JP2008231384A - Cyclic olefin resin film, polarizing plate and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cyclic olefin resin film which has superior optical characteristics although it is a thin film, is reduced in the change in optical properties due to the environmental moisture change and realizes a high quality visibility being little in the dependency on the visibility angle, a polarizing plate and a liquid crystal display containing the cyclic olefinic resin film and a cyclic olefinic resin film being reduced in the area defects during manufacturing. <P>SOLUTION: The cyclic olefin resin film comprises one kind of organic rod-like compound having at least one aromatic ring. The polarizing plate and the liquid crystal display uses the film. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a cyclic olefin resin film, and a polarizing plate and a liquid crystal display device including the cyclic olefin resin film.

A polarizing plate is usually produced by laminating a film mainly composed of cellulose triacetate as a protective film on both sides of a polarizer obtained by orientation-adsorbing iodine or dichroic dye on polyvinyl alcohol. Cellulose triacetate has characteristics such as toughness, flame retardancy, and high optical isotropy (low retardation), and is widely used as the protective film for polarizing plates described above.
The liquid crystal display device is composed of a polarizing plate and a liquid crystal cell. At present, in a TN mode TFT liquid crystal display device which is the mainstream of liquid crystal display devices, a liquid crystal display device with high display quality is realized by inserting an optical compensation sheet between a polarizing plate and a liquid crystal cell.
However, cellulose triacetate has a large amount of moisture absorption and transmission, and therefore has a problem that the optical compensation performance is likely to change and the polarizer is liable to deteriorate. On the other hand, cyclic olefin-based resin films are attracting attention as films that can improve the hygroscopicity and moisture permeability of cellulose triacetate film and have small changes in optical properties with respect to environmental temperature and humidity changes. Development as a film for display devices is being carried out. Patent Document 1 discloses an optical film made of a cyclic olefin-based ring-opening polymer, and Patent Document 2 discloses an optical film made of a cyclic olefin-based addition polymer.
Further, it is disclosed that the cellulose ester can improve the optical properties by using a retardation increasing agent. For example, Patent Document 3 discloses that an organic rod-shaped compound is effective, but has a problem that the compatibility with a cellulose ester is small and a surface failure is likely to occur.
Japanese Patent Laid-Open No. 2005-43740 Japanese Patent Laid-Open No. 2002-114827 JP 2002-363343 A

  As the screen of liquid crystal display devices is increasing, liquid crystal display devices for television applications that are expected to be viewed from various angles have not been able to meet the strict requirement for viewing angle dependency. Therefore, liquid crystal display devices different from the TN mode, such as an IPS (In-Plane Switching) mode, an OCB (Optically Compensatory Bend) mode, and a VA (Vertically Aligned) mode, have been studied. In particular, the VA mode is attracting attention as a liquid crystal display device for TV because of its high contrast and relatively high manufacturing yield.

  However, in the VA mode, although almost complete black display is possible in the normal direction of the panel, there is a problem that light leakage occurs when the panel is observed from an oblique direction, and the viewing angle is narrowed. In order to solve this problem, it has been proposed to improve the viewing angle characteristics of the VA mode by using an optically biaxial retardation film having different refractive indexes in the three-dimensional direction. On the other hand, these retardation films are required to be further thinned, and a means for realizing a three-dimensional optical characteristic and a thin film in a cyclic olefin resin film has been demanded.

  An object of the present invention is a cyclic olefin-based resin film that has excellent optical properties while being a thin film, has small optical property changes due to environmental humidity changes, and realizes high-quality visibility with little viewing angle dependency, A polarizing plate and a liquid crystal display device including a cyclic olefin resin film are provided. A further object of the present invention is to provide an excellent cyclic olefin resin film with less surface failure in the production process.

That is, the object of the present invention is achieved by the following means.
1. A cyclic olefin-based resin film comprising at least one organic rod-shaped compound having at least one aromatic ring.
2. 2. The cyclic olefin-based resin film as described in 1 above, wherein the organic rod-shaped compound contains at least one compound represented by the following general formula (1).

(In the formula, Ar ¹ and Ar ³ each independently represents an aryl group or an aromatic heterocycle, Ar ² represents an arylene group or an aromatic heterocycle, and L ¹ and L ² each independently represent a single bond, or .n representing the divalent linking group is an integer of 3 or more, Ar ^2, L ² respectively have different all Ar ² and L ² in may be the same or different. repeat units in the same May be.)
3. The cyclic olefin-based resin film as described in 1 or 2 above, wherein the organic rod-like compound or the compound represented by the general formula (1) has an octanol / water partition coefficient (log P) of 8 or more and 20 or less.
4). 4. The cyclic olefin-based resin film as described in any one of 1 to 3, wherein the cyclic olefin-based resin film has a thickness of 65 μm or less.
5. The cyclic olefin resin film according to any one of 1 to 4, wherein the cyclic olefin resin film is stretched.
6). 6. The cyclic olefin-based resin film as described in 5 above, wherein the draw ratio is from 1% to 30%.
7). Any one of 1 to 6 above, which is formed using a cyclic olefin-based resin that is at least one selected from the group consisting of [A-1], [A-2] and [A-3] below. The cyclic olefin-type resin film of crab.
[A-1] An addition copolymer containing at least one type of repeating unit represented by the following general formula (I) and at least one type of repeating unit represented by the following general formula (II):
[A-2] an addition (co) polymer containing at least one repeating unit represented by the following general formula (II), and
[A-3] A ring-opening (co) polymer containing at least one repeating unit represented by the following general formula (III).

Wherein R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X ¹ and Y ¹ each independently represent a hydrogen atom or a hydrocarbon having 1 to 10 carbon atoms. Group, halogen atom, C 1-10 hydrocarbon group substituted with halogen atom, — (CH ₂ ) _n COOR ⁵¹ , — (CH ₂ ) _n OCOR ⁵² , — (CH ₂ ) _n NCO, — (CH _{2) n NO 2, - (} CH 2) n CN, - (CH 2) n CONR 53 R 54, - (CH 2) n NR 53 R 54, - (CH 2) n OZ, - (CH 2) n Represents W, or (—CO) ₂ O or (—CO) ₂ NR ⁵⁵ composed of X ¹ and Y ¹ , wherein R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , and R ⁵⁵ represent a hydrogen atom or Represents a hydrocarbon group having 1 to 20 carbon atoms, Z represents a hydrocarbon group or a hydrocarbon group substituted with a halogen, and W represents Si. R ⁵⁶ _p D _3-p (R ⁵⁶ represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom, —OCOR ⁵⁶ or —OR ⁵⁶ , and p represents an integer of 0 to 3) ), N represents an integer of 0 to 10.)

(In the formula, m represents an integer of 0 to ^4. R ³ and R ⁴ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X ² and Y ² each independently represent a hydrogen atom, hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen _{atom, - (CH 2) n COOR} 51, - (CH 2) n OCOR 52, - (CH _{2) n NCO, - (CH} 2) n NO 2, - (CH 2) n CN, - (CH 2) n CONR 53 R 54, - (CH 2) n NR 53 R 54, - (CH 2) n OZ, — (CH ₂ ) _n W, or (—CO) ₂ O or (—CO) ₂ NR ⁵⁵ composed of X ² and Y ² represents R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ And R ⁵⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and Z represents a hydrocarbon group or a hydrocarbon substituted with a halogen. Represents the original, W is represents _{^{SiR 56 p D 3-p,}} (R 56 represents a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom, -OCOR ⁵⁶ or -OR ^56, p is N represents an integer of 0 to 3, and n represents an integer of 0 to 10.)

(In the formula, m represents an integer of 0 to 4. R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X ³ and Y ³ each independently represent a hydrogen atom, hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen _{atom, - (CH 2) n COOR} 51, - (CH 2) n OCOR 52, - (CH _{2) n NCO, - (CH} 2) n NO 2, - (CH 2) n CN, - (CH 2) n CONR 53 R 54, - (CH 2) n NR 53 R 54, - (CH 2) n OZ, — (CH ₂ ) _n W, or (—CO) ₂ O or (—CO) ₂ NR ⁵⁵ composed of X ³ and Y ³ represents R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ And R ⁵⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and Z is a hydrocarbon group or a hydrocarbon substituted with a halogen. Represents the original, W is represents _{^{SiR 56 p D 3-p,}} (R 56 represents a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom, -OCOR ⁵⁶ or -OR ^56, p is N represents an integer of 0 to 3, and n represents an integer of 0 to 10.)
8). The said cyclic olefin resin film satisfy | fills the relationship of following Numerical formula (1), The cyclic olefin resin film in any one of said 1-7 characterized by the above-mentioned.
Formula (1) Re (550)> 20 and Rth (550)> 50
(In the formula, Re (λ) is an in-plane retardation value of the film with respect to light of wavelength λ nm, and Rth (λ) is a retardation value of the film in the thickness direction with respect to light of wavelength λ nm (unit: : Nm).)
9. In the polarizing plate comprising a polarizer and a pair of protective films disposed on both sides thereof, at least one of the protective films is the cyclic olefin-based resin film according to any one of 1 to 8 above. A polarizing plate.
10. A liquid crystal display device comprising at least one of the cyclic olefin-based resin film according to any one of 1 to 8 and the polarizing plate according to 9 above.
11. A VA mode liquid crystal display device comprising a liquid crystal cell and a pair of polarizing plates disposed on both sides of the liquid crystal cell, wherein the polarizing plate is the polarizing plate described in 9 above.

  According to the present invention, a cyclic olefin-based resin film that has excellent optical properties while being a thin film, has small changes in optical properties due to environmental humidity changes, and realizes high-quality visibility with little viewing angle dependency, A polarizing plate and a liquid crystal display device including a cyclic olefin resin film can be provided. Furthermore, according to the present invention, it is possible to provide an excellent cyclic olefin-based resin film with few planar failures in the production process.

  Hereinafter, the present invention will be described in detail.

(Cyclic olefin resin)
The cyclic olefin resin forming the cyclic olefin resin film of the present invention includes (1) a norbornene polymer, (2) a monocyclic olefin polymer, (3) a cyclic conjugated diene polymer, (4 ) Vinyl alicyclic hydrocarbon polymers and hydrides of (1) to (4).

  Among them, the cyclic olefin resin suitable for the present invention is at least one selected from the group consisting of the following [A-1], [A-2] and [A-3].

[A-1] An addition copolymer containing at least one type of repeating unit represented by the following general formula (I) and at least one type of repeating unit represented by the following general formula (II):
[A-2] an addition (co) polymer containing at least one repeating unit represented by the following general formula (II), and
[A-3] A ring-opening (co) polymer containing at least one repeating unit represented by the following general formula (III).

Wherein R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X ¹ and Y ¹ each independently represent a hydrogen atom or a hydrocarbon having 1 to 10 carbon atoms. Group, halogen atom, C 1-10 hydrocarbon group substituted with halogen atom, — (CH ₂ ) _n COOR ⁵¹ , — (CH ₂ ) _n OCOR ⁵² , — (CH ₂ ) _n NCO, — (CH _{2) n NO 2, - (} CH 2) n CN, - (CH 2) n CONR 53 R 54, - (CH 2) n NR 53 R 54, - (CH 2) n OZ, - (CH 2) n W or (—CO) ₂ O or (—CO) ₂ NR ⁵⁵ composed of X ¹ and Y ¹ is represented by R ⁵¹ , R ⁵² ,
R ⁵³ , R ⁵⁴ , and R ⁵⁵ represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, Z represents a hydrocarbon group or a hydrocarbon group substituted with halogen, and W represents SiR ⁵⁶ _p D _{3− p} represents (R ⁵⁶ represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom, —OCOR ⁵⁶ or —OR ⁵⁶ , p represents an integer of 0 to 3), and n represents 0 to 0 Represents an integer of 10. )

(In the formula, m represents an integer of 0 to ^4. R ³ and R ⁴ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X ² and Y ² each independently represent a hydrogen atom, hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen _{atom, - (CH 2) n COOR} 51, - (CH 2) n OCOR 52, - (CH _{2) n NCO, - (CH} 2) n NO 2, - (CH 2) n CN, - (CH 2) n CONR 53 R 54, - (CH 2) n NR 53 R 54, - (CH 2) n OZ, — (CH ₂ ) _n W, or (—CO) ₂ O or (—CO) ₂ NR ⁵⁵ composed of X ² and Y ² represents R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ And R ⁵⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and Z represents a hydrocarbon group or a hydrocarbon substituted with a halogen. Represents the original, W is represents _{^{SiR 56 p D 3-p,}} (R 56 represents a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom, -OCOR ⁵⁶ or -OR ^56, p is N represents an integer of 0 to 3, and n represents an integer of 0 to 10.)

(In the formula, m represents an integer of 0 to 4. R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X ³ and Y ³ each independently represent a hydrogen atom, hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen _{atom, - (CH 2) n COOR} 51, - (CH 2) n OCOR 52, - (CH _{2) n NCO, - (CH} 2) n NO 2, - (CH 2) n CN, - (CH 2) n CONR 53 R 54, - (CH 2) n NR 53 R 54, - (CH 2) n OZ, — (CH ₂ ) _n W, or (—CO) ₂ O or (—CO) ₂ NR ⁵⁵ composed of X ³ and Y ³ represents R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ And R ⁵⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and Z is a hydrocarbon group or a hydrocarbon substituted with a halogen. Represents the original, W is represents _{^{SiR 56 p D 3-p,}} (R 56 represents a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom, -OCOR ⁵⁶ or -OR ^56, p is N represents an integer of 0 to 3, and n represents an integer of 0 to 10.)

By the substituents ^{X 1 ~X 3, Y 1 ~Y} 3 for introducing the polarizable large functional group, a thickness direction retardation of the film (Rth) is increased, the in-plane retardation (Re) The expression of can be increased. A film having a high Re developability can increase the Re value by stretching in the film forming process. Moreover, it is advantageous to interact with the organic rod-shaped compound of the present invention, and the orientation of the organic rod-shaped compound during stretching can be improved.

