JP5278306B2 - Polymerizable composition, resin molded body, and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable composition which has an extremely low dielectric dissipation factor in a high frequency region and is useful for production of a laminate excellent in wiring embedding property and heat resistance; a crosslinkable resin molded product; a crosslinked resin molded product; and a laminate obtained by using them. <P>SOLUTION: The polymerizable composition comprises a cycloolefin monomer; a polymerization catalyst; a crosslinking agent; a monofunctional compound having one vinylidene group; a bifunctional compound having two vinylidene groups; and a trifunctional compound having three vinylidene groups. The content ratio of the monofunctional compound, the bifunctional compound, and the trifunctional compound is 10-80:10-80:5-40 (monofunctional compound: bifunctional compound: trifunctional compound) in weight ratio. The crosslinkable resin molded product and crosslinked resin molded product formed by using the polymerizable composition, and the laminate having a layer formed of the crosslinkable resin molded product or the crosslinked resin molded product are also provided. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a polymerizable composition, a resin molded body, and a laminate. Specifically, a polymerizable composition, a crosslinkable resin molded body, a crosslinkable resin molded body, and those useful for the production of a laminate having a very low dielectric loss tangent in a high frequency region and excellent wiring embedding property and heat resistance, and those It is related with the laminated body obtained using this.

  In recent years, with the advent of advanced information technology, information transmission has begun to increase in speed and frequency, and microwave communication and millimeter wave communication have become a reality. For these circuit boards in the high frequency era, a material having a low dielectric loss tangent is required in order to reduce transmission loss at high frequencies to the limit. As a resin material having a small dielectric loss tangent, a cycloolefin polymer obtained by polymerizing a cycloolefin monomer has attracted attention.

  As a circuit board material using a cycloolefin polymer, for example, in Patent Document 1, a reinforcing fiber is impregnated with a polymerizable composition containing a cycloolefin monomer, a metathesis polymerization catalyst, a crosslinking agent, a chain transfer agent, and a dimethacrylate compound. A prepreg obtained by subsequent polymerization and a laminate obtained by laminating and curing the prepreg are disclosed. Such a prepreg uses a cycloolefin polymer as a base resin, and exhibits excellent resin fluidity (fluidity of the base resin) at the time of heat-curing, and the obtained laminate includes a cured product of the prepreg and a circuit board. It is described that it is excellent in peeling strength (peel strength).

  By the way, regarding the insulation treatment of electrical equipment, Patent Document 2 discloses a highly moisture-resistant resin composition for electrical insulation using unsaturated polyester as a base resin, which is excellent in moisture resistance of a cured product and is suitably used for the treatment. Is disclosed. Acrylic acid ester or methacrylic acid ester contained as a reactive monomer in the composition may be used in combination of two or more as appropriate in consideration of the adhesion between the cured product of the composition and the adherend. Is described.

JP 2009-242568 A JP 2005-285424 A

The inventors of the present invention obtained a prepreg and a laminate according to Patent Document 1 and investigated their characteristics. The resin fluidity of the prepreg and the wiring embedding property of the laminate were good, but the heat resistance of the laminate was Became inferior. On the other hand, in Patent Document 2, a cycloolefin polymer is used as a base resin, and a reactive monomer is appropriately combined to obtain a resin composition. Using such a composition, the method described in Patent Document 1 is used. When a laminate was obtained and its properties were examined, the composition did not provide sufficient resin fluidity at the time of heat curing, and the resulting laminate was inferior in wiring embedding and insufficient in heat resistance. It became clear that there was.
An object of the present invention is to provide a polymerizable composition, a crosslinkable resin molded article, and a crosslinked resin molded article useful for the production of a laminate having a very low dielectric loss tangent in a high frequency region and excellent wiring embedding property and heat resistance. And it is providing the laminated body obtained by using them.

  As a result of intensive studies in view of the above-mentioned problems, the present inventors have obtained a polymerizable compound containing a monofunctional, bifunctional, and trifunctional methacrylate compound at a predetermined ratio as a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, and a crosslinking aid. According to the composition, a prepreg excellent in resin fluidity at the time of heat curing can be obtained. According to the prepreg, a laminate having an extremely small dielectric loss tangent in a high frequency region, excellent in wiring embedding property, and heat resistance can be obtained. It was found that it can be obtained. Based on this knowledge, the inventors have completed the present invention.

That is, according to the present invention,
[1] a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, a monofunctional compound having one vinylidene group, a bifunctional compound having two vinylidene groups, and a trifunctional compound having three vinylidene groups, and Polymerization in which the content ratio of the monofunctional compound, the bifunctional compound, and the trifunctional compound is 10 to 80:10 to 80: 5 to 40 by weight ratio (monofunctional compound: bifunctional compound: trifunctional compound) Sex composition,
[2] The polymerizable composition according to [1], wherein the monofunctional compound is a monofunctional methacrylate compound, the bifunctional compound is a bifunctional methacrylate compound, and the trifunctional compound is a trifunctional methacrylate compound,
[3] The polymerizable composition according to [1] or [2], further containing a filler,
[4] The polymerizable composition according to any one of [1] to [3], further containing a chain transfer agent,
[5] A crosslinkable resin molded article obtained by bulk polymerization of the polymerizable composition according to any one of [1] to [4],
[6] A crosslinked resin molded product obtained by crosslinking a polymer obtained by bulk polymerization of the polymerizable composition according to any one of [1] to [4], and [7] at least in the above [5]. Or a laminate comprising a layer made of the crosslinked resin molded article according to [6],
Is provided.

  According to the present invention, a polymerizable composition, a crosslinkable resin molded body, and a crosslinked resin molded body, which are useful for producing a laminate having an extremely small dielectric loss tangent in a high frequency region and excellent wiring embedding property and heat resistance, And the laminated body which has the said characteristic can be provided. The laminate of the present invention can be suitably used for the production of high-frequency circuit boards such as microwaves or millimeter waves used for communication equipment applications.

  The polymerizable composition of the present invention comprises a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, a monofunctional compound having one vinylidene group, a bifunctional compound having two vinylidene groups, and a trifunctional compound having three vinylidene groups. The content ratio of the monofunctional compound, the bifunctional compound, and the trifunctional compound is 10 to 80:10 to 80: 5 in a weight ratio (monofunctional compound: bifunctional compound: trifunctional compound). ~ 40.

