JP5428286B2 - Thermally conductive filler-containing polymerizable composition, prepreg, and laminate - Google Patents

Description

  The present invention relates to a polymerizable composition, a prepreg, and a laminate. More specifically, a polymerizable composition and a prepreg that are extremely excellent in thermal conductivity, useful for producing a laminate having excellent high-frequency characteristics, fine wiring embedding properties, heat resistance, and crack resistance in a thermal shock test, and It relates to the laminate.

  Due to higher wiring density, higher electronic component mounting density, and higher integration of semiconductor elements for multilayer circuit boards, the amount of heat generated by multilayer circuit boards has increased, improving the heat dissipation of multilayer circuit boards. It is strongly desired.

  Various techniques for increasing the heat dissipation of the resin layer of the multilayer circuit board have been proposed so far. For example, Patent Document 1 includes an epoxy resin, a curing agent, and an epoxy resin that are excellent in moisture resistance, heat resistance, insulation reliability, crack resistance, and flexibility in addition to the compatibility of thermal conductivity and adhesiveness. A heat-sensitive adhesive composition comprising a specific amount of a soluble high molecular weight resin having a specific molecular weight, a high molecular weight resin having a reactive functional group, a curing accelerator, and an inorganic filler, and the heat A thermally conductive adhesive film obtained by applying or sticking a conductive adhesive composition onto a metal foil is disclosed. Further, Patent Document 2 discloses a norbornene-based monomer, a metathesis polymerization catalyst, and thermal conductivity that can easily and inexpensively provide a highly thermally conductive member having excellent thermal conductivity and excellent shape followability and electrical insulation. A polymerizable composition for a highly thermally conductive resin comprising a filler, and a highly thermally conductive member comprising a norbornene-based polymer and a thermally conductive filler using the composition are disclosed.

Japanese Patent Laid-Open No. 10-183086 JP 2001-261944 A

However, in a multilayer circuit board with higher frequency, higher sensitivity, and higher functionality, the technique described in Patent Document 1 cannot provide sufficient dielectric characteristics, heat dissipation, and the like. According to the present inventors, it is still inadequate in terms of the wiring embedding property for fine wiring and the crack resistance during repeated use under the assumed use environment of the multilayer circuit board. It became clear.
An object of the present invention is to provide a polymerizable composition and a prepreg that are extremely useful in the production of a laminate having excellent thermal conductivity, high frequency characteristics, fine wiring embedding, heat resistance, and crack resistance in a thermal shock test. And providing the laminate.

  As a result of intensive studies in view of the above problems, the present inventors have developed a polymerizable composition comprising a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, and a combination of a compound that functions as a reactive fluidizing agent and a crosslinking aid. Furthermore, by blending a thermally conductive filler, according to the composition, a dry film or prepreg excellent in fluidity can be easily produced, and such a dry film or prepreg can be appropriately made into other material layers, etc. It was found that a laminate having excellent dielectric properties, fine wiring embedding properties, heat resistance, and crack resistance in a thermal shock test can be efficiently obtained by curing (crosslinking) after lamination. Based on these findings, the inventors have completed the present invention.

That is, according to the present invention,
[1] A polymerizable composition comprising a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, a reactive fluidizing agent, a crosslinking aid, and a thermally conductive filler ,
Reactive fluidizer does not have an aliphatic carbon-carbon unsaturated bond that can participate in ring-opening polymerization, and can participate in a crosslinking reaction induced by a crosslinking agent to bind to a polymer. A polymerizable composition characterized by being a monofunctional compound having one unsaturated bond ;
[2] The polymerizable composition according to [1], wherein the reactive fluidizing agent is a monofunctional compound having one methacryl group ,
[3] The polymerizable composition according to [1] or [2], wherein the amount of the thermally conductive filler is 50 parts by weight or more with respect to 100 parts by weight of the cycloolefin monomer,
[4] The polymerizable composition according to any one of [1] to [3], wherein the thermally conductive filler is at least one selected from the group consisting of inorganic oxides, inorganic nitrides, and inorganic carbides,
[5] The above-mentioned [1] to [4], wherein the blending ratio of the reactive fluidizing agent and the crosslinking aid is in the range of 15/85 to 70/30 by weight ratio (reactive fluidizing agent / crosslinking aid). Any one of the polymerizable compositions,
[6] The polymerizable composition according to any one of [1] to [5], further comprising a chain transfer agent,
[7] A dry film obtained by polymerizing the polymerizable composition according to any one of [1] to [6],
[8] A prepreg obtained by polymerizing after impregnating a reinforcing fiber with the polymerizable composition according to any one of [1] to [6],
[9] A laminate having a layer made of a cured product of the dry film according to [7] and / or the prepreg according to [8], and [10] the laminate according to [9]. Heat dissipation printed circuit board,
Is provided.

