JPH10120768A - Cyclic olefin polymer and crosslinkable polymer composition - Google Patents

Abstract

(57) [Abstract] (with revision) [Problem] To improve electrical characteristics, heat resistance, solder resistance, chemical resistance,
Provided is a cyclic olefin polymer having excellent properties such as mechanical strength. SOLUTION: A cyclic olefin polymer containing at least one kind of repeating unit derived from a specific norbornene monomer and having a number average molecular weight (Mn) in the range of 500 to 20,000 ( i), a production method thereof, a ring-opening (co) polymer of at least one cyclic olefin monomer, a hydrogenated (co) polymer of the ring-opening (co) polymer, and the at least one cyclic olefin monomer. Selected from the group consisting of addition copolymers with vinyl compounds, and having a number average molecular weight (Mn) of 50
A crosslinkable polymer composition comprising at least one kind of cyclic olefin polymer (ii) in the range of 0 to 20,000 and a crosslinking agent; a sheet-like molded product obtained by molding the composition; Prepreg obtained by impregnating a reinforcing substrate with the composition,
And laminates.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel cyclic olefin polymer, a method for producing the same, a crosslinkable polymer composition, a sheet-like molded product obtained by using the crosslinkable polymer composition,
It relates to a prepreg and a laminate. More specifically, the present invention is excellent in electrical properties, heat resistance, solder resistance, chemical resistance, mechanical strength, etc., can be a high concentration solution, and furthermore, a compounding agent such as a flame retardant in the solution The present invention relates to a low molecular weight cyclic olefin polymer and a crosslinkable polymer composition having excellent uniform dispersibility. Further, the present invention relates to a sheet-like molded product, a prepreg, a laminate, and a metal-clad laminate excellent in electrical properties, heat resistance, solder resistance, chemical resistance, mechanical strength, and the like.

[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, phenol resins, epoxy resins, polyimide resins, fluororesins, polybutadiene resins, and the like 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 a dielectric loss tangent of 0.01 or more and have insufficient electrical characteristics. However, it has been difficult to increase the speed and reliability of arithmetic processing. On the other hand, a circuit board using a thermoplastic resin such as a fluororesin or polybutadiene resin has poor heat resistance. Was also difficult.

Recently, there has been proposed a method of improving heat resistance, solvent resistance, etc. by crosslinking a thermoplastic norbornene resin with an organic peroxide. For example, JP
JP-A-34924 discloses that addition polymerization of a norbornene-based cyclic olefin and ethylene causes 135
C, the intrinsic viscosity [η] measured in decalin is 1.15 to
Method of synthesizing 2.22 norbornene-based resin, kneading the norbornene-based resin and a crosslinking aid, pulverizing the mixture, impregnating it with an organic peroxide solution, removing the solution, and press-molding to crosslink. Is disclosed. However, in this method, in addition to the complicated process, it is difficult to make the norbornene-based resin a high-concentration solution,
Further, there is a problem that the organic peroxide and other compounding agents are not uniformly dispersed. Therefore, to prepare a prepreg using the resin solution obtained by this method,
Although it is necessary to have a low-concentration solution, when the low-concentration solution is impregnated into the reinforcing substrate, the drying time is long until it does not stick at room temperature, and it must be allowed to stand so as not to deform during this time. There is a problem that productivity is poor. Also,
It is necessary to add various compounding agents according to various applications.However, because the viscosity of the solution is high, uniform dispersion cannot be achieved. There is a disadvantage of separation. 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.

JP-A-6-248164 discloses a thermoplastic hydrogenated ring-opened norbornene resin, an organic peroxide,
After dispersing a flame retardant such as a crosslinking aid and a brominated bisphenol in a solvent, the resulting solution is cast or impregnated into a reinforcing substrate, and then the solvent is removed.
A method for producing a sheet, a prepreg, or the like by thermal crosslinking is disclosed. However, when a norbornene-based resin having a number average molecular weight (Mn) of 28,000, which is specifically disclosed in the publication, is used, it is difficult to sufficiently increase the solid content, and the productivity of the drying step is reduced. Not enough. Furthermore, in this method, there is a limitation in the kind and amount of the compounding agent that can be uniformly dispersed, so that there is a problem that it cannot be applied sufficiently depending on the application field.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high-concentration solution having excellent properties such as electric properties, heat resistance, solder resistance, chemical resistance, and mechanical strength. An object of the present invention is to provide a cyclic olefin-based polymer having excellent uniform dispersibility of a compounding agent such as a flame retardant therein. Another object of the present invention is to provide a crosslinkable polymer composition containing such a cyclic olefin polymer and a crosslinking agent as essential components. Another object of the present invention is to use such a crosslinkable polymer composition, electrical properties, heat resistance, solder resistance, chemical resistance, sheet-like moldings having excellent properties such as mechanical strength, prepreg, It is to provide a laminate and a metal-clad laminate.

The present inventors have conducted intensive studies to overcome the problems of the prior art as described above, and as a result, by using a cyclic olefin polymer having a relatively low molecular weight,
Because the viscosity is low, it is possible to sufficiently increase the resin solution concentration, to be able to uniformly disperse even high-concentration compounding agents, to increase the types of compounding agents that can be uniformly dispersed, and to further improve the prepreg, laminate, and metal-clad laminate. It has been found that properties such as electric properties, heat resistance, solder resistance, chemical resistance, and mechanical strength are sufficiently excellent without lowering. Furthermore, the molecular weight distribution of this cyclic olefin polymer (Mw /
It has been found that by reducing Mn), the strength properties are further improved, and the decrease in strength properties due to the reduction in molecular weight can be sufficiently compensated. The present invention has been completed based on these findings.

[0008]

According to the present invention, the formula (A ₃ )

[0009]

Embedded image [In the formula, the meaning of each symbol is as follows. n is 0 or 1. p: 0 or a positive integer, preferably 0 or 1 to 1
It is an integer of 3. q is 0 or 1. R _{1 to} R ₁₈ each independently represent 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, an alkoxy group, a cyano group, an amide group, an imide group, or Hydrocarbon group substituted with a silyl group). R _{a to} R _b each independently represent a hydrogen atom, a hydrocarbon group,
Halogen atom, hydroxyl group, ester group, alkoxy group, cyano group, amide group, imide group, silyl group, or polar group (halogen atom, hydroxyl group, ester group, alkoxy group,
A hydrocarbon group substituted with a cyano group, an amide group, an imide group, or a silyl group). However, R _{15 to} R ₁₈ may combine with each other to form an unsaturated bond, a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond. At R ₁₅ and R ₁₆ or at R ₁₇ and R ₁₈ ,
An alkylidene group may be formed. When q is 0, each bond is bonded to form a 5-membered ring. ... : represents a carbon-carbon single bond or a double bond. ]
And the formula (B ₃ )

[0010]

Embedded image [In the formula, the meaning of each symbol is as follows. m: 0 or a positive integer, preferably 0 or 1 to 1
It is an integer of 3. h: 0 or a positive integer, preferably 0 or 1 to 1
It is an integer of 3. j: 0, 1 or 2. k: 0, 1 or 2. R ^{1 to} R ¹¹ each independently represent 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, an alkoxy group, a cyano group, an amide group, an imide group, or Hydrocarbon group substituted with a silyl group). R ^{12 to} R ²⁰ each independently represent 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, an alkoxy group, a cyano group, an amide group, an imide group, or Hydrocarbon group substituted with a silyl group). However, the carbon atom to which R ¹⁰ 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 ²⁰ may combine with each other to form a monocyclic or polycyclic aromatic ring. ... : represents a carbon-carbon single bond or a double bond. ]
At least one kind of repeating unit selected from the group consisting of repeating units represented by
There is provided a cyclic olefin-based polymer (i), wherein n) is in the range of 500 to 20,000.

