JPH10158367A - Norbornene polymer containing epoxy group and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polymer capable of exhibiting excellent dielectric characteristics, water resistance and dispersibility of a compounding agent, etc., by hydrogenating a part of C-C double bonds in the main chain structure of a ring-opened polymer of a norbornene monomer and epoxidizing the remaining part of the double bonds. SOLUTION: This polymer contains epoxy groups in the main chain structure of a ring-opened polymer of a norbornene monomer and has a C-C double bond content of <=30mol% in the main chain structure and a number-average molecular weight of 500-500,000. The polymer can be produced by hydrogenating and saturating a part of the C-C double bonds in the main chain structure of the ring-opened polymer of the norbornene monomer and epoxidizing the remaining part of the C-C double bonds. The obtained polymer has excellent water- resistance, thermal stability, dielectric constant and peeling strength of metallic foil, exhibits excellent uniform dispersibility of a compounding agent in a solution and facilitates the control of the epoxy-modification ratio.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel epoxy group-containing norbornene-based polymer, a method for producing the same, and a crosslinkable polymer composition containing the polymer, and more particularly, to water resistance and heat stability. An epoxy group-containing norbornene-based polymer having excellent dielectric constant, excellent peeling strength with a metal foil, and excellent uniform dispersibility of a compounding agent in a solution, a method for producing the same, and a polymer and a crosslinking agent. A crosslinkable polymer composition comprising:

[0002]

2. Description of the Related Art With the advancement of technology, demands for higher speed, higher reliability, higher densities, etc. of arithmetic processing have increased for circuits equipped in precision equipment such as electronic computers and communication equipment. Higher performance such as multi-layering, higher precision, and miniaturization is progressing. Such a circuit board is prepared, for example, by impregnating a resin base material such as a glass cloth with a resin varnish, producing a dried semi-cured sheet (prepreg), and then forming a copper foil or a copper-clad board for an outer layer, a prepreg. It is manufactured by laying up an inner layer copper-clad plate or the like between mirror plates in order and then pressurizing and heating to completely cure the resin.
Conventionally, thermosetting resins such as phenolic resins, epoxy resins, and polyimide resins have been used as resin materials.

However, phenolic resins, epoxy resins,
Thermosetting resins such as polyimide resins generally have a high dielectric constant of 4.0 or more and do not have sufficient electrical characteristics. Therefore, it is difficult to speed up arithmetic processing on a circuit board using these thermosetting resins. Met. In recent years, a crosslinked product having excellent electrical properties such as a dielectric constant has been proposed by crosslinking a thermoplastic norbornene-based resin with an organic peroxide. For example,
JP-A-62-34924 discloses a synthesis of a norbornene-based resin obtained by addition polymerization of ethylene and a norbornene-based monomer, kneading of the norbornene-based resin and a crosslinking aid, pulverization, and addition of an organic peroxide. A method is disclosed in which a solution is impregnated, the solution is removed, and then press-molded and crosslinked.

However, in this method, in addition to the complicated steps, it is difficult to make the norbornene-based resin a high-concentration solution, and the organic peroxide and other compounding agents are not uniformly dispersed. There is a problem. Therefore, in order to prepare a prepreg using the resin solution obtained by this method, it is necessary to use a low-concentration solution, but when the low-concentration solution is impregnated into the reinforcing substrate, it does not stick at room temperature. The drying time is long, and it is necessary to stand still so as not to be deformed during this time, so that there is a problem that productivity is poor. In addition, it is necessary to add various compounding agents according to various uses. There is a disadvantage that it will.
Even if the reinforcing base material is immersed in the two-phase separated solution, it is not possible to obtain a prepreg uniformly impregnated with each component. Furthermore, even if a copper foil is laminated on the thus obtained molded body such as a prepreg, the peeling strength is not sufficient and there is a problem in durability.

JP-A-6-248164 discloses that a flame retardant such as a hydrogenated product of a ring-opened polymer of a norbornene-based monomer, an organic peroxide, a crosslinking aid, and a brominated bisphenol is dispersed in a solvent. After that, the obtained solution is cast or impregnated in a reinforcing base material, and then the solvent is removed and thermally crosslinked to produce a sheet or a prepreg, and further laminate a copper foil. A method is disclosed.

However, according to this method, when the polymer and various additives are dispersed in a solvent, the uniform dispersibility of the additives is poor. Further, in this method, a large amount of a crosslinking aid such as diallyl phthalate must be used, and the crosslinking aid causes a decrease in dielectric properties. On the other hand, if the blending ratio of the crosslinking assistant is small or not blended, the crosslinking reaction of the norbornene-based polymer does not proceed sufficiently, and only a laminate having insufficient peel strength with copper foil can be obtained. Has problems.

Conventionally, as norbornene-based polymers having an epoxy group, for example, JP-A-62-27412 discloses ethylene and 2-methyl-1,4,5,8-dimethano-1,2,3. An epoxy-modified norbornene-based polymer in which an addition polymer with 4,4a, 5,8,8a-octahydronaphthalene is graft-modified with glycidyl methacrylate in the presence of dicumyl peroxide is disclosed. However, in this method, gelation of the polymer easily occurs at the time of graft modification, and it is difficult to obtain a modified polymer having a sufficiently high epoxy group content. Moreover,
Since glycidyl methacrylate as a modifier has a polar group other than an epoxy group, there is a problem that the obtained epoxy-modified norbornene-based polymer has poor electrical properties and water resistance.

JP-A-2-298510 discloses a norbornene monomer having a carbon-carbon unsaturated group such as an ethylidene group, or a carbon-carbon double bond not involved in addition polymerization in a molecule such as dicyclopentadiene. An epoxy group-containing norbornene-based polymer obtained by subjecting a norbornene-based monomer to addition polymerization and then epoxidizing 100% of carbon-carbon double bonds in the obtained addition polymer is disclosed. However, in this method, the obtained epoxy group-containing norbornene-based polymer has an excessively high epoxy group content, so that electrical properties and water resistance are reduced. Also,
In this method, when the carbon-carbon double bond is partially epoxidized, a large amount of the carbon-carbon double bond will remain in the obtained epoxy group-containing norbornene-based polymer, so that the heat stable There was a problem that it was inferior in nature.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide excellent dielectric properties, water resistance, and thermal stability, as well as excellent dispersibility with a compounding agent and peel strength with a copper foil. An object of the present invention is to provide an epoxy group-containing norbornene-based polymer in which the rate of group modification can be easily controlled, a method for producing the same, and a crosslinkable polymer composition containing the polymer and a crosslinking agent. The present inventors have conducted intensive studies in order to overcome the problems of the prior art as described above, and as a result, found that a part of the carbon-carbon double bond in the main chain structure of the ring-opened polymer of a norbornene-based monomer. Hydrogenation, and then epoxidation of the remaining carbon-carbon double bonds, thereby controlling the residual amount of carbon-carbon double bonds and the epoxy group content within an appropriate range. Was found to be easily obtainable. Therefore, the epoxy group-containing norbornene-based polymer obtained by this method has excellent dielectric properties, water resistance, and thermal stability, and also has excellent dispersibility with a compounding agent and excellent peel strength with a copper foil. Was found. The present invention has been completed based on these findings.

[0010]

Thus, according to the present invention, there is provided a ring-opened polymer of a norbornene-based monomer having an epoxy group in the main chain structure and a carbon-carbon double bond in the main chain structure. An epoxy group-containing norbornene-based polymer having a content of 30 mol% or less and a number average molecular weight (Mn) of 500 to 500,000 is provided. According to the present invention, a part of the carbon-carbon double bond in the main chain structure of the ring-opened polymer of the norbornene-based monomer is hydrogenated, and then the carbon-carbon double bond is epoxidized with an epoxidizing agent. A method for producing an epoxy group-containing norbornene-based polymer, characterized in that Furthermore, according to the present invention, the ring-opened polymer of the norbornene-based monomer has an epoxy group in the main chain structure, and has a carbon-carbon double bond content of 30 mol% or less in the main chain structure. Accordingly, there is provided a crosslinkable polymer composition comprising an epoxy group-containing norbornene-based polymer having a number average molecular weight (Mn) of 500 to 500,000, and a crosslinking agent.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Epoxy group-containing norbornene-based polymer The epoxy group-containing norbornene-based polymer of the present invention has an epoxy group in the main chain structure, and has a carbon atom in the main chain structure.
It is characterized by a low content of carbon double bonds. When the norbornene-based monomer is subjected to ring-opening polymerization, a ring-opened polymer having a carbon-carbon double bond in the main chain structure is obtained. That is, the main chain structure of the ring-opened polymer of the norbornene-based monomer has a structure in which a 5-membered ring formed by opening the norbornene ring and a carbon-carbon double bond portion are connected. When the norbornene-based monomer has a substituent or is a polycyclic norbornene-based monomer, a polymer having a structure in which the substituent and the remaining cyclic structure are bonded to the 5-membered ring in the main chain structure is obtained. . The epoxy group-containing norbornene-based polymer of the present invention is saturated by hydrogenating a part of the carbon-carbon double bond in the main chain structure of the ring-opened polymer of the norbornene-based monomer, and the remaining carbon-carbon double bond. It can be produced by epoxidizing the bond. The ring-opening polymer of the norbornene-based monomer is not particularly limited, and examples thereof include JP-A-2-227424 and JP-A-2-27.
No. 6,842, JP-A-5-97719, JP-A-7-41550, JP-A-8-72210 and the like can be used.

