JP4799320B2 - Negative A retardation film and liquid crystal display device using the same - Google Patents

Description

The present invention relates to a negative A retardation film and a liquid crystal display device using the same, and more specifically, a negative 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 relates to an A retardation film and 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. Conventionally, positive birefringence such as polycarbonate and cyclic polyolefin is mainly used. Materials with properties have been used.

  Under such circumstances, a norbornene-based ring-opening polymer having a highly reactive norbornene derivative as a precursor among cyclic polyolefins has been developed. For example, JP 2003-255102 A (Patent Document 1), JP-A-2004-176051 (Patent Document 2) and JP-A-2004-323489 (Patent Document 3) disclose optical films made of a specific norbornene-based ring-opening polymer. However, the conventional norbornene-based ring-opening polymers described in Patent Documents 1 to 3 are not sufficiently high in adhesion to other materials, and are expected to be used for reverse wavelength dispersion films and the like. The negative birefringence that can be achieved is not sufficiently achieved.

  On the other hand, US Pat. No. 5,612,801 (Patent Document 4) discloses a so-called negative A retardation film exhibiting specific optical characteristics among negative birefringence. However, such conventional materials having negative birefringence such as polystyrene and polymethyl methacrylate are not sufficiently high in heat resistance, and it is difficult to obtain a negative A retardation film with such materials. there were.

  Further, a phase difference film (broadband phase difference plate: reverse) that gives a phase difference of ¼ wavelength in a wide wavelength range of the entire visible light range (400 to 800 nm) required for applications such as LCD and optical disk pickups. Various studies have also been made on wavelength-dispersing films. For example, JP-A-10-68816 (Patent Document 5) discloses a retardation film in which two retardation films are laminated in a substantially orthogonal direction and laminated. JP 2002-48919 A (Patent Document 6) discloses a retardation film obtained by polycondensation of two types of monomers exhibiting positive or negative intrinsic birefringence. Furthermore, JP-A-2001-194527 (Patent Document 7) discloses a retardation film obtained by alloying polymers exhibiting positive and negative intrinsic birefringence, and JP-A-2005-36201 ( Patent Document 8) 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 5, it is necessary to bond two films using an adhesive during 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 6 to 8, when blended during production, the polymers are difficult to mix with each other, so phase separation often causes white turbidity, 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.
JP 2003-255102 A JP 2004-176051 A JP 2004-323489 A US Pat. No. 5,612,801 JP-A-10-68816 JP 2002-48919 A JP 2001-194527 A JP 2005-36201 A

The present invention has been made in view of the above-described problems of the prior art, has a single layer with high transparency and excellent wavelength dispersion characteristics, and can give a specific phase difference to broadband light. , is very high adhesion with other materials, moreover negative Rukoto also possible negative a retardation film forming us optical characteristics as a specific negative a among birefringence, as well, using the same An object is to provide a liquid crystal display device.

As a result of intensive studies to achieve the above-mentioned object, the present inventors used a norbornene-based ring-opening polymer containing a structural unit represented by a specific structural formula, and contained in the polymer. By making the ratio of the exo isomer of the structural unit within a specific range, it has a single layer with high transparency and excellent wavelength dispersion characteristics, and can give a specific phase difference to broadband light. of very high adhesion to the material, moreover found that negative Rukoto also possible negative a retardation forming us optical characteristics as a specific negative a among birefringent film is obtained, the present invention It came to complete.

That is, the negative A retardation film of the present invention has 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 , and R ⁴ may be the same or different and are each at least one 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 proportion of the structural units in which the wavy line c of the structural units represents the exo configuration is in the range of more than 65 mol% to 100 mol% The film is formed by stretching.

In addition, the optical characteristics as the so-called negative A referred to herein are defined as the X-axis stretching direction defined by uniaxial stretching of the film, and the Y-axis and Z-axis directions defined orthogonal to the X-axis. The X-axis refractive index (Nx), the Y-axis refractive index (Ny), and the Z-axis refractive index (Nz) are expressed by the following formula (2):
Ny = Nz> Nx (2)
Satisfying the relationship represented by Therefore, the negative A retardation film of the present invention preferably satisfies the condition represented by the above formula (2). Then, according to the negative A retardation film satisfying such conditions, it is possible to improve the viewing angle and the tint of TFT-LCD and TN-TFT, which have been difficult in the past.