The cyclic olefin polymer (i) is a hydrogenated polymer in which 95% or more of the carbon-carbon double bonds in the main chain are hydrogenated, and the carbon-carbon dibond non-conjugated to the side chain. When there is a heavy bond, 95% or more thereof is hydrogenated, and when there is an aromatic ring in the side chain, 20% of the aromatic ring is present.
It is preferable that about 100% remain without hydrogenation. The ratio (Mw) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of this cyclic olefin polymer
/ Mn) is preferably 4 or less.

According to the present invention, the formula (A)

[0013]

Embedded image [In the formula, the meaning of each symbol is as follows. n is 0 or 1. p: 0 or a positive integer, preferably 0 or 1 to 1
It is an integer of 3. q is 0 or 1. R _{1 to} R ₁₈ each independently represent 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, an alkoxy group, a cyano group, an amide group, an imide group, or Hydrocarbon group substituted with a silyl group). R _{a to} R _b each independently represent a hydrogen atom, a hydrocarbon group,
Halogen atom, hydroxyl group, ester group, alkoxy group, cyano group, amide group, imide group, silyl group, or polar group (halogen atom, hydroxyl group, ester group, alkoxy group,
A hydrocarbon group substituted with a cyano group, an amide group, an imide group, or a silyl group).

However, R _{15 to} R ₁₈ are bonded to each other,
It may form an unsaturated bond, a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond. R
₁₅ and R ₁₆ or R ₁₇ and R ₁₈ may form an alkylidene group. When q is 0, each bond is bonded to form a 5-membered ring. And formula (B)

[0015]

Embedded image [In the formula, the meaning of each symbol is as follows. m: 0 or a positive integer, preferably 0 or 1 to 1
It is an integer of 3. h: 0 or a positive integer, preferably 0 or 1 to 1
It is an integer of 3. j: 0, 1 or 2. k: 0, 1 or 2. R ^{1 to} R ¹¹ each independently represent 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, an alkoxy group, a cyano group, an amide group, an imide group, or Hydrocarbon group substituted with a silyl group). However, the carbon atom to which R ¹⁰ 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 ²⁰ may combine with each other to form a monocyclic or polycyclic aromatic ring. The ring-opening polymerization of at least one cyclic olefin monomer selected from the group consisting of cyclic olefin monomers represented by It contains at least one type of repeating unit selected from the group consisting of (A ₃ ) and a repeating unit represented by the formula (B ₃ ), and has a number average molecular weight (Mn) of 500 to 20,000.
A method for producing a cyclic olefin polymer (i) in the range of 0 is provided.

Further, according to the present invention, a ring-opening (co) polymer of at least one cyclic olefin monomer selected from the group consisting of the cyclic olefin monomers represented by the formulas (A) and (B) , A hydrogenated (co) polymer of the ring-opened (co) polymer, and an addition copolymer of the at least one cyclic olefin monomer and a vinyl compound, and having a number average molecular weight (Mn). )
Is within the range of 500 to 20,000, and at least one cyclic olefin polymer (ii), and a crosslinkable polymer composition comprising a crosslinking agent. According to the present invention, a sheet-like molded product obtained by molding the cross-linkable polymer composition, a prepreg obtained by impregnating a reinforcing base material with the cross-linkable polymer composition, a sheet-shaped molded product thereof, and / or Provided are a laminate obtained by laminating a prepreg and crosslinking a crosslinkable polymer composition, and a laminate in which a metal layer is further laminated on the laminate.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Cyclic olefin polymer (i) (1) Polymer The cyclic olefin polymer (i) of the present invention has the formula (A)
It is a relatively low molecular weight polymer containing at least one type of repeating unit selected from the group consisting of the repeating units represented by ₃ ) and (B ₃ ). In these formulas, ...
* Represents a carbon-carbon single bond (CC) or a double bond (C = C). The cyclic olefin polymer (i) is
It can be obtained by ring-opening (co) polymerizing at least one cyclic olefin selected from the group consisting of the cyclic olefin monomers represented by the formulas (A) and (B), and hydrogenating as necessary. The ring-opened (co) polymer has a carbon-carbon double bond in the main chain. When this ring-opened (co) polymer is hydrogenated, the double bond in the main chain is hydrogenated to form a carbon-carbon single bond. In this case, the hydrogenation rate is 1
If it does not reach 00%, a carbon-carbon single bond and a double bond will coexist. ... represents all unhydrogenated parts, hydrogenated product and partially hydrogenated product.

The carbon-carbon double bond in the main chain may be hydrogenated at a hydrogenation rate of 95% or more. If non-conjugated carbon-carbon double bonds are present in the side chains, they are likewise hydrogenated during hydrogenation of the main chain double bonds. When there is an aromatic ring in the side chain, when the selective hydrogenation of the carbon-carbon double bond of the main chain is performed, the aromatic ring remains without hydrogenation, but the carbon-carbon double bond of the main chain and the aromatic ring remain. When hydrogenation of the conjugated double bond of the ring is performed simultaneously, the aromatic ring is also saturated by hydrogenation. However, in the cyclic olefin-based polymer (i) of the present invention, when an aromatic ring is present in the side chain, 20 to 100% of the aromatic ring remains without hydrogenation, which indicates that the uniform dispersibility of various compounding agents It is preferable from the viewpoint of. The hydrogenation will be described later in detail. Further, the more specific contents of the symbols in the other formulas will be described in detail in the description of the production method of the cyclic olefin polymer (i).

The molecular weight of the cyclic olefin polymer (i) of the present invention can be expressed as a number average molecular weight (Mn) in terms of polystyrene of 500 as determined by gel permeation chromatography (GPC) using toluene as a solvent.
~ 20,000, preferably 1,000 ~ 15,000
0, more preferably from 2,000 to 10,000, most preferably from 3,000 to 9,000. The cyclic olefin polymer (i) of the present invention is characterized in that it is a polymer having a relatively small specific range of molecular weight. The cyclic olefin-based polymer (i) can have a higher polymer concentration when a solution having the same viscosity is used as compared with the case where a conventionally known high molecular weight polymer is used. It can significantly improve productivity, has good impregnating property to the reinforcing base material, has excellent uniform dispersibility of various compounding agents, and has almost no deterioration in physical properties of molded articles. If the number average molecular weight of the cyclic olefin polymer (i) is too small, the mechanical strength is not sufficient, and conversely,
If it is too large, the dispersibility of the compounding agent is not sufficient, and both are not preferred.

The molecular weight distribution of the cyclic olefin polymer (i) of the present invention is determined by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene measured by GPC using toluene as a solvent. ) Is usually 4 or less,
When preferably 3 or less, more preferably 2 or less,
This is preferable because the mechanical strength can be sufficiently increased, and a slight decrease in mechanical strength caused by reducing the molecular weight can be sufficiently compensated. The cyclic olefin polymer (i) of the present invention comprises a ring-opened polymer of a cyclic olefin monomer having a repeating unit represented by the formula (A ₃ ) or a hydrogenated polymer thereof (hydrogenated product), a compound represented by the formula (B) ₃ ) A ring-opened polymer of a cyclic olefin-based monomer having a repeating unit represented by formula ( ₃ ) or a hydrogenated product thereof, and a cyclic olefin-based polymer containing both repeating units represented by formulas (A ₃ ) and (B ₃ ) It is a ring-opened copolymer of a monomer or a hydrogenated product thereof. The cyclic olefin polymer (i) of the present invention
Is a ring-opening copolymer or a hydrogenated product thereof containing both the repeating units represented by the formulas (A ₃ ) and (B ₃ ), and the aromatic ring-containing ring represented by the formula (B ₃ ) The proportion of the repeating unit derived from the olefin-based monomer is usually at least 10% by weight, preferably at least 30% by weight, more preferably at least 50% by weight, from the viewpoint of uniform dispersibility of various additives.

