JP2009167433A - Ring-opened copolymer, hydrogenated product of ring-opened copolymer, method for producing the same, and composition thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a ring-opened metathesis copolymer having low water absorption, excellent adhesiveness to other materials such as metals and compatibility with other compounds such as a curing agent, exhibiting high heat-resistance and causing little delay and noise of a signal in a high-frequency range, and to provide a hydrogenated product of the copolymer. <P>SOLUTION: The ring-opened metathesis copolymer and the hydrogenated product of the ring-opened metathesis copolymer having a hydroxy group, a desired monomer composition and high molecular weight can be produced by the ring-opening metathesis copolymerization of a norbornene monomer having a hydroxy group and a non-substituted norbornene monomer having three or more rings in the presence of a catalyst principally composed of an organic ruthenium compound having a coordinated neutral electron-donative ligand and hydrogenating the copolymerization product. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel norbornene-based ring-opening metathesis copolymer (hereinafter referred to as “ring-opening metathesis copolymer” or “copolymer”) and a hydride of the copolymer. More specifically, the present invention relates to a ring-opening metathesis copolymer having excellent balance between low water absorption and electrical properties, metal adhesion and compatibility with other materials, and excellent heat resistance, and a hydride thereof.

  A ring-opening metathesis polymer of a norbornene-based monomer that does not contain a polar group and its hydride are widely used in electrical insulation applications because of their excellent heat resistance, electrical properties, and low water absorption. However, adhesion to other materials such as metals such as copper and silicon or glass is low, and compatibility with other compounds such as curing agents and epoxy resins is low.

On the other hand, what polymerized the norbornene-type monomer containing a polar group is proposed. Specifically, a norbornene monomer having an ester group or a hydroxyl group such as acetate of 5,6-dihydroxymethyl-bicyclo- [2.2.1] -hept-2-ene is added in the presence of a tungsten catalyst. A polymer having a large number of polar groups such as hydroxyl groups obtained by ring-opening polymerization and hydrogenation (see Patent Document 1); 8-methoxycarbonyltetracyclo [4.4] obtained using a tungsten-based catalyst .0.1 ^2,5 . 1, ¹⁰ ] -3-dodecene homo-ring-opening polymer or 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . A polymer having a hydroxycarbonyl group obtained by hydrogenating and further hydrolyzing a ring-opening copolymer of 1 ^7,10 ] -3-dodecene and bicyclo [2.2.1] hept-2-ene ( Patent Document 2) is disclosed. These polymers have slightly improved adhesion compared to polymers that do not contain polar groups, but have a high water absorption rate, a long propagation delay time for high-frequency signals in the GHz band, and are easy to pick up signal noise. Further, as described above, a high molecular weight copolymer comprising a norbornene monomer having a polar group and a bicyclic norbornene monomer has a low glass transition temperature (Tg) and insufficient heat resistance. .

Japanese Patent Laid-Open No. 5-155888 Japanese Patent Laid-Open No. 11-52574

  An object of the present invention is to provide a ring-opening metathesis copolymer having excellent electrical characteristics and low water absorption, excellent adhesion to other materials such as metals, compatibility with other compounds such as curing agents, and high heat resistance. And providing a hydride thereof.

The present inventors have disclosed 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] -3-Dodecene, a norbornene-based monomer having three or more rings that gives a high Tg was copolymerized using a tungsten-based catalyst, but a side reaction occurred, resulting in a desired molecular weight. And a ring-opening copolymer having a repeating unit ratio could not be obtained.

  Therefore, as a result of further studies to achieve the above-mentioned object, the present inventors have desired a repeating unit consisting of a repeating unit having a hydroxyl group and a nonpolar group only by using a specific ruthenium-based catalyst. High-molecular-weight norbornene-based ring-opening metathesis copolymer and hydride thereof can be obtained, and the copolymer and hydride can adhere to other materials such as metals and glass, and hardeners. The present inventors have found that it is excellent in compatibility with other compounds and has a good balance of heat resistance, electrical properties and low water absorption properties, and has completed the present invention.

  Thus, according to the present invention, the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) or the repeating unit represented by the general formula (3) are all repeating units. Provided is a ring-opening metathesis copolymer having a ratio of the number of hydroxyl groups to 5 to 100% and a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography of 1,000 to 500,000. .

（１）
（式（１）中、Ｒ^１〜Ｒ^４の少なくとも一つがヒドロキシル基を含む置換基（ヒドロキシカルボニル基は除く）であり、その他は水素原子、炭素数１〜２０の炭化水素基又はハロゲン原子、ケイ素原子、酸素原子もしくは窒素原子を含む基（ヒドロキシル基及びヒドロキシカルボニル基を除く）を示す。ｍは０〜２の整数を表す。）

(1)
(In the formula (1), at least one of R ^{1 to} R ⁴ is a substituent containing a hydroxyl group (excluding a hydroxycarbonyl group), and the other is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen atom, A group containing a silicon atom, an oxygen atom or a nitrogen atom (excluding a hydroxyl group and a hydroxycarbonyl group). M represents an integer of 0 to 2.)

（２）
（式（２）中、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は、それぞれ独立に、水素原子又は炭素数１〜２０の炭化水素基を示し、Ｒ^５またはＲ^６がＲ^７またはＲ^８と結合して環を形成しても構わない。ｎは１〜２の整数を表す。）

(2)
(In the formula ^(2), R ^5, R 6, ^{R 7} and ^{R 8} each independently represent a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 20, ^{R 5} or ^{R 6 R 7} or ^{R 8} And n may represent an integer of 1 to 2).

（３）
（式（３）中、Ｒ^９、Ｒ^１０、Ｒ^１１およびＲ^１２は、それぞれ独立に、水素原子又は炭素数１〜２０の炭化水素基を示し、Ｒ^９またはＲ^１０がＲ^１１またはＲ^１２と結合して環を形成している。）

(3)
(In Formula (3), R < ⁹ >, R < ¹⁰ >, R < ¹¹ > and R < ¹² > show a hydrogen atom or a C1-C20 hydrocarbon group each independently, and R < ⁹ > or R < ¹⁰ > is R < ¹¹ > or R <^12>. To form a ring.)

  According to the present invention, the repeating unit represented by the general formula (1), the repeating unit represented by the general formula (2) or (3), the repeating unit represented by the general formula (5), It consists of repeating units represented by formula (6) or (7), and the total of repeating units represented by general formulas (1), (2) and (3) is 50 to 0% of all repeating units. The total number of repeating units represented by the general formulas (5), (6) and (7) is 50 to 100% of all repeating units, and the ratio of the number of hydroxyl groups to all repeating units is 5 to 100%. A ring-opening metathesis copolymer hydride having a polystyrene-equivalent weight average molecular weight of 1,000 to 500,000 as measured by gel permeation chromatography is provided.

（５）
（式（５）中、Ｒ^１〜Ｒ^４の少なくとも一つがヒドロキシル基を含む置換基（ヒドロキシカルボニル基を除く）であり、その他は水素原子、炭素数１〜２０の炭化水素基又はハロゲン原子、ケイ素原子、酸素原子もしくは窒素原子を含む基（ヒドロキシル基及びヒドロキシカルボキシル基を除く）を示す。ｍは０〜２の整数を表す。）

(5)
(In Formula (5), at least one of R ^{1 to} R ⁴ is a substituent containing a hydroxyl group (excluding a hydroxycarbonyl group), and the other is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, A group containing a silicon atom, oxygen atom or nitrogen atom (excluding hydroxyl group and hydroxycarboxyl group), m represents an integer of 0-2.

（６）
（式（６）中、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は、それぞれ独立に、水素原子又は炭素数１〜２０の炭化水素基を示し、Ｒ^５またはＲ^６がＲ^７またはＲ^８と結合して環を形成しても構わない。ｎは１〜２の整数を表す。）

(6)
(In Formula (6), R < ⁵ >, R < ⁶ >, R < ⁷ > and R < ⁸ > show a hydrogen atom or a C1-C20 hydrocarbon group each independently, and R < ⁵ > or R < ⁶ > is R < ⁷ > or R <^8>. And n may represent an integer of 1 to 2).

（７）
（式（７）中、Ｒ^９、Ｒ^１０、Ｒ^１１およびＲ^１２は、それぞれ独立に、水素原子又は炭素数１〜２０の炭化水素基を示し、Ｒ^９またはＲ^１０がＲ^１１またはＲ^１２と結合して環を形成している。）

(7)
(In Formula (7), R < ⁹ >, R < ¹⁰ >, R < ¹¹ > and R < ¹² > show a hydrogen atom or a C1-C20 hydrocarbon group each independently, and R < ⁹ > or R < ¹⁰ > is R < ¹¹ > or R <^12>. To form a ring.)

