WO1998005715A1 - Cross-linking polymer composition - Google Patents

Abstract

A cross-linking polymer composition containing an aromatic norbornene polymer with a number-average molecular weight (Mn) of 500 to 500,000 and a cross-linking agent; sheets and prepregs produced therefrom; and laminates produced by laminating the sheets and/or the prepregs.

Description

 Description Crosslinkable polymer composition <Technical field>

 The present invention relates to a crosslinkable polymer composition containing an aromatic ring-containing norbornene-based polymer and a crosslinking agent as essential components, a sheet-shaped molded article comprising the composition, and a glass cross-linked composition. TECHNICAL FIELD The present invention relates to a prepreg impregnated in a reinforcing base material such as steel, and a laminate obtained by laminating the prepreg. More specifically, the present invention has excellent electrical properties, heat resistance, hang resistance, chemical resistance, and mechanical strength, and can uniformly disperse a compounding agent such as a flame retardant. And a crosslinkable polymer composition. Further, the present invention provides a crosslinked molded article, prepreg, laminated body, which is excellent in electric properties, heat resistance, solder resistance, chemical resistance, and mechanical strength, and in which a compounding agent is uniformly dispersed. And a metal-clad laminate. Background technology>

 Circuits installed in precision equipment such as electronic computers and communication equipment are required to have higher speed, higher reliability and higher density in arithmetic processing as technology advances. High performance such as miniaturization, high precision, and miniaturization is progressing.

For such a circuit board, for example, a reinforcing base material such as glass cross is impregnated with a resin varnish, and a dried semi-cured sheet (that is, a pre-preda) is produced. Alternatively, it is manufactured by laying out a copper clad board for outer layer, prepreg, copper clad board for inner layer, etc. in order between the mirror-finished plates, and then pressurizing and heating to completely cure the resin. You. Conventionally, as a resin material, X-nor resin, epoxy resin, polyimide resin, fluorine resin, polybutadiene resin, and the like have been used.

 However, thermosetting resins such as phenolic resins, epoxy resins, and polyimide resins generally have a high dielectric constant of 4.0 or more and a high dielectric loss tangent of 0.01 or more. Since the electrical characteristics are not sufficient, it has been difficult for circuit boards using these thermosetting resins to achieve high-speed and high-reliability arithmetic processing. On the other hand, a circuit board using a thermoplastic resin such as a fluororesin or a polybutadiene resin has poor heat resistance, so that cracks and peeling may occur at the time of hang-up. In addition, the dimensional stability was poor, and multilayering was difficult.

Recently, there has been proposed a method for improving heat resistance, solvent resistance, and the like by crosslinking a thermoplastic norbornane resin with an organic peroxide. For example, Japanese Patent Application Laid-Open No. Sho 62-34924 describes that decalin is obtained by addition polymerization of norbornane-based cyclic olefin and ethylene. A norbornane resin having an intrinsic viscosity [] of 1.15 to 2.22 was synthesized in the reactor, kneaded with the norbornane resin and a crosslinking agent, and then pulverized. A method is disclosed in which a solution is impregnated, a solvent is removed, and then press molding is performed to perform crosslinking. However, in this method, in addition to the complicated process, there is a problem that the organic peroxide and other compounding agents are not uniformly dispersed. Japanese Unexamined Patent Publication No. 6-24816 discloses flame retardants such as thermoplastic hydrogenated ring-opened norpolene-based resins, organic peroxides, crosslinking aids, and brominated bisphenols. A method has been disclosed in which, after uniformly dispersing in a solvent, the solvent is removed and the resin is thermally crosslinked. According to this method, it is possible to obtain a cross-linked molded article having excellent heat resistance and low dielectric constant and dielectric loss tangent. You. However, in this method, the type and amount of the compounding agent to be dispersed are limited, so that it may not be sufficient depending on the application field. Disclosure of the invention)

 An object of the present invention is to provide an excellent electric property, heat resistance, solder resistance, chemical resistance, and mechanical strength, and to uniformly disperse a compounding agent such as a flame retardant. An object of the present invention is to provide a crosslinkable polymer composition having various properties suitable as a resin for a circuit board and a resin material for a circuit board.

 More specifically, an object of the present invention is to use a norbornene-based resin excellent in dielectric constant, dielectric loss tangent, moisture resistance (in other words, water absorption resistance) and the like, and to provide a crosslinkable material having excellent physical properties as described above. An object of the present invention is to provide a polymer composition, a prepreg made of the composition, and a laminate suitable as a circuit board. The present inventors have conducted intensive studies to overcome the problems of the prior art, and as a result, as a norbornene resin, it has a specific number average molecular weight range and has an aromatic ring. Using a norbornane-based polymer, it was found that a large amount of a crosslinking agent and various compounding agents can be uniformly dispersed in a solution state. Therefore, when the solution containing the compounding agent is impregnated with a reinforcing base material such as glass cloth, a prepreg in which each component is uniformly impregnated can be produced. Moreover, by using a crosslinkable polymer composition containing an aromatic ring-containing norbornene polymer and a crosslinking agent as essential components, electrical properties, heat resistance, hang resistance, chemical resistance, It is possible to obtain molded articles, prepregs, laminates, etc. with excellent mechanical strength. The present invention has been completed based on these findings.

Thus, according to the present invention, the number average molecular weight (M n) 500 to 500, The present invention provides a crosslinkable polymer composition comprising: a benzene-containing norbornane-based polymer having a molecular weight of 0.001; and a crosslinking agent.

 According to the present invention, a crosslinkable polymer composition containing an aromatic ring-containing norbornene-based polymer having a number average molecular weight (Mn) of 500 to 500,000 and a crosslinking agent is formed. A sheet will be provided.

 According to the present invention, a crosslinkable polymer composition containing an aromatic ring-containing norbornane-based polymer having a number average molecular weight (Mn) of 500 to 500,000 and a crosslinking agent is used as a reinforcing base material. A prepreg impregnated with a prepreg is provided. According to the present invention, there is provided a laminate obtained by laminating the sheets and / or prepregs and crosslinking the crosslinkable polymer composition.

 According to the present invention, there is provided a metal-clad laminate in which a metal layer is further laminated on the laminate.

<Best mode for carrying out the invention>

Aroma-containing norbornane polymer

 (1) Polymers and monomers

 The aromatic ring-containing norbornane-based polymer used in the present invention is a thermoplastic norbornane-based polymer as long as it has at least one aromatic ring in the molecule. Although there is no particular limitation, a polymer containing an aromatic ring-containing monomer unit is preferably used. Examples of the aromatic ring-containing monomer include an aromatic ring-containing norbornane-based monomer and an aromatic vinyl compound, and among these, the content of the aromatic ring and the norbornane-based monomer are included. For increasing the unit content, an aromatic ring-containing norbornane-based monomer is preferred.

Examples of the aromatic ring-containing norbornane-based polymer having an aromatic ring-containing monomer unit include (1) an aromatic ring-containing norbornene-based monomer. Ring-opening polymers, (2) ring-opening copolymers of an aromatic ring-containing norbornane-based monomer and an aromatic ring-free norbornane-based monomer, and (3) hydrogenated products thereof. . Examples of the aromatic ring-containing norbornene-based polymer include: (4) an addition polymer of an aromatic ring-containing norbornene-based monomer and an aromatic vinyl compound; and (5) an aromatic ring-containing norbornene-based monomer. (6) Addition polymer of a norbornane monomer containing no aromatic ring and an aromatic vinyl compound and an aromatic vinyl compound containing no aromatic ring (7) an addition polymer of an aromatic ring-containing norbornane-based monomer and a vinyl compound other than an aromatic vinyl compound (eg, ethylene); and (8) a hydrogenated product thereof. Can be used.

 The hydrogenated product is usually a (co) polymer having a carbon-carbon double bond formed in the main chain and / or a (co) polymer having a non-conjugated carbon-carbon double bond in a side chain. Hydrogenated carbon-carbon double bonds. This hydrogenated product may be hydrogenated up to a hydrogenation rate of 99% or more for the carbon-carbon double bond in the main chain and the non-conjugated carbon-carbon double bond in the side chain. Not all of the rings are hydrogenated. The hydrogenation rate of the aromatic ring is appropriately selected depending on the content of the aromatic ring-containing monomer, but is usually 90% or less, preferably 80% or less, and more preferably 70%. Below, the most preferred is 60% or less.

There is no particular limitation on the aromatic ring-containing norbornene monomer used in the present invention. For example, JP-A-5-97719, JP-A-7-415550 And those described in JP-A-8-72210 can be used. A typical example of the aromatic ring-containing monomer is a compound represented by the following formula (I).

In the formula (I), the meaning of each symbol is as follows.

m: 0 or a positive integer.

h: 0 or a positive integer.

 j: 0, 1 or 2.

k: 0, 1 or 2.

R ′ R ¹ ′: each independently represents a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, an ester group (eg, an alkyl ester group), a cyano group, an amide group, an imido group, Selected from hydrocarbon groups substituted with a lilyl group and a polar group (halogen atom, alkoxy group, hydroxyl group, ester group, cyano group, amide group, imido group, or silyl group) It is. R ¹² ~R ^2. : Independently of each other, a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, an ester group (eg, an alkyl ester group), a cyano group, an amide group, an imide group, a silyl group, and a polar group The group is selected from hydrocarbon groups substituted with a group (halogen atom, alkoxy group, hydroxyl group, ester group, cyano group, amide group, imido group, or silyl group). In formula (I), the carbon atom to which R '° and R ¹¹ are attached, the carbon atom to which carbon atoms or R ¹² R ¹⁴ is bonded is bonded, have in direct carbon atoms It may be bonded through 1-3 alkylene groups. j = in the case of k = 0 is the R ¹⁶ and R ¹³ or R ¹⁶ and R ² °, sintered to each other Together, they may form a monocyclic or polycyclic aromatic ring.

 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms; and 2 to 20 carbon atoms. Preferably 2 to 10 or more preferably 2 to 6 alkenyl groups; having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 6 alkynyl groups Groups; alkylidene groups having 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms; 3 to 15 carbon atoms, preferably 3 to 8 carbon atoms And more preferably a cycloalkyl group having 5 to 6 carbon atoms; and an aromatic hydrocarbon having 6 to 20 carbon atoms, preferably 6 to 16 carbon atoms, and more preferably 6 to 10 carbon atoms. Group; and the like. Examples of the hydrocarbon group substituted with a polar group include a halogenated alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Can be.

