JPH10251343A - Thermoplastic norbornene-based polymer and epoxy group-containing norbornene-based polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polymer excellent in electric insulation, heat resistance, etc., by compounding specific two kinds of recurrent units at a specific ratio and specifying a number average molecular weight. SOLUTION: This polymer has a recurrent unit A of formula I [(a) and (b) are each 0-2; (c) is 1, 2; R<1> to R<14> are each H or a (polar group-substituted) hydrocarbon, etc., one or more of R<1> to R<14> are alkenyl, etc., or R<5> and R<6> , R<11> and R<12> or R<13> and R<14> are linked to each other to form one or more alkylidene, etc.] and a recurrent unit B of formula II [(d) and (g) are each 0-2; R<15> to R<25> are each H or a (polar group-substituted) hydrocarbon, etc., one or more of R<15> to R<25> are alkenyl, etc., or R<19> and R<20> , and R<22> , R<23> and R<24> or R<25> and R<26> are linked to each other to form one or more alkylidene, etc., or R<24> and R<25> are linked to each other and form a CC double bond between two carbons on which the R<24> and the R<25> are respectively linked] at a ratio A:B=(100:0) to (30:70), and a number-average molecular weight of 500 to 500,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel thermoplastic norbornene-based polymer and an epoxy-group-containing norbornene-based polymer, and a method for producing the same. More specifically, the present invention relates to an epoxy group-containing polymer suitable as a sealant for various electronic parts. The present invention relates to a norbornene-based polymer, a thermoplastic norbornene-based polymer suitable for the production thereof, and a method for producing the same. The present invention also relates to a crosslinkable polymer composition containing a novel epoxy group-containing norbornene-based polymer and a crosslinking agent, and an electronic component using the same.

2. Description of the Related Art Conventionally, transistors, diodes,
Various electronic components such as ICs, capacitors, resistors, and capacitors are generally used for the purpose of maintaining electrical insulation, preventing physical property changes due to an external atmosphere, improving productivity, and reducing costs.
Sealing with a synthetic resin is performed. For example, JP
Japanese Patent Application Laid-Open No. -202218 discloses that a thermoplastic norbornene-based resin obtained by polymerizing ethylene and a norbornene-based monomer is used as a sealing material. However, although this method has excellent electrical insulation properties, it has a problem that the resin sealing portion is likely to be deformed due to thermal stress at the time of sealing molding or soldering because of its heat resistance. In addition, this thermoplastic norbornene-based resin does not have sufficient adhesion to the lead frame or bonding wire of the electronic component, and moisture permeates from the interface between the resin sealing portion and the lead frame or the bonding wire, and the electrical insulation property is reduced. It causes deterioration and corrosion of the lead frame or the bonding wire, thereby deteriorating the electrical characteristics of the electronic component. JP-A-2-298510 discloses that an epoxy group-containing norbornene resin obtained by homopolymerizing vinyl norbornene or ethylidene norbornene and then epoxidizing all vinyl groups or ethylidene groups is suitable as a sealant. Have been reported. However, in this method, although the adhesiveness is excellent, the heat resistance is not sufficient, the electrical insulation performance such as the dielectric constant and the dielectric loss tangent and the moisture resistance are poor, or the resin is sealed by a long-term heat history or heat cycle. There is a problem that cracks and denaturation occur in the part.

The present inventors have conducted intensive studies to solve the above-mentioned problems of the prior art, and as a result, as a sealing material, a norbornene-based material having a repeating unit of a specific structure and having a carbon-carbon double bond. By using an epoxy group-containing norbornene-based polymer in which at least a part of the carbon-carbon double bond of the (co) polymer is epoxidized, electric insulation such as dielectric constant and dielectric tangent, heat resistance, moisture resistance, Further, the present inventors have found that an electronic component having excellent adhesion to other materials and also excellent in heat history and crack resistance due to a heat cycle can be obtained, thereby completing the present invention.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide excellent electrical insulating properties such as dielectric constant and dielectric loss tangent, heat resistance, moisture resistance, and adhesion to other materials, as well as resistance to heat history and heat cycling. An object of the present invention is to provide an epoxy group-containing norbornene-based copolymer having excellent cracking properties. Another object of the present invention is to provide an electronic component sealed with a thermoplastic resin composition having such excellent characteristics.

[0004]

According to the present invention, as a first invention, a repeating unit [A] represented by the following formula (A) and a repeating unit [B] represented by the following formula (B) are provided. ] [A]: [B] = 100: 0 to 30:70, and the number average molecular weight (Mn) is 500 to 50.
000 thermoplastic norbornene-based polymers are provided.

[0005]

Embedded image

(In the formula (A), a is 0, 1 or 2, b is 0, 1 or 2, c is 1 or 2,
^{1 to} R ¹⁴ each independently represent a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, an ester group, a cyano group, an amide group, an imide group, a silyl group, or a polar group (halogen atom, alkoxy group, ester group, Represents a hydrocarbon group substituted with a cyano group, an amide group, an imide group, or a silyl group). However, R ¹ or at least one to R ¹⁴ is an alkenyl group substituted with an alkenyl group or polar group, or R ⁵ and and R ^6, R ¹¹ and R ¹² or R ^{1 3} R ¹⁴
Are bonded to each other to form at least one alkylidene group or an alkylidene group substituted with a polar group. )

[0007]

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[0008] (In the formula (B), each symbol, d is 0, 1 or 2, e is 0, 1 or 2, f is 0, 1 or 2, g is 0, 1 or 2, R ¹⁵ To R ²⁶ are each independently
Hydrogen atom, alkyl group, halogen atom, alkoxy group,
Represents an alkyl group substituted with an ester group, a cyano group, an amide group, an imide group, a silyl group, or a polar group (a halogen atom, an alkoxy group, an ester group, a cyano group, an amide group, an imide group, or a silyl group). However, R ^{15 to} R
^At least one of ²⁶ is an alkenyl group or an alkenyl group substituted with a polar group, or R ¹⁹ and R ²⁰ , R
²¹ and R ²² , R ²³ and R ²⁴ or R ²⁵ and R ²⁶ are bonded to each other to form at least one alkylidene group or an alkylidene group substituted with a polar group, or
R ^{24 to} R ²⁵ are bonded to each other to form a carbon-carbon double bond between the two carbon atoms formed by the bonding of R ^{24 to} R ²⁵ . )

According to the present invention, as a second invention, a norbornene-based monomer [a] represented by the following formula (a):
And a norbornene-based monomer [b] represented by the following formula (b) at a ratio of [a]: [b] = 100: 0 to 30:70 to form a transition metal compound belonging to Group VIII of the periodic table. There is provided a method for producing a thermoplastic norbornene-based polymer, characterized by performing addition polymerization using a polymerization catalyst contained therein.

[0010]

Embedded image

(In the formula (a), a is 0, 1 or 2, b is 0, 1 or 2, c is 1 or 2,
^{1 to} R ¹⁴ each independently represent a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, an ester group, a cyano group, an amide group, an imide group, a silyl group, or a polar group (halogen atom, alkoxy group, ester group, Represents a hydrocarbon group substituted with a cyano group, an amide group, an imide group, or a silyl group). However, R ¹ or at least one to R ¹⁴ is an alkenyl group substituted with an alkenyl group or polar group, or R ⁵ and and R ^6, R ¹¹ and R ¹² or R ^{1 3} R ¹⁴
Are bonded to each other to form at least one alkylidene group or an alkylidene group substituted with a polar group. )

[0012]

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[0013] (In the formula (b), each symbol, d is 0, 1 or 2, e is 0, 1 or 2, f is 0, 1 or 2, g is 0, 1 or 2, R ¹⁵ To R ²⁶ are each independently
Hydrogen atom, alkyl group, halogen atom, alkoxy group,
Represents an alkyl group substituted with an ester group, a cyano group, an amide group, an imide group, a silyl group, or a polar group (a halogen atom, an alkoxy group, an ester group, a cyano group, an amide group, an imide group, or a silyl group). However, R ^{15 to} R
^At least one of ²⁶ is an alkenyl group or an alkenyl group substituted with a polar group, or R ¹⁹ and R ²⁰ , R
R ²¹ and R ²² , R ²³ and R ²⁴ or R ²⁵ and R ²⁶ are bonded to each other to form at least one alkylidene group or an alkylidene group substituted with a polar group;
^{24 to} R ²⁵ are bonded to each other to form a carbon-carbon double bond between the two carbon atoms formed by the bonding of R ^{24 to} R ²⁵ . )

According to the present invention, as a third invention, a repeating unit [C] represented by the following formula (C) and a repeating unit [D] represented by the following formula (D) are represented by [C] : [D] =
An epoxy group-containing norbornene-based polymer having a ratio of 100: 0 to 30:70 and a number average molecular weight (Mn) of 500 to 500,000 is provided.