  Norbornene type addition (co) polymers preferably used in the present invention are disclosed in JP-A-10-7732, JP-T 2002-504184, US200429129157A1, WO2004 / 070463A1, and the like. It can be obtained by addition polymerization of norbornene-based polycyclic unsaturated compounds. If necessary, norbornene-based polycyclic unsaturated compounds and conjugated dienes such as ethylene, propylene, butene, butadiene and isoprene; non-conjugated dienes such as ethylidene norbornene; acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride It is also possible to carry out addition polymerization with linear diene compounds such as acid, acrylic acid ester, methacrylic acid ester, maleimide, vinyl acetate and vinyl chloride. This norbornene-based addition (co) polymer is sold under the name of Apel by Mitsui Chemicals, Inc., and has different glass transition temperatures (Tg) such as APL8008T (Tg70 ° C), APL6013T (Tg125 ° C) or APL6015T ( Grades such as Tg145 ° C). Pellets are sold under the trade names such as TOPAS 8007, 6013, and 6015 from Polyplastics. Further, Appear 3000 is sold by Ferrania.

The norbornene polymer hydride preferably used in the present invention is disclosed in JP-A-1-240517, JP-A-7-196736, JP-A-60-26024, JP-A-62-19801, JP-A-2003-159767. As disclosed in Japanese Patent Laid-Open No. 2004-309979 and the like, the polycyclic unsaturated compound is produced by addition polymerization or metathesis ring-opening polymerization and then hydrogenation. In the norbornene-based ring-opening (co) polymer used in the present invention, R ^{5 to} R ⁶ are preferably a hydrogen atom or —CH ₃ , X ³ and Y ³ are preferably a hydrogen atom, Cl, —COOCH ₃ , and other groups Is appropriately selected. This norbornene-based resin is sold under the trade name Arton G or Arton F by JSR Corporation, and from Zeon Corporation Zeonor ZF14, ZF16, Zeonex 250 or Zeonex. They are commercially available under the trade name 280 and can be used.

(Organic rod-shaped compound)
The cyclic olefin resin film of the present invention contains at least one organic rod-shaped compound having at least one aromatic ring.
The organic rod-shaped compound of the present invention further preferably has at least two aromatic rings. Further, it preferably has 4 to 8 aromatic rings, and most preferably has 4 to 6 aromatic rings.

  The organic rod-shaped compound preferably has a linear molecular structure. The linear molecular structure means that the molecular structure of the rod-like compound is linear in the most thermodynamically stable structure. The most thermodynamically stable structure can be obtained by crystal structure analysis or molecular orbital calculation. For example, molecular orbital calculation can be performed using molecular orbital calculation software (eg, WinMOPAC2000, manufactured by Fujitsu Limited) to obtain a molecular structure that minimizes the heat of formation of a compound. The molecular structure being linear means that the angle of the molecular structure is 140 degrees or more in the thermodynamically most stable structure obtained by calculation as described above.

The organic rod-like compound of the present invention preferably has an octanol / water partition coefficient (log P) of 8 or more and 20 or less. More preferably, it is 9 or more and 15 or less.
In the case of cellulose ester, logP is preferably 1 or more and 8 or less from the viewpoint of planar failure such as bleed-out, but cyclic olefin-based resins are relatively hydrophobic as can be seen from their low hygroscopicity and moisture permeability. The cyclic olefin resin can be used while avoiding a planar failure even in the above range.

  The octanol-water partition coefficient (log P value) can be measured by a flask immersion method described in JIS Japanese Industrial Standard Z7260-107 (2000). Further, the octanol-water partition coefficient (log P value) can be estimated by a computational chemical method or an empirical method instead of the actual measurement. As a calculation method, Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987).), Viswanadhan's fragmentation method (J. Chem. Inf. Comput. Sci., 29, 163 (1989).) Broto's fragmentation method (Eur. J. Med. Chem.- Chim. Theor., 19, 71 (1984).) And the like are preferably used, but Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27 , 21 (1987). When the log P value of a certain compound varies depending on the measurement method or calculation method, it is preferable to determine whether or not the compound is within the scope of the present invention by the Crippen's fragmentation method.

The addition amount of the organic rod-shaped compound of the present invention is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 1 to 10% by mass with respect to the cyclic olefin resin. When using 2 or more types, it is preferable that the total amount satisfy | fills said range.
Examples of the organic rod-shaped compound of the present invention include compounds described in JP-A Nos. 2004-4450 and 2006-96876, which have been proposed as retardation developers.

  The organic rod-like compound of the present invention is preferably a compound represented by the following general formula (1).

The compound represented by the general formula (1) will be described in detail.
In general formula (1), Ar ¹ and Ar ³ each independently represents an aryl group or an aromatic heterocycle, Ar ² represents an arylene group or an aromatic heterocycle, and L ¹ and L ² each independently represent a single group. It represents a bond or a divalent linking group. n represents an integer of 3 or more, and Ar ² and L ² may be the same or different.

Ar ¹ and Ar ³ each independently represents an aryl group or an aromatic heterocycle. Ar ¹ and Ar ³ may be different or the same. The aryl group represented by Ar ¹ or Ar ³ is preferably an aryl group having 6 to 30 carbon atoms, and may be a single ring or may form a condensed ring with another ring. Further, if possible, it may have a substituent, and the substituent T described later can be applied as the substituent.
In general formula (1), the aryl group represented by Ar ¹ or Ar ³ is more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl group, p-methylphenyl group, naphthyl Group and the like.

Ar ² represents an arylene group or an aromatic heterocycle, and all Ar ² in the repeating unit may be the same or different. The arylene group is preferably an arylene group having 6 to 30 carbon atoms, and may be a single ring or may form a condensed ring with another ring. Further, if possible, it may have a substituent, and the substituent T described later can be applied as the substituent.
In the general formula (1), the arylene group represented by Ar ² is more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms. Can be mentioned.

In the general formula (1), the aromatic heterocycle represented by Ar ¹ , Ar ² , Ar ³ can be an aromatic heterocycle containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom, An aromatic heterocycle containing at least one of a 5- to 6-membered oxygen atom, nitrogen atom or sulfur atom is preferred. Moreover, you may have a substituent further if possible. Substituent T described later can be applied as the substituent.

Specific examples of the aromatic heterocycle represented by Ar ¹ , Ar ² , Ar ³ in the general formula (1) include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine. , Indole, indazole, purine, thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole Benzthiazole, benzotriazole, tetrazaindene, pyrrolotriazole, pyrazolotriazole and the like. Preferred as the aromatic heterocycle are benzimidazole, benzoxazole, benzthiazole, and benzotriazole.

In general formula (1), L ¹ and L ² each independently represent a single bond or a divalent linking group. L ¹ and L ² may be the same or different. Further, all L ² in the repeating unit may be the same or different.
A preferable example of the divalent linking group is a group represented by —NR ⁷ — (R ⁷ represents a hydrogen atom, an alkyl group or an aryl group which may have a substituent), —SO ₂ —. , —CO—, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, —O—, —S—, —SO— and a group obtained by combining two or more of these divalent groups. , -O preferable than them -, - CO -, - SO 2 NR 7 -, - NR 7 SO 2 -, - CONR 7 -, - NR 7 CO -, - COO-, and -OCO-, alkynylene Group, most preferably —CONR ⁷ —, —NR ⁷ CO—, —COO—, and —OCO—, an alkynylene group.

In the compound represented by the general formula (1) of the present invention, Ar ² is bonded to L ¹ and L ^{2. When} Ar ² is a phenylene group, L ¹ -Ar ² -L ² and L ^2- Ar ² -L ² is most preferably in a para-position (1,4-position) to each other.

  In general formula (1), n represents an integer greater than or equal to 3, Preferably it is 3-7, More preferably, it is 3-5.

  Among the compounds represented by the general formula (1), a compound represented by the general formula (2) is preferable.

  Next, the compound represented by the general formula (2) will be described in detail.

In the general formula (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent. Ar ² represents an arylene group or an aromatic heterocycle, and L ² and L ³ each independently represent a single bond or a divalent linking group. n represents an integer of 3 or more, and Ar ² and L ² may be the same or different.

Ar ² , L ² , and n are as described for formula (1), L ³ represents a single bond or a divalent linking group, and preferably —NR ⁷ as an example of a divalent linking group. A group represented by — (R ⁷ represents a hydrogen atom, an alkyl group or an aryl group which may have a substituent), an alkylene group, a substituted alkylene group, —O—, and these divalent groups are represented by 2 a one or more combination obtained group, -O is preferred from them ^{-, - NR 7 -, -} NR 7 SO 2 -, and -NR ⁷ is CO-.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom, carbon An alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, and an isopropyl group) and an aryl group having 6 to 12 carbon atoms (for example, a phenyl group and a naphthyl group), and more preferably 1 to 4 carbon atoms. It is an alkyl group.

R ²¹ , R ²² , R ²³ and R ²⁴ each independently represents a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group, an alkoxy group or a hydroxyl group, more preferably a hydrogen atom or an alkyl group (preferably Is an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

The aforementioned substituent T will be described below.
The substituent T is preferably a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, Isopropyl group, t-butyl group, n-octyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms such as cyclohexyl group, cyclopentyl group, 4 -N-dodecylcyclohexyl group), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. For example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane 3-yl), an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group or an allyl group), a cycloalkenyl group (preferably a substituted or unsubstituted group having 3 to 30 carbon atoms) That is, a monovalent group in which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms has been removed (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), bicycloalkenyl Group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond) For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] oct-2-ene-4- ), An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group or a propargyl group), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms) A phenyl group, a p-tolyl group, a naphthyl group, a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted, aromatic or non-aromatic heterocyclic compound with one hydrogen atom removed. A 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and 2-benzothiazolyl. Group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as meth Xy group, ethoxy group, isopropoxy group, t-butoxy group, n-octyloxy group, 2-methoxyethoxy group), aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, For example, phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group), silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, For example, a trimethylsilyloxy group, a tert-butyldimethylsilyloxy group), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, a 1-phenyltetrazole-5-oxy group, 2 -Tetrahydropyranyloxy group), acyloxy group (preferably formyloxy group) C2-C30 substituted or unsubstituted alkylcarbonyloxy group, C6-C30 substituted or unsubstituted arylcarbonyloxy group, for example, formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyl Oxy group, p-methoxyphenylcarbonyloxy group), carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N, N-diethyl) A carbamoyloxy group, a morpholinocarbonyloxy group, an N, N-di-n-octylaminocarbonyloxy group, an Nn-octylcarbamoyloxy group), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted group having 2 to 30 carbon atoms) Substituted alkoxycarbonyloxy Group, for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, n-octylcarbonyloxy group), aryloxycarbonyloxy group (preferably substituted or unsubstituted aryloxy having 7 to 30 carbon atoms) A carbonyloxy group, for example, a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, a pn-hexadecyloxyphenoxycarbonyloxy group, an amino group (preferably an amino group, a substituted or unsubstituted group having 1 to 30 carbon atoms) Substituted alkylamino group, substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group), acylamino group (Preferably formyl Amino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino group, acetylamino group, pivaloylamino group, lauroylamino Group, benzoylamino group), aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N -Diethylaminocarbonylamino group, morpholinocarbonylamino group), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms such as methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxy A carbonylamino group, an n-octadecyloxycarbonylamino group, an N-methyl-methoxycarbonylamino group), an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, Phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino group), sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms) , For example, sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn-octylaminosulfonylamino group, alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted having 1 to 30 carbon atoms) Alkylsulfonyl Mino, substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methyl Phenylsulfonylamino group), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio group, ethylthio group, n-hexadecylthio group), arylthio group (preferably 6 carbon atoms) -30 substituted or unsubstituted arylthio groups, for example, phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group), heterocyclic thio group (preferably a substituted or unsubstituted heterocycle having 2 to 30 carbon atoms) Thio group, for example, 2-benzothiazolylthio group 1-phenyltetrazol-5-ylthio group), sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl Group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N′phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl and arylsulfinyl group (preferably Is a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, or a p-methylphenylsulfinyl group. ), Alkyls and aryls A sulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms such as a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group, p- Methylphenylsulfonyl group), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as acetyl group, A valoylbenzoyl group), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, an m-nitrophenoxycarbonyl group, p-tert-butylphenoxycarbonyl group ), An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, an n-octadecyloxycarbonyl group), a carbamoyl group ( Preferably, the substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, for example, carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (Methylsulfonyl) carbamoyl group), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo Group, p-chlorophenylazo group, 5-ethylthio- , 3,4-thiadiazol-2-ylazo group), imide group (preferably N-succinimide group, N-phthalimide group), phosphino group (preferably substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, For example, dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group), phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl group, dioctyloxyphosphinyl group , Diethoxyphosphinyl group), phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy group, dioctyloxyphosphinyl) An oxy group), a phosphinylamino group (preferably a C2-C30 substituent or A substituted phosphinylamino group such as a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group, a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms such as a trimethylsilyl group , Tert-butyldimethylsilyl group, phenyldimethylsilyl group).

  Among the above-mentioned substituents, those having a hydrogen atom may be substituted with the above-mentioned group after removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

  Moreover, when there are two or more substituents, they may be the same or different. If possible, they may be linked together to form a ring.

As a preferred embodiment of the compound represented by the general formula (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or an alkyl group, preferably 1 to 4 carbon atoms. R ²¹ , R ²² , R ²³ , R ²⁴ are all hydrogen atoms; Ar ² is a substituted or unsubstituted arylene group, preferably substituted or unsubstituted. An arylene group having 6 to 20 carbon atoms, more preferably a substituted or unsubstituted phenylene group; L ² is a single bond, —COO—, —OCO—, —CONR ⁷ —, —NR ⁷ CO—, —NR ⁷ —, —CONR ⁷ — (R ⁷ represents a hydrogen atom, an alkyl group or an aryl group which may have a substituent, preferably a hydrogen atom), —O—, or an alkynylene group. There; L ³ is -O- or NR ⁷ - (R ⁷ is a hydrogen atom, an optionally substituted alkyl group or an aryl group.) Can be exemplified those which are.

  Hereinafter, the compounds represented by the general formula (1) and the general formula (2) will be described in detail with specific examples, but the present invention is not limited to the following specific examples.

