CN101512397B - Retardation film, and liquid crystal display device using the same - Google Patents

Abstract

The present invention provided is a retardation film produced by stretching a film comprising a norbornene ring-opening polymer, wherein the norbornene ring-opening polymer contains a constituent unit (A) represented by the general formula (1) and the constituent unit (A) contains 35 to 100 mol% inclusive of a constituent unit (A-1) which is a type of the constituent unit (A) wherein the wavy line c in the formula (1) shows an exo-type configuration. (1) wherein n represents an integer of 0 or 1; X<1> represents a group represented by the formula: -CH=CH- or a group represented by the formula: -CH2CH2-; R<1>, R<2>, R<3> and R<4> independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have at least one linking group selected from an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom, and a polar group; the wavy lines a and b independently represents an endo- or exo-type configuration; and the wavy line c represents an endo- or exo-type configuration.

Description

Retardation film and liquid crystal display device using same

technical field

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

Background technique

In liquid crystal display devices such as liquid crystal displays (LCDs), for the purpose of optical compensation, retardation films that control optical anisotropy are used. Conventionally, materials with positive birefringence, such as polycarbonate and cyclic polyolefin, have been mainly used. .

Under such circumstances, a norbornene-based ring-opening polymer using norbornene derivatives with particularly high reactivity among cyclic polyolefins as a precursor has been developed. 1), JP-A-2004-176051 (Document 2) and JP-A-2004-323489 (Document 3) disclose optical films made of specific norbornene-based ring-opening polymers. However, conventional norbornene-based ring-opening polymers, as described in Documents 1 to 3, do not have sufficiently high adhesion to other materials, and cannot sufficiently achieve the negative birefringence expected to be utilized in reverse wavelength dispersion films, etc. .

On the other hand, U.S. Patent No. 5,612,801 (Document 4) discloses a so-called negative A retardation film that exhibits specific optical properties even in negative birefringence. However, such materials having negative birefringence, which are known conventionally as polystyrene and polymethyl methacrylate, do not have sufficiently high heat resistance, and it is difficult to obtain a negative A retardation film using such materials.

In addition, a retardation film (wide-range retardation plate: reverse wavelength Dispersive film) of various studies. For example, JP-A-10-68816 (Document 5) discloses a retardation film in which two retardation films are bonded and laminated in directions substantially perpendicular to each other. In addition, JP-A-2002-48919 (Document 6) discloses a retardation film obtained by polycondensing two types of monomers showing positive or negative intrinsic birefringence. Also disclosed in JP-A-2001-194527 (Document 7) is a retardation film obtained by alloying polymers showing positive and negative intrinsic birefringence, and in JP-A-2005-36201 (Document 8). A retardation film obtained by ring-opening (co)polymerizing two types of norbornene-based monomers showing positive or negative intrinsic birefringence after polymerization was obtained.

However, the retardation film described in Document 5 requires bonding of two films using an adhesive during production, and there are problems in terms of productivity such as complicated production steps, decreased yield, and increased cost. In addition, with regard to the conventional retardation films described in Documents 6 to 8, when they are mixed during production, the polymers are difficult to mix, so phase separation often occurs and cloudiness occurs, and it is difficult to use them in optical applications. retardation film. In addition, monomers exhibiting negative birefringence used in the production of these retardation films have a special structure, so there are also problems in that the production is difficult and expensive.

Contents of the invention

The present invention is made in view of the above-mentioned problems in the prior art, and aims to provide a single layer with high transparency and excellent wavelength dispersion characteristics, which can give a specific retardation to a wide range of light, and provide a close bond with other materials. Retardation film and liquid crystal display device using the retardation film and the retardation film that can make the wavelength dispersion characteristic of birefringence reversely dispersed even in the negative birefringence, and can achieve the optical characteristic of specific negative A, which is very high. .

The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, have found that the shape of the above-mentioned structural unit contained in the polymer can be changed by using a norbornene-based ring-opening polymer containing a structural unit represented by a specific structural formula. By setting the conformational ratio in a specific range, a single layer with high transparency and excellent wavelength dispersion characteristics can be obtained, and a specific retardation can be given to a wide range of light, and the adhesion with other materials is very high, and even in The present invention has been accomplished so far with a retardation film that can achieve specific negative A optical characteristics even in negative birefringence, and can make the wavelength dispersion characteristics of birefringence into inverse dispersion.

That is, the retardation film of the present invention is obtained by stretching a film formed of a norbornene-based ring-opening polymer,

This norbornene-based ring-opening polymer contains a structural unit (A) represented by the following general formula (1), and in the above-mentioned structural unit (A), the following wavy line c represents the structure of the external stereo configuration The content ratio of the unit (A-1) is in the range of 35 mol% or more and 100 mol% or less,

[in formula (1), n represents the integer of 0 or 1,

X ¹ 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 represent any atom or group selected from a hydrogen atom, a halogen atom, a hydrocarbon group and a polar group, and the above hydrocarbon group may have A substituted or unsubstituted hydrocarbon group with 1 to 30 carbon atoms of at least one linking group of atom, sulfur atom and silicon atom,

The wavy lines a and b indicate the three-dimensional configuration of the inner or outer shape,

The wavy line c indicates the three-dimensional configuration of the endo- or exo-shape. ]

Such a retardation film of the present invention can make the wavelength dispersion characteristic of birefringence reverse dispersion. Then, from the viewpoint of exhibiting such reverse dispersion, as the above-mentioned retardation film of the present invention, in the above-mentioned structural unit (A), the above-mentioned wavy line c represents a structural unit (A-1) of an external stereo configuration. The content ratio of is in the range of not less than 35 mol % and not more than 65 mol %, and the retardation film is preferably a reverse dispersion retardation film.

Regarding the retardation film of the present invention described above, the optical characteristic of specific negative A can be achieved even in negative birefringence. And, from the viewpoint of achieving the optical characteristics as negative A, as the above-mentioned phase difference film of the present invention, in the above-mentioned structural unit (A), the above-mentioned wavy line c represents the structural unit of the stereo configuration of the external shape (A-1 ) is in the range of more than 65 mol % and 100 mol % or less, and the retardation film is preferably a negative A retardation film.

In addition, the so-called negative A optical characteristics mean that when the stretching direction of the uniaxial stretching of the above-mentioned film is defined as the X axis, and the direction perpendicular to the X axis is defined as the Y axis and the Z axis, the X The refractive index (Nx) of the axis, the refractive index (Ny) of the Y axis and the refractive index (Nz) of the Z axis satisfy the relationship shown in the following relational formula (1):

Ny=Nz>Nx(1).

Therefore, the retardation film of the present invention preferably satisfies the condition represented by the above relational expression (1). Furthermore, if a negative A retardation film satisfying such conditions is used, it becomes possible to improve the viewing angle and color tone of TFT-LCD and TN-TFT, which were difficult in the past.

In addition, in the retardation film of the present invention described above, X ¹ in the above general formula (1) is a content ratio of a structural unit of a group represented by the formula -CH ₂ CH ₂ -, with respect to the above-mentioned norbornene-based ring-opening polymerization The total structural units in the compound are preferably 90 mol% or more.

In addition, regarding the retardation film of the present invention described above, the norbornene-based ring-opening polymer may be a norbornene-based ring-opening copolymer that further contains a structural unit (B) represented by the following general formula (3). When, the above-mentioned structural unit (A) is a structural unit (A') represented by the following general formula (2), and the stereo configuration of the substituted or unsubstituted phenyl group in the following general formula (2) is exo The content ratio of the coordinated structural unit (A'-1) is preferably in the range of 90 mol% or more relative to the total amount of the structural unit (A'). That is, with respect to the retardation film of the present invention, the norbornene-based ring-opening polymer is preferably a norbornene-based ring-opening copolymer, and the norbornene-based ring-opening copolymer preferably contains the following general formula (2): The structural unit (A') shown and the structural unit (B) represented by the following general formula (3). In addition, in the retardation film of the present invention, the above-mentioned norbornene-based ring-opening polymer, in the above-mentioned structural unit (A'), the stereo configuration of the substituted or unsubstituted phenyl group in the above-mentioned general formula (2) The content ratio of the structural unit (A'-1) which coordinates to an exo form is in the range of 90 mol% or more.

[In formula (2), n, X ¹ , R ¹ , R ² , R ³ , R ⁴ and wavy line c are the same as n, X ¹ , R ¹ , R ² , R ³ , R ⁴ has the same meaning as the wavy line c. ]

[In formula (3), n represents the integer of 0 or 1,

X ² represents a group represented by the formula -CH=CH- or a group represented by the formula -CH ₂ CH ₂ -,

R ⁵ , R ⁶ , R ⁷ , and R ⁸ may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 1 to 20 carbon atoms, and a carbon Any atom or group in an alkylcarbonyl group with 1 to 20 atoms and an ester group with a hydrocarbon group with 1 to 20 carbon atoms,

Two or more of R ⁵ to R ⁸ are bonded to each other to form a monocyclic hydrocarbon with 3 to 20 carbon atoms that may have an unsaturated bond, or a polycyclic hydrocarbon with 4 to 20 carbon atoms that may have an unsaturated bond. hydrocarbon,

R ⁵ and R ⁶ , or R ⁷ and R ⁸ may together form an alkylene group having 1 to 20 carbon atoms. ]

Thus, in the present invention, as the above-mentioned norbornene-based ring-opening polymer, a compound containing the structural unit (A') represented by the above general formula (2) and the structural unit (B) represented by the above general formula (3) is used , and when the ratio of the above-mentioned structural unit (A'-1) is a norbornene-based ring-opening copolymer in a specific range, the single layer has high transparency and excellent wavelength dispersion characteristics, and can give specific light to a wide range of light. The phase difference and the adhesiveness with other materials are very high, and even in the negative birefringence, it can achieve the specific negative A optical characteristic, and the wavelength dispersion characteristic of the birefringence can be reversed dispersion.

In addition, regarding the above-mentioned retardation film of the present invention, even when the above-mentioned norbornene-based ring-opening polymer is the above-mentioned norbornene-based ring-opening copolymer containing a structural unit (A') and a structural unit (B), It is also possible to make the wavelength dispersion characteristic of birefringence reverse dispersion. Furthermore, when the above-mentioned norbornene-based ring-opening polymer is the above-mentioned norbornene-based ring-opening copolymer containing a structural unit (A') and a structural unit (B), from the viewpoint of exerting such reverse dispersibility , as the above-mentioned phase difference film of the present invention, the ratio of the above-mentioned structural unit (A'-1) is in the range of 40 mol% or more and less than 80 mol% with respect to all the structural units in the above-mentioned norbornene-based ring-opening copolymer In addition, the aforementioned retardation film is preferably a reverse dispersion retardation film.

In addition, regarding the above-mentioned retardation film of the present invention, even when the above-mentioned norbornene-based ring-opening polymer is the above-mentioned norbornene-based ring-opening copolymer containing a structural unit (A') and a structural unit (B), The optical characteristic as a specific negative A can be achieved even with negative birefringence. Moreover, in the case where the above-mentioned norbornene-based ring-opening polymer is the above-mentioned norbornene-based ring-opening copolymer containing a structural unit (A') and a structural unit (B), from the viewpoint of achieving the optical characteristics as negative A In the retardation film of the present invention described above, the ratio of the structural unit (A'-1) to all structural units in the norbornene-based ring-opening copolymer is in the range of 80 mol% or more and 99 mol% or less. In addition, the aforementioned retardation film is preferably a negative A retardation film.

In addition, as mentioned above, the so-called negative A optical characteristics means satisfying the relationship shown in the above-mentioned relational formula (1), so even if the above-mentioned norbornene-based ring-opening polymer contains the structural unit (A') In the case of the above-mentioned norbornene-based ring-opening copolymer with the structural unit (B), it is preferable that the retardation film of the present invention satisfies the condition represented by the above-mentioned relational formula (1).

In addition, when the above-mentioned norbornene-based ring-opening polymer is the above-mentioned norbornene-based ring-opening copolymer containing a structural unit (A') and a structural unit (B), regarding the above-mentioned retardation film of the present invention, the above-mentioned X ¹ in the general formula (2) is a structural unit of a group represented by the formula -CH ₂ CH ₂ - and X ² in the above general formula (3) is a structural unit of a group represented by the formula -CH ₂ CH ₂ - The content ratio of is preferably 90 mol% or more with respect to all the structural units in the above-mentioned norbornene-based ring-opening polymer.

Moreover, the liquid crystal display device of this invention is characterized by including the retardation film of this invention mentioned above.

According to the present invention, it is possible to provide a single layer having high transparency and excellent wavelength dispersion characteristics, a specific phase difference can be given to a wide range of light, and the adhesion with other materials is very high, and even in negative birefringence A retardation film capable of achieving a specific negative A optical characteristic and making the wavelength dispersion characteristic of birefringence inversely dispersed, and a liquid crystal display device using the retardation film.

In addition, such a retardation film of the present invention can be thinned. The retardation film of the present invention also has simplified manufacturing steps, and can be manufactured with high yield and low cost.

Description of drawings

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

2 is an NMR chart of the hydrogenated product (HpB) of the norbornene-based ring-opening polymer obtained in Synthesis Example 1. FIG.

3 is an NMR chart of the hydrogenated product (HpC) of the norbornene-based ring-opening polymer obtained in Synthesis Example 2. FIG.

4 is an NMR chart of a hydrogenated product (HpD) of a norbornene-based ring-opening polymer obtained in Synthesis Example 2. FIG.

5 is an NMR chart of the hydrogenated product (HpE) of the norbornene-based ring-opening polymer obtained in Synthesis Example 3. FIG.

6 is an NMR chart of a hydrogenated product (HpF) of a norbornene-based ring-opening polymer obtained in Synthesis Example 4. FIG.

7 is a graph showing the relationship between the external shape ratio and birefringence of the stretched films obtained in Examples 1 to 4 and Examples 6 to 7.

8 is a graph showing the relationship between the external shape ratio and the birefringence wavelength dispersion value of stretched films obtained in Examples 1 to 4 and Examples 6 to 7.

9 is an NMR chart of a hydrogenated product (HpI) of a norbornene-based ring-opening polymer obtained in Synthesis Example 7. FIG.

10 is an NMR chart of a hydrogenated product (HpJ) of a norbornene-based ring-opening polymer obtained in Synthesis Example 8. FIG.

11 is an NMR chart of the hydrogenated product (HpK) of the norbornene-based ring-opening polymer obtained in Synthesis Example 9. FIG.

12 is a graph showing the relationship between the copolymerization ratio and birefringence of the stretched films obtained in Examples 8 to 12.

13 is a graph showing the relationship between the copolymerization ratio and the birefringence wavelength dispersion value of stretched films obtained in Examples 8 to 12.

14 is a graph showing the relationship between the copolymerization ratio and Tg of stretched films obtained in Examples 8 to 12.

Detailed ways

Hereinafter, the present invention will be described in detail based on its preferred embodiments.

First, the retardation film of the present invention will be described. That is, the retardation film of the present invention is obtained by stretching a film formed of a norbornene-based ring-opening polymer,

This norbornene-based ring-opening polymer contains a structural unit (A) represented by the following general formula (1), and in the above-mentioned structural unit (A), the following wavy line c represents the structure of the external stereo configuration The content ratio of the unit (A-1) is in the range of 35 mol% or more and 100 mol% or less,

[in formula (1), n represents the integer of 0 or 1,

X ¹ 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 represent any atom or group selected from a hydrogen atom, a halogen atom, a hydrocarbon group and a polar group, and the above hydrocarbon group may have A substituted or unsubstituted hydrocarbon group with 1 to 30 carbon atoms of at least one linking group of atom, sulfur atom and silicon atom,

The wavy lines a and b indicate the three-dimensional configuration of the inner or outer shape,

The wavy line c indicates the three-dimensional configuration of the endo- or exo-shape. ]

Examples of the norbornene-based ring-opening polymers involved in the present invention include structural units (A) represented by the above-mentioned general formula (1), the substituents of which have aromatic rings, and ring-opening polymerization of norbornene monomers. The obtained norbornene ring-opening polymer is a norbornene-based ring-opening polymer in which the cyclopentane ring and the aromatic ring are directly bonded or bonded via two rings.

