JP2012214589A - Polymerizable composition, method for preparing the same, crosslinkable resin molding, crosslinked resin molding, and laminate - Google Patents

Abstract

【Task】
Useful for the production of cross-linked resin moldings and laminates with high flame retardancy, a polymerizable composition with low thixotropy and good moldability, its preparation method, cross-linkable resin molding, and flame retardancy It is an object of the present invention to provide an excellent crosslinked resin molded body and laminate.
[Solution]
Containing aluminum hydroxide and / or magnesium hydroxide having an average particle size increased by treatment with a cycloolefin monomer, a metathesis polymerization catalyst, a crosslinking agent, and a silane coupling agent, The storage elastic modulus (G ′) is 5 when the average particle diameter of magnesium hydroxide after treatment with the silane coupling agent is in the range of 3 to 100 μm and the shear strain (γ) is 0.1. Polymeric composition which is -1000 Pa, its preparation method, crosslinkable resin molding, crosslinked resin molding, and laminate.
[Selection figure] None.

Description

  The present invention relates to a polymerizable composition having low thixotropy and good moldability, a method for preparing the same, a crosslinkable resin molded body, and a crosslinked resin molded body and laminate having high flame retardancy.

  In recent years, electronic devices tend to be smaller, lighter, higher performance, and more diverse. Following these trends, electronic components used in electronic devices have been increased in frequency, and electronic materials excellent in moldability capable of obtaining low dielectric properties and a fine structure in a high frequency region have been demanded. Under such circumstances, a cycloolefin resin obtained by bulk polymerization of a polymerizable composition (varnish) containing a cycloolefin monomer has attracted attention as an electronic material excellent in electrical characteristics and workability.

Since the cycloolefin resin itself is flammable, a flame retardant is added to the polymerizable composition when flame retardancy is required. Conventionally, flame retardants containing halogen have been used as flame retardants. Such a flame retardant can provide a flame retardant effect even if the amount added is relatively small, but since a toxic gas is generated when the molded body that has become unnecessary is incinerated, conversion to a flame retardant containing no halogen is required. .
However, when using flame retardants that do not contain halogens, a large amount of flame retardants must be used to obtain high flame retardant properties, which increases the viscosity of the varnish and reduces moldability. Or the strength of the resulting molded product may be reduced.

  On the other hand, Patent Document 1 discloses a resin composition having high flame retardancy by blending an inorganic compound that does not contain halogen and phosphorus and has a predetermined softening point with an average particle size of 0.1 to 30 μm. Has been. However, the resin composition described in this document has high thixotropic properties of the varnish, and the coatability sometimes deteriorated. In addition, the insulating layer formed of the composition takes time to melt the inorganic compound during incineration, and the fire extinguishing action may be delayed.

  Further, Patent Document 2 discloses a polymerizable composition having a high flame retardancy and good moldability including a compound that releases moisture by heating and a Group 6 metal oxide in a predetermined ratio. Yes. According to the polymerizable composition described in this document, an insulating layer excellent in flame retardancy can be formed, but when a fine wiring structure is formed in the insulating layer, an oxide of a Group 6 metal is included. Therefore, it has been difficult to exhibit good insulation performance.

JP 2003-206406 A JP 2008-143958 A

  The present invention has been made in view of the above-described prior art, and is useful for the production of highly flame-retardant crosslinked resin molded articles and laminates. The polymerizable composition has low thixotropic properties and good moldability. It is an object of the present invention to provide a preparation method thereof, a crosslinkable resin molded article, and a crosslinked resin molded article and a laminate excellent in flame retardancy.

  As a result of diligent research to solve the above-mentioned problems, the present inventor has increased the average particle size as compared with before treatment by treating with a cycloolefin monomer, a metathesis polymerization catalyst, a crosslinking agent, and a silane coupling agent. The polymerizable composition containing aluminum hydroxide and / or magnesium hydroxide and having a storage elastic modulus (G ′) of 5 to 1000 Pa when the shear strain (γ) is 0.1 is thixotropic. The present invention has been completed by finding that it is useful for the production of a crosslinked resin molded body and laminate having low properties, good moldability and high flame retardancy.

  Thus, according to the present invention, the following polymerizable compositions (1) to (4), a method for preparing the polymerizable composition (5), a crosslinkable resin molded article (6), and a crosslinked resin mold (7) And a laminate of (8) are provided.

(1) Containing aluminum hydroxide and / or magnesium hydroxide whose average particle size is increased by treatment with a cycloolefin monomer, a metathesis polymerization catalyst, a crosslinking agent, and a silane coupling agent, and water Storage elastic modulus (G ′) when average particle diameter of aluminum oxide and / or magnesium hydroxide after treatment with silane coupling agent is in the range of 3 to 100 μm and shear strain (γ) is 0.1 ) Is a polymerizable composition having a viscosity of 5 to 1000 Pa.
(2) The polymerizable composition according to (1), wherein the total amount of aluminum hydroxide and magnesium hydroxide is 50 to 500 parts by weight with respect to 100 parts by weight of the cycloolefin monomer.

(3) The polymerization according to (1) or (2), wherein the mixing ratio of aluminum hydroxide and magnesium hydroxide is (aluminum hydroxide / magnesium hydroxide) = 100/0 to 10/90 by weight ratio. Sex composition.
(4) The initial average particle diameter of the aluminum hydroxide and / or magnesium hydroxide is 1 to 10 μm, and the average particle diameter after being treated with the silane coupling agent is 1.2 times or more of the initial average particle diameter. The polymerizable composition as set forth in any one of (1) to (3), wherein

(5) Aluminum hydroxide and / or magnesium hydroxide having an initial average particle diameter of 1 to 10 μm is treated with a silane coupling agent, and the average particle diameter is 1.2 times or more of the initial average particle diameter. The preparation method of the polymeric composition in any one of (1)-(4) which has the process to do.

