JP2010168487A - Polymerizable composition, crosslinked body, and crosslinked resin composite object - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable composition giving a crosslinked body being excellent in high frequency characteristic, heat-resistance and anti-crack property at cold heat impact test and a crosslinked resin composite, and a crosslinked body and a crosslinked resin composite object obtained by using this. <P>SOLUTION: The polymerizable composition contains a norbornene based monomer, a metathesis polymerization catalyst, a chain transfer agent, a crosslinking agent, and a crosslinked rubber particle. Preferably, an average particle diameter of the crosslinked rubber particle is 10-2,000 nm, and further, a containing ratio of the crosslinked rubber particle is 0.1-100 pts.wt. based on 100 pts.wt. of the norbornene based monomer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polymerizable composition, a crosslinked product, and a crosslinked resin composite, and more particularly, a polymerizable composition that provides a crosslinked product and a crosslinked resin composite excellent in high-frequency characteristics, heat resistance, and crack resistance in a thermal shock test. And a crosslinked body and a crosslinked resin composite obtained using the same.

  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) The selection of body materials has become an important issue.

  For example, in Patent Document 1, as a material for constituting the dielectric layer of such a circuit board, 100 parts by weight of a thermoplastic resin or a mixture of a thermoplastic resin and a thermosetting resin, and a layered silicate 0 An insulating substrate material containing 1 to 100 parts by weight is disclosed. In addition, this patent document 1 describes that an epoxy-modified butadiene rubber, which is a liquid rubber component, is added to an insulating substrate material. However, in the insulating substrate material obtained using the thermoplastic resin described in Patent Document 1 or a mixture of a thermoplastic resin and a thermosetting resin, the dielectric loss tangent is not necessarily kept sufficiently low, For this reason, there is a problem that it cannot cope with high frequency.

  On the other hand, a cycloolefin polymer obtained by bulk polymerization of cycloolefin monomers has attracted attention as a resin material having a small dielectric loss tangent. For example, Patent Document 2 discloses a polymerizable composition for a dielectric layer of a circuit board containing a cycloolefin monomer, a metathesis polymerization catalyst, a crosslinking agent, a chain transfer agent, and a specific liquid diene rubber. Yes. In Patent Document 2, the flowability of the polymerizable composition is improved by adding a liquid diene rubber to the polymerizable composition containing a cycloolefin monomer.

  Similarly to Patent Document 2, as a technique for blending rubber into a resin material, Patent Document 3 includes an epoxy resin having an average particle size in the range of 20 to 500 nm, a uniform structure, and a gel content. Has disclosed a reinforced thermosetting resin comprising 75% by weight or more of rubber particles. In Patent Document 3, the toughness of the epoxy resin is improved by blending the predetermined rubber particles with the epoxy resin.

JP 2003-26939 A JP 2008-133417 A JP 2005-510613 A

  However, as a result of studies by the present inventors, the insulating substrate material described in Patent Document 1 and the polymerizable composition described in Patent Document 2 are inferior in heat resistance, and further, under the expected use environment of a circuit board. The problem that it was inferior also to the crack resistance at the time of repeated use of was recognized. Further, the reinforced thermosetting resin described in Patent Document 3 has a problem that the dielectric loss tangent is not suppressed sufficiently low, a problem that the operability is poor because of high viscosity, and a repeated use under an environment where the circuit board is assumed to be used. The problem of inferior crack resistance during use was observed.

  An object of the present invention is to provide a crosslinked composition and a crosslinked resin composite excellent in high-frequency characteristics, heat resistance and crack resistance in a thermal shock test, and a crosslinked composition and a crosslinked resin obtained using the same. It is to provide a complex.

  As a result of intensive studies in view of the above problems, the present inventors have incorporated high-frequency characteristics by incorporating crosslinked rubber particles into a polymerizable composition containing a norbornene-based monomer, a metathesis polymerization catalyst, a crosslinking agent, and a chain transfer agent. It has been found that a polymerizable composition giving a crosslinked body and a crosslinked resin composite excellent in heat resistance and crack resistance in a thermal shock test can be obtained, and the present invention has been completed based on this finding.