  The compounds represented by general formula (1) and general formula (2) can be synthesized by known methods. For example, a method described in JP 2006-96876 A can be mentioned.

  Specific examples of the organic rod-like compound other than the compounds represented by the general formula (1) and the general formula (2) are given below, but the present invention is not limited to the following specific examples.

[Optical properties of film]
In the present specification, Re (λ) is an in-plane retardation value of the film with respect to light having a wavelength of λnm, and Rth (λ) is a retardation value in the thickness direction of the film with respect to light having a wavelength of λnm (unit: nm). Re (λ) is measured with an automatic birefringence meter such as “KOBRA 21ADH” (manufactured by Oji Scientific Instruments Co., Ltd.) or the like, with light having a wavelength of λ nm incident in the normal direction of the film. Rth (λ) is relative to the film normal direction with Re (λ) and the in-plane slow axis (determined by an automatic birefringence meter such as “KOBRA 21ADH”) as the tilt axis (rotation axis). From the direction inclined by −40 ° with respect to the normal direction of the film, with the retardation value measured by making light of wavelength λnm incident from the direction inclined + 40 ° and the slow axis in the plane as the inclination axis (rotation axis) An automatic birefringence meter such as “KOBRA 21ADH” calculates based on the retardation values measured in a total of three directions of the retardation values measured by making light having a wavelength λ nm incident.

Here, as the assumed value of the average refractive index, values in the polymer handbook (John Wiley & Sons, Inc.) and catalogs of various optical films can be used. If the average refractive index is not known, it can be measured with an Abbe refractometer. Examples of the average refractive index values of main optical films are given below:
Cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), polystyrene (1.59).
Further, by inputting the assumed average refractive index values and thicknesses, n _x (slow axis direction of the refractive index) by an automatic double refractometer such as KOBRA 21ADH, n _y (refractive index of the fast axis direction) , N _z (refractive index in the thickness direction) is calculated. Further, an automatic birefringence meter such as “KOBRA 21ADH” has an angle β with respect to the film normal direction at which the retardation value is minimum with respect to the light propagating through the film when the in-plane slow axis is the tilt axis. Is also calculated.

The film of the present invention can be preferably used as a retardation film corresponding to various liquid crystal modes.
When the film of the present invention is used as a retardation film, its preferable optical properties vary depending on the liquid crystal mode.
For the OCB mode, Re (550) is preferably 10 to 100, and more preferably 20 to 70. Rth (550) is preferably 50 to 300, more preferably 100 to 250.
For TN, Re (550) is preferably 0-50, more preferably 2-30. Rth (550) is preferably 10-200, more preferably 30-150.
Moreover, in the mode for OCB and the mode for TN, an optical anisotropic layer can be apply | coated on the film which has the said retardation value, and it can use as an optical compensation film.

When using the film of this invention for the polarizing plate protective film of the liquid crystal display device of VA mode, it is preferable to satisfy | fill following numerical formula (1).
Formula (1) Re (550)> 20 nm and Rth (550)> 50 nm

  A form in which the film of the present invention is used in total on a cell side of a VA mode liquid crystal display device, one on each side (two sheets type), and a form in which only one of the upper and lower sides of the cell is used (one sheet type) The preferable optical characteristics are different in the two cases.

  In the case of the single sheet type or IPS mode used for the VA mode, Re (550) is preferably 30 to 150 nm, and more preferably 40 to 100 nm. Rth (550) is preferably from 100 to 300 nm, more preferably from 150 to 250 nm.

In the case of the single sheet type used for the VA mode, it is preferable that the following expressions (1) and (2) are further satisfied.
(1) Re (550)> 20 nm and Rth (550)> 50 nm
(2) −2.5 × Re (550) +300 <Rth (550) <− 2.5 × Re (550) +500

The film of the present invention more preferably satisfies the following formulas (1a) and (2a).
(1a) Re (550)> 30 nm and Rth (550)> 50 nm
(2a) −2.5 × Re (550) +320 <Rth (550) <− 2.5 × Re (550) +480

In the case of the single sheet type, it is preferable to satisfy the following formulas (3) to (6).
(3) 0.60 <Re (450) / Re (550) <1.0
(4) 1.0 <Re (650) / Re (550) <1.25
(5) 0.60 <Rth (450) / Rth (550) <1.0
(6) 1.0 <Rth (650) / Rth (550) <1.25
Furthermore, it is more preferable to satisfy the following formulas (3a) to (6a).
(3a) 0.70 <Re (450) / Re (550) <1.0
(4a) 1.0 <Re (650) / Re (550) <1.15
(5a) 0.70 <Rth (450) / Rth (550) <1.0
(6a) 1.0 <Rth (650) / Rth (550) <1.15

  When it is used on both sides of a liquid crystal cell as an optical compensation film of a VA mode liquid crystal display device and compensated with two sheets, Re (550) is in the range of 20 to 100 nm and Rth (550) is in the range of 100 to 200 nm. Preferably, Re (550) is 25 to 80 nm and Rth (550) is 100 to 150 nm.

The film of the present invention preferably satisfies the following formulas (A) to (D).
(A) 0.1 <Re (450) / Re (550) <0.95
(B) 1.03 <Re (650) / Re (550) <1.93
(C) 0.4 <(Re / Rth (450)) / (Re / Rth (550)) <0.95
(D) 1.05 <(Re / Rth (650)) / (Re / Rth (550)) <1.9
(In the formula, Re / Rth (λ) is the ratio of the in-plane retardation value of the film to the retardation value in the thickness direction with respect to light of wavelength λ nm (unit: nm).)

The above formulas (A) to (D) are also preferable in a single sheet type used in the VA mode.
When compensating with two films of the present invention, it is more preferable to satisfy the following formulas (A1) to (D1).
(A1) 0.6 <Re (450) / Re (550) <0.95
(B1) 1.05 <Re (650) / Re (550) <1.25
(C1) 0.45 <(Re / Rth (450)) / (Re / Rth (550)) <0.95
(D1) 1.05 <(Re / Rth (650)) / (Re / Rth (550)) <1.7
The film of the present invention more preferably satisfies the following formulas (A2) to (D2).
(A2) 0.5 <Re (450) / Re (550) <0.95
(B2) 1.10 <Re (650) / Re (550) <1.25
(C2) 0.50 <(Re / Rth (450)) / (Re / Rth (550)) <0.95
(D2) 1.05 <(Re / Rth (650)) / (Re / Rth (550)) <1.5

  The birefringence (Δn: nx−ny) of the film is preferably in the range of 0.00 to 0.002 μm. The birefringence {(nx + ny) / 2-nz} in the thickness direction of the support film and the counter film is preferably in the range of 0.00 to 0.04.

(Additive)
To the cyclic olefin-based resin film of the present invention, various additives (for example, deterioration preventing agents, ultraviolet absorbers, fine particles, peeling accelerators, infrared absorbers, etc.) depending on the application are added in each preparation step. They can be solid or oily. That is, the melting point and boiling point are not particularly limited. For example, mixing of an ultraviolet absorbing material at 20 ° C. or lower and 20 ° C. or higher, and a mixture of deterioration preventing agents are also possible. Furthermore, infrared absorbing dyes are described, for example, in JP-A No. 2001-194522. In addition, the addition time may be added at any stage in the cyclic olefin resin solution (dope) preparation process, but it is performed by adding an additive to the final preparation process of the dope preparation process. Also good. Furthermore, the amount of each material added is not particularly limited as long as the function is manifested. Moreover, when a cyclic olefin resin film is formed by a multilayer structure, the kind and addition amount of the additive of each layer may differ.

(Deterioration inhibitor)
A known deterioration (oxidation) inhibitor, for example, a phenol-based or hydroquinone-based antioxidant can be added to the cyclic olefin-based resin film of the present invention. Furthermore, it is preferable to use a phosphorus-based antioxidant. As for the addition amount of antioxidant, it is preferable to add 0.05-5.0 mass parts with respect to 100 mass parts of cyclic olefin resin.

(UV absorber)
For the cyclic olefin-based resin film of the present invention, an ultraviolet absorber is preferably used from the viewpoint of preventing deterioration of a polarizing plate or liquid crystal. As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties. Specific examples of ultraviolet absorbers preferably used in the present invention include, for example, hindered phenol compounds, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds Etc. Examples of hindered phenol compounds include 2,6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert) -Butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate and the like. Examples of benzotriazole compounds include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), (2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5- Triazine, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-tert-butyl-4- Hydroxy-hydrocinnamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2 (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, (2 (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) -5 -Chlorbenzotriazole, 2,6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like. The addition amount of these ultraviolet light inhibitors is preferably 1 ppm to 100,000 ppm, more preferably 10 to 1000 ppm by mass with respect to the cyclic olefin resin.

(Fine particles)
The cyclic olefin-based resin film of the present invention may contain organic and / or inorganic fine particles (matting agent) to prevent scratching or deterioration of transportability, and may be so-called matted. preferable.

  In order to keep the cyclic olefin-based resin film from being too rough, to keep the haze low and to maintain transparency, the average particle size and content of the matting agent are preferably in the following ranges.

  The average particle size of the matting agent described in the present specification is the average size of the matting agent present in the film or on the film surface. Whether the matting agent is aggregated or non-aggregated. Regardless of this, the particle diameter can be determined from the average of the particle diameters of 100 particles obtained by SEM imaging and TEM imaging of the film surface and the slice.

  The matting agent used in the present invention is preferably inorganic fine particles or polymer fine particles having an average particle size of 0.1 μm to 3.0 μm, more preferably 0.15 μm to 2.0 μm, still more preferably 0.2 μm to 1. 0 μm.

  The average particle size of the matting agent in the present invention means the average size (average secondary particle size) of the aggregate if it is agglomerated fine particles, and will be described later if manufactured by the solution casting film forming method. The particle size in the dispersion can be controlled by the dispersion formulation. In the case of non-aggregating fine particles, it means an average value obtained by measuring the size of one particle.

  The matting agent used in the present invention is preferably a fine particle having an average primary particle size of 0.05 μm to 0.5 μm, more preferably 0.08 μm to 0.3 μm, and even more preferably 0.1 μm, as long as it is a coherent fine particle. ˜0.25 μm.

  The polymer fine particles are preferable because a desired refractive index can be obtained by selecting a polymer species. Furthermore, since the polymer fine particles have high compatibility with the cyclic olefin resin and can suppress haze, refraction, and scattering when a film is formed using the polymer fine particles, when using the polymer fine particles as a matting agent, Rather than using inorganic fine particles as a matting agent, it is possible to select a grade having a large size and enhance the matting effect.

  Further, the content is preferably 0.03 to 1.0% by mass, more preferably 0.05 to 0% with respect to the cyclic olefin-based resin, regardless of, for example, spherical shape, indefinite shape, inorganic fine particles, or polymer matting agent. 0.6% by mass, and more preferably 0.08-0.4% by mass.

  The preferable haze range of the cyclic olefin resin film containing the matting agent in the present invention is 4.0% or less, more preferably 2.0% or less, and particularly preferably 1.0% or less. The haze value can be measured according to JIS K-6714 using a haze meter (for example, HGM-2DP, Suga Test Instruments) at 25 ° C. and 60% RH for a sample of 40 mm × 80 nm.

  The preferable static friction coefficient of the cyclic olefin resin film containing the matting agent in the present invention is 0.8 or less, and particularly preferably 0.5 or less.

  The value of the static friction coefficient of the cyclic olefin-based resin film is set in a Tensilon (tensile tester) after preparing samples of two sizes of 7.5 × 10 cm (small sample) and 10 × 20 cm (large sample). Set a large sample on the table, place a small sample on it, apply a load of 200 g to the small sample, pull the small sample with Tensilon, and measure the load (f) from which the small sample started to slide. It can be calculated from the formula of f / 200.

  There is no restriction | limiting in particular in the composition of the mat agent used, These mat agents can also be used in mixture of 2 or more types. Examples of the inorganic compound used for the inorganic fine particles of the matting agent of the present invention include inorganic fine powders such as barium sulfate, manganese colloid, titanium dioxide, strontium barium sulfate, and silicon dioxide. Examples thereof include silicon dioxide such as synthetic silica obtained by gelation of silicic acid and titanium dioxide (rutile type or anatase type) produced by titanium slug and sulfuric acid. It can also be obtained by pulverizing from an inorganic substance having a relatively large particle size, for example, 20 μm or more, and then classifying (vibration filtration, wind classification, etc.). The inorganic compound used for the inorganic fine particles of the matting agent of the present invention includes an inorganic compound whose surface is modified with a methyl group or a hydroxyl group.

  In addition, polymer compounds (polymer fine particles) include polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate, starch and the like, and pulverized and classified products thereof. Alternatively, a polymer compound synthesized by a suspension polymerization method, a polymer compound made spherical by a spray dry method or a dispersion method, or an inorganic compound can be used.

  Moreover, the polymer compound which is a polymer of one kind or two or more kinds of monomer compounds described below may be formed into particles by various means. Specific examples of the monomer compound of the polymer compound include acrylic acid ester, methacrylic acid ester, itaconic acid diester, crotonic acid ester, maleic acid diester, and phthalic acid diester. Examples of ester residues include methyl, Ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylhexyl, 2-chloroethyl, cyanoethyl, 2-acetoxyethyl, dimethylaminoethyl, benzyl, cyclohexyl, furfuryl, phenyl, 2-hydroxyethyl, 2-ethoxyethyl, glycidyl, ω -Methoxypolyethylene glycol (addition mole number 9) etc. are mentioned.

  Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate, etc. Can be mentioned. Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene.

  Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, trifluoromethyl styrene, vinyl. And benzoic acid methyl ester.

  Acrylamides include acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide, tert-butyl acrylamide, phenyl acrylamide, dimethyl acrylamide, etc .; methacrylamides such as methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacryl Amides, tert-butylmethacrylamide, etc .; allyl compounds such as allyl acetate, allyl caproate, allyl laurate, allyl benzoate, etc .; vinyl ethers such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethyl Aminoethyl vinyl ether and the like; vinyl ketones such as methyl vinyl , Phenyl vinyl ketone, methoxyethyl vinyl ketone, etc .; vinyl heterocycles such as vinyl pyridine, N-vinyl imidazole, N-vinyl oxazolidone, N-vinyl triazole, N-vinyl pyrrolidone, etc .; unsaturated nitriles such as , Acrylonitrile, methacrylonitrile and the like; polyfunctional monomers such as divinylbenzene, methylenebisacrylamide, and ethylene glycol dimethacrylate.

