JP2013129717A - Polymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable composition that can obtain a crosslinking resin, a crosslinking resin composite or a crosslinking resin laminate that is suitable for an electric circuit board or the like, in which a dielectric loss tangent in a high-frequency region is small, and that are excellent in the characteristics of insulation, adhesion, mechanical strength, heat resistance, a wiring embedding property, a dielectric property or the like.SOLUTION: The polymerizable composition includes: a cycloolefin-based monomer (A); a metathesis polymerization catalyst (B); and a compound (C) that has a carbon-carbon double bond in the terminal and has a benzocyclobutene structure in the molecular, and optionally includes a crosslinking agent. A crosslinkable resin, a crosslinkable resin composite or a crosslinkable resin laminate is obtained by massiveness polymerizing the polymerizable composition. The crosslinking resin, the crosslinking resin composite or the crosslinking laminate is obtained by crosslinking the crosslinkable resin, the crosslinkable resin composite or the crosslinkable resin laminate.

Description

  The present invention relates to a polymerizable composition. More specifically, the present invention is suitable for electric circuit boards and the like, has a small dielectric loss tangent in a high frequency region, and is excellent in characteristics such as electric insulation, adhesion, mechanical strength, heat resistance, wiring embedding, and dielectric characteristics. The present invention relates to a polymerizable composition capable of obtaining a crosslinked resin, a crosslinked resin composite, or a crosslinked resin laminate.

  A molded article of a crosslinked resin is obtained by crosslinking a thermoplastic norbornene resin obtained by ring-opening metathesis polymerization of a norbornene monomer with a crosslinking agent such as an organic peroxide. For example, in Patent Document 1, an organic peroxide and a crosslinking aid are added to a thermoplastic hydrogenated ring-opening norbornene-based resin and uniformly dispersed to obtain a norbornene-based resin composition. It is described that it was molded into a prepreg, laminated with a substrate, and then subjected to heat and pressure molding, followed by crosslinking and heat fusion to obtain a crosslinked resin molded product. Patent Document 1 describes that the crosslinked resin molded body is useful as an interlayer insulating film, a moisture-proof layer forming film, and the like.

  Patent Document 2 discloses a method in which a norbornene monomer is subjected to metathesis polymerization in the presence of a ruthenium carbene complex as a metathesis polymerization catalyst and a crosslinking agent, and then post-cured (post-crosslinked). The method of Patent Document 2 teaches that a polymer crosslinked at high density can be obtained.

  In Patent Document 3, a polymerizable composition containing a norbornene-based monomer, a metathesis polymerization catalyst, a chain transfer agent and a crosslinking agent is bulk-polymerized to obtain a crosslinkable thermoplastic resin, and this crosslinkable thermoplastic resin is used as a substrate or the like. It is disclosed that it was laminated and cross-linked to obtain a composite material.

  In Patent Document 4, a macrothesis polymerizable monomer, a metathesis polymerization catalyst, and an allyl compound such as allyl alcohol, allyl isocyanate, allyl isothiocyanate, allylamine, allyl acrylate, etc. are used when performing ring-opening metathesis polymerization. Monomer production methods are disclosed.

In Patent Document 5, in a polymerizable composition containing a norbornene-based monomer, a metathesis polymerization catalyst, a chain transfer agent, and a crosslinking agent, the chain transfer agent is represented by the formula (A): CH ₂ ═CH—Y—OCO—CR ¹ ═CH. _{By using the} compound represented by ₂ (in formula (A), Y represents a divalent hydrocarbon group having 3 to 20 carbon atoms, and R ¹ represents a hydrogen atom or a methyl group), It is disclosed that a crosslinked body or composite having excellent adhesion, mechanical strength, heat resistance and the like was obtained.

JP-A-6-248164 WO97 / 003096 WO2004 / 003052 JP 2001-226466 A WO2008 / 047895

  However, due to the rapid progress of technological development in recent years, even in a composite obtained by laminating a crosslinked body and a substrate, obtained by the method disclosed in Patent Document 5, the adhesion between the substrate and the crosslinked body. There is a need for further improvement of the above, further reduction of dielectric loss tangent in the high frequency region, and further improvement of heat resistance and wiring embedding.

  The object of the present invention is a bridge having a small dielectric loss tangent in a high frequency region suitable for an electric circuit board and the like, and having excellent characteristics such as electrical insulation, adhesion, mechanical strength, heat resistance, wiring embedding, and dielectric properties. The object is to provide a polymerizable composition capable of obtaining a resin, a crosslinked resin composite or a crosslinked resin laminate.

  The inventor has intensively studied to achieve the above object. As a result, in the polymerizable composition containing a cycloolefin monomer, a metathesis polymerization catalyst and a chain transfer agent, the chain transfer agent has a carbon-carbon double bond at the terminal and a benzocyclobutene structure in the molecule. It has been found that by using a compound, a cross-linked resin having a small dielectric loss tangent in a high frequency region and excellent properties such as electrical insulation, adhesion, mechanical strength, heat resistance, wiring embedding property, and dielectric properties 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), a metathesis polymerization catalyst (B), and a compound (C) having a carbon-carbon double bond at a terminal and a benzocyclobutene structure in the molecule object.
[2] The polymerizable composition according to [1], wherein the cycloolefin monomer (A) is a norbornene monomer.
[3] The benzocyclobutene structure is bicyclo [4.2.0] octa-1 (6), 2,4-trien-3-yl, or bicyclo [4.2.0] octa-1 (6), The polymerizable composition according to [1] or [2], which is 2,4-trien-2-yl.
[4] The polymerizable composition according to any one of [1] to [3], further including a crosslinking agent (D).
[5] A crosslinkable resin obtained by bulk polymerization of the polymerizable composition according to any one of [1] to [4].
[6] The crosslinkable resin according to [5], wherein the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 3 or less.