(6) A crosslinkable resin molded article obtained by bulk polymerization of the polymerizable composition according to any one of (1) to (4).
(7) A crosslinked resin molded article obtained by crosslinking a polymer obtained by bulk polymerization of the polymerizable composition according to any one of (1) to (4).
(8) A laminate having at least a layer formed of the crosslinkable resin molded article according to (6) or the crosslinked resin molded article according to (7).

The polymerizable composition of the present invention has a low thixotropic property, a good moldability, and is useful for the production of a crosslinked resin molded product or laminate having high flame retardancy.
The crosslinkable resin molded article of the present invention is useful for producing a crosslinked resin molded article or laminate having high flame retardancy.
The crosslinked resin molded body and laminate of the present invention are excellent in flame retardancy.
According to the preparation method of the present invention, the polymerizable composition of the present invention having a low thixotropic property and good moldability can be easily obtained.

  Hereinafter, the present invention is divided into 1) a polymerizable composition, 2) a method for preparing the polymerizable composition, 3) a crosslinkable resin molded article, 4) a crosslinked resin molded article, and 5) a laminate. This will be described in detail.

1) Polymerizable composition The polymerizable composition of the present invention comprises (a) a cycloolefin monomer, (b) a metathesis polymerization catalyst, (c) a crosslinking agent, and (d) an average particle by treatment with a silane coupling agent. Aluminum hydroxide and / or magnesium hydroxide having an increased diameter, and having an average particle diameter of 3 to 100 μm after being treated with a silane coupling agent of aluminum hydroxide and / or magnesium hydroxide The storage elastic modulus (G ′) when the shear strain (γ) is 0.1 is 5 to 1000 Pa.

(A) Cycloolefin monomer The cycloolefin monomer used in the present invention is a compound having an alicyclic structure and a carbon-carbon double bond in the molecule. Specific examples include norbornene monomers and monocyclic cycloolefins.

  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, and (ii) an unsaturated bond other than the carbon-carbon unsaturated bond involved in the polymerization reaction. (Iii) norbornene monomers having a polar group, (iv) norbornene monomers not containing a polar group other than the above (i) and (ii), and the like.

Examples of the norbornene-based monomer (i) include norbornene, tetracyclododecene, and alkyl-substituted products thereof.
Examples of the norbornene-based monomer (ii) include ethylidene norbornene, vinyl norbornene, ethylidene tetracyclododecene, and dicyclopentadiene.
Examples of the norbornene-based monomer (iii) include methoxycarbonylnorbornene, methoxycarbonyltetracyclododecene, and 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.

As the norbornene-based monomer that does not contain the polar group (iv), that is, is composed of only a carbon atom and a hydrogen atom, 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);
Dicyclopentadienes having an aromatic ring such as dicyclopentadiene, methyldicyclopentadiene, dihydrodicyclopentadiene (also referred to as tricyclo [5.2.1.0 ^2,6 ] dec-8-ene);

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 . ^02,7 ] 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] pentacyclic body more cyclic olefins such as heptadeca-4-ene; and the like.

  Examples of the monocyclic cycloolefin include cyclobutene, cyclopentene, cyclooctene, cyclododecene, and 1,5-cyclooctadiene. These may have a substituent.

  These cycloolefin 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.

  Moreover, when using a monocyclic cycloolefin, it is preferable to use together with a norbornene-type monomer, The usage-amount is with respect to a norbornene-type monomer, Preferably it is 40 mass% or less, More preferably, it is 20 mass% or less. If the amount used exceeds 40% by mass, the heat resistance of the polymer obtained by bulk polymerization may be insufficient.

  Among these, since it is possible to obtain a crosslinked product having excellent electrical characteristics, (iv) norbornene-based monomers containing no polar group other than the above (i) and (ii) are preferable, and a crosslinked product having excellent flame retardancy. Etc., norbornene monomers having an aromatic ring are more preferable.

(B) Metathesis Polymerization Catalyst The metathesis polymerization catalyst used in the present invention is not particularly limited as long as it allows the cycloolefin monomer to undergo metathesis ring-opening polymerization.
Specific examples of the metathesis polymerization catalyst include a complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds around a transition metal atom. As the transition metal atom, a Group 8 transition metal atom is preferable, and ruthenium and osmium are more 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.
The ruthenium carbene complex is represented by the following formula (1) or formula (2).

In the formulas (1) and (2), R ¹ and R ² may each independently contain a hydrogen atom, a halogen atom, or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. A hydrocarbon group having 1 to 20 carbon atoms is represented.
Examples of the hydrocarbon group having 1 to 20 carbon atoms of R ¹ and R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, n- C1-C20 alkyl group such as hexyl group; C2-C20 alkenyl group such as vinyl group, 1-propenyl group, 2-propenyl group and crotyl group; C2-C2 such as ethynyl group and propargyl group 20 alkynyl group; aryl groups having 6 to 20 carbon atoms such as phenyl group, 1-naphthyl group, 2-naphthyl group; and the like.

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.

X ¹ and X ² are ligands having a negative charge when separated from a central metal atom, such as a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a diketonate group, a substituent A cyclopentadienyl group, an alkoxy group, an aryloxy group, a carboxyl group, etc. are mentioned. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

In the hetero atom-containing carbene compound of L ¹ and L ² , the hetero atom means an atom of Groups 15 and 16 of the periodic table, specifically, N, O, P, S, As, Se atom etc. are mentioned. Among these, from the viewpoint of obtaining a stable carbene compound, N, O, P, S atoms and the like are preferable, and N atom is 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 the above formula, R ^{3 to} R ⁶ are each independently a hydrogen atom, a halogen atom, or a C 1 -C 1 that may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. 20 hydrocarbon groups are represented. R ^{3 to} R ⁶ may be bonded to each other in any combination to form a ring.