  Further, according to the present invention, there is provided a curable resin composition containing at least one copolymer selected from the ring-opening metathesis copolymer and the hydrogenated ring-opening metathesis copolymer, and a curing agent. .

  Furthermore, according to the present invention, the monomer represented by the general formula (9) and the monomer represented by the general formula (10) or the monomer represented by the general formula (11) Of ring-opening metathesis copolymer comprising ring-opening metathesis copolymerization in the presence of a catalyst mainly composed of an organoruthenium compound coordinated with a neutral electron-donating ligand, and this production A method for producing a hydride of a ring-opening metathesis copolymer comprising hydrogenating a main chain double bond of the ring-opening metathesis copolymer obtained by the method is provided.

（９）
（式（９）中、Ｒ^１〜Ｒ^４の少なくとも一つが、−ＯＨ（すなわち、ヒドロキシル基）を含む置換基（ヒドロキシカルボニル基は除く）であり、その他は水素原子、炭素数１〜２０の炭化水素基又はハロゲン原子、ケイ素原子、酸素原子もしくは窒素原子を含む基（ヒドロキシル基及びヒドロキシカルボキシル基を除く）を示す。ｍは０〜２の整数を表す。）

(9)
(In Formula (9), at least one of R ^{1 to} R ⁴ is a substituent (excluding a hydroxycarbonyl group) containing —OH (ie, a hydroxyl group), and the others are a hydrogen atom and a C 1-20 carbon atom. A hydrocarbon group or a group containing a halogen atom, a silicon atom, an oxygen atom or a nitrogen atom (excluding a hydroxyl group and a hydroxycarboxyl group), and m represents an integer of 0 to 2.

（１０）
（式（１０）中、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は、それぞれ独立に、水素原子又は炭素数１〜２０の炭化水素基を示し、Ｒ^５またはＲ^６がＲ^７またはＲ^８と結合して環を形成しても構わない。ｎは１〜２の整数を表す。）

(10)
(In the formula (10), R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁵ or R ⁶ is R ⁷ or R ^8. And n may represent an integer of 1 to 2).

（１１）
（式（１１）中、Ｒ^９、Ｒ^１０、Ｒ^１１およびＲ^１２は、それぞれ独立に、水素原子又は炭素数１〜２０の炭化水素基を示し、Ｒ^９またはＲ^１０がＲ^１１またはＲ^１２と結合して環を形成している。）

(11)
(In formula (11), R < ⁹ >, R < ¹⁰ >, R < ¹¹ > and R < ¹² > show a hydrogen atom or a C1-C20 hydrocarbon group each independently, and R < ⁹ > or R < ¹⁰ > is R < ¹¹ > or R <^12>. To form a ring.)

  According to the production method of the present invention, ring-opening metathesis copolymerization of a norbornene-based monomer having a hydroxyl group and a norbornene-based monomer having three or more rings can be carried out at a desired monomer composition ratio. A molecular weight product is obtained. Further, the ring-opening metathesis copolymer and the hydride thereof according to the present invention have a low water absorption, low signal delay and signal noise, excellent adhesiveness with copper and silicon, and a conventional curing agent with low compatibility. Excellent compatibility with. The composition containing the copolymer and hydride of the present invention and a curing agent can be suitably used as an electrical insulating material for electronic components, multilayer circuit boards and the like by curing the composition.

  The ring-opening metathesis copolymer of the present invention comprises a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2) or (3).

  The ring-opening metathesis copolymer hydride of the present invention is represented by the repeating unit represented by the general formula (1), the repeating unit represented by the general formula (2) or (3), and the general formula (5). And a repeating unit represented by the general formula (6) or (7).

  The preferred ring-opening metathesis copolymer and hydride of the ring-opening metathesis copolymer of the present invention are substantially free of repeating units other than the above repeating units.

  The repeating units represented by the general formulas (1) and (5) constituting the ring-opening metathesis copolymer and the ring-opening metathesis copolymer hydride of the present invention are those in which a hydroxyl group is bonded as a substituent. is there. On the other hand, the repeating units represented by the general formulas (2), (3), (6) and (7) have no substituent or have a hydrocarbon group bonded as a substituent.

  The number of hydroxyl groups (excluding the hydroxyl group in the hydroxycarbonyl group) is 5 to 100%, preferably 8 to 90, based on the repeating units constituting the ring-opening metathesis copolymer or hydride of the ring-opening metathesis copolymer. %, More preferably 10 to 80%. By making the ratio of the number of hydroxyl groups in the copolymer within the above range, the adhesiveness with other materials and compatibility with other compounds are excellent, and furthermore, the heat resistance, electrical properties and low water absorption properties are balanced. .

  The group containing a hydroxyl group in the repeating units represented by the general formulas (1) and (5) may be already bonded in the monomer used at the time of copolymerization or copolymerization. It may be introduced later or after hydrogenation by a hydrolysis reaction or the like.

  In the hydrogenated ring-opening metathesis copolymer of the present invention, the total of repeating units represented by the general formulas (1), (2) and (3) is 50 to 0%, preferably 30 to 0%, more preferably 20 to 0%, particularly preferably 10 to 0%, and the total of the repeating units represented by the general formulas (5), (6) and (7) is 50 to 100%, preferably 70 to 100%. Preferably it is 80 to 100%, and particularly preferably 90 to 100%.

  The repeating units represented by the general formulas (1) to (3) are units derived from a norbornene-based monomer, and are obtained by copolymerizing the norbornene-based monomer in the presence of a catalyst described later by ring-opening metathesis copolymerization. can get.

  The repeating units represented by the general formulas (5) to (7) are also units derived from norbornene monomers, and the norbornene monomers were copolymerized by ring-opening metathesis in the presence of a catalyst described later. Later, it is obtained by hydrogenating unsaturated bonds of the main chain.

  The norbornene-based monomer includes a bicycloheptene derivative in which m or n is 0, a tetracyclododecene derivative in which m or n is 1, a hexacycloheptadecene derivative in which m or n is 2. Also included are those in which a ring is further formed by a substituent. Examples of the substituent for ring formation include vinylene group, methylene group, dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group and the like.

  The repeating unit represented by the general formulas (2), (3), (6) and (7) is a norbornene system having a tricyclic or higher structure in which there is no substituent or a hydrocarbon group is bonded as a substituent. Derived from the monomer.

Specific examples of the unsubstituted or hydrocarbyl-substituted tricyclic body more norbornene monomers, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8- methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-ethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca - 3-ene, 8-cyclohexyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-cyclopentyl-tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] dodeca-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] dodeca-3-ene, 8-ethylidene tetracyclo [4.4.0 .1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8- flop Bae cycloalkenyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-cyclohexenyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-cyclopentenyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-phenyl-tetracyclo [4.4.0.1 ^{2, 5.1 7,10]} dodeca-3-tetracyclododecene derivatives and such as ene; hexacyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-ene, 11-methyl-hexa cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-ene, 11-phenyl-hexa cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-ene unsubstituted or a monomer of the hydrocarbon group substituted as represented by the general formula, such as hexamethylene cycloheptanone decene derivative (10) such as; tricyclo [4.3.1 ^2,5 .0] -3-decene, tricyclo [4.3.12,5.0] - deca-3,7-diene (also known as dicyclopentadiene), tetracyclo [6.5.1 ^2,5. 0 ^1,6 .0 ^8,13] tetradeca -3,8,10,12- tetraene (alias: 1,4-methano -1,4,4a, 9a- tetrahydrofluorene), tetracyclo [6.6.1 ^{2 5} .0 ^1,6 .0 ^8,13] pentadeca -3,8,10,12- tetraene (also known as 1,4-methano -1,4,4a, 5,10,10a- hexahydro-anthracene) of Unsubstituted or carbonized as represented by general formula (11) Monomers containing groups substituted and the like.

The unsubstituted or hydrocarbon group-substituted norbornene monomers can be used alone or in combination of two or more. In order to obtain a ring-opening copolymer having excellent heat resistance and solubility in a solvent, an unsubstituted or hydrocarbon group-substituted monomer represented by the general formula (11) and a tetracyclododecene derivative are used. Specifically, specifically, tricyclo [4.3.1 ^2,5 . 0] -3-decene, tricyclo [4.3.2 ^2,5 . 0] - deca-3,7-diene, tetracyclo ^{[8.6.1 2,5.} 0 ^1,6 . 0 ^8,13] pentadeca -3,8,10,12- tetraene; tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-dodecene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene is preferred.