(Norbornene-based monomer) Specific examples of the norbornene-based monomer include, for example, bicyclo [2.
2.1] hept-2-ene derivative, tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene derivative, hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0
^9,14] -4-heptadecene derivatives, octacyclo [8.
8.0.1 ^2,9 . ^14,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0
^12,17 ] -5-docosene derivative, pentacyclo [6.
6.1.1 ^3,6 . 0 ^2,7 . 0 ^9,14] -4-hexadecene derivative, heptacyclo-5-eicosene derivatives, heptacyclo-5-heneicosene derivatives, tricyclo [4.
3.0.1 ^2,5 ] -3-decene derivative, tricyclo [4.4.0.1 ^2,5 ] -3-undecene derivative, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-
Pentadecene derivative, pentacyclopentadecadiene derivative, pentacyclo [7.4.0.1 ^2,5 . ^19,12 . 0
^8,13] -3-pentadecene derivatives, heptacyclo [8.
7.0.1 ^3,6 . 1 ^10,17 . 1 ^12,15 . 0 ^2,7 . 0 ^11,16 ]
-4-eicosene derivative, nonacyclo [10.9.1.
^14,7 . 1 ^13,20 . 1 ^15,18 . 0 ^3,8 . 0 ^2,10 . 0 ^12,21 .
0 ^14,19] -5-pentacosene derivatives, pentacyclo [8.4.0.1 ^{2,5. 19,12} . 0 ^8,13] -3-hexadecene derivative, heptacyclo [8.8.0.1 ^4,7. 1
^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5- ^heneicosene derivative, nonacyclo [10.10.1.1 ^5,8 . 1
^14,21 . 1 ^16,19 . 0 ^2,11 . 0 ^4,9 . 0 ^13,22 . 0 ^15,20 ]
-5-hexacocene derivative, 1,4-methano-1,4,
4a, 9a-tetrahydrofluorene derivative, 1,4-
Methano-1,4,4a, 5,10,10a-hexahydroanthracene derivative, cyclopentadiene-acenaphthylene adduct and the like.

More specifically, for example, bicyclo [2.
2.1] Hept-2-ene, 6-methylbicyclo [2.
2.1] Hept-2-ene, 5,6-dimethylbicyclo [2.2.1] hept-2-ene, 1-methylbicyclo [2.2.1] hept-2-ene, 6-ethylbicyclo [2.2.1] Hept-2-ene, 6-n-butylbicyclo [2.2.1] hept-2-ene, 6-isobutylbicyclo [2.2.1] hept-2-ene, 7 Bicyclo [2.2.1] hept-2-ene derivatives such as -methylbicyclo [2.2.1] hept-2-ene; tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
Propyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-dodecene, 8-butyltertracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isobutyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-hexyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclohexyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-stearyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 5,10-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 2,10-dimethyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -3-dodecene, 8,9-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethyl-9-methyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 11,12-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
3-dodecene, 2,7,9-trimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 9-
Ethyl-2,7-dimethyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -3-dodecene, 9-isobutyl-
2,7-dimethyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10] -3-dodecene, 9,11,12- trimethyl tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-dodecene, 9-ethyl-11,12-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 9
-Isobutyl-11,12-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 5,
8,9,10-tetramethyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10] -3-dodecene, 8-ethylidene-9-methyl-tetracyclo [4.4.0.1 ^{2, 5.} 1
^7,10 ] -3-dodecene, 8-ethylidene-9-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethylidene-9-isopropyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
Ethylidene-9-butyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 8-n-propylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-n-propylidene-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8
-N-propylidene-9-ethyltetracyclo [4.
4.0.1 ^{2, 5} . 1 ^7,10 ] -3-dodecene, 8-n-propylidene-9-isopropyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-n-propylidene-9-butyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 8-isopropylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isopropylidene-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8
-Isopropylidene-9-ethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isopropylidene-9-isopropyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isopropylidene-9-butyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -3-dodecene, 8-chlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-bromotetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene, 8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,
9-dichlorotetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-dodecene, tetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene derivative; hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14 ]
-4-heptadecene, 12-methylhexacyclo [6.
6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, 12-ethylhexanoate cyclo [6.6.1.1
^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene,
12-isobutylhexacyclo [6.6.1.1 ^3,6 .
1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, 1,
6,10-trimethyl-12-isobutylhexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14 ] -4
Hexacyclo [6.6.1.1], such as heptadecene,
^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene derivatives; octacyclo [8.8.0.1 ^{2,9. 14,7} . 1
^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5-docosene, 1
5-methyloctacyclo [8.8.0.1 ^2,9 . ^14,7 .
1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5-docosene,
15-ethyloctacyclo [8.8.0.1 ^2,9 .
^14,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . Octacyclo [8.8.0.1 ^{2,9 .0,12,17} ] -5-docosene. 1
^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5-docosene derivative; pentacyclo [6.6.1.1 ^3,6 .
0 ^2,7 . 0 ^9,14 ] -4-hexadecene, 1,3-dimethylpentacyclo [6.6.1.1 ^3,6 . 0 ^2,7 . 0 ^9,14 ]
-4-hexadecene, 1,6-dimethylpentacyclo [6.6.1.1 ^3,6 . 0 ^2,7 . ^09,14 ] -4-Hexadecene, 15,16-dimethylpentacyclo [6.6.
1.1 ^3,6 . 0 ^2,7 . 0 ^9,14] -4-hexadecene, pentacyclo such as [6.6.1.1 ^3,6. 0 ^2,7 . 0 ^9,14 ]
-4-hexadecene derivative; heptacyclo [8.7.
0.1 ^2,9 . ^14,7 . 1 ^11,17 . 0 ^3,8 . 0 ^12,16 ] −5
Eicosene, heptacyclo [8.8.0.1 ^2,9 .
^14,7 . 1 ^11,18 . 0 ^3,8 . ^Heptacyclo -5-eicosene derivative or heptacyclo-5-heneicosene derivative such as 0 ^12,17 ] -5- ^heneicosene ; tricyclo [4.3.0.1 ^2,5 ] -3-decene, 2-methyltricyclo [ 4.3.0.1 ^2,5 ] -3-decene, 5-methyltricyclo [4.3.0.1 ^2,5 ] -3-decene,
Tricyclo [4.3.0.1 ^2,5 ] -3-decene derivative; tricyclo [4.4.0.1 ^2,5 ] -3-undecene, 10-methyltricyclo [4.4.0] .
1 ^2,5] -3-undecene, tricyclo such [4.
4.0.1 ^2,5 ] -3-undecene derivative; pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene, 1,3-dimethylpentacyclo [6.5.1.
^13-6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene, 1,6-
Dimethylpentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0
^9,13 ] -4-pentadecene, 14,15-dimethylpentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-
Pentacyclo [6.5.1.1] such as pentadecene,
^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene derivative; pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4,
A diene compound such as 10-pentadecadiene; pentacyclo [7.4.0.1 ^2,5 . ^19,12 . 0 ^8,13 ] -3-
Pentadecene, methyl-substituted pentacyclo [7.4.0.
^12.5 . ^19,12 . 0 ^8,13] -3-pentadecene, pentacyclo such [7.4.0.1 ^{2,5. 19,12} . 0 ^8,13 ]
-3-pentadecene derivative; heptacyclo [8.7.
0.1 ^3,6 . 1 ^10,17 . 1 ^12,15 . 0 ^2,7 . 0 ^11,16 ] -4
-Eicosene, dimethyl-substituted heptacyclo [8.7.
0.1 ^3,6 . 1 ^10,17 . 1 ^12,15 . 0 ^2,7 . 0 ^11,16 ] -4
Heptacyclo [8.7.0.1, e.g.
^3,6 . 1 ^10,17 . 1 ^12,15 . 0 ^2,7 . 0 ^11,16] -4-eicosene derivatives; Nonashikuro [10.9.1.1 ^{4, 7.} 1
^13,20 . 1 ^15,18 . 0 ^3,8 . 0 ^2,10 . 0 ^12,21 . 0 ^14,19 ]
-5-pentacocene, trimethyl-substituted nonacyclo [1
0.9.1.1 ^4,7 . 1 ^13,20 . 1 ^15,18 . 0 ^3,8 .
0 ^2,10 . 0 ^12,21 . 0 ^{14, 19]} -5-pentacosenoic, Nonashikuro such as [10.9.1.1 ^4,7. 1 ^13,20 . 1
^15,18 . 0 ^3,8 . 0 ^2,10 . 0 ^12,21 . 0 ^14,19] -5-pentacosene derivatives; pentacyclo [8.4.0.1 ^2,5.
19,12 . 0 ^8,13] -3-hexadecene, 11-methyl-penta cyclo [8.4.0.1 ^{2,5. 19,12} . 0 ^8,13 ] −
3-hexadecene, 11-ethyl-pentacyclo [8.
4.0.1 ^2,5 . ^19,12 . 0 ^8,13 ] -3-hexadecene, 10,11-dimethyl-pentacyclo [8.4.
0.1 ^2,5 . ^19,12 . 0 ^8,13] -5-hexadecene, pentacyclo such [8.4.0.1 ^{2,5. 19,12} . 0
^8,13] -3-hexadecene derivatives; heptacyclo [8.
8.0.1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ]
-5-heneicosene, 15-methyl-heptacyclo [8.8.0.1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0
^12,17 ] -5- ^heneicosene , trimethyl-heptacyclo [8.8.0.1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 .
Heptacyclo [8.8.0.1 ^4,7 .0 ^12,17 ] -5-heneicosene. 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0
^12,17 ] -5- ^heneicosene derivative; nonacyclo [1
0.10.1.1.1 ^5,8 . 1 ^14,21 . 1 ^16,19 . 0 ^2,11 . 0
^4,9 . 0 ^13,22 . 0 ^15,20] -6-hexacosenoic, Nonashikuro such as [10.10.1.1 ^5,8. 1 ^14,21 . 1
^16,19 . 0 ^2,11 . 0 ^4,9 . 0 ^13,22 . 0 ^15,20] -6-hexacosenoic derivatives; pentacyclo [6.5.1.1 ^{3, 6.}
0 ^2,7 . 0 ^9,13 ] -4,11-pentadecadiene, methyl-substituted pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0
^9,13 ] -4,11-pentadecadiene, methyl-substituted pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4,
11-pentadecadiene, methyl-substituted pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4,11-pentadecadiene, trimethyl-substituted pentacyclo [4.
7.0.1 ^2,5 . 0 ^8,13 . 1 ^9,12 ] -3-pentadecene, pentacyclo [4.7.0.1 ^2,5 . 0 ^8,13 . 1
^9,12 ] -3,10-pentadecadiene, methyl-substituted pentacyclo [4.7.0.1 ^2,5 . 0 ^8,13 . 1 ^9,12 ] −
3,10-pentadecadiene, methyl-substituted pentacyclo [4.7.0.1 ^2,5 . 0 ^8,13 . 1 ^9,12 ] -3,10-
Pentadecadiene, methyl-substituted pentacyclo [4.7.
0.1 ^2,5 . 0 ^8,13 . 1 ^9,12 ] -3,10-pentadecadiene, methyl-substituted heptacyclo [7.8.0.
^13-6 . 0 ^2,7 . 1 ^10,17 . 0 ^11,16 . 1 ^12,15] -4-eicosene, trimethyl-substituted heptacyclo [7.8.0.
^13-6 . 0 ^2,7 . 1 ^10,17 . 0 ^11,16 . 1 ^12,15] -4-eicosene, tetramethyl-substituted heptacyclo [7.8.
0.1 ^3,6 . 0 ^2,7 . 1 ^10,17 . 0 ^11,16 . 1 ^12,15 ] -4
-Eicosene, tricyclo [4.3.0.1 ^2,5 ]-
3,7-decadiene (ie dicyclopentadiene), 2,3-dihydrodicyclopentadiene, 5-phenyl-bicyclo [2.2.1] hept-2-ene (ie 5-phenyl-2-norbornene) , 5-Methyl-5-phenyl-bicyclo [2.2.1] hept-2
-Ene, 5-benzyl-bicyclo [2.2.1] hept-2-ene, 5-tolyl-bicyclo [2.2.1] hept-2-ene, 5- (ethylphenyl) -bicyclo [2. 2.1] Hept-2-ene, 5- (isopropylphenyl) -bicyclo [2.2.1] hept-2-ene, 8-phenyl-tetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-phenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-dodecene, 8-benzyl-tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-tolyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Dodecene, 8- (ethylphenyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
(Isopropylphenyl) -tetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-diphenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
3-dodecene, 8- (biphenyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
(Β-naphthyl) -tetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -3-dodecene, 8- (α-naphthyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
3-dodecene, 8- (anthracenyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 11
-Phenyl-hexacyclo [6.6.1.1 ^3,6 .
0 ^2,7 . 0 ^9,14] -4-heptadecene, 6- (alpha-naphthyl) - bicyclo [2.2.1] - hept-2-ene, 5
-(Anthracenyl) -bicyclo [2.2.1] -hept-2-ene, 5- (biphenyl) -bicyclo [2.
2.1] -Hept-2-ene, 5- (β-naphthyl)-
Bicyclo [2.2.1] -hept-2-ene, 5,6-
Diphenyl-bicyclo [2.2.1] -hept-2-ene, 9- (2-norbornen-5-yl) -carbazole, 1,4-methano-1,4,4a, 4b, 5,8,8
a, 9a-octahydrofluorenes; 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, 1,
4-methano-8-methyl-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-8-chloro-1,
1,4-methano-1,4,4a, 9a- such as 4,4a, 9a-tetrahydrofluorene and 1,4-methano-8-bromo-1,4,4a, 9a-tetrahydrofluorene
Tetrahydrofluorenes; 1,4-methano-1,4,4
4a, 9a-tetrahydrodibenzofurans; 1,4-
Methano-1,4,4a, 9a-tetrahydrocarbazole, 1,4-methano-9-phenyl-1,4,4a, 9
1,4-methano- such as a-tetrahydrocarbazole
1,4,4a, 9a-tetrahydrocarbazoles;
1,4-methano-1, such as 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene,
4,4a, 5,10,10a-hexahydroanthracenes; 7,10-methano-6b, 7,10,10a-tetrahydrofluorancenes; compounds obtained by further adding cyclopentadiene to cyclopentadiene-acenaphthylene adduct; 11,12-benzo-pentacyclo [6,
5,1,1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene,
11,12-benzo-pentacyclo [6,6,1,1
^3,6 . 0 ^2,7 . 0 ^9,14 ] -4-hexadecene, 14,15
-Benzo-heptacyclo [8.7.0.1 ^2,9 . ^14,7 .
1 ^11,17 . 0 ^3,8 . 0 ^12,16 ] -5-eicosene, cyclopentadiene-acenaphthylene adduct and the like. These norbornene-based monomers can be used alone or in combination of two or more.

