JP2009098682A - Liquid crystal panel, optical film, and optical film set for liquid crystal panel - Google Patents

Abstract

The present invention provides a liquid crystal panel excellent in display performance capable of achieving a large contrast ratio, an optical film having a highly controlled optical performance over the entire surface, and an optical film set for a liquid crystal panel, suitable for the use of the liquid crystal panel.
An optical film having a specific optical film (A) and a polarizer (i), and an angle 90 + s between the maximum refractive index direction in the film plane of the optical film (A) and the absorption axis direction of the polarizer (i). A polarizing plate (1) whose (degree) satisfies | s | ≦ 1, the product of the retardation R0 (nm) in the film plane of the optical film (A) and | s | An optical film (B) and a polarizer (ii) are included, and an angle 90 + t (degree) between the maximum refractive index direction in the film plane of the optical film (B) and the absorption axis direction of the polarizer (ii) is | t A liquid crystal panel having a retardation R0 (nm) in the film plane of the optical film (B) and a polarizing plate (2) having a product of | t | .
[Selection figure] None

Description

  The present invention relates to a liquid crystal panel having two types of polarizing plates exhibiting different retardations, an optical film that can constitute the polarizing plate, and an optical film set for a liquid crystal panel.

  The optical film constituting the liquid crystal display device is required to have properties such as heat resistance and moisture resistance in addition to optical properties such as transparency. The applicant of the present application has found that a cyclic olefin-based optical film can be suitably used for such applications, and has already proposed (see Patent Documents 1 and 2).

  In recent years, liquid crystal display devices have been required to be larger, and uniform display performance has been required over the entire surface of large liquid crystal display devices. On the other hand, a liquid crystal display device is required to display a clear image and is required to exhibit a higher contrast ratio. The contrast ratio is represented by the luminance when white is displayed with respect to the luminance 1 when black is displayed on the monitor in a dark room, and is generally about 500 to 2000 in a commercially available liquid crystal display device. However, at present, there has been a demand for a liquid crystal display device capable of displaying a clearer image, for example, having a contrast ratio of 5000 or more.

  However, even if a conventionally known optical film that simply specifies the range of retardation is used, it is possible to obtain a large liquid crystal display device that can display homogeneously on the entire surface and exhibits an extremely high contrast ratio. It was not realized.

As a result of intensive studies in such a situation, the present inventor has obtained a liquid crystal panel having two types of polarizing plates made of a cyclic olefin resin and obtained by using two types of specific optical films having different retardations. The inventors have found that a high contrast ratio can be realized, and have completed the present invention.
JP 2001-350017 A Japanese Patent Application Laid-Open No. 2004-309979

  The present invention provides a liquid crystal panel excellent in display performance capable of achieving a large contrast ratio, an optical film having a highly controlled optical performance over the entire surface, and an optical film set for a liquid crystal panel, suitable for the use of the liquid crystal panel. Is an issue.

The liquid crystal panel of the present invention is
The following optical film (A) and polarizer (i) are included, and the angle 90 + s (degree) between the maximum refractive index direction in the film plane of the optical film (A) and the absorption axis direction of the polarizer (i) is | Polarizing plate (1) satisfying s | ≦ 1, and having a product of retardation R0 (nm) in the film plane of optical film (A) and | s |
The following optical film (B) and polarizer (ii) are included, and the angle 90 + t (degree) between the maximum refractive index direction in the film plane of the optical film (B) and the absorption axis direction of the polarizer (ii) is | It is characterized by having a polarizing plate (2) satisfying t | ≦ 1, a retardation R0 (nm) in the film plane of the optical film (B), and a product of | t |
Optical film (A): made of cyclic olefin resin,
The retardation R0 in the film plane is 15 to 60 nm, and
An optical film having a retardation Rxz in the film thickness direction of 150 to 250 nm.
Optical film (B): made of a cyclic olefin resin,
The in-plane retardation R0 is 70 to 120 nm,
An optical film having a ratio (Rxz / R0) of retardation Rxz to R0 in the film thickness direction of 1.2 to 1.5.
(Here, the retardation R0 in the film plane and the retardation Rxz in the film thickness direction are the maximum refractive index in the film plane at a light wavelength of 550 nm, nx, and in the direction orthogonal to nx in the film plane, respectively. (If the refractive index is ny and the film thickness is d (nm), this is a value determined by the formula R0 = (nx−ny) × d and the formula Rxz = (nx−nz) × d).
In such a liquid crystal panel of the present invention, it is preferable that the cyclic olefin-based resin constituting the optical film (A) and the optical film (B) has a structural unit represented by the following formula (I).

［式（Ｉ）中、ｍは１以上の整数であり、ｐは０または１以上の整数であり、Ｄは−ＣＨ＝ＣＨ−または−ＣＨ₂ＣＨ₂−で表される基であり、Ｒ¹〜Ｒ⁴はそれぞれ独立に水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子もしくはケイ素原子を含む連結基；置換もしくは非置換の炭素原子数１〜３０の炭化水素基；極性基よりなる群から選ばれる原子もしくは基を表し、Ｒ¹およびＲ²は一体化して２価の炭化水素基を形成してもよく、Ｒ³
およびＲ⁴は一体化して２価の炭化水素基を形成してもよい。Ｒ¹およびＲ²は互いに結合
して炭素環または複素環を形成してもよく、Ｒ³およびＲ⁴は互いに結合して炭素環または複素環を形成してもよく、該炭素環または複素環は単環でも多環でもよい。］
本発明の液晶パネルでは、偏光板（１）が、光学フィルム（Ａ）、偏光子（ｉ）、トリアセチルセルロースフィルムがこの順に積層されてなることが好ましく、また、偏光板（２）が、光学フィルム（Ｂ）、偏光子（ｉｉ）、トリアセチルセルロースフィルムがこの順に積層されてなることが好ましい。

[In the formula (I), m is an integer of 1 or more, p is 0 or an integer of 1 or more, D is a group represented by —CH═CH— or —CH ₂ CH ₂ —, R ^{1 to} R ⁴ are each independently a hydrogen atom; a halogen atom; a linking group containing an oxygen atom, sulfur atom, nitrogen atom or silicon atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms; a polar group represents an atom or a group selected from the group, R ¹ and R ² may form a divalent hydrocarbon group are integrated, R ³
And R ⁴ may be integrated to form a divalent hydrocarbon group. R ¹ and R ² may be bonded to each other to form a carbocyclic or heterocyclic ring, and R ³ and R ⁴ may be bonded to each other to form a carbocyclic or heterocyclic ring. May be monocyclic or polycyclic. ]
In the liquid crystal panel of the present invention, the polarizing plate (1) is preferably formed by laminating the optical film (A), the polarizer (i), and the triacetyl cellulose film in this order, and the polarizing plate (2) The optical film (B), the polarizer (ii), and the triacetyl cellulose film are preferably laminated in this order.

The optical film (a) of the present invention is
Made of cyclic olefin resin,
The retardation R0 in the film plane is 15-60 nm,
The thickness direction retardation Rxz is 150 to 250 nm,
The angle α (degrees) between the maximum refractive index direction in the film plane and the film width direction satisfies | α | ≦ 1, and
The product of | α | and R0 (nm) is 30 or less.

The optical film (b) of the present invention is
Made of cyclic olefin resin,
The in-plane retardation R0 is 70 to 120 nm,
The ratio (Rxz / R0) of retardation Rxz and R0 in the film thickness direction is 1.2 to 1.5,
The angle β (degrees) between the maximum refractive index direction in the film plane and the film width direction satisfies | β | ≦ 1, and
The product of | β | and R0 (nm) is 30 or less.

  The optical film set for a liquid crystal panel of the present invention is characterized by comprising the optical film (a) and the optical film (b).

  According to the present invention, a liquid crystal panel that can achieve a large contrast ratio, has no display unevenness, and exhibits stable display characteristics regardless of the use environment, and is suitable for the use of the liquid crystal panel, has high optical performance over the entire surface. A controlled optical film and an optical film set for a liquid crystal panel can be provided.

Hereinafter, the present invention will be specifically described.
<Cyclic olefin resin>
First, the cyclic olefin resin constituting the optical film according to the present invention will be described.

  The optical film according to the present invention, that is, the optical films (A) and (B) constituting the liquid crystal panel of the present invention, and the optical films (a) and (b) of the present invention are each made of a cyclic olefin resin. These optical films may be comprised from the same kind of cyclic olefin resin, and may be comprised from different cyclic olefin resin.

  The cyclic olefin resin constituting the optical film according to the present invention is not particularly limited, and a ring-opening (co) polymer or ring-opening (co) polymer of a cyclic olefin monomer having a norbornene skeleton. And hydrogenated products, addition (co) polymers, copolymers of cyclic olefin monomers with other monomers copolymerizable, and hydrogenated products thereof.

Specifically, a ring-opening (co) polymer of a cyclic olefin monomer represented by formula (I ′) and formula (II ′) described later, and a hydride of the ring-opening (co) polymer. , Addition (co) polymers, addition copolymers of cyclic olefin monomers and α-olefins, and the like. Among these, a hydride of a ring-opening (co) polymer is preferable, and a polymer having a structural unit represented by the following general formula (I) is particularly preferable. The polymer may be a homopolymer having a structural unit represented by the following general formula (I), or a copolymer having a structural unit represented by the following general formula (II) together with the formula (I). It may be a coalescence.

［式（Ｉ）中、ｍは１以上の整数であり、ｐは０または１以上の整数であり、Ｄは−ＣＨ＝ＣＨ−または−ＣＨ₂ＣＨ₂−で表される基であり、Ｒ¹〜Ｒ⁴はそれぞれ独立に水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子もしくはケイ素原子を含む連結基；置換もしくは非置換の炭素原子数１〜３０の炭化水素基；極性基よりなる群から選ばれる原子もしくは基を表し、Ｒ¹およびＲ²は一体化して２価の炭化水素基を形成してもよく、Ｒ³
およびＲ⁴は一体化して２価の炭化水素基を形成してもよい。Ｒ¹およびＲ²は互いに結合
して炭素環または複素環を形成してもよく、Ｒ³およびＲ⁴は互いに結合して炭素環または複素環を形成してもよく、該炭素環または複素環は単環でも多環でもよい。］

[In the formula (I), m is an integer of 1 or more, p is 0 or an integer of 1 or more, D is a group represented by —CH═CH— or —CH ₂ CH ₂ —, R ^{1 to} R ⁴ are each independently a hydrogen atom; a halogen atom; a linking group containing an oxygen atom, sulfur atom, nitrogen atom or silicon atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms; a polar group represents an atom or a group selected from the group, R ¹ and R ² may form a divalent hydrocarbon group are integrated, R ³
And R ⁴ may be integrated to form a divalent hydrocarbon group. R ¹ and R ² may be bonded to each other to form a carbocyclic or heterocyclic ring, and R ³ and R ⁴ may be bonded to each other to form a carbocyclic or heterocyclic ring. May be monocyclic or polycyclic. ]

［式（ＩＩ）中、Ｅは−ＣＨ＝ＣＨ−または−ＣＨ₂ＣＨ₂−で表される基であり、Ｒ⁵〜
Ｒ⁸はそれぞれ独立に水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子もしくは
ケイ素原子を含む連結基を有する置換もしくは非置換の炭素原子数１〜３０の炭化水素基；置換もしくは非置換の炭素原子数１〜３０の炭化水素基；極性基よりなる群から選ばれる原子もしくは１価の基、Ｒ⁵およびＲ⁶が一体化して形成される２価の炭化水素基、Ｒ⁷
およびＲ⁸が一体化して形成される２価の炭化水素基、Ｒ⁵〜Ｒ⁸から選ばれる２つの基が
互いに結合して形成される単環の脂環式炭化水素環または複素環を表す。］
環状オレフィン系樹脂のガラス転移温度をフィルム加工に適した領域にし、同時に複屈折制御性を確保するため、上記一般式（Ｉ）におけるｍは好ましくは１〜５、より好ましくは１〜３であり、ｐは好ましくは０〜４、より好ましくは０〜２である。また、Ｒ¹〜
Ｒ⁴の炭素原子数は好ましくは１〜２５、より好ましくは１〜２０である。さらに、上記
一般式（ＩＩ）におけるＲ⁵〜Ｒ⁸の炭素原子数は好ましくは１〜２５、より好ましくは１〜２０である。

[In Formula (II), E is a group represented by —CH═CH— or —CH ₂ CH ₂ —, and R ⁵ to
Each R ⁸ is independently a hydrogen atom; a halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms having a linking group containing an oxygen atom, sulfur atom, nitrogen atom or silicon atom; substituted or unsubstituted A hydrocarbon group having 1 to 30 carbon atoms; an atom selected from the group consisting of polar groups or a monovalent group; a divalent hydrocarbon group formed by integrating R ⁵ and R ⁶ ; R ⁷
And R ⁸ represents a monovalent alicyclic hydrocarbon ring or a heterocyclic ring formed by combining two groups selected from R ^{5 to} R ⁸ together with a divalent hydrocarbon group formed integrally with R ^8. . ]
In order to make the glass transition temperature of the cyclic olefin resin suitable for film processing and at the same time to ensure birefringence controllability, m in the above general formula (I) is preferably 1 to 5, more preferably 1 to 3. , P is preferably 0-4, more preferably 0-2. R ¹ to
R ⁴ preferably has 1 to 25 carbon atoms, more preferably 1 to 20 carbon atoms. Furthermore, the number of carbon atoms of R ^{5 to} R ⁸ in the general formula (II) is preferably 1 to 25, more preferably 1 to 20.

