosslinking. Such a crosslinked resin molded body can be obtained, for example, by crosslinking the above-described crosslinkable resin molded body of the present invention. Crosslinking of the crosslinkable resin molded body can be performed by maintaining the molded body at a temperature equal to or higher than a temperature at which a crosslinking reaction occurs in the base resin. The heating temperature is usually equal to or higher than the temperature at which a crosslinking reaction is induced by the radical generator. Specifically, the temperature is one minute half-life temperature of the radical generator or more, preferably 5 ° C. or more higher than the one-minute half-life temperature, more preferably 10 ° C. or more higher than the one-minute half-life temperature. Typically, it is in the range of 100 to 300 ° C, preferably 150 to 250 ° C. The heating time is in the range of 0.1 to 180 minutes, preferably 0.5 to 120 minutes, more preferably 1 to 60 minutes. Further, by maintaining the polymerizable composition of the present invention at a temperature equal to or higher than the temperature at which the crosslinkable resin molded article is crosslinked, specifically, by heating at the temperature and time described herein, the cycloolefin monomer It is also possible to produce the crosslinked resin molded article of the present invention by proceeding together with the bulk polymerization of the polymer and the crosslinking reaction in the cycloolefin polymer produced by the polymerization. Thus, when manufacturing a crosslinked-resin molded object, according to the method of said (a), if copper foil is used as a support body, a copper clad laminated board [Copper Clud Laminates (CCL)] can be obtained, for example. .

(Laminate)
The laminate of the present invention comprises at least a layer comprising the above-described crosslinkable resin molded product of the present invention or the above-described crosslinked resin molded product of the present invention. Both molded bodies may be continuously laminated or indirectly laminated with another layer interposed therebetween.
As a laminated body formed by laminating the crosslinkable resin molded body of the present invention, for example, RCC obtained by integrating the copper foil and the crosslinkable resin molded body in a layered manner obtained by the method (a) can be mentioned. . Moreover, as a laminated body formed by laminating the cross-linked resin molded body of the present invention, for example, CCL obtained by integrating the copper foil and the cross-linked resin molded body in a layered manner is obtained according to the method (a). Can be mentioned. In the method (a), if a separately obtained crosslinked resin molded body is used as the support, a laminate of the crosslinkable resin molded body and the crosslinked resin molded body can be obtained.

  In addition, a sheet-like or film-like crosslinkable resin molded article and, if desired, a sheet-like or film-like crosslinked resin molded article are optionally laminated, or further, for example, the metal foil is laminated and hot-pressed. By cross-linking, the laminate of the present invention obtained by laminating the cross-linked resin molded product is obtained. In that case, you may laminate | stack laminated bodies, such as said RCC and CCL. The pressure at the time of hot pressing is usually 0.5 to 20 MPa, preferably 3 to 10 MPa. The hot pressing may be performed in a vacuum or a reduced pressure atmosphere. The hot pressing can be performed using a known press having a press frame mold for flat plate forming, a press molding machine such as a sheet mold compound (SMC) or a bulk mold compound (BMC).

  The laminate of the present invention has a layer made of the crosslinkable resin molded body or the crosslinked resin molded body of the present invention. Since the crosslinkable resin molded body or the crosslinked resin molded body of the present invention is obtained by using the above-described polymerizable composition of the present invention, the laminate of the present invention has a low dielectric loss and is a machine. The mechanical strength, heat resistance and peel strength are excellent in balance, and can be suitably used for the production of a multilayer circuit board for high frequency.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, unless otherwise indicated, the part and% in each example are a basis of weight. Various physical properties were evaluated according to the following methods.

(1) Peel strength The strength when the copper foil was peeled from the copper clad laminate was measured according to JIS C6481, and the peel strength was evaluated according to the following criteria.
〔Evaluation criteria〕
A: More than 0.4 kN / m B: More than 0.35 kN / m, 0.4 kN / m or less C: 0.35 kN / m or less

(2) Heat resistance After etching the copper-clad laminate to remove the copper foil from the copper-clad laminate, the glass transition point of the crosslinked resin molded product (SS6100 standard type, manufactured by SII Nanotechnology Inc.) ( Tg) was measured, and the heat resistance was evaluated according to the following criteria.
〔Evaluation criteria〕
A: Tg is over 180 ° C B: Tg is over 175 ° C, 180 ° C or less C: Tg is 175 ° C or less

