JP2011074292A - Polymerizable composition, resin molded product and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable composition, a crosslinkable resin molded product, and a crosslinked resin molded product that are useful for production of a laminate having very low dielectric loss tangent in a high-frequency region and excellent wire embedding properties, and a laminate obtained by using them. <P>SOLUTION: The polymerizable composition contains a cycloolefin monomer, a metathesis polymerization catalyst, a crosslinking agent, and an N-substituted monomaleimide compound. The crosslinkable resin molded product and the crosslinked resin molded product are obtained by using the composition. The laminate is obtained by laminating at least the crosslinkable resin molded product or the crosslinked resin molded product. <P>COPYRIGHT: (C)2011,JPO&INPIT

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.

  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. In these high frequency era circuit boards, a material having a small 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, Patent Document 1 describes a cycloolefin-based crosslinked resin molded article and a crosslinked resin composite material having excellent heat resistance. This document also describes a polymerizable composition and a crosslinkable resin molded article (prepreg) that are preferably used in the production thereof, and the composition contains a crosslinking aid for the purpose of improving the crosslinking reaction rate. It is described that, for example, an imide compound such as maleimide is used as a crosslinking aid. On the other hand, Patent Document 2 discloses that a bismaleimide compound is suitably used as a crosslinking aid from the viewpoint of obtaining a thermoplastic elastomer composition excellent in injection fusion property. It is described that by using a maleimide compound, the viscosity of the resin composition (varnish) can be specifically reduced, and the dielectric loss tangent of a cured product obtained by using it together with quartz glass fiber / polyolefin fiber can be reduced.

International Publication No. 2005/016991 Pamphlet JP 2003-171511 A JP 2008-266408 A

The present inventor describes the polymerizable composition described in Patent Documents 2 and 3 for the purpose of obtaining a laminate having an extremely small dielectric loss tangent in a high-frequency region and an excellent wiring embedding property. A polymerizable composition is prepared by applying such a bismaleimide compound, and then a prepreg is prepared using the composition, and the prepreg is laminated on a printed wiring board manufacturing substrate, followed by heat crosslinking to produce a laminate. As a result, it was revealed that the bismaleimide compound has poor compatibility with the base resin, and the obtained laminate cannot be used practically.
An object of the present invention is to provide a polymerizable composition, a crosslinkable resin molded body, a crosslinkable resin molded body, and a crosslinkable 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 properties. It is providing the laminated body which uses this.

  As a result of intensive studies in view of the above problems, the present inventor prepared a polymerizable composition using an N-substituted monomaleimide compound that is a monomaleimide compound instead of a bismaleimide compound, and the composition was made into glass cloth or the like. It was found that a laminate having desired characteristics can be obtained by impregnating a fibrous reinforcing material and then polymerizing to prepare a prepreg, and then laminating the prepreg and heating and crosslinking. The present inventor has completed the present invention based on such knowledge.

That is, according to the present invention,
[1] A polymerizable composition comprising a cycloolefin monomer, a metathesis polymerization catalyst, a crosslinking agent, and an N-substituted monomaleimide compound,
[2] The polymerizable composition according to [1], wherein the cycloolefin monomer includes a cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond,
[3] The polymerizable composition according to the above [1] or [2], further comprising a filler,
[4] The polymerizable composition according to the above [3], wherein the blending amount of the filler is 50 parts by weight or more with respect to 100 parts by weight of the cycloolefin monomer,
[5] The polymerizable composition according to any one of [1] to [4], further comprising a chain transfer agent,
[6] A crosslinkable resin molded article obtained by bulk polymerization of the polymerizable composition according to any one of [1] to [5],
[7] A crosslinked resin molded article obtained by bulk polymerization of the polymerizable composition according to any one of [1] to [5] and crosslinking, and [8] at least the crosslinkable resin according to [6]. A laminate formed by laminating the molded product or the crosslinked resin molded product according to [7],
Is provided.

  According to the present invention, the polymerizable composition, the crosslinkable resin molded body, the crosslinkable resin molded body, and the laminate are useful for producing a laminate having an extremely small dielectric loss tangent in a high frequency region and excellent wiring embedding properties. The body is obtained. Since the laminate of the present invention exhibits excellent dielectric properties and excellent wiring embedding properties, it can be suitably used as a printed wiring board material.