(Cycloolefin monomer)
The cycloolefin monomer used in the present invention is a compound having an alicyclic structure formed of carbon atoms and having one polymerizable carbon-carbon double bond in the alicyclic structure. As used herein, “polymerizable carbon-carbon double bond” refers to a carbon-carbon double bond capable of chain polymerization (ring-opening polymerization). There are various types of ring-opening polymerization, such as ionic polymerization, radical polymerization, and metathesis polymerization. In the present invention, it generally refers to metathesis ring-opening polymerization.

Examples of the alicyclic structure of the cycloolefin monomer include monocycles, polycycles, condensed polycycles, bridged rings, and combination polycycles thereof. Although there is no limitation in particular in carbon number which comprises each alicyclic structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces.
The cycloolefin monomer has a hydrocarbon group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkylidene group, and an aryl group, and a polar group such as a carboxyl group or an acid anhydride group as a substituent. However, from the viewpoint of making the obtained laminate a low dielectric loss tangent, those having no polar group, that is, comprising only carbon atoms and hydrogen atoms are preferable.

  As the cycloolefin monomer, either a monocyclic cycloolefin monomer or a polycyclic cycloolefin monomer can be used. From the viewpoint of highly balancing the dielectric properties and heat resistance properties of the resulting laminate, polycyclic cycloolefin monomers are preferred. As the polycyclic cycloolefin monomer, a norbornene-based monomer 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.

As the cycloolefin monomer, any of those having no crosslinkable carbon-carbon unsaturated bond and those having one or more crosslinkable carbon-carbon unsaturated bonds can be used. As used herein, “crosslinkable carbon-carbon unsaturated bond” refers to a carbon-carbon unsaturated bond that does not participate in ring-opening polymerization and can participate in a crosslinking reaction. The cross-linking reaction is a reaction that forms a bridge structure, and there are various forms such as a condensation reaction, an addition reaction, a radical reaction, and a metathesis reaction. It refers to a 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 one or more crosslinkable carbon-carbon unsaturated bonds, the position of the unsaturated bond is not particularly limited, and in addition to the alicyclic structure formed by carbon atoms, other than the alicyclic structure It may be present at any position of, for example, at the end or inside of the side chain. For example, the aliphatic carbon-carbon double bond may exist as a vinyl group (CH ₂ ═CH—), a vinylidene group (CH ₂ ═C <), or a vinylene group (—CH═CH—). Since it exhibits radical crosslinking reactivity, it is preferably present as a vinyl group and / or vinylidene group, and more preferably as a vinylidene group.

  Examples of cycloolefin monomers having no crosslinkable carbon-carbon unsaturated bond include cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, and 3-chlorocyclopentene. Monocyclic cycloolefin monomers such as cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, and cycloheptene; norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-propyl-2-norbornene, 5,6-dimethyl-2-norbornene, 1-methyl-2-norbornene, 7-methyl-2-norbornene, 5,5,6-trimethyl- 2-norbornene, 5- Enyl-2-norbornene, tetracyclododecene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene (TCD), 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, , 5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 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-dihydrodicyclopentadiene, 5-chloro-2-norbornene, 5,5-dichloro-2-norbornene, 5-fluoro- 2-norbornene, 5,5,6-trifluoro-6-tri Fluoromethyl-2-norbornene, 5-chloromethyl-2-norbornene, 5-methoxy-2-norbornene, 5,6-dicarboxyl-2-norbornene anhydrate, 5-dimethylamino-2-norbornene, and 5- Norbornene monomers such as cyano-2-norbornene; and norbornene monomers having no crosslinkable carbon-carbon unsaturated bond are preferable.

Examples of the cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds 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, and 1,3-cyclooctadiene; 5-ethylidene-2-norbornene, 5- Methylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 5,6-diethylidene-2-norbornene, dicyclopentadiene, and 2,5- Norbornene-based monomers such as norbornadiene; Ku crosslinkable carbon - is a norbornene-based monomer having one or more carbon unsaturated bond.
These cycloolefin monomers can be used alone or in combination of two or more.

The cycloolefin monomer used in the present invention preferably includes a cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds. When such a cycloolefin monomer is used, the reliability of the obtained laminate is improved, which is preferable.
In the cycloolefin monomer blended in the polymerizable composition of the present invention, a blend of a cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds and a cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bonds The ratio may be appropriately selected as desired, but the weight ratio value (cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond / cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond). Usually, it is in the range of 5/95 to 100/0, preferably 10/90 to 90/10, more preferably 15/85 to 70/30. If the said mixture ratio exists in this range, in the laminated body obtained, heat resistance can be improved highly and it is suitable.

  In addition, as long as expression of the effect of this invention is not inhibited, the polymerizable composition of this invention may contain the arbitrary monomers copolymerizable with the above cycloolefin monomer.

(Polymerization catalyst)
The polymerization catalyst used in the present invention is not particularly limited as long as it can polymerize the cycloolefin monomer, but the polymerizable composition of the present invention is directly agglomerated in the production of a crosslinkable resin molded article described later. It is preferable to use it for polymerization, and it is usually preferable to use a metathesis polymerization catalyst.

  Examples of the metathesis polymerization catalyst include a complex formed by bonding a plurality of ions, atoms, polyatomic ions, compounds, etc. with a transition metal atom as a central atom, which is capable of metathesis ring-opening polymerization of the cycloolefin monomer. It is done. As transition metal atoms, atoms of Group 5, Group 6, and Group 8 (according to the long-period periodic table; the same applies hereinafter) are used. Although the atoms of each group are not particularly limited, examples of the Group 5 atom include tantalum, examples of the Group 6 atom include molybdenum and tungsten, and examples of the Group 8 atom include: Examples include ruthenium and osmium. Among them, the group 8 ruthenium or osmium is preferable as the transition metal atom. 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. As the complex having ruthenium as a central atom, a ruthenium carbene complex in which a carbene compound is coordinated to ruthenium is preferable. Here, the “carbene compound” is a general term for compounds having a methylene free group, and refers to a compound having an uncharged divalent carbon atom (carbene carbon) as represented by (> C :). Since the ruthenium carbene complex is excellent in catalytic activity during bulk polymerization, when the crosslinkable resin molded body is obtained by subjecting the polymerizable composition of the present invention to bulk polymerization, the resulting molded body is derived from unreacted monomers. A molded article with low odor and good productivity can be obtained. In addition, it is relatively stable to oxygen and moisture in the air and is not easily deactivated, so that it can be used even in the atmosphere.