  According to the present invention, a polymerizable composition and a prepreg that are extremely excellent in thermal conductivity, useful for producing a laminate having excellent high-frequency characteristics, fine wiring embedding properties, heat resistance, and crack resistance in a thermal shock test. As well as the laminate. The laminate of the present invention is excellent in thermal conductivity, dielectric properties, fine wiring embedding property, heat resistance, and crack resistance in a thermal shock test. Can be suitably used.

  The polymerizable composition of the present invention comprises a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, a reactive fluidizing agent, a crosslinking aid, and a thermally conductive filler. The dry film and prepreg of the present invention are obtained by polymerizing the polymerizable composition, and the laminate of the present invention has a layer made of a cured product of the dry film and / or the prepreg.

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

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

  As the cycloolefin monomer, either a monocyclic cycloolefin monomer or a polycyclic cycloolefin monomer can be used. From the viewpoint of highly balancing the dielectric properties and heat resistance properties of the resulting laminate, polycyclic cycloolefin monomers are preferred. As the polycyclic cycloolefin monomer, a norbornene-based monomer is particularly preferable. The “norbornene monomer” refers to a cycloolefin monomer having a norbornene ring structure in the molecule. For example, norbornenes, dicyclopentadiene, tetracyclododecene and the like can be mentioned.

  Cycloolefin monomers are divided into those having no crosslinkable carbon-carbon unsaturated bonds 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. In particular, it refers to a radical crosslinking reaction. Examples of the crosslinkable carbon-carbon unsaturated bond include carbon-carbon unsaturated bonds other than aromatic carbon-carbon unsaturated bonds, that is, aliphatic carbon-carbon double bonds or triple bonds. Usually refers to an aliphatic carbon-carbon double bond. In the cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds, the position of the unsaturated bond is not particularly limited, and within the ring structure formed of carbon atoms, any other than the ring structure For example, at the end or inside of the side chain.

  Examples of cycloolefin monomers having no crosslinkable carbon-carbon unsaturated bond include cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, and 3-chlorocyclopentene. , Cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene and other monocyclic cycloolefin monomers; 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-Fe Lu-2-norbornene, tetracyclododecene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5 , 8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5 , 8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-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-di Tano-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 monomers such as norbornene; and the like, preferably norbornene monomers having no crosslinkable carbon-carbon unsaturated bond.

Examples of the cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds include 3-vinylcyclohexene, 4-vinylcyclohexene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4- Monocyclic cycloolefin monomers such as cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene; 5-ethylidene-2-norbornene, 5-methylidene -2-norbornene, 5-isopropylidene-2-norbornene, 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 5,6-diethylidene-2-norbornene, dicyclopentadiene, 2,5-norbornadiene, etc. Norbornene-based monomers; Sexual carbon - is a norbornene-based monomer having one or more carbon unsaturated bond.
These cycloolefin monomers can be used alone or in combination of two or more.

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

(Polymerization catalyst)
The polymerization catalyst used in the present invention is not particularly limited as long as it can polymerize the cycloolefin monomer, but the polymerizable composition of the present invention is directly bulk polymerization in the production of a dry film or prepreg described later. In general, it is preferable to use a metathesis polymerization catalyst.

  Examples of the metathesis polymerization catalyst include a complex formed by bonding a plurality of ions, atoms, polyatomic ions, compounds, etc. with a transition metal atom as a central atom, which is capable of metathesis ring-opening polymerization of the cycloolefin monomer. It is done. As transition metal atoms, atoms of Group 5, Group 6 and Group 8 (according to the long-period periodic table; the same shall apply 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. Examples of the Group 8 atom include Examples thereof include ruthenium and osmium. Among them, group 8 ruthenium and osmium are preferable as the transition metal atom. That is, the metathesis polymerization catalyst used in the present invention is preferably a complex having ruthenium or osmium as a central atom, and more preferably a complex having ruthenium as a central atom. As the complex having ruthenium as a central atom, a ruthenium carbene complex in which a carbene compound is coordinated to ruthenium is preferable. Here, the “carbene compound” is a general term for compounds having a methylene free group, and refers to a compound having an uncharged divalent carbon atom (carbene carbon) as represented by (> C :). Since ruthenium carbene complex is excellent in catalytic activity during bulk polymerization, when the prepreg is obtained by subjecting the polymerizable composition of the present invention to bulk polymerization, the resulting prepreg has little odor derived from unreacted monomers and is produced. Good quality prepreg can be obtained. In addition, it is relatively stable to oxygen and moisture in the air and is not easily deactivated, so that it can be used even in the atmosphere.

  The ruthenium carbene complex preferably has at least one carbene compound having a heterocyclic structure as a ligand because the mechanical strength and impact resistance of the resulting prepreg and laminate can be highly balanced. As a hetero atom which comprises a heterocyclic structure, an oxygen atom, a nitrogen atom, etc. are mentioned, for example, Preferably it is a nitrogen atom. Moreover, as a heterocyclic structure, an imidazoline ring structure or an imidazolidine ring structure is preferable. Specific examples of the compound having such a heterocyclic structure include 1,3-di (1-adamantyl) imidazolidin-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1,3- Di (1-phenylethyl) -4-imidazoline-2-ylidene, 1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5-ylidene, 1 , 3-Dicyclohexylhexahydropyrimidin-2-ylidene, N, N, N ′, N′-tetraisopropylformamidinylidene, 1,3-dimesitylimidazolidine-2-ylidene, 1,3-dicyclohexylimidazolidine 2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzi Such as imidazole-2-ylidene and the like.

