JP4356516B2 - Norbornene ring-opening polymer - Google Patents

Description

  The present invention is a norbornene-based ring-opening polymer having excellent transparency, water resistance (low water absorption) and heat resistance, exhibiting positive birefringence, particularly having an extremely large absolute value of birefringence, and The present invention relates to a norbornene-based ring-opening polymer having a large retardation wavelength dispersion.

In the present specification, the term “birefringence” is used in a normal sense. Further, the value of birefringence (this is assumed to be Δn) is a stretched film obtained by uniaxially stretching a film formed from a polymer and orienting polymer molecular chains in one direction. This plane perpendicular to the y-axis with respect to the refractive index of the x-axis direction n _x, the refractive index in the y-axis direction as n _y, the following formula:
Δn = n _x -n _y
The absolute value varies depending on the wavelength of incident light.
The positive (or negative) birefringence means the property of the molded article when Δn is positive (or negative).

Next, the phase difference (Retardation, which is referred to as Re) is the following formula:
Re = Δn × d
(Where d is the optical path length of the transmitted light, and is usually the thickness of the stretched film)
The absolute value varies depending on the wavelength of incident light.
The wavelength dispersion of the phase difference means the correlation between the Re value and the wavelength of incident light. In addition, “the wavelength dispersion of the phase difference is large” means that the difference between the absolute value of Re for short-wavelength incident light and the absolute value of Re for long-wavelength incident light is large.

  Conventionally, transparent resin has been used as a transparent material that is usually required in the fields of automobile parts, lighting equipment, electrical parts, and the like, and particularly recently as an optical material that requires high optical properties. Applications are also being considered. As general transparent resins used for such applications, acrylic resins and polycarbonate resins are known. However, these resins do not sufficiently satisfy all the properties of transparency, heat resistance and water resistance. In contrast, a large number of cyclic olefin resins having excellent transparency, water resistance and heat resistance and low birefringence have been proposed as transparent resins for various optical materials. Polarizing plate protective films, transparent conductive substrates It is actually used as a retardation film or the like (see Patent Documents 1 to 9).

  A cyclic olefin-based resin obtained by ring-opening polymerization of a norbornene-based monomer having an aromatic carbonyloxy group bonded to a ring, and hydrogenating an olefinically unsaturated bond as necessary; There has also been proposed one having a characteristic that the absolute value of birefringence increases as the wavelength of incident light increases (see Patent Documents 10 and 11).

  However, with the advancement of functions of optical instruments and the widespread use, there are cases where optical properties such as the absolute value of birefringence is particularly large and the wavelength dispersion of retardation is actively used. The conventional cyclic olefin resin is difficult to cope with. In addition to this, development of resins having more various optical characteristics such as positive / negative of birefringence value, magnitude of absolute value thereof, and magnitude of wavelength dispersion of phase difference is desired in response to various demands. .

Japanese Patent Laid-Open No. 1-132625 JP-A-1-132626 JP-A-2-133413 JP-A-4-245202 JP-A-5-2108 Japanese Patent Laid-Open No. 5-64865 Japanese Patent Laid-Open No. 5-212828 JP-A-6-511117 JP-A-7-77608 JP 2003-255102 A JP 2003-321535 A

  The present invention is a norbornene-based ring-opening polymer having excellent transparency, water resistance (low water absorption) and heat resistance, exhibiting positive birefringence, particularly having an extremely large absolute value of birefringence, and An object of the present invention is to provide a norbornene-based ring-opening polymer having a large wavelength difference in retardation.

As a result of intensive studies to achieve the above object, the inventors of the present invention are alicyclic unsaturated compounds having a norbornene-based skeleton, in which the aromatic oxy group is an ethylene group (—CH ₂ CH ₂ —). A polymer obtained by ring-opening polymerization of a monomer having a structure bonded to a ring via an alkylene group-oxycarbonyl group, etc., shows an extremely large absolute value of birefringence, The present invention has been completed based on the findings.
That is, the present invention provides the following general formula (1):

（１）
［式中、ａは０〜２の整数であり、Ｘは式：−ＣＨ＝ＣＨ−で表される基または式：−ＣＨ₂ＣＨ₂−で表される基であり、Ｒ¹〜Ｒ⁶は、独立に、水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子もしくはケイ素原子を含む連結基を有してもよい、置換もしくは非置換の炭素原子数１〜30の炭化水素基；または極性基を表し、但し、Ｒ³〜Ｒ⁶の少なくとも１つは下記一般式（１−１）で表される芳香環を有する基および一般式（１−２）で表される芳香環を有する基からなる群から選ばれる基である。]
で表される構造単位（１）を有し、複数存在するＸは同一または異なるノルボルネン系開環重合体を提供する。

(1)
[Wherein, a is an integer of 0 to 2, X is a group represented by the formula: —CH═CH— or a group represented by the formula: —CH ₂ CH ₂ —, and R ^{1 to} R ^6] Are independently a hydrogen atom; a halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, which may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom; or Represents a polar group, provided that at least one of R ^{3 to} R ⁶ has a group having an aromatic ring represented by the following general formula (1-1) and an aromatic ring represented by the general formula (1-2) It is a group selected from the group consisting of groups. ]
And a plurality of Xs present the same or different norbornene-based ring-opening polymers.

（１−１）
［式中、Ｒ⁷〜Ｒ¹⁵は、独立に、水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子またはケイ素原子を含む連結基を有してもよい、置換または非置換の炭素原子数１〜30の炭化水素基；または極性基を表し、ｂは１〜10の整数であり、ｃおよびｄは独立に０〜３の整数であり、但し、ｃ＝ｄ＝０の場合は、Ｒ⁸とＲ¹¹、および／またはＲ¹⁵とＲ¹¹は相互に結合して炭素環または複素環（これらの炭素環または複素環は単環構造でもよいし、他の環が縮合して多環構造を形成してもよい。）を形成してもよい。］

(1-1)
[Wherein R ^{7 to} R ¹⁵ independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon atom that may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom. Represents a hydrocarbon group of 1 to 30; or a polar group, b is an integer of 1 to 10, c and d are independently an integer of 0 to 3, provided that when c = d = 0, R ⁸ and R ¹¹ , and / or R ¹⁵ and R ¹¹ are bonded to each other to form a carbocyclic or heterocyclic ring (these carbocyclic or heterocyclic rings may have a monocyclic structure, or other rings may be condensed to form a polycyclic structure. May be formed). ]

（１−２）
［式中、Ｒ¹⁶〜Ｒ²⁴は、独立に、水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子またはケイ素原子を含む連結基を有してもよい、置換または非置換の炭素原子数１〜30の炭化水素基；または極性基を表し、ｅは１〜10の整数であり、ｆは０〜３の整数である。］

(1-2)
[Wherein, R ^{16 to} R ²⁴ independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon atom which may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. 1 to 30 hydrocarbon group; or a polar group, e is an integer of 1 to 10, and f is an integer of 0 to 3. ]

  The ring-opening polymer of the present invention is excellent in transparency, water resistance and heat resistance, exhibits positive birefringence, particularly has an extremely large absolute value of birefringence and a large wavelength dispersion of retardation. is there. And the said absolute value and wavelength dispersion can be adjusted by setting the kind of monomer to be used, a copolymerization ratio, etc.

  Further, by combining the ring-opening polymer of the present invention with another type of transparent resin, for example, a cyclic olefin polymer exhibiting negative birefringence, and setting its composition, desired birefringence and retardation can be set. It is possible to obtain a composition having a wavelength dispersibility of. Therefore, it is particularly useful for obtaining optical films, optical components, etc. that actively utilize birefringence. For example, optical disks, magneto-optical disks, optical lenses (fθ lenses, pickup lenses, laser printer lenses, camera lenses, etc. Etc.), eyeglass lens, optical film (display film, retardation film, polarizing film, transparent conductive film, optical pickup film, etc.), liquid crystal alignment film, optical sheet, optical fiber, light guide plate, light diffusion plate, optical card, light It can be suitably used as a material such as a mirror, or a sealing material for IC, LSI or LED.