  Bicyclic [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2. 2.1] Hept-2-ene, 5-propylbicyclo [2.2.1] hept-2-ene, 5-butylbicyclo [2.2.1] hept-2-ene, 5-pentylbicyclo [2] 2.2.1] Hept-2-ene, 5-hexylbicyclo [2.2.1] hept-2-ene, 5-heptylbicyclo [2.2.1] hept-5-ene, 5-octylbicyclo [ 2.2.1] Hept-2-ene, 5-nonylbicyclo [2.2.1] hept-2-ene, 5-decylbicyclo [2.2.1] hept-2-ene, 5-vinylbicyclo [2.2.1] hept-2-ene, 5-ethylidenebicyclo [2.2.1] hept-2-ene, 5-cyclohexylbicyclo [2.2.1] hept- - ene, 5-cyclo to Kisenirubishikuro [2.2.1] hept-2-ene, such as 5-phenyl-bicyclo [2.2.1] hept-2-ene bicycloheptene derivatives. These can be copolymerized as long as the heat resistance does not decrease. However, when high heat resistance is required, it is better not to copolymerize a bicyclic norbornene monomer.

  The repeating unit represented by the general formulas (1) and (5) is a norbornene monomer to which a substituent containing a hydroxyl group is bonded, or a group that can be chemically changed to a hydroxyl group by hydrolysis or the like. It is derived from a norbornene monomer bonded, preferably a monomer represented by the general formula (9). As long as the hydroxyl group is contained, the substituent containing a hydroxyl group has a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, a silicon atom, an oxygen atom or a nitrogen atom in addition to the hydroxyl group. It does not matter.

Examples of norbornene-based monomers having a hydroxyl group include 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5,6 -Dihydroxymethylbicyclo [2.2.1] hept-2-ene, 5-hydroxyethoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-hydroxyethoxycarbonylbicyclo [2.2 .1] Hept-2-ene, 5-hydroxybutoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-hydroxypropoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl Bicycloheptene derivatives such as -5-hydroxypropoxycarbonylbicyclo [2.2.1] hept-2-ene; 8-hydroxytet Cyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene, 8-hydroxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-dihydroxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-hydroxyethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-hydroxyethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-hydroxybutoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-hydroxypropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-hydroxypropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . Tetracyclododecene derivatives such as 1 ^7,10 ] dodec- ³ -ene; 11-hydroxyhexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] - heptadeca-4-ene, 11-hydroxy methylhexahydrophthalic cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] - heptadeca-4-ene, 11,12-dihydroxy-methylhexahydrophthalic cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] - heptadeca-4-ene, 11-hydroxy ethoxycarbonyl hexamethylene cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] - heptadeca-4-ene, 11-methyl-11-hydroxy-ethoxycarbonyl hexamethylene cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] - heptadeca-4-ene, 11-hydroxy-butoxycarbonyl hexamethylene cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] - heptadeca-4-ene, 11-hydroxy-propoxycarbonyl hexamethylene cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] - heptadeca-4-ene, 11-methyl-11-hydroxy-propoxycarbonyl hexamethylene cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] - heptadeca-4-ene can be exemplified hexamethylene cycloheptanone decene derivatives such as.

  The group that can be chemically changed to a hydroxyl group may be any group that can be converted into a hydroxyl group by decomposition or reduction, and examples thereof include -OCOR, -COOR, and a dicarboxylic anhydride group. Here, R may be any of a linear, branched, or cyclic saturated hydrocarbon group or unsaturated hydrocarbon group, and a group containing a halogen atom, silicon atom, oxygen atom or nitrogen atom (excluding the hydroxyl group). ) May be substituted.

  Examples of the norbornene-based monomer to which —OCOR is bound include formate such as the aforementioned bicycloheptene derivative, tetracyclododecene derivative, and hexacycloheptadecene derivative, acetate, propionate, butyrate, barate, and benzoate.

  Examples of norbornene monomers to which —COOR is bonded include methyl esters, ethyl esters, isopropyl esters, n-butyl esters, t-butyl esters such as the aforementioned bicycloheptene derivatives, tetracyclododecene derivatives, and hexacycloheptadecene derivatives. , Phenyl ester, benzyl ester and the like.

Examples of the norbornene-based monomer to which a dicarboxylic anhydride group is bonded include bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, 5-methylbicyclo [2.2.1]. Bicycloheptene derivatives such as hept-2-ene-5,6-dicarboxylic anhydride, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8,9-dicarboxylic anhydride, 8-methyltetracyclo [4.4.0.1 ^2,5 . Tetracyclododecene derivatives such as 1 ^7,10 ] dodec- ³ -ene-8,9-dicarboxylic anhydride, hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] - heptadeca-4-ene-11,12-dicarboxylic acid anhydride, 11-methyl-hexa cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] - heptadeca-4-ene-11,12-F, such as dicarboxylic acid anhydride hexa can be given cycloheptanone decene derivatives.

  The norbornene monomers having the above substituents can be used independently or in combination of two or more. In order to obtain a ring-opening copolymer having excellent heat resistance and solubility in a solvent, a bicyclic to tetracyclic norbornene-based monomer is preferable. Specifically, in the general formula (9), m is A bicycloheptane derivative having 0 or a tetracyclododecene derivative in which m is 1 is preferable.

  The ring-opening metathesis copolymer and the ring-opening metathesis copolymer hydride of the present invention have a weight average molecular weight of 1,000 to 500,000, preferably 2,000 to 400,000, more preferably 4,000 to 200,000. If the molecular weight is small, the mechanical strength is insufficient, and if it is large, the hydrogenation reaction after copolymerization may be difficult. Moreover, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is usually 1 to 4, preferably 1.5 to 3. The weight average molecular weight and the number average molecular weight are values in terms of polystyrene measured by gel permeation chromatography.

  Preferred ring-opening metathesis copolymers and hydrides of ring-opening metathesis copolymers of the present invention are amorphous resins. The preferred ring-opening metathesis copolymer and hydride of the ring-opening metathesis copolymer of the present invention have a glass transition temperature of 100 ° C. or higher, preferably 120 ° C. or higher. The suitable ring-opening metathesis copolymer and hydride of the ring-opening metathesis copolymer of the present invention have a melt index (according to ASTM D1238) at 280 ° C. of about 1 to about 200, preferably about 5 to 100. It is.

  The preferred ring-opening metathesis copolymer and hydride of the ring-opening metathesis copolymer of the present invention have a dielectric constant and dielectric loss tangent of 3.2 or less and 0.015 or less, respectively, as measured at 1 MHz according to JIS C2330. Are 3.0 or less and 0.01 or less, respectively. The copolymer and copolymer hydride of the present invention whose relative dielectric constant and dielectric loss tangent are in the above ranges have no signal delay and low signal noise even for high frequency signals of 1 GHz.

  The method for producing a ring-opening metathesis copolymer of the present invention comprises the above-described norbornene-based monomer in the presence of a catalyst mainly composed of an organic ruthenium compound having a neutral electron-donating ligand. The copolymer is copolymerized and further subjected to hydrolysis or the like as necessary to modify the substituent.

  The method for producing a hydride of a ring-opening metathesis copolymer according to the present invention comprises the above-described norbornene monomer in the presence of a catalyst mainly composed of an organic ruthenium compound having a neutral electron donating ligand. Is subjected to ring-opening metathesis copolymerization, and then the main chain double bond of the obtained copolymer is hydrogenated and further subjected to hydrolysis or the like as necessary to modify the substituent.

  The catalyst used in the present invention is a catalyst mainly composed of an organic ruthenium compound coordinated with a neutral electron donating ligand.

  The neutral electron donating ligand constituting the organic ruthenium compound is a ligand having a neutral charge when pulled away from the central metal (ie, ruthenium).

  In addition, an anionic ligand is coordinated with a suitable organic ruthenium compound used in the present invention. Anionic ligands are ligands that have a negative charge when pulled away from ruthenium. Further, a counter anion may be present. The counter anion refers to an anion that forms an ion pair with a ruthenium cation, and is not particularly limited as long as it is an anion that can form such a pair.

  Representative examples of suitable organic ruthenium compounds used in the present invention include those represented by general formulas (13) to (15).

（１３）
（式（１３）中、Ｙ^１はそれぞれ独立に任意のアニオン性配位子を示し、Ｌ^１はそれぞれ独立に中性電子供与性配位子を示す。Ｙ^１および／またはＬ^１の２個、３個または４個はお互いに結合して多座キレート配位子を形成してもよい。ａ及びｂはそれぞれ独立に１〜４の整数で、ｘは１〜６の整数である。）

(13)
(In formula (13), Y ¹ independently represents an arbitrary anionic ligand, and L ¹ independently represents a neutral electron-donating ligand. Two of Y ¹ and / or L ¹ 3 or 4 may be bonded to each other to form a multidentate chelate ligand, wherein a and b are each independently an integer of 1 to 4, and x is an integer of 1 to 6.