Method for Producing Cyclic Olefin Resin The cyclic olefin resin according to the present invention has a structural unit represented by the above formula (I) and, if necessary, a structural unit represented by the above formula (II).

  The structural unit represented by the above formula (I) is derived from a cyclic olefin monomer represented by the following formula (I ′) by ring-opening (co) polymerization.

（式（Ｉ’）中、ｍおよびＲ¹〜Ｒ⁴は、前記式（Ｉ）と同様である。）
式（Ｉ）または式（Ｉ’）において、極性基としては、たとえば、水酸基、炭素原子数１〜１０のアルコキシ基、カルボニルオキシ基、アルコキシカルボニル基、アリーロキシカルボニル基、シアノ基、アミド基、イミド基、トリオルガノシロキシ基、トリオルガノシリル基、アミノ基、アシル基、アルコキシシリル基、スルホニル基、およびカルボキシル基などが挙げられる。さらに具体的には、上記アルコキシ基としては、たとえばメトキシ基、エトキシ基などが挙げられ；カルボニルオキシ基としては、たとえばアセトキシ基、プロピオニルオキシ基などのアルキルカルボニルオキシ基、およびベンゾイルオキシ基などのアリールカルボニルオキシ基が挙げられ；アルコキシカルボニル基としては、たとえばメトキシカルボニル基、エトキシカルボニル基などが挙げられ；アリーロキシカルボニル基としては、たとえばフェノキシカルボニル基、ナフチルオキシカルボニル基、フルオレニルオキシカルボニル基、ビフェニリルオキシカルボニル基などが挙げられ；トリオ
ルガノシロキシ基としては、たとえばトリメチルシロキシ基、トリエチルシロキシ基などが挙げられ；トリオルガノシリル基としてはトリメチルシリル基、トリエチルシリル基などが挙げられ；アミノ基としては第１級アミノ基が挙げられ、アルコキシシリル基としては、たとえばトリメトキシシリル基、トリエトキシシリル基などが挙げられる。

(In formula (I ′), m and R ^{1 to} R ⁴ are the same as those in formula (I).)
In the formula (I) or the formula (I ′), examples of the polar group include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbonyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an amide group, Examples thereof include an imide group, a triorganosiloxy group, a triorganosilyl group, an amino group, an acyl group, an alkoxysilyl group, a sulfonyl group, and a carboxyl group. More specifically, examples of the alkoxy group include a methoxy group and an ethoxy group; examples of the carbonyloxy group include an alkylcarbonyloxy group such as an acetoxy group and a propionyloxy group, and an aryl such as a benzoyloxy group. 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, a fluorenyloxycarbonyl group, Examples of the triorganosiloxy group include trimethylsiloxy group and triethylsiloxy group; examples of the triorganosilyl group include trimethyl Silyl groups, such as triethylsilyl group and the like; examples of the amino group include primary amino group, the alkoxysilyl group, for example a trimethoxysilyl group, a triethoxysilyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the hydrocarbon group having 1 to 10 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, allyl group, and propenyl group. Group and the like.

In addition, the 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)); oxygen , A linking group containing nitrogen, sulfur or silicon (for example, a carbonyl group (—CO—), an oxycarbonyl group (—O (CO) —), a sulfone group (—S
O ₂ -), ether bond (-O-), thioether bond (-S-), an imino group (-NH-), amide bond (-NHCO -, - CONH-), siloxane bond (-OSi (R ₂₎ -(Wherein R is an alkyl group such as methyl or ethyl)), etc., and a linking group containing a plurality of these may be used.

Specific examples of the cyclic olefin monomer (I ′) include the following compounds.
Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
Pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- pentadecene,
8-methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-ethyl tetracyclo [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-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-
Dodecene,
8-methyl-8-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-
Dodecene,
8-methyl -8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10]
-3-dodecene,
8-methyl-8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10]
-3-dodecene,
8-methyl -8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -
3-dodecene,
8-cyano-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-cyano-8-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-phenyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-fluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-fluoro-methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 difluoromethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 pentafluoroethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8-difluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-difluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-
Dodecene,
8,8,9- trifluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -
3-dodecene,
8,8,9,9- tetrafluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9,9- tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- trifluoro-9-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene,
8,8,9- trifluoro-9-pentafluoro propoxy tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-Fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-difluoro-8-heptafluoroisopropyl-9-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-Chloro -8,9,9- trifluoro tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-
Dodecene,
8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene,
8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.
4.0.1, ^{2.5.1 7,10} ] -3-dodecene These may be used alone or in combination of two or more.

In the present invention, the structural unit represented by the formula (I) preferably has a polar group, and the polar group is preferably a group represented by the following formula (III). That is, in the structural olefin monomer represented by the formula (I) or the cyclic olefin monomer represented by the formula (I ′), at least one of R ^{1 to} R ⁴ is represented by the following formula (III). It is preferably a group.

_{- (CH 2) p COOR '} ... (III)
(In formula (III), p is 0 or an integer of 1 to 5, and R ′ is a hydrocarbon group having 1 to 15 carbon atoms.)
In the above formula (III), the smaller the value of p and the smaller R ′ the number of carbon atoms, the higher the glass transition temperature of the resulting copolymer and the better the heat resistance. That is, p is usually 0 or an integer of 1 to 5, preferably 0 or 1, and R 'is usually a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 carbon atom. Desirably, it is an alkyl group of ˜3.

  Further, in the above formula (I) or (I ′), when an alkyl group is further bonded to the carbon atom to which the polar group represented by the general formula (III) is bonded, the heat resistance of the resulting copolymer is reduced. This is preferable for achieving a balance between the property and water absorption (wet) property. Moreover, it is preferable that the carbon atom number of an alkyl group is 1-5, More preferably, it is 1-2, Most preferably, it is 1.

  The structural unit represented by the formula (II) is derived from a cyclic olefin monomer (II) represented by the following formula (II ′) by ring-opening copolymerization.

（式（ＩＩ’）中、Ｒ⁵〜Ｒ⁸は前記式（ＩＩ）と同様である。）
このような環状オレフィン系単量体としては、具体的には次のような化合物が挙げられる。

(In Formula (II ′), R ^{5 to} R ⁸ are the same as those in Formula (II).)
Specific examples of such cyclic olefin monomers include the following compounds.

Bicyclo [2.2.1] hept-2-ene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-propylbicyclo [2.2.1] hept-2-ene,
5-butylbicyclo [2.2.1] hept-2-ene,
5-pentylbicyclo [2.2.1] hept-2-ene,
5-hexylbicyclo [2.2.1] hept-2-ene,
5-heptylbicyclo [2.2.1] hept-2-ene,
5-octylbicyclo [2.2.1] hept-2-ene,
5-nonylbicyclo [2.2.1] hept-2-ene,
5-decylbicyclo [2.2.1] hept-2-ene,
5-undecylbicyclo [2.2.1] hept-2-ene,
5-dodecylbicyclo [2.2.1] hept-2-ene,
5-tridecylbicyclo [2.2.1] hept-2-ene,
5-tetradecylbicyclo [2.2.1] hept-2-ene,
5-pentadecylbicyclo [2.2.1] hept-2-ene,
5-hexadecylbicyclo [2.2.1] hept-2-ene,
5-heptadecylbicyclo [2.2.1] hept-2-ene,
5-octadecylbicyclo [2.2.1] hept-2-ene,
5-nonadecylbicyclo [2.2.1] hept-2-ene,
5-icosylbicyclo [2.2.1] hept-2-ene,
5-phenylbicyclo [2.2.1] hept-2-ene,
5-cyanobicyclo [2.2.1] hept-2-ene,
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methoxycarbonyl-5-methylbicyclo [2.2.1] hept-2-ene,
5-ethoxycarbonyl-5-methylbicyclo [2.2.1] hept-2-ene,
5-cyano-5-methylbicyclo [2.2.1] hept-2-ene 5-ethylidenebicyclo [2.2.1] hept-2-enespiro [fluorene-9,8'-tricyclo [4.3. 0.1 ^2.5 ] [3] Decene],
Tricyclo [4.3.0.1 ^2,5 ] dec-3-ene Tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (dicyclopentadiene).

These can be used alone or in combination of two or more. In the present invention, among these, bicyclo [2.2.1] hept-2-ene, (norbornene), tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (dicyclopentadiene) Is preferably used in terms of the slidability and retardation of the film.

The cyclic olefin resin according to the present invention can be produced by ring-opening copolymerization of one or more cyclic olefin monomers (I ′) and cyclic olefin monomers (II ′). . The cyclic olefin resin according to the present invention is obtained by using 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and bicyclo [2.2.1] hept-2-ene (norbornene), or 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . It is particularly preferable that the copolymer be composed of 1 ^7,10 ] -3-dodecene and tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (dicyclopentadiene).

  In the present invention, the copolymerization ratio of the cyclic olefin monomer (compound represented by formula (I ′)) and the cyclic olefin monomer (compound represented by formula (II ′)) is the sum of these. Is usually 0 to 40 parts by weight, preferably 0 to 30 parts by weight, based on 100 parts by weight of the cyclic olefin monomer (II ′). If the copolymerization ratio of the cyclic olefin monomer (II ′) exceeds 30 parts by weight, the glass transition temperature may be lowered, and the heat resistance stability of various film properties such as retardation and dimensions may be lowered. On the other hand, if it is less than 3 weights, the slidability and retardation development property of the resulting molded article, film or sheet may be lowered.

In the present invention, in addition to these cyclic olefin monomers (I ′) and (II ′), other cyclic olefin monomers or other copolymerizable monomers may be used without departing from the object of the present invention. A small amount of a monomer can be used as a copolymerization raw material monomer, and the cyclic olefin resin according to the present invention can contain structural units other than the structural units represented by the formulas (I) and (II). Such a structural unit is formed, for example, by ring-opening copolymerization of a cycloolefin monomer such as cyclobutene, cyclopentene, cycloheptene, or cyclooctene together with the cyclic olefin monomers (I ′) and (II ′). can do. In addition, in the presence of an unsaturated hydrocarbon polymer having an olefinically unsaturated bond in the main chain, such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-nonconjugated diene copolymer, polynorbornene, etc. Olefin monomer (I ')
And (II ′) can also be formed by ring-opening copolymerization, and when having such a structural unit, the impact resistance of the copolymer of the present invention tends to be improved.

  However, in the present invention, it is preferable to carry out copolymerization using only the cyclic olefinic monomers (I ′) and (II ′). That is, the cyclic olefin-based resin according to the present invention may have other structural units in addition to the structural units represented by the formulas (I) and (II) as long as the object of the present invention is not impaired. However, it is preferable not to have structural units other than the structural units represented by the formulas (I) and (II).

A ring-opening copolymer obtained by ring-opening copolymerization of each cyclic olefin-based monomer has an olefinic unsaturated bond in the molecule and has problems such as heat-resistant coloring. The olefinically unsaturated bond is preferably hydrogenated, but a known method can be applied to the hydrogenation reaction. Further, when tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (dicyclopentadiene) is used as the cyclic olefin monomer (II ′), a ring-opening copolymer In addition to the main chain structure in the molecule, the side chain structure also has an olefinically unsaturated bond and is preferably hydrogenated for the same reason, but a known method can be applied to such a hydrogenation reaction. .

  For example, the catalyst, solvent, temperature conditions, etc. described in JP-A-63-218726, JP-A-1-132626, JP-A-1-240517, JP-A-2-10221 and the like are applied. The ring-opening polymerization reaction and the hydrogenation reaction can be carried out.

  The hydrogenation rate of the olefinically unsaturated bond is usually 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more. The hydrogenation reaction in the present invention is for olefinic unsaturated bonds in the molecule as described above, and when the cyclic olefin resin according to the present invention has an aromatic group, the aromatic group is refracted. Since it may have an advantageous effect on optical properties such as the rate and heat resistance, hydrogenation is not necessarily required.

As the molecular weight of the cyclic olefin resin according to the present invention, the polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is usually 3 × 10 ^{3 to} 5 × 10 ⁵ , preferably 5 × 10 ^{3 to} 3 × 10 ⁵ , more preferably 1 × 10 ⁴ to
A 2 × 10 ^5, The weight average molecular weight (Mw) in terms of polystyrene is usually ^{5 × 10 3 ~1 × 10 6} , preferably ^{1 × 10 4 ~5 × 10 5} , more preferably 2 × 10 ⁴ It is desirable to be in the range of ˜4 × 10 ⁵ .

  If the molecular weight is too small, the strength of the resulting film may be low, or the retardation development property during stretching may be reduced. On the other hand, when the molecular weight is excessive, the solution viscosity becomes too high, and the productivity and processability of the copolymer of the present invention may deteriorate.