In the negative A 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 structure in the norbornene-based ring-opening polymer. It is preferable that it is 90 mol% or more with respect to the unit.

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

According to the present invention, a single layer has high transparency and excellent wavelength dispersion characteristics, can give a specific phase difference to broadband light, and has very high adhesion to other materials, Moreover negative Rukoto also possible negative a retardation film forming us optical characteristics as a specific negative a among birefringence, as well, it is possible to provide a liquid crystal display device using the same.

Further, such a negative A retardation film of the present invention can be thinned. Furthermore, the negative A retardation film of the present invention has a simplified manufacturing process, and can be manufactured with a high yield and a 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, the negative A retardation film of the present invention has 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 , and R ⁴ may be the same or different and are each at least one 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. ]
From the wavy line c is in the range ratio than less 100 mol% 65 mol% of the structural unit indicating the configuration of exo norbornene ring-opening polymer of in represented containing structural unit and the structural unit The film is formed by stretching.

  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 thereof, and further opens the norbornene monomer. A cyclopentane ring and an aromatic ring obtained by 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 35 to 100 mol%. More preferably, it is 65-100 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 35%, the reverse dispersion characteristic tends not to be exhibited, and on the other hand, when it is 65% or less, the negative A property is not exhibited. There is a tendency.

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 ratio of the structural units in which the wavy line c indicates the exo configuration is more than 65 mol% and 100 mol% or less .

  In the retardation film of the present invention, from the viewpoint of achieving reverse wavelength dispersion, the proportion of the structural units in which the wavy line c of the structural units exhibits the exo configuration is 35 mol%. It is preferably in the range of less than 65 mol% (more preferably in the range of 40 to 60). That is, as the retardation film of the present invention, the retardation film is made to have an inverse dispersion retardation by setting the ratio of the structural units in which the wavy line c exhibits the exo configuration to a range of 35 mol% or more and less than 65 mol%. It can be a film. When the ratio of the structural units in which the wavy line c indicates the exo configuration is 65 mol% or more, it is difficult to achieve reverse wavelength dispersion.

In the negative A retardation film of the present invention, from the viewpoint of achieving the optical characteristics of negative A, the ratio of the structural units in which the wavy line c exhibits the exo configuration is in the norbornene-based ring-opening polymer. Of all the structural units, it is preferable to be in the range of more than 65 mol% and 100 mol% or less (more preferably 70 to 100 mol%). That is, as the retardation film of the present invention, the retardation film is made to have a negative A retardation by setting the ratio of structural units in which the wavy line c exhibits a configuration of exo to a range of more than 65 mol% and 100 mol% or less. It can be a film. When the ratio of the structural units in which the wavy line c indicates the exo configuration is less than 65 mol% of the total structural units in the norbornene-based ring-opening polymer, a specific negative among the negative birefringences. There is a tendency that the optical characteristics as A cannot be achieved. And as such a negative A phase difference film, when the stretching direction by uniaxial stretching of the film is defined as the X axis, and the directions orthogonal to the X axis are defined as the Y axis and the Z axis, the X axis The refractive index (Nx), the Y-axis refractive index (Ny), and the Z-axis refractive index (Nz) are represented by the following formula (2):
Ny = Nz> Nx (2)
What satisfies the relationship represented by these is preferable.

