JPWO2008013022A1 - Cyclic olefin ring-opening copolymer and use thereof - Google Patents

Abstract

[Solution] The cyclic olefin-based ring-opening copolymer of the present invention has an essential structural unit (1) represented by the following formula (1) and two or more other specific structural units. It is a feature. [Chemical Formula 1] [Effect] According to the present invention, heat resistance and workability are excellent, and transparency is excellent, so that it can be suitably used for various optical film applications. Novel norbornene-based ring-opening copolymer capable of controlling the size and wavelength dependence of the phase difference), an optical member obtained from the copolymer, a film, a stretched film, a polarizing plate using the stretched film, and a liquid crystal A display device can be provided.

Description

  The present invention relates to a cyclic olefin ring-opening copolymer and its use. Specifically, the present invention uses a novel copolymer containing a specific cyclic olefin-based structural unit, an optical member obtained from the copolymer, a film, a stretched film having a positive wavelength dependency, and the stretched film. The present invention relates to a polarizing plate and a liquid crystal display device.

  The cyclic olefin-based resin is excellent in transparency, heat resistance, moisture resistance, and the like, and thus is suitably used for applications such as an optical film. In recent years, films made of cyclic olefin-based resins are expected to be used for polarizing plate protective films, liquid crystal substrate materials, etc. due to their relatively low birefringence, and because they have retardation stability, It is expected to be used for optical compensation films such as phase difference films.

  For example, Patent Documents 1 to 4 describe retardation plates using a cyclic olefin-based resin film. Patent Documents 5 and 6 describe using a film of a cyclic olefin resin as a protective film for a polarizing plate, and using a polarizing plate using a cyclic olefin resin film for liquid crystal display applications. Is described.

  In these conventional techniques, a retardation film made of a cyclic olefin resin is given a function of giving a retardation (birefringence) to transmitted light by stretching orientation, but a retardation (birefringence) depending on the wavelength of the transmitted light. ) The change in absolute value was not a problem.

  However, at present, particularly in applications such as liquid crystal displays and optical disk pickups, the phase difference (birefringence) of transmitted light due to the wavelength of transmitted light is controlled in a wide wavelength range such as the entire visible light range (400 to 800 nm). It has actually been sought.

  And the development of the reverse wavelength dispersible stretched film and its resin in which the phase difference (birefringence) of the transmitted light increases as the transmitted light becomes longer wavelength has been developed.

  However, the development of a stretched film and its resin that uses a cyclic olefin resin and whose transmission light has a longer wavelength, the retardation (birefringence) of the transmitted light becomes smaller (positive dispersion). Almost no study or report has been made, and there is no known resin that can be made into a film by extrusion, including molding.

  For this reason, conventionally, when it is required to use a film having positive wavelength dispersion, it is necessary to use a material other than the cyclic olefin-based material. For example, although thin films such as polycarbonate films and polyimide polymer coatings are known to have positive retardation wavelength dispersion, they have a very high photoelastic coefficient, and are cyclic olefin resins in terms of water absorption and workability. When used as an optical film, it has been considered as a major problem in quality.

  Under such circumstances, the emergence of a single-layer optical film made of a cyclic olefin resin that can control the phase difference (birefringence) of transmitted light depending on the wavelength of transmitted light and has excellent processing characteristics in a wide range of wavelengths. In addition, the appearance of a resin capable of producing such an optical film is demanded.

  On the other hand, as a result of research on a cyclic olefin polymer suitable for an optical material, the applicant of the present application has found that a ring-opening copolymer of a specific cyclic olefin monomer is excellent in transparency and heat resistance and is resistant to solvents. It has been found that the solubility is high (see Patent Document 7).

As a result of diligent research in view of such circumstances, the present inventor has found that a specific novel norbornene-based ring-opening copolymer and its hydrogenated product can be processed by designing the polymerization composition and the substituent of the monomer. It has been found that when a retardation film is formed, not only the birefringence (phase difference) can be controlled, but also the wavelength dispersion can be controlled, and the present invention has been completed.
JP-A-4-245202 JP-A-4-36120 JP-A-5-2108 Japanese Patent Laid-Open No. 5-64865 Japanese Patent Laid-Open No. 5-212828 JP-A-6-511117 JP 2003-165828 A

  The present invention is excellent in heat resistance and workability, excellent in transparency, and can be suitably used for optical film applications. When a retardation film is formed, the birefringence (retardation) size and wavelength dependency are reduced. A novel norbornene-based ring-opening copolymer that can be controlled, an optical member obtained from the copolymer, a film suitably used as an optical film, a stretched film having positive wavelength dispersion, and the stretched film were used. It is an object to provide a polarizing plate and a liquid crystal display device.

The cyclic olefin ring-opening copolymer of the present invention is:
A structural unit (1) represented by the following formula (1):
It has at least 2 sort (s) of structural units chosen from the group which consists of the structural unit (2) represented by following formula (2), and the structural unit (3) represented by following formula (3).

(In Formula (1), a and b represent 0 or 1, and R ^{1 to} R ⁶ and a plurality of R ⁷ are each independently a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. Represents a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, which may have a linking group containing, or a polar group, and X represents —CH═CH— or —CH ₂ CH ₂ —. )

(In the formula (2), a represents 0 or 1, and R ^{1 to} R ⁴ each independently have a hydrogen atom; a halogen atom; a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or a polar group, X represents —CH═CH— or —CH ₂ CH ₂ —, and a plurality of Xs are the same. But it may be different.)

(In the formula (3), a represents 0 or 1, and R ¹ and R ² each independently have a linking group containing a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or a polar group, X represents —CH═CH— or —CH ₂ CH ₂ —, and a plurality of Xs are the same. Or Y may be —CH═CH—, —CH ₂ CH ₂ —, or

Represents. )
Such a cyclic olefin-based ring-opening copolymer of the present invention has a total of a plurality of X in the formulas (1), (2) and (3) of 100 mol%, and 80 mol% or more of X is —CH. A group represented by ₂ CH ₂ — is preferable.

  The cyclic olefin ring-opening copolymer of the present invention preferably contains 5 to 50 mol% of the structural unit (1) in 100 mol% of the total amount of the structural units (1), (2) and (3). .

In the cyclic olefin ring-opening copolymer of the present invention, R ¹ and R ² in the formula (2) are hydrogen atoms, R ³ is a hydrogen atom or a methyl group, R ⁴ is a hydrogen atom, alkoxycarbonyl It is preferable to have the structural unit (2) which is a group or a phenyl group.

  The cyclic olefin-based ring-opening copolymer of the present invention preferably has at least one structural unit (2) selected from structural units represented by the following formulas (2-1) to (2-5).