(Ring-Opening Polymerization Method) A ring-opening polymer of a norbornene-based monomer can be obtained by ring-opening polymerization or ring-opening copolymerization of at least one kind of norbornene-based monomer by a known polymerization method. Therefore, the ring-opened polymer includes not only a homopolymer but also a ring-opened copolymer. Examples of the ring-opening polymerization catalyst include, for example, a catalyst comprising a halide, nitrate or acetylacetone compound of a metal selected from ruthenium, rhodium, palladium, osmium, iridium, platinum and the like, and a reducing agent; or titanium, vanadium, zirconium A catalyst comprising a metal halide or an acetylacetone compound selected from tungsten, molybdenum and molybdenum, and an organoaluminum compound can be used.

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

The ring-opening (co) polymerization can be carried out without using a solvent, but can also be carried out in an inert organic solvent. As the solvent, for example, benzene, toluene, aromatic hydrocarbons such as xylene, n-pentane, hexane,
Examples thereof include aliphatic hydrocarbons such as heptane, alicyclic hydrocarbons such as cyclohexane, halogenated hydrocarbons such as styrene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, dichlorobenzene, and trichlorobenzene. The polymerization temperature is usually -50C to 100C, preferably -30C to 80C,
More preferably -20 ~ 60 ℃, the polymerization pressure,
Usually 0 to 50 kg / cm ² , preferably 0 to 20 kg
/ Cm ² .

(Hydrogenation method) The hydrogenation method of the ring-opened polymer of norbornene-based monomer is carried out by hydrogenating the ring-opened polymer with molecular hydrogen in the presence of a hydrogenation catalyst according to a conventional method. be able to. As the hydrogenation catalyst, a catalyst comprising a combination of a transition metal compound and an alkyl metal compound, for example, cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyl Lithium, a combination of tetrabutoxytitanate / dimethylmagnesium and the like can be mentioned.

The hydrogenation reaction is usually carried out in an inert organic solvent. As the organic solvent, a hydrocarbon-based solvent is preferable, and a cyclic hydrocarbon-based solvent is more preferable, because the resulting hydrogenated product is excellent in solubility. Examples of such hydrocarbon solvents include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as n-pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decalin; and tetrahydrofuran and ethylene glycol dimethyl ether. Ethers; and the like, and two or more of these can be used as a mixture. Usually, it may be the same as the polymerization reaction solvent, and the reaction may be carried out by adding a hydrogenation catalyst to the polymerization reaction solution as it is.

The present invention is characterized in that a part of the carbon-carbon double bond in the main chain structure of the ring-opening polymer is hydrogenated, and the hydrogenation ratio is usually 30 to 99.9%, preferably. Is in the range of 50 to 99%, more preferably 65 to 95%. When there is a non-conjugated carbon-carbon double bond such as an alkylidene group in the side chain, the carbon-carbon double bond in the side chain is hydrogenated at the same time when the carbon-carbon double bond in the main chain is hydrogenated. You. In the case of a ring-opened polymer of a norbornene-based monomer having an aromatic ring in the side chain, the aromatic ring may be left or partially hydrogenated during hydrogenation. The carbon-carbon double bond in the main chain structure and the conjugated double bond in the aromatic ring structure can be distinguished and recognized by analysis by ¹ H-NMR.

