JP2008143956A - Polymerizable composition, crosslinkable resin and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable composition from which a crosslinkable resin suitable for an electric material or the like used for an electric circuit board can be obtained, to provide the crosslinkable resin obtained by using the composition, and to provide a crosslinked product or the like having excellent heat resistance, flame retardancy, dielectric characteristics or the like. <P>SOLUTION: The polymerizable composition contains (a) a cycloolefin monomer, (b) a metathesis polymerization catalyst containing a group 8 transition metal, (c) a crosslinking agent, (d) a compound releasing water when being heated, and (e) an oxide of a group 6 metal, wherein the ratio (e)/(d) of (e) the metal oxide to (d) the compound releasing the water when being heated is 0.001-0.1 by mass. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polymerizable composition, a crosslinkable resin, and a crosslinked product. More specifically, a polymerizable composition capable of obtaining a crosslinkable resin and a crosslinked product having excellent electrical characteristics, heat resistance and flame retardancy, and a crosslinkable resin and a crosslinkable obtained using the polymerizable composition About the body.

  In recent years, electronic devices tend to be smaller, lighter, higher performance, and more diversified. Following these trends, electronic components used in electronic devices have become higher in frequency, and have low dielectric properties and fine structures in the high frequency region. There is a demand for an electronic material with excellent moldability for forming a glass. Under such demands, cycloolefin resins obtained by bulk polymerization of a polymerizable composition containing a cycloolefin monomer are attracting attention as materials having excellent electrical characteristics and processability. Such a cycloolefin-based resin itself is flammable, and flame retardant properties are required depending on the purpose of use thereof. In recent years, it has been proposed to add a flame retardant to a polymerizable composition. As the flame retardant, conventionally, a flame retardant having a halogen has been used (Patent Document 1). However, when such a flame retardant is used, a flame retardant effect can be obtained even if the amount added is relatively small, but a toxic gas is generated when the molded body that is no longer needed is incinerated. Conversion was required.

  In response to this, a flame retarding technique using a flame retardant containing no halogen has been reported. For example, Patent Document 2 discloses a polynorbornene resin containing at least one of a flame retardant containing a phosphorus atom-containing flame retardant and a nitrogen atom-containing flame retardant, and a flame retardant containing a phosphorus atom and a nitrogen atom in the molecule. A molded article is disclosed.

  In Patent Document 3, a cycloolefin monomer having an aromatic ring, a ruthenium-based metathesis polymerization catalyst, a polymerizable composition comprising a peroxide as a crosslinking agent and a flame retardant, and the polymerizable composition as a support. A film-like molded article obtained by impregnation and heat polymerization is disclosed.

  However, when using a flame retardant that does not contain halogen, it is often necessary to add a large amount in order to obtain high flame retardancy, which reduces moldability and the strength of the resulting molded product. There was a case. Further, when a flame retardant containing phosphorus is used as a flame retardant containing no halogen, high flame retardancy may be obtained with a small amount of addition. However, when a molded product obtained using a flame retardant containing phosphorus is used as an electrical insulating material, electrical characteristics may be insufficient.

JP-A-7-227863 JP 2001-234039 A WO2005 / 014690 pamphlet

  An object of the present invention is to provide a polymerizable composition capable of obtaining a crosslinkable resin suitable as an electric material used for an electric circuit board, a crosslinkable resin obtained using the same, and heat resistance, flame retardancy, An object of the present invention is to provide a crosslinked body excellent in dielectric characteristics and the like.

  As a result of intensive studies to achieve the above-mentioned object, the present inventor further released water into the polymerizable composition containing a cycloolefin monomer, a metathesis polymerization catalyst containing a Group 8 transition metal, and a crosslinking agent by heating. It was found that a molded article excellent in heat resistance, flame retardancy, dielectric properties, and the like can be obtained by blending the compound to be added and the Group 6 metal oxide in a specific quantitative ratio. The present invention has been further studied and completed based on this finding.

Thus, according to the first aspect of the present invention, (a) a cycloolefin monomer, (b) a metathesis polymerization catalyst containing a Group 8 transition metal, (c) a crosslinking agent, (d) a compound that releases moisture upon heating, and (E) comprising an oxide of a Group 6 metal;
There is provided a polymerizable composition in which the ratio (e) / (d) of (d) a compound that releases moisture by heating and (e) a metal oxide is 0.001 to 0.1 by mass ratio. .

The polymerizable composition preferably further contains (f) a chain transfer agent.
The (a) cycloolefin monomer is preferably a norbornene-based monomer having an aromatic ring.
The Group 6 metal is preferably molybdenum.

According to the second aspect of the present invention, there is provided a method for producing a crosslinkable resin characterized by polymerizing the polymerizable composition, and a crosslinkable resin obtained by polymerizing the polymerizable composition.
The polymerization is preferably bulk polymerization.

According to a third aspect of the present invention, there is provided a crosslinkable resin composite obtained by coating or impregnating the above polymerizable composition on a support and polymerizing.
According to the fourth aspect of the present invention, there is provided a cross-linked product obtained by cross-linking the cross-linkable resin.
According to a fifth aspect of the present invention, there is provided a cross-linked resin composite obtained by cross-linking the cross-linkable resin composite. Is provided.

  When the polymerizable composition of the present invention is bulk polymerized and then crosslinked, a crosslinked product having excellent characteristics such as heat resistance, flame retardancy, and dielectric properties can be obtained. The crosslinked body and composite obtained using the polymerizable composition of the present invention are suitable as an electrical material used for an electrical circuit board.

[Polymerizable composition]
The polymerizable composition of the present invention comprises (a) a cycloolefin monomer, (b) a metathesis polymerization catalyst containing a Group 8 (long-period periodic table, the same applies hereinafter) transition metal, (c) a crosslinking agent, (d) It contains a compound that releases moisture by heating, and (e) a Group 6 metal oxide.

(A) Cycloolefin monomer The cycloolefin monomer which comprises a polymeric composition is a compound which has an alicyclic structure and a carbon-carbon double bond in a molecule | numerator. Specific examples include norbornene monomers and monocyclic cycloolefins, and norbornene monomers are preferred. The norbornene-based monomer is a monomer having a norbornene ring structure in the molecule. Specifically, (i) a norbornene-based monomer having no unsaturated bond other than the carbon-carbon unsaturated bond involved in the polymerization reaction, such as norbornene, tetracyclododecene, and alkyl-substituted products thereof; (ii) Norbornene monomers having unsaturated bonds other than carbon-carbon unsaturated bonds involved in the polymerization reaction, such as ethylidene norbornene, vinyl norbornene, ethylidenetetracyclododecene, dicyclopentadiene, and the like. (Iii) norbornene-based monomers having an aromatic ring Monomers, (iv) norbornene monomers having a polar group such as methoxycarbonylnorbornene, methoxycarbonyltetracyclododecene, and the like.

