JP2008163249A - Polymerizable composition, crosslinkable resin, and method for producing the same - Google Patents

Polymerizable composition, crosslinkable resin, and method for producing the same Download PDF

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JP2008163249A
JP2008163249A JP2006355921A JP2006355921A JP2008163249A JP 2008163249 A JP2008163249 A JP 2008163249A JP 2006355921 A JP2006355921 A JP 2006355921A JP 2006355921 A JP2006355921 A JP 2006355921A JP 2008163249 A JP2008163249 A JP 2008163249A
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polymerizable composition
crosslinkable resin
crosslinking
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Junji Odemura
Akihiko Yoshihara
明彦 吉原
順司 小出村
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Nippon Zeon Co Ltd
日本ゼオン株式会社
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable composition suitable as electrical materials and the like used for electric circuit substrates, a crosslinkable resin obtained by using the same, a method for production thereof, and applications thereof to crosslinked products, composites, laminates and the like, excellent in characteristics such as electric insulation, tight adhesiveness, mechanical strengths, heat resistance, dielectric characteristics and the like. <P>SOLUTION: The polymerizable composition is prepared by mixing a metathesis polymerization catalyst containing benzilidene(1,3-dimethyl-4-imidazolidin-2-ylidene)(tricyclohexylphosphine)ruthenium dichloride and the like, a cycloolefin monomer such as 2-norbornene, tetracyclo[6.2.1.1<SP>3,6</SP>.0<SP>2,7</SP>]dodeca-4-ene, a chain transfer agent such as allyl methacrylate and a porous material such as porous silica. The crosslinked resin composite is prepared by coating or impregnating a support with the polymerizable composition, polymerizing in bulk to prepare the crosslinkable resin composite and crosslinking the composite. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polymerizable composition, a crosslinkable resin, and a method for producing the same. More specifically, 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 composition, a method for producing the crosslinkable resin, and the like, and The present invention relates to uses such as a crosslinked body, a composite, and a laminate excellent in electrical insulation, heat resistance, dielectric properties and the like.

A crosslinked molded article is obtained by crosslinking the thermoplastic resin with a crosslinking agent such as an organic peroxide. Various crosslinkable thermoplastic resins for obtaining this cross-linked molded article have been studied.
For example, Patent Document 1 discloses a polymerizable composition containing a norbornene monomer, a metathesis polymerization catalyst, a chain transfer agent, and a crosslinking agent. According to Patent Document 1, since this polymerizable composition has fluidity, it can be soaked into a nonwoven fabric as a support or formed into a film. Then, a crosslinkable thermoplastic resin can be obtained by bulk polymerization of the polymerizable composition. Further, Patent Document 1 discloses that various cross-linked resin composites can be obtained by laminating a cross-linkable thermoplastic resin with a base material such as a metal foil and performing cross-linking.
Japanese Patent Laid-Open No. 2004-244609

Patent Document 2 discloses an insulating resin composition containing porous inorganic fine particles having an average particle diameter of 1 to 50 μm, a porosity of 0.2 or more, and an average pore diameter of 10 to 100 nm, and an insulating resin. Things are disclosed. It is disclosed that a curing agent or a crosslinking agent is blended in the insulating resin composition to be cured or solidified. Such an insulating resin composition is produced by adding other components to the porous inorganic fine particles and the insulating resin as necessary, and uniformly mixing with a solvent, or by melt-kneading.
JP 2006-77172 A

  According to the study of the present inventor, the cross-linked product obtained with the resin disclosed in the above-mentioned patent document does not have a sufficiently low relative dielectric constant that affects high-frequency electrical conduction characteristics, and has a low dielectric constant and low linear expansion. It was difficult to balance the rate. Moreover, it was poor in solder heat resistance (a property in which blistering hardly occurs due to solder).

  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, and a method for producing a crosslinkable resin, a crosslinkable resin and the like obtained by using the polymerizable composition, In addition, an object of the present invention is to provide uses such as a cross-linked body, a composite body, and a laminated body excellent in electrical insulation, heat resistance, dielectric characteristics, and the like.

  As a result of intensive studies to achieve the above object, the present inventors have found that a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst contains a chain transfer agent and a porous material. It was found that by using a crosslinkable resin obtained by bulk polymerization of the polymer, a crosslinked product excellent in electrical insulation, heat resistance, dielectric properties and the like can be obtained. The present invention has been further studied and completed based on this finding.

