JP5625304B2 - Polymerizable composition, resin molded body, and laminate - Google Patents

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.

  A circuit board is generally composed of a dielectric layer and a conductor layer. In recent years, with the advent of advanced information technology, information transmission has begun to move toward higher speeds and higher frequencies, and microwave communication and millimeter wave communication are becoming reality. The dielectric layers of circuit boards in these high frequency eras need to reduce noise and transmission loss at high frequencies to the limit. Therefore, as a material for forming such a dielectric layer, a dielectric having a low dielectric loss tangent (tan δ) Body materials are sought.

  As a material for constituting such a dielectric layer of a circuit board, a cycloolefin polymer obtained by bulk polymerization of cycloolefin monomers has attracted attention. For example, Patent Document 1 discloses a polymerizable composition containing a norbornene monomer, a metathesis polymerization catalyst, a chain transfer agent, and a crosslinking agent. Since the polymerizable composition disclosed in Patent Document 1 has fluidity, the polymerizable composition is soaked into a nonwoven fabric as a support or formed into a film shape, and the polymerizable composition is subjected to bulk polymerization. It is possible to obtain a crosslinkable thermoplastic resin. Then, the obtained thermoplastic resin is used as a dielectric layer, laminated with a base material such as a metal foil as a conductor layer, and crosslinked to obtain various crosslinked resin composites.

Japanese Patent Laid-Open No. 2004-244609

However, when the present inventors examined, when the polymeric composition of patent document 1 was used as a dielectric material layer for circuit boards, although an electrical property was favorable, crack resistance and heat resistance are good. It has been observed that may not be sufficient.
An object of the present invention is to provide a crosslinked resin molded article and a crosslinkable resin molded article that have a low dielectric loss tangent in a high-frequency region and provide a cross-linked resin molded article and laminate excellent in crack resistance and heat resistance, and using these It is to provide a cross-linked resin molded article and a laminate obtained.

  As a result of diligent research to achieve the above object, the present inventors have found that a monomer mixture containing a cycloolefin monomer having a (meth) acryloyl group and a cycloolefin monomer having a vinyl group and / or a vinylidene group, A cross-linked resin molded article and laminate obtained using a metathesis polymerization catalyst and a polymerizable composition containing a cross-linking agent are found to have a low dielectric loss tangent and excellent crack resistance and heat resistance. The present invention has been completed.

That is, according to the present invention,
[1] A cycloolefin monomer (A) having a (meth) acryloyl group and a cycloolefin monomer (B) having a vinyl group and / or a vinylidene group (excluding those having a (meth) acryloyl group). A polymerizable composition comprising a monomer mixture containing, a metathesis polymerization catalyst, and a crosslinking agent, wherein the cycloolefin monomer (A) content in the monomer mixture is 0.1-10. A polymerizable composition having a content by weight of 5 to 95% by weight of the cycloolefin monomer (B),
[2] The polymerizable composition according to [1], further including a chain transfer agent,
[3] A crosslinkable resin molded article obtained by bulk polymerization of the polymerizable composition according to any one of [1] or [2],
[4] A cycloolefin monomer (A) having a (meth) acryloyl group and a cycloolefin monomer (B) having a vinyl group and / or a vinylidene group (excluding those having a (meth) acryloyl group). A crosslinkable resin molded article for a dielectric layer of a circuit board, which is obtained by bulk polymerization of a polymerizable composition comprising a monomer mixture, a metathesis polymerization catalyst, and a crosslinking agent, For dielectric layers of circuit boards in which the content of the cycloolefin monomer (A) in the mixture is 0.1 to 10% by weight and the content of the cycloolefin monomer (B) is 5 to 95% by weight. A crosslinkable resin molded product of
[ 5 ] A crosslinked resin molded product obtained by crosslinking a polymer obtained by bulk polymerization of the polymerizable composition according to any one of [1] or [2], and
[ 6 ] At least a crosslinkable resin molded article according to [3] or [4] , or a laminate obtained by laminating the crosslinked resin molded article according to [ 5 ],
Is provided.

  According to the present invention, a polymerizable composition and a crosslinkable resin molded body that give a crosslinked resin molded body and a laminate having a small dielectric loss tangent in a high frequency region and excellent in crack resistance and heat resistance, and using these The resulting crosslinked resin molded body and laminate are provided. Since the crosslinked resin molded body and laminate of the present invention have a small dielectric loss tangent in a high frequency region and are excellent in crack resistance and heat resistance, they can be suitably used as a high frequency substrate material in a wide range of applications.

  The polymerizable composition of the present invention includes a monomer mixture containing a cycloolefin monomer (A) having a (meth) acryloyl group and a cycloolefin monomer (B) having a vinyl group and / or a vinylidene group, a crosslinking agent, And a metathesis polymerization catalyst.