[7] A crosslinkable resin composite comprising a support and the crosslinkable resin according to [5] impregnated or coated on the support.
[8] A crosslinkable resin laminate comprising a substrate and the crosslinkable resin according to [5] or the crosslinkable resin composite according to [7] laminated on the substrate.
[9] A crosslinked resin obtained by crosslinking the crosslinkable resin according to [5].
[10] A crosslinked resin composite comprising a support and the crosslinked resin according to [9] impregnated or coated on the support.
[11] A crosslinked resin laminate comprising a substrate and the crosslinked resin according to [9] or the crosslinked resin composite according to [10] laminated on the substrate.
[12] A method for producing a crosslinkable resin, comprising a step of bulk polymerization of the polymerizable composition according to [4].
[13] A method for producing a crosslinkable resin composite, comprising the steps of impregnating or coating the polymerizable composition according to [4] on a support and then performing bulk polymerization.
[14] A method for producing a crosslinked resin, comprising a step of crosslinking the crosslinkable resin according to [5].
[15] A method for producing a crosslinked resin laminate, comprising a step of laminating the crosslinkable resin according to [5] or the crosslinkable resin composite according to [8] on a substrate and then crosslinking.
[16] A method for producing a crosslinked resin composite, comprising a step of crosslinking the crosslinkable resin composite according to [7].

The polymerizable composition of the present invention can provide a resin or a crosslinkable resin having excellent insulating properties by bulk polymerization. By crosslinking a crosslinkable resin obtained from the polymerizable composition of the present invention, a crosslinkable resin suitable as an electric material used for an electric circuit board can be obtained.
Since the polymerizable composition of the present invention is suitable for coating and impregnation, the support can be easily impregnated or coated. A crosslinkable resin composite can be easily obtained by bulk polymerization of a polymerizable composition impregnated or coated on a support, and a crosslinkable resin laminate by laminating a crosslinkable resin composite on a substrate. Can be obtained. By crosslinking the crosslinkable resin composite or the crosslinkable resin laminate, a crosslinkable resin composite or a crosslinkable resin laminate can be obtained. These cross-linked resins, cross-linked resin composites and cross-linked resin laminates have low dielectric loss tangents in the high frequency region, electrical insulation, adhesion, mechanical strength, heat resistance, adhesion to the support, wiring embedding, dielectric Excellent characteristics such as characteristics.

[Polymerizable composition]
The polymerizable composition of the present invention comprises a cycloolefin monomer (A), a metathesis polymerization catalyst (B), and a compound (C) having a carbon-carbon double bond at the terminal and a benzocyclobutene structure in the molecule. Is included. Moreover, the crosslinking composition (D) may further be contained in the polymerizable composition, and other additives (E) may further be contained.
Hereinafter, the substances (A) to (E) used in the polymerizable composition of the present invention will be described.

(A) Cycloolefin monomer The cycloolefin monomer (A) constituting the polymerizable composition of the present invention has an alicyclic structure formed of carbon atoms in the molecule, and a carbon-carbon in the ring. It is a compound having a double bond. A cycloolefin polymer is obtained by polymerizing a cycloolefin monomer.

  Examples of the alicyclic structure constituting the cycloolefin monomer (A) include monocyclic, polycyclic, condensed polycyclic, bridged ring, and combination polycyclic thereof. Although there is no special restriction | limiting in carbon number which comprises an alicyclic structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces.

  In the present invention, a norbornene monomer is preferably used as the cycloolefin monomer (A). The norbornene monomer is a cycloolefin monomer having a norbornene ring structure in the molecule. Specific examples include norbornenes, dicyclopentadiene, and tetracyclododecenes. These may have 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 double bond in the norbornene ring, it may further have a double bond. Examples of the norbornene-based monomer include the following.

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.

  Among these norbornene-based monomers, a norbornene-based monomer that does not contain a polar group, that is, only composed of carbon atoms and hydrogen atoms, can obtain a crosslinked resin, crosslinked resin composite, or crosslinked resin laminate having a small dielectric loss tangent. It is preferable because it is possible.

  These norbornene monomers can be used alone or in combination of two or more. It is possible to control the glass transition temperature and melting temperature of the resulting crosslinkable resin by using two or more monomers in combination and changing the amount ratio.

  Examples of other cycloolefin monomers (A) include monocyclic cycloolefin monomers. Examples of the monocyclic cycloolefin monomer include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, and the like. Of these monocyclic cycloolefin monomers, monocyclic cycloolefin monomers having no polar group are preferred.

  In the present invention, a norbornene monomer and another cycloolefin monomer may be copolymerized. The amount of the other cycloolefin monomer is preferably 40 parts by mass or less, more preferably 20 parts by mass or less with respect to 100 parts by mass of the norbornene monomer to be used. When the amount of the other cycloolefin monomer exceeds 40 parts by mass, the heat resistance of the polymer obtained by bulk polymerization may be insufficient.

(B) Metathesis polymerization catalyst The metathesis polymerization catalyst (B) constituting the polymerizable composition of the present invention is not particularly limited as long as it causes a metathesis ring-opening polymerization of a cycloolefin monomer.
A transition metal complex is mentioned as a metathesis polymerization catalyst (B). The complex is formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds to transition metal atoms. The transition metal atom used in the metathesis polymerization catalyst is not particularly limited, but atoms belonging to Groups 5, 6, and 8 in the long-period periodic table are preferred. Preferable atoms belonging to Group 5 include tantalum. Preferable atoms belonging to Group 6 include molybdenum and tungsten, and preferable atoms belonging to Group 8 include ruthenium and osmium.

  Among these, as the metathesis polymerization catalyst (B), a complex containing ruthenium or osmium is preferable, and a ruthenium carbene complex is particularly preferable. A complex containing ruthenium or osmium is hardly deactivated by oxygen or moisture in the air and is relatively stable, so that a crosslinkable resin can be produced even in the air. In addition to the above features, the ruthenium carbene complex is excellent in polymerization activity and can reduce the amount of residual unreacted monomer, so that a crosslinkable resin with less odor can be obtained.