The molecular weight distribution (Mw / Mn) of the cyclic olefin-based resin according to the present invention is usually 1.5 to 10, preferably 2 to 7, and more preferably 2 to 5.
The cyclic olefin resin according to the present invention has a saturated water absorption at 23 ° C. of usually 0.05 to 1% by weight, preferably 0.07 to 0.8% by weight, and more preferably 0.1 to 0.7% by weight. % Is desirable. When the saturated water absorption rate of the cyclic olefin resin according to the present invention is within the above range, various optical properties, transparency, retardation and retardation uniformity, or dimensional accuracy of the obtained film are high temperature and high humidity. In addition to being stably maintained even under such conditions, it is excellent in adhesion and adhesion to other materials, so that peeling does not occur during use, and it is compatible with additives such as antioxidants. Since solubility is also favorable, the freedom degree of selection of the kind and addition amount of an additive becomes large.

  When this saturated water absorption is less than 0.05% by weight, the resulting film has low adhesion and adhesiveness to other materials, tends to cause peeling during use, and an antioxidant. The amount of additives such as these may be limited. On the other hand, when the saturated water absorption exceeds 1% by weight, the water absorption tends to cause changes in optical characteristics and dimensional changes.

Here, the saturated water absorption is a value obtained by immersing in 23 ° C. water for 1 week and measuring an increased weight according to ASTM D570.
The glass transition temperature (Tg) of the cyclic olefin-based resin according to the present invention is usually 70 to 250 ° C, preferably 90 to 200 ° C, more preferably 100 to 180 ° C. A Tg of 150 ° C. or higher is preferred because of having excellent heat resistance. When Tg is less than 90 ° C., the heat distortion temperature becomes low, which may cause a problem in heat resistance, and there may be a problem that a change in optical characteristics due to temperature in the obtained film becomes large. is there. On the other hand, when Tg exceeds 200 ° C., the processing temperature becomes too high during stretching, and the copolymer of the present invention may be thermally deteriorated.

  Here, the Tg of the cyclic olefin-based resin is the maximum peak temperature of the differential differential scanning calorimetry curve obtained when measured in a nitrogen atmosphere using a differential scanning calorimeter (DSC) at a heating rate of 20 ° C./min ( A point) and a temperature of −20 ° C. from the maximum peak temperature (B point) are plotted on the differential scanning calorimetry curve, and the intersection of the tangent line on the baseline starting from B point and the tangent line starting from A point Desired.

Polymerization catalyst As a catalyst used for the production of the cyclic olefin-based resin according to the present invention, for example,
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, for example, WCl ₆ , MoCl ₅ , ReOCl ₃ , V
Examples thereof include compounds described in JP-A-1-240517 such as OCl ₃ and TiCl ₄ . These can be used singly or in combination of two or more.

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

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

The amount of the metathesis catalyst used in combination with the component (a) is such that the molar ratio of the component (a) to the total monomer is usually 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 of Group 4 to Group 8 of the periodic table or a metallacyclobutane complex can be used.

Specific examples of the catalyst (II) include, for example, W (= N-2,6-C ₆ H ₃ ⁱ Pr ₂ ) (= CH ^tert Bu) (O ^tert Bu) ₂ , Mo (= N-2, 6-C ₆ H ₃ ⁱ Pr ₂ ) (= CH ^tert
Bu) (O ^tert Bu) ₂ , Ru (= CHCH = CPh ₂ ) (PPh ₃ ) ₂ Cl ₂ , Ru (= C
HPh 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.
The molecular weight of the copolymers (A) and (B) used in 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 polymerization reaction system. 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.

  Examples of the solvent used in the ring-opening copolymerization reaction (that is, a solvent that dissolves a monomer, a ring-opening polymerization catalyst, a molecular weight regulator, etc.) include alkanes such as pentane, hexane, heptane, octane, nonane, and decane. ; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene , Compounds such as halogenated alkanes such as chloroform and tetrachloroethylene, aryl halides; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate; dibutyl ether Tetrahydrofuran, include ethers such as dimethoxyethane, aromatic hydrocarbons are preferred among these. 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.

  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.

The reaction time for carrying out the ring-opening copolymerization reaction is usually 0.1 to 10 hours, preferably 0.1 to 9 hours, more preferably 0.1 to 8 hours.
A ring-opening copolymer obtained by ring-opening copolymerization of each cyclic olefin-based monomer has an olefinic unsaturated bond in the molecule and has problems such as heat-resistant coloring. The olefinically unsaturated bond is preferably hydrogenated, but a known method can be applied to the hydrogenation reaction. For example, the catalyst, solvent, temperature conditions, etc. described in JP-A-63-218726, JP-A-1-132626, JP-A-1-240517, JP-A-2-10221 and the like are applied. The ring-opening polymerization reaction and the hydrogenation reaction can be carried out.

  The hydrogenation rate of the olefinically unsaturated bonds of the copolymers (A) and (B) is usually 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more. The hydrogenation reaction in the present invention is for olefinic unsaturated bonds in the molecule as described above. When the cyclic olefin resin used in the present invention has an aromatic group, the aromatic group is refracted. Since there may be an advantageous effect on optical characteristics such as the rate and heat resistance, hydrogenation is not necessarily required.

<Additives>
Various additives can be blended with the cyclic olefin resin according to the present invention as required. For example, an antioxidant selected from a phenolic antioxidant, a lactone antioxidant, a phosphorus antioxidant and a sulfur antioxidant may be added to improve oxidation stability and prevent coloring and deterioration. it can.

The antioxidant may be blended at a ratio of 0.001 to 5 parts by weight per 100 parts by weight of the polymer. Specific examples of antioxidants include
1) 2,6-di-tert-butyl-4-methylphenol, 4,4′-thiobis- (6
-Tert-butyl-3-methyl-phenyl), 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), tetrakis [methylene-3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid stearate, 2,5-di-tert- Phenolic antioxidants or hydroquinone antioxidants such as butylhydroquinone and pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl)] propionate,
2) Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert) -Butyl-5-methylphenyl) 4,4'-biphenylenediphosphonite, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis (2,4-di-tert-butylphenyl) Phosphorus secondary antioxidants such as pentaerythritol diphosphite, tris (4-methoxy-3,5-diphenyl) phosphite and tris (nonylphenyl) phosphite, and 3) dilauryl-3,3′-thiodipro Sulfur-based secondary antioxidants such as pionate and 2-mercaptobenzimidazole Rukoto can.

Moreover, a flame retardant can also be mix | blended with the cyclic olefin resin which concerns on this invention. Known flame retardants can be used, and examples thereof include halogen flame retardants, antimony flame retardants, phosphate ester flame retardants and metal hydroxides. Among these, phosphate ester-based flame retardants that are effective with a small amount of blending and can minimize deterioration of water absorption, low dielectric constant, and transparency are preferable, and 1,3-bis (phenylphosphoryl) benzene, 1 , 3-bis (diphenylphosphoryl) benzene, 1,3-bis [di (alkylphenyl) phosphoryl] benzene, 1,3-bis [di (2 ′, 6′-dimethylphenyl) phosphoryl] benzene, 1,3- Bis [di (2 ′, 6′-diethylphenyl) phosphoryl] benzene, 1,3-bis [di (2 ′, 6′-diisopropylphenyl) phosphoryl] benzene, 1,3-bis [di (2 ′, 6) '-Dibutylphenyl) phosphoryl] benzene, 1,3-bis [di (2'-tert-butylphenyl) phosphoryl] benzene, 1,3-bis [di (2'-isopropylphenyl) Phosphoryl] benzene 1,3-bis [di (2′-methylphenyl) phosphoryl] benzene, 1,4-bis (diphenylphosphoryl) benzene, 1,4-bis [di (2 ′, 6′-dimethylphenyl) phosphoryl Benzene, 1,4-bis [di (2 ′, 6′-diethylphenyl) phosphoryl] benzene, 1,4-bis [di (2 ′, 6′-diisopropylphenyl) phosphoryl] benzene, 1,4-bis [Di (2′-tert-butylphenyl) phosphoryl] benzene, 1,4-bis [di (2′-isopropylphenyl) phosphoryl] benzene, 1,4-bis [di (2′-methylphenyl) phosphoryl] benzene And condensed phosphate ester flame retardants such as 4,4′-bis [di (2 ″, 6 ″ -dimethylphenyl) phosphorylphenyl] dimethylmethane are more preferred. . The blending amount depends on the selected flame retardant and the required degree of flame retardancy, but is preferably 0.5 to 40 parts by weight, more preferably 2 to 30 parts by weight, based on 100 parts by weight of the cyclic olefin polymer. -20 parts by weight is particularly preferred. When the amount of the flame retardant is less than 0.5 parts by weight, the effect is insufficient. On the other hand, when the amount exceeds 40 parts by weight, transparency is impaired, and electrical characteristics such as dielectric constant are deteriorated. Or the water absorption increases or the heat resistance deteriorates.

  If necessary, the cyclic olefin-based resin according to the present invention may further contain a known lubricant, ultraviolet absorber, leveling agent, antistatic agent, retardation adjusting agent, plasticizer and dye.

<Optical film>
Optical film (A)
The optical film (A) is a film constituting the polarizing plate (1) of the liquid crystal panel of the present invention, and is made of a cyclic olefin-based resin. The in-plane retardation R0 is 15 to 60 nm, preferably 20 to 40 nm. The retardation Rxz in the film thickness direction is 150 to 250 nm, preferably 180 to 240 nm.

  In the present invention, the in-plane retardation R0 is the maximum refractive index in the film plane at a light wavelength of 550 nm, nx, the refractive index in the direction perpendicular to nx in the film plane, ny, and the film thickness in d (nm). In this case, the value is obtained by the formula R0 = (nx−ny) × d. Hereinafter, R0 may also be referred to as “R0 (550)”.

  In the present invention, the retardation Rxz in the film thickness direction is represented by nx as the maximum refractive index in the film plane at a light wavelength of 550 nm, ny in the direction perpendicular to nx in the film plane, and the film thickness. When d (nm), it is a value obtained by the formula Rxz = (nx−nz) × d.

In such an optical film (A), the maximum refractive index direction may be either the longitudinal direction or the width direction of the film, but is preferably the width direction.
As the optical film (A), it is particularly preferable to use the following optical film (a).

Optical film (a)
The optical film (a) of the present invention comprises a cyclic olefin resin,
The in-plane retardation R0 is 15-60 nm, preferably 20-40 nm,
The thickness direction retardation Rxz is 150 to 250 nm, preferably 160 to 240 nm,
The angle α (degrees) between the maximum refractive index direction in the film plane and the film width direction satisfies | α | ≦ 1, and
The product of | α | and R0 (nm) is 30 or less, preferably 20 or less.

  The optical film (a) is not particularly limited, but the width is preferably 1300 mm or more, more preferably 1500 mm or more, particularly preferably 2000 mm or more, and the thickness is preferably 30 to 80 μm, more preferably 35. ˜70 μm.

Further, the optical film (a) has a variation in the in-plane retardation R0 (550) of preferably 2 nm or less, more preferably 1.5 nm or less, and even more preferably 1 nm or less over the entire film surface.
When the optical film (a) satisfies such characteristics, it is suitable for forming the polarizing plate (1).

Optical film (B)
The optical film (B) is a film constituting the polarizing plate (2) of the liquid crystal panel of the present invention, and is made of a cyclic olefin-based resin. The in-plane retardation R0 is 70 to 120 nm, preferably 75 to 115 nm. The ratio (Rxz / R0) of retardation Rxz and R0 in the film thickness direction is 1.2 to 1.5, preferably 1.3 to 1.5.

In such an optical film (B), the maximum refractive index direction may be either the longitudinal direction or the width direction of the film, but is preferably the width direction.
As the optical film (B), it is particularly preferable to use the following optical film (b).

Optical film (b)
The optical film (b) of the present invention comprises a cyclic olefin resin,
The in-plane retardation R0 is 70 to 120 nm, preferably 75 to 115 nm,
The ratio (Rxz / R0) of retardation Rxz and R0 in the film thickness direction is 1.2 to 1.5, preferably 1.3 to 1.5,
The angle β (degrees) between the maximum refractive index direction in the film plane and the film width direction satisfies | β | ≦ 1, and
The product of | β | and R0 (nm) is 30 or less, preferably 20 or less.

  The optical film (b) is not particularly limited, but the width is preferably 1200 mm or more, more preferably 1300 mm or more, particularly preferably 2000 mm or more, and the thickness is preferably 30 to 60 μm, more preferably 35. ~ 55 μm.

  The optical film (b) has a variation in the in-plane retardation R0 (550) of preferably 2 nm or less, more preferably 1.5 nm or less, and even more preferably 1 nm or less over the entire film surface.

When the optical film (b) satisfies such characteristics, it is suitable for forming the polarizing plate (2).
The optical film (a) and the optical film (b) described above have little optical axis deviation, and can be suitably used as a set for liquid crystal panel applications by combining them.

Each of the optical film (a) and the optical film (b) described above has, for example, a width of 13
It is also suitable for the film roll to be 00 mm or more, more preferably 1500 mm or more, and still more preferably 2000 mm or more. In such an optical film (a) or (b), since the maximum refractive index direction is in the range of ± 1 degree in the width direction, a polarizer film roll having an absorption axis direction in the width direction, and a viscosity as necessary. A laminated film can be obtained by continuously laminating roll-to-roll through an adhesive. Such a laminated film can be suitably used as a polarizing plate by further laminating a protective film as necessary.