In addition, in such a structural unit (A), n in the above general formula (1) represents an integer of 0 or 1. Moreover, as the above-mentioned norbornene-based ring-opening polymer, it may be a homopolymer composed of a structural unit (A) in which n is 0 or 1 in the above-mentioned general formula (1), or may be the above-mentioned general formula (1) A copolymer of a structural unit (A) in which n is 0 in ) and a structural unit (A) in which n is 1 in the above general formula (1). Such a value of n is used to control the optical characteristics and various physical properties of the obtained norbornene-based ring-opening polymer in a well-balanced manner, and can be appropriately adjusted according to the intended design. That is, by appropriately changing such a value of n, different norbornene-based ring-opening copolymers can be appropriately formed according to the purpose.

In addition, the wavy lines a and b in the above general formula (1) represent internal or external three-dimensional configurations. In the present invention, among all the structural units (A) in the above-mentioned norbornene-based ring-opening polymer (relative to the total amount of the structural units (A)), the three-dimensional configurations represented by the above-mentioned wavy lines a and b are external. The ratio of the type structural unit is preferably 35 to 100 mol%, more preferably 65 to 100 mol. When the content ratio of the structural unit whose stereo configuration represented by such wavy lines a and b is less than 35 mol%, there is a tendency not to show reverse dispersion characteristics, and when it is 65 mol% or less, there is no tendency to show negative dispersion characteristics. A sexual orientation.

The wavy line c in the above general formula (1) also represents an endo-shape or exo-shape three-dimensional configuration. In the present invention, in all the structural units (A) in the norbornene-based ring-opening polymer, the content ratio of the structural unit (A-1) in which the wavy line c represents an external stereo configuration is 35 to 100 mol %. Such a wavy line c represents the ratio of the structural unit (A-1) of the external stereo configuration, and when the total amount of the structural unit (A) is less than 35 mol%, the wavelength dispersion value (D=Δn(λ=481nm) /Δn(λ=589nm)) is in the range of 0.92 or more and less than 1.0, and it is not possible to obtain a film exhibiting specific optical properties such that the wavelength dispersion value is less than 0.92 or the wavelength dispersion value becomes inverse dispersion (D is 1.0 or more). In addition, the wavy line c represents an external stereo configuration, which means that the stereo configuration of the substituted or unsubstituted phenyl group bonded to the wavy line c is external coordination. In addition, as a method of measuring the birefringence Δn, a method of measuring using a product name: "KOBRA21DH" manufactured by Oji Scientific Co., Ltd. as a measuring device can be employed.

In addition, regarding such a retardation film of the present invention, from the viewpoint of attaining reverse wavelength dispersibility, the wavy line c represents the ratio of the structural unit (A-1) in the stereo configuration of the external form, with respect to the norbornene The total amount of structural units (A) in the quasi-ring-opening polymer is preferably in the range of 35 mol% to 65 mol% (more preferably in the range of 40 mol% to 60 mol%). That is, as the phase difference film of the present invention, the ratio of the structural unit (A-1) in which the above-mentioned wavy line c represents an external shape is 35 mol % or more, 65 mol % or more with respect to the total amount of the structural unit (A). mol% or less, the retardation film can be made into a reverse dispersion retardation film. When the proportion of the structural unit of such a wavy line c representing the external configuration exceeds 65 mol% relative to the total amount of the structural unit (A), it is difficult to achieve reverse wavelength dispersibility.

In addition, regarding the retardation film of the present invention, from the viewpoint of achieving the optical characteristics of negative A, the above-mentioned wavy line c represents the ratio of the structural unit (A-1) in the stereo configuration of the external shape, and the above-mentioned norbornene-based It is preferably in the range of more than 65 mol% and 100 mol% or less (more preferably 70 to 100 mol%) of all the structural units (A) in the cyclic polymer. That is, as the retardation film of the present invention, the structural unit (A- The ratio of 1) is in the range of more than 65 mol % and 100 mol % or less, whereby the above retardation film can be made into a negative A retardation film. Such a wavy line c represents the ratio of the structural unit (A-1) of the external stereo configuration, when the total amount of the structural unit (A) in the above-mentioned norbornene-based ring-opening polymer is 65 mol% or less , there is a tendency that the specific negative A optical characteristic cannot be achieved even in negative birefringence. And, as such a negative A retardation film, when the stretching direction of the uniaxial stretching of the above-mentioned film is defined as the X-axis, and the direction perpendicular to the X-axis is defined as the Y-axis and the Z-axis, the X-axis The refractive index (Nx), the refractive index (Ny) of the Y axis and the refractive index (Nz) of the Z axis preferably satisfy the relationship shown in the following relational formula (1):

Ny=Nz>Nx(1).

In addition, as a method for measuring the above-mentioned refractive index (Nx, Ny, and Nz), a method of measuring the refractive index using a product name "2010 PrismCoupler" manufactured by Metricon Co., Ltd. as a refractive index measuring device can be used.

In addition, the three-dimensional configuration represented by such wavy lines a, b, and c can be appropriately adjusted by the reaction conditions at the time of monomer production, the reaction treatment after production, and the like. For example, the three-dimensional configuration of wavy lines a and b can be easily controlled by isomerization treatment after production, and the three-dimensional configuration of wavy line c can be controlled by reaction conditions during monomer production and heat treatment after production.

In addition, the substituents represented by R ¹ , R ² , R ³ , and R ⁴ in the above general formula (1) may be the same or different, and they are any one selected from a hydrogen atom, a halogen atom, a hydrocarbon group, and a polar group. Atom or group, the above-mentioned hydrocarbon group is a substituted or unsubstituted hydrocarbon group with 1 to 30 carbon atoms (more preferably 1 to 10) that may have at least one linking group selected from an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom .

In addition, such R ¹ , R ² , R ³ , and R ⁴ can be selected, and may have a substituted or non-substituted carbon atom number of at least one linking group selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. The hydrocarbon group having 1 to 30 carbon atoms is more preferably the above-mentioned hydrocarbon group having 1 to 10 carbon atoms. In addition, such a hydrocarbon group may be a linear, branched or cyclic hydrocarbon group and is not particularly limited, and examples thereof include alkyl, cycloalkyl, alkenyl, alkynyl, phenyl, aryl and the like. In addition, such a hydrocarbon group is preferably an alkyl group, a cycloalkyl group, a phenyl group, an aryl group, etc. from the viewpoint of transparency and weather resistance. Among the above-mentioned substituents, an alkyl group such as a t-butyl group is particularly preferable. In addition, such a hydrocarbon group is preferably a linear hydrocarbon group having 1 to 5 carbon atoms or a branched hydrocarbon group having 3 to 7 carbon atoms. In addition, such a hydrocarbon group is preferably a saturated hydrocarbon group.

In addition, examples of polar groups that can be selected for R ¹ , R ² , R ³ , and R ⁴ include hydroxyl group, mercapto group, cyano group, amino group, carboxyl group, sulfonic acid group, ester group, and the like. From the viewpoint of imparting high heat resistance to the obtained retardation film, as the substituents represented by R ¹ , R ² , R ³ , and R ⁴ in the general formula (1), among the above-mentioned substituents A cyano group and the like are preferable, and an ester group and the like are preferable from the viewpoint of transparency and weather resistance.

In addition, from the viewpoint of easiness of availability (production efficiency) of monomers used in the production of the above-mentioned norbornene-based ring-opening polymer, it is more preferable that R ¹ , R ² , and R ³ in the above-mentioned general formula (1) be respectively are independently a hydrogen atom, a fluorine atom, and a chlorine atom, particularly preferably a hydrogen atom. In addition, from the standpoint of ease of availability (production efficiency) of monomers used in the production of the above-mentioned norbornene-based ring-opening polymer, as R ⁴ in the above-mentioned general formula (1), it is more preferable to have a carbon number of 3 to 7 branched hydrocarbon group (more preferably a branched hydrocarbon group having 3 to 5 carbon atoms, particularly preferably a tert-butyl group).

In addition, X ¹ in the above general 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 (A) contained may be composed of only one of the above-mentioned groups, or may be composed of structural units (A) each having the above-mentioned groups. ) are mixed together. In addition, the norbornene-based ring-opening polymer of the present invention becomes a more stable polymer with a higher hydrogenation ratio, that is, with fewer double bonds in the main chain. Therefore, as the norbornene-based ring-opening polymer according to the present invention, a sufficiently hydrogenated polymer having few double bonds in the main chain is preferable. From such a viewpoint, X ¹ in the general formula (1) is preferably a group represented by the formula -CH ₂ CH ₂ -. In addition, X ¹ in the above-mentioned general formula (1) is a ratio of structural units (A) represented by the formula -CH ₂ CH ₂ -, and in all structural units (A) of the above-mentioned norbornene-based ring-opening polymer It is preferably 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 decreases, and it tends to be difficult to suppress coloring and deterioration due to heat.

In addition, in the present invention, the above-mentioned norbornene-based ring-opening polymer preferably contains a structural unit (A') represented by the following general formula (2) and a structural unit (B') represented by the following general formula (3). ) norbornene-based ring-opening copolymer. In addition, in the above-mentioned norbornene-based ring-opening polymer, in the above-mentioned structural unit (A'), the stereo configuration of the substituted or unsubstituted phenyl group in the above-mentioned general formula (2) is a structural unit that is externally coordinated The content ratio of (A'-1) exists in the range of 90 mol% or more.

[In formula (2), n, X ¹ , R ¹ , R ² , R ³ , R ⁴ and wavy line c are the same as n, X ¹ , R ¹ , R ² , R ³ , R ⁴ has the same meaning as the wavy line c. ]

[In formula (3), n represents the integer of 0 or 1,

X ² represents a group represented by the formula -CH=CH- or a group represented by the formula -CH ₂ CH ₂ -,

R ⁵ , R ⁶ , R ⁷ , and R ⁸ may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 1 to 20 carbon atoms, and a carbon Any atom or group in an alkylcarbonyl group with 1 to 20 atoms and an ester group with a hydrocarbon group with 1 to 20 carbon atoms,

Two or more of R ⁵ to R ⁸ are bonded to each other to form a monocyclic hydrocarbon with 3 to 20 carbon atoms that may have an unsaturated bond, or a polycyclic hydrocarbon with 4 to 20 carbon atoms that may have an unsaturated bond. hydrocarbon,

R ⁵ and R ⁶ , or R ⁷ and R ⁸ may together form an alkylene group having 1 to 20 carbon atoms. ]

In the above general formula (2), n, X ¹ , R ¹ , R ² , R ³ , R ⁴ and the wavy line c are the same as n, X ¹ , R ¹ , R ² , R ³ in the above general formula (1). , R ⁴ and wavy line c have the same meaning. In addition, the above-mentioned structural unit (A'-1) is a structural unit in which the wavy line c in the above-mentioned general formula (2) represents an external shape.

In addition, n in the above general formula (3) has the same meaning as n in the above general formula (1). In addition, X ² in the above general formula (3) has the same meaning as X ¹ in the above general formula (1).

In addition, the substituents represented by R ⁵ , R ⁶ , R ⁷ , and R ⁸ in the above general formula (3) may be the same or different, and they are respectively selected from hydrogen atoms, halogen atoms, cyano groups, carbon atoms having 1 to 20 Any atom or group in an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 1 to 20 carbon atoms, and an ester group having a hydrocarbon group having 1 to 20 carbon atoms. In addition, two or more of R ⁵ to R ⁸ are bonded to each other to form a monocyclic hydrocarbon with 3 to 20 carbon atoms that may have an unsaturated bond, or a polycyclic hydrocarbon with 4 to 20 carbon atoms that may have an unsaturated bond. Cyclic hydrocarbon, R ⁵ and R ⁶ may together form an alkylene group with 1 to 20 carbon atoms, or R ⁷ and R ⁸ may together form an alkylene group with 1 to 20 carbon atoms.

Such an alkyl group having 1 to 20 carbon atoms (more preferably 1 to 10) may be a linear, branched or cyclic alkyl group and is not particularly limited, but from the viewpoint of transparency and weather resistance , preferably methyl and ethyl etc. In addition, if the number of carbon atoms of such an alkyl group exceeds the above-mentioned upper limit, it will be difficult to purify by methods such as distillation and recrystallization.

In addition, the above-mentioned alkenyl group having 1 to 20 carbon atoms (more preferably 1 to 10) may be a linear, branched or cyclic alkenyl group and is not particularly limited, but from the viewpoint of transparency and weather resistance Starting from, ethylene and the like are preferred. In addition, if the number of carbon atoms of such an alkenyl group exceeds the above-mentioned upper limit, purification by methods such as distillation and recrystallization becomes difficult.

In addition, the above-mentioned alkylcarbonyl group having 1 to 20 carbon atoms (more preferably 1 to 10) may be a linear, branched or cyclic alkylcarbonyl group and is not particularly limited, but from the perspective of transparency and weather resistance From the standpoint, methylcarbonyl, ethylcarbonyl and the like are preferable. In addition, if the number of carbon atoms of such an alkylcarbonyl group exceeds the above upper limit, it will be difficult to purify by methods such as distillation and recrystallization.

In addition, the above-mentioned ester group having a hydrocarbon group having 1 to 20 carbon atoms (more preferably 1 to 10) may be a linear, branched or cyclic ester group, and is not particularly limited, but from the perspective of transparency and weather resistance From the viewpoint of sex, methoxycarbonyl, ethoxycarbonyl and the like are preferable. In addition, if the number of carbon atoms of such an ester exceeds the above-mentioned upper limit, it will be difficult to purify by methods such as distillation and recrystallization.

In addition, the above-mentioned monocyclic hydrocarbon having 3 to 20 carbon atoms (more preferably 3 to 10) that may have an unsaturated bond is not particularly limited, and may have other substituents. From the viewpoint of transparency and weather resistance, cyclopentene, cyclohexene, and the like are preferable as such monocyclic hydrocarbons. In addition, when the number of carbon atoms of such a monocyclic hydrocarbon exceeds the above-mentioned upper limit, it becomes difficult to purify by methods such as distillation and recrystallization.

In addition, the polycyclic hydrocarbon having 4 to 20 carbon atoms (more preferably 4 to 12) that may have an unsaturated bond is not particularly limited, and may have other substituents. Naphthalene, biphenyl, and the like are preferable as such polycyclic hydrocarbons from the viewpoint of transparency and weather resistance. In addition, when the number of carbon atoms of such polycyclic hydrocarbons exceeds the above-mentioned upper limit, it becomes difficult to purify them by methods such as distillation and recrystallization.

The alkylene group having 1 to 20 carbon atoms (more preferably 1 to 10 carbon atoms) is not particularly limited, but indane, tetralin, and the like are preferred from the viewpoint of transparency and weather resistance. In addition, if the number of carbon atoms of such an alkylene group exceeds the above-mentioned upper limit, it will be difficult to purify by methods such as distillation and recrystallization.

In addition, when the norbornene-based ring-opening polymer according to the present invention is the above-mentioned norbornene-based ring-opening copolymer containing the above-mentioned structural unit (A') and the above-mentioned structural unit (B), the above-mentioned norbornene-based ring-opening copolymer The compound has a phenyl group or a substituted phenyl group derived from the above structural unit (A') in the substituent. Also because such a norbornene-based ring-opening copolymer is a copolymer that can be obtained by ring-opening polymerization of norbornene monomers (the raw materials of the above-mentioned structural unit (A') and the above-mentioned structural unit (B)), it becomes A copolymer in which a cyclopentane ring and the above-mentioned phenyl or substituted phenyl are directly bonded or bonded via a bicyclic ring.

In the above-mentioned norbornene-based ring-opening copolymer containing such a structural unit (A') and a structural unit (B), the substituted or unsubstituted phenyl group (the benzene ring to which R ⁴ is bound) in the above-mentioned general formula (2) The content ratio of the structural unit (A'-1) whose stereo configuration is external coordination is 90 mol % ( More preferably, it exists in the range of 95 mol% or more. In such a norbornene-based ring-opening copolymer, when the content ratio of the structural unit (A'-1) in the structural unit (A') is less than the above lower limit, it is difficult for the obtained film to exhibit the intended optical properties.