  Examples of the compound represented by the formula (3) or the 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 the formula (3) or formula (4), 1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5 -Iridene, 1,3-dicyclohexylhexahydropyrimidin-2-ylidene, N, N, N ', N'-tetraisopropylformamidinylidene, 1,3,4-triphenyl-4,5-dihydro-1H- Hetero atom-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.

The neutral electron donating compound of L ¹ and L ² may be any ligand as long as it has a neutral charge when pulled away 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) Tyrimidazolidin-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) L ¹ and L ² such as phosphine) ruthenium dichloride, (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) (2-pyrrolidone-1-ylmethylene) (tricyclohexylphosphine) ruthenium dichloride One There to a hetero atom-containing carbene compounds, ruthenium complex compounds 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, etc. A ruthenium complex compound which is a contained carbene compound;

Among these, a ruthenium complex compound represented by the 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 is particularly preferable. preferable.

  These ruthenium complex compounds are described in Org. Lett. 1999, Vol. 1, p. 953, Tetrahedron. Lett. 1999, Vol. 40, page 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: cycloolefin 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 and mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane , Cycloaliphatic hydrocarbons such as decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile Oxygen-containing hydrocarbons such as diethyl ether and tetrahydrofuran; Among these, it is preferable to use industrially general-purpose aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons. Moreover, as long as the activity as a metathesis polymerization catalyst is not lowered, a liquid anti-aging agent, a plasticizer or an 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.

Specific examples of the activator include trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium. , Tetraalkoxytin, tetraalkoxyzirconium and the like.
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 crosslink after bulk polymerization to obtain a crosslinked resin.
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 alone or in combination of two or more. 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-butylperoxy) ) -2-peroxyketals such as 2-methylcyclohexane and 1,1-di (t-butylperoxy) cyclohexane; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; t-butylperoxyisopropylcarbonate; And 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 alone or in combination of two or more thereof. Moreover, it is possible to control freely the glass transition temperature and molten state of the crosslinkable resin obtained by using together 2 or more types of radical generating agents, and changing the blend ratio.

  The usage-amount of a crosslinking agent is 0.1-10 mass parts normally with respect to 100 mass parts of cycloolefin 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.

Moreover, in this invention, when using a radical generating agent as a crosslinking agent, in order to promote the crosslinking reaction, a crosslinking adjuvant can be used together.
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) Aluminum hydroxide and / or magnesium hydroxide The polymerizable composition of the present invention further comprises aluminum hydroxide and / or magnesium hydroxide whose average particle size is increased by treatment with a silane coupling agent. contains.
“Contains aluminum hydroxide and / or magnesium hydroxide” means that it contains only aluminum hydroxide, contains only magnesium hydroxide, and may contain both aluminum hydroxide and magnesium hydroxide. Means.

The average particle diameter (initial average particle diameter) at the beginning (before the treatment) of aluminum hydroxide and / or magnesium hydroxide (hereinafter sometimes referred to as “aluminum hydroxide or the like”) to be used is usually 1 to 10 μm. It is. On the other hand, the average particle diameter of aluminum hydroxide and the like after being treated with the silane coupling agent is in the range of 3 to 100 μm. The average particle diameter of the treated aluminum hydroxide or the like is usually 1.2 times or more, preferably 1.2 to 20 times the initial average particle diameter.
The average particle diameter of aluminum hydroxide or the like can be measured by, for example, a known laser diffraction type particle size distribution measuring device.

  Aluminum hydroxide or the like used in the present invention is generally used as a flame retardant for resin molded products. When these particle diameters are small, a high flame retardant effect is obtained because the resin molded product melts rapidly when it is burned, but the viscosity of the resin varnish used during the preparation of the resin molded product increases, so that the moldability decreases. On the other hand, when the particle diameter is large, an increase in the viscosity of the resin varnish can be suppressed, but when the resin molded product is burned, the melting is slow and the flame retardant effect is reduced. In the present invention, aluminum hydroxide or the like is agglomerated by treatment with a silane coupling agent, and apparently the particle size is increased and blended into the polymerizable composition, so that the viscosity of the polymerizable composition is increased. In addition to being suppressed, it is presumed that excellent flame retardancy can be obtained in the obtained molded body and laminate.

  The total amount of aluminum hydroxide and magnesium hydroxide used is preferably 50 to 500 parts by weight, more preferably 70 to 300 parts by weight, and 100 to 280 parts by weight based on 100 parts by weight of the cycloolefin monomer. More preferably, it is part. By setting the total amount of aluminum hydroxide and magnesium hydroxide to be in such a range, the polymerizable composition targeted by the present invention can be obtained more easily.

  The mixing ratio of aluminum hydroxide and magnesium hydroxide is usually 100/0 to 10/90, preferably 100/0 to 50/50, by weight ratio of (aluminum hydroxide / magnesium hydroxide). By setting the blending ratio of aluminum hydroxide and magnesium hydroxide in such a range, the polymerizable composition targeted by the present invention can be obtained more easily.

As the silane coupling agent, for example, styryl silane, vinyl silane, epoxy silane, acryloxy silane, amino silane, ureido silane, chloropropyl silane, mercapto silane, sulfide silane, isocyanate silane and the like can be used.
Examples of styrylsilane include 2-styrylethyltrimethoxysilane and p-styryltrimethoxysilane.