Hereinafter, the present invention will be specifically described.
<Norbornene-based ring-opening polymer>
The norbornene-based ring-opening polymer of the present invention contains the structural unit (1) as an essential structural unit, and if necessary, the following general formula (2):

（２）
［式中、ｇおよびｈは独立に０または１であり、但し、これらの少なくとも一方は１であり、ｉおよびｊは独立に０〜２の整数であり、Ｙは式：−ＣＨ＝ＣＨ−で表される基または式：−ＣＨ₂ＣＨ₂−で表される基であり、Ｒ²⁵〜Ｒ³⁴は、独立に、水素原子；ハロゲン原子；前記一般式（１−１）で表される芳香環を有する基および一般式（１−２）で表される芳香環を有する基以外の、酸素原子、硫黄原子、窒素原子もしくはケイ素原子を含む連結基を有してもよい、置換もしくは非置換の炭素原子数１〜30の炭化水素基；または極性基を表し、Ｒ³¹とＲ³²、および／またはＲ³³とＲ³⁴は一体化して２価炭化水素基を形成してもよく、Ｒ³¹またはＲ³²と、Ｒ³³またはＲ³⁴とは相互に結合して炭素環または複素環（これらの炭素環または複素環は単環構造でもよいし、他の環が縮合して多環構造を形成してもよい。）を形成してもよい。]
で表される構造単位（２）を有していてもよいし、前記構造単位（２）以外の構造単位を更に有していてもよい。

(2)
[Wherein g and h are independently 0 or 1, provided that at least one of them is 1, i and j are each independently an integer of 0 to 2, and Y is a formula: —CH═CH— Or a group represented by the formula: —CH ₂ CH ₂ —, wherein R ^{25 to} R ³⁴ are independently a hydrogen atom; a halogen atom; represented by the general formula (1-1). Other than the group having an aromatic ring and the group having an aromatic ring represented by formula (1-2), it may have a linking group containing an oxygen atom, sulfur atom, nitrogen atom or silicon atom, substituted or non-substituted A substituted hydrocarbon group having 1 to 30 carbon atoms; or a polar group, R ³¹ and R ³² , and / or R ³³ and R ³⁴ may be combined to form a divalent hydrocarbon group; ³¹ or R ³² and R ³³ or R ³⁴ are bonded to each other to form a carbocyclic or heterocyclic ring (these carbocyclic or heterocyclic rings). The prime ring may be a monocyclic structure, or other rings may be condensed to form a polycyclic structure. ]
Or a structural unit other than the structural unit (2).

In general formula (1), general formula (1-1), general formula (1-2), and general formula (2), a halogen atom represented by R ^{1 to} R ³⁴ ; an oxygen atom, a nitrogen atom, a sulfur atom Alternatively, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing a silicon atom; and a polar group will be described.
As a halogen atom, a fluorine atom, a chlorine atom, and a bromine atom are mentioned, for example.

Examples of the hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as methyl group, ethyl group and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group and allyl group; Group, alkylidene group such as propylidene group; aryl group such as phenyl group, naphthyl group, anthracenyl group; formula: — (CH ₂ ) m—R ′ (wherein R ′ is the cycloalkyl group or the aryl group) , M is an integer of 1 to 10), for example, aralkyl groups such as benzyl group and 2-phenylethyl group, and the like. A hydrogen atom bonded to a carbon atom in these groups may be substituted with, for example, a halogen atom such as fluorine, chlorine or bromine; a phenylsulfonyl group; a cyano group or the like.

The substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure, or may be bonded to the ring structure via a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom. Good. The linking group may include one or more of oxygen atom, nitrogen atom, sulfur atom, and silicon atom. Examples of the linking group include a carbonyl group (—CO—); a carbonyloxy group (—COO—), an oxycarbonyl group (—OCO—); a sulfonyl group (—SO ₂ —); a sulfonyloxy group (—SO ₂ ). O—); oxysulfonyl group (—OSO ₂ —); ether bond (—O—); thioether bond (—S—); imino group (—NH—), amide bond (—NHCO—, —CONH—); Formula: —Si (R) ₂ —, Formula: —Si (OR) ₂ O—, Formula: —OSi (R) ₂ —, or Formula: —OSi (OR) ₂ — (wherein R is carbon A bond containing a silicon atom represented by a hydrocarbon group having 1 to 10 atoms, preferably an alkyl group such as a methyl group or an ethyl group; or a combination of two or more of these Things.

  Examples of the structure in which the substituted or unsubstituted hydrocarbon group is bonded to the ring structure through the linking group include, for example, an alkoxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyloxy Group, arylcarbonyloxy group, triorganosilyl group, triorganosiloxy group and the like.

  More specifically, examples of the alkoxy group include a methoxy group and an ethoxy group; examples of the acyl group include an acetyl group and a benzoyl group; examples of the alkylcarbonyloxy group include: An acetoxy group, a propionyloxy group, and the like; examples of the arylcarbonyloxy group include a benzoyloxy group; examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and the like; Examples of the carbonyl group include a phenoxycarbonyl group, a naphthyloxycarbonyl group, a fluorenyloxycarbonyl group, a biphenylyloxycarbonyl group, and the like; examples of the triorganosiloxy group include a trimethylsiloxy group and a triethylsiloxy group. And trialkoxysiloxy groups such as trimethoxysiloxy group and triethoxysiloxy group; examples of the triorganosilyl group include trialkylsilyl groups such as trimethylsilyl group and triethylsilyl group; Examples include trialkoxysilyl groups such as silyl groups and triethoxysilyl groups.

Next, examples of the polar group include a hydroxyl group; a cyano group; an amide group; an imino group (═NH); an amino group such as a primary amino group (—NH ₂ ); a sulfonic acid group (—SO ₃ H); And sulfino group (—SO ₂ H); carboxyl group (—COOH) and the like.

  The norbornene-based ring-opening polymer of the present invention has the following general formula (3):

（３）
[式中、ａおよびＲ¹〜Ｒ⁶は、前記一般式（１）に関して定義のとおりである。]
で表されるノルボルネン系単量体（以下、「単量体（１）」という。）を、必要に応じて、下記一般式（４）：

(3)
[Wherein, a and R ^{1 to} R ⁶ are as defined in relation to the general formula (1). ]
A norbornene monomer represented by the following (hereinafter referred to as “monomer (1)”) is optionally represented by the following general formula (4):

（４）
[式中、ｇ、ｈ、ｉ、ｊおよびＲ²⁵〜Ｒ³⁴は、前記一般式（２）に関して定義のとおりである。]
で表されるノルボルネン系単量体（以下、「単量体（２）」という。）とともに、更に必要に応じて前記単量体（２）と他の共重合可能な単量体とともに、開環重合もしくは共重合し、次いで必要に応じて上記構造単位中の式：−ＣＨ＝ＣＨ−で表されるオレフィン性不飽和結合を水素添加することにより得ることができる。

(4)
[Wherein, g, h, i, j and R ^{25 to} R ³⁴ are as defined for the general formula (2). ]
In addition to the norbornene-based monomer represented by (hereinafter referred to as “monomer (2)”), the monomer (2) and other copolymerizable monomers as necessary. It can be obtained by ring polymerization or copolymerization, and then hydrogenating an olefinically unsaturated bond represented by the formula: —CH═CH— in the structural unit, if necessary.