(In formulas (2-1) to (2-5), X is as defined in general formula (2).)
The cyclic olefin ring-opening copolymer of the present invention preferably has at least one structural unit (3) selected from structural units represented by the following formulas (3-1) to (3-3).

(In formulas (3-1) to (3-3), X is as defined in general formula (3).)
The cyclic olefin-based ring-opening copolymer of the present invention preferably has an extrapolated glass transition start temperature measured according to Japanese Industrial Standard K7121 in the range of 110 to 170 ° C., and in an chloroform using an Ubbelohde viscometer. The logarithmic viscosity measured at a sample concentration of 0.5 g / dL and a temperature of 30 ° C. is preferably 0.4 to 0.8 dL / g.

  The optical component of the present invention is obtained by molding the cyclic olefin-based ring-opening copolymer of the present invention.

  The film of the present invention is obtained by forming the cyclic olefin ring-opening copolymer of the present invention by a casting method or an extrusion method.

  The stretched film of the present invention is formed by stretching the cyclic olefin-based ring-opening copolymer of the present invention by casting or extrusion.

  Such a stretched film of the present invention preferably satisfies the optical properties of the following formulas (a), (b) and (c).

Re550> 0 (a)
Re450 / Re550> 1.022 (b)
Re650 / Re550 <0.990 (c)
(In the above formulas (a) to (c), Re450, Re550, and Re650 represent in-plane retardations at wavelengths of 450 nm, 550 nm, and 650 nm, respectively.)
The polarizing plate or the liquid crystal display device of the present invention is characterized by including the stretched film of the present invention.

  According to the present invention, in addition to excellent heat resistance and workability, it has excellent transparency and can be suitably used for optical film applications. When a retardation film is formed, the magnitude of birefringence (retardation) and wavelength dispersion New norbornene-based ring-opening copolymer that can control the property, optical member obtained from the copolymer, film suitably used as an optical film, positive wavelength dispersion, suitable as a retardation film A stretched film that can be used for the present invention, a polarizing plate using the stretched film, and a liquid crystal display device can be provided.

  The cyclic olefin-based ring-opening copolymer according to the present invention is very useful as an optical material, and includes optical disks, magneto-optical disks, optical lenses (Fθ lenses, pickup lenses, laser printer lenses, camera lenses, etc.), spectacle lenses. , Optical film / sheet (display film, retardation film, polarizing film, polarizing plate protective film, diffusion film, antireflection film, liquid crystal substrate, EL substrate, electronic paper substrate, touch panel substrate, PDP front plate, etc.), transparent The present invention can be applied to optical materials that require very high-precision optical design, such as conductive film substrates, optical fibers, light guide plates, optical cards, optical mirrors, ICs, LSIs, and LED sealing materials.

  In particular, the cyclic olefin ring-opening copolymer according to the present invention can be used for an optical film, and is suitable for production of a film formed by a casting method or an extrusion method and a stretched film obtained by stretching the film. The stretched film is suitable as a retardation film and can be suitably used for applications such as a polarizing plate and a liquid crystal display device.

FIG. 1 shows an infrared absorption (IR) spectrum of the ring-opening copolymer hydrogenated product (D) obtained in Example 1. FIG. 2 shows the ¹ H-NMR spectrum of the hydrogenated ring-opening copolymer (D) obtained in Example 1.

  Hereinafter, the present invention will be specifically described.

In the present specification, the term birefringence is used in the ordinary sense. In addition, the birefringence value (this is assumed to be Δn) is a stretched film obtained by uniaxially, biaxially, and Z-axis-stretching a film formed from a polymer and orienting polymer molecular chains in one direction. (direction of larger draw ratio in biaxial stretching, shrinking direction in the Z-axis stretching) stretching direction x-axis and the plane perpendicular contrast to the y-axis, the refractive index of the x-axis direction n _x, y If the refractive index of the axial direction is n _y, the following formula:
Δn = n _x -n _y
The absolute value is different depending on the wavelength of incident light.

  And positive (or negative) birefringence means the property of the stretched film when the Δn is positive (or negative).

Next, the phase difference (Retardation, which is referred to as Re) is the following formula:
Re = Δn × d (where d is the optical path length (nm) of transmitted light, and is usually the thickness of the stretched film), and is a positive to negative value, and its absolute value Depends on the wavelength of the incident light. Further, “the phase difference is ¼λ” means that a phase difference corresponding to ¼ of the incident light wavelength (λ) is developed.

  The wavelength dispersion of the phase difference means the correlation between the value of Re and the wavelength of the incident light, and “the wavelength dispersion of the phase difference is large” means the absolute value of Re with respect to the incident light of a short wavelength. This means that there is a large difference from the absolute value of Re for incident light having a long wavelength. Also, “reverse wavelength dispersion” means a characteristic that the phase difference increases as the incident light wavelength becomes longer, and “positive wavelength dispersion” means that the incident light wavelength becomes shorter as the incident wavelength becomes shorter. It means the characteristic that the phase difference becomes large.

<Cyclic olefin ring-opening copolymer>
The cyclic olefin-based ring-opening copolymer of the present invention contains the structural unit (1) represented by the above formula (1) as an essential structural unit, and the structural unit (2) represented by the above formula (2). ) And at least two structural units selected from the group consisting of the structural unit (3) represented by the formula (3) are contained as essential structural units. The cyclic olefin-based ring-opening copolymer of the present invention may be composed of only these structural units (1) and structural units (2) and / or (3), and further structural units other than these may be included. You may have.

Here, a hydrogen atom represented by R ^{1 to} R ⁷ in the formula (1) and R ^{1 to} R ⁴ in the formulas (2) and (3); a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom or A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing a silicon atom; or a polar group will be described.

  As a halogen atom, a fluorine atom, a chlorine atom, and a bromine atom are mentioned, for example.

  Examples of the hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as methyl group, ethyl group and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group and allyl group; Groups, alkylidene groups such as propylidene groups; aromatic groups such as phenyl groups, naphthyl groups, anthracenyl groups, and the like. A hydrogen atom bonded to a carbon atom in these groups may be substituted with, for example, a halogen atom such as fluorine, chlorine or bromine, a phenylsulfonyl group, a cyano group or the like.

The above substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure, or may be bonded via a linking group. Examples of the linking group include a divalent hydrocarbon group having 1 to 10 carbon atoms (for example, an alkylene group represented by — (CH ₂ ) _m — (wherein m is an integer of 1 to 10)); A linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom (for example, a carbonyl group (—CO—), a carbonyloxy group (—COO—), a sulfonyl group (—SO ₂ —), a sulfonyloxy group (—SO ₂ ). ₂ -O-), an ether bond (-O-), thioether bond (-S-), an imino group (-NH-), amide bond (-NHCO-), siloxane bond (-Si (R) ₂ O-) (Wherein, R is an alkyl group such as a methyl group or an ethyl group); or a combination of two or more of these groups.