That is, according to the present invention,
[1] A polymerizable composition comprising a norbornene-based monomer, a metathesis polymerization catalyst, a chain transfer agent, a crosslinking agent, and crosslinked rubber particles,
[2] The polymerizable composition according to [1], wherein the crosslinked rubber particles have an average particle size of 10 to 2,000 nm.
[3] The polymerizable composition according to [1] or [2], wherein the content ratio of the crosslinked rubber particles is 0.1 to 100 parts by weight with respect to 100 parts by weight of the norbornene monomer.
[4] The polymerizable composition according to any one of [1] to [3], wherein the gel content of the crosslinked rubber particles is 50 to 99.9% by weight,
[5] A crosslinkable resin obtained by bulk polymerization of the polymerizable composition according to any one of [1] to [4],
[6] A crosslinkable resin composite obtained by coating or impregnating the polymerizable composition according to any one of the above [1] to [4] on a support and performing bulk polymerization,
[7] A crosslinked product obtained by crosslinking the crosslinkable resin according to [5], and
[8] A crosslinked resin composite comprising the crosslinked body according to [7] and a support,
Is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the polymeric composition which gives the crosslinked body and crosslinked resin composite excellent in the high frequency characteristic, heat resistance, and the crack resistance in a thermal shock test, and the crosslinked body and crosslinked resin obtained using this A complex is provided. The crosslinked body and crosslinked resin composite of the present invention are excellent in high-frequency characteristics, heat resistance, and crack resistance in a thermal shock test, and therefore suitable for high-frequency circuit boards such as microwaves or millimeter waves for communication equipment applications. Can be used.

  The polymerizable composition of the present invention comprises a norbornene monomer, a metathesis polymerization catalyst, a chain transfer agent, a crosslinking agent, and crosslinked rubber particles.

(Norbornene monomer)
The norbornene-based monomer used in the present invention is a monomer containing a norbornene ring. Specific examples include norbornenes, dicyclopentadiene, and tetracyclododecenes. These may contain a hydrocarbon group 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 addition to the norbornene ring double bond, it may further have a double bond. Among these, those having no polar group, that is, norbornene monomers composed only of carbon atoms and hydrogen atoms are preferable.

  Here, norbornene-based monomers are classified into those having no crosslinkable carbon-carbon unsaturated bond and those having one or more crosslinkable carbon-carbon unsaturated bonds. As used herein, “crosslinkable carbon-carbon unsaturated bond” refers to a carbon-carbon unsaturated bond that does not participate in ring-opening polymerization and can participate in a crosslinking reaction. The 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. In the norbornene-based monomer having one or more crosslinkable carbon-carbon unsaturated bonds, the position of the unsaturated bond is not particularly limited, and any other than the ring structure other than the ring structure formed by carbon atoms. For example, at the end or inside of the side chain.

  Examples of the norbornene-based monomer having no crosslinkable carbon-carbon unsaturated bond 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- Methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2, 3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-Fluoro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano- 1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8, 8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4 4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2- Dihydrodicyclopentadiene, 5-chloro-2-norbornene, 5,5-dichloro-2-norbornene, 5-fluoro-2-norbornene, 5,5,6-trifluoro-6-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, etc. be able to.

  Examples of norbornene monomers having one or more crosslinkable carbon-carbon unsaturated bonds include 5-ethylidene-2-norbornene, 5-methylidene-2-norbornene, 5-isopropylidene-2-norbornene, and 5-vinyl- Examples include 2-norbornene, 5-allyl-2-norbornene, 5,6-diethylidene-2-norbornene, dicyclopentadiene, 2,5-norbornadiene, and the like.

  The norbornene-based monomers described above can be used alone or in combination of two or more.

(Metathesis polymerization catalyst)
The metathesis polymerization catalyst used in the present invention is not particularly limited as long as it can perform a metathesis ring-opening polymerization of a norbornene-based monomer, but usually a plurality of ions, atoms, polyatomic ions and / or a transition metal atom as a central atom. Examples include complexes formed by bonding 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 the productivity of the crosslinkable resin, and the resulting crosslinkable resin 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 represents an arbitrary anionic ligand independently. 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 represents a hetero atom-containing carbene compound or a neutral electron donating 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, it is possible to use a ruthenium catalyst having a compound having a heterocyclic structure as a ligand as a metathesis polymerization catalyst. The resulting crosslinked product and crosslinked resin composite have high-frequency characteristics, heat resistance and resistance to thermal shock tests. 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: 5,000 to 1: 1, in a molar ratio of (metal atom in catalyst: norbornene monomer). In the range of 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.

(Chain transfer agent)
The chain transfer agent used in the present invention is not particularly limited as long as it can participate in the metathesis ring-opening polymerization. However, the chain transfer agent is used at the end of the crosslinkable resin obtained by polymerizing the polymerizable composition of the present invention. Compounds having one bondable aliphatic carbon-carbon double bond are preferred. Examples of such bondable aliphatic carbon-carbon double bonds include terminal vinyl groups. Moreover, the chain transfer agent may have one or more crosslinkable carbon-carbon unsaturated bonds.