  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-phenyl tetracyclo [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- heptaene, tetracyclo [7.4.1 ^{10 , 13} .0 ^1,9 .0 ^2,7 ] tetradeca-2,4,6,11-tetraene, 2-oxotetracyclo [7. 4.1 ^10,13 .0 ^1,9 .0 ^3,8] tetradeca -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-methylphenyl) 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) bi Chlo [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-aminophenyl) -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-carboxyl Tilbicyclo [2.2.1] -2-heptene, 5- (o-bromophenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (o-bromophenyl) -6-carboxymethylbicyclo [ 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-carboxylic acid 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-hepte 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-heptene 5-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-carboxyphenylbicyclo [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-carboxyethylbicycle [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-carboxycholesteryl 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-carboxyallylbisic B [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-carvone Bicyclo [2.2.1] -2-heptene, 5- (2-chloro-5-nitrophenyl) -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-hepte 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-carboxymethylbicyclo [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-carboxymethyl Bicyclo [2.2.1] -2-heptene, 5- (3,5-Dimethoxy-4-hydroxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (2,5-dimethoxyphenyl) -6-carboxylic acid 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-carboxymethylbicyclo [ 2.2.1] -2-heptene, 5- (2,3-dimethoxyphenyl) -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- Methoxyphenyl) -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 bicyclo [2.2.1] -2-heptene, 5- (4-fluorophenyl) -6-carboxymethylbicyclo [2.2.1] -2-heptene, 5- (4-fluoro Phenyl) -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-he , 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-hydroxy-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-Carboki Cyethylbicyclo [2.2.1] -2-heptene, 5- (3-methoxyphenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (3-methoxyphenyl) -6-carboxymethyl Bicyclo [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-methoxyphenyl) -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-methylenedioxy Enyl) -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-methyl Phenyl) -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-carboxy Ethylbicyclo [2.2.1] -2-heptene, 5- (3- Tylphenyl) -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-carboxy Methylbicyclo [2.2.1] -2-heptene, 5-methyl-5-phenyl-6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (3-nitrophenyl) -6-carboxylic acid bicyclo [ 2.2.1] -2-heptene, 5- (3-nitrophenyl) -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-carboxyethylbicyclo [2.2.1] ] -2-heptene, 5- (2-nitrophenyl) -6-carboxylic acid bicyclo [2.2.1] -2-heptene, 5- (2-nitrophenyl) -6-carboxymethylbicyclo [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-octadecyloxyphenyl) -6-carboxy Ethylbicyclo [2.2.1] -2-heptene, 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-trimethoxyphenyl) -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-carboxymethylbicyclo [2.2.1] -2-heptene 5- (2,4,5-trimethoxyphenyl) -6-carboxyethylbicyclo [2.2.1] -2-heptene, 5- (3-trifluoromethylphenyl) -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-cal Carboxyethyl bicyclo [2.2.1] -2-heptene, 5- (4-cyano-methylphenyl) 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-tetraphenylbicyclo [2.2.1] -2-heptene, 8,8,9,9-tetraphenyltetracyclo [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- tri phenyl tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 5,5,6 triphenyl [2.2.1] -2-heptene, 8,8,9- triphenyl Tetracyclo [4.4.1 ^2,5 .1 ^7,1 .0] -3-dodecene and 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 200 ° 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-methoxy cinnamic 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 benzylcyanide, 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 ratio of these isomers contained in the film is appropriately selected according to the target optical properties. For example, a film in which birefringence does not substantially occur can be obtained by appropriately changing the content ratio of these isomers. 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. Moreover, negative A property means the property which satisfy | fills the above-mentioned Formula (2), and means the property in which the refractive index of an extending | stretching direction becomes smaller than the refractive index of the orthogonal | vertical direction with respect to an extending | stretching direction. In addition, such isomers can be easily changed in the ratio in the product, for example, by appropriately changing the reaction conditions during the production of the monomer, The ratio can also 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).
The metathesis polymerization catalyst described in Press 1997) 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; benzene, toluene, xylene, ethylbenzene, cumene, etc. aromatic hydrocarbons; 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 they can be used as heterogeneous catalysts or homogeneous catalysts. 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, and the like. The form of such a hydrogenation catalyst may be powder or granular.

Furthermore, such a hydrogenation catalyst needs to be adjusted in the amount added 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 negative A 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, the biaxial stretching method includes a tenter method, a tube method, etc., and the uniaxial stretching method includes a water tank stretching method, a radiation stretching method, 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 above negative A retardation film of the present invention.

The negative A retardation film of the present invention is a retardation film that has high transparency and excellent wavelength dispersion, and can give a specific retardation to broadband light. In addition, it is possible to achieve a specific optical characteristic as negative A among negative birefringences, so that a quarter λ plate in a reflective liquid crystal display device and 1 in a liquid crystal projector device can be achieved. / 2λ plate and 1 / 4λ plate, 1 / 2λ plate and 1 / 4λ plate in transmissive liquid crystal display device, protective film for polarizing film used in liquid crystal display device, antireflection film and the like.

  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.

Further, the negative A 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 is transparent in a touch panel or a liquid crystal display device. It can also be used as an electrode film.

  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>
Retardation (Re) and birefringence defined by the following formulas using a retardation measuring device (trade name: KOBRA21DH, manufactured by Oji Scientific Co., Ltd.) for the retardation films obtained in each Example and Comparative Example. The chromatic dispersion value (D) of 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).