(Monomer mixture)
The monomer mixture used in the present invention is a cycloolefin monomer (A) having a (meth) acryloyl group and a cycloolefin monomer (B) having a vinyl group and / or a vinylidene group (however, having a (meth) acryloyl group). Excluding those).

  The cycloolefin monomer (A) having a (meth) acryloyl group (hereinafter abbreviated as “cycloolefin monomer (A)” as appropriate) has a (meth) acryloyl group (acryloyl group and / or methacryloyl group in the molecule). ) And an alicyclic structure, and a carbon-carbon double bond in the alicyclic structure.

  Examples of the alicyclic structure constituting the cycloolefin monomer (A) include a monocyclic ring, a polycyclic ring, a condensed polycyclic ring, a bridged ring, and a combination polycyclic ring. Although there is no special restriction | limiting in carbon number which comprises an alicyclic structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces. Examples of such cycloolefin monomers (A) include monocyclic cycloolefin monomers having a (meth) acryloyl group, norbornene monomers having a (meth) acryloyl group, and norbornene monomers having a (meth) acryloyl group Is preferred.

  Specific examples of the cycloolefin monomer (A) having a (meth) acryloyl group include 5-norbornen-2-yl methacrylate, 5-norbornen-2-yl acrylate, 5-norbornen-2-ylmethyl methacrylate, and acrylic. 5-norbornen-2-ylmethyl acid, 5-norbornen-2-ylethyl methacrylate, 5-norbornen-2-ylethyl acrylate, 5-norbornen-2-ylpropyl methacrylate, 5-norbornen-2-ylpropyl acrylate , 5-norbornen-2-ylbutyl methacrylate, 5-norbornen-2-ylbutyl acrylate, 5-norbornen-2-ylhexyl methacrylate, 5-norbornen-2-ylhexyl acrylate, 5-norbornen-2-yloctyl methacrylate , Le acid 5-norbornene-2-Iruokuchiru, methacrylic acid 5-norbornene-2-Irudeshiru and acrylic acid 5-norbornene-2-Irudeshiru. These can be used alone or in combination of two or more. Among these, 5-norbornen-2-yl methacrylate and 5-norbornen-2-yl acrylate are preferable, and 5-norbornene methacrylate is preferable because the effects of the present invention become more remarkable. 2-yl is particularly preferred.

  The content ratio of the cycloolefin monomer (A) in the monomer mixture used in the present invention is preferably 0.1 to 10% by weight, more preferably in all monomers constituting the monomer mixture. It is 0.5-9 weight%, More preferably, it is 1-7 weight%, Most preferably, it is 1.5-6 weight%. In the present invention, when the content ratio of the cycloolefin monomer (A) is within the above range, the polymerizable composition is bulk-polymerized to form a crosslinkable resin molded product, and thus is derived from the cycloolefin monomer (A). The proportion of (meth) acryloyl groups present in the polymer chain of the polymer can be increased, thereby improving the crack resistance and heat resistance of the resulting crosslinked resin molded product and laminate. It can be further increased. If the content of the cycloolefin monomer (A) is too small, the crack resistance of the resulting crosslinked resin molded product and laminate may be reduced. On the other hand, if the content is too large, the cycloolefin monomer (A) is excessively present. In some cases, the ratio of heat treatment increases and heat resistance decreases.

A cycloolefin monomer (B) having a vinyl group and / or a vinylidene group (hereinafter abbreviated as “cycloolefin monomer (B)” where appropriate) has a vinyl group (CH ₂ ═CH—) in the molecule and / or a vinylidene group (CH 2 = _{C <),} and a alicyclic structure, and carbon atoms in the alicyclic structure - are those having a carbon-carbon double bond.

  Examples of the alicyclic structure constituting the cycloolefin monomer (B) include a monocyclic ring, a polycyclic ring, a condensed polycyclic ring, a bridged ring, and a combination polycyclic ring. Although there is no special restriction | limiting in carbon number which comprises an alicyclic structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces. Examples of the cycloolefin monomer (B) include a monocyclic cycloolefin monomer having a vinyl group and / or a vinylidene group, a norbornene monomer having a vinyl group and / or a vinylidene group, and the vinyl group and / or vinylidene. A norbornene-based monomer having a group is preferred.

Specific examples of the cycloolefin monomer (B) having a vinyl group and / or vinylidene group include 9-methylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-10-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-10-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-10-isopropyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-10-butyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-10-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-10-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-10-isopropyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-10-butyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-propylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-propylidene-10-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-propylidene-10-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-propylidene-10-isopropyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-propylidene-10-butyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-isopropylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-isopropylidene-10-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-isopropylidene-10-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-isopropylidene-10-isopropyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-isopropylidene-10-butyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-vinyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-propenyltetracyclo [6.2.1.1 ^3,6 . ^{Tetracyclododecenes} such as 0 ^2,7 ] dodec-4-ene; 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, n-propylidene-2-norbornene , Norbornenes such as 5-vinyl-2-norbornene, 5-allyl-2-norbornene, and 5,6-diethylidene-2-norbornene; These can be used alone or in combination of two or more. Among these, tetracyclododecenes are preferable from the viewpoint that the effects of the present invention become more remarkable, and 9-ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene is particularly preferred.