 Specific examples of the aromatic ring-containing norbornane-based monomer represented by the formula (I) include norbornane having an aromatic substituent represented by the following formulas (1) to (23). And a norbornane-based monomer having a norbornane ring structure and an aromatic ring structure in a polycyclic structure represented by the following formulas (24) to (30). Can be mentioned.

CO CO

〇 ϋι

CO 00 4 ^ CO ο

SZLZ0 / L6d £ / JLDd SUSO / 86 OAV

twenty five

Ten

20

twenty five

A compound name of an aromatic ring-containing norbornane-based monomer having an aromatic substituent is, for example, 5—phenyl bicyclo [2.2.1] hept-2-ene [ Formula (1); 5-vinyl 2-norbornane], 5-methyl 5-vinyl bicyclo [2.2.1] hept 2-phen [formula (2)], 5 —Benzil-bicyclo [2.2.1] hept — 2 —ene [Equation (3)], 5 — Trirubicyclo [2.2.1] —Ene [Formula (4); eg, 5— (4—methylfurenyl) —2-nonorbornene], 5— (ethynolefenyl) —bicyclo [2.2.1] heptogram — 2-ene [Equation (5)], 5 — (Isopropyl phenyl) — Bicyclo [2,2,1] hept 2 —ene [Equation (6)), 8 — ENEIRUTE TRACE CYCL [4.4.0 I ² ' ^5. I ^{7. 10} ] — 3—dodecene (Equation (7)), 8—methyl 1-8—Fe-N 2 -tetracyclo [4.4.0. I ² ' ^{. 5 I 7 '10] -} 3 -. dodec emissions [formula (8)], 8-base emissions Giroux Te preparative La consequent b [4.4.1 0.1 ^2-5 1 ^7-0] one 3- dodecene [equation (9)], 8 Application Benefits root Te preparative La shea click b [4.4.1 0.1 ^{2 '5.1 7' 10]} one 3-dodecenyl down [formula (1 0)] 8- (Echirufu Weniru) - Te DOO La shea click b ^{[4. 4. 0. I 2 '5} I 7.' 10] - 3- dodec emissions [formula (1 1)], 8 - (Lee Seo Pro Pirufu d sulfonyl) Ichite preparative La shea click b ^{[4. 4. 0. I 2 · 5} I 7 '10.] - 3 - dodec emissions [formula (1 2)], 8, 9 - di full et two Lou Te Bok La shea click b ^{[4. 4. 0. I 2 '5} I 7.' 10] - 3- dodec emissions [equation (1 3)], 8- (Biff enyl) over Te preparative La shea click b [ 4.4.1 0.1 ^{2 '5} 1 ^{7.' 10]} - 3 - dodec [Equation (1 4)], 8- (/ 3-naphthyl) Ichite preparative La consequent b [4. ^{4. 0. 1 2 · B I 7} . '10] - 3 - dodec emissions [Equation (1 5)], 8 - (α - naphthyl) Ichite Bok La consequent b [4. 4. 0. I ^{2' . 5 I 7 '10] -} 3 - dodecene [equation (1 6)], 8 - (en preparative Raseniru) over Te preparative La consequent b ^{[4. 4. 0. I 2'.} 5 I 7 '10 ] - 3 - dodec emissions [formula (1 7)], 1 1 -... full et two routes to Kisashiku b ^{[6. 6. 1 I 3 '6} 0 2 · 7 0 9 · 1] one 4 heptene data Decene (Formula (18)), 6 — (α-naphthyl) -bicyclo [2.2.1] — Hept — 2 — (Formula (19)), 5-( (Trathenyl)-bicyclo [2.2.1]-hept — 2-ene [formula (20)], 5-(biphenyl)-bicyclo [2.2.1]-heb 1- 2 -ene [Equation (2 1)], 5-(yS-naphthyl) 1-bicyclo [2.2.1] -Hept 2 -ene [Equation (2 2)], 5 , 6 — Ziff Enil Cycle mouth [2.2.1]-hept-2-ene [formula (23)], 9- (2-norbornane-5-yl), one-pot rubazole, etc. it can.

Compound names of aromatic ring-containing norbornane-based monomers having a norbornane ring structure and an aromatic ring structure in the polycyclic structure are, for example, 1,41-metano-1, 4,4a, 4b, 5,8,8a, 9a —Octahydrofluorenes; 1,4-metanones 1,4,4a, 9a —Teto Lahydrofluorene [Equation (24)], 1.4-Methanol 8-Methyl 1, 4, 4a, 9a-Tetrahydrofrenolene, 1, 4 One methanol 8 — Black mouth 1, 4, 4a, 9 a — Tetrahydrofluorene, 1, 4 — Metano 8 — Bromo 1, 4, 4 a, 9 a — 1,4-metano-1,4,4a, 9a, such as tetrahydrofluorene, etc. —Tetrahydrofolenolen, 1,4-metano-1, 4, 4 a, 9 a — Tetrahydridene dibenzofuranones; 1, 4 — Metanoichi 1,4,4a, 9a—Tetrahydrocarbazole, 1,4-metanone 91-vinyl-1,4, 4a, 9a — 1, 4 such as tetrahydrocarbazole, etc. 1, 4, 4, 4a, 9a — Tetrahydropower compounds; 1,4,4,4a, 5,10,10a — 1,4,1 meta such as hexahydroanthracene (formula (25)) Nos 1, 4, 4a, 5, 10 and 10a —hexahydranthranes; 7, 10 —Metano 6b, 7,10, 1Oa — Tetra Compounds obtained by further adding cyclopentadiene to (hydrophenolenolansane); (cyclopentagen-acenaphthylene adduct) [Formula (26)], 11, 12 - Ben zone - penta sheet click b [6, 5, 1, l 3 '6 0 2.' 7 0 9 '13.] - 4 - pentadecene [formula (2 7)], 1 1, 1 2 - base down Zope te shea click b [6, 6, 1, 1 ^{3 '6} 0 ^{2.' 7} 0 ^{9 '14.]} one 4 - to Kisadese emissions [formula (28)], 1 4 , 1 5 - base down zone - hepta consequent b ^{[8. 7. 0. I 2 '9} I 4 · 7 1 "· 17 0 3...' 8 0 12 · 16.] - 5 - Ei co Se emissions [Formula (29)], cyclopentagen-l-acenaphthylene adduct [Formula (30)] and the like can be mentioned.

 These aromatic ring-containing norbornane-based monomers include alkyl, alkylidene, and alkenyl-substituted derivatives, and halogen, hydroxyl, and ester groups of these substituted or unsubstituted compounds, in addition to the above compound examples. For example, polar substituents such as an alkyl ester group), an alkoxy group, a cyano group, an amide group, an imido group, and a silyl group may be used.

 Examples of the aromatic vinyl compound include styrene, α-methylstyrene, ο—methinorestylene, ρ—methylstyrene, 1,3-dimethylstyrene, vinylna Examples include phthalene.

These aromatic ring-containing monomers can be used alone or in combination of two or more. The content (bonding amount) of the aromatic ring-containing monomer in the aromatic ring-containing norbornene-based polymer is appropriately selected according to the purpose of use, but is usually 10% by weight or more, preferably 10% by weight or more. It is at least 30% by weight, more preferably at least 50% by weight. By including the aromatic ring-containing monomer unit, the dispersibility of various compounding agents is highly improved.

 Other norbornane-based monomers containing no aromatic ring include, for example, Japanese Patent Application Laid-Open Nos. 2-222744, 2-276428, and 8-88. A known monomer disclosed in, for example, Japanese Patent Publication No. 722010 can be used. The norbornane-based monomer containing no aromatic ring is typically a compound represented by the following formula (II).

In the formula (II), the meaning of each symbol is as follows.

n: 0 or 1

P: 0 or a positive integer.

q: It is 0 or 1.

 R! R: each independently represents a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, an ester group (eg, an alkyl ester group), a cyano group, an amide group, an imido group, or a silyl group. And a hydrocarbon group substituted with a polar group (halogen atom, alkoxy group, hydroxyl group, ester group, cyano group, amide group, imido group, or silyl group).

R _{A to} R _B independently represent a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, an ester group (eg, an alkyl ester group), a cyano group, an amide group, an imido group, and a silyl group. And polar groups (halogen It is selected from a hydrocarbon group substituted by an atom, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amide group, an imido group, or a silyl group. In formula (II), R ₁₅ ~R _l8 is rather good also form a monocyclic or polycyclic bonded to each other, and monocyclic or polycyclic This also have a double bond Good. In the R ₁₆ and R _l6, or the R ₁₇ and R _ie may form a alkylene re den group. When q is 0, each bond is combined to form a 5-membered ring.

 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms; and 2 to 20 carbon atoms. Preferably 2 to 10, more preferably 2 to 6 alkenyl groups; having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 6 alkynyl groups A cycloalkyl group having 3 to 15 carbon atoms, preferably 3 to 8 carbon atoms, more preferably 5 to 6 carbon atoms; and 6 to 20 carbon atoms, preferably 6 to 16 carbon atoms. And more preferably 6 to 10 aromatic hydrocarbon groups; and the like. Examples of the hydrocarbon group substituted with a polar group include a halogenated alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Can be.

 Examples of the norbornene-based monomer having no aromatic ring include norbornane, its alkyl, alkylidene, aromatic-substituted derivatives, and halogen or hydroxyl group of these substituted or unsubstituted norbornene. Examples of the substituent include polar groups such as a ester group, an alkoxy group, a cyano group, an amido group, an imido group, and a silyl group.

More specifically, examples of norbornane-based monomers having no aromatic ring include, for example, 2-norbornane [that is, bicyclo [2.2.1]]. Pt 1 2 — ene), 5 — methyl 1 2 — norebornane, 5, 6 — dimethyl 1 2 — norbornane, 5 — ethyl 1 2 — norbornane, 5 — butyl 1 2 — Norbornane, 5 — ethylidene-1 2 — Norbornane, 5 — Metika Norrebonisole 2 — Norrebornine, 5 — Ciano 1 2 — Norbornene, 5 — Methinole 5 — Methoxyka Noreponinole 2 — Norbornane, 5 — Hexinoleone 2 — Nozolebornane, 5 — Oksylvolune 2 — Nozolebolne, 5 — Oktadecylous 2 — Norbornane No.