In order to partially hydrogenate the carbon-carbon double bond in the main chain structure of the ring-opened polymer of the norbornene-based monomer, the ring-opened polymer should be at -20 ° C to 120 ° C, preferably 0 ° C to 120 ° C.
At a temperature of 100 ° C, more preferably 20-80 ° C.
1 to 50 kg / cm ² , preferably 0.5 to 30 kg / cm ²
It is desirable to carry out the hydrogenation reaction at a hydrogen pressure of cm ² , more preferably 1 to 20 kg / cm ² . To hydrogenate the aromatic ring, for example, the hydrogenation temperature is set to 150 to 250 ° C.
About high temperature. Partially hydrogenated product of the ring-opened polymer of norbornene-based monomer obtained by hydrogenation, for example,
Epoxidation can be performed by reacting with a peroxide as an epoxidizing agent. As the peroxide, carbon-
There is no particular limitation as long as it is used as an epoxidizing agent for a carbon double bond. For example, peracids such as peracetic acid, perbenzoic acid, metachloroperbenzoic acid, and trifluoroperacetic acid; hydrogen peroxide, Hydroperoxides such as l-butyl hydroperoxide and cumene peroxide; and the like.

The epoxidation reaction may be performed by mixing a partial hydrogenated product of the ring-opening polymer and a peroxide and heating the mixture.
It is performed in the presence of a solvent. The solvent is not particularly limited as long as it can dissolve or disperse the partially hydrogenated product of the ring-opening polymer, and for example, the same as the solvent exemplified in the method for producing the ring-opening polymer of the norbornene-based monomer Can be used. The amount of the solvent used is not particularly limited as long as it can dissolve or disperse the partially hydrogenated product of the ring-opening polymer, but is usually 1 to 100 times by weight relative to the partially hydrogenated product of the ring-opening polymer. Amount, preferably 2-80 times amount,
More preferably, it is in the range of 5 to 50 times. The reaction conditions may be appropriately selected according to the type of peroxide, but the reaction temperature is usually 0 to 300 ° C, preferably 50 to 200 ° C.
The reaction temperature is usually 0.1 to 10 hours, preferably 0.5 to 5 hours. After completion of the reaction, a large amount of a poor solvent such as methanol is added to the reaction system to precipitate the polymer, and the polymer is separated by filtration, washed, and dried under reduced pressure to obtain an epoxy-modified polymer.

(Structure of Polymer) The epoxy group-containing norbornene-based polymer of the present invention is obtained by saturating a part of the carbon-carbon double bond in the main chain structure of the ring-opened polymer of norbornene-based monomer by hydrogenation. The remaining carbon-carbon double bond has a structure in which the carbon-carbon double bond is epoxidized, and the carbon-carbon double bond may remain at a ratio of 30 mol% or less, if desired. The structure of the epoxy group-containing norbornene-based polymer of the present invention will be described with reference to specific examples of a norbornene-based monomer, a repeating unit of a ring-opening polymer of a norbornene-based monomer, and a repeating unit of an epoxy group-containing norbornene-based polymer. In the present invention, the norbornene-based monomers as described above are used. When these are represented by a general formula, for example, they can be represented by the formula (a1).

[0023]

Embedded image [Wherein the symbols have the following meanings. R ¹ ~
R ⁸ is independently a hydrogen atom, a hydrocarbon group, a halogen atom, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an amide group, an imide group, a silyl group, or a polar group (that is, a halogen atom, a hydroxyl group, an ester group). Group, an alkoxy group, a cyano group, an amide group, an imide group, or a silyl group). However, R ^{5 to} R ⁸
And two or more may be bonded to each other to form a monocyclic or polycyclic ring, and this monocyclic or polycyclic ring may form an aromatic ring even if it has a carbon-carbon double bond. You may. Further, R ⁵ and R ⁶ , or R ⁷ and R ⁸ may form an alkylidene group. ]

The halogen atom in the formula (a1) includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As the hydrocarbon group, for example, 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1
-6 alkyl groups, 2-20, preferably 2-10, more preferably 2-6 alkenyl groups, and 3-15, preferably 3-8, more preferably 5-6 carbon atoms. And the like. Examples of the hydrocarbon group substituted with a polar group include a halogenated alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms. As the hydrocarbon group, those not substituted with a polar group are suitable for applications where low water absorption is highly required.
As the alkylidene group, a lower alkylidene group such as a methylidene group, an ethylidene group, a propylidene group, and an isopropylidene group is preferable. Preferred examples of the norbornene-based monomer include a monomer represented by the formula (a2).

[0025]

Embedded image [Wherein the symbols have the following meanings. R ⁹ ~
R ²⁰ is independently a hydrogen atom, a hydrocarbon group, a halogen atom, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an amide group, an imide group, a silyl group, or a polar group (that is, a halogen atom, a hydroxyl group, an ester group). Group, an alkoxy group, a cyano group, an amide group, an imide group, or a silyl group). However, R ^{17 to} R
²⁰ may form a monocyclic or polycyclic ring by bonding two or more to each other, and this monocyclic or polycyclic ring may form an aromatic ring even if it has a carbon-carbon double bond. May be. Further, R ¹⁷ and R ¹⁸ or R ¹⁹ and R ²⁰ may form an alkylidene group. ]

The halogen atom in the formula (a2) includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As the hydrocarbon group, for example, 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1
-6 alkyl groups, 2-20, preferably 2-10, more preferably 2-6 alkenyl groups, and 3-15, preferably 3-8, more preferably 5-6 carbon atoms. And the like. Examples of the hydrocarbon group substituted with a polar group include a halogenated alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms. As the hydrocarbon group, those not substituted with a polar group are suitable for applications where low water absorption is highly required.

R ^{9 to} R ²⁰ in the formula (a2) are preferably a hydrogen atom, a lower alkyl group or a lower alkenyl group, more preferably a hydrogen atom or a lower alkyl group. The carbon number of the lower alkyl group is appropriately selected according to the purpose, but is usually in the range of 1 to 6, preferably 1 to 4, and more preferably 1 to 3. Specific examples of the lower alkyl group include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group,
n-amyl group, n-hexyl group and the like. Among them, methyl group, ethyl group, n-propyl group, i-
A propyl group is preferred. The carbon number of the lower alkenyl group is appropriately selected according to the purpose, but is usually in the range of 2 to 6, preferably 2 to 4, and more preferably 2 to 3. Specific examples of the lower alkenyl group include, for example, a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group and the like. Among these, a vinyl group and a propenyl group are preferable.

R ^{17 to} R ²⁰ in the formula (a2) may be preferably such that two or more of them are bonded to each other to form a single ring, or R ¹⁷ and R ¹⁸ are R ¹⁹ and R ²⁰
And may form a lower alkylidene group. R ¹⁷ ~
The number of carbon atoms of the monocyclic ring in which two or more of R ²⁰ are bonded to each other is appropriately selected depending on the purpose, but is usually 3 to 8, preferably 4
~ 6, more preferably 5. Specific examples of the formed single ring include, for example, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a methylcyclopentane ring, a cyclohexane ring, a cyclooctene ring and the like, and usually a cyclopentane ring. The number of carbon atoms of the lower alkylidene group is appropriately selected according to the purpose of use, but is usually 1 to
6, preferably from 1 to 4, more preferably from 1 to 3. Preferred examples of the lower alkylidene group include, for example, a methylidene group, an ethylidene group, a propylidene group, an isopropylidene group and the like. Another preferred example of the norbornene-based monomer includes a monomer represented by the formula (a3).

[0029]

Embedded image [Wherein the symbols have the following meanings. R ²¹ ~
R ³⁰ is independently a hydrogen atom, a hydrocarbon group, a halogen atom, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an amide group, an imide group, a silyl group, or a polar group (that is, a halogen atom, a hydroxyl group, an ester group). Group, an alkoxy group, a cyano group, an amide group, an imide group, or a silyl group). However, R ^{25 to} R
²⁸ may form a monocyclic or polycyclic ring by bonding two or more to each other, and the monocyclic or polycyclic ring may form an aromatic ring even if it has a carbon-carbon double bond. May be. Also, R ²⁵ and R ²⁶ or R ²⁷ and R ²⁸ may form an alkylidene group. Further, R ²⁶ and R ²⁷ may be bonded to each other to form a double bond between two carbon atoms in the 5-membered ring to which R ²⁶ and R ²⁷ are bonded. ]

The halogen atom in the formula (a3) includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As the hydrocarbon group, for example, 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1
-6 alkyl groups, 2-20, preferably 2-10, more preferably 2-6 alkenyl groups, and 3-15, preferably 3-8, more preferably 5-6 carbon atoms. And the like. Examples of the hydrocarbon group substituted with a polar group include a halogenated alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms. As the hydrocarbon group, those not substituted with a polar group are suitable for applications where low water absorption is highly required.

R ^{21 to} R ³⁰ in the formula (a3) are preferably a hydrogen atom, a lower alkyl group or a lower alkenyl group, and more preferably a hydrogen atom or a lower alkyl group. The carbon number of the lower alkyl group is appropriately selected according to the purpose, but is usually in the range of 1 to 6, preferably 1 to 4, and more preferably 1 to 3. Specific examples of the lower alkyl group include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, and n
-Amyl group, n-hexyl group and the like. Among them, methyl group, ethyl group, n-propyl group, i-propyl group and the like are preferable. The carbon number of the lower alkenyl group is appropriately selected according to the purpose, but is usually in the range of 2 to 6, preferably 2 to 4, and more preferably 2 to 3. Specific examples of the lower alkenyl group include, for example, a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group and the like. Among these, a vinyl group and a propenyl group are preferable.