(2) Cyclic olefin-based monomer The cyclic olefin-based polymer (i) has the formula (A) or (B)
At least one cyclic olefin-based monomer selected from the group consisting of the cyclic olefin-based monomers represented by the following formula (I), is subjected to ring-opening (co) polymerization in the presence of a metathesis catalyst, and is optionally hydrogenated. Examples of the cyclic olefin-based monomer represented by the formulas (A) and (B) include, for example, bicyclo [2.2.1] hept-
2-ene derivative, tetracyclo [4.4.0.1 ^2,5 .
17, 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.
^13-6 . 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 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-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-hexacosenoic derivatives, 1,4-methano -1,4,4a, 9a- tetrahydrofluorene derivatives, 1,4-methano-1,4,
Examples thereof include 4a, 5,10,10a-hexahydroanthracene derivatives and cyclopentadiene-acenaphthylene adducts. More specifically, it is as shown below.

<Cyclic Olefin Monomer Represented by Formula (A)> The symbols in the formula (A) correspond to the symbols in the formula (A ₃ ). In the formula (A), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. As the hydrocarbon group, for example, an alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms, and having 2 to 2 carbon atoms.
0, preferably 2 to 10, more preferably 2 to 6 alkenyl groups, having 2 to 20 carbon atoms, preferably 2 to 1 carbon atoms.
0, more preferably 2-6 alkynyl groups, 3-15 carbon atoms, preferably 3-8, more preferably 5-6 cycloalkyl groups, and 6-20 carbon atoms, preferably 6-16, More preferably, there may be mentioned 6 to 10 aromatic hydrocarbon groups. 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.

Specific examples of the cyclic olefin monomer represented by the formula (A) include, for example, JP-A-2-22742.
4, JP-A-2-276842, JP-A-8-
Known monomers disclosed in, for example, Japanese Patent No. 72210 can be used. Specifically, the following norbornene-based monomers can be exemplified. 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.
^12.5 . 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 . 1
^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . Octacyclo [8.8.0.1 ^{2,9 .0,12,17} ] -5-docosene.
^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, 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-methyl-tricyclo [4.3.0.1 ^2,5] -3-decene, 5-methyl-tricyclo [4.3.0.1 ^{2 ,} 5] -3-decene, tricyclo such [4.3.0.1 ^{2, 5]} -3-decene derivatives;
Tricyclo [4.4.0.1 ^2,5 ] -3-undecene,
10-methyltricyclo [4.4.0.1 ^2,5 ] -3-
Tricyclo [4.4.0.1 ^2,5 ] such as undecene
-3-undecene derivative; pentacyclo [6.5.1.
^13-6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene, 1,3-
Dimethylpentacyclo [6.5.1.1 ^3,6 . 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-pentadecene,
Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0
^9,13 ] -4-pentadecene derivative; pentacyclo [6.
5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] 4,10 penta decadiene, diene compounds, such as pentacyclo [7.
4.0.1 ^2,5 . ^19,12 . 0 ^8,13] -3-pentadecene, methyl-substituted pentacyclo [7.4.0.1 ^2,5. 1
^9,12 . 0 ^8,13] -3-pentadecene, pentacyclo such [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, dimethyl-substituted heptacyclo [8.7.0.1 ^3,6 .
1 ^10,17 . 1 ^12,15 . 0 ^2,7 . 0 ^11,16 ] -4-eicosene, etc., and heptacyclo [8.7.0.1 ^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 [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-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, 10,1
1-dimethyl-pentacyclo [8.4.0.1 ^2,5 . 1
^9,12 . 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.
^14,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . Heptacyclo [8.8.0.1], such as 0 ^12,17 ] -5-heneicosene.
^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]} -6-hexacosenoic, Nonashikuro such as [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 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-penta-octadecadienoic, trimethyl replacement 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.
^12.5 . 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 [7.8.0.1 ^3,6 . 0 ^2,7 . 1
^10,17 . 0 ^11,16 . 1 ^12,15] -4-eicosene, trimethyl-substituted heptacyclo [7.8.0.1 ^3,6. 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. Further, as other specific examples, a monomer having a polycyclic structure which is a multimer of cyclopentadiene and a derivative or a substituent thereof,
For example, tricyclo [4.3.0.1 ^2,5 ] -3,7-
Decadiene (ie, dicyclopentadiene), 2,
3-dihydrodicyclopentadiene and the like.

<Cyclic Olefin Monomer Represented by Formula (B)> Each symbol in the above formula (B) corresponds to each symbol in the formula (B ₃ ). In the formula (B), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. As the hydrocarbon group, for example, an alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms, and having 2 to 2 carbon atoms.
0, preferably 2 to 10, more preferably 2 to 6 alkenyl groups, having 2 to 20 carbon atoms, preferably 2 to 1 carbon atoms.
0, more preferably 2 to 6 alkynyl groups, 2 to 20 carbon atoms, preferably 2 to 10, more preferably 2 to
6, an alkylidene group, a cycloalkyl group having 3 to 15, preferably 3 to 8, more preferably 5 to 6 carbon atoms, and a cycloalkyl group having 6 to 20, preferably 6 to 16, more preferably 6 to 10 carbon atoms. Examples thereof include an aromatic hydrocarbon group. 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 cyclic olefin monomer represented by the formula (B), for example, known monomers described in JP-A-5-97719, JP-A-7-41550, JP-A-8-72210 and the like can be used. Can be used.

Specific examples of the monomer having an aromatic substituent in the cyclic olefin monomer represented by the formula (B) are as follows. 5-phenyl-bicyclo [2.2.1] hept-2-ene (i.e., 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 0.1 ^2,5 . 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.
^12.5 . 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.
^12.5 . 1 ^7,10 ] -3-dodecene, 8- (biphenyl)
-Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Dodecene, 8- (β-naphthyl) -tetracyclo [4.
4.0.1 ^2,5 . 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.

Specific examples of the cyclic olefin monomer represented by the formula (B) having a norbornene ring structure and an aromatic ring structure in a polycyclic structure are as follows. 1,4-methano-1,4,4a, 4b, 5,8,8a,
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.

(3) Polymerization Method These cyclic olefin monomers can be used alone or in combination of two or more. In the case of a ring-opening copolymer, the proportion (bonding amount) of the aromatic ring-containing norbornene-based monomer represented by the formula (B) is appropriately selected according to the purpose of use, but is usually 10% by weight or more, preferably 30% by weight or more. % By weight or more, more preferably 50% by weight or more. By containing the aromatic ring-containing norbornene-based monomer unit, the dispersibility of various compounding agents is highly improved. The ring-opening polymer or ring-opening copolymer of the cyclic olefin-based monomer (norbornene-based monomer) represented by the formula (A) and / or (B) can be obtained by a known polymerization method.

As the ring-opening polymerization catalyst, 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, A catalyst comprising a halide or acetylacetone compound of a metal selected from zirconium, tungsten and molybdenum and an organoaluminum compound can be used. By adding a third component to the 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,
Aliphatic or aromatic tertiary amines are preferred 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 . The ring-opened polymer of the cyclic olefin monomer represented by the formula (A) is a polymer containing a repeating unit represented by the following formula (A ₁ ).