That is, the present invention includes the following aspects.
(1) A polymerizable composition comprising a cycloolefin monomer, a metathesis polymerization catalyst, a chain transfer agent, and a porous material.
(2) The polymerizable composition as described above, wherein the median diameter of the primary particles of the porous body is 50 μm or less.
(3) The said polymerizable composition whose average pore diameter of a porous body is 0.1-100 nm.
(4) The said polymerizable composition whose porosity of a porous body is 10 volume% or more.
(5) The polymerizable composition as described above, wherein the metathesis polymerization catalyst is a ruthenium carbene complex.
(6) The polymerizable composition further comprising a crosslinking agent.

(7) A crosslinkable resin obtained by bulk polymerization of the polymerizable composition.
(8) A method for producing a crosslinkable resin, comprising a step of bulk polymerization of the polymerizable composition.
(9) A method for producing a crosslinkable resin composite, comprising a step of coating or impregnating the above-mentioned polymerizable composition on a support and subjecting it to bulk polymerization.
(10) A method for producing a crosslinked product, comprising a step of crosslinking the crosslinkable resin.
(11) A method for producing a crosslinked resin composite, comprising a step of crosslinking the molded article of the crosslinkable resin on a support.
(12) A method for producing a crosslinked resin composite, comprising a step of crosslinking the crosslinkable resin composite obtained by the method for producing a crosslinkable resin composite.
(13) The manufacturing method of the said crosslinked resin composite which performs the said bridge | crosslinking on another support body.

When the polymerizable composition of the present invention is bulk polymerized and then crosslinked, a crosslinked product having excellent properties such as electrical insulation, heat resistance, and dielectric properties and having both a low dielectric constant and a low linear expansion coefficient can be obtained. .
By laminating this cross-linked body on a film-like base material or by combining it with a fiber material, a composite body having the above characteristics 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 includes a cycloolefin monomer, a metathesis polymerization catalyst, a chain transfer agent, and a porous material.

(1) Cycloolefin monomer The cycloolefin monomer constituting the polymerizable composition is a compound having a ring structure formed of carbon atoms and having a carbon-carbon double bond in the ring. Examples thereof include norbornene monomers. The norbornene-based monomer is a monomer containing a norbornene ring. Specific examples include norbornenes, dicyclopentadiene, and tetracyclododecenes. These may contain a hydrocarbon group such as an alkyl group, an alkenyl group, an alkylidene group or an aryl group, or a polar group such as a carboxyl group or an acid anhydride group as a substituent. In addition to the norbornene ring double bond, it may further have a double bond. Among these, norbornene-based monomers that do not contain a polar group, that is, are composed only of carbon atoms and hydrogen atoms are preferable.

Examples of the norbornene-based monomer that does not contain a polar group include dicyclopentadiene, methyldicyclopentadiene, dihydrodicyclopentadiene (also referred to as tricyclo [5.2.1.0 2,6 ] dec-8-ene). Cyclopentadiene;

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 ] dodec-4-ene, 9-phenyltetracyclo [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- norbornene, 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);

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.

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 ] dodec-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, 5-norbornene-2 acetate -Yl, 5-norbornene-2-methanol, 5-norbornene-2-ol, 5-norbornene-2-carbonitrile, 2-acetyl-5-norbornene, 7-oxa-2-norbornene and the like.

  Further, in the present invention, a monocyclic cycloolefin such as cyclobutene, cyclopentene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, or a derivative thereof having a substituent is added to the norbornene-based monomer for polymerization. Can do. 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. The addition amount of monocyclic cycloolefins and derivatives thereof is preferably 40% by mass or less, more preferably 20% by mass or less, based on the total amount of the cycloolefin monomer. When the addition amount exceeds 40% by mass, the heat resistance of the polymer obtained by bulk polymerization may be insufficient.

(2) Metathesis polymerization catalyst The metathesis polymerization catalyst constituting the polymerizable composition is not particularly limited as long as it causes the cycloolefin monomer to undergo metathesis ring-opening polymerization.
Examples of the metathesis polymerization catalyst include a complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds around a transition metal atom. As transition metal atoms, atoms of Group 5, Group 6, and Group 8 (long period periodic table, the same applies hereinafter) are used. The atoms of each group are not particularly limited, but preferable group 5 atoms include tantalum, preferable group 6 atoms include molybdenum and tungsten, and preferable group 8 atoms include ruthenium and osmium. Can be mentioned.

  Among these, a group 8 ruthenium or osmium complex is preferably used as a metathesis polymerization catalyst, and a ruthenium carbene complex is particularly preferable. Since the ruthenium carbene complex 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, the group 8 ruthenium and osmium complexes are relatively stable to oxygen and moisture in the air and are not easily deactivated, so that a crosslinkable resin can be produced even in the air.