(Synthesis Example 1)
<Synthesis of aromatic norbornenes A and 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 (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 and a fraction B of 165 to 170 ° C./1 mmHg. The yield of fraction A was 640 g (53% yield, based on tBu-styrene), and the yield of fraction B was 97 g (6% yield, based on tBu-styrene). As a result of performing gas chromatographic analysis and NMR analysis of fraction A, 5- (p-tBu phenyl) bicyclo [2.2.1] -2-heptene (endo / exo ratio (isomer ratio)) of 79/21 ( The following general formula (8) was confirmed.

Further, as a result of gas chromatographic analysis and NMR analysis of the fraction B, 8- (p-tBu phenyl) tetracyclo [4.4.1 ^2,5 ... With an endo-endo / endo-exo ratio of 87/13. 1 ^7,10 . 0] -3-dodecene (the following general formula (9)).

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. When 30 g of fraction B was dissolved in 150 ml of isopropyl alcohol by heating and allowed to cool naturally, 8- (p-tBuphenyl) tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 18 g of 0] -3-dodecene (B) crystals were obtained. The purity of the obtained crystal was 99%, and the endo-endo / endo-exo ratio was 100/0.

<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) was added an anhydrous toluene solution (2 ml) of 1-hexene (2.5 μl: 0.2 mol%) and Grubbs I catalyst (4.1 mg: 0.05 mol%), and the mixture was stirred at room temperature for 20 hours. 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.

<Polymerization of aromatic type norbornene B>
8- (p-tBuphenyl) tetracyclo [4.4.1 ^2,5 . With an endo-endo / endo-exo ratio of 100/0 in a nitrogen atmosphere. 1 ^7,10 . 0] -3-dodecene (B) (2.90 g: 0.01 mol) in anhydrous toluene (20 ml) and 1-hexene (2.5 μl: 0.2 mol%) and Grubbs I catalyst (4.1 mg: 0.1 mol). (05 mol%) in anhydrous toluene (2 ml) was added and stirred at room temperature for 20 hours. 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 2.84 g of B ring-opening polymer (pB) (yield 98%). When the obtained product was confirmed by GPC, the weight average molecular weight (Mw) in terms of polystyrene was 125000 and Mw / Mn was 1.5.

<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, 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 obtained reaction solution was cooled 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.

<Hydrogenation of Ring-Opening Polymer (pB) of Aromatic Norbornene B>
In a 0.2 L autoclave, 8- (p-tBuphenyl) tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -3-dodecene ring-opening polymer (pB) 2.0 g, xylene (150 ml) and RuHCl (CO) (PPh ₃ ) ₃ (20 mg) were charged, and the atmosphere was replaced with nitrogen. Subsequently, 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 release the hydrogen gas. Next, this reaction solution is poured into 3000 ml of methanol, and the precipitate is separated and recovered. The obtained precipitate is dried to obtain 8- (p-tBuphenyl) tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -3-dodecene ring-opened polymer hydrogenated product (HpB) 1.99 g (yield 99.5%) was obtained.

  When the product thus obtained was confirmed by GPC, the polystyrene-reduced average weight molecular weight (Mw) was 96400, 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. The obtained NMR chart is shown in FIG. On the other hand, as a result of measuring Tg using DSC, Tg was 226 ° C.

(Synthesis Example 2)
<Synthesis of aromatic norbornenes C and D with different endo / exo ratios>
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 (endo / exo = 79/21) 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 (C) 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 (D) having an endo / exo ratio of 24/76 was obtained at a yield of 13%. Obtained.

<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 50/50 under a nitrogen atmosphere ( 20 ml) was added an anhydrous toluene solution (2 ml) of 1-hexene (2.5 μl: 0.2 mol%) and Grubbs I catalyst (4.1 mg: 0.05 mol%), and the mixture was stirred at room temperature for 20 hours. 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 2.19 g of C ring-opening polymer (pC) (yield 97%). 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 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 24/76 in a nitrogen atmosphere ( 20 ml) was added an anhydrous toluene solution (2 ml) of 1-hexene (2.5 μl: 0.2 mol%) and Grubbs I catalyst (4.1 mg: 0.05 mol%), and the mixture was stirred at room temperature for 20 hours. 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 (pD) of D 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 (pC) of aromatic type norbornene C>
An autoclave having a capacity of 0.2 L was charged with 2.0 g of a ring-opening polymer (pC) of 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene having an endo / exo ratio of 50/50, xylene ( 150 ml) and RuHCl (CO) (PPh ₃ ) ₃ (20 mg) were charged, and the atmosphere was replaced with nitrogen. Subsequently, 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 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 (HpC) 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. The obtained NMR chart is shown in FIG. On the other hand, as a result of measuring Tg using DSC, Tg was 107 ° C.