In addition, when the above-mentioned norbornene-based ring-opening polymer is the above-mentioned norbornene-based ring-opening copolymer containing the above-mentioned structural unit (A') and the above-mentioned structural unit (B), in the above-mentioned norbornene-based ring-opening copolymer The content ratio of the above-mentioned structural unit (A') and the above-mentioned structural unit (B) is preferably 99:1 to 40:60 in terms of molar ratio (structural unit (A'):structural unit (B), more preferably 99:1 to 50:50 mol%. When the content ratio of such a structural unit (A') is less than the said lower limit, there exists a tendency for optical characteristics, such as reverse dispersion characteristic, to not be exhibited.

When the above-mentioned norbornene-based ring-opening polymer is the above-mentioned norbornene-based ring-opening copolymer containing the above-mentioned structural unit (A') and the above-mentioned structural unit (B), relative to the above-mentioned norbornene-based ring-opening copolymer The content ratio of the above-mentioned structural unit (A'-1) is preferably 40 to 99 mol%, more preferably 50 to 99 mol% of all the structural units contained. When the content ratio of the structural unit (A'-1) in such a norbornene-based ring-opening copolymer is less than 40 mol%, reverse dispersion characteristics tend not to be exhibited. In addition, when the above-mentioned norbornene-based ring-opening polymer is the above-mentioned norbornene-based ring-opening copolymer, if the content ratio of the above-mentioned structural unit (A'-1) is 80 mol% or less, the negative A property may not be exhibited. Propensity. In addition, when the above-mentioned norbornene-based ring-opening polymer is the above-mentioned norbornene-based ring-opening copolymer containing the above-mentioned structural unit (A') and the above-mentioned structural unit (B), the above-mentioned structural unit (A') in all structural units -1) When the ratio is less than 40 mol%, the wavelength dispersion value (D = Δn (λ = 481nm) / Δn (λ = 589nm)) is in the range of 0.92 or more and less than 1.0, and the display wavelength dispersion value of less than 0.92 may not be obtained. Or, the wavelength dispersion value tends to be a film having specific optical characteristics with high dispersion (D is 1.0 or more).

In addition, when the above-mentioned norbornene-based ring-opening polymer is the above-mentioned norbornene-based ring-opening copolymer containing the above-mentioned structural unit (A') and the above-mentioned structural unit (B), regarding the obtained retardation film, from reaching the reverse wavelength From the viewpoint of dispersibility, the three-dimensional configuration of the above-mentioned substituted or unsubstituted phenyl group is the content ratio of the structural unit (A'-1) that is externally coordinated, relative to the content ratio of the above-mentioned norbornene-based ring-opening copolymer. The total structural units of are preferably in the range of 40 mol% or more and less than 80 mol% (more preferably in the range of 50 to 70 mol%). That is, when the above-mentioned norbornene-based ring-opening polymer is the above-mentioned norbornene-based ring-opening copolymer, the ratio of the above-mentioned structural unit (A'-1) is in the range of 40 mol % or more and less than 80 mol %, thereby The aforementioned retardation film can be made into a reverse dispersion retardation film. When the ratio of the structural unit (A'-1) in which the stereo configuration of the benzene ring is exo is 80 mol% or more, it is difficult to achieve reverse wavelength dispersibility.

In addition, when the above-mentioned norbornene-based ring-opening polymer is the above-mentioned norbornene-based ring-opening copolymer containing the above-mentioned structural unit (A') and the above-mentioned structural unit (B), regarding the obtained retardation film, from reaching negative From the viewpoint of the optical properties of A, the stereo configuration of the substituted or unsubstituted phenyl group in the above-mentioned general formula (2) is an exo-coordinated structural unit (A'-1) content ratio, relative to the above-mentioned norbornanol The total structural units contained in the ethylenic ring-opened copolymer are preferably in the range of 80 to 99 mol % (more preferably 90 to 99 mol %). That is, when the above-mentioned norbornene-based ring-opening polymer is the above-mentioned norbornene-based ring-opening copolymer containing the above-mentioned structural unit (A') and the above-mentioned structural unit (B), the above-mentioned structural unit (A'-1) When the content ratio is in the range of 80 to 99 mol %, the above retardation film can be made into a negative A retardation film. When the content ratio of the above-mentioned structural unit (A'-1) is less than 80 mol% with respect to all the structural units in the above-mentioned norbornene-based ring-opening copolymer, the obtained retardation film may have negative birefringence even in negative birefringence. There is also a tendency not to achieve the specific negative A optical characteristic. And, it is preferable that such a negative A retardation film satisfies the relationship represented by the above-mentioned relational expression (1).

When the above-mentioned norbornene-based ring-opening polymer is the above-mentioned norbornene-based ring-opening copolymer, X in _the above-mentioned general formula ( ² ₎ is the above-mentioned structural unit (A ') and the content ratio of the above-mentioned structural unit (B) in which X ² in the above-mentioned general formula (3) is a group represented by the formula -CH ₂ CH ₂ -, relative to the total amount of the norbornene-based ring-opening polymer The structural unit is preferably 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 copolymer decreases, and it tends to be difficult to suppress coloring and deterioration due to heat.

In addition, in the present invention, the weight average molecular weight of the norbornene-based ring-opening polymer is preferably 1,000 to 1,000,000, more preferably 10,000 to 1,000,000. When the weight-average molecular weight of the norbornene-based ring-opened polymer is less than the above-mentioned lower limit, the strength of the obtained norbornene-based ring-opened polymer tends to be lowered, and if it exceeds the above-mentioned upper limit, the obtained norbornene-based ring-opened polymer tends to be low. The melt viscosity of the cyclic polymer tends to become too high.

A method suitable as a method for producing the norbornene-based ring-opening polymer according to the present invention will be described below. The method for producing such a norbornene-based ring-opening polymer is not particularly limited, and for example, a method represented by the following reaction formula (1) can be suitably employed.

[Reaction formula (I)]

[In the above reaction formula (I), R ¹ , R ² , R ³ , R ⁴ , wavy line a, wavy line b, wavy line c, and n are respectively related to R ¹ , R ² , R ³ , R ⁴ , wavy a, wavy b, wavy c, and n have the same meaning. ]

In the method represented by such reaction formula (1), specifically, the norbornene monomer represented by the above-mentioned general formula (I-1) is ring-opened and polymerized to obtain norbornene represented by the above-mentioned general formula (I-2). After the vinyl ring-opened polymer, the obtained ring-opened polymer is hydrogenated to obtain the norbornene-based ring-opened polymer represented by the above-mentioned general formula (I-2'). In addition, the structural units represented by the above-mentioned general formulas (I-2) and (I-2') respectively correspond to the above-mentioned structural units (A).

In addition, when producing the above-mentioned norbornene-based ring-opening copolymer containing the above-mentioned structural unit (A') and the above-mentioned structural unit (B) as the above-mentioned norbornene-based ring-opening polymer, for example, the following reaction formula ( II) The method shown.

[Reaction formula (II)]

[R ¹ , R ² , R ³ , R ⁴ , n and the wavy line c in the reaction formula (II) are respectively related to R ¹ , R ² , R ³ , R ⁴ , n and the wavy line in the above general formula (1) Line c has the same meaning, and R ⁵ , R ⁶ , R ⁷ , R ⁸ and n in the reaction formula (II) are respectively the same as R ⁵ , R ⁶ , R ⁷ , R ⁸ and n in the above general formula (3). have the same meaning. ]

The method represented by such reaction formula (II) is specifically to make the norbornene monomer shown in the general formula (II-1) in the reaction formula (II) and the norbornene monomer shown in the general formula (II-2) After carrying out ring-opening copolymerization of the norbornene monomer to obtain a norbornene-based ring-opening copolymer containing structural units represented by the above general formulas (II-3) and (II-4), hydrogenation is carried out on the obtained ring-opening copolymer. A method for obtaining a norbornene-based ring-opening copolymer containing structural units represented by the above general formulas (II-3') and (II-4'). In addition, the structural units represented by the above-mentioned general formulas (II-3) and (II-3') are structural units respectively corresponding to the above-mentioned structural unit (A'), and the above-mentioned general formulas (II-4) and (II-4 The structural units represented by ') are structural units corresponding to the above-mentioned structural units (B), respectively.

As the norbornene monomer represented by the general formula (I-1) in the above reaction formula (I) or the norbornene monomer represented by the general formula (II-1) in the above reaction formula (II), for example Examples of norbornene monomers 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 tert-butylphenyl)bicyclo[2.2.1]-2-heptene, 8-(p-tert-butylphenyl)tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-deca Dicarbene, 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)tetra Cyclo[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-heptane ene, 8-(p-isopropylphenyl)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)di Cyclo[2.2.1]-2-heptene, 8-(p-bromophenyl)tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene, 5-(o-bromo Phenyl)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, 5.17,10.0} ]-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-heptane ene, 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-chloromethyl Phenyl)bicyclo[2.2 .1]-2-heptene, 8-(m-chloromethylphenyl)tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene, 5-(p-chloromethyl phenyl)bicyclo[2.2.1]-2-heptene, 8-(p-chloromethylphenyl)tetracyclo[4.4.1 ^2,5 .1 ^7,0 .0]-3-dodeca ene, 5-(p-cyanomethylphenyl)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-fluorophenyl)-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-deca Dicarbene, 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-(pentafluorophenyl)bicyclo[2.2.1]-2-heptene, 8-(pentafluorophenyl)tetracyclo[4.4.1 ^2,5 .1 ^{7, 10} .0]-3-dodecene, 5-(o-methoxyphenyl)bicyclo[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-ethoxy Phenyl)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-methoxy phenyl)bicyclo[2.2.1]-2-heptene, 8-(p-methoxyphenyl)tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodeca Alkenes, 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-methylbenzene base) 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-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, 5.17,10.0} ]-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 phenyl)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-(p-n-octylphenyl)bicyclo[2.2. 1]-2-heptene, 8-(p-n-octylphenyl)tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene, 5-trimethylsilane Oxy-5-phenylbicyclo[2.2.1]-2-heptene, 8-(trimethylsilyloxy)-8-phenyltetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene, 5-(2,4,6-trimethylphenyl)bicyclo[2.2.1]-2-heptene, 8-(2,4,6-trimethyl phenyl)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-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-dimethylphenyl)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-iodophenyl)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-dodeca Carbene, 5-(p-sulfophenyl)bicyclo[2.2.1]-2-heptene, 8-(p-sulfophenyl)tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0 ]-3-dodecene, 5-(p-sulfonyl chloride phenyl)bicyclo[2.2.1]-2-heptene, 8-(p-sulfonyl 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-diphenylbicyclo[2.2.1]-2-heptene, 8,9-diphenyltetracyclo[4.4 .1 ^2,5 .1 ^7,10 .0]-3-dodecene, 5,5-diphenylbicyclo[2.2.1]-2-heptene, 8,8-diphenyltetracyclo [4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene, 5-(1-naphthyl)bicyclo[2.2.1]-2-heptene, 8-(1-naphthalene base) 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-heptane ene, 8-(9-anthracenyl)tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene, 5-(m-isopropenylphenyl)-5-methyl Bicyclo[2.2.1]-2-heptene, 8-(m-isopropenylphenyl)-8-methyltetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodeca Carbene, 5-(p-isopropyl Alkenylphenyl)-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-methylenebis Oxophenyl)-6-methylbicyclo[2.2.1]-2-heptene, 8-(3,4-methylenedioxophenyl)-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-phenylbicyclo[2.2.1]-2-heptene , 9-acetyl-8-phenyltetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene, 6-benzoyl-5-phenylbicyclo[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} ] Pentacycline-4,6,8,12-tetraene, Pentacyclo[7.6.1 ^{11,14.1 1,9} .0 ^{10, 15 .0 5, 17} ] heptadeca-1, 3, 5, 6, 8, 12-hexaene, pentacyclo [10.6.1 14, ¹⁷ .0 13, ¹⁸ .0 1 ^{, 6} .0 ^7,12 ] nineteen-1,3,5,7,9,11,15-heptacene, tetracyclo[7.4.1 ^{10,13.0 1,9.0 2,7} ] fourteen-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-methoxy phenyl)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)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-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-carboxymethylbis Cyclo[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-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) Phenyl)-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-carboxyethyl Bicyclo[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-chlorobenzene Base)-6-carboxybicyclo[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-carboxy Phenylbicyclo[2.2.1]-2-heptene, 5-phenyl-6-carboxymethylbicyclo[2.2.1]-2-heptene, 5-(p-hydroxyphenyl)-6-carboxy 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 Base)-6-carboxymethylbicyclo[2.2.1]-2-heptene, 5-(o-hydroxyphenyl)-6-carboxyethylbicyclo[2.2.1]-2-heptene, 5- Cyano-5-phenyl-6-carboxylic 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-carboxycholesterylbicyclo[ 2.2.1]-2-heptene, 5-(m-hydroxyphenyl)-6-carboxylic acid bicyclo[2.2.1]-2-heptene, 5-(m-hydroxyphenyl)-6-carboxymethyl Bicyclo[2.2.1]-2-heptene, 5-(m-hydroxyphenyl)-6-carboxyethylbicyclo[2.2.1]-2-heptene, 5-phenyl-6-carboxyallyl Bicyclo[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-nitrophenyl) -6-carboxymethylbicyclo[2.2.1]-2-heptene, 5-(2-chloro-5-nitrophenyl)-6-carboxyethylbicyclo[2.2.1]-2-heptene ene, 5-cyano-5-(p-hydroxyphenyl)-6-carboxylic acid bicyclo[2.2.1]-2-heptene, 5-cyano-5-(p-hydroxyphenyl)-6-carboxy Methylbicyclo[2.2.1]-2-heptene, 5-cyano-5-(p-hydroxyphenyl)-6-carboxyethylbicyclo[2.2.1]-2-heptene, 5-benzene Base-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-di Methoxyphenyl)-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-carboxymethylbicyclo[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 bicyclo[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-carboxyethyl Bicyclo[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 bicyclo[2.2.1]-2 -heptene, 5-(4-fluorophenyl)-6-carboxymethylbicyclo[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-carboxy Ethylbicyclo[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-carboxy Methylbicyclo[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-carboxyethylbicyclo[2.2.1]-2-heptene, 5-(3-methoxyphenyl)-6-carboxybicyclo[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-carboxybicyclo[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-methylenedioxophenyl)-6-carboxylic acid bicyclo[2.2.1]-2-heptene , 5-(3,4-methylenedioxophenyl)-6-carboxymethylbicyclo[2.2.1]-2-heptene, 5-(3,4-methylenedioxophenyl) Base)-6-carboxyethylbicyclo[2.2.1]-2-heptene, 5-(4-methylphenyl)-6-carboxylic acid bicyclo[2.2.1]-2-heptene, 5 -(4-Methylphenyl)-6-carboxymethyl Bicyclo[2.2.1]-2-heptene, 5-(4-methylphenyl)-6-carboxyethylbicyclo[2.2.1]-2-heptene, 5-(4-mercaptobenzene Base)-6-carboxybicyclo[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-carboxyethylbis Cyclo[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 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-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-carboxybicyclo[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-octadecyloxy Phenyl)-6-carboxybicyclo[2.2.1]-2-heptene, 5-(4-n-octadecyloxyphenyl)-6-carboxymethylbicyclo[2.2.1]-2 -heptene, 5-(4-n-octadecyloxyphenyl)-6-carboxyethylbicyclo[2.2.1]-2-heptene, 5-(4-stearyloxyphenyl) -6-carboxybicyclo[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-carboxy Methylbicyclo[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-carboxybicyclo[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-trifluoromethyl Oxyphenyl)-6-carboxybicyclo[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-trimethoxybenzene Base)-6-carboxybicyclo[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-cyanomethylphenyl)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-triphenylbicyclo[2.2.1]-2-heptene, 9-bromo-8,8,9-triphenyltetra cyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene, 5,5,6-triphenylbicyclo[2.2.1]-2-heptene, 8,8, ⁹ -triphenyltetracyclo[ ^{4.4.12,5.17,10.0} ]-3-dodecene, etc.

In addition, examples of the norbornene monomer represented by the general formula (II-2) in the above reaction formula (II) include the following norbornene monomers.

Bicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene, 5-methylbicyclo[2.2.1]heptene -2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-methoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-methyl-5-methoxy ylcarbonylbicyclo[2.2.1]hept-2-ene, 5-cyanobicyclo[2.2.1]hept-2-ene, 8-methoxycarbonyltetracyclo[4.4.1 ^2,5 .1 ^{7 ,10} .0]-3-dodecene, 8-ethoxycarbonyltetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene, 8-n-propoxy Carbonyl tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene, 8-isopropoxycarbonyl tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 8-n-butoxycarbonyltetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene, 8-methyl-8-methoxy Carbonyltetracyclo[ ^{4.4.12,5.17,10.0} ]-3-dodecene, 8-methyl-8 ^- ethoxycarbonyltetracyclo[ ^{4.4.12,5.17 , 10} .0]-3-dodecene, 8-methyl-8-n-propoxycarbonyltetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene, 8 -Methyl-8-isopropoxycarbonyl tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene, 8-methyl-8-n-butoxycarbonyl tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene, 5-ethylenebicyclo[2.2.1]hept-2-ene, 8-ethylenetetracyclo[4.4 .1 ^2,5 .1 ^7,10 .0]-3-dodecene, 8-methyltetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene, 8-Ethyl tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene, 8-propyl tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene, 8-isopropyltetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene, 8-n-butyltetracyclo[4.4.1 ^{2 , 5} .1 7 ^{, 10} .0]-3-dodecene, 5-n-butylbicyclo[2.2.1]hept-2-ene, 5-n-hexylbicyclo[2.2.1]hept-2 -ene, 5-cyclohexylbicyclo[2.2.1]hept-2-ene, 5-(2-cyclohexenyl)bicyclo[2.2.1]hept-2-ene, 5-n-octylbicyclo [2.2.1] Hept-2-ene, 5-n-decylbicyclo[2.2.1]hept-2-ene, 5-isopropylbicyclo[2.2.1]hept-2-ene, 5-cyclo Hexenylbicyclo[2.2.1]hept-2-ene, 5-fluorobicyclo[2.2.1]hept-2-ene, 5,5 -Difluorobicyclo[2.2.1]hept-2-ene, 5,6-difluorobicyclo[2.2.1]hept-2-ene, 5,5,6-trifluorobicyclo[2.2.1] Hept-2-ene, 5,5,6,6-tetrafluorobicyclo[2.2.1]hept-2-ene, 8-fluorotetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]- 3-dodecene, 8,8-difluorotetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene, dicyclopentadiene, tricyclopentadiene, Tetracyclopentadiene, indene-cyclopentadiene adduct (1,4-methylene-1,4,4a,9a-tetrahydrofluorene), etc.

In addition, the method for producing the norbornene monomer represented by the general formula (I-1) is not particularly limited, and for example, the method represented by the following reaction formula (III) can be suitably used.

[Reaction formula (III)]

[In the above-mentioned reaction formula (III), R ¹ , R ² , R ³ , R ⁴ , and the wavy line c are respectively related to R ¹ , R ² , R ³ , R ⁴ , and the wavy line c in the above-mentioned general formula (1). have the same meaning. ]

In the method represented by such reaction formula (III), specifically, the cyclopentadiene represented by the above formula (III-1) and the styrene derivative represented by the above formula (III-2) are subjected to Diels-Alder reaction method, whereby the norbornene monomers represented by the above formulas (III-3) and (III-3') can be obtained.

Examples of the styrene derivative represented by the general formula (III-2) used in the above reaction formula (III) include styrene, cinnamic acid, and the like. Such a styrene derivative functions as an excellent dienophile in the Diels-Alder reaction, and a desired reaction rate can be obtained in industrial production. That is, by reacting the above-mentioned styrene derivatives with cyclopentadiene under the temperature (160 to 200°C) conditions at which cyclopentadiene is produced from the precursor of cyclopentadiene (dicyclopentadiene), high-yield The objective norbornene monomer can be obtained efficiently. The method of obtaining such styrene derivatives is not particularly limited, but it is easy to obtain because there are products that can be produced industrially, and published books (Polymer Data Hand Book) can be used for compounds that are not commercially available industrially. Fundamentals, Polymer Society, 1986, Peifengkan, etc.) were synthesized.

In addition, examples of such styrene derivatives include the following styrene derivatives.

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-chloro Styrene, m-chloromethylstyrene, p-chloromethylstyrene, cyanomethylstyrene, o-chloromethylstyrene, 2,6-dichlorostyrene, 4-fluoro-α-methylstyrene , 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, pentafluorostyrene, 2-methoxystyrene, 4-ethoxystyrene, p-phenoxystyrene, p-vinyl Benzyl alcohol, 4-methoxystyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, cis-β-methylstyrene, 3 -Nitrostyrene, 4-nitrostyrene, 4-cyanostyrene, 4-n-octylstyrene, β-methylstyrene, 2,3,4,5,6-pentafluorostyrene, α-(trimethylsilyloxy)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 (cis-stilbene), trans-stilbene ( trans-stilbene), 1,1-diphenylethylene, 1-vinylnaphthalene, 2-vinylnaphthalene, 9-vinylanthracene, m-diisopropenylbenzene, p-diisopropenylbenzene, p-chloro-α -Methylstyrene, α-cyano-p-methylstyrene, allylbenzene, anethole, isoeugenol, isosafrole, β-bromostyrene, cinnamaldehyde ( cinnamaldehyde), benzalacetone, benzalacetophenone, β-cyanostyrene, β-nitrostyrene, 1,2-dihydronaphthalene, acenaphthylene, Phenanthrene, Indene, Methylenebenzoindene, Benzofuran, 4-Aminocinnamic Acid, 4-Bromocinnamic Acid, 2-Bromocinnamic Acid, Trans-3-Bromocinnamic Acid, 3,4-Dihydroxycinnamic Acid , 4-chlorocinnamic acid, trans-cinnamic acid, benzyl cinnamate, ethyl cinnamate, phenyl cinnamate, methyl cinnamate, trans-4-hydroxycinnamic acid, trans-2-hydroxycinnamate , α-cyanocinnamic acid, ethyl α-cyanocinnamate, trans-cholesteryl cinnamate, trans-3-hydroxycinnamic acid, allyl cinnamate, vinyl cinnamate, cinnamon cinnamate Esters, 2-chlorocinnamic acid, 3-chlorocinnamic acid, 4-chloro-3-nitrocinnamic acid, 2-chloro-5-nitrocinnamic acid Acid, methyl 4-chlorocinnamate, α-cyano-4-hydroxycinnamic acid, isopropyl cinnamate, α,β-ethyl dibromocinnamate, 3,4-dimethoxycinnamic acid, 3 , 5-dimethoxy-4-hydroxycinnamic acid, 3,4-dimethoxycinnamic acid, 2,5-dimethoxycinnamic acid, trans-2,3-dimethoxycinnamic acid, 2,4-difluorocinnamic acid, 2,4-dimethoxycinnamic acid, trans-2,4-dichlorocinnamic acid, α,β-dibromocinnamic acid, 3,5-dimethoxy- 4-Hydroxycinnamic acid, 4-fluorocinnamic acid, 2-fluorocinnamic acid, 3-fluorocinnamic acid, cinnamic acid, trans-4-hydroxy-3-methoxycinnamic acid, 3-hydroxy-4-methoxy Cinnamic acid, 4-hydroxycinnamic acid, 3-methoxycinnamic acid, trans-2-methoxycinnamic acid, 4-methoxycinnamic acid, 3,4-methylenedioxocinnamic acid, 4-methylcinnamic acid, cis-2-methoxycinnamic acid, 4-mercaptocinnamic acid, 2-ethylhexyl 4-methoxycinnamate, octyl 4-methoxycinnamate, 4- Ethyl methoxycinnamate, 2-methylcinnamic acid, 3-methylcinnamic acid, α-methylcinnamic acid, 3-nitrocinnamic acid, 4-nitrocinnamic acid, 2-nitrocinnamic acid, 4-nitrocinnamic acid ethyl ester, 4-n-octadecyloxycinnamic acid, 4-stearyloxycinnamic acid, α-phenylcinnamic acid, 3,4,5-trimethoxycinnamic acid, 2 , 4,5-trimethoxycinnamic acid, 3-(trifluoromethyl)cinnamic acid, 3-(trifluoromethoxy)cinnamic acid, 2,3,4-trimethoxycinnamic acid, coumarin ( coumarin), vinylbenzyl cyanide, tetraphenylethylene, 2-bromo-1,1,2-triphenylethylene, triphenylethylene, etc.

In addition, in the norbornene monomer obtained by the method shown in the above-mentioned reaction formula (III), there are exo isomers and endo isomers as stereoisomers at the site where the aromatic structure and the bicyclic structure are connected. isomer. Moreover, the exo isomer of such a norbornene monomer imparts "negative A-ness" to the obtained norbornene-based ring-opening polymer, while the endo isomer imparts "negative A-ness" to the obtained norbornene-based ring-opening polymer. The ring-opened polymer imparts "positive A-ness". Therefore, in the retardation film of the present invention, the ratio of these isomers contained in the film is appropriately selected according to the desired optical characteristics. For example, by appropriately changing the content ratio of these isomers, a film substantially free from birefringence can be obtained. In addition, the positive A property here refers to the property that the refractive index in the stretching direction is larger than the refractive index in the direction perpendicular to the stretching direction obtained from the change in refractive index that occurs when the film is uniaxially stretched. In addition, the negative A property refers to the property satisfying the condition of the above-mentioned relational expression (1), and refers to the property that the refractive index in the extending direction is smaller than the refractive index in the direction perpendicular to the extending direction. In addition, such isomers, for example, can be easily changed in the ratio of the product by appropriately changing the reaction conditions at the time of monomer production. In addition, even after the monomer is produced, it can be obtained by performing heat treatment and changing the conditions of the heat treatment. Easily change its ratio.

In addition, as a method for producing the norbornene monomer represented by the general formula (I-1) or (II-1), for example, a method represented by the following reaction formula (IV) can be suitably employed.

[Reaction formula (IV)]

[In the reaction formula (IV), n has the same meaning as n in the above general formula (1), and X represents a chlorine atom, a bromine atom or an iodine atom. ]

The method represented by such reaction formula (IV) is to utilize the reductive Heck reaction to make the norbornadiene derivative represented by the general formula (IV-1) and the halogenated benzene derivative represented by the general formula (IV-2) Reaction, obtains the method for the norbornene monomer shown in general formula (IV-3). By such a reaction, a norbornene monomer in which the stereo configuration of the benzene ring in the general formula (IV-3) is exo-coordinated can be obtained.

In addition, when the value of n in the above reaction formula (IV) is 0 (for norbornadiene), only a norbornene monomer in which the stereo configuration of the benzene ring is in the external form can be obtained. On the other hand, when the n value in the above-mentioned reaction formula (IV) is 1 (when it is tetracyclic [4.4.0.1 ^2,5 .1 ^7,10 ]-3,8-dodecadiene), it can be compared with n When = 0, the stereo configuration of the benzene ring is an exo configuration with respect to the norbornene ring, but there are two types of stereoisomers at the position where the norbornene rings are connected to each other: an exo isomer and an endo isomer isomer. The content ratio of such isomers can be easily changed by, for example, appropriately changing the reaction conditions for producing the norbornadiene derivative represented by the above-mentioned general formula (IV-1) as a raw material. In addition, even after the norbornene monomer represented by the general formula (IV-3) is produced, the content ratio of the above isomers can be changed by performing an isomerization treatment and changing the conditions of the isomerization treatment.

In addition, the catalyst for the ring-opening polymerization used in the reaction of ring-opening polymerization of such a norbornene monomer (the reaction described in the reaction formula (I) or the reaction described in the reaction formula (II)) does not have Particularly limited, for example, a metathesis polymerization catalyst described in Olefin Metathesis and Metathesis Polymerization (KJIVIN, JCMOL, Academic Press 1997) can be used. That is to say, (a) at least one compound selected from compounds containing W, Mo, Re, V and Ti, and (b) compounds containing Li, Na, K, Mg, Ca, Zn, Cd, Hg, B, a compound of an element such as Al, Si, Sn, Pb, etc., a catalyst composed of a combination of at least one compound selected from the group consisting of at least one element-carbon bond or element-hydrogen bond. When such a catalyst is used to advance the above-mentioned ring-opening polymerization, an additive (c) described later may be added in order to increase the activity of the catalyst. In addition, examples of other catalysts include (d) metathesis catalysts composed of transition metal-carbene complexes and metallocyclobutane complexes of Groups 4 to 8 of the Periodic Table that do not use a co-catalyst. In addition, the above-mentioned (a) component includes WCl ₆ , MoCl ₅ , ReOCl ₃ , VOCl ₃ , TiCl ₄ and the like as typical examples of compounds containing W, Mo, Re, V or Ti as appropriate. In addition, specific examples of the compound used as the component (b) include nC 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 ) Compounds such as AlCl ₂ , methylaluminoxane, LiH, etc. Alcohols, aldehydes, ketones, amines, etc. can be used as a representative example of the additive of (c)component. In addition, representative examples of the component (d) include 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 generation and second generation) and so on.

As the amount of such a metathesis catalyst used, the ratio of the above-mentioned component (a) to the total amount of the above-mentioned norbornene monomer (in the reaction formula (I), referred to as the above-mentioned component (a) and the above-mentioned formula (I-1) The ratio of the norbornene monomer shown in the reaction formula (II) is referred to as the ratio of the total amount of the norbornene monomer shown in the above-mentioned component (a) and the above-mentioned formula (II-1) and (II-2) Ratio) is preferably in the range of 1:500 to 1:500000, more preferably in the range of 1:1000 to 1:100000 in terms of molar ratio "(a) component: total amount of norbornene monomer". In addition, as the ratio of (a) component and (b) component, "(a) component: (b) component" is preferably in the range of 1:1 to 1:100 in terms of metal atomic ratio, more preferably 1:2 to 1:50 range. The ratio of component (a) to component (c) is preferably in the range of 0.005:1 to 15:1, more preferably 0.05:1 to 10:1 in molar ratio "(c) component: (a) component" range. In addition, as the amount of the catalyst (d) used, the ratio of the (d) component to the total amount of the norbornene monomer (in the above reaction formula (I), referred to as the above-mentioned (d) component and the formula (I-1) The ratio of the total amount of norbornene monomers shown in the above reaction formula (II) is referred to as the total amount of norbornene monomers shown in the above-mentioned (d) component and (II-1) and (II-2). The ratio of the amount) is preferably in the range of 1:30 to 1:100000, more preferably in the range of 1:50 to 1:50000 in terms of molar ratio "(d) component: total amount of norbornene monomer".

In addition, in the reaction (the reaction described in the reaction formula (I) or the reaction described in the reaction formula (II)) of ring-opening polymerization of the above-mentioned norbornene monomer, the obtained norbornene-based ring-opening polymerization The method of determining the molecular weight of the compound is not particularly limited, and for example, a method of appropriately adjusting the molecular weight by changing the polymerization temperature, the type of catalyst, the type of solvent, and the like can be employed. Furthermore, as such a method of adjusting the molecular weight, a method of making a molecular weight modifier coexist in the reaction system can be suitably employed. Examples of suitable molecular weight modifiers for such a molecular weight modifier include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1- α-olefins such as -decene, and styrene, among which 1-butene and 1-hexene are particularly preferable. These molecular weight modifiers can be used individually or in mixture of 2 or more types. The usage-amount of such a molecular weight modifier is preferably 0.005-1.0 mol, more preferably 0.02-0.5 mol with respect to 1 mol of the said norbornene monomer.

In addition, as a solvent usable in the reaction of ring-opening polymerization of the above-mentioned norbornene monomer (the reaction described in the reaction formula (I) or the reaction described in the reaction formula (II)), it is preferable that the above-mentioned norbornene can be dissolved. Solvents for norbornene monomers, metathesis catalysts, and molecular weight modifiers, for example, paraffins such as pentane, hexane, heptane, octane, nonane, and decane; cyclohexane, cycloheptane, and cyclooctane , decalin, norbornane and other cycloalkanes; benzene, toluene, xylene, ethylbenzene, cumene and other aromatic hydrocarbons; chlorobutane, bromohexane, dichloromethane, dichloroethane, hexamethylene Dibromide, chlorobenzene, chloroform, tetrachloroethylene and other halogenated alkanes; aryl and other compounds; ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate, dimethoxyethane, γ - saturated carboxylic acid esters such as butyrolactone; ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane, among which aromatic hydrocarbons are preferred. These solvents can be used individually or in mixture of 2 or more types. The amount of such a solvent used is preferably an amount of 1:1 to 30:1, more preferably an amount of 1:1 to 20:1 in terms of mass ratio of "solvent:norbornene monomer".

