JP6866737B2 - Polymers, compositions and moldings - Google Patents

Description

The present invention relates to novel polymers, compositions and molded articles. More specifically, the present invention relates to a novel polymer having a high glass transition temperature and an excellent balance of heat resistance, high refractive index, and mechanical properties, and compositions and molded articles using this polymer.

Conventionally, inorganic materials such as glass and ceramics have been widely used for optical parts such as lenses, but due to the growing need for weight reduction and price reduction in recent years, material replacement from inorganic materials to resins is used in many applications. Is progressing. Optical polymers are at the center of the optical technology field, which is responsible for recording, displaying, and transmitting information, such as high-performance lenses, antireflection coatings, flat displays, optical disks, and optical fibers. High refractive index and mechanical properties are required.

Examples of such a resin material include a composition capable of forming a thin film having a high refractive index and excellent transparency, and a composition containing a triazine ring-containing polymer (see Patent Documents 1 to 3) and heat resistance. A polymer having a good balance of properties, high refractive index, and moldability, and containing a specific structural unit in which a pyrimidine skeleton and a benzene ring skeleton are bonded with an oxygen atom or a sulfur atom (see Patent Document 4). ) Etc. are known.

Japanese Patent No. 5712921 Japanese Patent No. 5598258 International Publication No. 2015/098788 JP 2015-209510

However, there is still room for improvement in conventional resin materials, and the current situation is that further improvement in heat resistance, further improvement in heat resistance, high refractive index, and performance balance of mechanical properties is required. Is. The present invention has been made in view of the above circumstances, and provides a novel polymer, composition and molded product having a high glass transition temperature and an excellent balance of heat resistance, high refractive index, and mechanical properties. This is an issue.

〔式（１−１）〜（１−３）中、Ｒ^１は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、ニトロ基、シアノ基、１〜３級アミノ基、又は１〜３級アミノ基の塩である。ｎは、それぞれ独立して、０〜２の整数である。ｎが２の場合、複数のＲ^１は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成していてもよい。〕
［２］前記第２構造単位は、下記式（２）で表される構造単位である前記［１］に記載の重合体。

〔式（２）中、Ｒ^２及びＲ^３は、それぞれ独立して、水素原子、又は炭素数１〜２０の１価の炭化水素基である。Ｘは２価の有機基である。〕
［３］前記式（２）における前記Ｘが、下記式（２−１）〜（２−８）で表される基、炭素数１〜２０の２価の炭化水素基、炭素数１〜２０の２価のハロゲン化炭化水素基、又は環員数３〜１０の２価の複素環基である前記［２］に記載の重合体。

〔式（２−１）中、Ｒ^４及びＲ^５は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルチオ基、ニトロ基、シアノ基、カルボキシ基、スルホン酸基、ホスホン酸基、リン酸基、ヒドロキシ基、１〜３級アミノ基、カルボキシ基の塩、スルホン酸基の塩、ホスホン酸基の塩、リン酸基の塩、ヒドロキシ基の塩、又は１〜３級アミノ基の塩である。ｃ及びｄは、それぞれ独立して、０〜２の整数である。ａ及びｂは、それぞれ独立して、０〜８の整数である。ａが２以上の場合、複数のＲ^４は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成してもよい。ｂが２以上の場合、複数のＲ^５は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成してもよい。Ｑ及びＺは、それぞれ独立して、単結合、−Ｏ−、−Ｓ−、又は、−Ｎ（Ｒ^１７）−である。Ｒ^１７は、水素原子、炭素数１〜２０の１価の炭化水素基、又は炭素数１〜２０の１価のハロゲン化炭化水素基で
ある。Ｌは、単結合、又は２価の有機基である。ｙは、０〜５の整数である。ｙが２以上の場合、複数のＱ、Ｌ及びＺは、それぞれ、同一であっても異なっていてもよい。ｙが２以上且つａが１以上の場合、複数のＲ^４は、同一であっても異なっていてもよい。Ｒ^６及びＲ^７は、それぞれ独立して、単結合、メチレン基、又は炭素数２〜４のアルキレン基である。〕

〔式（２−２）中、Ｒ^ａ及びＲ^ｂは、それぞれ独立して、環員数５〜３０の２価の脂環式炭化水素骨格である。Ｒ^８及びＲ^９は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルチオ基、ニトロ基、シアノ基、カルボキシ基、スルホン酸基、ホスホン酸基、リン酸基、ヒドロキシ基、１〜３級アミノ基、カルボキシ基の塩、スルホン酸基の塩、ホスホン酸基の塩、リン酸基の塩、ヒドロキシ基の塩、又は１〜３級アミノ基の塩である。ｅ及びｆは、それぞれ独立して、０〜２０の整数である。ｅが２以上の場合、複数のＲ^８は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成してもよい。ｆが２以上の場合、複数のＲ^９は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成してもよい。Ｑ及びＺは、それぞれ独立して、単結合、−Ｏ−、−Ｓ−、又は、−Ｎ（Ｒ^１８）−である。Ｒ^１８は、水素原子、炭素数１〜２０の１価の炭化水素基、又は炭素数１〜２０の１価のハロゲン化炭化水素基である。Ｌは、単結合、又は２価の有機基である。ｙは、０〜５の整数である。ｙが２以上の場合、複数のＱ、Ｌ及びＺは、それぞれ、同一であっても異なっていてもよい。ｙが２以上且つｅが１以上の場合、複数のＲ^８は、同一であっても異なっていてもよい。Ｒ^１０及びＲ^１１は、それぞれ独立して、単結合、メチレン基、又は炭素数２〜４のアルキレン基である。〕

〔式（２−３）中、Ｒ^１２は、水素原子、炭素数１〜２０の１価の炭化水素基、又は炭素数１〜２０の１価のハロゲン化炭化水素基である。Ｒ^１３及びＲ^１４は、それぞれ独立して、炭素数１〜２０の２価の鎖状又は脂環式の炭化水素基、又は炭素数１〜２０の２価の鎖状又は脂環式のハロゲン化炭化水素基である。ｇは、０又は１である。ｈは、１〜１０の整数である。ｈが２以上の場合、複数のＲ^１２及びＲ^１４は、それぞれ、同一であっても異なっていてもよい。〕

〔式（２−４）中、Ｒ^１５及びＲ^１６は、それぞれ独立して、炭素数１〜２０の２価の鎖状又は脂環式の炭化水素基、又は炭素数１〜２０の２価の鎖状又は脂環式のハロゲン化炭化水素基である。ｉは、０又は１である。ｊは、１〜１０の整数である。ｊが２以上の場合、複数のＲ^１６は、同一であっても異なっていてもよい。〕

〔式（２−５）中、Ｒ^２１及びＲ^２２は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルチオ基、ニトロ基、シアノ基、カルボキシ基、スルホン酸基、ホスホン酸基、リン酸基、ヒドロキシ基、１〜３級アミノ基、カルボキシ基の塩、スルホン酸基の塩、ホスホン酸基の塩、リン酸基の塩、ヒドロキシ基の塩、又は１〜３級アミノ基の塩である。ｋ及びｌは、それぞれ独立して、０〜３の整数である。ｋが２又は３の場合、複数のＲ^２１は、同一であっても異なっていてもよい。ｌが２又は３の場合、複数のＲ^２２は、同一であっても異なっていてもよい。Ｒ^２３は、単結合、−Ｏ−、−Ｓ−、−Ｃ（Ｏ）−、−Ｓ（Ｏ）−、又は、−Ｓ（Ｏ）_２−である。〕

〔式（２−６）中、Ｒ^２４及びＲ^２５は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルチオ基、ニトロ基、シアノ基、カルボキシ基、スルホン酸基、ホスホン酸基、リン酸基、ヒドロキシ基、１〜３級アミノ基、カルボキシ基の塩、スルホン酸基の塩、ホスホン酸基の塩、リン酸基の塩、ヒドロキシ基の塩、又は１〜３級アミノ基の塩である。ｍ及びｎは、それぞれ独立して、０〜３の整数である。ｍが２又は３の場合、複数のＲ^２４は、同一であっても異なっていてもよい。ｎが２以上の場合、複数のＲ^２５は、同一であっても異なっていてもよい。Ｒ^２６及びＲ^２７は、それぞれ独立して、単結合、−Ｏ−、−Ｓ−、−Ｃ（Ｏ）−、−Ｓ（Ｏ）−、又は、−Ｓ（Ｏ）_２−である。〕

〔式（２−７）中、Ｒ^２８及びＲ^２９は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルチオ基、ニトロ基、シアノ基、カルボキシ基、スルホン酸基、ホスホン酸基、リン酸基、ヒドロキシ基、１〜３級アミノ基、カルボキシ基の塩、スルホン酸基の塩、ホスホン酸基の塩、リン酸基の塩、ヒドロキシ基の塩、又は１〜３級アミノ基の塩である。ｏは、０〜３の整数である。ｐは、０〜４の整数である。ｏが２以上の場合、複数のＲ^２８は、同一であっても異なっていてもよい。ｐが２以上の場合、複数のＲ^２９は、同一であっても異なっていてもよい。ｎは、０〜６の整数である。Ｒ^３０は、炭素数１〜２０の１価の炭化水素基、又は炭素数１〜２０の１価のハロゲン化炭化水素基である。ｑは、０〜１５の整数である。ｑが２以上の場合、複数のＲ^３０は、同一であっても異なっていてもよい。〕

〔式（２−８）中、Ｒ^３１及びＲ^３２は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルチオ基、ニトロ基、シアノ基、カルボキシ基、スルホン酸基、ホスホン酸基、リン酸基、ヒドロキシ基、１〜３級アミノ基、カルボキシ基の塩、スルホン酸基の塩、ホスホン酸基の塩、リン酸基の塩、ヒドロキシ基の塩、又は１〜３級アミノ基の塩である。ｒ及びｓは、それぞれ独立して、０〜４の整数である。ｒが２以上の場合、複数のＲ^３１は、同一であっても異なっていてもよい。ｓが２以上の場合、複数のＲ^３２は、同一であっても異なっていてもよい。ｍは、１〜５の整数である。ｎは、０〜５の整数である。Ｒ^３３は、炭素数１〜２０の１価の炭化水素基、又は炭素数１〜２０の１価のハロゲン化炭化水素基である。ｔは、０〜２０の整数である。ｔが２以上の場合、複数のＲ^３３は、同一であっても異なっていてもよい。〕
［４］前記式（２）における前記Ｘが、前記式（２−１）〜（２−４）で表される基、前記炭素数１〜２０の２価の炭化水素基、炭素数１〜２０の２価のハロゲン化炭化水素基、又は環員数３〜１０の２価の複素環基である前記［３］に記載の重合体。
［５］ポリスチレン換算の重量平均分子量が、５００以上６００，０００以下である前記［１］乃至［４］のうちのいずれかに記載の重合体。
［６］前記［１］乃至［５］のいずれかに記載の重合体と、有機溶媒と、を含有することを特徴とする組成物。
［７］前記［１］乃至［５］のいずれかに記載の重合体を含有することを特徴とする成形体。 The present invention is as follows.
[1] A first structural unit represented by at least one of the following formulas (1-1), (1-2) and (1-3), and
A polymer characterized by having a second structural unit having any one of a secondary amino structure and a tertiary amino structure at two or more terminals.

[In formulas (1-1) to (1-3), R ¹ is independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a monovalent halogen having 1 to 20 carbon atoms. A salt of a hydrocarbon group, a nitro group, a cyano group, a 1st to 3rd amino group, or a 1st to 3rd amino group. n is an integer of 0 to 2 independently of each other. When n is 2, the plurality of R ^1s may be the same or different, and may be combined in any combination to form a part of the ring structure. ]
[2] The polymer according to the above [1], wherein the second structural unit is a structural unit represented by the following formula (2).

[In the formula (2), R ² and R ³ are independently hydrogen atoms or monovalent hydrocarbon groups having 1 to 20 carbon atoms. X is a divalent organic group. ]
[3] The X in the formula (2) is a group represented by the following formulas (2-1) to (2-8), a divalent hydrocarbon group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. The polymer according to the above [2], which is a divalent halogenated hydrocarbon group of the above, or a divalent heterocyclic group having 3 to 10 ring members.