R ^{25 to} R ²⁸ in the formula (a3) are preferably such that two or more of them may be bonded to each other to form a monocyclic or aromatic ring, or R ²⁵ to R ²⁶ , or R ²⁷
And R ²⁸ may form a lower alkylidene group.
Further, it is also preferable that R ²⁶ and R ²⁷ are bonded to each other to form a double bond between two carbon atoms in the 5-membered ring to which R ²⁶ and R ²⁷ are bonded. Among these, those in which two or more of R ^{25 to} R ²⁸ are bonded to each other to form an aromatic ring are preferable. The number of carbon atoms of the lower alkylidene group is appropriately selected according to the purpose of use, but is usually 1 to
6, preferably from 1 to 4, more preferably from 1 to 3. Preferred examples of the lower alkylidene group include, for example, a methylidene group, an ethylidene group, a propylidene group, an isopropylidene group and the like. The repeating unit of the ring-opened polymer of these norbornene monomers is represented by the formula (b)
1) to (b3).

[0033]

Embedded image [The meaning of each symbol in the formula is the same as that in the formula (a1). ]

[0034]

Embedded image [The meaning of each symbol in the formula is the same as that in the formula (a2). ]

[0035]

Embedded image [The meaning of each symbol in the formula is the same as that in the formula (a3). ]

In the case of a ring-opening copolymer of two or more norbornene-based monomers, there will be a plurality of repeating units derived from each norbornene-based monomer.
Each of these ring-opened polymers of norbornene-based monomers has a structure in which a 5-membered ring formed by ring-opening of a norbornene ring and a carbon-carbon double bond are connected in a main chain structure. In the present invention, a part of the carbon-carbon double bond in the main chain structure of the ring-opening polymer is hydrogenated, and the remainder is epoxidized. In the case of a ring-opening polymer of a norbornene-based monomer having an alkenyl group or an alkylidene group as a substituent, or a norbornene-based monomer having a monocyclic or polycyclic ring having a non-conjugated carbon-carbon double bond, Similarly, at the time of hydrogenation of the carbon-carbon double bond therein, at least a portion may be hydrogenated, and the remainder may be epoxidized. The epoxy group-containing norbornene-based polymer of the present invention is obtained by, for example, hydrogenating a carbon-carbon double bond in a main chain structure of a ring-opened polymer having a repeating unit of the formula (b1),
And when it is epoxidized, a repeating unit represented by the formula (A1) is formed.

[0037]

Embedded image

The meanings of the symbols in the formula (A1) are basically the same as those in the formulas (a1) and (b1), but as described above, when the substituent is an alkenyl group or an alkylidene group. Or, when a monocyclic or polycyclic ring having a carbon-carbon double bond is present in the side chain, at least a part of the carbon-carbon double bond in the main chain structure is similarly hydrogenated, The remainder may be epoxidized. The formula (A
In 1), the formula (A1-1) represents a repeating unit in which a carbon-carbon double bond in the main chain structure is hydrogenated, and the formula (A1)
-2) shows an epoxidized repeating unit. When the carbon-carbon double bond in the main chain structure of the ring-opened polymer having the repeating unit of the formula (b2) is hydrogenated and epoxidized, the repeating unit represented by the formula (A2) A unit will be formed.

[0039]

Embedded image

The meaning of each symbol in the formula (A2) is basically the same as that in the formulas (a2) and (b2), but as described above, when the substituent is an alkenyl group or an alkylidene group. Or, when a monocyclic or polycyclic ring having a carbon-carbon double bond is present in the side chain, at least a part of the carbon-carbon double bond in the main chain structure is similarly hydrogenated, The remainder may be epoxidized. The formula (A
In 2), the formula (A2-1) represents a repeating unit in which a carbon-carbon double bond in the main chain structure is hydrogenated, and the formula (A2)
-2) shows an epoxidized repeating unit. Further, when the carbon-carbon double bond in the main chain structure of the ring-opened polymer having the repeating unit of the formula (b3) is hydrogenated and epoxidized, the repeating unit represented by the formula (A3) A unit will be formed.

[0041]

Embedded image

The meaning of each symbol in the formula (A3) is basically the same as in the formulas (a3) and (b3), but as described above, when the substituent is an alkenyl group or an alkylidene group. Or, when a monocyclic or polycyclic ring having a carbon-carbon double bond is present in the side chain, at least a part of the carbon-carbon double bond in the main chain structure is similarly hydrogenated, The remainder may be epoxidized. The formula (A
In 3), formula (A3-1) represents a repeating unit in which a carbon-carbon double bond in the main chain structure is hydrogenated, and formula (A3)
-2) shows an epoxidized repeating unit. These repeating units represented by formula (A1), formula (A2) or formula (A3) can be used alone or in combination of two or more. When a carbon-carbon double bond which is neither hydrogenated nor epoxidized remains in the main chain structure, in addition to the repeating unit shown in each of these formulas, formula (A1) contains the above formula (b1) , Equation (B
In (2), each repeating unit of the formula (b3) exists in the formula (b2), and in the formula (A3), each repeating unit of the formula (b3) exists.

The epoxy group content (epoxy modification rate) of the epoxy group-containing norbornene group polymer of the present invention is appropriately selected depending on the purpose of use, but is usually 0 based on the total number of monomer units in the polymer. 0.1 to 70 mol%, preferably 1 to 50 mol%, more preferably 5 to 35 mol%. When the epoxy group content of the epoxy group-containing norbornene-based polymer is in this range, dielectric properties, water absorption, dispersibility of the compounding agent, and properties such as peel strength with copper foil are highly balanced and suitable. is there. If the epoxy group content is too large, the water absorption tends to increase. The epoxy group content is represented by the following formula (1). Epoxy group content (mol%) = (X / Y) × 100 (1) X: Total number of moles of epoxy group (measured by ¹ H-NMR) Y: Total number of monomer units of polymer (weight average molecular weight of polymer) / Average molecular weight of monomer)

The content of carbon-carbon double bonds in the main chain structure of the epoxy group-containing norbornene polymer of the present invention is 3%.
0 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less, and most preferably 5 mol% or less. The content of carbon-carbon double bonds in the main chain structure is 10%.
It can be calculated by 0- (hydrogenation rate + epoxy group content). If the carbon-carbon double bond ratio in the main chain structure in the epoxy group-containing norbornene-based polymer is excessively high, thermal stability is inferior.

The molecular weight of the epoxy group-containing norbornene-based polymer of the present invention is determined by gel permeation chromatography (GPC) using toluene as a solvent, and is calculated as polystyrene-equivalent number average molecular weight (Mn) or norbornene-based polymer. If does not dissolve in toluene,
The number average molecular weight (Mn) in terms of polyisoprene measured by GPC using cyclohexane as a solvent is 500 to 5
00,000, preferably 1,000-200,00
0, more preferably in the range of 5,000 to 100,000. Number average molecular weight (Mn) of norbornene-based polymer
If the is too small, the mechanical strength is inferior.On the contrary, if it is too large, the viscosity when dissolved in a solvent increases, so that the solid content concentration including the compounding agent cannot be increased, and the metal foil and Has insufficient peeling strength, and neither is preferable.
The molecular weight distribution of the epoxy group-containing norbornene-based polymer of the present invention may be appropriately selected according to the purpose of use, and the weight average molecular weight (M
w) and the number average molecular weight (Mn) ratio (Mw / Mn) is
When it is usually 4.0 or less, preferably 3.0 or less, more preferably 2.5 or less, the mechanical strength is particularly high and is suitable.

Crosslinkable Polymer Composition The crosslinkable polymer composition of the present invention is characterized by containing the epoxy group-containing norbornene-based polymer and a crosslinking agent. Crosslinking of the crosslinkable polymer composition of the present invention is not particularly limited, and can be performed using, for example, heat, light, and radiation, and the type of the crosslinking agent is appropriately selected by those means. When the epoxy group-containing norbornene-based polymer is used, the dispersibility becomes good even for various crosslinking agents. The crosslinkable polymer composition of the present invention may contain, in addition to the crosslinking agent, a crosslinking assistant, a flame retardant, other polymer components, other compounding agents, a solvent, and the like, if desired.

(1) Crosslinking Agent The crosslinking agent is not particularly limited, but generally, an organic peroxide is used. Examples of the organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide;
Peroxy ketals such as bis (t-butylperoxy) 3,3,5-trimethylcyclohexane and 2,2-bis (t-butylperoxy) butane; t-butyl hydroperoxide, 2,5-dimethylhexane −2,
Hydroperoxides such as 5-dihydroperoxide; dicumyl peroxide, 2,5-dimethyl-2,
5-di (t-butylperoxy) hexyne-3, α,
dialkyl peroxides such as α'-bis (t-butylperoxy-m-isopropyl) benzene; diacyl peroxides such as octanoyl peroxide and isobutyryl peroxide; peroxyesters such as peroxydicarbonate; Is mentioned. Among them, dialkyl peroxide is preferable in view of the performance of the cured resin, and the type of the alkyl group is preferably changed depending on the molding temperature.