  As vinyl silane, vinyl trimethoxy silane, vinyl triethoxy silane, γ-methacryloxypropyl trimethoxy silane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyl trimethoxy silane hydrochloride, vinyl trimethoxy silane And vinyltriacetoxysilane.

Examples of the epoxy silane include 3-glycidoxypropyltrimethoxysilane and 3,4-glycidoxycyclocyclohexyltrimethylsilane.
As acryloxysilane, γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyl Examples include tripropoxysilane and γ- (meth) acryloxypropylmethyldimethoxysilane.

Examples of the aminosilane include 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, and the like.
Examples of ureidosilane include methyldimethoxy (N, N ′, N′-trimethylureido) silane, methyldimethoxy (N-allyl-N ′, N-dimethylureido) silane, and methyldimethoxy (N-phenyl-N ′, N ′). -Dimethylureido) silane etc. are mentioned.

Examples of chloropropylsilane include γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropylmethyldimethoxysilane, and γ-chloropropylmethyldiethoxysilane.
Examples of mercaptosilane include γ-mercaptopropylmethyldimethoxysilane.
Examples of the isocyanate silane include methyldimethoxyisocyanatosilane and dimethoxydiisocyanatosilane.

  A silane coupling agent can be used individually by 1 type or in combination of 2 or more types. Especially, as a silane coupling agent used by this invention, since an average particle diameter can be increased more simply, a styryl silane is preferable.

  The usage-amount of a silane coupling agent is 0.3-2 weight part normally with respect to 100 weight part of total usage of aluminum hydroxide and magnesium hydroxide, Preferably it is 0.3-1 weight part.

  The method of treating aluminum hydroxide or the like with a silane coupling agent is not particularly limited as long as it uses a known kneader to bring aluminum hydroxide or the like into contact with the silane coupling agent at a predetermined temperature. From the viewpoint of obtaining a polymerizable composition having low thixotropic properties and good moldability, both are mixed and stirred at a low temperature (10 to 25 ° C.), and the temperature is raised to a predetermined temperature (70 to 150 ° C.). A method of stirring is preferred.

  In addition, after performing these operations (step 1), the temperature is returned to a low temperature, aluminum hydroxide and the silane coupling agent are additionally added and mixed and stirred, and then the temperature is raised again and stirred at a predetermined temperature (step 2). ) Is preferable. By performing this step 2, the increase rate of the average particle diameter of aluminum hydroxide or the like can be further increased.

In either case of Step 1 or Step 2, the stirring time is usually 30 minutes to several hours after the temperature is raised by several tens of minutes at a low temperature, depending on the scale.
The use ratio of aluminum hydroxide or the like and the silane coupling agent is the same as that described above in either case of Step 1 or Step 2.

The stirring rotation speed of the kneader is usually 15 to 100 rpm, preferably 20 to 50 rpm, although it depends on the kneader to be used. If the rotational speed is too slow, the stirring efficiency is poor, and if the rotational speed is too fast, it tends to be difficult to increase the particle size.
After completion of stirring, the temperature is returned to a low temperature and dried with a dryer. As described above, aluminum hydroxide or the like having an increased average particle diameter can be obtained.

  When aluminum hydroxide and magnesium hydroxide are used in combination as aluminum hydroxide or the like, (i) a mixture of aluminum hydroxide and magnesium hydroxide treated by the above method may be used, or (ii) water Aluminum oxide and magnesium hydroxide may be separately treated by the above-mentioned method, and each of the obtained treatment products may be used in combination in a necessary amount, or (iii) aluminum hydroxide (or magnesium hydroxide) is used. After performing step 1, magnesium hydroxide (or aluminum hydroxide) may be added to perform step 2, and the resulting mixture of aluminum hydroxide and magnesium hydroxide may be used. Among them, the methods (ii) and (iii) are preferable, and the method (ii) is more preferable because the average particle diameter can be increased more easily.

  The rate of increase of the average particle diameter of aluminum hydroxide and the like relative to the initial average particle diameter is empirically determined by the addition of aluminum hydroxide and the like, the use ratio of the silane coupling agent, the processing time, the processing temperature, and the rotational speed of the kneader. It can control by adjusting etc.

  By using such aluminum hydroxide having an increased average particle diameter, the storage elastic modulus (G ′) when the shear strain (γ) is 0.1 is 5 to 1000 Pa, as will be described later. Thus, a polymerizable composition excellent in moldability can be easily obtained.

(E) Other additives The polymerizable composition of the present invention may contain other additives in addition to the components (a) to (d). Examples of other additives include polymerization reaction retarders, radical crosslinking retarders, dispersants, fillers, reinforcing materials, modifiers, antioxidants, colorants, and light stabilizers. These can be used by dissolving or dispersing in a monomer liquid or catalyst liquid described later.

  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, chain diene compounds, aryl phosphines, alkyl phosphines, and cycloolefin monomers having a diene structure or triene structure are preferred, alkyl phosphines, cycloolefin monomers having two double bonds in the ring, and A cycloolefin monomer having a double bond inside and outside the ring is particularly preferable.
What is necessary is just to adjust suitably the compounding quantity of a polymerization reaction retarder in the case of using a polymerization reaction retarder as needed.

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. The blending ratio is usually 0.001 to 1 mol, preferably 0.01 to 1 mol, with respect to 1 mol of the radical generator.