  Specific examples of such chain transfer agents include 1-hexene, 2-hexene, styrene, vinylcyclohexane, allylamine, glycidyl acrylate, allyl glycidyl ether, ethyl vinyl ether, methyl vinyl ketone, 2- (diethylamino) ethyl acrylate, A chain transfer agent having no crosslinkable carbon-carbon unsaturated bond, such as 4-vinylaniline; divinylbenzene, vinyl 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; Chain transfer agent having two or more crosslinkable carbon-carbon unsaturated bonds, such as allyltrivinylsilane and tetraallylsilane Is It is. Among these, the crosslinkable carbon-carbon unsaturated bond is used from the viewpoint that the high-frequency characteristics, heat resistance, and crack resistance in the thermal shock test of the obtained crosslinked body and crosslinked resin composite can be highly balanced. Those having 1 or more are preferable. Among these chain transfer agents, chain transfer agents having one vinyl group and one methacryl group are preferable, and vinyl methacrylate, allyl methacrylate, styryl methacrylate, undecenyl methacrylate, and the like are particularly preferable.

  These chain transfer agents can be used alone or in combination of two or more. The blending amount of the chain transfer agent in the polymerizable composition of the present invention is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the norbornene monomer.

(Crosslinking agent)
The crosslinking agent used in the present invention is used for the purpose of inducing a crosslinking reaction in a crosslinkable resin obtained by bulk polymerization of the polymerizable composition of the present invention. Therefore, the crosslinkable resin obtained by bulk polymerization of the polymerizable composition of the present invention becomes a postcrosslinkable thermoplastic resin. 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 the condition for curing (crosslinking of the crosslinkable resin and the crosslinkable resin composite 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, still more preferably 100 parts by weight of the norbornene monomer. The range is 0.5 to 5 parts by weight.

(Crosslinked rubber particles)
The crosslinked rubber particles are rubber particles having a crosslinked structure at least partially. By blending the crosslinked rubber particles with the polymerizable composition of the present invention, the heat resistance and crack resistance in the thermal shock test of the resulting crosslinked body and crosslinked resin composite can be improved. The type of rubber constituting the crosslinked rubber particles is not particularly limited. For example, natural rubber, styrene-butadiene rubber, carboxyl styrene-butadiene rubber, nitrile rubber, carboxyl nitrile rubber, chloroprene rubber, polybutadiene rubber, acrylic rubber, butadiene -Styrene-vinyl pyridine rubber, isoprene rubber, butyl rubber, ethylene-propylene rubber, polysulfide rubber, acrylate-butadiene rubber, urethane rubber, silicone rubber, fluorine rubber and the like. Among these, styrene-butadiene rubber, nitrile rubber, acrylic rubber, polybutadiene rubber, and silicone rubber are preferable from the viewpoint of high electrical insulation and workability, and styrene-butadiene rubber, polybutadiene rubber, and isoprene rubber. Silicone rubber is more preferable, and styrene-butadiene rubber and silicone rubber are particularly preferable.

  The average particle diameter of the crosslinked rubber particles is preferably 10 to 2,000 nm, more preferably 20 to 1,500 nm, still more preferably 30 to 1,000 nm, and particularly preferably 50 to 500 nm. The average particle diameter of the crosslinked rubber particles can be measured by a scanning electron microscope (Scanning EIeotron Microscopy). If the average particle size of the crosslinked rubber particles is too small, the viscosity may increase when blended into the polymerizable composition. On the other hand, if it is too large, the effect of improving the heat resistance and crack resistance of the resulting crosslinked product and crosslinked resin composite may not be obtained.

The gel content of the crosslinked rubber particles is preferably 50% to 99.9% by weight, more preferably 75 to 99.9% by weight, and still more preferably 90 to 99.9% by weight. If the gel content of the crosslinked rubber particles is too small, it may be compatible with the resin, and the effect of improving the heat resistance and crack resistance of the resulting crosslinked body and crosslinked resin composite may not be obtained. The gel content of the crosslinked rubber particles can be measured by the following method. That is, first, the crosslinked rubber particles (the weight of the crosslinked rubber particles is set to W ₀ ) are wrapped with lens paper, and then wrapped in a 200 mesh copper screen cloth, and then the copper screen cloth and contents (lens The total weight of the paper and the crosslinked rubber particles (this weight is designated as W ₁ ) is measured. The copper screen cloth and contents are then placed in boiling toluene for about 6 hours. Next, the boiled copper screen cloth and the contents are completely dried, and the total weight of these is measured (this weight is referred to as W ₂ ). And the gel content of a crosslinked rubber particle can be calculated | required according to a following formula.
Gel content (%) = {W ₀ − (W ₁ −W ₂ )} / W ₀ × 100

  The glass transition temperature (Tg) of the crosslinked rubber particles is not particularly limited, but is preferably 0 ° C. or lower, more preferably −10 ° C. or lower, and further preferably −20 ° C. or lower.