[0030]

Embedded image [Wherein the symbols have the same meanings as in the expression (A). The ring-opened polymer of the cyclic olefin monomer represented by the formula (B) is a polymer containing a repeating unit represented by the following formula (B ₁ ).

[0031]

Embedded image [In the formula, the meaning of each symbol is the same as in Formula (B). The ring-opening copolymer is a copolymer containing the repeating units represented by the formulas (A ₁ ) and (B ₁ ).

(4) Hydrogenation The cyclic olefin polymer (i) is an unhydrogenated product containing a repeating unit represented by the above formula (A ₁ ) and / or (B ₁ ), May remain, but from the viewpoint of heat resistance, weather resistance, etc., it is preferable that at least the carbon-carbon double bond of the main chain is hydrogenated. . The hydrogenated product can be obtained by a method of hydrogenating a ring-opened (co) polymer with hydrogen in the presence of a hydrogenation catalyst according to a conventional method. 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 cyclic olefin polymer (i) of the present invention
Is preferably high in weather resistance and light deterioration resistance. Therefore, the unsaturated bond in the main chain structure of the ring-opened (co) polymer is usually 95% or more, preferably 98% or more, more preferably 99%. The above is preferably saturated. When there is a non-conjugated unsaturated bond such as an alkylidene group in the side chain,
Hydrogenation occurs simultaneously with hydrogenation of unsaturated bonds in the main chain. In the case of a ring-opened (co) polymer having an aromatic ring in the side chain,
20% or more, preferably 30% or more of the aromatic ring structure,
Preferably, 40% or more, and most preferably, 100% remains. Unsaturated bonds in the main chain structure and unsaturated bonds in the aromatic ring structure can be distinguished and recognized by ¹ H-NMR analysis.

In order to mainly hydrogenate unsaturated bonds in the main chain structure, the temperature is preferably from -20 ° C to 120 ° C, more preferably from 0 to 10 ° C.
0 ° C, more preferably at a temperature of 20 to 80 ° C, 0.1 to
50 kg / cm ² , preferably 0.5 to 30 kg / c
The hydrogenation reaction is desirably performed at a hydrogen pressure of m ² , more preferably 1 to 20 kg / cm ² . In order to hydrogenate the aromatic ring, for example, the hydrogenation temperature is increased to about 150 to 250 ° C. The hydrogenated product of the ring-opened polymer of the cyclic olefin monomer represented by the formula (A) is a polymer containing a repeating unit represented by the following formula (A ₂ ) in which an unsaturated bond in the main chain is hydrogenated. It is.

[0036]

Embedded image [Wherein the symbols have the same meanings as in the expression (A). The hydrogenated product of the ring-opened polymer of the cyclic olefin monomer represented by the formula (B) contains a repeating unit represented by the following formula (B ₂ ) in which the unsaturated bond in the main chain is hydrogenated. It is a polymer.

[0037]

Embedded image [In the formula, the meaning of each symbol is the same as in Formula (B). The hydrogenated product of the ring-opening copolymer is a copolymer containing the repeating units represented by the formulas (A ₂ ) and (B ₂ ). However, these are hydrogenated ring-opened (co) polymers,
Those having a small hydrogenation rate have the side chain double bond represented by the formula (A ₁ ) and / or (B ₁ ) remaining. On the other hand, when part of the aromatic ring in the side chain is hydrogenated, in the repeating unit represented by the formula (B ₂ ), part of the aromatic ring is hydrogenated and saturated.

Crosslinkable Polymer Composition (1) Cyclic Olefin Polymer (ii) The crosslinkable polymer composition of the present invention comprises a resin containing the cyclic olefin polymer (ii) and a crosslinking agent as essential components. A composition. The cyclic olefin polymer (i)
The i) includes, in addition to the cyclic olefin polymer (i), an addition polymer of a cyclic olefin monomer and a vinyl compound. Therefore, the cyclic olefin polymer (ii) is a ring-opened (co) polymer of at least one cyclic olefin monomer selected from the group consisting of the cyclic olefin monomers represented by the formulas (A) and (B). And a hydrogenated product thereof, and an addition copolymer of the cyclic olefin monomer and a vinyl compound. These polymers can be used alone or in combination of two or more.

The number average molecular weight (Mn) and the molecular weight distribution of the cyclic olefin polymer (ii) are the same as those of the cyclic olefin polymer (i). That is, the number average molecular weight (Mn) of the cyclic olefin polymer (ii) is in the range of 500 to 20,000 in terms of polystyrene measured by GPC using toluene as a solvent, and preferably 1,000 to 15 2,000, more preferably 2,000
-10,000, most preferably 3,000-900
It is within the range of 0. Cyclic olefin polymer (ii)
However, by being in the specific low-molecular-weight region as described above, a high-concentration solution can be obtained, the productivity in the drying step can be increased, the impregnation property of the reinforcing base material and uniformity of various compounding agents can be improved. Dispersibility can also be increased. If the number average molecular weight is too small, the mechanical strength of a molded product will be reduced. The molecular weight distribution of the cyclic olefin polymer (ii) is not particularly limited, but the ratio (Mw) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene measured by GPC using toluene as a solvent. / M
When n) is usually 4 or less, preferably 3 or less, more preferably 2 or less, it is desirable because the mechanical strength is increased.

The addition polymer is obtained by subjecting at least one cyclic olefin monomer selected from the group consisting of the cyclic olefin monomers represented by the formulas (A) and (B) to an addition polymerization with a vinyl compound. Obtainable. Examples of the vinyl compound include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, and 4-methyl. -1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene,
-Ethyl-1-hexene, 3-ethyl-1-hexene,
C2-C20 ethylene or α-olefins such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; cyclobutene, cyclopentene, cyclohexene, 3,4 Cycloolefins such as -dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene; 4-hexadiene, 4-methyl-
Non-conjugated dienes such as 1,4-hexadiene, 5-methyl-1,4-hexadiene and 1,7-octadiene; styrene, α-methylstyrene, o-methylstyrene, p-
Aromatic vinyl compounds such as methylstyrene, 1,3-dimethylstyrene, and vinylnaphthalene; and the like. These vinyl compounds can be used alone or in combination of two or more.

In order to produce an addition copolymer of a cyclic olefin-based monomer and a vinyl compound, a known method can be employed. For example, the monomer component can be prepared in a hydrocarbon solvent or under a solvent-free condition. And a method of copolymerizing in the presence of a catalyst comprising a vanadium compound soluble in a solvent or a norbornene-based monomer and an organic aluminum compound, preferably a halogen-containing organic aluminum compound. As a hydrocarbon catalyst, for example,
Aliphatic hydrocarbons such as hexane, heptane, octane and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene and xylene.

The polymerization temperature is usually -50 ° C to 100 ° C, preferably -30 ° C to 80 ° C, more preferably -20 ° C to
60 ° C. and the polymerization pressure is usually 0 to 50 kg / cm
² , preferably 0 to 20 kg / cm ² . The cyclic olefin polymer (ii) can be prepared by a method known in JP-A-3-95235 or the like, using an α, β-unsaturated carboxylic acid,
It may be modified using a derivative thereof, a styrene-based hydrocarbon, an organosilicon compound having an olefin-based 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 thereof such as acid anhydrides or alkyl esters of unsaturated carboxylic acids are preferable.