  The content ratio of the cycloolefin monomer (B) in the monomer mixture used in the present invention is preferably 5 to 95% by weight, more preferably 20 to 20% in all monomers constituting the monomer mixture. 80% by weight, more preferably 35 to 65% by weight. If the content ratio of the cycloolefin monomer (B) is too small, the crack resistance of the resulting crosslinked resin molded product and laminate may be reduced. On the other hand, if the content is too large, the laminate property of the resulting crosslinked resin molded product may be reduced. May decrease.

  In addition to the cycloolefin monomer (A) and the cycloolefin monomer (B) described above, the monomer mixture used in the present invention is a cycloolefin monomer having a crosslinkable carbon-carbon unsaturated bond in the alicyclic structure. (C) (however, excluding those having a (meth) acryloyl group, a vinyl group or a vinylidene group) is preferable.

  The cycloolefin monomer (C) having a crosslinkable carbon-carbon unsaturated bond in the alicyclic structure (hereinafter abbreviated as “cycloolefin monomer (C)” as appropriate) has an alicyclic structure in the molecule. And having a crosslinkable carbon-carbon unsaturated bond in the alicyclic structure.

  In the present invention, the “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 crosslinking 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. In the present invention, usually, a radical crosslinking reaction or a metathesis crosslinking reaction is performed. In particular, it refers to a radical crosslinking reaction. Crosslinkable carbon-carbon unsaturated bonds include carbon-carbon unsaturated bonds other than aromatic carbon-carbon unsaturated bonds, that is, aliphatic carbon-carbon double bonds or aliphatic carbon-carbon triple bonds. In the present invention, it usually means an aliphatic carbon-carbon double bond. And the cycloolefin monomer (C) used by this invention consists of what all carbon atoms which comprise such a crosslinkable carbon-carbon unsaturated bond comprise a part of alicyclic structure. .

  Examples of the alicyclic structure constituting the cycloolefin monomer (C) having a crosslinkable carbon-carbon unsaturated bond in the alicyclic structure include monocyclic, polycyclic, condensed polycyclic, bridged ring, and combinations thereof. Etc. Although there is no special restriction | limiting in carbon number which comprises an alicyclic structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces. As such a cycloolefin monomer (C), a monocyclic cycloolefin monomer having a crosslinkable carbon-carbon unsaturated bond in the alicyclic structure, and a crosslinkable carbon-carbon unsaturated bond in the alicyclic structure. Examples thereof include norbornene monomers, and norbornene monomers having a crosslinkable carbon-carbon unsaturated bond in the alicyclic structure are preferred.

  Specific examples of the cycloolefin monomer (C) include dicyclopentadiene, methyl-dicyclopentadiene, dimethyldicyclopentadiene, ethyldicyclopentadiene, 2,5-norbornadiene, 5-methyl-2,5-norbornadiene, 5- Examples thereof include compounds having two carbon-carbon unsaturated bonds in the alicyclic structure such as phenyl-2,5-norbornadiene and 5,6-dimethyl-2,5-norbornadiene. These can be used alone or in combination of two or more. Among these, dicyclopentadiene is preferable from the viewpoint that the effects of the present invention become more remarkable.

  When the cycloolefin monomer (C) is contained in the monomer mixture used in the present invention, the content ratio of the cycloolefin monomer (C) is preferably 5 to 95 in all monomers constituting the monomer mixture. % By weight, more preferably 15 to 80% by weight, still more preferably 25 to 65% by weight.

  In addition to the cycloolefin monomer (A), cycloolefin monomer (B) and cycloolefin monomer (C), the monomer mixture used in the present invention contains a monomer copolymerizable with these. May be. Although it does not specifically limit as a monomer which can be copolymerized, Other cycloolefin monomers (D) other than the said cycloolefin monomer (A), a cycloolefin monomer (B), and a cycloolefin monomer (C) are mentioned.

  Specific examples of the other cycloolefin monomer (D) include 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-phenyl-2-norbornene, tetracyclododecene, 1,4,5,8-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 , 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-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- Kutahydronaphthalene, 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-trifluoromethyl-2-norbornene, 5-chloromethyl-2-norbornene , 5-methoxy-2-norbornene, 5,6-dicarboxyl-2-norbornene anhydrate, 5-dimethylamino-2-norbornene, 5-cyano-2-norbornene and the like. These can be used alone or in combination of two or more.