Further, a photo-crosslinking agent which generates a radical by light can be used as the cross-linking agent. Examples of the photocrosslinking agent include benzoin alkyl ether compounds such as benzoin ethyl ether and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl orthobenzoyl benzoate and 4,4'-dichlorobenzophenone; dibenzyl and benzyl methyl ketal. Benzyl compounds; 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone,
Acetophenone-based compounds such as 2,2-diethoxyacetophenone and 4'-phenoxy-2,2-dichloroacetophenone; thioxanthone-based compounds such as 2-chlorothioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone; 2-ethylanthraquinone; 2-
Anthraquinone-based compounds such as chloroanthraquinone and naphthoquinone; propiophenone-based compounds such as 2-hydroxy-2-methylpropiophenone and 4'-dodecyl-2-hydroxy-2-methylpropiophenone; cobalt octenoate, naphthenic acid Organic acid metal salts such as cobalt, manganese octenoate, and manganese naphthenate; and photo-crosslinking agents.

These crosslinking agents can be used alone or in combination of two or more. The compounding amount of the crosslinking agent is as follows.
0.001 part by weight, usually 0.001 to 30 parts by weight,
Preferably it is in the range of 0.001 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, most preferably 0.5 to 5 parts by weight. When the compounding amount of the crosslinking agent is within this range, the properties such as the crosslinkability and the electrical properties and water resistance of the crosslinked product are highly balanced and 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 increased. The crosslinking aid used in the present invention is not particularly limited, but may be any of those known in JP-A-62-34924, and examples thereof include quinone dioxime, benzoquinone dioxime, and p-nitrosophenol. An oxime / nitroso-based crosslinking aid; maleimide-based crosslinking aids such as N, N-m-phenylenebismaleimide; allyl-based crosslinking aids such as diallyl phthalate, triallyl cyanurate and triallyl isocyanurate; ethylene glycol dimethacrylate And methacrylate-based crosslinking aids such as trimethylolpropane trimethacrylate; and vinyl-based crosslinking aids such as vinyltoluene, ethylvinylbenzene, and divinylbenzene. Among these, an allyl-based crosslinking assistant and a methacrylate-based crosslinking assistant are preferred because they can be uniformly dispersed. The addition amount of the crosslinking aid 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 5 parts by weight, based on 1 part by weight of the crosslinking agent.
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) Flame Retardant The flame retardant is not particularly limited, but is preferably one that does not decompose, modify or degrade with a crosslinking agent, and a halogen-based flame retardant is usually used. As the halogen-based flame retardant, various chlorine-based and bromine-based flame retardants can be used, but the flame retardant effect, heat resistance at the time of molding, dispersibility in the resin, influence on the physical properties of the resin, etc. are considered. From, hexabromobenzene, pentabromoethylbenzene, hexabromobiphenyl, decabromodiphenyl, hexabromodiphenyl oxide,
Octabromodiphenyl oxide, decabromodiphenyl oxide, pentabromocyclohexane, tetrabromobisphenol A, and derivatives thereof [for example, tetrabromobisphenol A-bis (hydroxyethyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl) Ether), tetrabromobisphenol A-bis (bromoethyl ether), tetrabromobisphenol A-bis (allyl ether)
Etc.], tetrabromobisphenol S and derivatives thereof [eg, tetrabromobisphenol S-bis (hydroxyethyl ether), tetrabromobisphenol S-bis (2,3-dibromopropyl ether) and the like],
Halogenated bisphenol epoxy resin, tetrabromophthalic anhydride, and derivatives thereof [eg, tetrabromophthalimide, ethylenebistetrabromophthalimide, etc.], ethylenebis (5,6-dibromonorbornene-
2,3-dicarboximide), tris- (2,3-dibromopropyl-1) -isocyanurate, an adduct of Diels-Alder reaction of hexachlorocyclopentadiene, tribromophenyl glycidyl ether, tribromophenyl acrylate, ethylenebistriene Bromophenyl ether, ethylene bispentabromophenyl ether, tetradecabromodiphenoxybenzene, brominated polystyrene, brominated polyphenylene oxide, brominated epoxy resin, brominated polycarbonate, polypentabromobenzyl acrylate, octabromonaphthalene, hexabromocyclododecane , Bis (tribromophenyl) fumaramide, N-methylhexabromodiphenylamine and the like are preferably used.

These flame retardants can be used alone or in combination of two or more. The amount of the flame retardant to be added is as follows.
The amount is usually 3 to 150 parts by weight, preferably 10 to 140 parts by weight, particularly preferably 15 to 120 parts by weight with respect to 00 parts by weight. As a flame retardant aid for more effectively exhibiting the flame retardant effect of the flame retardant, for example, antimony trioxide,
Antimony-based flame retardants such as antimony pentoxide, sodium antimonate, and antimony trichloride can be used. These flame retardant aids are used in a proportion of usually 1 to 30 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the flame retardant.

(4) Other Polymer Components In the present invention, a rubbery polymer or other thermoplastic resin can be added to the crosslinkable polymer composition, if necessary. The rubbery polymer is a polymer having a glass transition temperature of 0 ° C. or lower, and includes ordinary rubbery polymers and thermoplastic elastomers. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the rubbery polymer is appropriately selected depending on the purpose of use, and is usually 5 to 200.

As the rubbery polymer, for example, ethylene-
α-olefin-based rubbery polymer; ethylene-α-olefin-polyene copolymer rubber; copolymer of ethylene and unsaturated carboxylic acid ester such as ethylene-methyl methacrylate and ethylene-butyl acrylate; ethylene-vinyl acetate Copolymer of ethylene and a fatty acid vinyl; a polymer of an alkyl acrylate such as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate;
Polybutadiene, polysoprene, styrene-butadiene or styrene-isoprene random copolymer, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene- (meth) acrylic acid alkyl ester copolymer, butadiene- (meth) acrylic Diene rubbers such as acid alkyl ester-acrylonitrile copolymer, butadiene- (meth) acrylic acid alkyl ester-acrylonitrile-styrene copolymer; and butylene-isoprene copolymer.

Examples of the thermoplastic elastomer include aromatic vinyl such as styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene-isoprene block copolymer, and hydrogenated styrene-isoprene block copolymer. -Conjugated diene-based block copolymers, low-crystalline polybutadiene resins, ethylene-propylene elastomers, styrene-grafted ethylene-propylene elastomers, thermoplastic polyester elastomers, ethylene ionomer resins, and the like. Of these thermoplastic elastomers, preferably, hydrogenated styrene-butadiene block copolymer,
And hydrogenated styrene-isoprene block copolymers. Specific examples thereof include JP-A-2-133406, JP-A-2-305814, JP-A-3-72512, and JP-A-3-74409. Can be mentioned.

As other thermoplastic resins, for example,
Low density polyethylene, high density polyethylene, linear low density polyethylene, ultra low density polyethylene, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, polystyrene, polyphenylene sulfide, polyphenylene ether, polyamide, polyester, polycarbonate, Cellulose triacetate and the like can be mentioned. These rubbery polymers and other thermoplastic resins can be used alone or in combination of two or more, and the compounding amount is appropriately selected within a range that does not impair the object of the present invention.

(5) Other Ingredients 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 antifogging agent, Lubricants, dyes, pigments, natural oils,
An appropriate amount of various compounding agents such as synthetic oils, waxes, and organic or inorganic fillers can be added. Specifically, for example, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di-t-butyl-4-hydroxyphenyl) Propionic acid alkyl ester, 2,2'-oxamidobis [ethyl-3 (3,5-di-t-butyl-
4-hydroxyphenyl) propionate]; trisnonylphenyl phosphite, tris (2,4-di-t-brylphenyl) phosphite, tris (2,4-di-t-butylphenyl) Phosphorus stabilizers such as phosphite; fatty acid metal salts such as zinc stearate, calcium stearate and calcium 12-hydroxystearate; glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol Polyhydric alcohol fatty acid esters such as distearate and pentaerythritol tristearate;
Synthetic hydrotalcite; Amine-based antistatic agent; Coupling agent such as silane coupling agent, titanate coupling agent, aluminum-based coupling agent, zircoaluminate coupling agent; Plasticizer; Colorant such as pigment or dye And the like.

Examples of the organic or inorganic filler include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, basic magnesium carbonate, dowamite, calcium sulfate, potassium titanate, and barium sulfate. , Calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, Examples thereof include polyester fibers and polyamide fibers.

For the purpose of adjusting the mechanical properties, different thermoplastic resins such as polycarbonate, polystyrene, polyphenylene sulfide, polyetherimide, polyester, polyamide, polyarylate 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 the respective functions and the intended use, but the smaller the ratio, the better.

(6) Solvent In the present invention, an epoxy group-containing norbornene-based polymer is dissolved in a solvent to prepare an impregnating solution for prepreg, or a sheet (film) is produced by a solution casting method. be able to. As described above, when dissolving the epoxy group-containing norbornene-based polymer using a solvent, for example, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, n-pentane, hexane, aliphatic hydrocarbons such as heptane, Examples thereof include alicyclic hydrocarbons such as cyclohexane, and halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene. The solvent is an epoxy group-containing norbornene-based polymer,
And, the components to be blended as necessary are used in a ratio sufficient to uniformly dissolve or disperse them. Usually, the solid content concentration is 1
It is adjusted so as to be 80% by weight, preferably 5% to 60% by weight, more preferably 10% to 50% by weight.

