JP2010097089A - Optical retardation film and liquid crystal display using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical retardation film which is composed of a single layer film and has wavelength dispersion characteristics of birefringence showing inverse dispersion characteristics and a sufficiently high total light transmittance. <P>SOLUTION: The optical retardation film is produced by stretching a film comprising a norbornene ring-opening polymer, wherein the norbornene ring-opening polymer has structure units represented by general formula (1). In the structure units, the ratio of the structure units wherein the wavy line c represents an exo-type configuration is within the range of 5-35 mol%. The total light transmittance of the optical retardation film is ≥86%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a retardation film and a liquid crystal display device using the same, and more specifically, a retardation film that can be suitably used for a 1 / 2λ plate, a 1 / 4λ plate, a protective film, an antireflection film, and the like. The present invention also relates to a liquid crystal display device using the same.

  A liquid crystal display device such as a liquid crystal display (LCD) uses a retardation film with controlled optical anisotropy for the purpose of optical compensation. For example, various researches have been made on retardation films (broadband retardation plates: reverse wavelength dispersive films) that provide a quarter-wave retardation in a wide wavelength region in the entire visible light region (400 to 800 nm). For example, JP-A-10-68816 (Patent Document 1) discloses a retardation film in which two retardation films are laminated in a substantially orthogonal direction and laminated. Japanese Patent Laid-Open No. 2002-48919 (Patent Document 2) discloses a retardation film obtained by polycondensation of two types of monomers exhibiting positive or negative intrinsic birefringence. Furthermore, JP 2001-194527 A (Patent Document 3) discloses a retardation film obtained by alloying polymers exhibiting positive and negative intrinsic birefringence, and JP 2005-36201 A ( Patent Document 4) discloses a retardation film obtained by ring-opening (co) polymerizing two types of norbornene-based monomers exhibiting positive or negative intrinsic birefringence after polymerization.

  However, in the retardation film as described in Patent Document 1, it is necessary to bond two films using an adhesive at the time of production, and the production process is complicated and the yield decreases, There was a problem in terms of productivity, such as high costs. In addition, in the conventional retardation films as described in Patent Documents 2 to 4, since the polymers are difficult to mix when blended at the time of production, they are often phase-separated and clouded, and the obtained retardation film Is difficult to use for optical applications. Furthermore, since the monomer exhibiting negative birefringence used for producing these retardation films has a special structure, the production thereof is difficult and expensive.

On the other hand, as a retardation film that solves the problem of productivity and the deterioration of optical properties, the endo / exo ratio of a norbornene derivative as a raw material was adjusted in Japanese Patent Application Laid-Open No. 2008-52119 (Patent Document 5). A retardation film made of a norbornene-based ring-opening polymer is disclosed. However, in the retardation film as described in Patent Document 5, the total light transmittance is not always sufficient.
JP-A-10-68816 JP 2002-48919 A JP 2001-194527 A JP 2005-36201 A JP 2008-52119 A

  The present invention has been made in view of the above-described problems of the prior art, and is made of a single layer film. The birefringent wavelength dispersion property exhibits reverse dispersion, and further has a sufficiently high total light transmittance. An object of the present invention is to provide a retardation film and a liquid crystal display device using the same.

  As a result of intensive studies to achieve the above object, the present inventors have used a norbornene-based ring-opening polymer containing a structural unit represented by the following general formula (1), and are contained in the polymer. When the ratio of the exo isomer of the structural unit is 5 mol% or more and 35 mol% or less, surprisingly the wavelength dispersion characteristic of birefringence exhibits reverse dispersion characteristics and sufficiently high total light transmittance. The inventors have found that a single layer retardation film can be obtained, and have completed the present invention.

That is, the retardation film of the present invention is a retardation film formed by stretching a film made of a norbornene-based ring-opening polymer,
The norbornene-based ring-opening polymer is represented by the following general formula (1):

[In the formula (1), n represents an integer of 0 or 1,
X represents a group represented by the formula: —CH═CH— or a group represented by the formula: —CH ₂ CH ₂ —.
R ¹ , R ² , R ³ , R ⁴ may be the same or different and each is at least 1 selected from the group consisting of a hydrogen atom; a halogen atom; an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms optionally having a linking group; and an atom or group selected from the group consisting of polar groups;
Wavy lines a and b indicate the configuration of endo or exo,
The wavy line c indicates the configuration of endo or exo. ]
A norbornene-based ring-opening polymer in which the ratio of the structural units containing the structural unit represented by the formula (1) and the wavy line c of the structural units exhibit the exo configuration is in the range of 5 mol% to 35 mol%. Yes,
The total light transmittance of the retardation film is 86% or more,
It is characterized by.

In the retardation film of the present invention, the ratio of the structural units in which X is a group represented by the formula: —CH ₂ CH ₂ — is the total structural unit in the norbornene-based ring-opening polymer. It is preferable that it is 90 mol% or more with respect to it.

  In addition, a liquid crystal display device of the present invention includes the retardation film of the present invention.

  According to the present invention, a retardation film comprising a single-layer film, birefringent wavelength dispersion characteristics exhibiting reverse dispersion, and a sufficiently high total light transmittance, and a liquid crystal display device using the same Can be provided.

  Moreover, such a retardation film of the present invention can be thinned. Furthermore, the manufacturing process of the retardation film of the present invention is also simplified, and it can be manufactured with a high yield and low cost.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

First, the retardation film of the present invention will be described. That is, a retardation film formed by stretching a film made of a norbornene-based ring-opening polymer,
The norbornene-based ring-opening polymer is represented by the following general formula (1):

[In the formula (1), n represents an integer of 0 or 1,
X represents a group represented by the formula: —CH═CH— or a group represented by the formula: —CH ₂ CH ₂ —.
R ¹ , R ² , R ³ , R ⁴ may be the same or different and each is at least 1 selected from the group consisting of a hydrogen atom; a halogen atom; an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms optionally having a linking group; and an atom or group selected from the group consisting of polar groups;
Wavy lines a and b indicate the configuration of endo or exo,
The wavy line c indicates the configuration of endo or exo. ]
A norbornene-based ring-opening polymer in which the ratio of the structural units containing the structural unit represented by the formula (1) and the wavy line c of the structural units exhibit the exo configuration is in the range of 5 mol% to 35 mol%. Yes,
The total light transmittance of the retardation film is 86% or more,
It is characterized by.

Thus, the total light transmittance of the retardation film of the present invention is 86% or more (more preferably 90% or more). When the total light transmittance is less than the lower limit, when used as a retardation film of a liquid crystal display device, the liquid crystal display screen becomes dark and the visibility tends to be lowered. Further, such total light transmittance is obtained by using an integrating sphere light transmittance measuring device (for example, trade name “CM3700d” manufactured by Minolta Co., Ltd.) after passing through the incident light amount T _{1 of} visible light and the film. It can be measured by obtaining the total light amount T _{2 of} visible light and obtaining the ratio (T ₂ / T ₁ ) of the light amount T ₂ to the light amount T ₁ (total light transmittance: Tt = T ₂ / T ₁ ). In addition, the measurement by such an integrating sphere type light transmittance measuring apparatus is performed using a test piece having a length of 40 mm, a width of 20 mm, and a thickness of 50 to 150 μm cut out from the retardation film.

  The norbornene-based ring-opening polymer according to the present invention contains the structural unit represented by the general formula (1), has an aromatic ring as a substituent, and further contains a norbornene monomer. A cyclopentane ring and an aromatic ring obtained by ring-opening polymerization are bonded directly or via a bicyclo ring. Moreover, as such a structural unit, n in the said Formula (1) shows the integer of 0 or 1. The norbornene-based ring-opening polymer may be a single polymer in which n is 0 or 1, or a copolymer in which n is 0 and 1. Such a value of n can be appropriately adjusted according to the intended design in order to control optical properties and various physical properties in a balanced manner.

  Moreover, the wavy lines a and b in the formula (1) indicate the endo or exo configuration. In the present invention, among all the structural units in the norbornene-based ring-opening polymer, the ratio of the structural units in which the configuration indicated by the wavy lines a and b is exo is preferably 1 to 60 mol%. More preferably, it is 5-35 mol%. When the content ratio of the structural unit whose steric configuration indicated by the wavy lines a and b is exo is less than 1%, the reverse dispersion characteristics tend not to be exhibited. The transmittance tends to decrease.

  Furthermore, the wavy line c in the formula (1) also indicates the endo or exo configuration. In the present invention, among all the structural units in the norbornene-based ring-opening polymer, the proportion of the structural units in which the configuration indicated by the wavy line c is exo is 5 to 35 mol% (more preferably 15 to 30 mol%). ). When the ratio of the structural units in which the wavy line c indicates the exo configuration is less than 5 mol%, the wavelength dispersion value (D = Δn (λ = 481 nm) / Δn (λ = 589 nm)) is in the range of 1.0 or more. Thus, since the wavelength dispersion characteristic becomes normal dispersion, a film showing reverse dispersion characteristic cannot be obtained. On the other hand, the chromatic dispersion value (D = Δn (λ = 481 nm) / Δn (λ = 589 nm)) is from 1 as the ratio of the structural unit whose steric configuration indicated by the wavy line c is exo is larger than 5 mol%. It becomes smaller and reverse dispersion characteristics are developed. However, when the ratio of the structural unit whose steric configuration indicated by the wavy line c is exo exceeds 35 mol%, the total light transmittance of the obtained retardation film is lowered, and the optical performance of the film tends to be lowered. . Thus, in the present invention, the retardation film has reverse dispersion by setting the ratio of the structural unit whose steric configuration indicated by the wavy line c is exo to 5 to 35 mol%, It is possible to simultaneously achieve the total light transmittance of the retardation film to be 86% or more, and to obtain a high-quality film having unique optical characteristics.

  The steric configuration represented by the wavy lines a, b, and c can be appropriately adjusted depending on the reaction conditions during the production of the monomer, the reaction treatment after the production, and the like. For example, the configuration of the wavy lines a and b can be easily controlled by isomerization after the production, and the configuration of the wavy line c is controlled by the reaction conditions during the production of the monomer and the heat treatment after the production. It is possible.