  Hereinafter, unless otherwise specified, a ring-opening polymer of the monomer (1), a copolymer of the monomer (1) and the monomer (2), etc., and hydrogenated products thereof are used. They are collectively referred to as “norbornene-based ring-opening polymers” without distinction.

<Monomer (1)>
As said monomer (1), since the manufacture is easy,
(A) Only one of R ^{3 to} R ^{6 in} the general formula (3) is a group having an aromatic ring represented by the general formula (1-1), or the general formula (1) -2), and (B) b in the group having an aromatic ring represented by the above general formula (1-1), and the above general formula (1-2). E in the group having an aromatic ring represented, or b and e are 2,
Of these, those satisfying at least one requirement are preferred, and those satisfying both of these requirements are more preferred.

  Specific examples of the monomer (1) are shown below, but are not limited to these specific examples.

２−(ナフタレン−１−イルオキシ)−エチル ５−メチル−ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

2- (Naphthalen-1-yloxy) -ethyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate

２−(ナフタレン−１−イルオキシ)−エチル ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

2- (Naphthalen-1-yloxy) -ethyl bicyclo [2.2.1] hept-2-ene-5-carboxylate

２−(ナフタレン−２−イルオキシ)−エチル ５−メチル−ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

2- (Naphthalen-2-yloxy) -ethyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate

２−(ナフタレン−2−イルオキシ)−エチル ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

2- (Naphthalen-2-yloxy) -ethyl bicyclo [2.2.1] hept-2-ene-5-carboxylate

２−(ビフェニル−４−イルオキシ)−エチル ５−メチル−ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

2- (Biphenyl-4-yloxy) -ethyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate

２−(ビフェニル−４−イルオキシ)−エチル ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

2- (Biphenyl-4-yloxy) -ethyl bicyclo [2.2.1] hept-2-ene-5-carboxylate

２−(ビフェニル−２−イルオキシ)−エチル ５−メチル−ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

2- (Biphenyl-2-yloxy) -ethyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate

２−(ビフェニル−２−イルオキシ)−エチル ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

2- (Biphenyl-2-yloxy) -ethyl bicyclo [2.2.1] hept-2-ene-5-carboxylate

２−[４−(１−メチル−１−フェニルエチル)−フェニルオキシ]−エチル ５−メチル−ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

2- [4- (1-Methyl-1-phenylethyl) -phenyloxy] -ethyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate

２−[４−(１−メチル−１−フェニルエチル)−フェニルオキシ]−エチル ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

2- [4- (1-Methyl-1-phenylethyl) -phenyloxy] -ethyl bicyclo [2.2.1] hept-2-ene-5-carboxylate

２−(９Ｈ−フルオレン−９−イルオキシ)−エチル ５−メチル−ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

2- (9H-Fluoren-9-yloxy) -ethyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate

２−(９Ｈ−フルオレン−９−イルオキシ)−エチル ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

2- (9H-Fluoren-9-yloxy) -ethyl bicyclo [2.2.1] hept-2-ene-5-carboxylate

２−(９−メチルフルオレン−９−イルオキシ)−エチル ５−メチル−ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

2- (9-Methylfluoren-9-yloxy) -ethyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate

２−(９−メチルフルオレン−９−イルオキシ)−エチル ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

2- (9-Methylfluoren-9-yloxy) -ethyl bicyclo [2.2.1] hept-2-ene-5-carboxylate

２−(アントラセン−９−イルオキシ)−エチル ５−メチル−ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

2- (Anthracen-9-yloxy) -ethyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate

２−(アントラセン−９−イルオキシ)−エチル ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

2- (Anthracen-9-yloxy) -ethyl bicyclo [2.2.1] hept-2-ene-5-carboxylate

２−(ナフタレン−１−イルオキシ)−エチル ８−メチル−テトラシクロ[４.４.０.１^2,5.１^7,10]−３−ドデセン−８−カルボキシレート

2- (naphthalen-1-yloxy) - ethyl 8-methyl - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 8-carboxylate

２−(ナフタレン−１−イルオキシ)−エチル テトラシクロ[４.４.０.１^2,5.１^7,10]−３−ドデセン−８−カルボキシレート

2- (naphthalen-1-yloxy) - ethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 8-carboxylate

２−(ナフタレン−２−イルオキシ)−エチル ８−メチル−テトラシクロ[４.４.０.１^2,5.１^7,10]−３−ドデセン−８−カルボキシレート

2- (naphthalen-2-yloxy) - ethyl 8-methyl - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 8-carboxylate

２−(ナフタレン−２−イルオキシ)−エチル テトラシクロ[４.４.０.１^2,5.１^7,10]−３−ドデセン−８−カルボキシレート

2- (naphthalen-2-yloxy) - ethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 8-carboxylate

２−[４−(１−メチル−１−フェニルエチル)−フェニルオキシ]−エチル ８−メチル−テトラシクロ[４.４.０.１^2,5.１^7,10]−３−ドデセン−８−カルボキシレート

2- [4- (1-methyl-1-phenylethyl) - phenyloxy] - ethyl 8-methyl - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 8- Carboxylate

２−[４−(１−メチル−１−フェニルエチル)−フェニルオキシ]−エチル テトラシクロ[４.４.０.１^2,5.１^7,10]−３−ドデセン−８−カルボキシレート

2- [4- (1-methyl-1-phenylethyl) - phenyloxy] - ethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 8-carboxylate

２−(ビフェニル−４−イルオキシ)−エチル ８−メチル−テトラシクロ[４.４.０.１^2,5.１^7,10]−３−ドデセン−８−カルボキシレート

2- (biphenyl-4-yloxy) - ethyl 8-methyl - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 8-carboxylate

２−(ビフェニル−４−イルオキシ)−エチル テトラシクロ[４.４.０.１^2,5.１^7,10]−３−ドデセン−８−カルボキシレート

2- (biphenyl-4-yloxy) - ethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 8-carboxylate

２−(９Ｈ−フルオレン−９−イルオキシ)−エチル ８−メチル−テトラシクロ[４.４.０.１^2,5.１^7,10]−３−ドデセン−８−カルボキシレート

2-(9H-fluoren-9-yloxy) - ethyl 8-methyl - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 8-carboxylate

２−(９Ｈ−フルオレン−９−イルオキシ)−エチル テトラシクロ[４.４.０.１^2,5.１^7,10]−３−ドデセン−８−カルボキシレート

2-(9H-fluoren-9-yloxy) - ethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 8-carboxylate

２−(９−メチルフルオレン−９−イルオキシ)−エチル ８−メチル−テトラシクロ[４.４.０.１^2,5.１^7,10]−３−ドデセン−８−カルボキシレート

2- (9-methyl-9-yloxy) - ethyl 8-methyl - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 8-carboxylate

２−(９−メチルフルオレン−９−イルオキシ)−エチル テトラシクロ[４.４.０.１^2,5.１^7,10]−３−ドデセン−８−カルボキシレート

2- (9-methyl-9-yloxy) - ethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 8-carboxylate

２−(アントラセン−９−イルオキシ)−エチル ８−メチル−テトラシクロ[４.４.０.１^2,5.１^7,10]−３−ドデセン−８−カルボキシレート

2- (anthracene-9-yloxy) - ethyl 8-methyl - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 8-carboxylate

２−(アントラセン−９−イルオキシ)−エチル テトラシクロ[４.４.０.１^2,5.１^7,10]−３−ドデセン−８−カルボキシレート

2- (anthracene-9-yloxy) - ethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 8-carboxylate

