JP2010054804A - Laminate film, method for manufacturing laminate film, polarizing plate having laminate film, and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate film excellent in economic efficiency and durability performance without using an orientation material, a method for manufacturing the laminate film, a polarizing plate using the laminate film as a protective film, and a liquid crystal display element using the polarizing plate. <P>SOLUTION: The laminate film has a cyclic olefin series resin layer (A) and a liquid crystal orientation layer (B) made by photopolymerizing a rod-shaped liquid crystal having a photopolymerizable group, in which the cyclic olefin series resin layer (A) and the liquid crystal orientation layer (B) are in direct contact with each other. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a laminated film having a liquid crystal layer (B) obtained by photopolymerizing a cyclic olefin resin layer (A) and a rod-like liquid crystal having a photopolymerizable group, a method for producing the laminated film, and a protective film for the laminated film. The present invention relates to a polarizing plate used in the above and a liquid crystal display device including the polarizing plate.

  In recent years, liquid crystal display elements are required to have a larger size, and display performance with uniform and high contrast over the entire surface of the liquid crystal display element. In addition, display performance with a wider range of viewing angles is required as screens become larger. In order to obtain such a wide viewing angle, generally a polarizing plate having a retardation film and a polarizer. Is provided outside the liquid crystal cell to provide a viewing angle compensation function.

  In a TN mode liquid crystal display element, a method of compensating the viewing angle by using a polarizing plate using a laminated optical film in which a discotic liquid crystal (disc-shaped liquid crystal) is coated on a transparent film as a retardation film is generally used. (Patent Document 1). A method of using a transparent film having a rod-like polymer liquid crystal layer as a retardation film is also known for compensating the viewing angle of a TN mode liquid crystal display element (Patent Document 2).

  However, any of the above retardation films uses an alignment material such as an alignment film in order to align the liquid crystal material in a desired direction. By using the alignment material, the alignment material itself is not only expensive, but also ensures the adhesion between the alignment material and the transparent film or liquid crystal material, establishes the coating condition of the alignment material, or rubs. It is necessary to establish the conditions. In addition, the product yield decreases due to foreign matter generated by rubbing cloth falling off during rubbing, foreign matter generated by scraping the alignment material, and environmental foreign matter attached by charging, so a washing facility such as a water washing device is installed to remove foreign matter. Must-have. For this reason, there is a problem that the number of processes increases, resulting in a problem that the product yield is lowered, which is disadvantageous in terms of cost.

In recent years, durability performance required for liquid crystal display elements has become increasingly severe. For example, liquid crystal display elements are used for automobile instrument panels, car navigation, and the like, but in order to ensure safety during driving, liquid crystal display elements are required to have further durability performance. Conventionally, a TAC (triacetyl cellulose) film is generally used as a transparent film of a retardation film for a TN mode liquid crystal display element, but has a wide viewing angle particularly in an environment of high humidity and high temperature. In addition, a retardation film whose display performance does not change has been eagerly desired.
JP-A-7-333597 JP 2000-66192 A

  The inventors of the present invention have a cyclic olefin resin layer (A) and a liquid crystal layer (B) obtained by photopolymerizing a rod-like liquid crystal having a photopolymerizable group, and the cyclic olefin resin layer (A). And a liquid crystal layer (B) formed by photopolymerizing a rod-like liquid crystal having a photopolymerizable group are laminated in direct contact with each other, so that a laminated film having excellent economy and durability can be obtained. I found it. The present invention provides a laminated film excellent in economic efficiency and durability, a method for producing the laminated film, a polarizing plate using the laminated film as a protective film, and a liquid crystal display device using the polarizing plate. This is the issue.

  The laminated film of the present invention comprises a cyclic olefin resin layer (A) having a repeating unit represented by the following formula (I) and a liquid crystal layer (B) formed by photopolymerizing a rod-like liquid crystal having a photopolymerizable group. And the cyclic olefin resin layer (A) and the liquid crystal layer (B) are in direct contact with each other.

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

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

  In the laminated film of the present invention, it is also preferred that the cyclic olefin resin further has a repeating unit represented by the following formula (II).

[式（ＩＩ）中、Ｄ^１は−ＣＨ＝ＣＨ−または−ＣＨ₂ＣＨ₂−で表される基であり、Ｒ¹〜Ｒ⁴はそれぞれ独立に水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子もしくはケイ素原子を含む連結基；置換もしくは非置換の炭素原子数１〜３０の炭化水素基；極性基よりなる群から選ばれる原子もしくは基を表し、Ｒ¹およびＲ²は一体化して２価の炭化水素基を形成してもよく、Ｒ³およびＲ⁴は一体化して２価の炭化水素基を形成してもよい。Ｒ¹〜Ｒ⁴から選ばれる２つの基が互いに結合して単環の脂環式炭化水素環または複素環を形成してもよい。］

[In Formula (II), D ¹ is a group represented by —CH═CH— or —CH ₂ CH ₂ —, and R ^{1 to} R ⁴ each independently represent a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom. A linking group containing a nitrogen atom or a silicon atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms; an atom or group selected from the group consisting of polar groups, wherein R ¹ and R ² are combined A divalent hydrocarbon group may be formed, and R ³ and R ⁴ may be integrated to form a divalent hydrocarbon group. Two groups selected from R ^{1 to} R ⁴ may be bonded to each other to form a monocyclic alicyclic hydrocarbon ring or heterocyclic ring. ]

  The cyclic olefin-based resin layer (A) of the present invention preferably has a phase difference.

  In the laminated film of the present invention, the liquid crystal layer (B) formed by photopolymerizing a rod-like liquid crystal having a photopolymerizable group is preferably hybrid-aligned.

The method for producing a laminated film of the present invention comprises a liquid crystal composition containing a rod-like liquid crystal having a photopolymerizable group on at least one side of a cyclic olefin resin layer (A) having a repeating unit represented by the formula (I). It includes a step (I-2) of forming a rod-like liquid crystal-containing layer having a photopolymerizable group by coating, and a step (II) of irradiating light to the rod-like liquid crystal layer having the photopolymerizable group.

The manufacturing method of the laminated | multilayer film of this invention performs the process (I-1) which performs a rubbing process on the surface which touches the liquid crystal layer (B) of a cyclic olefin resin layer (A) before the said process (I-2). It is also preferable to have it.

In the method for producing a laminated film of the present invention, the liquid crystal composition containing a rod-like liquid crystal having a photopolymerizable group preferably contains a compound represented by the following formula (A).

[式（Ａ）中、Ｒ^５は炭素数２〜５の炭化水素基を表し、Ｒ^６、Ｒ^７は相互に独立に水素、炭素数１〜１０の炭化水素基、炭素数６〜２０の芳香族炭化水素基、−Ｃ（Ｏ）Ｒ^８を表し、Ｒ^８は炭素数１〜１０の炭化水素基を表す。]

[In the formula (A), R ⁵ represents a hydrocarbon group having 2 to ⁵ carbon atoms, R ⁶ and R ⁷ are each independently hydrogen, a hydrocarbon group having 1 to 10 carbon atoms, or a carbon group having 6 to 20 carbon atoms. An aromatic hydrocarbon group, —C (O) R ⁸ is represented, and R ⁸ represents a hydrocarbon group having 1 to 10 carbon atoms. ]

In the method for producing a laminated film of the present invention, a liquid crystal composition containing a rod-like liquid crystal having a photopolymerizable group is added to a compound represented by the following formula (B) in addition to the compound represented by the above formula (A). It is also preferable to include.

[式（Ｂ）中、Ｒ^９、Ｒ^１０は相互に独立に水素、炭素数１〜１０の炭化水素基、炭素数６〜２０の芳香族炭化水素基を表す。]

[In Formula (B), R ⁹ and R ¹⁰ each independently represent hydrogen, a hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. ]

In the method for producing a laminated film of the present invention, a liquid crystal composition containing a rod-like liquid crystal having a photopolymerizable group is used as a compound represented by the formula (A) as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol. It is also preferable to contain at least one selected from monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, and ethylene glycol mono t-butyl ether.

In the method for producing a laminated film of the present invention, a liquid crystal composition containing a rod-like liquid crystal having a photopolymerizable group is added as a compound represented by the formula (B) in addition to the compound represented by the formula (A). It is also preferable to contain at least one selected from acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone.

  According to the present invention, it is possible to provide a laminated film for a liquid crystal display element excellent in economic efficiency and durability, a polarizing plate using the laminated film as a protective film, and a liquid crystal display element using the polarizing plate. it can. In particular, it can be suitably used for a TN mode liquid crystal display element.

Hereinafter, the present invention will be specifically described.
<Cyclic olefin resin layer (A)>
The cyclic olefin resin layer (A) of the present invention contains a cyclic olefin resin having a cyclic olefin and a repeating unit represented by the formula (I).

<Cyclic olefin resin>
The cyclic olefin resin contained in the laminated film according to the present invention has a repeating unit represented by the formula (I).

Method for Producing Cyclic Olefin Resin The cyclic olefin resin according to the present invention has a repeating unit represented by the formula (I). It is also preferable to have a repeating unit represented by the formula (II) from the viewpoint of laminated film slidability and retardation development.
The repeating unit represented by the formula (I) is derived from a cyclic olefin monomer represented by the following formula (I ′) by ring-opening (co) polymerization.

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

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the hydrocarbon group having 1 to 10 carbon atoms include alkyl groups such as methyl group, ethyl group, and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group, allyl group, and propenyl group. Groups and the like.

In addition, the substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure, or may be bonded via a linking group. Examples of the linking group include a divalent hydrocarbon group having 1 to 10 carbon atoms (for example, an alkylene group represented by — (CH ₂ ) _m — (wherein m is an integer of 1 to 10)); oxygen , A linking group containing nitrogen, sulfur or silicon (for example, a carbonyl group (—CO—), an oxycarbonyl group (—O (CO) —), a sulfone group (—SO ₂ —), an ether bond (—O—), Thioether bond (—S—), imino group (—NH—), amide bond (—NHCO—, —CONH—), siloxane bond (—OSi (R) ₂ — (wherein R is an alkyl such as methyl or ethyl) Group)) and the like, and a linking group containing a plurality of these may be used.

In order to ensure the birefringence controllability of the cyclic olefin resin, m in the formula (I) is preferably 0 to 4, more preferably 0 to 2, further preferably 0 to 1, and p is preferably 0 to 0. 4, More preferably, it is 0-2, More preferably, it is 0-1. The number of carbon atoms of R ^{1 to} R ⁴ is preferably 1 to 25, more preferably 1 to 20, and still more preferably 1 to 10. Furthermore, the number of carbon atoms of R ^{1 to} R ⁴ in the formula (II) is preferably 1 to 25, more preferably 1 to 20.