Moreover, the substituents represented by R ¹ , R ² , R ³ and R ⁴ in the formula (1) may be the same or different, and are each a hydrogen atom; a halogen atom; an oxygen atom, a nitrogen atom A substituted or unsubstituted hydrocarbon group having 1 to 30 (more preferably 1 to 10) carbon atoms, which may have at least one linking group selected from the group consisting of a sulfur atom and a silicon atom; And an atom or group selected from the group consisting of polar groups. Examples of such polar groups include a hydroxyl group, a mercapto group, a cyano group, an amino group, a carboxyl group, and a sulfonic acid group. Furthermore, as the substituent represented by R ¹ , R ² , R ³ , R ⁴ in the formula (1), a high heat resistance can be imparted by the obtained retardation film. Of these substituents, a cyano group and the like are preferable.

X in the formula (1) is a group represented by the formula: —CH═CH— or a group represented by the formula: —CH ₂ CH ₂ —. In the norbornene-based ring-opening polymer according to the present invention, X in all the structural units contained may consist of only one of the aforementioned groups, and the structural units each having the aforementioned groups are mixed. It may be. The norbornene-based ring-opening polymer according to the present invention becomes a more stable polymer as the hydrogenation ratio is higher, that is, as the number of double bonds in the main chain is smaller. Therefore, the norbornene-based ring-opening polymer according to the present invention is preferably a polymer to which hydrogen is sufficiently added and the number of double bonds in the main chain is small. From such a point of view, the ratio of the structural units in which X in the formula (1) is a group represented by the formula: —CH ₂ CH ₂ — is in all the structural units of the norbornene ring-opening polymer. 90 mol% (more preferably 95 mol%, particularly preferably 98 mol%) or more. When such a ratio is less than 90 mol%, the stability of the polymer is lowered, and it tends to be difficult to suppress coloring and deterioration due to heat.

  The weight average molecular weight of the norbornene-based ring-opening polymer represented by the general formula (1) is preferably 1000 to 10000000, and more preferably 10000 to 1000000. When the weight average molecular weight of the norbornene-based ring-opening polymer represented by the general formula (1) is less than the lower limit, the strength of the obtained aromatic norbornene-based ring-opening polymer tends to be low. If it exceeds 1, the melt viscosity of the resulting norbornene-based ring-opening polymer tends to be too high.

  The method for producing such a norbornene-based ring-opening polymer according to the present invention is not particularly limited. For example, the following reaction formula (I):

[In the reaction formula (I), R ¹ , R ² , R ³ , R ⁴ , a, b, c, and n are R ¹ , R ² , R ³ , R ^{4 in the} general formula (1), respectively. , A, b, c, n. ]
In accordance with the present invention, the aromatic norbornene monomer represented by the formula (3) is subjected to ring-opening polymerization to obtain a norbornene-based ring-opening polymer represented by the formula (4). A method of obtaining a norbornene-based ring-opening polymer represented by the above formula (4 ′) by hydrogenating the polymer can be suitably employed.

  Examples of the aromatic norbornene monomer represented by the formula (3) include the following.