ナフタレン−２−イルオキシメチル ５−メチル−ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

Naphthalen-2-yloxymethyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate

ナフタレン−２−イルオキシメチル ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

Naphthalen-2-yloxymethyl bicyclo [2.2.1] hept-2-ene-5-carboxylate

ナフタレン−１−イルオキシメチル ５−メチル−ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

Naphthalen-1-yloxymethyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate

ナフタレン−１−イルオキシメチル ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

Naphthalen-1-yloxymethyl bicyclo [2.2.1] hept-2-ene-5-carboxylate

ビフェニル−４−イルオキシメチル ５−メチル−ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

Biphenyl-4-yloxymethyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate

ビフェニル−４−イルオキシメチル ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

Biphenyl-4-yloxymethyl bicyclo [2.2.1] hept-2-ene-5-carboxylate

４−(１−メチル−１−フェニルエチル)−フェノキシ−メチル ５−メチル−ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

4- (1-Methyl-1-phenylethyl) -phenoxy-methyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate

４−(１−メチル−１−フェニルエチル)−フェノキシ−メチル ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

4- (1-Methyl-1-phenylethyl) -phenoxy-methyl bicyclo [2.2.1] hept-2-ene-5-carboxylate

３−(ナフタレン−２−イルオキシ)−プロピル ５−メチル−ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

3- (Naphthalen-2-yloxy) -propyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate

３−(ナフタレン−２−イルオキシ)−プロピル ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

3- (Naphthalen-2-yloxy) -propyl bicyclo [2.2.1] hept-2-ene-5-carboxylate

３−(ナフタレン−１−イルオキシ)−プロピル ５−メチル−ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

3- (Naphthalen-1-yloxy) -propyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate

３−(ナフタレン−１−イルオキシ)−プロピル ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

3- (Naphthalen-1-yloxy) -propyl bicyclo [2.2.1] hept-2-ene-5-carboxylate

３−(ビフェニル−４−イルオキシ)−プロピル ５−メチル−ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

3- (Biphenyl-4-yloxy) -propyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate

３−(ビフェニル−４−イルオキシ)−プロピル ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

3- (Biphenyl-4-yloxy) -propyl bicyclo [2.2.1] hept-2-ene-5-carboxylate

３−[４−(１−メチル−１−フェニルエチル)−フェノキシ]−プロピル ５−メチル−ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

3- [4- (1-Methyl-1-phenylethyl) -phenoxy] -propyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate

３−[４−(１−メチル−１−フェニルエチル)−フェノキシ]−プロピル ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート

3- [4- (1-Methyl-1-phenylethyl) -phenoxy] -propyl bicyclo [2.2.1] hept-2-ene-5-carboxylate

  The monomer (1) can be used alone or in combination of two or more.

<Monomer (2)>
Among the monomers (2) represented by the general formula (4), it is possible to improve the balance of solubility of the obtained polymer, adhesion to other types of substrates, adhesion, and the like. In the general formula (4), at least one of R ^{31 to} R ³⁴ has the formula: — (CH ₂ ) _n COOR ³⁵ (where R ³⁵ represents a hydrocarbon group having 1 to 20 carbon atoms, n is an integer of 0 to 10).

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ³⁵ include alkyl groups such as methyl group, ethyl group and propyl group, aryl groups such as phenyl group, and aralkyl groups such as benzyl group. It is done. Among them, preferred are a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and a phenyl group, and particularly preferred are a methyl group and an ethyl group.

Specific examples of the monomer (2) including the monomer having a group represented by the above formula: — (CH ₂ ) _n COOR ³⁵ are shown below, but are limited to these specific examples. It is not a thing.

Bicyclo [2.2.1] hept-2-enetricyclo [5.21.0 ^2,6 ] -8-decene tricyclo [5.2.1.0 ^2,6 ] deca-3, 8- diene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 2,10-dimethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene, 2,9-dimethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, pentacyclo [6.5.1.1 ^3,6 .0 ^{2 , 7.0 9, 13]} -4-pentadecene, pentacyclo ^{[7.4.0.1 2,5 .1 8,11 .0 7,12]} -3- pentadecene-tricyclo [4.4.0.1 ^2,5 ] -3-undecene, 7-methyltricyclo [4.4.0.1 ^2,5 ] -3-undecene, 5-methylbicyclo [2.2.1] hept-2-ene, 1- Methylbicyclo [2.2.1] hept-2-ene, 7-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbisi Chlo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept- 2-ene, 5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [ 2.2.1] Hept-2-ene-5-methyl-5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene

· 5- Shianobishikuro [2.2.1] hept-2-ene-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene · 8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] - 3-dodecene-8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^{2 , 5.1 7,10]} -3-dodecene, 8-phenoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] -3-dodecene, 8- (1-naphthoxy) carbonyl tetra cyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8- (2-naphthoxy) carbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-dodecene 8- (4-phenyl) Phenoxy) carbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] -3-dodecene, 8-methyl-8-ethoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] -3-dodecene, 8-methyl -8-n-propoxy carbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-methyl-8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^{7 , 10]} -3-dodecene, 8-methyl -8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-methyl-8-phenoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-methyl-8- (1-naphthoxy) carbonyl tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] 3-dodecene-8-methyl-8- (2-naphthoxy) carbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-methyl-8- (4-phenyl phenoxy) carbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene

- pentacyclo ^{[8.4.0.1 2,5 .1 9,12 .0 8,13]} -3- hexadecene heptacyclo [8.7.0.1 ^3,6 .1 ^10,17 .1 ^{12, 15.0 2,7} .0 ^{11, 16]} -4-eicosene, heptacyclo ^{[8.8.0.1 4,7 .1 11,18 .1 13,16 .0} 3,8 .0 12,17] 5-heneicosene-5-ethylidene bicyclo [2.2.1] hept-2-ene-8-ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 5 -Phenylbicyclo [2.2.1] hept-2-ene · 5-phenyl-5-methylbicyclo [2.2.1] hept-2-ene · 8-phenyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-dodecene, 8-phenyl-8-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-dodecene, 5-n-butyl Bicyclo [2.2.1] hept-2-ene, 5-n-hexylbicyclo [2.2.1] hept-2-ene, 5- Cyclohexylbicyclo [2.2.1] hept-2-ene · 5- (3-cyclohexenyl) bicyclo [2.2.1] hept-2-ene · 5-n-octylbicyclo [2.2.1] Hept-2-ene, 5-n-decylbicyclo [2.2.1] hept-2-ene, 5-isopropylbicyclo [2.2.1] hept-2-ene, 5- (1-naphthyl) bicyclo [2.2.1] Hept-2-ene · 5- (1-naphthyl) -5-methylbicyclo [2.2.1] hept-2-ene · 5- (2-naphthyl) bicyclo [2.2 .1] Hept-2-ene-5- (2-naphthyl) -5-methylbicyclo [2.2.1] hept-2-ene-5- (biphenyl-4-yl) bicyclo [2.2.1 ] Hept-2-ene-5- (biphenyl-4-yl) -5-methylbicyclo [2.2.1] hept-2-ene

5-aminomethylbicyclo [2.2.1] hept-2-ene, 5-trimethoxysilylbicyclo [2.2.1] hept-2-ene, 5-triethoxysilylbicyclo [2.2.1 ] Hept-2-ene, 5-trin-propoxysilylbicyclo [2.2.1] hept-2-ene, 5-trin-butoxysilylbicyclo [2.2.1] hept-2-ene, 5 -Chloromethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5-fluorobicyclo [2.2.1] hept-2- Ene, 5-fluoromethylbicyclo [2.2.1] hept-2-ene, 5-trifluoromethylbicyclo [2.2.1] hept-2-ene, 5-pentafluoroethylbicyclo [2.2. 1] Hept-2-ene, 5,5-difluorobicyclo [2.2.1] hept-2-ene, 5,6-di Fluorobicyclo [2.2.1] hept-2-ene-5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene / 5-bis (trifluoromethyl) bicyclo [2.2.1] Hept-2-ene · 5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene · 5,5,6-trifluorobicyclo [2.2. 1] Hept-2-ene-5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene-5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2. 2.1] Hept-2-ene-5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene

- 8-fluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-fluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene, 8-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-pentafluoroethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-dodecene, 8,8-difluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-dodecene, 8,9-difluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] 3-dodecene-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene-8,8,9- trifluoro tetracyclo [4 .4.0.1 ^2,5 .1, ^7,10 ] -3-dodecene 8,8,9,9-tetra Fluoro tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene-8,8,9,9- tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^{2, 5.1 7,10]} -3-dodecene, 8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] -3-dodecene

Among these, 5-phenylbicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 ^2,6 ] deca- 3,8-diene and 5-ethylidenebicyclo [2.2.1] hept-2-ene are preferred because they are inexpensive and readily available. Furthermore, as a monomer having a group represented by the above formula: — (CH ₂ ) _n COOR ³⁵ , since it can be easily produced, 5-methyl-5-methoxycarbonylbicyclo [2.2.1]. ] Hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-ethoxy Carbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-phenoxycarbonylbicyclo [2.2.1] hept 2-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-methoxycarbonyltetracyclo [4.4.0. 1 ^2,5 .1 ^7,10] -3-dodecene, 8-methyl-8-ethoxycarbonyl Rutetorashikuro [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene , 8-methyl -8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-methyl-8-isopropoxycarbonyl tetracyclo [4.4 .0.1 ^2,5 .1 ^7,10] -3-dodecene, 8-methyl -8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3 dodecene, 8-phenoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-methyl-8-phenoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5.1 7,10]} -3-dodecene is preferable.

Furthermore, since it is possible to improve the heat resistance of the resulting ring-opened norbornene polymer, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3 - dodecene, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-methyl-8-ethoxycarbonyl tetracyclo [4.4.0.1 ^{2 , 5.1 7,10]} -3-dodecene, 8-ethoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] -3-dodecene, 8-methyl -8-n-propoxy carbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-methyl-8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^{7 , 10]} -3-dodecene, 8-methyl -8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene is particularly preferred .
The monomer (2) can be used alone or in combination of two or more.

  Furthermore, as long as the effects of the present invention are not impaired, other copolymerizable monomers that can be used as needed together with the monomer (1) and the monomer (2) include, for example, Examples thereof include cyclic olefins such as cyclobutene, cyclopentene, cyclooctene and cyclododecene; and non-conjugated cyclic polyenes such as 1,4-cyclooctadiene and cyclododecatriene. The copolymerizable monomers can be used singly or in combination of two or more.

  In addition, the ring-opening polymerization is performed by opening a norbornene monomer other than polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-nonconjugated diene polymer, monomer (1), and monomer (2). The reaction may be performed in the presence of an unhydrogenated ring polymer (that is, an unhydrogenated product).

<Monomer usage ratio, etc.>
In the present invention, as described above, the norbornene-based ring-opening polymer is composed of one kind of homopolymer of the monomer (1), two or more kinds of copolymers of the monomer (1), and the single monomer. Any of a copolymer of the body (1) and the monomer (2), etc., or a hydrogenated product of the homopolymer or copolymer may be used. In the case where two or more combinations of the monomers (1) are subjected to ring-opening polymerization, the amount ratio is not particularly limited.

  When the norbornene-based ring-opening polymer of the present invention is a copolymer with the monomer (1), the monomer (2), etc., the use ratio of these monomers, that is, the copolymerization ratio is The obtained copolymer should be appropriately adjusted as necessary so as to exhibit a desired absolute value of birefringence and / or wavelength dispersion of retardation, The proportion of the monomer (1) to the body is usually 2 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more. When the proportion of the monomer (1) is 2 mol% or more, the absolute value of the birefringence and the wavelength dispersion of the retardation of the norbornene ring-opening polymer of the present invention can be easily obtained as desired. It becomes possible to adjust to.

  In addition, when a copolymerizable monomer other than the monomer (1) and the monomer (2) is also used, the ratio of the copolymerizable monomer to the total monomer is Usually, it is preferably 50 mol% or less, more preferably 30 mol% or less, and particularly preferably 20 mol% or less.

<Polymerization>
Hereinafter, the polymerization conditions in the method for producing a norbornene-based ring-opening polymer of the present invention will be further described.
Ring-opening polymerization catalyst Examples of the ring-opening polymerization catalyst used in the present invention include:
(I) A catalyst described in “Olefin Metathesis and Metathesis Polymerization” (KJIVIN, JCMOL, Academic Press 1997) is preferably used. Examples of such a catalyst include (a) at least one selected from compounds of W, Mo, Re, V and Ti, and (b) an alkali metal element (for example, Li, Na, K), alkaline earth. Group metal elements (eg Mg, Ca), Group 12 elements (eg Zn, Cd, Hg), Group 13 elements (eg B, Al), Group 14 elements (eg Si, Sn, Pb) And a metathesis catalyst composed of a combination with at least one selected from those having at least one element-carbon bond or the element-hydrogen bond. This catalyst may be added with an additive (c) described later in order to enhance the catalytic activity.

Specific examples of the component (a) include compounds described in JP-A-1-240517 such as WCl ₆ , MoCl ₅ , ReOCl ₃ , VOCl ₃ , TiCl _{4 and the} like. These can be used singly or in combination of two or more.

Specific examples of the component (b) include, for example, n-C ₄ H ₉ Li, (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , ( Examples thereof include compounds described in JP-A-1-240517 such as C ₂ H ₅ ) AlCl ₂ , methylalumoxane (MAO), and LiH. These can be used singly or in combination of two or more.

  As the additive of the component (c), for example, alcohols, aldehydes, ketones, amines and the like can be suitably used, and further, compounds described in JP-A-1-240517 can be used. it can. These can be used singly or in combination of two or more.

The amount of the metathesis catalyst used in combination with the component (a) is such that the component (a) and all monomers (monomer (1), monomer (2) and other copolymerizable monomers are used. The molar ratio of “(a) component: all monomers” is usually in the range of 1: 500 to 1: 500,000, preferably 1: 1,000 to 1: 100,000. It is a range. Further, the ratio of the component (a) to the component (b) is such that the metal atom (mole) ratio of “(a) :( b)” is usually 1: 1 to 1:50, preferably 1: 2. It is in the range of ˜1: 30. When the additive (c) is added to this metathesis catalyst, the ratio of the component (a) to the component (c) is usually such that the molar ratio of “(c) :( a)” is 0.005: 1-15. : 1, preferably in the range of 0.05: 1 to 7: 1.

As other catalysts,
(II) A metathesis catalyst composed of a transition metal-carbene complex or a metallacyclobutane complex of Groups 4 to 8 of the periodic table can be used. Specific examples of the catalyst (II), W (= N -2,6-C 6 H 3 i Pr 2) (= CH t Bu) (O t Bu) 2, Mo (= N-2,6- ^{_{C 6 H 3 i Pr 2)}} (= CH t Bu) (O t Bu) 2, Ru (= CHCH = CPh 2) (PPh 3) 2 Cl 2, Ru (= CHPh) (PC 6 H 11) 2 Cl ₂ etc. are mentioned. These can be used singly or in combination of two or more.

  The amount of the catalyst (II) used is such that the molar ratio of “catalyst (II): total monomer” is usually in the range of 1:50 to 1: 50,000, preferably 1: 100 to 1: 10,000. It is a range. The catalysts (I) and (II) may be used in combination.