  Moreover, the film roll of an optical film (a) or an optical film (b), the film roll of a polarizer, and the film which can be used as a surface protection film, Preferably, the film roll of a triacetyl cellulose film is used as needed. Thus, the polarizing plate can be continuously produced by laminating with an adhesive. According to such a method, the polarizing plate (1) or (2) can be produced with high production efficiency.

Method for Producing Optical Films (a) and (b) The optical film (a) described above is obtained by uniaxially stretching a raw film made of a cyclic olefin resin under heating in the film longitudinal direction and then uniaxially stretching in the film width direction. It can manufacture suitably by doing. The optical film (b) can be preferably produced by uniaxially stretching a raw film made of a cyclic olefin resin in the film width direction.

  As the raw film, a film made of a cyclic olefin resin and having a film in-plane retardation R0 (550) of 20 nm or less, preferably 0 to 15 nm, more preferably 0 to 10 nm can be preferably used.

In the raw film, the maximum refractive index direction in the film plane is preferably in the range of 0 ± 30 degrees, more preferably in the range of 0 ± 20 degrees with respect to the film longitudinal direction.
This raw film is usually an unstretched film, and is obtained by forming a film or a sheet by dissolving a cyclic olefin resin in an appropriate solvent and casting it. It can also be obtained by forming a film by a known method such as a melt extrusion method.

  The raw film used for producing the optical film (a) or (b) is made of a cyclic olefin resin, so that optical properties such as transparency, chemical resistance, heat resistance, water resistance and moisture resistance are provided. Excellent balance. Although the thickness of the raw film is not particularly limited, the film thickness is usually 100 to 250 μm, preferably 120 to 220 μm, and the difference between the maximum thickness and the minimum thickness of the film is within 3 μm, preferably within 2 μm. It is desirable that

  When such a raw film is uniaxially stretched in the longitudinal direction of the film, it is preferable that the heating temperature at the time of stretching is precisely controlled over the entire stretched portion of the film. For example, the uniaxial stretching in the longitudinal direction, that is, the longitudinal uniaxial stretching, has a temperature distribution within a set temperature ± 0.6 ° C, preferably within a set temperature ± 0.4 ° C, more preferably within a set temperature ± 0.2 ° C. It is preferably done in a controlled oven.

  Here, the set temperature may be equal in all regions in the oven, or may be a temperature in which distribution is provided stepwise or in a gradient manner. When the set temperature is a temperature having a distribution, the actual temperature distribution in the oven and the set temperature distribution are within ± 0.6 ° C., preferably within ± 0.4 ° C., more preferably It is desirable to be within ± 0.2 ° C.

The set temperature of the uniaxial stretching in the longitudinal direction may be set depending on the type of the cyclic olefin resin constituting the film, the stretching ratio and the stretching speed, the thickness of the film, the desired retardation of the film after stretching, and the like. However, for example, it is usually in the range of (Tg−10 ° C.) to (Tg + 70 ° C.), preferably (Tg ±) based on the glass transition temperature (Tg) of the cyclic olefin resin constituting the raw film. 0 ° C.) to (Tg + 50 ° C.). Such a temperature range is preferable because the film can be stretched without causing thermal degradation and without breaking the film. Here, Tg is a value obtained using a differential scanning calorimeter (DSC).

  When the optical film (a) is produced, the draw ratio of the uniaxial stretching in the longitudinal direction is, for example, 1.3 to 3.0 times, preferably 1.4 to 2.8 times, particularly preferably 1.5 to 2.5. Double the range.

In the production of the optical film (a), the stretching speed of the uniaxial stretching in the longitudinal direction is, for example, in the range of 2 to 100 m / min, preferably 5 to 50 m / min.
When producing the optical film (a), the film uniaxially stretched in the longitudinal direction has a film in-plane retardation R0 (550) of usually 200 to 400 nm, preferably 250 to 400 nm, more preferably 300 to 400 nm. .

  The variation of the in-plane retardation R0 (550) in the film uniaxially stretched in the longitudinal direction is usually within ± 3 nm, preferably within ± 2 nm, and more preferably within ± 1 nm. Further, the maximum refractive index direction in the film plane of the film uniaxially stretched in the longitudinal direction is usually in the range of 0 ± 3 degrees, preferably in the range of 0 ± 2 degrees, more preferably 0 ± 1 with respect to the film longitudinal direction. In the range of degrees.

  When manufacturing the optical film (a), the film obtained by uniaxially stretching the original film in the longitudinal direction as described above is then uniaxially stretched in the width direction. Moreover, when manufacturing an optical film (b), a raw film is uniaxially stretched in the width direction. By performing this uniaxial stretching in the width direction, that is, lateral uniaxial stretching under temperature control more precise than uniaxial stretching in the longitudinal direction, an optical film (a) or optical film (b) that is homogeneous over the entire surface is suitably obtained. be able to. For example, uniaxial stretching in the width direction is performed in an oven in which the temperature distribution is controlled within a set temperature ± 0.5 ° C, preferably within a set temperature ± 0.3 ° C, more preferably within a set temperature ± 0.2 ° C. It is desirable to do it.

  Here, the set temperature of the uniaxial stretching in the width direction may be the same temperature in the whole region in the oven as in the case of the uniaxial stretching in the longitudinal direction, or a temperature in which the distribution is provided stepwise or in a gradient. Also good. When the set temperature is a temperature having a distribution, the actual temperature distribution in the oven and the set temperature distribution are within ± 0.5 ° C, preferably within ± 0.3 ° C, more preferably It is desirable to be within ± 0.2 ° C. The set temperature in the width direction uniaxial stretching may be the same as or different from the set temperature in the longitudinal direction uniaxial stretching process.

  The set temperature of the uniaxial stretching in the width direction is not particularly limited as in the case of the uniaxial stretching in the longitudinal direction. For example, usually, (Tg-10) on the basis of the glass transition temperature (Tg) of the cyclic olefin resin. ° C) to (Tg + 70 ° C), preferably (Tg ± 0 ° C) to (Tg + 50 ° C).

  The draw ratio of the uniaxial stretching in the width direction may be determined according to the desired characteristics of the optical film to be produced, but when producing the optical film (a), for example, 1.3 to 3.0 times, preferably 1 In the case of producing the optical film (b), for example, 1.5 to 4.0 times, preferably 1.times.2.8 times, particularly preferably 1.5 to 2.5 times. It is desirable to be in the range of 8 to 3.8 times, particularly preferably 2.0 to 3.5 times.

In the production of the optical film (a) and the optical film (b), the stretching speed of the uniaxial stretching in the width direction is, for example, 2 to 100 m / min, preferably 5 to 50 m / min.
In the production of the optical film (a), the obtained optical film (a) is stretched at a stretch ratio of, for example, 2.5 to 6.5 times, preferably 2.8 to 6.3 times with respect to the original film. It is desirable that This draw ratio is a product of the draw ratio of uniaxial stretching in the longitudinal direction and the draw ratio of uniaxial stretching in the width direction.

  The optical film (a) or the optical film (b) thus obtained has a variation in the in-plane retardation R0 (550) of preferably 2 nm or less, more preferably 1.5 nm or less over the entire film surface. More preferably, it is 1.0 nm or less. Further, when the angle between the maximum refractive index direction in the film plane and the film width direction is α degrees (optical film (a)) or β degrees (optical film (b)), α or β indicating an optical axis shift Is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less, and the product of α and R0 or the product of β and R0 is preferably 30 or less, more preferably 25 or less, and further Preferably it is 20 or less.

  In the method for producing such an optical film (a) or optical film (b), characteristics such as the type of cyclic olefin resin constituting the film, that is, monomer type, copolymerization ratio, molecular weight distribution, glass transition temperature, etc. are taken into consideration. Characteristics of the optical film obtained by selecting the selected cyclic olefin resin, selecting the set temperature in the oven, selecting the stretching ratio and stretching speed, etc. in each step of uniaxial stretching in the longitudinal direction and uniaxial stretching in the width direction of the film Can be controlled.

<Polarizing plate>
The polarizing plate (1) according to the present invention has the optical film (A) and the polarizer (i) described above, and the polarizing plate (2) includes the optical film (B) and the polarizer (ii) described above. ). Each of the polarizing plates (1) and (2) further has a protective film for protecting the polarizer as necessary.

In the polarizing plate (1) according to the present invention, the angle 90 + s (degrees) between the maximum refractive index direction in the film plane of the optical film (A) and the absorption axis direction of the polarizer (i) satisfies | s | ≦ 1. The product of the retardation R0 in the film plane of the optical film (A) and | s | is 30 or less, preferably 25 or less. In the polarizing plate (2) according to the present invention, the angle 90 + t (degree) between the maximum refractive index direction in the film plane of the optical film (B) and the absorption axis direction of the polarizer (ii) is | t | ≦ 1 and the product of retardation R0 in the film plane of the optical film (B) and | t | is 30 or less, preferably 25 or less.
Such polarizing plates (1) and (2) have little shift of the optical axis, and can be suitably used for liquid crystal panel applications by combining them.

The polarizer constituting the polarizing plate according to a polarizer present invention, can be used without limitation a film having a function as a polarizer, typically a polymer film, adsorbing and orienting iodine or a dichroic dye The polarizer formed by making it use is used. The polarizer constituting the polarizing plate of the present invention is preferably made of a polyvinyl alcohol (PVA) film.

  In the present invention, the polarizer (i) constituting the polarizing plate (1) and the polarizer (ii) constituting the polarizing plate (2) may be the same or different. Both are preferably made of a PVA film.

The polarizer made of a PVA film is not particularly limited as long as it has a function as a polarizer. For example, iodine is adsorbed to a PVA film, and then uniaxially stretched in a boric acid bath. PVA / iodine polarizing film obtained; PVA film obtained by diffusing and adsorbing a direct dye having high dichroism and then uniaxially stretching; PVA film adsorbing iodine and stretching to polyvinylene Structured PVA / polyvinylene polarizing film; PVA film with gold, silver, mercury, iron and other metals adsorbed on PVA film; PVA film with boric acid solution containing potassium iodide and sodium thiosulfate A near-ultraviolet polarizing film treated with a dichroic dye on the surface and / or inside of a PVA-based film comprising a modified PVA containing a cationic group in the molecule Such as the polarizing film can be given to.

  The method for producing a polarizer comprising a PVA-based film is not particularly limited. For example, a method of adsorbing iodine ions after stretching a PVA-based film; a method of stretching a PVA-based film after dyeing with a dichroic dye A method in which a PVA film is stretched and dyed with a dichroic dye; a method in which a dichroic dye is printed on a PVA film and then stretched; a method in which a PVA film is stretched and then a dichroic dye is printed. Can be mentioned. More specifically, iodine is dissolved in an iodine potassium solution to prepare higher-order iodine ions, the iodine ions are adsorbed on a PVA film and stretched, and then a 1 to 4% boric acid aqueous solution has a bath temperature of 30. A method for producing a polarizing film by immersing at ~ 40 ° C, or treating a PVA film with boric acid in the same manner and stretching it about 3 to 7 times in a uniaxial direction, and bathing in a 0.05 to 5% dichroic dye aqueous solution Examples include a method of producing a polarizing film by immersing at a temperature of 30 to 40 ° C. to adsorb a dye, drying at 80 to 100 ° C., and heat fixing.

  The polarizers (i) and (ii) according to the present invention preferably both have an absorption axis in the longitudinal direction (longitudinal direction). A polarizer having an absorption axis in the longitudinal direction can be produced by stretching a polymer film by longitudinal uniaxial stretching.

Protective Film Layer Each of the polarizing plates (1) and (2) according to the present invention may have a protective film layer as necessary in order to maintain the durability and mechanical properties of the polarizer. The protective film layer can be a film excellent in transparency, water resistance and low moisture absorption, and is not particularly limited. For example, triacetyl cellulose (TAC), polyethylene terephthalate resin, polycarbonate resin, acrylic A film made of a resin, an acrylic / styrene copolymer resin, a polyolefin resin, a norbornene resin resin, or the like is preferably used. In the present invention, among these, a film of triacetyl cellulose (TAC) can be preferably used.

  In the present invention, the polarizing plate (1) is preferably formed by laminating the optical film (A), the polarizer (i) and the protective film in this order, and the protective film is more preferably a triacetyl cellulose film. Moreover, it is preferable that a polarizing plate (2) is formed by laminating an optical film (B), a polarizer (ii), and a protective film in this order, and the protective film is more preferably a triacetyl cellulose film.

Adhesive / Adhesive In the present invention, when the polarizing plate (1) is produced by adhering the optical film (A) and the polarizer (i) and, if necessary, the protective film layer, the optical film ( When producing the polarizing plate (2) by adhering B) and the polarizer (ii), and further, if necessary, the protective film layer, a pressure-sensitive adhesive or an adhesive can be used as necessary. As the pressure-sensitive adhesive or adhesive, any one that does not inhibit the optical properties of the obtained polarizing plate after pressure-sensitive adhesion or adhesion is suitably used.