5-phenylbicyclo [2.2.1] -2-heptene, 8- ^{phenyltetracyclo} [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene, 8- (p-tBuphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (p-aminophenyl) bicyclo [2.2 .1] -2-heptene, 8- (p-aminophenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (o-acetoxyphenyl) bicyclo [2.2.1 ] -2-heptene, 8- (o-acetoxyphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (p-acetoxyphenyl) bicyclo [2.2.1]- 2-heptene, 8- (p-acetoxyphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 6-bromo-5-phenyl-bicyclo [2.2.1] -2- Heptene, 8-phenyl-9- ^{bromotetracyclo} [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (p-isopropylphenyl) bicyclo [2.2.1] -2-heptene, 8- (p-isopropyl Eniru) tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 5-(m-bromophenyl) bicyclo [2.2.1] -2-heptene, 8- (m-bromophenyl) Tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (p-bromophenyl) bicyclo [2.2.1] -2-heptene, 8- (p-bromophenyl) tetracyclo [ 4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (o-bromophenyl) bicyclo [2.2.1] -2-heptene, 8- (o-bromophenyl) tetracyclo [4.4. 1 ^2,5 .1 ^7,10.0 ) -3-dodecene, 6,6-difluoro-5- (p-bromophenyl) bicyclo [2.2.1] -2-heptene, 8- (p-bromophenyl) -9,9-difluorotetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (p-chlorophenyl) -5-methylbicyclo [2.2.1] -2-heptene, 8- (p-chlorophenyl) -9-methyltetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (o-chlorophenyl) bicyclo [2.2.1] -2-heptene 8- (o-chlorophenyl) tetracyclo [4.4.1 ^2,5 . 1 ^7,10 .0] -3-dodecene, 5- (m-chlorophenyl) bicyclo [2.2.1] -2-heptene, 8- (m-chlorophenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 5- (p-chlorophenyl) bicyclo [2.2.1] -2-heptene, 8- (p-chlorophenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ]- 3-dodecene, 5- (m-chloromethylphenyl) bicyclo [2.2.1] -2-heptene, 8- (m-chloromethylphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ]- 3-dodecene, 5- (p-chloromethylphenyl) bicyclo [2.2.1] -2-heptene, 8- (p-chloromethylphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ]- 3- dodecene, 5-(p-cyano-methylphenyl) bicyclo [2.2.1] -2-heptene, 8- (p-cyanomethylphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] - 3-dodecene, 5- (o-chloromethylphenyl) bicyclo [2.2.1] -2-heptene, 8- (o-chloromethylphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ]- 3-dodecene, 5- (2,6 -Dichlorophenyl) bicyclo [2.2.1] -2-heptene, 8- (2,6-dichlorophenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (p-fluoro Phenyl) -5-methylbicyclo [2.2.1] -2-heptene, 8- (p-fluorophenyl) -9-methyltetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene 5- (o-fluorophenyl) bicyclo [2.2.1] -2-heptene, 8- (o-fluorophenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5 - (m-fluorophenyl) bicyclo [2.2.1] -2-heptene, 8- (m-fluorophenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 5- ( p-fluorophenyl) bicyclo [2.2.1] -2-heptene, 8- (p-fluorophenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (pentafluoro phenyl) bicyclo [2.2.1] -2-heptene, 8- (pentafluorophenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 5-(o-methoxyphenyl) bicycloaryl Black [2.2.1] -2-heptene, 8- (o-methoxyphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 5-(p-ethoxyphenyl) bicyclo [ 2.2.1] -2-heptene, 8- (p-ethoxyphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (p-phenoxyphenyl) bicyclo [2.2. 1] -2-heptene, 8- (p-phenoxyphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (p-hydroxymethylphenyl) bicyclo [2.2.1 ] -2-heptene, 8- (p-hydroxymethylphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (p-methoxyphenyl) bicyclo [2.2.1] -2-heptene, 8- (p-methoxyphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (o-methylphenyl) bicyclo [2.2.1] -2 -Heptene, 8- (o-methylphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (m-methylphenyl) bicyclo [2.2.1] -2-heptene , 8- (m-methyl Eniru) tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 5-(p-methylphenyl) bicyclo [2.2.1] -2-heptene, 8- (p-methylphenyl) Tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5-methyl-5-phenylbicyclo [2.2.1] -2-heptene, 8-methyl-8-phenyltetracyclo [4.4 .1 ^2,5 .1 ^7,10 .0] -3-dodecene, 6-methyl-5-phenylbicyclo [2.2.1] -2-heptene, 9-methyl-8-phenyltetracyclo [4.4.1 ^{2 , 5.1} 7,10.0] -3-dodecene, 5- (m-nitrophenyl) bicyclo [2.2.1] -2-heptene, 8- (m-nitrophenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (p-nitrophenyl) bicyclo [2.2.1] -2-heptene, 8- (p-nitrophenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (p-cyanophenyl) bicyclo [2.2.1] -2-heptene, 8- (p-cyanophenyl) tetracyclo [4.4.1 ^2,5 .1 ^{7, 10.0]} -3-dodecene, 5-(pn-octylphenyl) Bishiku [2.2.1] -2-heptene, 8- (pn-octylphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 5-trimethylsiloxy-5-phenyl-bicyclo [2.2 .1] -2-heptene, 8- (trimethylsiloxy) -8- ^{phenyltetracyclo} [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (2,4,6-trimethyl Phenyl) bicyclo [2.2.1] -2-heptene, 8- (2,4,6-trimethylphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (o -Methylphenyl) bicyclo [2.2.1] -2-heptene, 8- (o-methylphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (m-methyl Phenyl) bicyclo [2.2.1] -2-heptene, 8- (m-methylphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (p-methylphenyl) Bicyclo [2.2.1] -2-heptene, 8- (p-methylphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (2,4-dimethylphenyl) Bicyclo [2.2.1] -2-heptene, 8- (2,4-dimethyl Butylphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 5- (2,5-dimethylphenyl) bicyclo [2.2.1] -2-heptene, 8- (2,5 -Dimethylphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (2,5-dichlorophenyl) bicyclo [2.2.1] -2-heptene, 8- (2, 5-dichlorophenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (2,6-dichlorophenyl) bicyclo [2.2.1] -2-heptene, 8- (2, 6-dichlorophenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (3,4-dichlorophenyl) bicyclo [2.2.1] -2-heptene, 8- (3, 4-dichlorophenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (o-iodophenyl) bicyclo [2.2.1] -2-heptene, 8- (o-iodo Phenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (biphenyl) bicyclo [2.2.1] -2-heptene, 8- (biphenyl) tetracyclo [4.4.1 ^{2 , 5.1 7,10} .0] -3-dodecene, 5-(p- Sulfonic acid phenyl) bicyclo [2.2.1] -2-heptene, 8- (p-phenyl sulfonate) tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 5-(p- acid chloride phenyl) bicyclo [2.2.1] -2-heptene, 8- (p-sulfonic acid chloride phenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 5- ( p-carboxyphenyl) bicyclo [2.2.1] -2-heptene, 8- (p-carboxyphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5,6-diphenyl bicyclo [2.2.1] -2-heptene, 8,9-diphenyl-tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 5,5-diphenyl [2.2.1] - 2-heptene, 8,8-diphenyl-tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 5- (1-naphthyl) bicyclo [2.2.1] -2-heptene, 8 -(1-Naphtyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (2-naphthyl) bicyclo [2.2.1] -2-heptene, 8- (2- Naphthyl) tetracyclo [4.4. 1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (9-anthracenyl) bicyclo [2.2.1] -2-heptene, 8- (9-anthracenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 5- (m-isopropenylphenyl) -5-methylbicyclo [2.2.1] -2-heptene, 8- (m-isopropenylphenyl) -8-methyl Tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (p-isopropenylphenyl) -5-methylbicyclo [2.2.1] -2-heptene, 8- (p -Isopropenylphenyl) -8-methyltetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (p-chlorophenyl) -5-methylbicyclo [2.2.1] -2 -Heptene, 8- (p-chlorophenyl) -8-methyltetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5-cyano-5- (p-methylphenyl) bicyclo [ 2.2.1] -2-heptene, 8-cyano-8- (p-methylphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 6-methyl-5-phenylbicyclo [2.2.1] -2-heptene, 9-methyl-8 ^{-Phenyltetracyclo} [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (p-methoxyphenyl) -6-methylbicyclo [2.2.1] -2-heptene, 8- ( p-methoxyphenyl) -9-methyltetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (p-hydroxy-o-methoxyphenyl) -6-methylbicyclo [2.2 .1] -2-heptene, 8- (p-hydroxy-o-methoxyphenyl) -9-methyltetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 5- (3 , 4-Methylenedioxyphenyl) -6-methylbicyclo [2.2.1] -2-heptene, 8- (3,4-methylenedioxyphenyl) -9-methyltetracyclo [4.4.1 ^{2,5.1 7,10} .0] -3-dodecene, 6-bromo-5-phenylbicyclo [2.2.1] -2-heptene, 8-phenyl-9- ^{bromotetracyclo} [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 6-formyl-5-phenylbicyclo [2.2.1] -2-heptene, 9-formyl-8- ^{phenyltetracyclo} [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 6-acetyl-5-pheny Bicyclo [2.2.1] -2-heptene, 9-acetyl-8-phenyl-tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 6-benzoyl-5-phenyl bicyclo [2.2 .1] -2-heptene, 8-phenyl-9-benzoyltetracyclo [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 6-cyano-5-phenylbicyclo [2.2.1] -2-heptene, 9-cyano-8- ^{phenyltetracyclo} [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, 6-nitro-5-phenylbicyclo [2.2.1] -2- Heptene, 9-nitro-8- ^{phenyltetracyclo} [4.4.1 ^2,5 .1 ^7,10.0 ] -3-dodecene, tetracyclo [8.4.1 ^11,14.0
1,10 .0 ^4,9] pentadeca -4,6,8,12- tetraene, pentacyclo [7.6.1 ^{11, 14} .1 ^1,9 .0 ^{10, 15} .0 ^5,17] -heptadec 1,3 , 5,6,8,12- hexaene, pentacyclo [10.6.1 ^{14 and 17} .0 ^{13, 18} .0 ^1,6 .0 ^7,12] nonadec -1,3,5,7,9,11,15 - heptaenes, tetracyclo [7.4.1 ^10,13 .0 ^1,9 .0 ^2,7] tetradeca -2,4,6,11- tetraene, 2-oxo tetracyclo [7.4.1 ^10,13 .0 ^{1, 9.0 3,8]} tetradec -3,5,7,11- tetraene, 3-oxo tetracyclo [8.4.1 ^11,14 .0 ^1,10 .0 ^4,9] pentadeca -4,6,8, 12-tetraen-2-one, 5-phenyl-6-carboxy (p-methoxyphenyl) bicyclo [2.2.1] -2-heptene, 5-phenyl-6-carboxy (m-methoxyphenyl) bicyclo [2.2.1] ] -2-heptene, 5-phenyl-6-carboxy (o-methoxyphenyl) bicyclo [2.2.1] -2-heptene, 5-phenyl-6-carboxy (p-methylphenyl) bicyclo [2.2.1]- 2-heptene, 5-phenyl-6-carboxy (m-methyl Nyl) bicyclo [2.2.1] -2-heptene, 5-phenyl-6-carboxy (o-methylphenyl) bicyclo [2.2.1] -2-heptene, 5-phenyl-6-carboxy (p-chlorophenyl) bicyclo [2.2.1] -2-heptene, 5-phenyl-6-carboxy (m-chlorophenyl) bicyclo [2.2.1] -2-heptene, 5-phenyl-6-carboxy (o-chlorophenyl) bicyclo [2.2.1] ] -2-heptene, 5-phenyl-6-carboxy (p-nitrophenyl) bicyclo [2.2.1] -2-heptene, 5-phenyl-6-carboxy (m-nitrophenyl) bicyclo [2.2.1]- 2-heptene, 5-phenyl-6-carboxy (o-nitrophenyl) bicyclo [2.2.1] -2-heptene, 5-phenyl-6-carboxy (p-bromophenyl) bicyclo [2.2.1] -2- Heptene, 5-phenyl-6-carboxy (m-bromophenyl) bicyclo [2.2.1] -2-heptene, 5-phenyl-6-carboxy (o-bromophenyl) bicyclo [2.2.1] -2-heptene, 5- (p-amino Enyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (p-aminophenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (p-bromophenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (p-bromophenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (p-bromophenyl) -6 -Carboxyethylbicyclo [2.2.1] -2-heptene, 5- (o-bromophenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (o-bromophenyl) -6-carboxy Methylbicyclo [2.2.1] -2-heptene, 5- (o-bromophenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (m-bromophenyl) -6-carboxylic acid bicyclo [2.2.1] -2-Heptene 5- (m-bromophenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (m-bromophenyl) -6-carboxyethylbicyclo [2.2. 1] -2-heptene, 5- (p-chlorophenyl) -6-carvone Bicyclo [2.2.1] -2-heptene, 5- (p-chlorophenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (p-chlorophenyl) -6-carboxyethylbicyclo [2.2. 1] -2-heptene, 5- (m-chlorophenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (m-chlorophenyl) -6-carboxymethylbicyclo [2.2.1] -2 -Heptene, 5- (m-chlorophenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (o-chlorophenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5 -(o-chlorophenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (o-chlorophenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene5-phenyl-6- Carboxylic acid bicyclo [2.2.1] -2-heptene, 5-phenyl-6-carboxybenzylbicyclo [2.2.1] -2-heptene, 5-phenyl-6-carboxyethylbicyclo [2.2.1] -2-heptene , 5-Phenyl-6-carbo Cyphenylbicyclo [2.2.1] -2-heptene, 5-phenyl-6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (p-hydroxyphenyl) -6-carboxylic acid bicyclo [2.2.1 ] -2-heptene, 5- (p-hydroxyphenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (p-hydroxyphenyl) -6-carboxyethylbicyclo [2.2.1]- 2-heptene, 5- (o-hydroxyphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (o-hydroxyphenyl) -6-carboxymethylbicyclo [2.2.1] -2- Heptene, 5- (o-hydroxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5-cyano-5-phenyl-6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5 -Cyano-5-phenyl-6-carboxymethylbicyclo [2.2.1] -2-heptene, 5-cyano-5-phenyl-6-carboxyethylbicyclo [2.2.1] -2-heptene, 5-cyano-5 -Phenyl-6-carboki Cholesteryl bicyclo [2.2.1] -2-heptene, 5- (m-hydroxyphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (m-hydroxyphenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (m-hydroxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5-phenyl-6-carboxyallylbicyclo [2.2.1] -2 -Heptene, 5-phenyl-6-carboxyvinylbicyclo [2.2.1] -2-heptene, 5-phenyl-6-carboxycinnamylbicyclo [2.2.1] -2-heptene, 5- (p-chloro-m -Nitrophenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (p-chloro-m-nitrophenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (p-chloro-m-nitrophenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (2-chloro-5-nitrophenyl) -6-carboxylic acid bicyclo [2.2.1]- 2-heptene, 5- (2-chloro-5-nitro Enyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5--2-chloro-5-nitrophenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5-cyano-5 -(p-Hydroxyphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5-cyano-5- (p-hydroxyphenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene 5-cyano-5- (p-hydroxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5-phenyl-6-carboxyisopropylbicyclo [2.2.1] -2-heptene, 5, 6-dibromo-5-phenyl-6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5,6-dibromo-5-phenyl-6-carboxymethylbicyclo [2.2.1] -2-heptene, 5, 6-dibromo-5-phenyl-6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (3,4-dimethoxyphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5 -(3,4-Dimethoxyphenyl) -6-ca Boxymethylbicyclo [2.2.1] -2-heptene, 5- (3,4-dimethoxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (3,5-dimethoxy-4 -Hydroxyphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (3,5-dimethoxy-4-hydroxyphenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (3,5-Dimethoxy-4-hydroxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (2,5-dimethoxyphenyl) -6-carboxylate methylbicyclo [2.2. 1] -2-heptene, 5- (2,5-dimethoxyphenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (2,5-dimethoxyphenyl) -6-carboxyethylbicyclo [ 2.2.1] -2-heptene, 5- (2,3-dimethoxyphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (2,3-dimethoxyphenyl) -6-carboxymethyl Bicyclo [2.2.1] -2-heptene, 5- (2,3- Methoxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (2,4-difluorophenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (2, 4-difluorophenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (2,4-difluorophenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- ( 2,4-dimethoxyphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (2,4-dimethoxyphenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5 -(2,4-dimethoxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (2,4-dichlorophenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (2,4-dichlorophenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (2,4-dichlorophenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (4-Fluorophenyl) -6-carboxylic acid Chlo [2.2.1] -2-heptene, 5- (4-fluorophenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (4-fluorophenyl) -6-carboxyethylbicyclo [ 2.2.1] -2-heptene, 5- (2-fluorophenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (2-fluorophenyl) -6-carboxymethylbicyclo [2.2. 1] -2-heptene, 5- (2-fluorophenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (3-fluorophenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (3-fluorophenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (3-fluorophenyl) -6-carboxyethylbicyclo [2.2.1] -2 -Heptene, 5- (4-Hydroxy-3-methoxyphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (4-Hydroxy-3-methoxyphenyl) -6-carboxymethylbicyclo [ 2.2.1] -2-heptene, 5- (4-hydride Roxy-3-methoxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (3-hydroxy-4-methoxyphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene 5- (3-hydroxy-4-methoxyphenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (3-hydroxy-4-methoxyphenyl) -6-carboxyethylbicyclo [2.2. 1] -2-heptene, 5- (3-methoxyphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (3-methoxyphenyl) -6-carboxymethylbicyclo [2.2.1] 2-heptene, 5- (3-methoxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (2-methoxyphenyl) -6-carboxylic acid bicyclo [2.2.1] -2 -Heptene, 5- (2-methoxyphenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (2-methoxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene , 5- (4-Methoxy Phenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (4-methoxyphenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (4-methoxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (3,4-methylenedioxyphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (3,4 -Methylenedioxyphenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (3,4-methylenedioxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (4-methylphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (4-methylphenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (4-Methylphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (4-mercaptophenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (4 -Mercaptophenyl) -6-carboxymethylbicyclo [2.2. 1] -2-heptene, 5- (4-mercaptophenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (2-methylphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (2-methylphenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (2-methylphenyl) -6-carboxyethylbicyclo [2.2.1] -2 -Heptene, 5- (3-methylphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (3-methylphenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene 5- (3-methylphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5-methyl-5-phenyl-6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- Methyl-5-phenyl-6-carboxymethylbicyclo [2.2.1] -2-heptene, 5-methyl-5-phenyl-6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (3-nitro Phenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (3-nitrate Phenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (3-nitrophenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (4-nitrophenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (4-nitrophenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (4-nitrophenyl) -6 -Carboxyethyl bicyclo [2.2.1] -2-heptene, 5- (2-nitrophenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (2-nitrophenyl) -6-carboxy Methylbicyclo [2.2.1] -2-heptene, 5- (2-nitrophenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (4-n-octadecyloxyphenyl) -6 -Carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (4-n-octadecyloxyphenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (4-n-octa (Decyloxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2- Butene, 5- (4-stearyloxyphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (4-stearyloxyphenyl) -6-carboxymethylbicyclo [2.2.1] -2- Heptene, 5- (4-stearyloxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5,5-diphenyl-6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5, 5-diphenyl-6-carboxymethylbicyclo [2.2.1] -2-heptene, 5,5-diphenyl-6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (3,4,5-tri Methoxyphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (3,4,5-trimethoxyphenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (3,4,5-trimethoxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (2,4,5-trimethoxyphenyl) -6-carboxylic acid bicyclo [2.2.1 ] -2-heptene, 5- (2,4,5-trimethoxyphenyl) -6-cal Boxymethylbicyclo [2.2.1] -2-heptene, 5- (2,4,5-trimethoxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (3-trifluoro Methylphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (3-trifluoromethylphenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (3- Trifluoromethylphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (3-trifluoromethoxyphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- ( 3-trifluoromethoxyphenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (3-trifluoromethoxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5 -(2,3,4-Trimethoxyphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (2,3,4-trimethoxyphenyl) -6-carboxymethylbicyclo [2.2. 1] -2-heptene 5- (2,3,4-trimethoxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (4-cyanomethylphenyl) bicyclo [2.2.1] -2-heptene, 8- (4-cyano-methylphenyl) tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 5,5,6,6- tetraphenyl [2.2.1] -2-heptene , 8,8,9,9- tetraphenyl tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 6-bromo -5,5,6- triphenyl [2.2.1 ] -2-heptene, 9-bromo -8,8,9- triphenyl cyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 5,5,6 triphenyl bicyclo [ 2.2.1] -2-heptene, 8,8,9- triphenyltetrazolium cyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene or the like.