  The content ratio of the copolymerizable monomer in the monomer mixture used in the present invention is preferably 30% by weight or less, more preferably 20% by weight or less, based on all monomers constituting the monomer mixture. More preferably, it is 10% by weight or less.

(Metathesis polymerization catalyst)
The metathesis polymerization catalyst used in the present invention is not particularly limited as long as it can metathesis ring-opening polymerize the monomers constituting the monomer mixture described above, but usually a plurality of ions, atoms with a transition metal atom as a central atom. And a complex formed by bonding polyatomic ions and / or compounds. As transition metal atoms, atoms of Group 5, Group 6, and Group 8 (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 ruthenium and osmium. Can be mentioned. Among these, a group 8 ruthenium or osmium complex is preferably used as a metathesis polymerization catalyst, and a ruthenium carbene complex is particularly preferable. Since the ruthenium carbene complex has excellent catalytic activity during bulk polymerization, it is excellent in productivity of the crosslinkable resin molded article, and the resulting crosslinkable resin molded article has less odor derived from unreacted monomers and is excellent in workability. The ruthenium carbene complex is relatively stable to oxygen and moisture in the air and is not easily deactivated, so that it can be used for production in the atmosphere.

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

In the general formula (1) and the general formula (2), R ¹ and R ² each independently represents 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. The C1-C20 hydrocarbon group which may be included is represented.

X ¹ and X ² each independently represents an arbitrary anionic ligand. An anionic ligand is a ligand having a negative charge when pulled away from a central metal atom, such as a halogen atom, a diketonate group, a substituted cyclopentadienyl group, an alkoxyl group, an aryloxy group, A carboxyl group etc. can be mentioned. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

L ¹ and L ² each independently represent a heteroatom-containing carbene compound or a neutral electron-donating compound other than a heteroatom-containing carbene compound. A hetero atom means an atom of Group 15 and Group 16 of the Periodic Table, and specific examples thereof include N, O, P, S, As, and Se atoms. Among these, from the viewpoint of obtaining a stable carbene compound, N, O, P, S atoms and the like are preferable, and N atoms are particularly preferable.

Examples of the heteroatom-containing carbene compound include compounds represented by the following general formula (3) or general formula (4).

In the formula, R ^{3 to} R ⁶ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms that may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Represents a hydrogen group. R ^{3 to} R ⁶ may be bonded to each other in any combination to form a ring.

  The neutral electron donating compound may be any ligand as long as it has a neutral charge when separated from the central metal. Specific examples thereof include phosphines, ethers and pyridines, and trialkylphosphine is more preferable.

In the above formulas (1) and (2), R ¹ and R ² may be bonded to each other to form a ring, and further 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.

  In the present invention, the use of a ruthenium catalyst having as a ligand a compound having a heterocyclic structure as a metathesis polymerization catalyst, high-frequency characteristics, heat resistance, and resistance to resistance in a thermal shock test of the resulting crosslinked resin molded body and laminate. Since each characteristic of crack property can be highly balanced, it is preferable. Examples of the hetero atom constituting the heterocyclic structure include an O atom and an N atom, and an N atom is preferable. Moreover, as a heterocyclic structure, an imidazoline structure and an imidazolidine structure are preferable.

As a ruthenium catalyst having such a compound having a heterocyclic structure as a ligand, a ligand composed of a heteroatom-containing carbene compound represented by the above formula (1) or (2) is used as L ¹ or L ^2. The ruthenium catalyst which has can be used suitably. As a hetero atom constituting the hetero atom-containing carbene compound, an N atom is preferable. Specific examples of such heteroatom-containing carbene compounds include, for example, 1,3-di (1-adamantyl) imidazolidin-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1 , 3-di (1-phenylethyl) -4-imidazoline-2-ylidene, benzylidene (1,3-dimesitylimidazolidin-2-ylidene), 1,3-dimesitylimidazolidin-2-ylidene, Examples include 1,3-dicyclohexylimidazolidine-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene, and the like.

  Specific examples of the ruthenium catalyst having a ligand composed of a heteroatom-containing carbene compound include benzylidene (1,3-dimesityrylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3 -Dimesitylimidazolidin-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octahydrobenzimidazol-2-ylidene) Tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydro Imidazole-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole -5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityloimidazolidine-2-ylidene) Examples thereof include a ruthenium complex compound in which a hetero atom-containing carbene compound and a neutral electron donating compound are bonded as a ligand, such as pyridine ruthenium dichloride.

  These metathesis polymerization catalysts are used alone or in combination of two or more. The use amount of the metathesis polymerization catalyst is usually 1: 2,000 to 1: 2,000,000, preferably 1 in terms of a molar ratio of (metal atoms in the catalyst: all monomers contained in the monomer mixture). : 5,000 to 1: 1,000,000, more preferably 1: 10,000 to 1: 500,000.