Specific examples of the cyclic olefin monomer (I ′) include the following compounds.
Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
Pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- pentadecene,
8-methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-ethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl -8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl -8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,

8-cyano-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-cyano-8-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-phenyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-fluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-fluoro-methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 difluoromethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 pentafluoroethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8-difluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-difluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- trifluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9,9- tetrafluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,

8,8,9,9- tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- trifluoro-9-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- trifluoro-9-trifluoromethoxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- trifluoro-9-pentafluoro propoxy tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-Fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-difluoro-8-heptafluoroisopropyl-9-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-Chloro -8,9,9- trifluoro tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8- (2,2,2-trifluoroethoxy-carbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8- (2,2,2-trifluoroethoxy-carbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
These can be used alone or in combination of two or more.

Examples of the cyclic olefin monomer (I ′) include 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . It is particularly preferable that the polymer has 1 ^7,10 ] -3-dodecene.

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

（式（ＩＩＩ）中、ｐは０または１〜５の整数であり、Ｒ’は炭素原子数１〜１５の炭化水素基である。）
前記式（ＩＩＩ）において、ｐの値が小さいものほど、また、Ｒ’が炭素数の小さいほど、得られる共重合体のガラス転移温度が高くなり、耐熱性が向上するので好ましい。すなわち、ｐは通常０または１〜５の整数であるが、好ましくは０または１であり、また、Ｒ’は通常炭素原子数１〜１５の炭化水素基であるが、好ましくは炭素原子数１〜３のアルキル基であるのが望ましい。

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

  Further, in the formula (I) or (I ′), when an alkyl group is further bonded to the carbon atom to which the polar group represented by the formula (III) is bonded, the heat resistance of the resulting copolymer is increased. And water absorption (wet) properties are preferable. Moreover, it is preferable that the carbon atom number of an alkyl group is 1-5, More preferably, it is 1-2, Most preferably, it is 1.

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

(In formula (II ′), R ^{1 to} R ⁴ are the same as those in formula (II).)
Specific examples of such cyclic olefin monomers include the following compounds.
Bicyclo [2.2.1] hept-2-ene (norbornene),
Bicyclo [2.2.1] hepta-2,5-diene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-propylbicyclo [2.2.1] hept-2-ene,
5-butylbicyclo [2.2.1] hept-2-ene,
5-pentylbicyclo [2.2.1] hept-2-ene,
5-hexylbicyclo [2.2.1] hept-2-ene,
5-heptylbicyclo [2.2.1] hept-2-ene,
5-octylbicyclo [2.2.1] hept-2-ene,
5-nonylbicyclo [2.2.1] hept-2-ene,
5-decylbicyclo [2.2.1] hept-2-ene,
5-undecylbicyclo [2.2.1] hept-2-ene,
5-dodecylbicyclo [2.2.1] hept-2-ene,
5-tridecylbicyclo [2.2.1] hept-2-ene,
5-tetradecylbicyclo [2.2.1] hept-2-ene,
5-pentadecylbicyclo [2.2.1] hept-2-ene,

5-hexadecylbicyclo [2.2.1] hept-2-ene,
5-heptadecylbicyclo [2.2.1] hept-2-ene,
5-octadecylbicyclo [2.2.1] hept-2-ene,
5-nonadecylbicyclo [2.2.1] hept-2-ene,
5-icosylbicyclo [2.2.1] hept-2-ene,
5-phenylbicyclo [2.2.1] hept-2-ene,
5-cyanobicyclo [2.2.1] hept-2-ene,
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methoxycarbonyl-5-methylbicyclo [2.2.1] hept-2-ene,
5-ethoxycarbonyl-5-methylbicyclo [2.2.1] hept-2-ene,
5-Cyano-5-methylbicyclo [2.2.1] hept-2-ene 5-ethylidenebicyclo [2.2.1] hept-2-entylcyclo [4.3.0.1 ^2,5 ] deca -3,7-diene (dicyclopentadiene)
These can be used alone or in combination of two or more. Among these, the presence of bicyclo [2.2.1] hept-2-ene and tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (dicyclopentadiene) is also considered to be a slip of the laminated film. It is preferable in terms of mobility and retardation development and alignment control of the liquid crystal alignment layer.

  In the present invention, when the cyclic olefin monomer (II ′) is used, the copolymerization ratio is usually 100% by mass when the total of the structural units constituting the cyclic olefin resin is 100 parts by mass. It is desirable that the body (II ′) is in the range of 0 to 40 parts by mass, preferably 3 to 30 parts by mass. When the copolymerization ratio of the cyclic olefin monomer (II ′) exceeds 30 parts by mass, the glass transition temperature may be lowered, and the heat resistance stability of various film properties such as retardation and dimensions may be lowered. If it is less than 3 masses, the slidability and retardation development property of the resulting molded article, film or sheet may deteriorate.

  In the present invention, in addition to these cyclic olefin monomers (I ′) and (II ′), other cyclic olefin monomers or other copolymerizable monomers may be used as long as the object of the present invention is not impaired. A small amount of a monomer can be used as a copolymer raw material monomer, and the cyclic olefin resin according to the present invention can contain a repeating unit other than the repeating units represented by the formulas (I) and (II). Such repeating units are formed, for example, by ring-opening copolymerization of cycloolefin monomers such as cyclobutene, cyclopentene, cycloheptene, and cyclooctene together with the cyclic olefin monomers (I ′) and (II ′). can do. In addition, in the presence of an unsaturated hydrocarbon polymer having an olefinically unsaturated bond in the main chain, such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-nonconjugated diene copolymer, polynorbornene, etc. It can also be formed by ring-opening copolymerization of the olefinic monomers (I ′) and (II ′), and when having such a repeating unit, the impact resistance of the copolymer of the present invention is as follows. Tend to be improved.

  As the cyclic olefin-based resin contained in the laminated film according to the present invention, a cyclic olefin-based monomer having a norbornene skeleton other than the formula (I) in addition to the cyclic olefin resin, as long as the effects of the present invention are not impaired. Ring-opening (co) polymers, hydrogenated products of ring-opening (co) polymers, addition (co) polymers, or other monomers copolymerizable with cyclic olefin monomers other than the above formula (I) A copolymer with a monomer, a hydrogenated product thereof, and the like can be used in combination.

  However, in the present invention, it is preferable to carry out copolymerization using only the cyclic olefinic monomers (I ′) and (II ′). That is, the cyclic olefin resin according to the present invention may have other repeating units within a range not impairing the object of the present invention in addition to the repeating units represented by the formulas (I) and (II). However, it is preferable that it does not have repeating units other than the repeating unit represented by the said formula (I) and (II).

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

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

  The hydrogenation rate of the olefinically unsaturated bond is usually 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, and particularly preferably 99 mol% or more. As described above, the hydrogenation reaction in the present invention is for olefinic unsaturated bonds in the molecule, and when the cyclic olefin resin according to the present invention has an aromatic group, the aromatic group is refracted. Since there may be an advantageous effect on optical characteristics such as the rate and heat resistance, hydrogenation is not necessarily required.

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

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

  The molecular weight distribution (Mw / Mn) of the cyclic olefin-based resin according to the present invention is usually 1.5 to 10, preferably 2 to 7, and more preferably 2 to 5.

  The cyclic olefin resin according to the present invention has a saturated water absorption at 23 ° C. of usually 0 to 1% by mass, preferably 0.05 to 0.8% by mass, and more preferably 0.1 to 0.7% by mass. It is desirable. If the saturated water absorption of the cyclic olefin-based resin according to the present invention is within the above range, various optical properties, transparency, retardation and retardation uniformity, or dimensional accuracy of the obtained film are high temperature and high humidity. In addition to being stably maintained even under such conditions, it is excellent in adhesion and adhesion to other materials, so that peeling does not occur during use, and it is compatible with additives such as antioxidants. Since solubility is also favorable, the freedom degree of selection of the kind and addition amount of an additive becomes large.

When this saturated water absorption is less than 0.05% by mass, the resulting film has low adhesion and adhesiveness to other materials, and is liable to cause peeling during use. The amount of additives such as these may be limited. On the other hand, when the saturated water absorption exceeds 1% by mass, the water absorption tends to cause changes in optical characteristics and dimensional changes.
Here, the saturated water absorption is a value obtained by immersing in water at 23 ° C. for 1 week and measuring an increased mass in accordance with ASTM D570.

  The glass transition temperature (Tg) of the cyclic olefin resin according to the present invention is usually 70 to 250 ° C, preferably 90 to 200 ° C, more preferably 100 to 180 ° C. A Tg of 120 ° C. or higher is preferable because of having excellent heat resistance. When Tg is less than 90 ° C., the heat distortion temperature becomes low, which may cause a problem in heat resistance, and a problem that a change in optical characteristics due to temperature in the obtained film becomes large may occur. is there. On the other hand, when Tg exceeds 200 ° C., the processing temperature becomes too high during the stretching process, and the copolymer of the present invention may be thermally deteriorated, and productivity and workability may be deteriorated.

In this specification, the Tg of the cyclic olefin-based resin is the maximum peak of the differential differential scanning calorimetry curve obtained when measured with a differential scanning calorimeter (DSC) in a nitrogen atmosphere at a heating rate of 20 ° C./min. Plot the temperature (point A) and -20 ° C from the maximum peak temperature (point B) on the differential scanning calorimetry curve, and the tangent on the baseline starting from point B and the tangent starting from point A It is required as an intersection.
The cyclic olefin resin according to the present invention preferably has transparency and heat resistance, and preferably has a glass transition temperature of 120 ° C. or higher and a linear expansion coefficient of 7.0 × 10 ⁻⁵ / ° C. or lower.

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

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

  Examples of the solvent used in the ring-opening copolymerization reaction (that is, a solvent that dissolves a monomer, a ring-opening polymerization catalyst, a molecular weight regulator, etc.) include, for example, alkanes, cycloalkanes, aromatic hydrocarbons, and halogenated alkanes. , Compounds such as aryl halides, saturated carboxylic acid esters and ethers, among which aromatic hydrocarbons are preferred. These can be used singly or in combination of two or more.

  A ring-opening copolymer obtained by ring-opening copolymerization of each cyclic olefin monomer has an olefinic unsaturated bond in the molecule and has problems such as heat-resistant coloring. The olefinically unsaturated bond is preferably hydrogenated. The hydrogenation method and the preferred hydrogenation rate are as described above.

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

The said antioxidant can be mix | blended in the ratio of 0.001-5 mass parts per 100 mass parts of said polymers. Specific examples of antioxidants include
A phenolic antioxidant or a hydroquinone antioxidant, a phosphorus secondary antioxidant, a sulfur secondary antioxidant, etc. can be mentioned.