  The crosslinked rubber particles used in the present invention may be hollow particles. By using hollow particles, it is possible to improve the electrical properties of the resulting crosslinked product and crosslinked resin composite. The porosity in the case of using hollow particles as the crosslinked rubber particles is usually 10% by volume or more, preferably 20 to 90% by volume, more preferably 25 to 80% by volume, and further preferably 30 to 70% by volume. The porosity is in accordance with “porosity (%) = {(specific gravity of rubber material constituting crosslinked rubber particles−specific gravity of crosslinked rubber particles themselves) / specific gravity of rubber material constituting crosslinked rubber particles} × 100”. Can be sought.

  The crosslinked rubber particles can be obtained, for example, by a method of chemically performing a crosslinking reaction when a corresponding rubber latex is produced by an emulsion polymerization method or the like. In the emulsion polymerization method, an anionic, cationic, nonionic or amphoteric surfactant is used as an emulsifier. Usually, in the presence of a molecular weight regulator, the polymerization reaction of each monomer is initiated by a radical polymerization initiator, When the polymerization conversion rate is reached, a polymerization terminator is added if necessary to stop the polymerization reaction, and then the unreacted monomer in the system is removed by steam distillation or the like as necessary. The particulate polymer thus obtained can be obtained as a latex.

  Alternatively, for example, in order to increase the degree of crosslinking, the crosslinked rubber particles are crosslinked by irradiating a pre-prepared rubber latex with high energy rays in the presence of a crosslinking agent or in a condition where no crosslinking agent is used. It may be obtained as a latex of particulate polymer. Examples of the high energy ray include a cobalt source, X-rays, ultraviolet rays, and a high energy electron beam, and a cobalt source is preferable. The total irradiation amount of the high energy rays is preferably 0.1 to 30 megarads, more preferably 0.5 to 20 megarads.

  And the crosslinked rubber particle | grains can be obtained by drying the latex of the crosslinked particulate polymer obtained by said each method by the method of drying with a spray dryer, or the precipitation drying method. In addition, when drying using a spray dryer, normally, inlet temperature is adjusted to 100-200 degreeC, and outlet temperature is adjusted to 20-80 degreeC, and it drys.

  In addition, as a crosslinking agent used when manufacturing a crosslinked rubber particle, monofunctional crosslinking agents, such as octyl (meth) acrylate, isooctyl (meth) acrylate, glycidyl (meth) acrylate; 1,4-butanediol di ( Bifunctional crosslinking agents such as (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diglycol di (meth) acrylate, triglycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, divinylbenzene; Trifunctional crosslinking agents such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate; tetrafunctional crosslinking such as pentaerythritol tetra (meth) acrylate and ethoxylated pentaerythritol tetra (meth) acrylate ; And 5 or more functional groups of the crosslinking agents, such as dipentaerythritol penta (meth) acrylate. These may be used alone or in combination of two or more. The usage-amount of a crosslinking agent is 0.1-10 weight part normally with respect to 100 weight part of rubber components, Preferably it is 0.5-9 weight part, More preferably, it is 0.7-7 weight part.

  The amount of the crosslinked rubber particles in the polymerizable composition of the present invention is preferably 0.01 to 100 parts by weight, more preferably 1 to 75 parts by weight, and still more preferably 100 parts by weight of the norbornene monomer. It is in the range of 10 to 15 parts by weight. If the blended amount of the crosslinked rubber particles is too small, the effect of improving the heat resistance and crack resistance of the resulting crosslinked body and crosslinked resin composite may not be obtained. On the other hand, if it is too much, molding may be difficult in the case of using a crosslinkable resin.

(Polymerizable composition)
The polymerizable composition of the present invention contains the norbornene-based monomer, a metathesis polymerization catalyst, a chain transfer agent, a crosslinking agent, and crosslinked rubber particles. Moreover, a filler, a polymerization regulator, a polymerization reaction retarding agent, an antiaging 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 adding a filler to the polymerizable composition of the present invention, it is possible to improve the mechanical strength and heat resistance of the resulting crosslinked product and crosslinked resin composite.

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

  The blending amount of the filler is usually in the range of 1 to 1,000 parts by weight, preferably 10 to 500 parts by weight, more preferably 50 to 350 parts by weight with respect to 100 parts by weight of the norbornene monomer.