Examples of polar groups include hydroxyl groups, alkoxy groups having 1 to 10 carbon atoms, alkylcarbonyloxy groups, arylcarbonyloxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, cyano groups, nitro groups, amide groups, imino groups ( ═NH), triorganosiloxy group, triorganosilyl group, amino group, acyl group, alkoxysilyl group, sulfino group (—SO ₂ H), carboxyl group and the like.

  More specifically, examples of the alkoxy group include methoxy group and ethoxy group; examples of the alkylcarbonyloxy group include acetoxy group and propionyloxy group; and examples of the arylcarbonyloxy group include Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group; examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a naphthyloxycarbonyl group, and a fullyl group. Examples of the triorganosiloxy group include trimethylsiloxy group and triethylsiloxy group; examples of the triorganosilyl group include trimethylsilyl group. Examples of the amino group, for example, primary amino group or the like; group, triethylsilyl group, etc. Examples of the alkoxysilyl group, for example, trimethoxysilyl groups, triethoxysilyl group, and the like.

In the cyclic olefin ring-opening copolymer of the present invention, as the structural unit (2), a in the formula (2) is 0 or 1, and when a is 0, R ¹ and R ² are hydrogen atoms. And a structural unit in which R ³ is a hydrogen atom or a methyl group and R ⁴ is a hydrogen atom, an alkoxycarbonyl group or a phenyl group is preferred. As such a structural unit (2), structural units represented by the following formulas (2-1) to (2-5) are particularly preferable.

In the above formulas (2-1) to (2-5), X is as defined in the general formula (2) and represents —CH═CH— or —CH ₂ CH ₂ —, It may be the same or different.

In the cyclic olefin ring-opening copolymer of the present invention, as the structural unit (3), a in the formula (3) is 0 or 1, and when a is 1, R ¹ and R ² are hydrogen. A structural unit that is an atom is preferable, and a structural unit in which a is 0 is more preferable. Examples of the structural unit (3) include structural units represented by the following formulas (3-1), (3-2), and (3-3).

In the above formula (3-1) ~ (3-3), X is a as defined in the general formula (3), -CH = CH- or represents -CH ₂ CH ₂ -, X-presence of a plurality of It may be the same or different.

In the cyclic olefin-based ring-opening copolymer of the present invention, as described above, X in the structural units (1), (2) and (3) is —CH═CH— or —CH ₂ CH ₂ —. A plurality of Xs may be the same or different. That is, the cyclic olefin ring-opening copolymer of the present invention may be a copolymer obtained by ring-opening copolymerization of a cyclic olefin monomer capable of forming the structural units (1), (2) and (3). It may be well hydrogenated. A copolymer obtained by copolymerizing a cyclic olefin monomer is in the state of an olefinically unsaturated group in which X is represented by —CH═CH—. From the viewpoint of heat resistance stability, It is preferable that the saturated group is hydrogenated and X is a group converted to a group represented by —CH ₂ CH ₂ —. In the cyclic olefin copolymer of the present invention, the total of X in the structural units (1), (2) and (3) is 100 mol%, usually 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol. % Or more is preferably —CH ₂ CH ₂ —. The higher the ratio of X being —CH ₂ CH ₂ —, that is, the higher the hydrogen conversion rate of the copolymer, the more stable the copolymer and the more preferable coloring and deterioration due to heat and oxygen are suppressed.

In the structural unit (3), Y in the formula (3) is —CH═CH—, —CH ₂ CH ₂ —, or

And preferably, —CH ₂ CH ₂ —, or

Is a structural unit represented by

  The cyclic olefin ring-opening copolymer of the present invention has the structural unit (1) as an essential structural unit and at least two structural units selected from the group consisting of the structural units (2) and (3). Have That is, together with one or more of the structural units (1), the structural unit (2) may have two or more, the structural unit (3) may have two or more, and the structure You may have 1 or more types of a unit (2) and 1 or more types of the said structural unit (3).

  In the cyclic olefin-based ring-opening copolymer of the present invention, the proportion of the structural unit (1) is in the range of 5 to 50 mol% in the total amount of 100 mol% of the structural units (1), (2) and (3). It is preferable that the ratio of the structural unit (1) is more preferably in the range of 7 to 50 mol%. The higher the proportion of the structural unit (1), the higher the retardation development. However, when the proportion is higher than 50 mol%, the solubility of the resulting polymer in a general organic solvent is remarkably lowered, and the transparency of the film is increased. Is also significantly reduced. On the other hand, in the case where the proportion of the structural unit (1) is less than 5 mol%, the effect of developing positive wavelength dispersibility in the stretched film obtained from the obtained polymer may be significantly reduced.

  In the cyclic olefin-based ring-opening copolymer of the present invention, the total of the structural units (1), (2) and (3) is 70 mol% or more, preferably 80 mol% or more in all the structural units. desirable. As structural units other than the structural units (1), (2) and (3), ring-opening polymerization of cyclic olefinic monomers other than the monomers (1), (2) and (3) described later is carried out. Examples of the structural unit to be formed.

  The cyclic olefin-based ring-opening copolymer of the present invention has an extrapolated glass transition start temperature measured according to Japanese Industrial Standard (JIS) K7121, preferably 110 to 170 ° C, more preferably 115 to 165 ° C, and still more preferably 120. It is ˜160 ° C., has sufficient heat resistance, and has excellent moldability capable of melt molding such as extrusion molding.

  Further, the cyclic olefin ring-opening copolymer of the present invention has a logarithmic viscosity measured at a sample concentration of 0.5 g / dL and a temperature of 30 ° C. in chloroform using an Ubbelohde viscometer, preferably 0.4 to It is 0.80 dL / g, More preferably, it is 0.42-0.70 dL / g, More preferably, it is 0.42-0.65 dL / g. Moreover, in the measurement of the average molecular weight by gel permeation chromatography (GPC, tetrahydrofuran solvent, polystyrene conversion value), the number average molecular weight (Mn) of the ring-opening polymer is usually 1000 to 500,000, preferably 2000 to 30. More preferably, it is 5000-300,000, and a weight average molecular weight (Mw) is 5000-2 million normally, Preferably it is 10,000-1 million, More preferably, it is 30,000-500,000.