  The polymerizable composition of the present invention comprises a cycloolefin monomer, a metathesis polymerization catalyst, a crosslinking agent, and an N-substituted monomaleimide compound.

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

  Examples of the alicyclic structure of the cycloolefin monomer include monocycles, polycycles, condensed polycycles, bridged rings, and combination polycycles thereof. The cycloolefin monomer used in the present invention is preferably a polycyclic cycloolefin monomer from the viewpoint of improving the mechanical strength of the resulting crosslinked resin molded article. Although there is no limitation in particular in the carbon atom 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 may have a hydrocarbon group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkylidene group or an aryl group, or a polar group such as a carboxyl group or an acid anhydride group as a substituent. .

  In the present invention, the cycloolefin monomer is a cyclohexane having at least one crosslinkable carbon-carbon unsaturated bond from the viewpoint of improving mechanical strength and heat resistance by improving the crosslinking density of the resulting crosslinked resin molded article. Olefin monomers are preferably used. As used herein, “crosslinkable carbon-carbon unsaturated bond” refers to a carbon-carbon unsaturated bond that does not participate in metathesis ring-opening polymerization but participates in a crosslinking reaction. “Crosslinking reaction” refers to a reaction that forms a bridge structure. In the present invention, the crosslinking reaction usually means a radical crosslinking reaction or a metathesis crosslinking reaction, particularly a radical crosslinking reaction.

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

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

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

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

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

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

  In the cycloolefin monomer blended in the polymerizable composition of the present invention, the blending ratio of the cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond and the cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond May be appropriately selected as desired, but is usually 5% by weight ratio (cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond / cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond). / 95 to 100/0, preferably 10/90 to 95/5, more preferably 15/85 to 90/10. If the said mixture ratio exists in this range, in the crosslinked resin molding obtained, heat resistance and mechanical strength will improve with sufficient balance, 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.

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

  Among these, a group 8 ruthenium or osmium complex is preferable, and a ruthenium carbene complex is particularly preferable. Since the ruthenium carbene complex is excellent in catalytic activity at the time of bulk polymerization, it is possible to obtain a crosslinkable resin that is excellent in productivity of the crosslinkable resin and has less odor derived from residual unreacted monomers. In addition, the group 8 ruthenium and osmium complexes are relatively stable to oxygen and moisture in the air and are not easily deactivated, so that a crosslinkable resin can be produced even in the air.

  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 may each independently contain 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. A cyclic or chain hydrocarbon group having 1 to 20 carbon atoms is represented. X ¹ and X ² each independently represent an arbitrary anionic ligand. L ¹ and L ² each independently represent a hetero atom-containing carbene compound or a neutral electron donating compound other than the hetero atom-containing carbene compound. R ¹ and R ² may be bonded to each other to form an aliphatic ring or an aromatic ring that may contain a hetero atom. Furthermore, R ¹ , R ² , X ¹ , X ² , L ¹ and L ² may be bonded together in any combination to form a multidentate chelating ligand.

  A hetero atom refers to an atom of Groups 15 and 16 of the periodic table. Specific examples of the hetero atom include a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, an arsenic atom, and a selenium atom. Among these, from the viewpoint of obtaining a stable carbene compound, a nitrogen atom, an oxygen atom, a phosphorus atom and a sulfur atom are preferable, and a nitrogen atom is particularly preferable.

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

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

In Formula (3) or Formula (4), R ^{3 to} R ⁶ may 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 cyclic or chain hydrocarbon group having 1 to 20 carbon atoms. R ^{3 to} R ⁶ may be bonded to each other in any combination to form a ring.

  Specific examples of the compound represented by Formula (3) or Formula (4) include 1,3-dimesitylimidazolidin-2-ylidene and 1,3-di (1-adamantyl) imidazolidine-2- Iridene, 1-cyclohexyl-3-mesitylimidazolidine-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3 -Di (1-phenylethyl) -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 metal atom, for example, Examples thereof include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, diketonate group, substituted cyclopentadienyl group, alkoxy group, aryloxy group and carboxyl group. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

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

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

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

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

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

  Among these complex compounds, those having one compound represented by the formula (1) and represented by the formula (4) as a ligand are most preferable.

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

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

  In addition, when a complex of transition metal atoms of Group 5 and Group 6 is used as the metathesis polymerization catalyst, the metathesis polymerization catalyst is preferably used by dissolving in a monomer, but does not substantially impair the properties of the product. If so, it can be suspended or dissolved in a small amount of solvent.