[In the formula (2-1), R ⁴ and R ⁵ are independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a monovalent halogenated hydrocarbon having 1 to 20 carbon atoms. Group, alkoxy group with 1 to 20 carbon atoms, alkylthio group with 1 to 20 carbon atoms, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group, 1-3 amino group , A carboxy group salt, a sulfonic acid group salt, a phosphonic acid group salt, a phosphoric acid group salt, a hydroxy group salt, or a 1st to 3rd grade amino group salt. c and d are independently integers of 0 to 2. a and b are independently integers from 0 to 8. When a is 2 or more, the plurality of R ^4s may be the same or different, and may be combined in any combination to form a part of the ring structure. When b is 2 or more, the plurality of R ^5s may be the same or different, and may be combined in any combination to form a part of the ring structure. Q and Z are independently single bonds, -O-, -S-, or -N (R ¹⁷ )-, respectively. R ¹⁷ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. L is a single bond or divalent organic group. y is an integer from 0 to 5. When y is 2 or more, the plurality of Q, L, and Z may be the same or different, respectively. When y is 2 or more and a is 1 or more, the plurality of R ^4s may be the same or different. R ⁶ and R ⁷ are independently single bonds, methylene groups, or alkylene groups having 2 to 4 carbon atoms. ]

[In formula (2-2), ^Ra and R ^b are independently divalent alicyclic hydrocarbon skeletons having 5 to 30 ring members. Independently, R ⁸ and R ⁹ have a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and an alkoxy having 1 to 20 carbon atoms. Group, alkylthio group with 1 to 20 carbon atoms, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group, 1-3 amino group, carboxy group salt, sulfonic acid group Salt, phosphonic acid group salt, phosphoric acid group salt, hydroxy group salt, or 1-3 amino group salt. e and f are each independently an integer of 0 to 20. When e is 2 or more, the plurality of R ^8s may be the same or different, and may be combined in any combination to form a part of the ring structure. When f is 2 or more, the plurality of R ^9s may be the same or different, and may be combined in any combination to form a part of the ring structure. Q and Z are independently single bonds, -O-, -S-, or -N (R ¹⁸ )-, respectively. R ¹⁸ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. L is a single bond or divalent organic group. y is an integer from 0 to 5. When y is 2 or more, the plurality of Q, L, and Z may be the same or different, respectively. When y is 2 or more and e is 1 or more, the plurality of R ^8s may be the same or different. R ¹⁰ and R ¹¹ are independently single bonds, methylene groups, or alkylene groups having 2 to 4 carbon atoms. ]

[In the formula (2-3), R ¹² is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. R ¹³ and R ¹⁴ are independently divalent chain or alicyclic hydrocarbon groups having 1 to 20 carbon atoms, or divalent chain or alicyclic halogens having 1 to 20 carbon atoms. It is a hydrocarbon group. g is 0 or 1. h is an integer from 1 to 10. When h is 2 or more, the plurality of R ¹² and R ¹⁴ may be the same or different, respectively. ]

[In formula (2-4), R ¹⁵ and R ¹⁶ are independently divalent chain or alicyclic hydrocarbon groups having 1 to 20 carbon atoms, or divalent groups having 1 to 20 carbon atoms. It is a chain or alicyclic halogenated hydrocarbon group. i is 0 or 1. j is an integer from 1 to 10. When j is 2 or more, the plurality of R ^16s may be the same or different. ]

[In the formula (2-5), R ²¹ and R ²² are independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a monovalent halogenated hydrocarbon having 1 to 20 carbon atoms. Group, alkoxy group with 1 to 20 carbon atoms, alkylthio group with 1 to 20 carbon atoms, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group, 1-3 amino group , A carboxy group salt, a sulfonic acid group salt, a phosphonic acid group salt, a phosphoric acid group salt, a hydroxy group salt, or a 1st to 3rd grade amino group salt. k and l are independently integers of 0 to 3. When k is 2 or 3, the plurality of R ^21s may be the same or different. When l is 2 or 3, the plurality of R ^22s may be the same or different. R ²³ is a single bond, -O-, -S-, -C (O)-, -S (O)-, or -S (O) _2- . ]

[In the formula (2-6), R ²⁴ and R ²⁵ are independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a monovalent halogenated hydrocarbon having 1 to 20 carbon atoms. Group, alkoxy group with 1 to 20 carbon atoms, alkylthio group with 1 to 20 carbon atoms, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group, 1-3 amino group , A carboxy group salt, a sulfonic acid group salt, a phosphonic acid group salt, a phosphoric acid group salt, a hydroxy group salt, or a 1st to 3rd grade amino group salt. m and n are independently integers of 0 to 3. When m is 2 or 3, the plurality of R ^24s may be the same or different. When n is 2 or more, the plurality of R ^25s may be the same or different. R ²⁶ and R ²⁷ are independently single bonds, -O-, -S-, -C (O)-, -S (O)-, or -S (O) _2- . ]

[In the formula (2-7), R ²⁸ and R ²⁹ are independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a monovalent halogenated hydrocarbon having 1 to 20 carbon atoms. Group, alkoxy group with 1 to 20 carbon atoms, alkylthio group with 1 to 20 carbon atoms, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group, 1-3 amino group , A carboxy group salt, a sulfonic acid group salt, a phosphonic acid group salt, a phosphoric acid group salt, a hydroxy group salt, or a 1st to 3rd grade amino group salt. o is an integer from 0 to 3. p is an integer from 0 to 4. When o is 2 or more, the plurality of R ^28s may be the same or different. When p is 2 or more, the plurality of R ^29s may be the same or different. n is an integer from 0 to 6. R ³⁰ is a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. q is an integer from 0 to 15. When q is 2 or more, the plurality of R ^30s may be the same or different. ]

[In the formula (2-8), R ³¹ and R ³² are independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a monovalent halogenated hydrocarbon having 1 to 20 carbon atoms, respectively. Group, alkoxy group with 1 to 20 carbon atoms, alkylthio group with 1 to 20 carbon atoms, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group, 1-3 amino group , A carboxy group salt, a sulfonic acid group salt, a phosphonic acid group salt, a phosphoric acid group salt, a hydroxy group salt, or a 1st to 3rd grade amino group salt. r and s are independently integers from 0 to 4. When r is 2 or more, the plurality of R ^31s may be the same or different. When s is 2 or more, the plurality of R ^32s may be the same or different. m is an integer of 1-5. n is an integer from 0 to 5. R ³³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. t is an integer from 0 to 20. When t is 2 or more, the plurality of R ^33s may be the same or different. ]
[4] The X in the formula (2) is a group represented by the formulas (2-1) to (2-4), a divalent hydrocarbon group having 1 to 20 carbon atoms, and 1 to 1 carbon atoms. The polymer according to the above [3], which is a 20 divalent halogenated hydrocarbon group or a divalent heterocyclic group having 3 to 10 ring members.
[5] The polymer according to any one of the above [1] to [4], wherein the polystyrene-equivalent weight average molecular weight is 500 or more and 600,000 or less.
[6] A composition comprising the polymer according to any one of [1] to [5] above and an organic solvent.
[7] A molded product containing the polymer according to any one of the above [1] to [5].

Here, the "hydrocarbon group" includes a chain hydrocarbon group and a cyclic hydrocarbon group unless otherwise specified. This "hydrocarbon group" may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The "chain hydrocarbon group" refers to a hydrocarbon group that does not contain a cyclic structure and is composed only of a chain structure, and includes both a linear hydrocarbon group and a branched hydrocarbon group. The "cyclic hydrocarbon group" refers to a hydrocarbon group containing a cyclic structure, and includes both an alicyclic hydrocarbon group and an aromatic hydrocarbon group. The "alicyclic hydrocarbon group" refers to a hydrocarbon group containing only an alicyclic structure as a cyclic structure and not an aromatic ring structure, and refers to a monocyclic alicyclic hydrocarbon group and a polycyclic alicyclic hydrocarbon. Contains both hydrocarbon groups. However, it does not have to be composed only of an alicyclic structure, and a chain structure may be included as a part thereof. The "aromatic hydrocarbon group" refers to a hydrocarbon group having an aromatic ring structure as a cyclic structure, and includes both a monocyclic aromatic hydrocarbon group and a polycyclic aromatic hydrocarbon group. However, it does not have to be composed only of an aromatic ring structure, and a chain structure or an alicyclic structure may be included as a part thereof. The “number of ring members” means the number of atoms constituting the cyclic structure, and in the case of a polycycle, it means the number of atoms constituting this polycycle.

According to the present invention, a novel polymer having a high glass transition temperature and an excellent balance of mechanical properties such as heat resistance, high refractive index, and tensile strength, and a composition and a molded product using this polymer. Can be provided. In particular, a novel polymer having a high glass transition temperature, excellent heat resistance, a high refractive index, and excellent mechanical properties (CTE, elastic modulus, and tensile strength), and this polymer are used. The composition and the molded product can be provided.

Hereinafter, the polymer, composition and molded product of the present invention will be described in detail.
<Polymer>
The polymer of the present invention (hereinafter, also referred to as “[A] polymer”) is a polymer having the first structural unit and the second structural unit. The polymer [A] may have two or more of the above structural units. As long as the polymer [A] has the first and second structural units, the arrangement of each structural unit and other structures are not particularly limited. For example, the [A] polymer may have structural units other than the first and second structural units. Further, the polymer [A] may have a repeating unit (a), (b) or (c) containing the first and second structural units, as will be described later, and further has other repeating units. You may.

[First structural unit]
The first structural unit in the polymer [A] is represented by at least one of the following formulas (1-1), (1-2) and (1-3).

〔式（１−１）〜（１−３）中、Ｒ^１は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、ニトロ基、シアノ基、１〜３級アミノ基、又は１〜３級アミノ基の塩である。ｎは、それぞれ独立して、０〜２の整数である。ｎが２の場合、複数のＲ^１は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成していてもよい。〕

[In formulas (1-1) to (1-3), R ¹ is independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a monovalent halogen having 1 to 20 carbon atoms. It is a salt of a hydrocarbon group, a nitro group, a cyano group, a 1st to 3rd amino group, or a 1st to 3rd amino group. n is an integer of 0 to 2 independently of each other. When n is 2, the plurality of R ^1s may be the same or different, and may be combined in any combination to form a part of the ring structure. ]

Examples of the halogen atom represented by R ¹ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ include a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group. And so on.

Examples of the monovalent chain hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group and a t-butyl group. Alkyl groups such as n-pentyl group; alkenyl groups such as ethenyl group, propenyl group, butenyl group and pentenyl group; alkynyl groups such as ethynyl group, propynyl group, butyl group and pentynyl group can be mentioned.

Examples of the monovalent alicyclic hydrocarbon group include a monocyclic cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group; and a polycyclic cycloalkyl group such as a norbornyl group and an adamantyl group; Examples thereof include a monocyclic cycloalkenyl group such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group and a cyclohexenyl group; a polycyclic cycloalkenyl group such as a norbornenyl group and the like.

Examples of the monovalent aromatic hydrocarbon group include an aryl group such as a phenyl group, a trill group, a xsilyl group, a naphthyl group and an anthryl group; and an aralkyl group such as a benzyl group, a phenethyl group, a phenylpropyl group and a naphthylmethyl group. And so on.

The monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms represented by ^{R 1} is, for example, the hydrogen of the monovalent hydrocarbon group having 1 to 20 carbon atoms exemplified as the group represented by ^{R 1.} Examples thereof include a group in which a part or all of the atoms are replaced with halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The substituent in the secondary amino group and the tertiary amino group represented by R ¹ is not particularly limited, and for example, a monovalent hydrocarbon group having 1 to 20 carbon atoms exemplified as the group represented by ^{R 1 is used.} Can be mentioned. The cation constituting the cation moiety in the salt of the 1st to 3rd amino group represented by R ¹ is not particularly limited, and a known cation such as ^{Na + can be used.}

R ¹ includes a halogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, and 1 of 1 to 6 carbon atoms from the viewpoint of improving the polymerization reactivity and solubility of the monomer giving the first structural unit. Valuable halogenated hydrocarbon groups, nitro groups, cyano groups, 1-3-class amino groups, or 1-3-class amino group salts are preferred, with fluorine atoms, chlorine atoms, nitro groups, cyano groups, t-butyl groups, A phenyl group and an amino group are more preferable. From the same viewpoint, as n, 0 or 1 is preferable, and 0 is more preferable.

The position of the other bond with respect to one of the first structural units is not particularly limited, but the meta position is preferable from the viewpoint of improving the polymerization reactivity of the monomer giving the first structural unit.

As the first structural unit, the above formula (1-2) having a pyrimidine skeleton is used from the viewpoint of improving the polymerization reactivity of the monomer giving the first structural unit and improving the solubility in various organic solvents. The structural unit represented by is preferable.

Examples of the monomer giving the first structural unit in the [A] polymer include 4,6-dichloropyrimidine, 4,6-dibromopyrimidine, 2,4-dichloropyrimidine, and 2,5-dichloropyrimidine. 2,5-Dibromopyrimidine, 5-bromo-2-chloropyrimidine, 5-bromo-2-fluoropyrimidine, 5-bromo-2-iodopyrimidine, 2-
Chloro-5-fluoropyrimidine, 2-chloro-5-iodopyrimidine, 2,4-dichloro-5-fluoropyrimidine, 2,4-dichloro-5-iodopyrimidine, 5-chloro-2,4,6-trifluoro Pyrimidine, 2,4,6-trichloropyrimidine, 4,5,6-trichloropyrimidine, 2,4,5-trichloropyrimidine, 2,4,5,6-tetrachloropyrimidine, 2-phenyl-4,6-dichloro Pyrimidine, 2-methylthio-4,6-dichloropyrimidine, 2-methylsulfonyl-4,6-dichloropyrimidine, 5-methyl-4,6-dichloropyrimidine, 2-amino-4,6-dichloropyrimidine, 5-amino -4,6-dichloropyrimidine, 2,5-diamino-4,6-dichloropyrimidine, 4-amino-2,6-dichloropyrimidine, 5-methoxy-4,6-dichloropyrimidine, 5-methoxy-2,4 -Dichloropyrimidine, 5-fluoro-2,4-dichloropyrimidine, 5-bromo-2,4-dichloropyrimidine, 5-iodo-2,4-dichloropyrimidine, 2-methyl-4,6-dichloropyrimidine, 5- Methyl-4,6-dichloropyrimidine, 6-methyl-2,4-dichloropyrimidine, 5-methyl-2,4-dichloropyrimidine, 5-nitro-2,4-dichloropyrimidine, 4-amino-2-chloro- 5-fluoropyrimidine, 2-methyl-5-amino-4,6-dichloropyrimidine, 5-bromo-4-chloro-2-methylthiopyrimidine; 3,6-dichloropyrimidine, 3,5-dichloropyrimidine, 4-methyl -3,6-dichloropyrimidine; 2,3-dichloropyrimidine, 2,6-dichloropyrimidine, 2,5-dibromopyrimidine, 2,6-dibromopyrimidine, 2-amino-3,5-dibromopyrimidine, 5,6 − Dicyano-2,3-dichloropyrimidine and the like can be mentioned. These monomers may be used alone or in combination of two or more.