  As a ruthenium carbene complex, the complex compound represented by Formula (1) or Formula (2) is mentioned, for example.

R ² and R ^{3 in} formulas (1) and (2) may each independently contain a hydrogen atom, a halogen atom, or a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom or silicon atom. A hydrocarbon group having 1 to 20 carbon atoms is represented. R ² and R ³ may be bonded to each other to form a ring.

In the formulas (1) and (2), X ¹ and X ² each independently represent an arbitrary anionic ligand. An anionic (anionic) ligand is a ligand that has a negative charge when pulled away from a central metal atom. Examples thereof 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.

In formulas (1) and (2), L ¹ and L ² each independently represents a heteroatom-containing carbene compound or a neutral electron donating compound. R ² , R ³ , X ¹ , X ² , L ¹ and L ² may be bonded together in any combination to form a chelated multidentate ligand.

  Here, the hetero atom means an atom belonging to Group 15 and Group 16 in the periodic table, and specifically includes N, O, P, S, As, Se, and the like. Among these, N, O, P, and S are preferable from the viewpoint of obtaining a stable carbene compound, and N (nitrogen atom) is particularly preferable.

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

  Examples of the heteroatom-containing carbene compound include 1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5-ylidene, 1,3-dicyclohexylhexahydropyrimidine- 2-ylidene, N, N, N ′, N′-tetraisopropylformamidinylidene, 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole-5-ylidene, 3- (2,6-diisopropylphenyl) -2,3-dihydrothiazol-2-ylidene, or a compound represented by formula (3) or formula (4) may be mentioned.

In formulas (3) and (4), R ^{4 to} R ⁷ 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. This represents a hydrocarbon group having a number of 1 to 20. R ^{4 to} R ⁷ 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-mesitylimidazolidine-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.

  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 carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, thiocyanates, and the like. Among these, phosphines, ethers and pyridines are preferable, and trialkylphosphines are 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-octahydrobenz Imidazole-2-ylide ) (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-dimesity Imidazolidine-2-ylidene) pyridine ruthenium dichloride, (1,3-dimesitylmimidazolidine-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] (tricyclohexylphosphine ) ^One of L ¹ and L ² such as ruthenium dichloride, (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) (2-pyrrolidone-1-ylmethylene) (tricyclohexylphosphine) ruthenium dichloride But A hetero atom-containing carbene compounds, ruthenium complex compounds other is an electron-donating compound neutral;

Ruthenium in which 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 Complex compounds;

Both L ¹ and L ² such as benzylidenebis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride, benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride contain heteroatoms And ruthenium complex compounds which are carbene compounds.

Further, in the formula (1), as a complex compound to which R ² and L ¹ is attached, the compound of formula (5) to (7) below. Mes is a group represented by the formula (8).

（式（８）中の＊は、式（５）〜（７）中のＮ原子に結合する部分を示す。）

(* In the formula (8) represents a moiety bonded to the N atom in the formulas (5) to (7).)

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

  These metathesis polymerization catalysts (B) can be produced by the method described in Org. Lett., 1999, Vol. 1, page 953, Tetrahedron. Lett., 1999, Vol. 40, page 2247, etc. it can.

  The use amount of the metathesis polymerization catalyst (B) is usually 1: 2,000 to 1: 2,000,000, preferably 1: 5,000, in a molar ratio of (metal atom in catalyst: cycloolefin monomer). ˜1: 1,000,000, more preferably in the range of 1: 10,000 to 1: 500,000.

  The metathesis polymerization catalyst (B) can be used as dissolved or suspended in a small amount of an inert solvent, if necessary. 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; and aromatic rings such as indene, indane and tetrahydronaphthalene Hydrocarbons having a condensed ring with an alicyclic ring; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, and acetonitrile; oxygen-containing hydrocarbons such as diethyl ether and tetrahydrofuran;Among these, it is preferable to use industrially general-purpose 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 (B) can be used in combination with an activator (cocatalyst) for the purpose of controlling the polymerization activity and improving the polymerization reaction rate. Activators may include aluminum, scandium or tin alkylates, halides, alkoxylates or aryloxygenates. 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 1 in terms of a molar ratio of (metal atom in the catalyst: activator). : It is the range of 0.5-1: 10.

  Further, when a transition metal atom complex belonging to Groups 5 and 6 is used as the metathesis polymerization catalyst (B), it is preferable to use both the metathesis polymerization catalyst (B) and the activator dissolved in a monomer. However, it can be used by suspending or dissolving in a small amount of solvent as long as the properties of the product are not essentially impaired.

(C) Compound having a carbon-carbon double bond at the terminal and having a benzocyclobutene structure in the molecule. A compound having a carbon-carbon double bond at the terminal constituting the polymerizable composition and having a benzocyclobutene in the molecule. The compound (C) having a structure (hereinafter sometimes referred to as “compound (C)”) is used as a chain transfer agent. The carbon-carbon double bond of compound (C) may be further present at a position other than the terminal as long as at least one carbon-carbon double bond exists at the terminal. It is sufficient that at least one benzocyclobutene structure exists in the molecule of the compound (C). Of these, the compound represented by the formula (9) is particularly preferable.

R ⁸ in the formula (9) is a hydrogen atom or an alkyl group. Here, the alkyl group is preferably a methyl group.
A represents a single bond, a saturated or unsaturated divalent hydrocarbon group (—R—), an oxy group (—O—), a carbonyl group (—CO—), a carbonyloxy group (—COO—), an oxycarbonyl group. (—OCO—) or a group formed by combining two or more of these (for example, —R—OCO—, —R—COO—, etc.). Specific examples of the saturated or unsaturated divalent hydrocarbon group include alkanediyl groups such as methylene group, ethanediyl group, propane-1,2-diyl group, propane-1,3-diyl group; 2-butene-1 Alkenediyl groups such as, 4-diyl group and the like. The carbon number of the saturated or unsaturated divalent hydrocarbon group is preferably 1 to 15, more preferably 1 to 12, still more preferably 1 to 11, and particularly preferably 1 to 8. Among these, A is preferably a single bond or a saturated or unsaturated divalent hydrocarbon group, and more preferably a single bond.