  Moreover, a flame retardant can also be mix | blended with the cyclic olefin resin which concerns on this invention. A well-known thing can be used as a flame retardant, For example, a halogen flame retardant, an antimony flame retardant, a phosphate ester flame retardant, a metal hydroxide, etc. can be mentioned. Among them, a phosphate ester flame retardant that exhibits an effect with a small amount of blending and can minimize deterioration of water absorption, low dielectric constant, and transparency is preferable, and a condensed phosphate ester flame retardant is more preferable. The blending amount depends on the selected flame retardant and the required degree of flame retardancy, but is preferably 0.5 to 40 parts by weight, more preferably 2 to 30 parts by weight, based on 100 parts by weight of the cyclic olefin polymer. ˜20 parts by mass is particularly preferred. When the blended amount of the flame retardant is less than 0.5 parts by mass, the effect is insufficient. On the other hand, when it exceeds 40 parts by mass, the transparency is impaired or the electrical properties such as the dielectric constant are deteriorated. Or the water absorption increases or the heat resistance deteriorates.

  If necessary, the cyclic olefin-based resin of the present invention further includes a heat stabilizer, a light stabilizer, a phase difference adjusting agent, an ultraviolet absorber, an antistatic agent, a dispersant, a workability improver, a chlorine scavenger, and a crystal. Nucleating agents, antiblocking agents, antifogging agents, mold release agents, pigments, organic or inorganic fillers, neutralizing agents, lubricants, decomposition agents, metal deactivators, antifouling agents, antibacterial agents and other resins Moreover, well-known additives, such as a thermoplastic elastomer, can be added in the range which does not impair the effect of invention.

<Cyclic olefin resin layer (A) constituting the laminated film>
The cyclic olefin-based resin layer (A) contained in the laminated film according to the present invention is obtained by molding the above-mentioned cyclic olefin-based resin in a suitable solvent and casting it into a film shape or a sheet shape. It can also be obtained by forming into a film shape or a sheet shape by a known method such as a melt extrusion method (hereinafter referred to as a raw film). Further, a retardation film (I) obtained by appropriately stretching these raw films may be used as the cyclic olefin resin layer (A).

  When the cyclic olefin resin layer (A) contains the cyclic olefin resin, the optical properties such as transparency, chemical resistance, heat resistance, water resistance and moisture resistance are excellent in a well-balanced manner.

  The thickness of the cyclic olefin resin layer (A) is 30 to 250 μm, preferably 40 to 200 μm, and the difference between the maximum thickness and the minimum thickness of the film is 3 μm or less, preferably 2 μm or less.

  When the retardation film (I) is used as the cyclic olefin-based resin layer (A) contained in the laminated film according to the present invention, the in-plane retardation R0 is 150 nm or less, preferably 140 nm or less, particularly preferably 130 nm or less. The NZ coefficient NZ is 1.0 to 4.3, preferably 1.1 to 3.9, particularly preferably 1.2 to 3.0. When R0 exceeds 150 nm, there is a problem that the viewing angle becomes narrow. In addition, even if NZ is less than 1.0 or exceeds 4.3, there is a problem that the viewing angle is narrowed.

  In the present invention, the in-plane retardation R0 and the NZ coefficient NZ of the cyclic olefin resin layer (A) contained in the laminated film are the maximum refractive index in the film plane at a light wavelength of 590 nm, nx, and in the film plane, respectively. When the refractive index in the direction orthogonal to nx is ny, the refractive index in the film thickness direction is nz, and the film thickness is d (nm), the formula R0 = (nx−ny) × d and the formula NZ = (nx -Nz) / (nx-ny).

  In the cyclic olefin resin layer (A) contained in the laminated film according to the present invention, the maximum refractive index direction may be either the longitudinal direction or the width direction of the film, but it may be the width direction. preferable.

  The polarizing plate using the cyclic olefin-based resin layer (A) contained in the laminated film of the present invention exhibits stable optical characteristics because retardation variation due to retardation unevenness and environment is suppressed. . As a result, when the polarizing plate of the present invention is used, a liquid crystal display element having no display unevenness and no bright spot can be obtained.

Method of Stretching Cyclic Olefin Resin Layer (A) Contained in Laminate Film The cyclic olefin resin layer (A) contained in the laminate film according to the present invention is the above-described raw film, (1) film length The film can be suitably manufactured by biaxial stretching under heating in the direction and then uniaxial stretching in the film width direction, or (2) uniaxial stretching in the film width direction.

  When the raw film is stretched, it is preferable that the heating temperature during stretching is precisely controlled throughout the stretched portion of the film. For example, in the uniaxial stretching in the longitudinal direction in the method (1), that is, longitudinal uniaxial stretching, the temperature distribution is within the set temperature ± 0.6 ° C., preferably within the set temperature ± 0.4 ° C., more preferably the set temperature ± It is desirable to carry out in an oven controlled within 0.2 ° C.

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

  The set temperature of the uniaxial stretching in the longitudinal direction may be set according to the type of thermoplastic resin constituting the film, the stretching ratio and the stretching speed, the thickness of the film, the desired retardation of the film after stretching, and the like. However, it is usually in the range of (Tg−10 ° C.) to (Tg + 70 ° C.), preferably (Tg ± 0 ° C.), based on the glass transition temperature (Tg) of the thermoplastic resin constituting the raw film. ) To (Tg + 50 ° C.). Such a temperature range is preferable because the film can be stretched without causing thermal degradation and without breaking the film.

When the retardation film (I) is used as the cyclic olefin-based resin layer (A) contained in the laminated film according to the present invention, the stretching ratio of the uniaxial stretching in the longitudinal direction is, for example, 1.1 to 2.5 times, preferably The range is 1.1 to 2.0 times, particularly preferably 1.2 to 1.5 times.
Further, the stretching speed of the uniaxial stretching in the longitudinal direction when the retardation film according to the present invention is produced is, for example, in the range of 2 to 100 m / min, preferably 5 to 50 m / min.

When a retardation film is produced by the method (1), the film uniaxially stretched in the longitudinal direction has a film in-plane retardation R0 of usually 100 to 400 nm, preferably 150 to 300 nm.
Variation in the in-plane retardation R0 in the retardation film (I) uniaxially stretched in the longitudinal direction is usually within ± 3 nm, preferably within ± 2 nm, and more preferably within ± 1 nm. The maximum refractive index direction in the film plane of the retardation film (I) uniaxially stretched in the longitudinal direction is usually in the range of 0 ± 3 degrees, preferably in the range of 0 ± 2 degrees, with respect to the film longitudinal direction. Preferably it is in the range of 0 ± 1 degree.

  When the cyclic olefin-based resin layer (A) contained in the laminated film is produced by the method (1) above, a film obtained by uniaxially stretching the original film in the longitudinal direction as described above, and then uniaxially in the width direction. Stretch. Moreover, when manufacturing retardation film by the method of said (2), a raw film is uniaxially stretched in the width direction. By carrying out this uniaxial stretching in the width direction, that is, lateral uniaxial stretching under temperature control more precise than uniaxial stretching in the longitudinal direction, a uniform retardation film can be suitably obtained over the entire surface. For example, uniaxial stretching in the width direction is performed in an oven in which the temperature distribution is controlled within a set temperature ± 0.5 ° C, preferably within a set temperature ± 0.3 ° C, more preferably within a set temperature ± 0.2 ° C. It is desirable to do it.

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

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

The draw ratio of the uniaxial stretching in the width direction may be determined according to the desired characteristics of the optical film to be produced, but in the case of the method (1), for example, 1.2 to 2.5 times, preferably 1. The range is 3 to 2.0 times, particularly preferably 1.4 to 1.7 times. In the case of the method (2), for example, 1.5 to 4 times, preferably 1.7 to 3. It is desirable that the range is 7 times, particularly preferably 2 to 3.5 times.
The stretching speed of the uniaxial stretching in the width direction is, for example, 2 to 100 m / min, preferably 5 to 50 m / min.

  When the retardation film is produced by the method (1), the obtained retardation film is, for example, 1.3 to 6.0 times, preferably 1.7 to 3.0 times the original film. It is desirable that the film is stretched at a stretch ratio. This draw ratio is a product of the draw ratio of uniaxial stretching in the longitudinal direction and the draw ratio of uniaxial stretching in the width direction.

In the method for producing the cyclic olefin-based resin layer (A) constituting such a retardation film (I), characteristics such as the type of cyclic olefin-based resin, that is, polymer type, copolymerization ratio, molecular weight distribution, glass transition temperature, etc. The cyclic olefin resin layer obtained by selecting the resin in consideration of the thickness, selecting the set temperature in the oven, selecting the stretching ratio and the stretching speed in each step of uniaxial stretching in the longitudinal direction and uniaxial stretching in the width direction of the film The characteristic of (A) can be controlled.
<Liquid crystal layer (B) formed by photopolymerizing rod-like liquid crystal>

  The liquid crystal layer formed by photopolymerizing the rod-like liquid crystal constituting the liquid crystal layer (B) according to the present invention can be obtained by photopolymerizing a rod-like liquid crystal compound having a photopolymerizable group. The rod-like liquid crystal compound having a photopolymerizable group constituting a liquid crystal layer obtained by photopolymerizing rod-like liquid crystal is not particularly limited, and nematic liquid crystal and smectic liquid crystal have 1 acrylate group and / or methacrylate group. Those introduced more than one can be used. In the case of the TN type liquid crystal cell and the STN type liquid crystal cell, those made of rod-like liquid crystal molecules having positive dielectric anisotropy for forming a nematic type liquid crystal are preferable. Examples of the rod-like liquid crystal compound having a photopolymerizable group constituting the liquid crystal layer (B) obtained by photopolymerizing such rod-like liquid crystal include azoxy-type liquid crystal, cyanobiphenyl-type liquid crystal, Schiff-type liquid crystal, and cyanophenyl ester-type. One or more acrylate and / or methacrylate groups are introduced into low-molecular liquid crystals such as liquid crystal, cyanophenylcyclohexane liquid crystal, benzoic acid phenyl ester liquid crystal, cyclohexanecarboxylic acid phenyl ester liquid crystal, phenylpyrimidine liquid crystal, and phenyldioxane liquid crystal. The thing which was done is mentioned. These rod-like liquid crystal compounds having a photopolymerizable group may be used alone or in combination of two or more.

As a method for forming the liquid crystal layer (B) obtained by photopolymerizing the rod-like liquid crystal according to the present invention, a rod-like liquid crystal compound having a photopolymerizable group or a mixture of rod-like liquid crystal compounds and a compound containing the following formula (A) as a solvent It is preferable to obtain a liquid crystal composition containing a rod-like liquid crystal compound having a photopolymerizable group dissolved as follows by casting it on the cyclic olefin-based resin layer (A) and then evaporating the solvent by heating to dry it. .