The lower limit of the content ratio of the first structural unit in the [A] polymer is preferably 5 mol%, more preferably 10 when the total of all structural units in the [A] polymer is 100 mol%. It is mol%, more preferably 20 mol%, and particularly preferably 33 mol%. The upper limit of the content ratio is preferably 95 mol%, more preferably 67 mol%, further preferably 60 mol%, and particularly preferably 50 mol%. By setting the content ratio in the above range, heat resistance, high refractive index, mechanical properties and solubility in various organic solvents can be further improved.

[Second structural unit]
[A] The second structural unit in the polymer is a structural unit having any one of a secondary amino structure and a tertiary amino structure at two or more terminals. The location where the terminal is either a secondary amino structure or a tertiary amino structure is not particularly limited as long as it is two or more, but is preferably 2 to 15 and more preferably 2 to 10. More preferably, there are 2 to 5 locations. When the number of these portions is within the above range, it is preferable from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit.

The secondary amino structure can be a divalent structure represented by −NH−. Further, the tertiary amino structure can be a divalent structure represented by −N (R) − (R is a monovalent hydrocarbon group having 1 to 20 carbon atoms). Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R include the carbon numbers 1 to 1 exemplified as the group represented by ^{R 1 in the above formulas (1-1) to (1-3).} 20 monovalent hydrocarbon groups and the like can be mentioned. As R, a monovalent hydrocarbon group having 1 to 10 carbon atoms is preferable from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit.

The second structural unit can be represented by the following formula (2).

〔式（２）中、Ｒ^２及びＲ^３は、それぞれ独立して、水素原子、又は炭素数１〜２０の１価の炭化水素基である。Ｘは２価の有機基である。〕

[In the formula (2), R ² and R ³ are independently hydrogen atoms or monovalent hydrocarbon groups having 1 to 20 carbon atoms. X is a divalent organic group. ]

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ² and R ³ are exemplified as the group represented by ^{R 1 in the above formulas (1-1) to (1-3).} Examples thereof include monovalent hydrocarbon groups having 1 to 20 carbon atoms.

As R ² and R ³ , hydrogen atoms or monovalent hydrocarbon groups having 1 to 10 carbon atoms are preferable from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit, respectively.

Examples of the divalent organic group represented by X in the above formula (2) include a group represented by the following formula (2-1).

〔式（２−１）中、Ｒ^４及びＲ^５は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルチオ基、ニトロ基、シアノ基、カルボキシ基、スルホン酸基、ホスホン酸基、リン酸基、ヒドロキシ基、１〜３級アミノ基、カルボキシ基の塩、スルホン酸基の塩、ホスホン酸基の塩、リン酸基の塩、ヒドロキシ基の塩、又は１〜３級アミノ基の塩である。ｃ及びｄは、それぞれ独立して、０〜２の整数である。ａ及びｂは、それぞれ独立して、０〜８の整数である。ａが２以上の場合、複数のＲ^４は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成してもよい。ｂが２以上の場合、複数のＲ^５は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成してもよい。Ｑ及びＺは、それぞれ独立して、単結合、−Ｏ−、−Ｓ−、又は、−Ｎ（Ｒ^１７）−である。Ｒ^１７は、水素原子、炭素数１〜２０の１価の炭化水素基、又は炭素数１〜２０の１価のハロゲン化炭化水素基である。Ｌは、単結合、又は２価の有機基である。ｙは、０〜５の整数である。ｙが２以上の場合、複数のＱ、Ｌ及びＺは、それぞれ、同一であっても異なっていてもよい。ｙが２以上且つａが１以上の場合、複数のＲ^４は、同一であっても異なっていてもよい。Ｒ^６及びＲ^７は、それぞれ独立して、単結合、メチレン基、又は炭素数２〜４のアルキレン基である。〕

[In the formula (2-1), R ⁴ and R ⁵ are independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a monovalent halogenated hydrocarbon having 1 to 20 carbon atoms. Group, alkoxy group with 1 to 20 carbon atoms, alkylthio group with 1 to 20 carbon atoms, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group, 1-3 amino group , A carboxy group salt, a sulfonic acid group salt, a phosphonic acid group salt, a phosphoric acid group salt, a hydroxy group salt, or a 1st to 3rd grade amino group salt. c and d are independently integers of 0 to 2. a and b are independently integers from 0 to 8. When a is 2 or more, the plurality of R ^4s may be the same or different, and may be combined in any combination to form a part of the ring structure. When b is 2 or more, the plurality of R ^5s may be the same or different, and may be combined in any combination to form a part of the ring structure. Q and Z are independently single bonds, -O-, -S-, or -N (R ¹⁷ )-, respectively. R ¹⁷ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. L is a single bond or divalent organic group. y is an integer from 0 to 5. When y is 2 or more, the plurality of Q, L, and Z may be the same or different, respectively. When y is 2 or more and a is 1 or more, the plurality of R ^4s may be the same or different. R ⁶ and R ⁷ are independently single bonds, methylene groups, or alkylene groups having 2 to 4 carbon atoms. ]

Examples of the halogen atom represented by R ⁴ and R ⁵ include the above formulas (1-1) to (1-3).
), The same halogen atoms as those exemplified as the halogen atoms represented by ^{R 1 can be mentioned.}

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴ and R ⁵ are exemplified as the group represented by ^{R 1 in the above formulas (1-1) to (1-3).} Examples thereof include monovalent hydrocarbon groups having 1 to 20 carbon atoms.

Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴ and R ⁵ include the group represented by ^{R 1 in the above formulas (1-1) to (1-3).} Examples thereof include a group in which a part or all of hydrogen atoms of a monovalent hydrocarbon group having 1 to 20 carbon atoms is replaced with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Examples of the alkoxy group having 1 to 20 carbon atoms represented by R ⁴ and R ⁵ include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a 2-methylpropoxy group, and 1 -Methylpropoxy group, t-butoxy group, n-pentyloxy group and the like can be mentioned.

The alkylthio group having 1 to 20 carbon atoms represented by R ⁴ and ^{R 5,} for example, methylthio group, ethylthio group, n- propylthio group, i- propylthio group, n- butylthio group, 2-methylpropylthio group, Examples thereof include 1-methylpropylthio group, t-butylthio group, n-pentylthio group and the like.

The substituents in the secondary amino group and the tertiary amino group represented by R ⁴ and R ⁵ are not particularly limited, but for example, the group represented by ^{R 1 in the above formulas (1-1) to (1-3).} Examples thereof include monovalent hydrocarbon groups having 1 to 20 carbon atoms. The ^{secondary amino group and the tertiary amino group represented by R 4} and R ⁵ may form a terminal composed of any of the above-mentioned secondary amino structure and tertiary amino structure.

Salts of a carboxyl group represented by R ⁴ and R ^5, a salt of a sulfonic acid group, a salt of phosphonic acid group, salts of the phosphate group, a salt of hydroxy group, and the cation sites in the primary to tertiary salts of amino groups The constituent cations are not particularly limited, and known cations such as ^{Na + can be used.}

R ⁴ and R ⁵ are a halogen atom, a monovalent hydrocarbon group having 1 to 3 carbon atoms, and 1 to 3 carbon atoms, respectively, from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit. Monovalent halogenated hydrocarbon group, alkoxy group with 1-3 carbon atoms, alkylthio group with 1-3 carbon atoms, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy Group, 1-3-amino group, carboxy group salt, sulfonic acid group salt, phosphonic acid group salt, phosphoric acid group salt, hydroxy group salt, or 1-3-amino group salt is preferable, and fluorine Atomic, chlorine atom, methyl group, ethyl group, fluoromethyl group, methoxy group, methylthio group, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group, 1-3 amino More preferably, a group, a salt of a carboxy group, a salt of a sulfonic acid group, a salt of a phosphonic acid group, a salt of a phosphoric acid group, a salt of a hydroxy group, or a salt of a primary amino group. From the same viewpoint, a and b are 0 to 8, preferably 0 to 4, and more preferably 0 to 2, respectively. Further, from the same viewpoint, c and d are 0 to 2, respectively, and 0 or 1 is preferable.

-N ^{(R 17)} represented by Q and Z - ^{R 17} in the hydrogen atom, a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms Is. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁷ include the carbon number exemplified as the group represented by ^{R 1 in the above formulas (1-1) to (1-3).} Examples thereof include 1 to 20 monovalent hydrocarbon groups. Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁷ are exemplified as the group represented by ^{R 1 in the above formulas (1-1) to (1-3).} Examples thereof include a group in which a part or all of hydrogen atoms of a monovalent hydrocarbon group having 1 to 20 carbon atoms are replaced with halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As R ¹⁷ , a hydrogen atom, a monovalent hydrocarbon group having 1 to 3 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 3 carbon atoms is preferable.

Examples of the divalent organic group represented by L include -O-, -S-, -C (O)-, -S (O)-, -S (O) _2- , and -C (O). Examples thereof include -NH-, -C (O) -O-, a methylene group, an alkylene group having 2 to 20 carbon atoms, a methylene halide group, an alkylene halide group having 2 to 20 carbon atoms, and a divalent cardo structure. ..

Examples of the alkylene group having 2 to 20 carbon atoms represented by L include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a sec-butylene group, a t-butylene group, a neopentylene group, and 4-. Examples thereof include methyl-pentane-2,2-diyl group and nonan-1,9-diyl group.

Examples of the halogenated methylene group represented by L include a group in which a part or all of the hydrogen atom of the methylene group is replaced with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As the halogenated alkylene group having 2 to 20 carbon atoms represented by L, for example, a part or all of the hydrogen atoms of the alkylene group having 2 to 20 carbon atoms exemplified as the group represented by L may be a fluorine atom or chlorine. Examples thereof include groups substituted with halogen atoms such as an atom, a bromine atom and an iodine atom.

The divalent cardo structure represented by L includes a divalent group derived from fluorene (that is, a group excluding two hydrogen atoms in fluorene) and a divalent group derived from phenolphthalein (that is, phenol). Groups excluding two hydrogen atoms in phthalein), groups represented by the following formula (L1), and the like can be mentioned. In the divalent group derived from fluorene and the divalent group derived from phenolphthaline, a part or all of hydrogen atoms are substituted with monovalent chain hydrocarbon groups having 1 to 20 carbon atoms. Further, a part or all of the hydrogen atom including the substituent may be substituted with a fluorine atom.

〔式（Ｌ１）中、Ｒ^ｃは、環員数５〜３０の２価の脂環式炭化水素基である。〕

[In the formula (L1), R ^c is a divalent alicyclic hydrocarbon group having 5 to 30 ring members. ]

Examples of the divalent alicyclic hydrocarbon group having 5 to 30 ring members represented by R ^c include a monocyclic alicyclic hydrocarbon group having 5 to 15 ring members and a single ring having 5 to 15 ring members. Examples thereof include fluorinated alicyclic hydrocarbon groups, polycyclic alicyclic hydrocarbon groups having 7 to 30 ring members, and polycyclic fluorinated alicyclic hydrocarbon groups having 7 to 30 ring members.

Examples of the monocyclic alicyclic hydrocarbon group having 5 to 15 ring members include cyclopentane-1,1-diyl group, cyclohexane-1,1-diyl group, and 3,3,5-trimethylcyclohexane-1. , 1-diyl group, cyclopentene-3,3-diyl group, cyclohexene-3,3-diyl group, cyclooctane-1,1-diyl group, cyclodecane-1,1-diyl group, cyclododecane-1,1- Diyl groups, some or all of the hydrogen atoms in these groups have 1 to 1 carbon atoms
Examples thereof include a group substituted with 20 monovalent chain hydrocarbon groups.

The monocyclic fluorinated alicyclic hydrocarbon group having 5 to 15 ring members includes, for example, a part of the hydrogen atom of the group exemplified as the monocyclic alicyclic hydrocarbon group having 5 to 15 ring members or. Examples thereof include groups in which all are substituted with fluorine atoms.

Examples of the polycyclic alicyclic hydrocarbon group having 7 to 30 ring members include norbornane, norbornene, adamantan, tricyclo [5.2.1.0 ^2,6 ] decane, and tricyclo [5.2.1. 0 ^2,6 ] Polycyclic fats such as heptane, pinan, camphor, decalin, norbornene, perhydroanthracene, perhydroazulene, cyclopentanohydrophenanthrene, bicyclo [2.2.2] -2-octene A group excluding two hydrogen atoms bonded to one carbon atom of a cyclic hydrocarbon, and a part or all of the hydrogen atoms of these groups are monovalent chain hydrocarbon groups having 1 to 20 carbon atoms. Substituted groups and the like can be mentioned.