  In addition, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate (for example, monoethyl itaconate, etc.); monoalkyl maleate (for example, monomethyl maleate; styrene sulfonic acid, vinyl benzyl sulfonic acid, vinyl Sulfonic acid, acryloyloxyalkyl sulfonic acid (for example, acryloyloxymethyl sulfonic acid); methacryloyloxyalkyl sulfonic acid (for example, methacryloyloxyethyl sulfonic acid); acrylamide alkyl sulfonic acid (for example, 2-acrylamido-2-methylethane) Sulfonic acid, etc.); methacrylamide alkyl sulfonic acid (eg, 2-methacrylamide-2-methylethanesulfonic acid, etc.); acryloyloxyalkyl phosphate (eg, These acids may be alkali metal (eg, Na, K, etc.) or ammonium ion salts, and other monomeric compounds include those described in US Pat. 459,790, 3,438,708, 3,554,987, 4,215,195, 4,247,673, JP-A-57-205735 The crosslinkable monomer described in the document can be preferably used, and specific examples of such a crosslinkable monomer include N- (2-acetoacetoxyethyl) acrylamide, N- (2- (2 -Acetoacetoxyethoxy) ethyl) acrylamide and the like.

  These monomer compounds may be used alone as polymer particles, or may be used as copolymer particles obtained by combining a plurality of monomers. Among these monomer compounds, acrylic acid esters, methacrylic acid esters, vinyl esters, styrenes, and olefins are preferably used. In the present invention, particles having fluorine atoms or silicon atoms as described in JP-A Nos. 62-14647, 62-17744, and 62-17743 may be used.

  Among these, particle compositions preferably used are polystyrene, polymethyl (meth) acrylate, polyethyl acrylate, poly (methyl methacrylate / methacrylic acid (95/5, molar ratio), poly (styrene / styrene sulfonic acid (95/5, (Molar ratio), polyacrylonitrile, poly (methyl methacrylate / ethyl acrylate / methacrylic acid (50/40/10, molar ratio), silica, and the like.

  As the matting agent in the present invention, particles having reactive (particularly gelatin) groups described in JP-A No. 64-77052 and European Patent No. 307855 can also be used. Further, a large amount of an alkaline or acidic group capable of dissolving can be contained.

Next, the method of incorporating the matting agent into the film is not particularly limited, but there are a method of casting a solution containing a polymer and a matting agent to form a film, and a method of applying a matting agent dispersion to the formed film. Can be mentioned. Among these, the method of casting a solution containing a polymer and a matting agent to form a film is preferable from the viewpoint of cost. As a polymer, cyclic olefin resin itself may be used, and another polymer may be used.
In the case of casting a solution containing a polymer and a matting agent, the matting agent may be dispersed when preparing the polymer solution, or the matting agent dispersion may be added immediately before casting the polymer solution. It may be added. In order to disperse the matting agent in the polymer solution, a small amount of a surfactant or polymer may be added as a dispersion aid. In addition to the above method, a matting agent layer may be applied after film formation. In this case, it is preferable to use a binder for forming the matting agent layer. The binder for the layer containing the matting agent of the present invention is not particularly limited, and may be a lipophilic binder or a hydrophilic binder. As the lipophilic binder, known thermoplastic resins, thermosetting resins, radiation curable resins, reactive resins, and mixtures thereof can be used. The Tg of the resin is preferably 80 ° C to 400 ° C, more preferably 120 ° C to 350 ° C. The mass average molecular weight of the resin is preferably 10,000 to 1,000,000, and more preferably 10,000 to 500,000.

  Examples of the thermoplastic resin include vinyl chloride / vinyl acetate copolymers, vinyl chloride, copolymers of vinyl acetate and vinyl alcohol, maleic acid and / or acrylic acid, vinyl chloride / vinylidene chloride copolymers, vinyl chloride / Acrylonitrile copolymer, vinyl copolymer such as ethylene / vinyl acetate copolymer, cellulose derivatives such as nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate resin, cyclic olefin resin resin, acrylic resin, polyvinyl acetal Resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene butadiene resin, butadiene Rubber-based resins such as acrylonitrile resin, silicone resin, and fluorine resins.

  When the matting agent is incorporated into the cyclic olefin resin film by coating, a conventionally known coating method (for example, die coater (extrusion coater, slide coater), roll coater (forward roll coater, reverse roll coater, gravure coater). ), Rod coater, blade coater and the like can be preferably used. In order to carry out at a temperature at which deformation of the support carrying the coating layer, alteration of the coating solution, etc. do not occur, coating is preferably performed at a temperature of 10 ° C to 100 ° C, more preferably 20 ° C to 80 ° C. The coating speed is determined by appropriately adjusting depending on the viscosity of the coating solution and the coating temperature, but it is preferably performed at 10 m / min to 100 m / min, more preferably 20 m / min to 80 m / min.

  The coating layer containing the matting agent can be formed by applying a coating solution obtained by dissolving the matting agent in a suitable organic solvent to a cyclic olefin resin film and drying it. The matting agent can also be added to the coating liquid in the form of a dispersion. Solvents used include water, alcohols (such as methanol, ethanol, isopropanol), ketones (such as acetone, methyl ethyl ketone, cyclohexanone), esters (methyl such as acetic acid, formic acid, oxalic acid, maleic acid, succinic acid, Ethyl, propyl, butyl ester, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.) and amides (dimethylformamide, dimethylacetamide, n-methylpyrrolidone, etc.) are preferred.

  In the coating, it can be used together with a binder having a film forming ability. As such a polymer, known thermoplastic resins, thermosetting resins, radiation curable resins, reactive resins, mixtures thereof, and hydrophilic binders such as gelatin can be used.

  In both the method of casting the solution containing the polymer and the matting agent to form a film and the method of applying the matting agent dispersion to the formed film, the cyclic olefin resin film to be produced and / or Alternatively, the average particle size of the matting agent fine particles on the film surface is the average primary particle size of the matting agent fine particles, the amount of addition of the matting agent fine particles, the type of solvent to be dispersed, and the solvent to be dispersed. Addition amount, dispersion method, disperser type, disperser size, dispersion time, energy per unit time the disperser gives to the dispersion, mixing method, binder type, binder addition amount, order of addition and It can be controlled by changing conventionally known dispersion conditions such as the amount of dispersion charged.

  Even when a non-aggregating matting agent is used, it is preferable to prevent unexpected aggregation by controlling the dispersion conditions as in the case of the aggregating matting agent.

  The matting agent used in the present invention is preferably dispersed so that the average particle diameter r (μm) of the fine particles contained in the film is 0.1 μm to 3.0 μm using the above dispersion formulation. More preferably, they are 0.15 micrometer-2.0 micrometers, More preferably, they are 0.2 micrometer-1.0 micrometer.

(Peeling accelerator)
As additives for reducing the peeling resistance of the cyclic olefin-based resin film, many surfactants having a remarkable effect are found. Preferable peeling accelerators include phosphate ester surfactants, carboxylic acid or carboxylate surfactants, sulfonic acid or sulfonate surfactants, and sulfate ester surfactants. . A fluorine-based surfactant in which part of the hydrogen atoms bonded to the hydrocarbon chain of the surfactant is substituted with fluorine atoms is also effective.

  The addition amount of the peeling accelerator is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, and 0.1 to 0.5 parts by mass with respect to 100 parts by mass of the cyclic olefin resin. Most preferred.

(Formation of cyclic olefin resin film)
Examples of the method for forming a cyclic olefin-based resin film of the present invention include a hot melt film forming method and a solution film forming method, both of which are applicable. First, a solution casting method will be described.

(Organic solvent)
Next, the organic solvent in which the cyclic olefin-based resin is dissolved during the solution casting of the present invention will be described. In the present invention, the organic solvent that can be used is not particularly limited as long as the object can be achieved as long as the cyclic olefin-based resin can be dissolved, cast, and formed into a film. The organic solvent used in the present invention is a solvent selected from, for example, a chlorinated solvent such as dichloromethane and chloroform, a chain hydrocarbon having 3 to 12 carbon atoms, a cyclic hydrocarbon, an aromatic hydrocarbon, an ester, a ketone, and an ether. Is preferred. The ester, ketone and ether may have a cyclic structure. Examples of chain hydrocarbons having 3 to 12 carbon atoms include hexane, octane, isooctane, decane, and the like. Examples of cyclic hydrocarbons having 3 to 12 carbon atoms include cyclopentane, cyclohexane, decalin and derivatives thereof. Examples of the aromatic hydrocarbon having 3 to 12 carbon atoms include benzene, toluene, xylene and the like. Examples of esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate. Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone. Examples of ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phenetole. Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol. The preferable boiling point of the organic solvent is 35 ° C. or more and 200 ° C. or less. The solvent used in the present invention can be used by mixing two or more solvents for adjusting the solution physical properties such as drying property, viscosity, etc. Further, as long as the cyclic olefin resin is dissolved in the mixed solvent, It is also possible to add a poor solvent.

  A preferred poor solvent can be appropriately selected depending on the type of polymer used. When a chlorinated organic solvent is used as the good solvent, alcohols can be preferably used. Alcohols may preferably be linear, branched or cyclic, and among them, saturated aliphatic hydrocarbons are preferred. The hydroxyl group of the alcohol may be any of primary to tertiary. As the alcohol, fluorine-based alcohol is also used. Examples thereof include 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and the like. Among the poor solvents, particularly monovalent alcohols have an effect of reducing the peeling resistance and can be preferably used. Particularly preferred alcohols vary depending on the good solvent to be selected, but considering the drying load, alcohols having a boiling point of 120 ° C. or lower are preferred, monohydric alcohols having 1 to 6 carbon atoms are more preferred, and those having 1 to 4 carbon atoms are preferred. Alcohol can be used particularly preferably. A particularly preferable mixed solvent for preparing the cyclic olefin-based resin solution is a combination in which dichloromethane is the main solvent and one or more alcohols selected from methanol, ethanol, propanol, isopropanol, or butanol are used as poor solvents.

(Dope preparation)
Next, regarding the preparation of the cyclic olefin-based resin solution (also referred to as dope) according to the present invention, a method by stirring and dissolving at room temperature, stirring at room temperature to swell the polymer, cooling from −20 ° C. to −100 ° C., and again 20 There are a cooling dissolution method in which the solution is heated to 100 ° C. for dissolution, a high temperature dissolution method in which the temperature is higher than the boiling point of the main solvent in a sealed container, and a method in which the solution is dissolved at a high temperature and high pressure up to the critical point of the solvent. A polymer having good solubility is preferably dissolved at room temperature, but a polymer having poor solubility is preferably dissolved by heating in a closed container. In the case of a polymer whose solubility is not so bad, it is easier in terms of process to select a temperature as low as possible.

The viscosity of the cyclic olefin resin solution according to the present invention is preferably in the range of 1 to 500 Pa · s at 25 ° C. More preferably, it is the range of 5-200 Pa.s. The viscosity was measured as follows. 1 mL of the sample solution was placed on a rheometer (CLS 500) with a diameter of 4 cm.
/ 2 degree Steel Cone (both manufactured by TA Instruments) was used for measurement. Measurement was started after the sample solution was kept warm at the measurement start temperature until the liquid temperature became constant.

  The cyclic olefin resin solution is characterized in that a high concentration of dope can be obtained by appropriately selecting the solvent to be used, and the cyclic olefin resin having high concentration and excellent stability without depending on the means of concentration. A solution is obtained. Furthermore, in order to make it easy to melt | dissolve, after making it melt | dissolve at a low density | concentration, you may concentrate using a concentration means. The concentration method is not particularly limited. For example, the low-concentration solution is guided between the cylindrical body and the rotation trajectory of the outer periphery of the rotating blade rotating in the circumferential direction, and the temperature between the solution and the solution. A method of obtaining a high-concentration solution while evaporating the solvent by giving a difference (for example, Japanese Patent Laid-Open No. 4-259511), blowing a heated low-concentration solution into the container from the nozzle, and until the solution hits the inner wall of the container from the nozzle In which the solvent is flash evaporated and the solvent vapor is withdrawn from the container and the concentrated solution is withdrawn from the bottom of the container (eg, US Pat. No. 2,541,012, US Pat. No. 2,858,229, US Pat. No. 4,414,341, US Pat. No. 4,504,355, etc.).

Prior to casting, it is preferable to filter off foreign matters such as undissolved matter, dust, and impurities using a suitable filter medium such as a wire mesh or flannel. For the filtration of the cyclic olefin resin solution, a filter having an absolute filtration accuracy of 0.1 to 100 μm is preferably used, and a filter having an absolute filtration accuracy of 0.5 to 25 μm is preferably used. The thickness of the filter is preferably 0.1 to 10 mm, and more preferably 0.2 to 2 mm. In that case, the filtration pressure is preferably 1.6 MPa or less, more preferably 1.3 MPa or less, further 1.0 MPa or less, and particularly preferably 0.6 MPa or less. As the filter medium, conventionally known materials such as glass fibers, cellulose fibers, filter paper, and fluororesins such as tetrafluoroethylene resin can be preferably used, and ceramics and metals are also preferably used.
The viscosity of the cyclic olefin-based resin solution immediately before film formation may be in a range that can be cast during film formation, and is usually preferably adjusted to a range of 5 Pa · s to 1000 Pa · s, preferably 15 Pa · s to 500 Pa · s is more preferable, and 30 Pa · s to 200 Pa · s is still more preferable. In addition, although the temperature at this time will not be specifically limited if it is the temperature at the time of the casting, Preferably it is -5-70 degreeC, More preferably, it is -5-35 degreeC.