  Among these, norbornene-based monomers that do not contain a polar group, that is, are composed of only carbon atoms and hydrogen atoms, are preferable because they are excellent in electrical characteristics of the obtained crosslinked product and the like. Moreover, since it is excellent in flame retardance of the obtained crosslinked body etc., the norbornene-type monomer which has (iii) an aromatic ring is especially preferable.

(Iii) As the norbornene-based monomer having an aromatic ring, 9-phenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7] tetracyclododecene such as dodeca-4-ene; 5-phenyl-2-norbornene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), tetracyclo [10.2.1.0. ^2,11 . Norbornenes such as 0 ^4,9 ] pentadeca-4,6,8,13-tetraene (also referred to as 1,4-methano-1,4,4a, 9,9a, 10-hexahydroanthracene); It is done.

Other norbornene-based monomers that do not contain a polar group include dicyclopentadiene, methyldicyclopentadiene, dihydrodicyclopentadiene (also referred to as tricyclo [5.2.1.0 ^2,6 ] dec-8-ene), and the like. Of dicyclopentadiene;

Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyclohexyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyclopentyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-vinyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-propenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyclohexenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyclopentenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] tetracyclododecenes such as dodec-4-ene;

  2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-cyclohexyl-2- Norbornene, 5-cyclopentyl-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-cyclohexenyl-2-norbornene, 5-cyclopentenyl-2- Norbornenes such as norbornene;

Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-4,10-diene, pentacyclo [9.2.1.1 ^4,7. 0 ^2,10 . 0 ^3,8 ] pentadeca-5,12-diene, hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4 pentacyclic body more cyclic olefins such as ene; and the like.

(Iv) As the norbornene-based monomer containing a polar group, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] methyl dodeca-9-ene-4-carboxylate, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-methanol, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic acid, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic anhydride, methyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate, acetic acid 5-norbornene-2 -Yl, 5-norbornene-2-methanol, 5-norbornene-2-ol, 5-norbornene-2-carbonitrile, 2-acetyl-5-norbornene, 7-oxa-2-norbornene and the like.

  These norbornene monomers can be used alone or in combination of two or more. By using two or more monomers in combination and changing the blend ratio, it is possible to freely control the glass transition temperature and melting temperature of the resulting crosslinkable resin molded article.

  Examples of the monocyclic cycloolefin include cyclobutene, cyclopentene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, and the like, which may have a substituent. The amount of the monocyclic cycloolefin to be used is preferably 40% by mass or less, more preferably 20% by mass or less, based on the total amount of the norbornene-based monomer. When the addition amount exceeds 40% by mass, the heat resistance of the polymer obtained by bulk polymerization may be insufficient.

(B) Metathesis polymerization catalyst containing a Group 8 transition metal The metathesis polymerization catalyst constituting the polymerizable composition is particularly limited as long as it contains a Group 8 transition metal and metathesis ring-opening polymerization of a cycloolefin monomer. Not.
Examples of the metathesis polymerization catalyst include a complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds around a Group 8 transition metal atom. Although the group 8 atom is not particularly limited, ruthenium and osmium are preferable.

  Among these, a ruthenium carbene complex is particularly preferable. Since the ruthenium carbene complex is excellent in catalytic activity during bulk polymerization, it is excellent in productivity of a crosslinkable resin that can be post-crosslinked, and a crosslinkable resin having little odor derived from residual unreacted monomers can be obtained. In addition, ruthenium carbene complexes are relatively stable to oxygen and moisture in the air and are not easily deactivated, so that a crosslinkable resin can be produced even in the atmosphere.

  A ruthenium carbene complex is represented by the following formula (1) or formula (2).

In the formulas (1) and (2), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, or a carbon atom that may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. The hydrocarbon group of number 1-20 is represented. X ¹ and X ² each independently represent an arbitrary anionic ligand. L ¹ and L ² each independently represents a hetero atom-containing carbene compound or a neutral electron donating compound. R ¹ and R ² may be bonded to each other to form a ring. Furthermore, R ¹ , R ² , X ¹ , X ² , L ¹ and L ² may be bonded together in any combination to form a multidentate chelating ligand.

  A hetero atom 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.

  The heteroatom-containing carbene compound preferably has adjacent heteroatoms bonded to both sides of the carbene carbon, and more preferably has a heterocycle including a carbene carbon atom and heteroatoms on both sides thereof. . Moreover, it is preferable that the hetero atom adjacent to the carbene carbon has a bulky substituent.

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

In said formula, R < ³ > -R < ⁶ > is C1-C20 which may contain a hydrogen atom, a halogen atom, or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom each independently. Represents a hydrocarbon group. R ^{3 to} R ⁶ may be bonded to each other in any combination to form a ring.

  Examples of the compound represented by Formula (3) or Formula (4) include 1,3-dimesitylimidazolidin-2-ylidene, 1,3-di (1-adamantyl) imidazolidin-2-ylidene, 1 -Cyclohexyl-3-mesitylimidazolidin-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-di ( 1-phenylethyl) -4-imidazoline-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene and the like.

  In addition to the compound represented by formula (3) or formula (4), 1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5 -Iridene, 1,3-dicyclohexylhexahydropyrimidin-2-ylidene, N, N, N ', N'-tetraisopropylformamidinylidene, 1,3,4-triphenyl-4,5-dihydro-1H- Heteroatom-containing carbene compounds such as 1,2,4-triazole-5-ylidene and 3- (2,6-diisopropylphenyl) -2,3-dihydrothiazol-2-ylidene can also be used.