  If necessary, the metathesis polymerization catalyst can be used by dissolving or suspending in a small amount of an inert solvent. Examples of 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, Alicyclic hydrocarbons such as diethylcyclohexane, decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; and alicyclic rings such as indene and tetrahydronaphthalene 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 aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and hydrocarbons having an alicyclic ring and an aromatic ring.

(Crosslinking agent)
The cross-linking agent used in the present invention is used for the purpose of inducing a cross-linking reaction in a cross-linkable resin molded product obtained by bulk polymerization of the polymerizable composition of the present invention. Therefore, the obtained molded body is made of 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. Since the crosslinkable resin molded product of the present invention using the resin as a base resin melts by heating and has a high viscosity, its shape is maintained, while when an arbitrary member is brought into contact with the surface, Exhibits followability to the shape of the member, and finally crosslinks and cures. Such characteristics of the crosslinkable resin molded product of the present invention are considered to contribute to the improvement of interlayer adhesion in a laminate obtained by laminating, melting, and crosslinking the crosslinkable resin molded product of the present invention. .

  In the present invention, a radical generator is usually preferably used as the crosslinking agent. 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, 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; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, 3,6,9-triethyl-3 , 6,9-trimethyl-1,4,7-triperoxonane, cyclic peroxides such as 3,6-diethyl-3,6-dimethyl-1,2,4,5-tetroxane; 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, 1,1,1- And triphenyl-2-phenylethane.

  When a radical generator is used as the crosslinking agent, the half-life temperature for 1 minute is appropriately selected depending on the conditions of curing (crosslinking of the crosslinkable resin molded product obtained by bulk polymerization of the polymerizable composition of the present invention). However, it is usually in the range of 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. For example, it is 186 ° C. for di-t-butyl peroxide and 194 ° C. for 2,5-dimethyl-2,5-bis (t-butylperoxy) -3-hexyne.

  These crosslinking agents can be used alone or in combination of two or more. The amount of the crosslinking agent to be added to the polymerizable composition of the present invention is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, further preferably 100 parts by weight of the monomer mixture. Is in the range of 0.5 to 5 parts by weight.

(Chain transfer agent)
The polymerizable composition of the present invention preferably contains a chain transfer agent in addition to the monomer mixture, the metathesis polymerization catalyst, and the crosslinking agent.

  When a chain transfer agent is blended in the polymerizable composition of the present invention, the followability at the time of heating and melting can be further improved on the surface of the crosslinkable resin molded body obtained by bulk polymerization of the composition. Therefore, in a laminate obtained by laminating a crosslinkable resin molded article obtained by using a polymerizable composition containing a chain transfer agent, heating and melting, and crosslinking, the interlayer adhesion is further improved. This is preferable because the peel strength is further improved. The chain transfer agent may further have one or more crosslinkable carbon-carbon unsaturated bonds. Such a crosslinkable carbon-carbon unsaturated bond is preferably present as a vinyl group and / or vinylidene group.

  Specific examples of such chain transfer agents include hydrocarbon compounds having no hetero atom such as 1-hexene, 2-hexene, styrene, vinylcyclohexane, divinylbenzene; allylamine, glycidyl acrylate, allyl glycidyl ether, ethyl vinyl ether. , Methyl vinyl ketone, 2- (diethylamino) ethyl acrylate, 4-vinylaniline, vinyl methacrylate, allyl methacrylate, styryl methacrylate, allyl acrylate, undecenyl methacrylate, styryl acrylate, ethylene glycol diacrylate, allyltrivinylsilane And hydrocarbon compounds having a heteroatom such as tetraallylsilane. These can be used alone or in combination of two or more. Among these, a hydrocarbon compound having no hetero atom is preferable from the viewpoint that the obtained crosslinked resin molded body and laminate can be made more excellent in crack resistance and crack resistance. More preferred.

  The compounding ratio of the chain transfer agent to the polymerizable composition of the present invention is preferably 0.2 to 10 mol, more preferably 0.5 to 8 mol, relative to 1 mol of the cycloolefin monomer (A). More preferably, it is 1-6 mol. When the blending ratio of the chain transfer agent is too small, the laminate property of the resulting crosslinkable resin molded product tends to be lowered. On the other hand, when it is too much, the peel strength of the obtained laminate tends to be lowered.

(Polymerizable composition)
The polymerizable composition of the present invention comprises the monomer mixture, a metathesis polymerization catalyst, a crosslinking agent, and optionally a chain transfer agent. Moreover, a filler, a flame retardant, a polymerization regulator, a polymerization reaction retarder, an anti-aging agent, other compounding agents, and the like can be added to the polymerizable composition used in the present invention as desired.

  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 improvement of the mechanical strength and heat resistance of the crosslinked resin molding and laminated body which are obtained becomes possible.