 Another specific example of a norbornane-based monomer having no aromatic ring is a monomer having a structure in which norbornane is added with one or more cycle-opening pentangens. Derivatives and substitutes similar to those described above, and more specifically, for example, 1,4: 5,8—dimethanol 1,2,3,4,4a, 5,8,8a-2 , 3 — cyclopentane dinonaphthalene, 6 — methyl 1,4: 5,8 — dimethano 1, 4,4a, 5,6,7,8,8 a — Octahydronaphthalene, 1,4: 5,10: 6,9 Trimetano 1,2,3,4,4a, 5,5a, 6 , 9, 9a, 10, 10 a-Dodecahydro 2,3 — Cyclopentadienenoanthracene, etc .; polycyclic, which is a multimer of cyclopententagen Monomers of the structure, derivatives and substitutions similar to those described above, and more specifically, dicyclopentanes Gene, 2, 3-dihydroxycyclopentene and the like; adducts of cyclopentene and tetrahydroidene, etc., and their derivatives and substitutes as described above , More specifically, 1,4-metano-1,4,4a, 4b, 5,8,8a, 9a — octahydrofluorene, 5,8 — 1,2,3,4,4a, 5,8,8a—metahydro 2,3—cyclopentadienonaphthalene, etc .;

Norbornene monomer (aromatic ring-containing and / or other norbornene monomer) in the aromatic ring-containing norbornene polymer The amount (binding amount) is appropriately selected according to the purpose of use, but is usually at least 30% by weight, preferably at least 50% by weight, more preferably at least 70% by weight. If the content of norbornane-based monomer units is too small, properties such as electrical properties, heat resistance, solder resistance, chemical resistance, and mechanical strength may not be sufficient. , Not preferred.

 Examples of vinyl compounds other than aromatic vinyl compounds include, for example, ethylene, propylene, 1-butene, 11-pentene, 11-hexene, 31-methyl-1--1 Butene, 3 — Methinole 1 — Penten, 3 — Methinole 1 Penten, 4 — Methinole 1 Penten, 4 — Methyl 1 1 — Hexen, 4,4 Chinolay 1 — hexene, 4, 4 1 dimethyltin I 1 pentene, 4 1 ethyl 1 1 hexene, 3 — echinolay 1 1 hexene, 1 octene, 1 — decene 1-decadene, 1-tetradecane, 1-hexadecene, 1-year-old octadecene, 1-eicosene, etc. Or α — Orrefin; cyclobutene, cyclopentene, cyclohexene, 3, 4 — dimethinolate cyclo 1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetraten-, 3-methylcyclohexene, 2- (2-methylbutyl) LAHIDRO 4, 7 — METANO 1H — Cycloolefin such as indene; 1, 4 — hexagen; 4 — methyl 1, 4 — hexane Conjugates such as gen, 5—methyl—1, 4—hexagen, and 1,7—octagen. These vinyl compounds can be used alone or in combination of two or more.

 (2) Polymerization method

 The ring-opening polymer or ring-opening copolymer of norbornene-based monomer can be obtained by a known polymerization method.

Ruthenium, rhodium, palladium, ozone Catalyst system comprising a halide, nitrate or acetylacetonate compound of a metal selected from the group consisting of platinum, platinum, platinum, and the like, and a reducing agent; titanium, titanium dioxide, zinoleconium, tungsten A catalyst system comprising a halide or acetylacetonate compound of a metal selected from benzene, and molybdenum, and an organic aluminum compound can be used.

 By adding a third component to the above catalyst system, the polymerization activity and the selectivity of ring-opening polymerization can be increased. Specific examples of the third component include molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound, and the like. Examples include sulfur compounds, halogen-containing compounds, molecular iodine, and other Lewis acids. As the nitrogen-containing compound, an aliphatic or aromatic tertiary amine is preferred, and specific examples thereof include triethylamine, dimethylethylaniline, and tri-n-butylamine. , Pyridine, α-picolin and the like.

The ring-opening (co) polymerization is possible without using a solvent, but is preferably carried out in an inert organic solvent. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene; η-pentane, hexane, heptane, and other aliphatic hydrocarbons; cyclohexane; Which alicyclic hydrocarbons; halogenated hydrocarbons such as styrene dichloride, dichloroethane, dichloroethylene, tetrachlorethane, chlorobenzene, dichlorobenzene and trichlorobenzene; No. The polymerization temperature is usually in the range of —50 to 100, preferably —30 to 80, more preferably 120 to 60, and the polymerization pressure is ^{Usually, 0~ 5 0 k gZ cm 2} , is preferred properly in the range of 0~ ² 0 kg / cm 2.

Norbornene monomer and aromatic vinyl compound and / or aromatic In order to produce an addition copolymer with a vinyl compound other than the aromatic vinyl compound, a known method can be employed. Specifically, for example, a vanadium compound and an organic aluminum compound, which are soluble in a solvent or a norbornene monomer, in a hydrocarbon solvent or in the absence of a solvent in a hydrocarbon solvent, preferably An example is a method of copolymerizing in the presence of a catalyst system comprising a halogen-containing organic aluminum compound. Examples of the hydrocarbon catalyst include aliphatic hydrocarbons such as hexane, heptane, octane and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Aromatic hydrocarbons such as benzene, toluene and xylene; and the like.

The polymerization temperature is usually in the range of —50 to 100 ° C, preferably —30 to 80 ° C, more preferably 120 to 60 ° C. The polymerization pressure is usually in the range of 0 to 50 kg Z cm ² , preferably 0 to 20 kg / cm ² .

 (3) Hydrogenation method

 The hydrogenated product (hydrogenated polymer) of an aromatic ring-containing norbornane-based polymer is obtained by converting an aromatic ring-containing norbornane-based polymer into molecular hydrogen in the presence of a hydrogenated catalyst according to a conventional method. It can be obtained by a hydrogenation method. The aromatic ring-containing norbornane-based polymer to be hydrogenated is often the aforementioned ring-opening polymer or ring-opening copolymer having a carbon-carbon double bond (unsaturated bond) in the main chain structure. is there.

As the hydrogenation catalyst, a catalyst system composed of a combination of a transition metal compound and an alkyl metal compound, for example, cobalt triethylamine acetate, nickel acetylase toner toner triisobutyl aluminum, titanonium Sensory chloride / n — butyllithium, zircono Sensory chloride / sec — butyllithium, tetrabutyl toxititane Combinations of dimethylmagnesium and the like can be mentioned.

 The hydrogenation reaction is usually performed in an inert organic solvent. As the organic solvent, a hydrocarbon-based solvent is preferred, and a cyclic hydrocarbon-based solvent is more preferred, because of excellent solubility of the generated hydrogenated product. Examples of such hydrocarbon solvents include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as n-pentane and hexane; cyclohexane, decalin and the like. Alicyclic hydrocarbons: ethers such as tetrahydrofuran and ethyl glycol dimethyl ether; and the like, and two or more of these can be used in combination. Usually, it is the same as the polymerization reaction solvent, and the hydrogenation catalyst may be added to the polymerization reaction solution as it is to cause the reaction.

 The aromatic ring-containing norbornene-based polymer used in the present invention preferably has high weather resistance and light deterioration resistance. Therefore, the ring-opened (co) polymer has an unsaturated bond in the main chain structure. Usually, it is preferably at least 95%, preferably at least 98%, more preferably at least 99% saturated. If there is a non-conjugated carbon-carbon double bond in the side chain, it is also preferably highly saturated. However, in order to achieve the object of the present invention, the aromatic ring structure is usually at least 10%, preferably at least 20%, more preferably at least 30%, particularly preferably at least 4%. It is desirable that 0% or more remain. Unsaturated bonds in the aromatic ring structure can be recognized and distinguished from unsaturated bonds in the main chain structure and non-conjugated unsaturated bonds in the side chain structure by 1H-NMR analysis.

For hydrogenation mainly at carbon-carbon double bonds in the main chain structure, it is usually — 20 to 120 ° C, preferably 0 to: 100 ° C, more preferably. At a temperature of 20 to 80 ° C, usually 0.1 l SO kg Z cm ² , preferably 0.5 to 30 kg / cm ² , more preferably l to 20 kg gZcm ^Two It is desirable to carry out the hydrogenation reaction at this hydrogen pressure. Due to this hydrogenation reaction, when a non-conjugated carbon-carbon double bond exists in the side chain, hydrogenation is performed in the same manner.

 (4) Aroborn-containing norbornane-based polymer

 The molecular weight of the aromatic ring-containing norbornane-based polymer used in the present invention is as follows. One Measuring Chromatography

The number average molecular weight (Mn) in terms of polystyrene by the (GPC) method is 50,000 to 500,000, preferably 1, 0000 to 100,000. , More preferably in the range of 2,000 to 500,000, and most preferably in the range of 5,000 to 35,000.

 If the number average molecular weight of the aromatic ring-containing norbornene-based polymer is too small, the mechanical strength is not sufficient. Conversely, if the number average molecular weight is too large, the dispersibility of the compounding agent is not sufficient, and both are favorable. Absent.

 The molecular weight distribution (M w / n) of the aromatic ring-containing norbornane polymer used in the present invention is usually 4 or less, preferably 3 or less, more preferably 2 or less. The mechanical strength can be increased by reducing the molecular weight distribution.

 The aromatic ring-containing norbornane-based polymer can be prepared by a method known in Japanese Unexamined Patent Publication (Kokai) No. 3-92553, such as a, / S-unsaturated carboxylic acid, a derivative thereof, and a styrene-based polymer. It may be modified using a hydrocarbon, an organic gayne compound having an olefinic unsaturated bond and a hydrolyzable group, an unsaturated epoxy monomer, or the like. As the modifier, unsaturated carboxylic acids such as maleic anhydride, and derivatives of such acid anhydrides or alkyl esters of unsaturated carboxylic acids are preferred.

Crosslinkable polymer composition

The composition of the present invention has a number average molecular weight (Mn) of 500 to 500,000. A crosslinkable polymer composition containing the aromatic ring-containing norbornane-based polymer and a crosslinking agent as essential components.

 The method for crosslinking the crosslinkable polymer composition of the present invention is not particularly limited. For example, the crosslinking can be performed using heat, light, radiation, or the like. Is selected as appropriate. When an aromatic ring-containing norbornane-based polymer is used as the thermoplastic norbornane-based resin, its dispersibility is improved even with various crosslinking agents.

 The crosslinkable polymer composition of the present invention may contain, in addition to a crosslinking agent, a crosslinking aid, a thermosetting resin, a flame retardant, other compounding agents, a solvent, and the like, if desired. .

 (1) Crosslinking agent

 The crosslinking agent is not particularly limited, and examples thereof include an organic peroxide, a photocrosslinking agent that generates radicals by light, and a thermosetting crosslinking agent that exerts its ability by heating. Can be mentioned.