(Crosslinking agent)
The crosslinking agent is used for the purpose of inducing a crosslinking reaction in a polymer obtained by subjecting the polymerizable composition of the present invention to a polymerization reaction. Accordingly, the polymer becomes 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 polymer as a base resin is melted by heating and has a high viscosity, while maintaining its shape, when any member is brought into contact with the surface, It 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. .

  As the crosslinking agent, a radical generator is preferably used. 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 and 1,1-di (t-hexylperoxy) cyclohexane 1,1-di (t-butylperoxy) -2- Peroxyketals such as methylcyclohexane 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; and the like. Among these, dialkyl peroxides, peroxyketals, and cyclic peroxides are preferable in that there are few obstacles to the metathesis polymerization reaction.

Examples of the diazo compound include 4,4′-bisazidobenzal (4-methyl) cyclohexanone, 2,6-bis (4′-azidobenzal) cyclohexanone, and the like.
Examples of the nonpolar radical generator include 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1,1,2-triphenylethane, 1,1,1. -Triphenyl-2-phenylethane and the like.
These radical generators can be used alone or in combination of two or more.

  When the cross-linking agent used in the present invention is a radical generator, its one minute half-life temperature 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). However, it is usually in the range of 100 to 300 ° C, preferably 120 to 250 ° C, more preferably 150 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. About the 1 minute half life temperature of a radical generator, what is necessary is just to refer to the catalog and homepage of each radical generator manufacturer (for example, Nippon Oil & Fat Co., Ltd.), for example.

  The compounding amount of the crosslinking agent 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 0 to 100 parts by weight of the cycloolefin monomer. The range is from 5 to 5 parts by weight.

(N-substituted monomaleimide compound)
The N-substituted monomaleimide compound used in the present invention functions as a reactive fluidizing agent. As described above, the polymer obtained by subjecting the polymerizable composition of the present invention to a polymerization reaction becomes a post-crosslinkable thermoplastic resin. In the present invention, the “reactive fluidizing agent” refers to the crosslinkability of the present invention that lowers the glass transition temperature (Tg) of the polymer as a fluidizing agent and uses the polymer as a base resin. When the resin molded body is heated and melted, it improves the followability of the surface of the molded body with respect to the shape of any member that is in contact with the surface, but is involved in the reaction after the crosslinking reaction is induced by the crosslinking agent. A monofunctional compound exhibiting binding reactivity to a polymer.

  Since the N-substituted monomaleimide compound functions as a reactive fluidizing agent, for example, when laminating the crosslinkable resin molded product of the present invention having the polymer containing the compound as a base resin, with a circuit board or the like, The molded body can be easily melted and laminated by heating, and sufficient laminate adhesion and wiring embedding can be obtained in the obtained laminated body. Furthermore, since the N-substituted monomaleimide compound is involved in the crosslinking reaction induced by the crosslinking agent by heating during lamination and exhibits binding reactivity to the polymer, it is released in the polymer as the crosslinking reaction proceeds. It is considered that there is a decrease in the amount of the compound existing in the state of (2), and there is substantially no component in the free state at the end of the crosslinking reaction. Therefore, unlike what is called a plasticizer, it does not become a factor which reduces the heat resistance of the laminated body obtained. Rather, the N-substituted monomaleimide compound can exhibit the effect of improving heat resistance and crack resistance in the resulting laminate.

  Specifically, the N-substituted monomaleimide compound used in the present invention has the following formula:

When a crosslinking reaction is induced by a crosslinking agent, the compound reacts with a crosslinkable carbon-carbon double bond or the like in a polymer (cycloolefin polymer) to form a polymer. It is thought that it is combined with.

  In the above formula, R is not particularly limited as long as it does not inhibit the expression of the effects of the present invention, but is usually substituted or unsubstituted, 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1-10, an alkyl group, a cycloalkyl group, or an aryl group is shown. Examples of the substituent include, for example, an alkyl group, a cycloalkyl group, or an aryl group having 1 to 10 carbon atoms; a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; a carboxyl group; an amino group; a nitro group; Examples include heterocyclic substituents such as imidazole.