The crosslinkable polymer composition of the present invention, such as a molded article, a prepreg, or a laminate, can be molded and then crosslinked to form a crosslinkable molded article. The method of molding the crosslinkable polymer composition is performed by dissolving in a solvent and molding, or at a temperature at which crosslinking is not performed, or at a sufficiently low crosslinking speed, so that deterioration in moldability does not occur due to crosslinking during molding. Melt and mold. Specifically, the crosslinkable polymer composition dissolved in a solvent is cast to remove the solvent, and then molded into a sheet (sheet or film) or impregnated into a substrate to be molded.

(1) Prepreg A prepreg, which is a specific example of a cross-linked molded article, is prepared by uniformly dissolving or dispersing a cross-linkable polymer composition and various compounding agents in a solvent such as toluene, cyclohexane or xylene. After being impregnated with the reinforcing base material, it is dried to remove the solvent, and thus is manufactured. Generally, the prepreg is 50-
Preferably, the thickness is about 500 μm. As the solvent, those described above can be used. The amount of the solvent used is such that the solid concentration is usually 1 to 90% by weight, preferably 5 to 85% by weight, more preferably 10 to 90% by weight.
It is adjusted to be 80% by weight, most preferably 20 to 80% by weight. As the reinforcing substrate, for example, a paper substrate (linter paper, kraft paper, etc.), a glass substrate (glass cloth, glass mat, glass paper quartz fiber, etc.) and a synthetic resin fiber substrate (polyester fiber,
Aramid fiber). These reinforcing base materials may be surface-treated with a treating agent such as a silane coupling agent. These reinforcing substrates can be used alone or in combination of two or more. The amount of the modified norbornene-based polymer with respect to the reinforcing substrate is appropriately selected depending on the purpose of use, but is in the range of 1 to 90% by weight, preferably 10 to 60% by weight based on the reinforcing substrate.

(2) Sheet A method for producing a sheet, which is one of specific examples of the crosslinkable molded article, is not particularly limited, but generally, a casting method is used. For example, in a solvent such as toluene, xylene, or cyclohexane, the crosslinkable resin composition of the present invention is dissolved and dispersed so as to have a solid concentration of about 5 to 50% by weight, and is cast or coated on a smooth surface. The solvent is removed by drying or the like, and the sheet is peeled off from the smooth surface to obtain a sheet. When the solvent is removed by drying, it is preferable to select a method that does not cause foaming by rapid drying. do it.

As the smooth surface, a mirror-finished metal plate, a resin carrier film or the like can be used. When a resin carrier film is used, the solvent to be used and the drying conditions are determined while paying attention to the solvent resistance and heat resistance of the material of the carrier film. The sheet obtained by the casting method generally has a thickness of about 10 μm to 1 mm. 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 product, is formed by laminating the above-mentioned prepreg and / or uncross-linked sheets, and heat-compressing them to form a cross-linked / heat-fused sheet. By doing so, the required thickness is obtained. When the laminate is used as a circuit board, for example, a circuit is formed by laminating a conductive layer for wiring made of metal foil or the like, or by etching the surface. The wiring conductive layer may be laminated not only on the outer surface of the finished laminate, but also inside the laminate depending on the purpose or the like. In order to prevent warpage at the time of secondary processing such as an etching process, it is preferable to stack the layers in a vertically symmetrical manner. For example, the surface of the laminated prepreg and / or sheet is heated at a temperature not lower than the heat fusion temperature corresponding to the norbornene resin used, usually 150 to 300 ° C.
About 30-80 kgf / cm ² , cross-linking and heat-sealing between each layer to obtain a laminate. Other methods of applying metals to these insulating layers or substrates are evaporation, electroplating, sputtering, ion-mecca, spraying and layering. Commonly used metals include copper, nickel, tin, silver, gold, aluminum, platinum, titanium, zinc and chromium. In the wiring board,
Copper is the most frequently used.

(4) Crosslinking In the present invention, a crosslinked molded article can be obtained by singly or laminating the crosslinked molded articles, and by heating them at a certain temperature or more to crosslink. The temperature at which the cross-linking reaction occurs is determined mainly by the combination of the organic peroxide and the cross-linking aid, but is usually 80 to 350 ° C., preferably 1 to 350 ° C.
Crosslinking is carried out by heating to a temperature of from 20C to 300C, more preferably from 150C to 250C. The crosslinking time is preferably about four times the half-life of the organic peroxide, and is usually 5 to 120 minutes, preferably 10 to 90 minutes, and more preferably 20 to 60 minutes. When a photo-crosslinking agent is used as the cross-linking agent, crosslinking can be performed by light irradiation. When cross-linking is performed by laminating cross-linkable molded articles, heat fusion and cross-linking occur between the respective layers, and an integrated cross-linked molded article is obtained.

(5) Crosslinked Molded Product Examples of the crosslinked molded product include a laminate, a circuit board, an interlayer insulating film, a film for forming a moisture-proof layer, and the like. The cross-linked molded article is 1
The dielectric constant at MHZ is usually 4.0 or less, and it is excellent in electrical characteristics as compared with a conventional thermosetting resin molded product. Heat resistance is equal to or higher than that of conventional thermosetting resin molded products. It is not allowed. In addition, the peel strength with copper foil is 1.5k.
g / cm ² or more, preferably 2.0 kg / cm ² or more. For these reasons, the laminate that is the crosslinked molded article of the present invention is also preferable as a circuit board. Further, the cross-linked molded article is excellent in flame retardancy, specifically, UL-
In the 94 standard, those showing V-2 or better flame retardancy are preferable, those showing V-1 or V-0 flame retardancy are more preferable, and those showing V-0 flame retardancy are more preferable. Particularly preferred. In order to obtain a flame-retardant cross-linked molded article,
What is necessary is just to use the crosslinking resin composition containing a flame retardant as mentioned above.

[0068]

The present invention will be described more specifically below with reference to examples and comparative examples. The measuring methods of the physical properties are as follows. (1) Unless otherwise specified, the molecular weight was measured as a value in terms of polystyrene by gel permeation chromatography (GPC) using toluene as a solvent. (2) The hydrogenation rate was measured by ¹ H-NMR. (3) The epoxy group content was measured by ¹ H-NMR and calculated by the above formula (1). (4) The dielectric constant at 1 MHz is JIS C6481.
It measured according to. (5) The copper foil peeling strength was determined by taking out a test piece having a width of 20 mm and a length of 100 mm from the laminate and a width of 10 mm on the copper foil surface.
Was cut in parallel by a tensile tester at a speed of 50 mm / min at a speed of 50 mm / min, and the lowest value of the stress at that time was shown.

Example 1 A 1-liter flask purged with nitrogen was charged with 8-methyl-tetracyclo [4.4.0.
^12.5 . 1 ^7,10] -3-dodecene (hereinafter, MTD for short) and 5g, toluene 120g was added, as a polymerization catalyst, 1-hexene 3 triisobutylaluminum 0.287 mmol and isobutyl alcohol 0.287 mmol, as a molecular weight modifier. 83 mmol was added. To this, 0.057 mmol of tungsten hexachloride was added and stirred at 40 ° C. for 5 minutes. Then, MTD 45g
And 0.086 mmol of tungsten hexachloride were continuously dropped into the system in about 30 minutes, and after completion of the dropping, the mixture was further stirred for 30 minutes to terminate the polymerization. The polymerization reaction solution was transferred to a 1-liter autoclave, and 160 g of toluene was added.
A mixture of 0.5 g of nickel acetylacetonate and 5.15 g of a 30% by weight toluene solution of triisobutylaluminum was added, the atmosphere in the reactor was replaced with hydrogen, and the temperature was raised to 40 ° C. with stirring. When the temperature was stabilized, the hydrogen pressure was increased to 30 kg / cm ² , and the reaction was performed for 1 hour while replenishing the hydrogen consumed in the reaction process. Then
4.2 g of water and activated alumina (surface area 320 cm ² /
g, a pore volume of 0.8 cm ³ / g, an average particle diameter of 15 μm, and 2.5 g of Mizusawa Chemical's Neobead D powder).
After stirring at 1 ° C. for 1 hour, the hydrogenation reaction solution from which solids were removed by filtration was poured into 3 liters of isopropyl alcohol to precipitate out, and the resin was recovered by filtration. The recovered resin was dried at 100 ° C. and 1 Torr or less for 48 hours. The hydrogenation rate of the main chain of the obtained hydrogenated ring-opened polymer was 89.
%Met. To 50 parts by weight of this polymer, 50 parts by weight of m-chloroperbenzoic acid and 300 parts by weight of toluene were mixed, and the mixture was stirred at 40 ° C. for 3 hours. A modified polymer was obtained. This polymer is designated as A. No olefinic protons were observed in the polymer after epoxidation. Table 1 shows the respective physical properties.

Example 2 A hydrogenated ring-opened polymer having a main chain hydrogenation rate of 82% was prepared in the same manner as in Example 1 except that the hydrogenation reaction time was changed from 2 hours to 1.5 hours. Obtained. This polymer was used in the same manner as in Example 1 to obtain an epoxy-modified polymer. This polymer is designated as B. No olefinic protons were observed in the polymer after epoxidation. Table 1 shows the respective physical properties.