  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 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 50 to 350 parts by weight with respect to 100 parts by weight of the monomer mixture.

  As the flame retardant, any industrially used flame retardant can be used without any particular limitation. Examples of the flame retardant include tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, chlorinated polystyrene, chlorinated polyethylene, highly chlorinated polypropylene, chlorosulfonated polyethylene, hexabromobenzene. , Decabromodiphenyl oxide, bis (tribromophenoxy) ethane, 1,2-bis (pentabromophenyl) ethane, tetrabromobisphenol S, tetradecabromodiphenoxybenzene, 2,2-bis (4-hydroxy-3, 5-dibromophenylpropane), halogenated flame retardants such as pentabromotoluene; non-halogenated flame retardants such as phosphorus-containing flame retardants, nitrogen-containing flame retardants, antimony compounds such as antimony trioxide; and the like. These flame retardants can be used alone or in combination of two or more.

  The compounding amount of the flame retardant is usually in the range of 10 to 300 parts by weight, preferably 20 to 200 parts by weight, more preferably 30 to 150 parts by weight with respect to 100 parts by weight of the monomer mixture.

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

  A polymerization reaction retarder can suppress an increase in viscosity of the polymerizable composition of the present invention. 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. What is necessary is just to adjust suitably the compounding quantity of a polymerization reaction retarder in the case of using a polymerization reaction retarder as needed.

  Examples of the anti-aging agent include phenol-based anti-aging agents, amine-based anti-aging agents, phosphorus-based anti-aging agents, sulfur-based anti-aging agents and the like. By blending these anti-aging agents, a crosslinking reaction can be performed. It is preferable because the heat resistance of the resulting crosslinked resin molded body and laminate can be improved to a high degree without hindering. 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. In the case of using an anti-aging agent, the amount of the anti-aging agent used is preferably 0.0001 to 10 parts by weight, more preferably 0.001 to 5 parts by weight, and more preferably 100 parts by weight of the monomer mixture. Preferably it is the range of 0.01-2 weight part.

  Moreover, other compounding agents other than the above-mentioned compounding agents can be blended in the polymerizable composition of the present invention. As other compounding agents, colorants, light stabilizers, pigments, foaming agents and the like can be used. As the colorant, dyes, pigments and the like are 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 metathesis polymerization catalyst is dissolved or dispersed in an appropriate solvent is prepared, and separately a monomer mixture and essential components such as a crosslinking agent. In addition, if necessary, a liquid (monomer liquid) containing other compounding agents is prepared, and a catalyst liquid is added to the monomer liquid, followed by 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.

  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 article 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 a method for heating an impregnated product obtained by impregnating a fibrous reinforcing material with a polymerizable composition include, for example, a method in which an 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) above, 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.

  As described above, the polymer constituting the crosslinkable resin molded product obtained by bulk polymerization of the polymerizable composition of the present invention 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 possibility 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 polymerization of the 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 higher than the 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 above the temperature at which the above-mentioned crosslinkable resin molded article is crosslinked, specifically, by heating at the above-mentioned temperature and time, a lump of cycloolefin monomer is obtained. It is also possible to produce the crosslinked resin molded article of the present invention by proceeding together with the polymerization and the crosslinking reaction in the cycloolefin polymer produced by the polymerization. In the case of producing a crosslinked resin molded body in this manner, 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 is formed by laminating at least the crosslinkable resin molded product or the crosslinked resin molded product. 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 layers 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.

  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 The laminate of the present invention is obtained by laminating and cross-linking by hot pressing to form a crosslinked resin molded body. 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 small dielectric loss tangent in a high frequency region, and is excellent in crack resistance (particularly crack resistance in a thermal shock test) and heat resistance. Can do. Specifically, the laminate of the present invention can be suitably used for a microwave or millimeter wave high-frequency circuit board for use in communication equipment.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. Parts and% in each example are based on weight unless otherwise specified.
In addition, the definition and evaluation method of each characteristic are as follows.

(1) Crack resistance About the laminated body, the heat cycle test was done using the thermal shock apparatus (ESPEC company, TSA-100SW). The conditions of the heat cycle test were as follows: high temperature exposure: + 150 ° C., 30 minutes, normal temperature exposure: 5 minutes, low temperature exposure: −65 ° C., 30 minutes. Then, at each predetermined cycle of the heat cycle test, the surface of the laminate is observed using a digital microscope (KEYENCE, HX-900), and the crack index is calculated by dividing the crack generation area by the total area. When the crack index was 0.1 or more, it was determined that a crack occurred, and the crack resistance was evaluated according to the following criteria.
○: In the sample after 1000 cycles, the occurrence of cracks was not confirmed.
(Triangle | delta): Generation | occurrence | production of a crack was not confirmed in the sample after completion | finish of 500 cycles.
X: Generation of cracks was confirmed in the sample after 500 cycles.