Organic peroxides include, for example, ketone peroxides such as methylethyl ketone peroxide and cyclohexanone peroxide; 1,11 bis (t- Butyloxy) 3,3,5—Trimethyltincyclohexane, 2,2—Bisoxy (t-butylperoxy) butane, etc .; ,. Oxides, 2, 5 — dimethylhexane 1, 2, 5 — dihydronox, such as dihydroxide peroxide, ⁰ — oxides; dicumyl peroxide, 2, 5 — dimethyl 1, 2, 5 — Di (t-butylperoxy) hexine-13, a, a 'Bis (t-butylno, .oxy-1 m — isopropyl) Dialkyl peroxides such as benzene: octa Diaryloxides such as ylperoxide and isobutyrylperoxide; and peroxyesters such as carboxylic dicarbonate. Among these However, from the performance of the cured resin, dialkyl peroxide is preferred, and the type of the alkyl group may be changed depending on the molding temperature.

 Examples of the photocrosslinking agent that generates a radical by light include benzoquinethyl ether, benzoinquinobutyl ether and other benzoinquinol ether-based conjugates; Benzophenone, benzophenone-based compounds such as dibenzobenzophenone; benzyl-based compounds such as dibenzyl and benzylmethyl ketone; 2, 2—Jetoxyacetphenone, 2—Hydroxy 2—Methyl propionone, 4 —Isopropyl 1 2—Hyd mouth 1—Methyl propionone, 1, 1-Cycloacetophenone, 2, 2-Jexoxyacetophenone, 4'-Phenoxy2, 2-Dichloroacetophenone, etc. Tovonon-based compound Thioxanthonone, 2—methylthioxanthone, 2—isopropylthioxanthone, and other thioxanthonone compounds; 2—ethylanthraquinone; Anthraquinone-based compounds such as anthraquinone and naphthoquinone; 2 — hydroxy — 2 — methylpropionoff; Non-propionic X-non-compounds such as nonan; organic acid gold salts such as cobalt octanoate, cobalt cobalt naphthenate, manganese octanoate and manganese naphthenate; Photocrosslinking agents can be mentioned.

Examples of thermosetting crosslinking agents that exhibit their ability by heating include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, bisazides, and acid anhydrides. , Dicarboxylic acid, polyhydric phenol, polyamide, diiso cyanate, and the like. More specifically, examples of the thermosetting crosslinking agent include, for example, hexamethylenediamine, triethylenetetramine, diethylethylenetriamine, tetraethylene. Aliphatic ports such as lempentamine Li A Mi emissions; Jia Mi Bruno shea click b to hexa down, 3 (4), 8 (9) Single-bis (§ Mi Bruno methylation) Application Benefits shea click b [5, 2, 1, 0 ^{2 '6]} Decane; 1, 3 — (diaminomethyl) cyclohexane, mensendiamine, isophoronediamine, N—aminoethylpiperazine, bis (4-amino-3-cyclohexyl) methane, bis (41-aminocyclohexyl) methane, and other aliphatic polyamines; 4, 4 '-diamino diphenyl ethereolene, 4, 4'-diamino diphenyle acetane, a, '-bis (4-diamino diphenylene 1, 3-diisopropirbe A'-bis (4-aminopropyl) 1,4-diisopropylbenzene, 4,4'-diaminodiphenylsulfur , Aromatic polyamines such as metaphenylenediamine; 4,4'-bisazidobenzaru (4-methinole) cyclohexanone, 4,4 'ー Diazidocanolecon, 2,6 bis (4 '1 azidobenzar) cyclohexanone, 2, 6 — bis (4' 1 azidobenzal) 1 4 — methinolac Bis-azide such as rohexanone, 4,4'-diazidodiphenylsulfone, 4,4'-diazidodiphenylmethane, 2,2'-diazidostilbene Phthalic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, nadic anhydride, 1,2-cyclohexane dicarbohydrate Acid anhydride, maleic anhydride-modified polypropylene, maleic anhydride-modified cyclic olefin resin, etc. Acid anhydrides; fumaric acid, phthalic acid, maleic acid, trimellitic acid, and dicarboxylic acids such as hymic acid; phenolic boric resin, cresolnoic acid Polyvalent phenols such as boric resin; Nylon-16, Nylon-66, Nylon-610, Nylon-11, Nylon-6 11 , Nylon 1-12, Nylon 1 46, methoxymethylated polyamide, polyhexamethylene diamine terephthalamide, polyhexamethyl Polyamide, such as rain soft amide And the like; diisocyanates such as hexamethylene diisocyanate and tridenzene diisocyanate; and the like. These may be used alone or as a mixture of two or more. Among these, aliphatic polyamines and aromatic polyamines are preferred because they are easily dispersed uniformly.

 These cross-linking agents can be used alone or in combination of two or more. The mixing ratio of the crosslinking agent is usually from 0.01 to 30 parts by weight, preferably from 0.001 to 15 parts by weight, based on 100 parts by weight of the aromatic ring-containing norbornene-based polymer. Heavy! : Part, more preferably 0.1 to 10 parts by weight, most preferably 0.5 to 5 parts by weight. When the compounding ratio of the crosslinking agent is in this range, the properties such as cross-linking property and electric properties, chemical resistance, and water resistance of the cross-linked product are highly balanced and are suitable.

 (2) Crosslinking aid

 In the present invention, the use of a crosslinking aid is preferable because the crosslinking property and the dispersibility of the compounding agent can be further enhanced.

The crosslinking aid used in the present invention is not particularly limited, and for example, a polyfunctional monomer, a photosensitizer, a curing accelerator and the like can be used according to the type of each crosslinking agent. More specifically, known crosslinking aids such as those disclosed in Japanese Patent Application Laid-Open No. Sho 62-34924 may be used, such as quinone dioxime, benzoquinone dioxime, and the like. p—Oxim, such as dinitrophenol; dinitro-type crosslinking aid; N, N—m — Murine-mid crosslinking, such as fuirylene bismuthamide Auxiliaries; aryl cross-linking assistants such as diaryl phthalate, trilinolecinurate, and trilinoleocyanate; ethylene glycol dimethacrylate, Methacrylate-based crosslinking aids such as trimethylolpropane trimethacrylate; vinyl Vinyl-based crosslinking aids such as rutoluene, ethylvinylbenzene, divinylbenzene, and the like; and the like. These crosslinking aids are mainly used in combination with an organic peroxide or a photocrosslinking agent. Of these, aryl crosslinkers and methacrylate crosslinkers are preferred because they are easily dispersed uniformly.

 Examples of the curing accelerator used in combination with the thermosetting crosslinking agent include, for example, pyridin, pentanoresinethylamine, triethanolanoreamin, trietinoreamin, tributylamine. , Tribenzilamine, dimethinoleformamide, imidazoles, and other amines to control the curing rate and improve the efficiency of the crosslinking reaction. It is added for the purpose of doing.

 The amount of the crosslinking aid to be added is appropriately selected depending on the type of the crosslinking agent, but is usually 0.1 to 10 parts by weight, preferably 0.2 to 10 parts by weight, per part by weight of the crosslinking agent. 5 parts by weight. If the amount of the crosslinking aid is too small, crosslinking is unlikely to occur. Conversely, if the amount is too large, the electrical properties, water resistance, moisture resistance, etc. of the crosslinked resin may be reduced.

 (3) Thermosetting resin

 In the crosslinkable polymer composition of the present invention, it is preferable to add a thermosetting resin such as an epoxy resin because the adhesive strength of the laminate is highly improved.

 The thermosetting resin is not particularly limited, and generally used ones can be used. Examples thereof include epoxy resins, urea resins, melanin resins, phenol resins, and unsaturated polyester resins. And a tellurium resin. Of these, epoxy resins are preferred.

Thermosetting resins usually consist of a low molecular weight raw material and a curing agent. For example, in the case of epoxy resin, it consists of an epoxy compound and various curing agents Is done.

The epoxy compound is not particularly limited as long as it is a compound having an epoxy group in a molecule, and includes a bisphenol type, a novolak type, a fl cyclic type, a heterocyclic type, and a glycerol type. Examples include compounds used as epoxy resins such as phosphorus type and dicyclopentadiene type. Among them, a halogenated bisphenol type epoxy compound represented by the formula (E1) is preferable.

(In the formula, X is a halogen atom, R is a divalent hydrocarbon group, m is an integer of 1 to 3, and n is 0 or an integer of 1 or more.)

 In the epoxy compound of the formula (E 1), those in which m is all 2, n is substantially 0, a halogen atom X is a bromine atom, and R is an isopropylidene group are preferred. New

 Further, a novolak type epoxy compound represented by the formula (E2) is preferably used.

(E2)

(In the formula, R ′ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and p is 0 or an integer of 1 or more.)

In the epoxy compound of the formula (E 2), it is preferable that the average value of p is 0 to 5 and R ′ is a hydrogen atom or a methyl group. These epoxy compounds can be used alone or in combination of two or more. When importance is placed on flame retardancy, the bisphenol type epoxy compound of the formula (E1) is preferred, and when heat resistance and chemical resistance are to be improved, the formula (E2) Novolak type epoxy compounds are preferred. As a specific example of the epoxy compound of the formula (E1), a compound represented by the formula (E3) can be mentioned.

As the halogenated bisphenol-type epoxy compound represented by the formula (E3), for example, those having a Br content of 20% by weight or 50% by weight are commercially available. Have been.

 Examples of the curing agent for the epoxy resin include, for example, an amine compound, an imidazole compound, a nitrogen-containing heterocyclic compound such as diazabicyclodecene, an organic phosphine, and an organic boron complex. And quaternary ammonium compounds, quaternary phosphoniums and the like.

 The mixing ratio of the thermosetting resin is usually 3 to 150 parts by weight, preferably 10 to 140 parts by weight, more preferably 100 to 100 parts by weight of the aromatic ring-containing norbornene-based polymer. The amount is 15 to 120 parts by weight.

 (4) Flame retardant

 There is no particular limitation on the flame retardant used in the present invention, but those which do not decompose, modify or degrade with the crosslinking agent are preferred.