Example 3 The hydrogenation reaction time was reduced from 2 hours to 1 hour.
A hydrogenated ring-opened polymer having a main chain hydrogenation ratio of 74% was obtained in the same manner as in Example 1 except that the time was changed. This polymer was used in the same manner as in Example 1 to obtain an epoxy-modified polymer. This polymer is designated as C. No olefinic protons were observed in the polymer after epoxidation. Table 1 shows the respective physical properties.

Example 4 The hydrogenation reaction time was reduced from 2 hours to 3 hours.
A hydrogenated ring-opened polymer having a main chain hydrogenation ratio of 62% was obtained in the same manner as in Example 1 except that the time was changed to 0 minutes. This polymer was used in the same manner as in Example 1 to obtain an epoxy-modified polymer. This polymer is designated as D. No olefinic protons were observed in the polymer after epoxidation. Table 1 shows the respective physical properties.

Example 5 The MTD was 1,4-methano-
1,4,4a, 9a-tetrahydrofluorene (hereinafter, referred to as
An epoxy-modified polymer was obtained in the same manner as in Example 1, except that MTF was abbreviated. This polymer is designated as E. No olefinic protons were observed in the polymer after epoxidation. Table 1 shows the respective physical properties.

Example 6 An epoxy-modified polymer was obtained in the same manner as in Example 1, except that the MTD was changed to MTF and the hydrogenation reaction time was changed from 2 hours to 1.5 hours. This polymer is designated as F. No olefinic protons were observed in the polymer after epoxidation. Table 1 shows the respective physical properties.

Example 7 MTD was converted to 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . Epoxy-modified polymer was obtained in the same manner as in Example 1 except that [ ^17,10 ] -3-dodecene (hereinafter abbreviated as ETD) was changed. This polymer is G
And No olefinic protons were observed in the polymer after epoxidation. Table 1 shows the respective physical properties.

Example 8 An epoxy-modified polymer was obtained in the same manner as in Example 2 except that MTD was changed to ETD. This polymer is designated as H. No olefinic protons were observed in the polymer after epoxidation. Table 1 shows the respective physical properties.

Example 9 MTD was converted to tricyclo [4.
3.2.1 ^2,5 ] -3,7-decadiene (hereinafter referred to as DCP
An epoxy-modified polymer was obtained in the same manner as in Example 1, except that the above was changed. This polymer is designated as I. No olefinic protons were observed in the polymer after epoxidation. Table 1 shows the respective physical properties.

Example 10 An epoxy-modified polymer was obtained in the same manner as in Example 2, except that the MTD was changed to DCP. This polymer is designated as J. No olefinic protons were observed in the polymer after epoxidation. Table 1 shows the respective physical properties.

Example 11 MTD was 50% by weight of MTF
And an epoxy-modified polymer was obtained in the same manner as in Example 1, except that DCP was changed to 50% by weight. This polymer is designated as K. No olefinic protons were observed in the polymer after epoxidation. Table 1 shows the respective physical properties.

[Example 12] 50% by weight of MTF
And an epoxy-modified polymer was obtained in the same manner as in Example 2, except that DCP was changed to 50% by weight. This polymer is designated as L. No olefinic protons were observed in the polymer after epoxidation. Table 1 shows the respective physical properties.

Example 13 A hydrogenated ring-opened polymer having a main chain hydrogenation rate of 42% was obtained in the same manner as in Example 1 except that the hydrogenation reaction time was changed from 2 hours to 15 minutes. . This polymer was used in the same manner as in Example 1 to obtain an epoxy-modified polymer. This polymer is designated as M. No olefinic protons were observed in the polymer after epoxidation. Table 1 shows the respective physical properties.

[Comparative Example 1] The hydrogenation reaction temperature was increased from 40 ° C to 8
A hydrogenation reaction was carried out in the same manner as in Example 1 except that the hydrogenation time was changed from 2 hours to 3 hours at 0 ° C. to obtain a hydrogenated ring-opened polymer. This polymer is designated as N. Table 1 shows the respective physical properties.

[Comparative Example 2] The hydrogenation reaction temperature was increased from 40 ° C to 8
A hydrogenation reaction was carried out in the same manner as in Example 1 except that the hydrogenation time was changed from 2 hours to 3 hours at 0 ° C. to obtain a hydrogenated ring-opened polymer. To 50 parts by weight of the obtained polymer, 3 parts by weight of allyl glycidyl ether, 0.8 part by weight of dicumyl peroxide, and 120 parts by weight of tert-butylbenzene were mixed, and reacted at 150 ° C. for 3 hours in an autoclave. After performing, the reaction solution is coagulated and dried in the same manner as described above,
An epoxy-modified polymer was obtained. This polymer is designated as O. Table 1 shows the respective physical properties.

Comparative Example 3 A hydrogenation reaction was not carried out, and 50 parts by weight of m-chloroperbenzoic acid was changed to 10 parts by weight.
An epoxy-modified polymer was obtained in the same manner as in Example 1. This polymer is designated as P. Table 1 shows the respective physical properties.

[0085]

[Table 1]

[Examples 14 to 38 and Comparative Examples 4 and 5] Each of the resins obtained in Examples 1 to 13 and Comparative Examples 1 and 2 was mixed with various components according to the compositions shown in Tables 2 and 3. Then, each was dissolved in toluene so that the concentration of the solid content became 20 to 40% by weight to obtain a solution (varnish). Uniformity of the solution After the solution was allowed to stand for 30 minutes, the uniformity of the solution was visually observed and evaluated according to the following criteria. ：: Completely homogeneous system, ×: Phase separation system. Uniformity of impregnation For each solution, width 10cm, length 10cm, thickness about 0.5m
m glass cloth was immersed for 10 seconds, then slowly pulled up and left for 1 minute. Only the solid content of the obtained resin-impregnated glass cloth was dissolved again in toluene, poured into a large amount of isopropyl acetate, and only the cyclic polyolefin component was coagulated and collected by filtration. On the other hand, the filtered liquid was poured into a large amount of methanol, and the flame retardant was recovered in the same manner as described above. These were dried at 70 ° C. × 1 Torr for 48 hours, and the weight of each was measured. At this time, the difference between the weight ratio of the two components and the weight ratio of the two components in the varnish state was calculated and evaluated according to the following criteria. ◎: less than 2%, ：: 2% to less than 5%, Δ: 5% to less than 10%, ×: 10% or more. Laminate E glass cloth was immersed in each of the above-mentioned solutions (varnish) for impregnation, and then dried in an air oven to prepare a curable composite material (prepreg). The weight of the base material in the prepreg was 40% based on the weight of the prepreg.
A plurality of the above prepregs are laminated as necessary so that the thickness after molding becomes 0.8 mm, and a copper foil having a thickness of 35 μm is placed on both surfaces thereof, and is molded and cured by a hot press molding machine to laminate the resin. I got a body. When the physical properties of the resin laminate thus obtained were measured, all of the resin laminates of the examples exhibited good dielectric constant and copper foil peeling strength. However, as seen in Example 38, when an epoxy-containing norbornene-based polymer having an epoxy content (modification rate) as high as 58 mol% was used, the water absorption and the dielectric constant tended to decrease. Therefore, it is understood that the epoxy group content is preferably 1 to 50 mol%, more preferably 5 to 35 mol%. The results are shown in Tables 2 and 3.

[0087]

[Table 2]

[0088]

[Table 3]

(Footnote) (1) Peroxide a: 2,5-dimethyl-2,5-di (t
-Butylperoxy) hexyne-3 (2) TAIC: triallyl isocyanurate (3) Epoxy flame retardant: bisphenol A type epoxy resin (AER 8010) manufactured by Asahi Ciba Co., Ltd. (4) Imidazole: 2-ethyl-4 -Methylimidazole

Example 39 and Comparative Example 6 <Evaluation of Thermal Stability> The thermal decomposition temperatures of the polymers C and P obtained in Example 3 and Comparative Example 3 were measured. Polymer P was at 350 ° C., indicating that Polymer P was inferior in thermal stability.

[0091]

According to the present invention, water resistance, thermal stability, dielectric constant, peel strength with metal foil are excellent, uniform dispersibility of a compounding agent in a solution is excellent, and epoxy modification rate is excellent. Provided are an epoxy group-containing norbornene-based polymer that can be easily controlled, a method for producing the same, and a crosslinkable polymer composition containing the polymer and a crosslinking agent. The epoxy group-containing norbornene-based polymer of the present invention is suitable for use in, for example, circuit boards of electric / electronic devices by utilizing these various properties.

Claims (3)

[Claims] 1. A ring-opened polymer of a norbornene-based monomer having an epoxy group in the main chain structure and having a carbon-carbon double bond content of 30 mol% or less in the main chain structure. An epoxy group-containing norbornene-based polymer having an average molecular weight (Mn) of 500 to 500,000. 2. A method of hydrogenating a part of a carbon-carbon double bond in a main chain structure of a ring-opened polymer of a norbornene-based monomer,
Next, a method for producing an epoxy group-containing norbornene-based polymer, which comprises epoxidizing a carbon-carbon double bond with an epoxidizing agent. 3. A ring-opened polymer of a norbornene-based monomer having an epoxy group in the main chain structure and having a carbon-carbon double bond content of 30 mol% or less in the main chain structure. A crosslinkable polymer composition comprising an epoxy group-containing norbornene-based polymer having an average molecular weight (Mn) of 500 to 500,000, and a crosslinking agent.