  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 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 body and crosslinked resin composite 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, further preferably 100 parts by weight of the norbornene monomer. Is in the range of 0.01 to 2 parts by weight.

  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 used. For example, a liquid (catalyst liquid) in which a metathesis polymerization catalyst is dissolved or dispersed in an appropriate solvent is prepared, and a norbornene monomer, a chain transfer agent, a crosslinking agent, and a crosslinked rubber It can be prepared by preparing a liquid (monomer liquid) containing essential components such as particles and other compounding agents as required, adding a catalyst liquid to the monomer liquid, and stirring.

(Crosslinkable resin, crosslinkable resin composite)
The crosslinkable resin of the present invention can be obtained by bulk polymerization of the above-described polymerizable composition of the present invention. As a method for bulk polymerization of the polymerizable composition, (a) a method of pouring or coating the polymerizable composition on a support and bulk polymerization, (b) pouring the polymerizable composition into a mold, Examples thereof include a polymerization method, (c) a method in which a polymerizable composition is impregnated into a support made of a fiber material, and bulk polymerization is performed.

  According to the method (a), a crosslinkable resin composite formed from a crosslinkable resin and a support is obtained. Although it does not specifically limit as a support body, A metal foil or a resin film is preferable. Examples of the material constituting the metal foil include iron, stainless steel, copper, aluminum, nickel, chromium, gold, and silver. Examples of the material constituting the resin film include polyethylene terephthalate, polypropylene, polyethylene, polycarbonate, polyethylene naphthalate, polyarylate, and nylon. In the case of using a metal foil or a resin film as the support, these thicknesses are preferably 1 to 150 μm, more preferably 2 to 100 μm, and still more preferably 3 to 75 μm from the viewpoint of workability and the like. The surface of these supports is preferably smooth. In addition, the surface of these supports is preferably surface-treated with a known silane coupling agent or the like.

  In the method (a), the method for applying the polymerizable composition onto the support is not particularly limited, and may be a spray coating method, a dip coating method, a roll coating method, a curtain coating method, a die coating method, a slit coating method, or the like. A well-known coating method is mentioned.

  In the method (a), bulk polymerization is initiated by heating the polymerizable composition to a temperature at which the metathesis polymerization catalyst functions. The method of heating the polymerizable composition to a predetermined temperature is not particularly limited, and is a method of heating by placing on a heating plate, a method of heating (hot pressing) while applying pressure using a press, and pressing with a heated roller. Examples thereof include a method and a method using a heating furnace.

  Moreover, according to the method (b), a molded article of a crosslinkable resin 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. Further, the shape, material, size and the like of the mold are not particularly limited. Alternatively, 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. As a result, a sheet-like or film-like molded product of the crosslinkable resin can be obtained.

  In the method (b), 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, transfer of the transfer surface formed on the inner peripheral surface of the cavity tends not to be performed well. On the other hand, if the filling pressure is too high, it is not economical because the rigidity of the mold must be increased. The mold clamping pressure is usually in the range of 0.01 to 10 MPa.

According to the method (c), a prepreg that is a crosslinkable resin composite formed by impregnating reinforcing fibers with a crosslinkable resin can be obtained. Although it does not specifically limit as a reinforced fiber, For example, organic fibers, such as PET (polyethylene terephthalate) fiber, aramid fiber, ultra high molecular polyethylene fiber, polyamide (nylon) fiber, and liquid crystal polyester fiber; Glass fiber, carbon fiber, alumina fiber , Tungsten fibers, molybdenum fibers, budene fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, silica fibers, and other inorganic fibers. Among these, organic fibers and glass fibers are preferable, and aramid fibers, liquid crystal polyester fibers, and glass fibers are particularly preferable. As the glass fiber, fibers such as E glass, NE glass, S glass, D glass, and H glass can be suitably used.
These reinforcing fibers can be used alone or in combination of two or more, and the amount used is appropriately selected as desired, but is preferably 10 to 90 in the prepreg (crosslinkable resin composite). % By weight, more preferably 20 to 80% by weight, still more preferably 30 to 70% by weight. When the use amount of the reinforcing fiber is within this range, the dielectric property and mechanical strength of the obtained prepreg are highly balanced, which is preferable.

  In the method (c), the impregnation of the polymerizable composition into the reinforcing fiber may be performed by, for example, applying a predetermined amount of the polymerizable composition by spray coating, dip coating, roll coating, curtain coating, die coating, It can apply by applying to a fiber material by well-known methods, such as a slit coat method, putting a protective film on it as needed, and pressing with a roller etc. from the upper side. After impregnating the polymerizable composition into the fiber material, the polymerizable composition can be bulk polymerized by heating the impregnated product to a predetermined temperature, thereby obtaining a prepreg impregnated with the crosslinkable resin. Moreover, when impregnation is performed in a mold, reinforcing fibers are placed in the mold, and the polymerizable composition is poured into the mold. As the mold used in this case, the same mold as used in the method (b) can be used, and the filling pressure when filling the polymerizable composition into the cavity of the mold is also the above ( What is necessary is just to be the same as the method of b).