  Further, the method for producing such an aromatic norbornene monomer is not particularly limited, and for example, the following reaction formula (II):

[In the above reaction formula ^{(II), R 1, R} 2, R 3, R 4 are the same meanings as ^{R 1, R 2, R 3} , R 4 in the general formula (1). ]
According to the method, a Diels-Alder reaction of the cyclopentadiene represented by the above formula (5) and the styrene derivative represented by the above formula (6) can be suitably employed, whereby the above formula (7) and An aromatic norbornene monomer represented by (7 ′) can be obtained.

  Examples of the styrene derivative represented by the formula (6) in the reaction formula (II) include styrene and cinnamic acid. Such a styrene derivative acts as an excellent dienophile in the Diels-Alder reaction, and is capable of obtaining a reaction rate desirable for industrial production. That is, by reacting the styrene derivative with cyclopentadiene under the temperature (160 to 230 ° C.) at which cyclopentadiene is generated from a cyclopentadiene precursor (dicyclopentadiene), the desired aromatic norbornene unit is obtained. A monomer can be obtained with good yield. The method for obtaining such a styrene derivative is not particularly limited, but it is easy to obtain because some are industrially produced. , Edited by Polymer Society, 1986, Baifukan etc.).

Examples of such styrene derivatives include the following.
4-aminostyrene, 2-acetoxystyrene, 4-acetoxystyrene, β-bromostyrene, 4-tert-butylstyrene, 4-isopropylstyrene, 3-bromostyrene, 4-bromostyrene, 2-bromostyrene, 4-bromo- β, β-difluorostyrene, 4-chloro-α-methylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, m-chloromethylstyrene, p-chloromethylstyrene, cyanomethylstyrene, o-chloro Methylstyrene, 2,6-dichlorostyrene, 4-fluoro-α-methylstyrene, 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, pentafluorostyrene, 2-methoxystyrene, 4-ethoxystyrene, p- Phenoxystyrene, p-vinylbenzyl alcohol, 4-methoxystyrene, 2-methylstyrene, 3-methylstyrene, 4- Tylstyrene, α-methylstyrene, cis-β-methylstyrene, 3-nitrostyrene, 4-nitrostyrene, 4-cyanostyrene, 4-n-octylstyrene, β-methylstyrene, 2,3,4,5,6 -Pentafluorostyrene, α- (trimethylsiloxy) styrene, styrene, 2,4,6-trimethylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5- Dimethylstyrene, 2,4,6, -trimethylstyrene, 2,5-dichlorostyrene, 2,6-dichlorostyrene, 3,4-dichlorostyrene, o-iodostyrene, p-phenylstyrene, p-styrenesulfonic acid, p-styrenesulfonyl chloride, 4-carboxystyrene, cis-stilbene, trans-stilbene, 1,1-diphenylethylene, 1-vinylnaphthalene, 2-vinylnaphthalene, 9-vinylanthracene, m-diisopropenylben P-diisopropenylbenzene, p-chloro-α-methylstyrene, α-cyano-p-methylstyrene, propenylbenzene, anethole, isoeugenol, isosafrole, β-bromostyrene, cinnamaldehyde, benzalacetone, Benzalacetophenone, β-cyanostyrene, β-nitrostyrene, 1,2-dihydronaphthalene, acenaphthylene, phenanthrene, indene, methylenebenzoindene, coumarone, 4-aminocinnamic acid, 4-bromocinnamic acid, 2-bromocinnamic acid Trans-3-bromocinnamic acid, 3,4-dihydroxycinnamic acid, 4-chlorocinnamic acid, trans-cinnamic acid, cinnamic acid benzyl ester, cinnamic acid ethyl ester, cinnamic acid phenyl ester, cinnamic acid methyl ester, trans -4-hydroxycinnamic acid, trans-2-hydroxycinnamic acid, α-cyanocinnamic acid, α-cyanocinnamic acid ethyl ester Trans-cinnamic acid cholesterol ester, trans-3-hydroxycinnamic acid, cinnamic acid allyl ester, cinnamic acid vinyl ester, cinnamic acid cinnamyl ester, 2-chlorocinnamic acid, 3-chlorocinnamic acid, 4-chloro-3 -Nitrocinnamic acid, 2-chloro-5-nitrocinnamic acid, 4-chlorocinnamic acid methyl ester, α-cyano-4-hydroxycinnamic acid, cinnamic acid isopropyl ester, α, β-dibromocinnamic acid ethyl ester, 3, 4-dimethoxycinnamic acid, 3,5-dimethoxy-4-hydroxycinnamic acid, 3,4-dimethoxycinnamic acid, 2,5-dimethoxycinnamic acid, trans-2,3-dimethoxy cinnamic acid, 2,4-difluorocinnamic acid Acid, 2,4-dimethoxycinnamic acid, trans-2,4-dichlorocinnamic acid, α, β-dibromocinnamic acid, 3,5-dimethoxy-4-hydroxycinnamic acid, 4-fluorocinnamic acid, 2-fluoro cinnamic acid Acid, 3-fluorocinnamic acid, cinnamic acid, trans-4-hydroxy-3-methoxycinnamic acid 3-hydroxy-4-methoxycinnamic acid, 4-hydroxycinnamic acid, 3-methoxycinnamic acid, trans-2-methoxycinnamic acid, 4-methoxycinnamic acid, 3,4-methylenedioxycinnamic acid, 4-methylcinnamic acid Acid, cis-2-methoxycinnamic acid, 4-mercaptocinnamic acid, 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid octyl ester, 4-methoxycinnamic acid ethyl ester, 2-methyl cinnamic acid, 3- Methyl cinnamic acid, α-methyl cinnamic acid, 3-nitro cinnamic acid, 4-nitro cinnamic acid, 2-nitro cinnamic acid, 4-nitro cinnamic acid ethyl ester, 4-n-octadecyloxy cinnamic acid, 4-stearyloxy cinnamic Acid, α-phenylcinnamic acid, 3,4,5-trimethoxy cinnamic acid, 2,4,5-trimethoxy cinnamic acid, 3- (trifluoromethyl) cinnamic acid, 3- (trifluoromethoxy) cinnamic acid, 2, 3,4-trimethoxycinnamic acid, coumarin, vinyl benzyl cyanide, tetraphenyl Ethylene, 2-bromo-1,1,2-triphenylethylene, triphenylethylene and the like.