-Molecular weight regulator The molecular weight of the ring-opening polymer can be adjusted by adjusting the polymerization temperature, the type of catalyst, the type of solvent, etc., but in the present invention, the molecular weight regulator coexists in the reaction system. It is preferable to adjust by adjusting. Examples of the molecular weight regulator include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene, and styrene, 4 -Vinyl aromatic compounds such as vinylbiphenyl, 1-vinylnaphthalene and 2-vinylnaphthalene are preferred, and among these, 1-butene and 1-hexene are particularly preferred. These molecular weight regulators can be used singly or in combination of two or more. The amount of the molecular weight regulator used is usually 0.001 to 0.6 mol, preferably 0.02 to 0.5 mol, per mol of all monomers.

-Solvent for ring-opening polymerization reaction As a solvent used in the ring-opening polymerization reaction (that is, a solvent that dissolves a monomer, a metathesis catalyst, a molecular weight regulator, etc.), for example, pentane, hexane, heptane, octane, nonane, decane Alkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane, etc .; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene Halogenated alkanes such as dibromide, chloroform and tetrachloroethylene; aryl halides such as chlorobenzene; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate and methyl propionate; dimethoxyethane, dibuty Ether, tetrahydrofuran and the like. Among these, aromatic hydrocarbons are preferred. These can be used alone or in combination of two or more. The amount of the solvent used for the ring-opening polymerization reaction is such that the weight ratio of “solvent: total monomer” is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1. Is the amount.

<Hydrogenation reaction>
In the norbornene-based ring-opening polymer obtained by the above ring-opening polymerization, X in the structural unit (1) and Y in the structural unit (2) optionally contained are represented by the formula: —CH═CH—. It has an olefinically unsaturated group structure. This ring-opening polymer can be used as it is.

In order to further improve the heat resistance stability of the ring-opening polymer, further reduce the burning (coloring) / gel generated when the polymer is processed into a molded body, and to improve the weather resistance of the resulting molded body, The olefinically unsaturated group is preferably hydrogenated and converted to a group represented by the formula: —CH ₂ CH ₂ — to obtain a hydrogenated product of a ring-opening polymer. However, the hydrogenated product as used in the present invention is limited to those in which the olefinically unsaturated group is hydrogenated, and the monomer (1), monomer ( It is particularly preferable that the intracyclic conjugated double bond in an aromatic ring skeleton such as a benzene ring derived from the structure 2) is not substantially hydrogenated.

It should be noted that the hydrogenation rate (that is, X when the ring-opening polymer has the structural unit (1) and no structural unit (2), and the ring-opening polymer has the structural unit (1) and the structural unit ( 2), the ratio of X and Y being converted into a group represented by the formula: —CH ₂ CH ₂ —) is a plurality of the above X or the total of X and Y It is at least mol%, preferably at least 60 mol%, more preferably at least 90 mol%. A higher hydrogenation rate is preferable because coloration and deterioration under high temperature conditions are suppressed.

  The hydrogenation reaction needs to be carried out under the condition that the intracyclic conjugated double bond in the aromatic ring skeleton is not substantially hydrogenated. For example, a hydrogenation reaction catalyst is added to the ring-opening polymer solution, and hydrogen gas at atmospheric pressure to 30 MPa, preferably 3 to 20 MPa is usually added thereto, and usually 0 to 220 ° C., preferably 20 to 20 ° C. It is carried out by reacting at 200 ° C.

  As the hydrogenation reaction catalyst, those used for the usual hydrogenation reaction of olefinic compounds can be used, and heterogeneous catalysts and homogeneous catalysts are known. Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, or ruthenium is supported on a carrier such as carbon, silica, alumina, or titania. Examples of homogeneous catalysts include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium. Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, and the like. The form of these catalysts may be powdery or granular. Further, the hydrogenation reaction catalyst can be used alone or in combination of two or more.

These hydrogenation reaction catalysts need to be adjusted in the amount of addition so that the intraconjugated conjugated double bond in the aromatic ring skeleton is not substantially hydrogenated. The weight ratio of the “addition reaction catalyst” is usually used at a ratio of 1: 1 × 10 ⁻⁶ to 1: 2.

  The norbornene-based ring-opening polymer of the present invention or its hydrogenated product is an Ubbelohde viscometer, and the intrinsic viscosity [η] measured in chloroform is usually 0.2 to 5.0, preferably 0.3 to 4.0, more preferably 0.35 to 2.0. Further, in the molecular weight measurement by gel permeation chromatography (GPC, tetrahydrofuran solvent, polystyrene conversion), the number average molecular weight (Mn) of the ring-opening polymer is usually 1,000 to 500,000, preferably 2,000 to 300,000, more preferably The weight average molecular weight (Mw) is usually 5,000 to 2,000,000, preferably 10,000 to 1,000,000, and more preferably 20,000 to 500,000.

When the intrinsic viscosity [η] is less than 0.2, the number average molecular weight (Mn) is less than 1,000, or the weight average molecular weight (Mw) is less than 5,000, the norbornene-based ring-opening polymer of the present invention In some cases, the strength of the resulting molded product is significantly reduced. On the other hand, when the intrinsic viscosity [η] is 5.0 or more, the number average molecular weight (Mn) is 500,000 or more, or the weight average molecular weight (Mw) is 2,000,000 or more, the melt viscosity of the ring-opening polymer or The solution viscosity becomes too high, and it may be difficult to obtain a desired molded product.

  Various known additives can be added to the norbornene-based ring-opening polymer of the present invention. Examples of the additive include 2,6-di-t-butyl-4-methylphenol, 2,2′-methylenebis (4-ethyl-6-t-butylphenol), 2,5-di-t-butyl. Hydroquinone, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis- (6-tert-butyl-3-methylphenol), 1, 1-bis (4-hydroxyphenyl) cyclohexane, octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,3 ', 3 ", 5,5', 5" -hexa Phenolic and hydroquinone antioxidants such as -t-butyl-a, a ', a "-(mesitylene-2,4,6-triyl) tri-p-cresol; tris (4-methoxy-3,5- Diphenyl) phosphite, tris ( And phosphorous antioxidants such as Nylphenyl) phosphite, Tris (2,4-di-t-butylphenyl) phosphite, etc. By adding one or more of these antioxidants, The oxidation degradation resistance of the ring polymer can be improved.

  Further, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzo Light resistance can also be improved by adding an ultraviolet absorber such as triazol-2-yl) phenol]]. Furthermore, in addition to a lubricant for improving processability, known additives such as a flame retardant, an antibacterial agent, a petroleum resin, a plasticizer, a colorant, a release agent, and a foaming agent can be added as necessary. These additives can be used singly or in combination of two or more.

  The norbornene-based ring-opening polymer of the present invention can be obtained, for example, by setting the structure / kind of the substituent and the copolymerization ratio of the monomer (1) (and the monomer (2)). It is possible to adjust the absolute value of birefringence and the wavelength dispersion of the retardation of a combined film or the like. Also, by properly blending the norbornene-based ring-opening polymer of the present invention with a known cyclic olefin-based resin or the like, the birefringence value of the polymer film or the like formed from the obtained resin composition can be positive or negative. The absolute value of refraction and the wavelength dispersion of the phase difference can be adjusted.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to a following example. Hereinafter, unless otherwise specified, “part” means part by weight, “%” means weight%, and “room temperature” means 25 ° C.

  Various measurements, evaluations, and the like described in Examples and Comparative Examples were performed as follows.

<Measurement and evaluation method>
1. Glass transition temperature (Tg)
Using a differential scanning calorimeter (manufactured by Seiko Instruments Inc., trade name: DSC6200), measurement was performed under a nitrogen stream under a temperature increase rate of 20 ° C./min.

2. Weight average molecular weight and molecular weight distribution Gel permeation chromatography (GPC, manufactured by Tosoh Corporation, trade name: HLC-8020 / four columns: manufactured by Tosoh Corporation, trade name: TSK gel G7000HxL, TSK gel GMHxL, TSK gel GMHxL, TSK gel G2000xL), tetrahydrofuran (THF) as a solvent, and polystyrene-equivalent weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured. The Mn is a number average molecular weight.