Specific examples of the group having a carbon-carbon double bond at the terminal include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an acryloxy group, and a methacryloxy group. Of these, vinyl groups or allyl groups are preferred.
The benzocyclobutene structure is bicyclo [4.2.0] octa-1 (6), 2,4-trien-3-yl, or bicyclo [4.2.0] octa-1 (6), 2,4. -Trien-2-yl is preferred.

  Specific examples of the compound (C) include 3-vinyl-bicyclo [4.2.0] octa-1 (6), 2,4-triene, 3-allyl-bicyclo [4.2.0] octa- 1 (6), 2,4-triene, 3- (3-butenyl) -bicyclo [4.2.0] octa-1 (6), 2,4-triene, 3- (4-pentenyl) -bicyclo [ 4.2.0] octa-1 (6), 2,4-triene, 3- (5-hexenyl) -bicyclo [4.2.0] octa-1 (6), 2,4-triene, 3- (6-heptenyl) -bicyclo [4.2.0] octa-1 (6), 2,4-triene, 3- (7-octenyl) -bicyclo [4.2.0] octa-1 (6), 2,4-triene, 3- (8-nonenyl) -bicyclo [4.2.0] octa-1 (6), 2,4-triene, 3- Acryloyl-bicyclo [4.2.0] octa-1 (6), 2,4-triene, 3-methacrylolyl-bicyclo [4.2.0] octa-1 (6), 2,4-triene, 3- Acryloyloxy-bicyclo [4.2.0] octa-1 (6), 2,4-triene, 3-methacryloyloxy-bicyclo [4.2.0] octa-1 (6), 2,4-triene, 2-vinyl-bicyclo [4.2.0] octa-1 (6), 2,4-triene, 2-allyl-bicyclo [4.2.0] octa-1 (6), 2,4-triene, 2- (3-Butenyl) -bicyclo [4.2.0] octa-1 (6), 2,4-triene, 2- (4-pentenyl) -bicyclo [4.2.0] octa-1 (6 ), 2,4-triene, 2- (5-hexenyl) -bicyclo [4.2.0] o 1- (6), 2,4-triene, 2- (6-heptenyl) -bicyclo [4.2.0] octa-1 (6), 2,4-triene, 2- (7-octenyl)- Bicyclo [4.2.0] octa-1 (6), 2,4-triene, 2- (8-nonenyl) -bicyclo [4.2.0] octa-1 (6), 2,4-triene, 2-acryloyl-bicyclo [4.2.0] octa-1 (6), 2,4-triene, 2-methacrylolyl-bicyclo [4.2.0] octa-1 (6), 2,4-triene, 2-acryloyloxy-bicyclo [4.2.0] octa-1 (6), 2,4-triene, 2-methacryloyloxy-bicyclo [4.2.0] octa-1 (6), 2,4- And triene. These can be used alone or in combination of two or more.

  This compound (C) acts as a chain transfer agent in the metathesis polymerization reaction, and can improve the melt fluidity of the resulting crosslinkable resin and the embedding property of the resin on the support or substrate surface. In the compound (C), the benzocyclobutene structure portion can be a starting point for the crosslinking reaction. The compound (C) can improve the heat resistance of the cross-linked resin, cross-linked resin composite or cross-linked resin laminate obtained from the cross-linkable resin, particularly the solder heat resistance.

  The amount of the compound (C) is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the cycloolefin monomer (A). When the amount of the compound (C) is within this range, the polymerization reaction rate is high and a crosslinkable resin can be obtained efficiently. Further, since the residual amount of the compound (C) is small after polymerization, a resin having a small dielectric loss tangent (tan δ) can be obtained.

  Compound (C) can be produced by applying a reaction for forming a carbon-carbon bond as described in Kiso et al., J. Am. Chem. Soc., 1972, 4374-4376. . For example, a halogenated benzocyclobutene and a transition metal compound are dissolved in a solvent. This solution is maintained at a low temperature, preferably about 0 ° C., and an organometallic solution having a double bond at the terminal is added dropwise over 10 minutes or more and refluxed for 10 hours or more. After the reaction is complete, acid and solvent are added for extraction. The obtained organic layer is washed with water, dried using a desiccant, and concentrated to obtain the desired product. If necessary, it can be purified by chromatographic separation, distillation or the like.

The polymerizable composition of the present invention may contain a chain transfer agent other than the compound (C).
As the chain transfer agent, a compound having at least one vinyl group can be used. Specific examples include aliphatic olefins such as 1-hexene and 2-hexene; aromatic olefins such as styrene, divinylbenzene and stilbene; alicyclic olefins such as vinylcyclohexane; vinyl ethers such as ethyl vinyl ether; Vinyl ketones such as vinyl ketone, 1,5-hexadien-3-one, 2-methyl-1,5-hexadien-3-one; a compound represented by the formula: CH ₂ ═CH—Q (where Q is And a group having at least one group selected from a methacryloyl group, an acryloyl group, a vinylsilyl group, an epoxy group, and an amino group). These chain transfer agents can be used alone or in combination of two or more.

Among these, it is preferable to use a compound represented by the formula: CH ₂ ═CH—Q as a chain transfer agent. Formula: Specific examples of the compound represented by CH ₂ = CH-Q is vinyl methacrylate, allyl methacrylate, 3-buten-1-yl, methacrylic acid 3-buten-2-yl, styryl methacrylate Compounds wherein Q is a group having a methacryloyl group; allyl acrylate, 3-buten-1-yl acrylate, 3-buten-2-yl acrylate, 1-methyl-3-butene-2-acrylate Compounds in which Q is a group having an acryloyl group, such as yl, styryl acrylate, and ethylene glycol diacrylate; compounds in which Q is a group having a vinylsilyl group, such as allyltrivinylsilane, allylmethyldivinylsilane, and allyldimethylvinylsilane; Q has an epoxy group, such as glycidyl acrylate and allyl glycidyl ether A compound wherein Q is a group having an amino group, such as allylamine, 2- (diethylamino) ethanol vinyl ether, 2- (diethylamino) ethyl acrylate, 4-vinylaniline; 3-vinyl-bicyclo [4.2.0 ] Compounds wherein Q is a benzocyclobutenyl group, such as octa-1 (6), 2,4-triene, 2-vinyl-bicyclo [4.2.0] octa-1 (6), 2,4-triene Is mentioned.

