JP6627869B2 - Liquid crystal display device with touch panel and method of manufacturing the same - Google Patents

Description

  The present invention relates to a liquid crystal display device with a touch panel and a method for manufacturing the same. More specifically, the present invention relates to a liquid crystal display device with a touch panel having excellent front contrast and a method of manufacturing the same.

  In recent years, the spread of liquid crystal display devices equipped with a touch panel has progressed, and it is expected that the number will increase in the future.

  For example, in a capacitance type touch panel module used for a touch panel, an X electrode pattern extending in the X direction by a transparent conductive layer (also referred to as a transparent electrode) is formed on a transparent substrate, and in the Y direction by another transparent conductive layer. Some have an extended Y electrode pattern. When the finger on the surface of the touch panel touches the X electrode pattern and the Y electrode pattern, the change in capacitance at that position is detected by the X and Y electrode patterns.

  As a configuration in which such a transparent conductive layer having two electrodes is combined with a polarizing plate and a liquid crystal cell, for example, there is an out-cell type touch panel module.

  FIG. 1 is a schematic view showing an example of a liquid crystal display device with a touch panel having a conventional out-cell touch panel module.

  Although details will be described later, a polarizing plate in which a polarizer is sandwiched between two protective films is arranged adjacent to the liquid crystal cell, and an ITO (indium oxide) is formed on a transparent base film via an adhesive layer on the polarizing plate. A transparent electrode containing tin oxide) and a film sensor (also referred to as a touch panel module) formed with a protective layer for protecting the transparent electrode, and a front plate such as glass or an acrylic plate via an adhesive layer. Pasted.

  In such a configuration, since the polarizing plate and the film sensor are independent of each other, the touch panel has a certain thickness.

  In the future, as display devices become thinner, further reduction in thickness of touch panels, which are main members, is required.

  As a touch panel configuration for meeting the demand for thinness, integration of a film sensor and a polarizing plate has been attempted, and there is a so-called mid-cell type or inner-cell type touch panel module as opposed to an out-cell type (for example, Patent Document 1). And Patent Document 2.). These polarizing plate integrated type touch panel modules correspond to a reduction in thickness of members by forming the transparent electrode on an optical compensation film or a protective film which is a component of the polarizing plate.

  On the other hand, one of the main members of the liquid crystal display device is a liquid crystal cell.

  There are a plurality of types of liquid crystal cells according to liquid crystal molecules to be used. At present, a VA (vertical alignment) mode and an IPS (in-plane switching) mode are mainly used. Generally, it is said that the VA mode is superior in the front contrast as compared with the IPS mode. This is because the liquid crystal molecules of the VA mode liquid crystal molecules are vertically aligned when the electric field is off, so that it is possible to further suppress the backlight light from leaking to the viewing side during black display.

  The present inventor combined the so-called mid-cell type or inner-cell type polarizing plate integrated touch panel module with a VA mode liquid crystal display cell. And the effect of improving the front contrast could not be obtained.

JP 2011-81810 A JP 2013-104847 A

  The present invention has been made in view of the above-described problems and circumstances, and a problem to be solved is to provide a liquid crystal display device with a touch panel having a VA mode liquid crystal cell having excellent front contrast and a method of manufacturing the same. is there.

  In order to solve the above problems, the present inventor, in the course of studying the causes of the above problems, has a liquid crystal with a touch panel equipped with a polarizing plate integrated touch panel module having a transparent conductive layer on the viewing side of the VA mode liquid crystal cell. In the display device, the polarizing plate-integrated touch panel module includes an optical compensation film having a transparent conductive layer on at least one surface, a polarizer, and a protective film in this order from the VA mode liquid crystal cell toward a viewing side. And found that the object of the present invention can be solved when the glass transition temperature Tg of the optical compensation film is equal to or higher than a specific value.

  That is, the above object according to the present invention is solved by the following means.

1. A liquid crystal display device with a touch panel, comprising a polarizing plate-integrated touch panel module having a transparent conductive layer on the viewing side of a VA mode liquid crystal cell,
A polarizing plate integrated touch panel module having the transparent conductive layer,
An optical compensation film having a transparent conductive layer on at least one surface, a polarizer, and a protective film in this order from the VA mode liquid crystal cell toward the viewing side, and
A liquid crystal display device with a touch panel, wherein the glass transition temperature Tg of the optical compensation film is in the range of 155 to 250 ° C.

  2. 2. The liquid crystal display device with a touch panel according to claim 1, wherein the optical compensation film contains one of a cycloolefin-based resin, a polyimide-based resin, and a polyarylate-based resin.

  3. When the optical compensation film is heat-treated at 150 ° C. for 1 hour, the variation of the in-plane retardation value Ro is within ± 3.0%, and the variation of the thickness direction retardation value Rt is less than ± 3.0%. 3. The liquid crystal display device with a touch panel according to item 1 or 2, wherein the value is within a range of ± 4.0%.

  4. 4. The liquid crystal display device with a touch panel according to claim 1, wherein a thickness of the optical compensation film is in a range of 10 to 40 μm. 5.

  5. 5. The optical compensation film according to any one of items 1 to 4, wherein the optical compensation film contains a nitrogen-containing heterocyclic compound having a structure represented by the following general formula (3) as a retardation increasing agent. A liquid crystal display device with a touch panel according to the above item.