[0015]

Embedded image

(In the formula (C), a is 0, 1 or 2, b is 0, 1 or 2, c is 1 or 2,
^{1 to} R ¹⁴ each independently represent a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, an ester group, a cyano group, an amide group, an imide group, a silyl group, or a polar group (halogen atom, alkoxy group, ester group, Represents a hydrocarbon group substituted with a cyano group, an amide group, an imide group, or a silyl group). However, at least one of R ^{1 to} R ¹⁴ is an alkyl group having an epoxy skeleton or an alkyl group substituted with a polar group having an epoxy skeleton, or R ⁵ and R ⁶ , R ¹¹ and R ¹² , or R ¹³ And R ¹⁴ are bonded to each other to form at least one of the following formulas (d)

[0017]

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(In the formula (d), R ⁶⁵ is a hydrogen atom, an alkyl group, a polar group, or an alkyl group substituted with a polar group.) . )

[0019]

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[0020] (In the formula (D), each symbol, d is 0, 1 or 2, e is 0, 1 or 2, f is 0, 1 or 2, g is 0, 1 or 2, R ¹⁵ To R ²⁶ are each independently
Hydrogen atom, alkyl group, halogen atom, alkoxy group,
Represents an alkyl group substituted with an ester group, a cyano group, an amide group, an imide group, a silyl group, or a polar group (a halogen atom, an alkoxy group, an ester group, a cyano group, an amide group, an imide group, or a silyl group). However, R ^{15 to} R
^At least one of ²⁶ is an alkyl group having an epoxy skeleton or an alkyl group substituted with a polar group having an epoxy skeleton, or R ²⁴ and R ²⁵ are bonded via an oxygen atom to form an oxy group; Or R ¹⁹ and R ²⁰ , R ²¹ and R ²² , R ²³ and R ²⁴ , or R ²⁵ and R ²⁶ are bonded to each other, and at least one of the following formulas (d)

[0021]

Embedded image

(In the formula (d), R ⁶⁵ is a hydrogen atom, an alkyl group, a polar group, or an alkyl group substituted with a polar group.) . )

According to a fourth aspect of the present invention, there is provided an epoxy resin according to the fourth aspect, wherein at least a part of the non-conjugated carbon-carbon double bond of the thermoplastic norbornene-based polymer is epoxidized with a peroxide. A method for producing a group-containing norbornene-based polymer is provided. According to the present invention, further, as a fifth invention, a crosslinkable polymer composition containing the epoxy group-containing norbornene-based polymer and a crosslinking agent, and as a sixth invention, the crosslinkable polymer An electronic component encapsulated with the composition is provided.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Thermoplastic norbornene-based polymer (1) Polymer It is a copolymer of (A) alone or a copolymer of (A) and (B), which comprises a repeating unit. The norbornene-based repeating unit is a unit structure derived from a tetracyclododecene structure having two norbornene ring skeletons.
It has an alkylidene or alkenyl unsaturated bond or an unsaturated bond derived from a cyclopentadiene ring in a side chain.

In the formula (A), the meaning of each code is as follows. a and b are each independently 0, 1 or 2, and c is 1 or 2. R ^{1 to} R ¹⁴ each independently represent a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, an ester group (for example, an alkyl ester group),
Represents a hydrocarbon group substituted with a cyano group, an amide group, an imide group, a silyl group, or a polar group (a halogen atom, an alkoxy group, an ester group, a cyano group, an amide group, an imide group, or a silyl group). Provided that at least one of R ^{1 to} R ¹⁴ is an alkenyl group or an alkenyl group substituted with a polar group, or R ⁵ and R ⁶ , R ¹¹ and R ¹² or R
¹³ and R ¹⁴ are bonded to each other to form at least one alkylidene group or an alkylidene group substituted with a polar group.

The halogen atom in the formula (A) includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As the hydrocarbon group, for example, 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to
A chain alkyl group of 6; an alkenyl group having 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms; and 3 to 15, preferably 3 to 8, more preferably 5 to 5 carbon atoms. 6, a cyclic alkyl group having 6 to 12 carbon atoms,
Preferably, 6 to 8, more preferably 6, aryl groups and the like can be mentioned. Examples of the hydrocarbon group substituted with a polar group include, for example, 1 to 20 carbon atoms, preferably 1 to
10, and more preferably 1 to 6 halogenated alkyl groups. As the hydrocarbon group, those which are not substituted with a polar group are suitable for highly enhancing the moisture-proof property.

The alkylidene group in the formula (A) includes, for example, a methylidene group, an ethylidene group, a propylidene group,
And lower alkyl groups such as isopropylidene. Examples of the alkylidene group substituted with a polar group include those obtained by halogenating these lower alkylidene groups. However, an alkylidene group which is not substituted with a polar group is preferable in order to highly enhance the moisture-proof property.
Preferred examples of the norbornene-based repeating unit [A] include a repeating unit represented by the formula (A1).

[0028]

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Each symbol in the formula (A1) is such that h is 0 or 1, i is 0 or 1, j is 1, and R ^{27 to} R ³² are each independently a hydrogen atom or a carbon atom having 1 to 1 carbon atoms. 6 represents a hydrocarbon group. However, R ²⁷ and R ²⁸ , R ²⁹ and R ³⁰ , or R ³¹ and R ³² are bonded to each other to form an alkylidene group having 1 to 6 carbon atoms. Preferably, R ³¹ and R ³²
Are bonded to each other to form an alkylidene group having 1 to 6 carbon atoms, or R ³⁰ and R ³¹ are bonded to each other to form a carbon-carbon double bond. Examples of the alkylidene group include a methylidene group, an ethylidene group, a propylidene group, and an isopropylidene group.

The norbornene repeating unit [A]
As a preferable example, a repeating unit represented by the formula (A2) can be exemplified.

[0031]

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In the formula (A2), k is 0 or 1, m is 0 or 1, n is 1, and R ^{33 to} R ³⁶ are each independently a hydrogen atom or a carbon atom having 1 to 1 carbon atoms. R ³⁷ and R which represent an alkyl group of 6 and are preferably a hydrogen atom
³⁸ has one of 2 to 6, preferably 2 to 2 carbon atoms
3 is an alkenyl group, and the other is a hydrogen atom. These norbornene-based repeating units [A] can be used alone or in combination of two or more. In the formula (B), the meaning of each symbol is as follows. d, e, f, and g are each independently 0, 1, or 2. R ^{15 to} R ²⁶ each independently represent a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, an ester group (eg, an alkyl ester group), a cyano group, an amide group, an imide group, a silyl group, or a polar group (halogen). Atom, alkoxy group, ester group, cyano group, amide group,
Imide group or silyl group). Provided that at least one of R ^{15 to} R ²⁶ is an alkenyl group or an alkenyl group substituted with a polar group,
Alternatively R ¹⁹ and R ^20, R ²¹ and R ^22, R ^{2 3} and R ²⁴ or R
²⁵ and R ²⁶ are bonded to each other to form at least one alkylidene group or an alkylidene group substituted with a polar group, or R ²⁴ and R ²⁵ are bonded to each other,
R ²⁴ and R ²⁵ form a carbon-carbon double bond between the two carbon atoms to which each is bonded.

The halogen atom in the formula (B) includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As the alkyl group, for example, 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to
And a chain alkyl group having 6 and a cyclic alkyl group having 3 to 15, preferably 3 to 8, and more preferably 5 to 6 carbon atoms. Examples of the alkyl group substituted with a polar group include, for example, 1 to 20 carbon atoms, preferably 1
And, more preferably, 1 to 6 halogenated alkyl groups. As the alkyl group, those which are not substituted with a polar group are suitable for highly enhancing the moisture-proof property.

Provided that at least one of R ^{15 to} R ²⁶ is
An alkenyl group having 2 to 10, preferably 2 to 6, more preferably 3 to 4 carbon atoms, or 2 to 10, preferably 2 to 6, more preferably 3 to 4 carbon atoms substituted with an alkenyl group or a polar group; A alkenyl group, or R ¹⁹ and R ²⁰ , R ²¹ and R ²² , R ²³ and R ²⁴ or R ²⁵ and R ²⁶ bonded to each other to form at least one carbon atom having 2 to 10, preferably 2 6 to 6, more preferably 3 to 4 carbon atoms substituted with an alkylidene group or a polar group having 2 to 10 carbon atoms;
Preferably 2 to 6, or whether more preferably forms an alkylidene group is 3-4, and bound and R ^{2 4} and R ²⁵ to each other, R ²⁴ and R ²⁵ are two attached respectively Preferably, a carbon-carbon double bond is formed between carbon atoms. Further, norbornene-based repeating unit [B]
As a preferable example, there can be mentioned, for example, a repeating unit represented by the formula (B1).