  Specific examples of the ruthenium carbene complex include complexes represented by the following formula (1) or formula (2).

In the formulas (1) and (2), R ¹ and R ² each independently include a hydrogen atom; a halogen atom; or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. It represents a good cyclic or chain hydrocarbon group having 1 to 20 carbon atoms. X ¹ and X ² each independently 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 heteroatom means an atom of groups 15 and 16 of the periodic table, and specifically, a nitrogen atom (N), an oxygen atom (O), a phosphorus atom (P), a sulfur atom (S), an arsenic atom (As), a selenium atom (Se), etc. can be mentioned. Among these, N, O, P, and S are preferable from the viewpoint of obtaining a stable carbene compound, and N is particularly preferable.

  As the ruthenium carbene complex, the mechanical strength and impact resistance of the resulting crosslinked resin molded product and laminate can be highly balanced, so that a carbene compound having a heterocyclic structure is coordinated as a heteroatom-containing carbene compound. What has at least 1 child is preferable. As the heterocyclic structure, an imidazoline ring structure or an imidazolidine ring structure is preferable.

  Examples of the carbene compound having a heterocyclic structure include compounds represented by the following formula (3) or formula (4).

In the formulas (3) and (4), R ^{3 to} R ⁶ each independently include a hydrogen atom; a halogen atom; or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Represents a good 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.

  Examples of the compound represented by the formula (3) or the formula (4) include 1,3-dimesitylimidazolidin-2-ylidene, 1,3-di (1-adamantyl) imidazolidin-2-ylidene, 1 , 3-dicyclohexylimidazolidine-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-di (1-phenyl) Ethyl) -4-imidazoline-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene, and the like.

  In addition to the compound represented by the formula (3) or formula (4), 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- 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 formulas (1) and (2), the anionic (anionic) ligands X ¹ and X ² are ligands having a negative charge when separated from the central atom. For example, halogen atoms such as fluorine atom (F), chlorine atom (Cl), bromine atom (Br), and iodine atom (I), diketonate group, substituted cyclopentadienyl group, alkoxy group, aryloxy group, and carboxyl Examples include groups. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

  The neutral electron-donating compound may be any ligand as long as it has a neutral charge when it is separated from the central atom. 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 ruthenium carbene complex represented by the formula (1) include benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-4, 5-dibromo-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4-imidazoline-2-ylidene) (3-phenyl-1H-indene-1-ylidene) (tri Cyclohexylphosphine) ruthenium dichloride, (1,3-dimesitylimidazolidine-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl- Octahydrobenzi Dazol-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-triazol-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylid (1,3-Dimesitylimidazolidin-2-ylidene) pyridine ruthenium dichloride, (1,3-Dimesitylimidazolidin-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 and (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) (2-pyrrolidone-1-ylmethylene) (tricyclohexylphosphine) ruthenium Dichloride Which is a ruthenium carbene complex in which a heteroatom-containing carbene compound and a neutral electron-donating compound are each bonded;

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

  Two heteroatom-containing carbene compounds such as benzylidenebis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride and benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride bonded together Ruthenium carbene complex; and the like.

  Examples of the ruthenium carbene complex represented by the formula (2) include (1,3-dimesitylmimidazolidine-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 ruthenium carbene complexes, those having one compound represented by the formula (1) and represented by the formula (4) as a ligand are most preferable.

  These ruthenium carbene complexes can be produced by the methods described in Org. Lett., 1999, Vol. 1, page 953, Tetrahedron. Lett., 1999, Vol. 40, page 2247, and the like.

  The metathesis polymerization catalysts may be used alone or in combination of two or more. The amount of the metathesis polymerization catalyst used is a molar ratio (metal atom in the metathesis polymerization catalyst: cycloolefin monomer) and is usually from 1: 2,000 to 1: 2,000,000, preferably from 1: 5,000 to 1. : 1,000,000, more preferably in the range of 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, diethyl Cycloaliphatic hydrocarbons such as cyclohexane, decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; alicyclic rings such as indene and tetrahydronaphthalene And hydrocarbons having an aromatic ring; 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 a chain aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, and a hydrocarbon having an alicyclic ring and an aromatic ring.

(Crosslinking agent)
The crosslinking agent used in the present invention is used for the purpose of inducing a crosslinking reaction in a polymer (cycloolefin polymer) obtained by subjecting the polymerizable composition of the present invention to a polymerization reaction. Accordingly, the polymer can be a post-crosslinkable thermoplastic resin. Here, “after-crosslinking is possible” means that the resin can be heated to advance a crosslinking reaction to form a crosslinked resin. Although the crosslinkable resin molded product of the present invention using the polymer as a base resin melts by heating, it retains its shape because of its high viscosity. On the other hand, when an arbitrary member is contacted, , Exhibit followability to the shape of the member, and finally crosslink and cure. Such characteristics of the crosslinkable resin molded article of the present invention contribute to the development of interlayer adhesion and wiring embedding in a laminate obtained by laminating, melting, and crosslinking the crosslinkable resin molded article of the present invention. It is considered a thing.

  Although it does not specifically limit as a crosslinking agent in this invention, Usually, a radical generator is used suitably. Examples of the radical generator include organic peroxides, diazo compounds, and nonpolar radical generators, and organic peroxides and nonpolar radical generators are preferable.

  Examples of the organic peroxide include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, and 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, and 2,5-dimethyl-2,5- Dialkyl peroxides such as di (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)- Peroxyketals such as 2-methylcyclohexane and 1,1-di (t-butylperoxy) cyclohexane; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; t-butylperoxyisopropylcarbonate and di Peroxycarbonates such as (isopropylperoxy) dicarbonate; alkylsilyl peroxides such as t-butyltrimethylsilyl peroxide; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, 3,6,9- Cyclic peroxides such as triethyl-3,6,9-trimethyl-1,4,7-triperoxonan and 3,6-diethyl-3,6-dimethyl-1,2,4,5-tetroxane; Is mentioned. Among these, dialkyl peroxides, peroxyketals, and cyclic peroxides are preferable in that there are few obstacles to the polymerization reaction.