Dispersants include aluminate coupling agents, silane coupling agents, titanate coupling agents, silazanes, organosiloxane coupling agents; anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric interfaces Surfactants such as activators; resins; and the like.
Among these dispersants, it is excellent in dispersibility and has excellent electrical properties and mechanical strength such as a crosslinked product, so that coupling agents such as aluminate coupling agents, silane coupling agents, and titanate coupling agents are used. And nonionic surfactants are preferred, and aluminate coupling agents and nonionic surfactants are particularly preferred.

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

  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, σ-methacryloxybutyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ- Mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltritrimethoxysilane Etc.

  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 ester polyoxyethylene ether, sorbitan ester polyoxyethylene ether, sorbitol ester polyoxyethylene ether; fatty acid polyhydric alcohol ester type; polyethylene glycol fatty acid ester, glycerin ester, polyglycerin ester, sorbitan ester, Ester types such as propylene glycol ester and sucrose ester, fatty acid alkanolamine , Polyoxyethylene fatty acid amides, polyoxyethylene alkyl amines, nitrogen-containing type such as amine oxides like.

These dispersants can be used alone or in combination of two or more.
The amount of the dispersing agent is usually 0.01 to 10 parts by mass, preferably 0.05 to 6 parts by mass, and more preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the cycloolefin monomer. .

  Examples of the filler include organic fillers such as polyethylene powder; inorganic fillers such as glass powder, ceramic powder, and silica; These fillers can be used alone or in combination of two or more. Moreover, what was surface-treated with the silane coupling agent etc. can also be used as a filler. The blending 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.

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, amine-based antioxidants for plastics and rubber. These antioxidants may be used alone or in combination of two or more.

  Examples of the colorant include dyes and pigments. There are various kinds of dyes, and known ones may be appropriately selected and used.

  The method for preparing the polymerizable composition is not particularly limited. For example, (b) a liquid in which a metathesis polymerization catalyst is dissolved or dispersed in an appropriate solvent (hereinafter sometimes referred to as “catalyst liquid”) is prepared, and (a) a cycloolefin monomer is added to (c) a crosslinking agent. (D) A liquid (hereinafter sometimes referred to as “monomer liquid”) containing a filler such as aluminum hydroxide treated with a silane coupling agent and other additives as required is prepared, and the monomer is prepared. The method of preparing by mixing and stirring a liquid and a catalyst liquid is mentioned.

The polymerizable composition of the present invention has a storage elastic modulus (G ′) when the shear strain (γ) is 0.1, usually 5 to 1000 Pa, preferably 5 to 700 Pa, more preferably 6 to 500 Pa. It is.
Since the polymerizable composition of the present invention has a storage elastic modulus (G ′) in such a range, it has thixotropic properties (although it exhibits high viscosity when allowed to stand, but exhibits extremely high fluidity during stirring. Properties) are low and the moldability is good.

  In addition, the polymerizable composition having the storage elastic modulus (G ′) in such a range is, for example, the type and amount of the components (a) to (d), particularly, a filler such as aluminum hydroxide. It can be easily obtained by empirically controlling the increase ratio of the average particle size.

2) Preparation method of polymerizable composition The preparation method of the polymerizable composition of the present invention is obtained by treating aluminum hydroxide and / or magnesium hydroxide having an initial average particle diameter of 1 to 10 μm with a silane coupling agent. And a step of setting the average particle diameter to 1.2 times or more of the initial average particle diameter.
As a method of treating aluminum hydroxide or the like having an initial average particle diameter of 1 to 10 μm in this step with a silane coupling agent and setting the average particle diameter to 1.2 times the initial average particle diameter or more, The method similar to the method of processing aluminum hydroxide etc. by the silane coupling agent described in the said 1) term is mentioned.
When aluminum hydroxide or the like treated in this step is used, the polymerizable composition of the present invention having low thixotropic properties and excellent molding processability can be easily obtained.

3) Crosslinkable resin molded body The crosslinkable resin molded body of the present invention is a molded body obtained by bulk polymerization of the polymerizable composition of the present invention.
As a method for bulk polymerization of the polymerizable composition of the present invention, (A) a method of pouring (casting) or coating the polymerizable composition on a support and applying bulk polymerization; (B) a polymerizable composition; And a bulk polymerization method, and (C) a method in which a polymerizable composition is impregnated into a support and bulk polymerization is performed.

  The material of the support used in the method (A) is a resin such as polyethylene terephthalate, polypropylene, polyethylene, polycarbonate, polyethylene naphthalate, polyarylate, nylon; iron, stainless steel, copper, aluminum, nickel, chromium, gold, silver Metal materials such as, and the like. Although the shape of a molded object is not specifically limited, A film form (sheet form) is preferable like a metal foil or a resin film.

  The thickness of the support is usually 1 to 150 μm, preferably 2 to 100 μm, from the viewpoint of workability and the like. The surface of these supports is preferably smooth. Moreover, when it is desired to enhance the adhesion, the surface of the support is preferably surface-treated with a silane coupling agent or the like in advance.

  The method for applying the polymerizable composition to the support is not particularly limited, and examples thereof include known application 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. The heating temperature is a temperature at which the metathesis polymerization catalyst functions, and 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 10 seconds to 5 minutes.

This polymerization reaction is an exothermic reaction, and once the polymerization starts, the temperature of the reaction solution rises rapidly and reaches the peak temperature in a short time (eg, about 10 seconds to 5 minutes). If the maximum temperature during the polymerization reaction is too high, a crosslinking reaction occurs to form a crosslinked resin (crosslinked product), and there is a possibility that a crosslinkable resin that can be postcrosslinked 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 more than the 1 minute half-life temperature of the radical generator, preferably not more than 230 ° C., more preferably Is preferably controlled below 200 ° C.
The term “crosslinkable resin that can be post-crosslinked” herein means a resin that can be converted into a crosslinked body by heating the resin to cause a crosslinking reaction. The crosslinkable resin molded article of the present invention is a molded article that can be post-crosslinked.