  The amount of the chain transfer agent other than the compound (C) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the cycloolefin monomer (A).

(D) Crosslinking agent The polymerizable composition may further contain a crosslinking agent (D).

  Examples of the crosslinking agent (D) include a radical generator, an epoxy compound, an isocyanate group-containing compound, a carboxyl group-containing compound, an acid anhydride group-containing compound, an amino group-containing compound, and a Lewis acid. 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.
Examples of the organic peroxide include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide; dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis (t- Butylperoxy-m-isopropyl) benzene, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2,5-di ( dialkyl peroxides such as t-butylperoxy) hexane; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; 2,2-di (t-butylperoxy) butane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -2-methyl Peroxyketals such as cyclohexane and 1,1-di (t-butylperoxy) cyclohexane; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; t-butylperoxyisopropylcarbonate, di (isopropylperoxy) Peroxycarbonates such as dicarbonate; alkylsilylperoxasides such as t-butyltrimethylsilyl peroxide; and the like. 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, 4,5-dimethyl-4,5-diphenyloctane, 1,1,1-triphenylpropane, 1,1,1-triphenylbutane 1,1,1-triphenylpentane, 1,1,1-triphenyl-2-propene, 1,1,1-triphenyl-4-pentene, 1,1,1-triphenyl-2-phen Ruetan and the like.

  These radical generators can be used alone or in combination of two or more. It is possible to arbitrarily control the glass transition temperature and the molten state of the resulting crosslinkable resin by using two or more kinds of radical generators in combination and changing the amount ratio thereof. The radical generator preferably has a 1 minute half-life temperature of 150 to 350 ° C, more preferably 200 to 300 ° C. In the present invention, the 1-minute half-life temperature represents a temperature at which the radical generator decomposes and becomes half in one minute. Of these radical generators, organic peroxides are preferably used.

  The usage-amount of a crosslinking agent (D) is 0.1-10 mass parts normally with respect to 100 mass parts of cycloolefin type monomers (A), 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 crosslinkable resin and a crosslinked resin having desired physical properties cannot be obtained.

  Moreover, when using a radical generating agent as a crosslinking agent (D), in order to promote the crosslinking reaction, a crosslinking adjuvant can be used. The crosslinking aid is preferably a compound having two or more crosslinkable carbon-carbon unsaturated bonds that do not participate in ring-opening polymerization and can participate in a crosslinking reaction induced by the crosslinking agent. Such a crosslinkable carbon-carbon unsaturated bond is preferably present as a terminal vinylidene group, particularly as an isopropenyl group or a methacryl group, more preferably as a methacryl group, in the compound constituting the crosslinking aid. preferable.

  Specific examples of the crosslinking aid include polyfunctional compounds having two or more isopropenyl groups, such as p-diisopropenylbenzene, m-diisopropenylbenzene, o-diisopropenylbenzene; ethylene dimethacrylate, 1, 3 -Butylene dimethacrylate, 1,4-butylene dimethacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 2,2 2 or more methacrylic groups such as' -bis (4-methacryloxydiethoxyphenyl) propane, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate Such as a polyfunctional compound having may be mentioned. Among these, as the crosslinking aid, a polyfunctional compound having two or more methacryl groups is preferable from the viewpoint of improving the heat resistance and crack resistance of the resulting multilayer substrate. Among polyfunctional compounds having two or more methacryl groups, polyfunctional compounds having three methacryl groups such as trimethylolpropane trimethacrylate and pentaerythritol trimethacrylate are more preferable.

  The crosslinking aids can be used alone or in combination of two or more. The amount of crosslinking aid is usually an error! Link is not correct for 100 parts by weight of cycloolefin monomer. Heavy part, preferably an error! The link is incorrect. Heavy part, more preferably an error! The link is incorrect. Parts by weight.

(E) Other additives The polymerizable composition of the present invention may contain an additive (E) in addition to the substances listed above. Examples of the additive (E) include a polymerization reaction retarder, a radical crosslinking retarder, a reinforcing material, a modifier, an antioxidant, a flame retardant, a filler, a colorant, and a light stabilizer. These can be used by dissolving or dispersing in a monomer solution or a catalyst solution described later.

Examples of the polymerization reaction retarder include phosphines such as triphenylphosphine, tributylphosphine, trimethylphosphine, triethylphosphine, dicyclohexylphosphine, and vinyldiphenylphosphine; Lewis bases such as aniline and pyridine. Among these, phosphines are preferable because the pot life of the polymerizable composition of the present invention can be efficiently controlled and the polymerization reaction is hardly inhibited.
Among cycloolefin monomers, cycloolefin monomers having a 1,5-diene structure or a 1,3,5-triene structure in the molecule such as 1,5-cyclooctadiene and 5-vinyl-2-norbornene The monomer also functions as a retarder for the metathesis polymerization reaction of the norbornene monomer.

  Examples of radical crosslinking retarders include alkoxyphenols, catechols, and benzoquinones. Of these, alkoxyphenols such as 3,5-di-t-butyl-4-hydroxyanisole are preferred.