In the formulas (1) and (2), the anionic (anionic) ligands X ¹ and X ² are ligands having a negative charge when separated from the central metal atom, for example, Examples include halogen atoms such as F, Cl, Br, and I, diketonate groups, substituted cyclopentadienyl groups, alkoxy groups, aryloxy groups, and carboxyl groups. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

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

Examples of the complex compound represented by the formula (1) include benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-4,5- Dibromo-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4-imidazoline-2-ylidene) (3-phenyl-1H-indene-1-ylidene) (tricyclohexylphosphine) ) Ruthenium dichloride, (1,3-dimesitylimidazolidine-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octahydro Benzimidazol-2-y Den) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2, 3-dihydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2, 4-triazole-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimethyl) Tyrimidazolidine-2-ylidene) pyridine ruthenium dichloride, (1,3-dimesitylimididine-2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4- Imidazoline-2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) [(phenylthio) methylene] (tricyclohexyl) phosphine) ruthenium dichloride, (1,3-dimesityl-4,5-dibromo-4-imidazolin-2-ylidene) (2-pyrrolidone-1-ylmethylene) (tricyclohexylphosphine), such as ruthenium dichloride, ^{L 1} and ^{L 2} One is a hetero atom-containing carbene compound to a ruthenium complex compound other is an electron-donating compound neutral;

Both L ¹ and L ² are neutral electron donating compounds such as benzylidenebis (tricyclohexylphosphine) ruthenium dichloride, (3-methyl-2-buten-1-ylidene) bis (tricyclopentylphosphine) ruthenium dichloride. A ruthenium compound;

Both L ¹ and L ² are heteroatoms, such as benzylidenebis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride, benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride A ruthenium complex compound which is a carbene compound.

Among these complex compounds, a ruthenium complex represented by the above formula (1) and ^one of L ¹ and L ² is represented by the formula (4), and the other is a neutral electron donating compound. Compounds are most preferred.

  These ruthenium complex catalysts are described in Org. Lett. 1999, Vol. 1, p. 953, Tetrahedron. Lett. 1999, Vol. 40, p. 2247, and the like.

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

  The metathesis polymerization catalyst can be used in combination with an activator (cocatalyst) for the purpose of controlling the polymerization activity and improving the polymerization reaction rate. Examples of the activator include aluminum, scandium, tin alkylates, halides, alkoxylates, and aryloxylates.

Activators include trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium, tetraalkoxy Tin, tetraalkoxyzirconium, etc. are mentioned.
The use amount of the activator is usually 1: 0.05 to 1: 100, preferably 1: 0.2 to 1:20, more preferably (molar ratio of metal atom in the metathesis polymerization catalyst: activator). Is in the range of 1: 0.5 to 1:10.

(C) Crosslinking agent The polymerizable composition of the present invention contains a crosslinking agent in order to obtain a resin having crosslinkability after bulk polymerization.
Examples of the crosslinking agent include radical generators, epoxy compounds, isocyanate group-containing compounds, carboxyl group-containing compounds, acid anhydride group-containing compounds, amino group-containing compounds, Lewis acids, and the like. These can be used individually by 1 type or in combination of 2 or more types. Among these, use of a radical generator, an epoxy compound, an isocyanate group-containing compound, a carboxyl group-containing compound, and an acid anhydride group-containing compound is preferable, and use of a radical generator, an epoxy compound, and an isocyanate group-containing compound is more preferable. The use of a generator is particularly preferred.

  Examples of the radical generator include organic peroxides, diazo compounds, and nonpolar radical generators. Although it does not specifically limit as an organic peroxide, For example, hydroperoxides, such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide; Dicumyl peroxide, t-butyl cumyl peroxide, (alpha), (alpha) '- Bis (t-butylperoxy-m-isopropyl) benzene, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2, Dialkyl peroxides such as 5-di (t-butylperoxy) hexane; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; 2,2-di (t-butylperoxy) butane and 1,1-di (t-hexyl) Peroxy) cyclohexane, 1,1-di (t-butylper) Peroxyketals such as oxy) -2-methylcyclohexane and 1,1-di (t-butylperoxy) cyclohexane; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; t-butylperoxyisopropylcarbonate Peroxycarbonates such as di (isopropylperoxy) dicarbonate, alkylsilylperoxasides such as t-butyltrimethylsilyl peroxide, and peroxyketals; Among these, dialkyl peroxides and peroxyketals are preferable in that there are few obstacles to the metathesis polymerization reaction.

  Examples of the diazo compound include 4,4′-bisazidobenzal (4-methyl) cyclohexanone, 4,4′-diazidochalcone, 2,6-bis (4′-azidobenzal) cyclohexanone, and 2,6-bis. (4′-azidobenzal) -4-methylcyclohexanone, 4,4′-diazidodiphenylsulfone, 4,4′-diazidodiphenylmethane, 2,2′-diazidostilbene and the like.

  Non-polar radical generators include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diphenylbutane, 1,4-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1, 1,2,2-tetraphenylethane, 2,2,3,3-tetraphenylbutane, 3,3,4,4-tetraphenylhexane, 1,1,2-triphenylpropane, 1,1,2- Triphenylethane, triphenylmethane, 1,1,1-triphenylethane, 1,1,1-triphenylpropane, 1,1,1-triphenylbutane, 1,1,1-triphenylpentane, 1, Examples include 1,1-triphenyl-2-propene, 1,1,1-triphenyl-4-pentene, 1,1,1-triphenyl-2-phenylethane, and the like.

  These radical generators can be used singly or in a mixture of two or more radical generators. By using two or more kinds of radical generators in combination and changing the blend ratio thereof, it is possible to freely control the glass transition temperature and the molten state of the resulting crosslinkable resin.

  The usage-amount of a crosslinking agent is 0.1-10 mass parts normally with respect to 100 mass parts of norbornene-type monomers, Preferably it is 0.5-5 mass parts. If the amount of the crosslinking agent is too small, crosslinking may be insufficient, and a crosslinked resin having a high crosslinking density may not be obtained. When the amount of the crosslinking agent is too large, the crosslinking effect is saturated, but there is a possibility that a thermoplastic resin and a crosslinked resin having desired physical properties cannot be obtained.

  In the present invention, when a radical generator is used as the crosslinking agent, a crosslinking aid can be used to promote the crosslinking reaction. Examples of crosslinking aids include dioxime compounds such as p-quinonedioxime; methacrylate compounds such as lauryl methacrylate and trimethylolpropane trimethacrylate; fumaric acid compounds such as diallyl fumarate: phthalic acid compounds such as diallyl phthalate, triallylcia And cyanuric acid compounds such as nurate; imide compounds such as maleimide; and the like. Although the usage-amount of a crosslinking adjuvant is not restrict | limited in particular, It is 0-100 mass parts normally with respect to 100 mass parts of norbornene-type monomers, Preferably it is 0-50 mass parts.