  Specific examples of a suitable ruthenium carbene complex used as a metathesis polymerization catalyst in the present invention 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- Hydrobenzimidazol-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 ) Ruthenium carbene complexes having a carbene compound having a heterocyclic structure and other neutral electron donors as ligands such as pyridine ruthenium dichloride. Here, the “neutral electron donor” refers to a ligand having a neutral charge when separated from a central metal atom.

  The metathesis polymerization catalysts may be used alone or in combination of two or more. The amount of the metathesis polymerization catalyst used is a molar ratio (metal atom in the metathesis polymerization catalyst: cycloolefin monomer) and is usually from 1: 2,000 to 1: 2,000,000, preferably from 1: 5,000 to 1. : 1,000,000, more preferably in the range of 1: 10,000 to 1: 500,000.

  If desired, the metathesis polymerization catalyst can be used dissolved or suspended in a small amount of an inert solvent. Such solvents include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin and mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane , Decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene, cyclooctane and other alicyclic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; indene, tetrahydronaphthalene and other alicyclic and aromatic rings A nitrogen-containing hydrocarbon such as nitromethane, nitrobenzene, and acetonitrile; an oxygen-containing hydrocarbon such as diethyl ether and tetrahydrofuran; and the like. Among these, it is preferable to use a chain aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, and a hydrocarbon having an alicyclic ring and an aromatic ring.

(Crosslinking agent)
The crosslinking agent used in the present invention is used for the purpose of inducing a crosslinking reaction in a polymer obtained by subjecting the polymerizable composition of the present invention to a polymerization reaction. Accordingly, the polymer becomes a post-crosslinkable 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 a crosslinking agent, the half-life temperature for 1 minute is appropriately selected depending on the conditions of curing (crosslinking of a polymer obtained by subjecting the polymerizable composition of the present invention to a polymerization reaction). , 100 to 300 ° C, preferably 150 to 250 ° C, more preferably 160 to 230 ° C. Here, the half-life temperature for 1 minute is a temperature at which half of the radical generator decomposes in 1 minute. The 1-minute half-life temperature of the radical generator may be referred to, for example, a catalog or homepage of each radical generator manufacturer (for example, Nippon Oil & Fats Co., Ltd.).

  The radical generators can be used alone or in combination of two or more. The blending amount of the radical generator in the polymerizable composition of the present invention is usually 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, with respect to 100 parts by weight of the cycloolefin monomer to be blended. More preferably, it is the range of 0.5-5 weight part.

(Reactive fluidizer)
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 compound used as the reactive fluidizing agent in the present invention decreases the glass transition temperature (Tg) of the polymer as a fluidizing agent, and after the crosslinking reaction is induced by the crosslinking agent. Is preferably a compound having reactivity to participate in the reaction and bind to the polymer. For example, when the polymer containing a reactive fluidizing agent is used as a base material for a prepreg described later, when the prepreg is laminated with a metal material layer, it can be easily melt-laminated by heating the prepreg. In addition, sufficient interlayer adhesion can be obtained in the obtained laminate. Furthermore, since the reactive fluidizing agent can participate in the crosslinking reaction induced by the crosslinking agent by heating during lamination, it can bind to the polymer after the heating. Therefore, unlike the so-called plasticizer, it does not become a factor that decreases the heat resistance of the obtained laminate. Rather, the resulting laminate can have the effect of increasing heat resistance and crack resistance.

  The reactive fluidizing agent used in the present invention includes an aliphatic carbon-carbon that can participate in a ring-opening polymerization reaction, such as a polymerizable aliphatic carbon-carbon double bond in a cycloolefin structure or a vinyl group. A monofunctional compound having no unsaturated bond and having an aliphatic carbon-carbon unsaturated bond or one organic group that can be bonded to a polymer by participating in a crosslinking reaction induced by a crosslinking agent, A monofunctional compound having no polymerizable aliphatic carbon-carbon unsaturated bond and having one crosslinkable aliphatic carbon-carbon unsaturated bond is preferred. The crosslinkable aliphatic carbon-carbon unsaturated bond that can be bonded to the polymer by participating in the cross-linking reaction induced by the cross-linking agent is, for example, as a terminal vinylidene group in the compound constituting the reactive fluidizing agent. In particular, it is preferably present as an isopropenyl group or a methacryl group, and more preferably as a methacryl group. Examples of the organic group include an epoxy group, an isocyanate group, and a sulfo group.