(Solution casting)
A method for producing a film using a cyclic olefin resin solution will be described. As the method and equipment for producing the cyclic olefin-based resin film of the present invention, the same solution casting film forming method and solution casting film forming apparatus as those conventionally used for cellulose triacetate film production are preferably used. A preferred solution casting film forming method will be described below, but is not limited thereto.
The dope (cyclic olefin resin solution) prepared from the dissolving machine (kettle) is temporarily stored in a storage kettle, and the foam contained in the dope is defoamed for final preparation. The dope is sent from the dope discharge port to the pressure die through a pressure metering gear pump capable of delivering a constant amount of liquid with high accuracy, for example, by the number of rotations, and the dope is run endlessly from the die (slit) of the pressure die. The dry-dried dope film (also referred to as web) is peeled off from the metal support at a peeling point that is uniformly cast on the metal support and substantially rounds the metal support. Both ends of the obtained web are sandwiched between clips, transported with a tenter and dried, then transported with a roll group of a drying device, dried, and wound up to a predetermined length with a winder. The combination of the tenter and the roll group dryer varies depending on the purpose. In the solution casting film forming method used for the functional protective film for electronic displays, in addition to the solution casting film forming apparatus, surface processing on films such as an undercoat layer, an antistatic layer, an antihalation layer, a protective layer, etc. Therefore, a coating device is often added. Although each manufacturing process is described briefly below, it is not limited to these.

First, when the prepared cyclic olefin-based resin solution (dope) is prepared as a cyclic olefin-based resin film by a solvent cast method, the dope is formed on an endless metal support, for example, a metal drum or a metal support (band or belt). It is preferable to cast the film on top and evaporate the solvent to form a film. It is preferable to adjust the concentration of the dope before casting so that the amount of the cyclic olefin-based resin is 10 to 35% by mass. The surface of the drum or band is preferably finished in a mirror state. The dope is preferably cast on a drum or band having a surface temperature of 30 ° C. or lower, and particularly preferably a metal support temperature of −10 to 20 ° C.
Further, JP-A Nos. 2000-301555, 2000-301558, 7-032391, JP-A-3-193316, JP-A-5-086212, JP-A-62-237113, JP-A-2-276607. The cellulose acylate film-forming techniques described in JP-A-55-014201, JP-A-2-111511 and JP-A-2-208650 can be applied in the present invention.

  The casting film forming speed in the present invention is preferably 20 m / min or more, more preferably 25 m / min or more, and more preferably 30 m / min or more in order to improve productivity and surface quality. It is particularly preferred.

(Co-casting)
For example, the cyclic olefin resin solution may be cast as a single layer liquid on a smooth band or a drum as a metal support, or a plurality of cyclic olefin resin solutions of two or more layers may be cast. Good.

  When casting a plurality of cyclic olefin resin solutions, a solution containing a cyclic olefin resin is cast and laminated from a plurality of casting ports provided at intervals in the traveling direction of the metal support (sequentially). Laminate co-casting) films may be prepared, and for example, the methods described in JP-A Nos. 61-158414, 1-122419, and 11-198285 can be applied.

  Alternatively, the cyclic olefin resin solution may be cast from two casting ports (simultaneous lamination co-casting) to form a film.

  Alternatively, a casting method may be used in which a flow of a high-viscosity cyclic olefin resin solution is wrapped with a low-viscosity cyclic olefin resin solution and the high- and low-viscosity cyclic olefin resin solution is simultaneously extruded. Furthermore, it is also a preferable embodiment that the outer solution contains a larger amount of an alcohol component that is a poor solvent than the inner solution. Alternatively, the film is formed by peeling the film formed on the metal support using the first casting port and performing the second casting on the side in contact with the metal support surface using the two casting ports. It may be produced.

  The cyclic olefin resin solution to be cast may be the same solution or different cyclic olefin resin solutions, and is not particularly limited. In order to give a function to a plurality of cyclic olefin-based resin layers, a cyclic olefin-based resin solution corresponding to the function may be extruded from each casting port. Furthermore, the cyclic olefin resin solution may be cast simultaneously with other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, a matting agent layer, a UV absorbing layer, a polarizing layer). sell.

  In the case of co-casting, the inner and outer thicknesses are not particularly limited, but preferably the outer side is preferably 1 to 50% of the total film thickness, and more preferably 2 to 30%. Here, in the case of co-casting with three or more layers, the total thickness of the layer in contact with the metal support and the layer in contact with the air side is defined as the outer thickness. In the case of co-casting, a cyclic olefin resin film having a laminated structure may be produced by co-casting the cyclic olefin resin solutions having different additive concentrations such as the aforementioned deterioration inhibitor, ultraviolet absorber, and matting agent. it can. For example, a cyclic olefin resin film having a structure of skin layer / core layer / skin layer can be produced. For example, the matting agent can be contained in the skin layer in a large amount or only in the skin layer. The deterioration inhibitor and the ultraviolet absorber can be contained in the core layer more than the skin layer, and may be contained only in the core layer. It is also possible to change the type of deterioration inhibitor and ultraviolet absorber between the core layer and the skin layer. For example, the skin layer may contain a low volatility deterioration inhibitor and / or an ultraviolet absorber so that the core layer is plastic. It is also possible to add an excellent plasticizer or an ultraviolet absorber excellent in ultraviolet absorption. Moreover, it is also a preferable aspect to contain a peeling accelerator only in the skin layer on the metal support side. It is also preferable to add more alcohol, which is a poor solvent, to the skin layer than the core layer in order to cool the metal support by the cooling drum method to gel the solution. The Tg of the skin layer and the core layer may be different, and the Tg of the core layer is preferably lower than the Tg of the skin layer. The viscosity of the solution containing the cyclic olefin resin during casting may be different between the skin layer and the core layer, and the viscosity of the skin layer is preferably smaller than the viscosity of the core layer. It may be smaller than the viscosity of the layer.

  Any of the simultaneous lamination co-casting method and the sequential lamination co-casting method may be used for the multilayer casting of the cyclic olefin resin film. However, in general, it is more preferable to store the film by the simultaneous lamination co-casting method because of the ease of maintaining the flatness of the film, the simplicity of the process and the high productivity.

(Casting)
As a solution casting method, a method in which the prepared dope is uniformly extruded from a pressure die onto a metal support, and a method using a doctor blade in which the film thickness of the dope once cast on the metal support is adjusted with a blade. Alternatively, there is a method using a reverse roll coater that adjusts with a reverse rotating roll, and a method using a pressure die is preferable. The pressure die includes a coat hanger type and a T die type, and any of them can be preferably used. In addition to the methods listed here, it can be carried out by various methods of casting a cellulose triacetate solution known in the art, and by setting each condition in consideration of differences in the boiling point of the solvent used, etc. The same effects as described in the above publication can be obtained. The endlessly running metal support used for producing the cyclic olefin resin film of the present invention includes a drum whose surface is mirror-finished by chrome plating and a stainless steel belt (which is called a band) whose surface is mirror-finished by surface polishing. May be suitably used. The pressure die used for the production of the cyclic olefin-based resin film of the present invention may be one or two or more installed above the metal support. Preferably 1 or 2 groups. When two or more units are installed, the amount of dope to be cast may be divided into various ratios for each die, or the dope may be fed to the dies from each of a plurality of precision quantitative gear pumps. The temperature of the cyclic olefin resin solution used for casting is preferably −10 to 55 ° C., more preferably 25 to 50 ° C. In that case, all of the processes may be the same, or may be different at various points in the process. If they are different, the temperature may be a desired temperature just before casting.

(Dry)
Drying of the dope on the metal support involved in the production of the cyclic olefin-based resin film is generally performed by applying hot air from the surface side of the metal support (eg, drum or band), that is, from the surface of the web on the metal support. Method, method of applying hot air from the back of the drum or band, contact the temperature-controlled liquid from the back of the band or drum opposite the dope casting surface, and heat the drum or band by heat transfer to control the surface temperature However, the back surface liquid heat transfer method is preferable. The surface temperature of the metal support before casting may be any number as long as it is not higher than the boiling point of the solvent used for the dope. However, in order to promote drying and to lose fluidity on the metal support, the temperature should be set to 1 to 10 degrees lower than the boiling point of the lowest boiling solvent used. Is preferred. This is not the case when the casting dope is cooled and peeled off without drying.

(Peeling)
When peeling a raw dry film from a metal support, if the peeling resistance (peeling load) is large, the film may be irregularly stretched in the film forming direction, resulting in optical anisotropic unevenness. In particular, when the peeling load is large, a portion stretched stepwise in the film forming direction and a portion unstretched are alternately generated, resulting in a distribution in retardation. When loaded in a liquid crystal display device, the line or strip becomes uneven. In order not to cause such a problem, it is preferable to set the peeling load of the film to 0.25 N or less per 1 cm of the film peeling width. As a method of reducing the peeling load, there are a method of adding a release agent as described above and a method of selecting a solvent composition to be used.

  The preferable residual volatile content concentration at the time of peeling is 5 to 60% by mass. 10-50 mass% is still more preferable, and 20-40 mass% is especially preferable. Peeling with a high volatile content is preferable because the drying rate can be increased and the productivity is improved. On the other hand, when the volatile content is high, the strength and elasticity of the film are small, and the film is cut or stretched against the peeling force. Further, the self-holding force after peeling is poor, and deformation, wrinkles and nicks are likely to occur. It also causes distribution in the retardation.

(Extension process)
When the cyclic olefin resin film of the present invention is stretched, it is preferably carried out in a state where the solvent still remains in the film immediately after peeling. The general purpose of stretching is (1) to obtain a film having excellent flatness without wrinkles and deformation and uniform retardation in the in-plane direction and / or (2) to increase the in-plane retardation of the film. To do.

  In the stretching in the production method of the present invention, the preferred residual volatile content concentration in the raw dry film at the start of stretching is 15 to 60% by mass, more preferably 20 to 50% by mass, and particularly preferably 25 to 40% by mass. . The draw ratio is preferably 1 to 30%, more preferably 3 to 25%, and particularly preferably 5 to 20%. Because it is not rigid and flexible, it can not only give uniform stretching in the in-plane direction of the film, but also the distribution of retardation in the in-plane direction varies due to the progress of orientational relaxation of the cyclic olefin molecules in the film. In terms of decreasing, the residual solvent amount is preferably 15% by mass or more. On the other hand, the amount of residual solvent is preferably 60% by mass or less in that the strength and elasticity of the film are large, unintentional cutting and elongation are unlikely to occur, and the distribution of retardation in the in-plane direction is unlikely to vary. Furthermore, the self-holding force is sufficient under these conditions, and there is an advantage that it is difficult to cause deformation, wrinkles and nicks, and is useful as an optical film.

  The stretching of the film may be uniaxial stretching only in the longitudinal or transverse direction with respect to the film conveying direction, or simultaneous or sequential biaxial stretching, but simultaneous or sequential biaxial stretching is preferable in terms of optical property development and uniform control. The birefringence of the retardation film for a VA liquid crystal cell or OCB liquid crystal cell is preferably such that the refractive index in the width direction is larger than the refractive index in the length direction. Therefore, it is preferable to stretch more in the width direction (lateral direction).

  In stretching in the method for producing the cyclic olefin resin film of the present invention, the stretched film can be contracted by relaxing the film after stretching.

  When relaxation is performed, for example, it is preferable that the stretched film is contracted by holding the horizontally stretched thermoplastic resin film at a predetermined temperature for a predetermined time. The relaxation rate is preferably within 20%, more preferably within 15%, and particularly preferably within 10%. If the relaxation rate is too high, the film being transported is loosened, so that the running property is deteriorated and handling is not only worsened, but also the optical characteristic variation is increased due to the variation of the transport tension. If the holding temperature is too low, the molecular orientation in the stretching process is frozen and it becomes difficult to make the retardation value uniform, so that it is preferably held at 100 ° C. or higher, more preferably 120 ° C. or higher. The holding time is preferably 10 to 300 seconds, more preferably 30 to 180 seconds. If the holding time is too short, the stress relaxation effect is small and the retardation value cannot be made uniform, and if it is too long, the variation of the retardation value in the film thickness direction increases.

(After drying)
The cyclic olefin-based resin film is preferably further dried after stretching, and wound up with a residual volatile content of 2% or less. It is preferable to knurle both ends of the film before winding. The width of the knurling is 3 mm to 50 mm, more preferably 5 mm to 30 mm, and the height is 1 to 50 μm, preferably 2 to 20 μm, more preferably 3 to 10 μm. This may be a single push or a double push.

The thickness of the finished cyclic olefin-based resin film of the present invention (after drying) is, for example, 65 μm or less, preferably in the range of 20 to 65 μm, particularly preferably 30 to 45 μm.
The thickness of the film may be adjusted by adjusting the solid content concentration contained in the dope, the slit gap of the die base, the extrusion pressure from the die, the metal support speed, and the like. The width of the cyclic olefin-based resin film obtained as described above is preferably 0.5 to 3 m, more preferably 0.6 to 2.5 m, and still more preferably 0.8 to 2.2 m. The length is preferably 100 to 10000 m per roll, more preferably 500 to 7000 m, and still more preferably 1000 to 6000 m. When winding, knurling is preferably applied to at least one end, the width is 3 mm to 50 mm, more preferably 5 m to 30 mm, and the height is 0.5 to 500 μm, and more preferably 1 to 200 μm. This may be a single push or a double push.

  The variation in the Re (590) value in the width direction of the film is preferably ± 5 nm, and more preferably ± 3 nm. Further, the variation in the Rth (590) value in the width direction is preferably ± 10 nm, and more preferably ± 5 nm. Moreover, it is preferable that the variation in the Re value and the Rth value in the length direction is also within the range of the variation in the width direction.

  The variation of the slow axis angle in the film plane of the film preferred in the present invention is preferably in the range of −2 ° to + 2 ° with respect to the reference direction of the roll film, and in the range of −1 ° to + 1 °. More preferably, it is most preferably in the range of -0.5 ° to + 0.5 °. Here, the reference direction is the longitudinal direction of the roll film when the cyclic olefin-based resin film is longitudinally stretched, and the width direction of the roll film when it is laterally stretched.