(2) Heat resistance After performing an etching process about a laminated body, the glass transition point was measured using TMA (SII nanotechnology company, S6100 standard type), and the heat resistance was evaluated on the following references | standards.
○: Glass transition point is over 150 ° C. Δ: Glass transition point is over 130 ° C. and 150 ° C. or less. X: Glass transition point is 130 ° C. or less.

Example 1
Benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) 0.05 part of ruthenium dichloride and 0.01 part of triphenylphosphine were dissolved in 1.51 part of indene to form a catalyst. A liquid was prepared. Apart from this, as cycloolefin monomer, ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (ETD) 100 parts, 2.4 parts methacrylate 5-norbornen-2-yl (MAc-NB), and 2,6-bis (1 , 1-Dimethylethyl) -4-methylphenol 0.28 part is added to a glass container, and silica as a filler (manufactured by Admatechs, product name SO-E2, silane coupling agent treated product) 100 parts of an average particle size of 0.5 μm), 20 parts of antimony oxide (PATOX-M, manufactured by Nippon Seiko Co., Ltd.) and ethane-1,2-bis (pentabromophenyl) (SAYTEX 8010, manufactured by Albemarle) as a flame retardant ) 40 parts was added and mixed uniformly. Next, 1.8 parts of divinylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) as a chain transfer agent and di-t-butyl peroxide (manufactured by Kayaku Akzo Co., Ltd., Kayabutyl D (registered trademark)) 1 14 parts were added to obtain a monomer solution. Then, 1.6 ml of the metathesis catalyst solution per 100 parts of cycloolefin monomer was added to this monomer solution and stirred to obtain a polymerizable composition. In addition, the content rate of divinylbenzene was 1 mol with respect to 1 mol of 5-norbornen-2-yl methacrylate (MAc-NB).

  Next, the obtained polymerizable composition was impregnated into glass cloth (E glass, 2112), and this was subjected to a polymerization reaction at 120 ° C. for 3.5 minutes to obtain a prepreg having a thickness of 0.13 mm (crosslinkable resin molding). Body). Furthermore, 16 prepregs were sandwiched between electrolytic copper foils (Type F0, treated with a silane coupling agent, thickness 0.012 mm, manufactured by Furukawa Electric Co., Ltd.), and hot-pressed while maintaining a flat plate shape with a hot press machine. A laminate having a thickness of 2 mm was obtained, in which the cross-linked resin molded bodies were laminated. The conditions for hot pressing were a temperature of 200 ° C., 15 minutes, and a pressure of 3 MPa.

  And according to the above-mentioned method, each evaluation of crack resistance and heat resistance was performed using the obtained laminated body. The results are shown in Table 1.

Example 2
Ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-4-ene (ETD) was changed from 100 parts to 80 parts, and 20 parts of dicyclopentadiene (DCP) was used. A polymerizable composition and a laminate were produced and evaluated in the same manner. The results are shown in Table 1.

Example 3
Ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-4-ene (ETD) was changed from 80 parts to 60 parts and dicyclopentadiene (DCP) was changed from 20 parts to 40 parts. In the same manner as in Example 2, a polymerizable composition and a laminate were produced and evaluated in the same manner. The results are shown in Table 1.

Example 4
Ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-4-ene (ETD) was changed from 80 parts to 40 parts, and dicyclopentadiene (DCP) was changed from 20 parts to 60 parts. In the same manner as in Example 2, a polymerizable composition and a laminate were produced and evaluated in the same manner. The results are shown in Table 1.

Example 5
Ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-4-ene (ETD) was changed from 80 parts to 20 parts and dicyclopentadiene (DCP) was changed from 20 parts to 80 parts. In the same manner as in Example 2, a polymerizable composition and a laminate were produced and evaluated in the same manner. The results are shown in Table 1.

Example 6
Ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-4-ene (ETD) was changed from 80 parts to 5 parts, and dicyclopentadiene (DCP) was changed from 20 parts to 95 parts. In the same manner as in Example 2, a polymerizable composition and a laminate were produced and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 1
Ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (ETD) instead of 100 parts tetracyclo [6.2.1.1 ^3,6 . [0 ^2,7 ] A polymerizable composition and a laminate were produced in the same manner as in Example 1 except that 100 parts of dodeca-4-ene (TCD) was used, and evaluation was performed in the same manner. The results are shown in Table 1.

Comparative Example 2
A polymerizable composition and a laminate were produced and evaluated in the same manner as in Example 4 except that 2.4 parts of 5-norbornen-2-yl methacrylate (MAc-NB) was not blended. It was. The results are shown in Table 1.

Comparative Example 3
The blending amount of 5-norbornen-2-yl methacrylate (MAc-NB) was changed from 2.4 parts to 100 parts, and ethylidenetetracyclo [6.2.1.1 ^3,6 . [0 ^2,7 ] A polymerizable composition and a laminate were produced and evaluated in the same manner as in Example 1 except that 100 parts of dodeca-4-ene (ETD) was not blended. The results are shown in Table 1.