(2) Crosslinking agent The crosslinking of the crosslinkable polymer composition of the present invention is not particularly limited, and can be performed using, for example, heat, light, radiation, and the like. Is appropriately selected by the means. When the cyclic olefin-based polymer (ii) 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 thermosetting resin, a flame retardant, other compounding agents, a solvent, and the like, if desired. 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; 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, Peroxy ketals such as 2-bis (t-butylperoxy) butane; hydroperoxides such as t-butyl hydroperoxide and 2,5-dimethylhexane-2,5-dihydroperoxide; dicumylper Oxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, α, α′-bis (t-
Dialkyl peroxides such as butylperoxy-m-isopropyl) benzene; diacyl peroxides such as octanoyl peroxide and isobutyryl peroxide; and peroxyesters such as peroxydicarbonate. 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, as the cross-linking agent, a photo-crosslinking agent that generates a radical by light can be used. 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 amount of the cross-linking agent to be added is 100% of the cyclic olefin polymer (ii).
0.001-30 parts by weight, preferably 0.001-15 parts by weight, more preferably 0.1
10 to 10 parts by weight, most preferably 0.5 to 5 parts by weight. When the compounding amount of the cross-linking agent is within this range, the properties such as cross-linkability and electric properties, chemical resistance and water resistance of the cross-linked product are highly balanced and suitable.

(3) 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, 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.

(4) Thermosetting Resin In the crosslinkable polymer composition of the present invention, when a thermosetting resin such as an epoxy resin is added, the adhesive strength of the laminate is highly improved, which is preferable. The thermosetting resin is not particularly limited, and generally used resins are used, for example, epoxy resin, urea resin, melanin resin,
Examples include phenolic resins, polyaminobismaleimide resins, modified imide resins, bismaleimide / triazine resins, unsaturated polyester resins, and the like. Among these,
Epoxy resins are preferred.

The thermosetting resin usually comprises a low molecular weight raw material and a curing agent. For example, in the case of an epoxy resin, it is composed of an epoxy compound and various curing agents. The epoxy compound is not particularly limited as long as it has an epoxy group in the molecule, and is a bisphenol type, a novolak type,
Compounds used as epoxy resins such as alicyclic type, heterocyclic type, glycerin type and dicyclopentadiene type can be mentioned. Among them, the halogenated bisphenol type epoxy compound represented by the formula (E1) is preferable.

[0050]

Embedded image (Wherein, X is a halogen atom, R is a divalent hydrocarbon group, m is 1-3, and n is 0 or an integer of 1 or more.) In the epoxy compound of the formula (E1), , M are all 2, n is substantially 0, a halogen atom X is a bromine atom, and R is an isopropylidene group. Further, a novolak type epoxy compound represented by the formula (E2) is preferably used.

[0051]

Embedded image (In the formula, R ′ is a hydrogen atom, 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 (E2), the average value of p is 0.
And R 'is preferably a hydrogen atom or a methyl group. These epoxy compounds can be used alone or in combination of two or more. The bisphenol-type epoxy compound of the formula (E1) is preferable when the flame retardancy is important, and the novolak-type epoxy compound of the formula (E2) is preferable when the heat resistance and the chemical resistance are to be improved. Specific examples of the epoxy compound of the formula (E1) include a compound represented by the formula (E3).

[0052]

Embedded image As the halogenated bisphenol type epoxy compound represented by the formula (E3), for example, the Br content is 20% by weight.
And 50% by weight are commercially available. As a curing agent for the epoxy resin, for example, an amine compound,
Known compounds such as an imidazole compound, a nitrogen-containing heterocyclic compound such as diazabicycloundecene, an organic phosphine, an organic boron complex, a quaternary ammonium compound, and a quaternary phosphonium can be used. The addition amount of the thermosetting resin is usually 3 to 150 parts by weight, preferably 10 to 10 parts by weight based on 100 parts by weight of the cyclic olefin polymer (ii).
It is 140 parts by weight, particularly preferably 15 to 120 parts by weight.

(5) Flame Retardant The flame retardant is not particularly limited, but is preferably one that does not decompose, modify or degrade with a crosslinking agent. 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 [eg, tetrabromobisphenol A-bis (hydroxyethyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromo Bisphenol 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), etc.], tetrabromophthalic anhydride, and derivatives thereof [eg, tetrabromophthalimide, ethylenebistetrabromophthalate Imide], ethylenebis (5,6-dibromo-norbornene-2,3-dicarboximide), tris - (2,3-dibromopropyl -
1) -Isocyanurate, adduct of Diels-Alder reaction of hexachlorocyclopentadiene, tribromophenyl glycidyl ether, tribromophenyl acrylate, ethylenebistribromophenyl ether,
Ethylene bispentabromophenyl ether, tetradecabromodiphenoxybenzene, brominated polystyrene,
It is preferable to use brominated polyphenylene oxide, brominated epoxy resin, brominated polycarbonate, polypentabromobenzyl acrylate, octabromonaphthalene, hexabromocyclododecane, bis (tribromophenyl) fumaramide, N-methylhexabromodiphenylamine and the like. . Particularly preferred flame retardants among the flame retardants used in the present invention will be described with reference to chemical formulas. Preferred examples of the flame retardant which is hardly decomposed, denatured or deteriorated by the organic peroxide in the resin composition in the uniform dispersibility or the crosslinking reaction step include the compounds represented by the following formulas.

[0054]

Embedded image

[0055]

Embedded image

[0056]

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

[0057]

Embedded image

[0058]

Embedded image (In the formula, n is an integer of 0 or 1 or more, and m1 to m4
Is an integer of 1 or more, 1 ≦ m1 ≦ 5, 1 ≦ m2 ≦ 4,
1 ≦ m3 ≦ 4, 1 ≦ m4 ≦ 5, preferably 2 ≦ m1 ≦
4, 5 ≦ m2 ≦ 3, 2 ≦ m3 ≦ 3, 2 ≦ m4 ≦ 4, particularly preferably m1 = 3, m2 = 2, m3 = 2, m4 = 3. )

[0059]

Embedded image (Where n is 0 or an integer of 1 or more, and m1 to m6
Is an integer of 1 or more, 1 ≦ m1 ≦ 5, 1 ≦ m2 ≦ 5,
1 ≦ m3 ≦ 4, 1 ≦ m4 ≦ 4, 1 ≦ m5 ≦ 5, 1 ≦ m6
≦ 5, preferably 2 ≦ m1 ≦ 4, 2 ≦ m2 ≦ 4, 2 ≦ m
3 ≦ 3, 2 ≦ m4 ≦ 3, 2 ≦ m5 ≦ 3, 2 ≦ m6 ≦ 4,
Particularly preferably, m1 = 3, m2 = 2, m3 = 2, m4 =
2, m5 = 3 and m6 = 3. )

[0060]

Embedded image (This is a specific example of Formula N5.)

[0061]

Embedded image (This is a specific example of Formula N6.)

[0062]

Embedded image Incidentally, the halogenated bisphenol type epoxy compound in the thermosetting resin is also a kind of flame retardant. The amount of the flame retardant to be added is usually 3 to 150 parts by weight, preferably 10 to 14 parts by weight, per 100 parts by weight of the aromatic ring-containing norbornene polymer.
0 parts by weight, particularly preferably 15 to 120 parts by weight.
As a flame retardant aid for more effectively exhibiting the flame retardant effect of the flame retardant, for example, an antimony-based flame retardant aid such as antimony trioxide, antimony pentoxide, sodium antimonate, and antimony trichloride may be used. it can. These flame retardant aids are usually 1 to 3 parts by weight based on 100 parts by weight of the flame retardant.
0 parts by weight, preferably 2 to 20 parts by weight.