（式中Ａはピラゾール環を表す。Ａｒ_１及びＡｒ_２はそれぞれ芳香族炭化水素環又は芳香族複素環を表し、置換基を有してもよい。Ｒ_１は水素原子、アルキル基、アシル基、スルホニル基、アルキルオキシカルボニル基、又はアリールオキシカルボニル基を表す。ｑは１又は２を表す。ｎ及びｍはそれぞれ１〜３の整数を表す。）
６．第１項から第５項までのいずれか一項に記載のタッチパネル付き液晶表示装置を製造するタッチパネル付き液晶表示装置の製造方法であって、
前記光学補償フィルムの少なくとも一方の面に前記透明導電層を形成した後、１５０℃以上で熱処理する工程と、
偏光子を前記透明導電層を形成した光学補償フィルムと保護フィルムとで挟持するように貼合して、偏光板一体型タッチパネルモジュールを作製する工程と、
前記偏光板一体型タッチパネルモジュールの前記光学補償フィルム側を前記ＶＡモード型液晶セルに貼合する工程と、を備えることを特徴とするタッチパネル付き液晶表示装置の製造方法。

(In the formula, A represents a pyrazole ring. Ar ₁ and Ar ₂ each represent an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and may have a substituent. R ₁ is a hydrogen atom, an alkyl group, or an acyl group. , A sulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. Q represents 1 or 2. n and m each represent an integer of 1 to 3.)
6. A method for manufacturing a liquid crystal display device with a touch panel for manufacturing the liquid crystal display device with a touch panel according to any one of the first to fifth items,
After forming the transparent conductive layer on at least one surface of the optical compensation film, a step of heat treatment at 150 ° C. or more,
Laminating the polarizer so as to be sandwiched between the optically compensatory film and the protective film on which the transparent conductive layer is formed, and a step of producing a polarizing plate integrated type touch panel module,
Laminating the optical compensation film side of the polarizing plate-integrated touch panel module to the VA mode liquid crystal cell.

  By the above means of the present invention, it is possible to provide a liquid crystal display device with a touch panel having a VA mode liquid crystal cell having excellent front contrast and a method of manufacturing the same.

  Although the mechanism of the effect or the mechanism of action of the present invention has not been clarified, it is speculated as follows.

  Generally, in the case of an IPS mode liquid crystal cell, a film having no retardation in the optical compensation film, that is, a film having a retardation value Ro in the in-plane direction and a retardation value Rt in the thickness direction near zero is used. Is desirable. On the other hand, in the case of a VA mode type liquid crystal cell, as the optical compensation film, a film having a high retardation value Ro and Rt, for example, a retardation film in which Ro is in the range of 20 to 70 nm and Rt is in the range of 70 to 200 nm is used. It is desirable to be.

  Such a film having a high retardation value is usually subjected to a stretching treatment in a manufacturing process, and the polymer molecules constituting the film are highly oriented to obtain the retardation value.

  To provide a transparent conductive layer on the optical compensation film in order to produce a polarizing plate integrated type touch panel module called a so-called mid-cell type or inner-cell type, after forming the transparent conductive layer, the conductive layer Heat treatment (also referred to as annealing treatment) is required to reduce the resistance value. For example, specifically, a heat treatment at about 150 ° C. for about 30 minutes is performed, whereby the orientation of the polymer molecules in the optical compensation film is disturbed, and as a result, the required optical compensation performance becomes insufficient. It is assumed that the contrast is reduced.

  According to the configuration of the present invention, in order to cope with the above-described phenomenon, the use of a heat-resistant optical compensation film having a glass transition point Tg of 155 ° C. or more suppresses the retardation value fluctuation due to the heat treatment, and the VA mode It is presumed that excellent front contrast, which is a unique feature of the liquid crystal, can be achieved.

  Further, as described above, in order to reduce the thickness of the touch panel, the optical compensation film may be required to have a thickness of 40 μm or less. At this time, since the retardation value and the film thickness are in a reciprocal relationship, in the case of a thin film having a thickness of 40 μm or less, an additive capable of increasing the retardation value by adding the additive (in this application, both of the retardation increasing agent). Is added to the film. The present inventors have studied various phase difference increasing agents, and have found a phase difference increasing agent having a specific structure capable of obtaining more excellent effects. By adding this additive, at the time of the heat treatment, the orientation of the phase difference increasing agent itself is disturbed, and the phase difference variation derived from the compound occurs, thereby canceling the phase difference variation derived from the polymer molecules constituting the film. It is presumed that excellent retardation value and heat treatment fluctuation resistance can be realized even with a thin film.

Schematic diagram showing an example of the configuration of a conventional liquid crystal display device with an out-cell touch panel module Schematic diagram showing an example of the configuration of a liquid crystal display device with a touch panel including the polarizing plate integrated type touch panel module of the present invention. The schematic diagram which shows another example of the structure of the liquid crystal display device with a touch panel provided with the polarizing plate integrated type touch panel module of this invention. The schematic diagram which shows another example of the structure of the liquid crystal display device with a touch panel provided with the polarizing plate integrated type touch panel module of this invention. The schematic diagram which shows another example of the structure of the liquid crystal display device with a touch panel provided with the polarizing plate integrated type touch panel module of this invention. The schematic diagram which shows another example of the structure of the liquid crystal display device with a touch panel provided with the polarizing plate integrated type touch panel module of this invention.

  The liquid crystal display device with a touch panel according to the present invention is a liquid crystal display device with a touch panel including a polarizing plate integrated type touch panel module having a transparent conductive layer on the viewing side of a VA mode liquid crystal cell, wherein the polarized light having the transparent conductive layer is provided. A plate-integrated touch panel module has an optical compensation film, a polarizer, and a protective film having a transparent conductive layer on at least one surface in this order from the VA mode liquid crystal cell toward the viewing side, and the optical compensation The glass transition temperature Tg of the film is in the range of 155 to 250C. This feature is a technical feature common to the claimed inventions.

  As an embodiment of the present invention, from the viewpoint of achieving the effects of the present invention, the optical compensation film may contain any of a cycloolefin-based resin, a polyimide-based resin, or a polyarylate-based resin, It is preferable from the viewpoint of satisfying the glass transition temperature Tg.

  Further, when the optical compensation film is heat-treated at 150 ° C. for 1 hour, the variation of the in-plane retardation value Ro is within a range of ± 3.0%, and the variation of the retardation value Rt in the thickness direction is less than ± 3.0%. When the variation is within the range of ± 4.0%, the optical compensation function is sufficiently exhibited, the phase difference variation due to the heat treatment is suppressed, and the excellent front contrast when using the VA mode liquid crystal cell is obtained. This is a preferable performance from the viewpoint of achievement.