  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 represents 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 the formula, R 3 to R 6 each independently represent 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, which may contain 1 to 20 carbon atoms. Represents a hydrocarbon group, and 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, 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.

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

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

  These ruthenium complex catalysts can be produced by the methods described in Org. Lett., 1999, Vol. 1, page 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, mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane. , Decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene, cyclooctane and other alicyclic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; nitromethane, nitrobenzene, acetonitrile and other nitrogen-containing hydrocarbons Oxygen-containing hydrocarbons such as diethyl ether and tetrahydrofuran; Among these, it is preferable to use industrially general-purpose aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons. Further, as long as the activity as a metathesis polymerization catalyst is not lowered, a liquid anti-aging agent, a liquid plasticizer, or a liquid elastomer may be used as a solvent.

  The metathesis polymerization catalyst can be used in combination with an activator (cocatalyst). The activator is added 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.

  In addition, when using a complex of transition metal atoms of Group 5 and Group 6 as the metathesis polymerization catalyst, it is preferable to use both the metathesis polymerization catalyst and the activator dissolved in the monomer. As long as it is essentially not damaged, it can be suspended or dissolved in a small amount of solvent.

(3) Chain transfer agent The polymerizable composition of the present invention further 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. In particular, the formula (A): a compound represented by CH 2 = CH-Y-OCO -CR 7 = CH 2 are preferred. Y in the formula (A) is an alkylene group, and R 7 is 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 (A) 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.

(4) Porous body The porous body used in the present invention has a large number of small pores, and some of the pores are open on the particle surface. The shape of the porous body is not particularly limited, and examples thereof include a spherical shape, a plate shape, an irregular shape, a rod shape, and a fibrous shape, and a spherical or irregular shape is preferable. When these are used, the filling property is excellent, and variation in the dielectric constant depending on the location of the obtained crosslinked body or the like can be reduced.

In the porous body, the median diameter in the number-based particle size distribution of the primary particles is usually 50 μm or less, preferably 0.01 to 50 μm, more preferably 0.05 to 25 μm, still more preferably 0.05 to 10 μm, particularly preferably. 0.1 to 5 μm.
A porous material having a median diameter that is too small is difficult to produce, and a sufficient porosity may not be obtained. In addition, the viscosity of the polymerizable composition and the monomer liquid described later may increase and the moldability may decrease. If the median diameter is too large, the variation of the dielectric constant depending on the location, such as the resulting crosslinked product, tends to increase. In addition, it is difficult to produce a thin crosslinked body or the like, and there is a possibility that drilling workability and plating ability may be lowered.

  The porosity of the porous body is preferably 10% by volume or more, more preferably 30% by volume or more, still more preferably 40 to 90% by volume, and particularly preferably 50 to 80% by volume. If the porosity is too small, the effect of reducing the relative permittivity tends to be small. When the porosity is too large, the strength of the porous body is insufficient and the porous body is easily broken. Here, the porosity is calculated from the total particle volume (ml / g) obtained by the impact method and the pore volume (ml / g) obtained by the BET method. The porosity (%) = [pore volume (ml / g g) / total particle volume (ml / g)] × 100.

  The average pore diameter of the porous body by the Dollimore-Heal method (DH method) is preferably 0.1 to 100 nm, more preferably 0.1 to 50 nm, and still more preferably 1 to 10 nm. Here, the DH method is an analysis method for obtaining the volume frequency distribution of the pore diameter from the increment of the relative pressure of the adsorbed gas and the amount of adsorption assuming that the pore is cylindrical. If the average pore diameter is too small, the effect of reducing the linear expansion coefficient tends to be small. On the other hand, if the average pore diameter is too large, the pores are filled with resin or the like, and the effect of reducing the relative dielectric constant tends to be small.

The pore volume is preferably 0.1 to 5 ml / g, more preferably 0.3 to 3 ml / g, and particularly preferably 0.5 to 2 ml / g.
If the pore volume is too small, the effect of reducing the dielectric constant tends to be small. If it is too large, it becomes difficult to produce a porous body.
BET specific surface area of the porous body is preferably 1~3,000m 2 / g, more preferably 100~1,000m 2 / g.

  The porous body may be dispersed as an aggregate of the porous body in the polymerizable composition, but it is preferable that the porous body is dispersed as primary particles.