（１４）
（式（１４）中、Ｌ^２はそれぞれ独立に中性の電子供与性配位子を表し、Ｙ^２はそれぞれ独立にアニオン性の配位子を表す。Ｑはそれぞれ独立に水素または炭素数１〜２０個の炭化水素基（ハロゲン原子、窒素原子、酸素原子、珪素原子、リン原子、硫黄原子を含んでいてもよい）を表す。ｃ、ｄ及びｙはそれぞれ独立に１〜４の整数を表し、ｅは０または１を表す。）

(14)
(In Formula (14), L ² each independently represents a neutral electron-donating ligand, Y ² each independently represents an anionic ligand. Q each independently represents hydrogen or carbon number 1. Represents 20 hydrocarbon groups (which may contain a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom), c, d and y each independently represents an integer of 1 to 4; E represents 0 or 1.)

（１５）
（式（１５）中、Ｌ^３はそれぞれ独立に中性電子供与性配位子を表し、Ｙ^３はそれぞれ独立にアニオン性配位子を表す。Ｘは対アニオンを表す。ｆ及びｇはそれぞれ独立に１〜４の整数を表し、ｚは１または２である。）

(15)
(In Formula (15), L ³ each independently represents a neutral electron-donating ligand, Y ³ each independently represents an anionic ligand, X represents a counter anion, and f and g each represent Independently represents an integer of 1 to 4, and z is 1 or 2.)

  Neutral electron donating ligands include oxygen, water, carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, phosphinites, phosphites, stibines, sulfoxides Thioethers, amides, aromatics, diolefins (may be cyclic), olefins (may be cyclic), isocyanides, thiocyanates, heterocyclic carbene compounds, etc. It is done. Among them, pyridines such as bipyridine; phosphines such as triphenylphosphine and tricyclohexylphosphine; aromatics such as p-cymene; cyclic diolefins such as cyclopentadiene; or 1,3-dimesitylimidazoline-2 -Copolymerization activity may become high when heterocyclic carbene compounds, such as-ylidene and 1, 3- dimesityl imidazolidine 2- ylidene, are coordinated.

  Examples of the anionic ligand include halogens such as F, Br, Cl and I, diketonate groups such as hydride and acetylacetonate groups, cyclopentadienyl groups, allyl groups, alkenyl groups, alkyl groups, aryl groups and alkoxy groups. , Aryloxy group, alkoxycarbonyl group, arylcarboxyl group, carboxyl group, alkyl or arylsulfonate group, alkylthio group, alkenylthio group, arylthio group, alkylsulfonyl group, alkylsulfinyl group and the like. Among these, when a halogen, a cyclopentadienyl group, an allyl group, an alkyl group or an aryl group is coordinated, it is excellent in terms of copolymerization activity.

  Specific examples of Q in the general formula (14) include hydrogen, alkenyl group, alkynyl group, alkyl group, alkylidene group, aryl group, carboxyl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group, alkoxy Examples thereof include a carbonyl group, an alkylthio group, an alkenylthio group, an arylthio group, an alkylsulfonyl group, and an alkylsulfinyl group. Especially, when the C1-C100 alkyl group, alkylidene group, aryl group, alkoxy group, aryloxy group, alkylthio group, or arylthio group is coordinated, the copolymerization activity of a catalyst may become high.

Examples of counter anions include BF ₄ ⁻ , B (C ₆ H ₆ ) ₄ ⁻ , B (C ₆ F ₆ ) ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , ClO ₄ ⁻ , IO ₄ ⁻ , p-toluene. Examples thereof include a sulfonate anion and a trifluoromethanesulfonate anion. Among these, when BF ₄ ⁻ , B (C ₆ H ₆ ) ₄ ⁻ , B (C ₆ F ₆ ) ₄ ⁻ , PF ₆ ^— or SbF ₆ ^— is present as a counter anion, the catalytic activity may be increased.

  Examples of the polymerization catalyst represented by the general formula (13) include bis (cyclopentadienyl) ruthenium, chloro (cyclopentadienyl) bis (triphenylphosphine) ruthenium, dichloro (1,5-cyclooctadiene). Ruthenium, dichlorotris (triphenylphosphine) ruthenium, cis-dichlorobis (2,2′-bipyridyl) ruthenium dihydrate, dichlorobis [(p-cymene) chlororuthenium]], dichloro (2,7-dimethylocta- 2,6-diene-1,8-diyl) ruthenium and the like.

  Examples of the polymerization catalyst represented by the general formula (14) include bis (tricyclohexylphosphine) benzylidene ruthenium dichloride, bis (triphenylphosphine) -3,3-diphenylpropenylidene ruthenium dichloride, bis (tricyclohexylphosphine). Phenylvinylidene ruthenium dichloride, bis (tricyclohexylphosphine) t-butylvinylidene ruthenium dichloride, bis (1,3-diisopropylimidazoline-2-ylidene) benzylidene ruthenium dichloride, bis (1,3-dicyclohexylimidazolin-2-ylidene) benzylidene ruthenium Dichloride, (1,3-dimesitylimidazoline-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dimene Such as chill imidazolidin-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride.

Examples of the polymerization catalyst represented by the general formula (15) include [(p-cymene) (CH ₃ CN) ₃ Ru] (BF ₄ ) ₂ , [(C ₆ H ₆ ) (CH ₃ CN) ₂ ( Cl) Ru] (BF ₄ ), [(C ₆ H ₆ ) (CH ₃ CN) ₃ Ru] (PF ₆ ) ₂ , [(CH ₃ CN) ₂ (Cl) (2,7-dimethylocta-2, 6-diene-1,8-diyl) Ru] (BF ₄ ), [(CH ₃ CN) ₃ (2,7-dimethylocta-2,6-diene-1,8-diyl) Ru] (BF ₄ ) ₂ etc. are mentioned.

  Further, as a method for increasing the copolymerization activity of the polymerization catalyst described above, complex compounds such as pyridines; phosphines; 1,3-diisopropylimidazoline-2-ylidene and 1,3-dimesitylimidazolidine-2-ylidene described above are used. A neutral electron donating compound such as a cyclic carbene compound may be added in a ratio of 1 to 100 times by weight with respect to the ruthenium metal.

Furthermore, when using the polymerization catalyst represented by the general formulas (13), (14) and (15), in order to increase the copolymerization activity, for example, a diazo compound such as N ₂ CHCOOEt, phenylacetylene, etc. An acetylene compound or a silyl compound such as Et ₂ SiH or Ph ₂ MeSiH can be added at a ratio of 1 to 100 times by weight with respect to the ruthenium metal. Et is an ethyl group, Ph is a phenyl group, and Me is a methyl group.

  Among the above-described catalysts, the polymerization catalyst represented by the general formula (14) is preferable because it exhibits high copolymerization activity.

  The ring-opening metathesis copolymerization reaction may be performed in a solvent or in the absence of a solvent, but after the copolymerization reaction, a hydrogenation reaction can be performed without isolating the polymer. Is preferred. The polymerization solvent is not particularly limited as long as it dissolves the copolymer and does not inhibit the copolymerization reaction. Polymerization solvents include aliphatic hydrocarbons such as pentane, hexane, heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydro Alicyclic hydrocarbons such as indenecyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, acetonitrile, propionitrile and benzonitrile; diethyl ether Ethers such as tetrahydrofuran, dioxane; chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, It includes halogen-containing hydrocarbons such as Li chlorobenzene. Among these solvents, the relative dielectric constant is 2 to 5, preferably 2.1 to 4.5, or a mixture of two or more solvents so that the relative dielectric constant is included in the above range. The mixed solvent is preferable. The dielectric constant of the solvent is disclosed in "Organic solvent" 2nd edition, John A. Riddick and Emory E. Toops Jr., 1955.

  When the copolymerization is performed in a solvent, the concentration of the norbornene monomer is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and 5 to 40% by weight. It is particularly preferred. When the concentration of the norbornene monomer is less than 1% by weight, the productivity of the copolymer may be deteriorated. When the concentration exceeds 50% by weight, the viscosity after the copolymerization is too high and subsequent hydrogenation is difficult. May be.