<Hydrogenation of Ring-Opening Polymer (pD) of Aromatic Norbornene D>
An autoclave having 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 24/76, xylene ( 150 ml) and RuHCl (CO) (PPh ₃ ) ₃ (20 mg) were charged, and the atmosphere was replaced with nitrogen. Subsequently, 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 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 (HpD) 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. The obtained NMR chart is shown in FIG. On the other hand, as a result of measuring Tg using DSC, Tg was 105 ° C.

(Synthesis Example 3)
<Synthesis of exo type aromatic norbornene E>
Angew. Chem. Int. Ed. 39, p 1946, 2000 and ibid. , 34, p1844, 1995, exo type aromatic norbornene E was synthesized. 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) The mixture was heated and stirred at 120 ° C. for 16 hours. Next, the obtained reaction solution was cooled, poured into 300 ml of ice water, and extracted with n-hexane (50 ml × 3 times) using a separatory funnel. Thereafter, the n-hexane solution was washed with saturated brine, dried over anhydrous magnesium sulfate, and the extract was filtered and concentrated to obtain 3.62 g of a crude product. Subsequently, the obtained crude product was purified by distillation to obtain a fraction E of 104 ° C./1 mmHg. The yield of fraction E was 2.45 g (55% yield). As a result of conducting gas chromatographic analysis and NMR analysis of fraction E, it was found that 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene having an endo / exo ratio (isomer ratio) of 0/100. It was confirmed that there was.

<Polymerization of aromatic type norbornene E>
An anhydrous toluene solution of 5- (p-tBuphenyl) bicyclo [2.2.1] -2-heptene (E) (2.61 g: 11.6 mmol) having an endo / exo ratio of 0/100 under 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 the mixture was stirred at room temperature for 20 hours. 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 ring-opened polymer (pE) of E. 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 (pE) of Aromatic Norbornene C>
An autoclave having a capacity of 0.2 L was charged with 2.3 g of a ring-opening polymer (pE) 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. Subsequently, 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 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 (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 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. The obtained NMR chart is shown in FIG. On the other hand, as a result of measuring Tg using DSC, Tg was 108 ° C.

(Synthesis Example 4)
<Synthesis of Aromatic Norbornene F>
(I) Synthesis of cinnamic acid phenyl ester A 1 L three-necked flask was charged with trans-cinnamic acid chloride (100 g, 0.60 mol), phenol (59.3 g, 0.63 mol), and THF (500 ml) in a nitrogen stream. Under cooling, a THF solution (100 ml) of triethylamine (63.8 g, 0.63 mol) was added dropwise using a dropping funnel. After completion of the dropwise addition, the mixture was stirred at room temperature for 12 hours, and then the reaction solution was put into a water bath. The resulting white precipitate was filtered and dried under reduced pressure, and the yield was 135.5 g (yield 99.9%). This was dissolved in about 200 ml of methanol by heating and cooled to obtain white crystals (112.6 g, yield 83.8%). In addition, it was confirmed by NMR structural analysis that the obtained crystal was trans-cinnamic acid phenyl ester which was the target product.

(Ii) Synthesis of Aromatic Norbornene F In a 0.3 L autoclave, trans-cinnamic acid phenyl ester (112 g, 0.5 mol) and dicyclopentadiene (36.4 g, 0.3 mol) obtained as described above were added. 55 mol) and toluene (100 ml) were added, and the mixture was stirred at 180 ° C. for 4 hours. Then, after the heating was stopped, the mixture was naturally cooled and cooled to room temperature, and then the autoclave was opened and the reaction product was taken out. Next, this reaction product was concentrated, and a part of the concentrate (1.2 g) was separated and purified by recycle preparative HPLC (LC-918, manufactured by Nippon Analytical Industrial Co., Ltd.), and the desired product, 5-phenyl-6-carboxyphenyl. 0.58 g (reaction yield 40%) of bicyclo [2.2.1] -2-heptene (F) was obtained (recycled 7 times). Moreover, such a fractionation operation was repeated 4 times to obtain 2.7 g of the target product. As a result of structural analysis by NMR, the target product thus obtained was a mixture having an isomer ratio endo / exo ratio of 60/40.