  The thickness of the optical compensation film is preferably in the range of 10 to 40 μm, which is a preferable thickness for reducing the thickness of the touch panel. In this case, the structure represented by the general formula (3) is used. It is preferable to contain a nitrogen-containing heterocyclic compound having the following formula, from the viewpoint of imparting a desired retardation value and further suppressing a variation in retardation due to heat treatment.

  The method for producing a liquid crystal display device with a touch panel according to the present invention includes, after forming the transparent conductive layer on at least one surface of the optical compensation film, a heat treatment at 150 ° C. or higher, and a polarizer formed with the transparent conductive layer. Affixing the optical compensation film and the protective film so as to be sandwiched therebetween, to produce a polarizing plate integrated touch panel module, and the optical compensation film side of the polarizing plate integrated touch panel module to the VA mode liquid crystal cell. And a step of bonding.

  Hereinafter, the present invention, its components, and embodiments and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning including the numerical value described before and after that as a lower limit and an upper limit.

<< Outline of Liquid Crystal Display Device with Touch Panel of the Present Invention >>
The liquid crystal display device with a touch panel according to the present invention is a liquid crystal display device with a touch panel including a polarizing plate integrated type touch panel module having a transparent conductive layer on the viewing side of a VA mode liquid crystal cell, wherein the polarized light having the transparent conductive layer is provided. Board integrated type touch panel module,
An optical compensation film having a transparent conductive layer on at least one surface, a polarizer, and a protective film in this order from the VA mode liquid crystal cell toward the viewing side, and
The glass transition temperature Tg of the optical compensation film is in the range of 155 to 250C.

  The liquid crystal display device with a touch panel according to the present invention is characterized in that it has a VA mode liquid crystal display cell as described above. By adopting the VA mode liquid crystal display cell, a conventional IPS mode liquid crystal display cell can be obtained. This is to improve the front contrast as compared with the liquid crystal display device with a touch panel used.

  The glass transition temperature Tg of the optical compensation film needs to be 155 ° C. or higher from the viewpoint of suppressing the fluctuation of the retardation value during the heat treatment and improving the contrast. When the temperature is lower than 155 ° C., in the heat treatment after the formation of the transparent conductive layer, the phase difference value fluctuates due to the disorder of the polymer molecules of the optical compensation film, and the optical compensation function is reduced, which is a characteristic characteristic of the VA mode liquid crystal. Excellent front contrast cannot be obtained.

  Further, various additives are added to the optical compensation film from the viewpoint of improving optical and physical functions, and it is necessary to satisfy the range of the glass transition temperature in a state in which various additives are contained. . For example, when a plasticizer or the like is added, the glass transition temperature may decrease depending on the type and the amount of addition, which is a design consideration.

  The glass transition temperature Tg can be determined by, for example, using a differential scanning calorimeter DSC220 manufactured by Seiko Instruments Inc. according to JIS K-7121. As a specific method, about 10 mg of a sample film is set in a container, and the temperature is raised from room temperature to 250 ° C. at a rate of 20 ° C./min under a nitrogen flow rate of 50 ml / min and held for 10 minutes (first scan). ) Then, the temperature was lowered to 30 ° C. at a rate of 20 ° C./min, held for 10 minutes (second scan), and further raised to 250 ° C. at 20 ° C./min (third scan) to prepare a DSC curve. The glass transition temperature Tg is determined from the obtained DSC curve of the third scan.

  Further, as described above, the optical compensation film according to the present invention preferably contains a retardation increasing agent having a structure represented by the general formula (3) for the purpose of further suppressing a change in retardation value during heat treatment. .

  In the course of the study of the present invention, as a result of various studies of a general-purpose resin film, the diacetyl cellulose film has a large dimensional change due to humidity, and when a transparent conductive layer is formed on the film, shrinkage or elongation occurs during storage, and the electrode Cracks and the like occurred, and it was difficult to use. In addition, the PET film has too large a phase difference, and has been difficult to use as an optical compensation film of a VA mode liquid crystal display device. Similarly, the polycarbonate (PC) film has a large photoelastic coefficient and is similarly unsuitable as an optical compensation film for a VA mode liquid crystal display device. Further, the acrylic resin film had a low glass transition temperature Tg and was unsuitable as the optical compensation film of the present invention.

<Configuration of liquid crystal display device with touch panel of the present invention>
The liquid crystal display device with a touch panel according to the present invention is a liquid crystal display device with a touch panel including a polarizing plate integrated type touch panel module having a transparent conductive layer on the viewing side of a VA mode liquid crystal cell, wherein the polarized light having the transparent conductive layer is provided. A plate-integrated touch panel module has an optical compensation film, a polarizer, and a protective film having a transparent conductive layer on at least one surface in this order from the VA mode liquid crystal cell toward the viewing side, and the optical compensation The glass transition temperature Tg of the film is in the range of 155 to 250 ° C., wherein the optical compensation film contains a cycloolefin-based resin, a polyimide-based resin, or a polyarylate-based resin. It is preferable from the viewpoints of controllability and phase difference value.

  The configuration of the liquid crystal display device with a touch panel of the present invention will be described with reference to the drawings, together with the configuration of a comparative example.

  FIG. 1 is a schematic diagram showing an example of a configuration of a liquid crystal display device with a touch panel including a conventional out-cell touch panel module.

  A liquid crystal display device with a touch panel 10 as a comparative example has a polarizing plate P1 in which a polarizer 2 is sandwiched between a protective film T1 and an optical compensation film T2 on one surface of a liquid crystal cell 1, and a conductive layer base film thereon. 4, a touch panel module T having a transparent conductive layer 5 and a protective layer 6 on both surfaces is bonded to the polarizing plate P1 via an adhesive layer 3, and a front plate 7 is bonded to the touch panel module T via the adhesive layer 3. . The other surface of the liquid crystal cell 1 has a polarizing plate P2 in which a polarizer 2 is sandwiched between an optical compensation film T3 and a protective film T4. The polarizing plate P1 side is the viewing side, and the polarizing plate P2 side is the backlight side. Here, the liquid crystal cell 1 is generally of the IPS mode type.