  The amount of the polymerization catalyst is a molar ratio of the norbornene-based monomer to the metal ruthenium in the polymerization catalyst (metal ruthenium: monomer =) 1: 100 to 1: 2,000,000, preferably 1: 500 to 1: 1,000,000, more preferably 1: 1,000-1: 500,000. If the amount of catalyst exceeds a ratio of 1: 100, catalyst removal may be difficult. When the ratio is less than 1: 2,000,000, sufficient copolymerization activity may not be obtained. The polymerization temperature is not particularly limited, but is usually -100 ° C to 200 ° C, preferably -50 ° C to 180 ° C, more preferably -30 ° C to 160 ° C, and most preferably 0 ° C to 140 ° C. The polymerization time is usually 1 minute to 100 hours, and can be appropriately adjusted depending on the progress of copolymerization.

In the present invention, a molecular weight modifier can be used to adjust the molecular weight of the copolymer and its hydride. Examples of molecular weight modifiers include α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrenes such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, i-butyl vinyl ether and allyl glycidyl ether. A halogen-containing vinyl compound such as allyl chloride; an oxygen-containing vinyl compound such as allyl acetate, allyl alcohol, and glycidyl methacrylate; and a nitrogen-containing vinyl compound such as acrylamide. The molecular weight modifier is 0.1% relative to the norbornene monomer.
A ring-opening metathesis copolymer having a desired molecular weight and a hydride thereof can be obtained by arbitrarily selecting the amount in the range of ˜100 mol%.

  The hydrogenation reaction is usually a reaction in which hydrogen is introduced in the presence of a hydrogenation catalyst so that the unsaturated double bond in the main chain of the ring-opening metathesis copolymer becomes a saturated single bond.

  The hydrogenation catalyst used in the hydrogenation reaction may be any one that is generally used for hydrogenation of olefin compounds.

  Examples of hydrogenation catalysts include cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, titanocene dichloride and n-butyllithium, zirconocene dichloride and sec-butyllithium, transition metal compounds such as tetrabutoxytitanate and dimethylmagnesium, and alkalis. Ziegler catalyst comprising a combination of metal compounds; organic ruthenium compounds represented by the above general formulas (13), (14) and (15), chlorotris (triphenylphosphine) rhodium, JP-A-7-2929, JP-A-7 -149823, JP-A-11-209460, JP-A-11-158256, JP-A-11-193323, JP-A-11-209460, and the like, such as ruthenium compounds, etc. Catalyst: heterogeneous catalyst in which a metal such as nickel, palladium, platinum, rhodium, ruthenium is supported on a carrier such as carbon, silica, diatomaceous earth, alumina, titanium oxide; specifically, nickel / silica, nickel / diatomaceous earth Soil, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like.

  Among these hydrogenation catalysts, no side reaction such as functional group modification occurs, and the carbon-carbon unsaturated bond in the copolymer can be selectively hydrogenated, so that noble metal complex catalysts such as rhodium and ruthenium can be used. The organic ruthenium compounds represented by the general formulas (13), (14), and (15) are more preferable, and the heterocyclic carbene compound having a high electron donating property or the ruthenium compound coordinated with phosphines is particularly preferable. .

  The organoruthenium compounds represented by the general formulas (13), (14), and (15) are also polymerization catalysts as described above. Therefore, after completion of the copolymerization reaction, the compounds are used as they are as hydrogenation catalysts, or ethyl vinyl ether, etc. After the catalyst modifier such as vinyl compound or α-olefin is added to activate the compound, it can be directly used for the hydrogenation reaction.

  The hydrogenation reaction is usually carried out in an organic solvent. The organic solvent can be appropriately selected depending on the solubility of the hydride to be produced, and the same organic solvent as the polymerization solvent can be used. Therefore, after the copolymerization reaction, the hydrogenation catalyst can be added and reacted without changing the solvent.

  Although suitable conditions for the hydrogenation reaction vary depending on the hydrogenation catalyst used, the hydrogenation temperature is usually -20 to 250 ° C, preferably -10 to 220 ° C, more preferably 0 to 200 ° C. The pressure is usually 0.01 to 10 MPa, preferably 0.05 to 8 MPa, more preferably 0.1 to 5 MPa. When the hydrogenation temperature is less than −20 ° C., the reaction rate is slow. Conversely, when the hydrogenation temperature exceeds 250 ° C., side reactions tend to occur. Further, when the hydrogen pressure is less than 0.01 MPa, the hydrogenation rate is slow, and when it exceeds 10 MPa, a high pressure reactor is required. The hydrogenation reaction time is appropriately selected in order to control the hydrogenation rate. When the hydrogenation reaction time is in the range of 0.1 to 50 hours, among the carbon-carbon double bonds of the main chain in the copolymer, 50% or more, preferably 70% or more, more preferably 80% or more, most Preferably 90% or more can be hydrogenated.

  In the production method of the ring-opening metathesis copolymer and the ring-opening metathesis copolymer hydride of the present invention, the functional group is modified by hydrolysis or the like, if necessary.

  For example, it can be modified to —OH by hydrolyzing —OCOR, —COOR, or a carboxylic anhydride group.

  This modification reaction can be performed by the same method as the method of decomposing a generally known ester or carboxylic acid anhydride into an alcohol. Examples of the modification reaction method include a hydrolysis method, a thermal decomposition method, and a hydrogenation reduction method.

  Specific examples of the ester or carboxylic acid anhydride hydrolysis method include: 1. a method of reacting directly with water; 2. a method of reacting with an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, or aqueous ammonia; 3. a method of reacting with an acid aqueous solution such as hydrochloric acid, sulfuric acid, phosphoric acid, and organic sulfonic acid; Examples thereof include a method of transesterification with a lower alcohol having 1 to 6 carbon atoms or a lower carboxylic acid having 1 to 6 carbon atoms. As a catalyst for the transesterification reaction, an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia, or an amine compound may be used. The hydrolysis reaction can be performed in the absence of a solvent or in the presence of a solvent. As the solvent, the same solvents as those used in the polymerization solvent and the hydrogenation reaction solvent can be used, and water, alcohol, ester and the like can be used in addition thereto.

  Pyrolysis is usually performed by heating a ring-opening metathesis copolymer or hydrogenation of a ring-opening metathesis copolymer having —OCOR, —COOR, or a carboxylic anhydride group to 100 ° C. or more and 400 ° C. or less for 1 second or more. Done. In particular, when R is a secondary or tertiary alkyl group such as isopropyl group, 2-ethylhexyl group, 2-phenylethyl group, t-butyl group, etc., it is preferable because the thermal decomposition reaction is accelerated. The heating temperature is preferably 150 ° C. or higher.

  The process by hydrogenation reduction is carried out by hydrogenating -OCOR or -COOR or by hydrogenating a carboxylic anhydride group. The hydrogenation catalyst used in this hydroreduction method is the same as the catalyst used for hydrogenating the main chain double bond of the ring-opening copolymer, and the procedure is also the main of the ring-opening copolymer. This can be done in substantially the same way as when hydrogenating chain double bonds. Therefore, when the main chain double bond of the ring-opening copolymer is hydrogenated, -OCOR, -COOR or carboxylic anhydride group may be simultaneously hydrogenated and reduced; Thereafter, -OCOR, -COOR or a carboxylic anhydride group may be subjected to hydrogen reduction; and after -OCOR, -COOR or a carboxylic anhydride group is subjected to hydrogen reduction, the main chain double bond may be reduced. You may hydrogenate.

  The ring-opening metathesis copolymer or the ring-opening metathesis copolymer hydride is a -OCOR, -COOR, or -OCOR in a ring-opening metathesis copolymer or hydride of a ring-opening metathesis copolymer having a carboxylic anhydride group. , -COOR or 50% or more, preferably 70% or more, more preferably 80% or more, and most preferably 90% or more of the carboxylic anhydride group is preferably converted to -OH.

  The ring-opening metathesis copolymer or hydride of the ring-opening metathesis copolymer of the present invention is excellent in electrical insulation, electrical properties, and low water absorption. For example, the water absorption rate is 2% or less, preferably 1.5% or less as measured by JIS K7209. The adhesiveness is 1.5 mm or less, preferably 1 mm or less, from the intersection of the X-cut portion with respect to copper, silicon and glass substrate by the X-cut tape method defined by JIS K5400.

  The ring-opening metathesis copolymer or hydride of the ring-opening metathesis copolymer of the present invention is excellent in electrical properties and low water absorption as described above, and also in excellent adhesion to other materials such as metals. Furthermore, the compatibility with a compound having a functional group such as a curing agent is also good.

  The curable resin composition of this invention contains the copolymer chosen from the said ring-opening metathesis copolymer and the ring-opening metathesis copolymer hydride, and a hardening | curing agent.