[0035]

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In each symbol in the formula (B1), p is 0 or
1, q is 0 or 1, r is 0 or 1, s is 0, 1, or
Is 2R³⁹~ R⁴⁴, R⁶³, R⁶⁴Are each independently a hydrogen source
And represents an alkyl group having 1 to 6 carbon atoms.
Or a hydrogen atom. Where R³⁹~ R⁴⁴, R⁶³, R
⁶⁴At least one is substituted with an alkenyl group or a polar group
Alkenyl group or R³⁹And R⁴⁰, R
^{Four 1}And R⁴², R⁴³ And R⁶³Or R⁴⁴And R⁶⁴And combine with each other
With at least one alkylidene group or polar group
Forming a substituted alkylidene group, or
R⁶³And R⁶⁴Combine with each other to form R⁶³And R⁶⁴Is each
A carbon-carbon double bond between the two bonded carbon atoms
Has formed. These unconjugated carbon-carbon unsaturated bonds
Each of the norbornene-based repeating units [B] having
Used alone or in combination of two or more
Can be.

The content ratio of the repeating units [A] and [B] in the thermoplastic norbornene-based polymer of the present invention can be appropriately selected according to the purpose of use. Usually 100: 0 to 30:70, preferably 90: 1.
0 to 40:60, more preferably 80:20 to 50: 5
It is in the range of 0. When the content of the repeating units [A] and [B] is within this range, the electrical properties of the epoxy group-containing norbornene-based polymer of the present invention described below obtained by epoxidizing the norbornene-based polymer with a peroxide. Properties such as heat resistance, moisture resistance, and adhesion to the metal layer are highly balanced.

The molecular weight of the thermoplastic norbornene-based copolymer of the present invention is expressed by polystyrene-equivalent number average molecular weight (Mn) of 50 as measured by gel permeation chromatography (GPC) using toluene as a solvent.
0-500,000, preferably 1,000-200,
000, more preferably 2,000 to 100,000,
Most preferably, it is in the range of If the number average molecular weight is excessively small, the strength of the molded body or film is reduced, which causes cracks and the like.On the contrary, if the number average molecular weight is excessively large, the viscosity of the copolymer is too large, and The processability of the coating film deteriorates, which is not preferable.

The glass transition temperature (Tg) of the thermoplastic norbornene-based polymer of the present invention may be appropriately selected according to the purpose of use.
The range is preferably from 00 to 400C, more preferably from 150 to 350C.

(2) Norbornene-based monomer (monomer) The method for producing the thermoplastic norbornene-based polymer of the present invention comprises:
There is no particular limitation. For example, the norbornene-based monomer [a] represented by the formula (a) and the formula (b)
Can be obtained by subjecting a norbornene-based monomer [b] represented by the following formula to addition polymerization using a polymerization catalyst containing a transition metal compound belonging to Group VIII of the periodic table. The norbornene-based monomer [a] has two or more norbornene rings and has a carbon-carbon double bond in a norbornene ring not involved in addition polymerization, in addition to a carbon-carbon double bond in the norbornene ring involved in addition polymerization. Those having a heavy bond are used.

The norbornene-based monomer [a] is represented by the formula (a)

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

Further, it has a ring structure other than the norbornene ring, and has a hydrocarbon group having a non-conjugated carbon-carbon double bond such as an alkylidene group or an alkenyl group in a side chain;
Alternatively, those having a non-conjugated carbon-carbon double bond in a cyclopentane ring or a cyclohexane ring are used.

Examples of the norbornene-based monomer [b] include (b)

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

Preferred examples of the norbornene-based monomer (a) include those represented by the formula (a1):

Embedded image (The meaning of each code in the formula (a1) is the same as that in the formula (A1).)

Equation (a2)

Embedded image (The meaning of each symbol in the formula (a2) is the same as that in the formula (A2).)

A preferred example of the norbornene monomer (b) is represented by the formula (b1)

Embedded image (The meaning of each symbol in the formula (b1) is the same as that in the formula (B1).)

[0047] As the norbornene-based monomer constituting the norbornene-based polymer [A], tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] -3-dodecene derivatives, pentacyclo -4, A 10-pentadecadiene derivative, a bicyclo [2.2.1] hept-2-ene derivative,
Tricyclo-3,7-decadiene derivatives and the like can be mentioned. More specifically, it is as shown below.

8-ethylidenetetracyclo [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-ethyl-tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] -3-dodecene, 8-ethylidene-9-isopropyl-tetracyclo [ 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-ethylidene tetracyclo [4,4,0,1 ^2,5 etc., 1 ^7,10] -3-dodecene derivatives; 8-n-propylidene Tetracyclo [4
4,0,1 ^2,5, 1 ^7,10] -3-dodecene, 8-n-propylidene-9-methyl-tetracyclo [4,4,0,1
^2,5, 1 ^7,10] -3-dodecene, 8-n-propylidene-9-ethyl-tetracyclo [4,4,0,1 ^2,5, 1
^7,10] -3-dodecene, 8-n-propylidene-9-isopropyl-tetracyclo [4,4,0,1 ^2,5,
1 ^7,10 ] -3-dodecene, 8-n-propylidene-9-
Butyl tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] -
3-dodecene, 8-n-propylidene-tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] etc. -3-dodecene derivatives; 8 isopropylidene tetracyclo [4,4,0,
1 ^{2, 5,} 1 ^7,10] -3-dodecene, 8-isopropylidene-9-methyl-tetracyclo [4,4,0,1 ^2,5, 1
^7,10] -3-dodecene, 8-isopropylidene-9-ethyl-tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] -3
- dodecene, 8-isopropylidene-9-isopropyl-tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] -3-dodecene, 8-isopropylidene-9-butyl tetracyclo [4,4, 0,1 ^2,5, 1 ^7,10] -3-dodecene, etc. 8 isopropylidene tetracyclo [4,4,0,1
^2,5, 1 ^{7, 10]} -3-dodecene derivatives; pentacyclo [6,5,1,1 ^3,6, 0 ^2,7, 0 ^9,13] 4,10 penta decadiene, pentacyclo etc. -4,10-pentadecadiene derivative; and the like.

Specific examples of the monomer other than the tetracyclododecene derivative of the formula (2) [b] are specifically shown below. 5-vinyl-bicyclo [2,2,1] hept-2-ene, 5-ethylidene-bicyclo [2,2,1]
Hept-2-ene, 5-n-propenyl-bicyclo [2,2,1] hept-2-ene, 5-n-propylidene-bicyclo [2,2,1] hept-2-ene, 5-n
-Isopropenyl-bicyclo [2,2,1] hept-2
-Ene, 5-n-isopropylidene-bicyclo [2,
2,1] hept-2-ene, bicyclo [2,2,
1] Hept-2-ene derivative tricyclo [4,3,0,
1 ^2,5] -3,7-decadiene (i.e. dicyclopentadiene), and the like tricyclo-3,7-decadiene derivative such.

These norbornene monomers [a] and [b] can be used alone or in combination of two or more. The ratio of the norbornene-based monomers [a] and [b] is appropriately selected so as to be the content of the repeating units [A] and [B] in the norbornene-based polymer. That is, in the weight ratio of [a]: [b],
Usually 100: 0 to 30:70, preferably 90:10
The ratio is in the range of 40:60, more preferably 80:20 to 50:50.

(3) Polymerization Method The method for producing the thermoplastic norbornene-based polymer may be a known method. Organomet. Che
m. , 358, 567-588 (1988);
-205408, JP-A-4-63807,
JP-A-5-262821, WO95 / 14048
For example, a catalyst and a polymerization method described in Japanese Patent Application Laid-Open No. H10-208 can be used. As the catalyst, a polymerization catalyst containing a transition metal compound belonging to Group VIII of the periodic table as a main component is used. Specific examples of such transition metals include iron, cobalt, nickel, ruthenium, rhodium, palladium, platinum and the like. Of these, cobalt, nickel and palladium are particularly preferred. Specific transition metal compounds are exemplified below.