  Examples of the diazo compound include 4,4'-bisazidobenzal (4-methyl) cyclohexanone and 2,6-bis (4'-azidobenzal) cyclohexanone.

  Nonpolar radical generators include 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1,1,2-triphenylethane, and 1,1,1 -Triphenyl-2-phenylethane and the like.

  When a radical generator is used as a crosslinking agent, the half-life temperature for 1 minute is appropriately selected depending on the conditions of curing (crosslinking of a polymer obtained by subjecting the polymerizable composition of the present invention to a polymerization reaction). , 100 to 300 ° C, preferably 150 to 250 ° C, more preferably 160 to 230 ° C. Here, the half-life temperature for 1 minute 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 radical generators can be used alone or in combination of two or more. The amount of radical generator added to the polymerizable composition of the present invention is usually 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 100 parts by weight of cycloolefin monomer. Is in the range of 0.5 to 5 parts by weight.

(Crosslinking aid)
The polymerizable composition of the present invention includes a monofunctional compound having one vinylidene group (hereinafter sometimes simply referred to as a monofunctional compound) and a bifunctional compound having two vinylidene groups (hereinafter simply referred to as a bifunctional compound). And trifunctional compounds having three vinylidene groups (hereinafter sometimes simply referred to as trifunctional compounds) are used, and these compounds function as a crosslinking aid. None of these compounds participate in the ring-opening polymerization reaction, but can participate in the crosslinking reaction induced by the crosslinking agent by the vinylidene group. In the polymerizable composition of the present invention, the monofunctional compound, the bifunctional compound, and the trifunctional compound are used in a weight ratio of 10 to 80:10 to 80: 5 to 40.

As described above, the polymer obtained by subjecting the polymerizable composition of the present invention to a polymerization reaction can be a post-crosslinkable thermoplastic resin. The crosslinkable resin molded article of the present invention uses such a polymer as a base resin.
All of the monofunctional compound, bifunctional compound and trifunctional compound used in the present invention are present in a substantially free state in the polymer constituting the crosslinkable resin molded article of the present invention. A plasticizing effect is exerted on the polymer. Therefore, when the molded body is heated, the polymer melts and exhibits an appropriate fluidity. On the other hand, when the molded body is continuously heated, a crosslinking reaction is induced by the crosslinking agent. However, the monofunctional compound, the bifunctional compound, and the trifunctional compound are all involved in the crosslinking reaction and have a binding reactivity to the polymer. As shown, as the cross-linking reaction proceeds, it is presumed that what is present in a free state decreases, and at the end of the cross-linking reaction, there is substantially no free state. Monofunctional compounds, bifunctional compounds and trifunctional compounds exhibit the properties as described above, but the binding reactivity to the polymer appears to be higher in the order of monofunctional compounds, bifunctional compounds and trifunctional compounds. The plastic effect can be expressed longer in the order of trifunctional compound, bifunctional compound, and monofunctional compound. The crosslinking aid is used for the purpose of increasing the crosslink density in the resulting laminate and improving the heat resistance of the laminate, but is a polymer that constitutes the molded body when the crosslinkable resin molded body is heated. When a cross-linked structure is formed, sufficient polymer fluidity cannot be obtained, and the followability of the cross-linkable resin molded body surface to other members decreases. In that regard, when a monofunctional compound, a bifunctional compound, and a trifunctional compound are used in combination, the plastic effect of the monofunctional compound or the bifunctional compound is lost even after the plastic effect of the trifunctional compound disappears in the polymer. In the laminated body obtained, the wiring embedding property and the heat resistance are improved in a very balanced manner. That is, the present invention contributes to improvement in wiring embedding property in the obtained laminate, exhibits appropriate fluidity of the base resin during curing, and contributes to improvement in heat resistance in the obtained laminate, after curing. The coexistence of the contradictory physical phenomenon of increasing the crosslinking density of the base resin is achieved by using a predetermined monofunctional compound, bifunctional compound, and trifunctional compound in combination in the above-mentioned content ratio. .
In the content ratio of monofunctional compound, bifunctional compound and trifunctional compound, if the proportion of monofunctional compound and bifunctional compound is excessive, the resulting laminate may have insufficient heat resistance. If the ratio between the compound and the bifunctional compound is insufficient, sufficient wiring embedding cannot be obtained in the laminate. If the proportion of the trifunctional compound is excessive, sufficient wiring embedding cannot be obtained with the obtained laminate, and if the proportion of the trifunctional compound is insufficient, sufficient heat resistance cannot be obtained with the laminate.

In the monofunctional compound, the bifunctional compound and the trifunctional compound used in the present invention, the vinylidene group is preferably present as an isopropenyl group or a methacryl group, and preferably present as a methacryl group, because of excellent crosslinking reactivity. More preferred.
Specific examples of monofunctional compounds having one vinylidene group include isopropenylbenzene, 2-isopropenyltoluene, 4-isopropenyltoluene, 2-isopropenylnaphthalene, isopropenyloxytrimethylsilane, and isopropenyl acetate. Monofunctional compounds having one isopropenyl group; and benzyl methacrylate, hexyl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate octenyl methacrylate, tolyl methacrylate, cyclohexyl methacrylate, adamantyl methacrylate, lauryl methacrylate, stearyl methacrylate, tetrahydrofurfuryl methacrylate, methoxydiethylene glycol Methacrylate, dicyclopentenyloxyethyl methacrylate, and di Such as black dicyclopentanyl methacrylate, monofunctional compound having one methacryl group; and the like. The monofunctional compound having one vinylidene group is preferably a monofunctional compound having one methacryl group (monofunctional methacrylate compound).
Specific examples of the bifunctional compound having two vinylidene groups include bifunctional compounds having two isopropenyl groups, such as p-diisopropenylbenzene, m-diisopropenylbenzene, and 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, bisphenol dimethacrylate, tricyclodecane dimethanol dimethacrylate, 1,3-adamantyl dimethanol dimethacrylate, 1,4-adapter Inch distearate dimethanol dimethacrylate, and 2,2'-bis (4-methacryloxydiethoxyphenyl Siji ethoxyphenyl) propane, and the like bifunctional compounds having two methacryl groups. As the bifunctional compound having two vinylidene groups, a bifunctional compound having two methacrylic groups (bifunctional methacrylate compound) is preferable.
Specific examples of trifunctional compounds having three vinylidene groups include trifunctional compounds having three methacrylic groups such as trimethylolpropane trimethacrylate and pentaerythritol trimethacrylate. The trifunctional compound having three vinylidene groups is preferably a trifunctional compound having three methacrylic groups (trifunctional methacrylate compound).