(6) Other Compounding Agents The resin composition of the present invention may contain, if necessary, an elastomer, a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, and a lubricant. Various additives such as dyes, pigments, natural oils, synthetic oils, waxes, and organic or inorganic fillers can be added in appropriate amounts.

Specifically, for example, natural rubber, polyisoprene rubber and its hydrogenated product, polybutadiene rubber and its hydrogenated product, butadiene-isoprene copolymer rubber and its hydrogenated product, styrene-butadiene random copolymer Rubber and its hydrogenated product, styrene-isoprene random copolymer and its hydrogenated product, acrylonitrile-butadiene copolymer rubber and its hydrogenated product, styrene-butadiene block copolymer rubber and its hydrogenated product, styrene-isoprene Elastomers such as block copolymers and hydrogenated products thereof, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber, ethylene-butene copolymer rubber, propylene-butene copolymer rubber; [Methylene-3
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] methane, β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2′-oxamidobis [ethyl-3 (3,3
5-di-t-butyl-4-hydroxyphenyl) propionate]; trisnonylphenyl phosphite, tris (2,4-di-t-brylphenyl) phosphite, tris (2,4 -Di-t
Phosphorus-based stabilizers such as -butylphenyl) phosphite; fatty acid metal salts such as zinc stearate, calcium stearate and calcium 12-hydroxystearate; glycerin monostearate, glycerin monolaurate;
Glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate,
Polyhydric alcohol fatty acid esters such as pentaerythritol tristearate; synthetic hydrotalcite; amine-based antistatic agents; cups such as silane coupling agents, titanate coupling agents, aluminum-based coupling agents, and zircoaluminate coupling agents. Ring agents; plasticizers; coloring agents such as pigments and dyes; 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.

(7) Solvent In the present invention, the cyclic olefin polymer (ii) is dissolved in a solvent to prepare an impregnation solution for prepreg,
A sheet (film) can be produced by a solution casting method. As described above, when the cyclic olefin polymer (ii) is dissolved using a solvent, for example, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, and aliphatic hydrocarbons such as n-pentane, hexane, and heptane And alicyclic hydrocarbons such as cyclohexane, and halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene. The solvent is used in an amount ratio sufficient to uniformly dissolve or disperse the aromatic ring-containing norbornene-based polymer and each component to be blended as required.

In the present invention, such as a molded article, a prepreg, and a laminate , after the crosslinkable polymer composition is molded,
Crosslinking is performed to obtain 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 one of the specific examples of the crosslinked molded article of the present invention, uniformly dissolves or disperses a crosslinkable polymer composition and various compounding agents in a solvent such as toluene, cyclohexane, or xylene. And then impregnated with a reinforcing substrate and dried to remove the solvent. Generally, it is preferable that the prepreg has a thickness of about 50 to 500 μm. As the solvent, those described above can be used. The amount of the solvent used is usually a solid concentration of 1 to 1.
90% by weight, preferably 5-85% by weight, more preferably 10-80% by weight, most preferably 20-80% by weight
It is adjusted to become.

Examples of the reinforcing base material include paper base materials (such as linter paper and kraft paper), glass base materials (such as glass cloth, glass mat and glass paper quartz fiber), and synthetic resin fiber base materials (such as polyester fiber and 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 norbornene-based polymer with respect to the reinforcing substrate is appropriately selected depending on the purpose of use.
It is in the range of from 90 to 90% by weight, preferably from 10 to 60% 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. 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 the cross-linked molded article of the present invention, is formed by stacking the above-mentioned prepreg and / or uncross-linked sheet, and heat-press molding to form a cross-linked sheet. The required thickness is obtained by heat fusion. 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 heat fusion temperature or higher depending on the norbornene resin used, usually 150 to 3
The laminate is heated to about 00 ° C., pressurized to about 30 to 80 kgf / cm ² , and crosslinked and thermally fused between the layers to obtain a laminate. Other methods of applying metal to these insulating layers or substrates include deposition, electroplating, sputtering, ion mecca,
Spraying and layering. Commonly used metals are copper, nickel, tin, silver, gold, aluminum, platinum,
Titanium, zinc, chromium and the like. Copper is most frequently used in wiring boards.

(4) Crosslinking In the present invention, a crosslinked molded article is obtained by singly or by laminating, and heating and crosslinking at a certain temperature or higher. The temperature at which the cross-linking reaction occurs is determined mainly by the combination of the organic peroxide and the cross-linking auxiliary, but is usually 80 to 350 ° C., preferably 120 to 300 ° C.
More preferably, it is crosslinked by heating to a temperature of 150 to 250 ° C. The crosslinking time is preferably about four times the half-life of the organic peroxide, and is usually 5 to 120 times.
Minutes, preferably 10 to 90 minutes, 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 of the present invention include a laminate, a circuit board, an interlayer insulating film, a film for forming a moisture-proof layer, and the like. Crosslinked molded article of the present invention is usually water absorption of 0.03% or less, insulation resistance 10 ¹⁵ to 10 ¹⁷ Omega, dielectric constant at 1 MH _Z, the dielectric loss tangent respectively 2.0～2.5,0. 001 to 0.0007
It is excellent in water resistance and electrical properties as compared with a conventional thermosetting resin molded article. On the other hand, the heat resistance is the same as that of a conventional thermosetting resin molded product. No abnormalities are observed. For these reasons, the laminate that is the crosslinked molded article of the present invention is also preferable as a circuit board. Further, the crosslinked molded article of the present invention is excellent in flame retardancy, specifically, UL-94.
In the standard, those showing V-2 or superior flame retardancy are preferred, those showing V-1 or V-0 flame retardancy are more preferred, and those showing V-0 flame retardancy are particularly preferred. preferable. In order to obtain such a crosslinkable molded article, a crosslinkable resin composition containing the above-described flame retardant may be used.

[0076]

The present invention will be specifically described below with reference to Synthesis Examples, Examples and Comparative Examples. In addition, the measuring method of physical properties is as follows. (1) The glass transfer temperature is determined by the differential scanning calorimetry (DSC method).
Was measured by (2) 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. (3) The hydrogenation rates of the main chain and side chains were measured by ¹ H-NMR. (4) The copolymerization ratio was measured by ¹ H-NMR. (5) Flame retardancy was measured according to the 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) Copper foil peel strength is 20m width from resin laminate
m, a test piece of 100 mm in length was taken out and a width of 10
mm, a copper foil was continuously peeled off at a speed of 50 mm / min in a direction perpendicular to the surface with a tensile tester, and the lowest value of the stress at that time was shown. (8) Toluene resistance was 25 m for the laminate from which the copper foil had been removed.
After cutting out to m-square and boiling in toluene for 5 minutes, the change in appearance was visually observed and evaluated according to the following criteria. ：: no change in appearance, ×: change in appearance. (9) Solder resistance was 25 mm for the laminate from which the copper foil had been removed.
After cutting into corners and floating in a 260 ° C. solder bath for 120 seconds, changes in appearance were visually observed and evaluated according to the following criteria. ：: no change in appearance, ×: change in appearance. (10) Crack resistance A hole having a diameter of 1 mm was made in the laminate using a drill, the cross section was observed, and judgment was made according to the following criteria. ：: no cracks, or even very small cracks, ○: small cracks, ×: cracks are clearly observed.