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

(Crosslinking aid)
The crosslinking aid used in the present invention is preferably a compound having two or more crosslinkable carbon-carbon unsaturated bonds that are not involved in ring-opening polymerization and can participate in a crosslinking reaction induced by the crosslinking agent. Such a crosslinkable carbon-carbon unsaturated bond is preferably present as a terminal vinylidene group, particularly as an isopropenyl group or methacryl group, and preferably as a methacryl group, in the compound constituting the crosslinking aid. More preferred.

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

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

  The mixing ratio of the reactive fluidizing agent and the crosslinking aid may be appropriately selected as desired, but is usually 5/95 to 90/10, preferably by weight ratio (reactive fluidizing agent / crosslinking aid). Is in the range of 10/90 to 70/30, more preferably 15/85 to 70/30. If the blending ratio is in such a range, the fluidity is improved in the dry film or prepreg, and in the laminate, the characteristics of fine wiring embedding, heat resistance and crack resistance in the thermal shock test are balanced, Is preferred.

  In the present invention, a particularly preferred combination of the reactive fluidizing agent and the crosslinking aid comprises benzyl methacrylate or adamantyl methacrylate (reactive fluidizing agent) and trimethylolpropane trimethacrylate (crosslinking aid). Combinations are mentioned. If this combination is used, the fluidity of dry film or prepreg is improved, and in the laminate, the characteristics of fine wiring embedding, heat resistance, and crack resistance in a thermal shock test are highly balanced, It is suitable for.

  The blending amount of the reactive fluidizing agent and the crosslinking aid in the polymerizable composition of the present invention (total blending amount of the reactive fluidizing agent and the crosslinking aid) is the cycloolefin monomer to be blended. Usually, it is 0.2-200 weight part with respect to 100 weight part, Preferably it is 1-100 weight part, More preferably, it is 2-60 weight part.

(Thermal conductive filler)
The thermally conductive filler used in the present invention is not particularly limited, but usually a filler having a thermal conductivity of 10 W / mK or more is preferred. The thermal conductivity can be measured by, for example, a hot disk method. Specific examples of the thermally conductive filler include inorganic oxides such as alumina, magnesium oxide, beryllium oxide, and titanium oxide; inorganic nitrides such as aluminum nitride, boron nitride, and silicon nitride; inorganic carbides such as silicon carbide; Examples thereof include metals or alloys such as copper, silver, iron, aluminum, nickel, and titanium; carbon-based compounds such as diamond, carbon fiber, and carbon black; and quartz and quartz glass. As the heat conductive filler, it is preferable to use at least one selected from the group consisting of inorganic oxides, inorganic nitrides, and inorganic carbides from the viewpoint of further improving the heat dissipation of the obtained laminate. It is preferable to use at least one selected from the group consisting of inorganic oxides and inorganic nitrides. As the inorganic oxide, alumina is preferable, and as the inorganic nitride, aluminum nitride and boron nitride are preferable. As the heat conductive filler used in the present invention, alumina, aluminum nitride, and boron nitride are generally preferable, and aluminum nitride and boron nitride are more preferable. These heat conductive fillers can be used alone or in combination of two or more. Moreover, as long as expression of the desired effect of this invention is not inhibited, well-known fillers other than a heat conductive filler can be used together.

  In addition, from the viewpoint of increasing the affinity with a polymer obtained by polymerizing a cycloolefin monomer, the thermally conductive filler may be surface-treated with a known silane coupling agent. The thermally conductive filler subjected to such surface treatment is available as a commercial product.

  The particle diameter (average particle diameter) of the thermally conductive filler 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, It is 0.001-50 micrometers, Preferably it is 0.01-10 micrometers, More preferably, it is the range of 0.1-5 micrometers.

  The amount of the thermally conductive filler added 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 parts by weight with respect to 100 parts by weight of the cycloolefin monomer. It is -750 weight part, More preferably, it is the range of 100-500 weight part. The polymerizable composition of the present invention has a low viscosity as compared with a polymer varnish that has been used in the production of prepregs and laminates, and has an epoxy resin or the like dissolved in a solvent. A high amount of the agent can be blended. Therefore, in the obtained dry film, prepreg, or laminate, the thermally conductive filler can be contained beyond the limit content of the conventional dry film, prepreg, or laminate, and the obtained laminate In that case, the heat dissipation excellent to the extent which is not in the past can be exhibited.

(Polymerizable composition)
In the polymerizable composition used in the present invention, the cycloolefin monomer, the polymerization catalyst, the crosslinking agent, the reactive fluidizing agent, the crosslinking auxiliary agent, and the heat conductive filler described above as essential components, if desired, A polymerization regulator, a polymerization reaction retarder, a chain transfer agent, an anti-aging agent, and other compounding agents can be added.

  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 the reinforcing fiber easily when preparing a prepreg. Polymerization reaction retarders include phosphine compounds such as triphenylphosphine, tributylphosphine, trimethylphosphine, triethylphosphine, dicyclohexylphosphine, vinyldiphenylphosphine, allyldiphenylphosphine, triallylphosphine, styryldiphenylphosphine; Lewis bases such as aniline and pyridine Etc. can be used. What is necessary is just to adjust the compounding quantity suitably as needed.