In addition, a preferable film of the present invention has a difference ΔRe (= Re _10% −Re _80% ) between Re value at 25 ° C. and 10% RH and Re value at 25 ° C. and 80% RH of 0 to ₁₀ nm, The difference ΔRth (= Rth _10% −Rth _80% ) between the Rth value at 25 ° C. and 10% RH and the Rth value at 25 ° C. and 80% RH is 0 to 30 nm. It is preferable for reducing the taste change.

Further, a preferable film of the present invention has an equilibrium water content of not more than 3.2% at 25 ° C. and 80% RH in order to reduce the color change with time of the liquid crystal display device.
The moisture content is measured by measuring a film sample 7 mm × 35 mm by a Karl Fischer method using a moisture measuring device and a sample drying apparatus {“CA-03”, “VA-05”, both Mitsubishi Chemical Corporation}. . It is calculated by dividing the amount of water (g) by the sample mass (g).

Furthermore, a preferable film of the present invention is a liquid crystal having a moisture permeability of 40 g, 90% RH and 24 hours (converted to a film thickness of 80 μm) of 10 g / m ² · 24 hr to 500 g / m ² · 24 hr. This is preferable for reducing a change in color of the display device over time.

  The measurement method of moisture permeability is "Polymer Physical Properties II" (Polymer Experiment Course 4, Kyoritsu Shuppan), pages 285-294: Measurement of vapor permeation (mass method, thermometer method, vapor pressure method, adsorption amount method) The method described in can be applied.

  The glass transition temperature is measured by adjusting a film sample (unstretched) 5 mm × 30 mm at 25 ° C. and 60% RH for 2 hours or more, and then measuring a dynamic viscoelasticity measuring device “Vibron: DVA-225” {IT measurement Measured at a distance between grips of 20 mm, a heating rate of 2 ° C./min, a measurement temperature range of 30 ° C. to 200 ° C. and a frequency of 1 Hz, the vertical axis is the logarithmic axis and the storage modulus is The glass transition temperature Tg was defined as the temperature at which the storage elastic modulus was observed when the storage elastic modulus shifted from the solid region to the glass transition region when the temperature (° C.) was taken as a linear axis. Specifically, on the obtained chart, when the straight line 1 is drawn in the solid region and the straight line 2 is drawn in the glass transition region, the intersection of the straight line 1 and the straight line 2 decreases rapidly when the temperature rises. The glass transition temperature Tg (dynamic viscoelasticity) was determined because the film started to soften and the temperature started to shift to the glass transition region.

  The elastic modulus was measured by adjusting a protective film sample 10 mm × 150 mm at 25 ° C. and 60% RH for 2 hours or more, and then using a tensile tester “Strograph-R2” {manufactured by Toyo Seiki Seisakusho}} The distance between chucks was 100 mm, the temperature was 25 ° C., and the stretching speed was 10 mm / min.

The measurement of the hygroscopic expansion coefficient is the value L _{80% obtained} by measuring the dimension of the film left at 25 ° C. and 80% RH for 2 hours or more with the pin gauge, and the dimension of the film left at 25 ° C. and 10% RH for 2 hours or more. Was obtained by the following formula (14) from the value L _10% measured with a pin gauge.
Formula (14): (L _80% -L _10% ) / (80% RH-10% RH) × 10 ⁶

  Furthermore, the preferable film of the present invention preferably has a mass change in the range of 0 to 5% by mass when left for 48 hours under the conditions of 80 ° C. and 90% RH.

  Furthermore, the preferred film of the present invention has a dimensional change when left at 60 ° C. and 95% RH for 24 hours, and a size when left at 90 ° C. and 5% RH for 24 hours. The degree of change is preferably in the range of 0 to 5%.

A preferable film of the present invention has a photoelastic coefficient of 50 × 10 ⁻¹³ cm ² / dyn (50 × 10 ⁻⁸ cm ² / N) or less in order to reduce color change with time of the liquid crystal display device. Is preferable. As a specific measuring method, a tensile stress is applied to the major axis direction of the protective film sample 10 mm × 100 mm, and the retardation at that time is measured with an ellipsometer, for example, “M150” {JASCO Corp.} A method of calculating the photoelastic coefficient from the amount of change in retardation with respect to stress is used.

[Melting]
The film production method of the present invention may be melt film formation. A raw material such as a polymer or an additive as a raw material may be heated and melted, and this may be extruded and formed into a film by injection molding, or the raw material may be sandwiched between two heated plates and pressed to form a film.

  The temperature for heating and melting is not particularly limited as long as the raw polymer is melted uniformly. Specifically, it is heated to a temperature equal to or higher than the melting point or softening point. In order to obtain a uniform film, the material is melted by heating to a temperature higher than the melting point of the starting polymer, preferably 5 to 40 ° C. higher than the melting point, particularly preferably 8 to 30 ° C. higher than the melting point. preferable.

[Alignment film]
When the film of the present invention is used as a part of the optical compensation film, the optical compensation film may have an alignment film between the film of the present invention and the optical anisotropic layer. In addition, an alignment film is used only when an optically anisotropic layer is produced, and after producing an optically anisotropic layer on the oriented film, only the optically anisotropic layer is transferred onto the film of the present invention. Also good.
In the present invention, the alignment film is preferably a layer made of a crosslinked polymer. The polymer used for the alignment film may be either a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent. The alignment film is formed by reacting a polymer having a functional group or a polymer having a functional group introduced therein with light, heat, pH change, or the like; or a cross-linking agent that is a highly reactive compound Can be formed by introducing a linking group derived from a cross-linking agent between polymers to cross-link between the polymers.

  The alignment film made of a crosslinked polymer can be usually formed by applying a coating solution containing the polymer or a mixture of the polymer and a crosslinking agent on a support, followed by heating. In the rubbing process described later, it is preferable to increase the degree of crosslinking in order to suppress the dust generation of the alignment film. A value (1- (Ma / Mb)) obtained by subtracting 1 from the ratio (Ma / Mb) of the amount (Ma) of the crosslinking agent remaining after crosslinking to the amount (Mb) of the crosslinking agent added to the coating solution. When Mb)) is defined as the degree of crosslinking, the degree of crosslinking is preferably 50% to 100%, more preferably 65% to 100%, and most preferably 75% to 100%.

In the present invention, the polymer used for the alignment film may be either a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent. Of course, a polymer having both functions can also be used. Examples of the polymer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleimide copolymer, polyvinyl alcohol and modified polyvinyl alcohol, poly (N-methylolacrylamide), styrene / vinyl toluene copolymer. , Chlorosulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, carboxymethyl cellulose, gelatin, polyethylene, polypropylene, polycarbonate, etc. Examples thereof include compounds such as polymers and silane coupling agents. Examples of preferred polymers are water-soluble polymers such as poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyville alcohol, and modified polyvinyl alcohol, and gelatin, polyville alcohol, and modified polyvinyl alcohol are preferred. Mention may be made of bil alcohol and modified polyvinyl alcohol.
When the polyvinyl alcohol and the modified polyvinyl alcohol are directly coated on the film of the present invention, a method of providing a hydrophilic undercoat layer or applying a saponification treatment is preferably used.

Among the above polymers, polyvinyl alcohol or modified polyvinyl alcohol is preferable.
Examples of the polyvinyl alcohol include those having a saponification degree of 70 to 100%, generally those having a saponification degree of 80 to 100%, and more preferably those having a saponification degree of 82 to 98%. The polymerization degree is preferably in the range of 100 to 3000.
Examples of the modified polyvinyl alcohol include those modified by copolymerization (modified groups such as COONa, Si (OX) ₃ , N (CH ₃ ) ₃ .Cl, C ₉ H ₁₉ COO, SO ₃ Na, C ₁₂ H _25, etc. Modified by chain transfer (for example, COONa, SH, SC ₁₂ H ₂₅ etc. are introduced as modifying groups), modified by block polymerization (modified groups such as COOH, for example) , CONH ₂ , COOR (wherein R is an alkyl group having 12 or less carbon atoms, C ₆ H ₅ or the like is introduced). As a polymerization degree, the range of 100-3000 is preferable. Among these, unmodified or modified polyvinyl alcohol having a saponification degree of 80 to 100% is preferable, and unmodified or alkylthio-modified polyvinyl alcohol having a saponification degree of 85 to 95% is more preferable.
In order to impart adhesion between the film of the present invention and the optically anisotropic layer, it is preferable to introduce a crosslinking / polymerization active group into the polyvinyl alcohol, and a preferable example thereof is JP-A-8-338913. It is described in detail in the publication.
When using a hydrophilic polymer such as polyvinyl alcohol for the alignment film, it is preferable to control the moisture content from the viewpoint of the degree of hardening, preferably 0.4% to 2.5%, 0.6% More preferably, it is -1.6%. The water content can be measured with a commercially available Karl Fischer moisture content measuring device.
The alignment film preferably has a thickness of 10 microns or less.

(Polarizer)
Next, the polarizing plate of the present invention will be described.
The polarizing plate of the present invention is a polarizing plate comprising a polarizer and two protective films disposed on both sides thereof, and at least one of the protective films is the above-mentioned cyclic olefin resin film of the present invention. It is characterized by that. The polarizing plate usually has a polarizer and two transparent protective films disposed on both sides thereof. The cyclic olefin resin film of the present invention is used as both or one protective film. A normal cellulose acetate film or the like may be used for the other protective film. Examples of the polarizer include an iodine polarizer, a dye polarizer using a dichroic dye, and a polyene polarizer. The iodine polarizer and the dye polarizer are generally produced using a polyvinyl alcohol film. When the cyclic olefin-based resin film of the present invention is used as a polarizing plate protective film, the film is subjected to surface treatment as described later, and then the film-treated surface and a polarizer are bonded together using an adhesive. Examples of the adhesive used include polyvinyl alcohol adhesives such as polyvinyl alcohol and polyvinyl butyral, vinyl latexes such as butyl acrylate, and gelatin. The polarizing plate is composed of a polarizer and a protective film that protects both surfaces of the polarizer, and is further constructed by laminating a protective film on one surface of the polarizing plate and a separate film on the opposite surface. The protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection. In this case, the protect film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. Moreover, a separate film is used in order to cover the contact bonding layer bonded to a liquid crystal plate, and is used for the surface side which bonds a polarizing plate to a liquid crystal plate.

  The method of laminating the cyclic olefin resin film of the present invention to the polarizer is preferably performed such that the transmission axis of the polarizer and the slow axis of the cyclic olefin resin film of the present invention coincide with each other. In addition, when the polarizing plate produced under polarizing plate crossed Nicols was evaluated, the orthogonal accuracy between the slow axis of the cyclic olefin resin film of the present invention and the absorption axis of the polarizer (axis orthogonal to the transmission axis) is It was found that when the angle was larger than 1 °, the polarization degree performance under the polarizing plate crossed Nicols was lowered and light leakage occurred. In this case, when combined with a liquid crystal cell, sufficient black level and contrast cannot be obtained. Therefore, the deviation between the direction of the main refractive index nx of the cyclic olefin resin film of the present invention and the direction of the transmission axis of the polarizing plate is preferably within 1 °, preferably within 0.5 °.

  A spectrophotometer such as UV3100PC (manufactured by Shimadzu Corporation) can be used to measure the single plate transmittance TT, parallel transmittance PT, and orthogonal transmittance CT of the polarizing plate. In the measurement, measurement is performed in the range of 380 nm to 780 nm, and the average value of 10 measurements can be used for both single plate, parallel and orthogonal transmittance.

(Surface treatment of cyclic olefin resin film)
In this invention, in order to improve the adhesiveness of a polarizer and a protective film, it is preferable to surface-treat the surface of a cyclic olefin resin protective film. As for the surface treatment, any method may be used as long as the adhesiveness can be improved. Preferred examples of the surface treatment include glow discharge treatment, ultraviolet irradiation treatment, corona treatment, and flame treatment. The glow discharge treatment here refers to so-called low temperature plasma that occurs under low pressure gas. In the present invention, plasma treatment under atmospheric pressure is also preferable. The details of the glow discharge treatment are described in US Pat. No. 3,462,335, US Pat. No. 3,761,299, US Pat. No. 4,072,769, and British Patent No. 891469. A method described in JP-A-59-556430 in which the discharge atmosphere gas composition is changed to only the gas species generated in the container by subjecting the polyester support itself to a discharge treatment after the start of discharge is also used. In addition, the method described in Japanese Patent Publication No. 60-16614, in which the surface temperature of the film is set to 80 ° C. or higher and 180 ° C. or lower when the vacuum glow discharge treatment is performed, can also be applied.

The vacuum degree during the glow discharge treatment is preferably 0.5 to 3000 Pa, more preferably 2 to 300 Pa. The voltage is preferably between 500 and 5000V, more preferably between 500 and 3000V. The discharge frequency to be used is from direct current to several thousand MHz, more preferably 50 Hz to 20 MHz, and further preferably 1 KHz to 1 MHz. The discharge treatment intensity is preferably 0.01 KV · A · min / m ^{2 to 5} KV · A · min / m ² , more preferably 0.15 KV · A · min / m ^{2 to 1} KV · A · min / m ² . is there.

In the present invention, it is also preferable to perform an ultraviolet irradiation method as the surface treatment. For example, it can be carried out by the processing methods described in JP-B 43-2603, JP-B 43-2604, and JP-B 45-3828. The mercury lamp is a high-pressure mercury lamp made of a quartz tube and preferably has an ultraviolet wavelength of 180 to 380 nm. As for the method of ultraviolet irradiation, a high pressure mercury lamp with a dominant wavelength of 365 nm can be used as long as the surface temperature of the protective film rises to around 150 ° C. in terms of the performance of the support. When low-temperature treatment is required, a low-pressure mercury lamp having a dominant wavelength of 254 nm is preferable. It is also possible to use an ozone-less high-pressure mercury lamp and a low-pressure mercury lamp. Regarding the amount of processed light, the greater the amount of processed light, the better the adhesive strength between the thermoplastic saturated alicyclic structure-containing polymer resin film and the polarizer, but there is a problem that the film becomes colored and becomes brittle as the amount of light increases. appear. Therefore, a high-pressure mercury lamp having a main wavelength of 365 nm has a good irradiation light quantity of 20 to 10000 (mJ / cm ² ), more preferably 50 to 2000 (mJ / cm ² ). In the case of low-pressure mercury lamp for a 254nm main wavelength, the irradiation light amount 100~10000 (mJ / cm ²⁾ C., more preferably 300~1500 (mJ / cm ^2).