[Synthesis Example 1] 8-methyltetracyclo [4.4.0.1] was placed in a 1-liter flask purged with nitrogen.
^2,5 . 1 ^7,10 ] -3-dodecene (hereinafter abbreviated as MTD)
5 g and 120 g of toluene were added, and 0.287 mmol of triisobutylaluminum and 0.287 mmol of isobutyl alcohol were added as polymerization catalysts, and 8.61 mmol of 1-hexene was added as a molecular weight regulator. here,
After adding 0.057 mmol of tungsten hexachloride, 40
Stirred at C for 5 minutes. Thereafter, 45 g of MTD 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 stirred for 30 minutes to complete the polymerization.

The polymerization reaction solution was transferred to a 1-liter autoclave, 160 g of toluene was added, and a mixture of 0.5 g of nickel acetylacetonate and 5.15 g of a 30% by weight toluene solution of triisobutylaluminum was added. Is replaced with hydrogen, and then stirred at 80 ° C.
The temperature rose. When the temperature is stable, increase the hydrogen pressure to 30k
The reaction was performed for 3 hours while increasing the pressure to g / cm ² and replenishing the hydrogen consumed during the reaction. Then, water of 4.2 g, activated alumina (surface 320 cm ² / g, pore volume 0.8 cm ² / g, average particle size 15 [mu] m, manufactured by Mizusawa Chemical Co., Neobido D powder) of 2.5g was added, 80 ° C. After stirring for 1 hour at, the hydrogenation reaction solution from which the solid content was removed by filtration was poured into 3 liters of isopropyl alcohol to precipitate out, and was collected by filtration. 100 ° C,
It was dried at 1 Torr or less for 48 hours. Table 1 shows the synthesis results.
It was shown to. This polymer is designated as A. The repeating unit of the polymer A is represented by the following formula.

[0079]

Embedded image (However, ... is almost a carbon-carbon single bond.)

[Synthesis Example 2] MTD was converted to 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . A white powder was obtained in the same manner as in Synthesis Example 1 except that the composition was changed to [ ^1,7,10 ] -3-dodecene (hereinafter abbreviated as ETD). The synthesis results are shown in Table 1. This polymer is designated as B. The repeating unit of the polymer B is represented by the following formula.

[0081]

Embedded image (However, ... is almost a carbon-carbon single bond.)

[Synthesis Example 3] MTD was converted to 1,4-methano-
1,4,4a, 9a-tetrahydrofluorene (hereinafter, referred to as
A white powder was obtained in the same manner as in Synthesis Example 1 except that MTF was abbreviated. The synthesis results are shown in Table 1. This polymer is designated as C. The repeating unit of the polymer C is represented by the following formula.

[0083]

Embedded image (However, ... is almost a carbon-carbon single bond.)

[Synthesis Example 4] MTD was converted to 5-phenyl-2
A white powder was obtained in the same manner as in Synthesis Example 1 except that -norbornene (hereinafter abbreviated as PNB) was used. The synthesis results are shown in Table 1. This polymer is designated as D. Polymer D
Is represented by the following formula.

[0085]

Embedded image (However, ... is almost a carbon-carbon single bond.)

[Synthesis Example 5] MTD was added to PNB at 50% by weight.
A white powder was obtained in the same manner as in Synthesis Example 1 except that the mixture was replaced with a mixed monomer of 50% by weight of TCD. The synthesis results are shown in Table 1. This polymer is designated as E. The repeating unit of the polymer E is as follows.

[0087]

Embedded image (However, ... is almost a carbon-carbon single bond.)

[Synthesis Example 6] In a 1-liter polymerization vessel purged with nitrogen, a cyclohexane solution of TCD and V
O (OC ₂ H ₅ ) Cl ₂ in cyclohexane and ethyl aluminum sesquichloride [Al (C ₂ H ₅ ) _1.5
Cl _1.5 ] in a polymerization vessel are supplied at concentrations of 60 g / l, 0.5 mmol / l, and 4.0 mmol / l, respectively. The solution was supplied at a rate of 5 L / Hr, and the inside of the system was controlled at 10 ° C. On the other hand, the polymerization solution in the flask was continuously extracted from the upper portion of the polymerization vessel so that the total amount of the polymerization solution was 1 liter and the average residence time was 0.5 hour. A small amount of isopropyl alcohol was added to the withdrawn polymerization solution to terminate the polymerization, and then an aqueous solution in which 5 ml of concentrated hydrochloric acid was added to 1 liter of water and the polymerization solution in a ratio of 1: 1 using a homogenizer under strong stirring. Contact was made and the catalyst residue was transferred to the aqueous phase. The mixture was allowed to stand, and after removing the aqueous phase, the mixture was further washed twice with distilled water, and the polymerization liquid was purified and separated. This polymerization solution was poured into 3 liters of acetone to precipitate, and was collected by filtration. The recovered resin was dried at 100 ° C. and 1 Torr or less for 48 hours to obtain a white powder. The synthesis results are shown in Table 1. This polymer is designated as F. The repeating unit of the polymer F is as follows.

[0089]

Embedded image

[Synthesis Example 7] A white powder was obtained in the same manner as in Synthesis Example 6, except that MTF was used instead of TCD. The synthesis results are shown in Table 1. This polymer is designated G. The repeating unit of the polymer G is represented by the following formula.

[0091]

Embedded image

[Synthesis Example 8] Except that the supply amount of hydrogen was changed from 2.5 L / Hr to 0.5 L / Hr,
A white powder was obtained in the same manner as in Synthesis Example 6. The synthesis results are shown in Table 1. This polymer is designated as H.

[Synthesis Example 9] The number average molecular weight (Mn) was the same as in Synthesis Example 1, except that MTD was changed to ETD and 1-hexene was changed from 8.61 mmol to 2.30 mmol.
Is 28,500 and the weight average molecular weight (Mw) is 57,80.
0, a hydrogenated product having a main chain hydrogenation rate of 99% or more was obtained. The synthesis results are shown in Table 1. This polymer is designated as I.

[0094]

[Table 1] (* 1) It is a molar ratio.

[Examples 1 to 14] Each of the resins obtained in Synthesis Examples 1 to 7 and various components were blended according to the compositions shown in Table 2 so that the solid content was 60 to 70% by weight. Was dissolved in toluene to form a varnish. For all formulations,
The solution was homogeneous without precipitation. E glass cloth was immersed in these solutions 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% by weight based on the weight of the prepreg. A plurality of the above prepregs are stacked as needed 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 form a resin laminate. I got When the physical properties of the resin laminate thus obtained were measured, any of the resin laminates had good dielectric properties,
Shows water absorption, heat resistance, solvent resistance, copper foil peel strength,
The flame retardancy was V-0. Table 2 shows the results.

[0096]

[Table 2]

(Footnote) (1) Peroxide a: 2,5-dimethyl-2,5-di (t
-Butylperoxy) hexyne-3 (2) TAIC: triallyl isocyanurate (3) imidazole: 2-ethyl-4-methylimidazole (4) N3: flame retardant of the formula (N3) (5) E3: Asahi Chiba Made, brominated bisphenol A type epoxy resin (AER 8010), Br content = 50% by weight

[Comparative Examples 1 to 4] As a resin component, the polymer I obtained in Synthesis Example 9 (Mn = 28,500, Mw =
57,800, a main chain hydrogenation rate of 99% or more), or the polymer H (cycloolefin-based addition polymer) obtained in Synthesis Example 8, and various components were blended in the composition shown in Table 3. The varnish was dissolved in toluene so that the concentration of the total solid content became 20% by weight, but the varnish was separated into two phases. Table 3 shows the results.