  In the method (c), the heating method of the impregnated product is not particularly limited, and the same method as the method (a) can be adopted, and the impregnated product may be placed on the substrate and heated. Alternatively, the polymerizable composition may be poured into a mold provided with a fiber material and impregnated with the polymerizable composition, and then bulk polymerization may be performed according to the method (b). Since the polymerizable composition of the present invention has a lower viscosity than conventional resin varnishes and is excellent in impregnation properties for reinforcing fibers, the reinforcing fibers can be uniformly impregnated with a crosslinkable resin. In addition, since the polymerizable composition of the present invention has a low content of a solvent that does not participate in the reaction, a step of removing the solvent after impregnating the reinforcing fiber is unnecessary, and the productivity is excellent and the residual solvent Odors and blisters do not occur.

  The thickness of the prepreg obtained by the method (c) is appropriately selected according to the purpose of use, but is usually 0.001 to 10 mm, preferably 0.005 to 1 mm, more preferably 0.01. It is the range of -0.5mm. If it exists in this range, since the shapeability at the time of lamination | stacking and characteristics, such as a mechanical strength and toughness of the crosslinked resin composite obtained by bridge | crosslinking, are fully exhibited, it is suitable. The amount of volatile components of the prepreg obtained by the method (c) is an amount that volatilizes when heated at 200 ° C. for 1 hour, and is usually 30% by weight or less, preferably 10% by weight or less, more preferably 5% by weight. Hereinafter, it is particularly preferably 1% by weight or less. When the amount of the volatile component of the prepreg is excessively large, the prepreg becomes sticky and the operability and storage stability tend to be poor.

  In any of the above methods (a), (b) and (c), the heating temperature for polymerizing the polymerizable composition is usually 50 to 250 ° C, preferably 80 to 200 ° C, more preferably 90. In the range of ˜150 ° C., less than 1 minute half-life temperature of the crosslinking agent, usually radical generator, preferably less than 10 ° C. of 1 minute half-life temperature, more preferably less than 20 ° C. of 1 minute half-life temperature. is there. The polymerization time may be appropriately selected, but is usually 10 seconds to 60 minutes, preferably within 20 minutes. Heating the polymerizable composition under the above conditions is preferable because a crosslinkable resin and a crosslinkable resin composite with little unreacted monomer can be obtained.

  The crosslinkable resin of the present invention and the crosslinkable resin portion constituting the crosslinkable resin composite of the present invention have substantially no crosslink structure, for example, are soluble in toluene, and the molecular weight thereof is gel- The weight average molecular weight in terms of polystyrene measured by permeation chromatography (eluent: tetrahydrofuran), and is usually 1,000 to 1,000,000, preferably 5,000 to 500,000, more preferably 10, The range is from 000 to 100,000.

(Crosslinked product)
The crosslinked product of the present invention is obtained by crosslinking the crosslinkable resin of the present invention.
Crosslinking of the crosslinkable resin can be carried out, for example, by heating and melting the crosslinkable resin of the present invention to maintain the crosslinkable resin at a temperature at which the crosslinkable reaction occurs. For example, when a radical generator is used as the crosslinking agent, the heating temperature for crosslinking the crosslinkable resin is usually at least 1 minute half-life temperature of the radical generator, preferably at least 5 ° C. higher than the 1-minute half-life temperature. The temperature is more preferably 10 ° C. or more higher than the 1 minute half-life temperature. Specifically, 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 1 to 120 minutes, more preferably 2 to 60 minutes.

  In the case where the crosslinkable resin is a sheet-like or film-like molded body, a method of laminating the crosslinkable resin on the substrate and hot pressing as necessary is preferable. 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).

(Crosslinked resin composite)
The crosslinked resin composite of the present invention comprises a crosslinked body and a support, and is obtained by crosslinking the crosslinkable resin composite produced by the method (a) or (c). can get. Alternatively, the cross-linked resin composite of the present invention is obtained by laminating the cross-linkable resin composite produced by the method (a) or (c) above on another support by hot pressing. It can also be obtained by heating and crosslinking. Furthermore, the crosslinked resin composite of the present invention can also be obtained by laminating the crosslinkable resin produced by the method (b) above on a support by hot pressing and crosslinking by heating on the support. Can do. Note that a plurality of cross-linked resin composites may be laminated.