When the logarithmic viscosity (ηinh) is less than 0.4, the number average molecular weight (Mn) is less than 1000, or the weight average molecular weight (Mw) is less than 5000, the norbornene-based ring opening of the present invention is performed. The strength of the molded product obtained from the polymer may be significantly reduced. On the other hand, when the logarithmic viscosity (ηinh) is 0.81 or more, the number average molecular weight (Mn) is 500,000 or more, or the weight average molecular weight (Mw) is 2 million or more, the ring-opening weight Since the melt viscosity or solution viscosity of the coalescence increases, it may be difficult to obtain a desired molded product such as a sheet, film, or optical component.
<Method for producing cyclic olefin-based ring-opening copolymer>
Such a cyclic olefin ring-opening copolymer of the present invention can be produced, for example, as follows.

Ring- Opening Copolymer / Monomer The cyclic olefin-based ring- opening copolymer of the present invention includes a monomer (1m) represented by the following formula (1m) and a monomer represented by the following formula (2m). (2m) and a monomer composition containing at least two monomers selected from the monomers (3m) represented by the following formula (3m) are subjected to ring-opening copolymerization and optionally hydrogenated. Can be manufactured.

(In the formula (1m), a, b and R ^{1 to} R ⁷ are as defined for the formula (1).)

(In the formulas (2m) and (3m), a, Y and R ^{1 to} R ⁴ are as defined for the formula (2) or (3).)
The structural unit (1) of the cyclic olefin ring-opening polymer of the present invention is from the monomer (1m), the structural unit (2) is from the monomer (2m), and the structural unit (3) is the monomer (3m). ).

  The monomer (1m) for deriving the structural unit (1) can be produced by performing a Diels-Alder type reaction using acenaphthylene or a derivative thereof and cyclopentadiene or a derivative thereof as raw materials. Examples of such a monomer (1m) include the following.

  As the monomer (1m), among these,

Is preferable because it is easy to obtain and the extrapolated glass transition temperature can be easily controlled. In addition, the mutual configuration of the above compound with the norbornene ring and the acenaphthene ring may be an endo isomer, an exo isomer, or an endo-exo isomer mixture, and is not particularly limited.

Examples of the monomer (2m) for deriving the structural unit (2) include the following.
Bicyclo [2.2.1] hept-2-ene

5-Methylbicyclo [2.2.1] hept-2-ene

5-ethylbicyclo [2.2.1] hept-2-ene

5-Butylbicyclo [2.2.1] hept-2-ene

5-Phenylbicyclo [2.2.1] hept-2-ene

5- (Biphenyl-4-yl) bicyclo [2.2.1] hept-2-ene

5- (Naphthalen-2-yl) bicyclo [2.2.1] hept-2-ene

5- (Naphthalen-1-yl) bicyclo [2.2.1] hept-2-ene

5-Cyclohexylbicyclo [2.2.1] hept-2-ene

5- (Cyclohexen-4-yl) bicyclo [2.2.1] hept-2-ene

5-Methoxycarbonylbicyclo [2.2.1] hept-2-ene

5-Ethoxycarbonylbicyclo [2.2.1] hept-2-ene

5-Butoxycarbonylbicyclo [2.2.1] hept-2-ene

5-Cyanobicyclo [2.2.1] hept-2-ene

5-Methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene

5-Methyl-5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene

5-Methyl-5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene

5-Fluorobicyclo [2.2.1] hept-2-ene

5-Trifluoromethylbicyclo [2.2.1] hept-2-ene

Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-phenyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-phenoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8- (1-Naphoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8- (2-Naphoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8- (4-Phenylphenoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-methyl-8-phenoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-methyl-8- (1-naphthoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-methyl-8- (2-naphthoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-methyl-8- (4-phenylphenoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-fluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-pentafluoroethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8,8-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

As the monomer (2m), among these, R ¹ and R ² in the formula (2m) are hydrogen atoms, R ³ is a hydrogen atom or a methyl group, R ⁴ is a hydrogen atom, alkoxycarbonyl A compound which is a group or a phenyl group is preferred, among these,

Preferably, at least one selected from the compounds represented by:

Examples of the monomer (3m) for deriving the structural unit (3) include the following.
Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene

Tricyclo [5.2.1.0 ^2,6 ] -8-decene

Tricyclo [5.2.1.0 ^2,6 ] -deca-3,8-diene

  As the monomer (3m), among these,

It is preferable that

  In producing the cyclic olefin ring-opening copolymer according to the present invention, a monomer (1m) and two types of monomers selected from the monomer (2m) and the monomer (3m) are prepared. It is preferable to use it. In the case where there is one kind of monomer selected from the monomers (2m) and (3m), it is difficult to achieve both the physical properties of the polymer (glass transition temperature) and the film optical properties (retardation). Although the copolymer of the monomer (1m) and one monomer selected from the monomer (2m) and the monomer (3m) can control the glass transition temperature, that is, processability. In the copolymerization system of these two types of monomers, the optical characteristics are determined when the copolymer composition ratio is set to a desired glass transition temperature, and the glass transition temperature and the optical characteristics can be controlled simultaneously. Have difficulty. Accordingly, it is preferable to use two types of monomers selected from the monomer (2m) and the monomer (3m), and the homopolymers of these two types of monomers have different glass transition temperatures. Is preferred. By using the monomer (1m) and two monomers selected from the monomer (2m) and the monomer (3m), the wavelength dispersion of the retardation with the content of the monomer (1m) The glass transition temperature can be controlled by the content of the two monomers selected from the property, monomer (2m) and monomer (3m).

  The total amount of the monomer (1m), monomer (2m) and monomer (3m) in the monomer composition is 100 mol%, and the monomer (1m) is in the range of 5 to 50 mol%. Is preferable, and it is more preferable that it is the range of 10-50 mol%. By using the monomer (1m) at such a copolymerization ratio, the resulting cyclic olefin-based ring-opening copolymer of the present invention has optical characteristics such as anisotropy of refractive index and wavelength dispersion, and Physical properties such as glass transition temperature can be easily controlled without problems.

  In addition to the monomer (1m), monomer (2m) and monomer (3m) described above, the monomer composition may contain other copolymerizable monomers as long as the object of the present invention is not impaired. It may contain a monomer. Examples of the copolymerizable monomer include cyclic olefins such as cyclobutene, cyclopentene, cyclooctene, and cyclododecene; and non-conjugated cyclic polyenes such as 1,4-cyclooctadiene and cyclododecatriene. The copolymerizable monomers can be used singly or in combination of two or more. In the present invention, the copolymerizable monomer in the monomer composition is preferably 30 mol% or less, and more preferably 20 mol% or less.