Comparative Example 4
Example 1 except that the cycloolefin monomer used was changed to 80 parts dicyclopentadiene (DCP) and 20 parts styrylnorbornene (ST-NB), and the compounding amount of divinylbenzene was changed to 0.3 parts. In the same manner, a polymerizable composition and a laminate were produced and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 5
The cycloolefin monomer used was ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (ETD) 67.8 parts, vinyl norbornene (Vinyl-NB) 10 parts, and norbornene 22.2 parts, and the compounding amount of divinylbenzene to 0.3 parts A polymerizable composition and a laminate were produced and evaluated in the same manner as in Example 1 except for the change. The results are shown in Table 1.

Comparative Example 6
The cycloolefin monomer used was tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] 67.5 parts dodec-4-ene (TCD) and 32.5 parts styrylnorbornene (ST-NB), and 0.68 parts styrene instead of 1.8 parts divinylbenzene A polymerizable composition and a laminate were produced and evaluated in the same manner as in Example 1 except that was used. The results are shown in Table 1.

表１中、それぞれ、「ＭＡｃ−ＮＢ」はメタクリル酸５−ノルボルネン−２−イル、「ＥＴＤ」はエチリデンテトラシクロ［６．２．１．１^３，６．０^２，７］ドデカ−４−エン、「ＤＣＰ」はジシクロペンタジエン、「ＴＣＤ」はテトラシクロ［６．２．１．１^３，６．０^２，７］ドデカ−４−エン、「ＳＴ−ＮＢ」はスチリルノルボルネン、「Ｖｉｎｙｌ−ＮＢ」はビニルノルボルネンを、示している。

In Table 1, “MAc-NB” is 5-norbornen-2-yl methacrylate and “ETD” is ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, “DCP” is dicyclopentadiene, and “TCD” is tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, “ST-NB” represents styrylnorbornene, and “Vinyl-NB” represents vinylnorbornene.

As shown in Table 1, in cycloolefin monomer (B) having 5-norbornen-2-yl methacrylate which is cycloolefin monomer (A) having (meth) acryloyl group and vinyl group and / or vinylidene group Some ethylidenetetracyclo [6.2.1.1 ^3,6 . When a polymerizable composition having a monomer mixture containing 0 ^2,7 ] dodec-4-ene is used, the resulting laminate is excellent in crack resistance and heat resistance in a thermal shock test. Results were obtained (Examples 1 to 3).

On the other hand, when the cycloolefin monomer (B) having a vinyl group and / or vinylidene group was not used, the result was inferior in crack resistance in a thermal shock test (Comparative Example 1).
Even when the cycloolefin monomer (A) having a (meth) acryloyl group was not used, the results were inferior in crack resistance in the thermal shock test (Comparative Examples 2, 5, 6).
Moreover, when only the cycloolefin monomer (A) which has a (meth) acryloyl group was used as a monomer which comprises a monomer mixture, it became a result inferior to heat resistance (comparative example 3).
Furthermore, even when neither the cycloolefin monomer (A) having a (meth) acryloyl group and the cycloolefin monomer (B) having a vinyl group and / or a vinylidene group were used, the heat resistance was poor. (Comparative Example 4).

Claims (6)

A single amount comprising a cycloolefin monomer (A) having a (meth) acryloyl group and a cycloolefin monomer (B) having a vinyl group and / or a vinylidene group (excluding those having a (meth) acryloyl group). A polymerizable composition comprising a body mixture, a metathesis polymerization catalyst, and a crosslinking agent,
The polymerizable composition in which the content of the cycloolefin monomer (A) is 0.1 to 10% by weight and the content of the cycloolefin monomer (B) is 5 to 95% by weight in the monomer mixture. object.   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 single amount comprising a cycloolefin monomer (A) having a (meth) acryloyl group and a cycloolefin monomer (B) having a vinyl group and / or a vinylidene group (excluding those having a (meth) acryloyl group). A crosslinkable resin molded body for a dielectric layer of a circuit board, which is obtained by bulk polymerization of a polymerizable composition comprising a body mixture, a metathesis polymerization catalyst, and a crosslinking agent,
In the monomer mixture, the content ratio of the cycloolefin monomer (A) is 0.1 to 10% by weight and the content ratio of the cycloolefin monomer (B) is 5 to 95% by weight. A crosslinkable resin molding for a dielectric layer.   A crosslinked resin molded article obtained by crosslinking a polymer obtained by bulk polymerization of the polymerizable composition according to claim 1. A laminate formed by laminating at least the crosslinkable resin molded article according to claim 3 or 4 , or the crosslinked resin molded article according to claim 5 .