Example 1
A catalyst solution was prepared by dissolving 51 parts of benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and 79 parts of triphenylphosphine in 952 parts of toluene. Separately, 80 parts of tetracyclododecene (TCD) as a cycloolefin monomer, 20 parts of dicyclopentadiene, and silicon oxide particles as a filler (manufactured by Admatechs, trade name SOC02, average particle size 0.5 μm) 200 5 parts of 9-trans-eicosenyl-1,20-dimethacrylate (chain transfer agent having a methacryloxy group at both ends) as a chain transfer agent, di-t-butyl peroxide (1 minute half-life as a radical generator) A monomer solution was prepared by mixing 3.4 parts of a temperature of 186 ° C. and 42 parts of trimethylolpropane trimethacrylate as a crosslinking aid. And the catalyst liquid prepared above was added to the obtained monomer liquid in the ratio of 0.12 mL per 100 g of cycloolefin monomers, and it stirred, and prepared the polymeric composition.

  Then, the polymerizable composition obtained above was impregnated into a glass cloth (E glass) having a thickness of 70 μm and maintained at 120 ° C. for 5 minutes, and the polymerizable composition was subjected to bulk polymerization to obtain a thickness of 0. A prepreg of 11 mm (crosslinkable resin molded product) was obtained. The glass cloth content of the obtained prepreg was 25% by volume.

  Next, 6 sheets of the prepreg obtained above were stacked and laminated with 2 sheets of 12 μm thick F2 copper foil (silane coupling agent-treated electrolytic copper foil, roughness Rz = 1,600 nm, manufactured by Furukawa Circuit Foil Co., Ltd.). The prepreg sheet thus obtained was sandwiched and heated and pressed at 3 MPa for 20 minutes at 205 ° C. to obtain a copper-clad laminate (a laminate in which cross-linked resin molded bodies were laminated). And each evaluation of peel strength and heat resistance was performed using the obtained copper clad laminated board. The results are shown in Table 1.

Example 2
A polymerizable composition and a copper clad laminate were prepared in the same manner as in Example 1 except that the amount of 9-trans-eicosenyl-1,20-dimethacrylate as a chain transfer agent was changed from 5 parts to 10 parts. Obtained and evaluated in the same manner. The results are shown in Table 1.

Example 3
A polymerizable composition and a copper clad laminate were prepared in the same manner as in Example 1 except that the amount of 9-trans-eicosenyl-1,20-dimethacrylate as a chain transfer agent was changed from 5 parts to 20 parts. Obtained and evaluated in the same manner. The results are shown in Table 1.

Example 4
As a chain transfer agent, in place of 5 parts of 9-trans-eicosenyl-1,20-dimethacrylate, 5 parts of 4-cis-octenyl-1,8-dimethacrylate (chain transfer agent having methacryloxy groups at both ends) Except having used, it carried out similarly to Example 1, and obtained the polymeric composition and the copper clad laminated board, and evaluated it similarly. The results are shown in Table 1.

Comparative Example 1
As chain transfer agent, instead of 5 parts of 9-trans-eicosenyl-1,20-dimethacrylate, undecenyl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK Economer ML”, methacryloxy group only at one end Polymeric composition and copper clad laminate were obtained and evaluated in the same manner as in Example 1 except that 2.7 parts of chain transfer agent) were used. The results are shown in Table 1.

  From Table 1, it can be seen that the laminates produced using the polymerizable compositions obtained in Examples 1 to 4 are excellent in balance between peel strength and heat resistance (high glass transition point). On the other hand, in Comparative Example 1, when the chain transfer agent having functional groups at both ends was not added to the polymerizable composition, the obtained laminate was peel strength compared to the laminates of Examples 1 to 4. Is equivalent, but it is understood that the heat resistance is inferior.

Claims (6)

A polymerizable composition comprising a cycloolefin monomer, a metathesis polymerization catalyst, a radical generator, and a chain transfer agent represented by the following general formula (1).
Q ¹ -A-CH = CH-BQ ² (1)
(In the general formula (1), Q ¹ and Q ² are each independently a methacryloxy group, an acryloxy group, or an ethynyl group, and A and B each independently contain a vinyl group and a vinylene group in the chemical structure. There are no divalent organic groups.)   The polymerizable composition according to claim 1, wherein the divalent organic group is a C 1-10 divalent hydrocarbon group which may contain a hetero atom.   The polymerizable composition according to claim 1 or 2, wherein the cycloolefin monomer has a crosslinkable carbon-carbon unsaturated bond.   A crosslinkable resin molded article obtained by bulk polymerization of the polymerizable composition according to claim 1.   A crosslinked resin molded article obtained by bulk polymerization of the polymerizable composition according to claim 1 and crosslinking.   A laminate comprising at least a layer comprising the crosslinkable resin molded article according to claim 4 or the crosslinked resin molded article according to claim 5.