As the pressure-sensitive adhesive or adhesive, a water-based adhesive in which polyvinyl alcohol (PVA) is dissolved in water is preferably used. It is also preferable to use a pressure-sensitive adhesive having a polar group or an adhesive having a polar group (hereinafter, these are also collectively referred to as “polar group-containing adhesive”).

  Examples of polar groups possessed by the polar group-containing adhesive include halogen atoms and halogen atom-containing groups, carboxyl groups, carbonyl groups, hydroxyl groups, ester groups such as alkyl ester groups and aromatic ester groups, amino groups, amide groups, cyano groups. Group, ether group, acyl group, silyl ether group, thioether group and the like. Among these, a carboxyl group, a carbonyl group, a hydroxyl group, and an ester group are preferable. Moreover, it is preferable that a polar group containing adhesive is an aqueous adhesive or an aqueous adhesive. As a suitable polar group-containing adhesive used for attaching a specific resin film, an aqueous dispersion of an acrylate-based polymer can be exemplified.

  The acrylic ester polymer constituting the polar group-containing adhesive can be obtained by polymerizing a monomer composition containing an acrylic ester and a polar group-containing monomer. Examples of the acrylate ester include ethyl acrylate, propyl acrylate, cyclohexyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. The polar group-containing monomer has polar groups such as halogen atoms and halogen atom-containing groups, carboxyl groups, carbonyl groups, hydroxyl groups, ester groups such as alkyl ester groups and aromatic ester groups, amino groups, amide groups, A cyano group, an ether group, an acyl group, a silyl ether group, a thioether group, and the like can be mentioned. Of these, a carboxyl group, a carbonyl group, a hydroxyl group, and an ester group are preferable, and a hydroxyl group and a carboxyl group are particularly preferable. Specific examples of preferable polar group-containing monomers include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid, and methacrylic acid. The ratio of the acrylate ester used for the synthesis of the acrylate ester polymer to the polar group-containing monomer was such that the polar group-containing monomer was 0.1% relative to 100 parts by weight of the acrylate ester polymer. The amount is preferably about 5 to 15 parts by weight.

  Furthermore, it is preferable to use a diene monomer such as divinylbenzene as the monomer used for the synthesis of the acrylate polymer. An acrylic ester polymer obtained by polymerizing a composition containing an acrylic ester, a polar group-containing monomer, and a diene monomer can form a high-strength adhesive layer. Here, the amount of the diene monomer used is desirably 0 to 10 parts by weight with respect to 100 parts by weight of the acrylate polymer. When the usage-amount of a diene monomer exceeds 10 weight part, an adhesive layer or an adhesive bond layer will become hard.

  Examples of the polymerization method for obtaining the acrylic ester polymer include an emulsion polymerization method, a suspension polymerization method, and a solution polymerization method. If a nonpolar solvent such as toluene or xylene is used as the polymerization solvent, it is not preferable because, when the resulting pressure-sensitive adhesive is used, a deviation or the like tends to occur between the polarizer to be bonded and the optical film. .

  As the molecular weight of the acrylate ester-based polymer constituting the polar group-containing adhesive, the number average molecular weight (Mn) in terms of polystyrene measured by GPC analysis is preferably 5,000 to 500,000. The molecular weight distribution is preferably 10,000 to 200,000, and the weight average molecular weight (Mw) is preferably 15,000 to 1,000,000, more preferably 20,000 to 500,000. (Mw / Mn) is preferably 1.2 to 5, and more preferably 1.4 to 3.6.

The polar group-containing adhesive that can be used in the present invention may contain a crosslinking agent such as isocyanate or butylated melamine, an ultraviolet absorber, and the like. Here, the addition of the crosslinking agent to the polar group-containing adhesive is usually performed immediately before the polar group-containing adhesive is applied.

Manufacturing method of polarizing plate The polarizing plate (1) according to the present invention has an optical film (A) and a polarizer (i), and preferably the optical film (A), the polarizer (i), and the protective film. More preferably, the protective film is a triacetyl cellulose film. Further, the polarizing plate (2) according to the present invention has an optical film (B) and a polarizer (ii), and preferably an optical film (B), a polarizer (ii), and a protective film are laminated in this order. More preferably, the protective film is a triacetyl cellulose film.

Such polarizing plates (1) and (2) can be produced by adhering each film constituting each polarizing plate through an adhesive or a pressure-sensitive adhesive as necessary.
In the polarizing plate (1) or (2) according to the present invention, the optical film (A) or (B) is preferably adhered or bonded to one surface of the polarizer (i) or (ii) made of a PVA film or the like. It can be manufactured by laminating using an agent, heating and pressure bonding. More preferably, the polarizing plate (1) or (2) is formed by applying the optical film (A) or (B) to the polarizer (i) on one surface of the polarizer (i) or (ii) made of a PVA film or the like. Alternatively, a protective film such as a triacetyl cellulose film can be bonded to the surface on the opposite side of (ii) by using a pressure-sensitive adhesive or an adhesive, and this can be heated and pressure-bonded.

  In the production of the polarizing plate, the optical film (A) or (B) is bonded together so that the maximum refractive index direction in the film plane is orthogonal to the absorption axis of the polarizer (i) or (ii). .

  In the case where the optical films (A) and (B) according to the present invention are the optical films (a) and (b) obtained by the above-described preferred production method, the film is stretched in the width direction after stretching in the longitudinal direction. By stretching, the maximum refractive index direction in the film plane is the width direction and is usually obtained as a film roll. Therefore, a polarizer film roll having an absorption axis in the longitudinal direction, and a triacetyl cellulose film as necessary A protective film such as “roll to roll” can be continuously bonded. That is, the longitudinal direction of the optical film (A) or (B), the longitudinal direction of the polarizer (i) or (ii) having an absorption axis in the longitudinal direction, and a protective film such as a triacetyl cellulose film as necessary Are prepared, and these can be stuck continuously to produce a polarizing plate. In the case of producing a polarizing plate in this way, a retardation film having an optical axis in the longitudinal direction is cut according to the width of the polarizer, and then the direction of the retardation film is perpendicular to the absorption axis of the polarizer. As described above, it is possible to continuously manufacture a polarizing plate according to a conventional method that has to be individually bonded, and the manufacturing efficiency can be significantly improved.

<LCD panel>
The liquid crystal panel of the present invention has the polarizing plate (1) and the polarizing plate (2) described above. Preferably, the liquid crystal cell is composed of the polarizing plate (1) and the polarizing plate (2). It is desirable to have a sandwiched structure. More preferably, the structure is such that the polarizing plate (1) and the polarizing plate (2) are in this order from the backlight side, and the optical films (A) and (B) are on the liquid crystal panel side.

For example, the liquid crystal panel of the present invention comprises a polarizing plate (1) in which an optical film (A), a polarizer (i) and a triacetyl cellulose film are laminated in this order, an optical film (B), a polarizer (ii) and When the triacetyl cellulose film has the polarizing plate (2) laminated in this order, one side of the liquid crystal cell is bonded to the optical film (A) side surface of the polarizing plate (1), and the other side of the liquid crystal cell However, the structure adhered to the optical film (B) side surface of the polarizing plate (2) is preferably employed. For the adhesion between the liquid crystal cell and each polarizing plate, the above-mentioned pressure-sensitive adhesive or adhesive that can be used for production of the polarizing plate can be used. In addition, a pressure-sensitive adhesive layer may be further provided on the surface of each polarizing plate to be bonded to the liquid crystal cell in advance, thereby bonding the polarizing plate and the liquid crystal cell.

  The liquid crystal panel according to the present invention has a highly controlled optical performance over the entire surface, and even if it is a wide panel, the entire surface is homogeneous, so it is particularly suitable for applications such as a liquid crystal monitor equipped with a large display. Can be used.

  The liquid crystal panel of the present invention is excellent in display performance by having the polarizing plate (1) and the polarizing plate (2) described above, and the contrast ratio is preferably 4000 or more, more preferably 5000 or more, and further preferably 6000 or more. The difference between the maximum value and the minimum value is preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less on the entire panel surface. Can be.

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.
In the following examples or comparative examples, each property was measured or evaluated as follows.

(1) Measuring method of R0, Rxz and maximum refractive index direction Using “KOBRA-21ADH” manufactured by Oji Scientific Instruments Co., Ltd. The maximum refractive index direction was measured. The measurement was performed every 10 cm in the film width direction. From this, the angle (α degree and β degree) between the maximum refractive index direction and the film width direction is obtained, the product of R0 and | α | and the product of R0 and | β | Adopted as product value. Further, the polarizing plate is also measured every 10 cm in the film width direction, and the angles (90 + s degrees and 90 + t degrees) between the absorption axis of the polarizer and the maximum refractive index direction in the film plane are obtained, and R0 and | s | The product and the product of R0 and | t | were calculated, and the maximum value was adopted as the value of each product.

(2) Polarization degree of polarizing plate Using V-7300 manufactured by JASCO Corporation, the polarization degree of the polarizing plate was measured by making it incident from the adhesive / adhesive side of the optical film. In this measurement, the position of the polarizing plate corresponding to the measurement position in Measurement Example (1) was similarly measured every 10 cm.

(3) Contrast ratio measurement of liquid crystal display device The brightness, viewing angle, and contrast ratio of the liquid crystal panel were measured in a dark room with an illuminance of 1 lx or less using “EZ contrast-XL88” manufactured by ELDIM Corporation. In this measurement, the same position as that of the polarizing plate measured in the measurement example (2) was measured.

(4) Glass transition temperature (Tg )
Using a DSC6200 manufactured by Seiko Instruments Inc., the temperature increase rate was measured at 20 ° C. per minute under a nitrogen stream. Tg is the tangent line on the baseline starting from point B, plotting the differential peak scanning calorie maximum peak temperature (point A) and the temperature at −20 ° C. from the maximum peak temperature (point B) on the differential scanning calorimetry curve. And the intersection of the tangent starting from point A.

(5) Hydrogenation rate A magnetic magnetic resonance spectrometer (NMR) was an AVANCE 500 manufactured by Bruker, and ¹ H-NMR was measured using d-chloroform as a measurement solvent. 5.1-5.8 ppm vinylene group, 3
. The hydrogenation rate was calculated after calculating the monomer composition from the integrated value of 7 ppm methoxy group and 0.6 to 2.8 ppm aliphatic proton.

(6) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Gel permeation chromatography (manufactured by Tosoh Corporation HLC-8220GPC, column: Tosoh Corporation guard column _{H XL -H, TSK gelG7000H XL,} TSKgel GMH XL 2 present, sequentially connecting the TSK gel G2000H _XL, solvent: tetrahydrofuran Flow rate: 1 mL / min, sample concentration: 0.7 to 0.8% by weight, injection amount: 70 μL, measurement temperature: 40 ° C., detector: RI (40 ° C.), standard material: TSK manufactured by Tosoh Corporation Standard polystyrene) was used to measure the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn). The Mn is a number average molecular weight.

(7) Residual solvent amount The sample was dissolved in methylene chloride, and the resulting solution was analyzed using gas chromatography (Shimadzu GC-7A).

(8) Logarithmic viscosity Using an Ubbelohde viscometer, in chloroform (sample concentration: 0.5 g / dL), 30 ° C.
Measured with

(9) Saturated water absorption Based on ASTM D570, the sample was immersed in water at 23 ° C. for 1 week, and the change in weight before and after immersion was measured.

(10) total light transmittance was measured using a haze manufactured by Suga Test Instruments Co., Ltd. haze meter (HGM-2DP type).
(11) Film thickness distribution It measured using the film thickness distribution measuring apparatus (made by MOCON).

(12) NZ coefficient The NZ coefficient of the optical film (retardation film) is measured by “KOBRA-21ADH” manufactured by Oji Scientific Instruments Co., Ltd. The refractive index nx in the X-axis direction of the optical film, in the Y-axis direction It calculated | required by the following formula from refractive index ny and refractive index nz of the Z-axis direction.
NZ = (nx-nz) / (nx-ny)

[Preparation Example 1] (Preparation of cyclic olefin resin A)
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
Using 225 parts of 3-dodecene and 25 parts of bicyclo [2.2.1] hept-2-ene as monomers, 27 parts of 1-hexene (molecular weight regulator) and toluene (solvent for ring-opening polymerization reaction) ) Along with 750 parts, the reaction vessel was purged with nitrogen, and this solution was heated to 60 ° C. Next, in the solution in the reaction vessel, as a polymerization catalyst, 0.62 part of a toluene solution of triethylaluminum (1.5 mol / liter), tungsten hexachloride modified with tert-butanol and methanol (tert-butanol: methanol: tungsten) = 0.35 mol: 0.3 mol: 1 mol) of a toluene solution (concentration 0.05 mol / liter) 3.7 parts was added, and this solution was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction. A ring-opening polymer solution was obtained. The polymerization conversion rate in this polymerization reaction was 97%.

1,000 parts of the ring-opening polymer solution thus obtained was charged into an autoclave, and 0.12 part of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. Then, the hydrogenation reaction was performed by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C.

  After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover a coagulated product, which was dried to obtain a hydrogenated polymer (hereinafter referred to as “resin A”).