Examples of the reinforcing material include short fiber powders such as chopped strands and milled fibers. Examples of the types of fibers include glass fibers, paper base materials, carbon fibers, metal fibers, and aramid fibers.
Examples of the modifier include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), Examples include ethylene-propylene-diene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), and elastomers such as hydrides thereof.
Examples of the antioxidant include various hindered phenol-based, phosphorus-based and amine-based antioxidants for plastics and rubbers. These antioxidants are preferably 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. The flame retardant is preferably used singly or in combination of two or more.

  Examples of the filler include glass powder, ceramic powder, and silica. Two or more kinds of these fillers may be used in combination. As the filler, one that has been surface-treated with a silane coupling agent or the like can also be used. The amount of the filler is usually 0 to 600 parts by mass, preferably 50 to 500 parts by mass, more preferably 50 to 400 parts by mass with respect to 100 parts by mass of the cycloolefin monomer (A).

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

  The polymerizable composition of the present invention is not particularly limited by the method for preparing it. The polymerizable composition is prepared, for example, by preparing a liquid in which the metathesis polymerization catalyst (B) is dissolved or dispersed in an appropriate solvent (hereinafter sometimes referred to as “catalyst liquid”), and separately from the cycloolefin monomer (A). Prepared by adding a filler, a flame retardant, and other additives as necessary (hereinafter sometimes referred to as “monomer liquid”), adding the catalyst liquid to the monomer liquid, and stirring the mixture. it can. Mixing of the monomer liquid and the catalyst liquid is preferably performed immediately before the bulk polymerization described below. Further, the compound (C), the crosslinking agent (D), the radical crosslinking retarder, etc., which are chain transfer agents, may be added to the monomer liquid and / or the catalyst liquid before mixing the monomer liquid and the catalyst liquid, You may add, after mixing a monomer liquid and a catalyst liquid.

[Crosslinkable resin, crosslinkable resin composite and crosslinkable resin laminate]
The crosslinkable resin of the present invention can be obtained by bulk polymerization of the polymerizable composition.
As a method for bulk polymerization of the polymerizable composition,
(A) A method in which the support is coated with the polymerizable composition by a method such as pouring or coating the polymerizable composition on the support, and bulk polymerization is performed,
(B) a method of impregnating a polymerizable composition into a support and performing bulk polymerization;
(C) A method of pouring the polymerizable composition into a mold and performing bulk polymerization,
Etc.

According to the method (a) or (b), a crosslinkable resin composite comprising a support and a crosslinkable resin impregnated or coated on the support is obtained.
Examples of the support used in the method (a) include resins such as polyethylene terephthalate, polypropylene, polyethylene, polycarbonate, polyethylene naphthalate, polyarylate, and nylon; iron, stainless steel, copper, aluminum, nickel, chromium, gold, Examples thereof include a metal material such as silver. The shape of the support is not particularly limited, but a metal foil or a resin film is preferably used as the support.
For example, when a copper foil is used as the support, a copper foil with a crosslinkable resin (Resin Coated Copper (RCC)) can be obtained. The thickness of the metal foil or the resin film as the support 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. In addition, the surface of these supports is preferably surface-treated with a silane coupling agent such as styryltrimethoxysilane.

  The method for coating the support with the polymerizable composition 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 metathesis polymerization proceeds.
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 while pressing using a press machine (hot pressing method), and pressing with a heated roller. And a method using a heating furnace.
The crosslinkable resin film formed on the surface of the support thus obtained has a thickness of usually 15 mm or less, preferably 10 mm or less, more preferably 5 mm or less, and particularly preferably 1 mm or less.

The support used in the method (b) is a porous material or a fiber material, and a fiber material is frequently used. According to this method, for example, a prepreg that is a crosslinkable resin composite including a fiber material and a crosslinkable resin impregnated in the fiber material can be obtained.
Examples 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 fibers constituting the fiber material may be either organic fibers or inorganic fibers, such as aramid fibers, polyethylene terephthalate fibers, vinylon fibers, polyester fibers, polyamide fibers, poly (paraphenylenebenzobisoxazole); glass fibers , Carbon fiber, metal fiber, ceramic fiber and the like. These can be used alone or in combination of two or more.

  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, or a slit coating method. Can be applied by applying to a fiber material, and if necessary, a protective film is 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, thereby including the fiber material and the crosslinkable resin impregnated therein. A prepreg consisting of

  The heating method for bulk polymerization of the impregnated product is not particularly limited, and the same method as the method (a) may be employed, and the impregnated product may be placed on a heating plate 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 (c) below.

Since the polymerizable composition of the present invention has a low viscosity as compared with a conventional resin varnish and is excellent in impregnation property to a support such as a 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 small content of a solvent 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. Odor and bulge are not generated. Furthermore, since the crosslinkable resin of the present invention is excellent in storage stability, the obtained prepreg is excellent in storage stability.

  According to the method (c), a molded body of a crosslinkable resin having an arbitrary shape can be obtained. Examples of the shape of the cross-linked resin molding include a sheet shape, a film shape, a column shape, a columnar shape, and a polygonal column shape.

  As a mold for obtaining a cross-linked resin molded body, 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. The polymerizable composition is injected into the void (cavity) of the mold to perform bulk polymerization. The core mold and the cavity mold are produced so as to form a void portion that matches the shape of the target cross-linked resin molded body. 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 molded product of the crosslinkable resin 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.

  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 the bulk polymerization reaction starts, the temperature of the reaction solution rapidly increases 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 resin, and a post-cross-linkable resin may not 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 crosslinking agent, preferably not more than 230 ° C., more preferably It is preferable to control the temperature below 200 ° C.

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

Since the bulk polymerization reaction of the polymerizable composition described above proceeds almost completely, most of the compound (C) as a chain transfer agent is also consumed in the polymerization reaction. As a result, the crosslinkable resin obtained by the bulk polymerization has a small residual amount of the compound (C), a very low dielectric loss tangent (tan δ), and good electrical characteristics.
The amount of the compound (C) contained in the crosslinkable resin is usually 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass with respect to the amount of the compound (C) contained in the polymerizable composition. Hereinafter, it is most preferably 1.5% by mass or less. The amount of the compound (C) contained in the crosslinkable resin can be determined, for example, by analyzing a solution obtained by dissolving the crosslinkable resin in a solvent with a gas chromatograph.