  As the curing agent, for example, an ionic curing agent, a radical curing agent, or a curing agent having both ionic and radical properties is used.

Examples of the ionic curing agent include aliphatic polyamine compounds such as hexamethylenediamine, triethylenetetramine, diethylenetriamine, and tetraethylenepentamine; diaminocyclohexane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [ 5.2.1.0 ^2,6 ] decane, 1,3- (diaminomethyl) cyclohexane, mensendiamine, isophoronediamine, N-aminoethylpiperazine, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) alicyclic polyamine compounds such as methane; 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, α, α′-bis (4-aminophenyl) -1,3-diisopropylbenzene , Α, α′-bis (4-aminophenyl) -1, -Aromatic polyamine compounds such as diisopropylbenzene, 4,4'-diaminodiphenylsulfone, metaphenylenediamine, metaxylylenediamine; 4,4'-bisazidobenzal (4-methyl) cyclohexanone, 4,4'-di Azido chalcone, 2,6-bis (4′-azidobenzal) cyclohexanone, 2,6-bis (4′-azidobenzal) -4-methylcyclohexanone, 4,4′-diazidodiphenylsulfone, 4,4′-diazide Bisazide compounds such as diphenylmethane and 2,2′-diazidostilbene; phthalic anhydride, pyroperitric anhydride, benzophenonetetracarboxylic anhydride, nadic anhydride, 1,2-cyclohexanedicarboxylic anhydride, maleic anhydride modified polypropylene Acid anhydrides such as fumaric acid, phthalic acid, malein Dicarboxylic acid compounds such as acid, trimellitic acid and hymic acid;

  Diol compounds such as 1,3-butanediol, 1,4-butanediol, hydroquinone dihydroxyethyl ether, and tricyclodecane dimethanol; Triols such as 1,1,1-trimethylolpropane; and many compounds such as phenol novolac and cresol novolac Polyhydric phenol; nylon-6, nylon-66, nylon-610, nylon-11, nylon-612, nylon-12, nylon-46, methoxymethylated polyamide, polyhexamethylenediamine terephthalamide, polyhexamethyleneisophthalamide, etc. Polyamide compounds; diisocyanate compounds such as hexamethylene diisocyanate, toluylene diisocyanate, triglycidyl isocyanurate; phenol novolac type epoxy compounds, cresol novolac Glycidyl ether type epoxy compounds such as epoxy compounds, cresol type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, brominated bisphenol A type epoxy compounds, brominated bisphenol F type epoxy compounds; alicyclic epoxy compounds, glycidyl And polyvalent epoxy compounds such as ester type epoxy compounds, glycidylamine type epoxy compounds, and isocyanurate type epoxy compounds. Among these, a diol compound, a polyhydric phenol compound, and a polyvalent epoxy compound are preferable, and a polyvalent epoxy compound is particularly preferable.

  Examples of the radical curing agent include methyl ethyl ketone peroxide, cyclohexanone peroxide, 1,1- (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, and t-butyl. Hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, α, α'-bis ( and organic peroxides such as t-butylperoxy-m-isopropyl) benzene, octanoyl peroxide, isobutyryl peroxide, and peroxydicarbonate.

  Examples of the curing agent having both ionic and radical properties include cyanurates such as triallyl cyanurate; 1-allyl isocyanurate, 1,3-diallyl isocyanurate, 1,3-diallyl-5-benzyl isocyanurate, Isocyanurates such as triallyl isocyanurate, 1-allyl-3,5-dibenzyl isocyanurate, 1-allyl-3,5-diglycidyl isocyanurate, 1,3-diallyl-5-glycidylyl isocyanurate It is done.

  These curing agents can be used alone or in combination of two or more. Of these curing agents, isocyanurate curing agents are preferred because cured products having excellent flame retardancy can be obtained. The amount of the curing agent is appropriately selected depending on the purpose of use, and is usually 0.1 to 200 parts by weight, preferably 100 parts by weight of the ring-opening metathesis copolymer or 100 parts by weight of the ring-opening metathesis copolymer hydride. Is in the range of 1 to 150 parts by weight, more preferably 10 to 100 parts by weight.

  A preferred curable resin composition of the present invention is one in which a ring-opening metathesis copolymer or a hydrogenation of a ring-opening metathesis copolymer and a curing agent are uniformly compatible. When in a compatible state, the composition does not separate into two layers, and the composition itself does not become opaque. In addition to the above components, the composition of the present invention includes rubber, other resins, flame retardants, fillers, heat stabilizers, anti-aging agents, weathering stabilizers, ultraviolet absorbers, leveling agents, antistatic agents, and slip agents. Antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, emulsifiers, and the like can be contained, and the amount thereof is appropriately selected within a range not impairing the object of the present invention.

  Since the curable composition of the present invention has excellent electrical characteristics when cured, it is an insulating material for multilayer substrates, electronic components, IC chips, wirings, etc .; prepreg; solder mask; print Suitable for protective films and interlayer insulating films for substrates, electronic components, IC chips, display elements, etc .; materials for display devices such as EL devices and liquid crystal devices; and for multilayer circuit boards with built-in elements.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples. “Part” is based on weight unless otherwise specified.
(1) The molecular weight was measured as a polystyrene equivalent value by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.
(2) The monomer composition ratio in the copolymer was measured by ¹ H-NMR spectrum.
(3) The hydrogenation rate was measured by ¹ H-NMR spectrum.
(4) The hydrolysis rate was measured by IR spectrum (KBr method).

[Example 1]
Equipped with a stirrer glass reactor, tetrahydrofuran 311 parts, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene 77.8 parts of 5-hydroxy-ethoxycarbonyl bicyclo [2.2. 1] 22.2 parts of hept-2-ene and 0.51 parts of 1-hexene were charged. 0.05 parts of (1,3-dimesitymimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride dissolved in 44.9 parts of tetrahydrofuran was added, and copolymerization was carried out at 70 ° C. After 2 hours, the copolymerization reaction solution was poured into a large amount of isopropanol to precipitate a solid, washed by filtration, and then dried under reduced pressure at 40 ° C. for 18 hours to obtain a ring-opening metathesis copolymer. The yield of the obtained ring-opening metathesis copolymer was 98 parts, and the molecular weight (in terms of polystyrene) was number average molecular weight (Mn) = 22,100 and weight average molecular weight (Mw) = 44,400. Monomer ratio in the copolymer was tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene / 5-hydroxy-ethoxycarbonyl bicyclo [2.2.1] hept - 2-ene = 80/20 (mol / mol). The ratio of the number of hydroxyl groups to all repeating units was 20%.

[Example 2]
Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene 77.8 parts, and 5-hydroxy-ethoxycarbonyl bicyclo [2.2.1] hept-2-ene 22.2 the Department, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene 37 parts of 5-hydroxy-ethoxycarbonyl bicyclo [2.2.1] hept-2-ene 63 parts A ring-opening metathesis copolymer was obtained in the same manner as in Example 1 except for changing. The yield of the obtained ring-opening metathesis copolymer was 63 parts, and the molecular weight (in terms of polystyrene) was number average molecular weight (Mn) = 26,200 and weight average molecular weight (Mw) = 58,600. Monomer ratio in the copolymer was tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene / 5-hydroxy-ethoxycarbonyl bicyclo [2.2.1] hept - 2-ene = 42/58 (mol / mol). The ratio of the number of hydroxyl groups to all repeating units was 58%.

[Example 3]
Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene 77.8 parts, and 5-hydroxy-ethoxycarbonyl bicyclo [2.2.1] hept-2-ene 22.2 the parts, 8-ethylidene tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] dodeca-3-ene 80.3 parts, and 5-hydroxy-ethoxycarbonyl bicyclo [2.2.1] hept A ring-opening metathesis copolymer was obtained in the same manner as in Example 1 except that the amount was changed to 19.7 parts of 2-ene. The yield of the obtained ring-opening metathesis copolymer was 95.1 parts, and the molecular weight (in terms of polystyrene) was number average molecular weight (Mn) = 21,600 and weight average molecular weight (Mw) = 44,100. Monomer ratio in the copolymer was 8 ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene / 5-hydroxy-ethoxycarbonyl bicyclo [2.2. 1] Hept-2-ene = 82/18 (mol / mol). The ratio of the number of hydroxyl groups to all repeating units was 18%.