  FIG. 2 is a schematic diagram illustrating an example of the configuration of a liquid crystal display device with a touch panel including the polarizing plate integrated touch panel module of the present invention.

  The liquid crystal display device with a touch panel 20 of the present invention has a polarizing plate P1 in which a polarizer 2 is sandwiched between a protective film T1 and an optical compensation film T2 on one surface of a liquid crystal cell 1, and the optical compensation film T2 is on both sides thereof. A polarizer-integrated touch panel module having a so-called mid-cell or inner-cell structure in which a transparent conductive layer 5 is formed. With such a configuration, the liquid crystal display device with the touch panel can be made thinner than the out-cell type. It is preferable that the adhesion between the respective films and layers is performed by appropriately forming the adhesive layer 3.

  The other surface of the liquid crystal cell 1 similarly has a polarizing plate P2 in which a polarizer 2 is sandwiched between an optical compensation film T3 and a protective film T4. Here, the liquid crystal cell 1 is of a VA mode type.

  Further, the above is the minimum configuration, and a functional layer (a hard coat layer, an intermediate layer, an antistatic layer, a smoothing layer, an ultraviolet absorbing layer, an anti-curl layer, and the like) may be provided between the members as necessary. Forming a hard coat layer as a protective layer of the film and forming an antistatic layer are preferred embodiments.

  The thickness of the entire polarizing plate-integrated touch panel module according to the present invention is not particularly limited, but is preferably in the range of 7 to 80 μm, more preferably from the viewpoints of prevention of bending, good resistance value, handleability, and the like. It is in the range of 10 to 60 μm.

  FIG. 3 is a schematic diagram illustrating another example of the configuration of a liquid crystal display device with a touch panel including the polarizing plate integrated touch panel module of the present invention.

  In the configuration of FIG. 3, the transparent conductive layer 5 is formed as an upper layer of the protective film T1 and the optical compensation film T2.

  FIG. 4 is a schematic diagram showing another example of the configuration of a liquid crystal display device with a touch panel including the polarizing plate integrated touch panel module of the present invention.

  In the configuration of FIG. 4, the transparent conductive layer 5 is formed as an upper layer of the protective film T1 and a lower layer of the optical compensation film T2.

  FIG. 5 is a schematic view showing another example of the configuration of a liquid crystal display device with a touch panel including the polarizing plate integrated touch panel module of the present invention.

  In the configuration of FIG. 5, the transparent conductive layer 5 is formed as a single layer, and is disposed below the optical compensation film T2. In this case, the transparent conductive layer preferably has a configuration in which the X electrode pattern and the Y electrode pattern are provided via an insulating layer.

  FIG. 6 is a schematic diagram showing another example of the configuration of the liquid crystal display device with a touch panel including the polarizing plate integrated touch panel module of the present invention.

In the configuration of FIG. 6, the transparent conductive layer 5 is formed as a single layer, and is disposed above the optical compensation film T2. Similarly, the transparent conductive layer in this case has a configuration in which an X electrode pattern and a Y electrode pattern are interposed in the layer with an insulating layer interposed therebetween. Hereinafter, each element constituting the polarizing plate integrated touch panel module of the present invention will be described in detail. explain.

[1] Optical Compensation Film The glass transition temperature Tg of the optical compensation film according to the present invention is in the range of 155 to 250 ° C., and the lower limit of Tg needs to be 155 ° C. or more. The optical compensation film usually contains a resin, a plasticizer, various additives, a matting agent, and the like, but the present invention is characterized in that the glass transition temperature Tg of the finished film is 155 ° C. or higher.

  The glass transition temperature Tg is required to be 155 ° C. or higher from the viewpoint of suppressing the phase difference fluctuation with respect to the heat treatment when the film forms the transparent conductive layer, and the upper limit of the glass transition temperature Tg is as follows. 250 ° C. or less. If the Tg exceeds 250 ° C., the adhesion and the crack resistance may decrease with an increase in the internal stress. Therefore, the present invention is directed to an optical compensation film having a glass transition temperature Tg of up to 250 ° C.

  The preferred resin used in the optical compensation film according to the present invention preferably has a glass transition temperature Tg of a resin alone of 155 ° C. or higher, and in consideration of the development of phase difference and stability, among others, a cellulose ester resin Preferably, it contains any of cycloolefin resin, polyimide resin or polyarylate resin, more preferably contains any of cycloolefin resin, polyimide resin or polyarylate resin, cycloolefin It is particularly preferable to contain a system resin.

[1.1] Cellulose Ester Resin A cellulose ester resin having a glass transition temperature Tg of 155 ° C. or higher when contained in an optical compensation film (hereinafter, also referred to as a cellulose ester) is a lower fatty acid ester of cellulose. Is preferred. Above all, it is preferable to use a mixed fatty acid ester such as cellulose acetate propionate or cellulose acetate butyrate from the viewpoint of easily producing a phase difference and dimensional stability against humidity.

  Among the above, the lower fatty acid ester of cellulose that is particularly preferably used is cellulose acetate propionate (also referred to as CAP in the present application).

  Cellulose acetate propionate and cellulose acetate butyrate have an acyl group having 2 to 4 carbon atoms as a substituent, the degree of substitution of an acetyl group is X, and the degree of substitution of a propionyl group or a butyryl group is Y And those satisfying the following formulas (I) and (II) at the same time are preferable.

Formula (I) 2.0 ≦ X + Y ≦ 3.0
Formula (II) 1.0 ≦ X ≦ 2.0 and 0.1 ≦ Y ≦ 1.0
It is preferable that

  The method for measuring the degree of substitution of the acyl group can be measured according to ASTM-D817-96.