  Examples of the support used in this case include copper foil, aluminum foil, nickel foil, chrome foil, gold foil, silver foil and other metal foils; printed wiring boards; conductive polymer films, films such as other resin films; Can be mentioned. Moreover, when a printed wiring board is used as the support, a multilayer printed wiring board can be manufactured. The surface of the conductive layer on the metal foil such as copper foil or printed wiring board is preferably treated with a silane coupling agent, a thiol coupling agent, a titanate coupling agent, or various adhesives. Of these, those treated with a silane coupling agent are particularly preferred.

  The cross-linked body and cross-linked resin composite of the present invention thus obtained are excellent in high-frequency characteristics, heat resistance, and crack resistance in a thermal shock test, and thus can be widely and suitably used as a high-frequency substrate material. . Specifically, the crosslinked body and crosslinked resin composite of the present invention can be suitably used for microwave or millimeter wave high frequency circuit boards for communication equipment applications.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on weight unless otherwise specified.
The test and evaluation were as follows.

(1) Crack resistance The laminated plate was subjected to a thermal shock test a predetermined number of times in the temperature range of −40 ° C. to + 150 ° C., the appearance of the laminated plate after the thermal shock test was visually observed, and the laminate plate was resistant to the following criteria. The crack property was evaluated. In addition, the thermal shock test was done with the thermal shock test apparatus (The product made by ESPEC company, model number; TSA-71H-W).
A: Generation of cracks was not confirmed in the sample after 300 cycles.
B: Generation of cracks was not confirmed in the sample after the end of 200 cycles.
C: Cracks were confirmed in the sample after the end of 200 cycles.
D: Generation of cracks was confirmed in the sample after the end of 100 cycles.
(2) Glass transition temperature (Tg)
The glass transition temperature (Tg) of the crosslinked resin constituting the laminate was determined from the peak temperature of loss tangent of dynamic viscoelasticity analysis (DMA method), and the heat resistance of the crosslinked resin was evaluated according to the following criteria.
A: Glass transition temperature is 155 ° C. or higher B: Glass transition temperature is 150 ° C. or higher and lower than 155 ° C. C: Glass transition temperature is lower than 150 ° C. (3) Solder heat resistance A test piece is cut out by cutting a laminated plate into 2 cm × 2 cm. The prepared test piece was immersed in a solder bath at 260 ° C. for 10 seconds, and the heat cycle test was performed for 3 cycles with the operation of pulling it up and allowing it to stand at room temperature for 60 seconds. The shape change was observed and the solder heat resistance was evaluated according to the following criteria.
○: No blistering occurred on the test piece ×: Blistering occurred on the test piece (4) Dielectric loss tangent (tan δ)
With respect to the laminated plate, the dielectric loss tangent (tan δ) at a frequency of 1 GHz was measured at 20 ° C. using an impedance analyzer (manufactured by Agilent Technologies, model number E4991A), and evaluated according to the following criteria.
A: 0.0018 or less B: More than 0.0018

Example 1
In a glass flask, 51 parts of benzylidene (1,3-dimethyl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and 79 parts of triphenylphosphine were dissolved in 952 parts of toluene to form a catalyst. A liquid was prepared. Separately, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7] dodeca-4-ene (TCD) 80 parts of tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (MTF) (20 parts) was added, and the chain transfer agent was 2.2 parts of allyl methacrylate and the crosslinking agent was di-tert-butyl peroxide (halved for 1 minute). 1.2 parts at an initial temperature of 186 ° C., 100 parts of silica (average particle size 0.5 μm, silane coupling agent treated product, manufactured by Admatechs), and crosslinked styrene-butadiene rubber particles (Narpow VP-108) as crosslinked rubber particles A monomer liquid was prepared by adding and mixing 30 parts of a gel content of 98% by weight and an average particle size of 100 nm. And the catalyst liquid prepared above was added to the obtained monomer liquid in the ratio of 0.12mL per 100g of norbornene-type monomers, and it stirred, and prepared the polymeric composition.

  Next, 100 parts of the obtained polymerizable composition was cast on a polyethylene naphthalate film (type Q51, thickness 75 μm, manufactured by Teijin DuPont Films), and a glass cloth (product number 2116, thickness 92 μm) was spread thereon. Further, 80 parts of the polymerizable composition was cast thereon. Then, a polyethylene naphthalate film was further covered from above, and the entire glass cloth was impregnated with the polymerizable composition using a roller. Next, this was heated in a heating furnace heated to 150 ° C. for 1 minute to bulk polymerize the polymerizable composition, thereby obtaining a prepreg having a thickness of 0.13 mm.