  In the present invention, it is particularly preferable to use a combination of a monofunctional methacrylate compound, a bifunctional methacrylate compound and a trifunctional methacrylate compound. Specific examples of the combination include benzyl methacrylate, hexyl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate octenyl. At least one compound selected from the group consisting of methacrylate, tolyl methacrylate, cyclohexyl methacrylate, adamantyl methacrylate, lauryl methacrylate, stearyl methacrylate, tetrahydrofurfuryl methacrylate, methoxydiethylene glycol methacrylate, dicyclopentenyloxyethyl methacrylate, and dicyclopentanyl methacrylate ( Above, monofunctional methacrylate compound) , 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, bisphenol dimethacrylate, tricyclodecane dimethanol dimethacrylate, 1,3-adamantyl dimethanol dimethacrylate, 1,4-adamantyl dimethanol dimethacrylate, and 2,2′-bis (4-methacryloxydi) At least one compound selected from the group consisting of ethoxyphenyl) propane (above, a bifunctional methacrylate compound) and tri Chiro - Le propane trimethacrylate (or, trifunctional methacrylate compound) and a combination consisting of a. According to such a combination, in the crosslinkable resin molded body, the resin fluidity at the time of heat curing is improved, the followability of the surface of the molded body to other members is increased, and in the laminate, the wiring embedding property is increased. , And heat resistance is highly balanced and very suitable.

  In the polymerizable composition of the present invention, the content ratio of the monofunctional compound, the bifunctional compound, and the trifunctional compound increases the resin fluidity of the resulting crosslinkable resin molded product, and improves the heat resistance of the resulting laminate. From the viewpoint of making it, it is preferably 10-75: 15-75: 5-35, more preferably 10-70: 20-70: 5-30.

  The monofunctional compound, the bifunctional compound, and the trifunctional compound can be used alone or in combination of two or more. The total compounding amount of the monofunctional compound, bifunctional compound and trifunctional compound in the polymerizable composition of the present invention is usually 0.1 to 100 parts by weight, preferably 0.1 to 100 parts by weight of the cycloolefin monomer. 5 to 50 parts by weight, more preferably 1 to 40 parts by weight.

(Polymerizable composition)
In the polymerizable composition of the present invention, the cycloolefin monomer, the polymerization catalyst, the crosslinking agent, the monofunctional compound, the bifunctional compound, and the trifunctional compound described above as essential components, if necessary, a filler, a polymerization regulator, Polymerization reaction retarders, chain transfer agents, anti-aging agents, and other compounding agents can be added.

  In the present invention, it is preferable to add a filler to the polymerizable composition from the viewpoint of enhancing the functionality of the laminate. The polymerizable composition of the present invention has a low viscosity as compared with a polymer varnish obtained by dissolving an epoxy resin or the like in a solvent, which has been conventionally used in the production of prepregs and laminates. Can be blended. Therefore, in the obtained crosslinkable resin molded body or laminate, the filler may be contained exceeding the limit content of the conventional prepreg or laminate.

  As the filler, any of organic fillers and inorganic fillers can be used. Although it may be appropriately selected as desired, an inorganic filler is usually preferably used. Examples of such inorganic fillers include high dielectric fillers, low linear expansion fillers, and non-halogen flame retardants.

High dielectric fillers are inorganic fillers that are generally highly dielectric. By blending with the polymerizable composition of the present invention, the resulting laminate can have a low dielectric loss tangent and a large dielectric constant. For example, according to such a laminate, a circuit board with low loss and small device design can be obtained. Etc. are obtained and suitable.
The high dielectric filler can be used without particular limitation as long as it is industrially used, but the relative dielectric constant measured particularly at 1 GHz at 20 ° C. is usually 5 or more, preferably 10 or more. More preferably, 15 or more are suitable. Such high dielectric fillers include, for example, zircon oxides such as calcium zirconate, strontium zirconate, lead zirconate, and zirconia; barium titanate, strontium titanate, calcium titanate, cobalt titanate, zinc titanate, and And titanium oxides such as titania;

A low linear expansion filler is an inorganic filler having a generally low linear expansion coefficient. By mix | blending with the polymeric composition of this invention, mechanical strength can improve in the laminated body obtained, a linear expansion coefficient can be reduced, and it is suitable.
The linear expansion coefficient of the low linear expansion filler is usually 15 ppm / ° C. or less. The linear expansion coefficient of the low linear expansion filler can be measured by a thermomechanical analyzer (TMA). As such a low linear expansion filler, any industrially used filler can be used without any particular limitation. For example, inorganic oxides such as silica, silica balloon, alumina, iron oxide, zinc oxide, magnesium oxide, tin oxide, beryllium oxide, barium ferrite, and strontium ferrite; inorganic carbonates such as calcium carbonate, magnesium carbonate, and sodium bicarbonate Salt; inorganic sulfates such as calcium sulfate; inorganic silicates such as talc, clay, mica, kaolin, fly ash, montmorillonite, calcium silicate, glass, and glass balloon; and the like, preferably silica.