As the iron compound, iron (II) chloride, chloride
Iron (III), iron (II) acetate, iron (II) acetyl
Setonat, ferrocene, and the like. Cobaltization
Compounds include cobalt (II) acetate, cobalt (I
I) acetylacetonate, cobalt (II) tetraf
Ruboroborate, cobalt chloride, cobalt (II) ben
Zoate and the like. As nickel compounds,
Nickel acetate, nickel acetylacetonate,
Nickel, nickel chloride, nickel ethyl hexanoe
G, nickelocene, NiCl_Two(PPh_Three)_Two, Bis ants
Nickel oxide and nickel oxide. Paraziu
Palladium chloride, palladium bromide,
Palladium oxide, PdCl_Two(PPh_Three)_Two, PdCl
_Two(PhCN)_Two, PdCl_Two(CH_ThreeCN)_Two, [Pd
(CH_ThreeCN)_Four] [BF_Four]_Two, [Pd (C_Two H_FiveC
N)_Four] [BF_Four]_Two, Palladium acetylacetona
And palladium acetate. Above all, chloride
Palladium, nickel acetylacetonate, PdCl
_Two(PhCN)_Two, [Pd (CH_ThreeCN)_Four] [BF_Four]_TwoWhat
Which is particularly preferred. The amount of catalyst used is usually
In a molar ratio of 1 / 1,000,000 to 1/1
0, more preferably 1 / 100,000 to 1/100
It is.

These catalysts may be used alone or in combination of two or more. The amount of the catalyst to be used may be appropriately selected depending on the polymerization conditions and the like.
1,000,000 to 1/10, preferably 1/100,
000 to 1/100. In the present invention, a co-catalyst such as aluminoxane may be used as necessary.
Methylaluminoxane is particularly preferred as the aluminoxane. The cocatalyst may be used alone or in combination of two or more. When the aluminoxane is used, the ratio of the aluminoxane and the transition metal compound can be selected arbitrarily according to various conditions. The ratio (molar ratio) of aluminum / transition metal is 1 to 100,000, preferably 5 to 1
It may be set to 0000.

The polymerization reaction may be bulk polymerization without using a solvent or polymerization in an inert organic solvent. Examples of the solvent medium include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as n-pentane, hexane and heptane, alicyclic hydrocarbons such as cyclohexane, styrene dichloride, dichloroethane, and dichloroethylene. And halogenated hydrocarbons such as tetrachloroethane, chlorobenzene, dichlorobenzene, and trichlorobenzene; and nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, acetonitrile, and benzonitrile.

The polymerization temperature is generally -50 ° C to 200 ° C, preferably -30 ° C to 150 ° C, more preferably -20 ° C.
To 100 ° C., and the polymerization pressure is usually 0 to 50 kg /
cm ² , preferably 0 to 20 kg / cm ² .

Epoxy group-containing norbornene-based polymer The epoxy group-containing norbornene-based polymer of the present invention is obtained by epoxidizing the non-conjugated carbon-carbon double bond portion of the thermoplastic norbornene-based polymer of the present invention described above. Which contains the epoxy group-containing norbornene-based repeating unit [C] represented by the formula (C). The epoxy group-containing norbornene-based polymer may further contain a norbornene-based repeating unit [D] represented by the formula (D). Further, the epoxy group-containing norbornene-based polymer of the present invention may optionally have the above-mentioned formula [A]
Or the norbornene-based repeating unit represented by the formula [B], that is, the non-conjugated carbon-carbon double bond portion in these formulas is not completely epoxidized, and the non-conjugated carbon-carbon A polymer having a carbon double bond may be used.

The meaning of each symbol in the expression (C) is as follows. a and b are each independently 0, 1 or 2, and c is 1 or 2. R ^{1 to} R ¹⁴ each independently represent a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, an ester group (eg, an alkyl ester group), a cyano group, an amide group, an imide group, a silyl group, or a polar group (halogen). Atom, alkoxy group, ester group,
Represents an alkyl group substituted with a cyano group, an amide group, an imide group, or a silyl group). However, at least one of R ^{1 to} R ¹⁴ is an alkyl group having an epoxy skeleton or an alkyl group substituted with a polar group having an epoxy skeleton, or R ⁵ and R ⁶ , R ¹¹ and R ¹² , or R ¹³ And R
¹⁴ and at least one of the following formulas

Embedded image (In the formula (d), R ⁶⁵ is a hydrogen atom, an alkyl group, a polar group, or an alkyl group substituted with a polar group.)

The halogen atom in the formula (C) includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As the alkyl group, for example, 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to
And a cyclic alkyl group having 6 to 15 carbon atoms, preferably 4 to 10, and more preferably 5 to 6 carbon atoms. Examples of the alkyl group substituted with a polar group include, for example, 1 to 20 carbon atoms, preferably 1 to 1 carbon atoms.
0, and more preferably 1 to 6 halogenated alkyl groups. An alkyl group which is not substituted with a polar group other than an epoxy group is preferable in order to highly enhance moisture resistance.

The feature of the formula (C) is that an epoxy group is introduced. An alkyl group having an epoxy skeleton or a group having an epoxy skeleton that is not substituted with a polar group is preferable in order to highly enhance moisture resistance. R
¹⁵ is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and is preferably 1 hydrogen atom or 1 carbon atom.
Alkyl groups of 4 to 4 are more preferred.

The meaning of each code in the formula (D) is as follows.
It is. d, e, f and g are each independently 0, 1,
Or 2. R^Fifteen~ R²⁶Is, independently of each other, hydrogen
Atom, alkyl group, halogen atom, alkoxy group, S
Ter groups (eg, alkyl ester groups), cyano groups,
Imide group, imide group, silyl group, or polar group (halogen
Atom, alkoxy group, ester group, cyano group, amide
Substituted with an alkyl group, an imide group, or a silyl group)
Represents a group. Where R^Fifteen~ R²⁶At least one of the epo
Has an alkyl group having a xy skeleton or an epoxy skeleton
An alkyl group substituted with a polar group,
^{twenty four} , R^{twenty five}Are linked via an oxygen atom to form an oxy group
Or R¹⁹And R²⁰, R^{twenty one}And R^{twenty two}, R^{twenty three}And R
^{twenty four}Or R^{twenty five}And R²⁶Are combined with each other, at least
One lower formula

Embedded image (In the formula (d), R ¹⁵ is a hydrogen atom, an alkyl group, a polar group, or an alkyl group substituted with a polar group.)

The halogen atom in the formula (D) includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As the alkyl group, for example, 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to
And a cyclic alkyl group having 6 to 15 carbon atoms, preferably 4 to 10, and more preferably 5 to 6 carbon atoms. Examples of the alkyl group substituted with a polar group include, for example, those having 1 to 20 carbon atoms, preferably 1
And, more preferably, 1 to 6 halogenated alkyl groups. As the alkyl group, those which are not substituted with a polar group are suitable for highly enhancing the moisture-proof property.

Provided that at least one of R ^{15 to} R ²⁶ is
An alkyl group having an epoxy skeleton having 2 to 10, preferably 2 to 6, more preferably 3 to 4 carbon atoms, or a C2 to 10 carbon atom, preferably 2 substituted with a polar group.
Or more preferably an alkyl group having an epoxy skeleton of 3 to 4, or R ¹⁹ and R ²⁰ , R ²¹ and R
²² , R ²³ and R ²⁴ or R ²⁵ and R ²⁶ are bonded to each other;
R ⁶⁵ is 0 to 8 carbon atoms, preferably 0-4, at least one of the formula R ⁶⁵ carbon atoms which is substituted with a group or a polar group represented by (d) is more preferably 1 to 2 0
To 8, preferably 0 to 4, more preferably 1 to 2 or a group represented by the formula (d), or R ²⁴ and R ²⁵ are bonded to each other to form R ²⁴ and R ^It is preferred that ²⁵ forms a carbon-carbon double bond between the two carbon atoms to which each is bonded.

Preferred examples of the epoxy group-containing norbornene-based repeating unit [C] include, for example, the formulas (C1) and (C2). Preferred examples of the epoxy-group-containing norbornene-based repeating unit [D] include: The formula (D
1) Each repeating unit represented can be mentioned.

[0064]

Embedded image

(The meaning of each code in the formula (C1) is that α is 0
Or 1, β is 0 or 1, γ is 1, and R ^{45 to} R ⁴⁸
Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom, and R ^{49 to} R ⁵⁰ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or a carbon atom. It is an alkyl group having 1 to 3 atoms. )

[0066]

Embedded image

(The meaning of each symbol in the formula (C2) is that δ is 0
Or 1, ε is 0 or 1, ζ is 1, and R ^{51 to} R ⁵⁵
Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and is preferably a hydrogen atom, and R ⁵⁶ is a group represented by the following formula (e).