The hydrogenation rate measured by ¹ H-NMR of the resin A thus obtained was 99.9%.
, Tg measured by DSC method is 130 ° C., Mn by polystyrene conversion measured by GPC method is 20,800, Mw is 62,000, Mw / Mn is 3.00, and saturated water absorption at 23 ° C. is 0.21%. The logarithmic viscosity in chloroform at 30 ° C. was 0.51 dl / g.

[Preparation Example 2] (Preparation of cyclic olefin resin B)
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Using 1 part of dodecene (DNM), 15 parts of dicyclopentadiene (DCP), and 1 part of bicyclo [2.2.1] hept-2-ene (NB) as monomers, Along with 18 parts of hexene and 200 parts of toluene, the reaction vessel was purged with nitrogen and heated to 100 ° C.

To this, 0.005 part of triethylaluminum and 0.005 part of methanol-modified WCl ₆ (anhydrous methanol: PhPOCl ₂ : WCl ₆ = 103: 630: 427 weight ratio) were added and reacted for 1 minute, and then 10 parts of DCP and 3 parts of NB Was further added in 5 minutes, and the mixture was further reacted for 45 minutes to obtain a copolymer of DNM / DCP / NB = 69.77 / 26.01 / 4.23 (wt%).

Next, the obtained copolymer solution was placed in an autoclave, and 200 parts of toluene was further added. Next, 1 part of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a reaction modifier and RuHCl (CO) [P (C ₆ H ₅ )] as a hydrogenation catalyst _After adding 0.006 part of ₃ and heating to 155 ° C, hydrogen gas was charged into the reactor,
The pressure was 10 MPa. Thereafter, the reaction was carried out at 165 ° C. for 3 hours while maintaining the pressure at 10 MPa. After completion of the reaction, 100 parts by weight of toluene, 3 parts by weight of distilled water, 0.72 part by weight of lactic acid and 0.00214 parts by weight of hydrogen peroxide were added and heated at 60 ° C. for 30 minutes. Thereafter, 200 parts by weight of methanol was added and heated at 60 ° C. for 30 minutes. When this was cooled to 25 ° C., it was separated into two layers. Remove 500 parts by weight of the supernatant, add 350 parts by weight of toluene and 3 parts by weight of water again, heat at 60 ° C. for 30 minutes, then add 240 parts by weight of methanol, heat at 60 ° C. for 30 minutes, and cool to 25 ° C. Separated into two layers. Remove 500 parts by weight of the supernatant, add 350 parts by weight of toluene and 3 parts by weight of water, heat at 60 ° C. for 30 minutes, then add 240 parts by weight of methanol, heat at 60 ° C. for 30 minutes, and cool to 25 ° C. Separated into two layers. Finally, after removing 500 parts by weight of the supernatant, the remaining polymer solution was filtered using 2.0 μm, 1.0 μm, and 0.2 μm filters. Thereafter, the solid content of the polymer was concentrated to 55%, the solvent was removed at 250 ° C., 4 torr, and a residence time of 1 hour, and the polymer was passed through a 10 μm polymer filter to obtain a copolymer (hereinafter “resin B”). That said.) When the polymer solution before the solvent removal treatment was continuously filtered and the change in filtration rate with time was followed, the filter was not clogged after 1000 hours and the filtration rate did not decrease.

The hydrogenation rate measured by ¹ H-NMR of the resin B thus obtained was 99.9%.
, Tg measured by DSC method is 131 ° C., Mn by polystyrene conversion measured by GPC method is 16,000, Mw is 61,000, Mw / Mn is 3.81, and saturated water absorption at 23 ° C. is 0.18%. The logarithmic viscosity in chloroform at 30 ° C. was 0.52 dl / g.

[Preparation Example 3] (Preparation of aqueous adhesive)
A reaction vessel was charged with 250 parts of distilled water, and 90 parts of butyl acrylate, 8 parts of 2-hydroxyethyl methacrylate, 2 parts of divinylbenzene, and 0.1 part of potassium oleate were added to the reaction vessel. The dispersion was stirred with a stirring blade made of Teflon (registered trademark).

  After replacing the inside of the reaction vessel with nitrogen, the temperature of the system was raised to 50 ° C., and 0.2 part of potassium persulfate was added to initiate polymerization. After 2 hours, 0.1 part of potassium persulfate was further added, the system was heated to 80 ° C., and the polymerization reaction was continued for 1 hour to obtain a polymer dispersion.

  Next, by using an evaporator, the polymer dispersion is concentrated until the solid content concentration becomes 70%, whereby an aqueous adhesive (adhesive having a polar group) composed of an aqueous dispersion of an acrylic ester polymer. Got.

  The acrylic ester polymer constituting the water-based pressure-sensitive adhesive thus obtained was measured for polystyrene-reduced number average molecular weight (Mn) and weight average molecular weight (Mw) by the GPC method (solvent: tetrahydrofuran). Mn was 69,000, Mw was 135,000, and the logarithmic viscosity measured in chloroform at 30 ° C. was 1.2 dl / g.

[Production Example 1] (Production of raw film A)
Resin A obtained in Preparation Example 1 is dissolved in toluene so as to have a concentration of 30% (solution viscosity at room temperature is 30,000 mPa · s), and pentaerythrityl tetrakis [3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate] was added in an amount of 0.1 part by weight with respect to 100 parts by weight of the resin, and a metal fiber sintered filter having a pore diameter of 5 μm manufactured by Nippon Pole was used. Filtration was performed while controlling the flow rate of the solution so that it was within 4 MPa.

  The resin solution produced by the above method is extruded downstream using a gear pump while degassing toluene with a 3-stage vent using a twin screw extruder (manufactured by Toshiba Machine Co., Ltd .; TEM-48). The resin flown out of the strand die was cooled in a cooling water tank, then sent to a strand cutter, and cut into rice grains to obtain a granulated resin.

  This granulated resin was dried at 100 ° C. for 4 hours in a nitrogen atmosphere, then sent to a single-screw extruder (90 mmΦ), and melted at 260 ° C., and quantitative extrusion was performed with a gear pump, with a nominal opening of 10 μm. Using a metal fiber sintered filter manufactured by Nippon Seisen Co., Ltd., melt filtration is performed, and a coat hanger die (1700 mm width) is used to form a film at 260 ° C. with a gap at the coat hanger die outlet of 0.5 mm. Extruded. The die land length (the length of the parallel part of the die exit) of the die used at this time was 20 mm. The distance from the die exit to the roll crimping point is set to 65 mm, and the extruded film is sandwiched between a 250 mmφ mirror surface roll with a surface roughness of 0.1 S and a metal belt with a thickness of 0.3 mm to gloss the film surface. Transferred to the surface. The metal belt (width 1650 mm) is held by a rubber-coated roll (the diameter of the roll to be held is 150 mmΦ) and a cooling roll (roll diameter 150 mm), and a commercially available sleeve type transfer roll (manufactured by Chiba Machine Industry) is used. And transcribed. The roll interval during transfer was 0.35 mm, and the transfer pressure was 0.35 MPa.

  The peripheral speed of the outer periphery of the mirror surface roll at this time was 10 m / min. At this time, the temperature of the mirror surface roll was set to 125 ° C. using an oil temperature controller, and the temperature of the rubber coating roll was set to 115 ° C.

  A cooling roll 1 having a diameter of 250 mm is arranged on the downstream side of the mirror surface roll, and the film peeled off from the mirror surface roll is cooled for 2.1 seconds until the film is pressure-bonded to the cooling roll 1 set at 115 ° C. .

  After the cooling roll 2, the film is peeled off at a peeling tension of 0.4 MPa · cm, a masking film is bonded on one side, wound up by a winder, and a resin having a thickness of 150 μm, a width of 1500 mm and a length of 2000 m A film was obtained (hereinafter referred to as “resin film A”). The residual solvent amount of the obtained film was 0.1%, the total light transmittance was 93%, and the glass transition temperature (Tg) was 130 ° C. The film thickness variation was 1 μm (0.7%).

[Production Example 2] (Production of raw film B)
A resin film having a thickness of 150 μm, a width of 1500 mm, and a length of 2000 m was obtained in the same manner as in Production Example 1 except that the resin B obtained in Preparation Example 2 was used in place of the resin A (hereinafter referred to as “resin film”). B ”). The film obtained had a residual solvent amount of 0.1%, a total light transmittance of 93%, and a glass transition temperature (Tg) of 131 ° C. The film thickness variation was 1 μm (0.7%).

[Production Example 3] (Production of polarizer)
A film made of roll-shaped polyvinyl alcohol (hereinafter also referred to as “PVA”) having a thickness of 120 μm is a 30 ° C. aqueous solution having an iodine concentration of 0.03% by weight and a potassium iodide concentration of 0.5% by weight. In the dye bath, the aqueous solution having a boric acid concentration of 5% by weight and a potassium iodide concentration of 8% by weight at 55 ° C. was continuously uniaxially stretched (pre-stretched) in the longitudinal direction at a stretching ratio of 3 times. In the cross-linking bath, the film was further uniaxially stretched (post-stretched) in the longitudinal direction at a stretch ratio of 2 times, dried and wound up to obtain a roll-shaped polarizer (used as polarizers (i) and (ii)). .

[Example 1]
Using the resin film A obtained in Production Example 1, in the tank in which the temperature distribution in the stretching machine furnace is controlled within 153 ± 0.2 ° C., the furnace speed is 8.0 m / min and the length is 2.2. The film was uniaxially stretched in the film longitudinal direction without fixing the film width direction to obtain a uniaxially stretched film having R0 of 351 nm, R0 variation of ± 3 nm, and optical axis of 0 ± 1 degree with respect to the film longitudinal direction. Further, using the obtained uniaxially stretched film, in a tenter in which the temperature distribution in the stretching machine furnace is controlled within 143 ± 0.2 ° C., the furnace speed is 8.0 m / min in the direction perpendicular to the film longitudinal direction. 2.3 times uniaxial stretching with the film longitudinal direction fixed, slitting both ends of the film, R0 20.5 nm, R0 variation ± 0.8 nm, Rxz 196 nm, Rxz variation ± 1. A roll-shaped optical film (a) -1 having a product of 4 nm, an angle α with respect to the film width direction and R0 of 8.1 to 18.5 nm, a film width of 2000 mm, and a length of 2000 m was obtained.

  Similarly, a film in which the resin film A is previously slit to a width of 750 mm is used, and the in-furnace speed is 8.0 m in a tenter-conveying horizontal stretching furnace in which the temperature distribution in the stretching machine furnace is controlled within 155 ± 0.2 ° C. Uniaxial stretching in the film width direction with the film longitudinal direction fixed at a magnification of 3.1 times in the direction perpendicular to the film longitudinal direction at / min, R0 is 100.0 nm, R0 variation is 1.0 nm, Rxz is 130 nm, An optical film (b) -1 having a variation of Rxz of 1.2 nm, a product of an angle β with respect to the film width direction and R0 of 0 to 20.0 nm, a film width of 2000 mm, and a length of 1800 m was obtained.

[Example 2]
Using the resin film B obtained in Production Example 2, in the tank in which the temperature distribution in the stretching machine furnace is controlled within 154 ± 0.2 ° C., the furnace speed is 8.0 m / min and the length is 2.2. The film was uniaxially stretched in the longitudinal direction of the film without fixing the film width direction to obtain a uniaxially stretched film having R0 of 352 nm, a variation of R0 of ± 3 nm, and an optical axis of 0 ± 1 degree with respect to the longitudinal direction of the film. Further, using the obtained uniaxially stretched film, the temperature distribution in the stretching machine furnace was controlled within 144 ± 0.2 ° C., and the furnace speed was 8.0 m / min in the direction perpendicular to the film longitudinal direction. The film was uniaxially stretched with the film longitudinal direction fixed to 2.4 times, slitted at both ends of the film, R0 was 20.2 nm, R0 variation was ± 0.7 nm, and Rxz was 198 nm.
An optical film (a) -2 having a variation of Rxz of 2.1 nm and an angle α with respect to the film width direction of R0 of 0 to 20.0 nm was obtained.

  Similarly, a film in which a resin film B is slit in advance to a width of 750 mm is used, and the in-furnace speed is 8.0 m in a tenter-conveying horizontal stretching furnace in which the temperature distribution in the stretching machine furnace is controlled within 155 ± 0.2 ° C. Uniaxial stretching in the film width direction with the film longitudinal direction fixed to 3.0 times in the direction perpendicular to the film longitudinal direction at / min, R0 is 100.4 nm, R0 variation is ± 0.9 nm, and Rxz is 131 nm. A roll-shaped optical film (b) -2 having a variation of Rxz of ± 1.1 nm, a product of an angle β with the film width direction and R0 of 0 to 20.1, a film width of 2000 mm, and a length of 1800 m was obtained. .