The polycyclic fluorinated alicyclic hydrocarbon group having 7 to 30 ring members includes, for example, a part of the hydrogen atom of the group exemplified as the polycyclic alicyclic hydrocarbon group having 7 to 30 ring members or. Examples thereof include groups in which all are substituted with fluorine atoms.

As L, from the viewpoint of structural stability of the [A] polymer, single bond, −O−, −S−, −C (O) −, −S (O) −, −S (O) ₂₋ , -C (O) -NH-, -C (O) -O-, methylene group, alkylene group having 2 to 10 carbon atoms, methylene halide group, alkylene group having 2 to 10 carbon atoms, or divalent A cardo structure is preferred. From the same viewpoint, y is preferably 0 to 4, more preferably 0 to 3.

Examples of the alkylene group having 2 to 4 carbon atoms represented by R ⁶ and R ⁷ include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a sec-butylene group and a t-butylene group. Can be mentioned. As R ⁶ and R ⁷ , a single bond, a methylene group, or an ethylene group is preferable from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit, respectively.

Further, examples of the divalent organic group represented by the above X in the above formula (2) include a group represented by the following formula (2-2).

〔式（２−２）中、Ｒ^ａ及びＲ^ｂは、それぞれ独立して、環員数５〜３０の２価の脂環式炭化水素骨格である。Ｒ^８及びＲ^９は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルチオ基、ニトロ基、シアノ基、カルボキシ基、スルホン酸基、ホスホン酸基、リン酸基、ヒドロキシ基、１〜３級アミノ基、カルボキシ基の塩、スルホン酸基の塩、ホスホン酸基の塩、リン酸基の塩、ヒドロキシ基の塩、又は１〜３級アミノ基の塩である。ｅ及びｆは、それぞれ独立して、０〜２０の整数である。ｅが２以上の場合、複数のＲ^８は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成してもよい。ｆが２以上の場合、複数のＲ^９は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成して
もよい。Ｑ及びＺは、それぞれ独立して、単結合、−Ｏ−、−Ｓ−、又は、−Ｎ（Ｒ^１８）−である。Ｒ^１８は、水素原子、炭素数１〜２０の１価の炭化水素基、又は炭素数１〜２０の１価のハロゲン化炭化水素基である。Ｌは、単結合、又は２価の有機基である。ｙは、０〜５の整数である。ｙが２以上の場合、複数のＱ、Ｌ及びＺは、それぞれ、同一であっても異なっていてもよい。ｙが２以上且つｅが１以上の場合、複数のＲ^８は、同一であっても異なっていてもよい。Ｒ^１０及びＲ^１１は、それぞれ独立して、単結合、メチレン基、又は炭素数２〜４のアルキレン基である。〕

[In formula (2-2), ^Ra and R ^b are independently divalent alicyclic hydrocarbon skeletons having 5 to 30 ring members. Independently, R ⁸ and R ⁹ have a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and an alkoxy having 1 to 20 carbon atoms. Group, alkylthio group with 1 to 20 carbon atoms, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group, 1-3 amino group, carboxy group salt, sulfonic acid group Salt, phosphonic acid group salt, phosphoric acid group salt, hydroxy group salt, or 1-3 amino group salt. e and f are each independently an integer of 0 to 20. When e is 2 or more, the plurality of R ^8s may be the same or different, and may be combined in any combination to form a part of the ring structure. When f is 2 or more, the plurality of R ^9s may be the same or different, and may be combined in any combination to form a part of the ring structure. Q and Z are independently single bonds, -O-, -S-, or -N (R ¹⁸ )-, respectively. R ¹⁸ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. L is a single bond or divalent organic group. y is an integer from 0 to 5. When y is 2 or more, the plurality of Q, L, and Z may be the same or different, respectively. When y is 2 or more and e is 1 or more, the plurality of R ^8s may be the same or different. R ¹⁰ and R ¹¹ are independently single bonds, methylene groups, or alkylene groups having 2 to 4 carbon atoms. ]

Examples of the divalent alicyclic hydrocarbon skeleton having 5 to 30 ring members represented by R ^a and R ^b include a monocyclic alicyclic hydrocarbon skeleton having 5 to 15 ring members and 7 to 30 ring members. Examples thereof include a polycyclic alicyclic hydrocarbon skeleton. The position of the other bond relative to one bond in the divalent alicyclic hydrocarbon skeleton having 5 to 30 ring members represented by ^Ra and R ^{b is not particularly limited.}

Examples of the monocyclic alicyclic hydrocarbon skeleton having 5 to 15 ring members include a cyclopentane-diyl group, a cyclohexane-diyl group, a cyclopentene-diyl group, a cyclohexene-diyl group, a cyclooctane-diyl group, and a cyclodecane-. Examples thereof include a diyl group and a cyclododecane-diyl group.

Examples of the polycyclic alicyclic hydrocarbon skeleton having 7 to 30 ring members include norbornane, norbornene, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, and tricyclo [5.2.1. 0 ^2,6 ] Polycyclic fats such as heptane, pinan, camphor, decalin, norbornene, perhydroanthracene, perhydroazulene, cyclopentanohydrophenanthrene, bicyclo [2.2.2] -2-octene Examples thereof include groups of cyclic hydrocarbons excluding two hydrogen atoms.

The ^{divalent alicyclic hydrocarbon skeleton having 5 to 30 ring members represented by R a} and R ^b is a cyclopentane-diyl group from the viewpoint of maintaining high heat resistance, high refractive index, and mechanical properties, respectively. , Cyclohexane-diyl groups, groups excluding two hydrogen atoms in norbornene, or groups in which some or all of the hydrogen atoms in these groups are substituted with ^{R 8} or R ^{9 are preferred.}

^{For R 8} and R ⁹ in the formula (2-2), ^{all the explanations regarding R 4} in the formula (2-1) can be applied as they are. e and f are preferably 0 to 10, more preferably 0 to 5, from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit.

^{Regarding Q, Z, R 18} , L, and y in the formula (2-2), ^{all the explanations regarding Q, Z, R 17} , L, and y in the formula (2-1) can be applied as they are. it can.

^{For R 10} and R ¹¹ in equation (2-2), ^{all the explanations for R 6} in equation (2-1) can be applied as they are.

Further, as the divalent organic group represented by the above X in the above formula (2), a group represented by the following formula (2-3) can be mentioned.

〔式（２−３）中、Ｒ^１２は、水素原子、炭素数１〜２０の１価の炭化水素基、又は炭素数１〜２０の１価のハロゲン化炭化水素基である。Ｒ^１３及びＲ^１４は、それぞれ独立して、炭素数１〜２０の２価の鎖状又は脂環式の炭化水素基、又は炭素数１〜２０の２価の鎖状又は脂環式のハロゲン化炭化水素基である。ｇは、０又は１である。ｈは、１〜１０の整数である。ｈが２以上の場合、複数のＲ^１２及びＲ^１４は、それぞれ、同一であっても異なっていてもよい。〕

[In the formula (2-3), R ¹² is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. R ¹³ and R ¹⁴ are independently divalent chain or alicyclic hydrocarbon groups having 1 to 20 carbon atoms, or divalent chain or alicyclic halogens having 1 to 20 carbon atoms. It is a hydrocarbon group. g is 0 or 1. h is an integer from 1 to 10. When h is 2 or more, the plurality of R ¹² and R ¹⁴ may be the same or different, respectively. ]

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ¹² include the carbon number exemplified as the group represented by ^{R 1 in the above formulas (1-1) to (1-3).} Examples thereof include 1 to 20 monovalent hydrocarbon groups.

Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹² are exemplified as the group represented by ^{R 1 in the above formulas (1-1) to (1-3).} Examples thereof include a group in which a part or all of hydrogen atoms of a monovalent hydrocarbon group having 1 to 20 carbon atoms are replaced with halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

R ¹² has a hydrogen atom, a monovalent hydrocarbon group having 1 to 3 carbon atoms, or a monovalent group having 1 to 3 carbon atoms from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit. Halogenated hydrocarbon groups are preferred.

Examples of the divalent chain hydrocarbon group having 1 to 20 carbon atoms represented by R ¹³ and R ¹⁴ include a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group and a tetra. Methylene group, pentamethylene group, hexamethylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 1-methyl-1, Examples thereof include a linear or branched alkylene group such as a 4-butylene group and a 2-methyl-1,4-butylene group.

Examples of the divalent alicyclic hydrocarbon group (number of carbon atoms; 3 to 20) represented by R ¹³ and R ^{14 include a cyclobutylene group such as a cyclopropylene group and a 1,3-cyclobutylene group, and 1} , Cyclopentylene group such as 3-cyclopentylene group, monocyclic hydrocarbon group such as cyclohexylene group such as 1,4-cyclohexylene group; 1,4-norbornylene group, 2,5-norbornylene group, etc. Examples thereof include a polycyclic hydrocarbon group such as an adamantylene group such as a norbornylene group, a 1,5-adamantylene group and a 2,6-adamantylene group.

Examples of the divalent chain or alicyclic halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹³ and ^{R 14,} for example, exemplified as the group represented by ^{R 13} and ^{R 14} carbons Examples thereof include a group in which a part or all of hydrogen atoms in a divalent chain or alicyclic hydrocarbon group of numbers 1 to 20 are replaced with halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. ..

R ¹³ and R ¹⁴ are divalent chain hydrocarbon groups having 1 to 3 carbon atoms and 4 to 10 carbon atoms, respectively, from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit. Divalent alicyclic hydrocarbon group, divalent chain halogenated hydrocarbon group having 1 to 3 carbon atoms, or 4 to 4 carbon atoms.
A 10-divalent alicyclic halogenated hydrocarbon group is preferred. From the same viewpoint, h is preferably 0 to 5, more preferably 0 to 3.

Further, examples of the divalent organic group represented by the above X in the above formula (2) include a group represented by the following formula (2-4).

〔式（２−４）中、Ｒ^１５及びＲ^１６は、それぞれ独立して、炭素数１〜２０の２価の鎖状又は脂環式の炭化水素基、又は炭素数１〜２０の２価の鎖状又は脂環式のハロゲン化炭化水素基である。ｉは、０又は１である。ｊは、１〜１０の整数である。ｊが２以上の場合、複数のＲ^１６は、同一であっても異なっていてもよい。〕

[In formula (2-4), R ¹⁵ and R ¹⁶ are independently divalent chain or alicyclic hydrocarbon groups having 1 to 20 carbon atoms, or divalent groups having 1 to 20 carbon atoms. It is a chain or alicyclic halogenated hydrocarbon group. i is 0 or 1. j is an integer from 1 to 10. When j is 2 or more, the plurality of R ^16s may be the same or different. ]

^{For R 15} and R ¹⁶ in the formula (2-4), ^{all the explanations regarding R 13} in the above formula (2-3) can be applied as they are. j is preferably 0 to 5, more preferably 0 to 3, from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit.

Further, examples of the divalent organic group represented by the above X in the above formula (2) include a group represented by the following formula (2-5).

〔式（２−５）中、Ｒ^２１及びＲ^２２は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルチオ基、ニトロ基、シアノ基、カルボキシ基、スルホン酸基、ホスホン酸基、リン酸基、ヒドロキシ基、１〜３級アミノ基、カルボキシ基の塩、スルホン酸基の塩、ホスホン酸基の塩、リン酸基の塩、ヒドロキシ基の塩、又は１〜３級アミノ基の塩である。ｋ及びｌは、それぞれ独立して、０〜３の整数である。ｋが２又は３の場合、複数のＲ^２１は、同一であっても異なっていてもよい。ｌが２又は３の場合、複数のＲ^２２は、同一であっても異なっていてもよい。Ｒ^２３は、単結合、−Ｏ−、−Ｓ−、−Ｃ（Ｏ）−、−Ｓ（Ｏ）−、又は、−Ｓ（Ｏ）_２−である。〕

[In the formula (2-5), R ²¹ and R ²² are independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a monovalent halogenated hydrocarbon having 1 to 20 carbon atoms. Group, alkoxy group with 1 to 20 carbon atoms, alkylthio group with 1 to 20 carbon atoms, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group, 1-3 amino group , A carboxy group salt, a sulfonic acid group salt, a phosphonic acid group salt, a phosphoric acid group salt, a hydroxy group salt, or a 1st to 3rd grade amino group salt. k and l are independently integers of 0 to 3. When k is 2 or 3, the plurality of R ^21s may be the same or different. When l is 2 or 3, the plurality of R ^22s may be the same or different. R ²³ is a single bond, -O-, -S-, -C (O)-, -S (O)-, or -S (O) _2- . ]

^{For R 21} and R ²² in the formula (2-5), ^{all the explanations regarding R 4} in the above formula (2-1) can be applied as they are. K and l in the formula (2-5) are preferably 0 to 2, more preferably 0 to 1, respectively, from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit.

Further, examples of the divalent organic group represented by the above X in the above formula (2) include a group represented by the following formula (2-6).