  As the molecular weight of cellulose acetate propionate and cellulose acetate butyrate, the number average molecular weight (Mn) is from 100,000 to less than 180,000, Mw is from 200,000 to less than 360,000, and Mw / Mn is from 1.8 to 2.0. Is preferred.

  The number average molecular weight (Mn) and molecular weight distribution (Mw) of the cellulose ester can be measured using high performance liquid chromatography. The measurement conditions are as follows.

Solvent: dichloromethane Column: Shodex K806, K805, K803G
(Three Showa Denko KK products were connected and used.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (GL Science)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 500 to 1,000,000 A calibration curve using 13 samples was used. The 13 samples are preferably used at substantially equal intervals.

[1.2] Cycloolefin-based resin As the cycloolefin-based resin, polymers of various cycloolefin monomers can be used, and a cycloolefin monomer having a norbornene skeleton is homopolymerized or copolymerized. It is preferable to use the obtained polymer.

  Hereinafter, the cycloolefin monomer used in the present invention will be described.

  The cycloolefin resin according to the present invention is preferably a polymer obtained by homopolymerization or copolymerization from cycloolefin monomers represented by the following general formulas (A-1) and (A-2). .

  The cycloolefin monomer having a structure represented by the general formula (A-1) will be described.

（一般式（Ａ−１）中、Ｒ^１〜Ｒ^４は、それぞれ独立に水素原子又はハロゲン原子を表す。又は、酸素原子、窒素原子、イオウ原子若しくはケイ素原子を含む連結基を有していてもよい、置換又は非置換の炭素原子数１〜３０の炭化水素基、若しくは極性基を表す。ｐは、０〜２の自然数を表す。）
上記極性基は、酸素、硫黄、窒素、ハロゲンなど電気陰性度の高い原子によって分極が生じている官能基のことをいう。上記極性基としては、カルボキシ基、ヒドロキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、アミノ基、アミド基、シアノ基、ハロゲン原子などが挙げられ、これら極性基はメチレン基などの連結基を介して結合していてもよい。また、酸素原子、窒素原子、イオウ原子又はケイ素原子を含む連結基を有していてもよい置換又は非置換の炭素原子数１〜３０の炭化水素基、例えばカルボニル基、エーテル基、シリルエーテル基、チオエーテル基、イミノ基など極性を有する２価の有機基が連結基となって結合している炭素原子数１〜３０の炭化水素基なども極性基として挙げられる。これらの中では、カルボキシ基、ヒドロキシ基、アルコキシカルボニル基又はアリールオキシカルボニル基が好ましく、特にアルコキシカルボニル基又はアリールオキシカルボニル基であることが、溶液製膜時の溶解性を確保する観点で好ましい。

(In the general formula (A-1), R ^{1 to} R ⁴ each independently represent a hydrogen atom or a halogen atom. Alternatively, R ^{1 to} R ⁴ each have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom. Represents a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or a polar group. P represents a natural number of 0 to 2)
The polar group refers to a functional group in which polarization is caused by atoms having high electronegativity such as oxygen, sulfur, nitrogen, and halogen. Examples of the polar group include a carboxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an amide group, a cyano group, a halogen atom, and the like.These polar groups are formed through a linking group such as a methylene group. They may be combined. Further, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom, for example, a carbonyl group, an ether group, a silyl ether group And a hydrocarbon group having 1 to 30 carbon atoms to which a divalent organic group having polarity such as a thioether group and an imino group is bonded as a linking group. Among these, a carboxy group, a hydroxy group, an alkoxycarbonyl group, or an aryloxycarbonyl group is preferable, and an alkoxycarbonyl group or an aryloxycarbonyl group is particularly preferable from the viewpoint of securing solubility during solution film formation.

  Next, the cycloolefin monomer represented by the general formula (A-2) will be described.

（一般式（Ａ−２）中、Ｒ^５は、独立に水素原子、炭素数１〜５の炭化水素基、又は炭素数１〜５のアルキル基を有するアルキルシリル基を表す。Ｒ^６は、カルボキシ基、ヒドロキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、アミノ基、アミド基、シアノ基、フッ素原子、塩素原子、臭素原子、又はヨウ素原子を表す。ｐは、０〜２の整数を表す。）
本発明においては、一般式（Ａ−２）で表されるように、置換基Ｒ^５及びＲ^６が片側炭素に置換されたシクロオレフィン単量体を用いることで、分子の対称性が崩れたためか溶媒揮発時の樹脂と添加剤同士の拡散運動を促進し、それに伴い添加剤の製膜フィルム表面への移動を促すことから、添加剤の偏在の観点から好ましい。

(In the general formula (A-2), R ⁵ independently represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or an alkylsilyl group having an alkyl group having 1 to 5 carbon atoms. R ⁶ represents Represents a carboxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an amide group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and p represents an integer of 0 to 2. )
In the present invention, as represented by the general formula (A-2), by using a cycloolefin monomer in which the substituents R ⁵ and R ⁶ are substituted on one side carbon, the symmetry of the molecule is lost. This is preferable from the viewpoint of uneven distribution of the additive, because it promotes the diffusion movement between the resin and the additive when the solvent is volatilized, thereby promoting the movement of the additive to the surface of the film-forming film.

R ⁵ is a hydrocarbon group having 1 to 3 carbon atoms, and R ⁶ is preferably a carboxy group, a hydroxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, and particularly preferably an alkoxycarbonyl group or an aryloxycarbonyl group. It is also preferable from the viewpoint of ensuring solubility during film formation.

  Hereinafter, the structures of the general formulas (A-1) and (A-2) in the present application are specifically shown, but are not limited to the following specific examples.