Furthermore, in the present invention, it is also preferable to perform a corona discharge treatment as the surface treatment. For example, it can be carried out by the processing methods described in JP-B-39-12838, JP-A-47-19824, JP-A-48-28067, and JP-A-52-42114. As the corona discharge treatment apparatus, a solid state corona treatment machine manufactured by Pillar, a LEPEL type surface treatment machine, a VETAPHON type treatment machine, or the like can be used. The treatment can be performed at normal pressure in air. The discharge frequency during the treatment is 5 to 40 KV, more preferably 10 to 30 KV, and the waveform is preferably an AC sine wave. The gap transparent lance between the electrode and the dielectric roll is 0.1 to 10 mm, more preferably 1.0 to 2.0 mm. Discharge is processed above a dielectric support roller provided in the discharge zone, and the treatment amount is 0.3 to 0.4 KV · A · min / m ² ,
More preferably, it is 0.34 to 0.38 KV · A · min / m ² .

In the present invention, it is also preferable to perform a flame treatment as the surface treatment. The gas used may be natural gas, liquefied propane gas, or city gas, but the mixing ratio with air is important.
This is because the effect of surface treatment by flame treatment is thought to be brought about by plasma containing active oxygen, and the point is how much plasma activity (temperature) and oxygen are important properties of flame. is there. The governing factor of this point is the gas / oxygen ratio. When the reaction is carried out without excess or deficiency, the energy density is the highest and the plasma activity is increased. Specifically, the preferable mixing ratio of natural gas / air is 1/6 to 1/10, preferably 1/7 to 1/9 in volume ratio. In the case of liquefied propane gas / air, 1/14 to 1/22, preferably 1/16 to 1/19, and in the case of city gas / air, 1/2 to 1/8, preferably 1/3 to 1. / 7. Further, the flame treatment amount is 1 to 50 Kcal / m ² , more preferably 3 to 20 Kcal / m ² . The distance between the burner tip and the film is 3
It should be ˜7 cm, more preferably 4-6 cm. The burner nozzle shapes are: Flynburner (US) ribbon type, Wise (US) multi-hole type, Aerogen (UK) ribbon type, Kasuga Electric (Japan) staggered multi-hole type, Koike Oxygen ( Japan) is preferred. The backup roll that supports the film for the flame treatment is a hollow roll, and is preferably cooled at a constant temperature of 20 to 50 ° C. by cooling with cooling water.

  As for the degree of surface treatment, the preferred range varies depending on the type of surface treatment and the type of cyclic olefin resin, but as a result of the surface treatment, the contact angle of the surface of the protective film subjected to the surface treatment with pure water is 50 It is preferable to be less than °. The contact angle is more preferably 25 ° or more and less than 45 °. When the contact angle of the protective film surface with pure water is in the above range, the adhesive strength between the protective film and the polarizer becomes good.

(adhesive)
When laminating a polarizer made of polyvinyl alcohol and a protective film made of a surface-treated cyclic olefin resin, it is preferable to use an adhesive containing a water-soluble polymer.
Water-soluble polymers preferably used for the adhesive include N-vinyl pyrrolidone, acrylic acid, methacrylic acid, maleic acid, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, vinyl alcohol, methyl vinyl ether, vinyl acetate. , Acrylamide, methacrylamide, diacetone acrylamide, vinyl imidazole and other homopolymers or copolymers having ethylenically unsaturated monomers as constituents, polyoxyethylene, polyoxypropylene, poly-2-methyloxazoline, methylcellulose, hydroxy Examples thereof include ethyl cellulose and hydroxypropyl cellulose gelatin. Of these, polyvinyl alcohol (PVA) and gelatin are preferred in the present invention.

  In the present invention, when PVA is used as an adhesive, it is preferable to use a crosslinking agent in combination. Examples of the cross-linking agent preferably used in combination with PVA as an adhesive include boric acid, polyvalent aldehyde, polyfunctional isocyanate compound, polyfunctional epoxy compound, and the like, but boric acid is particularly preferred in the present invention.

  When the above-mentioned crosslinking agent is used in combination, the preferred addition amount of the crosslinking agent is 0.1% by mass or more and less than 40% by mass, more preferably 0.5% by mass with respect to the water-soluble polymer in the adhesive. As mentioned above, it is less than 30 mass%. It is preferable to apply an adhesive to at least one surface of the protective film or the polarizer to form an adhesive layer, and to bond the adhesive film. Is preferably bonded to the surface of the polarizer.

(Antireflection layer)
It is preferable to provide a functional film such as an antireflection layer on the transparent protective film disposed on the opposite side of the polarizing plate from the liquid crystal cell. In particular, in the present invention, at least the light scattering layer and the low refractive index layer are laminated in this order on the transparent protective film, or the medium refractive index layer, the high refractive index layer, and the low refractive index layer are formed on the transparent protective film. An antireflection layer laminated in order is preferably used.

  It is preferable that mat particles are dispersed in the light scattering layer. The light scattering layer may have both antiglare properties and hard coat properties, and may be a single layer or may be composed of a plurality of layers, for example, 2 to 4 layers.

  The optical properties of the antireflection layer are such that the specular reflectance is 2.5% or less, the transmittance is 90% or more, and the 60 ° glossiness is 70% or less, so that reflection of external light can be suppressed and visibility is improved. Therefore, it is preferable. In particular, the specular reflectance is more preferably 1% or less, and most preferably 0.5% or less. Haze 20% to 50%, internal haze / total haze value (ratio) is 0.3 to 1, haze value after formation of low refractive index layer from haze value to light scattering layer is within 15%, comb width Prevents glare on a high-definition LCD panel by setting the transmitted image sharpness at 0.5 mm to 20% to 50% and the transmittance ratio of the vertical transmitted light / at a 2 degree tilt from the vertical to 1.5 to 5.0. Reduction of blurring of characters and the like is achieved, which is preferable.

  The low refractive index layer preferably contains a fluorine-containing polymer as a low refractive index binder. The fluorine polymer is preferably a fluorine-containing polymer that is crosslinked by heat or ionizing radiation with a coefficient of dynamic friction of 0.03 to 0.20, a contact angle with water of 90 to 120 °, and a sliding angle of pure water of 70 ° or less. When the antireflection film is attached to an image display device, the lower the peel strength from a commercially available adhesive tape, the easier it is to peel off after sticking a seal or memo, preferably 500 gf or less, more preferably 300 gf or less, and more preferably 100 gf or less. Most preferred. Further, the higher the surface hardness measured with a micro hardness tester, the harder it is to scratch, preferably 0.3 GPa or more, more preferably 0.5 GPa or more.

(Other layers of antireflection layer)
Further, a hard coat layer, a forward scattering layer, a primer layer, an antistatic layer, an undercoat layer, a protective layer, and the like may be provided.

(Liquid crystal display device)
Next, the liquid crystal display device of the present invention will be described.
The liquid crystal display device of the present invention has at least one of the above-mentioned cyclic olefin resin film of the present invention and the above-mentioned polarizing plate of the present invention.
The cyclic olefin resin film of the present invention, a retardation film comprising the film, and a polarizing plate using the film can be used for liquid crystal cells and liquid crystal display devices in various display modes. TN (Twisted Nematic), IPS (In-Plane Switching), ECB (Electrically Controled Birefringence), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-ferroelectric Liquid Crystal), OCB (Optically Compensatory Bend), STN (Supper Twisted Nematic) Various display modes such as VA (Vertically Aligned) and HAN (Hybrid Aligned Nematic) have been proposed. Of these, the IPS mode, OCB mode, or VA mode can be preferably used.

  In an IPS mode liquid crystal cell, rod-like liquid crystal molecules are aligned substantially parallel to the substrate, and the liquid crystal molecules respond in a planar manner when an electric field parallel to the substrate surface is applied. In the IPS mode, black is displayed when no electric field is applied, and the transmission axes of the pair of upper and lower polarizing plates are orthogonal. JP-A-10-54982, JP-A-11-202323, and JP-A-9-292522 are methods for reducing leakage light at the time of black display in an oblique direction and improving a viewing angle using an optical compensation sheet. No. 11-133408, No. 11-305217, No. 10-307291, and the like.

  The OCB mode liquid crystal cell is a liquid crystal display device using a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in a substantially opposite direction (symmetrically) between an upper portion and a lower portion of the liquid crystal cell. OCB mode liquid crystal cells are disclosed in US Pat. Nos. 4,583,825 and 5,410,422. Since the rod-like liquid crystal molecules are aligned symmetrically between the upper part and the lower part of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. For this reason, this liquid crystal mode is also called an OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device has an advantage of high response speed.

In a VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied.
The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). 176625 (in Japanese Patent Publication No. 176625), and (2) a liquid crystal cell (SID97, Digest of tech. Papers (Proceedings) 28 (1997) 845 in which the VA mode is converted into a multi-domain (for MVA mode) in order to enlarge the viewing angle. ), (3) A liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary collections 58-59 of the Japan Liquid Crystal Society) (1998)) and (4) SURVAVAL mode liquid crystal cells (announced at LCD International 98).
The VA mode liquid crystal display device includes a liquid crystal cell and two polarizing plates disposed on both sides thereof. The liquid crystal cell carries a liquid crystal between two electrode substrates. In one aspect of the transmissive liquid crystal display device of the present invention, the cyclic olefin resin film of the present invention is disposed between the liquid crystal cell and one polarizing plate, or the liquid crystal cell and both polarizing plates. Two are placed between the two.

  In another aspect of the transmissive liquid crystal display device of the present invention, a retardation film made of the cyclic olefin resin film of the present invention is used as a transparent protective film of a polarizing plate disposed between a liquid crystal cell and a polarizer. . The above retardation film may be used only for the transparent protective film (between the liquid crystal cell and the polarizer) of one polarizing plate, or between the polarizing plates (between the liquid crystal cell and the polarizer). The retardation film may be used for the two transparent protective films. When the retardation film is used for only one polarizing plate, it is particularly preferable to use it as a liquid crystal cell side protective film for a backlight side polarizing plate of a liquid crystal cell. The lamination to the liquid crystal cell is preferably performed on the VA cell side of the cyclic olefin resin film of the present invention. The protective film may be a normal cell rate acylate film. For example, 40-80 μm is preferable, and examples thereof include, but are not limited to, commercially available KC4UX2M (40 μm manufactured by Konica Capto), KC5UX (60 μm manufactured by Konica Capto), TD80 (80 μm manufactured by Fuji Film), and the like.

  In an OCB mode liquid crystal display device or a TN liquid crystal display device, an optical compensation film is used to expand the viewing angle. As the optical compensation film for OCB cell, a film provided with an optically anisotropic layer in which a discotic liquid crystal is hybrid-aligned and fixed on an optically uniaxial or biaxial film is used. As the optical compensation film for TN cell, a film in which an optical anisotropic layer in which a discotic liquid crystal is fixed in a hybrid orientation is fixed on a film having optical isotropy or an optical axis in the thickness direction. The cyclic olefin resin film of the present invention is useful for the production of the above-mentioned OCB cell optical compensation film and TN cell optical compensation film.

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

[Example 1]
The following composition was put into a mixing tank and stirred to dissolve each component, and then filtered through a filter paper having an average pore size of 34 μm and a sintered metal filter having an average pore size of 10 μm to prepare a dope for film formation.

(Creation of cyclic olefin resin film 101)
The following composition was put into a mixing tank, stirred to dissolve each component, and then filtered through a filter paper having an average pore size of 34 μm and a sintered metal filter having an average pore size of 10 μm.

―――――――――――――――――――――――――――――――――
Cyclic polyolefin solution D-1
―――――――――――――――――――――――――――――――――
Appear 3000 (manufactured by Ferrania) 150 parts by weight Exemplary compound (1) 6.0 parts by weight dichloromethane 380 parts by weight methanol 70 parts by weight ----------- ―――――――――

  Next, the following composition containing the cyclic polyolefin solution D-1 produced by the above method was charged into a disperser to prepare a matting agent dispersion.

――――――――――――――――――――――――――――――――――
Matting agent dispersion M-1
――――――――――――――――――――――――――――――――――
Silica particles having an average primary particle size of 16 nm (aerosil R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass Dichloromethane 73 parts by mass Methanol 10 parts by mass Cyclic polyolefin solution D-1 10 parts by mass ――――――――――― ――――――――――――――――――――――

100 parts by mass of the cyclic polyolefin solution D-1 and 1.43 parts by mass of the matting agent dispersion M-1 were mixed to prepare a dope for film formation.
The above dope was cast using a band casting machine. The film peeled off from the band with a residual solvent amount of about 30% by mass was stretched in the width direction at a stretch ratio of 10% using a tenter, and hot air was applied while holding the film so as not to cause wrinkles. Dried. Then, the tenter transport was shifted to the roll transport, and further dried at 120 to 140 ° C. and wound up. Thus, a resin film 101 having a film thickness of 45 μm was obtained.

(Creation of cyclic olefin-based tree films 102 to 107)
Cyclic olefin-based resin films 101 to 107 were produced in the same manner except that the organic rod-like compound, the draw ratio, and the thickness of the film 101 were polarized as shown in Table 1.

(Preparation of comparative cellulose ester film 201)
An optical film 201 described in Japanese Patent Application Laid-Open No. 2006-91807 was produced in the same manner as the method described in the publication, and used as a comparative cellulose ester film 201. The film uses a cellulose ester having an acetyl substitution degree of 1.95, a propionyl substitution degree of 0.7, and a total substitution degree of 2.65, and the organic rod-shaped compound (45) of the present invention.

(Preparation of comparative cellulose ester film 202)
The cellulose ester film 101 described in WO2006 / 121026A1 was produced in the same manner as the method described in the publication, and a comparative cellulose ester film 202 having a thickness of 40 μm was obtained. This film uses a cellulose ester having an acetyl substitution degree of 1.7, a propionyl substitution degree of 0.9, and a total substitution degree of 2.6, and does not use the organic rod-shaped compound of the present invention.