-Ring-opening polymerization catalyst As a catalyst for ring-opening polymerization that can be suitably used for producing the cyclic olefin-based ring-opening copolymer of the present invention, for example,
(I) A catalyst described in Olefin Metathesis and Metathesis Polymerization (KJIVIN, JCMOL, Academic Press 1997) is preferably used. Examples of such a catalyst include (a) at least one selected from compounds of W, Mo, Re, V and Ti, and (b) an alkali metal element (for example, Li, Na, K), alkaline earth. Group metal elements (eg, Mg, Ca), Group 12 elements (eg, Zn, Cd, Hg), Group 13 elements (eg, B, Al), Group 14 elements (eg, Si, Sn, Pd) And a metathesis catalyst comprising a combination with at least one selected from those having at least one of the element-carbon bond or the element-hydrogen bond. In order to enhance the activity of the catalyst, the additive (c) described later may be added.

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

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

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

  The amount of the metathesis catalyst formed by combining the component (a) and the like includes the component (a) and all monomers (the monomers (1m), (2m), (3m) and other copolymers described above). The molar ratio of “(a) component: all monomers” is generally in the range of 1: 500 to 1: 500,000, preferably 1: 1. , 000 to 1: 100,000. Further, the ratio of the component (a) to the component (b) is such that the metal atom (mole) ratio of “(a) :( b)” is usually 1: 1 to 1:50, preferably 1: 2. It is in the range of ˜1: 30. When the additive (c) is added to the metathesis catalyst, the ratio of the component (a) to the component (c) is such that the molar ratio of “(c) :( a)” is usually 0.005: 1 to The range is 15: 1, preferably 0.05: 1 to 7: 1.

As other catalysts,
(II) A metathesis catalyst composed of a transition metal-carbene complex or a metallacyclobutane complex of Groups 4 to 8 of the periodic table can be used.

Specific examples of the catalyst (II), W (= N -2,6-C 6 H 3 i Pr 2) (= CH t Bu) (O t Bu) 2, Mo (= N-2,6- ^{_{C 6 H 3 i Pr 2)}} (= CH t Bu) (O t Bu) 2, Ru (= CHCH = CPh 2) (PPh 3) 2 Cl 2, Ru (= CHPh 2) [P (C 6 H 11 ₃ ] ₂ Cl _{2 and the} like. These can be used singly or in combination of two or more.

  The amount of the catalyst (II) used is such that the molar ratio of “catalyst (II): total monomer” is usually 1: 500 to 1: 50,000, preferably 1: 100 to 1:10, 000.

  The catalysts (I) and (II) may be used in combination.

-Molecular weight regulator The molecular weight of the cyclic olefin ring-opening copolymer according to the present invention can be adjusted by adjusting the polymerization temperature, the type of catalyst, the type of solvent, etc. It is preferable to adjust by making it coexist in the reaction system of ring copolymerization. As the molecular weight regulator, for example, α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and styrene are preferable. Of these, 1-butene and 1-hexene are particularly preferred. These molecular weight regulators can be used singly or in combination of two or more. The amount of the molecular weight regulator used is usually 0.005 to 0.6 mol, preferably 0.02 to 0.5 mol, per mol of all monomers.

-Ring-opening polymerization reaction solvent Solvents used in the ring-opening copolymerization reaction (that is, solvents that dissolve monomers, ring-opening polymerization catalysts, molecular weight regulators, etc.) include, for example, pentane, hexane, heptane, octane, and nonane. , Alkanes such as decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride, dichloroethane, Compounds such as halogenated alkanes and aryl halides such as hexamethylene dibromide, chlorobenzene, chloroform, and tetrachloroethylene; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, and methyl propionate; dibutyl ether Ethers such as sulfur, tetrahydrofuran and dimethoxyethane, among which aromatic hydrocarbons are preferred. These can be used singly or in combination of two or more. The use amount of the solvent for the ring-opening polymerization reaction is such that the weight ratio of “solvent: total monomer” is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1. Is desirable.

-Ring-opening polymerization reaction temperature The ring-opening copolymerization reaction is usually an exothermic reaction, and it is not always necessary to keep the reaction temperature constant during the polymerization reaction, but the temperature at the start of the polymerization, that is, the monomer solution when the catalyst is added It is preferable to control the temperature. The temperature of the monomer solution when adding the catalyst is preferably 30 to 200 ° C, more preferably 50 to 180 ° C. When the temperature is lower than 30 ° C, the yield of the polymer may be lowered, and when it exceeds 200 ° C, it may be difficult to control the molecular weight.

Hydrogenated cyclic olefin-based ring-opening copolymer obtained by the above ring-opening copolymer is an olefinically unsaturated group in which X in the structural units (1) to (3) is represented by the formula: —CH═CH—. It has the following structure. This ring-opened polymer can be used as it is, but in order to further improve the heat stability, a group represented by the formula: —CH ₂ —CH ₂ — in which the olefinically unsaturated group is hydrogenated. It is preferably obtained as a hydrogenated ring-opening polymer (hydrogenated product). However, the hydrogenated product referred to in the present invention is a product obtained by hydrogenating the olefinically unsaturated group generated by ring-opening copolymerization, and in an aromatic ring skeleton such as a benzene ring derived from a monomer structure. The intracyclic conjugated double bond is preferably not substantially hydrogenated.

Hydrogenation rate of the cyclic olefin-based ring-opening copolymer of the present invention, that is, a ratio in which X in the structural units (1) to (3) is converted into a group represented by the formula: —CH ₂ —CH ₂ — Is 80 mol% or more, preferably 85 mol% or more, and more preferably 90 mol% or more of the total of the above-mentioned X. The higher the hydrogenation rate, the more preferable the occurrence of coloring and deterioration of the cyclic olefin copolymer under high temperature conditions.

  The hydrogenation reaction is desirably carried out under the condition that the intracyclic conjugated double bond in the aromatic ring skeleton is not substantially hydrogenated. For example, a hydrogenation reaction catalyst is added to a ring-opening polymer solution, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, is usually added thereto, and usually 0 to 200 ° C., preferably It can carry out by making it react at 50-200 degreeC.

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

These hydrogenation reaction catalysts need to be added in an amount so that the intraconjugated conjugated double bond in the aromatic ring skeleton is not substantially hydrogenated, and “ring-opening copolymer: The “hydrogenation reaction catalyst” is generally used at a ratio by weight of 1: 1 × 10 ⁻⁶ to 1: 2.

<Molding of cyclic olefin copolymer>
The cyclic olefin-based ring-opening copolymer of the present invention is excellent in moldability, and is suitably molded into a desired shape by any of melt molding such as extrusion molding and injection molding and molding by a solution casting method (cast method). be able to.