[式（Ａ）中、Ｒ^５は炭素数２〜５の炭化水素基を表し、Ｒ^６、Ｒ^７は相互に独立に水素、炭素数１〜１０の炭化水素基、炭素数６〜２０の芳香族炭化水素基、-C(O)Ｒ^８を表し、Ｒ^８は炭素数１〜１０の炭化水素基を表す。]
前記式（Ａ）で表される溶剤として、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテル、エチレングリコールモノブチルエーテルアセテート、エチレングリコールモノｔ−ブチルエーテルなどをあげることができる。これらの化合物は１種または２種以上の組み合わせで用いることができる。

[In the formula (A), R ⁵ represents a hydrocarbon group having 2 to ⁵ carbon atoms, R ⁶ and R ⁷ are each independently hydrogen, a hydrocarbon group having 1 to 10 carbon atoms, or a carbon group having 6 to 20 carbon atoms. An aromatic hydrocarbon group, —C (O) R ⁸ is represented, and R ⁸ represents a hydrocarbon group having 1 to 10 carbon atoms. ]
Examples of the solvent represented by the formula (A) include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol mono t-butyl ether and the like. be able to. These compounds can be used alone or in combination of two or more.

The content of the compound (A) is usually 60 to 90%, preferably 65 to 80% when the liquid crystal composition is 100% by mass. It is preferable for the compound (A) to be in the above range because the liquid crystal layer has a hybrid orientation and the adhesion between the liquid crystal layer (B) and the cyclic olefin resin layer (A) becomes good.

In addition to the above formula (A), the liquid crystal composition containing a rod-like liquid crystal compound having a photopolymerizable group used in the present invention preferably further uses a compound of the following formula (B) as a solvent.

[式（Ｂ）中、Ｒ^９、Ｒ^１０は相互に独立に水素、炭素数１〜１０の炭化水素基、炭素数６〜２０の芳香族炭化水素基を表す。]
前記式（Ｂ）で表される溶剤としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルアミルケトンなどをあげることができる。これらの化合物はなかでも、プロピレングリコールモノメチルエーテルとメチルエチルケトンの組み合わせが最も好ましい。

[In Formula (B), R ⁹ and R ¹⁰ each independently represent hydrogen, a hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. ]
Examples of the solvent represented by the formula (B) include acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone. Among these compounds, a combination of propylene glycol monomethyl ether and methyl ethyl ketone is most preferable.

When a rod-like liquid crystal compound having a photopolymerizable group or a mixture of rod-like liquid crystal compounds is appropriately selected and the above solvent is used, the obtained liquid crystal layer is preferably in a hybrid alignment. Moreover, when using said solvent, since the adhesiveness between a liquid crystal layer (B) and a cyclic olefin resin layer (A) becomes favorable, it is preferable.
When using the said compound (B) together, a liquid crystal composition shall be 100 mass%, and the sum total of content of the said compound (A) and the said compound (B) is 60 to 90% normally, Preferably it is 65 to 80%. The mass ratio of the compound (A) to the compound (B) is usually (90:10) to (50:50), preferably (80:20) to (60:40). It is preferable that the compound (A) and the compound (B) satisfy the above range because the liquid crystal layer has a hybrid alignment and the adhesion between the liquid crystal layer (B) and the cyclic olefin resin layer (A) becomes good.

Moreover, it is preferable that a photopolymerization initiator is added to the liquid crystal composition of the present invention. The photopolymerization initiator is not particularly limited as long as it can efficiently initiate photopolymerization at the wavelength of light provided for curing, and a known one can be used. The addition amount is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 3% by mass or less with respect to the mass of the liquid crystal composition of the present invention. If the addition amount exceeds 10% by mass, the influence of the unreacted photopolymerization initiator on the physical properties of the cured film such as the liquid crystal transition temperature cannot be ignored. Furthermore, the liquid crystal composition of the present invention may contain known additives such as an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antistatic agent, an antifoaming agent, and a surfactant as necessary. It can add in the range which does not impair the effect of invention.

As the rod-like liquid crystal compound used in the present invention, Licrive ^™ RMM19B (trade name) manufactured by Merck Co., Ltd. can be preferably used.

<Method for producing laminated film>

The laminated film of the present invention is obtained by applying a liquid crystal composition containing a rod-like liquid crystal having a photopolymerizable group on at least one surface of the cyclic olefin resin layer (A) having the repeating unit represented by the formula (I). It can be obtained by a step (I-2) of forming a rod-like liquid crystal-containing layer having a polymerizable group and a step (II) of irradiating the rod-like liquid crystal layer having a photopolymerizable group. Moreover, it can have the process (I-1) which performs a rubbing process on the surface which contacts the liquid-crystal layer (B) of a cyclic olefin resin layer (A) before the said process (I-2) as needed. .

In particular, when the cyclic olefin-based resin layer (A) of the present invention has a retardation, the liquid crystal can be aligned without performing the step (I-1) for performing the rubbing treatment. Generally, when a liquid crystal composition dissolved in a solvent is applied without rubbing, the base material is dissolved and the liquid crystal is not aligned, or a transparent laminated film cannot be obtained. In such a laminated film, such a phenomenon does not occur, and liquid crystal alignment and transparency can be secured, which is preferable. In addition, the laminated film according to the present invention is characterized in that the optical axes in the film planes of the cyclic olefin resin layer (A) and the liquid crystal layer (B) are accurately orthogonal. This means that the optical axis in the film plane is always orthogonal regardless of the application direction of the liquid crystal composition. For example, when rubbing, since the alignment direction of the liquid crystal coincides with the rubbing direction, the liquid crystal cannot be aligned in a desired direction unless the rubbing direction is accurately controlled with respect to the substrate. On the other hand, in the laminated film according to the present invention, the optical axes of the cyclic olefin resin layer (A) and the liquid crystal layer (B) are controlled to be orthogonal even when the rubbing treatment (I-1) is not performed. Therefore, it is preferable from the viewpoint of uniformity of optical characteristics and reduction of unevenness.

Method for producing liquid crystal layer (B) obtained by photopolymerizing rod-like liquid crystal The cyclic olefin resin layer (A) according to the present invention is directly rubbed on the surface in contact with the liquid crystal layer (B) in advance. There may be. The rubbing process may be performed by a known technique and is not particularly limited. As a typical rubbing treatment, there is one in which a rubbing cloth such as cotton or rayon is wound around the surface of a metal roll, and the roll is rotated and brought into contact with the surface of the cyclic olefin resin layer (A). . Although it does not specifically limit as processing conditions, 100-2000 rpm is preferable, as for roll rotation speed, More preferably, it is 200-1500 rpm, Most preferably, it is 300-900 rpm. 1-50 m / min is preferable and, as for the conveyance speed of a cyclic olefin resin layer (A), More preferably, it is 5-30 m / min. The roll push-in amount is preferably 0.1 to 0.5 mm, more preferably 0.2 to 0.4 mm. These rubbing conditions are preferable because uniform rubbing treatment can be performed over the entire surface of the cyclic olefin-based resin layer (A). The rubbing direction is determined by an angle formed by the rotation axis direction of the rubbing roll and the longitudinal direction of the film, but is not particularly limited as long as the rubbing roll can cover the entire film width. Since the rubbing direction determines the alignment direction of the liquid crystal molecules, the rubbing may be performed by setting it to a desired direction. When the cyclic olefin-based resin layer (A) does not have a phase difference, it is preferable to perform rubbing treatment (I-1).

The rubbing process generally involves generation of foreign matter. This is because the fibers of the rubbing cloth have fallen off, the film surface material used for rubbing has been scraped off and the surrounding environmental foreign matter adheres due to the generated static electricity. Therefore, it is necessary to remove these foreign substances, and it is preferable to blow off the foreign substances or to wash them. Of these, washing with water is preferably used. However, when washing with water, the rubbing effect is lost unless the rubbed film has resistance to water. For example, it is not preferable to use a film coated with polyvinyl alcohol as the alignment film material because the liquid crystal layer cannot be aligned because polyvinyl alcohol is dissolved in water.

When the cyclic olefin-based resin layer (A) of the present invention is used, the liquid crystal layer is aligned without impairing the rubbing effect even if washed with water because of its high resistance to water derived from the structure of the cyclic olefin-based resin. It is preferable because Further, when the cyclic olefin resin layer (A) of the present invention is used, the film dimensional change due to water absorption is small due to the structure of the cyclic olefin resin, and the water absorption rate is small, so that the film can be easily dried after washing with water. This is preferable because there is an advantage of being. When a film having a relatively large dimensional change due to water absorption such as triacetylcellulose is used, it is necessary to perform sufficient drying before forming the liquid crystal layer, which is not preferable because the process becomes longer.

  The rod-like liquid crystal layer (B) according to the present invention is a cyclic olefin resin obtained by subjecting a liquid crystal composition in which a rod-like liquid crystal compound having a photoreactive group or a mixture of rod-like liquid crystal compounds is dissolved in a solvent to a mechanical rubbing treatment. It is obtained by coating on layer (A) and photopolymerizing. As a coating method, a known coating method can be employed without limitation. Specific coating methods include, for example, spin coating, lip coating, comma coating, roll coating, die coating, blade coating, dip coating, bar coating, casting film formation, gravure coating Method and printing method.

  In order to evaporate the solvent from the layer containing the rod-like liquid crystal having the photopolymerizable group cast on the cyclic olefin resin layer (A), the cyclic olefin resin layer (A) is heated together. good. The heating temperature is preferably raised to a temperature higher than the liquid crystal transition temperature of the liquid crystal to be used, but in view of the heat resistance of the cyclic olefin-based resin layer (A), it is preferably 50 to 120 ° C., more preferably. Is 70-100 ° C. If the heating temperature exceeds 120 ° C, the cyclic olefin resin layer (A) as a substrate may be deformed, which is not preferable. Conversely, if the heating temperature is less than 50 ° C, evaporation of the solvent becomes insufficient, and the desired liquid crystal layer Is not preferred because it cannot be obtained. Further, within the above temperature range, the heating temperature may be increased stepwise.

  The light source for photocuring the layer containing a rod-like liquid crystal having a photopolymerizable group is not particularly limited as long as the photopolymerization initiator efficiently initiates photopolymerization, and a known light source can be used. Those that generate the acid are preferably used in the industry. Examples of the light source that generates ultraviolet rays include those using a metal halide lamp or a high-pressure mercury lamp. Light irradiation is performed from the liquid crystal layer (B) side obtained by photopolymerizing a rod-like liquid crystal having a photopolymerizable group, or from the cyclic olefin resin layer (A) side through the cyclic olefin resin layer (A). It can be carried out.