  Non-halogen flame retardants consist of flame retardant compounds that do not contain halogen atoms. When blended with the polymerizable composition of the present invention, the flame retardancy of the resulting laminate can be improved, and there is no concern of dioxin generation when the laminate is burned, which is preferable. Any non-halogen flame retardant can be used without particular limitation as long as it is industrially used. For example, metal hydroxide flame retardants such as aluminum hydroxide and magnesium hydroxide; phosphinate flame retardants such as aluminum dimethylphosphinate and aluminum diethylphosphinate; metal oxide flame retardants such as magnesium oxide and aluminum oxide; triphenyl Phosphorus containing other than phosphinates such as phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, and bisphenol A bis (dicresyl) phosphate Flame retardants; Nitrogen-containing flame retardants such as melamine derivatives, guanidines and isocyanurs; ammonium polyphosphate, melamine phosphate, melamine polyphosphate, melam polyphosphate, guanidinium phosphate , And flame retardants containing both phosphorus and nitrogen phosphazene and the like; and the like. As the non-halogen flame retardant, metal hydroxide flame retardant, phosphinate flame retardant, and phosphorus-containing flame retardant other than phosphinate are preferable. As the phosphorus-containing flame retardant, tricresyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, and bisphenol A bis (dicresyl) phosphate are particularly preferable.

  The particle size (average particle size) of the filler used in the present invention may be appropriately selected as desired, but as an average value of the length in the longitudinal direction and the short direction when the particles are viewed three-dimensionally, Usually, it is 0.001-50 micrometers, Preferably it is 0.01-10 micrometers, More preferably, it is the range of 0.1-5 micrometers.

  The above fillers can be used alone or in combination of two or more. The compounding amount in the polymerizable composition of the present invention is usually 50 parts by weight or more, preferably 50 to 1,000 parts by weight, more preferably 50 to 750 parts by weight, based on 100 parts by weight of the cycloolefin monomer. Preferably it is the range of 100-500 weight part.

  The polymerization regulator is blended for the purpose of controlling the polymerization activity or improving the polymerization reaction rate. For example, trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkyl Examples include aluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium, tetraalkoxytin, and tetraalkoxyzirconium. These polymerization regulators can be used alone or in combination of two or more. The blending amount of the polymerization regulator is, for example, in a molar ratio (metal atom in the metathesis polymerization catalyst: polymerization regulator), usually 1: 0.05 to 1: 100, preferably 1: 0.2 to 1:20. More preferably, it is in the range of 1: 0.5 to 1:10.

  A polymerization reaction retarder can suppress an increase in viscosity of the polymerizable composition of the present invention. Therefore, a polymerizable composition obtained by blending a polymerization reaction retarder is preferable because, for example, when a prepreg is produced as a crosslinkable resin molded article, the fibrous reinforcing material can be easily impregnated uniformly. Polymerization retarders include phosphine compounds such as triphenylphosphine, tributylphosphine, trimethylphosphine, triethylphosphine, dicyclohexylphosphine, vinyldiphenylphosphine, allyldiphenylphosphine, triallylphosphine, and styryldiphenylphosphine; Lewis such as aniline and pyridine Base; etc. can be used. What is necessary is just to adjust the compounding quantity suitably as needed.

  A chain transfer agent can be blended with the polymerizable composition of the present invention as desired. In the resulting crosslinkable resin molded article, the surface followability can be improved during the heat curing. Therefore, in the laminate obtained by laminating, melting, and crosslinking such a molded article, interlayer adhesion and wiring embedding are obtained. Increased properties are preferable.

The chain transfer agent may have one or more crosslinkable carbon-carbon unsaturated bonds. Specific examples of the chain transfer agent include 1-hexene, 2-hexene, styrene, vinylcyclohexane, allylamine, glycidyl acrylate, allyl glycidyl ether, ethyl vinyl ether, methyl vinyl ketone, 2- (diethylamino) ethyl acrylate, and 4- Chain transfer agents without crosslinkable carbon-carbon unsaturated bonds, such as vinylaniline; divinylbenzene, vinyl methacrylate, allyl methacrylate, styryl methacrylate, allyl acrylate, undecenyl methacrylate, styryl acrylate, and ethylene Chain transfer agent having one crosslinkable carbon-carbon unsaturated bond, such as glycol diacrylate; Chain transfer agent having two or more crosslinkable carbon-carbon unsaturated bonds, such as allyltrivinylsilane and allylmethyldivinylsilane Na And the like. Among these, in the obtained laminate, from the viewpoint of highly balancing wiring embedding property and heat resistance, those having one or more crosslinkable carbon-carbon unsaturated bonds are preferable. Those having one bond are more preferred. Among such chain transfer agents, chain transfer agents having one vinyl group and one methacryl group are preferable, and vinyl methacrylate, allyl methacrylate, styryl methacrylate, and undecenyl methacrylate are particularly preferable.
These chain transfer agents can be used alone or in combination of two or more. As the blending amount of the chain transfer agent to the polymerizable composition of the present invention, the balance between the wiring embedding property and the heat resistance of the obtained laminate is taken into consideration, and is usually 0. 01 to 10 parts by weight, preferably 0.1 to 5 parts by weight.

  Moreover, as an anti-aging agent, blending at least one anti-aging agent selected from the group consisting of a phenol-based anti-aging agent, an amine-based anti-aging agent, a phosphorus-based anti-aging agent and a sulfur-based anti-aging agent is a cross-linking. It is preferable because the heat resistance of the obtained laminate can be improved to a high degree without inhibiting the reaction. Among these, a phenolic antiaging agent and an amine antiaging agent are preferable, and a phenolic antiaging agent is more preferable. These anti-aging agents can be used alone or in combination of two or more. The amount of the anti-aging agent is appropriately selected as desired, but is usually 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, and more preferably 0 to 100 parts by weight of the cycloolefin monomer. .01 to 2 parts by weight.

  Other compounding agents can be blended in the polymerizable composition of the present invention. As other compounding agents, colorants, light stabilizers, foaming agents and the like can be used. As the colorant, a dye or a pigment is used. There are various kinds of dyes, and known ones may be appropriately selected and used. These other compounding agents can be used alone or in combination of two or more, and the amount used is appropriately selected within a range not impairing the effects of the present invention.

  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 liquid) in which a polymerization catalyst is dissolved or dispersed in an appropriate solvent is prepared, and other essential components such as a cycloolefin monomer and a crosslinking agent are optionally added. It can be prepared by preparing a liquid (monomer liquid) containing other compounding agents, adding the catalyst liquid to the monomer liquid, and stirring.