〔式（２−６）中、Ｒ^２４及びＲ^２５は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルチオ基、ニトロ基、シアノ基、カルボキシ基、スルホン酸基、ホスホン酸基、リン酸基、ヒドロキシ基、１〜３級アミノ基、カルボキシ基の塩、スルホン酸基の塩、ホスホン酸基の塩、リン酸基の塩、ヒドロキシ基の塩、又は１〜３級アミノ基の塩である。ｍ及びｎは、それぞれ独立して、０〜３の整数である。ｍが２又は３の場合、複数のＲ^２４は、同一であっても異なっていてもよい。ｎが２以上の場合、複数のＲ^２５は、同一であっても異なっていてもよい。Ｒ^２６及びＲ^２７は、それぞれ独立して、単結合、−Ｏ−、−Ｓ−、−Ｃ（Ｏ）−、−Ｓ（Ｏ）−、又は、−Ｓ（Ｏ）_２−である。〕

[In the formula (2-6), R ²⁴ and R ²⁵ are independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a monovalent halogenated hydrocarbon having 1 to 20 carbon atoms. Group, alkoxy group with 1 to 20 carbon atoms, alkylthio group with 1 to 20 carbon atoms, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group, 1-3 amino group , A carboxy group salt, a sulfonic acid group salt, a phosphonic acid group salt, a phosphoric acid group salt, a hydroxy group salt, or a 1st to 3rd grade amino group salt. m and n are independently integers of 0 to 3. When m is 2 or 3, the plurality of R ^24s may be the same or different. When n is 2 or more, the plurality of R ^25s may be the same or different. R ²⁶ and R ²⁷ are independently single bonds, -O-, -S-, -C (O)-, -S (O)-, or -S (O) _2- . ]

^{For R 24} and R ²⁵ in the formula (2-6), ^{all the explanations regarding R 4} in the above formula (2-1) can be applied as they are. M and n in the formula (2-6) are preferably 0 to 2, more preferably 0 to 1, respectively, from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit.

Further, examples of the divalent organic group represented by the above X in the above formula (2) include a group represented by the following formula (2-7).

〔式（２−７）中、Ｒ^２８及びＲ^２９は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルチオ基、ニトロ基、シアノ基、カルボキシ基、スルホン酸基、ホスホン酸基、リン酸基、ヒドロキシ基、１〜３級アミノ基、カルボキシ基の塩、スルホン酸基の塩、ホスホン酸基の塩、リン酸基の塩、ヒドロキシ基の塩、又は１〜３級アミノ基の塩である。ｏは、０〜３の整数である。ｐは、０〜４の整数である。ｏが２以上の場合、複数のＲ^２８は、同一であっても異なっていてもよい。ｐが２以上の場合、複数のＲ^２９は、同一であっても異なっていてもよい。ｎは、０〜６の整数である。Ｒ^３０は、炭素数１〜２０の１価の炭化水素基、又は炭素数１〜２０の１価のハロゲン化炭化水素基である。ｑは、０〜１５の整数である。ｑが２以上の場合、複数のＲ^３０は、同一であっても異なっていてもよい。〕

[In the formula (2-7), R ²⁸ and R ²⁹ are independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a monovalent halogenated hydrocarbon having 1 to 20 carbon atoms. Group, alkoxy group with 1 to 20 carbon atoms, alkylthio group with 1 to 20 carbon atoms, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group, 1-3 amino group , A carboxy group salt, a sulfonic acid group salt, a phosphonic acid group salt, a phosphoric acid group salt, a hydroxy group salt, or a 1st to 3rd grade amino group salt. o is an integer from 0 to 3. p is an integer from 0 to 4. When o is 2 or more, the plurality of R ^28s may be the same or different. When p is 2 or more, the plurality of R ^29s may be the same or different. n is an integer from 0 to 6. R ³⁰ is a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. q is an integer from 0 to 15. When q is 2 or more, the plurality of R ^30s may be the same or different. ]

^{For R 28} and R ²⁹ in the formula (2-7), ^{all the explanations regarding R 4} in the above formula (2-1) can be applied as they are. O and p in the formula (2-7) are preferably 0 to 2, more preferably 0 to 1, respectively, from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit.

The monovalent hydrocarbon group having 1 to 20 carbon atoms represented by ^{R 30} in the formula (2-7) is ^{represented by, for example, the above R 1} in the above formulas (1-1) to (1-3). Examples of the group include monovalent hydrocarbon groups having 1 to 20 carbon atoms.

Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R ³⁰ are exemplified as the group represented by ^{R 1 in the above formulas (1-1) to (1-3).} Examples thereof include a group in which a part or all of hydrogen atoms of a monovalent hydrocarbon group having 1 to 20 carbon atoms are replaced with halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The R ³⁰ has a hydrogen atom, a monovalent hydrocarbon group having 1 to 3 carbon atoms, or a monovalent group having 1 to 3 carbon atoms from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit. Halogenated hydrocarbon groups are preferred. From the same viewpoint, n is preferably 0 to 4, more preferably 0 to 2. From the same viewpoint, q is preferably 0 to 11, more preferably 0 to 7.

Further, examples of the divalent organic group represented by X in the above formula (2) include a group represented by the following formula (2-8).

〔式（２−８）中、Ｒ^３１及びＲ^３２は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルチオ基、ニトロ基、シアノ基、カルボキシ基、スルホン酸基、ホスホン酸基、リン酸基、ヒドロキシ基、１〜３級アミノ基、カルボキシ基の塩、スルホン酸基の塩、ホスホン酸基の塩、リン酸基の塩、ヒドロキシ基の塩、又は１〜３級アミノ基の塩である。ｒ及びｓは、それぞれ独立して、０〜４の整数である。ｒが２以上の場合、複数のＲ^３１は、同一であっても異なっていてもよい。ｓが２以上の場合、複数のＲ^３２は、同一であっても異なっていてもよい。ｍは、１〜５の整数である。ｎは、０〜５の整数である。Ｒ^３３は、炭素数１〜２０の１価の炭化水素基、又は炭素数１〜２０の１価のハロゲン化炭化水素基である。ｔは、０〜２０の整数である。ｔが２以上の場合、複数のＲ^３３は、同一であっても異なっていてもよい。〕

[In the formula (2-8), R ³¹ and R ³² are independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a monovalent halogenated hydrocarbon having 1 to 20 carbon atoms, respectively. Group, alkoxy group with 1 to 20 carbon atoms, alkylthio group with 1 to 20 carbon atoms, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group, 1-3 amino group , A carboxy group salt, a sulfonic acid group salt, a phosphonic acid group salt, a phosphoric acid group salt, a hydroxy group salt, or a 1st to 3rd grade amino group salt. r and s are independently integers from 0 to 4. When r is 2 or more, the plurality of R ^31s may be the same or different. When s is 2 or more, the plurality of R ^32s may be the same or different. m is an integer of 1-5. n is an integer from 0 to 5. R ³³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. t is an integer from 0 to 20. When t is 2 or more, the plurality of R ^33s may be the same or different. ]

^{For R 31} and R ³² in the formula (2-8), ^{all the explanations regarding R 4} in the above formula (2-1) can be applied as they are. r and s are preferably 0 to 2, more preferably 0 to 1, from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit. From the same viewpoint, m is preferably 1 to 3, more preferably 1 to 2. From the same viewpoint, n is preferably 0 to 3, more preferably 0 to 2.

As a monovalent hydrocarbon group having 1 to 20 carbon atoms represented by ^{R 33} in the formula (2-8),
For example, a monovalent hydrocarbon group having 1 to 20 carbon atoms, which is exemplified as the group represented by ^{R 1} in the above formulas (1-1) to (1-3), can be mentioned.

Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R ³³ are exemplified as the group represented by ^{R 1 in the above formulas (1-1) to (1-3).} Examples thereof include a group in which a part or all of hydrogen atoms of a monovalent hydrocarbon group having 1 to 20 carbon atoms are replaced with halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The R ³³ has a hydrogen atom, a monovalent hydrocarbon group having 1 to 3 carbon atoms, or a monovalent group having 1 to 3 carbon atoms from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit. Halogenated hydrocarbon groups are preferred. From the same viewpoint, t is preferably 0 to 12, more preferably 0 to 8.

Further, examples of the divalent organic group represented by X in the above formula (2) include a divalent hydrocarbon group having 1 to 20 carbon atoms. Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 2 having 6 to 20 carbon atoms. Valuable aromatic hydrocarbon groups and the like can be mentioned.

Examples of the divalent chain hydrocarbon group include a divalent chain hydrocarbon group having 1 to 20 carbon atoms exemplified as the group represented by ^{R 13 in the above formula (2-3).} Be done. Examples of the divalent alicyclic hydrocarbon group, for example, a divalent alicyclic hydrocarbon group exemplified C3-20 group represented by the R ¹³ in the formula (2-3) or the like Can be mentioned. Examples of the divalent aromatic hydrocarbon group include an arylene group such as a phenylene group, a trilene group, a naphthylene group and an anthrylene group.

When the divalent organic group represented by X is a divalent hydrocarbon group having 1 to 20 carbon atoms, the carbon number is 1 from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit. A divalent chain hydrocarbon group having ~ 16 to 16, a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable.

Further, examples of the divalent organic group represented by X in the above formula (2) include a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms. The divalent halogenated hydrocarbon group having 1 to 20 carbon atoms includes, for example, a part or all of the hydrogen atoms in the divalent hydrocarbon group having 1 to 20 carbon atoms exemplified as the group represented by X. Examples thereof include groups in which the above is substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

When the divalent organic group represented by X is a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, carbon is used from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit. A chain halogenated hydrocarbon group having a number of 1 to 16, an alicyclic halogenated hydrocarbon group having 3 to 10 carbon atoms, or a halogenated aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable.

Further, examples of the divalent organic group represented by X in the above formula (2) include a divalent heterocyclic group having 3 to 10 ring members. Examples of the divalent heterocyclic group having 3 to 10 ring members include pyrrole, 2H-pyrrole, imidazole, pyrazole, isothiazole, isooxazole, pyridine, pyrazine, pyrimidine, pyridazine, indridin, isoindole, and 3H-. Indol, indol, 1H-indazole, purine, 4H-quinolidine, quinoline, isoquinoline, phthalazine, naphthylidine, quinoxalin, quinazoline, cinnoline, pteridine, carbazole, carboline, phenanthridin, acredin, perimidine, phenanthroline, phenazine, phenothiazine, flazan Phenoxazine, pyrrolidine, pyrrolin, imidazoline, imidazolidine, pyrazolidine, pyrazoline, piperidine, piperazin, indolin, isoindolin, quinuclidine, oxazole, benzoxazole, 1,3,5-triazine, tetrazole, tetrazine, triazole, phenalzazine, benzoimidazole. , Benzoliazole, thiazole, benzothiazole, thiazazole, benzothiazazole and other nitrogen-containing heterocyclic compounds excluding two hydrogen atoms and the like.

The hydrogen atom in this heterocyclic group is a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. , Alkylthio group, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group, 1-3 amino group, carboxy group salt, sulfonic acid group It may be substituted with a salt, a salt of a phosphonic acid group, a salt of a phosphoric acid group, a salt of a hydroxy group, or a salt of a primary amino group. Note that these substituents can be applied to the description of R ⁴ in the formula (2-1).

When the divalent organic group represented by X is a divalent heterocyclic group having 3 to 10 ring members, the number of ring members is 3 from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit. It is preferably a divalent nitrogen-containing heterocyclic group of 10 to 10.

The second structural unit in the polymer [A] is preferably a structural unit represented by the formula (2). In particular, from the viewpoint of further improving heat resistance, high refractive index, and mechanical properties, X in the formula (2) is a group represented by the above formulas (2-1) to (2-4), and the above carbon. It is preferably a divalent hydrocarbon group having a number of 1 to 20, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or a divalent heterocyclic group having 3 to 10 ring members, and the formula ( The fact that X in 2) is a group represented by the above formula (2-1), a group represented by the above formula (2-2), or a divalent heterocyclic group having 3 to 10 ring members. preferable.

Further, as the monomer giving the second structural unit in the [A] polymer, for example,
Mononuclear aromatic diamine compounds such as the following compounds (M-1) to (M-17);
Dinuclear aromatic diamine compounds such as the following compounds (M-18) to (M-34);
Aromatic diamine compounds with three or more nuclei such as the following compounds (M-35) to (M-43);
Condensation ring-containing diamine compounds such as the following compounds (M-44) to (M-46);
Cardo-structure-containing diamine compounds such as the following compounds (M-47) to (M-48);
Alicyclic diamine compounds such as the following compounds (M-49) to (M-53);
Aliphatic diamine compounds such as the following compounds (M-54) to (M-59);
Examples thereof include other diamine compounds such as the following compounds (M-60) to (M-65). These monomers may be used alone or in combination of two or more.

The lower limit of the content ratio of the second structural unit in the [A] polymer is preferably 5 mol%, more preferably 10 when the total of all structural units in the [A] polymer is 100 mol%. It is mol%, more preferably 20 mol%, and particularly preferably 33 mol%. The upper limit of the content ratio is preferably 95 mol%, more preferably 67 mol%, further preferably 60 mol%, and particularly preferably 50 mol%. By setting the content ratio in the above range, heat resistance, high refractive index, and mechanical properties can be further improved.

[Other structural units]
The polymer may have other structural units different from the first and second structural units, for example, for adjusting the molecular weight, as long as the above-mentioned effects are not impaired. Examples of the other structural unit include a third structural unit represented by the following formula (3) in which the ^{NR 2} and NR ³ sites in the above formula (2) are replaced with oxygen atoms, respectively. In addition, X in the formula (3) is synonymous with X in the above formula (2).