  Variation in the in-plane retardation R0 of the liquid crystal layer (B) obtained by photopolymerizing the rod-like liquid crystal according to the present invention is usually within ± 5 nm, preferably within ± 3 nm, and more preferably within ± 1 nm. The maximum refractive index direction in the film plane is usually in the range of 0 ± 3 degrees, preferably in the range of 0 ± 2 degrees, more preferably in the range of 0 ± 1 degrees with respect to the film longitudinal direction. Moreover, the absolute value of the β value representing the hybrid characteristics (Nz tilt angle) is preferably 10 to 50 degrees, more preferably 20 to 40 degrees. When the absolute value of the β value is smaller than 10 degrees or larger than 50 degrees, the viewing angle compensation effect of the TN mode liquid crystal display element is deteriorated, which is not preferable.

A laminated film comprising a cyclic olefin resin layer (A) comprising a cyclic olefin resin obtained as described above and a liquid crystal layer (B) obtained by photopolymerizing a rod-like liquid crystal is a retardation for a TN mode liquid crystal display element. It is suitably used as a film.
<Laminated film>

  The laminated film according to the present invention comprises the liquid crystal layer (B) formed by photopolymerizing the cyclic olefin resin layer (A) and the rod-like liquid crystal having a photopolymerizable group as described above. The form of the laminated film is, for example, a film roll having a width of 1300 mm or more, more preferably 1500 mm or more, and further preferably 2000 mm or more. Such a film roll can be laminated | stacked continuously by the roll-to-roll through a film roll of a polarizer and an adhesive agent as needed, and a laminated polarizing film can be obtained. Such a laminated polarizing film can be suitably used as a polarizing plate by further laminating a protective film as necessary.

  In addition, using a film roll of a laminated film, a film roll of a polarizer, and a film roll of a film that can be used as a protective film, it is continuously polarized by laminating via an adhesive as necessary. A board can be manufactured. According to such a method, a polarizing plate can be produced with high production efficiency. As said protective film, Preferably a cyclic olefin resin film (the said raw film of this invention) or a triacetyl cellulose film can be used.

  The polarizing plate using the laminated film of the present invention exhibits stable optical characteristics because the retardation unevenness and the change in retardation due to the environment are suppressed. As a result, when the polarizing plate of the present invention is used, a liquid crystal display element having no display unevenness and no bright spot can be obtained.

<Polarizing plate>
The polarizing plate which concerns on this invention has the laminated film and polarizer which were mentioned above. Moreover, it has a protective film which protects a polarizer further as needed.

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

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

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

  Any of the polarizers according to the present invention preferably has an absorption axis in the longitudinal direction (longitudinal direction). A polarizer having an absorption axis in the longitudinal direction can be produced by stretching a polymer film by longitudinal uniaxial stretching.

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

  The polarizing plate according to the present invention is preferably formed by laminating a retardation film, a polarizer, and a protective film in this order.

Adhesive / Adhesive In the present invention, when a polarizing plate is produced by adhering a laminated film and a polarizer, and further, if necessary, a protective film, an adhesive or an adhesive can be used as necessary. As the pressure-sensitive adhesive or adhesive, any one that does not inhibit the optical properties of the obtained polarizing plate after pressure-sensitive adhesion or adhesion is suitably used.

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

  The polar group-containing adhesive is preferably an aqueous pressure-sensitive adhesive or an aqueous adhesive. As a suitable polar group-containing adhesive used for attaching a specific resin film, an aqueous dispersion of an acrylate-based polymer can be exemplified.

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

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

Manufacturing method of polarizing plate The polarizing plate according to the present invention is preferably manufactured by laminating a laminated film on one surface of a polarizer made of a PVA film or the like using an adhesive or an adhesive, and heating and pressing it. be able to. More preferably, it can be produced by laminating a phase difference on one surface of the polarizer and a protective film on the opposite surface of the polarizer using an adhesive or an adhesive, respectively, and heating and pressure-bonding them. .

  In the production of the polarizing plate, both are bonded so that the maximum refractive index direction in the film plane of the laminated film and the absorption axis of the polarizer are parallel or orthogonal.

<Liquid crystal display element>
The liquid crystal display element of the present invention has the polarizing plate described above, and is usually a TN mode liquid crystal display element having a structure in which a liquid crystal cell is sandwiched between two polarizing plates. The TN mode liquid crystal display element is a display element having a liquid crystal cell using a TN type liquid crystal.

  For example, when the liquid crystal display element of the present invention has two laminated polarizing plates, a polarizer, and a protective film in this order, both surfaces of the liquid crystal cell are bonded to the retardation film side surface of the polarizing plate, respectively. Such a structure is preferably employed. For the adhesion between the liquid crystal cell and each polarizing plate, the above-mentioned pressure-sensitive adhesive or adhesive that can be used for production of the polarizing plate can be used. Further, a pressure-sensitive adhesive layer may be further provided on the surface of each polarizing plate to be bonded to the liquid crystal cell in advance, thereby bonding the polarizing plate and the liquid crystal cell.

  The liquid crystal display element according to the present invention has a highly controlled optical performance over the entire surface, and the entire surface is uniform even with a wide panel. Therefore, the liquid crystal display element is particularly used for a TN mode liquid crystal monitor equipped with a large display. In addition to being suitable for use, the use of a cyclic olefin-based resin layer (A) made of a cyclic olefin-based resin as a retardation film provides excellent durability, so that it can be used for in-vehicle TN mode liquid crystal monitors, etc. Can be suitably used.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. Each property was measured and evaluated as follows.

(1) Measuring method of in-plane retardation R0 and orientation angle θ, tilt angle β Using “KOBRA-21ADH” manufactured by Oji Scientific Instruments Co., Ltd., the retardation R0 in the film plane of the retardation film at a wavelength of 590 nm and The absolute value of the orientation angle θ (the film flow direction is defined as 0 degree) and the tilt angle β of the refractive index in the Z-axis direction were measured. The measured value was determined as an average value of values measured at 10 cm intervals in the film width direction.

(2) Polarization degree of polarizing plate V-7300 manufactured by JASCO Corporation was used to make the light incident from the adhesive / adhesive side of the retardation film, and the polarizing degree of the polarizing plate was measured.

(3) Contrast ratio measurement of liquid crystal display element Using “EZContrast-XL88” manufactured by ELDIM Corporation, the luminance, viewing angle and contrast ratio of the liquid crystal display element were measured in a dark room with an illuminance of 1 lx or less.

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

(5) Hydrogenation rate As a nuclear magnetic resonance spectrometer (NMR), AVANCE 500 manufactured by Bruker was used, and ¹ H-NMR was measured using d-chloroform as a measurement solvent. The hydrogenation rate was calculated after calculating the monomer composition from the integral value of 5.1 to 5.8 ppm of vinylene group, 3.7 ppm of methoxy group, and 0.6 to 2.8 ppm of aliphatic proton.

(6) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Gel permeation chromatography (Tosoh Co., Ltd. HLC-8220GPC, Column: Tosoh Co., Ltd. guard column H _XL- H, TSK gel G7000H _XL , TSKgel GMH _XL , TSK gel G2000H _XL , sequentially connected, solvent: Tetrahydrofuran, flow rate: 1 mL / min, sample concentration: 0.7 to 0.8% by mass, injection amount: 70 μL, measurement temperature: 40 ° C., detector: RI (40 ° C.), standard material: manufactured by Tosoh Corporation Using TSK standard polystyrene), the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured. The Mn is a number average molecular weight.

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

(8) Logarithmic viscosity Using a Ubbelohde viscometer, the viscosity was measured in chloroform (sample concentration: 0.5 g / dL) at 30 ° C.

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

(10) total light transmittance was measured using a haze manufactured by Suga Test Instruments Co., Ltd. haze meter (HGM-2DP type).

(11) <Wet heat test>
After pasting a polarizing plate having an adhesive layer on glass for LCD, it was stored for 1000 hours in an environment of a temperature of 60 ° C. and a relative humidity of 90%, and then the degree of polarization was measured. The degree of polarization was evaluated according to the following criteria from the amount of change in the degree of polarization before and after the durability test represented by the following formula.

(12) <Dry heat test>
After pasting the polarizing plate having the adhesive layer on the glass for LCD, it was stored in an environment at a temperature of 95 ° C. for 1000 hours, and then the degree of polarization was measured. The degree of polarization was evaluated according to the following criteria from the amount of change in the degree of polarization before and after the durability test represented by the following formula.

<Standard>
A: Change in polarization degree is less than 0.5% B: Change in polarization degree is 0.5% or more and less than 2.0% X: Change in polarization degree is 2.0% or more [Change in polarization degree ] = (1− [degree of polarization after test] / [initial degree of polarization]) × 100 (%)

(13) <Adhesion>
Using an adhesive tape specified in JIS Z1522, the adhesion between the cyclic olefin-based resin layer (A) and the liquid crystal layer (B) was evaluated in a 25 square cross-cut peeling tape test in accordance with JIS K5400. The remaining film rate was evaluated.

[Synthesis Example 1] (Production of Cyclic Olefin Resin A)
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (DNM) 225 parts by mass and bicyclo [2.2.1] hept-2-ene (NB) 25 parts by mass are used as monomers, and 1-hexene (molecular weight adjustment) Agent) 27 parts by mass and toluene (solvent for ring-opening polymerization reaction) 750 parts by mass were charged into a nitrogen-substituted reaction vessel, and this solution was heated to 60 ° C. Subsequently, 0.62 parts by mass of a toluene solution of triethylaluminum (1.5 mol / liter) as a polymerization catalyst and tungsten hexachloride modified with tert-butanol and methanol (tert-butanol: methanol: Ring addition polymerization reaction was performed by adding 3.7 parts by mass of a toluene solution (concentration 0.05 mol / liter) of tungsten = 0.35 mol: 0.3 mol: 1 mol) and heating and stirring this solution at 80 ° C. for 3 hours. To obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

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

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

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

[Synthesis Example 2] (Production of Cyclic Olefin Resin B)
Using DNM 71 parts by mass, dicyclopentadiene (DCP) 15 parts by mass and NB 1 part by mass as a monomer, together with 18 parts by mass of molecular weight regulator 1-hexene and 200 parts by mass of toluene, The mixture was charged and heated to 100 ° C.