3. Polymer molecular structure ¹ H-NMR was measured in deuterated chloroform using a superconducting nuclear magnetic resonance absorber (NMR, manufactured by Bruker, trade name: AVANCE500). Furthermore, an infrared absorption (IR) spectrum was measured using an infrared spectrophotometer (IR, manufactured by JASCO Corporation, trade name: FT / IR-420). From the obtained data, the hydrogenation rate was calculated and the molecular structure was identified.

4). Evaluation of retardation and birefringence A methylene chloride solution (concentration: 25%) of the ring-opening polymer obtained in each of the following examples and comparative examples was cast on a glass plate having a smooth surface and dried to obtain a residual solvent of 0.5 % Or less film was made. The obtained film was uniaxially stretched 2.0 times at a temperature described in each of the following Examples and Comparative Examples using a tensile testing machine with a thermostatic bath (manufactured by Instron, MODEL5567 type). Using this stretched film as a sample, the retardation (Re) in the wavelength range of 400 to 800 nm was continuously measured using a retardation measuring instrument (trade name: KOBRA21DH, manufactured by Oji Scientific Co., Ltd.).

Measurement wavelength: Phase difference values at 400 nm, 550 nm, and 800 nm (respectively, Re400, Re550, and Re800) were obtained. Next, Re550 was divided by the film thickness (d) to obtain a birefringence value (Δn550) at a measurement wavelength of 550 nm.
Moreover, the value of the ratio of Re400 / Re550 and the value of the ratio of Re800 / Re550 were determined. Further, the difference between the value of (Re400 / Re550) and the value of (Re800 / Re550) was calculated, and the absolute value (| (Re800 / Re550)-(Re400 / Re550) |) was obtained.
Table 1 shows the values of Δn550 (× 10 ⁻⁴ ), Re400 / Re550, Re800 / Re550, and | (Re800 / Re550) − (Re400 / Re550) |.

[Synthesis Example 1]
<Synthesis of 2- (naphthalen-2-yloxy) -ethyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate>

エチレンカーボネート 110ｇ（1.25mol）と２−ナフトール 90ｇ（0.624mol）をフラスコに仕込み、系内を窒素置換した後、オイルバス中、195℃で1.5時間加熱して反応させた。反応物を冷却した後、240mLのエタノールで希釈し、これを３Ｎ水酸化ナトリウム氷冷水溶液900mL中に投入した。得られた沈殿物をろ過し、冷水でよく洗浄した後、トルエン中で結晶化させて、２−(２−ヒドロキシエチルオキシ)ナフタレン 111.6ｇを得た。

A flask was charged with 110 g (1.25 mol) of ethylene carbonate and 90 g (0.624 mol) of 2-naphthol, and the system was purged with nitrogen, and then reacted by heating at 195 ° C. for 1.5 hours in an oil bath. After the reaction was cooled, it was diluted with 240 mL of ethanol and poured into 900 mL of 3N sodium hydroxide ice-cold aqueous solution. The obtained precipitate was filtered, washed well with cold water, and then crystallized in toluene to obtain 111.6 g of 2- (2-hydroxyethyloxy) naphthalene.

  Next, 109 g (0.578 mol) of 2- (2-hydroxyethyloxy) naphthalene and 48 g (0.289 mol) of 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene were charged into the flask. Further, 8.5 mL (0.0289 mol) of titanium tetraisopropoxide and 20 mL of toluene were added thereto, and transesterification was carried out at 100 ° C. for 7 hours while distilling off the methanol produced by the reaction. After the reaction, toluene was distilled off, and this was subjected to column purification (developing solvent: methylene chloride / hexane, filler: alumina), and liquid chromatography purity 97.6%, colorless transparent viscous liquid 2- (naphthalene- There were obtained 22.9 g (0.0710 mol, yield: 24.6%) of 2-yloxy) -ethyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate.

[Synthesis Example 2]
<Synthesis of 2- (naphthalen-1-yloxy) -ethyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate>

上記合成例１に記載の２−ナフトールに代えて１−ナフトール 90ｇ（0.624mol）を使用したこと以外は、合成例１と同じにして、液体クロマトグラフィー純度 99.１％、無色透明粘性液体状の２−(ナフタレン−１−イルオキシ)−エチル ５−メチル−ビシクロ[２.２.１]ヘプト−２−エン−５−カルボキシレート 28.0ｇ（0.0867mol，収率：30％）を得た。

The same as in Synthesis Example 1 except that 90 g (0.624 mol) of 1-naphthol was used instead of 2-naphthol described in Synthesis Example 1, and the liquid chromatographic purity was 99.1%, colorless transparent viscous liquid state 28.0 g (0.0867 mol, yield: 30%) of 2- (naphthalen-1-yloxy) -ethyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate was obtained.

[Example 1]
2- (Naphthalen-2-yloxy) -ethyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate obtained in Synthesis Example 1 4.55 g (0.0141 mol) as a molecular weight regulator A reaction vessel purged with nitrogen was added to 0.09 mL of 1-hexene and 20 mL of toluene, and heated to 80 ° C. Of a toluene solution (concentration: 0.6 mol / L) of triethylaluminum 0.15 mL, toluene solution (concentration: 0.025 mol / L) of methanol-modified WCl ₆ 0.45 mL was added, opening heavy by reacting for 2 hours at 80 ° C. A combined toluene solution was obtained.
The resulting ring-opening polymer had a weight average molecular weight (Mw) of 1.96 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 2.57.

Subsequently, the obtained toluene solution of the ring-opening polymer was put in an autoclave, and 480 mL of toluene was further added to the solution to make a total amount of about 500 mL. 50 mg of RuHCl (CO) (PPh ₃ ) ₃ was added thereto as a hydrogenation catalyst, and then reacted at 160 to 165 ° C. for 3 hours at a hydrogen gas pressure of 9.5 to 10 MPa. After completion of the reaction, re-precipitation in a large amount of methanol solution gave a hydrogenated ring-opened polymer (polymer yield: 1.0 g, yield: 22%). The hydrogenated product of the obtained ring-opening polymer had a weight average molecular weight (Mw) = 3.03 × 10 ⁴ , a molecular weight distribution (Mw / Mn) = 1.72, an intrinsic viscosity [η] = 0.33, a glass transition temperature (Tg) = It was 47.5 ° C. The ¹ H-NMR spectrum of the hydrogenated product of this ring-opening polymer is shown in FIG. 1, and the infrared absorption (IR) spectrum is shown in FIG.

As a result of NMR measurement, a group represented by the formula: —CH═CH— contained in the ring-opening polymer before the hydrogenation reaction was converted to a group represented by the formula: —CH ₂ CH ₂ —. The ratio (hereinafter referred to as “hydrogenation rate”) is 90%, while the conjugated double ring in an aromatic ring skeleton such as a benzene ring contained in the ring-opening polymer before the hydrogenation reaction. The proportion of bonds remaining without being hydrogenated after the reaction (hereinafter referred to as “aromatic ring residual ratio”) was 100%.
A cast film having a thickness of 60 μm was prepared from the hydrogenated product of the ring-opening polymer, and uniaxially stretched at 48 ° C. to obtain a retardation measurement sample.

[Example 2]
8.4 g (0.0261 mol) of 2- (naphthalen-1-yloxy) -ethyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate obtained in Synthesis Example 2 5-Methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene 5.6 g (0.0337 mol) as a monomer, 1-hexene 0.38 mL as a molecular weight regulator, and toluene 32 mL in a reaction vessel substituted with nitrogen And heated to 80 ° C. Toluene solution (concentration: 0.6 mol / L) of this triethylaluminum 0.16 mL, toluene solution (concentration: 0.025 mol / L) of methanol-modified WCl ₆ 0.48 mL was added, ring-opening copolymerization by reacting for 2 hours at 80 ° C. A toluene solution of the polymer was obtained.