In addition, the norbornene-based ring-opened polymer obtained in the ring-opening polymerization state as described above is a norbornene-based polymer containing a structural unit represented by the formula (I-2) when the above-mentioned reaction formula (I) is adopted. The ring-opened polymer is a norbornene-based ring-opened polymer containing structural units represented by formulas (II-3) and (II-4) when the above reaction formula (II) is used. In addition, the norbornene-based ring-opened polymer obtained in this way has a vinylidene group in its structural unit. Such a norbornene-based ring-opening polymer can be used as it is in the retardation film of the present invention for various applications, but from the viewpoint of improving the heat resistance stability of the obtained retardation film, it is preferable to react as described above. In the formula (I) and (II), a part or all of the vinylidene group of the norbornene ring-opening polymer is hydrogenated, so that it becomes a hydride (formula (I) containing the vinylidene group converted to vinyl - A norbornene-based ring-opening polymer having a structural unit represented by 2')), or a norbornene-based ring-opening polymer containing a structural unit represented by (II-3') and (II-4'). In addition, in such a hydride, the aromatic ring of the side chain in the structural unit represented by the above formula (I-2') or (II-3') is not substantially hydrogenated. In addition, the hydrogenation rate of the vinylene group is preferably 90% or higher, more preferably 95% or higher, and particularly preferably 98% or higher. The higher the hydrogenation rate of the vinylidene group, the higher the heat resistance of the obtained norbornene-based ring-opening polymer, and the tendency to sufficiently suppress coloring and deterioration due to heat.

In addition, the norbornene-based ring-opening polymer containing the structural unit represented by the above general formula (I-2) or norbornene containing the structural unit represented by the above general formula (II-3) and (II-4) The hydrogenation reaction of the olefinic ring-opening copolymer is not particularly limited, but as mentioned above, it is necessary to carry out under the condition that the aromatic ring of the side chain is not substantially hydrogenated, and usually contains the above-mentioned general formula (I-2) The solution of the norbornene ring-opening polymer of the structural unit shown or the solution of the norbornene ring-opening copolymer containing the structural unit represented by the above general formula (II-3) and (II-4) is added The hydrogenation catalyst is performed at 0 to 200°C, preferably at 20 to 180°C, by allowing hydrogen gas at normal pressure to 30 MPa, preferably 3 to 20 MPa, to act on it.

In addition, as a hydrogenation catalyst used in such a hydrogenation reaction, a catalyst used in a general hydrogenation reaction of an olefinic compound can be used, and a heterogeneous system catalyst or a homogeneous system catalyst can be used. Specific examples of such heterogeneous catalysts include solid catalysts in which noble metal catalyst substances such as palladium, platinum, nickel, rhodium, and ruthenium are supported on supports such as carbon, silica, alumina, and titania. In addition, as specific examples of homogeneous system catalysts, nickel naphthenate/triethylaluminum, nickel acetylacetonate/triethylaluminum, cobalt octoate/n-butyllithium, titanocene dichloride/diethylaluminum, Ethyl aluminum monochloride, rhodium acetate, tris(triphenylphosphine)rhodium chloride, tris(triphenylphosphine)ruthenium dichloride, tris(triphenylphosphine)ruthenium dichlorocarbonyl, tris(triphenylphosphine)dichlorocarbonyl Phosphine) ruthenium, etc. The form of such a hydrogenation catalyst may be powder or granular.

Such a hydrogenation catalyst is a norbornene-based ring-opening polymer containing a structural unit represented by the above formula (I-2) or a norbornene-based ring-opening polymer containing a structural unit represented by the above formulas (II-3) and (II-4). The side-chain aromatic rings in the norbornene-based ring-opening copolymer are not substantially hydrogenated, and the amount of addition must be adjusted. The weight ratio of "ring-opening polymer:hydrogenation catalyst" is preferably 1:1×10 ^-6 to 1: A ratio of 2 is used.

In addition, the retardation film of the present invention is a film formed by stretching a film composed of the norbornene-based ring-opening polymer according to the present invention. The method for producing a film composed of such a norbornene-based ring-opening polymer is not particularly limited, and known methods can be appropriately used. In addition, when making such a film, other macromolecules, surfactants, polymer electrolytes, conductive materials, etc. Sexual coordination compounds, silica, alumina, pigment materials, heat stabilizers, ultraviolet absorbers, antistatic agents, antiblocking agents, lubricants, plasticizers, oils, etc. In addition, the method of stretching after forming the norbornene-based ring-opening polymer into a film is not particularly limited, and conventionally known stretching methods can be suitably used.

In addition, suitable methods for producing such a norbornene-based ring-opening polymer film include known and commonly used methods such as casting method (solution casting method), melt extrusion method, calendering method, and compression molding method. . In addition, as a molding device used in such a casting method, a dry casting machine, a belt casting machine, a spin coater, or the like can be used. In addition, examples of the melt extrusion method include a T-die method and blow molding method.

In addition, specific examples of the solvent used in the casting method include, for example, cyclic ketones such as cyclohexanone and cyclopentanone; lactones such as γ-butyrolactone and δ-valerolactone; benzene, toluene, and the like; , xylene, ethylbenzene, cumene and other aromatic hydrocarbons; dichloromethane, dichloroethane, chlorobenzene, dichlorobenzene, chloroform, tetrachloroethylene and other halogenated paraffins; aryl and other compounds, dibutyl ether, Ethers such as tetrahydrofuran and dimethoxyethane, polar solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethylsulfoxide, among which preferred Aromatic hydrocarbons, halogenated paraffins, aryls. In addition, these solvents can be used individually or in mixture of 2 or more types.

In addition, as a method of stretching the above-mentioned norbornene-based ring-opening polymer into a film, examples of the biaxial stretching method include a tenter method, a tube method, and the like, and examples of a uniaxial stretching method include a water tank stretching method. , Radiation stretching method, hot air heating method, hot plate heating method, roller heating method, etc.

The thickness of the retardation film of the present invention thus obtained is not particularly limited, but is desirably 10 to 500 μm, more preferably 30 to 200 μm. When the thickness of the retardation film is less than 10 μm, the mechanical properties and the handleability at the time of secondary processing tend to decrease, and when it exceeds 500 μm, problems tend to arise in flexibility. Moreover, although the draw ratio at the time of obtaining the retardation film of this invention is not specifically limited, It is preferable that it is about 1.1-5.0 times.

The phase difference value of the retardation film of the present invention is the scope of 5～2000nm, is the scope that should be selected according to the purpose, when using as 1/2 lambda plate, the phase difference in the visible light of wavelength 550nm hope is 200～400nm, in as When the 1/4λ plate is used, the phase difference in visible light with a wavelength of 550nm is desirably 90 to 200nm.

In addition, the retardation film of the present invention may include a thin film for the purpose of imparting functions such as gas barrier properties, scratch resistance, chemical resistance, and antiglare properties. The method of forming such a film, for example, is based on various thermoplastic resins, thermosetting resins having amino groups, imino groups, epoxy groups, silyl groups, etc., radiation-curable resins having acryloyl groups, methacryloyl groups, vinyl groups, etc., or Add polymerization inhibitors, waxes, dispersants, pigment materials, solvents, plasticizers, ultraviolet absorbers, inorganic fillers, etc. to the mixture of these resins. Coating method, dip coating method, air knife coating method, roll coating method, extrusion coating method, contact coating method, blowing coating method, spray coating method, spin coating method and other methods Method of coating. These thin films may be cured by radiation or by heating as necessary after coating to form a cured thin film layer. In addition, when printing is performed when forming such a thin film, methods such as a gravure method, a transfer method, a flex method, and a screen printing method 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-tightness or the like. Such a metal oxide layer is formed by a vacuum evaporation method, a sputtering method, an ion plating method, a plasma CVD method, or the like.

In addition, the retardation film of the present invention and other films may be laminated. As a method for laminating the retardation film of the present invention and other films in this way, conventionally known methods can be appropriately adopted, for example, thermal bonding such as heat sealing, surge current sealing, ultrasonic bonding, high frequency bonding, etc. Lamination methods such as extrusion lamination, hot melt lamination, dry pressing, wet pressing, solvent-free adhesive lamination, thermal lamination, co-extrusion, etc. In addition, the laminated film includes, for example, polyester resin film, polyvinyl alcohol ester 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, etc.

Next, the liquid crystal display device of the present invention will be described. That is, the liquid crystal display device of the present invention is characterized by comprising the retardation film of the present invention described above.

The above-mentioned retardation film of the present invention is a retardation film that has high transparency and excellent wavelength dispersion, can give a specific retardation to a wide range of light, and has very high adhesion to other materials, and even in negative birefringence In nature, it can also achieve the optical characteristics of a specific negative A, and can achieve the reverse dispersion of the birefringence wavelength dispersion characteristic, so it can be used as a 1/4λ plate in a reflective liquid crystal display device and a 1/2λ plate in a liquid crystal projection device. plate and 1/4λ plate, 1/2λ plate and 1/4λ plate in a transmissive liquid crystal display device, a protective film for a polarizing film used in a liquid crystal display device, an antireflection film, and the like.

Therefore, the liquid crystal display device of the present invention may include the retardation film of the present invention described above as a 1/2λ plate, a 1/4λ plate, a protective film, an antireflection film, etc., and other structures may be the same as those of conventionally known liquid crystal display devices.

In addition, the retardation film of the present invention can be used as a film in touch panels, liquid crystal display devices, etc. Transparent electrode film is used.

Example

Hereinafter, the present invention will be more specifically described based on examples and comparative examples, but the present invention is not limited to the following examples.

First, the method of evaluating the properties 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 flow at a heating rate of 20° C. per minute.

<Molecular weight and molecular weight distribution>

As the measuring device, gel permeation chromatography (GPC, produced by Tosoh Co., Ltd., trade name: HLC-8020/4 columns: produced by Tosoh Co., Ltd., trade name: TSK gelGMH _HR ) was used, and tetrahydrofuran (THF) was used as the solvent. Polystyrene-equivalent weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the polymer obtained in each synthesis example. In addition, Mn represents a number average molecular weight.

<Monomer and Polymer Molecular Structure>

¹ H-NMR and ¹³ C-NMR of the polymers obtained in each synthesis example were measured in deuterated chloroform using a superconducting nuclear magnetic resonance absorption apparatus (NMR, manufactured by VARIAN, trade name: UNITY INOVA-600). From the obtained data, the internal shape/external shape ratio of the monomer and the hydrogenation rate of the polymer ( ^X1 in the norbornene-based ring-opening polymer containing the structural unit represented by the above general formula (1) or containing the above general formula (1) were calculated. X ¹ and X ² in the norbornene-based ring-opening copolymer of structural units shown in formulas (2) and (3) are transformed into the ratio of groups shown in formula -CH ₂ CH ₂ -) calculation and molecular structure identification.

<Evaluation of phase difference, birefringence, wavelength dispersion value of birefringence>

The retardation (Re) defined by the following formula and the wavelength dispersion value (D) of the birefringence were measured with respect to the retardation films obtained in the respective examples and comparative examples using a retardation meter (manufactured by Oji Scientific Co., Ltd., trade name: KOBRA21DH). .

Re=(nx-ny)×d

nx: Refractive index in stretching direction

ny: Refractive index in the direction perpendicular to the stretching direction

d: film thickness (nm)

D: wavelength dispersion value Δn(λ=481 nm)/Δn(λ=589 nm) of birefringence.

(Synthesis Example 1)

<Synthesis of norbornene monomer (monomer) A, B>

Put 4-tert-butylstyrene (856g, 5.36mol), dicyclopentadiene (709g, 5.36mol), 4-tert-butylcatechol (44.6g, 0.27mol), toluene into a 2L autoclave (200mol), heated and stirred at 185°C for 4 hours. A pressure of 0.4 MPa was displayed at the initial stage of the reaction, and the pressure decreased as time passed, and finally 0.2 MPa was displayed. Then, after the heating was stopped, it was left to cool naturally, and after dropping to room temperature, the lid of the autoclave was opened to take out the reactants.

Next, the reactant thus obtained was purified by distillation to obtain Fraction A at 118 to 120° C./1 mmHg and Fraction B at 165 to 170° C./1 mmHg. The yield of Fraction A was 640 g (53% yield based on tert-butylstyrene) and the yield of Fraction B was 97 g (6% yield based on tert-butylstyrene). Fraction A was analyzed by gas chromatography and NMR, and as a result, it was confirmed that it was a 5-(p-tert-butylphenyl) bicyclic compound with an endo/exo ratio (isomer ratio) of 79/21. [2.2.1]-2-Heptene (general formula (4) below).

[fraction A]

In addition, Fraction B was also subjected to gas chromatography analysis and NMR analysis, and as a result, it was confirmed that it was 8-(para-tert) with an endo-endo/endo-exo ratio of 87/13. butylphenyl)tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene (general formula (5) below).

[fraction B]

Next, 300 g of fraction A was heated and dissolved in 1200 ml of methanol, and allowed to cool naturally to obtain 165 g of crystals of 5-(p-tert-butylphenyl)bicyclo[2.2.1]-2-heptene (A). The crystals obtained had a purity of 98% and an endo/exo ratio of 80/20. In addition, dissolve 30 g of fraction B in 150 ml of isopropanol, and let it cool naturally to obtain 18 g of 8-(p-tert-butylphenyl)tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]- Crystallization of 3-dodecene (B). The purity of the obtained crystals was 99%, and the endo-endo/endo-exo ratio was 100/0.

<Polymerization of Norbornene Monomer A>

Under a nitrogen atmosphere, the endo/exo ratio of 5-(p-tert-butylphenyl)bicyclo[2.2.1]-2-heptene (A) (2.26g, 0.01mol) of 80/20 Anhydrous toluene solution (2 ml) of 1-hexene (2.5 μl, 0.2 mol%) and Grubbs I catalyst (4.1 mg, 0.05 mol%) was added to anhydrous toluene solution (20 ml), and stirred at room temperature for 20 hours. Next, the viscous polymerization solution was diluted with 100 ml of toluene, poured into 3000 ml of methanol, and the obtained precipitate was filtered. Next, the precipitate was dried with a vacuum dryer to obtain 1.90 g (85% yield) of the ring-opened polymer of A (pA). The obtained product was confirmed by GPC, and the polystyrene conversion weight average molecular weight (Mw) was 90000, and Mw/Mn was 1.6.

<Polymerization of Norbornene Monomer B>

8-(p-tert-butylphenyl)tetracyclo[4.4.1 2, ^{5 .1 7 , 10} .0] with an endo-endo/endo-exo ratio of 100/0 under nitrogen atmosphere -1-hexene (2.5 μl, 0.2mol%) and Grubbs I catalyst (4.1mg, 0.05mol%) were added in anhydrous toluene solution (20ml) of 3-dodecene (B) (2.90g, 0.01mol%) ) in anhydrous toluene (2ml), stirred at room temperature for 20 hours. Next, the viscous polymerization solution was diluted with 100 ml of toluene, poured into 3000 ml of methanol, and the obtained precipitate was filtered. Next, the precipitate was dried with a vacuum dryer to obtain 2.84 g (98% yield) of the ring-opened polymer of B (pB). The obtained product was confirmed by GPC, and the polystyrene-equivalent weight average molecular weight (Mw) was 125000, and Mw/Mn was 1.5.