Examples of the porous body include an inorganic porous body and an organic porous body.
As an inorganic porous body, what consists of a conventionally well-known material can be used as an inorganic filler. Examples thereof include oxides, nitrides, borides, hydroxides, and hydrates thereof. Among these, oxides, nitrides, and borides are preferable, and the production of a porous body is easy, and since the linear expansion coefficient is small, oxides are more preferable.
The constituent elements of the inorganic hollow particles are at least selected from the group consisting of Si, Al, B, Zr, Ti, Fe, Ca, Sn, Ce, P, Mo, Zn, W, Ni, Cu, Nb and Mg. One element is mentioned.

Specifically, silica (SiO 2 ), alumina (Al 2 O 3 ), zirconium oxide (ZrO 2 ), zeolite, titanium oxide (TiO 2 ), aluminum nitride (AlN), silicon carbide (SiC), silicon nitride ( Si 3 N 4 ), barium titanate (BaTiO 3 ), shirasu, strontium titanate (SrTiO 3 ), calcium titanate (CaTiO 3 ), shirasu, aluminum borate, boronite, calcium carbonate, lead oxide, tin oxide, oxide Examples thereof include porous materials such as cerium, calcium oxide, trimanganese tetroxide, magnesium oxide, cerium zirconate, calcium silicate, zirconium silicate, ITO, and titanium silicate.
Furthermore, the porous body which sintered inorganic material powder, such as a silicon oxide and aluminum oxide, can be mentioned.
These can be used alone or in combination of two or more. Among these, those containing Si are preferable, those containing SiO 2 , SiC, Si 3 N 4 , shirasu, and glass as main components are more preferable, and SiO 2 , shirasu, and glass are particularly preferable.

  Further, as the inorganic porous body, an aggregate composed of inorganic fine particles having a number average particle diameter of 100 nm or less determined by observation with a scanning electron microscope can be used. The median diameter as an aggregate of inorganic fine particles is usually 50 μm or less, more preferably 0.01 to 50 μm. Further, particles synthesized by a sol-gel method using a micelle of a surfactant as a template can also be used.

It does not specifically limit as an organic porous body, What consists of an elastomer, a thermoplastic resin, a thermosetting resin etc. can be used. Specifically, polyethylene, polypropylene, polystyrene, polydivinylbenzene, polycycloolefin, polyphenylene oxide, polyphenylene sulfide, polysulfone, acrylic resin, silicone, polyamide, polyamideimide, polyarylate, thermoplastic polyimide, polyetheretherketone, poly Fluorine resin such as ether nitrile, polyethylene oxide, polyethylene terephthalate, Teflon (registered trademark), epoxy resin, polyimide resin, aramid resin, triazine resin, phenol resin, melamine resin, polybenzoxazole, polybenzimidazole, polybenzocyclobutene, The porous body which consists of polyepoxy acrylate etc. is mentioned. Among these, those made of an organic material having a crosslinked structure are preferable in terms of heat resistance.
These may be used alone or in combination of two or more.
The molecular weight of these organic materials is not particularly specified. As the organic material, a resin having few polar groups is preferable. In particular, those that do not completely dissolve in the cycloolefin monomer are preferred. A resin having a low dielectric constant is preferable. Furthermore, a thermosetting resin is preferable because the linear expansion coefficient decreases.

  The manufacturing method of these organic porous bodies is not particularly limited. For example, it may be produced by a known method such as emulsion polymerization or suspension polymerization.

  The amount of water adsorbed on the surface of the porous body is measured as a loss on heating by drying in a hot air dryer at 150 ° C. for 1 hour. The content of surface adsorbed water is usually 5% by mass or less, preferably 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably 0.05% by mass or less. If the amount is too large, the production efficiency is lowered, for example, a drying step is required, and problems such as insufficient polymerization of the cycloolefin monomer tend to occur.

  The porous body may be surface-treated with a reactive compound such as a silane coupling agent, an aluminate coupling agent, a titanate coupling agent, silazanes, or an organosiloxane, or a resin. By using a porous body that has been subjected to such a surface treatment, the interfacial adhesion between the porous body and a resin obtained by polymerizing a cycloolefin monomer can be controlled, thereby improving the mechanical strength. Can be expected.

  A well-known thing can be used as a coupling agent. Specifically, allyltrimethoxysilane, 3-butenyltrimethoxysilane, styryltrimethoxysilane, N-β- (N- (vinylbenzyl) aminoethyl) -γ-aminopropyltrimethoxysilane and salts thereof, allyltri Chlorosilane, allylmethyldichlorosilane, styryltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltrichlorosilane, β-methacryloxyethyltrimethoxysilane, β- Methacryloxyethyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, δ-methacryloxybutyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxy Examples include silane, γ-mercaptopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane. .