The method of heating the polymerizable composition is not particularly limited, and is a method of heating by placing on a heating plate, a method of heating while applying pressure using a press (hot pressing), a method of pressing with a heated roller, heating Examples include a method using a furnace.
The thickness of the crosslinkable resin molded product (film) obtained as described above is usually 10 mm or less, 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 polymerization temperature, polymerization time, etc. are the same as described in (A) above.

The support used in the method (C) is a fiber material. According to the method (C), a prepreg in which a fiber material is impregnated with a crosslinkable resin can be obtained.
The material of the fiber material is organic and / or inorganic fiber. Examples thereof include glass fiber, carbon fiber, aramid fiber, polyethylene terephthalate fiber, vinylon fiber, polyester fiber, amide fiber, metal fiber, and ceramic fiber. 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. By applying to a fiber material, if necessary, a protective film may be stacked thereon and pressed from above with a roller or the like. After impregnating the polymerizable composition into the fiber material, the polymerizable composition can be bulk polymerized by heating the impregnated material to a predetermined temperature, whereby the fiber material is impregnated with the crosslinkable resin. Is obtained.
As a protective film, the thing similar to having illustrated as a support body used with the method of said (A) can be used.

The heating method of the impregnated product is not particularly limited, and the same method as the method (A) can be adopted. The polymerization temperature, polymerization time, etc. are the same as described in (A) above.
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).

  Further, the method (A) and the method (C) may be combined. For example, casting a polymerizable composition on a support, laying a fiber material thereon, casting the polymerizable composition again, overlaying a protective film thereon, pressing with a roller or the like from above, heating By doing so, a prepreg in which the fiber material is sufficiently impregnated with the crosslinkable resin can be obtained.

Since the polymerizable composition of the present invention has a low viscosity as compared with conventional resin varnishes and is excellent in impregnation with respect to the fiber material, the fiber material can be uniformly impregnated with the polymerizable composition.
In addition, since the polymerizable composition of the present invention has a low content of a solvent or the like that does not participate in the reaction, a step such as removing the solvent after impregnating the fiber material is unnecessary, and it is excellent in productivity and depends on the residual solvent. Odors and bulges do not occur. Furthermore, since the crosslinkable resin molded article of the present invention is excellent in storage stability, the obtained prepreg is excellent in storage stability.

  Since the crosslinkable resin molded article of the present invention is obtained by almost completely proceeding the bulk polymerization reaction of the polymerizable composition described above, there are few residual monomers, and the working environment deteriorates due to odors etc. derived from the monomers. There is nothing to do. In addition, when a radical generator 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 property in a wiring board are good. Become.

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

  The crosslinkable resin molded product of the present invention may be a partially crosslinked product. 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 crosslinkable resin that can be post-crosslinked, the effects of the crosslinkable resin molded article of the present invention can be fully enjoyed.

  Since the crosslinkable resin molded article of the present invention is obtained by almost completely proceeding bulk polymerization, there is no fear that the polymerization reaction further proceeds during storage. Although the crosslinkable resin molded article of the present invention contains a crosslinking agent, unless it is heated to a temperature higher than that causing a crosslinking reaction, problems such as change in surface hardness do not occur, and the storage stability is excellent.

4) Crosslinked resin molded article The crosslinked resin molded article of the present invention is obtained by crosslinking a polymer obtained by bulk polymerization of the polymerizable composition of the present invention (hereinafter sometimes referred to as "crosslinkable resin"). It is.
Crosslinking can be performed by, for example, heating and melting the crosslinkable resin 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.

As a method for melting the crosslinkable resin by heating, when the crosslinkable resin is a sheet-shaped or film-shaped molded body, a method of laminating the molded body on a support 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 press having a press frame mold for flat plate forming, a press molding machine such as a sheet mold compound (SMC) or a bulk mold compound (BMC).
As the support, those similar to those exemplified in the section 3) Crosslinkable resin molded article can be used.
The obtained crosslinked resin molded article of the present invention is excellent in flame retardancy. It can confirm that it is excellent in a flame retardance by the test based on UL-94 specification.

5) Laminate The laminate of the present invention has at least a layer formed of the crosslinkable resin molded product of the present invention or the crosslinked resin molded product of the present invention.
As a specific example of a laminate having a layer composed of the crosslinkable resin molded body of the present invention, a support and a crosslinkable resin molded article in which a sheet-like or film-like crosslinkable resin is laminated on the support described above. A laminate composed of a body is exemplified.

  As a specific example of a laminate having a layer made of the crosslinked resin molded article of the present invention, a support obtained by laminating a sheet-like or film-like crosslinkable resin on the above-described support and hot pressing the laminate. And a laminate composed of a crosslinked resin molded body, a laminate obtained by hot pressing a prepreg, and the like. The conditions for hot pressing are the same as those for crosslinking the crosslinkable resin.

Moreover, the laminated body of this invention may have another support body other than the said support body. Examples of other supports 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; Further, when a printed wiring board is used as the support, a multilayer printed wiring board can be manufactured.
The metal foil such as copper foil and the conductive layer on the printed wiring board are preferably those whose surfaces are treated with a silane coupling agent, a thiol coupling agent, a titanate coupling agent, various adhesives, Those treated with a silane coupling agent are particularly preferred.