  In the present invention, blending a chain transfer agent is preferable because the resulting laminate can highly balance fine wire embedding properties, heat resistance, and crack resistance in a thermal shock test. Moreover, the polymer obtained can be made to be excellent in fluidity while having high viscosity, and the dry film or prepreg described later comprising the polymer is, for example, laminated with another material. Melting lamination is possible.

  The chain transfer agent can usually participate in metathesis ring-opening polymerization and has one aliphatic carbon-carbon double bond that can be bonded to the terminal of a polymer obtained by subjecting the polymerizable composition of the present invention to a polymerization reaction. Compounds are preferred. Examples of the double bond include a terminal vinyl group. 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, 4- Chain transfer agents without crosslinkable carbon-carbon unsaturated bonds, such as vinylaniline; divinylbenzene, vinyl methacrylate, allyl methacrylate, styryl methacrylate, allyl acrylate, undecenyl methacrylate, styryl acrylate, ethylene glycol Chain transfer agent having one crosslinkable carbon-carbon unsaturated bond, such as diacrylate; Chain transfer agent having two or more crosslinkable carbon-carbon unsaturated bonds, such as allyltrivinylsilane and allylmethyldivinylsilane And the like. Among these, in the obtained laminate, those having one or more crosslinkable carbon-carbon unsaturated bonds are preferable from the viewpoint of highly balancing the characteristics of fine wiring embedding, heat resistance, and crack resistance, Those having one crosslinkable carbon-carbon unsaturated bond are more preferred. Among such chain transfer agents, chain transfer agents having one vinyl group and one methacryl group are preferable, and vinyl methacrylate, allyl methacrylate, styryl methacrylate, undecenyl methacrylate, and the like are particularly preferable.
These chain transfer agents can be used alone or in combination of two or more. As a compounding quantity of the chain transfer agent to the polymeric composition of this invention, it is 0.01-10 weight part normally with respect to 100 weight part of cycloolefin monomers to mix | blend, Preferably it is 0.1-5 weight part. is there.

  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 compounding agents, adding the catalyst liquid to the monomer liquid, and stirring.

(Dry film)
The dry film of the present invention is obtained by polymerizing the polymerizable composition of the present invention. The polymerization is preferably carried out by bulk polymerization because it is excellent in dry film production efficiency. Examples of a method for producing a dry film by bulk polymerization of the polymerizable composition of the present invention include, for example, (i) a method in which a polymerizable composition is applied on a support and bulk polymerization, or (ii) a polymerizable composition. A method of bulk polymerization of the product in a mold is mentioned. Examples of the support used in the method (i) include resins such as polyethylene terephthalate, polypropylene, polyethylene, polycarbonate, polyethylene naphthalate, polyarylate, and nylon; iron, stainless steel, copper, aluminum, nickel, chromium, gold, Examples thereof include a metal material such as silver. The shape is not particularly limited, but it is preferable to use a metal foil or a resin film. The thickness of the metal foil or resin film is usually 1 to 150 μm, preferably 2 to 100 μm, from the viewpoint of workability and the like. The method for applying the polymerizable composition to the support is not particularly limited. For example, a known application method such as a spray coating method, a dip coating method, a roll coating method, a curtain coating method, a die coating method, or a slit coating method can be employed. . After apply | coating a polymeric composition on a support body, a polymeric composition is heated and block polymerization is performed and a dry film is obtained. On the other hand, the method (ii) can be carried out in the same manner as the prepreg described later, except for the step of impregnating the reinforcing fiber with the polymerizable composition of the present invention. The thickness of the obtained dry film is not particularly limited, but is usually 100 μm or less, preferably 50 μm or less. If it exists in this range, it is suitable at the point of size reduction, low profile, and heat dissipation of the laminated body obtained.

(Reinforced fiber)
The reinforcing fiber used in the present invention is not particularly limited. For example, organic fibers such as PET (polyethylene terephthalate) fiber, aramid fiber, ultrahigh molecular polyethylene fiber, polyamide (nylon) fiber, and liquid crystal polyester fiber; And inorganic fibers such as glass fibers, carbon fibers, alumina fibers, tungsten fibers, molybdenum fibers, budene fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, silica fibers, and the like. 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 usually 10 to 90% by weight in the prepreg or laminate, preferably Is in the range of 20 to 80% by weight, more preferably in the range of 30 to 70% by weight. Within this range, the dielectric properties and mechanical strength of the resulting laminate are highly balanced, which is preferable.