Various chlorinated and bromine-based flame retardants can be used as the lipogen-based flame retardant, but the flame retardant effect, heat resistance during molding, dispersibility in the polymer, polymer Hexabromobenzene, pentabromoethylbenzen, hexibopen mobilifnil, de Cabromo diphenyl, Hexa-sub-modulofluxide, Octapromo-modulofluxide, Dekabu-flux modifoxy-fluxide, Pentabu-flux microcyclohexane, Tetrabromo Bisphenol 8 and its derivatives [eg, tetrabromobisphenol A—bis (hydroxyxethyl ether), tetrabromobisphenol A—bis (2,3— Jib mouth mopro propyl ether), tetrabromobisphenol A—bis (promoethyl), tetrabromobisphenol A—bis (aryl ether), etc. Bromobisphenol S and derivatives thereof [eg, tetrabromobisphenol S—bis (hydroxixethyl), tetrabromobis Phenol S-bis (2,3-dibromopropyl ether), etc.), tetrabromobromophthalic anhydride, and derivatives thereof [eg, tetrabromophthalimide, ethylene bis Tribromophthalimid, etc.), ethylenebis (5, 6-dibromomonobornane-1,2,3—dicarboximid), tris (2,3—dibromopropyl-1) iso Cyanurate, adduct of Diels-Alder reaction of hexacyclocyclopentagen, trib mouth ninoleregisyl ether, trib mouth morphine crelate , Ethylene bistribromophenyl ether, Ethylene bispentabromophenyl ether, Tetradecab modifoxy benzene, Brominated polystyrene , Brominated polyphenylene oxide, brominated epoxy resin, brominated polycarbonate, polypentabromobenzyl acrylate, octabutamonaphthalene, hexabole Preference is given to cyclodecane, bis (triphenylamine) fumaric acid, N-methylhexadiphenyldiphenylamine and the like.

Among the flame retardants used in the present invention, particularly preferred flame retardants will be described with reference to chemical formulas. Uniform dispersibility in polymer composition, crosslinking In the reaction step, compounds represented by the following formulas (N1) to (N9) are preferable as flame retardants that are not easily decomposed, denatured, and altered by a crosslinking agent such as an organic peroxide. It can be mentioned as a thing.

 (In the formula, n is 0 or an integer of 1 or more.)

(Where n is an integer of 0 or 1 or more, and ml to m4 are integers of 1 or more, and l ≤ ml ≤ 5, 1 ≤ m 2 ≤ 4, 1 ≤ m 3 ≤ 4, 1 ≤ πι 4 ≤ 5, preferably 2 ≤ ml 4, 5 ≤ m 2 ≤ 3, 2 ≤ m 3 ≤ 3, 2 ≤ m 4 ≤ 4, especially preferably ml = 3, m 2 = 2, m 3 = 2, m 4 = 3.)

(Where n is an integer of 0 or 1 or more, ml to m 6 are integers of 1 or more, and l ≤ ml ≤ 5, 1 ≤ m 2 ≤ 5, 1 ≤ m 3 ≤ 4 , 1 ≤ m 4 ≤ 4. 1 ≤ m 5 ≤ 5, l ≤ m 6 ≤ 5 and preferably 2

≤ m 1 ≤ 4 ^ 2 ≤ m 2 ≤ 4.2 .2 ≤ m 3 ≤ 3, 2 ≤ m 4 ≤ 3.2 ≤ m 5 ≤ 3.2 .2 ≤ 111 6 ≤ 4, especially preferred 111 1 = 3, m2 = 2, m3 = 2, m4 = 2, m5 = 3, m6 = 3. )

(The compound of formula N 7 is a specific example of a compound of formula N 5

Br

(N8)

(The compound of formula N8 is a specific example of a compound of formula N6.)

The halogenated bisphenol-type epoxy compound in the thermosetting resin is also a kind of flame retardant. The compounding ratio of the flame retardant is usually 3 to 150 parts by weight, preferably 10 to 140 parts by weight, more preferably 100 to 140 parts by weight, based on 100 parts by weight of the aromatic ring-containing norbornane polymer. It is preferably 15 to 120 parts by weight.

 In order to more effectively exhibit the flame retardant effect of the flame retardant, as a flame retardant aid, for example, antimony trioxide, antimony pentoxide, sodium antimonate, Antimony flame retardant aids such as antimony chloride can be used. These flame retardant auxiliaries are usually used in a proportion of 1 to 30 parts by weight, preferably 2 to 20 parts by weight, per 100 parts by weight of the flame retardant.

 (5) Other compounding agents

 The crosslinkable polymer composition of the present invention may contain, if necessary, a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an anti-violation agent, a lubricant, a dye, a pigment, Various compounding agents such as natural oils, synthetic oils, waxes, organic or inorganic fillers can be added in appropriate amounts.

Specifically, for example, tetrakis [methylen-3 (3.5-di-t-butynole 4-hydroxyhydroxy) propionate] methane, β— (3,5— Di-t-butyl-4-hydroxypropyl) propionic acid alkyl ester, 2, 2'-diazamidbis [ethyl-3 (3,5—di-t-butyl-4-hydroxyphenyl) ) Probionate] and other phenolic antioxidants; trisnonylphenylphosphite, tris (2,4-di-t-brenylphenyl) phosphite, Phosphorus stabilizers such as lys (2,4—g-t-butylbenzyl) phosphite; zinc stearate, calcium stearate, and 12—calcium hydroxycarboxylate Fatty acid metal salt; glycerine monoester Les over door, grayed Li cell Li Nmono La cormorant rate, grayed Li cell Li down Jisutea rate, Bae Ntae re-scan Li door Rumono steer rate, Pentae re-scan Li Polyhydric alcohol fatty acid esters such as tonorestearate, pentaerythritol and tristearate: synthetic hydrotalcite; amine-based antistatic agents; silane coupling agents, Coupling agents such as titanate coupling agents, aluminum-based coupling agents, zirconate coupling agents; plasticizers; coloring agents such as pigments and dyes; Can be mentioned.

 As the organic or inorganic filler, various fillers such as powder, granules, and arrowheads can be used. Specifically, as the filler, for example, silica, gay alga earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, basic magnesium carbonate, Dolomite, sulfated calcium, potassium titanate, barium sulfate, sulfite, talc, creed, my strength, asbestos, glass fibers, glass flakes, glass beads, Calcium gaymate, Monmorillonite, Bentonite, Graphite, Aluminum powder, Molybdenum sulfide, Boron fiber, Silicon carbide fiber, Polyethylene fiber , Polypropylene fibers, polyester fibers, and polyamide fibers.

 For the purpose of adjusting physical properties such as mechanical properties within the range not impairing the object of the present invention, the crosslinkable polymer composition is added to a polycarbonate, a polystyrene, a polyphenylene sulfone, or the like. Different kinds of thermoplastic resins such as sulfide, polyetherimide, polyester, polyamide, polyacrylate, and polysulfone can be blended.

 These compounding agents can be used alone or in combination of two or more. The mixing ratio can be appropriately determined according to each function and purpose of use.

(6) Solvent In the present invention, an aromatic ring-containing norbornane-based polymer is dissolved in a solvent to prepare an impregnating solution for prepreg, or a sheet (including a film) is produced by a solution casting method. You can do it.

 In the case of dissolving an aromatic ring-containing norbornane-based polymer using a solvent as described above, the solvent used may be, for example, an aromatic hydrocarbon such as toluene, xylene, or ethylbenzene. N-pentane, hexane, heptane and other aliphatic hydrocarbons; cyclohexane and other alicyclic hydrocarbons; cyclobenzene benzene, dichlorobenzen, trichloronoben Halogenated hydrocarbons such as benzene; and the like.

 The solvent is used in an amount sufficient to uniformly dissolve or disperse the aromatic ring-containing norbornene-based polymer, the crosslinking agent, and, if necessary, each component.

Molded body, pre-pre-spreader, sperm body

 In the present invention, the crosslinkable polymer composition is molded and then crosslinked to obtain a crosslinkable molded article. The method of molding the crosslinkable polymer composition is either dissolved in a solvent or molded so as not to cause deterioration in moldability due to crosslinking in the course of molding, or a crosslinking reaction does not occur. Melting and molding at a temperature where the temperature or crosslinking rate is sufficiently slow. Specifically, the crosslinkable polymer composition dissolved in a solvent is cast on a flat support, and the solvent is removed, and then molded into a sheet or impregnated into a substrate to be molded.

 (1) Pre-preg

The pre-preda, which is one of the specific examples of the cross-linked molded article of the present invention, comprises a norbornene-based polymer, a cross-linking agent, and, if necessary, a solvent such as toluene, cyclohexane, or xylene. It is manufactured by uniformly dissolving or dispersing various compounding agents, then impregnating the reinforcing base material, and then drying to remove the solvent. Generally, the pre-reader is about 50 to 500 m. Thickness is preferred.

 As the solvent, those described above can be used. The proportion of the solvent used is usually 1 to 90% by weight of solid content, preferably 5 to 85% by weight, more preferably 10 to 80% by weight, and most preferably 20 to 8% by weight. Adjusted to be 0% by weight.

 As the reinforcing base material, for example, a paper base material (for example, a lint paper, a craft paper), a glass base material (for example, a glass cross, a glass mat, a glass paper quartz) Fibers) and synthetic resin fiber base materials (for example, polyester fibers and aramid fibers) can be used. These reinforcing base materials may be surface-treated with a treating agent such as a silane coupling agent. These reinforcing base materials can be used alone or in combination of two or more.

 The impregnation ratio of the crosslinkable polymer composition to the reinforcing base material is appropriately selected according to the purpose of use, but is usually 1 to 90% by weight, preferably 10 to 80% by weight, based on the total amount of the prepreg. % By weight, more preferably in the range of 20 to 70% by weight.

 (2) Sheet

A method for producing a sheet, which is one of the specific examples of the crosslinkable molded article of the present invention, is not particularly limited, but generally, a casting method is used. Specifically, for example, the crosslinkable polymer composition of the present invention is dissolved in a solvent such as toluene, xylene, or cyclohexane so as to have a solid content concentration of about 5 to 50% by weight. Alternatively, the sheet is cast or coated on the smooth surface of the support, the solvent is removed by drying or the like, and the sheet is obtained by peeling off the smooth surface. When removing the solvent by drying, it is preferable to select a method that does not cause foaming due to rapid drying.For example, after evaporating the solvent at a low temperature to some extent, And increase the solvent It may be volatilized.

 As the support, a mirror-finished metal plate, a resin carrier film, or the like can be used. When using a resin carrier film, determine the solvent to be used and the drying conditions while paying attention to the solvent resistance and heat resistance of the resin material.

 Sheets obtained by the casting method are generally 1! It has a thickness of about lmm. These sheets can be used as an interlayer insulating film, a film for forming a moisture-proof layer, etc. by crosslinking. Further, it can be used for manufacturing a laminate described below.