  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.

Examples of silazanes include hexamethyldisilazane, divinyltetramethyldisilazane, dibutyltetramethyldisilazane, and diphenyltetramethyldisilazane.
Among these, a silane coupling agent having a reactive group such as a double bond or silazane is preferable in terms of adhesion.

When surface coating is performed with a resin, the coating method and the like may be performed by a known method. Specifically, the porous body is added to the resin solution and dispersed, and then the solvent is removed, or the porous body is added to the solution containing the monomer and polymerized in a dispersed state to form a coating. Examples thereof include a method for forming a resin to be used.
The solvent used in these methods is not particularly limited.

The content of the porous material in the polymerizable composition is usually 0.1 to 80% by volume, preferably 0.5 to 60% by volume, more preferably 1 to 50% by volume, and particularly preferably 5 to 40% by volume. %.
Moreover, it is 0.01-95 mass% normally, Preferably it is 0.1-75 mass%, More preferably, it is 1-60 mass%, Especially preferably, it is 5-50 mass%, Most preferably, it is 5-40 mass%.

(5) Crosslinking agent The polymerizable composition preferably 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.
The organic peroxide is not particularly limited. For example, hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide; dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis (T-butylperoxy-m-isopropyl) benzene, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2,5 Dialkyl peroxides such as di (t-butylperoxy) hexane; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; 2,2-di (t-butylperoxy) butane and 1,1-di (t-hexylperoxy) ) Cyclohexane, 1,1-di (t-butylperoxy) Peroxyketals such as 2-methylcyclohexane and 1,1-di (t-butylperoxy) cyclohexane; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; t-butylperoxyisopropylcarbonate, di And peroxycarbonates such as (isopropylperoxy) dicarbonate and alkylsilylperoxasides and peroxyketals such as t-butyltrimethylsilyl peroxide. 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.

  Examples of the nonpolar radical generator used in the present invention include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diphenylbutane, 1,4-diphenylbutane, and 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 1,1,2-triphenylethane, triphenylmethane, 1,1,1-triphenylethane, 1,1,1-triphenylpropane, 1,1,1-triphenylbutane, 1,1,1-triphenyl Examples include phenylpentane, 1,1,1-triphenyl-2-propene, 1,1,1-triphenyl-4-pentene, 1,1,1-triphenyl-2-phenylethane, and the like.

  These crosslinking agents can be used alone or in combination of two or more. By using two or more kinds of crosslinking agents in combination and changing the blend ratio, 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 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.

  In the present invention, 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 cycloolefin monomers, Preferably it is 0-50 mass parts.

(6) Other additives The polymerizable composition includes various additives such as polymerization reaction retarders, radical crosslinking retarders, reinforcing materials, modifiers, antioxidants, flame retardants, colorants, and light. Stabilizers and the like can be included. Moreover, you may add fillers other than the said porous body. The shape is not particularly limited, and examples thereof include a spherical shape, an indeterminate shape, a rod shape, a plate shape, and a hollow shape. The material of the filler is not particularly limited, and the same material as the porous body can be used. These can be used by dissolving or dispersing in advance in a monomer solution or a catalyst solution described later.

Examples of the polymerization reaction retarder include phosphines such as triphenylphosphine, tributylphosphine, trimethylphosphine, and triethylphosphine; Lewis bases such as aniline and pyridine. Among these, phosphines are preferred because the pot life of the polymerizable composition of the present invention can be controlled efficiently and the inhibition of the polymerization reaction is small.
Of the cyclic olefin monomers copolymerizable with the norbornene monomer, the cyclic olefin having a 1,5-diene structure or a 1,3,5-triene structure in the molecule also functions as a polymerization reaction retarder. Examples of such a compound include 1,5-cyclooctadiene and 5-vinyl-2-norbornene.

  Examples of the radical crosslinking retarder include alkoxyphenols, catechols, and benzoquinones, and alkoxyphenols such as 3,5-di-t-butyl-4-hydroxyanisole are preferable.

  Examples of the reinforcing material include inorganic reinforcing materials such as glass fibers, and organic reinforcing materials such as paper base materials and aramid fibers.

  As the modifier, natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), ethylene -Elastomers such as propylene-diene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA) and 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 flame retardant include phosphorus flame retardants, nitrogen flame retardants, halogen flame retardants, metal hydroxide flame retardants such as aluminum hydroxide, and antimony compounds such as antimony trioxide. Although the flame retardant may be used alone, it is preferable to use a combination of two or more.