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

Next, the obtained copolymer solution was placed in an autoclave, and 200 parts of toluene was further added. Next, 1 part by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a reaction modifier and RuHCl (CO) [P (C ₆ H ₅ ) as a hydrogenation catalyst ] After adding 0.006 parts by mass of ₃ and heating to 155 ° C., hydrogen gas was charged into the reactor, and the pressure was adjusted to 10 MPa. Thereafter, the reaction was carried out at 165 ° C. for 3 hours while maintaining the pressure at 10 MPa. After completion of the reaction, 100 parts by mass of toluene, 3 parts by mass of distilled water, 0.72 parts by mass of lactic acid, and 0.00214 parts by mass of hydrogen peroxide were added and heated at 60 ° C. for 30 minutes.

Thereafter, 200 parts by mass of methanol was added and heated at 60 ° C. for 30 minutes. When this was cooled to 25 ° C., it was separated into two layers. Remove 500 parts by mass of the supernatant, again add 350 parts by mass of toluene and 3 parts by mass of water and heat at 60 ° C. for 30 minutes, then add 240 parts by mass of methanol and heat at 60 ° C. for 30 minutes to cool to 25 ° C. Separated into two layers. Remove 500 parts by mass of the supernatant, further add 350 parts by mass of toluene and 3 parts by mass of water, heat at 60 ° C. for 30 minutes, then add 240 parts by mass of methanol and heat at 60 ° C. for 30 minutes to cool to 25 ° C. Separated into two layers. Finally, after removing 500 parts by mass of the supernatant, the remaining polymer solution was filtered using 2.0 μm, 1.0 μm, and 0.2 μm filters. Thereafter, the solid content of the polymer was concentrated to 55%, the solvent was removed at 250 ° C., 4 torr, and a residence time of 1 hour, and the polymer was passed through a 10 μm polymer filter to obtain a copolymer (hereinafter “resin B”). That said.)

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

[Synthesis Example 3] (Production of Cyclic Olefin Resin C)
In Synthesis Example 1, a hydrogenated polymer (hereinafter referred to as “resin C”) was prepared in the same manner as in Synthesis Example 1 except that the amount of DNM was 250 parts by mass and the amount of 1-hexene added was 18 parts by mass. Got. The hydrogenation rate measured by ¹ H-NMR of the resin C thus obtained was 99.9%, the Tg measured by the DSC method was 165 ° C., the Mn in terms of polystyrene measured by the GPC method was 32,000, Mw was 137,000 and Mw / Mn was 4.29, the saturated water absorption at 23 ° C was 0.3%, and the logarithmic viscosity in chloroform at 30 ° C was 0.78 dl / g.

[Adjustment Example 1] (Preparation of a liquid crystal composition containing a rod-like liquid crystal having a photopolymerizable group)
A solvent in which propylene glycol monomethyl ether acetate and methyl ethyl ketone were mixed at a mass ratio of 75:25 was prepared. This mixed solvent was added to a mixture of rod-shaped liquid crystals having a photopolymerizable group (RMM19B) manufactured by Merck Co., Ltd. so as to have a solid concentration of 30% by mass, and dissolved under stirring in an ambient environment of 35 ° C. By doing so, a liquid crystal composition was prepared.

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

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

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

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

[Production Example 1] (Production of raw film A)
Resin A obtained in Synthesis Example 1 and pentaerythrityltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] as an antioxidant were mixed with a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.). TEM-48), and the resin strands that flowed out from the strand die were cooled in a cooling water tank, then sent to a strand cutter, and cut into rice grains to obtain a granulated resin. The amount of antioxidant added was 0.1 parts by mass with respect to 100 parts by mass of the resin.

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

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

  On the downstream side of the mirror roll, a cooling roll having a diameter of 250 mm was arranged, and the film peeled off from the mirror roll was cooled for 2.1 seconds until it was pressure-bonded to the cooling roll set at 115 ° C. Thereafter, the film was peeled off at a peel tension of 0.4 MPa · cm, a masking film was bonded to one side, and the film was wound up by a winder to obtain a resin film having a thickness of 130 μm (hereinafter referred to as “raw film A”). Called). The residual solvent amount of the obtained film was 0.1%, the total light transmittance was 93%, and the glass transition temperature (Tg) was 130 ° C.

[Production Example 2] (Production of raw film B)
In Production Example 1, a resin film having a thickness of 130 μm was obtained in the same manner as in Production Example 1 except that Resin B obtained in Synthesis Example 2 was used instead of Resin A (hereinafter referred to as “raw film B”). "). The film obtained had a residual solvent amount of 0.1%, a total light transmittance of 93%, and a glass transition temperature (Tg) of 131 ° C.

[Production Example 3] (Production of raw film C)
Resin C obtained in Synthesis Example 3 is dissolved in toluene so as to have a concentration of 30% (solution viscosity at room temperature is 30,000 mPa · s), and pentaerythrityl tetrakis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate] is added in an amount of 0.1 parts by mass with respect to 100 parts by mass of the polymer, and a metal fiber sintered filter having a pore diameter of 5 μm manufactured by Nippon Pole is used. Filtration was performed while controlling the flow rate of the solution so that it was within 0.4 MPa. The obtained polymer solution was treated with an acrylic acid-based INVEX lab coater installed in a Class 1000 clean room and made hydrophilic with an acrylic acid (surface-adhesive) surface-treated PET film having a thickness of 100 μm (Toray Industries, Inc.) By applying the film thickness after drying onto Lumirror U94 (manufactured by Co., Ltd.) so that the film thickness is 130 μm, and after first drying at 50 ° C., peeling off from the PET film and performing secondary drying at 90 ° C. A resin film was obtained (hereinafter referred to as “film C”). The amount of residual solvent of the obtained film C was 0.1%, the total light transmittance was 93%, and the glass transition temperature (Tg) was 165 ° C.

[Production Example 4] (Production of protective film)
Using a twin screw extruder, 0.3 parts by mass of (pentaerythrityltetrakis-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate: melting point 115 ° C.) with respect to 100 parts by mass of resin A As a benzotriazole compound, (2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol]: melting point 199 ° C.) 1 After melt-kneading at 270 ° C. at a blending ratio of 5 parts by mass, the mixture was extruded onto a strand, cooled with water, and then pellets were obtained through a feeder ruder. The obtained pellets were circulated and dehumidified and dried at 100 ° C. for 3 hours under nitrogen, then sent to a hopper and melted at a resin temperature of 270 ° C. using a single screw extruder having a screw diameter of 75 mmφ.

  This molten resin was guided to a 700 mm wide coat hanger die through a polymer filter (aperture 5 μm) heated to 280 ° C. at a rate of 30 kg / hr by a double shaft discharge type gear pump. The differential pressure between the inlet and outlet of the filter was 3 MPa. The die heater was set to 250 ° C. using an aluminum cast heater, and a lip heater was installed in addition to the front lip portion to control the die lip temperature to 250 ± 0.4 ° C.

  The lip opening was set to 0.5 mm in the width direction, and fine adjustment was performed by measuring thickness unevenness with an on-line thickness gauge installed on the downstream side of melt extrusion. The resin coming out of the die was dropped in the lead direct wire direction of a 250 mmφ cast roll (surface roughness: 0.1 μm) and crimped, and then pressed in order with two cooling rolls installed horizontally to the cast roll axis, and then peeled off. The tension was controlled at 4 kgf and the film was taken out to obtain a protective film α having a thickness of 80 μm.

[Production Example 5] (Production of polarizer)
A 120 μm-rolled polyvinyl alcohol (hereinafter also referred to as “PVA”) film is a 30 ° C. aqueous dyeing bath having an iodine concentration of 0.03% by mass and a potassium iodide concentration of 0.5% by mass. In a 55 ° C. cross-linking bath of an aqueous solution having a boric acid concentration of 5 mass% and a potassium iodide concentration of 8 mass% after continuously uniaxially stretching (pre-stretching) in the longitudinal direction at a stretching ratio of 3 times Then, the film was further uniaxially stretched (post-stretched) in the longitudinal direction at a stretch ratio of 2 times, dried and wound up to obtain a 27 μm roll-shaped polarizer.

[Example 1]
Using the raw film A obtained in Production Example 1, tenter transverse stretching was performed at a stretching speed of 5.0 m / min and a stretching ratio of 3.0 times in a tank having a furnace furnace temperature of 155 ° C., and a thickness of 37 μm. A roll-like retardation film A was obtained. The in-plane retardation R0 of the obtained retardation film A was 130.2 nm, and the NZ coefficient was 1.31.

  On one side of the obtained retardation film A, the rubbing process is performed with a rubbing direction in which the rubbing process is performed with a rubbing machine manufactured by Iinuma Gauge Co., Ltd. After performing so that it might become parallel to a direction, the liquid crystal composition obtained by the adjustment example 1 was coated using the 250 mesh small diameter gravure roll in INVEX laboratory coater by Inoue Metal Industry. At the time of coating, filtration was performed with a 0.2 μm PTFE filter, and after coating, the solvent was evaporated and dried by passing through a dryer.

Drying was performed under stepwise conditions of 30 seconds at 60 ° C. and 30 seconds at 100 ° C. A film containing rod-like liquid crystal formed by drying the solvent was irradiated with UV light using a high-pressure mercury lamp to obtain a laminated film A ′ in which a liquid crystal layer cured by photopolymerization was laminated on the retardation film A. . When the thickness and retardation of the formed liquid crystal alignment film were analyzed, the thickness was 1.7 μm, the in-plane retardation R0 = 85.2 nm, the orientation angle θ = 0.2 degrees, and the tilt angle β = 32.2 degrees. It was. Further, the adhesion was 25/25, which was good.

  The surface of the obtained laminated film A ′ on which the liquid crystal layer is not laminated is aligned with the roll film on one side of the polarizer obtained in Production Example 5 (longitudinal direction which is the absorption axis of the polarizer). And the longitudinal direction of the laminated film A ′ are parallel to each other), both are continuously pasted using the aqueous adhesive obtained in Preparation Example 2, and obtained in Production Example 4 on the other surface of the polarizer. The protective film α was pasted using the aqueous adhesive obtained in Preparation Example 2 to obtain a polarizing plate A-1. When the single transmittance and degree of polarization of the obtained polarizing plate were examined, they were 42.0% and 99.9%, respectively. Further, the obtained polarizing plate A-1 was subjected to a wet heat test and a dry heat test, respectively. The results are shown in Table 1.

  The polarizing plate on the viewer side and the back side of the TN mode liquid crystal display element of a liquid crystal television (model code: LS20BRDBBV / XSJ) manufactured by Samsung Electronics Co., Ltd. is peeled off, and the polarizing plate A-1 is placed on both sides of the peeled portion. The polarizing plate was attached so that the retardation film surface of the polarizing plate was on the liquid crystal cell side in the same manner as the transmission axis of the polarizing plate originally attached.

  When the viewing angle (region having a contrast ratio of 150 or more) was confirmed in all directions of the obtained TN mode liquid crystal display element, it was confirmed to be 65 degrees in the vertical direction and 120 degrees in the horizontal direction. The results are shown in Table 1.