<Polymerization of aromatic type norbornene F>
An anhydrous THF solution of 5-phenyl-6-carboxyphenylbicyclo [2.2.1] -2-heptene (F) (2.67 g, 9.2 mmol) having an endo / exo ratio of 60/40 under a nitrogen atmosphere ( 25 ml) was added a solution of Grubbs II catalyst (3.9 mg, 0.05 mol%) in anhydrous THF (5 ml), and the mixture was stirred at room temperature for 20 hours. Subsequently, the viscous polymerization solution was diluted with 200 ml of THF, and the resulting precipitate was put into 3000 ml of methanol and filtered. Next, the precipitate was dried by a vacuum dryer, and 2.3 g (yield 87%) of a ring-opening polymer (pF) of 5-phenyl-6-carboxyphenylbicyclo [2.2.1] -2-heptene (F). ) When the obtained product was confirmed by GPC, the weight average molecular weight (Mw) in terms of polystyrene was 3096000, and Mw / Mn was 2.7.

<Hydrogenation of Ring-Opening Polymer (pF) of Aromatic Norbornene F>
In a 0.2 L autoclave, a ring-opening polymer of 5-phenyl-6-carboxyphenylbicyclo [2.2.1] -2-heptene (pF) 2.20 g, xylene (150 ml), RuHCl (CO) (PPh ₃ ) ₃ (22 mg) was charged and purged with nitrogen. Subsequently, 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 release the hydrogen gas. Next, this reaction solution is poured into 3000 ml of methanol to separate and recover the precipitate, and the obtained precipitate is dried to open 5-phenyl-6-carboxyphenylbicyclo [2.2.1] -2-heptene. 1.97 g (yield 89.5%) of a hydrogenated product (HpF) of a ring polymer was obtained.

  When the product thus obtained was confirmed by GPC, the polystyrene-reduced average weight molecular weight (Mw) was 3920000, and Mw / Mn was 1.8. 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. The obtained NMR chart is shown in FIG. On the other hand, as a result of measuring Tg using DSC, Tg was 103 ° C.

(Examples 1-2 and Reference Examples 1-6 )
Aromatic norbornene ring-opening polymers obtained in Synthesis Examples 1 to 4 {HpA ( Reference Example 1), HpB ( Reference Example 2), HpC ( Reference Example 3), HpD (Example 1 ), HpE (implementation) Example 2 ), HpF ( Reference Example 4 )} were used to prepare retardation films ( Examples 1-2 and Reference Examples 1-4 ). Furthermore, position of HPA (0.925 g) and HPC the HpG a polymer solution blend (0.695 g) (Reference Example 5), hph a polymer solution blend of HPC (0.462 g) and HpD (0.420 g) (Reference Example 6) Phase difference films ( Reference Examples 5 to 6 ) were prepared. That is, first, a chlorobenzene solution containing each polymer at a concentration of 5 wt% was prepared, cast on a glass plate by a casting method, and naturally dried for 24 hours. Next, after peeling off the obtained film from the glass plate, respectively, using a vacuum dryer maintained at a temperature around the 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. The films thus obtained were sufficiently high in transparency. Moreover, the film thickness of the obtained film was 30-150 micrometers. Next, the obtained film was cut into strips (size: 5.0 × 4.0 cm), and each film was used using a biaxial stretching apparatus (trade name “SS-60 type” manufactured by Shibayama Kagaku). 50 mm / min. At a temperature condition of Tg + 10 ° C. Performed uniaxially stretched 200% (2.0 times) at a pulling speed of, to obtain a phase difference film (Examples 1-2 and Reference Examples 1-6).

<Evaluation of optical properties of retardation films obtained in Examples 1-2 and Reference Examples 1-6 >
The birefringence of the retardation films obtained in Examples 1-2 and Reference Examples 1-6 was measured with a retardation measuring device. The obtained results are shown in Table 1. The refractive index was measured with an Abbe refractometer. Further, a stretching direction by uniaxial stretching of the film is defined as an X-axis, and directions perpendicular to the X-axis are defined as a Y-axis and a Z-axis (Y-axis and Z-axis are also orthogonal), and the X-axis refractive index (Nx ), The refractive index (Ny) of the Y axis, and the refractive index (Nz) of the Z axis.