(D) Compound that releases moisture by heating The polymerizable composition of the present invention contains a compound that releases moisture by heating (hereinafter, also referred to as “water-releasing compound”) as a flame retardant. A water-releasing compound is a compound that does not release water at room temperature, but dehydrates and releases crystal water when heated or releases water by chemical decomposition. The amount of water to be released is usually 10 to 70% by mass, preferably 20 to 60% by mass in the compound. The temperature at which moisture is released is usually 150 to 800 ° C, preferably 150 to 600 ° C. If the temperature when releasing moisture is too low, moisture may be released during polymerization or crosslinking, which may inhibit the polymerization reaction or crosslinking reaction, or may generate bubbles in the crosslinked resin obtained by generating gas. is there. On the other hand, if the temperature when releasing moisture is too high, the flame retardancy may be insufficient.

Specific examples of the compound that dehydrates and releases crystal water when heated include FeSO ₄ · 7H ₂ O, MgSO ₄ · 7H ₂ O, CaCl ₂ · 6H ₂ O, zinc borate (2ZnO · 3B ₂ O ₃ -Inorganic salt hydrates stable at room temperature, such as 3.5H ₂ O), dihydrate gypsum (CaSO ₄ · 2H ₂ O), calcium aluminate hydrate, and the like. Compounds that release water by chemical decomposition when heated include magnesium hydroxide (Mg (OH) ₂ ), aluminum hydroxide (Al (OH) ₃ ), manganese hydroxide (Mn (OH) ₂ ), and water Metal water such as sodium tin oxide Na ₂ [Sn (OH) ₆ ], zinc stannate (ZnSn (OH) ₆ ), basic magnesium carbonate, dosonite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide An oxide is mentioned. Among these, metal hydroxide is preferable, and magnesium hydroxide and aluminum hydroxide are more preferable from the viewpoint of ease of handling due to low toxicity.

  Moreover, these water-releasing compounds may contain surface adsorbed water. The amount of water adsorbed on the surface is measured as a loss on heating by drying in a hot air dryer at 150 ° C. for 1 hour. The content of the surface adsorbed water is usually 0.01 to 5% by mass, preferably 0.1 to 3% by mass, and particularly preferably 0.4 to 2% by mass. If the amount is too large, the production efficiency is lowered, for example, a drying step of the water-releasing compound is required.

  The shape of the water-releasing compound is not particularly limited, but usually a particulate one is used. The size of the particle is not particularly limited, but is an average value of the length in the longitudinal direction and the short direction when the particle is viewed three-dimensionally, and the particle diameter is usually 0.001 to 100 μm, preferably 0.01. 10 to 10 μm, more preferably 0.01 to 5 μm. When the particle size is within this range, the productivity of the molded body and the flame retardancy of the obtained molded body are excellent, which is preferable. Further, the water-releasing compound may be used with the same particle diameter, or a mixture of a large particle diameter and a small particle diameter may be used. In order to make the particle diameter of the water-releasing compound uniform, classification may be performed as necessary.

The bulk specific gravity of the water-releasing compound is not particularly limited, but is preferably 0.2 to 30.0 g / cm ³ , and particularly preferably 0.3 to 10.0 g / cm ³ . When the bulk specific gravity of the water-releasing compound is within this range, the productivity of the molded body and the flame retardancy of the obtained molded body are excellent and preferable.

  These water-releasing compounds can be used alone or in combination of two or more, and the amount used is usually 10 to 500 parts by weight, preferably 100 parts by weight of (a) cycloolefin monomer, It is 50-300 mass parts, More preferably, it is 50-200 mass parts.

(E) Group 6 Metal Oxide The polymerizable composition of the present invention contains a Group 6 metal oxide. By containing a Group 6 metal oxide, a crosslinkable resin or the like obtained from the polymerizable composition exhibits high flame retardancy. Such a metal oxide may be a complex oxide of a Group 6 metal and another metal. Specifically, the Group 6 metal represents chromium, molybdenum, and tungsten. The metal oxide is not limited by its valence or the like, and is a compound represented by the chemical formula M _x O _y (wherein M represents a Group 6 metal atom, O is an oxygen atom, x represents an integer of 1 to 3, and y represents an integer of 1 to 4). Specific examples of the compound include CrO, CrO ₃ , Cr ₂ O ₃ , Cr ₂ O ₅ , MoO ₂ , MoO ₃ , WoO ₂ , and WoO ₃ . Among these, an oxide containing molybdenum or tungsten is preferable, an oxide containing molybdenum is more preferable, and MoO ₃ is particularly preferable because an excellent flame retardant effect can be obtained.

  These metal oxides can be used alone or in combination of two or more, and the amount used is usually 0.01 to 50 parts by mass, preferably 100 parts by mass of (a) cycloolefin monomer. Is 0.03 to 15 parts by mass, more preferably 0.05 to 5 parts by mass.

  The shape of these metal oxides is not particularly limited, but usually a particulate one is used. The particle size is not particularly limited, but is usually 0.01 to 50 μm, preferably 0.01 to 10 μm, particularly preferably as an average value of the length in the longitudinal direction and the short direction when the particle is viewed three-dimensionally. Is 0.1 to 5 μm.

  In the polymerizable composition of the present invention, the ratio (e) / (d) of (d) the compound that releases moisture by heating and (e) the metal oxide is 0.001 to 0.1 in terms of mass ratio. is there. (E) / (d) is preferably 0.003 to 0.03, more preferably 0.005 to 0.01. If (e) / (d) is too small or too large, sufficient flame retarding effect cannot be obtained. Moreover, when (e) / (d) is too large, the moldability of the crosslinkable resin obtained and the electrical characteristics of the crosslinkable resin may deteriorate.

(F) Chain transfer agent The polymerizable composition of the present invention preferably contains a chain transfer agent for the polymerization reaction.
As the chain transfer agent, chain olefins which may have a substituent can be usually used.
Specifically, aliphatic olefins such as 1-hexene and 2-hexene; olefins having an aromatic group such as styrene, divinylbenzene and stilbene; olefins having an alicyclic hydrocarbon group such as vinylcyclohexane; Vinyl ethers such as ethyl vinyl ether; vinyl ketones such as methyl vinyl ketone, 1,5-hexadien-3-one, 2-methyl-1,5-hexadien-3-one; styryl acrylate, ethylene glycol diacrylate; Vinyl silane, allyl methyl divinyl silane, allyl dimethyl vinyl silane; glycidyl acrylate, allyl glycidyl ether; allyl amine, 2- (diethylamino) ethanol vinyl ether, 2- (diethylamino) ethyl acrylate, 4-vinylaniline And the like.