[Example 2]
Using the raw film B obtained in Production Example 2, a tenter transverse stretch was performed at a stretch rate of 5 m / min and a stretch ratio of 4.2 times in a tank at a temperature of 160 ° C. in a stretching machine furnace, and a roll having a thickness of 31 μm. A phase difference film B was obtained. The in-plane retardation R0 of the obtained retardation film B was 119.8 nm, and the NZ coefficient was 1.24.

A laminated film B ′ was obtained in the same manner as in Example 1 except that the retardation film B was used instead of the retardation film A in Example 1. When the thickness and retardation of the formed liquid crystal layer were analyzed, the thickness was 1.7 μm, the in-plane retardation R0 = 84.9 nm, the orientation angle θ = 0.1 degree, and the tilt angle β = 33.2 degrees. . Further, the adhesion was 25/25, which was good. Further, in Example 1, a polarizing plate B-1 was obtained in the same manner as in Example 1 except that the laminated film B ′ was used instead of the laminated film A ′. When the single transmittance and degree of polarization of the obtained polarizing plate were examined, they were 42.1% and 99.9%, respectively. Moreover, when the wet heat test and the dry heat test were conducted in the same manner as in Example 1, they were evaluated as ◎.
When a TN mode liquid crystal display element was obtained and evaluated in the same manner as in Example 1, the viewing angle was 60 degrees vertically and 120 degrees horizontally. The results are shown in Table 1.

[Example 3]
Using the raw film C obtained in Production Example 3, in a tank at a stretching machine furnace temperature of 169 ° C., a stretching speed of 5 m / min, a stretching ratio of 1.4 times, and a film longitudinal direction that does not fix the film width direction After uniaxial stretching, a tenter transverse stretching was performed at a stretching speed of 5 m / min and a stretching ratio of 1.7 times in a tank at a temperature of 183 ° C. in a stretching machine, and a roll-like retardation film C having a thickness of 73 μm was obtained. Obtained. The in-plane retardation R0 of the obtained retardation film C was 40.4 nm, and the NZ coefficient was 2.9.

In Example 1, a laminated film C ′ was obtained in the same manner as in Example 1 except that the retardation film C was used instead of the retardation film A. When the thickness and retardation of the formed liquid crystal layer were analyzed, the thickness was 1.7 μm, the in-plane retardation R0 = 86.1 nm, the orientation angle θ = 0.1 degree, and the tilt angle β = 30.2 degree. . Further, the adhesion was 25/25, which was good. Further, in Example 1, a polarizing plate C-1 was obtained in the same manner as in Example 1 except that the laminated film C ′ was used instead of the laminated film A ′. When the single transmittance and degree of polarization of the obtained polarizing plate were examined, they were 42.1% and 99.9%, respectively. Moreover, when the wet heat test and the dry heat test were conducted in the same manner as in Example 1, they were evaluated as ◎.
When a TN mode liquid crystal display element was obtained and evaluated in the same manner as in Example 1, the viewing angle was 65 degrees vertically and 115 degrees horizontally. The results are shown in Table 1.

[Example 4]
In Example 1, a polarizing plate A-2 was obtained in the same manner as in Example 1 except that a film made of triacetyl cellulose (hereinafter also referred to as “TAC”) was used instead of the protective film α. When the single transmittance and polarization degree of the obtained polarizing plate were examined, they were 41.6% and 99.9%, respectively. Further, the wet heat test and the dry heat test were conducted in the same manner as in Example 1, and the results were ○ and ◎, respectively.
When a TN mode liquid crystal display element was obtained and evaluated in the same manner as in Example 1, the viewing angle was 60 degrees vertically and 115 degrees horizontally. The results are shown in Table 1.

[Example 5]
In Example 2, a polarizing plate B-2 was obtained in the same manner as in Example 2 except that a TAC film was used instead of the protective film α. When the single transmittance and degree of polarization of the obtained polarizing plate were examined, they were 41.8% and 99.9%, respectively. Further, the wet heat test and the dry heat test were conducted in the same manner as in Example 1, and the results were ○ and ◎, respectively.
When a TN mode liquid crystal display element was obtained and evaluated in the same manner as in Example 1, the viewing angle was 60 degrees vertically and 115 degrees horizontally. The results are shown in Table 1.

[Example 6]
In Example 3, a polarizing plate C-2 was obtained in the same manner as in Example 3 except that a TAC film was used instead of the protective film α. When the single transmittance and degree of polarization of the obtained polarizing plate were examined, they were 41.5% and 99.9%, respectively. Further, the wet heat test and the dry heat test were conducted in the same manner as in Example 1, and the results were ○ and ◎, respectively.
When a TN mode liquid crystal display element was obtained and evaluated in the same manner as in Example 1, the viewing angle was 65 degrees vertically and 120 degrees horizontally. The results are shown in Table 1.

[Example 7]
In Example 1, a laminated film E was obtained in the same manner as in Example 1 except that the raw film A that was not stretched instead of the retardation film A was used. When the thickness and retardation of the formed liquid crystal layer were analyzed, the thickness was 1.7 μm, the in-plane retardation R0 = 84.4 nm, the orientation angle θ = 0.0 degrees, and the tilt angle β = 30.0 degrees. . Further, the adhesion was 25/25, which was good. Furthermore, the protective film α obtained in Production Example 4 was continuously pasted on both surfaces of the polarizer obtained in Production Example 5 using the water-based adhesive obtained in Preparation Example 2 to obtain a polarizing plate γ. The side of the polarizing plate γ where the liquid crystal layer of the obtained laminated film E is not laminated is cut so that the longitudinal direction which is the absorption axis of the polarizer and the longitudinal direction of the laminated film E are perpendicular to each other. And it bonded using the water-system adhesive obtained by the preparation example 2, and obtained polarizing plate A-3. When the single transmittance and degree of polarization of the obtained polarizing plate were examined, they were 42.1% and 99.9%, respectively. Moreover, when the wet heat test and the dry heat test were conducted in the same manner as in Example 1, they were evaluated as ◎.
When a TN mode liquid crystal display element was obtained and evaluated in the same manner as in Example 1, the viewing angle was 60 degrees vertically and 120 degrees left and right. The results are shown in Table 1.

[Example 8]
In Example 1, a laminated film F was obtained in the same manner as in Example 1 except that the raw film B which was not stretched instead of the retardation film A was used. When the thickness and retardation of the formed liquid crystal layer were analyzed, the thickness was 1.7 μm, the in-plane retardation R0 = 84.7 nm, the orientation angle θ = 0.2 degrees, and the tilt angle β = 31.5 degrees. . Further, the adhesion was 25/25, which was good. Further, in Example 7, a polarizing plate B-3 was obtained in the same manner as in Example 7 except that the laminated film F was used instead of the laminated film E. When the single transmittance and degree of polarization of the obtained polarizing plate were examined, they were 42.0% and 99.9%, respectively. Moreover, when the wet heat test and the dry heat test were conducted in the same manner as in Example 1, they were evaluated as ◎.
When a TN mode liquid crystal display element was obtained and evaluated in the same manner as in Example 1, the viewing angle was 60 degrees vertically and 115 degrees horizontally. The results are shown in Table 1.

[Example 9]
In Example 1, a laminated film G was obtained in the same manner as in Example 1 except that the raw film C which was not stretched instead of the retardation film A was used. When the thickness and retardation of the formed liquid crystal layer were analyzed, the thickness was 1.7 μm, the in-plane retardation R0 = 85.1 nm, the orientation angle θ = 0.2 degrees, and the tilt angle β = 32.3 degrees. . Further, the adhesion was 25/25, which was good. Further, in Example 7, a polarizing plate C-3 was obtained in the same manner as in Example 7 except that the laminated film E was used instead of the laminated film E. When the single transmittance and degree of polarization of the obtained polarizing plate were examined, they were 42.1% and 99.9%, respectively. Moreover, when the wet heat test and the dry heat test were conducted in the same manner as in Example 1, they were evaluated as ◎.
When a TN mode liquid crystal display element was obtained and evaluated in the same manner as in Example 1, the viewing angle was 60 degrees vertically and 115 degrees horizontally. The results are shown in Table 1.

[Example 10]
In Example 2, a laminated film B ′ ′ was obtained in the same manner as in Example 2 except that the rubbing treatment was not performed. When the thickness and retardation of the formed liquid crystal layer were analyzed, the thickness was 1.7 μm, the in-plane retardation R0 = 85.4 nm, the orientation angle θ = 0.1 degree, and the tilt angle β = 32.7 degree. Although the rubbing treatment was not performed, good alignment of the liquid crystal layer was observed, and the haze was also good at 0.5%. Further, the in-plane retardation R0 of the laminated film B ′ ′ is 34.2 nm, and the difference between the in-plane retardation R0 of the phase difference film B = 119.8 nm and the in-plane retardation of the liquid crystal layer R0 = 85.4 nm. Since it was substantially equal, it was found that the in-plane optical axis of the retardation film B and the in-plane optical axis of the liquid crystal layer were orthogonal. Further, the adhesion was 25/25, which was good. Further, in Example 1, a polarizing plate B-4 was obtained in the same manner as in Example 1 except that the laminated film B ′ ′ was used instead of the laminated film A ′. When the single transmittance and degree of polarization of the obtained polarizing plate were examined, they were 42.0% and 99.9%, respectively. Moreover, when the wet heat test and the dry heat test were conducted in the same manner as in Example 1, they were evaluated as ◎.
When a TN mode liquid crystal display element was obtained and evaluated in the same manner as in Example 1, the viewing angle was 60 degrees vertically and 115 degrees horizontally. The results are shown in Table 1.

[Comparative Example 1]
In Example 1, polarizing plate A-4 was obtained in the same manner as Example 1 except that the retardation film A that was not coated with the liquid crystal composition was used instead of the laminated film A ′. When the single transmittance and degree of polarization of the obtained polarizing plate were examined, they were 42.1% and 99.9%, respectively. Moreover, when the wet heat test and the dry heat test were conducted in the same manner as in Example 1, they were evaluated as ◎.
When a TN mode liquid crystal display element was obtained and evaluated in the same manner as in Example 1, the viewing angle was 20 degrees vertically and 115 degrees horizontally, and the viewing angle in the vertical direction was narrow. The results are shown in Table 1.

[Comparative Example 2]
In Example 2, a polarizing plate B-5 was obtained in the same manner as in Example 2 except that the retardation film B in which the liquid crystal composition was not applied was used instead of the laminated film B ′. When the single transmittance and degree of polarization of the obtained polarizing plate were examined, they were 42.0% and 99.9%, respectively. Further, when the wet heat test and the dry heat test were conducted in the same manner as in Example 1, they were evaluated as ◎.
When a TN mode liquid crystal display element was obtained and evaluated in the same manner as in Example 1, the viewing angle was 20 degrees up and down and 120 degrees left and right, and the viewing angle in the up and down direction was narrowed. The results are shown in Table 1.