  Next, the obtained prepreg was cut to a size of 100 mm square, the polyethylene naphthalate film was peeled off, and 8 sheets thereof were stacked, and an electrolytic copper foil (Type-F0 silane coupling agent-treated product, Furukawa, on both outermost surfaces) Circuit foil) was laminated, and heat-pressed under conditions of 3 MPa and 200 ° C. for 15 minutes by a hot press to produce a laminated board. And according to the said method, each evaluation of crack resistance, glass transition temperature (Tg), solder heat resistance, and dielectric loss tangent was performed about the obtained laminated board. The results are shown in Table 1.

Example 2
A prepreg and a laminate were prepared and evaluated in the same manner as in Example 1 except that the blending amount of the crosslinked styrene-butadiene rubber particles was changed from 30 parts to 50 parts. The results are shown in Table 1.

Example 3
In the same manner as in Example 1, except that 30 parts of crosslinked silicone rubber particles (Narpow VP-601A, gel content 98 wt%, average particle diameter 150 nm) were used instead of 30 parts of crosslinked styrene-butadiene rubber particles. A prepreg and a laminate were prepared and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 1
A prepreg and a laminate were prepared and evaluated in the same manner as in Example 1 except that the crosslinked styrene-butadiene rubber particles were not used. The results are shown in Table 1.

Comparative Example 2
In the same manner as in Example 1 except that 5 parts of liquid polybutadiene rubber (PO-110, manufactured by Nippon Zeon Co., Ltd., gel content: 0% by weight) was used instead of 30 parts of the crosslinked styrene-butadiene rubber particles, A laminate was prepared and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 3
A prepreg and a laminate were prepared and evaluated in the same manner as in Comparative Example 2 except that the blending amount of the liquid polybutadiene rubber was changed from 5 parts to 20 parts. The results are shown in Table 1.

Comparative Example 4
In the same manner as in Example 1 except that 5 parts of liquid silicone (KF-50, manufactured by Shin-Etsu Chemical Co., Ltd., gel content: 0% by weight) was used instead of 30 parts of the crosslinked styrene-butadiene rubber particles, A laminate was prepared and evaluated in the same manner. The results are shown in Table 1.

表１中、「ＴＣＤ」は、テトラシクロ［６．２．１．１^３，６．０^２，７］ドデカ−４−エンであり、「ＭＴＦ」は、テトラシクロ［９．２．１．０^２，１０．０^３，８］テトラデカ−３，５，７，１２−テトラエンである。

In Table 1, “TCD” is tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7] is a dodeca-4-ene, "MTF" is, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene.

As shown in Table 1, the laminate obtained by blending crosslinked rubber particles with the polymerizable composition is excellent in crack resistance and heat resistance in a thermal shock test (high glass transition temperature, solder heat resistance). In addition, the results show that the film has excellent high frequency characteristics (dielectric loss tangent is kept low) (Examples 1 to 3).
On the other hand, when the crosslinked rubber particles were not blended, and when 5 parts of liquid butadiene was used instead of the crosslinked rubber particles, the crack resistance in the thermal shock test was inferior (Comparative Example). 1, 2).
Moreover, when the compounding quantity of liquid butadiene was increased to 20 parts, it became a result inferior to the crack resistance in a thermal shock test, and heat resistance (comparative example 3).
Furthermore, when liquid silicone rubber was used instead of the crosslinked rubber particles, the results were inferior to all of crack resistance, heat resistance and high frequency characteristics in the thermal shock test (Comparative Example 4).

Claims (8)

  A polymerizable composition comprising a norbornene-based monomer, a metathesis polymerization catalyst, a chain transfer agent, a crosslinking agent, and crosslinked rubber particles.   The polymerizable composition according to claim 1, wherein the crosslinked rubber particles have an average particle size of 10 to 2,000 nm.   The polymerizable composition according to claim 1, wherein a content ratio of the crosslinked rubber particles is 0.1 to 100 parts by weight with respect to 100 parts by weight of the norbornene-based monomer.   The polymerizable composition according to claim 1, wherein the gel content of the crosslinked rubber particles is 50 to 99.9 wt%.   A crosslinkable resin obtained by bulk polymerization of the polymerizable composition according to claim 1.   A crosslinkable resin composite obtained by coating or impregnating the polymerizable composition according to any one of claims 1 to 4 on a support and performing bulk polymerization.   The crosslinked body formed by bridge | crosslinking the crosslinkable resin of Claim 5.   A crosslinked resin composite comprising the crosslinked body according to claim 7 and a support.