  Further, according to the present invention, a crosslinkable resin having a narrow molecular weight distribution can be obtained. Since the molecular weight is uniform, the fluidity range of the resin becomes uniform, and the embedding property to the wired support becomes good. The molecular weight distribution of the crosslinkable resin is a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), preferably 3.5 or less, more preferably 3.0 or less, most preferably 2 .8 or less. The range of the weight average molecular weight is preferably 5,000 to 80,000, more preferably 10,000 to 50,000, and most preferably 15,000 to 40,000. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the crosslinkable resin of the present invention are calculated by converting the measurement results by gel permeation chromatography using tetrahydrofuran as a developing solvent into the molecular weight of standard polystyrene. Can be sought. If the molecular weight of the crosslinkable resin is too low, the fluidity is too high, and it may be difficult to control the embedding property and flatness of the crosslinkable resin in the support or the substrate. On the other hand, if the molecular weight is too high, it may not flow in the temperature range during crosslinking.

  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. In addition, since the crosslinkable resin of the present invention exhibits thermoplasticity, it can be formed into various shapes by performing melt molding at a temperature that does not cause a crosslinking reaction.

  The molded product of the crosslinkable resin obtained by the method (c) may be one in which a part thereof is a crosslinked resin. 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 resin. However, if the surface portion that easily dissipates heat is formed of a post-crosslinkable resin, the effect of the crosslinkable resin of the present invention as a molded body can be fully enjoyed. Similarly, in the crosslinkable resin composite, a part of the crosslinkable resin may be a crosslinkable resin.

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

The crosslinkable resin laminate of the present invention comprises a substrate and a crosslinkable resin or a crosslinkable resin composite laminated on the substrate.
The crosslinkable resin laminate of the present invention can be obtained by laminating the crosslinkable resin or the crosslinkable resin composite on a substrate.
Examples of the substrate used for laminating the crosslinkable resin or the crosslinkable resin composite include those exemplified as the support used in the methods (a) and (b), printed wiring boards, conductive polymer films, and the like. Can be mentioned. Moreover, when a printed wiring board is used as the substrate, a multilayer printed wiring board having excellent wiring embedding properties can be manufactured. The surface of the conductive layer on the metal foil such as copper foil or printed wiring board is preferably treated with a silane coupling agent, a thiol coupling agent, a titanate coupling agent, or various adhesives. Of these, those treated with a silane coupling agent are particularly preferred.

  The crosslinkable resin or crosslinkable resin composite and the substrate can be laminated by one layer or a plurality of layers alternately and as necessary, and then hot-pressed. The pressure at the time of hot pressing is usually 0.5 to 20 MPa, preferably 3 to 10 MPa. The hot pressing may be performed in a vacuum or a reduced pressure atmosphere. The hot pressing can be performed using a known press having a press frame mold for flat plate forming, a press molding machine such as a sheet mold compound (SMC) or a bulk mold compound (BMC).

[Crosslinked resin, crosslinked resin composite and crosslinked resin laminate]
The crosslinked resin of the present invention is obtained by crosslinking the crosslinkable resin.
Crosslinking of the crosslinkable resin can be performed, for example, by heating the crosslinkable resin of the present invention and maintaining the temperature at or above the temperature at which the crosslinkable resin causes a crosslinking reaction. The temperature at which the crosslinkable resin is crosslinked is preferably 20 ° C. or more higher than the peak temperature at the time of bulk polymerization, and is usually 170 to 250 ° C., preferably 170 to 240 ° C. The crosslinking time is not particularly limited, but is usually from several minutes to several hours.

The crosslinked resin composite of the present invention comprises a support and a crosslinked resin impregnated or coated on the support.
The cross-linked resin composite of the present invention can be obtained by cross-linking the above cross-linkable resin composite by the same method as the cross-linking of the cross-linkable resin.

The crosslinked resin laminate of the present invention comprises a substrate and a crosslinked resin or a crosslinked resin composite laminated on the substrate.
The cross-linked resin laminate of the present invention is obtained by heating and cross-linking the cross-linkable resin laminate. As a method of heating and crosslinking the crosslinkable resin laminate, a method by hot pressing can be mentioned. For example, the crosslinkable resin can be crosslinked by laminating a molded body of a crosslinkable resin formed into a plate shape or a film shape on a substrate by hot pressing and further heating. The conditions for hot pressing are the same as those for crosslinking the crosslinkable resin.

  Since the crosslinkable resin of the present invention is excellent in fluidity and adhesion, the crosslinkable resin molded article, the crosslinkable resin composite, and the crosslinkable that are excellent in flatness and excellent in adhesion to a support or a substrate. A functional resin laminate can be obtained.

  The cross-linked resin, cross-linked resin composite, and cross-linked resin laminate of the present invention have a small dielectric loss tangent in the high-frequency region, and characteristics such as electrical insulation, adhesion, mechanical strength, heat resistance, wiring embedding, and dielectric properties Therefore, it is suitable as an electric material.

  For the dielectric loss tangent (tan δ), the dielectric loss tangent (tan δ) at a frequency of 1 GHz was measured by a capacitance method using an impedance analyzer (manufactured by Agilent Technologies, model number E4991).

  For electrical insulation, a sample of 10 via-lined via-holes arranged in a straight line with a spacing of 100 μm on a multi-layered board was prepared in parallel with a spacing of 100 μm. Used as a substrate. Time until a conduction is confirmed by applying a voltage of 100 V for a predetermined time between one via hole row and the other via hole row, which are insulated from each other in an environment of 85% RH at 130 ° C. Were measured and evaluated.

  Adhesiveness (peel strength) was measured and evaluated according to JIS C6481 for strength when the copper foil was peeled off from the crosslinked resin laminate.