<Hydrogenation of ring-opening polymer (pA) of norbornene monomer A>

In an autoclave with a capacity of 0.2 L, 1.9 g of ring-opened polymer (pA), xylene (150 ml), RuHCl ( CO)(PPh ₃ ) ₃ (19 mg), nitrogen replacement. Next, after hydrogenation reaction was carried out by heating for 30 hours under the conditions of a hydrogen pressure of 10 MPa and a reaction temperature of 165° C., the resulting reaction solution was cooled and the hydrogen pressure was released. Then, inject the reaction solution obtained in this way into 3000ml of methanol, separate and recover the precipitate, and dry the obtained precipitate to obtain the ring-opening polymerization of 5-(p-tert-butylphenyl)bicyclo[2.2.1]-2-heptene The hydride (HpA) of the product was 1.69 g (yield 89%).

The obtained product was confirmed by GPC, and the polystyrene-equivalent weight average molecular weight (Mw) was 97000, and Mw/Mn was 1.5. In addition, the hydrogenation rate of the olefinic unsaturated bond was measured using NMR for the obtained product, and it was confirmed to be 99.9%. In addition, since the signal from the aromatic ring did not change, it was confirmed that the aromatic ring was not substantially hydrogenated. The obtained NMR chart is shown in FIG. 1 . On the other hand, when Tg was measured using DSC, Tg was 118°C.

<Hydrogenation of ring-opening polymer (pB) of norbornene monomer B>

In an autoclave with ^a capacity ^of 0.2L, add the ring-opening polymer (pB ) 2.0 g, xylene (150 ml), RuHCl(CO)(PPh ₃ ) ₃ (20 mg), nitrogen replacement. Next, after hydrogenation reaction was carried out by heating for 30 hours under the conditions of a hydrogen pressure of 10 MPa and a reaction temperature of 165° C., the resulting reaction solution was cooled and the hydrogen pressure was released. Then, the reaction solution was injected into 3000ml of methanol, the precipitate was separated and recovered, and the obtained precipitate was dried to obtain 8-(p-tert-butylphenyl)tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3 - 1.99 g (99.5% yield) of a hydrogenated product (HpB) of a ring-opened polymer of dodecene.

The product obtained in this way was confirmed by GPC, and the polystyrene-equivalent weight average molecular weight (Mw) was 96400, and Mw/Mn was 1.5. In addition, the hydrogenation rate of the olefinic unsaturated bond was measured using NMR for the obtained product, and it was confirmed to be 99.9%. In addition, since the signal from the aromatic ring did not change, it was confirmed that the aromatic ring was not substantially hydrogenated. The obtained NMR chart is shown in FIG. 2 . On the other hand, when Tg was measured using DSC, Tg was 226°C.

(Synthesis Example 2)

<Synthesis of norbornene monomers C and D with different endo/exo ratios>

After inserting quartz wool into a straight glass tube (made of quartz) of about 10 cm, heat it to about 340-380°C, and add 5-(p-tert-butylphenyl)bicyclo[2.2 .1] -2-heptene (internal/external = 79/21), thermally decomposed. The reaction products are tert-butylstyrene, cyclopentadiene and 5-(p-tert-butylphenyl)bicyclo[2.2.1]-2-heptene with high exosome content. This is because the internal body is thermally unstable, and if the thermal decomposition temperature is increased, the content of the external body will increase. In addition, the yield of 5-(p-tert-butylphenyl)bicyclo[2.2.1]-2-heptene decreased while the temperature was increased. As a result of thermal decomposition at a thermal decomposition temperature of 340° C., 5-(p-tert-butylphenyl)bicyclo[2.2.1]-2 with an endo/exo ratio of 50/50 was obtained in a yield of 50%. - Heptene (C). In addition, if the thermal decomposition temperature is increased to 380 °C, 5-(p-tert-butylphenyl)bicyclo[2.2.1]-2- Heptene (D).

<Polymerization of Norbornene Monomer C>

Under a nitrogen atmosphere, 5-(p-tert-butylphenyl)bicyclo[2.2.1]-2-heptene (C) (2.26g, 0.01mol) with an endo/exo ratio of 50/50 Anhydrous toluene solution (2 ml) of 1-hexene (2.5 μl, 0.2 mol%) and Grubbs I catalyst (4.1 mg, 0.05 mol%) was added to anhydrous toluene solution (20 ml), and stirred at room temperature for 20 hours. Next, the viscous polymerization solution was diluted with 100 ml of toluene, poured into 3000 ml of methanol, and the obtained precipitate was filtered. Next, the precipitate was dried with a vacuum dryer to obtain 2.19 g (yield: 97%) of the ring-opened polymer of C (pC). The obtained product was confirmed by GPC, and the polystyrene-equivalent weight average molecular weight (Mw) was 113000, and Mw/Mn was 1.4.

<Polymerization of Norbornene Monomer D>

Under a nitrogen atmosphere, 5-(p-tert-butylphenyl)bicyclo[2.2.1]-2-heptene (D) (2.26g, 0.01mol) with an endo/exo ratio of 24/76 Anhydrous toluene solution (2 ml) of 1-hexene (2.5 μl, 0.2 mol%) and Grubbs I catalyst (4.1 mg, 0.05 mol%) was added to anhydrous toluene solution (20 ml), and stirred at room temperature for 20 hours. Next, the viscous polymerization solution was diluted with 100 ml of toluene, poured into 3000 ml of methanol, and the obtained precipitate was filtered. Next, the precipitate was dried with a vacuum dryer to obtain 1.74 g (yield: 77%) of the ring-opened polymer of D (pD). The obtained product was confirmed by GPC, and the polystyrene-equivalent weight average molecular weight (Mw) was 129000, and Mw/Mn was 1.7.

<Hydrogenation of ring-opening polymer (pC) of norbornene monomer C>

Add the ring-opening polymer (pC) of 5-(p-tert-butylphenyl)bicyclo[2.2.1]-2-heptene with an internal shape/external shape ratio of 50/50 in an autoclave with a capacity of 0.2L 2.0 g, xylene (150 ml), RuHCl(CO)(PPh ₃ ) ₃ (20 mg), nitrogen replacement. Next, after hydrogenation reaction was carried out by heating for 30 hours under the conditions of a hydrogen pressure of 10 MPa and a reaction temperature of 165° C., the resulting reaction solution was cooled and the hydrogen pressure was released. Then, inject the reaction solution in 3000ml methanol, separate and recover the precipitate, and dry the obtained precipitate to obtain a 5-(p-tert-butylphenyl)bicyclo[2.2.1]- Hydrogenated compound (HpC) of the ring-opened polymer of 2-heptene 1.96 g (98% yield).

The product obtained in this way was confirmed by GPC, and the polystyrene-equivalent weight average molecular weight (Mw) was 112000, and Mw/Mn was 1.5. The hydrogenation rate of the olefinic unsaturated bond of the obtained product was measured using NMR, and it was confirmed to be 99.9%. In addition, since the signal from the aromatic ring did not change, it was confirmed that the aromatic ring was not substantially hydrogenated. The obtained NMR chart is shown in FIG. 3 . On the other hand, when Tg was measured using DSC, Tg was 107°C.

<Hydrogenation of ring-opening polymer (pD) of norbornene monomer D>

Add the ring-opening polymer (pD) of 5-(p-tert-butylphenyl)bicyclo[2.2.1]-2-heptene with an endo/exo ratio of 24/76 in an autoclave with a capacity of 0.2L 2.0 g, xylene (150 ml), RuHCl(CO)(PPh ₃ ) ₃ (20 mg), nitrogen replacement. Next, after hydrogenation reaction was carried out by heating for 30 hours under the conditions of a hydrogen pressure of 10 MPa and a reaction temperature of 165° C., the resulting reaction solution was cooled and the hydrogen pressure was released. Then, inject the reaction solution in 3000ml methanol, separate and recover the precipitate, and dry the precipitate obtained to obtain a 5-(p-tert-butylphenyl)bicyclo[2.2.1]- The hydrogenated product (HpD) of the ring-opened polymer of 2-heptene was 1.70 g (yield: 85%).

The product obtained in this way was confirmed by GPC, and the polystyrene-equivalent weight average molecular weight (Mw) was 117000, and Mw/Mn was 1.5. In addition, the hydrogenation rate of the olefinic unsaturated bond was measured using NMR for the obtained product, and it was confirmed to be 99.9%. In addition, since the signal from the aromatic ring did not change, it was confirmed that the aromatic ring was not substantially hydrogenated. The obtained NMR chart is shown in FIG. 4 . On the other hand, when Tg was measured by DSC, Tg was 105°C.

(Synthesis Example 3)

<Synthesis of Exo Norbornene Monomer E>

The exo norbornene monomer E was synthesized according to the methods described in Angew. Chem. Int. Ed., 39, p1946 (published in 2000) and ibid., 34, p1844 (published in 1995). First, 4-tert-butyl iodobenzene (5g, 19.22mmol), dinorbornadiene (5.66g, 61.50mmol), trans-bis(μ-acetonato)bis[o-( Di-o-tolylphosphino)benzyl]dipalladium (II) (90mg, 0.5mol%), DMSO (82ml), _NEt3 (6.22g, 61.5mmol), formic acid (2.26g, 49.2mmol), at 120 It was heated and stirred at ℃ 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 separating 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. Next, the obtained crude product was purified by distillation to obtain Fraction E at 104° C./1 mmHg. The yield of Fraction E was 2.45 g (55% yield). Fraction E was subjected to gas chromatography and NMR analysis, and as a result, it was confirmed that 5-(p-tert-butylphenyl)bicyclo[2.2.1]-2 had an endo/exo ratio (isomer ratio) of 0/100. -heptene.

<Polymerization of Norbornene Monomer E>

Under nitrogen atmosphere, 5-(p-tert-butylphenyl)bicyclo[2.2.1]-2-heptene (E) (2.61g, 11.6mmol) with an endo/exo ratio of 0/100 Anhydrous toluene solution (2 ml) of 1-hexene (7.5 μl, 0.6 mol%) and Grubbs I catalyst (4.7 mg, 0.05 mol%) was added to anhydrous toluene solution (23 ml), and stirred at room temperature for 20 hours. Next, the viscous polymerization solution was diluted with 200 ml of toluene, poured into 3000 ml of methanol, and the obtained precipitate was filtered. Next, the precipitate was dried in a vacuum dryer to obtain 2.28 g (87% yield) of the ring-opened polymer of E (pE). The obtained product was confirmed by GPC, and the polystyrene-equivalent weight average molecular weight (Mw) was 174000, and Mw/Mn was 2.4.

<Hydrogenation of ring-opening polymer (pE) of norbornene monomer E>

Add the ring-opening polymer (pE) of 5-(p-tert-butylphenyl)bicyclo[2.2.1]-2-heptene with an internal shape/external shape ratio of 0/100 in an autoclave with a capacity of 0.2L 2.3 g, xylene (150 ml), RuHCl(CO)(PPh ₃ ) ₃ (23 mg), replaced with nitrogen. Next, after hydrogenation reaction was carried out by heating for 30 hours under the conditions of a hydrogen pressure of 10 MPa and a reaction temperature of 165° C., the resulting reaction solution was cooled and the hydrogen pressure was released. Then, inject the reaction solution in 2000ml of methanol, separate and recover the precipitate, and dry the obtained precipitate to obtain a 5-(p-tert-butylphenyl)bicyclo[2.2.1]- Hydrogenated product (HpE) of the ring-opened polymer of 2-heptene 2.0 g (yield 89%).

The product obtained in this way was confirmed by GPC, and the polystyrene-equivalent weight average molecular weight (Mw) was 173900, and Mw/Mn was 2.4. The hydrogenation rate of the olefinic unsaturated bond of the obtained product was measured using NMR, and it was confirmed to be 99.9%. In addition, since the signal from the aromatic ring did not change, it was confirmed that the aromatic ring was not substantially hydrogenated. The obtained NMR chart is shown in FIG. 5 . On the other hand, when Tg was measured using DSC, Tg was 108°C.

(Synthesis Example 4)

<Synthesis of Norbornene Monomer F>

(i) Synthesis of phenyl cinnamate

In a 1L three-necked flask, trans-cinnamoyl chloride (100g, 0.60mol), phenol (59.3g, 0.63mol), THF (500ml) were added under nitrogen flow, and triethylamine ( 63.8g, 0.63mol) in THF solution (100ml). After completion of the dropwise addition, the reaction solution was thrown into a water bath after stirring at room temperature for 12 hours. The obtained white precipitate was filtered and dried under reduced pressure. The yield was 135.5 g (yield 99.9%). When this was heated and dissolved in about 200 ml of methanol and cooled, white crystals (112.6 g, yield 83.8%) were obtained. In addition, the obtained crystal was confirmed to be the target trans-phenyl cinnamate by NMR structure analysis.

(ii) Synthesis of norbornene monomer F

Put trans-phenyl cinnamate (112g, 0.5mol), dicyclopentadiene (36.4g, 0.55mol) and toluene (100ml) obtained by the above operation into an autoclave with a capacity of 0.3L, and heat at 180°C Stir for 4 hours. Then, after the heating was stopped, it was left to cool naturally, and after dropping to room temperature, the lid of the autoclave was opened to take out the reactants. Next, the reactant was concentrated, and a part of the concentrate (1.2 g) was separated and purified by recycling fractionation HPLC (manufactured by Nippon Analytical Industry, LC-918) to obtain the target 5-phenyl-6-carboxyphenyl bicyclo [2.2.1] -2-heptene (norbornene monomer F: a compound represented by the following chemical formula (6)) 0.58 g (reaction yield 40%) (number of cycles 7 times)

In addition, such fractionation operation was repeated four times to obtain 2.7 g of the target object. As a result of NMR structural analysis of the target compound obtained in this way, the isomer ratio was a mixture with an endo-form/exo-ratio of 60/40.

<Polymerization of Norbornene Monomer F>

Under nitrogen atmosphere, 5-phenyl-6-carboxyphenylbicyclo[2.2.1]-2-heptene (F) (2.67g, 9.2mmol) with an endo/exo ratio of 60/40 Anhydrous THF solution (5 ml) of Grubbs II catalyst (3.9 mg, 0.05 mol%) was added to anhydrous THF solution (25 ml), and stirred at room temperature for 20 hours. Next, the viscous polymerization solution was diluted with 200 ml of THF, poured into 3000 ml of methanol, and the resulting precipitate was filtered. Then, the precipitate was dried by a vacuum dryer to obtain 2.3 g (pF) of the ring-opened polymer (pF) of 5-phenyl-6-carboxyphenylbicyclo[2.2.1]-2-heptene (F) (yield 87% ). The obtained product was confirmed by GPC, and the polystyrene-equivalent weight average molecular weight (Mw) was 3,096,000, and Mw/Mn was 2.7.

<Hydrogenation of ring-opening polymer (pF) of norbornene monomer F>

Add 2.20 g of ring-opening polymer (pF) of 5-phenyl-6-carboxyphenylbicyclo[2.2.1]-2-heptene, xylene (150 ml), RuHCl ( CO)(PPh ₃ ) ₃ (22 mg), nitrogen replacement. Next, after hydrogenation reaction was carried out by heating for 30 hours under the conditions of a hydrogen pressure of 10 MPa and a reaction temperature of 165° C., the resulting reaction solution was cooled and the hydrogen pressure was released. Then, the reaction solution was injected into 3000ml of methanol, the precipitate was separated and recovered, and the precipitate obtained was dried to obtain the hydrogenation of the ring-opened polymer of 5-phenyl-6-carboxyphenylbicyclo[2.2.1]-2-heptene Compound (HpF) 1.97g (yield 89.5%).

The product obtained in this way was confirmed by GPC, and the polystyrene-equivalent weight average molecular weight (Mw) was 3,920,000, and Mw/Mn was 1.8. The hydrogenation rate of the olefinic unsaturated bond of the obtained product was measured using NMR, and it was confirmed to be 99.9%. In addition, since the signal from the aromatic ring did not change, it was confirmed that the aromatic ring was not substantially hydrogenated. The obtained NMR chart is shown in FIG. 6 . On the other hand, when Tg was measured using DSC, Tg was 103°C.