Specific examples of the N-substituted monomaleimide compound include N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, and N-phenyl. Maleimide, N-methylphenylmaleimide, N-benzylmaleimide, N-chlorophenylmaleimide, N-carboxyphenylmaleimide, N-aminomaleimide, N-nitromaleimide, N- (1-pyrenyl) maleimide, N-methylphenylmaleimide, etc. Can be mentioned. Among these, N-phenylmaleimide, N-methylphenylmaleimide, N-benzylmaleimide, and N-cyclohexylmaleimide are preferable from the viewpoint of reducing the dielectric loss tangent of the obtained crosslinked resin molded body and laminate.
These N-substituted monomaleimide compounds can be used alone or in combination of two or more. The compounding amount of the compound may be appropriately selected as desired, but is usually 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, more preferably 1 to 100 parts by weight with respect to 100 parts by weight of cycloolefin monomer. 30 parts by weight.

(Polymerizable composition)
The polymerizable composition used in the present invention contains the above cycloolefin monomer, metathesis polymerization catalyst, crosslinking agent, and N-substituted monomaleimide compound as essential components, and optionally, a filler, a polymerization regulator, and a polymerization reaction. Other additives such as 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 for the purpose 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.

  The filler may be an inorganic substance or an organic substance, and may be appropriately selected as desired. Usually, an inorganic filler is preferably used. Such inorganic fillers can be classified into, for example, low linear expansion fillers, flame retardants, and the like according to their characteristics. In the present invention, the inorganic fillers can be used alone or in combination of two or more.

The low linear expansion filler is preferable because it can be added to the polymerizable composition of the present invention to improve the mechanical strength of the resulting laminate and reduce the linear expansion coefficient. The linear expansion coefficient of the low linear expansion filler is usually about 15 ppm / ° C. or less.
Examples of the low linear expansion filler include inorganic oxides such as silica, silica balloon, alumina, iron oxide, zinc oxide, magnesium oxide, tin oxide, beryllium oxide, barium ferrite, strontium ferrite; calcium carbonate, magnesium carbonate, hydrogen carbonate Inorganic carbonates such as sodium; inorganic sulfates such as calcium sulfate; inorganic silicates such as talc, clay, mica, kaolin, fly ash, montmorillonite, calcium silicate, glass, and glass balloon; Silica.

  By blending a flame retardant with the polymerizable composition of the present invention, the resulting laminate is flame retardant and is suitable. The flame retardant can be used without particular limitation as long as it is industrially used. Phosphorus-containing flame retardant, nitrogen-containing flame retardant, halogen-containing flame retardant, metal hydroxide flame retardant such as aluminum hydroxide And antimony compounds such as antimony trioxide. Among them, a halogen-containing flame retardant is preferable, and a brominated organic compound that contains a bromine atom as a halogen and does not have an unsaturated bond is more preferable because it does not affect the crosslinking reaction. As such brominated organic compounds, aromatic brominated compounds such as decabromodiphenylethane, 4,4-dibromobiphenyl, and ethylenebistetrabromophthalimide are particularly preferable. Furthermore, a halogenated triallyl isocyanurate, a fluorinated aliphatic resin, or the like can be used as the halogen-containing flame retardant. Moreover, as a flame retardant, what has a true specific gravity in the range of 2-3.5 is 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.

  These fillers can be used alone or in combination of two or more. The compounding amount with respect to 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, further preferably 100 parts by weight of the cycloolefin monomer. Is in the range of 100 to 500 parts by weight. When the filling amount is less than these ranges, the mechanical strength may be decreased or the linear thermal expansion coefficient may be increased. If the filling amount is larger than this, the wiring embedding property may be insufficient. On the other hand, when using a flame retardant as a filler, the usage-amount of a flame retardant is 1-200 weight part normally with respect to 100 weight part of cycloolefin monomers, Preferably it is 10-100 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 it can be easily impregnated into a fibrous reinforcing material when a crosslinkable resin molded article is prepared as described below. Polymerization 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 the compounding quantity suitably as needed.