  The physical property values of the cyclic olefin-based ring-opening copolymer of the present invention can be controlled by the copolymer composition ratio and the amount of the molecular weight regulator used, but the characteristics of the cyclic olefin copolymer of the present invention are not lost. Various additives may be added within the range. Moreover, well-known various additives can be added to the cyclic olefin ring-opening polymer of the present invention for other purposes.

  Examples of the additive include 2,6-di-t-butyl-4-methylphenol, 2,2′-methylenebis (4-ethyl-6-t-butylphenol), and 2,5-di-t-butylhydroquinone. Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis- (6-tert-butyl-3-methylphenol), 1, 1-bis (4-hydroxyphenyl) cyclohexane, octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa Phenolic and hydroquinone antioxidants such as -t-butyl-a, a ', a "-(mesitylene-2,4,6-triyl) tri-p-cresol; tris (4-methoxy-3,5- And phosphorous antioxidants such as phenyl) phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, etc. One or two of these antioxidants By adding the above, the oxidation degradation resistance of the ring-opening copolymer can be improved, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-methylenebis. Light resistance can be improved by adding an ultraviolet absorber such as [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol]]. Furthermore, additives such as lubricants can be added for the purpose of improving processability, and these additives can be used alone or in combination of two or more. Can be used.

  The cyclic olefin-based ring-opening polymer of the present invention can be molded into a desired shape, but is excellent in optical properties, and thus is useful for various optical materials. Especially, shaping | molding into a film or a sheet | seat (in this invention, these are named generically and a film) is preferable, and can use it suitably for the use of various optical films.

- cyclic olefin ring-opening polymer of the optical film present invention, substituents R ¹ to R ⁷ of the monomer (1 m), the monomer (2m), the substituents R ¹ of the monomer (3m) to R ⁴ structure-type, by setting the like copolymerization ratio, it is possible to prepare a wavelength dispersion of the absolute value and the phase difference of the molded article of the birefringence, such as the resulting film. Further, the absolute value or level of birefringence of a polymer film or the like formed from the resin composition obtained by appropriately blending the cyclic olefin ring-opening polymer of the present invention with a known cyclic olefin resin or the like, as appropriate. The wavelength dispersion of the phase difference can be adjusted.

  When the cyclic olefin-based ring-opening polymer of the present invention is selected and used, the absolute value of birefringence and the wavelength dispersion of retardation can be easily controlled, so that it can be obtained from the copolymer of the present invention. The film can be suitably used as an optical compensation film. For this reason, the cyclic olefin-based ring-opening copolymer of the present invention or a composition containing the same is preferably formed into an optical film by casting or extrusion. Furthermore, since the optical film exhibits its performance sufficiently by stretching, it can be applied to free-width uniaxial stretching (longitudinal stretching), width-constrained uniaxial stretching (lateral stretching), sequential biaxial stretching, simultaneous biaxial stretching, or optical film. It is preferable to apply a shrinkable film at the time of stretching or after stretching to perform a so-called Z-axis orientation (Z-axis stretching) for adjusting the refractive index in the film thickness direction to obtain a stretched film.

  Since the optical film of the present invention exhibits excellent transparency in a film formed by extrusion molding or cast molding, it can be suitably used as various protective films. In addition, a stretched film obtained by further stretching a film obtained by film formation has unique wavelength dispersibility, and therefore can be suitably used as a film constituting a retardation plate or a liquid crystal display device.

  A film obtained by stretching a film obtained by forming a film from the cyclic olefin-based ring-opening copolymer of the present invention or a resin composition containing the same, particularly a film obtained by stretching uniaxially stretching a free width, By selecting the type of copolymer and the resin composition, in the visible light region, a film having positive wavelength dispersion can be obtained in which the retardation Re decreases as the transmitted wavelength increases. Such a film can be suitably used as a retardation film, and is suitable as a film constituting a polarizing plate or a liquid crystal display device such as a large liquid crystal television or a monitor.

  The stretched film of the present invention can preferably satisfy the optical properties of the following formulas (a), (b) and (c) at the same time.

Re550> 0 (a)
Re450 / Re550> 1.022 (b)
Re650 / Re550 <0.990 (c)
(In the above formulas (a) to (c), Re450, Re550, and Re650 represent in-plane retardation (nm) at wavelengths of 450 nm, 550 nm, and 650 nm, respectively.)
In particular, the free-width uniaxially stretched film obtained by thermally stretching an optical film comprising the cyclic olefin-based ring-opening copolymer of the present invention with a stress of 1 to 150 kgf / cm ² is preferably the following optical characteristics (a ′), (B ′), (c ′) and (d) can be satisfied simultaneously.
(A ′) 0 nm ≦ Re550 ≦ 1000 nm
(B ′) 1.022 <Re450 / Re550 ≦ 1.200
(C ′) 0.900 ≦ Re650 / Re550 <0.990
(D) 10000 nm ≦ d ≦ 300000 nm
(In the above formula, Re450, Re550, and Re650 represent the in-plane retardation Re at wavelengths of 450 nm, 550 nm, and 650 nm, respectively, and are represented by Re = (nx−ny) × d, where nx and ny Represents the refractive index in the x-axis direction and the y-axis direction when the stretching direction is the x-axis and the vertical direction in the film plane is the y-axis, and d represents the thickness (nm) of the film.
When the stretched film according to the present invention satisfies the optical characteristics of the above (a ′), (b ′), (c ′) and (d) at the same time, the optical characteristics of monitors, televisions, mobile devices, etc. of various specifications It can be particularly suitably used as a compensation material.
[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified. The room temperature is about 25 ° C.

  The measuring method of various physical property values in the present invention is shown below.

・ Glass transition temperature (Tg)
Using a differential scanning calorimeter (trade name: DSC6200, manufactured by Seiko Instruments Inc.), an extrapolated glass transition start temperature was determined according to Japanese Industrial Standard K7121. Hereinafter, it is simply referred to as glass transition temperature (Tg).

Weight average molecular weight and molecular weight distribution Using gel permeation chromatography (GPC, manufactured by Tosoh Corporation, trade name: HLC-8020), tetrahydrofuran (THF) as a solvent, polystyrene equivalent weight average molecular weight (Mw) and Molecular weight distribution (Mw / Mn) was measured. The Mn is a number average molecular weight.

Polymer molecular structure Using a superconducting nuclear magnetic resonance absorber (NMR, manufactured by Bruker, trade name: AVANCE500), ¹ H-NMR was measured in deuterated chloroform to determine the copolymer composition ratio and hydrogenation rate. Calculated.