The cycloolefin resin is a polymer obtained by homopolymerizing or copolymerizing a cycloolefin monomer having a structure represented by the general formulas (A-1) and (A-2) having a norbornene skeleton. There are, for example, the following.
(1) Ring-opening polymer of cycloolefin monomer (2) Ring-opening copolymer of cycloolefin monomer and copolymerizable monomer (3) Ring-opening polymer of the above (1) or (2) ( Hydrogenated (co) polymer of (co) polymer (4) The ring-opened (co) polymer of (1) or (2) is cyclized by Friedel-Crafts reaction and then hydrogenated (co) polymer (5) Saturated polymer of cycloolefin monomer and unsaturated double bond-containing compound (6) Addition (co) polymer of cycloolefin monomer and hydrogenated (co) polymer thereof (7) Alternating copolymer of cycloolefin-based monomer and methacrylate or acrylate Any of the above polymers (1) to (7) can be obtained by known methods, for example, JP-A-2008-107534 and JP-A-2005-227606. Can be obtained by the method described in Japanese Unexamined Patent Publication No. For example, as the catalyst and the solvent used for the ring-opening copolymerization of the above (2), for example, those described in paragraphs 0019 to 0024 of JP-A-2008-107534 can be used. As the catalyst used for the hydrogenation of (3) and (6), for example, those described in paragraphs 0025 to 0028 of JP-A-2008-107534 can be used. As the acidic compound used in the Friedel-Crafts reaction (4), for example, those described in paragraph 0029 of JP-A-2008-107534 can be used. As the catalyst used for the addition polymerization of the above (5) to (7), for example, those described in paragraphs 0058 to 0063 of JP-A-2005-227606 can be used. The alternating copolymerization reaction of the above (7) can be performed, for example, by the method described in paragraphs 0071 and 0072 of JP-A-2005-227606.

  Among them, the polymers (1) to (3) and (5) are preferable, and the polymers (3) and (5) are more preferable.

  Preferred cycloolefin polymers according to the present invention include those having structural units represented by the following general formulas (B-1) and (B-2). Such a cycloolefin-based resin has only the structural unit represented by the general formula (B-1), only the structural unit represented by the general formula (B-2), and the general formula (B-1) and the general formula (B-1). A copolymer containing each structural unit of B-2) may be used.

  Preferably, it is a resin of a copolymer containing only a structural unit of the general formula (B-2) or a structural unit of both the general formulas (B-1) and (B-2). The obtained cycloolefin-based resin is preferable in that the glass transition temperature is high and the transmittance is excellent.

（一般式（Ｂ−１）中、Ｘは、−ＣＨ＝ＣＨ−で表される基又は式：−ＣＨ_２ＣＨ_２−で表される基である。Ｒ^１〜Ｒ^４は、それぞれ独立に水素原子；ハロゲン原子；酸素、窒素、イオウ又はケイ素を含む連結基を有していてもよい置換又は非置換の炭素原子数１〜３０の炭化水素基；又は極性基を表す。ｐは、０〜２の自然数を表す。）

（一般式（Ｂ−２）中、Ｘは、−ＣＨ＝ＣＨ−で表される基又は式：−ＣＨ_２ＣＨ_２−で表される基である。Ｒ^５は、それぞれ独立に水素原子、炭素数１〜５の炭化水素基、又は炭素数１〜５のアルキル基を有するアルキルシリル基を表す。Ｒ^６は、カルボキシ基、ヒドロキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、アミノ基、アミド基、シアノ基、フッ素原子、塩素原子、臭素原子、又はヨウ素原子を表す。ｐは、０〜２の整数を表す。）
本明細書では、本願に係るシクロオレフィン系樹脂の製造方法等については、特開２００８−１０７５３４号公報の記載を援用するものとし、その説明を省略する。

(In the general formula (B-1), X is a group represented by —CH ＝ CH— or a group represented by the formula: —CH ₂ CH ₂ —. R ^{1 to} R ⁴ are each independently A hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing oxygen, nitrogen, sulfur or silicon; Represents a natural number of ~ 2.)

(In the general formula (B-2), X is a group represented by —CH ＝ CH— or a group represented by the formula: —CH ₂ CH ₂ —. R ⁵ is each independently a hydrogen atom, Represents a hydrocarbon group having 1 to 5 carbon atoms or an alkylsilyl group having an alkyl group having 1 to 5 carbon atoms, and R ⁶ represents a carboxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an amide group. Represents a group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and p represents an integer of 0 to 2.)
In this specification, the description of JP-A-2008-107534 will be referred to for the method for producing the cycloolefin-based resin according to the present application, and the description thereof will be omitted.

The cycloolefin resins can be used alone or in combination of two or more.
The preferred molecular weight of the cycloolefin resin according to the present invention is such that the number average molecular weight (Mn) in terms of polystyrene measured by the gel permeation chromatography (GPC) is 8,000 to 100,000, more preferably 10,000 to 80,000, and particularly preferably 12,000. And a weight average molecular weight (Mw) of 20,000 to 300,000, more preferably 30,000 to 250,000, particularly preferably 40,000 to 200,000.

The glass transition temperature (Tg) of the cycloolefin resin according to the present invention is usually 110 ° C. or higher, preferably 110 to 350 ° C., more preferably 120 to 250 ° C., and particularly preferably 120 to 220 ° C. A case where Tg is 110 ° C. or higher is preferable because deformation is unlikely to occur due to use under high-temperature conditions or secondary processing such as coating and printing.
On the other hand, by setting the Tg to 350 ° C. or lower, it is possible to avoid the case where the molding process becomes difficult, and to suppress the possibility that the resin is deteriorated by heat during the molding process.
As long as the effects of the present invention are not impaired, specific hydrocarbon-based resins described in, for example, JP-A-9-221577 and JP-A-10-287732, or known heats may be used as the cycloolefin-based resin. Plastic resins, thermoplastic elastomers, rubbery polymers, organic fine particles, inorganic fine particles, etc. may be blended, specific wavelength dispersants, plasticizers, antioxidants, peeling accelerators, rubber particles, ultraviolet absorbers and the like It may contain additives.
Commercial products can be preferably used as the cycloolefin-based resin. Examples of the commercial products include trade names of ARTON (registered trademark) G, ARTON F, ARTON R, and ARTON RX from JSR Corporation. And can be used.