  Moreover, in the aromatic norbornene monomer obtained in this way, exo isomer and endo isomer exist as stereoisomers at the site where the aromatic structure and the bicyclo ring structure are linked. The exo isomer of such an aromatic norbornene monomer gives “negative A property” to the resulting norbornene-based ring-opening polymer, while the endo isomer is the obtained norbornene-based ring-opening polymer. Gives "Positive A". Therefore, in the retardation film of the present invention, the wavelength dispersion characteristic of birefringence can be adjusted by adjusting the ratio of these isomers contained in the film. In addition, positive A property here is calculated | required from the refractive index change generate | occur | produced when a film is uniaxially stretched, and means the property that the refractive index of a extending direction becomes larger than the refractive index perpendicular | vertical with respect to a extending direction. The negative A property refers to a property in which the refractive index in the stretching direction is smaller than the refractive index in the direction perpendicular to the stretching direction. From such a viewpoint, in the present invention, the ratio of the exo isomer is adjusted to 5 mol% or more and 35 mol% or less to obtain a reverse dispersible film. The ratio of such exo or endo isomers in the product can be easily changed, for example, by appropriately changing the reaction conditions during the production of the monomer. Even after manufacturing, it can be easily changed by applying heat treatment and changing the conditions of this heat treatment.

Further, as a catalyst for ring-opening polymerization used in a reaction for ring-opening polymerization of such an aromatic norbornene monomer, Olefin Metathesis and Metathesis Polymerization (KJ IVIN, JC MOL, Academic Press 1997). The metathesis polymerization catalyst described in) is used. That is, (a) at least one selected from W, Mo, Re, V and Ti compounds, and (b) Li, Na, K, Mg, Ca, Zn, Cd, Hg, B, Al, Si, It is a catalyst comprising a combination of at least one compound selected from the group consisting of Sn, Pb and the like and having at least one element-carbon bond or the element-hydrogen bond. In this case, an additive (c) described later may be added to increase the activity of the catalyst. Examples of the other catalyst include (d) a metathesis catalyst composed of a group 4 to group 8 transition metal-carbene complex, a metallacyclobutene complex, or the like that does not use a promoter. Representative examples of W, Mo, Re, V or Ti compounds suitable as the component (a) include WCl ₆ , MoCl ₅ , ReOCl ₃ , VOCl ₃ and TiCl ₄ . Specific examples of the compound used as the component (b) include 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 , (C ₂ H ₅ ) AlCl ₂ , methylalumoxane, LiH and the like can be mentioned. Furthermore, alcohols, aldehydes, ketones, amines and the like can be used as representative examples of the additive as component (c). As typical examples of the component (d), W (= N-2,6-C ₆ H ₃ iPr ₂ ) (= CHtBu) (OtBu) ₂ , Mo (= N-2,6-C ₆ H ₃ iPr ₂ ) (= CHtBu) (OtBu) ₂ , Ru (= CHCH = CPh ₂ ) (PPh ₃ ) ₂ Cl ₂ , Ru (= CHPh) (PC ₆ H ₁₁ ) ₂ Cl ₂ (Grubbs I (first generation) Catalyst), Grubbs II (second generation) catalyst, Hoveyda-Grubbs catalyst (first and second generation), and the like.

  The amount of such a metathesis catalyst used is such that the ratio of the component (a) to the aromatic norbornene monomer is "(a) component: aromatic norbornene monomer" in molar ratio. : The range which becomes 500-1: 500,000 is preferable, and the range which becomes 1: 1000-1: 100000 is more preferable. In addition, the ratio of the component (a) to the component (b) is preferably in a range in which “(a) component: (b) component” is 1: 1 to 1: 100 in terms of metal atomic ratio, and is 1: 2-1. : The range which becomes 50 is more preferable. Furthermore, the ratio of the component (a) to the component (c) is preferably in a range where the molar ratio of “(c) component: (a) component” is 0.005: 1 to 15: 1, 0.05: 1 A range of 10 to 10: 1 is more preferable. Further, the amount of the catalyst (d) used is such that the ratio of the component (d) to the aromatic norbornene monomer is 1:30 in the molar ratio “(d) component: aromatic norbornene monomer”. A range of ˜1: 100,000 is preferred, and a range of 1:50 to 1: 50000 is more preferred.

  Further, in the reaction for ring-opening polymerization of the aromatic norbornene monomer, the method for adjusting the molecular weight of the resulting norbornene-based ring-opening polymer is not particularly limited. For example, polymerization temperature, type of catalyst, type of solvent A method of appropriately adjusting the molecular weight by changing the above may be employed. And as a method of adjusting such molecular weight, the method of making a molecular weight regulator coexist in a reaction system can be employ | adopted suitably. Suitable examples of such molecular weight regulators include α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. As well as styrene, 1-butene and 1-hexene are particularly preferable. These molecular weight regulators can be used alone or in admixture of two or more. The amount of such a molecular weight regulator used is more preferably in the range of 0.005 to 1.0 mol, preferably 0.02 to 0.5 mol, per mol of the aromatic norbornene monomer.

  The solvent used in the reaction for ring-opening polymerization of the aromatic norbornene monomer is preferably a solvent that dissolves the aromatic norbornene monomer, the metathesis catalyst, and the molecular weight regulator, such as pentane, hexane, heptane. , Octane, nonane, decane, etc .; cyclohexane, cycloheptane, cyclooctane, decalin, norbornane, etc .; cycloalkanes such as benzene, toluene, xylene, ethylbenzene, cumene, etc .; chlorobutane, bromohexane, chloride Halogenated alkanes such as methylene, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform, tetrachloroethylene; compounds such as aryl; ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, dimethyl Kishietan, saturated carboxylic acid esters such as γ- butyrolactone; dibutyl ether, tetrahydrofuran, ethers such as dimethoxyethane. Of these, aromatic hydrocarbons are preferred. These solvents can be used alone or in admixture of two or more. The amount of such a solvent used is preferably such that the mass ratio of “solvent: aromatic norbornene monomer” is 1: 1 to 30: 1, and more preferably 1: 1 to 20: 1. preferable.

  Further, the norbornene-based ring-opening polymer obtained in the state of ring-opening polymerization as described above is a norbornene-based ring-opening polymer represented by the formula (4) in the reaction formula (I), and its structural unit. It has a vinylene group in it. Such a norbornene-based ring-opening polymer can be used as it is for the retardation film of the present invention for various uses, but from the viewpoint of improving the heat resistance stability of the obtained retardation film, the above reaction formula is used. As shown in (I), a hydrogenated product obtained by hydrogenating a part or all of the vinylene group of the norbornene-based ring-opening polymer and converting the vinylene group to an ethylene group (represented by the formula (4 ′)) Norbornene-based ring-opening polymer). Such a hydrogenated product is a product in which the aromatic ring in the side chain of the aromatic norbornene monomer is not substantially hydrogenated. The hydrogenation rate with respect to the vinylene group is preferably 90% or more, more preferably 95% or more, and particularly preferably 98% or more. As the hydrogenation rate with respect to the vinylene group is higher, the heat resistance of the resulting aromatic norbornene-based ring-opening polymer is improved and coloring and deterioration due to heat tend to be sufficiently suppressed.

  Further, as described above, the reaction for hydrogenating the norbornene-based ring-opening polymer represented by the formula (4) needs to be performed under the condition that the side chain aromatic ring is not substantially hydrogenated. In general, a hydrogenation catalyst is added to the solution of the norbornene-based ring-opening polymer represented by the formula (4), and hydrogen gas at normal pressure to 30 MPa, preferably 3 to 20 MPa is added thereto at 0 to 200 ° C. The reaction is preferably performed at 20 to 180 ° C.

  In addition, as the hydrogenation catalyst used in such a hydrogenation reaction, those used in the usual hydrogenation reaction of olefinic compounds can be used, and either a heterogeneous catalyst or a homogeneous catalyst can be used. Can do. Specific examples of such a heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania. . Specific examples of the homogeneous catalyst include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenyl Phosphine) rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, tricarbonyltris (triphenylphosphine) ruthenium, dihydrocarbonyltris (triphenyl) Phosphine) ruthenium, hydrocarbomethoxycarbonyltris (triphenylphosphine) ruthenium, etc. It can gel. The form of such a hydrogenation catalyst may be powder or granular.

Furthermore, such a hydrogenation catalyst needs to be adjusted in the amount of addition in order to prevent the side chain aromatic ring based on the aromatic norbornene monomer from being substantially hydrogenated. It is preferable to use “ring-opening polymer: hydrogenation catalyst” in a ratio of 1: 1 × 10 ⁻⁶ to 1: 2.

  The retardation film of the present invention is formed by stretching a film made of the norbornene-based ring-opening polymer according to the present invention. A method for producing a film comprising such a norbornene-based ring-opening polymer is not particularly limited, and a known method can be appropriately employed. Further, when producing such a film, other polymers, surfactants, polymer electrolytes, conductive complexes, silica, alumina, dye materials, heat stabilizers are within the scope of the present invention. UV absorbers, antistatic agents, antiblocking agents, lubricants, plasticizers, oils, and the like can be added. Further, the method of stretching after forming the above-described norbornene-based ring-opening polymer into a film is not particularly limited, and a conventionally known stretching method can be appropriately employed.

  Moreover, as a suitable method for producing such a norbornene-based ring-opening polymer film, for example, a publicly known and publicly available method such as a casting method (solution casting method), a melt extrusion method, a calendar method, a compression molding method, etc. A method is mentioned. Furthermore, as a molding apparatus used for such a casting method, a drum-type casting machine, a band-type casting machine, a spin coater, or the like can be used. Examples of the melt extrusion method include a T-die method and an inflation method.

  Specific examples of the solvent used in the casting method include cyclic ketones such as cyclohexanone and cyclopentanone; lactones such as γ-butyrolactone and δ-valerolactone; benzene, toluene, xylene, ethylbenzene, cumene and the like. Aromatic hydrocarbons such as methylene chloride, dichloroethane, chlorobenzene, dichlorobenzene, chloroform, tetrachloroethylene, etc .; compounds such as aryl, ethers such as dibutyl ether, tetrahydrofuran, dimethoxyethane, N-methylpyrrolidone, N, N -Polar solvents such as dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide and the like can be mentioned, among which aromatic hydrocarbons, halogenated alkanes and aryls are preferable. These solvents can be used alone or in admixture of two or more.