[Comparative Example 3]
In Example 3, a polarizing plate C-4 was obtained in the same manner as in Example 3 except that the retardation film C in which the liquid crystal composition was not applied was used instead of the laminated film C ′. When the single transmittance and degree of polarization of the obtained polarizing plate were examined, they were 41.8% and 99.9%, respectively. Further, when the wet heat test and the dry heat test were conducted in the same manner as in Example 1, they were evaluated as ◎.
When a TN mode liquid crystal display element was obtained and evaluated in the same manner as in Example 1, the viewing angle was 15 degrees up and down and 115 degrees left and right, and the viewing angle in the up and down direction was narrowed. The results are shown in Table 1.

[Comparative Example 4]
In Example 1, a polarizing plate A-5 was obtained in the same manner as in Example 1 except that instead of the laminated film A ′, a raw film A that was not coated with a liquid crystal composition and was not stretched was used. . When the single transmittance and degree of polarization of the obtained polarizing plate were examined, they were 42.1% and 99.9%, respectively. Moreover, when the wet heat test and the dry heat test were conducted in the same manner as in Example 1, they were evaluated as ◎.
When a TN mode liquid crystal display element was obtained and evaluated in the same manner as in Example 1, the viewing angle was 20 degrees in the vertical direction and 20 degrees in the horizontal direction, and the viewing angles in the vertical and horizontal directions were narrowed. The results are shown in Table 1.

[Comparative Example 5]
In Example 2, a polarizing plate B-6 was obtained in the same manner as in Example 2 except that instead of the laminated film B ′, a raw film B that was not coated with liquid crystal and was not stretched was used. When the single transmittance and degree of polarization of the obtained polarizing plate were examined, they were 42.0% and 99.9%, respectively. Further, when the wet heat test and the dry heat test were conducted in the same manner as in Example 1, they were evaluated as ◎.
When a TN mode liquid crystal display element was obtained and evaluated in the same manner as in Example 1, the viewing angle was 15 degrees up and down and 20 degrees left and right, and the viewing angles in the up and down and left and right directions were narrowed. The results are shown in Table 1.

[Comparative Example 6]
In Example 3, a polarizing plate C-5 was obtained in the same manner as in Example 3 except that instead of the laminated film C ′, a raw film C that was not coated with a liquid crystal composition and was not stretched was used. . When the single transmittance and degree of polarization of the obtained polarizing plate were examined, they were 42.1% and 99.9%, respectively. Further, when the wet heat test and the dry heat test were conducted in the same manner as in Example 1, they were evaluated as ◎.
When a TN mode liquid crystal display element was obtained and evaluated in the same manner as in Example 1, the viewing angle was 15 degrees up and down and 20 degrees left and right, and the viewing angles in the up and down and left and right directions were narrowed. The results are shown in Table 1.

[Comparative Example 7]
Cellulose-based resin unstretched film having a ratio of acetyl substitution degree / propionyl substitution degree of 70/30 is stretched at a stretching speed of 5 m / min and a stretching ratio of 1.6 times in a tank at a stretching machine furnace temperature of 138 ° C. After uniaxial stretching in the longitudinal direction of the film without fixing the film width direction, tenter transverse stretching is performed at a stretching speed of 5 m / min and a stretching ratio of 1.9 times in a tank having a temperature in a stretching machine furnace of 152 ° C. A roll-like retardation film H of 52 μm was obtained. The in-plane retardation R0 of the obtained retardation film H was 40.5 nm, and the NZ coefficient was 2.9.
In Example 1, except that the retardation film H was used instead of the retardation film A, an attempt was made to obtain a laminated film H ′ in the same manner as in Example 1. When the thickness and retardation of the formed liquid crystal layer were analyzed, the thickness was 1.7 μm, but the in-plane retardation R0 = 42 nm, the orientation angle θ = 3.5 degrees, and the tilt angle β = 2.6 degrees. Thus, a desired hybrid oriented retardation film could not be obtained.

[Comparative Example 8]
In Example 10, a laminated film H ′ ′ was obtained without rubbing in the same manner as in Example 10 except that the retardation film H was used instead of the retardation film B ′. When the thickness and retardation of the formed liquid crystal layer were analyzed, the thickness was 1.7 μm, but the in-plane retardation R0 was not exhibited, and a desired hybrid-aligned retardation film could not be obtained. .

[Comparative Example 9]
An alignment film composed of a modified PVA having a vinyl-based repeating unit having a bonding group in the side chain is formed on a triacetyl cellulose film having a thickness of 80 μm, and a discotic liquid crystal having a polymerizable group bonded to the alignment film. A composition having a compound and a photopolymerization initiator was applied and heated, and then irradiated with ultraviolet rays to obtain a laminated film J. The obtained laminated film J had an in-plane retardation R0 of 40.1 nm, an orientation angle of 0.1 degree, and β of 22.3 degree. Further, the adhesion was 25/25, which was good. A polarizing plate J-1 was obtained in the same manner as in Example 4 except that the retardation film J was used instead of the retardation film A in Example 4. When the single transmittance and polarization degree of the obtained polarizing plate were examined, they were 40.9% and 99.9%, respectively. Further, when the wet heat test and the dry heat test were conducted in the same manner as in Example 4, they were x and ◎, respectively. In particular, in the wet heat test, the polarizing plate was bent and its shape was changed, so that it could not be used.
When a TN mode liquid crystal display element was obtained and evaluated in the same manner as in Example 1, the viewing angle was 65 degrees vertically and 80 degrees horizontally. The results are shown in Table 1.

Claims (15)

A cyclic olefin-based resin layer (A) having a repeating unit represented by the following formula (I) and a liquid crystal layer (B) formed by photopolymerizing a rod-like liquid crystal having a photopolymerizable group; A laminated film, wherein the resin layer (A) and the liquid crystal layer (B) are in direct contact.

[In Formula (I), m is an integer of 0 or more, p is an integer of 0 or more, D is a group represented by —CH═CH— or —CH ₂ CH ₂ —, and R ¹ to Each R ⁴ independently represents a hydrogen atom; a halogen atom; a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms; a polar group; R ¹ and R ² may be combined to form a divalent hydrocarbon group, and R ³ and R ⁴ may be combined to form a divalent hydrocarbon group. Good. R ¹ and R ² may be bonded to each other to form a carbocyclic or heterocyclic ring, and R ³ and R ⁴ may be bonded to each other to form a carbocyclic or heterocyclic ring. May be monocyclic or polycyclic. ] 2. The laminated film according to claim 1, wherein the cyclic olefin resin further has a repeating unit represented by the following formula (II).

[In Formula (II), D ¹ is a group represented by —CH═CH— or —CH ₂ CH ₂ —, and R ^{1 to} R ⁴ each independently represent a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom. A linking group containing a nitrogen atom or a silicon atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms; an atom or group selected from the group consisting of polar groups, wherein R ¹ and R ² are combined A divalent hydrocarbon group may be formed, and R ³ and R ⁴ may be integrated to form a divalent hydrocarbon group. Two groups selected from R ^{1 to} R ⁴ may be bonded to each other to form a monocyclic alicyclic hydrocarbon ring or heterocyclic ring. ] The laminated film according to claim 1 or 2, wherein the cyclic olefin-based resin layer (A) has a phase difference. The laminated film according to claim 1, wherein a liquid crystal alignment layer made of a rod-like liquid crystal having a photopolymerizable group is hybrid-aligned. A rod-like shape having a photopolymerizable group by applying a liquid crystal composition containing a rod-like liquid crystal having a photopolymerizable group to at least one surface of a cyclic olefin-based resin layer (A) having a repeating unit represented by the following formula (I) A method for producing a laminated film comprising: a step (I-2) of forming a liquid crystal-containing layer; and a step (II) of irradiating light to the rod-like liquid crystal layer having the photopolymerizable group.

[In the formula (I), m is an integer of 0 or more, p is 0 or an integer of 1 or more, D is a group represented by —CH═CH— or —CH ₂ CH ₂ —, R ^{1 to} R ⁴ are each independently a hydrogen atom; a halogen atom; a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms; a polar group R ¹ and R ² may be combined to form a divalent hydrocarbon group, and R ³ and R ⁴ may be combined to form a divalent hydrocarbon group. May be. R ¹ and R ² may be bonded to each other to form a carbocyclic or heterocyclic ring, and R ³ and R ⁴ may be bonded to each other to form a carbocyclic or heterocyclic ring. May be monocyclic or polycyclic. ]   6. The method according to claim 5, further comprising a step (I-1) of performing a rubbing treatment on the surface of the cyclic olefin resin layer (A) in contact with the liquid crystal layer (B) before the step (I-2). The manufacturing method of laminated film of description. The said cyclic olefin resin layer (A) has a phase difference, The manufacturing method of the laminated | multilayer film of Claim 5 or 6 characterized by the above-mentioned. The method for producing a laminated film according to claim 5, wherein the liquid crystal composition containing a rod-like liquid crystal having a photopolymerizable group contains a compound represented by the following formula (A).

[In the formula (A), R ⁵ represents a hydrocarbon group having 2 to ⁵ carbon atoms, R ⁶ and R ⁷ are each independently hydrogen, a hydrocarbon group having 1 to 10 carbon atoms, or a carbon group having 6 to 20 carbon atoms. An aromatic hydrocarbon group, —C (O) R ⁸ is represented, and R ⁸ represents a hydrocarbon group having 1 to 10 carbon atoms. ] The method for producing a laminated film according to claim 8, wherein the liquid crystal composition containing a rod-like liquid crystal having a photopolymerizable group further contains a compound represented by the following formula (B).

[In Formula (B), R ⁹ and R ¹⁰ each independently represent hydrogen, a hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. ]   The compound represented by the formula (A) is at least selected from propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol mono t-butyl ether It is 1 type, The manufacturing method of the laminated | multilayer film of Claim 8 or 9 characterized by the above-mentioned.   The method for producing a laminated film according to claim 9 or 10, wherein the compound represented by the formula (B) is at least one selected from acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone. The method according to claim 5, wherein a liquid crystal alignment layer formed by photopolymerizing a rod-like liquid crystal having a photopolymerizable group is hybrid-aligned.   A polarizing plate comprising the laminated film according to claim 1 as a protective film.   A polarizing plate according to claim 13 is disposed on one side or both sides of a cell.   The liquid crystal cell is a TN mode. The liquid crystal display element according to claim 14.