 (3) Laminate

 A laminate such as a laminate, which is a specific example of a cross-linked molded article obtained by using the cross-linkable polymer composition of the present invention, comprises the above-described prepreg and the number of sheets of uncross-linked or uncross-linked. The required thickness is obtained by stacking, heat-compression molding, crosslinking and heat-sealing. When the laminate is a circuit board (for example, a printed wiring board, a multi-layer printed wiring board, a high-density wiring board, etc.), generally, a plurality of prepregs are stacked and heated and compression-molded to form an insulating layer. I do. The pre-preda and the sheet may be combined and laminated, or depending on the field of use, a plurality of sheets alone may be laminated.

When the laminate is used as a circuit board, for example, a wiring conductive layer (metal layer) made of gold foil or the like is further laminated, or the circuit is formed by etching the metal layer surface. Form. The wiring conductive layer may be laminated not only on the outer surface (one surface or both surfaces) of the finished laminate, but also on the inside of the laminate depending on the purpose of forming an inner layer circuit or the like. . In order to prevent warpage during secondary processing such as etching, prepreg and nose or sheet are combined vertically and laminated. I prefer to do it.

In order to obtain a laminate, for example, the surface of the required number of stacked pre-predaders and sheets or sheets is heated to a heat-sealing temperature or higher corresponding to the norbornane resin used, usually 150 to 300. Heat to about 30 to 80 kgf Z cm ² , and crosslink and heat fuse between each layer to obtain a laminate. In addition to gold foil lamination, other methods of forming a metal layer on the laminate include vapor deposition, electrical plating, sputter, ion plating, spraying, and layering. No. Commonly used metals include copper, nigel, tin, silver, gold, aluminum, platinum, titanium, zinc, and chromium. Copper is most frequently used on circuit boards

 (4) Crosslinking

 In the present invention, a crosslinked molded article is obtained by heating the crosslinkable molded article alone or by laminating it at a certain temperature or higher. The temperature at which the cross-linking reaction occurs is mainly determined by the combination of the organic peroxide and the crosslinking assistant, but is usually from 80 to 350 ° C, preferably 120 ° C. Crosslinking is achieved by heating to a temperature of from about 300 ° C to about 300 ° C, more preferably from about 150 ° C to about 250 ° C. The crosslinking time is preferably about 4 times the half-life of the organic peroxide, usually 5 to 120 minutes, more preferably 10 to 90 minutes, and more preferably. Or 20 to 60 minutes. When an optical cross-linking agent is used as a cross-linking agent, it can be cross-linked by light irradiation. When a thermosetting crosslinking agent is used, the crosslinking is carried out by heating to a temperature at which the crosslinking agent exerts its ability. When the crosslinkable molded articles are laminated and crosslinked, heat fusion and crosslinkage occur between each employee, and an integrated crosslinked molded article is obtained. (5) Crosslinked molded body

As the crosslinked molded article of the present invention, a laminated board, a circuit board, an interlayer insulating film, Examples include a film for forming a wet layer.

Crosslinked molded article of the present invention has water absorption 0.0 to ^{3%, 1 0 15 ~ 1 0 17} Ω, the dielectric constant and dielectric loss tangent at 1 MHz, respectively from 2.0 to 2.5, 0 .001 to 0.0007. Therefore, the crosslinked molded article of the present invention is superior in water resistance and electrical properties as compared with the conventional thermosetting resin molded article. On the other hand, the heat resistance of the crosslinked molded article of the present invention is equivalent to that of a conventional thermosetting resin molded article. For example, even if 260.degree. Solder is brought into contact with the laminate obtained by laminating the copper foil of the present invention for 30 seconds, no abnormality such as peeling of the copper foil or occurrence of flaking is observed.

 The crosslinked molded article of the present invention is preferably one having excellent flame retardancy, specifically, one having a flame retardancy of V-2 or better in the UL-94 standard. Those exhibiting a flame retardancy of —1 or V-0 are more preferred, and those exhibiting a flame retardancy of V-0 are particularly preferred. In order to obtain such a flame-retardant cross-linked molded article, a cross-linkable resin composition containing the above-described flame retardant may be used. Examples>

 Hereinafter, the present invention will be described specifically with reference to Synthesis Examples, Examples, and Comparative Examples. The methods for measuring physical properties are as follows.

 (1) The glass transfer temperature was measured by the differential scanning calorimetry (DSC method).

(2) Unless otherwise specified, molecular weights were measured as gel-no using toluene as a solvent, and as polystyrene equivalents by the ^0- Measion's chromatography (GPC) method. .

(3) The degree of hydrogenation of unconjugated carbon-carbon double bonds (unsaturated bonds) in the main chain and side chains was measured by —NMR. (4) The copolymerization ratio was measured by 'H-NMR.

 (5) Flame retardancy was measured according to US UL-94 test standard.

 (6) The dielectric constant, dielectric loss tangent, and water absorption at 1 MHz were measured according to JIS C6481.

 (7) The copper foil peel strength was determined by taking a test piece of width 100 mm and width 100 mm from the laminate, making a parallel cut of width 10 mm on the copper foil surface, and then applying a tensile tester. The copper foil was peeled off continuously at a speed of 5 O mmZ in the direction perpendicular to the surface, and the lowest value of stress at that time was shown.

 (8) Toluene resistance was measured by cutting out a 25 mm square piece of copper from which the copper foil had been removed, boiling it in toluene for 5 minutes, and visually observing the change in appearance. The evaluation was based on the following criteria.

：: No change in appearance,

X: Change in appearance.

 (9) The hang resistance was measured by cutting the laminate from which the copper foil had been removed into 25 mm squares, floating them in a 260 deg. Solder bath for 120 seconds, and then visually examining the change in appearance. And evaluated according to the following criteria.

：: No change in appearance,

X: Change in appearance.

 [Synthesis example 1]

1,4-Methanol 1,4,4a, 9a—Tetrahydrofluorene (hereinafter abbreviated as “MTF”) in a 1-liter flask filled with nitrogen gas g and toluene (120 g), and tris-butylanolamine (0.287 mmo1) and isobutyl alcohol (0.287 mmo1) as polymerization catalysts, and 1,287 mmo (1) as a molecular weight regulator. 5. 75 mmo 1 was added. Next, 0.057 mmol of tungsten hexachloride was added, and the mixture was stirred at 40 ° C. for 5 minutes. After that, 5 g of MTF and hexachloride 0.086 mmol of gungsten was continuously dropped into the system in about 30 minutes. After the completion of the dropwise addition, the mixture was further stirred for 30 minutes to complete the ring-opening polymerization reaction. The obtained polymerization reaction solution was transferred into a 1-liter autoclave, and toluene was added. g was added, followed by a mixture of 0.5 g of nickel acetyl acetate and 5.15 g of a 30% by weight solution of triisobutyl aluminum in toluene. After the inside of the autoclave was replaced with hydrogen gas, the temperature was raised to 80 ° C with stirring. When the temperature was stabilized, the hydrogen gas pressure was increased to 30 kg Z cm ² , and a hydrogenation reaction was performed for 3 hours while replenishing the hydrogen gas consumed in the reaction process. Next, 4.2 g of water and active alumina (surface area: 320 cm ² / g, pore volume: 0.8 cm ³ Zg, average particle size: 15 m; Mizusawa Chemical, Neo Bead) D powder) was added, and the mixture was stirred at 80 ° C. for 1 hour, and the solid content was removed by filtration. The hydrogenated reaction solution thus obtained was poured into 3 liters of isopropyl alcohol to cause precipitation, followed by filtration to collect a hydrogenated polymer. The recovered polymer was dried at 100 ° C. and 1 Torr or less for 48 hours. The obtained hydrogenated polymer (Polymer A) was determined by ¹ H-NMR measurement to have a hydrogenation rate of unsaturated bonds of the main chain of at least 99% and a hydrogenation rate of the benzene ring of almost 0%. It was a white powder having a number average molecular weight (Mn) of 13,200 and a weight average molecular weight (Mw) of 21,700.

 [Synthesis example 2]

1 A ring-opening polymerization reaction and a hydrogen addition reaction were carried out in the same manner as in Synthesis Example 1 except that the amount of hexane used was changed from 5.75 mmol to 3.83 mmo 1. The hydrogenation rate of the unsaturated bond in the chain is over 99%, the hydrogenation rate of the benzene ring is almost 0%, and the number average molecular weight (Mn) A hydrogenated polymer (polymer B) having a force of <17,500 and a weight average molecular weight (Mw) of 29,100 was obtained.

 [Synthesis example 3]

 1 The polymerization reaction and hydrogenation reaction were carried out in the same manner as in Synthesis Example 1 except that the amount of hexane used was changed to 5.75 mmol force and 2.30 mmo1. The hydrogenation rate of the unsaturated bond in the main chain is more than 99%, the hydrogenation rate of the benzene ring is almost 0%, the number average molecular weight (Mn) is 31,200, the weight average molecular weight ( A hydrogenated polymer (polymer C) having Mw) of 55,800 was obtained.

 [Synthesis example 4]

 1 Synthesis was performed except that the amount of hexane used was changed from 5.75 mmol to 2.30 mmo 1 and the reaction temperature in the hydrogenation reaction was changed from 80 ° C to 40. A polymerization reaction and a hydrogenation reaction were carried out in the same manner as in Example 1, and the hydrogenation rate of the unsaturated bond in the main chain was 99% or more, and the hydrogenation rate of the benzene ring was 51%. A hydrogenated polymer (polymer D) having an average molecular weight (Mn) of 28,500 and a weight average molecular weight (Mw) of 51,700 was obtained.

 [Synthesis example 5]

MTF was changed to a monomer mixture of 50% by weight of MTF and 50% by weight of tetracyclododecene (hereinafter abbreviated as “TCD”), and the amount of 1-hexene used was 5.75 mmol Polymerization reaction and hydrogenation reaction were carried out in the same manner as in Synthesis Example 1 except that the amount was changed to 2.30 mmol, and the hydrogenation rate of the unsaturated bond in the main chain was 99% or more. The hydrogenation rate of the benzene ring is almost 0%, the number average molecular weight (Mn) is 27,200, the weight average molecular weight (Mw) is 49, 100, and the MTF Hydrogenated polymer (polymer) in which the copolymerization ratio of TCD and TCD is 50:50 (weight ratio) E).