(Examples 1 to 7 and Comparative Example 1)

The norbornene-based ring-opening polymers {HpA (Example 1), HpB (Comparative Example 1), HpC (Example 2), HpD (Example 3), and HpE (Example 3) obtained in Synthesis Examples 1 to 4 were used respectively. Example 4), HpF (Example 5)} to make a retardation film (Examples 1-5 and Comparative Example 1). HpG (Example 6) made from a polymer solution mixture of HpA (0.925 g) and HpC (0.695 g), and HpH made from a polymer solution mixture of HpC (0.462 g) and HpD (0.420 g) were also used, respectively. (Example 7), a retardation film (Examples 6-7) was produced. That is, first, chlorobenzene solutions containing each polymer at a concentration of 5 wt % were prepared respectively, cast on a glass plate into a film form by casting method, and dried naturally for 24 hours. Next, after peeling the obtained films from the glass plate, they were dried until the residual solvent concentration became 1.0 wt. %the following. The films obtained in this way have high transparency. In addition, the film thickness of the obtained film was 30-150 micrometers. Next, the obtained film was cut into a thin rectangular shape (size: 5.0 × 4.0 cm), and a biaxial stretching device (manufactured by Shibayama Science and Technology Co., Ltd., trade name "SS-60 type") was used to cut the film into a polymer Tg of each film material. Under the temperature condition of +10 ℃, carry out 200% (2.0 times) uniaxial stretching with the drawing speed of 50mm/min, obtain retardation film (embodiment 1～7) of the present invention and retardation film (comparative example) 1).

(Evaluation of Optical Properties of Retardation Films Obtained in Examples 1 to 7 and Comparative Example 1)

The birefringence of the retardation films obtained in Examples 1 to 7 and Comparative Example 1 was measured with a retardation meter. Table 1 shows the obtained results. In addition, the refractive index was measured with a trade name "2010 Prism Coupler" manufactured by Metricon Corporation. In addition, the stretching direction of the uniaxial stretching of the above-mentioned film is defined as the X-axis, and the direction perpendicular to the X-axis is defined as the Y-axis and the Z-axis (the Y-axis and the Z-axis are also orthogonal), and the X-axis is measured. Refractive index (Nx), Y-axis refractive index (Ny), Z-axis refractive index (Nz).

In addition, regarding the retardation films obtained in Examples 1 to 4 and Examples 6 to 7, FIG. 7 shows a graph showing the relationship between the ratio of the external bodies contained and the birefringence. In addition, regarding the phase difference films obtained in Examples 1 to 4 and Examples 6 to 7, the ratio of exosomes and the wavelength dispersion value {D=(Δn: λ481nm)/(Δn: λ589nm)} relationship chart.

[Table 1]

*1Δn@481nm/Δn@589nm *2 Inner-inner/inner-outer ratio

From the results shown in Table 1 and FIG. 7 , it was confirmed that the retardation film obtained in each Example functioned favorably as a retardation film. Also, since the retardation films of HpD and HpE (Examples 3 and 4) satisfy the relationship represented by the following formula (2), it was confirmed that they function as so-called negative A retardation films.

Ny＝Nz＞Nx (2)

In addition, from the results shown in FIG. 8, it can be seen that the wavelength dispersion value {D=(Δn: λ481nm)/(Δn: λ589nm)} of the birefringence of each retardation film is confirmed, and the ratio of the inner shape to the outer shape of the monomer is confirmed. On the other hand, it was confirmed that the retardation films obtained in Examples 1, 2, 6, and 7 were inversely dispersed.

(Evaluation of Adhesion of Retardation Films Obtained in Examples 1 to 7 and Comparative Example 1)

On the surface of the triacetyl cellulose substrate, the retardation film obtained in Examples 1 to 7 and Comparative Example 1 was bonded with an ultraviolet curable adhesive (manufactured by Toagosei, UVX-1620), according to JIS-K5400 When these adhesiveness was evaluated by the method of description, it was confirmed that the adhesiveness of any retardation film and a triacetyl cellulose film was very high.

(Synthesis Example 5)

<Synthesis of Norbornene Monomer I-1>

Under a nitrogen atmosphere, 2-dicyclohexylphosphino-2'-methylbiphenyl (258mg, 0.708mmol), palladium acetate (13.3mg, 0.059mmol), DMSO (250ml), Norbornadiene (19ml, 190mmol), 4-tert-butylbromobenzene (10ml, 59mmol), NEt ₃ (26.7ml, 192mmol) and formic acid (5.9ml, 154mmol), heated and stirred at 80°C for 6 hours, a reaction solution was obtained. Next, the obtained reaction solution was cooled to 30° C., poured into 300 ml of ice water, and extracted with n-hexane (50 ml×3 times) using a separating funnel to obtain a n-hexane solution. Next, after washing with water and saturated brine, it was dried over anhydrous magnesium sulfate to obtain an extract. Then, the above extract was filtered and concentrated to obtain 13.4 g of a crude product.

Next, the above crude product was purified by distillation to obtain a fraction (product) at 104° C./1 mmHg. The yield of such a product was 10.7 g (yield 80%). In addition, as a result of gas chromatographic analysis and NMR analysis, it was confirmed that the obtained product was an exo-5-(p-tert-butylphenyl)bicyclic ring with an endo-exo ratio (isomer ratio) of 0/100. [2.2.1]-2-Heptene (norbornene monomer I: a compound represented by the following chemical formula (7)).

(Synthesis Example 6)

<Synthesis of Norbornene Monomer I-2>

Under a nitrogen atmosphere, 2-(dicyclohexylphosphino)biphenyl (248mg, 0.708mmol), palladium acetate (13.3mg, 0.059mmol), DMSO (250ml), norbornadiene were put into a 1.0L three-necked flask. (19ml, 190mmol), 4-tert-butylbromobenzene (10ml, 59mmol), NEt ₃ (26.7ml, 192mmol) and formic acid (5.9ml, 154mmol), heated and stirred at 80°C for 8 hours to obtain a reaction solution. Next, the reaction solution was cooled to 30° C., poured into 300 ml of ice water, and extracted with n-hexane (50 ml×3 times) using a separating funnel to obtain a n-hexane solution. Next, the n-hexane solution was washed with water and saturated brine, and dried over anhydrous magnesium sulfate to obtain an extract. Then, the above extract was filtered and concentrated to obtain 13.8 g of a crude product.

Next, the above crude product was purified by distillation to obtain a fraction (product) at 104° C./1 mmHg. The yield of such a product was 11.2 g (yield 84%). As a result of gas chromatographic analysis and NMR analysis, it was confirmed that the above-mentioned product is the exo-5-(p-tert-butylphenyl)bicyclo[2.2. 1]-2-Heptene (norbornene monomer I).

(Synthesis Example 7)

<Copolymerization of norbornene monomer I with tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene (norbornene monomer J)-1>

Under a nitrogen atmosphere, the norbornene monomer I (1.70 g, 7.5 mmol) obtained in Synthesis Example 5 and the norbornene monomer J (0.40 g, 2.5 mmol) represented by the following chemical formula (8) were prepared. Anhydrous toluene solution (23ml).

Add anhydrous toluene solution (2ml) containing 1-hexene (7.5 μl, 0.6mol%) and Grubbs I catalyst (4.1mg, 0.05mol%) to the above-mentioned anhydrous toluene solution, stir at room temperature (25°C) After 20 hours, a polymerization solution was obtained. Next, the obtained viscous polymerization solution was diluted with 200 ml of toluene, poured into 3000 ml of methanol, and the obtained precipitate was filtered. Next, the precipitate was dried in a vacuum dryer to obtain 1.71 g (yield: 82%) of a ring-opening copolymer (pI) of norbornene monomer I and norbornene monomer J. The obtained copolymer (pI) was confirmed by GPC, and the polystyrene-equivalent weight average molecular weight (Mw) was 290000, and Mw/Mn was 4.9.

<Hydrogenation of ring-opening polymer (pI) of norbornene monomer I and norbornene monomer J>

pi (1.68g), xylene (150ml), RuHCl(CO)(PPh ₃ ) ₃ (8.5mg, 0.5mass%) were added to a 0.2L autoclave, and replaced with nitrogen. Next, after hydrogenation reaction was carried out by heating for 30 hours under the conditions of a hydrogen pressure of 10 MPa and a reaction temperature of 165° C., the obtained reaction solution was cooled to 30° C., and the hydrogen pressure was released. Next, the reaction solution was poured into 2000 ml of methanol, the precipitate was separated and recovered, and the obtained precipitate was dried to obtain 1.4 g (yield: 81%) of a hydrogenated product of pI (copolymer (HpI)).

The product (HpI) thus obtained was confirmed by GPC, and the polystyrene-equivalent weight average molecular weight (Mw) was 263000, and Mw/Mn was 4.5. In addition, when Tg was measured using DSC, Tg was 123°C. The hydrogenation rate of the olefinic unsaturated bonds was also measured for the obtained copolymer (HpI) using NMR. The obtained NMR chart is shown in FIG. 9 . From the results shown in FIG. 9 , in the obtained copolymer (HpI), it was confirmed that the hydrogenation rate of olefinic unsaturated bonds was 99.9%. In addition, in the obtained copolymer (HpI), since the signal derived from the aromatic ring did not change, it was confirmed that the aromatic ring in the side chain was not substantially hydrogenated.

(Synthesis Example 8)

<Copolymerization of norbornene monomer I with tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene (norbornene monomer J)-2>

Under a nitrogen atmosphere, a compound containing norbornene monomer I (1.13 g, 5.0 mmol) obtained in Synthesis Example 5 and norbornene monomer J (0.80 g, 5.0 mmol) represented by the above chemical formula (8) was prepared. Anhydrous toluene solution (23ml), in above-mentioned anhydrous toluene solution, add the anhydrous toluene solution (2ml) that contains 1-hexene (7.5 μ l, 0.6mol%) and Grubbs I catalyst (4.1mg, 0.05mol%), The mixture was stirred at room temperature for 20 hours to obtain a polymerization solution. Next, the obtained viscous polymerization solution was diluted with 200 ml of toluene, poured into 3000 ml of methanol, and the obtained precipitate was filtered. Next, the above precipitate was dried with a vacuum dryer to obtain 1.70 g (yield: 88%) of a ring-opening copolymer (pJ) of norbornene monomer I and norbornene monomer J. The obtained copolymer (pJ) was confirmed by GPC, and the polystyrene-equivalent weight average molecular weight (Mw) was 160000, and Mw/Mn was 3.3.

<Hydrogenation of ring-opening copolymer (pJ) of norbornene monomer I and norbornene monomer J>

PJ (1.66g), xylene (150ml) and RuHCl(CO)(PPh ₃ ) ₃ (8.5mg, 0.5mass%) were added to a 0.2L autoclave, and replaced with nitrogen. Next, after hydrogenation reaction was carried out by heating for 30 hours under the conditions of a hydrogen pressure of 10 MPa and a reaction temperature of 165° C., the obtained reaction solution was cooled to 30° C., and the hydrogen pressure was released. Next, the above-mentioned reaction solution was poured into 2000 ml of methanol, the precipitate was separated and recovered, and the obtained precipitate was dried to obtain 1.6 g (98% yield) of a hydrogenated product of the copolymer (pJ) (copolymer (HpJ)).

The copolymer (HpJ) thus obtained was confirmed by GPC, and the polystyrene-equivalent weight average molecular weight (Mw) was 131000, and Mw/Mn was 3.6. In addition, when Tg was measured using DSC, Tg was 137°C. The hydrogenation rate of the olefinic unsaturated bond was also measured about the obtained copolymer (HpJ) using NMR. The NMR chart of the obtained copolymer (HpJ) is shown in FIG. 10 . From the results shown in FIG. 10 , it was confirmed that the hydrogenation rate of olefinic unsaturated bonds in the obtained hydrogenated product (HpJ) was 99.9%. In addition, in the obtained hydride (HpJ), since the signal from the aromatic ring did not change, it was confirmed that the aromatic ring in the side chain was not substantially hydrogenated.

(Synthesis Example 9)

<Copolymerization of norbornene monomer I with tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene (norbornene monomer J)-3>

First, a mixture containing norbornene monomer I (0.57 g, 2.5 mmol) obtained in Synthesis Example 5 and norbornene monomer J (1.20 g, 7.5 mmol) represented by the above chemical formula (8) was prepared under a nitrogen atmosphere. Anhydrous toluene solution (23ml) of above-mentioned anhydrous toluene solution (23ml), add the anhydrous toluene solution containing 1-hexene (7.5 μ l, 0.6mol%) and Grubbs I catalyst (4.1mg, 0.05mol%) (2 ml), stirred at room temperature for 20 hours to obtain a polymer solution. Next, the obtained viscous polymerization solution was diluted with 200 ml of toluene, poured into 3000 ml of methanol, and the obtained precipitate was filtered. Next, the precipitate was dried in a vacuum dryer to obtain 1.70 g (yield: 96%) of a ring-opening copolymer (pK) of norbornene monomer I and norbornene monomer J. As for the obtained copolymer (pK), it was confirmed by GPC that the polystyrene-equivalent weight average molecular weight (Mw) was 123000, and Mw/Mn was 2.6.

<Hydrogenation of ring-opening polymer (pK) of norbornene monomer I and norbornene monomer J>

PK (1.66g), xylene (150ml), RuHCl(CO)(PPh ₃ ) ₃ (8.5mg, 0.5mass%) were added to a 0.2L autoclave, and replaced with nitrogen. Next, after hydrogenation reaction was carried out by heating for 30 hours under the conditions of a hydrogen pressure of 10 MPa and a reaction temperature of 165° C., the obtained reaction solution was cooled to 30° C., and the hydrogen pressure was released. Next, this reaction solution was poured into 2000 ml of methanol, the precipitate was separated and recovered, and the obtained precipitate was dried to obtain 1.6 g (yield 98%) of a pK hydride (copolymer (HpK)).

The Tg of the copolymer (HpK) thus obtained was measured by DSC, and the Tg was 147°C. Moreover, the hydrogenation rate of an olefinic unsaturated bond was measured about a copolymer (HpK) using NMR. The obtained NMR chart is shown in FIG. 11 . From the results shown in FIG. 11 , in the obtained copolymer (HpK), it was confirmed that the hydrogenation rate of olefinic unsaturated bonds was 97.0%. In addition, in the obtained copolymer (HpK), since the signal derived from the aromatic ring did not change, it was confirmed that the aromatic ring was not substantially hydrogenated.

(Synthesis Example 10)

<Copolymerization of norbornene monomer I with tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene (norbornene monomer J)-4>

First, a mixture containing norbornene monomer I (1.98 g, 8.75 mmol) obtained in Synthesis Example 5 and norbornene monomer J (0.20 g, 1.25 mmol) represented by the above chemical formula (8) was prepared under a nitrogen atmosphere. Anhydrous toluene solution (23ml) of anhydrous toluene solution (23ml), in above-mentioned anhydrous toluene solution, add the anhydrous toluene solution (2ml) containing 1-hexene (7.5 μ l, 0.6mol%) and Grubbs I catalyst (4.1mg, 0.05mol%) , stirred at room temperature for 20 hours to obtain a polymer solution. Next, the obtained viscous polymerization solution was diluted with 200 ml of toluene, poured into 3000 ml of methanol, and the obtained precipitate was filtered. Next, the precipitate was dried in a vacuum dryer to obtain 1.74 g (yield: 80%) of a ring-opened copolymer (pL) of norbornene monomer I and norbornene monomer J.

<Hydrogenation of ring-opening copolymer (pL) of norbornene monomer I and norbornene monomer J>

pL (1.66g), xylene (150ml), RuHCl(CO)(PPh ₃ ) ₃ (8.5mg, 0.5mass%) were added to a 0.2L autoclave, and replaced with nitrogen. Next, after hydrogenation reaction was carried out by heating for 30 hours under the conditions of a hydrogen pressure of 10 MPa and a reaction temperature of 165° C., the obtained reaction solution was cooled to 30° C., and the hydrogen pressure was released. Next, this reaction solution was poured into 2000 ml of methanol, the precipitate was separated and recovered, and the obtained precipitate was dried to obtain 1.3 g (yield: 80%) of a pL hydrogenated product (copolymer (HpL)).

The Tg of the copolymer (HpL) thus obtained was measured by DSC, and the Tg was 116°C. Moreover, the hydrogenation rate of the olefinic unsaturated bond was measured using NMR about the obtained copolymer (HpL), and it confirmed that the said hydrogenation rate was 99.9%. In addition, in the obtained copolymer (HpL), since the signal derived from the aromatic ring did not change, it was confirmed that the aromatic ring was not substantially hydrogenated.