[0068]

Embedded image

(In the formula (e), n is an integer of 0 to 4 and m is 0
And n + m is 1 to 4. Preferably, n is 0 or 1 and m is 0 or 1. ))

[0070]

Embedded image

(The meaning of each symbol in the formula (D1) is as follows: η is 0 or 1, θ is 0 or 1, κ is 1
And λ is 0 or 1. R ^{57 to} R ⁶² represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom. )

The norbornene-based repeating units containing epoxy group [C] can be used alone or in combination of two or more. If necessary, one or two kinds of repeating units containing epoxy group-containing norbornene repeating units [D] can be used. These can be used in combination.

Specific examples of the norbornene-based repeating unit [B] having no non-conjugated carbon-carbon double bond and the norbornene-based repeating unit [A] are the same as those of the norbornene-based polymer.

In the epoxy group-containing norbornene-based polymer of the present invention, an epoxy group-containing repeating unit such as repeating units [C] and [D] and a non-conjugated carbon unit such as [A] and [B]. -The proportion of the repeating unit containing a carbon double bond is appropriately selected depending on the purpose of use and the type of the repeating unit, but is preferably from 0.20 mol / 100 g to an epoxy value representing the number of moles of the epoxy group in 100 g of the resin. 0.
90 mol / 100 g, preferably 0.30 mol / 1
00g to 0.80mol / 100g, more preferably 0.40mol / 100g to 0.70mol / 100g
It is. When the epoxy value is within this range, the properties such as electrical properties, moisture resistance, and adhesion to the metal layer are highly balanced and suitable. It is preferable that the content of [A] or [B] is small. If the content is excessively large, electric characteristics and moisture-proof property deteriorate, which is not preferable.

The molecular weight of the epoxy group-containing norbornene-based copolymer of the present invention is 50 as the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) using toluene as a solvent.
0-500,000, preferably 1,000-300,
000, more preferably in the range of 2,000 to 200,000. When the number average molecular weight (Mn) of the epoxy group-containing norbornene-based copolymer is too small, the mechanical strength is reduced. The glass transition temperature (Tg) of the epoxy group-containing norbornene-based copolymer of the present invention may be appropriately selected according to the purpose of use, but is usually 50 to 500 ° C, preferably 100 to 400 ° C, and more preferably 150 to 150 ° C. ~ 3
It is in the range of 50 ° C.

The method for producing the epoxy group-containing norbornene-based copolymer of the present invention is not particularly limited. For example, the norbornene-based copolymer produced by the above-mentioned production method is reacted with a peroxide as an epoxidizing agent. It can be done by doing. The peroxide is not particularly limited as long as it is conventionally used as an epoxidizing agent for a carbon-carbon double bond. Examples thereof include peracetic acid, perbenzoic acid, metachloroperbenzoic acid, and trifluoroperacetic acid. Peracids such as hydrogen peroxide, tertiary butyl hydroperoxide,
Hydroperoxides such as cumene peroxide; and the like.

The epoxidation reaction may be carried out by mixing a norbornene-based copolymer and a peroxide and heating the mixture, and is usually carried out in the presence of a solvent. The solvent is not particularly limited as long as it can dissolve or disperse the norbornene-based copolymer. For example, the same solvents as those exemplified in the production of the norbornene-based copolymer can be used. The amount of the solvent to be used is not particularly limited as long as the solvent can dissolve or disperse the norbornene-based copolymer. The amount is more preferably in the range of 5 to 50 times. The reaction conditions may be appropriately selected according to the type of peroxide, but the reaction temperature is usually 0 to 300 ° C, preferably 50 to 200 ° C, and the reaction time is usually 0.1 to 10 hours, preferably The range is 0.5 to 5 hours. After completion of the reaction, a large amount of a poor solvent such as methanol is added to the reaction system to precipitate a polymer, which can be obtained by filtration, washing, and drying under reduced pressure.

Crosslinkable Polymerizable Composition In the present invention, a rubbery polymer or other thermoplastic resin can be added to the crosslinkable polymer composition, if necessary. The rubbery polymer is a polymer having a glass transition temperature of 0 ° C. or less, and includes a usual rubbery polymer and a thermoplastic elastomer. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the rubbery polymer is appropriately selected according to the purpose of use, and is usually 5 to 200.

Examples of the rubbery polymer include ethylene-α-olefin-based rubbery polymers; ethylene-α-olefin-polyene copolymer rubbers; and ethylene and unsaturated compounds such as ethylene-methyl methacrylate and ethylene-butyl acrylate. Copolymer with carboxylic acid ester; Copolymer of ethylene and fatty acid vinyl such as ethylene-vinyl acetate; Acrylic acid such as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate Polymers of alkyl esters; polybutadienes, polysoprene, styrene-butadiene or styrene-isoprene random copolymers,
Acrylonitrile-butadiene copolymer, butadiene-
Isoprene copolymer, butadiene-alkyl (meth) acrylate copolymer, butadiene-alkyl (meth) acrylate-acrylonitrile copolymer,
Diene rubbers such as butadiene- (meth) acrylic acid alkyl ester-acrylonitrile-styrene copolymer; butylene-isoprene copolymer;

As the thermoplastic elastomer, for example,
Aromatic vinyl-conjugated diene block copolymers such as styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer, low Crystalline polybutadiene resin, ethylene-
Propylene elastomer, styrene grafted ethylene
Propylene elastomer, thermoplastic polyester elastomer, ethylene ionomer resin and the like can be mentioned. Among these thermoplastic elastomers, preferred are hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, and the like. Specifically, JP-A-2-133406,
JP-A-2-305814, JP-A-3-72512
And Japanese Patent Application Laid-Open No. 3-74409.

Other thermoplastic resins include, for example,
Low density polyethylene, high density polyethylene, linear low density polyethylene, ultra low density polyethylene, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, polystyrene, polyphenylene sulfide, polyphenylene ether, polyamide, polyester, polycarbonate, Cellulose triacetate and the like can be mentioned.

These rubbery polymers and other thermoplastic resins can be used alone or in combination of two or more, and the amount of the rubbery polymer or other thermoplastic resin is appropriately selected within a range not to impair the object of the present invention. You. The crosslinkable polymer composition used in the present invention is, in COB, TAB, MCM, etc., a semiconductor chip mounted on a glass / epoxy wiring board or a polyimide flexible board, etc., locally.
It can be used as a sealing resin crosslinkable polymer composition for molding by a potting method, and its configuration is based on the norbornene-based resin, a crosslinking agent and a crosslinking auxiliary agent whose effects are exhibited by heating, and an organic solvent. Be composed. In order to reduce the linear expansion coefficient (α) required for the sealing material, it is preferable to add an inorganic filler such as a fused silica powder.

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

Examples of the photocrosslinking agent that generates radicals by light include benzoin alkyl ether compounds such as benzoin ethyl ether and benzoin isobutyl ether; benzophenone, methyl orthobenzoyl benzoate, and 4,4′-dichlorobenzophenone. Benzophenone compounds; benzyl compounds such as dibenzyl and benzylmethyl ketal; 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, Acetophenone-based compounds such as 2,1-dichloroacetophenone, 2,2-diethoxyacetophenone, 4′-phenoxy-2,2-dichloroacetophenone; 2-chlorothioxanthone, 2-methylthioxanthone, Thioxanthone compounds such as isopropylthioxanthone; 2-ethylanthraquinone,
Anthraquinone-based compounds such as 2-chloroanthraquinone and naphthoquinone; propiophenone-based compounds such as 2-hydroxy-2-methylpropiophenone and 4'-dodecyl-2-hydroxy-2-methylpropiophenone; cobalt octenoate; Photocrosslinking agents such as organic acid metal salts such as cobalt naphthenate, manganese octenoate and manganese naphthenate;

These crosslinking agents can be used alone or in combination of two or more. The amount of the crosslinking agent is usually 0.001 to 30 parts by weight, preferably 0.001 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the epoxy group-containing norbornene-based addition copolymer. 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 the cross-linking property and the electric properties of the cross-linked product and moisture-proof property are highly balanced and suitable.

(2) Crosslinking Aid In the present invention, a crosslinking aid can be used to further enhance the crosslinking property and the dispersibility of the compounding agent. The crosslinking assistant is not particularly limited, but may be a known one disclosed in JP-A-62-34924, for example, quinone dioxime, benzoquinone dioxime, p-nitrosophenol and the like. 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.
0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight. If the amount of the crosslinking aid is too small, crosslinking is unlikely to occur. Conversely, if the amount is too large, the electrical properties, moisture resistance, etc. of the crosslinked resin may be reduced.