 [Synthesis example 6]

 MTF is converted to a monomer mixture of 20% by weight of MTF and 80% by weight of methyltetracyclodecene (hereinafter abbreviated as “MTD”), and the amount of used hexane is 11%. Polymerization reaction and hydrogenation reaction were carried out in the same manner as in Synthesis Example 1 except that the hydrogenation rate of unsaturated bonds in the main chain was changed from 5.75 mmol to 2.30 mmol. Above 99%, the hydrogenation rate of the benzene ring is almost 0%, the number average molecular weight (Mn) is 30,300, the weight average molecular weight (Mw) is 53,900, and Thus, a hydrogenated polymer (polymer F) having a copolymerization ratio of MTF and MTD of 20:80 (weight ratio) was obtained.

 [Synthesis example 7]

 The MTF was changed to a monomer mixture of MTF 10% by weight and] VLT D 90% by weight, and the amount of 1-hexene used was 5.75 mmol force, etc. A polymerization reaction and a hydrogenation reaction were carried out in the same manner as in Synthesis Example 1 except that the value was changed to mmo1, and the hydrogenation rate of the unsaturated bond in the main chain was 99% or more, and hydrogen in the benzene ring was obtained. The addition rate is almost 0%, the number average molecular weight (Mn) is 32,400, the weight average molecular weight (Mw) is 57,900, and the copolymerization ratio of MTF and MTD As a result, a hydrogenated polymer (polymer G) having a weight ratio of 10:90 was obtained.

 [Synthesis example 8]

The MTF was changed to a mixed monomer of 50% by weight of 50% by weight of TCD and 50% by weight of TCD, and the amount of 1-hexene used was 5%. A polymerization reaction and a hydrogenation reaction were carried out in the same manner as in Synthesis Example 1 except that the amount was changed from 75 mmol to 2.30 mmol, and the hydrogenation rate of unsaturated bonds in the main chain was 9 9% or more The hydrogenation rate of the benzene ring is almost 0%, the number average molecular weight (Mn) is 29,200, the weight average molecular weight (Mw) is 53,100, and both PNB and TCD A hydrogenated polymer (polymer H) having a polymerization ratio of 50:50 (weight ratio) was obtained.

 [Synthesis example 9]

A polymerization vessel having an internal volume of 1 liter was replaced with nitrogen gas, hexane solution MTF of consequent opening, catalyst and to VO (0 C ₂ H ₅₎ hexa emissions solution C 1 ₂ to Shik b, and Echiruarumi Niumusesukiku mouth Lai de _{[a 1 (C 2 H 5} ),. 5 C 1!. 5] the hexane solution consequent opening of the polymerization vessel at concentrations respectively 6 0 g / Li Tsu Bok Honoré, 0. 5 mmo 1 / litre, 4.0 mmo 1 liter, supplied with 15 liters of ethylene ZH r and 2.5 liters of hydrogen gas The system was supplied at a rate of H r and the system was controlled at 10 ° C. On the other hand, the polymerization liquid was continuously withdrawn from the upper part of the polymerization vessel so that the entire amount of the polymerization liquid in the flask became 1 liter and the average residence time was 0.5 hour.

 The polymerization was stopped by adding a small amount of isopropyl alcohol to the withdrawn polymerization solution, and then using a homogenizer at a ratio of 1: 1 of an aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water. Contact was made under strong stirring to transfer the catalyst residue to the aqueous phase. The mixture was allowed to stand, the aqueous phase was removed, and the mixture was further washed twice with distilled water to purify and separate the polymer solution.

The polymerization solution was poured into 3 liters of acetone to precipitate a polymer, which was collected by filtration. Next, the recovered polymer was dried at 100 ° C. and 1 Torr or less for 48 hours. The obtained polymer (Polymer I; MTF / ethylene addition copolymer) had an ethylene content of 62 mol%, a number average molecular weight (Mn) of 10, 500, and a weight average molecular weight. (Mw) was 37,800. [Synthesis example 10]

 Same as Synthesis Example 1 except that the MTF was changed to ethyltetracyclododecene (ETD) and the amount of 1-hexene was changed from 5.75 mmol to 2.30 mmol. As a result, a hydrogenated product having a number average molecular weight (Mn) of 28,500, a weight average molecular weight (Mw) of 57,800, and a hydrogenation rate of an unsaturated bond in the main chain of 9.9% or more was obtained. . Let J be this polymer.

 [Synthesis example 1 1]

 In the same manner as in Synthesis Example 1 except that the hydrogenation reaction temperature was changed from 80 ° C to 230, the number average was calculated in terms of polystyrene by GPC using cyclohexane as a solvent. Molecular weight (Mn) of 30,900, weight-average molecular weight (Mw) of 58,800, hydrogenation rate of unsaturated bond of main chain is more than 99%, hydrogenation of benzene ring A hydrogenated product having a rate of about 100% was obtained. Let K be this polymer.

Table 1 shows the composition, polymerization method, hydrogenation rate, molecular weight, etc. of each polymer obtained in Synthesis Examples 1 to 11 collectively.

table 1

[Example 1]

 Polymer II obtained in Synthesis Example 1 and various components shown in Table 2 were blended, and dissolved in toluene so as to have a solid content of 65% by weight to prepare a varnish. The varnish obtained was a homogeneous solution without phase separation and no precipitate.

This varnish is impregnated by immersing E glass cloth, and then It was dried in an air oven to produce a curable composite material (prepredder). The weight of the base material in the prepreg was 40% by weight based on the total amount of the prepreg. A plurality of the above prepregs are stacked as necessary so that the thickness after molding becomes 0.8 mm, and copper foil with a thickness of 35 μm is placed on both sides of the prepreg, and molded by a hot press molding machine It was cured to obtain a laminate.

 When the physical properties of the thus obtained laminate were measured, it showed good dielectric properties, water absorption, heat resistance, solvent resistance, copper foil peeling strength, and flame retardancy of V. -It was 0.

 [Examples 2 to 32]

 Each of the polymers obtained in Synthesis Examples 1 to 9 was blended with various components shown in Tables 2 and 3 and dissolved in toluene so that the solid content concentration became 20 to 65% by weight. A varnish was prepared. Each of the obtained varnishes was a uniform solution without phase separation, and had no precipitate.

 In the same manner as in Example 1, each varnish was immersed in and impregnated with E glass cloth to prepare a prepreg, and then a resin laminate was obtained. When the physical properties of each of the resin laminates thus obtained were measured, they showed good dielectric properties, water absorption, heat resistance, solvent resistance, and copper foil peeling strength. The flame retardancy was V-0.

Tables 2 and 3 show the compositions and results of Examples 1 to 32 collectively.

CO ο

Table 2

to

 〇 〇 ι

Table 3

(Footnote)

 (1) Peroxide a: Dicumyl peroxide

 (2) Peroxide b: 2,5—dimethyl-2,5—di (t-butylpropyl) hexine-3

 (3) T AIC: Trial Noi Cyanate

 (4) T AC: Trial Nori

 (5) TMPT: trimethylolpropane trimethacrylate

(6) Imidazole: 2—ethyl 45 imidazole

 (7) E 1: Asahi Ciba, brominated bisphenol A type epoxy resin (A ER 820)

 (8) E 2: Asahi Ciba, brominated bisphenol A type epoxy resin (AE R810)

 [Comparative Examples 1 to 7]

 Using the polymer J obtained in Synthesis Example 10 as a polymer, it was blended with the various components shown in Table 4, and the toluene was adjusted so that the solid content concentration was 20% by weight. To prepare a varnish.

 Each of the obtained varnishes was phase-separated into two phases, and a uniform solution could not be obtained. These varnishes were impregnated by impregnating E-galaxros, but the impregnating components differed between the upper and lower portions of E-galaxros, and uniform impregnation was not possible.

 [Comparative Examples 8 to 14]

As the polymer, a cyclic olefin addition polymer [APEL 515, manufactured by Mitsui Petrochemicals Co., Ltd .; number average molecular weight (Mn) 47, 200, weight average molecular weight (Mw) 83, 100], and various components shown in Table 4 were blended, and dissolved in toluene so that the solid content concentration became 20% by weight to prepare a varnish. Each of the obtained varnishes was phase-separated into two phases, and a uniform solution could not be obtained. These varnishes were impregnated with E glass cross by impregnation, but the impregnating components differed between the upper and lower portions of the E glass cross, and uniform impregnation was not possible.

 Table 4 summarizes the compositions of these comparative examples.

(footnote)

 (1) APL 515: APEL 515, manufactured by Mitsui Petrochemical Co., Ltd .; number average molecular weight (Mn) = 47, 200, weight average molecular weight (Mw) = 8 3. 3. Ι Ο ο 'Η— NMR confirmed that this polymer had no aromatic ring structure.

(2) Peroxide b: 2,5-dimethyl-2,5-di (t-butylperoxy) hexyl-3- (3) TAIC: Tri-Louis Soy Nurate

 (4) TMPT: Trimethylol propane trimethacrylate

(5) Imidazole: 2-ethyl-4 imidazole

 (6) E 1: Asahi Ciba, brominated bisphenol A type epoxy resin (AER8201)

 (7) E 2: Asahi Ciba, brominated bisphenol A type epoxy resin (AER81010)

 [Examples 33 to 41]

 Each polymer obtained in Synthesis Examples 1 to 9 was mixed with various components shown in Table 5 and dissolved in toluene to prepare a varnish so that the solid content concentration became 20% by weight. did. After each varnish obtained was allowed to stand at room temperature for 30 minutes, the presence or absence of phase separation was visually observed and evaluated according to the following criteria.

〇: Uniform, no phase separation,

 : With phase separation.

 After each varnish obtained above was allowed to stand at room temperature for 30 minutes, the varnish was added to the varnish in the width direction of E glass cross (width l O c mx length l O cm x thickness 0.5 mm). One end was held and immersed in a suspended state. After 10 seconds had elapsed, it was slowly pulled up and left for 1 minute. Only the solid content of the obtained resin-impregnated glass cloth was dissolved again in toluene. Next, a large amount of isopropyl acetate was poured into the toluene solution, and only the polymer component was coagulated and collected by filtration. On the other hand, the filtrate was poured into a large amount of methanol, and only the flame retardant component was coagulated, filtered and collected.

The weight of the recovered polymer component and flame retardant component after drying at 70 at 1 Torr for 48 hours was measured. At this time, the difference between the weight ratio of the polymer component and the flame retardant component and the weight ratio of these two components in the varnish used was calculated and evaluated according to the following criteria. ◎: Difference is 2% or less, excellent impregnation uniformity 極 め て: Difference is more than 2%, 5% or less, impregnation uniformity is excellent, △: Difference is more than 5% , Less than 10%, and good impregnation uniformity,

 X: The difference is 10% or more, and the impregnation uniformity is poor.