  In addition, as a method of stretching after forming the norbornene-based ring-opening polymer into a film, a biaxial stretching method includes a tenter method, a tube method, and the like, and a uniaxial stretching method includes a water tank stretching method, a radiation stretching method, and hot air heating. Method, hot plate overheating method, roll heating method and the like.

  The thickness of the retardation film of the present invention thus obtained is not particularly limited, but is preferably 10 to 500 μm, and more preferably 30 to 200 μm. When the thickness of the retardation film is less than 10 μm, mechanical properties and handling properties at the time of secondary processing tend to be reduced. On the other hand, when the thickness exceeds 500 μm, there is a tendency for flexibility to occur. Moreover, the draw ratio in obtaining the retardation film of the present invention is not particularly limited, but is preferably about 1.1 to 5.0 times.

  The retardation value of the retardation film of the present invention should be selected according to the purpose in the range of 5 to 2000 nm. When used as a 1 / 2λ plate, the phase difference value in the visible light having a wavelength of 550 nm is used. The phase difference is preferably 200 to 400 nm, and when used as a ¼λ plate, the phase difference in visible light having a wavelength of 550 nm is preferably 90 to 200 nm.

  The retardation film of the present invention may further include a thin film for the purpose of imparting functions such as gas barrier properties, scratch resistance, chemical resistance, and antiglare properties. Examples of the method for forming such a thin film include various thermoplastic resins, thermosetting resins having amino groups, imino groups, epoxy groups, silyl groups, etc., radiation having acryloyl groups, methacryloyl groups, vinyl groups, etc. Polymerization inhibitors, waxes, dispersants, pigment materials, solvents, plasticizers, UV absorbers, inorganic fillers, etc. are added to a curable resin or a mixture of these resins, and this is added to a gravure roll coating method or a Meyer bar coating method. , Reverse roll coating method, dip coating method, air knife coating method, calendar coating method, squeeze coating method, kiss coating method, phanten coating method, spray coating method, spin coating method, etc. can do. Further, such a thin film may be a cured thin film layer after coating by performing curing by irradiation with radiation or heat curing by heating as necessary. When printing is performed when such a thin film is formed, a gravure method, an offset method, a flexo method, a silk screen method, or the like can be used. In addition, the retardation film of the present invention may further include a metal oxide layer mainly composed of aluminum, silicon, magnesium, zinc or the like for the purpose of imparting gas sealing properties. Such a metal oxide layer is formed by a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, or the like.

  Moreover, you may laminate | stack the retardation film of this invention and another film. As a method for laminating as described above, a conventionally known method can be appropriately employed. For example, a heat sealing method such as a heat sealing method, an impulse sealing method, an ultrasonic bonding method, a high frequency bonding method, an extrusion laminating method, a hot melt laminating method. Laminating methods such as a method, a dry laminating method, a wet laminating method, a solventless adhesive laminating method, a thermal laminating method, and a coextrusion method. In addition, as a film to be laminated, for example, polyester resin film, polyvinyl alcohol resin film, cellulose resin film, polyvinyl fluoride resin film, polyvinylidene chloride resin film, polyacrylonitrile resin film, nylon resin film, polyethylene Resin film, polypropylene resin film, acetate resin film, polyimide resin film, polycarbonate resin film, polyacrylate resin film, and the like.

  Next, the liquid crystal display device of the present invention will be described. That is, the liquid crystal display device of the present invention comprises the retardation film of the present invention.

  The retardation film of the present invention is a retardation film comprising a single layer film, birefringent wavelength dispersion characteristics exhibiting reverse dispersion, and a high total light transmittance. 1 / 4λ plate in LCD, 1 / 2λ plate and 1 / 4λ plate in liquid crystal projector device, 1 / 2λ plate and 1 / 4λ plate in transmissive liquid crystal display device, protective film for polarizing film used in liquid crystal display device, reflection It is useful as a prevention film.

  Therefore, the liquid crystal display device of the present invention may be provided with the retardation film of the present invention as a 1 / 2λ plate, 1 / 4λ plate, protective film, antireflection film, etc. It may be the same as the display device.

  In addition, the retardation film of the present invention is formed by forming a ceramic thin film such as indium tin oxide or indium zinc oxide on the surface thereof by a plasma process using DC or glow discharge, and a transparent electrode film in a touch panel, a liquid crystal display device or the like. It can also be used.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

  First, the evaluation method of the characteristics of the polymer obtained in each synthesis example and the retardation film obtained in each example will be described.

<Glass transition temperature: Tg>
Using a differential scanning calorimeter (manufactured by Perkin-Elmer, trade name: DSC7), the glass transition temperature of the polymer obtained in each synthesis example was measured under a nitrogen stream at a heating rate of 20 ° C. per minute. It was.

<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 GMH _HR ) is used as a measuring apparatus, and tetrahydrofuran (THF) is used as a solvent. The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) in terms of polystyrene of the polymer obtained in each synthesis example were determined. Mn represents the number average molecular weight.

<Monomer and polymer molecular structure>
Using a superconducting nuclear magnetic resonance absorption apparatus (NMR, manufactured by Varian, trade name: UNITY INOVA-600), ¹ H, ¹³ C-NMR of the polymer obtained in each synthesis example was obtained in deuterated chloroform. It was measured. From the obtained data, the endo / exo ratio of the monomer and the hydrogenation rate of the polymer (X in the norbornene-based ring-opening polymer represented by the general formula (1) is represented by the formula: —CH ₂ CH ₂ — And the molecular structure were identified.

<Phase difference, birefringence evaluation, birefringence wavelength dispersion evaluation>
For the retardation films obtained in each Example and each Comparative Example, using a retardation measuring device (trade name: KOBRA21DH, manufactured by Oji Scientific Co., Ltd.) The wavelength dispersion value (D) of refraction was measured.
Re = (nx−ny) × d
nx: refractive index in the stretching direction ny: refractive index in the direction perpendicular to the stretching direction d: film thickness (nm)
D: Birefringence wavelength dispersion value Δn (λ = 481 nm) / Δn (λ = 589 nm).

<Total light transmittance evaluation>
The total light transmittance was measured using the retardation film obtained in each Example and Comparative Example. That is, first, test piece films (length: 40 mm, width: 20 mm, thickness: 60 to 100 μm) were prepared using each retardation film. Next, the test piece film is installed in an integrating sphere type light transmittance measuring device (CM3700d manufactured by Minolta Co., Ltd.), and then the test piece film is irradiated with visible light, and the incident light amount T _{1 of} visible light is obtained. The total amount of light T ₂ that passed through the test piece film was determined, and the total light transmittance (Tt = T ₂ / T ₁ ) was measured from these values.

(Synthesis Example 1)
<Synthesis of Aromatic Norbornene A>
To a 2 L autoclave, 4-tBu-styrene (856 g: 5.36 mol), dicyclopentadiene (709 g: 5.36 mol), 4-tBu-catechol (44.6 g: 0.27 mol), and toluene (200 ml) were added. The mixture was heated and stirred at 185 ° C. for 4 hours. The initial reaction showed a pressure of 0.4 MPa, but the pressure decreased with the passage of time and finally showed 0.2 MPa. Then, after the heating was stopped, the mixture was naturally allowed to cool to room temperature, and then the autoclave was opened, and the reaction product was taken out.

  Next, the reaction product thus obtained was purified by distillation to obtain a fraction A of 118 to 120 ° C./1 mmHg. The yield of fraction A was 640 g (53% yield, based on tBu-styrene). As a result of conducting gas chromatographic analysis and NMR analysis of fraction A, it was found that 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene having an endo / exo ratio (isomer ratio) of 79/21 was obtained. It was confirmed that there was.

  Next, when 300 g of fraction A was dissolved in 1200 ml of methanol by heating and allowed to cool naturally, 165 g of 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene (A) crystals were obtained. It was. The purity of the obtained crystal was 98%, and the endo / exo ratio was 80/20.

<Polymerization of aromatic type norbornene A>
An anhydrous toluene solution of 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene (A) (2.26 g: 0.01 mol) having an endo / exo ratio of 80/20 under a nitrogen atmosphere ( 20 ml), 1-hexene (2.5 μl: 0.2 mol%) and Grubbs I catalyst (4.1 mg: 0.05 mol%) in anhydrous toluene (2 ml) were added and stirred at room temperature for 20 hours to polymerize the solution. Got. Subsequently, the viscous polymerization solution was diluted with 100 ml of toluene, and the resulting precipitate was put into 3000 ml of methanol and filtered. Next, the precipitate was dried by a vacuum dryer to obtain 1.90 g (yield 85%) of the ring-opening polymer (pA) of A. When the obtained product was confirmed by GPC, the weight average molecular weight (Mw) in terms of polystyrene was 90000, and Mw / Mn was 1.6.

<Hydrogenation of Ring-Opening Polymer (pA) of Aromatic Norbornene A>
In a 0.2 L autoclave, 1.9 g of a ring-opening polymer (pA) of 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene, xylene (150 ml), RuHCl (CO) (PPh ₃ ) ₃ (19 mg) was charged and purged with nitrogen. Subsequently, after hydrogenation reaction was performed by heating for 30 hours under the conditions of a hydrogen gas pressure of 10 MPa and a reaction temperature of 165 ° C., the obtained reaction solution was cooled to 25 ° C., and the hydrogen gas was released. The reaction solution thus obtained is poured into 3000 ml of methanol, and the precipitate is separated and collected. The obtained precipitate is dried to give 5- (p-tBuphenyl) bicyclo [2.2.1]- 1.69 g (yield 89%) of hydrogenated product (HpA) of a ring-opening polymer of 2-heptene was obtained.