Among these chain transfer agents, those having a group that contributes to crosslinking are preferred as the substituent. The group that contributes to crosslinking is specifically a group having a carbon-carbon double bond, and examples thereof include a vinyl group, an acryloyl group, and a methacryloyl group. Among them, since a high crosslinking density is obtained, a chain transfer agent having an acryloyl group or a methacryloyl group is more preferable, and a compound represented by the formula (5): CH ₂ ═CH—Y—OCO—CR ⁴ ═CH ₂ is particularly preferable. preferable. In formula (5), Y represents an alkylene group, and R ⁴ represents a hydrogen atom or a methyl group.
The number of carbon atoms of the alkylene group is not particularly limited, but is usually 1-20, preferably 4-12. By using a chain transfer agent having this structure, it is possible to obtain a crosslinked resin molded product or a crosslinked resin composite having higher strength.

  Examples of the compound represented by the formula (5) include allyl methacrylate, 3-buten-1-yl methacrylate, allyl acrylate, 3-buten-1-yl acrylate, undecenyl methacrylate, hexenyl methacrylate, and the like. It is done. Of these, undecenyl methacrylate and hexenyl methacrylate are particularly preferred.

  The addition amount of the chain transfer agent is usually 0.01 to 10% by mass, preferably 0.1 to 5% by mass, based on the total amount of the cycloolefin monomer. When the addition amount of the chain transfer agent is within this range, a thermoplastic resin having a high polymerization reaction rate and capable of post-crosslinking can be obtained efficiently.

(G) Dispersant The polymerizable composition of the present invention preferably contains a dispersant. The dispersant exhibits an action of keeping the state stable by uniformly dispersing the (d) moisture releasing compound and (e) Group 6 metal oxide in the (a) cycloolefin monomer. The dispersant can be used by being dispersed or dissolved in (a) a cycloolefin monomer. Further, it may be used as a surface treating agent for (d) a moisture-releasing compound and / or (e) a Group 6 metal oxide. The dispersant is not particularly limited as long as it exhibits such an action. Specifically, coupling agents such as silane coupling agents, aluminate coupling agents, titanate coupling agents, and zircoaluminate coupling agents; anionic surfactants, cationic surfactants, nonionic surfactants, and And surfactants such as amphoteric surfactants.

  Examples of the silane coupling agent include allyltrimethoxysilane, 3-butenyltrimethoxysilane, styryltrimethoxysilane, N-β- (N- (vinylbenzyl) aminoethyl) -γ-aminopropyltrimethoxysilane, and Its salts, allyltrichlorosilane, allylmethyldichlorosilane, styryltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltrichlorosilane, β-methacryloxyethyltri Methoxysilane, β-methacryloxyethyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, δ-methacryloxybutyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ- Mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane And styryltrimethoxysilane.

  Examples of the aluminate coupling agent include acetoalkoxy aluminum diisopropylate, aluminum diisopropoxy monoethyl acetoacetate, aluminum trisethyl acetoacetate, aluminum trisacetylacetonate and the like.

  Examples of titanate coupling agents include triisostearoyl isopropyl titanate, di (dioctyl phosphate) diisopropyl titanate, didodecylbenzenesulfonyl diisopropyl titanate, diisostearyl diisopropyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, and bis (dioctyl pyrophosphate). ) Oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate and the like.

  Nonionic surfactants include, for example, ether types such as polyoxyethylene alkyl and alkylphenyl ether, alkylallyl formaldehyde condensed polyoxyethylene ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropyl alkyl ether; glycerin Ether ester type such as polyoxyethylene ether of ester, polyoxyethylene ether of sorbitan ester, polyoxyethylene ether of sorbitol ester; polyethylene glycol fatty acid ester, glycerin ester, polyglycerin ester, sorbitan ester, propylene glycol ester, sucrose ester Ester type such as fatty acid alkanolamide, polyoxyethylene fatty acid amino acid , Polyoxyethylene alkyl amines, nitrogen-containing type such as amine oxides and the like.

  Among these dispersants, (d) a water-releasing compound and (e) an excellent dispersibility of a Group 6 metal oxide, and excellent electrical properties and mechanical strength of the resulting crosslinked product, etc. Coupling agents such as ring agents, aluminate coupling agents, titanate coupling agents; and nonionic surfactants are preferred, and aluminate coupling agents are particularly preferred. These dispersants can be used alone or in combination of two or more.

  The amount of the dispersant is usually 0.01 to 30 parts by mass, preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, particularly 100 parts by mass of the (a) cycloolefin monomer. Preferably it is 0.1-5 mass parts. If the amount of the dispersant is too small, the dispersion of (d) the moisture-releasing compound and (e) the Group 6 metal oxide may be insufficient. In that case, the resulting crosslinkable resin or the like becomes non-uniform, and the flame retardancy may be reduced. On the other hand, when there is too much quantity of a dispersing agent, electrical characteristics, such as crosslinkable resin obtained, may deteriorate.

(Other additives)
The polymerizable composition contains various additives such as a polymerization reaction retarder, a radical crosslinking retarder, a reinforcing material, a modifier, an antioxidant, a filler, a colorant, and a light stabilizer. Can do. These can be used by dissolving or dispersing in a monomer solution or a catalyst solution described later in advance.

  The polymerization reaction retarder is a compound that controls the polymerization activity of the metathesis polymerization catalyst, extends the gelation time of the polymerizable composition, and improves processability. For example, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene, (cis, cis) -2,6-octadiene, (cis, trans) -2,6-octadiene, (trans, trans)- Chain diene compounds such as 2,6-octadiene; (trans) -1,3,5-hexatriene, (cis) -1,3,5-hexatriene, (trans) -2,5-dimethyl-1, Chain triene compounds such as 3,5-hexatriene and (cis) -2,5-dimethyl-1,3,5-hexatriene; aryl phosphines such as triphenylphosphine and methyldiphenylphosphine; tri-n-butyl Alkylphosphines such as phosphine and triethylphosphine; Lewis bases such as aniline; and the like.

  Furthermore, a cycloolefin monomer having a diene structure or a triene structure serves as a polymerization reaction retarder as well as a cycloolefin monomer. Examples of such cycloolefin monomers include cycloolefin monomers having two double bonds in the ring such as 1,5-cyclooctadiene and 1,5-dimethyl-1,5-cyclooctadiene; Cycloolefin monomers having three double bonds in the ring such as 3,5-cycloheptatriene and (cis, trans, trans) -1,5,9-cyclododecatriene; in the ring such as vinyl norbornene and ethylidene norbornene And cycloolefin monomers having a double bond outside the ring; and the like.

  Among these polymerization reaction retarders, chain diene compounds, aryl phosphines, alkyl phosphines, and cycloolefin monomers having a diene structure or a triene structure are preferable, and alkyl phosphines have two double bonds in the ring. Cycloolefin monomers and cycloolefin monomers having double bonds in and outside the ring are particularly preferred.