(Crosslinkable resin molding)
The crosslinkable resin molded article of the present invention can be obtained by bulk polymerization of the polymerizable composition. 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. 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 polytetrafluoroethylene, polyethylene terephthalate, polypropylene, polyethylene, polycarbonate, polyethylene naphthalate, polyarylate, and nylon; iron, stainless steel, copper, aluminum, nickel, chromium And films and plates made of metal materials such as gold, silver, and the like. 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) and is usually 10 μm or less, preferably 5 μm or less. Preferably it is 3 micrometers or less, More preferably, it is 2 micrometers or less. If the surface roughness of the metal foil is in the above range, for example, in the obtained high-frequency circuit board, generation of noise, delay, transmission loss and the like in high-frequency transmission is suppressed, which is preferable. The surface of the metal foil is preferably treated with a known coupling agent or adhesive such as a silane coupling agent, a thiol coupling agent, and a titanate coupling agent. 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. The thickness of the obtained molded body is usually in the range of 0.001 to 10 mm, preferably 0.005 to 1 mm, more preferably 0.01 to 0.5 mm. If it exists in this range, the shaping property at the time of lamination | stacking and the mechanical strength, toughness, etc. of a laminated body will improve, and it is suitable. 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. The content of the fibrous reinforcing material in the crosslinkable resin molded body is usually in the range of 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight. Within this range, the dielectric properties and mechanical strength of the resulting laminate are balanced, which is preferable.

  As the fibrous reinforcing material, inorganic and / or organic fibers can be used. For example, organic fibers such as PET (polyethylene terephthalate) fiber, aramid fiber, ultra-high molecular polyethylene fiber, polyamide (nylon) fiber, and liquid crystal polyester fiber; glass fiber, carbon fiber, alumina fiber, tungsten fiber, molybdenum fiber, and budene fiber , Inorganic fibers such as titanium fiber, steel fiber, boron fiber, silicon carbide fiber, and silica fiber. Among these, organic fibers and glass fibers are preferable, and aramid fibers, liquid crystal polyester fibers, and glass fibers are particularly preferable. As the glass fiber, fibers such as E glass, NE glass, S glass, D glass, and H glass can be suitably used. These can be used individually by 1 type or in combination of 2 or more types. The form 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).

  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. In the range of ˜150 ° C. and not more than 1 minute half-life temperature of the crosslinking agent, usually radical generator, preferably not more than 10 ° C. of 1 minute half-life temperature, more preferably not more than 20 ° C. of 1 minute half-life temperature It is. 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 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, if the surface part that easily dissipates heat is formed of a crosslinkable resin that can be postcrosslinked, the crosslinkable resin molded article of the present invention can sufficiently exhibit the desired effect.

The crosslinkable resin molded article of the present invention is obtained by completing bulk polymerization, and there is no fear that the polymerization reaction further proceeds during storage. In addition, the crosslinkable resin molded article of the present invention contains a crosslinking agent such as a radical generator, but does not cause a problem such as a change in surface hardness unless it is heated to a temperature at which a crosslinking reaction is caused or not. Excellent 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 product of the present invention is obtained by bulk polymerizing the polymerizable composition of the present invention and crosslinking the resulting polymer. Such a crosslinked resin molded body can be obtained, for example, by crosslinking the crosslinkable resin molded body. 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 polymer constituting the molded body. The heating temperature is usually equal to or higher than the temperature at which a crosslinking reaction is induced by the crosslinking agent. For example, when a radical generator is used as a crosslinking agent, it is usually at least 1 minute half-life temperature, preferably at least 5 ° C. above 1-minute half-life temperature, more preferably at least 10 ° C. above 1-minute half-life temperature. It is. 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. In the case of producing a crosslinked resin molded body in this way, a copper clad laminate (Copper Clad Laminates (CCL)) can be obtained in accordance with the method (a), for example, by using a copper foil as a support. .

(Laminate)
The laminate of the present invention comprises at least the crosslinkable resin molded body or a layer made of the crosslinked resin molded body. When there are a plurality of layers formed of a crosslinkable resin molded product or a crosslinked resin molded product, both molded products may be laminated continuously or indirectly with another layer interposed therebetween. .
As a laminated body which has a layer which consists of a crosslinkable resin molding of this invention, RCC obtained by the method of said (a) and which integrates copper foil and a crosslinkable resin molding in a layer form is mentioned, for example. . Moreover, as a laminated body which has a layer which consists of a crosslinked-resin molded object of this invention, CCL obtained by conforming to the method of said (a), and the copper foil and the crosslinked-resin molded object integrated in layered form, for example. Can be mentioned. In the method (a), if a separately obtained cross-linked resin molded body is used as the support, a laminate having a layer made of a cross-linkable resin molded body and a layer made of the cross-linked resin molded body can be obtained. .
Further, when the crosslinkable resin molded body is in the form of a sheet or film, the molded body and, optionally, the sheet-shaped or film-shaped crosslinked resin molded body is arbitrarily laminated, or further, for example, the metal foil Are laminated and hot-pressed for crosslinking to obtain a laminate of the present invention having a layer composed of a crosslinked resin molded article. 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 excellent electrical characteristics unique to cycloolefin polymers, such as low dielectric constant and low dielectric loss tangent, has low transmission loss in the high frequency region, and has excellent wiring embedding and heat resistance. Since it is excellent, it can be suitably used as a high-frequency substrate material having a wide range of uses.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. In addition, the part and% in an Example and a comparative example are a basis of weight unless there is particular notice.