Since the crosslinkable resin of the present invention is excellent in fluidity and adhesion, the laminate of the present invention is excellent in flatness and adhesion.
In addition, since the laminate of the present invention has the crosslinkable resin molded body of the present invention or a layer formed of the crosslinked resin molded body, mechanical characteristics such as low linear expansion coefficient and high strength; electrical characteristics such as low dielectric loss tangent; Excellent in fire resistance and flame retardancy.
Therefore, the laminate of the present invention can be suitably used as an electronic component material such as a resin-coated copper foil; 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.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples.

In Preparation Examples 1 to 6, a biaxial planetary mixing kneader (TK Hibismix 2P-1 type, manufactured by PRIMIX) was used as a mixing kneader.
The particle diameter was measured by dispersing the particles in isopropyl alcohol and using a laser diffraction particle size distribution analyzer (SALD 3000J, manufactured by Shimadzu Corporation).

(Preparation Example 1)
0.5 part of styrylsilane (KBM-1403 manufactured by Shin-Etsu Silicone Co., Ltd., the same below) was added to 100 parts of aluminum hydroxide (average particle size: 3.1 μm, the same applies hereinafter). After stirring at a temperature of 20 ° C. and a stirring speed of 50 rpm for 15 minutes, the stirring speed was set to 20 rpm, heated to 90 ° C., further stirred for 1 hour, and then cooled to 20 ° C.

  To the obtained mixture, 0.5 part of styrylsilane was further added. After stirring for 15 minutes at a temperature of 20 ° C. and a stirring rotational speed of 20 rpm, 100 parts of aluminum hydroxide was newly added. After stirring for 15 minutes at a temperature of 20 ° C. and a stirring rotation speed of 20 rpm, the mixture was heated to 90 ° C., further stirred for 1 hour, and then cooled to 20 ° C. The mixture was taken out into a vat and dried at 100 ° C. for 2 hours with a dryer to prepare aluminum hydroxide having an average particle size of 35 μm (11.3 times the initial average particle size).

(Preparation Example 2)
In Preparation Example 1, the average particle diameter was 30 μm (initial average particle diameter of 16 μm) in the same manner as in Preparation Example 1, except that aluminum hydroxide was changed to magnesium hydroxide (average particle diameter 1.8 μm, the same applies hereinafter). 0.7 times) magnesium hydroxide was prepared.

(Preparation Example 3)
In Preparation Example 1, 100 parts of aluminum hydroxide to be newly added was changed to 80 parts of magnesium hydroxide, and styrylsilane to be newly added was changed from 0.5 parts to 0.6 parts. Then, a mixture of aluminum hydroxide and magnesium hydroxide having an average particle size of 30 μm (1.2 times or more of the initial average particle size) was prepared.

(Preparation Example 4)
0.5 part of styrylsilane was added to 100 parts of aluminum hydroxide. After stirring for 15 minutes at a temperature of 20 ° C. and a stirring speed of 50 rpm, the stirring speed was changed to 200 rpm, heated to 90 ° C., further stirred for 1 hour, and then cooled to 20 ° C.
The obtained mixture was taken out into a vat and dried at 100 ° C. for 2 hours with a dryer to prepare aluminum hydroxide having an average particle size of 2.7 μm (0.87 times the initial average particle size).

(Preparation Example 5)
Magnesium hydroxide having an average particle diameter of 2 μm (1.11 times the initial average particle diameter) was prepared in the same manner as in Preparation Example 4 except that aluminum hydroxide was changed to magnesium hydroxide in Preparation Example 4.

(Preparation Example 6)
In Preparation Example 4, aluminum hydroxide having an average particle size of 4 μm (1.29 times the initial average particle size) was prepared in the same manner as in Preparation Example 4 except that the stirring rotation speed in the latter half was changed from 200 rpm to 20 rpm. .

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.
A polyethylene bottle, as cycloolefin monomers, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (MTF), 40 parts, and tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (TCD) 60 parts, where 0.74 part of allyl methacrylate as a chain transfer agent and di-t-butyl peroxide as a cross-linking agent (1 minute half-life temperature 186 ° C. 1.2 parts), 1.1 parts of acetoalkoxyaluminum diisopropylate (Plenact AL-M, manufactured by Ajinomoto Fine Techno Co.) as a dispersant, and 160 parts of aluminum hydroxide having an average particle size of 35 μm obtained in Preparation Example 1 80 parts of magnesium hydroxide having an average particle diameter of 30 μm obtained in Preparation Example 2 was added and stirred to prepare a polymerizable composition (1).

  Next, 100 parts of this polymerizable composition (1) was cast on a polyethylene naphthalate film (type Q51, thickness 75 μm, manufactured by Teijin DuPont Films, the same applies hereinafter), and a glass cloth (product number 2116) was formed thereon. , A thickness of 92 μm), and 80 parts of the polymerizable composition (1) was cast thereon. A polyethylene naphthalate film was further covered thereon, and the entire glass cloth was impregnated with the polymerizable composition (1) using a roller. Next, this was heated in a heating furnace heated to 150 ° C. for 1 minute, and the polymerizable composition (1) was bulk polymerized to obtain a laminate (1) having a thickness of 0.1 mm.

(Example 2)
In Example 1, instead of 160 parts of aluminum hydroxide obtained in Preparation Example 1 and 80 parts of magnesium hydroxide obtained in Preparation Example 2, aluminum hydroxide and water having an average particle diameter of 30 μm obtained in Preparation Example 3 were used. A polymerizable composition (2) was prepared in the same manner as in Example 1 except that 240 parts of magnesium oxide was used. Further, in the same manner as in Example 1, a laminate (2) having a thickness of 0.1 μm was prepared. Got.