[0099]

[Table 3] (Footnotes) (1) peroxide b: dicumyl peroxide (2) TAIC: triallyl isocyanurate (3) imidazole: 2-ethyl-4-imidazole (4) N3: flame retardant of the formula (N3) ( 5) E3: brominated bisphenol A type epoxy resin (AER 8010) manufactured by Asahi Ciba, Br content = 5% by weight

[Examples 15 to 21 and Comparative Examples 5 to 6]
Each resin obtained in Synthetic Examples 1 to 9 and various components were blended with the compositions shown in Table 4, and dissolved in toluene so that the concentration of various solid components became 20% by weight to form a varnish. After allowing this solution to stand for 30 minutes, the presence or absence of phase separation was visually observed,
Evaluation was made according to the following criteria. <Solution uniformity> ：: Uniform and no phase separation, ×: Phase separation. After leaving each varnish obtained above at room temperature for 30 minutes,
E-glass cloth (width 10 cm x length 10)
While holding one end in the width direction (cm × 0.5 mm in thickness), it was immersed in a suspended state, and after elapse of 10 seconds, 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, the mixture was poured into a large amount of isopropyl acetate in a toluene solution, and only the polymer component was coagulated, filtered and collected. Meanwhile, the filtrate was poured into a large amount of methanol, and only the flame retardant component was coagulated.
It was collected by filtration. The weight of the recovered polymer component and the flame retardant component after drying at 70 ° C. and 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 used varnish was calculated and evaluated according to the following criteria. <Uniformity of impregnation> ：: The difference is 2% or less and the impregnation uniformity is extremely excellent. ：: The difference is more than 2% and 5% or less, and the impregnation uniformity is excellent. : The difference is more than 5% and less than 10%, and the uniformity of impregnation is good. ×: The difference is 10% or more, and the uniformity of impregnation is poor. The results are shown in Table 4

[0101]

[Table 4] (Footnotes) (1) E3: Asahi Ciba, brominated bisphenol A type epoxy resin (AER 8010), Br content = 5% by weight

[0102]

According to the present invention, heat resistance, solder resistance,
Provided is a cyclic olefin-based polymer which is excellent in chemical resistance, mechanical strength, etc., can be used as a high-concentration solution, and is suitable for uniformly dispersing various compounding agents such as a flame retardant in the solution. You. Further, according to the present invention, there are provided a crosslinkable polymer composition having excellent physical properties, a molded article, a prepreg, a laminate, a metal-clad laminate, and the like using the composition.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 45/00 C08L 45/00 65/00 65/00

Claims (9)

[Claims] 1. A compound of the formula (A ₃ ) [In the formula, the meaning of each symbol is as follows. n is 0 or 1. p: 0 or a positive integer. q is 0 or 1. R _{1 to} R ₁₈ each independently represent 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, an alkoxy group, a cyano group, an amide group, an imide group, or Hydrocarbon group substituted with a silyl group). R _{a to} R _b each independently represent a hydrogen atom, a hydrocarbon group,
Halogen atom, hydroxyl group, ester group, alkoxy group, cyano group, amide group, imide group, silyl group, or polar group (halogen atom, hydroxyl group, ester group, alkoxy group,
A hydrocarbon group substituted with a cyano group, an amide group, an imide group, or a silyl group). However, R _{15 to} R ₁₈ may combine with each other to form an unsaturated bond, a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond. At R ₁₅ and R ₁₆ or at R ₁₇ and R ₁₈ ,
An alkylidene group may be formed. When q is 0, each bond is bonded to form a 5-membered ring. ... : represents a carbon-carbon single bond or a double bond. ]
And formula (B ₃ ) [In the formula, 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 ^{1 to} R ¹¹ each independently represent 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, an alkoxy group, a cyano group, an amide group, an imide group, or Hydrocarbon group substituted with a silyl group). R ^{12 to} R ²⁰ each independently represent 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, an alkoxy group, a cyano group, an amide group, an imide group, or Hydrocarbon group substituted with a silyl group). However, the carbon atom to which R ¹⁰ 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 ²⁰ may combine with each other to form a monocyclic or polycyclic aromatic ring. ... : represents a carbon-carbon single bond or a double bond. ]
At least one kind of repeating unit selected from the group consisting of repeating units represented by
(i) the cyclic olefin-based polymer (i), wherein n) is in the range of 500 to 20,000. 2. The cyclic olefin polymer (i) is a hydrogenated polymer, wherein 95% or more of carbon-carbon double bonds in the main chain are hydrogenated, and the non-conjugated carbon-carbon double bond in the side chain. When there is a heavy bond, 95% or more of the aromatic ring is hydrogenated, and when there is an aromatic ring in the side chain, 20 to 100% of the aromatic ring remains without hydrogenation in the cyclic olefin-based heavy. Coalescing. 3. The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 4 or less.
The cyclic olefin-based polymer according to the above. 4. Formula (A) [In the formula, the meaning of each symbol is as follows. n is 0 or 1. p: 0 or a positive integer. q is 0 or 1. R _{1 to} R ₁₈ each independently represent 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, an alkoxy group, a cyano group, an amide group, an imide group, or Hydrocarbon group substituted with a silyl group). R _{a to} R _b each independently represent a hydrogen atom, a hydrocarbon group,
Halogen atom, hydroxyl group, ester group, alkoxy group, cyano group, amide group, imide group, silyl group, or polar group (halogen atom, hydroxyl group, ester group, alkoxy group,
A hydrocarbon group substituted with a cyano group, an amide group, an imide group, or a silyl group). However, R _{15 to} R ₁₈ may combine with each other to form an unsaturated bond, a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond. At R ₁₅ and R ₁₆ or at R ₁₇ and R ₁₈ ,
An alkylidene group may be formed. When q is 0, each bond is bonded to form a 5-membered ring. ]
And formula (B) [In the formula, 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 ^{1 to} R ¹¹ each independently represent 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, an alkoxy group, a cyano group, an amide group, an imide group, or Hydrocarbon group substituted with a silyl group). R ^{12 to} R ²⁰ each independently represent 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, an alkoxy group, a cyano group, an amide group, an imide group, or Hydrocarbon group substituted with a silyl group). However, the carbon atom to which R ¹⁰ 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 ²⁰ may combine with each other to form a monocyclic or polycyclic aromatic ring. Wherein at least one cyclic olefin-based monomer selected from the group consisting of cyclic olefin-based monomers represented by the following formula is characterized by ring-opening polymerization in the presence of a metathesis catalyst, and then, if necessary, hydrogenation. It contains at least one kind of repeating unit selected from the group consisting of repeating units represented by (A ₃ ) and formula (B ₃ ), and has a number average molecular weight (Mn) of 500 to 20,000.
A method for producing a cyclic olefin polymer (i) in the range of 00. 5. A ring-opened (co) polymer of at least one cyclic olefin-based monomer selected from the group consisting of the cyclic olefin-based monomers represented by the formulas (A) and (B), A) hydrogenated (co) polymer of the polymer,
And a number-average molecular weight (Mn) of 500 to 20,000 selected from the group consisting of an addition copolymer of the at least one cyclic olefin monomer and a vinyl compound.
A crosslinkable polymer composition comprising at least one kind of cyclic olefin polymer (ii) in the range of 0 and a crosslinking agent. 6. A sheet-like molded product obtained by molding the crosslinkable polymer composition according to claim 5. 7. A prepreg obtained by impregnating a reinforcing substrate with the crosslinkable polymer composition according to claim 5. 8. The sheet-shaped molded product according to claim 6, and / or
A laminate obtained by laminating the prepreg according to claim 7 and crosslinking the crosslinkable polymer composition. 9. The laminate according to claim 8, further comprising a metal layer.