[Example 4]
Tetrahydrofuran as a polymerization solvent is toluene (dielectric constant = 2.379), 1-hexene is charged to 0.91 part, (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ) A ring-opening metathesis copolymer was obtained in the same manner as in Example 3 except that the amount of benzylidene ruthenium dichloride was changed to 0.02 part. The yield of the obtained ring-opening metathesis copolymer was 93.2 parts, and the molecular weight (polystyrene conversion) was number average molecular weight (Mn) = 13,400 and weight average molecular weight (Mw) = 24,200. Monomer ratio in the copolymer was 8 ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene / 5-hydroxy-ethoxycarbonyl bicyclo [2.2. 1] Hept-2-ene = 80/20 (mol / mol). The ratio of the number of hydroxyl groups to all repeating units was 20%.

100 parts of the ring-opening metathesis copolymer was dissolved in 400 parts of toluene, and then charged in an autoclave equipped with a stirrer. Next, 0.05 part of bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride and 0.39 part of ethyl vinyl ether were added to 20 parts of toluene. A hydrogenation catalyst solution dissolved in the part was added, and a hydrogenation reaction was performed at a hydrogen pressure of 4.5 MPa and 120 ° C. for 6 hours. The hydrogenation reaction solution was poured into a large amount of isopropanol to completely precipitate a solid content, washed by filtration, and then dried under reduced pressure at 90 ° C. for 18 hours to obtain a ring-opening copolymer hydride. The molecular weight (in terms of polystyrene) was number average molecular weight (Mn) = 18,100 and weight average molecular weight (Mw) = 32,800. It was confirmed by ¹ H-NMR that the hydroxyl group and the ester group were completely preserved, both were 20%, and 99% or more of the carbon-carbon double bonds in the main chain were hydrogenated.

[Example 5]
5-hydroxyethoxycarbonylbicyclo [2.2.1] hept-2-ene was converted to 8-hydroxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] A ring-opening metathesis copolymer was obtained in the same manner as in Example 2 except that it was changed to dodec-3-ene. The yield of the obtained ring-opening metathesis copolymer was 93 parts, and the molecular weight (polystyrene conversion) was number average molecular weight (Mn) = 20,600 and weight average molecular weight (Mw) = 36,600. Monomer ratio in the copolymer was tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene / 8-hydroxymethyl-tetracyclo [4.4.0.1 ^{2 , 5} . 1 ^7,10 ] dodec-3-ene = ^35/65 (mol / mol).

1 part of the obtained ring-opening copolymer was dissolved in 65.3 parts of tetrahydrofuran and charged into an autoclave equipped with a stirrer. Next, a hydrogenation catalyst solution prepared by dissolving 0.09 part of bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride and 0.8 part of ethyl vinyl ether in 16.3 parts of tetrahydrofuran was added, and the hydrogen pressure was 1 MPa, 100 ° C. for 4 hours. A hydrogenation reaction was performed. The hydrogenation reaction solution was poured into a large amount of isopropanol to completely precipitate the solid content, washed by filtration and dried under reduced pressure at 70 ° C. for 18 hours to obtain a ring-opening copolymer hydride. The molecular weight (polystyrene conversion) was number average molecular weight (Mn) = 27,300 and weight average molecular weight (Mw) = 48,800. It was confirmed by ¹ H-NMR that the hydroxyl groups were completely preserved, the ratio of the number of hydroxyl groups was 65%, and 99% or more of the carbon-carbon double bonds in the main chain were hydrogenated.

[Example 6]
Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene 77.8 parts, and 5-hydroxy-ethoxycarbonyl bicyclo [2.2.1] hept-2-ene 22.2 the Department, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene 50.8 parts, and 5,6-dihydroxy methyl bicyclo [2.2.1] hept-2 A ring-opening metathesis copolymer was obtained in the same manner as in Example 1 except that the amount of enene was changed to 49.2 parts. The yield of the obtained ring-opening metathesis copolymer was 68.3 parts, and the molecular weight (in terms of polystyrene) was number average molecular weight (Mn) = 32,100 and weight average molecular weight (Mw) = 59,500. Monomer ratio in the copolymer was tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene / 5,6-dihydroxy methyl bicyclo [2.2.1] hept -2-ene = 55/45 (mol / mol). The ratio of the number of hydroxyl groups to all repeating units was 90%.

[Example 7]
In a glass reactor equipped with a stirrer, 386 parts of cyclohexane, 91.3 parts of dicyclopentadiene, 8.7 parts of 5,6-diacetyloxymethylbicyclo [2.2.1] hept-2-ene, and 0. 1-hexene. 61 copies were prepared. 0.06 part of (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride dissolved in 13.3 parts of cyclohexane was added and copolymerization was carried out at 80 ° C. After 2 hours, the polymerization reaction solution was poured into a large amount of isopropanol to precipitate a solid content, washed by filtration, and then dried under reduced pressure at 40 ° C. for 18 hours to obtain a ring-opening copolymer. The yield of the ring-opening copolymer is 87.6 parts, the molecular weight (polystyrene conversion) is the number average molecular weight (Mn) = 15,900, the weight average molecular weight (Mw) = 29,700, The number was 12%.

1 part of the obtained ring-opening copolymer was dissolved in 39 parts of cyclohexane, and then charged into an autoclave equipped with a stirrer. Then, a hydrogenation catalyst solution prepared by dissolving 0.1 part of bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride and 0.88 part of ethyl vinyl ether in 7.8 parts of cyclohexane was added, and the hydrogen pressure was 10 MPa, 100 ° C. for 8 hours. A hydrogenation reaction was performed. The hydrogenation reaction solution was poured into a large amount of isopropanol to completely precipitate the solid content, washed by filtration, and dried under reduced pressure at 40 ° C. for 18 hours to obtain a ring-opening copolymer hydride. The molecular weight (in terms of polystyrene) was number average molecular weight (Mn) = 20,700 and weight average molecular weight (Mw) = 38,600. ¹ H-NMR spectrum measurement confirmed that the ester group was completely preserved and 99% or more of the carbon-carbon double bonds in the main chain were hydrogenated.

A glass reactor equipped with a stirrer was charged with 1 part of the obtained ring-opening copolymer hydride and 200 parts of tetrahydrofuran. Thereto was added 20 parts of a sodium methoxide (10%) methanol solution, and the mixture was heated to reflux for 12 hours. The reaction solution was poured into a large amount of isopropanol to completely precipitate the solid, washed by filtration, and dried under reduced pressure at 80 ° C. for 18 hours. It was confirmed by IR spectrum measurement that absorption derived from a broad alcohol OH stretching vibration in the vicinity of 3300 cm ⁻¹ appeared. Furthermore, since the absorption derived from the ester group C═O stretching vibration near 1740 cm ⁻¹ completely disappeared, it was confirmed that the hydrolysis rate was 100%. The ratio of the number of hydroxyl groups to all repeating units was 12%.

[Comparative Example 1]
The monomer is 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . The polymerization reaction was carried out in the same manner as in Example 4 using 100 parts of ^{17, 10} ] -3-dodecene. The yield of the obtained ring-opening polymer was 95 parts, and the molecular weight (polystyrene conversion) was number average molecular weight (Mn) = 15,400 and weight average molecular weight (Mw) = 34,200.

A hydrogenation reaction was carried out in the same manner as in Example 4 except that the obtained ring-opening polymer was used. The molecular weight (in terms of polystyrene) was number average molecular weight (Mn) = 18,600 and weight average molecular weight (Mw) = 38,200. ¹ H-NMR spectrum measurement confirmed that the ester group was completely preserved and 99% or more of the carbon-carbon double bonds in the main chain were hydrogenated. The number of ester groups with respect to all repeating units was 100%, and the ratio of the number of hydroxycarbonyl groups was 0%.

[Comparative Example 2]
10 parts of the polymer hydride obtained in Comparative Example 1, 10 parts of N-methylpyrrolidone, 50 parts of propylene glycol and 8 parts of potassium hydroxide were charged into a reactor and stirred at 190 ° C. for 5 hours. The obtained reaction solution was poured into a large amount of a mixed solution of water, tetrahydrofuran and hydrochloric acid to coagulate the hydrolyzate. The coagulated polymer was washed with water and dried to obtain a hydrolyzate. The hydrolysis rate was 95%. The number of ester groups with respect to all repeating units was 5%, and the ratio of the number of hydroxycarbonyl groups was 95%.

[Comparative Example 3]
The monomer is 8-ethyltetracyclo [4.4.0.1 ^2,5 . The polymerization reaction was carried out in the same manner as in Example 4 using 100 parts of ^{17, 10} ] -3-dodecene. The yield of the obtained ring-opened polymer was 99 parts, and the molecular weight (polystyrene conversion) was number average molecular weight (Mn) = 12,800 and weight average molecular weight (Mw) = 29,200.