When the [A] polymer contains the above other structural units, the lower limit of the total content of the other structural units is 1 when the total of all the structural units in the [A] polymer is 100 mol%. It is preferably mol%, more preferably 5 mol%, still more preferably 10 mol%. The upper limit of the content ratio is preferably 40 mol%, more preferably 30 mol%. By setting the content ratio within the above range, the molecular weight can be easily adjusted within a range that does not impair the above-mentioned effects.

When the [A] polymer contains the above-mentioned third structural unit, the lower limit of the content ratio of the third structural unit is 5 mol% when the total of all the structural units in the [A] polymer is 100 mol%. It is preferably 10 mol%, more preferably 20 mol%. The upper limit of the content ratio is preferably 40 mol%, more preferably 30 mol%. By setting the content ratio in the above range, the solubility in various organic solvents can be further improved.

[Array of each structural unit]
As long as the polymer has the first and second structural units, the arrangement of each structural unit is not limited, but from the viewpoint of further improving heat resistance, high refractive index, and mechanical properties, the polymer can further improve heat resistance, high refractive index, and mechanical properties. It is preferable to have the first and second structural units in the main chain. Here, the "main chain" refers to the relatively longest binding chain in the polymer.

Further, when the [A] polymer has the first and second structural units in the main chain, it is excellent in heat resistance and mechanical properties, so that, for example, thermal deterioration of the resin molded product obtained from the [A] polymer is suppressed. At the same time, high dimensional stability can be imparted.

[Repeat unit]
Examples of the polymer having the first and second structural units in the main chain include the repeating unit (a) represented by the following formula (a), the repeating unit (b) represented by the following formula (b), and the like. Examples thereof include a repeating unit (c) represented by the following formula (c), a polymer having a combination of these repeating units in the main chain, and the like.

In the above formulas (a) to (c), R ^{1 and n are synonymous with R 1} and n in the above formulas (1-1) to (1-3), respectively. R ^{2, R 3} and X are respectively the same meanings as ^R 2, ^{R 3} and X in the above formula (2).

<[A] Polymer synthesis method>
The method for synthesizing the polymer [A] in the present invention is not particularly limited, and for example, a monomer giving a first structural unit, a monomer giving a second structural unit, and other compounds as needed. , Can be synthesized by reacting in an organic solvent under predetermined conditions.

Examples of the other compounds include alkali metal compounds, terminal terminators, and monomers giving other structural units.

Examples of the alkali metal compound include alkali metal hydrides such as lithium hydride, sodium hydride and potassium hydride; alkali metals hydroxide such as lithium hydroxide, sodium hydroxide and potassium hydroxide; lithium carbonate and sodium carbonate. , Alkali metal carbonates such as potassium carbonate; and alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydride, potassium hydride and the like. Among these, alkali metal hydroxide and alkali metal carbonate are preferable, and sodium hydroxide and potassium carbonate are more preferable.

When the above alkali metal compound is used, the lower limit of the amount used is preferably 1 times equivalent as the amount of metal atoms in the alkali metal compound with respect to the amino groups of all the monomers used in the synthesis of the [A] polymer. A 1.1-fold equivalent is more preferred, a 1.2-fold equivalent is even more preferred, and a 1.5-fold equivalent is particularly preferred. On the other hand, as the upper limit of the amount used, a triple equivalent is preferable, and a double equivalent is more preferable.

Examples of the organic solvent include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, sulfolane, and dimethyl sulfoxide. , Diethyl sulfoxide, dimethyl sulfoxide, diethyl sulfone, diisopropyl sulfone, diphenyl sulfone, diphenyl ether, benzophenone, methylene chloride, benzene, toluene, xylene, dialkoxybenzene (alkoxy group carbon number 1 to 4), trialkoxybenzene (alkoxy group Examples thereof include carbon atoms 1 to 4). These organic solvents may be used alone or in combination of two or more.

In addition to the organic solvent exemplified above, a solvent that azeotropes with water such as hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole, and phenetol can also be used in combination. These solvents may be used alone or in combination of two or more.

[A] The reaction temperature at the time of synthesizing the polymer is, for example, 20 ° C. or higher and 250 ° C. or lower. The reaction time is, for example, 15 minutes or more and 100 hours or less. The polymer [A] can be obtained as a solution, powder or pellet. When obtained as a powder, it is obtained by coagulating in a poor solvent, filtering, washing and drying. In that case, it is coagulated after being pretreated with an aqueous solution or solvent containing an alkali metal compound or ammonia. May be. Alternatively, it can also be obtained by directly coagulating in an aqueous solution containing an alkali metal compound, ammonia or the like or a poor solvent.

<[A] Weight average molecular weight (Mw) of polymer>
[A] The lower limit of the weight average molecular weight (Mw) of the polymer is preferably 500, more preferably 1,000, still more preferably 5,000, still more preferably 10,000, and most preferably 30, It is 000. The upper limit of Mw is preferably 600,000, more preferably 400,000, still more preferably 300,000, and most preferably 200,000. By setting the Mw to the above lower limit or more, the heat resistance can be further improved. On the other hand, if the Mw exceeds the upper limit, the viscosity may become too high and the coatability and operability may deteriorate.

<[A] Polymer glass transition temperature (Tg)>
[A] The lower limit of the glass transition temperature of the polymer is preferably 150 ° C., more preferably 180 ° C. The upper limit of the glass transition temperature is not particularly limited, but for example, 320 ° C. is preferable, and 300 ° C. is more preferable. By setting the glass transition temperature to the above lower limit or higher, the heat resistance can be further improved. The glass transition temperature is, for example, a value measured at a heating rate of 20 ° C./min under a nitrogen atmosphere using a differential scanning calorimetry device.

<Composition>
The composition in the present invention may contain the above-mentioned [A] polymer and an organic solvent, and may contain other components as long as the effects of the present invention are not impaired. This composition has excellent solubility in various organic solvents and can be used as a highly versatile composition applicable to various uses. Further, since the composition in the present invention contains the [A] polymer having excellent heat resistance and mechanical properties, thermal deterioration of the molded product obtained from this composition can be suppressed, and high mechanical properties and high dimensional stability can be suppressed. Can be given.

Since the above composition is excellent in solubility in various organic solvents, it can be used regardless of whether it is a polar solvent or a non-polar solvent. Specific organic solvents include, for example, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidi. Amid solvents such as non; ester solvents such as γ-butyrolactone and butyl acetate; ether solvents such as cyclopentanone, cyclohexanone, methyl ethyl ketone and benzophenone; many such as 1-methoxy-2-propanol and propylene glycol methyl ether acetate. Functional solvent; In addition to sulfone solvents such as sulfolane, dimethylsulfoxide, diethylsulfoxide, dimethylsulfone, diethylsulfone, diisopropylsulfone, and diphenylsulfone, methylene chloride, benzene, toluene, xylene, and dialkoxybenzene (the number of carbon atoms in the alkoxy group; 1 to 4), trialkoxybenzene (number of carbon atoms of the alkoxy group; 1 to 4) and the like can be mentioned. These organic solvents may be used alone or in combination of two or more.

The content of the polymer [A] in the composition of the present invention can be, for example, 0.01% by mass or more and 100% by mass or less, and 1% by mass or more and 100% by mass or more, based on the total solid content of the composition. It can be mass% or less.

The content of the organic solvent in the composition of the present invention can be, for example, 50 parts by mass or more and 100,000 parts by mass or less with respect to 100 parts by mass of the polymer [A].

Examples of the other components include antioxidants, lubricants, flame retardants, antibacterial agents, colorants, mold release agents, foaming agents, polymers other than the [A] polymer, and the like. These other components may be used alone or in combination of two or more.

Examples of the antioxidant include hindered phenol compounds, phosphorus compounds, sulfur compounds, metal compounds, hindered amine compounds and the like. Among these, hindered phenolic compounds are preferable.

The hindered phenolic compound preferably has a molecular weight of 500 or more. Examples of hindered phenolic compounds having a molecular weight of 500 or more include triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] and 1,6-hexanediol-bis [ 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -3,5-triazine, pentaerythritol tetrakis [3- (3,5-t-butyl-4-hydroxyphenyl) propionate], 1,1,3-tris [2-methyl-4- [3- (3,3) 5-di-t-Butyl-4-hydroxyphenyl) propionyloxy] -5-t-butylphenyl] butane, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-) Hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-) Hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-) Butyl-4-hydroxybenzyl) -isocyanurate, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl]- 2,4,8,10-Tetraoxaspiro [5.5] undecane and the like can be mentioned.

When the composition in the present invention contains an antioxidant, the content of the antioxidant is, for example, 0.01 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymer [A].

The composition in the present invention is prepared by uniformly mixing the polymer [A], an organic solvent, and, if necessary, other components such as an antioxidant. This composition is prepared in the form of a liquid, a paste, or the like.

<Molded body>
The molded product in the present invention contains the polymer [A] and is obtained, for example, by the above composition. Since this molded product contains the [A] polymer having excellent heat resistance and mechanical properties, it is possible to suppress thermal deterioration and to impart high mechanical properties and high dimensional stability. The molded product can be manufactured by, for example, a mold molding method, an extrusion molding method, a solvent casting method, or the like. For example, a mold forming method is suitable for manufacturing a lens, an extrusion molding method and a solvent casting method are suitable for manufacturing an optical film or an insulating film for a printed wiring board, and an extrusion molding method is more preferable. .. Examples of the use of this molded body include encapsulants for electrical and electronic parts, interlayer insulating films, heat-resistant protective films; laminated boards (printed wiring boards, interlayer adhesives, solder resists, solder pastes); adhesives (conductive). Adhesives, heat conductive adhesives / adhesive sheets); Structural adhesives / prepregs used for various structural materials; Various coating optical components (optical films such as wavelength plates and retardation plates, conical lenses, spherical lenses, cylindrical lenses, etc. (Various special lenses, lens arrays, etc.), insulating films for printed wiring boards, etc. In particular, “Demonstration of 20 μm Pitch Micro-vias by Excimer Laser Ablation in Ultra-thin Dry-film Polymer Dielectrics for Multi-layer RDL on Glass Interposers”, “2015 IEEE Electronic Components & Technology”
Conference, 922-927 ”,“ Demonstration of enhanced system-level reliability of
ultra-thin BGA packages with doped polymer collars and doped solder alloys ”,“ 2016 IEEE 66th Electronic Components and Technology Conference, 1377-1385 ”,“ Modeling, Design, Fabrication and Demonstration of RF Front-End 3D IPAC Module with Ultra-thin Glass Substrates for LTE Applications ”,“ 2016 IEEE
66th Electronic Components and Technology Conference, 1297-1302 ”,“ Design, Demonstration and characterization of Ultra-thin Low-warpage Glass BGA Packages for Smart Mobile Application Processor ”,“ 2016 IEEE 66th Electronic Components
and Technology Conference, 1465-1470 ”,“ Design and Demonstration of Ultra-thin Glass 3D IPD Diplexers ”, 2016 IEEE 66th Electronic Components and Technology
It can be suitably used as a material for the mounting structure described in Conference, 2348-2352 ”and the like.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. In the following, parts and% are based on mass unless otherwise specified.

[1] Synthesis of polymer (Example 1)
Bis (4-aminophenyl) methane (19.8 g, 100.0 mmol) and 4,6-dichloropyrimidine (14.9 g, 100.0 mmol) were weighed into a four-neck separable flask equipped with a stirrer. N-Methyl-2-pyrrolidone (81 g) was added, and the mixture was reacted at 145 ° C. for 8 hours under a nitrogen atmosphere. After completion of the reaction, N-methyl-2-pyrrolidone (100 g) was added and the mixture was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 15 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-1). The polymer P-1 having the above was obtained (yield 26.3 g, yield 96%).

(Example 2)
Bis (4-aminocyclohexyl) methane (15.8 g, 75.0 mmol) and 4,6-dichloropyrimidine (11.2 g, 75.0 mmol) were weighed into a four-neck separable flask equipped with a stirrer. N-Methyl-2-pyrrolidone (63 g) was added, and the mixture was reacted at 145 ° C. for 7 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was added to methanol (2.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 12 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-2). The polymer P-2 having the above was obtained (yield 10.1 g, yield 47%).

(Example 3)
Α, α'-bis (4-aminophenyl) -1,4-diisopropylbenzene (17.2 g, 50.0 mmol), 4,6-dichloropyrimidine (7) in a four-neck separable flask equipped with a stirrer. .4 g, 50.0 mmol) was weighed in, N-methyl-2-pyrrolidone (58 g) was added, and the mixture was reacted at 145 ° C. for 12 hours under a nitrogen atmosphere. After completion of the reaction, N-methyl-2-pyrrolidone (80 g) was added and the mixture was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 12 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-3). The polymer P-3 having was obtained (yield 20.2 g, yield 96%).

(Example 4)
2,2-bis [4- (4-aminophenoxy) phenyl] propane (24.6 g, 60.0 mmol), 4,6-dichloropyrimidine (8.9 g) in a four-neck separable flask equipped with a stirrer. , 60.0 mmol) was added, N-methyl-2-pyrrolidone (78 g) was added, and the mixture was reacted at 145 ° C. for 8 hours under a nitrogen atmosphere. After completion of the reaction, N-methyl-2-pyrrolidone (100 g) was added and the mixture was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 12 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-4). The polymer P-4 having was obtained (yield 20.7 g, yield 71%).