Subsequently, the obtained ring-opening copolymer was hydrogenated in the same manner as in Example 1, weight average molecular weight (Mw) = 13.5 × 10 ⁴ , molecular weight distribution (Mw / Mn) = 3.75, intrinsic viscosity [η] = A hydrogenated product having a glass transition temperature (Tg) of 48.4 ° C. was obtained (polymer yield: 10.59 g, yield: 75.6%). The ¹ H-NMR spectrum of the hydrogenated product of this ring-opening copolymer is shown in FIG. 3, and the infrared absorption (IR) spectrum is shown in FIG. As a result of NMR measurement, the hydrogenation rate was 93% and the aromatic ring residual rate was 100%. In addition, 2- (naphthalen-1-yloxy) -ethyl 5-methyl-bicyclo [2.2.1] hept-2-ene-5-carboxylate and 5-methyl-5-methoxycarbonylbicyclo [ The copolymerization ratio (molar ratio) with 2.2.1] hept-2-ene was 44/56.
A cast film having a thickness of 65 μm was prepared from the hydrogenated product of the ring-opening copolymer, and uniaxially stretched at 48 ° C. to obtain a retardation measurement sample.

[Comparative Example 1]
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 50 g, as a molecular weight modifier 1-hexene 3.6 g, and toluene 100g with nitrogen The reaction vessel was charged and heated to 80 ° C. Toluene solution (concentration: 0.6 mol / L) of this triethylaluminum 0.09 mL, toluene solution (concentration: 0.025 mol / L) of methanol-modified WCl ₆ 0.29 mL was added, the ring-opening polymerization by 3 hours at 80 ° C. I let you. The obtained ring-opened polymer was hydrogenated in the same manner as in Example 1, and the hydrogenated product of the ring-opened polymer (weight average molecular weight (Mw) = 5.6 × 10 ⁴ , molecular weight distribution (Mw / Mn) = 3.20, glass transition temperature (Tg) = 167 ° C.). As a result of NMR measurement, the hydrogenation rate of this hydrogenated product was 99.6%.
A cast film having a thickness of 80 μm was prepared from the hydrogenated product of the ring-opening polymer, and uniaxially stretched at 167 ° C. to obtain a sample for phase difference measurement.

[Evaluation]
As is apparent from [Table 1], the stretched film of the ring-opening polymer obtained in Example 1 and Example 2 has a larger absolute value of birefringence than that of Comparative Example 1 even at the same stretch ratio. It is clear. Moreover, the magnitude | size of the absolute value of the birefringence of the stretched film of the ring-opening polymer of this invention seen from the numerical value of the Example of Table 1 is the said Formula (1-1) and Formula (1-2). It is clear that it can be adjusted by selecting the aromatic structure to be expressed and setting the copolymer composition ratio.

Furthermore, when the thing of an Example and the thing of the conventionally well-known norbornene-type ring-opening polymer which does not contain the aromatic ester bond of the comparative example 1 are compared, the structural unit containing the specific aromatic ester bond of an Example It is apparent that a stretched film of a ring-opening polymer having a difference in wavelength dispersion of retardation (value of | (Re800 / Re550) − (Re400 / Re550) |) is remarkably large.
Therefore, the ring-opening polymer of the present invention can be suitably applied to applications such as optical films that actively utilize birefringence.

2 is a ¹ H-NMR spectrum of a hydrogenated product of the ring-opening polymer obtained in Example 1. FIG. 2 is an infrared absorption (IR) spectrum of a hydrogenated product of the ring-opening polymer obtained in Example 1. 2 is a ¹ H-NMR spectrum of a hydrogenated product of a ring-opening polymer obtained in Example 2. 3 is an infrared absorption (IR) spectrum of a hydrogenated product of a ring-opening polymer obtained in Example 2.

Claims (9)

The following general formula (1):

(1)
[Wherein, a is an integer of 0 to 2, X is a group represented by the formula: —CH═CH— or a group represented by the formula: —CH ₂ CH ₂ —, and R ^{1 to} R ^6] Are independently a hydrogen atom; a halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, which may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom; or Represents a polar group, provided that at least one of R ^{3 to} R ⁶ has a group having an aromatic ring represented by the following general formula (1-1) and an aromatic ring represented by the general formula (1-2) It is a group selected from the group consisting of groups. ]
And a plurality of X's are the same or different norbornene-based ring-opening polymers :

(1-1)
Wherein, R ⁷ to R ¹⁵ are independently a hydrogen atom, a halogen atom, substitution or unsubstituted hydrocarbon group having 1 to 30 carbon atoms; represents or polar group, b is an integer of from 1 to 10 And c and d are each independently an integer of 0 to 3, provided that when c = d = 0, R ⁸ and R ¹¹ and / or R ¹⁵ and R ¹¹ are bonded to each other to form a carbocyclic ring Alternatively, a heterocyclic ring (these carbocycles or heterocyclic rings may have a monocyclic structure or other rings may be condensed to form a polycyclic structure) may be formed. ]

(1-2)
[Wherein, R ^{16 to} R ²⁴ independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon atom which may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. 1 to 30 hydrocarbon group; or a polar group, e is an integer of 1 to 10, and f is an integer of 0 to 3. ] The norbornene-based ring-opening polymer according to claim 1, wherein at least one of R ^{3 to} R ⁶ in the general formula (1) is a group having an aromatic ring represented by the general formula (1-1). . Following formula:

Or the following formula:

The norbornene-based ring-opening polymer according to claim 1 , which is a ring-opening polymer obtained by ring-opening polymerization or ring-opening copolymerization of a monomer represented by the formula: Furthermore, the following general formula (2):

(2)
[Wherein g and h are independently 0 or 1, provided that at least one of them is 1, i and j are each independently an integer of 0 to 2, and Y is a formula: —CH═CH— Or a group represented by the formula: —CH ₂ CH ₂ —, wherein R ^{25 to} R ³⁴ are independently a hydrogen atom; a halogen atom; represented by the general formula (1-1). Other than the group having an aromatic ring and the group having an aromatic ring represented by formula (1-2), it may have a linking group containing an oxygen atom, sulfur atom, nitrogen atom or silicon atom, substituted or non-substituted A substituted hydrocarbon group having 1 to 30 carbon atoms; or a polar group, R ³¹ and R ³² , and / or R ³³ and R ³⁴ may be combined to form a divalent hydrocarbon group; ³¹ or R ³² and R ³³ or R ³⁴ are bonded to each other to form a carbocyclic or heterocyclic ring (these carbocyclic or heterocyclic rings). The prime ring may be a monocyclic structure, or other rings may be condensed to form a polycyclic structure. ]
The norbornene-type ring-opening polymer according to any one of claims 1 to 3, wherein a plurality of Ys having the structural unit (2) represented by The norbornene-based ring-opening polymer according to claim 1, wherein 40 mol% or more of the plurality of Xs is a group represented by the formula: —CH ₂ CH ₂ —. 6. The norbornene-based ring-opening polymer according to claim 1, 2, 4 or 5, wherein b and / or e is 2 . More than 40 mol% of the total of the plurality of X and Y is represented by the formula: -CH ₂ CH ₂ The norbornene-based ring-opening polymer according to claim 4, which is a group represented by-. The norbornene-based ring-opening polymer according to any one of claims 4 to 7, wherein the proportion of the structural unit (1) in all the structural units constituting the polymer is 2 mol% or more. The norbornene-based ring-opening polymer. A molded product formed by molding the norbornene-based ring-opening polymer according to any one of claims 1 to 8.

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