  When a chain transfer agent is added to the polymerizable composition used in 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, melting, and crosslinking, interlayer adhesion is further enhanced. This is preferable because the wiring embedding property 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 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, 4-vinyl. A chain transfer agent having no crosslinkable carbon-carbon unsaturated bond, such as aniline; divinylbenzene, vinyl methacrylate, hexenyl methacrylate, allyl methacrylate, styryl methacrylate, allyl acrylate, undecenyl methacrylate, styryl acrylate, Chain transfer agent having one crosslinkable carbon-carbon unsaturated bond, such as ethylene glycol diacrylate; a chain having two or more crosslinkable carbon-carbon unsaturated bonds, such as allyltrivinylsilane and allylmethyldivinylsilane Such as transfer agents, and the like. From the viewpoint of improving the strength of the crosslinked resin molded product and the laminate, those having one or more crosslinkable carbon-carbon unsaturated bonds are preferable, and those having one crosslinkable carbon-carbon unsaturated bond are more preferable.
These chain transfer agents can be used alone or in combination of two or more. The amount of the chain transfer agent used is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the cycloolefin monomer.

  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, more preferably 100 parts by weight of the cycloolefin monomer to be blended. Is in the range of 0.01 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, 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 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 additives, 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, and in the method (c), the fibrous reinforcing material can be impregnated with the polymerizable composition quickly and uniformly.

  According to the method (a), a crosslinkable resin molded product such as a film or plate can be obtained. The thickness of the molded body is usually 15 mm or less, preferably 5 mm or less, more preferably 0.5 mm or less, and most preferably 0.1 mm or less. Examples of the support include films and plates made of resins such as 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), usually 10 μm or less, preferably 5 μm or less, more preferably Is 3 μm or less, more preferably 2 μm or less. The surface of the metal foil is preferably treated with a known coupling agent or adhesive. According to the method (a), for example, when a copper foil is used as the support, a resin-coated copper foil (Resin Coated Copper (RCC)) can be obtained.

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

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

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

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

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

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

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

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

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

  The crosslinkable resin molded article of the present invention is a post-crosslinkable resin molded article, but a part of the constituent resin may be crosslinked. For example, when the polymerizable composition is bulk-polymerized in the mold, the temperature of a part of the mold may become too high because the polymerization reaction heat hardly diffuses in the central part of the mold. In the high temperature part, a cross-linking reaction occurs, and cross-linking may occur. However, 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 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 crosslinkable resin molded body. 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 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 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 a layered manner is obtained according to the method (a). Can be mentioned. In the method (a), if a separately obtained crosslinked resin molded body is used as the support, a laminate of the crosslinkable resin molded body and the crosslinked resin molded body can be obtained.
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 excellent electrical characteristics unique to cycloolefin polymers, such as low dielectric constant and low dielectric loss tangent, and has extremely small dielectric loss tangent in the high frequency region and excellent wiring embedding properties. It is. The laminate of the present invention can be suitably used as a printed wiring board material, for example.

Each characteristic in an Example and a comparative example was measured and evaluated according to the following methods.
(1) Dielectric loss tangent Using a sample obtained by removing the copper foil from the laminate as a sample, the dielectric loss tangent (tan δ) at a frequency of 1 GHz at 20 ° C. using an impedance analyzer (manufactured by Agilent Technologies, model number E4991A) by the capacitance method. It was measured.
(2) Glass transition point (Tg)
A strip-shaped test piece (width 4 mm × length 35 mm) was cut out from the sample prepared in “(1) Dielectric loss tangent” and used as a test piece for measurement. The test piece was subjected to measurement by a dynamic viscoelasticity tester (model number: EXSTAR DMS6100, manufactured by Seiko Instruments Inc.), and Tg was determined from the peak value of tan δ.
(3) Wiring embedding property A prepreg sheet is stacked on a circuit board (a test board on which 15 wirings of L / S = 30 μm and thickness 18 μm are arranged), and heated and pressed at 3 MPa for 10 minutes at 200 ° C. Got. 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.
◎: No wiring is not embedded ×: No wiring is embedded

Example 1
A catalyst solution was prepared by dissolving 51 parts of benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and 79 parts of triphenylphosphine in 952 parts of toluene. Separately, 100 parts of tetracyclo [6.2.13, 6.02,7] dodec-4-ene (tetracyclododecene) as a cycloolefin monomer, 1.7 parts of divinylbenzene as a chain transfer agent, 2 parts of di-t-butyl peroxide (186 ° C., 1 minute half-life temperature) as a crosslinking agent, 125 parts of silica as a filler, and 6.8 parts of N-cyclohexylmaleimide as an N-substituted monomaleimide compound are mixed to prepare a monomer solution. Prepared. The said catalyst liquid was added here in the ratio of 0.12mL per 100g of cycloolefin monomers, and it stirred, and prepared polymeric composition.