  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 is dissolved or dispersed in an appropriate solvent (hereinafter, also referred to as “catalyst liquid”), and separately preparing a porous body and a flame retardant with a cycloolefin monomer. Can be prepared by preparing a liquid (hereinafter sometimes referred to as “monomer liquid”) in which additives such as these are blended as necessary, adding the catalyst liquid to the monomer liquid, and stirring. The addition of the catalyst solution is preferably performed immediately before the bulk polymerization described below. Further, a chain transfer agent, a crosslinking agent, a radical crosslinking retarder, etc. may be added to the monomer liquid and / or the catalyst liquid before mixing the monomer liquid and the catalyst liquid, or the monomer liquid and the catalyst liquid are mixed. It may be added later.

  When the porous body is used by being dispersed in the monomer liquid, it is preferable that the particle diameter of d90 is a fine particle having a particle diameter of 100 μm or less in the number-based particle size distribution of the porous body in the monomer liquid. Note that d90 is a particle diameter that includes 90% of the particles accumulated from the smallest in the number-based particle size distribution. d50 is the median diameter.

A well-known thing can be used for the dispersing apparatus for disperse | distributing a porous body to a monomer liquid. Specifically, a kneader, a bead mill, a ball mill, a triple roll, a homomixer, an ultrasonic disperser, a nanomizer, an optimizer, a film mix shear type wet jet mill, a collision type wet jet mill, a high speed shear stirrer, etc. can be used as appropriate. .
These may be used alone or in combination of two or more.
Further, it is more preferable to carry out a dispersion treatment in multiple stages in order to atomize the porous body in the monomer liquid. For example, it is preferable that the d90 particle size is lowered to 100 μm or less by the first stage dispersion treatment, and then further dispersion treatment is performed by another dispersion device.
Equipment that is preferably used for the dispersion treatment after the second stage is equipment that imparts high energy to the monomer liquid, such as a homomixer, a bead mill, an ultrasonic dispersion machine, a shear type wet jet mill such as a nanomizer, and a collision type such as an optimizer. High-speed shearing stirrers such as wet jet mills and fill mixes are preferred.

[Crosslinkable resin and crosslinkable resin composite]
The crosslinkable resin of the present invention can be obtained by bulk polymerization of the polymerizable composition.
As a method of 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 in which a polymerizable composition is impregnated into a support and bulk polymerization is performed. 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. The surface of these supports is preferably subjected to a surface treatment such as an oxidation treatment using plasma or the like; a chemical treatment such as a blackening treatment; a coupling agent treatment using a silane coupling agent or the like.

  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 body 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. As a result, 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, for example, glass fiber, carbon fiber, aramid fiber, polyethylene terephthalate fiber, vinylon fiber, polyester fiber, amide fiber, metal fiber, ceramic fiber, poly Well-known things, such as an arylate fiber and a fluororesin fiber, are 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 subjected to a surface treatment such as an oxidation treatment using plasma or the like; a chemical treatment such as a blackening treatment; a coupling agent treatment using 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 heating method of the impregnated product is not particularly limited, and the same method as the method (a) can be adopted, and the impregnated product may be placed on the substrate and heated. Alternatively, the polymerizable composition may be poured into a mold provided with a fiber material and impregnated with the polymerizable composition, and then bulk polymerization may be performed according to the method (b).

Since the polymerizable composition 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 more than the 1 minute half-life temperature of the peroxide, preferably not more than 230 ° C., more preferably Is preferably controlled below 200 ° C.

The crosslinkable resin of the present invention is a crosslinkable resin. Here, “crosslinkable” 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. Also, when a peroxide having a high decomposition temperature is used as the peroxide, the crosslinkable resin will flow appropriately during crosslinking, and the adhesion to a support such as a metal foil and embedding in a wiring board will be good. Become. In addition, the crosslinked product obtained from the above peroxide has a remarkably small dielectric loss (tan δ) and is excellent in electrical characteristics.

  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.

  The molded product of the crosslinkable resin 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 of the present invention as a molded article 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 peroxide having a structure represented by the formula (A), but does not cause problems such as change in surface hardness unless heated to a temperature at which a crosslinking reaction is caused. Excellent 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. Further, those subjected to chemical treatment such as blackening treatment are also preferable.

  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 is used as a support, the peel strength measured based on JIS C6481 is preferably 0.4 kN / m or more, more preferably 0. .6 kN / m or more.