The structure of the obtained polymer ^{was identified by 1 1} H-NMR. The chemical shift values at this time are shown below.
^{1 1} H-NMR (DMSO-d6, 400 MHz) δ (ppm): 1.60 (s, 6H), 6.07 (s, 1H), 6.88 (d, 4H), 7.00 (d, 4H) ), 7.20 (d, 4H), 7.46 (d, 4H), 8.31 (s, 1H), 9.81 (s, 2H)

(Example 5)
Bis (4-aminophenyl) sulfone (24.8 g, 100.0 mmol) and 4,6-dichloropyrimidine (14.9 g, 100.0 mmol) were weighed into a four-neck separable flask equipped with a stirrer. N-Methyl-2-pyrrolidone (93 g) was added, and the mixture was reacted at 160 ° C. for 14 hours under a nitrogen atmosphere. After completion of the reaction, N-methyl-2-pyrrolidone (100 g) was added and the mixture was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 14 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-5). The polymer P-5 having was obtained (yield 30.8 g, yield 95%).

(Example 6)
In a four-neck separable flask equipped with a stirrer, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (16.4 g, 40.0 mmol) and bis (4-aminophenyl) sulfone (9) .9 g, 40.0 mmol), 4,6-dichloropyrimidine (11.9 g, 80.0 mmol) were weighed, N-methyl-2-pyrrolidone (89 g) was added, and the reaction was carried out at 145 ° C. for 8 hours under a nitrogen atmosphere. I let you. After completion of the reaction, N-methyl-2-pyrrolidone (100 g) was added and the mixture was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 16 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-6). The polymer P-6 having was obtained (yield 12.5 g, yield 39%). The ratio (a: b) of the constituent units in this polymer is 50:50 (mol%).

The structure of the obtained polymer ^{was identified by 1 1} H-NMR. The chemical shift values at this time are shown below.
^{1 1} H-NMR (DMSO-d6, 400 MHz) δ (ppm): 1.59 (s, 6H), 6.07-6.30 (m, 2H), 6.84-6.87 (m, 4H) , 6.95-6.98 (m, 4H), 7.17-7.19 (m, 4H), 7.51-7.53 (m, 4H), 7.77-7.83 (m, 4H) 8H), 8.21-8.40 (m, 2H), 9.10-9.25 (m, 2H), 9.66-9.81 (m, 2H)

(Example 7)
Bis (3-aminophenyl) sulfone (12.4 g, 50.0 mmol) and 4,6-dichloropyrimidine (7.4 g, 50.0 mmol) were weighed into a four-neck separable flask equipped with a stirrer. N-Methyl-2-pyrrolidone (46 g) was added, and the mixture was reacted at 145 ° C. for 15 hours under a nitrogen atmosphere. After completion of the reaction, N-methyl-2-pyrrolidone (50 g) was added and the mixture was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 13 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-7). The polymer P-7 having was obtained (yield 14.9 g, yield 92%).

(Example 8)
In a four-neck separable flask equipped with a stirrer, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (16.4 g, 40.0 mmol) and bis (3-aminophenyl) sulfone (9) .9 g, 40.0 mmol), 4,6-dichloropyrimidine (11.9 g, 80.0 mmol) were weighed, N-methyl-2-pyrrolidone (89 g) was added, and the reaction was carried out at 145 ° C. for 7 hours under a nitrogen atmosphere. I let you. After completion of the reaction, N-methyl-2-pyrrolidone (100 g) was added and the mixture was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 13 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-8). The polymer P-8 having the above was obtained (yield 30.3 g, yield 93%). The ratio (a: b) of the constituent units in this polymer is 50:50 (mol%).

(Example 9)
4,4'-Diaminobenzanilide (18.2 g, 80.0 mmol) and 4,6-dichloropyrimidine (11.9 g, 80.0 mmol) were weighed into a four-neck separable flask equipped with a stirrer. N-Methyl-2-pyrrolidone (70 g) was added, and the mixture was reacted at 145 ° C. for 9 hours under a nitrogen atmosphere. After completion of the reaction, N-methyl-2-pyrrolidone (80 g) was added and the mixture was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 12 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-9). The polymer P-9 having the above was obtained (yield 8.7 g, yield 36%).

(Example 10)
In a four-neck separable flask equipped with a stirrer, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (20.5 g, 50.0 mmol), 2,2-bis (3-amino-) Weigh 4-hydroxyphenyl) propane (3.2 g, 12.5 mmol) and 4,6-dichloropyrimidine (9.3 g, 62.5 mmol), add N-methyl-2-pyrrolidone (77 g), and add a nitrogen atmosphere. The reaction was carried out at 145 ° C. for 8 hours. After completion of the reaction, N-methyl-2-pyrrolidone (100 g) was added and the mixture was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 16 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-10). The polymer P-10 having the above was obtained (yield 26.7 g, yield 94%). The ratio (a: b) of the constituent units in this polymer is 80:20 (mol%).

(Example 11)
2,2-bis [4- (4-aminophenoxy) phenyl] propane (20.5 g, 50.0 mmol), 1,4-phenylenediamine (5.4 g) in a four-neck separable flask equipped with a stirrer. , 50.0 mmol), 4,6-dichloropyrimidine (14.9 g, 100.0 mmol) was weighed, N-methyl-2-pyrrolidone (95 g) was added, and the reaction was carried out at 145 ° C. for 5.5 hours under a nitrogen atmosphere. I let you. After completion of the reaction, N-methyl-2-pyrrolidone (100 g) was added and the mixture was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 13 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-11). The polymer P-11 having the above was obtained (yield 32.6 g, yield 97%). The ratio (a: b) of the constituent units in this polymer is 50:50 (mol%).

(Example 12)
In a four-neck separable flask equipped with a stirrer, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (16.8 g, 40.9 mmol), N, N'-di-sec-butyl. Weigh -1,4-phenylenediamine (9.0 g, 40.9 mmol) and 4,6-dichloropyrimidine (12.2 g, 81.9 mmol), add N-methyl-2-pyrrolidone (87 g), and add nitrogen. The reaction was carried out at 145 ° C. for 7.5 hours in an atmosphere. After completion of the reaction, N-methyl-2-pyrrolidone (100 g) was added and the mixture was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 12 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-12). The polymer P-12 having the above was obtained (yield 9.9 g, yield 31%). The ratio (a: b) of the constituent units in this polymer is 50:50 (mol%).

(Example 13)
In a four-neck separable flask equipped with a stirrer, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (12.3 g, 30.0 mmol), N, N'-di-beta-naphthyl. Weigh -1,4-phenylenediamine (10.8 g, 30.0 mmol) and 4,6-dichloropyrimidine (8.9 g, 60.0 mmol), add N-methyl-2-pyrrolidone (75 g), and add nitrogen. The reaction was carried out at 145 ° C. for 7 hours in an atmosphere. After completion of the reaction, N-methyl-2-pyrrolidone (100 g) was added and the mixture was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 12 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-13). The polymer P-13 having the same was obtained (yield 18.6 g, yield 67%). The ratio (a: b) of the constituent units in this polymer is 50:50 (mol%).

(Example 14)
In a four-neck separable flask equipped with a stirrer, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (14.4 g, 35.0 mmol), 2,4-diethyl-6-methyl- Weigh 1,3-phenylenediamine (6.2 g, 35.0 mmol) and 4,6-dichloropyrimidine (10.4 g, 70.0 mmol), add N-methyl-2-pyrrolidone (72 g), and add a nitrogen atmosphere. The reaction was carried out at 145 ° C. for 13 hours. After the reaction is completed, N
-Methyl-2-pyrrolidone (100 g) was added and added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 12 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-14). The polymer P-14 having the above was obtained (yield 12.2 g, yield 47%). The ratio (a: b) of the constituent units in this polymer is 50:50 (mol%).

(Example 15)
2,2-bis [4- (4-aminophenoxy) phenyl] propane (20.5 g, 50.0 mmol), benzoguanamine (2.3 g, 12.5 mmol) in a four-neck separable flask equipped with a stirrer. , 4,6-Dichloropyrimidine (9.3 g, 62.5 mmol) was weighed, N-methyl-2-pyrrolidone (75 g) was added, and the mixture was reacted at 145 ° C. for 15.5 hours under a nitrogen atmosphere. After completion of the reaction, N-methyl-2-pyrrolidone (100 g) was added and the mixture was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 12 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-15). The polymer P-15 having the above was obtained (yield 11.6 g, yield 42%). The ratio (a: b) of the constituent units in this polymer is 80:20 (mol%).

(Example 16)
2,2-bis [4- (4-aminophenoxy) phenyl] propane (20.5 g, 50.0 mmol), 2,4-diamino-6-hydroxypyrimidine in a four-neck separable flask equipped with a stirrer Weigh (1.6 g, 12.5 mmol), 4,6-dichloropyrimidine (9.3 g, 62.5 mmol), add N-methyl-2-pyrrolidone (73 g), and add N-methyl-2-pyrrolidone (73 g) under a nitrogen atmosphere at 145 ° C. 8 Reacted for time. After completion of the reaction, N-methyl-2-pyrrolidone (100 g) was added and the mixture was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 12 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-16). The polymer P-16 having the above was obtained (yield 16.5 g, yield 62%). The ratio (a: b) of the constituent units in this polymer is 80:20 (mol%).

(Example 17)
2,2-bis [4- (4-aminophenoxy) phenyl] propane (8.2 g, 20.0 mmol), 4,6-dichloro-2-phenylpyrimidine in a four-neck separable flask equipped with a stirrer. (4.5 g, 20.0 mmol) was weighed, N-methyl-2-pyrrolidone (30 g) was added, and the mixture was reacted at 145 ° C. for 9.5 hours under a nitrogen atmosphere. After completion of the reaction, N-methyl-2-pyrrolidone (50 g) was added and the mixture was added to methanol (2.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 12 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-17). The polymer P-17 having the above was obtained (yield 10.7 g, yield 95%).

(Example 18)
2,2-bis [4- (4-aminophenoxy) phenyl] propane (24.6 g, 60.0 mmol), 3,6-dichloropyridazine (8.9 g) in a four-neck separable flask equipped with a stirrer. , 60.0 mmol), N-methyl-2-pyrrolidone (78 g) was added, and the mixture was reacted at 145 ° C. for 7 hours under a nitrogen atmosphere. After completion of the reaction, N-methyl-2-pyrrolidone (100 g) was added and the mixture was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 12 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-18). The polymer P-18 having the above was obtained (yield 15.1 g, yield 52%).

(Example 19)
2,2-bis [4- (4-aminophenoxy) phenyl] propane (20.5 g, 50.0 mmol), 2,6-dichloropyrazine (7.4 g) in a four-neck separable flask equipped with a stirrer. , 50.0 mmol) was weighed in, N-methyl-2-pyrrolidone (65 g) was added, and the mixture was reacted at 145 ° C. for 10 hours under a nitrogen atmosphere. After completion of the reaction, N-methyl-2-pyrrolidone (100 g) was added and the mixture was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 12 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-19). The polymer P-19 having the above was obtained (yield 6.8 g, yield 28%).

(Example 20)
2,2-bis [4- (4-aminophenoxy) phenyl] propane (28.7 g, 70.0 mmol), 4,6-dichloropyrimidine (5.2 g) in a four-neck separable flask equipped with a stirrer. , 35.0 mmol), 3,6-dichloropyrimidine (5.2 g, 35.0 mmol) was weighed, N-methyl-2-pyrrolidone (91 g) was added, and the reaction was carried out at 145 ° C. for 8.5 hours under a nitrogen atmosphere. I let you. After completion of the reaction, N-methyl-2-pyrrolidone (100 g) was added and the mixture was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 17 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-20). The polymer P-20 having the above was obtained (yield 30.8 g, yield 90%). The ratio (a: b) of the constituent units in this polymer is 50:50 (mol%).

(Example 21)
In a four-neck separable flask equipped with a stirrer, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (16.4 g, 40.0 mmol) and bis (4-aminophenyl) sulfone (9) .9 g, 40.0 mmol), 3,6-dichloropyridazine (11.9 g, 80.0 mmol) were weighed, N-methyl-2-pyrrolidone (89 g) was added, and the reaction was carried out at 145 ° C. for 18 hours under a nitrogen atmosphere. I let you. After completion of the reaction, N-methyl-2-pyrrolidone (100 g) was added and the mixture was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 17 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-21). The polymer P-21 having the same was obtained (yield 28.6 g, yield 88%). The ratio (a: b) of the constituent units in this polymer is 50:50 (mol%).

(Example 22)
In a four-neck separable flask equipped with a stirrer, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (16.4 g, 40.0 mmol) and bis (4-aminophenyl) sulfone (9) .9 g, 40.0 mmol), 4,6-dichloropyrimidine (6.0 g, 40.0 mmol), 3,6-dichloropyridazine (6.0 g, 40.0 mmol), and N-methyl-2-pyrrolidone. (89 g) was added, and the mixture was reacted at 145 ° C. for 14 hours under a nitrogen atmosphere. After completion of the reaction, N-methyl-2-pyrrolidone (100 g) was added and the mixture was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 14 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-22). The polymer P-22 having the above was obtained (yield 25.8 g, yield 80%). The ratio of the constituent units (a: b: c: d) in this polymer is 25:25:25:25 (mol%).