[1.3] Polyimide resin The polyimide resin according to the present invention is preferably a polyimide resin represented by the following formula (P1) obtained by chemically imidizing a polyimide precursor.

[Polymerization of polyimide precursor]
An example of a method for producing a polyimide precursor having a structure represented by the formula (P1) used in the present invention will be described below.

  First, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFMB) as a diamine is dissolved in a polymerization solvent in a polymerization vessel. To this diamine solution, a powder of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanoic acid dianhydride (6FDA) was gradually added, and a mechanical stirrer was used. Stir in the range, preferably in the range of 20-60 ° C for 1-72 hours. By using TFMB and 6FDA, the transmittance and solubility of visible light are improved. The number of moles of the diamine and the number of moles of the tetracarboxylic dianhydride are substantially equimolar. The total monomer concentration during the polymerization is 5 to 40% by mass, preferably 10 to 30% by mass. By performing polymerization in this monomer concentration range, a polyimide precursor solution having a uniform and high degree of polymerization can be obtained. If the polymerization is carried out at a concentration lower than the above monomer concentration range, the degree of polymerization of the polyimide precursor will not be sufficiently high, and the polyimide resin film finally obtained may be fragile, which is not preferable.

Although the polymerization solvent is not particularly limited, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, hexamethylphosphoramide, dimethylsulfoxide, γ- Butyrolactone, 1,3-dimethyl-2-imidazolidinone, 1,2-dimethoxyethane-bis (2-methoxyethyl)
Aprotic solvents such as ether, terahydrofuran, 1,4-dioxane, picoline, pyridine, acetone, chloroform, toluene, xylene, and phenol, o-cresol, m-cresol, p-cresol, o-chlorophenol; Protic solvents such as m-chlorophenol and p-chlorophenol can be used. These solvents may be used alone or as a mixture of two or more.

[Production method of polyimide resin]
The polyimide resin represented by the formula (P1) can be produced by a dehydration ring closure reaction (imidation reaction) of the polyimide precursor obtained by the above method. For the imidization reaction, a chemical imidization in which the obtained polyimide resin shows more excellent dimensional stability is used. Chemical imidization can be carried out using a dehydrating cyclizing agent (chemical imidizing agent) comprising an acid anhydride of an organic acid and an organic tertiary amine. For example, the polyimide precursor varnish may be used as it is or after being appropriately diluted with a solvent, a dehydration cyclization reagent may be added thereto, and the mixture is stirred at 0 to 100 ° C, preferably at 20 to 60 ° C for 0.5 to 48 hours. It can be easily imidized.

  The acid anhydride of the organic acid used at that time is not particularly limited, and acetic anhydride, propionic anhydride, maleic anhydride, phthalic anhydride and the like can be used, but the cost and the ease of post-treatment are possible. From the viewpoint of acetic acid, acetic anhydride is preferably used. The organic tertiary amine is not particularly limited, and pyridine, 1,5-dimethylpyridine, β-picoline, γ-picoline, lutidine, isoquinoline, triethylamine, N, N-dimethylaniline and the like can be used.

  At the time of the chemical imidization reaction, the amount of the acid anhydride used in the dehydration cyclization reagent is preferably in the range of 1 to 10 times mol of the theoretical dehydration amount of the polyimide precursor, The amount of the catalyst used is preferably in the range of 0.1 to 2 moles per mole of the acid anhydride. If the chemical imidization is performed outside these ranges, the imidization reaction may not be completed or the imidization may be insufficient due to the precipitation of a polyimide-based resin in which the imidization is not completed in the reaction solution.

  After completion of imidation, the reaction solution can be used as it is for coating, or the reaction solution is dropped into a large amount of poor solvent, or the poor solvent is added to the reaction solution to precipitate and wash the polyimide resin. After removing the reaction solvent and, in the case of chemical imidization, an excess of the chemical imidizing agent, drying under reduced pressure can give a polyimide resin powder. Usable poor solvents are not particularly limited as long as they do not dissolve the polyimide resin, and are not particularly limited, but water, methanol, and ethanol are preferred from the viewpoint of affinity with a reaction solvent or a chemical imidizing agent and ease of removal by drying. , N-propanol, isopropanol and the like are preferably used.

  The weight average molecular weight of the polyimide resin is not particularly limited, but is preferably 5,000 to 2,000,000, more preferably 10,000 to 1,000,000, and still more preferably 50,000 to 500,000. When the weight average molecular weight is 5,000 or more, sufficient strength is obtained when the film is formed, and dimensional stability tends to be improved, so that sufficient dimensional stability is obtained. On the other hand, if it is 2,000,000 or less, the solution viscosity does not become too high, and it is easy to handle. In addition, the said weight average molecular weight means the value of polyethylene glycol conversion by size exclusion chromatography (SEC).

[1.3] Polyarylate resin The polyarylate resin according to the present invention is preferably a polyarylate resin containing a bisphenol residue and an aromatic dicarboxylic acid residue.
The bisphenol residue has a structure represented by the general formula (P2).

  In the general formula (P2), X needs to be a divalent group containing a fluorine atom. By making X in the general formula (P2) a divalent group containing a fluorine atom, it is excellent in heat resistance and light transmittance in a visible light region and a shorter wavelength region (ultraviolet region). Thus, a polyarylate resin having better flame retardancy than the conventional one and suppressing yellowing due to ultraviolet rays can be obtained. When X is a divalent group containing no fluorine atom, flame retardancy is reduced, yellowing is caused by irradiation with ultraviolet rays, and light transmittance is reduced.

  The divalent group containing a fluorine atom is represented by, for example, a general formula (P2a).

In the general formula (P2a), R ^1a and R ^2a are each independently a trifluoromethyl group (CF ₃ group), a difluoromethyl group (CF ₂ H group), a monofluoromethyl group (CH ₂ F group), or It is a fluorine atom. Among them, R ^1a and R ^2a are preferably a trifluoromethyl group.
R ¹ and R ² represent a substituent bonded to the benzene ring in the general formula (P2).