  The wiring embedding property was evaluated by the following procedure. The copper foil of the cross-linked resin laminate was etched, and a prepreg that was a cross-linkable resin composite was layered on the surface on which 15 wires of L / S = 15 μm were formed. A multilayer board was obtained. The test multilayer board was arbitrarily cut at three points in a direction perpendicular to the wiring direction. The cut surface of the obtained test multilayer board was visually observed.

  Next, an Example and a comparative example are given and this invention is demonstrated concretely. However, the present invention is not limited to the following examples. In the following Examples and Comparative Examples, “parts” and “%” are based on mass unless otherwise specified.

  In this example, evaluation was performed according to the following method.

(Solder heat resistance)
The crosslinked resin laminate A was immersed in a solder bath at 280 ° C. for 1 minute. Thereafter, the appearance was observed. Evaluation was as follows.
A: No abnormality
B: Slight bulge
C: swelling, peeling

Production Example 4-Chlorobenzocyclobutene and [NiCl ₂ (dpe)] were dissolved in tetrahydrofuran. While maintaining this solution at 0 ° C., a tetrahydrofuran solution of CH ₂ ═CHMgBr was added dropwise over 10 minutes and then refluxed for 20 hours. After completion of the reaction, the mixture was extracted with dilute hydrochloric acid and ether. The organic layer obtained is washed with water, dried using calcium chloride, concentrated, purified by column chromatography and 3-vinyl-bicyclo [4.2.0] octa-1 (6), 2,4. -Triene [see formula (A)] was obtained.

Example 1
In a glass flask, 0.04 part of benzylidene (1,3-dimethyl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and 0.06 part of triphenylphosphine are added to 0.7 part of tetrahydrofuran. A catalyst solution was prepared by dissolution.
In a 200 ml metal container, tetracyclo [6.2.1.1 ^3.6 . ^02.7 ] 70 parts dodec-4-ene, 30 parts 2-norbornene, 100 parts silica particles, 10 parts antimony trioxide as a flame retardant and 26.7 parts ethane-1,2-bis (pentabromophenyl), The monomer liquid was obtained by mixing uniformly.

  Subsequently, in a polyethylene bottle having a capacity of 200 ml, 240 parts of the monomer liquid, 1.8 parts of 3-vinyl-bicyclo [4.2.0] octa-1 (6), 2,4-triene as a chain transfer agent, Then, 0.35 part of the catalyst solution was added with stirring to obtain a polymerizable composition.

  Subsequently, 70 parts of this polymerizable composition was cast on a polyethylene naphthalate film, a glass cloth was laid thereon, and 70 parts of the polymerizable composition was cast thereon. Further, a polyethylene naphthalate film was covered thereon, and the entire glass cloth was impregnated with the polymerizable composition using a roller. Subsequently, this was heated for 1 minute in the heating furnace heated at 130 degreeC, the polymerizable composition was block-polymerized, and the prepreg which is a crosslinkable resin composite was obtained.

This prepreg was cut into a size of 100 mm square, and 6 sheets of the prepreg were stacked. Both surfaces of the prepreg were sandwiched between copper foils, and heat-pressed at 3 MPa and 220 ° C. for 30 minutes with a hot press to prepare a crosslinked resin laminate A .
The obtained crosslinked resin laminate A was cut into a size of 50 mm × 50 mm, and the solder heat resistance was measured.

Comparative Example 1
Polymerizable composition, prepreg, cross-linked resin laminate in the same manner as in Example 1 except that styrene was used instead of 3-vinyl-bicyclo [4.2.0] octa-1 (6), 2,4-triene. Body A was obtained. The evaluation results are shown in Table 1.

  From the above results, it can be seen that the prepreg obtained by bulk polymerization of the polymerizable composition of the present invention was hot-pressed to crosslink the crosslinkable resin, resulting in a crosslinked body having high solder heat resistance.

Claims (16)

  A polymerizable composition comprising a cycloolefin monomer (A), a metathesis polymerization catalyst (B), and a compound (C) having a carbon-carbon double bond at a terminal and a benzocyclobutene structure in the molecule.   The polymerizable composition according to claim 1, wherein the cycloolefin monomer (A) is a norbornene monomer.   The benzocyclobutene structure is bicyclo [4.2.0] octa-1 (6), 2,4-trien-3-yl, or bicyclo [4.2.0] octa-1 (6), 2,4 The polymerizable composition according to claim 1, which is -trien-2-yl.   The polymerizable composition according to claim 1, further comprising a crosslinking agent (D).   Crosslinkable resin obtained by carrying out bulk polymerization of the polymeric composition as described in any one of Claims 1-4.   The crosslinkable resin according to claim 5, wherein the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 3 or less.   A crosslinkable resin composite comprising a support and the crosslinkable resin according to claim 5 impregnated or coated on the support.   A crosslinkable resin laminate comprising a substrate and the crosslinkable resin according to claim 5 or the crosslinkable resin composite according to claim 7 laminated on the substrate.   A crosslinked resin obtained by crosslinking the crosslinkable resin according to claim 5.   A crosslinked resin composite comprising a support and the crosslinked resin according to claim 9 impregnated or coated on the support.   A crosslinked resin laminate comprising a substrate and the crosslinked resin according to claim 9 or the crosslinked resin composite according to claim 10 laminated on the substrate.   A method for producing a crosslinkable resin, comprising a step of bulk polymerization of the polymerizable composition according to claim 4.   The manufacturing method of a crosslinkable resin composite including the process of impregnating or coat | covering the polymeric composition of Claim 4 to a support body, and carrying out block polymerization then.   The manufacturing method of crosslinked resin including the process of bridge | crosslinking the crosslinkable resin of Claim 5.   A method for producing a crosslinked resin laminate comprising the steps of laminating the crosslinkable resin according to claim 5 or the crosslinkable resin composite according to claim 8 on a substrate and then crosslinking.   The manufacturing method of a crosslinked resin composite including the process of bridge | crosslinking the crosslinkable resin composite of Claim 7.