(Prepreg)
The prepreg of the present invention is formed by impregnating the polymerizable composition into the reinforcing fiber and then polymerizing.
The impregnation of the polymerizable composition into the reinforcing fiber is, for example, a known method such as 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 in a predetermined amount of the polymerizable composition. Can be applied to the reinforcing fiber by applying a protective film thereon if desired, and pressing with a roller or the like from above. In the present invention, after impregnating the polymerizable composition into the reinforcing fiber, the polymerizable composition can be bulk-polymerized by heating the impregnated product to a predetermined temperature, whereby a sheet-like or film-like prepreg is obtained. Is obtained.
When impregnation is performed in a mold, reinforcing fibers are placed in the mold, and the polymerizable composition is poured into the mold. According to this method, a prepreg 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 prepreg. Further, the shape, material, size and the like of the mold are not particularly limited. Also, 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. A sheet-like or film-like prepreg can be obtained by curing in the mold.

  Since the polymerizable composition of the present invention has a lower viscosity than a conventional polymer varnish such as an epoxy resin and is excellent in impregnation properties for reinforcing fibers, the reinforcing fiber base material is uniformly impregnated with the resin obtained by polymerization. be able to.

  The thickness of the prepreg of the present invention is appropriately selected according to the purpose of use, but is usually in the range of 0.001 to 10 mm, preferably 0.005 to 1 mm, more preferably 0.01 to 0.5 mm. . If it exists in this range, the characteristics, such as the formability at the time of lamination | stacking, and the mechanical strength of a laminated body obtained by hardening, toughness, etc. are fully exhibited, and are suitable.

  The amount of the volatile component of the prepreg of the present invention 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 or less, and most 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.

  The polymer (cycloolefin monomer polymer) as the base resin of the dry film or prepreg of the present invention has substantially no cross-linked 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 polymerizable composition of the present invention usually comprises a metathesis polymerization catalyst. In any of the above methods, the heating temperature for polymerizing the polymerizable composition is usually 50 to 250 ° C., preferably 80. It is in the range of ˜200 ° C., more preferably in the range of 90 ° C. to 150 ° C., and is not more than the 1 minute half-life temperature of the crosslinking agent, usually a radical generator, preferably not more than 10 ° C., more preferably not more than 20 ° C. The polymerization time may be appropriately selected, but is usually 10 seconds to 60 minutes, preferably within 20 minutes. Heating the polymerizable composition under such conditions is preferable because a dry film or prepreg with less unreacted monomer can be obtained.

(Laminate)
The laminated body of this invention has a layer which consists of a hardened | cured material of the dry film of this invention, and / or the prepreg of this invention. The laminate is formed by laminating (a) a dry film, (b) a prepreg, and (c) any other material that can be laminated with them in any order in any combination, and further shaping if desired. Can be manufactured.
Other materials that can be laminated are appropriately selected depending on the purpose of use, and examples thereof include thermoplastic resin materials and metal materials, and metal materials are particularly preferably used. As a metal material, what is generally used with a circuit board can be used without a special restriction | limiting, Usually, metal foil, Preferably copper foil is used. Although the thickness of a metal material is suitably selected according to the intended purpose, it is 0.5-50 micrometers normally, Preferably it is 1-30 micrometers, More preferably, it is 3-20 micrometers, Most preferably, it is the range of 3-15 micrometers. The metal material is preferably one whose surface is treated with a silane coupling agent, a thiol coupling agent, a titanate coupling agent, various adhesives, or the like. Of these, those treated with a silane coupling agent are more preferred.
The roughness (Rz) of the surface of the layer made of the metal material at the adhesion interface between the prepreg of the present invention and the metal material is not particularly limited, but is usually 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less, and even more preferably. Is 2 μm or less. On the other hand, the lower limit of the roughness is not particularly limited, but is usually 10 nm or more, preferably 5 nm or more, more preferably 1 nm or more. If the roughness of the surface of the layer made of a metal material is in the above range, the occurrence of noise, delay, transmission loss, etc. in high frequency transmission is preferably suppressed. The adjustment of the roughness of the surface of the layer made of a metal material can be easily performed by selecting and using one having a roughness of the surface of the metal material to be laminated in a desired range. A metal material having such a surface roughness is available as a commercial product. The roughness (Rz) can be immediately measured with an AFM (atomic force microscope).

The method of laminating and curing may follow a conventional method. For example, the heat pressing can be performed using a known press machine having a press frame mold for flat plate molding, a press molding machine such as a sheet mold compound (SMC) or a bulk mold compound (BMC). The heating temperature is 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 1 to 120 minutes, more preferably 2 to 60 minutes. As a press pressure, it is 0.1-20 MPa normally, Preferably it is 0.1-10 MPa, More preferably, it is 1-5 MPa. Moreover, you may perform a hot press in a vacuum or a pressure-reduced atmosphere.
The laminate of the present invention thus obtained has extremely high thermal conductivity, exhibits excellent high frequency characteristics, particularly low dielectric loss tangent, has low transmission loss in the high frequency region, and has fine wiring embedding, heat resistance, and thermal shock. Since it is excellent in crack resistance in the test, it can be suitably used as a high-frequency substrate material having a wide range of uses.