  The crosslinked body and composite of the present invention are excellent in electrical insulation, mechanical strength, heat resistance, dielectric properties and the like. Further, the composite has good adhesion to the support and is suitable as an electric 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) Mixability After 30 seconds after impregnating the polymerizable composition with a glass cloth, it is determined whether or not the filler (porous body) in the polymerizable composition is lifted and separated on the surface of the polymerizable composition. Visual observation was performed.
No separation: ○
With separation: ×

(2) Relative permittivity The relative permittivity (ε) at a frequency of 1 GHz was measured by a capacitance method using an impedance analyzer (manufactured by Agilent Technologies, model number E4991A).
It was determined that ε was less than 3.5 as A, 3.5 or more and less than 3.6 as B, and 3.6 or more as C. It represents that it is excellent in an electrical property, so that (epsilon) is small.

(3) Solder heat resistance The laminate was floated in a 260 ° C. solder bath for 20 seconds, and the presence or absence of swelling and distortion of the laminate was observed.
Balloon, distortion; 0 to 1: A
Balloon, distortion; 2-3 pieces: B
Bulge, distortion; 4 or more: C

(4) Fluidity The laminate was etched, and the number of whitened portions (scratch due to poor fluidity) was counted by visual observation.
A: Zero, B: 1-3, C: 4 or more

(5) Linear expansion coefficient It measured using the thermal analyzer TMASS6100 by Seiko Instruments Inc. Using a laminate (thickness 1 mm) from which the copper foil was removed by etching, the linear expansion coefficient from 50 ° C to 100 ° C was measured. If the linear expansion coefficient was less than 70 ppm, it was A, 70 if it was less than 80 ppm, and C if it was 80 ppm or more.

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.
In a polyethylene bottle, 40 parts of 2-norbornene (NB) as a cycloolefin monomer and tetracyclo [6.2.1.1 3,6 . 0 2,7 ] 60 parts dodec-4-ene (TCD), 0.74 parts allyl methacrylate as chain transfer agent, di-t-butyl peroxide as cross-linking agent (1 minute half-life temperature 186 ° C.) 1 .2 parts, 1 part of tristearyl isopropoxy titanate (Plenact TTS, manufactured by Ajinomoto Fine Techno Co.) as a dispersant, and porous silica (E-6C, manufactured by Suzuki Yushi Co., Ltd., median diameter 2 μm, pore volume 1.3 ml / g, porosity 52 volume%, average pore diameter 1.06 nm) 27.7 parts were added and mixed. Next, the above catalyst solution was added at a rate of 0.12 ml per 100 g of cycloolefin monomer and stirred 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 Ltd.), and a glass cloth (product number 2112, thickness 69 μm) was laid on the polyethylene composition. On top of this, 80 parts of the polymerizable composition was cast. Further, a polyethylene naphthalate film was covered thereon, and the polymerizable composition was immersed in the entire glass cloth using a roller. Next, this was left in a heating furnace heated to 150 ° C. for 1 minute to bulk polymerize the polymerizable composition to obtain a prepreg having a thickness of 0.13 mm.

  This prepreg was cut to a size of 100 mm square, and the polyethylene naphthalate film was peeled off. Six of them 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 evaluation of this laminate.

Example 2
Instead of porous silica E-6C, porous silica (D-25C, manufactured by Suzuki Yushi Co., Ltd., median diameter 10 μm, pore volume 0.5 ml / g, porosity 30 volume%, average pore diameter 1.06 nm) 19 A polymerizable composition, a prepreg and a laminate were obtained in the same manner as in Example 1 except that 1 part was used. The results of evaluating each characteristic are shown in Table 1.

Example 3
In place of 40 parts of NB and 60 parts of TCD, 100 parts of dicyclopentadiene (DCP) (including about 10% cyclopentadiene trimer) was used in the same manner as in Example 2 to obtain a polymerizable composition, prepreg and A laminate was obtained. The results of evaluating each characteristic are shown in Table 1.

Comparative Example 1
The polymerizable composition was the same as in Example 1 except that 100 parts of spherical silica (FB-105, manufactured by Denki Kagaku Kogyo Co., Ltd., median diameter 12 μm, porosity 0%) was used instead of porous silica E-6C. Articles, prepregs and laminates were obtained. The results of evaluating each characteristic are shown in Table 1.

Comparative Example 2
A polymerizable composition, a prepreg, and a laminate were obtained in the same manner as in Comparative Example 1 except that the amount of spherical silica FB-105 used was 50 parts. The results of evaluating each characteristic are shown in Table 1.