(Example 23)
Bis (4-aminophenyl) methane (19.8 g, 100.0 mmol), 4,6-dichloropyrimidine (14.9 g, 100.0 mmol), potassium carbonate (19.8 g, 100.0 mmol) in a four-neck separable flask equipped with a stirrer. 18.7 g (135 mmol) was weighed in, N-methyl-2-pyrrolidone (81 g) was added, and the mixture was reacted at 130 ° C. for 8 hours under a nitrogen atmosphere. After completion of the reaction, N-methyl-2-pyrrolidone (100 g) was added for dilution, and the precipitate was removed by filtration. The filtrate was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 15 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-23). The polymer P-23 having the above was obtained (yield 10.4 g, yield 38%).

(Example 24)
Bis (4-aminophenyl) methane (19.8 g, 100.0 mmol), 4,6-dichloropyrimidine (14.9 g, 100) in a four-neck separable flask equipped with a stirrer.
.. 0 mmol) and potassium carbonate (18.7 g, 135 mmol) were weighed in, N-methyl-2-pyrrolidone (81 g) was added, and the mixture was reacted at 145 ° C. for 8 hours under a nitrogen atmosphere. After completion of the reaction, N-methyl-2-pyrrolidone (100 g) was added for dilution, and the precipitate was removed by filtration. The filtrate was added to methanol (3.0 kg). The precipitated solid is separated by filtration, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120 ° C. for 15 hours using a vacuum dryer to obtain the structural unit represented by the following formula (P-24). The polymer P-24 having the same was obtained (yield 17.0 g, yield 62%).

(Comparative Example 1)
Α, α'-bis (4-aminophenyl) -1,4-diisopropylbenzene (12.1 g, 35.0 mmol), and triethylamine (7.4 g, 72) were placed in a two-necked round bottom flask containing a stir bar. .8 mmol) was weighed and N-methyl-2-pyrrolidone (67 g) was added to prepare a diamine solution. Separately, terephthalic acid chloride (3.5 g, 17.3 mmol) and isophthalic acid chloride (3.5 g, 17.3 mmol) were dissolved in N-methyl-2-pyrrolidone (9 g) to prepare a carboxylic acid dihalide solution. This carboxylic acid dihalide solution was added to the diamine solution under stirring and reacted at room temperature for 1 hour. After completion of the reaction, the polymer solution was poured into an excess amount of methanol under strong stirring, and the precipitated solid was collected by filtration. The recovered solid was washed 3 times with an excess amount of ion-exchanged water, dried under reduced pressure at 120 ° C. for 13 hours using a vacuum dryer, and the polymer R- having a structural unit represented by the following formula (R-1). 1 was obtained (yield 14.8 g, yield 89%). The ratio (a: b) of the constituent units in this polymer is 50:50 (mol%).

(Comparative Example 2)
In a four-neck separable flask equipped with a stirrer, α, α'-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene (17.3 g, 50.0 mmol) and pt-butylphenol (0. Weigh 105 g, 0.7 mmol), sodium hydroxide (4.2 g, 105.7 mmol), and tri-n-butylbenzylammonium chloride (0.109 g, 0.35 mmol), and add ion-exchanged water (133 g). , Aqueous diol was prepared. Separately, terephthalic acid chloride (5.1 g, 25.2 mmol) and isophthalic acid chloride (5.1 g, 25.2 mmol) were dissolved in dichloromethane (96 mL) to prepare an organic solution of carboxylic acid dihalide. This dicarboxylic acid halide organic solution was added to the diol aqueous solution under strong stirring, and an interfacial polycondensation reaction was carried out at room temperature for 2 hours. After completion of the reaction, acetic acid was added to neutralize the remaining alkali metal compound. After allowing to stand to separate the aqueous phase and the organic phase, the aqueous phase was extracted by decantation. The operation of washing the remaining organic phase with an equal amount of ion-exchanged water was repeated three times. The washed organic phase was poured into an excess amount of methanol under strong stirring, and the precipitated solid was separated by filtration and recovered, and then dried under reduced pressure at 120 ° C. for 12 hours using a vacuum dryer to obtain the following formula (R-2). ) Was obtained (yield 21.6 g, yield 90%). The ratio (a: b) of the constituent units in this polymer is 50:50 (mol%).

(Comparative Example 3)
Α, α'-Bis (4-aminophenyl) -1,4-diisopropylbenzene (2.4 g, 7.0 mmol) was weighed into a screw vial containing a stir bar, and N-methyl-2-pyrrolidone (24 g) was added. ) Was added to prepare a diamine solution. Pyromellitic anhydride (1.5 g, 6.9 mmol) was added to the diamine solution under stirring, and the mixture was reacted at room temperature for 5 hours. The obtained polymer solution was applied onto a glass substrate using a spin coater, dried at 70 ° C. for 15 minutes, then dried at 120 ° C. for 15 minutes to form a film, and then peeled off from the glass substrate. The film was fixed to a gold frame and further fired at 350 ° C. under nitrogen for 1 hour to obtain a polymer R-3 (film (thickness 30 μm)) having a structural unit represented by the following formula (R-3).

(Comparative Example 4)
A polymer R-4 (trade name “ULTRASON S 3010” manufactured by BASF) having a structural unit represented by the following formula (R-4) was used.

<Structural analysis of polymer>
The structure of the polymer was identified by ¹ H-NMR using a nuclear magnetic resonance apparatus (“ECX400P” manufactured by JEOL Ltd.) and deuterated dimethylsulfoxide as a measurement solvent.

[2] Evaluation of physical properties of polymer In each polymer obtained as described above, "weight average molecular weight (Mw)", "glass transition temperature (Tg)", "refractive index", "mechanical characteristics (thermal expansion coefficient)" , Elastic modulus, and tensile strength) ”was evaluated according to the following method. The evaluation results are shown in Tables 1 and 2. In addition, "-" in the table means that the corresponding evaluation item is not measured.

<Weight average molecular weight (Mw)>
The weight average molecular weight (Mw) of each polymer was measured using a GPC apparatus (“HLC-8320 type” manufactured by Tosoh Corporation) under the following conditions.
Column: A concatenation of Tosoh's "TSKgel α-M" and Tosoh's "TSKgel guardcоlumn α" Developing solvent: N-methyl-2-pyrrolidone (with LiBr 10 mM added)
Column temperature: 40 ° C
Flow velocity: 1.0 mL / min Sample concentration: 0.75% by mass
Sample injection volume: 50 μL
Detector: Differential Refractometer Standard Material: Monodisperse Polystyrene

<Glass transition temperature (Tg)>
The glass transition temperature (Tg) of each polymer is a thermogram obtained at a heating rate of 20 ° C./min under a nitrogen atmosphere using a differential scanning calorimetry device (Rigaku DSC device "Thermo Plus DSC8230"). In the DSC temperature rise curve of, the temperature was set to correspond to the intersection of the baseline and the tangent at the inflection point. The inflection point was set to the temperature corresponding to the peak in the DDSC curve, which is the differential curve of the DSC temperature rise curve. Further, in order to confirm the baseline of DSC, the DDSC curve was appropriately referred to.

<Refractive index (nD)>
First, each polymer was redissolved in N-methyl-2-pyrrolidone to obtain a resin composition having a polymer concentration of 20% by mass. This resin composition was applied onto a glass substrate using a spin coater, dried at 70 ° C. for 15 minutes, then dried at 120 ° C. for 15 minutes to form a film, and then peeled off from the glass substrate. Then, the film was fixed to a metal frame and further dried at 150 ° C. for 12 hours to obtain an evaluation film having a film thickness of 30 μm. The film of Comparative Example 3 was used as it was for evaluation (the same applies hereinafter). Then, the refractive index of the evaluation film of each polymer was measured using a prism coupler (modelPC-2010) manufactured by Metallikon. At this time, the refractive index was measured using light having three wavelengths of 408, 633, and 828 nm, and the refractive index (nD) with respect to the D line (589 nm) was determined using the Cauchy equation.

<Mechanical characteristics>
(Coefficient of linear expansion (CTE))
A film similar to the evaluation film used for measuring the refractive index was prepared, and the linear expansion coefficient of the obtained evaluation film was measured using an SSC-5200 type TMA measuring device manufactured by Seiko Instruments Inc. At this time, the coefficient of linear expansion was calculated from the gradient of the TMA curve at 100 to 150 ° C. when the temperature of the evaluation film was raised at 5 ° C./min to a temperature 20 ° C. lower than the glass transition temperature.

(Elastic modulus and tensile strength)
A similar evaluation film as the one used for measuring the refractive index was prepared, and the elastic modulus and tensile strength of the obtained evaluation film at room temperature were measured using a tensile tester "EZ-LX" manufactured by Shimadzu Corporation. Then, a tensile test was carried out at a speed of 5 mm / min using a No. 7 dumbbell and the measurement was performed.

As is clear from Tables 1 and 2, the polymers of each example have a high glass transition temperature, a high refractive index, and excellent mechanical properties (CTE, elastic modulus, and tensile strength). Was confirmed. For example, the polymers of Examples 3, 4, 6, 8 and 17 showed a high glass transition temperature of 200 ° C. or higher, a high refractive index of 1.66 or higher, and excellent mechanical properties (CTE of 46). It is as low as below and the tensile strength is as high as 100 MPa or more). On the other hand, in Comparative Examples 1 to 4, the refractive index was as low as less than 1.65 and the tensile strength was as low as less than 100 MPa.

The novel polymer in the present invention has a high glass transition temperature, excellent heat resistance, a high refractive index, and excellent mechanical properties (CTE, elastic modulus, and tensile strength). Therefore, the polymer of the present invention, the composition containing the same, and the molded product can be suitably used in the fields of electrical and electronic materials, optical materials, and the like used in the electrical and electronic industry and the optical industry. In particular, encapsulants for electrical and electronic parts, interlayer insulating films, heat-resistant protective films; laminated boards (printed wiring boards, interlayer adhesives, solder resists, solder pastes, etc.); adhesives (conductive adhesives, thermally conductive adhesives, etc.) / Adhesive sheet, etc.); Various coatings, optical components (optical films such as wavelength plates and retardation plates, various special lenses such as conical lenses, spherical lenses, and cylindrical lenses, lens arrays, etc.), insulating films for printed wiring boards, etc. Can be suitably used for.

Claims (5)

The first structural unit represented by at least one of the following formulas (1-1), (1-2) and (1-3), and
The second structural unit, which is the structural unit represented by the following formula (2), and
It is a polymer having
A polymer characterized by having a repeating unit represented by the following formula (a), a repeating unit represented by the following formula (b), a repeating unit represented by the following formula (c), or a combination of these repeating units in the main chain. ..

[In formulas (1-1) to (1-3), R ¹ is independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a monovalent halogen having 1 to 20 carbon atoms. A salt of a hydrocarbon group, a nitro group, a cyano group, a 1st to 3rd amino group, or a 1st to 3rd amino group. n is an integer of 0 to 2 independently of each other. When n is 2, the plurality of R ^1s may be the same or different, and may be combined in any combination to form a part of the ring structure. ]

[In the formula (2), R ² and R ³ are independently hydrogen atoms or monovalent hydrocarbon groups having 1 to 20 carbon atoms. X is a group represented by the following formula (2-1). ]

[In the formula (2-1), R ⁴ and R ⁵ are independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a monovalent halogenated hydrocarbon having 1 to 20 carbon atoms. Group, alkoxy group with 1 to 20 carbon atoms, alkylthio group with 1 to 20 carbon atoms, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group, 1-3 amino group , A carboxy group salt, a sulfonic acid group salt, a phosphonic acid group salt, a phosphoric acid group salt, a hydroxy group salt, or a 1st to 3rd grade amino group salt. c and d are independently integers of 0 to 2. a and b are independently integers from 0 to 8. When a is 2 or more, the plurality of R ^4s may be the same or different, and may be combined in any combination to form a part of the ring structure. When b is 2 or more, the plurality of R ^5s may be the same or different, and may be combined in any combination to form a part of the ring structure. Q and Z are independently single bonds, -O-, -S-, or -N (R ¹⁷ )-, respectively. R ¹⁷ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. L is a single bond or divalent organic group. y is an integer from 0 to 5. When y is 2 or more, the plurality of Q, L, and Z may be the same or different, respectively. When y is 2 or more and a is 1 or more, the plurality of R ^4s may be the same or different. R ⁶ and R ⁷ are single bonds. ]

[In the formulas (a) to (c), R ^{1 and n are synonymous with R 1} and n in the above formulas (1-1) to (1-3) , respectively. R ^{2, R 3} and X are respectively the same meanings as ^R 2, ^{R 3} and X in the above formula (2). ] The polymer according to claim 1, wherein the polystyrene-equivalent weight average molecular weight is 500 or more and 600,000 or less. The polymer according to claim 1, wherein the polystyrene-equivalent weight average molecular weight is 30,000 or more and 200,000 or less. A composition comprising the polymer according to any one of claims 1 to 3 and an organic solvent. A molded product containing the polymer according to any one of claims 1 to 3.