(Example 3)
In Example 1, instead of 160 parts of aluminum hydroxide obtained in Preparation Example 1 and 80 parts of magnesium hydroxide obtained in Preparation Example 2, 200 parts of aluminum hydroxide having an average particle diameter of 4 μm obtained in Preparation Example 6 was used. A polymerizable composition (3) was prepared in the same manner as in Example 1 except that it was used, and a laminate (3) having a thickness of 0.1 μm was obtained in the same manner as in Example 1.

(Comparative Example 1)
In Example 1, instead of 160 parts of aluminum hydroxide obtained in Preparation Example 1 and 80 parts of magnesium hydroxide obtained in Preparation Example 2, 160 parts of aluminum hydroxide having an average particle diameter of 3 μm obtained in Preparation Example 4 and preparation were prepared. A polymerizable composition (4) was prepared in the same manner as in Example 1 except that 80 parts of magnesium hydroxide having an average particle diameter of 2 μm obtained in Example 5 was used. Further, in the same manner as in Example 1, A laminate (4) having a thickness of 0.1 mm was obtained.

(Comparative Example 2)
In Example 1, in place of 160 parts of aluminum hydroxide obtained in Preparation Example 1 and 80 parts of magnesium hydroxide obtained in Preparation Example 2, 200 parts of aluminum hydroxide having an average particle diameter of 3 μm obtained in Preparation Example 4 were used. A polymerizable composition (5) was prepared in the same manner as in Example 1 except that a laminate (5) having a thickness of 0.1 μm was obtained in the same manner as in Example 1.

(Comparative Example 3)
In Example 1, instead of 160 parts of aluminum hydroxide obtained in Preparation Example 1 and 80 parts of magnesium hydroxide obtained in Preparation Example 2, commercially available aluminum hydroxide (B303, average particle size of 30 μm, manufactured by Nippon Light Metal Co., Ltd.) ) A polymerizable composition (6) was prepared in the same manner as in Example 1 except that 200 parts were used as it was. Further, in the same manner as in Example 1, a laminate (6) having a thickness of 0.1 μm was prepared. Got.

  By the method shown below, the moldability and viscoelasticity were evaluated and measured for the polymerizable compositions (1) to (6) obtained in Examples 1 to 3 and Comparative Examples 1 to 3, and the laminate (1). Flame retardancy was evaluated for ~ (6).

<Molding processability>
1.5 L of each of the polymerizable compositions (1) to (6) was filled in a 2 L metal tank, and a pressure of 0.5 MP was applied. The metal tank and the T-shaped die were connected with a SUS tube having a diameter of 1.5 cm, and the polymerizable composition was pumped to the T-shaped die. The appearance of the polymerizable composition from a T-die having a height of 100 μm and a width of 50 cm was observed, and molding processability was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1 below.

〔Evaluation criteria〕
○: The whole amount comes out.
Δ: Clogged in the middle.
X: Not appearing.

<Viscoelasticity>
For the polymerizable compositions (1) to (6), linear viscoelasticity measurement is performed using a viscosity / viscoelasticity measuring device (Rheo Stress 6000, manufactured by HAAKE), and the shear strain (γ) is 0.1. The storage elastic modulus (G ′) was determined. The results are shown in Table 1 below.

<Flame retardance>
The digestion time (seconds) was measured for the laminates (1) to (6) based on the UL-94 standard. The measurement results are shown in Table 1 below.

From Table 1, the polymerizable compositions (1) to (3) of Examples 1 to 3 have a storage elastic modulus G ′ of 5 to 1000 Pa, excellent molding processability, and laminates (1) to (3). Was excellent in flame retardancy.
The polymerizable compositions (4) and (5) of Comparative Examples 1 and 2 having a storage elastic modulus G ′ of 5 to 1000 Pa have a small average particle diameter of the used aluminum hydroxide and the like, and are difficult to obtain. Although the flammability is high, the molding processability is inferior, and the polymerizable composition (6) of Comparative Example 3 has a large average particle diameter and the molding processability is excellent, but the flame retardancy is inferior.

Claims (8)

  Containing aluminum hydroxide and / or magnesium hydroxide having an average particle size increased by treatment with a cycloolefin monomer, a metathesis polymerization catalyst, a crosslinking agent, and a silane coupling agent, The storage elastic modulus (G ′) is 5 when the average particle diameter of magnesium hydroxide after treatment with the silane coupling agent is in the range of 3 to 100 μm and the shear strain (γ) is 0.1. Polymeric composition which is -1000Pa.   The polymerizable composition according to claim 1, wherein the total amount of aluminum hydroxide and magnesium hydroxide is 50 to 500 parts by weight based on 100 parts by weight of the cycloolefin monomer.   3. The polymerizable composition according to claim 1, wherein the mixing ratio of aluminum hydroxide and magnesium hydroxide is (aluminum hydroxide / magnesium hydroxide) = 100/0 to 10/90 by weight ratio.   The initial average particle diameter of the aluminum hydroxide and / or magnesium hydroxide is 1 to 10 μm, and the average particle diameter after being treated with the silane coupling agent is 1.2 times or more of the initial average particle diameter. The polymerizable composition according to any one of claims 1 to 3.   A step of treating aluminum hydroxide and / or magnesium hydroxide having an initial average particle diameter of 1 to 10 μm with a silane coupling agent so that the average particle diameter is 1.2 times or more of the initial average particle diameter. The preparation method of the polymeric composition in any one of Claims 1-4 which has.   A crosslinkable resin molded article obtained by bulk polymerization of the polymerizable composition according to claim 1.   A crosslinked resin molded article obtained by crosslinking a polymer obtained by bulk polymerization of the polymerizable composition according to claim 1.   A laminate having at least a layer comprising the crosslinkable resin molded article according to claim 6 or the crosslinked resin molded article according to claim 7.