Comparative Example 3
Example 1 except that 100 parts of dicyclopentadiene (DCP) (including about 10% cyclopentadiene trimer) was used instead of 40 parts of NB and 60 parts of TCD, and no chain transfer agent and crosslinking agent were used. In the same manner as in Example 1, a polymerizable composition, a prepreg and a laminate were obtained. The results of evaluating each characteristic are shown in Table 1.

As shown in Table 1, in the examples of the present invention, the filler does not protrude from the polymerizable composition, the solder heat resistance is high, and the linear expansion coefficient is low. In particular, tetracyclo [6.2.1.1 3,6 . [0 2,7 ] Examples 1 and 2 using a cycloolefin monomer not containing a polar group such as dodec-4-ene, that is, a norbornene-based monomer composed only of carbon atoms and hydrogen atoms, has excellent fluidity, Good balance of characteristics.
On the other hand, Comparative Example 1 and Comparative Example 2 using a non-porous body are difficult to achieve a balance of characteristics such as relative dielectric constant and linear expansion coefficient, and when attempting to lower the relative dielectric constant, the linear expansion coefficient is high. Therefore, if the coefficient of linear expansion is to be lowered, the relative dielectric constant is increased.

Claims (13)

  1.   A polymerizable composition comprising a cycloolefin monomer, a metathesis polymerization catalyst, a chain transfer agent, and a porous material.
  2.   The polymerizable composition according to claim 1, wherein the median diameter of the primary particles of the porous body is 50 μm or less.
  3.   The polymerizable composition according to claim 1 or 2, wherein the porous body has an average pore diameter of 0.1 to 100 nm.
  4.   The polymerizable composition according to claim 1, wherein the porosity of the porous body is 10% by volume or more.
  5.   The polymerizable composition according to claim 1, wherein the metathesis polymerization catalyst is a ruthenium carbene complex.
  6.   Furthermore, the polymeric composition in any one of Claims 1-5 containing a crosslinking agent.
  7.   A crosslinkable resin obtained by bulk polymerization of the polymerizable composition according to claim 6.
  8.   The manufacturing method of crosslinkable resin including the process of carrying out bulk polymerization of the polymeric composition of Claim 6.
  9.   The manufacturing method of a crosslinkable resin composite including the process of apply | coating or impregnating the polymeric composition of Claim 6 to a support body, and carrying out block polymerization.
  10.   The manufacturing method of a crosslinked body including the process of bridge | crosslinking the crosslinkable resin of Claim 7.
  11.   The manufacturing method of a crosslinked resin composite including the process of bridge | crosslinking the molded object of the crosslinkable resin of Claim 7 on a support body.
  12.   The manufacturing method of a crosslinked resin composite including the process of bridge | crosslinking the crosslinkable resin composite obtained by the manufacturing method of the crosslinkable resin composite of Claim 9.
  13.   The method for producing a crosslinked resin composite according to claim 12, wherein the crosslinking is performed on another support.
JP2006355921A 2006-12-28 2006-12-28 Polymerizable composition, crosslinkable resin, and method for producing the same Pending JP2008163249A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009235401A (en) * 2008-03-04 2009-10-15 Hitachi Chem Co Ltd Resin composition for prepreg, prepreg, laminate, and printed-wiring board
JP2012523323A (en) * 2009-04-09 2012-10-04 インダストリー−ユニバーシティ コオペレーション ファウンデーション ソギャン ユニバーシティIndustry−University Cooperation Foundation Sogang University Method for producing printed matter on which aligned fine particles are printed
US8956691B2 (en) 2010-01-21 2015-02-17 Canon Kabushiki Kaisha Methods for manufacturing organic-inorganic composite particles, optical material, optical element and lens, and organic-inorganic composite particles
JPWO2014050890A1 (en) * 2012-09-26 2016-08-22 Rimtec株式会社 Polymerizable composition and method for producing resin molded body

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009235401A (en) * 2008-03-04 2009-10-15 Hitachi Chem Co Ltd Resin composition for prepreg, prepreg, laminate, and printed-wiring board
JP2012523323A (en) * 2009-04-09 2012-10-04 インダストリー−ユニバーシティ コオペレーション ファウンデーション ソギャン ユニバーシティIndustry−University Cooperation Foundation Sogang University Method for producing printed matter on which aligned fine particles are printed
US8956691B2 (en) 2010-01-21 2015-02-17 Canon Kabushiki Kaisha Methods for manufacturing organic-inorganic composite particles, optical material, optical element and lens, and organic-inorganic composite particles
JPWO2014050890A1 (en) * 2012-09-26 2016-08-22 Rimtec株式会社 Polymerizable composition and method for producing resin molded body

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