  300 mm long, 300 mm wide, 0.08 mm thick glass fiber reinforced polytetrafluoroethylene (PTFE) resin film (product number 5310, manufactured by Saint-Gobain Norton) 200 mm long, 200 mm wide, 0.174 mm thick Two glass cloths (product number 7628 / AS891AW, manufactured by Asahi Schavel) were placed on top of each other, and the above polymerizable composition was poured thereon. Next, another glass fiber-reinforced PTFE resin film similar to the above was covered from above, and was squeezed with a roller to impregnate the polymerizable composition. The laminate obtained by sandwiching the upper and lower sides of the glass cloth impregnated material of the polymerizable composition thus obtained between the glass fiber reinforced PTFE resin films was attached to a hot plate heated to 145 ° C. for 1 minute for polymerization. Subsequently, the glass fiber reinforced PTFE resin films on the upper and lower surfaces were peeled off to obtain a prepreg sheet as a crosslinkable resin molded body.

  Next, 5 sheets of the prepared prepreg sheets were stacked, and the laminated prepreg sheets were sandwiched between 12 μm F2 copper foil (silane coupling agent-treated electrolytic copper foil, roughness Rz = 1,600 nm, manufactured by Furukawa Circuit Foil Co., Ltd.), 205 Heat pressing was performed at 3 MPa for 20 minutes at ° C. to obtain a laminated body in which crosslinked resin molded bodies were laminated. The copper foil was removed from the obtained laminate by etching, and the dielectric loss tangent and glass transition point were measured. On the other hand, the evaluation of wiring embedding was performed by separately obtaining a laminate by the method described in (3) Wiring embedding. The evaluation results are shown in Table 1.

Example 2
A laminate was obtained in the same manner as in Example 1 except that 9 parts of N-phenylmaleimide was used instead of N-cyclohexylmaleimide. The evaluation results are shown in Table 1.

Comparative Example 1
A laminate was obtained in the same manner as in Example 1 except that N-cyclohexylmaleimide was not used. The evaluation results are shown in Table 1.

Comparative Example 2
A laminate was obtained in the same manner as in Example 1 except that 10 parts of m-phenylenebismaleimide was used instead of N-cyclohexylmaleimide. Since m-phenylene bismaleimide does not show compatibility with the base resin in the crosslinked resin molded body constituting the laminate, and the dispersibility is poor, each evaluation of the laminate cannot be performed.

Comparative Example 3
A laminate was obtained in the same manner as in Example 1 except that 6 parts of 1,3-diisopropenylbenzene was used instead of N-cyclohexylmaleimide. The evaluation results are shown in Table 1.

  From Table 1, the laminate obtained using the N-substituted monomaleimide compound has a very low dielectric loss tangent (tan δ) in the high-frequency region, excellent wiring embedding properties, and a high Tg. (Examples 1 and 2). On the other hand, when no N-substituted monomaleimide compound was used (Comparative Example 1), the resulting laminate had poor wiring embedding properties, and could function as a crosslinking aid instead of the N-substituted monomaleimide compound. When 1,3-diisopropenylbenzene, which is a functional compound, is used (Comparative Example 3), the resulting laminate has good wiring embedding properties, but the dielectric loss tangent is slightly deteriorated and Tg is lowered, resulting in heat resistance. It turns out that it is inferior. On the other hand, when a bismaleimide compound was used instead of the N-substituted monomaleimide compound (Comparative Example 2), as described above, a practically usable laminate was not obtained.

Claims (8)

  A polymerizable composition comprising a cycloolefin monomer, a metathesis polymerization catalyst, a crosslinking agent, and an N-substituted monomaleimide compound.   The polymerizable composition according to claim 1, wherein the cycloolefin monomer comprises a cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond.   The polymerizable composition according to claim 1 or 2, further comprising a filler.   The polymerizable composition according to claim 3, wherein the blending amount of the filler is 50 parts by weight or more with respect to 100 parts by weight of the cycloolefin monomer.   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 bulk polymerization of the polymerizable composition according to claim 1 and crosslinking.   A laminate formed by laminating at least the crosslinkable resin molded article according to claim 6 or the crosslinked resin molded article according to claim 7.