(3) Flame Retardant The flame retardant is not particularly limited, but is preferably one that does not decompose, modify or degrade with a crosslinking agent, and a halogen-based flame retardant is usually used. As the halogen-based flame retardant, various chlorine-based and bromine-based flame retardants can be used, but the flame retardant effect, heat resistance at the time of molding, dispersibility in the resin, influence on the physical properties of the resin, etc. are considered. From, hexabromobenzene, pentabromoethylbenzene, hexabromobiphenyl, decabromodiphenyl, hexabromodiphenyl oxide,
Octabromodiphenyl oxide, decabromodiphenyl oxide, pentabromocyclohexane, tetrabromobisphenol A, and derivatives thereof [for example, tetrabromobisphenol A-bis (hydroxyethyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl) Ether), tetrabromobisphenol A-bis (bromoethyl ether), tetrabromobisphenol A-bis (allyl ether)
Etc.], tetrabromobisphenol S and derivatives thereof [eg, tetrabromobisphenol S-bis (hydroxyethyl ether), tetrabromobisphenol S-bis (2,3-dibromopropyl ether) and the like],
Tetrabromophthalic anhydride and derivatives thereof [for example,
Tetrabromophthalimide, ethylenebistetrabromophthalimide, etc.], ethylenebis (5,6-dibromonorbornene-2,3-dicarboximide), tris-
(2,3-dibromopropyl-1) -isocyanurate, an adduct of the Diels-Alder reaction of hexachlorocyclopentadiene, tribromophenylglycidyl ether, tribromophenyl acrylate, ethylenebistribromophenylether, ethylenebispentabromophenylether, Tetradecabromodiphenoxybenzene, brominated polystyrene, brominated polyphenylene oxide, brominated epoxy resin, brominated polycarbonate, polypentabromobenzyl acrylate, octabromonaphthalene, hexabromocyclododecane, bis (tribromophenyl) fumaramide, N- It is preferable to use methylhexabromodiphenylamine or the like.

The amount of the flame retardant to be added is usually 3 to 15 parts by weight per 100 parts by weight of the epoxy group-containing norbornene copolymer.
0 parts by weight, preferably 10 to 140 parts by weight, particularly preferably 15 to 120 parts by weight. As a flame retardant aid to more effectively exhibit the flame retardant effect of the flame retardant, for example,
Antimony-based flame retardants such as antimony trioxide, antimony pentoxide, sodium antimonate and antimony trichloride can be used. These flame retardant aids are flame retardant 1
It is used in an amount of usually 1 to 30 parts by weight, preferably 2 to 20 parts by weight, based on 00 parts by weight.

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

Examples of the rubbery polymer include ethylene-α-olefin-based rubbery polymers; ethylene-α-olefin-polyene copolymer rubbers; and ethylene and unsaturated monomers such as ethylene-methyl methacrylate and ethylene-butyl acrylate. Copolymer with carboxylic acid ester; Copolymer of ethylene and fatty acid vinyl such as ethylene-vinyl acetate; Acrylic acid such as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate Polymers of alkyl esters; polybutadienes, polysoprene, styrene-butadiene or styrene-isoprene random copolymers,
Acrylonitrile-butadiene copolymer, butadiene-
Isoprene copolymer, butadiene-alkyl (meth) acrylate copolymer, butadiene-alkyl (meth) acrylate-acrylonitrile copolymer,
Diene rubbers such as butadiene- (meth) acrylic acid alkyl ester-acrylonitrile-styrene copolymer; butylene-isoprene copolymer;

Examples of the thermoplastic elastomer include, for example,
Aromatic vinyl-conjugated diene block copolymers such as styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer, low Crystalline polybutadiene resin, ethylene-
Propylene elastomer, styrene grafted ethylene
Propylene elastomer, thermoplastic polyester elastomer, ethylene ionomer resin and the like can be mentioned. Among these thermoplastic elastomers, preferred are hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, and the like. Specifically, JP-A-2-133406,
JP-A-2-305814, JP-A-3-72512
And Japanese Patent Application Laid-Open No. 3-74409.

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

(5) Filler An organic or inorganic filler is blended with the crosslinkable polymer composition of the present invention in order to reduce the linear expansion coefficient (linear expansion coefficient) and increase dimensional stability. Is preferred. Examples of the organic filler include boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, and polyamide fiber.Examples of the inorganic filler include silica, alumina, kaolin, talc, clay, and silica alumina. Glass flake, glass beads, glass fiber, bentonite, graphite, montmorillonite aluminum powder, hydrotalcite, diatomaceous earth, pumice powder, pumice balloon, dolomite, carbon black, titanium oxide, magnesium oxide, calcium oxide, zinc oxide, zirconium oxide , Aluminum hydroxide, calcium hydroxide, magnesium hydroxide, calcium carbonate, basic magnesium carbonate, basic calcium carbonate, calcium silicate, magnesium silicate, calcium sulfate, barium sulfate Fillers such as magnesium sulfate, calcium sulfite, magnesium carbonate, magnesium chloride, magnesium phosphate, calcium phosphate, magnesium carbonate, magnesium chloride, magnesium phosphate, calcium phosphate, silicon nitride, potassium titanate, calcium titanate, and molybdenum sulfide are included. .

Each of these inorganic fillers is used alone.
Alternatively, two or more kinds can be used in combination.
Further, those obtained by treating these inorganic fillers with a silane coupling agent or a titanate coupling agent can be used. The inorganic filler material is usually 10 to 300 parts by weight, preferably 20 to 1 part by weight, based on 100 parts by weight of the polymer component.
50 parts by weight, more preferably 30 to 100 parts by weight. By blending the inorganic filler, the coefficient of linear expansion can be reduced, but if the blending ratio is too small, the decrease in the coefficient of linear expansion becomes insufficient, the thermal denaturation at high temperatures becomes large, and the moisture resistance increases. On the other hand, if the mixing ratio is too large, the viscosity of the composition increases and the formability decreases.

(6) Other Ingredients The crosslinkable polymer composition of the present invention may contain, as necessary, a heat stabilizer, a weather stabilizer, a leveling agent, an antistatic agent, a slip agent, an antiblocking agent, Clouding agents, lubricants, dyes,
Other compounding agents such as pigments, natural oils, synthetic oils and waxes can be added in appropriate amounts. Specifically, for example, tetrakis [methylene-3 (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate] methane, β-
(3,5-di-t-butyl-4-hydroxyphenyl)
Phenolic antioxidants such as alkyl propionate, 2,2'-oxamide bis [ethyl-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]; trisnonylphenyl phosphite, tris (2 , 4-di-t-brylphenyl) phosphite,
Phosphorus-based stabilizers such as tris (2,4-di-t-butylphenyl) phosphite; fatty acid metal salts such as zinc stearate, calcium stearate and calcium 12-hydroxystearate; glycerin monostearate, glycerin monolaurate; Polyhydric alcohol fatty acid esters such as glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate; synthetic hydrotalcite; amine-based antistatic agents; fluorine-based nonionic surfactants; Coating leveling agents such as acrylic resin-based leveling agents and silicone-based leveling agents; cups such as silane coupling agents, titanate coupling agents, aluminum-based coupling agents, and zircoaluminate coupling agents Ing agents; coloring agents such as pigments and dyes; plasticizers and the like.

(7) Solvent In the present invention, an epoxy group-containing norbornene-based copolymer is dissolved in a solvent to prepare an impregnation solution for prepreg, or a sheet (film) is produced by a solution casting method. can do. As described above, when the epoxy group-containing norbornene-based copolymer 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 epoxy group-containing norbornene-based copolymer and, if necessary, each component. The amount of the solvent used is such that the solid content concentration is usually 1 to 80% by weight, preferably 5 to
It is adjusted to be 60% by weight, more preferably 10 to 50% by weight.

Electronic Components / Norbornene-Based Resin Sealing Material The sealing material used in the present invention is composed of a norbornene-based resin and a crosslinking agent, a crosslinking aid, an organic solvent, an inorganic filler such as fused silica and the like. 0.1 ~ 20.0Pa ・
s, preferably 0.2 to 10.0 Pa · s, more preferably 0.3 to 5.0 Pa · s. The non-volatile content of the solution is usually 5 to 100%, preferably 10 to 90%.
%, More preferably 20 to 70%. If the concentration is too low, the surface tension of the sealing agent is reduced, and it cannot be sealed with a sufficient film thickness because it spreads over the substrate, and if the concentration is too high, the viscosity of the sealing agent becomes too high, There is a problem in that the resin does not sufficiently flow around the bonding wire or between the chip and the substrate, so that the resin is not completely filled, or voids are generated because bubbles are not completely removed.