[Example 3]
Using the resin film A obtained in Production Example 1, in a tank controlled within 152 ± 0.2 ° C. by the temperature distribution in the stretching machine furnace, the furnace speed was 8.0 m / min and the length was 2.2. Double uniaxially stretched in the film longitudinal direction without fixing the film width direction to obtain a uniaxially stretched film having R0 of 362 nm, R0 variation of ± 3 nm, and optical axis of 0 ± 1 degree with respect to the film longitudinal direction. Further, using the obtained uniaxially stretched film, the temperature distribution in the stretching machine furnace was controlled within 141 ± 0.2 ° C., and the furnace speed was 8.0 m / min in the direction perpendicular to the film longitudinal direction. The film was uniaxially stretched with the film longitudinal direction fixed 2.4 times, and both ends of the film were slit, R0 was 41.1 nm, R0 variation was ± 0.7 nm, Rxz was 198 nm, and Rxz variation was ± 1. A roll-shaped optical film (a) -3 having a film width of 2000 mm and a length of 2000 m having a product of 8 nm, an angle α with respect to the film width direction and R0 of 12.3 to 20.5 and a length of 2000 m was obtained.

  Similarly, a film in which the resin film A is previously slit to a width of 750 mm is used, and the in-furnace speed is 8.0 m in a tenter-conveying horizontal stretching furnace in which the temperature distribution in the stretching machine furnace is controlled within 154 ± 0.2 ° C. Uniaxially stretching in the film width direction with the film longitudinal direction fixed to 3.0 times in the direction perpendicular to the film longitudinal direction at / min, R0 is 100.9 nm, R0 variation is ± 0.8 nm, and Rxz is 131 nm. A roll-shaped optical film (b) -3 having a film width of 2000 mm and a length of 1800 m with a variation of Rxz of ± 2.5 nm and a product of the angle β to the film width direction and R0 of 10.1 to 20.2. Obtained.

[Comparative Example 1]
Using the resin film A obtained in Production Example 1, in the layer in which the temperature distribution in the stretching machine furnace is controlled within 153 ± 0.7 ° C., the furnace speed is 8.0 m / min and the vertical direction is 2.2 times. Further, the film was uniaxially stretched in the film longitudinal direction without fixing the film width direction to obtain a uniaxially stretched film having R0 of 352 nm, R0 variation of ± 3 nm, and an optical axis of 0 ± 3 degrees with respect to the film longitudinal direction. Further, using the obtained uniaxially stretched film, the temperature distribution in the stretching machine furnace was controlled within 143 ± 0.6 ° C. and the furnace speed was 8.0 m / min. .3 times, uniaxial stretching with the film longitudinal direction fixed, slitting both ends of the film, R0 is 20.2 nm, R0 variation is ± 3.6 nm, Rxz is 195 nm, Rx
A roll-shaped optical film (a) -4 having a film width of 2000 mm and a length of 2000 m with a variation of z of ± 5.1 nm, a product of the angle α with the film width direction and R0 of 6.1 to 60.2, and a length of 2000 m was obtained. .

  Similarly, a film in which the resin film A is previously slit to a width of 750 mm is used, and the in-furnace speed is 8.0 m in a tenter-conveying horizontal stretching furnace in which the temperature distribution in the stretching machine furnace is controlled within 155 ± 0.6 ° C. Uniaxial stretching in the film width direction with the film longitudinal direction fixed at a magnification of 3.1 times in the direction perpendicular to the film longitudinal direction at / min, R0 is 100.6 nm, R0 variation is ± 1.5 nm, and Rxz is 129 nm A roll-shaped optical film (b) -4 having a film width of 2000 mm and a length of 1800 m having a variation of Rxz of ± 4.1 nm and a product of the angle β with the film width direction of R0 of 10.2 to 30.2. Obtained.

[Comparative Example 2]
Using the resin film A obtained in Production Example 1, in the layer in which the temperature distribution in the stretching machine furnace is controlled within 152 ± 0.7 ° C., the furnace speed is 8.0 m / min and the vertical direction is 2.2 times. Further, the film was uniaxially stretched in the film longitudinal direction without fixing the film width direction to obtain a uniaxially stretched film having R0 of 364 nm, R0 variation of ± 4 nm, and optical axis of 0 ± 3 degrees with respect to the film longitudinal direction. Further, using the obtained uniaxially stretched film, the temperature distribution in the stretching machine furnace was controlled within 141 ± 0.7 ° C., and the speed in the furnace was 8.0 m / min. .4 times, uniaxial stretching with the film longitudinal direction fixed, slitting both ends of the film, R0 is 40.3 nm, R0 variation is ± 2.6 nm, Rxz is 210 nm, Rxz variation is ± 4.8 nm, A roll-shaped optical film (a) -5 having a film width of 2000 mm and a length of 2000 m having a product of the angle α and R0 with the film width direction of 8.2 to 71.4 was obtained.

  Similarly, a film in which the resin film A is previously slit to a width of 750 mm is used, and the in-furnace speed is 8.0 m in a tenter-conveying horizontal stretching furnace in which the temperature distribution in the stretching machine furnace is controlled within 157 ± 0.7 ° C. Uniaxial stretching in the film width direction with the film longitudinal direction fixed 2.1 times in a direction perpendicular to the film longitudinal direction at / min, R0 is 75.0 nm, R0 variation is ± 2.2 nm, and Rxz is 115 nm A roll-shaped optical film (b) -5 having a film width of 2000 mm and a length of 1800 m having a variation of Rxz of ± 3.1 nm and an angle β with the film width direction of 0 to 37.5 and a product of 0 to 37.5 was obtained. .

[Comparative Example 3]
Using resin film B obtained in Production Example 2, the temperature distribution in the stretching machine furnace is 2.1 times in the longitudinal direction at a furnace speed of 8.0 m / min in a layer controlled within 153 ± 1.0 ° C. Further, the film was uniaxially stretched in the film longitudinal direction without fixing the film width direction to obtain a uniaxially stretched film having an R0 of 256 nm, a variation of R0 of ± 4 nm, and an optical axis of 0 ± 4 degrees with respect to the film longitudinal direction. Further, using the obtained uniaxially stretched film, the temperature distribution in the stretching machine furnace was controlled within 140 ± 0.7 ° C., and the speed in the furnace was 8.0 m / min. .4 times, uniaxial stretching with the film longitudinal direction fixed, slitting both ends of the film, R0 is 58.1 nm, R0 variation is ± 2.7 nm, Rxz is 256 nm, Rxz variation is ± 7.1 nm, A roll-shaped optical film (a) -6 having a film width of 2000 mm and a length of 2000 m with a product of the angle α and R0 with the film width direction of 5.9 to 46.8 nm was obtained.

  Similarly, a film in which a resin film B is slit in advance to a width of 750 mm is used, and the in-furnace speed is 8.0 m in a tenter-conveying horizontal stretching furnace in which the temperature distribution in the stretching machine furnace is controlled within 155 ± 0.7 ° C. Uniaxially stretching in the film width direction with the film longitudinal direction fixed 2.2 times in the direction perpendicular to the film longitudinal direction at / min, R0 is 75.1 nm, R0 variation is ± 1.9 nm, and Rxz is 115 nm. A roll-shaped optical film (b) -6 having a film width of 2000 mm and a length of 1800 m, wherein the variation of Rxz is ± 4.3 nm and the product of the angle β with the film width direction and R0 is 7.5 to 45.1. Obtained.

[Comparative Example 4]
Using the resin film B obtained in Production Example 2, in the layer in which the temperature distribution in the stretching machine furnace is controlled within 154 ± 1.0 ° C., the furnace speed is 8.0 m / min and the vertical direction is 2.2 times. Further, the film was uniaxially stretched in the film longitudinal direction without fixing the film width direction to obtain a uniaxially stretched film having R0 of 346 nm, R0 variation of ± 4 nm, and optical axis of 0 ± 4 degrees with respect to the film longitudinal direction. Further, using the obtained uniaxially stretched film, the temperature distribution in the stretching machine furnace was controlled within 144 ± 1.0 ° C., and the speed in the furnace was 8.0 m / min. .4 times, uniaxial stretching with the film longitudinal direction fixed, slitting both ends of the film, R0 is 21.2 nm, R0 variation is ± 4.2 nm, Rxz is 206 nm, Rxz variation is ± 6.7 nm, A roll-shaped optical film (a) -7 having a film width of 2000 mm and a length of 2000 m with a product of an angle α and R0 with the film width direction of 2.2 to 63.6 nm was obtained.

  Similarly, a film in which the resin film B is slit in advance to a width of 750 mm is used, and the in-furnace speed is 8.0 m in a tenter-conveying horizontal stretching furnace in which the temperature distribution in the stretching machine is controlled within 152 ± 1.0 ° C. Uniaxial stretching in the film width direction with the film longitudinal direction fixed to 3.0 times in the direction perpendicular to the film longitudinal direction at / min, R0 is 99.8 nm, R0 variation is ± 3.1 nm, and Rxz is 130 nm. A roll-shaped optical film (b) -7 having a film width of 2000 mm and a length of 1800 m with a variation of ± 4.9 nm and an angle β with the film width direction of R0 of 9.7 to 58.2 was obtained. .

[Example 4] (Production of polarizing plate)
The optical film (a) -1 obtained in Example 1 is arranged so that a roll-shaped film is aligned on one side of the polarizer obtained in Production Example 4 (exists in the absorption axis of the polarizer and the width direction of the optical film). The optical axes are perpendicular to each other), and the above-mentioned water-based adhesive is used to continuously stick both together, and a film made of triacetyl cellulose (hereinafter also referred to as “TAC”) having a thickness of 80 μm is provided on the other surface. A polarizing plate (1) -1 was obtained by sticking using an adhesive composed of a PVA aqueous solution having a concentration of 5%. When the transmittance and degree of polarization of the obtained polarizing plate were examined, they were 44.0% and 99.9%, respectively. Further, the angle 90+ | s | (degree) of the optical axis deviation between the absorption axis direction of the polarizer and the optical film was examined, and the product of the in-plane retardation R0 (550) of the film and | s | 0.1-18.5.

[Example 5] (Production of polarizing plate)
In Example 4, in place of the optical film (a) -1, the optical film (b) -1 obtained in Example 1 was used, except that the polarizing plate (2)- 1 was obtained. When the transmittance and degree of polarization of the obtained polarizing plate were examined, they were 44.0% and 99.9%, respectively. Further, the angle 90+ | t | (degree) of the optical axis deviation between the absorption axis direction of the polarizer and the optical film was examined, and the product of the in-plane retardation R0 (550) of the film and | t | ~ 20.0.

[Example 6] (Production of liquid crystal panel)
In order to evaluate the characteristics of the polarizing plates obtained in Examples 5 and 6, polarizing plates and retardation films attached to the front and back of the liquid crystal panel of Samsung Electronics Co., Ltd. (model number LN40R81BD) on the viewer side The polarizing plate (1) -1 obtained in Example 4 was originally attached to the back surface, and the polarizing plate (2) -1 obtained in Example 5 was originally attached to the front surface. The film was attached so that the optical film (retardation film) of the polarizing plate was on the liquid crystal cell side in the same manner as the transmission axis of the polarizing plate.

When the front contrast ratio of the liquid crystal television having this polarizing plate was confirmed, it was a high value of 5950 at the minimum value and 6320 at the maximum value, and no unevenness was visually observed. Further, when viewing angles (regions with a contrast ratio of 10 or more) were confirmed in all directions, it was confirmed that the angles were 175 degrees or more in all directions, up and down, left and right, and oblique directions. In addition, when the color shift phenomenon at a polar angle of 0 to 80 degrees was visually confirmed at an azimuth angle of 45 degrees in the black display state, it was satisfactory without color loss.

[Example 7] (Production of polarizing plate)
In Example 4, in place of the optical film (a) -1, the optical film (a) -2 obtained in Example 2 was used, except that the polarizing plate (1)- 2 was obtained. The transmittance of the obtained polarizing plate, the degree of polarization, and the angle 90+ | s | (degree) of the optical axis deviation between the absorption axis direction of the polarizer (i) and the optical film are examined, and the in-plane retardation R0 (550) of the film ) And | s | were 44.0%, 99.99%, and 4.4 to 22.2, respectively.

[Example 8] (Production of polarizing plate)
In Example 5, in place of the optical film (b) -1, the optical film (b) -2 obtained in Example 2 was used, and the polarizing plate (2)- 2 was obtained. The transmittance of the obtained polarizing plate, the degree of polarization, and the angle 90+ | t | (degree) of the optical axis deviation between the absorption axis direction of the polarizer (ii) and the optical film were examined, and the in-plane retardation R0 (550) of the film ) And | t | were 44.0%, 99.98-99.99% and 0-20.1, respectively.

[Example 9] (Production of liquid crystal panel)
In Example 6, instead of the polarizing plate (1) -1, the polarizing plate (1) -2 obtained in Example 7 was used, and the polarizing plate obtained in Example 8 instead of the polarizing plate (2) -1. Except having used board (2) -2, it bonded to the liquid crystal panel similarly to Example 6, and evaluated. The front contrast ratio was 5870 at the minimum value and 6120 at the maximum value, and no unevenness was visually observed.

[Example 10] (Production of polarizing plate)
In Example 4, in place of the optical film (a) -1, the optical film (a) -3 obtained in Example 3 was used, except that the polarizing plate (1)- 3 was obtained. The transmittance of the obtained polarizing plate, the degree of polarization, and the angle 90+ | s | (degree) of the optical axis deviation between the absorption axis direction of the polarizer (i) and the optical film were examined, and the in-plane retardation R0 (550) of the film ) And | s | were 44.0%, 99.99%, and 12.3 to 20.5, respectively.