Each characteristic in an Example and a comparative example was measured and evaluated according to the following methods.
(1) Dielectric loss tangent 3 cm square is cut out and etched to remove the copper foil, and then the capacitance tangent (tan δ) at a frequency of 1 GHz is obtained at 20 ° C. using an impedance analyzer (manufactured by Agilent Technologies, model number E4991A). And measured according to the following criteria.
〔Evaluation criteria〕
A: Less than 0.0015 B: Less than 0.0015, less than 0.002 x: More than 0.002 (2) Wiring embedding On a circuit board (test board on which 15 wires of L / S = 30 μm are arranged) The laminate was obtained by heating and pressing at 3 MPa at 200 ° C. for 10 minutes. The laminate was arbitrarily cut at three points in a direction perpendicular to the wiring direction. The cut surface of the obtained laminate was visually observed, and the wiring embeddability into the resin layer on the circuit board was evaluated according to the following criteria. In addition, if it is evaluation of (circle) and (double-circle), a laminated body will function without a problem as a high frequency board material.
〔Evaluation criteria〕
A: There is no portion where the wiring is not embedded. ○: A portion of the wiring is not embedded. X: The wiring is not embedded. (3) Heat resistance After removing the copper foil by etching the laminate, TMA (SII The glass transition point (Tg) was measured using a nanotechnology company, SS6100 standard type, and the heat resistance was evaluated according to the following criteria.
〔Evaluation criteria〕
◎: Over 165 ° C ○: Over 155 ° C, 165 ° C or lower x 155 ° C or lower

Example 1
Benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride 0.05 part and triphenylphosphine 0.01 part are dissolved in indene 1.51 part to form a catalyst. A liquid was prepared.
Separately, 100 parts of tetracyclododecene (TCD) as a cycloolefin monomer; 1.6 parts of divinylbenzene as a chain transfer agent; di-t-butyl peroxide as a crosslinking agent (1 minute half-life temperature 186 ° C.) 1.14 parts; 10 parts benzyl methacrylate as monofunctional compound, 20 parts tricyclodecane dimethanol dimethacrylate as bifunctional compound, 4 parts trimethylolpropane trimethacrylate as trifunctional compound; 145 parts calcium titanate as high dielectric filler (Product of Kyoritsu Material Co., Ltd., product name CT-WA, average particle size 2.3 μm) 100 parts; 170 parts of magnesium hydroxide as a non-halogen flame retardant (product name KISUMA8, average particle size 1.8 μm, manufactured by Kyowa Chemical Industry Co., Ltd.) And 3,5-di as a phenolic anti-aging agent The monomer solution was prepared by mixing the t- butyl-4-hydroxyanisole 0.28 parts. The above catalyst solution was added thereto at a rate of 0.62 mL per 100 g of cycloolefin monomer and stirred to prepare a polymerizable composition.
Subsequently, the obtained polymerizable composition was impregnated into glass cloth (E glass), and this was subjected to bulk polymerization reaction at 120 ° C. for 3.5 minutes to obtain a prepreg having a thickness of 0.13 mm.
Next, 6 sheets of the prepared prepregs were laminated, then sandwiched between 12 μm F0 copper foil (silane coupling agent-treated electrolytic copper foil, manufactured by Furukawa Electric Co., Ltd.), and heated and pressed at 180 ° C. for 60 minutes at 3 MPa to obtain a laminate. Got. The dielectric tangent and heat resistance of the obtained laminate were evaluated. On the other hand, the wiring embedding property was evaluated by separately obtaining a laminate by the method described in (2) Wiring embedding property. The results are shown in Table 1.

Example 2
A prepreg and a laminate were obtained in the same manner as in Example 1 except that divinylbenzene was not used, the amount of tricyclodecane dimethanol dimethacrylate was 10 parts, and the amount of trimethylolpropane trimethacrylate was 9 parts. , Evaluated in the same way. The results are shown in Table 1.

Comparative Example 1
The prepreg and laminate as in Example 1 except that the amount of benzyl methacrylate was 29 parts, the amount of tricyclodecane dimethanol dimethacrylate was 3 parts, and the amount of trimethylolpropane trimethacrylate was 2 parts. And evaluated similarly. The results are shown in Table 1.

Comparative Example 2
The prepreg and laminate as in Example 1 except that the amount of benzyl methacrylate was 25 parts, the amount of tricyclodecane dimethanol dimethacrylate was 2 parts, and the amount of trimethylolpropane trimethacrylate was 7 parts. And evaluated similarly. The results are shown in Table 1.

Comparative Example 3
The prepreg and laminate as in Example 1 except that the amount of benzyl methacrylate was 5 parts, the amount of tricyclodecane dimethanol dimethacrylate was 5 parts, and the amount of trimethylolpropane trimethacrylate was 24 parts. And evaluated similarly. The results are shown in Table 1.

  From Table 1, it can be seen that the laminates obtained in Examples 1 and 2 have a low dielectric loss tangent and have excellent wiring embedding properties and heat resistance. On the other hand, in the laminate of Comparative Example 1 obtained using the polymerizable composition having an excessive content of benzyl methacrylate, the dielectric loss tangent and wiring embedding properties are the same as those in Example 1, but the heat resistance is improved. The laminate of Comparative Example 2 obtained using a polymerizable composition that is inferior and lacks the content of tricyclodecane dimethanol dimethacrylate has the same dielectric loss tangent and heat resistance as those of Example 1. However, in the laminate of Comparative Example 3 obtained by using the polymerizable composition inferior in the wiring embedding property and having an excessive content of trimethylolpropane trimethacrylate, the dielectric loss tangent and the heat resistance are those of Example 1. Although it is equivalent, it turns out that it is inferior to wiring embedding.

Claims (7)

  A cycloolefin monomer, a polymerization catalyst, a crosslinking agent, a monofunctional compound having one vinylidene group, a bifunctional compound having two vinylidene groups, and a trifunctional compound having three vinylidene groups. Polymeric composition whose content ratio of a compound, the said bifunctional compound, and the said trifunctional compound is 10-80: 10-80: 5-40 by weight ratio (monofunctional compound: bifunctional compound: trifunctional compound) .   The polymerizable composition according to claim 1, wherein the monofunctional compound is a monofunctional methacrylate compound, the bifunctional compound is a bifunctional methacrylate compound, and the trifunctional compound is a trifunctional methacrylate compound.   The polymerizable composition according to claim 1 or 2, further comprising a filler.   The polymerizable composition according to claim 1, further comprising a chain transfer agent.   A crosslinkable resin molded article obtained by bulk polymerization of the polymerizable composition according to claim 1.   A crosslinked resin molded article obtained by crosslinking a polymer obtained by bulk polymerization of the polymerizable composition according to claim 1.   A laminate comprising at least a layer formed of the crosslinkable resin molded article according to claim 5 or the crosslinked resin molded article according to claim 6.