(Synthesis Example 11)

<Copolymerization of norbornene monomer I with tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene (norbornene monomer J)-5>

First, a mixture containing norbornene monomer I (2.15 g, 9.50 mmol) obtained in Synthesis Example 5 and norbornene monomer J (0.08 g, 0.5 mmol) represented by the above chemical formula (8) was prepared under a nitrogen atmosphere. Anhydrous toluene solution (23ml) of anhydrous toluene solution (23ml), in above-mentioned anhydrous toluene solution, add the anhydrous toluene solution (2ml) containing 1-hexene (7.5 μ l, 0.6mol%) and Grubbs I catalyst (4.1mg, 0.05mol%) , stirred at room temperature for 20 hours to obtain a polymer solution. Next, the obtained viscous polymerization solution was diluted with 200 ml of toluene, poured into 3000 ml of methanol, and the obtained precipitate was filtered. Next, the precipitate was dried in a vacuum dryer to obtain 1.81 g (yield: 81%) of a ring-opening copolymer (pM) of norbornene monomer I and norbornene monomer J.

<Hydrogenation of ring-opening polymer (pM) of norbornene monomer I and norbornene monomer J>

PM (1.66g), xylene (150ml), RuHCl(CO)(PPh ₃ ) ₃ (8.5mg, 0.5mass%) were added to a 0.2L autoclave, and replaced with nitrogen. Next, after hydrogenation reaction was carried out by heating for 30 hours under the conditions of a hydrogen pressure of 10 MPa and a reaction temperature of 165° C., the obtained reaction solution was cooled to 30° C., and the hydrogen pressure was released. Next, this reaction solution was poured into 2000 ml of methanol, the precipitate was separated and recovered, and the obtained precipitate was dried to obtain 1.35 g (yield 82%) of pM hydride (copolymer (HpM)).

The Tg of the copolymer (HpM) thus obtained was measured by DSC, and the Tg was 112°C. Moreover, the hydrogenation rate of the olefinic unsaturated bond was measured using NMR about the obtained copolymer (HpM), and it confirmed that the said hydrogenation rate was 99.9%. In addition, in the obtained copolymer (HpM), since the signal derived from the aromatic ring did not change, it was confirmed that the aromatic ring was not substantially hydrogenated.

(Synthesis Example 12)

<Norbornene monomer I and 8-methoxycarbonyl-8-methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene (norbornene monomer K) copolymerization-1>

First, a mixture containing norbornene monomer I (1.13 g, 5.0 mmol) obtained in Synthesis Example 5 and norbornene monomer K (1.16 g, 5.0 mmol) represented by the following chemical formula (9) was prepared under a nitrogen atmosphere. , endoform/exoform ratio=79.2/20.8) in anhydrous toluene solution (23ml).

In above-mentioned anhydrous toluene solution (23ml), add the anhydrous toluene solution (2ml) containing 1-hexene (7.5 μ l, 0.6mol%) and Grubbs I catalyst (4.1mg, 0.05mol%), stir at room temperature for 20 hours, to obtain a polymer solution. Next, the obtained viscous polymerization solution was diluted with 200 ml of toluene, poured into 3000 ml of methanol, and the obtained precipitate was filtered. Next, the precipitate was dried in a vacuum dryer to obtain 1.88 g (yield: 82%) of a ring-opened copolymer (pN) of norbornene monomer I and norbornene monomer K. The obtained copolymer (pN) was confirmed by GPC, and the polystyrene-equivalent weight average molecular weight (Mw) was 147000, and Mw/Mn was 4.5.

<Hydrogenation of ring-opening copolymer (pN) of norbornene monomer I and norbornene monomer K>

PN (1.68g), xylene (150ml), RuHCl(CO)(PPh ₃ ) ₃ (8.5mg, 0.5mass%) were added to a 0.2L autoclave, and replaced with nitrogen. Next, after hydrogenation reaction was carried out by heating for 30 hours under the conditions of a hydrogen pressure of 10 MPa and a reaction temperature of 165° C., the resulting reaction solution was cooled and the hydrogen pressure was released. Next, this reaction solution was poured into 2000 ml of methanol, the precipitate was separated and recovered, and the obtained precipitate was dried to obtain 1.36 g (yield: 81%) of a pN hydride (copolymer (HpN)).

As for the copolymer (HpN) thus obtained, it was confirmed by GPC that the polystyrene-equivalent weight average molecular weight (Mw) was 129000, and Mw/Mn was 4.1. Moreover, when Tg was measured using DSC about the obtained copolymer (HpN), Tg was 147 degreeC. The hydrogenation rate of the olefinic unsaturated bond of the obtained copolymer (HpN) was also measured using NMR, and it was confirmed that the hydrogenation rate was 99.9%. In addition, in the obtained copolymer (HpN), since the signal derived from the aromatic ring did not change, it was confirmed that the aromatic ring was not substantially hydrogenated.

(comparative synthesis example 1)

<Polymerization of tetracyclo[4.4.1 ^2,5 .1 ^7,10 .0]-3-dodecene (norbornene monomer J)>

Under a nitrogen atmosphere, a solution of norbornene monomer J (1.60 g, 10.0 mmol) in anhydrous toluene (23 ml) was added containing 1-hexene (75 μl, 0.6 mol%) and Grubbs I catalyst (4.1 mg, 0.05 mol%) in anhydrous toluene (2ml), stirred at room temperature for 20 hours. However, the reaction system was not uniform, the polymer precipitated, and the obtained polymer (pO) was insoluble in chloroform, THF, and the like.

(Embodiments 8-13)

The copolymers obtained in Synthesis Examples 7 to 12 {HpI obtained in Synthesis Example 7 (Example 8), HpJ obtained in Synthesis Example 8 (Example 9), and HpK obtained in Synthesis Example 9 were used respectively. (Example 10), HpL obtained in Synthesis Example 10 (Example 11), HpM obtained in Synthesis Example 11 (Example 12), HpN obtained in Synthesis Example 12 (Example 13)}, prepared The phase difference film of this invention (Examples 8-13).

That is, first, chlorobenzene solutions containing each copolymer at a concentration of 5 wt % were prepared respectively, and the solutions were cast on a glass plate into a film form by casting method, and dried naturally for 24 hours to obtain a film precursor. Next, after peeling off the obtained film precursors from the glass plate, they were dried to a residual solvent concentration using a vacuum dryer maintained at a temperature near the Tg of the polymer used as the film material (Tg of each polymer - 10°C). It becomes 1.0 mass % or less, and the film which consists of each copolymer was obtained, respectively. The films obtained in this way have high transparency. In addition, the film thickness of the obtained film was 30 to 150 μm.

Next, the obtained films were cut into thin rectangular shapes (dimensions: 5.0×4.0 cm), and were cut at Tg+10° C. 200% (2.0 times) uniaxial stretching was carried out at a stretching speed of 50 mm/min under temperature conditions to obtain retardation films of the present invention (Examples 8-13).

(Evaluation of Optical Properties of Retardation Films Obtained in Examples 8 to 13)

The birefringence of the retardation films obtained in Examples 8 to 13 was measured with a retardation meter (manufactured by Oji Scientific Corporation, trade name "KOBRA21DH"). In addition, the refractive index was measured using a brand name "2010 Prism Coupler" manufactured by Metricon Corporation as a refractive index measuring device. In addition, the stretching direction of the uniaxial stretching of the above-mentioned film is defined as the X-axis, and the direction perpendicular to the X-axis is defined as the Y-axis and the Z-axis (the Y-axis and the Z-axis are also orthogonal), and the X-axis is measured. Refractive index (Nx), Y-axis refractive index (Ny), Z-axis refractive index (Nz). Table 2 shows the obtained results.

[Table 2]

Delay (nm) Nx Ny Nz Film Thickness (μm) Wavelength dispersion value D ^*1 (addition) ratio of monomer I Example 8 (HpI) 12.4 1.538 1.537 1.537 79 0.16 75 Example 9 (HpJ) 197.9 1.536 1.534 1.534 93 0.94 50 Example 10 (HpK) 307.5 1.533 1.529 1.529 75 1.02 25 Example 11 (HpL) 78.3 1.540 1.541 1.541 87 1.47 87.5 Example 12 (HpM) 102.1 1.541 1.543 1.543 60 1.20 95 Example 13 (HpN) 49.5 1.549 1.549 1.549 99 0.71 50

＊1Δn@481nm/Δn@589nm

In addition, regarding the retardation films obtained in Examples 8 to 12, a graph showing the relationship between the ratio of the norbornene monomer I contained and the birefringence is shown in FIG. 12 . In addition, regarding the retardation films obtained in Examples 8 to 12, the ratio of the norbornene monomer I contained and the wavelength dispersion value {D=(Δn: λ481nm)/(Δn: λ589nm) are shown in FIG. 13 } relationship diagram. On the other hand, for the retardation films obtained in Examples 8 to 12, a graph showing the relationship between the ratio of norbornene monomer I contained and Tg is shown in FIG. 14 . In FIG. 14 , Tg (162°C) at which the ratio of norbornene monomers I and J (norbornene monomer I/norbornene monomer J) is 0/100 is quoted from Journal of the Chemical Society of Japan 1998, No. 2, p. 81. In addition, the norbornene monomer I is a monomer in which the endo/exo ratio (isomer ratio) of the stereo configuration of the aromatic ring in the side chain is 0/100.

From the results shown in Table 2 and FIG. 12 , it was confirmed that the retardation film obtained in each Example functioned favorably as a retardation film. Also because the retardation film of HpL (Example 11) and the retardation film of HpM (Example 12) satisfy the relationship shown in the following relational formula (1), it was confirmed that they function as so-called negative A retardation films. membrane.

Ny＝Nz＞Nx (1)

In addition, from the results shown in FIG. 13 , it was confirmed that the wavelength dispersion value {D=(Δn: λ481nm)/(Δn: λ589nm)} of the birefringence of each retardation film differs depending on the copolymerization ratio. It was confirmed that the retardation film obtained in 9 was a reversely dispersed retardation film.

(Evaluation of Adhesion of Retardation Films Obtained in Examples 8 to 13)

The retardation films obtained in Examples 8 to 13 were bonded on the surface of a triacetylcellulose substrate with an ultraviolet curable adhesive (manufactured by Toagosei, UVX-1620), and their properties were evaluated according to the method described in JIS K5400. Regarding the adhesiveness of the retardation film, it was confirmed that the adhesiveness between any of the retardation films and the triacetyl cellulose film was very high.

Industrial availability

As explained above, according to the present invention, it is possible to provide a single layer with high transparency and excellent wavelength dispersion characteristics, which can give a specific phase difference to a wide range of light, and has very high adhesion with other materials, and even in negative double A retardation film that can achieve a specific negative A optical characteristic in refraction, and can make the wavelength dispersion characteristic of birefringence reversely dispersed, and a liquid crystal display device using the retardation film.

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, and the like used in liquid crystal display devices and the like.

Claims (12)

1. phase retardation film is characterized in that:

It stretches the film that is formed by norborene class ring-opening polymerization polymer and obtains,

This norborene class ring-opening polymerization polymer contains the structural unit (A) shown in the following general formula (1), and in described structural unit (A), following wave-like line c represent the spatial configuration of external form structural unit (A-1) contain ratio in 35 moles more than the %, the 100 moles scopes below the %

In the formula (1), n represents 0 or 1 integer,

X ¹Base shown in expression-CH=CH-or formula-CH ₂CH ₂-shown in base,

R ¹, R ², R ³And R ⁴Identical or different, expression is selected from any one atom or the base in hydrogen atom, halogen atom, alkyl and the polar group respectively, described alkyl is to have at least a kind of alkyl that is connected the carbon number 1～30 of basic replacement or non-replacement that is selected from oxygen atom, nitrogen-atoms, sulphur atom and the silicon atom

The spatial configuration of type or external form in wave-like line a, b represent,

The spatial configuration of type or external form in wave-like line c represents.

2. phase retardation film as claimed in claim 1 is characterized in that:

In described structural unit (A), described wave-like line c represent the spatial configuration of external form structural unit (A-1) contain ratio in 35 moles more than the %, the 65 moles scopes below the %, and described phase retardation film is the contrary phase retardation film that disperses.

3. phase retardation film as claimed in claim 1 is characterized in that:

In described structural unit (A), described wave-like line c represent the spatial configuration of external form structural unit (A-1) contain ratio in greater than 65 moles of %, 100 moles of scopes below the %, and described phase retardation film is negative A phase retardation film.

4. phase retardation film as claimed in claim 3 is characterized in that:

When the draw direction with the uniaxial tension of described film is defined as X-axis and will be defined as Y-axis and Z axle with the direction of X-axis quadrature, the refractive index (Ny) of the refractive index of X-axis (Nx), Y-axis and the refractive index (Nz) of Z axle satisfy the relation shown in the following relational expression (1)

Ny＝Nz＞Nx (1)。

5. phase retardation film as claimed in claim 1 is characterized in that:

X in the described general formula (1) ¹Be formula-CH ₂CH ₂-shown in base structural unit contain ratio, be 90 moles more than the % with respect to the entire infrastructure unit in the described norborene class ring-opening polymerization polymer.

6. phase retardation film as claimed in claim 1 is characterized in that:

Described norborene class ring-opening polymerization polymer is the norborene class ring opening copolymer thing that contains the structural unit (B) shown in structural unit (A ') shown in the following general formula (2) and the following general formula (3),

In the formula (2), n, X ¹, R ¹, R ², R ³, R ⁴With n, the X in wave-like line c and the described general formula (1) ¹, R ¹, R ², R ³, R ⁴With the same meaning of wave-like line c,

In the formula (3), n represents 0 or 1 integer,

X ²Base shown in expression-CH=CH-or formula-CH ₂CH ₂-shown in base,

R ⁵, R ⁶, R ⁷, R ⁸Identical or different, respectively expression be selected from alkyl, the carbon number 1～20 of hydrogen atom, halogen atom, cyano group, carbon number 1～20 thiazolinyl, carbon number 1～20 alkyl-carbonyl and have any one atom or base in the ester group of alkyl of carbon number 1～20

R ⁵～R ⁸In mutually combine more than 2, can form the monocyclic hydrocarbon of the carbon number 3～20 that can have unsaturated link, maybe can have the polycycle hydrocarbon of the carbon number 4～20 of unsaturated link,

R ⁵And R ⁶, or, R ⁷And R ⁸Can form the alkylidene of carbon number 1～20 together.

7. phase retardation film as claimed in claim 6 is characterized in that:

In described norborene class ring opening copolymer thing, the spatial configuration of the replacement in the described general formula (2) in the described structural unit (A ') or the phenyl of non-replacement be the external form coordination structural unit (A '-1) contain ratio in 90 moles of scopes more than the %.

8. phase retardation film as claimed in claim 6 is characterized in that:

The spatial configuration of the replacement in the described general formula (2) in the described structural unit (A ') or the phenyl of non-replacement be the external form coordination structural unit (A '-1) contain ratio, in 40 moles of scopes more than the %, less than 80 moles of %, and described phase retardation film is the contrary phase retardation film that disperses with respect to the entire infrastructure unit in the described norborene class ring opening copolymer thing.

9. phase retardation film as claimed in claim 6 is characterized in that:

The spatial configuration of the replacement in the described general formula (2) in the described structural unit (A ') or the phenyl of non-replacement be the external form coordination structural unit (A '-1) contain ratio, in 80 moles more than the %, the 99 moles scopes below the %, and described phase retardation film is negative A phase retardation film with respect to the entire infrastructure unit in the described norborene class ring opening copolymer thing.

10. phase retardation film as claimed in claim 8 is characterized in that:

Satisfy the relation shown in the described relational expression (1).

11. phase retardation film as claimed in claim 6 is characterized in that:

X in the described general formula (2) ¹Be formula-CH ₂CH ₂-shown in the structural unit of base and the X in the described general formula (3) ²Be formula-CH ₂CH ₂-shown in base structural unit contain ratio, be 90 moles more than the % with respect to the entire infrastructure unit in the described norborene class ring-opening polymerization polymer.

12. a liquid crystal indicator is characterized in that:

Has the described phase retardation film of claim 1.

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