 [Comparative Example 15]

 Operations were performed in the same manner as in Examples 33 to 41, except that the polymer J obtained in Synthesis Example 10 was used as the polymer, and evaluation was performed in the same manner.

 [Comparative Example 16]

 As the polymer, a cyclic olefin-based addition polymer [APEL 515, manufactured by Mitsui Petrochemical Co., Ltd .; number average molecular weight (Mn) 47, 200, weight average molecular weight (Mw) 83, 1 [0 0] was performed in the same manner as in Examples 33 to 41, and the same evaluation was performed.

 [Comparative Example 17]

 Operations were performed in the same manner as in Examples 33 to 41, except that the polymer K obtained in Synthesis Example 11 was used as the polymer, and the same evaluation was performed.

Table 5 shows the compositions and results of Examples 33 to 41 and Comparative Examples 15 to 17 collectively.

Table 5

(1) APL 515: APEL 515, manufactured by Mitsui Petrochemical Co., Ltd .; number average molecular weight (Mn) = 47, 200, weight average molecular weight (1 \ 4) = 83, 1 0 0. 'H-NMR confirmed that this polymer had no aromatic ring structure.

 (2) E 1: Industrial applicability of Asahi Ciba, brominated bisphenol A-type epoxy resin (AER8201)

 According to the present invention, a crosslinkable polymer composition having excellent heat resistance, hang resistance, chemical resistance, mechanical strength, and the like, and suitable for uniformly dispersing various compounding agents such as a flame retardant, A molded article, a prepreg, a two-layer body, a metal-clad laminate, and the like using the composition are provided.

Claims

The scope of the claims

1. A crosslinkable polymer composition containing an aromatic ring-containing norbornane-based polymer having a number average molecular weight (Mn) of 500 to 500,000 and a crosslinking agent.

2. The aromatic ring-containing norbornane-based polymer contains (（) an aromatic ring-containing norbornane-based monomer and (2) an aromatic ring-containing norbornane-based monomer and an aromatic ring. A ring-opening copolymer with a non-norbornene-based monomer which is not used, and (3) at least one kind of thermoplastic norbornane-based polymer selected from the group consisting of these hydrogenated products. 1. The crosslinkable polymer composition according to 1.

3. The ring-opening copolymer of an aromatic ring-containing norbornane-based monomer and an aromatic ring-containing norbornane-based monomer is 10 to 90% by weight of an aromatic ring-containing norbornane-based monomer. 3. The crosslinkable polymer composition according to claim 2, which is a ring-opened copolymer with 90 to 10% by weight of a norbornane-based monomer containing no ring.

4. The hydrogenated product has hydrogenated at least 95% of the carbon-carbon double bonds in the main chain of the ring-opening polymer or the ring-opening copolymer, and

3. The crosslinkable polymer composition according to claim 2, wherein 40% or more is left unhydrogenated.

5. The crosslinkable polymer composition according to claim 1, wherein the aromatic ring-containing norbornane-based polymer is an addition copolymer of an aromatic ring-containing norbornane-based monomer and a vinyl compound.

6. The crosslink according to claim 5, wherein the addition copolymer of the aromatic ring-containing norbornene-based monomer and the vinyl compound is an addition copolymer of an aromatic ring-containing norbornene-based monomer and ethylene. Polymer composition.

7. Addition of aromatic ring-containing norbornene-based monomer and vinyl compound Addition of 10-90% by weight of aromatic-ring-containing norbornene-based monomer to 90-10% by weight of vinyl compound 7. The crosslinkable polymer composition according to claim 5, which is a copolymer. 8. The crosslinkable polymer composition according to any one of claims 2 to 7, wherein the aromatic-containing norbornene-based monomer is a compound represented by the following formula (I).

(In the formula,

 m: 0 or a positive integer.

 h: 0 or a positive integer.

 j: 0, 1 or 2.

 k: 0, 1 or 2.

R 'R' ^1: independently, a hydrogen atom, a hydrocarbon group, androgenic atom, alkoxy group, hydroxyl group, ester group, Xia amino group, § de group, I Hydrocarbons substituted by mid groups, silyl groups, and polar groups (halogen atoms, alkoxy groups, hydroxyl groups, ester groups, cyano groups, amide groups, imido groups, or silyl groups) Selected from groups.

R ^{12 to} R ² °: independently of each other, a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amide group, an imide group, a silyl group, and It is selected from a hydrocarbon group substituted with a polar group (a halogen atom, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amide group, an imido group, or a silyl group).

The carbon atom to which R ^l ° and R ¹¹ are bonded and the carbon atom to which R ¹⁴ is bonded or the carbon atom to which R ¹² is bonded are directly or via an alkylene group having 1 to 3 carbon atoms. May be combined.

When j = k = 0, R ¹⁶ and R ¹³ or R ¹⁶ and R ² ° may combine with each other to form a monocyclic or polycyclic aromatic ring. 9. The crosslinkable polymer composition according to any one of claims 2 to 4, wherein the norbornene-based monomer having no aromatic ring is a compound represented by the following formula (II).

(In the formula,

 n: 0 or 1.

 P: 0 or a positive integer

q: 0 or 1 R, to R _ie independently represent a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amide group, an imide group, a silyl group, and It is selected from hydrocarbon groups substituted by polar groups (halogen atom, alkoxy group, hydroxyl group, ester group, cyano group, amide group, imido group, or silyl group).

R _a to R _b: each independently, a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, an ester group, Xia amino group, A Mi de group, I mi de group, shea Li group, and the polar The group is selected from a hydrocarbon group substituted with a group (halogen atom, alkoxy group, hydroxyl group, ester group, cyano group, amide group, imido group, or silyl group).

R ₁₅ to R _ie may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond.

In the R _l5 and R _l6, or the R ₁₇ and R, _8, they may form a Arukiri den group. When q is 0, each bond is combined to form a 5-membered ring. ]

10. Aromatic ring-containing norbornane-based polymer is a hydrogenated product of 1,4-monoethanol 1, 4, 4, 4a, 9a — ring-opened polymer of tetrahydrofluorene 5. The crosslinkable polymer composition according to any one of claims 1 to 4.

1 1. Aromatic ring-containing norbornene-based polymer is converted to 1,4-metano 1.4.4,4a, 9a — ring-opening reaction between tetrahydrohydronolene and tetracyclododecene. The crosslinkable polymer composition according to any one of claims 1 to 4, which is a hydrogenated product of a polymer.

1 2. Aromatic ring-containing norbornene-based polymers were converted to 1,4-metano-1,4,4a, 9a-tetrahydrofluorene and methyltetracyclododecane. 5. The crosslinkable polymer composition according to any one of claims 1 to 4, which is a hydrogenated product of the ring-opening copolymer.

1 3. The method according to claim 1 or 4, wherein the aromatic ring-containing norbornane-based polymer is a hydrogenated product of a ring-opening copolymer of 5-phenyl-2-norbornane and tetracyclododecene. The crosslinkable polymer composition according to any one of claims 1 to 7.

1 4. The claim that the aromatic ring-containing norbornene polymer is an addition copolymer of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene and ethylene. Item 6. The crosslinkable polymer composition according to item 6 or 7.

15. The crosslinkable polymer composition according to any one of claims 1 to 14, wherein the aromatic ring-containing norbornene-based polymer has a molecular weight distribution (MwZMn) of 4 or less.

16. The crosslinkable polymer composition according to any one of claims 1 to 15, wherein the crosslinker is an organic peroxide, a photocrosslinker or a thermosetting crosslinker.

17. The crosslinkable polymer composition according to any one of claims 1 to 16, further comprising a crosslinking aid.

1 8. Any one of claims 1 to 17 further comprising a flame retardant Crosslinkable polymer composition according to item

1 9. The flame retardant is of the formula (N 1)

A compound represented by the formula: (N 2)

(N2)

A compound represented by the formula (N 3)

(In the formula, n is 0 or an integer of 1 or more.)

Or a compound represented by the formula (N 4)

The crosslinkable polymer composition according to claim 18, which is a compound represented by the following formula:

20. The flame retardant has the formula (E 1)

H-S- H ₂ (El)

(In the formula, X is a halogen atom, R is a divalent hydrocarbon group, m is an integer of 13, and n is 0 or an integer of 1 or more.)

Or a compound represented by the formula (E 2)

(In the formula, R ′ is a hydrogen atom or an alkyl group having 120 carbon atoms, and ρ is 0 or an integer of 1 or more.)

19. The crosslinkable polymer composition according to claim 18, which is a compound represented by the formula:

21. The crosslinkable polymer composition according to any one of claims 1 to 20, further comprising a solvent.

2 2. With 100 parts by weight of the aromatic ring-containing norbornene polymer, 0.001 to 30 parts by weight of crosslinking agent, 310 parts by weight of flame retardant, and uniformly dissolve each component 22. The crosslinkable polymer composition according to claim 21, which contains a sufficient amount of a solvent.

2 3. A sheet formed by molding a crosslinkable polymer composition containing a norbornene polymer having an aromatic ring having a number average molecular weight (量 η) of 500,000 and a crosslinking agent.

2 4. A crosslinkable polymer composition containing an aromatic ring-containing norbornene-based polymer having a number average molecular weight (Μη) of 500.000 A prepreg made by impregnating a reinforcing base material.

2 5. Sheet formed by molding a crosslinkable polymer composition containing a norbornene-based polymer having an aromatic ring having a number average molecular weight (Mn) of 500 to 500,000 and a crosslinking agent. , And a cross-linkable polymer composition containing an aromatic ring-containing norbornene-based polymer having a number average molecular weight (Mn) of 500 to 500,000 and a cross-linking agent is impregnated into a reinforcing base material. A laminated body formed by stacking a plurality of at least one kind selected from the group consisting of prepregs and then heating and compression molding.

26. The hired body according to claim 25, wherein a metal layer is further laminated on one or both sides of the laminate.

27. The multilayer structure according to claim 25 or 26, wherein a metal layer is further provided in the middle of the ridge structure.

2 8. The crosslinkable polymer composition contains 0.001 to 30 parts by weight of a crosslinking agent with respect to 100 parts by weight of an aromatic ring-containing norbornane-based polymer, and a flame retardant of 3 to 28. The layered product according to any one of claims 25 to 27, further comprising 150 parts by weight and a solvent in an amount sufficient to uniformly dissolve each component.