Comparative compound A-1: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol) (Adeka Stub manufactured by Asahi Denka Kogyo Co., Ltd.) LA-31)

Comparative compound A-1 is described in JP-A No. 2004-325523.
Comparative compounds A-2 and A-3 are described in JP-A-2006-91807.

<Re, Rth of film>
Re and Rth at a wavelength of 550 nm of the produced film were measured with a KOBRA 21ADH (manufactured by Oji Scientific Instruments) birefringence meter (in an environment with a relative humidity of 60%) according to the method described above. Similarly, the change widths of Re (550) and Rth (550) measured in an environment with a relative humidity of 80% and a relative humidity of 10% were calculated as ΔRe and ΔRth, respectively.
The results are shown in Table 1 below. The cyclic olefin-based resin film has a greater optical property than the cellulose ester film, but when it is formed into a thin film, Re is insufficient. By using the organic rod-shaped compound of the present invention, the Re and Rth values can be preferably set at a low draw ratio even for a thin film of 45 μm. The ability to reduce the thickness is preferable because it can be provided at a low cost. When the draw ratio is increased, there is a failure such as breakage and the load on the manufacturing process is large. If the draw ratio is controlled according to the embodiment of the present invention, it is possible to achieve both preferable optical characteristics and reduction in fluctuation due to environmental humidity.

[Evaluation of sheet failure]
The film sample obtained in Example 1 was wound into a roll, and this original roll was stored at 35 ° C. and 90% RH for 2 months. Each cellulose acylate film was cut into a size of 100 mm × 100 mm, observed with a polarizing microscope under crossed Nicols at a magnification of 30 times, and the following evaluation was performed with the number of foreign matters.
○: Number of foreign matters 0 to 10 Δ: Number of foreign matters 11 to 50 ×: Number of foreign matters 51 or more When the organic rod-shaped compound of the present invention is used for a cyclic olefin resin, preferable optical characteristics and reduction of surface defects are reduced. It can be compatible.

(Film surface treatment)
The both sides of the film 101 obtained in Example 1 were imparted hydrophilicity by corona discharge produced by Kasuga Electric Co., Ltd. under the condition of 12 W · min / m ² .

(Preparation of adhesive)
Polyester urethane (Mitsui Takeda Chemical Co., Takelac XW-74-C154) 10 parts and isocyanate cross-linking agent (Mitsui Takeda Chemical Co., Takenate WD-725) 1 part are dissolved in water and the solid content is 20%. A solution adjusted to 1 was prepared. This was used as an adhesive.

(Preparation of polarizing plate)
A polarizer was produced by adsorbing iodine to a stretched polyvinyl alcohol film.
After the adhesive solution is applied to both sides of the polarizer, the film surface is in contact with the polarizer so that the polarizer is sandwiched between the film 101 and the saponified FUJITAC TD80UF (manufactured by FUJIFILM Corporation). Then, they were bonded together and dried and cured in an oven at 40 ° C. for 72 hours to produce a polarizing plate 101.
Further, using the films 102 to 107, polarizing plates were produced in the same manner as described above, and the polarizing plates were used as the polarizing plates 102 to 107, respectively.
The comparative cellulose ester films 201 and 202 were saponified and attached to one side of the polarizer using a polyvinyl alcohol-based adhesive. Saponified Fujitac TD80UF was attached to the opposite side of the polarizer and dried at 70 ° C. for 10 minutes or more. These were designated as polarizing plates 201 and 202.
The saponification treatment was performed under the following conditions.
A 1.5 mol / liter aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.01 mol / liter dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C. The produced cellulose acylate film was immersed in the aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to thoroughly wash away the aqueous sodium hydroxide solution. Subsequently, after being immersed in the above-mentioned dilute sulfuric acid aqueous solution for 1 minute, it was immersed in water to sufficiently wash away the dilute sulfuric acid aqueous solution. Finally, the sample was thoroughly dried at 120 ° C.

<Production of liquid crystal cell>
The liquid crystal cell has a cell gap between substrates of 3.6 μm, and a liquid crystal material having negative dielectric anisotropy (“MLC6608”, manufactured by Merck & Co., Inc.) is dropped and sealed between the substrates. Prepared by forming a layer. The retardation of the liquid crystal layer (that is, the product Δn · d of the thickness d (μm) of the liquid crystal layer and the refractive index anisotropy Δn) was set to 300 nm. The liquid crystal material was aligned so as to be vertically aligned.

<Mounting on VA panel>
(Polarizing plates 101 to 107)
A commercially available super high contrast product (HLC2-5618 manufactured by Sanlitz Co., Ltd.) was used for the upper polarizing plate (observer side) of the liquid crystal display device using the vertical alignment type liquid crystal cell. The polarizing plates 101 to 107 were placed on the lower polarizing plate (backlight side) so that the films 101 to 107 were on the liquid crystal cell side. The upper polarizing plate and the lower polarizing plate were attached to the liquid crystal cell via an adhesive. The crossed nicols were arranged so that the transmission axis of the upper polarizing plate was in the vertical direction and the transmission axis of the lower polarizing plate was in the horizontal direction.
(Polarizing plates 201 and 202)
The above polarizing plates 201 and 202 are placed in two places on the upper polarizing plate (observer side) and the lower polarizing plate (backlight side) of the liquid crystal display device using the vertical alignment type liquid crystal cell, and the cellulose ester films 201 and 202. Was placed on the liquid crystal cell side. The upper polarizing plate and the lower polarizing plate were attached to the liquid crystal cell via an adhesive. The crossed nicols were arranged so that the transmission axis of the upper polarizing plate was in the vertical direction and the transmission axis of the lower polarizing plate was in the horizontal direction.

A rectangular wave voltage of 55 Hz was applied to the liquid crystal cell. A normally black mode of white display 5V and black display 0V was set. The black display transmittance (%) at the azimuth angle of 45 degrees and the polar angle of 60 degrees and the color shift Δx between the azimuth angle of 45 degrees polar angle of 60 degrees and the azimuth angle of 180 degrees and polar angle of 60 degrees were obtained. .
Further, using the measuring device (EZ-Contrast 160D, manufactured by ELDIM) as the contrast ratio, the transmittance ratio (white display / black display), the visual field is displayed in eight stages from black display (L1) to white display (L8). The angle (a polar angle range with a contrast ratio of 10 or more and no black-side gradation inversion) was measured. The results are shown in Table 1.

Viewing angle (polar angle range with contrast ratio of 10 or more and no black-side gradation inversion)
○ Polar angle 80 ° or more in top / bottom / left / right ○ △ Polar angle 80 ° or more in three directions, top / bottom / left / right △ Polar angle 80 ° or more in two directions, top / bottom / right / left More than 80 degrees

  By using the film of the present invention, a good contrast can be realized in the front direction and the viewing angle direction of the liquid crystal panel.

[Example 2]
(Creation of cyclic olefin-based tree film 301)
The following composition was put into a mixing tank, stirred to dissolve each component, and then filtered through a filter paper having an average pore size of 34 μm and a sintered metal filter having an average pore size of 10 μm.

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Cyclic polyolefin solution D-2
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Cyclic polyolefin: 150 parts by weight of ARTON-G Liquid paraffin: Daphne Oil CP68 (Idemitsu Kosan Co., Ltd.) 10 parts by weight Exemplary compound (41) 6 parts by weight Dichloromethane 450 parts by weight -------- ――――――――――――――――――――

  Next, the following composition containing the cyclic polyolefin solution prepared by the above method was charged into a disperser to prepare a fine particle dispersion.

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Fine particle dispersion M-2
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Silica particles having a primary average particle size of 16 nm (aerosil R972 Nippon Aerosil Co., Ltd.) 2 parts by mass Dichloromethane 83 parts by mass Cyclic polyolefin solution D-1 10 parts by mass ――――――――――――――― ―――――――――――――――――

100 parts by mass of the cyclic polyolefin solution D-2 and 1.35 parts by mass of the fine particle dispersion M-2 were mixed to prepare a dope for film formation. The above dope was cast using a band casting machine, dried at 120 ° C. to a residual solvent content of 15%, and the film was peeled off. After drying to a residual solvent content of 5% at an ambient temperature of 100 ° C., it was further dried at 120 ° C. for 30 minutes, and stretched 30% in the width direction at 135 ° C. while being conveyed. The clip was removed and further dried at 120 ° C. for 30 minutes to produce a cyclic olefin-based tree film 301. The film 301 thus produced had a residual solvent amount of 0.1% and a film thickness of 50 μm.
The obtained film was evaluated in the same manner as in Example 1, and it was as good as the sample 102 in Re, Rth and its environmental humidity change, surface condition evaluation, and panel mounting evaluation.

Claims (11)

  A cyclic olefin-based resin film comprising at least one organic rod-shaped compound having at least one aromatic ring. The said cyclic | annular olefin resin film of Claim 1 whose said organic rod-shaped compound is a compound represented by following General formula (1).

(In the formula, Ar ¹ and Ar ³ each independently represent an aryl group or an aromatic heterocycle, Ar ² represents an arylene group or an aromatic heterocycle, and L ¹ and L ² each independently represent a single bond, or Represents a divalent linking group, n represents an integer of 3 or more, and Ar ² and L ² may be the same or different, respectively.   The cyclic olefin resin film according to claim 1 or 2, wherein an octanol / water partition coefficient (log P) of the organic rod-shaped compound or the compound represented by the general formula (1) is 8 or more and 20 or less.   The film thickness of the said cyclic olefin resin film is 65 micrometers or less, The cyclic olefin resin film in any one of Claims 1-3 characterized by the above-mentioned.   The cyclic olefin resin film according to claim 1, wherein the cyclic olefin resin film is stretched.   The cyclic olefin resin film according to claim 5, wherein the draw ratio is 1% or more and 30% or less. It is formed using the cyclic olefin resin which is at least 1 sort (s) chosen from the group which consists of following [A-1], [A-2], and [A-3]. The cyclic olefin-type resin film in any one.
[A-1] An addition copolymer containing at least one type of repeating unit represented by the following general formula (I) and at least one type of repeating unit represented by the following general formula (II):
[A-2] an addition (co) polymer containing at least one repeating unit represented by the following general formula (II), and
[A-3] A ring-opening (co) polymer containing at least one repeating unit represented by the following general formula (III).

Wherein R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X ¹ and Y ¹ each independently represent a hydrogen atom or a hydrocarbon having 1 to 10 carbon atoms. Group, halogen atom, C 1-10 hydrocarbon group substituted with halogen atom, — (CH ₂ ) _n COOR ⁵¹ , — (CH ₂ ) _n OCOR ⁵² , — (CH ₂ ) _n NCO, — (CH _{2) n NO 2, - (} CH 2) n CN, - (CH 2) n CONR 53 R 54, - (CH 2) n NR 53 R 54, - (CH 2) n OZ, - (CH 2) n Represents W, or (—CO) ₂ O or (—CO) ₂ NR ⁵⁵ composed of X ¹ and Y ¹ , wherein R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , and R ⁵⁵ represent a hydrogen atom or Represents a hydrocarbon group having 1 to 20 carbon atoms, Z represents a hydrocarbon group or a hydrocarbon group substituted with a halogen, and W represents Si. R ⁵⁶ _p D _3-p (R ⁵⁶ represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom, —OCOR ⁵⁶ or —OR ⁵⁶ , and p represents an integer of 0 to 3) ), N represents an integer of 0 to 10.)

(In the formula, m represents an integer of 0 to ^4. R ³ and R ⁴ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X ² and Y ² each independently represent a hydrogen atom, hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen _{atom, - (CH 2) n COOR} 51, - (CH 2) n OCOR 52, - (CH _{2) n NCO, - (CH} 2) n NO 2, - (CH 2) n CN, - (CH 2) n CONR 53 R 54, - (CH 2) n NR 53 R 54, - (CH 2) n OZ, — (CH ₂ ) _n W, or (—CO) ₂ O or (—CO) ₂ NR ⁵⁵ composed of X ² and Y ² represents R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ And R ⁵⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and Z represents a hydrocarbon group or a hydrocarbon substituted with a halogen. Represents the original, W is represents _{^{SiR 56 p D 3-p,}} (R 56 represents a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom, -OCOR ⁵⁶ or -OR ^56, p is N represents an integer of 0 to 3, and n represents an integer of 0 to 10.)

(In the formula, m represents an integer of 0 to 4. R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X ³ and Y ³ each independently represent a hydrogen atom, hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen _{atom, - (CH 2) n COOR} 51, - (CH 2) n OCOR 52, - (CH _{2) n NCO, - (CH} 2) n NO 2, - (CH 2) n CN, - (CH 2) n CONR 53 R 54, - (CH 2) n NR 53 R 54, - (CH 2) n OZ, — (CH ₂ ) _n W, or (—CO) ₂ O or (—CO) ₂ NR ⁵⁵ composed of X ³ and Y ³ represents R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ And R ⁵⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and Z is a hydrocarbon group or a hydrocarbon substituted with a halogen. Represents the original, W is represents _{^{SiR 56 p D 3-p,}} (R 56 represents a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom, -OCOR ⁵⁶ or -OR ^56, p is N represents an integer of 0 to 3, and n represents an integer of 0 to 10.) The said cyclic olefin resin film satisfy | fills the relationship of following Numerical formula (1), The cyclic olefin resin film in any one of Claims 1-7 characterized by the above-mentioned.
Formula (1) Re (550)> 20 and Rth (550)> 50
(In the formula, Re (λ) is an in-plane retardation value of the film with respect to light of wavelength λ nm, and Rth (λ) is a retardation value of the film in the thickness direction with respect to light of wavelength λ nm (unit: : Nm).)   A polarizing plate comprising a polarizer and a pair of protective films disposed on both sides thereof, wherein at least one of the protective films is the cyclic olefin-based resin film according to claim 1. A characteristic polarizing plate.   A liquid crystal display device comprising at least one of the cyclic olefin resin film according to claim 1 and the polarizing plate according to claim 9.   A VA mode liquid crystal display device comprising a liquid crystal cell and a pair of polarizing plates disposed on both sides of the liquid crystal cell, wherein the polarizing plate is the polarizing plate according to claim 9.