If the viscosity of the sealant is too low, it will spread too much during potting, causing the chip to protrude. If the viscosity is too high, the sealant will not flow smoothly between the bonding wires or voids will occur. And the like, which may cause cracks or the like during an environmental test.

Formation of Sealing Coat Film (1a) Potting Method A method of forming an overcoat film on an LSI chip using the sealing material of the present invention is a dropping method using a dispenser, or a method using a mold. In the dropping method, there are a method of forming a dam around the chip, a method of providing a dent, and a method of not providing a frame at all. In the case of the former two methods, high flow type sealing is used. In the latter case, a high-viscosity shape-retaining sealing material is used. There is also a method of sealing the tape carrier package by a dropping method. In this case, a sealing material having a low viscosity tape is used. As a casting method for sealing using a casting frame, a material having high fluidity and low viscosity is used.

(B) Curing The curing of the encapsulant is carried out, as a first step, usually at 70 to 250 ° C., preferably at 80 to 150 ° C. in order to remove the solvent by evaporation.
After pre-baking for 5 to 60 minutes, preferably 10 to 30 minutes, usually at 100 to 250 ° C, preferably at 150 to 200 ° C, usually 30 minutes to 5 hours, preferably 1 to 2 hours Let it cure completely. In the present invention, the materials of the lead wires and the lead frame of the electronic component are not particularly limited, but any material combining various metals such as iron, nickel, copper, aluminum, tin, zinc, cobalt, and zirconium can be used.

The electronic components that can be sealed by the method of the present invention include lead-through mounted products and surface mounted products, and specifically, ICs, LSIs, VLSIs, hybrid ICs, transistors, diodes, triodes, and the like. Capacitors, resistors, resistor networks, thyristors,
Chip inductors, transformers, motors, LC filters,
Connectors, coils, varistors, transducers, crystal oscillators, fuses, current detectors, power supplies, switches, relays,
Examples include a sensor, a Hall element, a surge absorber, an arrester, a bin grid array, a photocabler, and a composite component thereof.

[0102]

The present invention will be described more specifically below with reference to examples and comparative examples. (1) Glass transition temperature (Tg): Differential scanning calorimetry (DS)
C method). (2) Molecular weight (Mw, Mn): Unless otherwise specified, the molecular weight was measured in terms of polystyrene by gel permeation chromatography (GPC) using toluene as a solvent. (3) Copolymerization ratio: Measured by ¹ H-NMR spectrum. (4) Epoxy value: calculated according to JIS7236.
The epoxidation rate (conversion rate of epoxy group of carbon-carbon unsaturated bond) was measured by ¹ H-NMR.

(5) Adhesion: An overcoat film formed by the method described later and an LSI chip were subjected to a peeling test on the gobang pattern, and 100/100 were judged to be good. (6) Durability: After standing for 1000 hours at 90 ° C. and 95% humidity, abnormal appearance and discoloration of blisters and the like are observed to confirm the moisture resistance and the stability against heat history, and then −40.
℃ → 100 ℃ (holding time of each temperature is 30 minutes, heating and cooling time is 30 minutes), even in the heat cycle test of 1000 cycles, abnormal appearance and discoloration of blisters etc. are observed, and thermal stability by heat cycle It was confirmed. (7) Solder heat resistance: After contacting the solder at 300 ° C. for 1 minute, the external appearance was observed and judged according to the following criteria. Good: No peeling or blistering Bad: Peeling or blistering (8) Dielectric constant and dielectric loss tangent were measured according to JIS K6911.

Example 1 (Production of a cyclic olefin thermoplastic norbornene-based addition copolymer and epoxy modification)
Of a glass container, dichlorobis (benzonitrile) palladium 500mg and 8-ethylidene tetracyclo [4,4,0,1 ^{2, 5,} 1 ^7,10] -3-dodecene 75m
was added and a polymerization reaction was carried out at 90 ° C. for 4 hours. After completion of the reaction, the mixture was poured into a large amount of methanol to precipitate a polymer. The polymer was separated by filtration, washed, and dried under reduced pressure to obtain 32 g of a polymer (number average molecular weight (Mn) =
2,400, weight average molecular weight (Mw) = 3,400, glass transition temperature (Tg) = 320 ° C.).

(Epoxy Modification) 50 parts by weight of the obtained thermoplastic norbornene resin was added to 1000 parts by weight of xylene.
Dissolved at 30 ° C. Subsequently, 2 parts by weight of t-butyl hydroperoxide and 0.15 parts by weight of hexacarbonylmolybdenum were added and reacted at 130 ° C. for 1 hour. This was poured into a large amount of methanol to precipitate a polymer. The polymer was separated by filtration, washed, and dried under reduced pressure to obtain 50 parts by weight of an epoxy-modified thermoplastic norbornene-based resin polymer (code No. A). The molecular weight of this resin polymer A is Mn = 2,800
And Tg was 322 ° C. The epoxy value of this resin polymer A was 0.49 mol / 100 g. ¹ H-NM
The conversion of the olefinically unsaturated bond epoxy group measured by R was 92%, and the epoxy group introduction rate per repeating structural unit of the polymer was 92%. ＄

Example 2 (Epoxy Modification) 50 parts by weight of the thermoplastic norbornene resin obtained in Example 1 was added to 10 parts by weight of xylene.
Dissolved at 0 ° C. Subsequently, a solution prepared by dissolving 9 parts by weight of metachloroperbenzoic acid in 400 parts by weight of xylene was added, and 1
The reaction was performed at 00 ° C. for 3 hours. This was poured into a large amount of methanol to precipitate a polymer, and the polymer was separated by filtration, washed, and dried under reduced pressure to obtain 50 parts by weight of an epoxy-modified thermoplastic norbornene-based resin polymer (code No. B). The molecular weight of this resin polymer B is Mn = 2,700 and Tg is 321 ° C.
Met. The epoxy value of this resin polymer B is 0.41 m
ol / 100 g. Conversion of epoxy group of olefinically unsaturated bond measured by ¹ H-NMR is 81%.
The epoxy group introduction ratio per repeating structural unit of the polymer was 81%.

Example 3 (Production of Cyclic Norbornene-Based Polymer and Epoxy Modification) 500 mg of dichlorobis (benzonitrile) palladium and 5-
Vinyl-bicyclo [2,2,1] hept-2-ene (V
NB) and 8-ethylidenetetracyclo [4,4,
0,1 ^2,5, 1 ^{7, 10]} -3 mixtures dodecene 75ml
Was added and a polymerization reaction was performed at 90 ° C. for 4 hours. After the completion of the reaction, the mixture was poured into a large amount of methanol to precipitate a polymer,
After washing by filtration and drying under reduced pressure, 46.0 g of a polymer (VNB composition 54%, number average molecular weight (Mn) = 2,100 in terms of polystyrene, weight average molecular weight (Mw))
= 3,100, glass transition temperature (Tg) = 282 ° C)
I got

(Epoxy Modification) 50 parts by weight of the obtained thermoplastic norbornene resin was added to 1000 parts by weight of xylene in a proportion of 1 part.
Dissolved at 30 ° C. Subsequently, 2 parts by weight of t-butyl hydroperoxide and 0.15 parts by weight of hexacarbonylmolybdenum were added and reacted at 130 ° C. for 1 hour. This was poured into a large amount of methanol to precipitate a polymer, and the polymer was separated by filtration, washed, and dried under reduced pressure to obtain 50 parts by weight of an epoxy-modified thermoplastic norbornene-based resin polymer (code No. C). The molecular weight of this resin polymer C is Mn = 2,300
And Tg was 284 ° C. The epoxy value of the resin polymer C was 0.61 mol / 100 g. ¹ H-N
The conversion of the epoxy group of the olefinically unsaturated bond measured by MR was 98%, and the epoxy group introduction rate per repeating structural unit of the polymer was 98%.

REFERENCE EXAMPLE 1 To a 300 ml glass container purged with nitrogen, 100 ml of toluene, 6 mmol of methylaluminoxane and 0.3 mmol of bis (cyclopentadienyl) zirconium dichloride were added. Next, 15 ml of 5-vinyl-bicyclo [2,2,1] hept-2-ene was added,
The polymerization reaction was performed at 80 ° C. for 24 hours. After completion of the reaction, the mixture was poured into a large amount of methanol to precipitate a polymer.
(Weight average molecular weight (Mw) = 1,800, glass transition temperature (Tg) = 246 ° C.).