-Evaluation of phase difference and birefringence A toluene or methylene chloride solution (concentration: 25%) of a ring-opening polymer was cast on a smooth glass plate, dried, and then a thickness of 94 to 140 μm and a residual solvent of 0.5 to 0 An 8% colorless and transparent film was obtained. The film was uniaxially stretched 2.0 times at temperatures of 5, 10, and 15 ° C. higher than the extrapolated glass transition temperature (Tg). The retardation and birefringence values of the stretched film were measured using a retardation measuring device (manufactured by Oji Scientific Instruments, trade name: KOBRA21DH).
Logarithmic viscosity Using an Ubbelohde viscometer, the viscosity was measured in chloroform at a sample concentration of 0.5 g / dL and a temperature of 30 ° C.

[Example 1]
As the cyclic olefin monomer (1m), 2.00 g of 1,2- (2H, 3H- [1,3] epicyclopenta) -1,2-dihydroacenaphthylene represented by the following formula (A) , 8-methoxycarbonyl-8-methyltetracyclo [4.4.0.1 ^2,5 ... Represented by the following formula (B) as a cyclic olefin monomer (2 m). 1 ^7,10 ] -3-dodecene 16.00 g, bicyclo [2.2.1] hept-2-ene 2.00 g represented by the following formula (C), and toluene 40 g as a polymerization solvent were substituted with nitrogen. The reaction vessel was charged, and 2.09 g of 1-hexene was further added as a molecular weight regulator and heated to 80 ° C.

To this reaction system, 0.13 mL of a toluene solution of triethylaluminum (concentration 0.6 mol / L) and 0.40 mL of a methanol-modified WCl ₆ toluene solution (concentration 0.025 mol / L) were added as a catalyst and reacted for 3 hours. Then, the polymerization was stopped with methanol water. Subsequently, the entire amount of the polymerization solution was transferred to a 2 L autoclave, and further 40 g of toluene and an amount of RuHCl (CO) [P (C ₆ H] of 500 ppm with respect to the charged amount of all monomers as a hydrogenation catalyst. ₅ ) ₃ ] ₃ was added, and a hydrogenation reaction was performed for 3 hours under the conditions of a hydrogen gas pressure of 9 to 10 MPa and a temperature of 160 to 165 ° C. After completion of the reaction, the reaction solution was added to a large amount of methanol solution to cause precipitation, and dried in a vacuum dryer at 100 ° C. for 12 hours to obtain a cyclic olefin ring-opening copolymer hydrogenated product (hereinafter referred to as this cyclic product). The olefin ring-opening copolymer hydrogenated product is referred to as “ring-opening copolymer hydrogenated product (D)”. The obtained hydrogenated product (D) has a weight average molecular weight (Mw) = 73600, a molecular weight distribution (Mw / Mn) = 6.00, a logarithmic viscosity (ηinh) = 0.54, an extrapolated glass transition start temperature. It was (Tg) = 139.0 degreeC. The hydrogenation rate of this hydrogenated product (D) determined by NMR measurement was 99.7% or more, and the aromatic ring residual rate was 100%. The IR spectrum and ¹ H-NMR spectrum of the resulting hydrogenated ring-opening copolymer (D) are shown in FIGS.

  2.8 g of the obtained hydrogenated ring-opening polymer (D) was dissolved in 28 g of methylene chloride, and a solution obtained by filtering under reduced pressure (filter medium: GA200 manufactured by ADVANTEC) was a smooth glass petri dish (size: inner diameter 146 mm × depth). 30 mm). This film was peeled from the bathtub and then dried for 12 hours with a vacuum dryer at 100 ° C. to obtain a film having a thickness of 96 μm. The amount of residual solvent in the obtained film was 500 ppm.

  This film was cut into a width of 10 mm and a length of 70 mm, and stretched by heating with a tensile tester equipped with a thermostatic bath to prepare a stretched film. The film was stretched twice at 154, 149 and 144 ° C. at a speed of 220% / min. The film thicknesses of the obtained films were 85, 72, and 67 μm, respectively, and the phase difference was measured to be R550 = 393, 464, and 666 nm. Here, R550 represents a phase difference at a wavelength of 550 nm. Detailed results are shown in Table 1.

[Comparative Example 1]
Ring-opening polymerization in the same manner as in Example 1 except that the monomers (A) and (C) were not used, 100 g of the monomer (B) and 4.6 g of 1-hexene were used as the molecular weight regulator. Reaction, hydrogenation reaction, hydrogenated body recovery and drying, weight average molecular weight (Mw) = 13,000, molecular weight distribution (Mw / Mn) = 3.06, logarithmic viscosity (ηinh) = 0.78, extrapolation A ring-opening polymerization hydrogenated product having a glass transition start temperature (Tg) = 167.0 ° C. was obtained. The hydrogenation rate of this hydrogenated product determined by NMR measurement was 99.8% or more. The obtained ring-opening polymerization hydrogenated product was formed in the same manner as in Example 1 to obtain a 140 μm film. The amount of residual solvent in the obtained film was 530 ppm.

  This film was cut into a width of 10 mm and a length of 70 mm, and stretched by heating with a tensile tester equipped with a thermostatic bath to prepare a stretched film. The film was stretched twice at a speed of 220% / min at 177 ° C. The film thickness of the obtained film was 100 μm, and the phase difference was measured to be R450 = 396, R550 = 388, and R650 = 384 nm, respectively.

[Comparative Example 2]
Ring-opening polymerization reaction, hydrogen as in Example 1 except that 2.00 g of monomer (A) and 10.00 g of (B) were used and 1.09 g of 1-hexene was used as a molecular weight regulator. Addition reaction, recovery of hydrogenated product and drying, weight average molecular weight (Mw) = 115600, molecular weight distribution (Mw / Mn) = 3.52, logarithmic viscosity (ηinh) = 0.70, extrapolated glass transition temperature (Tg) ) = 175.0 ° C. A ring-opening polymerization hydrogenated product was obtained. The hydrogenation rate of this hydrogenated product determined by NMR measurement was 99.8% or more. The obtained ring-opening polymerization hydrogenated product was formed in the same manner as in Example 1 to obtain a 140 μm film. The amount of residual solvent in the obtained film was 530 ppm.

  This film was cut into a width of 10 mm and a length of 70 mm, and stretched by heating with a tensile tester equipped with a thermostatic bath to prepare a stretched film. The film was stretched twice at a speed of 220% / min at 185 ° C. The film thickness of the obtained film was 100 μm, and the phase difference was measured to be R450 = 510, R550 = 490, R650 = 480 nm.

  The results are summarized in Table 1.