  When the obtained product was confirmed by GPC, the average weight molecular weight (Mw) in terms of polystyrene was 97000, and Mw / Mn was 1.5. Moreover, when the hydrogenation rate of the olefinic unsaturated bond was measured about the obtained product using NMR, it was confirmed that it is 99.9%. In addition, since the signal originating in an aromatic ring did not change, it was confirmed that the aromatic ring is not substantially hydrogenated. The obtained NMR chart is shown in FIG. On the other hand, as a result of measuring Tg using DSC, Tg was 118 ° C.

(Synthesis Example 2)
<Synthesis of aromatic norbornene B>
To a 2 L autoclave, 4-tBu-styrene (856 g: 5.36 mol), dicyclopentadiene (709 g: 5.36 mol), 4-tBu-catechol (44.6 g: 0.27 mol), and toluene (400 ml) were added. The mixture was stirred at 220 ° C. for 4 hours. The initial reaction showed a pressure of 0.6 MPa, but the pressure decreased with the passage of time and finally showed 0.4 MPa. Then, after the heating was stopped, the mixture was naturally allowed to cool to room temperature, and then the autoclave was opened, and the reaction product was taken out.

  Next, the reaction product thus obtained was subjected to precision distillation using a distillation column having a theoretical plate number of 20 to obtain a fraction of 118 to 120 ° C./1 mmHg. The yield of this fraction was 193 g (yield 16%, based on tBu-styrene). The product was 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene (B) with an endo / exo ratio of 65/35, and the purity was 98%.

<Polymerization of aromatic type norbornene B>
An anhydrous toluene solution of 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene (B) (2.26 g: 0.01 mol) having an endo / exo ratio of 65/35 under a nitrogen atmosphere. 20 ml), 1-hexene (2.5 μl: 0.2 mol%) and Grubbs I catalyst (4.1 mg: 0.05 mol%) in anhydrous toluene (2 ml) were added and stirred at room temperature for 20 hours to polymerize the solution. Got. Subsequently, the viscous polymerization solution was diluted with 100 ml of toluene, and the resulting precipitate was put into 3000 ml of methanol and filtered. Next, the precipitate was dried by a vacuum dryer to obtain 2.01 g (yield 90%) of B ring-opening polymer (pB). When the obtained product was confirmed by GPC, the weight average molecular weight (Mw) in terms of polystyrene was 95,000, and Mw / Mn was 1.7.

<Hydrogenation of Ring-Opening Polymer (pB) of Aromatic Norbornene B>
In a 0.2 L autoclave, 1.9 g of the ring-opening polymer (pB) of 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene, xylene (150 ml), RuHCl (CO) ( PPh ₃ ) ₃ (19 mg) was charged and purged with nitrogen. Subsequently, after hydrogenation reaction was performed by heating for 30 hours under the conditions of a hydrogen gas pressure of 10 MPa and a reaction temperature of 165 ° C., the obtained reaction solution was cooled to 25 ° C., and the hydrogen gas was released. The reaction solution thus obtained is poured into 3000 ml of methanol, and the precipitate is separated and collected. The obtained precipitate is dried to give 5- (p-tBuphenyl) bicyclo [2.2.1]- 1.75 g (yield 92%) of a hydrogenated product (HpB) of a ring-opening polymer of 2-heptene was obtained. When the obtained product was confirmed by GPC, the average weight molecular weight (Mw) in terms of polystyrene was 101000, Mw / Mn was 1.6, and Tg was 115 ° C.

(Synthesis Example 3)
<Synthesis of Aromatic Norbornene C>
240 mL of 30 g of 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene (A) having an endo / exo ratio (isomer ratio) of 80/20 synthesized by the method described in Synthesis Example 1 When heated and dissolved in methanol at 64 ° C. and allowed to cool naturally, 14 g of 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene (C) crystals were obtained. The purity of the obtained crystal was 99%, and the endo / exo ratio was 90/10.

<Polymerization of aromatic type norbornene C>
An anhydrous toluene solution of 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene (C) (2.26 g: 0.01 mol) having an endo / exo ratio of 90/10 under a nitrogen atmosphere ( 20 ml), 1-hexene (2.5 μl: 0.2 mol%) and Grubbs I catalyst (4.1 mg: 0.05 mol%) in anhydrous toluene (2 ml) were added and stirred at room temperature for 20 hours to polymerize the solution. Got. Subsequently, the viscous polymerization solution was diluted with 100 ml of toluene, and the resulting precipitate was put into 3000 ml of methanol and filtered. Next, the precipitate was dried by a vacuum dryer to obtain 2.01 g of C ring-opening polymer (pC) (yield 89%). When the obtained product was confirmed by GPC, the polystyrene equivalent weight average molecular weight (Mw) was 50000, and Mw / Mn was 1.8.

<Hydrogenation of ring-opening polymer (pC) of aromatic type norbornene C>
In a 0.2 L autoclave, 1.9 g of the ring-opening polymer (pC) of 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene, 150 ml of xylene, RuHCl (CO) (PPh _{3 3} ) 19 mg was charged and purged with nitrogen. Subsequently, after hydrogenation reaction was performed by heating for 30 hours under the conditions of a hydrogen gas pressure of 10 MPa and a reaction temperature of 165 ° C., the obtained reaction solution was cooled to 25 ° C., and the hydrogen gas was released. The reaction solution thus obtained is poured into 3000 ml of methanol, and the precipitate is separated and collected. The obtained precipitate is dried to give 5- (p-tBuphenyl) bicyclo [2.2.1]- 1.79 g (94% yield) of a hydrogenated product (HpC) of a ring-opening polymer of 2-heptene was obtained. When the obtained product was confirmed by GPC, the polystyrene equivalent average weight molecular weight (Mw) was 52000, Mw / Mn was 1.8, and Tg was 121 ° C.

(Synthesis Example 4)
<Synthesis of aromatic norbornenes D and E having an exo body ratio of 50% or more>
After filling quartz wool into a glass straight tube (made of quartz) of about 10 cm, it is heated to about 340 to 380 ° C. and using a dropping funnel under vacuum conditions, and 5- (p-tBuphenyl) bicyclo [2.2. 1] -2-heptene (A) (endo / exo = 80/20) was added dropwise to perform thermal decomposition. The reaction product was 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene having a high content of tBu styrene, cyclopentadiene, and exo form. This is because the endo form is more thermally unstable, so that the content of the exo form is improved when the thermal decomposition temperature is raised. The yield of 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene decreased with increasing temperature. As a result of thermal decomposition at a thermal decomposition temperature of 340 ° C., 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene (D) having an endo / exo ratio of 50/50 was obtained in a yield of 50% It was. Further, when the thermal decomposition temperature was increased to 380 ° C., 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene (E) having an endo / exo ratio of 24/76 was obtained at a yield of 13%. Obtained.

<Polymerization of aromatic type norbornene D>
An anhydrous toluene solution of 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene (D) (2.26 g: 0.01 mol) having an endo / exo ratio of 50/50 under a nitrogen atmosphere ( 20 ml), 1-hexene (2.5 μl: 0.2 mol%) and Grubbs I catalyst (4.1 mg: 0.05 mol%) in anhydrous toluene (2 ml) were added and stirred at room temperature for 20 hours to polymerize the solution. Got. Subsequently, the viscous polymerization solution was diluted with 100 ml of toluene, and the resulting precipitate was put into 3000 ml of methanol and filtered. Subsequently, the precipitate was dried by a vacuum dryer, and 2.19 g (yield 97%) of the ring-opening polymer (pD) of D was obtained. When the obtained product was confirmed by GPC, the weight average molecular weight (Mw) in terms of polystyrene was 113000, and Mw / Mn was 1.4.

<Polymerization of aromatic type norbornene E>
An anhydrous toluene solution of 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene (E) (2.26 g: 0.01 mol) having an endo / exo ratio of 24/76 in a nitrogen atmosphere ( 20 ml), 1-hexene (2.5 μl: 0.2 mol%) and Grubbs I catalyst (4.1 mg: 0.05 mol%) in anhydrous toluene (2 ml) were added and stirred at room temperature for 20 hours to polymerize the solution. Got. Subsequently, the viscous polymerization solution was diluted with 100 ml of toluene, and the resulting precipitate was put into 3000 ml of methanol and filtered. Subsequently, the precipitate was dried by a vacuum dryer, and 1.74 g (yield 77%) of a ring-opening polymer (pE) of E was obtained. When the obtained product was confirmed by GPC, the polystyrene-reduced weight average molecular weight (Mw) was 129000, and Mw / Mn was 1.7.

<Hydrogenation of Ring-Opening Polymer (pD) of Aromatic Norbornene D>
An autoclave with a capacity of 0.2 L was charged with 2.0 g of a ring-opening polymer (pD) of 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene having an endo / exo ratio of 50/50, 150 ml) and RuHCl (CO) (PPh ₃ ) ₃ (20 mg) were charged, and the atmosphere was replaced with nitrogen. Next, the hydrogenation reaction was performed by heating for 30 hours under the conditions of a hydrogen gas pressure of 10 MPa and a reaction temperature of 165 ° C., and then the resulting reaction solution was cooled to 25 ° C. to release the hydrogen gas. Next, the reaction solution is poured into 3000 ml of methanol, and the precipitate is separated and recovered. The obtained precipitate is dried to give 5- (p-tBuphenyl) bicyclo [2.2] having an endo / exo ratio of 50/50. .1] 1.96 g (98% yield) of a hydrogenated product (HpD) of a ring-opening polymer of 2-heptene. When the product thus obtained was confirmed by GPC, the average weight molecular weight (Mw) in terms of polystyrene was 112000, and Mw / Mn was 1.5. When the hydrogenation rate of the olefinic unsaturated bond was measured about the obtained product using NMR, it was confirmed that it was 99.9%. In addition, since the signal originating in an aromatic ring did not change, it was confirmed that the aromatic ring is not substantially hydrogenated. On the other hand, as a result of measuring Tg using DSC, Tg was 107 ° C.