(Heat dissipation printed circuit board)
Since the laminate of the present invention has high thermal conductivity and extremely excellent heat dissipation, and can be used in a normal printed circuit board manufacturing method, a circuit board on which various semiconductor chip components are mounted, power It can be suitably used for manufacturing a semiconductor package substrate that requires high heat dissipation during semiconductor operation, such as an amplifier module, a semiconductor chip built-in substrate, a passive component built-in substrate, a multichip module, and a high-frequency module. Such a semiconductor package substrate is a heat-dissipating printed circuit board that has an excellent heat-dissipating property that has never existed before.
The heat-radiating printed circuit board constituted by the laminate of the present invention can be used, for example, for the production of SiP, SiM, BGA, COC, POP, CSP, and QFN represented by ordinary package substrates. In particular, the SiP is a complex semiconductor,
It is preferably used for a POP with a built-in SiM or semiconductor PKG, a BGA that operates at a very high temperature, or the like. From the viewpoint of further improving the heat dissipation of the package substrate, it is preferable to form a heat dissipation via hole in the package substrate in combination with the heat dissipation printed circuit board of the present invention.

According to the heat-radiating printed board of the present invention, for example, the board size is 50 mm × 30 mm, the thickness is 0.8 mm, the mounted semiconductor is operated at 10 W, and the board surface temperature after 12 minutes is measured. In this case, the substrate surface temperature can be reduced by 10 ° C. as compared with the conventional printed circuit board of the same form. The thermal conductivity of the heat-radiating printed board according to the present invention is preferably 1 W / mK or more, more preferably 1.2 W / mK or more.
By using the heat-radiating printed circuit board of the present invention for a semiconductor package substrate or the like, the thermal shock generated during operation / stopping of the semiconductor can be reduced, so that the board design is easy and the operation reliability is high, and the power consumption is low. An unprecedented package substrate group can be manufactured. The laminate of the present invention can be suitably used for the production of these package substrate groups.

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

Each characteristic in an Example and a comparative example was measured and evaluated according to the following methods.
(1) Dielectric loss tangent Using an impedance analyzer (manufactured by Agilent Technologies, model number E4991A), the dielectric loss tangent (tan δ) at a frequency of 1 GHz was measured at 20 ° C. by the capacitance method, and evaluated according to the following criteria.
(Double-circle): 0.003 or less (circle): More than 0.003, 0.008 or less x: More than 0.008 (2) Thermal conductivity The thermal conductivity of the laminated body was measured by the hot disk method, and evaluated according to the following criteria.
A: 1.2 W / mK or more B: 0.8 W / mK or more, less than 1.2 W / mK x: less than 0.8 W / mK (3) Fine wiring embedding circuit board (L / S = 15 μm) A laminate was obtained by stacking on a test substrate (fifteen wirings) and heating and pressing at 205 ° C. for 10 minutes at 3 MPa. 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 fine wiring embedding property in the resin layer on the circuit board was evaluated according to the following criteria.
A: There is no portion where the wiring is not embedded. X: The wiring is not embedded (4) Heat resistance The laminate was cut into 20 mm squares to obtain test pieces. The test piece was allowed to flow on a solder bath at 260 ° C. for 20 seconds. This operation was repeated three times using separate test pieces (n = 3), and the swelling of the surface of each test piece was visually observed and evaluated according to the following criteria.
◎: No expansion when n = 3 ○: No expansion when n = 2 x: Generation of expansion when n = 2 or more (5) Crack resistance A predetermined number of thermal shocks in the temperature range of −65 ° C. to 150 ° C. After the test, the appearance was observed and evaluated according to the following criteria. 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: No occurrence of crack in sample after 500 cycles. O: No occurrence of crack in sample after 300 cycles. X: Generation of crack in sample after 300 cycles.

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 tetracyclododecene as the cycloolefin monomer, 0.74 parts of styrene as the chain transfer agent, 3,3,5,7,7-pentamethyl-1,2,4-trioxepane (1 2 parts per minute half-life temperature 205 ° C) 15 parts benzyl methacrylate as reactive fluidizing agent, 20 parts trimethylolpropane trimethacrylate as crosslinking aid, 50 parts aluminum dimethylphosphinate as flame retardant, nitriding as thermally conductive filler A monomer solution was prepared by mixing 190 parts of boron and 1 part of 3,5-di-t-butyl-4-hydroxyanisole as a phenolic antioxidant. The said catalyst liquid was added here in the ratio of 0.12mL per 100g of cycloolefin monomers, and it stirred, and prepared the polymeric composition.

Next, the obtained polymerizable composition was impregnated into glass cloth (E glass), and this was subjected to a polymerization reaction at 120 ° C. for 5 minutes to obtain a prepreg having a thickness of 0.15 mm. The amount of volatile components of the prepreg was 0.7%, and the glass cloth content of the prepreg was 40%.
Next, 6 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 A laminated body was obtained by performing a heat press at 3 MPa at 20 ° C. for 20 minutes. The dielectric tangent, thermal conductivity, heat resistance, and crack resistance of the obtained laminate were evaluated. Regarding the fine wiring embedding property, a laminate was separately obtained and evaluated using the obtained prepreg sheet according to the method described in the section (3) Fine wiring embedding property. The results are shown in Table 1.