(Epoxy modification) 50 parts by weight of the obtained thermoplastic norbornene-based resin was added to 1000 parts by weight of xylene.
Dissolved at 30 ° C. Subsequently, 2 parts by weight of t-butyl hydroperoxide and 0.15 parts by weight of hexacarbonylmolybdenum were added and reacted at 130 ° C. for 1 hour. This was poured into a large amount of methanol to precipitate a polymer, which was separated by filtration, washed, and dried under reduced pressure to obtain 50 parts by weight of an epoxy-modified thermoplastic norbornene-based resin (code No. D). The molecular weight of this resin D is Mn = 1,200 and Tg is 2
48 ° C. The conversion of the olefinically unsaturated bond epoxy group of the resin D measured by ¹ H-NMR was 85.
%, The introduction ratio of epoxy groups per repeating structural unit of the polymer was 85%. ＄ (Examples 4 to 6, Comparative Example 1) Examples 1 to 3 and Reference Example 1
When 30 parts by weight of each of the epoxy-modified thermoplastic norbornene resins obtained in the above and 1.2 parts by weight of 4,4'-bisazidobenzal (4-methyl) cyclohexanone are dissolved in 50 parts by weight of xylene, precipitation occurs. A homogeneous solution was obtained.

<Formation of Overcoat Film for Encapsulating Semiconductor>
The above solution was applied on a component in which an LSI chip was bare-chip mounted on a substrate, and prebaked at 90 ° C. for 60 seconds to obtain a 300 μm-thick coating film on the LSI chip. This sample was heated and cured at 250 ° C. for 3 hours under nitrogen to form an overcoat film having a thickness of 300 μm.
The evaluation results are shown in Table 1.

[0112]

[Table 1]

In the table, "polymer" indicates a resin before epoxy modification, and "epoxy" indicates an epoxy value.

Claims (6)

[Claims] 1. A repeating unit [A] represented by the following formula (A) and a repeating unit [B] represented by the following formula (B): [A]: [B] = 100: 0 to 30:70 And a number average molecular weight (Mn) of 500 to 500,000. Embedded image (In the formula (A), a represents 0, 1 or 2, b represents 0, 1 or 2, c represents 1 or 2, and R ^{1 to} R ¹⁴ each independently represent a hydrogen atom, a hydrocarbon, Group, halogen atom, alkoxy group, ester group, cyano group, amide group,
Represents a hydrocarbon group substituted by an imide group, a silyl group, or a polar group (a halogen atom, an alkoxy group, an ester group, a cyano group, an amide group, an imide group, or a silyl group). However, at least one of either an alkenyl group substituted with an alkenyl group or polar group, or R ⁵ and R ^6, R ¹¹ and R ¹² or R ^{1 3} and R ¹⁴ are bonded to each other R ¹ to R ¹⁴ At least one alkylidene group or an alkylidene group substituted with a polar group. ) (In the formula (B), d is 0, 1 or 2, e is 0, 1 or 2, f is 0, 1 or 2, g is 0, 1 or 2, and R ^{15 to} R ²⁶ Is independently a hydrogen atom,
Alkyl group, halogen atom, alkoxy group, ester group, cyano group, amide group, imide group, silyl group, or polar group (halogen atom, alkoxy group, ester group, cyano group, amide group, imide group, or silyl group) Represents an alkyl group substituted with Provided that at least one of R ^{15 to} R ²⁶ is an alkenyl group or an alkenyl group substituted with a polar group, or R ¹⁹ and R ²⁰ , R ²¹ and R ²² ,
R ²³ and R ²⁴ or R ²⁵ and R ²⁶ are bonded to each other to form at least one alkylidene group or an alkylidene group substituted with a polar group, or R ^{24 to} R ²⁵ are bonded to each other, to form a carbon-carbon double bonds - R ²⁴ to R ²⁵ is a carbon between the two carbon atoms formed by combining each. ) 2. A norbornene-based monomer [a] represented by the following formula (a) and a norbornene-based monomer [b] represented by the following formula (b): [a]: [b] = 100 : 0 to 30: 70, a process for producing a thermoplastic norbornene-based polymer, which comprises carrying out addition polymerization using a polymerization catalyst containing a transition metal compound belonging to Group VIII of the periodic table. Embedded image (In the formula (a), a is 0, 1 or 2, b is 0, 1 or 2, c is 1 or 2, and R ^{1 to} R ¹⁴ are each independently a hydrogen atom, a hydrocarbon, Group, halogen atom, alkoxy group, ester group, cyano group, amide group,
Represents a hydrocarbon group substituted by an imide group, a silyl group, or a polar group (a halogen atom, an alkoxy group, an ester group, a cyano group, an amide group, an imide group, or a silyl group). However, at least one of either an alkenyl group substituted with an alkenyl group or polar group, or R ⁵ and R ^6, R ¹¹ and R ¹² or R ^{1 3} and R ¹⁴ are bonded to each other R ¹ to R ¹⁴ At least one alkylidene group or an alkylidene group substituted with a polar group. ) (In the formula (b), d is 0, 1 or 2, e is 0, 1 or 2, f is 0, 1 or 2, g is 0, 1 or 2, and R ^{15 to} R ²⁶ Is independently a hydrogen atom,
Alkyl group, halogen atom, alkoxy group, ester group, cyano group, amide group, imide group, silyl group, or polar group (halogen atom, alkoxy group, ester group, cyano group, amide group, imide group, or silyl group) Represents an alkyl group substituted with Provided that at least one of R ^{15 to} R ²⁶ is an alkenyl group or an alkenyl group substituted with a polar group, or R ¹⁹ and R ²⁰ , R ²¹ and R ²² ,
R ²³ and R ²⁴ or R ²⁵ and R ²⁶ are bonded to each other to form at least one alkylidene group or an alkylidene group substituted with a polar group, or R ^{24 to} R ²⁵
Are bonded to each other to form a carbon-carbon double bond between the two carbon atoms formed by bonding R ^{24 to} R ²⁵ . ) 3. The repeating unit [C] represented by the following formula (C) and the repeating unit [D] represented by the following formula (D) are represented by [C]: [D] = 100: 0 to 30:70. And the number average molecular weight (Mn) is 500 to 500,000.
Norbornene-based polymers having an epoxy group. Embedded image (In the formula (C), a represents 0, 1 or 2, b represents 0, 1 or 2, c represents 1 or 2, and R ^{1 to} R ¹⁴ each independently represent a hydrogen atom, a hydrocarbon, Group, halogen atom, alkoxy group, ester group, cyano group, amide group,
Represents a hydrocarbon group substituted by an imide group, a silyl group, or a polar group (a halogen atom, an alkoxy group, an ester group, a cyano group, an amide group, an imide group, or a silyl group). However, at least one of R ¹ to R ¹⁴ is an alkyl group substituted by a polar group having an alkyl group or an epoxy backbone having an epoxy skeleton, or R ¹² and R
¹³ is bonded via an oxygen atom to form an oxy group, or R ⁵ and R ⁶ , R ¹¹ and R ¹² , or R ¹³ and R
^{And 14} are bonded to each other to form at least one of the following formulas (d): (In the formula (d), R ⁶⁵ is a hydrogen atom, an alkyl group, a polar group, or an alkyl group substituted with a polar group.) ) (In the formula (D), d is 0, 1 or 2, e is 0, 1 or 2, f is 0, 1 or 2, g is 0, 1 or 2, and R ^{15 to} R ²⁶ Is independently a hydrogen atom,
Alkyl group, halogen atom, alkoxy group, ester group, cyano group, amide group, imide group, silyl group, or polar group (halogen atom, alkoxy group, ester group, cyano group, amide group, imide group, or silyl group) Represents an alkyl group substituted with Provided that at least one of R ^{15 to} R ²⁶ is an alkyl group having an epoxy skeleton or an alkyl group substituted with a polar group having an epoxy skeleton, or R ²⁴ and R ²⁵ are bonded via an oxygen atom. An oxy group is formed, or R ¹⁹ and R ²⁰ , R ²¹
And R ²² , R ²³ and R ²⁴ , or R ²⁵ and R ²⁶ are bonded to each other to form at least one of the following formulas (d): (In the formula (d), R ⁶⁵ is a hydrogen atom, an alkyl group, a polar group, or an alkyl group substituted with a polar group.) ) 4. The thermoplastic norbornene-based polymer according to claim 1, which is reacted with a peroxide as an epoxidizing agent.
A method for producing an epoxy group-containing norbornene-based polymer, wherein a non-conjugated carbon-carbon double bond in the copolymer is epoxidized with a peroxide. 5. A crosslinkable polymer composition comprising the epoxy group-containing norbornene polymer according to claim 4 and a crosslinking agent. 6. An electronic component encapsulated with the crosslinkable polymer composition according to claim 5.