<Hydrogenation of Ring-Opening Polymer (pE) of Aromatic Norbornene E>
An autoclave having a capacity of 0.2 L was charged with 2.0 g of a ring-opening polymer (pE) of 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene having an endo / exo ratio of 24/76, xylene ( 150 ml) and RuHCl (CO) (PPh ₃ ) ₃ (20 mg) were charged, and the atmosphere was replaced with nitrogen. Next, the hydrogenation reaction was performed by heating for 30 hours under the conditions of a hydrogen gas pressure of 10 MPa and a reaction temperature of 165 ° C., and then the resulting reaction solution was cooled to 25 ° C. to release the hydrogen gas. Next, the reaction solution is poured into 3000 ml of methanol, and the precipitate is separated and recovered. The obtained precipitate is dried to give 5- (p-tBuphenyl) bicyclo [2.2] having an endo / exo ratio of 24/76. .1] 1.70 g (yield 85%) of a hydrogenated product (HpE) of a ring-opening polymer of 2-heptene. When the product thus obtained was confirmed by GPC, the polystyrene-reduced average weight molecular weight (Mw) was 117,000, and Mw / Mn was 1.5. Moreover, when the hydrogenation rate of the olefinic unsaturated bond was measured about the obtained product using NMR, it was confirmed that it is 99.9%. In addition, since the signal originating in an aromatic ring did not change, it was confirmed that the aromatic ring is not substantially hydrogenated. On the other hand, as a result of measuring Tg using DSC, Tg was 105 ° C.

(Synthesis Example 5)
<Synthesis of exo type aromatic norbornene F>
Exo type aromatic norbornene F was synthesized according to the method described in Angew. Chem. Int. Ed., 39, p1946, 2000 and ibid., 34, p1844, 1995. That is, first, in a 0.3 L three-necked flask, 4-tBu-iodobenzene (5 g: 19.22 mmol), dinorbornadiene (5.66 g: 61.50 mmol), trans-di (μ-acetonato) bis [o- (Di-o-tolyl-phosphino) benzyl] dipalladium (II) (90 mg: 0.5 mol%), DMSO (82 ml), NEt ₃ (6.22 g: 61.5 mmol), formic acid (2.26 g: 49. 2 mmol) was added, and the mixture was stirred with heating at 120 ° C. for 16 hours. The reaction solution was cooled, poured into 300 ml of ice water, and extracted with n-hexane (50 ml × 3 times) using a separatory funnel. The n-hexane solution was washed with saturated brine, and dried over anhydrous magnesium sulfate. The extract was filtered and concentrated to obtain 3.62 g of a crude product. Next, this crude product was purified by distillation, and a fraction F of 104 ° C./1 mmHg was obtained. The yield of fraction F was 2.45 g (55% yield). As a result of conducting gas chromatographic analysis and NMR analysis of fraction F, 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene (endo / exo ratio (isomer ratio)) of 0/100 was obtained. F) was confirmed.

<Polymerization of aromatic type norbornene F>
An anhydrous toluene solution of 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene (F) (2.61 g: 11.6 mmol) having an endo / exo ratio of 0/100 in a nitrogen atmosphere ( 23 ml) was added 1-hexene (7.5 μl: 0.6 mol%) and Grubbs I catalyst (4.7 mg: 0.05 mol%) in anhydrous toluene (2 ml) and stirred at room temperature for 20 hours to polymerize the solution. Got. Subsequently, the viscous polymerization solution was diluted with 200 ml of toluene, and the resulting precipitate was put into 3000 ml of methanol and filtered. Next, the precipitate was dried by a vacuum dryer to obtain 2.28 g (yield 87%) of a ring-opening polymer (pF) of F. When the obtained product was confirmed by GPC, the weight average molecular weight (Mw) in terms of polystyrene was 174000, and Mw / Mn was 2.4.

<Hydrogenation of Ring-Opening Polymer (pF) of Aromatic Norbornene F>
An autoclave having a capacity of 0.2 L was charged with 2.3 g of a ring-opening polymer (pF) of 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene having an endo / exo ratio of 0/100, xylene ( 150 ml) and RuHCl (CO) (PPh ₃ ) ₃ (23 mg) were charged, and the atmosphere was replaced with nitrogen. Next, the hydrogenation reaction was performed by heating for 30 hours under the conditions of a hydrogen gas pressure of 10 MPa and a reaction temperature of 165 ° C., and then the resulting reaction solution was cooled to 25 ° C. to release the hydrogen gas. Next, this reaction solution is poured into 2000 ml of methanol, and the precipitate is separated and collected. The obtained precipitate is dried to give 5- (p-tBuphenyl) bicyclo [2.2 with an endo / exo ratio of 0/100. .1] 2.0 g (yield 89%) of a hydrogenated product (HpF) of a ring-opening polymer of 2-heptene.

  When the product thus obtained was confirmed by GPC, the polystyrene-reduced average weight molecular weight (Mw) was 173900, and Mw / Mn was 2.4. When the hydrogenation rate of the olefinic unsaturated bond was measured about the obtained product using NMR, it was confirmed that it was 99.9%. In addition, since the signal originating in an aromatic ring did not change, it was confirmed that the aromatic ring is not substantially hydrogenated. As a result of measuring Tg using DSC, Tg was 108 ° C.

(Examples 1-3)
Using the aromatic norbornene-based ring-opening polymer {HpA (Example 1), HpB (Example 2), HpC (Example 3)} obtained in Synthesis Examples 1 to 3, respectively, the retardation film of the present invention (Examples 1 to 3) were prepared. That is, first, a chlorobenzene solution containing each polymer at a concentration of 5 wt% was prepared. The chlorobenzene solution was cast onto a glass plate by a casting method so that the film thickness after drying was 100 to 200 μm, and then naturally dried for 24 hours. Then, after peeling off the obtained film from the glass plate, respectively, using a vacuum dryer kept at a temperature in the vicinity of Tg of the polymer that became the material of each film (Tg-10 ° C. of each polymer), It dried until the residual solvent density | concentration became 1.0 weight% or less. Next, the obtained film was cut into strips (size: 5.0 × 4.0 cm) and used as a material for each film using a biaxial stretching device (SS-60 model manufactured by Shibayama Kagaku). Under a temperature condition of Tg + 10 ° C. of the polymer, 50 mm / min. The film was subjected to uniaxial stretching of 200% (2.0 times) at a tensile speed of 1 to obtain retardation films of the present invention (Examples 1 to 3).

(Comparative Examples 1-3)
Example 1 except that the aromatic norbornene-based ring-opening polymer {HpD (Comparative Example 1), HpE (Comparative Example 2), HpF (Comparative Example 3)} obtained in Synthesis Examples 4 and 5 was used. A retardation film was produced using the same method.

<Evaluation of optical properties of retardation films obtained in Examples 1 to 3 and Comparative Examples 1 to 3>
The above evaluation method was employed to evaluate the total light transmittance, retardation, and wavelength dispersion value of the retardation films obtained in Examples 1 to 3 and Comparative Examples 1 to 3. That is, first, the retardation and wavelength dispersion value of the retardation films obtained in Examples 1 to 3 were measured using a retardation measuring instrument (trade name: KOBRA21DH, manufactured by Oji Scientific Co., Ltd.). The refractive index was measured with an Abbe refractometer. The refractive index is defined as an X-axis stretching direction by uniaxial stretching of the film, and a direction perpendicular to the X-axis is defined as a Y-axis and a Z-axis (Y-axis and Z-axis are also orthogonal), and the refraction in the X-axis direction. The refractive index was Nx, the refractive index in the Y-axis direction was Ny, and the refractive index in the Z-axis direction was Nz. The film thickness of the retardation film was measured with a micrometer manufactured by Mitutoyo. The results are shown in Table 1.

  As is apparent from the results shown in Table 1, the retardation films (Examples 1 to 3) of the present invention have birefringent wavelength dispersion characteristics, reverse dispersion characteristics, and a total light transmittance of 86. % Was sufficiently high, and it was confirmed that the film functions well as a retardation film. On the other hand, the retardation film (Comparative Examples 2 to 3) having an exo ratio of 76% or more exhibited normal dispersion characteristics and birefringence wavelength dispersion characteristics, and did not exhibit reverse dispersion characteristics. Further, the retardation film (Comparative Example 1) having an endo / exo ratio of 50/50 showed a reverse dispersion characteristic as a birefringence wavelength dispersion characteristic, but the light transmittance of the film was 85%. In comparison, the light transmittance was not sufficient. Moreover, from the results shown in Table 1, it was found that the total light transmittance of the film tends to decrease as the ratio of the exo body in the norbornene ring-opening polymer constituting the retardation film increases.

  As described above, according to the present invention, a retardation film comprising a single layer film, birefringent wavelength dispersion characteristics exhibit reverse dispersion, and a sufficiently high total light transmittance, and A liquid crystal display device using can be provided.

  Therefore, the retardation film of the present invention is particularly useful as a 1 / 2λ plate, a 1 / 4λ plate, a protective film, an antireflection film or the like used for a liquid crystal display device or the like.

2 is an NMR chart of a hydrogenated product (HpA) of an aromatic norbornene ring-opening polymer obtained in Synthesis Example 1. FIG.

Claims (3)

A retardation film formed by stretching a film made of a norbornene-based ring-opening polymer,
The norbornene-based ring-opening polymer is represented by the following general formula (1):

[In the formula (1), n represents an integer of 0 or 1,
X represents a group represented by the formula: —CH═CH— or a group represented by the formula: —CH ₂ CH ₂ —.
R ¹ , R ² , R ³ , R ⁴ may be the same or different and each is at least 1 selected from the group consisting of a hydrogen atom; a halogen atom; an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms optionally having a linking group; and an atom or group selected from the group consisting of polar groups;
Wavy lines a and b indicate the configuration of endo or exo,
The wavy line c indicates the configuration of endo or exo. ]
A norbornene-based ring-opening polymer in which the ratio of the structural units containing the structural unit represented by the formula (1) and the wavy line c of the structural units exhibit the exo configuration is in the range of 5 mol% to 35 mol%. Yes,
The total light transmittance of the retardation film is 86% or more,
A retardation film characterized by. The ratio of the structural unit in which X is a group represented by the formula: —CH ₂ CH ₂ — is 90 mol% or more based on all structural units in the norbornene-based ring-opening polymer. The retardation film according to claim 1.   A liquid crystal display device comprising the retardation film according to claim 1.

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