  The radical crosslinking retarder is a compound having a radical scavenging function and has an effect of delaying the radical crosslinking reaction by the radical generator. By adding a radical crosslinking retarder to the polymerizable composition, the flowability and storage stability of the resulting crosslinkable resin can be improved. Examples of the radical crosslinking retarder include 3-t-butyl-4-hydroxyanisole, 2-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyanisole, 2,5- Hydroxyanisols such as di-t-butyl-4-hydroxyanisole and bis-1,2- (3,5-di-t-butyl-4-hydroxyphenoxy) ethane; 2,6-dimethoxy-4-methylphenol Dialkoxyphenols such as 2,4-dimethoxy-6-t-butylphenol; catechols such as catechol, 4-t-butylcatechol, 3,5-di-t-butylcatechol; benzoquinone, naphthoquinone, methylbenzoquinone, etc. Benzoquinones; and the like. Among these, hydroxyanisoles, catechols, and benzoquinones are preferable, and hydroxyanisoles are particularly preferable. These radical crosslinking retarders can be used alone or in combination of two or more, and the blending ratio is usually 0.001 to 1 mole, preferably 0.001 to 1 mole of the radical generator. 01 to 1 mol.

  Examples of the reinforcing material include glass fiber and carbon fiber. Examples of the modifier include natural rubber, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), ethylene-propylene-dienter. Examples include polymers (EPDM), ethylene-vinyl acetate copolymers (EVA), and elastomers such as hydrides thereof. Examples of the antioxidant include various hindered phenol-based, phosphorus-based and amine-based antioxidants for plastics and rubbers. These antioxidants may be used alone or in combination of two or more.

  Examples of the filler include organic fillers such as polyethylene powder, inorganic fillers such as glass powder, ceramic powder, and silica. These fillers may be used alone or in combination of two or more. As the filler, one that has been surface-treated with a silane coupling agent or the like can also be used. The amount of the filler is usually 0 to 600 parts by mass, preferably 50 to 500 parts by mass, and more preferably 50 to 300 parts by mass with respect to 100 parts by mass of the norbornene monomer.

  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.

  The polymerizable composition is not particularly limited by the method for preparing the polymerizable composition. The polymerizable composition is prepared, for example, by preparing a liquid in which a metathesis polymerization catalyst containing a Group 8 transition metal is dissolved or dispersed in an appropriate solvent (hereinafter, sometimes referred to as “catalyst liquid”), and cycloolefin. By preparing a liquid (hereinafter sometimes referred to as “monomer liquid”) containing additives such as fillers and flame retardants as necessary, adding the catalyst liquid to the monomer liquid, and stirring. Can be prepared. The addition of the catalyst solution is preferably performed immediately before the bulk polymerization described below. Further, the timing of addition of (c) cross-linking agent, (d) moisture releasing compound, (e) Group 6 metal oxide, (f) chain transfer agent and other additives is not particularly limited. It may be added to the monomer solution and / or the catalyst solution before mixing the catalyst solution with the catalyst solution, or after mixing the monomer solution and the catalyst solution.

[Crosslinkable resin and crosslinkable resin composite]
The crosslinkable resin of the present invention can be obtained by polymerizing the polymerizable composition. The polymerization method is not particularly limited, but bulk polymerization is preferable.
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, and bulk polymerization. And (C) a method of impregnating a polymerizable composition into a support and bulk polymerization. In addition, when the polymerizable composition is bulk polymerized by the method (A) or (C), a crosslinkable resin composite including a support and a crosslinkable resin is obtained.

  According to the method (A), a crosslinkable resin composite formed from a crosslinkable resin and a support is obtained. As the support used here, resins such as polyethylene terephthalate, polypropylene, polyethylene, polycarbonate, polyethylene naphthalate, polyarylate, and nylon; metal materials such as iron, stainless steel, copper, aluminum, nickel, chromium, gold, and silver; etc. The thing which consists of is mentioned. The shape is not particularly limited, but it is preferable to use a metal foil or a resin film. For example, when a copper foil is used for the support, a resin-coated copper foil (Resin Coated Copper (RCC)) can be obtained. The thickness of these metal foil or resin film is usually 1 to 150 μm, preferably 2 to 100 μm, more preferably 3 to 75 μm, from the viewpoint of workability and the like. The surface of these supports is preferably smooth. Moreover, it is preferable that the surface of these supports is surface-treated with a silane coupling agent or the like in order to enhance the adhesion with the support.

  The method for applying the polymerizable composition to the support is not particularly limited, and examples thereof include known coating methods such as spray coating, dip coating, roll coating, curtain coating, die coating, and slit coating.

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.
The crosslinkable resin film obtained as described above has a thickness of usually 15 mm or less, preferably 10 mm or less, more preferably 5 mm or less.

  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 mold having a split mold structure, that is, a core mold and a cavity mold, can be used, and a polymerizable composition is injected into these voids (cavities). And bulk polymerization is performed. 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. 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. By this, a sheet-like or film-like crosslinkable resin molded product can be obtained.

  The filling pressure (injection pressure) when filling the polymerizable composition into the cavity of the mold is usually 0.01 to 10 MPa, preferably 0.02 to 5 MPa. If the filling pressure is too low, the transfer surface formed on the inner peripheral surface of the cavity tends not to be transferred well. If the filling pressure is too high, the mold must be rigid and economical. is not. The mold clamping pressure is usually in the range of 0.01 to 10 MPa.

  The support used in the method (C) is a fiber material. According to this method, it is possible to obtain a prepreg that is a crosslinkable resin composite in which a fiber material is impregnated with a crosslinkable resin. The material of the fiber material used here is an organic and / or inorganic fiber, such as glass fiber, carbon fiber, aramid fiber, polyethylene terephthalate fiber, vinylon fiber, polyester fiber, amide fiber, metal fiber, ceramic fiber, etc. A well-known thing is mentioned. These can be used alone or in combination of two or more. Examples of the shape of the fiber material include mat, cloth, and non-woven fabric. Moreover, it is preferable that the surface of these fiber materials is surface-treated with a silane coupling agent or the like.

  The impregnation of the polymerizable composition into the fiber material 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 with a predetermined amount of the polymerizable composition. Can be applied by applying to the fiber material, and if necessary, a protective film is stacked thereon and pressed from above with a roller or the like. After the fibrous material is impregnated with the polymerizable composition, the polymerizable composition can be bulk polymerized by heating the impregnated material to a predetermined temperature, thereby obtaining a prepreg impregnated with the crosslinkable resin.