Example 2
A prepreg and a laminate were obtained in the same manner as in Example 1 except that the cycloolefin monomer was changed to 80 parts of tetracyclododecene and 20 parts of dicyclopentadiene, and each characteristic was evaluated. The results are shown in Table 1.

Example 3
A prepreg and a laminate were obtained in the same manner as in Example 1 except that the chain transfer agent was changed to allyl methacrylate, and each characteristic was evaluated. The results are shown in Table 1.

Example 4
A glass cloth-reinforced PTFE resin film (300 mm × 300 mm cut with a roll coating method, the same polymerizable composition as that prepared in Example 1 except that alumina was used as the thermally conductive filler, thickness of 0. 08 mm, product name: 5310, manufactured by Saint-Gobain Norton), and another glass cloth reinforced PTFE resin film covered from above was brought into contact with an aluminum plate heated to 120 ° C. for 5 minutes. The composition was polymerized. Thereafter, the glass cloth reinforced PTFE resin film was peeled off to obtain a dry film having a thickness of 0.2 mm. A glass epoxy double-sided copper-clad laminate (thickness 1 mm, cut to 80 mm × 80 mm) obtained by microetching the surface of the copper foil (treated with a surface roughening agent (CZ-8100, manufactured by MEC)) was obtained. The laminate (double-sided copper-clad laminate) was obtained by sandwiching between the films and heating and pressing at 205 MPa for 15 minutes at 5.2 MPa. Each characteristic was evaluated about the obtained laminated body. The results are shown in Table 1.

Comparative Example 1
A prepreg and a laminate were obtained in the same manner as in Example 1 except that the reactive fluidizing agent and the crosslinking aid were not used, and each characteristic was evaluated. The results are shown in Table 1.

Comparative Example 2
A prepreg and a laminate were obtained in the same manner as in Example 1 except that the thermally conductive filler was not used, and each characteristic was evaluated. The results are shown in Table 1.

Comparative Example 3
A dry film and a laminate were obtained in the same manner as in Example 4 except that the thermally conductive filler was not used, and each characteristic was evaluated. The results are shown in Table 1.

Comparative Example 4
In the system of Example 1, the prepreg sheet was changed to BT resin (manufactured by Mitsubishi Gas Chemical Company, CCL-HL832-NX) to obtain a laminate, and each characteristic was evaluated. The results are shown in Table 1.

Comparative Example 5
In the system of Example 1, a prepreg sheet was changed to FR-4 (manufactured by Matsushita Electric Works, R-1766) to obtain a laminate, and each characteristic was evaluated. The results are shown in Table 1.

  The laminates obtained in Examples 1 to 4 generally exhibited low dielectric loss tangent, excellent thermal conductivity, fine wiring embedding, heat resistance and crack resistance. On the other hand, the laminate of Comparative Example 1 obtained using a polymerizable composition in which a reactive fluidizing agent and a crosslinking aid were not blended was inferior in fine wiring embedding property, heat resistance and crack resistance, and heat conduction. In the laminates of Comparative Examples 2 and 3 obtained using a polymerizable composition that did not contain a conductive filler, the thermal conductivity was inferior, and in the system of Example 1, the prepreg sheet was changed to another resin sheet. The laminates of Comparative Examples 4 and 5 were generally inferior to either property.

Claims (10)

A polymerizable composition comprising a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, a reactive fluidizing agent, a crosslinking aid, and a thermally conductive filler ;
Reactive fluidizer does not have an aliphatic carbon-carbon unsaturated bond that can participate in ring-opening polymerization, and can participate in a crosslinking reaction induced by a crosslinking agent to bind to a polymer. A monofunctional compound having one unsaturated bond,
A polymerizable composition characterized by the above . The polymerizable composition according to claim 1, wherein the reactive fluidizing agent is a monofunctional compound having one methacryl group .   The polymerizable composition according to claim 1 or 2, wherein the compounding amount of the thermally conductive filler is 50 parts by weight or more with respect to 100 parts by weight of the cycloolefin monomer.   The polymerizable composition according to any one of claims 1 to 3, wherein the thermally conductive filler is at least one selected from the group consisting of inorganic oxides, inorganic nitrides, and inorganic carbides.   The polymerization ratio according to any one of claims 1 to 4, wherein a mixing ratio of the reactive fluidizing agent and the crosslinking aid is in a range of 15/85 to 70/30 in terms of weight ratio (reactive fluidizing agent / crosslinking aid). Sex composition.   The polymerizable composition according to claim 1, further comprising a chain transfer agent.   A dry film obtained by polymerizing the polymerizable composition according to claim 1.   A prepreg obtained by polymerizing the reinforcing composition according to any one of claims 1 to 6 after impregnating the reinforcing fiber.   The laminated body which has a layer which consists of a hardened | cured material of the dry film of Claim 7, and / or the prepreg of Claim 8.   A heat dissipating printed board using the laminate according to claim 9.