[Example 11] (Production of polarizing plate)
In Example 5, in place of the optical film (b) -1, the optical film (b) -3 obtained in Example 3 was used, except that the polarizing plate (2)- 3 was obtained. The transmittance of the obtained polarizing plate, the degree of polarization, and the angle 90+ | t | (degree) of the optical axis deviation between the absorption axis direction of the polarizer (ii) and the optical film were examined, and the in-plane retardation R0 (550) of the film ) And | t | were 44.0%, 99.98-99.99%, and 10.20.2, respectively.

[Example 12] (Production of liquid crystal panel)
In Example 6, the polarizing plate (1) -1 obtained in Example 10 was used instead of the polarizing plate (1) -1, and the polarizing plate obtained in Example 11 instead of the polarizing plate (2) -1. Except having used board (2) -3, it bonded to the liquid crystal panel similarly to Example 6, and evaluated. The front contrast ratio was 5550 at the minimum value and 5980 at the maximum value, and no unevenness was visually observed.

[Comparative Example 5] (Production of polarizing plate)
In Example 4, in place of the optical film (a) -1, the optical film (a) -4 obtained in Comparative Example 1 was used, except that the polarizing plate (1)- 4 was obtained. The transmittance of the obtained polarizing plate, the degree of polarization, and the angle 90+ | s | (degree) of the optical axis deviation between the absorption axis direction of the polarizer (i) and the optical film were examined, and the in-plane retardation R0 (550) of the film ) And | s | were 44.0%, 99.87-99.99%, and 6.1-60.2, respectively.

[Comparative Example 6] (Production of polarizing plate)
In Example 5, in place of the optical film (b) -1, the optical film (b) -4 obtained in Comparative Example 1 was used, except that the polarizing plate (2)- 4 was obtained. The transmittance of the obtained polarizing plate, the degree of polarization, and the angle 90+ | t | (degree) of the optical axis deviation between the absorption axis direction of the polarizer (ii) and the optical film were examined, and the in-plane retardation R0 (550) of the film ) And | t | were found to be 44.0%, 99.92 to 99.99%, and 10.2 to 30.2, respectively.
Met.

[Comparative Example 7] (Production of liquid crystal panel)
In Example 6, the polarizing plate (1) -1 obtained in Comparative Example 5 was used in place of the polarizing plate (1) -1, and the polarizing plate obtained in Comparative Example 6 was used instead of the polarizing plate (2) -1. Except having used board (2) -4, it bonded to the liquid crystal panel similarly to Example 6, and evaluated. The front contrast ratio was 3110 at the minimum value and 5120 at the maximum value, and unevenness was visually observed.

[Comparative Example 8] (Production of polarizing plate)
In Example 4, in place of the optical film (a) -1, the optical film (a) -5 obtained in Comparative Example 2 was used, except that the polarizing plate (1)- 5 was obtained. The transmittance of the obtained polarizing plate, the degree of polarization, and the angle 90+ | s | (degree) of the optical axis deviation between the absorption axis direction of the polarizer (i) and the optical film were examined, and the in-plane retardation R0 (550) of the film ) And | s | were 44.0%, 99.79-99.99%, and 8.2-71.4, respectively.

[Comparative Example 9] (Production of polarizing plate)
In Example 5, in place of the optical film (b) -1, the optical film (b) -5 obtained in Comparative Example 2 was used, except that the polarizing plate (2)- 5 was obtained. The transmittance of the obtained polarizing plate, the degree of polarization, and the angle 90+ | t | (degree) of the optical axis deviation between the absorption axis direction of the polarizer (ii) and the optical film were examined, and the in-plane retardation R0 (550) of the film ) And | t | were 44.0%, 99.91 to 99.99%, and 0 to 37.5, respectively, and unevenness was visually observed.

[Comparative Example 10] (Production of liquid crystal panel)
In Example 6, the polarizing plate (1) -1 obtained in Comparative Example 8 was used instead of the polarizing plate (1) -1, and the polarizing plate obtained in Comparative Example 9 was used instead of the polarizing plate (2) -1. Except having used board (2) -5, it bonded to the liquid crystal panel similarly to Example 6, and evaluated. The front contrast ratio was 2990 at the minimum value and 4760 at the maximum value, and unevenness was confirmed visually.

[Comparative Example 11] (Production of Polarizing Plate)
In Example 4, in place of the optical film (a) -1, the optical film (a) -6 obtained in Comparative Example 3 was used, except that the polarizing plate (1)- 6 was obtained. The transmittance of the obtained polarizing plate, the degree of polarization, and the angle 90+ | s | (degree) of the optical axis deviation between the absorption axis direction of the polarizer (i) and the optical film were examined, and the in-plane retardation R0 (550) of the film ) And | s | were 44.0%, 99.90-99.99% and 5.9-46.8, respectively.

[Comparative Example 12] (Production of polarizing plate)
In Example 5, in place of the optical film (b) -1, the optical film (b) -6 obtained in Comparative Example 3 was used, except that the polarizing plate (2)- 6 was obtained. The transmittance of the obtained polarizing plate, the degree of polarization, and the angle 90+ | t | (degree) of the optical axis deviation between the absorption axis direction of the polarizer (ii) and the optical film were examined, and the in-plane retardation R0 (550) of the film ) And | t | were 44.0%, 99.91 to 99.99%, and 7.5 to 45.1, respectively, and unevenness was visually observed.

[Comparative Example 13] (Production of liquid crystal panel)
In Example 6, instead of the polarizing plate (1) -1, the polarizing plate (1) -6 obtained in Comparative Example 11 was used, and the polarizing plate obtained in Comparative Example 12 instead of the polarizing plate (2) -1. Except having used board (2) -6, it bonded to the liquid crystal panel similarly to Example 6, and evaluated. The front contrast ratio was 3420 at the minimum value and 4110 at the maximum value, and unevenness was visually observed.

[Comparative Example 14] (Production of polarizing plate)
In Example 4, in place of the optical film (a) -1, the optical film (a) -7 obtained in Comparative Example 4 was used, except that the polarizing plate (1)- 7 was obtained. The transmittance of the obtained polarizing plate, the degree of polarization, and the angle 90+ | s | (degree) of the optical axis deviation between the absorption axis direction of the polarizer (i) and the optical film were examined, and the in-plane retardation R0 (550) of the film ) And | s | were 44.0%, 99.78-99.99% and 2.2-63.6, respectively.

[Comparative Example 15] (Production of polarizing plate)
In Example 5, in place of the optical film (b) -1, the optical film (b) -7 obtained in Comparative Example 4 was used, and the polarizing plate (2)- 7 was obtained. The transmittance of the obtained polarizing plate, the degree of polarization, and the angle 90+ | t | (degree) of the optical axis deviation between the absorption axis direction of the polarizer (ii) and the optical film were examined, and the in-plane retardation R0 (550) of the film ) And | t | were 44.0%, 99.88 to 99.99% and 9.7 to 58.2, respectively.

[Comparative Example 16] (Production of liquid crystal panel)
In Example 6, instead of the polarizing plate (1) -1, the polarizing plate (1) -7 obtained in Comparative Example 14 was used, and the polarizing plate obtained in Comparative Example 15 instead of the polarizing plate (2) -1. Except having used board (2) -7, it bonded to the liquid crystal panel similarly to Example 6, and evaluated. The front contrast ratio was 2530 at the minimum value and 4210 at the maximum value, and unevenness was visually observed.

The optical film and optical film set of the present invention are suitably used for the production of liquid crystal panels, and the liquid crystal panels of the present invention can be used for various liquid crystal display devices such as mobile phones, notebook computers, car navigation systems, and liquid crystal televisions. it can. The liquid crystal panel according to the present invention has a highly controlled optical performance over the entire surface, and since the entire surface is uniform even with a wide panel, it is particularly suitable for applications such as a liquid crystal monitor equipped with a large display. Can be used.

Claims (7)

The following optical film (A) and polarizer (i) are included, and the angle 90 + s (degree) between the maximum refractive index direction in the film plane of the optical film (A) and the absorption axis direction of the polarizer (i) is | Polarizing plate (1) satisfying s | ≦ 1, and having a product of retardation R0 (nm) in the film plane of optical film (A) and | s |
The following optical film (B) and polarizer (ii) are included, and the angle 90 + t (degree) between the maximum refractive index direction in the film plane of the optical film (B) and the absorption axis direction of the polarizer (ii) is | A liquid crystal characterized by having a retardation R0 (nm) in the film plane of the optical film (B) and a polarizing plate (2) having a product of | t | panel.
Optical film (A): made of cyclic olefin resin,
The retardation R0 in the film plane is 15 to 60 nm, and
An optical film having a retardation Rxz in the film thickness direction of 150 to 250 nm.
Optical film (B): made of a cyclic olefin resin,
The in-plane retardation R0 is 70 to 120 nm,
An optical film having a ratio (Rxz / R0) of retardation Rxz to R0 in the film thickness direction of 1.2 to 1.5.
(Here, the retardation R0 in the film plane and the retardation Rxz in the film thickness direction are the maximum refractive index in the film plane at a light wavelength of 550 nm, nx, and in the direction orthogonal to nx in the film plane, respectively. (If the refractive index is ny and the film thickness is d (nm), this is a value determined by the formula R0 = (nx−ny) × d and the formula Rxz = (nx−nz) × d). 2. The liquid crystal panel according to claim 1, wherein the cyclic olefin-based resin constituting the optical film (A) and the optical film (B) has a structural unit represented by the following formula (I).

[In the formula (I), m is an integer of 1 or more, p is 0 or an integer of 1 or more, D is a group represented by —CH═CH— or —CH ₂ CH ₂ —, R ^{1 to} R ⁴ are each independently a hydrogen atom; a halogen atom; a linking group containing an oxygen atom, sulfur atom, nitrogen atom or silicon atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms; a polar group represents an atom or a group selected from the group, R ¹ and R ² may form a divalent hydrocarbon group are integrated, R ³
And R ⁴ may be integrated to form a divalent hydrocarbon group. R ¹ and R ² may be bonded to each other to form a carbocyclic or heterocyclic ring, and R ³ and R ⁴ may be bonded to each other to form a carbocyclic or heterocyclic ring. May be monocyclic or polycyclic. ]   The liquid crystal panel according to claim 1 or 2, wherein the polarizing plate (1) is formed by laminating an optical film (A), a polarizer (i), and a triacetyl cellulose film in this order.   The liquid crystal panel according to any one of claims 1 to 3, wherein the polarizing plate (2) is formed by laminating an optical film (B), a polarizer (ii), and a triacetyl cellulose film in this order. Made of cyclic olefin resin,
The retardation R0 in the film plane is 15-60 nm,
The thickness direction retardation Rxz is 150 to 250 nm,
The angle α (degrees) between the maximum refractive index direction in the film plane and the film width direction satisfies | α | ≦ 1, and
An optical film (a), wherein the product of | α | and R0 (nm) is 30 or less. (Here, the retardation R0 in the film plane and the retardation Rxz in the film thickness direction are the maximum refractive index in the film plane at a light wavelength of 550 nm, nx, and in the direction orthogonal to nx in the film plane, respectively. (If the refractive index is ny and the film thickness is d (nm), this is a value determined by the formula R0 = (nx−ny) × d and the formula Rxz = (nx−nz) × d). Made of cyclic olefin resin,
The in-plane retardation R0 is 70 to 120 nm,
The ratio (Rxz / R0) of retardation Rxz and R0 in the film thickness direction is 1.2 to 1.5,
The angle β (degrees) between the maximum refractive index direction in the film plane and the film width direction satisfies | β | ≦ 1, and
An optical film (b), wherein the product of | β | and R0 (nm) is 30 or less. (Here, the retardation R0 in the film plane and the retardation Rxz in the film thickness direction are the maximum refractive index in the film plane at a light wavelength of 550 nm, nx, and the direction perpendicular to nx in the film plane, respectively. (If the refractive index is ny and the film thickness is d (nm), this is a value determined by the formula R0 = (nx−ny) × d and the formula Rxz = (nx−nz) × d.) An optical film set for a liquid crystal panel comprising the following optical film (a) and the following optical film (b).
Optical film (a): made of cyclic olefin resin,
The retardation R0 in the film plane is 15-60 nm,
The thickness direction retardation Rxz is 150 to 250 nm,
The angle α (degrees) between the maximum refractive index direction in the film plane and the film width direction satisfies | α | ≦ 1, and
An optical film having a product of | α | and R0 (nm) of 30 or less.
Optical film (b): made of cyclic olefin resin,
The in-plane retardation R0 is 70 to 120 nm,
The ratio (Rxz / R0) of retardation Rxz and R0 in the film thickness direction is 1.2 to 1.5,
The angle β (degrees) between the maximum refractive index direction in the film plane and the film width direction satisfies | β | ≦ 1, and
An optical film, wherein the product of | β | and R0 (nm) is 30 or less.
(Here, the retardation R0 in the film plane and the retardation Rxz in the film thickness direction are the maximum refractive index in the film plane at a light wavelength of 550 nm, nx, and the direction perpendicular to nx in the film plane, respectively. (If the refractive index is ny and the film thickness is d (nm), this is a value determined by the formula R0 = (nx−ny) × d and the formula Rxz = (nx−nz) × d.)