  The method for heating the impregnated product is not particularly limited, and the same method as the method (A) may be employed, 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 has a lower viscosity than the conventional resin varnish and is excellent in impregnation with respect to the fiber material, the fiber material can be uniformly impregnated with the crosslinkable resin.
In addition, since the polymerizable composition has a low content of a solvent or the like that does not participate in the reaction, there is no need for a process such as removing the solvent after impregnating the fiber material. Etc. does not occur. Furthermore, since the crosslinkable resin of the present invention is excellent in storage stability, the obtained prepreg is excellent in storage stability.

  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 100 to 200 ° C. The polymerization time may be appropriately selected, but is usually 10 seconds to 20 minutes, preferably within 5 minutes.

  A polymerization reaction is started by heating the polymerizable composition to a predetermined temperature. This polymerization reaction is an exothermic reaction, and once bulk polymerization starts, the temperature of the reaction solution rises rapidly and reaches the peak temperature in a short time (for example, about 10 seconds to 5 minutes). If the maximum temperature during the polymerization reaction is too high, a cross-linking reaction occurs to form a cross-linked body, and there is a possibility that a cross-linkable resin that can be post-cross-linked cannot be obtained. Therefore, in order to allow only the polymerization reaction to proceed completely and to prevent the crosslinking reaction from proceeding, the peak temperature of the bulk polymerization is not higher than the 1 minute half-life temperature of the radical generator, preferably not higher than 230 ° C., more preferably Is preferably controlled below 200 ° C.

The crosslinkable resin of the present invention is a postcrosslinkable resin. Here, “after-crosslinking is possible” means that by heating the resin, the crosslinking reaction proceeds to form a crosslinked body.
The crosslinkable resin composite of the present invention is a composite material in which the crosslinkable resin and the support are integrated.

  In the crosslinkable resin of the present invention, since the bulk polymerization reaction of the polymerizable composition described above proceeds almost completely, the residual monomer is reduced, and the working environment is not deteriorated by odor derived from the monomer. In addition, when a radical decomposition agent having a high decomposition temperature is used, the crosslinkable resin flows appropriately during crosslinking, and the adhesion to a support such as a metal foil and the embedding in a wiring board are good. Become.

  The crosslinkable resin of the present invention is preferably soluble in solvents such as aromatic hydrocarbons such as benzene and toluene, ethers such as diethyl ether and tetrahydrofuran, and halogenated hydrocarbons such as dichloromethane and chloroform. Moreover, since it shows thermoplasticity, various shapes can be formed by performing melt molding at a temperature at which crosslinking reaction does not occur.

  When the crosslinkable resin of the present invention is used as a molded body, a part thereof may be a crosslinked body. For example, when the polymerizable composition is bulk-polymerized in the mold, the temperature of a part of the mold may become too high because the polymerization reaction heat hardly diffuses in the central part of the mold. In the high temperature part, a crosslinking reaction may occur, resulting in a crosslinked body. However, if the surface part that easily dissipates heat is formed of a cross-linkable resin that can be post-crosslinked, the effects as the cross-linkable resin of the present invention can be fully enjoyed. Similarly, in the crosslinkable resin composite, a part of the crosslinkable resin may be a crosslinked body.

  Since the crosslinkable resin of the present invention is obtained by almost completely proceeding bulk polymerization, there is no fear that the polymerization reaction further proceeds during storage. The crosslinkable resin of the present invention contains a crosslinker, but unless it is heated to a temperature higher than the temperature at which the crosslink reaction takes place, it does not cause problems such as changes in surface hardness and is excellent in storage stability.

[Crosslinked product]
The crosslinked product of the present invention is obtained by crosslinking the crosslinkable resin.
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 or higher. The temperature at which the crosslinkable resin is crosslinked is preferably 20 ° C. or more higher than the peak temperature during the bulk polymerization, and is usually 170 to 250 ° C., preferably 180 to 220 ° C. The time for crosslinking is not particularly limited, but is usually from several minutes to several hours.

  When the crosslinkable resin is a sheet-shaped or film-shaped molded body, a method of laminating the molded body on a substrate as necessary and hot pressing 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 pressing 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).

[Crosslinked resin composite]
The crosslinked resin composite of the present invention comprises the crosslinked body and a support.
The crosslinked resin composite of the present invention can be obtained by crosslinking the above-mentioned crosslinkable resin composite. It can also be obtained by heating and crosslinking the crosslinkable resin molded body on a support, or by heating and crosslinking the crosslinkable resin composite on another support.

As a method of crosslinking the crosslinkable resin molded body or the crosslinkable resin composite by heating on the support, a crosslinkable resin formed into a plate shape or a film shape is laminated on the support by hot pressing, and further By continuing the heating, the crosslinkable resin can be crosslinked. The conditions for hot pressing are the same as those for crosslinking the crosslinkable resin.
New supports used here include metal foils such as copper foil, aluminum foil, nickel foil, chrome foil, gold foil, and silver foil; printed wiring boards; films such as conductive polymer films and other resin films; Is mentioned. Further, 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.

  Since the crosslinkable resin of this invention is excellent in fluidity | liquidity and adhesiveness, the composite_body | complex excellent in flatness and excellent in adhesiveness with a support body can be obtained. In the composite of the present invention, for example, when an ultra-smooth (SLP) copper foil having a thickness of 12 μm is used as a support, the peel strength measured based on JIS C6481 is preferably 0.6 kN / m or more, More preferably, it is 0.8 kN / m or more.

  The crosslinkable resin, cross-linked product and cross-linked resin composite of the present invention are excellent in mechanical properties such as low linear expansion coefficient and high strength, electrical properties such as low dielectric loss tangent, heat resistance and flame retardancy. The composite is excellent in adhesion to the support.

  The crosslinkable resin, cross-linked product and composite of the present invention having such characteristics include a prepreg; a copper foil with resin; a printed wiring board, an insulating sheet, an interlayer insulating film, an overcoat, an antenna substrate, a radio wave absorber, and a radio wave shield. It is suitable as an electronic component material.

  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 mass references | standards unless there is particular notice.

Each characteristic in an Example and a comparative example was measured and evaluated according to the following method.
(1) Flame retardancy The flame retardancy of the laminate was measured and determined based on the UL-94 standard.
(2) Dissipation factor (tan δ)
The dielectric loss tangent (tan δ) at a frequency of 1 GHz was measured by a capacitance method using an impedance analyzer (manufactured by Agilent Technologies, model number E4991A). When tan δ was less than 0.0025, it was judged as A, 0.0025 or more and 0.0030 not yet B, and 0.0030 or more as C. It represents that it is excellent in an electrical property, so that tan-delta is small.
(3) Formability The laminate was visually observed. If the white portion due to poor adhesion between the prepregs was zero, it was judged as A, 1 to 3 as B, and 4 or more as C. The smaller the white portion due to poor adhesion, the better the moldability.