Moreover, about the retardation film obtained in Examples 1-2, Reference Example 1, Reference Example 3, and Reference Examples 5-6 , the graph which shows the ratio of the exo body to contain and the relationship with birefringence is shown in FIG. Show. Furthermore, for the retardation films obtained in Examples 1-2, Reference Example 1, Reference Example 3, and Reference Examples 5-6 , the ratio of the exo-forms contained and the wavelength dispersion value {D = (Δn: λ481 nm) / A graph showing the relationship with (Δn: λ589 nm)} is shown in FIG.

As is clear from the results shown in Table 1 and FIG. 7, it was confirmed that the retardation films obtained in each Example functioned well as a retardation film. Further, in the retardation films of HpD and HpE (Examples 1 and 2 ), the following formula (2):
Ny = Nz> Nx (2)
Therefore, it was confirmed that the film functions as a so-called negative A retardation film.

Further, as is apparent from the results shown in FIG. 8, the wavelength dispersion value {D = (Δn: λ481 nm) / (Δn: λ589 nm)} of the birefringence of each retardation film may vary depending on the endo / exo ratio of the monomer. It was confirmed that the retardation films obtained in Reference Examples 1, 3 , 5, and 6 were reverse dispersion retardation films.

<Evaluation of Adhesiveness of Retardation Films Obtained in Examples 1-2 and Reference Examples 1-6 >
The retardation films obtained in Examples 1 and 2 and Reference Examples 1 to 6 were adhered to the surface of a triacetyl cellulose substrate with an ultraviolet curable adhesive (UVX-1620 manufactured by Toagosei Co., Ltd.), and described in JIS-K5400. When the adhesiveness was evaluated based on the method, it was confirmed that all the retardation films had very high adhesiveness with the triacetylcellulose film.

As described above, according to the present invention, a single layer has high transparency and excellent wavelength dispersion characteristics, can give a specific phase difference to broadband light, and is in close contact with other materials. sex is very high and negative Rukoto also possible negative a retardation film forming us optical characteristics as a specific negative a among birefringence, as well as to provide a liquid crystal display device using the same Is possible.

  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. 3 is an NMR chart of a hydrogenated product (HpB) of an aromatic norbornene ring-opening polymer obtained in Synthesis Example 1. FIG. 4 is an NMR chart of a hydrogenated product (HpC) of an aromatic norbornene ring-opening polymer obtained in Synthesis Example 2. FIG. 4 is an NMR chart of a hydrogenated product (HpD) of an aromatic norbornene ring-opening polymer obtained in Synthesis Example 2. FIG. 4 is an NMR chart of a hydrogenated product (HpE) of an aromatic norbornene ring-opening polymer obtained in Synthesis Example 3. FIG. 6 is an NMR chart of a hydrogenated product (HpF) of an aromatic norbornene ring-opening polymer obtained in Synthesis Example 4. FIG. It is a graph which shows the relationship between the exo ratio and birefringence about the stretched film obtained in Examples 1-2, Reference Example 1, Reference Example 3, and Reference Examples 5-6 . It is a graph which shows the relationship between the exo ratio about the stretched film obtained by Example 1-2, Reference Example 1, Reference Example 3, and Reference Examples 5-6 , and the chromatic dispersion value of birefringence.

Claims (4)

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 , and R ⁴ may be the same or different and are each at least one 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. ]
From the wavy line c is in the range ratio than less 100 mol% 65 mol% of the structural unit indicating the configuration of exo norbornene ring-opening polymer of in represented containing structural unit and the structural unit A negative A phase difference film obtained by stretching a film. When the stretching direction by uniaxial stretching of the film is defined as the X axis and the directions orthogonal to the X axis are defined as the Y axis and the Z axis, the refractive index (Nx) of the X axis, the refractive index of the Y axis ( Ny) and the refractive index (Nz) of the Z axis are the following formula (2):
Ny = Nz> Nx (2)
The negative A retardation film according to claim 1 , satisfying a relationship represented 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 negative A phase difference film according to claim 1 or 2 . A liquid crystal display device comprising: a negative A retardation film according to any one of claims 1-3.

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