  A hydrogenation reaction was carried out in the same manner as in Example 4 except that the obtained ring-opening polymer was used. The molecular weight (in terms of polystyrene) was number average molecular weight (Mn) = 15,200 and weight average molecular weight (Mw) = 34,100. The hydrogenation rate was 99% or more. The number of functional groups for all repeating units was 0%.

[Example 8]
2 parts of the ring-opening metathesis copolymer or hydrogenated ring-opening metathesis copolymer obtained in Examples 1 to 7 and Comparative Examples 1 to 3 were dissolved in 6.5 parts of chlorobenzene.

  Each solution was filtered under pressure, and the filtrate was spin-coated on each of a copper substrate and a silicon substrate. These substrates were heated at 60 ° C. for 2 minutes and then heated and dried at 200 ° C. for 2 hours in a nitrogen stream, so that the thickness of 30 ± 1 micron adhered to the copper substrate and the silicon substrate (apparently). Polymer and copolymer hydride films were obtained.

  Further, spin coating conditions were adjusted appropriately and the same operation as described above was performed to obtain a film having a thickness of about 5 microns on a Teflon (registered trademark) substrate.

(Evaluation method)
The adhesion of each film adhered to the copper substrate and the silicon substrate was measured by an X-cut tape test in accordance with JIS K5400. ○: 1.0 mm or less, Δ: 1.0 to 2.0 mm, x: 2.0 mm or more It was.

  The film was carefully peeled from the Teflon substrate, and the water absorption, dielectric constant, and dielectric loss tangent of the peeled film were measured.

  The water absorption was measured according to JIS K7209, and ○: 1% or less, Δ: 1-2%, ×: 2% or more was used as an index.

  The dielectric constant and dielectric loss tangent were measured at a high frequency of 1 MHz in accordance with JIS C2330, and displayed with the following indices.

Dielectric constant ○: 3.0 or less, Δ: 3.0 to 3.5, X: 3.5 or more Dielectric loss tangent ○: 0.01 or less, Δ: 0.01 to 0.02, ×: 0.02 Add 2 parts hydrogenated bisphenol A type epoxy resin (trade name: EPICLON EXA-7015: manufactured by Dainippon Ink Co., Ltd.) as a curing agent to 2 parts of each solution prepared above, and after stirring well, let stand. The compatibility with the curing agent was evaluated by visually observing whether the solution was uniform. As an evaluation index, ○: uniform solution, x: turbidity, or with phase separation was used.

  Signal delay and signal noise were observed by curing a copolymer solution blended with a curing agent, forming a conductor layer wiring on the surface by plating, and flowing a high frequency signal of 1 GHz. The case where there was substantially no delay was evaluated as ◯, the case where it was present was evaluated as x, the case where there was no signal noise was evaluated as ○, and the case where it was present was evaluated as x. -Is not measured.

[Comparative Example 4]
The amount of 1-hexene added was 72 parts, and instead of (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, a cyclohexane solution of triethylaluminum (0.5 mol / l) _6. Cyclohexane solution (0.01 mol / l) of 0.74 parts of WCl ₆ modified with t-butanol / methanol (t-butanol / methanol / WCl ₆ = 0.35 / 0.3 / 1; molar ratio) 4 parts except for using as a catalyst solution, in the same manner as in example 7, 8-ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene / 5-t An attempt was made to copolymerize -butoxycarbonylbicyclo [2.2.1] hept-2-ene. In the course of the reaction, side reactions occurred simultaneously, the viscosity of the reaction solution increased rapidly and solidified, and an insoluble polymer was obtained, and the ring-opening copolymer of the present invention was not obtained.

[Comparative Example 5]
(1,3-Dimesitylimidazolidin-2-ylidene) (tricyclohexylphosphine) Instead of benzylidene ruthenium dichloride, 0.74 parts of a tetrahydrofuran solution (0.5 mol / l) of triethylaluminum, t-butanol / methanol Except that 7.4 parts of a tetrahydrofuran solution (0.01 mol / l) of modified WCl ₆ (t-butanol / methanol / WCl ₆ = 0.35 / 0.3 / 1; molar ratio) was added as a catalyst solution, in the same manner as in example 1, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene / 5-hydroxy-ethoxycarbonyl bicyclo [2.2.1] hept-2-ene Copolymerization of was attempted. After 6 hours, the polymerization reaction solution was poured into a large amount of isopropanol, but no solid content was precipitated. The ring-opening copolymer of the present invention was not obtained.

Claims (5)

The repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) or the repeating unit represented by the general formula (3). Is a ring-opening metathesis copolymer having a polystyrene-reduced weight average molecular weight of 1,000 to 500,000 as measured by gel permeation chromatography.

(1)
(In the formula (1), at least one of R ^{1 to} R ⁴ is a substituent (excluding a hydroxycarbonyl group) containing —OH (ie, a hydroxyl group), and the others are a hydrogen atom and having 1 to 20 carbon atoms. A hydrocarbon group or a group containing a halogen atom, a silicon atom, an oxygen atom or a nitrogen atom (excluding a hydroxyl group and a hydroxycarbonyl group), and m represents an integer of 0 to 2.)

(2)
(In the formula ^(2), R ^5, R 6, ^{R 7} and ^{R 8} each independently represent a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 20, ^{R 5} or ^{R 6 R 7} or ^{R 8} And n may represent an integer of 1 to 2).

(3)
(In Formula (3), R < ⁹ >, R < ¹⁰ >, R < ¹¹ > and R < ¹² > show a hydrogen atom or a C1-C20 hydrocarbon group each independently, and R < ⁹ > or R < ¹⁰ > is R < ¹¹ > or R <^12>. To form a ring.) The repeating unit represented by the general formula (1), the repeating unit represented by the general formula (2) or (3), the repeating unit represented by the general formula (5), and the general formula (6) or ( 7), the total of the repeating units represented by the general formulas (1), (2), and (3) is 50 to 0% of the total repeating units, and the general formula (5) The total number of repeating units represented by (6) and (7) is 50 to 100% of all repeating units, the ratio of the number of hydroxyl groups to all repeating units is 5 to 100%, and gel permeation. Hydrogenated ring-opening metathesis copolymer having a polystyrene-reduced weight average molecular weight of 1,000 to 500,000 as measured by chromatography.

(5)
(In formula (5), at least one of R ^{1 to} R ⁴ is a substituent containing a hydroxyl group (excluding a hydroxycarbonyl group), and the other is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen atom, A group containing a silicon atom, an oxygen atom or a nitrogen atom (excluding a hydroxyl group and a hydroxycarbonyl group). M represents an integer of 0 to 2.)

(6)
(In Formula (6), R < ⁵ >, R < ⁶ >, R < ⁷ > and R < ⁸ > show a hydrogen atom or a C1-C20 hydrocarbon group each independently, and R < ⁵ > or R < ⁶ > is R < ⁷ > or R <^8>. And n may represent an integer of 1 to 2).

(7)
(In Formula (7), R < ⁹ >, R < ¹⁰ >, R < ¹¹ > and R < ¹² > show a hydrogen atom or a C1-C20 hydrocarbon group each independently, and R < ⁹ > or R < ¹⁰ > is R < ¹¹ > or R <^12>. To form a ring.) A curable resin composition comprising at least one copolymer selected from the ring-opening metathesis copolymer according to claim 1 and the ring-opening metathesis copolymer hydride according to claim 2, and a curing agent. A neutral electron-donating coordination between the monomer represented by the general formula (9) and the monomer represented by the general formula (10) or the monomer represented by the general formula (11). A method for producing a ring-opening metathesis copolymer, which comprises carrying out ring-opening metathesis copolymerization in the presence of a catalyst mainly composed of an organoruthenium compound coordinated with a child.

(9)
(In formula (9), at least one of R ^{1 to} R ⁴ is a substituent containing —OH (excluding a hydroxycarbonyl group), and the other is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom. , A group containing a silicon atom, oxygen atom or nitrogen atom (excluding hydroxyl group and hydroxycarbonyl group), m represents an integer of 0-2.

(10)
(In the formula (10), R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁵ or R ⁶ is R ⁷ or R ^8. And n may represent an integer of 1 to 2).

(11)
(In formula (11), R < ⁹ >, R < ¹⁰ >, R < ¹¹ > and R < ¹² > show a hydrogen atom or a C1-C20 hydrocarbon group each independently, and R < ⁹ > or R < ¹⁰ > is R < ¹¹ > or R <^12>. To form a ring.) A method for producing a hydride of a ring-opening metathesis copolymer comprising hydrogenating a main chain double bond of the ring-opening metathesis copolymer obtained by the production method according to claim 4.