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.
Tetracyclo ^{[9.2.1.0 2,10} polyethylene bottle as cycloolefin monomers. 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (MTF), 40 parts, and tetracyclo [6.2.1.1 ^3,6 . ^0,7 ] dodec-4-ene (TCD) 60 parts, 0.74 part of allyl methacrylate as a chain transfer agent, di-t-butyl peroxide as a cross-linking agent (1 minute half-life temperature 186 ° C.) 1.2 parts, acetoalkoxyaluminum diisopropylate (Plenact AL-M, manufactured by Ajinomoto Fine-Techno) as a dispersant, and 159 aluminum hydroxide (particle diameter 1 μm) as a compound that releases moisture by heating Then, 1 part of molybdenum oxide (VI) was added as an oxide of Group 6 metal, and then the catalyst solution was added at a rate of 0.12 ml per 100 g of cycloolefin monomer to prepare a polymerizable composition.

  Next, 100 parts of this 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 laid on it. Further, 80 parts of the polymerizable composition was cast thereon. Further, a polyethylene naphthalate film was covered thereon, 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, and the polymerizable composition was bulk polymerized to obtain a prepreg having a thickness of 0.1 mm.

  This prepreg was cut out to a size of 100 mm square, and the polyethylene naphthalate film was peeled off. Then, 12 sheets thereof were stacked and heat-pressed with a hot press at 3 MPa and 200 ° C. for 15 minutes to produce a laminate. Table 1 shows the results of evaluating the flame retardancy, dielectric loss tangent, and moldability of this laminate.

Examples 2-4
A polymerizable composition was prepared in the same manner as in Example 1 except that the amount of molybdenum oxide (VI) was changed to the amount shown in Table 1, and a prepreg and a laminate were obtained using the polymerizable composition. Table 1 shows the results of evaluation of this laminate.

Example 5
A polymerizable composition was prepared in the same manner as in Example 1 except that 100 parts of dicyclopentadiene (DCP) was used instead of 40 parts of MTF and 60 parts of TCD as a cycloolefin monomer, and a prepreg and a laminate were prepared using this. I got a plate. Table 1 shows the results of evaluation of this laminate.

Comparative Example 1
A polymerizable composition was prepared in the same manner as in Example 1 except that molybdenum oxide (VI) was not used, and a prepreg and a laminate were obtained using the polymerizable composition. Table 1 shows the results of evaluation of this laminate.

Comparative Example 2
A polymerizable composition was prepared in the same manner as in Comparative Example 1 except that the amount of aluminum hydroxide was 250 parts, and a prepreg and a laminate were obtained using the polymerizable composition. Table 1 shows the results of evaluation of this laminate.

Comparative Examples 3 and 4
A polymerizable composition was prepared in the same manner as in Example 1 except that the amount of molybdenum oxide (VI) was changed to the amount shown in Table 1, and a prepreg and a laminate were obtained using the polymerizable composition. Table 1 shows the results of evaluation of this laminate.

Comparative Example 5
A polymerizable composition was prepared in the same manner as in Example 1 except that 1 part of melamine polyphosphate (PMP-100; manufactured by Nissan Chemical Industries, Ltd.) was used instead of 1 part of molybdenum (VI) oxide. A prepreg and a laminate were obtained. Table 1 shows the results of evaluation of this laminate.

Comparative Example 6
A polymerizable composition was prepared in the same manner as in Example 5 except that molybdenum oxide (VI) was not used, and a prepreg and a laminate were obtained using the polymerizable composition. Table 1 shows the results of evaluation of this laminate.

Comparative Example 7
A polymerizable composition was prepared in the same manner as in Example 1 except that 1 part of vanadium oxide (IV) was used instead of 1 part of molybdenum oxide (VI), and a prepreg and a laminate were obtained using the same. . Table 1 shows the results of evaluation of this laminate.

  As is clear from the above, when the polymerizable composition of the present invention was used, laminates having high flame retardancy, low dielectric loss tangent, and few adhesion failures could be obtained (Examples 1 to 5). In contrast, when (e) a Group 6 metal oxide is not used, the flame retardancy is low (Comparative Examples 1 and 6), and particularly when (a) DCP is used as the cycloolefin monomer, the moldability is low. (Comparative Example 6). Moreover, (d) When the usage-amount of the water | moisture-releasable compound was increased, although a flame retardance became high, the electrical property and the moldability deteriorated (comparative example 2).

  (E) Even when a Group 6 metal oxide is used, if (e) / (d) is too small, the flame retardancy is low (Comparative Example 3). The property was low (Comparative Example 4).

  (E) In the case of using a flame retardant containing phosphorus in place of the oxide of the Group 6 metal (Comparative Example 5) and in the case of using the oxide of vanadium which is a Group 5 metal (Comparative Example 7) In either case, the flame retardant effect of the present invention could not be obtained.

Claims (10)

(A) a cycloolefin monomer, (b) a metathesis polymerization catalyst containing a Group 8 transition metal, (c) a crosslinking agent, (d) a compound that releases moisture upon heating, and (e) an oxide of a Group 6 metal Comprising
(D) The polymerizable composition wherein the ratio (e) / (d) of the compound that releases moisture by heating and (e) the metal oxide is 0.001 to 0.1 in terms of mass ratio. The polymerizable composition according to claim 1, further comprising (f) a chain transfer agent. The polymerizable composition according to claim 1 or 2, wherein (a) the cycloolefin monomer is a norbornene-based monomer having an aromatic ring. The polymerizable composition according to claim 1, wherein the Group 6 metal is molybdenum. A method for producing a crosslinkable resin, comprising polymerizing the polymerizable composition according to claim 1. Crosslinkable resin obtained by superposing | polymerizing the polymeric composition in any one of Claims 1-4. The crosslinkable resin according to claim 6, wherein the polymerization is bulk polymerization. The crosslinkable resin composite obtained by apply | coating or impregnating the polymeric composition in any one of Claims 1-4 to a support body, and superposing | polymerizing. The crosslinked body formed by bridge | crosslinking the crosslinkable resin of Claim 6 or 7. A cross-linked resin composite obtained by cross-linking the cross-linkable resin composite according to claim 8.