表１に示されるように、単量体Ａを共重合成分とする開環共重合体水素添加物から得られた実施例１の延伸フィルムでは、従来のノルボルネン系樹脂では達成されていない短波長ほど位相差が顕著に大きくなり、長波長ほど位相差が顕著に小さくなる「正の波長分散性」を示し、さらに単量体Ｃを共重合成分とすることで補外ガラス転移開始温度が低くなることに起因して、延伸温度（加工温度）を低くしても、比較例１、２と同等の応力で延伸処理を行うことができ、同等の光学特性を発現することができる。また、延伸温度が低いために、加工時の熱劣化、変色を低減することが可能になる。また、補外ガラス転移開始温度が低いため、比較例１、２の重合体と異なり、溶融押出法によっても成形することが可能になる。このように、本発明の環状オレフィン系開環共重合体が、加工性および強度に優れ、且つそれから得られる延伸フィルムが顕著に「正の波長分散性」を有することが示されている。このような波長分散性および加工性の両立は、用いる単量体の種類およびその組成比を変えることにより調節することができる。

As shown in Table 1, in the stretched film of Example 1 obtained from the ring-opening copolymer hydrogenated product containing monomer A as a copolymerization component, the short wavelength not achieved by the conventional norbornene resin The phase difference becomes significantly larger as the wavelength increases, and the longer the wavelength, the smaller the phase difference becomes “positive wavelength dispersibility”, and the extrapolated glass transition start temperature is lowered by using monomer C as a copolymerization component. As a result, even if the stretching temperature (processing temperature) is lowered, the stretching process can be performed with the same stress as in Comparative Examples 1 and 2, and the same optical characteristics can be exhibited. Further, since the stretching temperature is low, it becomes possible to reduce thermal deterioration and discoloration during processing. Further, since the extrapolated glass transition start temperature is low, unlike the polymers of Comparative Examples 1 and 2, it can be molded by a melt extrusion method. As described above, it is shown that the cyclic olefin-based ring-opening copolymer of the present invention is excellent in processability and strength, and the stretched film obtained therefrom has remarkably “positive wavelength dispersion”. Such compatibility between wavelength dispersion and processability can be adjusted by changing the type of monomer used and its composition ratio.

Industrial applicability

  The cyclic olefin-based ring-opening copolymer according to the present invention is very useful as an optical material, and includes optical disks, magneto-optical disks, optical lenses (Fθ lenses, pickup lenses, laser printer lenses, camera lenses, etc.), spectacle lenses. , Optical film / sheet (display film, retardation film, polarizing film, polarizing plate protective film, diffusion film, antireflection film, liquid crystal substrate, EL substrate, electronic paper substrate, touch panel substrate, PDP front plate, etc.), transparent The present invention can be applied to optical materials that require very high-precision optical design, such as conductive film substrates, optical fibers, light guide plates, optical cards, optical mirrors, ICs, LSIs, and LED sealing materials.

  The film of the present invention is useful as an optical film, and exhibits excellent transparency in an unstretched film formed by extrusion molding or cast molding. Therefore, the film of the present invention can be suitably used as various protective films. Since the film exhibits unique wavelength dispersion, it can be suitably used as a film constituting a retardation plate or a liquid crystal display device.

Claims (14)

A structural unit (1) represented by the following formula (1):
A cyclic structure having at least two structural units selected from the group consisting of a structural unit (2) represented by the following formula (2) and a structural unit (3) represented by the following formula (3): Olefin ring-opening copolymer;

(In Formula (1), a and b represent 0 or 1, and R ^{1 to} R ⁶ and a plurality of R ⁷ are each independently a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. Represents a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, which may have a linking group containing, or a polar group, and X represents —CH═CH— or —CH ₂ CH ₂ —. A plurality of X may be the same or different.)

(In the formula (2), a represents 0 or 1, and R ^{1 to} R ⁴ each independently have a hydrogen atom; a halogen atom; a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or a polar group, X represents —CH═CH— or —CH ₂ CH ₂ —, and a plurality of Xs are the same. But it may be different.)

(In the formula (3), a represents 0 or 1, and R ¹ and R ² each independently have a linking group containing a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or a polar group, X represents —CH═CH— or —CH ₂ CH ₂ —, and a plurality of Xs are the same. Or Y may be —CH═CH—, —CH ₂ CH ₂ —, or

Represents. ). The total of a plurality of X present in the formulas (1), (2) and (3) is 100 mol%, and 80 mol% or more of X is a group represented by —CH ₂ CH ₂ —. The cyclic olefin ring-opening copolymer according to claim 1.   The cyclic olefin system according to claim 1 or 2, wherein 5 to 50 mol% of the structural unit (1) is contained in 100 mol% of the total amount of the structural units (1), (2) and (3). Ring-opening copolymer. Structural unit (2) wherein R ¹ and R ^{2 in} formula (2) are hydrogen atoms, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a hydrogen atom, an alkoxycarbonyl group or a phenyl group. The cyclic olefin-based ring-opening copolymer according to any one of claims 1 to 3, wherein It has at least 1 sort (s) of structural units (2) chosen from the structural units represented by following formula (2-1)-(2-5), The cyclic | annular form in any one of Claims 1-4 characterized by the above-mentioned. Olefin ring-opening copolymer;

(In formulas (2-1) to (2-5), X is as defined in general formula (2).) It has at least 1 sort (s) of structural units (3) chosen from a structural unit denoted by a following formula (3-1)-(3-3), The cyclic according to any one of claims 1-5 characterized by things Olefin ring-opening copolymer;

(In the formulas (3-1) to (3-3), X is as defined in the general formula (3).)   The cyclic olefin-based ring-opening copolymer according to any one of claims 1 to 6, wherein an extrapolated glass transition start temperature measured according to Japanese Industrial Standard K7121 is 110 to 170 ° C.   The logarithmic viscosity measured at a sample concentration of 0.5 g / dL at a temperature of 30 ° C. in chloroform using an Ubbelohde viscometer is 0.4 to 0.8 dL / g. The cyclic olefin ring-opening copolymer according to any one of the above.   The optical component obtained by shape | molding the cyclic olefin type | system | group ring-opening copolymer in any one of Claims 1-8.   A film obtained by forming the cyclic olefin-based ring-opening copolymer according to any one of claims 1 to 8 by a casting method or an extrusion method.   A stretched film obtained by forming and stretching the cyclic olefin-based ring-opening copolymer according to any one of claims 1 to 8 by a casting method or an extrusion method. The stretched film according to claim 11 satisfies the optical properties of the following formulas (a), (b) and (c);
Re550> 0 (a)
Re450 / Re550> 1.022 (b)
Re650 / Re550 <0.990 (c)
(In the above formulas (a) to (c), Re450, Re550, and Re650 represent in-plane phase differences at wavelengths of 450 nm, 550 nm, and 650 nm, respectively).   A polarizing plate comprising the stretched film according to claim 11.   A liquid crystal display device comprising the stretched film according to claim 11.

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