In the general formula (P2), R ¹ and R ^{2 each} independently have 1 carbon atom because bisphenol giving the structure represented by the general formula (P2) is easily available industrially or easily synthesized. To 6 hydrocarbon groups, halogenated alkyl groups or halogen atoms. Among these, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a phenyl group and a cyclohexyl group are preferred, and a bromine atom and a methyl group are more preferred.
p and q each represent the number of substituents R ¹ and R ² bonded to the benzene ring, and are each independently an integer of 0 to 4. For example, when p and q are 0, it indicates that all hydrogen atoms bonded to the benzene ring in the general formula (P2) are not substituted with R ¹ and R ² . When p is 2 to 4, a plurality of R ¹ may be the same substituent or different substituents. When q is 2 to 4, a plurality of R ² may be the same substituent or different substituents. It is preferable that p and q are 0 because bisphenol giving the structure represented by the general formula (P2) is industrially easily available or easily synthesized.

Examples of the bisphenol giving the structure represented by the general formula (P2) include 2,2-bis (4-hydroxyphenyl) hexafluoropropane [BisAF] and 2,2-bis (3,5-dimethyl-4- (Hydroxyphenyl) hexafluoropropane and 2,2-bis (tetramethyl-4-hydroxyphenyl) hexafluoropropane. Of these, BisAF is preferred because of its industrial availability. When BisAF is used, in the general formula (P2), p = 0, q = 0, and X = —C (CF ₃ ) ₂ —.

  In the present invention, the bisphenol residue may include a bisphenol residue other than the bisphenol that gives the structure of the general formula (P2) as long as the effects of the present invention are not impaired. Examples of bisphenols that provide such a residue include 2,2-bis (4-hydroxyphenyl) propane [BisA], 2,2-bis (3-methyl-4-hydroxyphenyl) propane [BisC], 9 , 9-bis (3-methyl-4-hydroxyphenyl) fluorene [BCF], 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1-bis (3-methyl-4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane, bis (3,5-dimethyl) 4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) hexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) Hexane is mentioned.

  In order to impart high flame retardancy to the polyarylate resin and further suppress yellowing due to ultraviolet rays, of the entire bisphenol residue present in the polyarylate resin, the bisphenol residue represented by the general formula (P2) Is preferably 50 to 100 mol%, more preferably 80 to 100 mol%, and even more preferably 100 mol%.

  The aromatic dicarboxylic acid residue preferably has a structure represented by the general formula (P3). By having the structure represented by the general formula (P3) together with the structure represented by the general formula (P2), excellent heat resistance, flame retardancy, visible light region and shorter wavelength region (ultraviolet light region) Region) and the suppression of yellowing due to ultraviolet rays can be realized at the same time. When the aromatic dicarboxylic acid residue does not have the structure of the general formula (P2), light transmittance in a short wavelength region (ultraviolet region) is reduced, or yellowing is easily caused by ultraviolet rays. For example, when only terephthalic acid which gives a structure not represented by the general formula (P3) is used as the aromatic dicarboxylic acid, the polyallylate resin has a reduced light transmittance in a short wavelength region (ultraviolet region) and yellows due to ultraviolet rays. Easier to do.

In the general formula (P3), R ³ and R ⁴ represent a substituent bonded to the benzene ring in the general formula (P3).

Since the aromatic dicarboxylic acid giving the structure represented by the general formula (P3) is industrially easily available or easily synthesized, R ³ and R ⁴ are each independently a carbon having 1 to 6 carbon atoms. It is a hydrogen group, a halogenated alkyl group or a halogen atom. Among these, chlorine, bromine, a methyl group, an ethyl group, a phenyl group, and a cyclohexyl group are preferable, and a bromine and a methyl group are more preferable.
r and s represent the number of substituents bonded to the benzene ring, and are each independently an integer of 0 to 4. For example, when r and s are 0, it indicates that all hydrogen atoms bonded to the benzene ring in the general formula (P2) are not substituted with R ³ and R ⁴ . When r is 2 to 4, a plurality of R ³ may be the same substituent or different substituents. When s is 2 to 4, a plurality of R ⁴ may be the same substituent or different substituents.

  Examples of the aromatic dicarboxylic acid giving the structure represented by the general formula (P3) include diphenyl ether-2,2'-dicarboxylic acid, diphenyl ether-2,3'-dicarboxylic acid, and diphenyl ether-2,4'-dicarboxylic acid And diphenyl ether-3,3'-dicarboxylic acid, diphenyl ether-3,4'-dicarboxylic acid, and diphenyl ether-4,4'-dicarboxylic acid. Of these, diphenyl ether-4,4'-dicarboxylic acid is preferred among them because it is industrially available. When diphenyl ether-4,4'-dicarboxylic acid is used, r = 0 and s = 0 in the general formula (P3).

  In the present invention, the aromatic dicarboxylic acid residue may include an aromatic dicarboxylic acid residue other than the aromatic dicarboxylic acid giving the structure of the general formula (P3) as long as the effects of the present invention are not impaired. Good. Examples of the aromatic dicarboxylic acid giving such a residue include terephthalic acid, isophthalic acid, and orthophthalic acid, and among them, isophthalic acid is preferable. By using isophthalic acid in combination, yellowing due to ultraviolet rays can be suppressed.

  In order to further suppress yellowing due to ultraviolet rays, of the entire aromatic dicarboxylic acid residues present in the polyarylate resin, an aromatic dicarboxylic acid residue having a structure represented by the general formula (P3) (isophthalic acid) In the case of containing a residue, the proportion occupied by the aromatic dicarboxylic acid residue having the structure represented by the general formula (P3) and the isophthalic acid residue) is preferably 35 to 100 mol%, The content is more preferably 50 to 100 mol%, further preferably 80 to 100 mol%, and most preferably 100 mol%.

  From the viewpoint of tensile elongation at break of the polyarylate resin, the proportion of the aromatic dicarboxylic acid residues having the structure represented by the general formula (P3) in the entire aromatic dicarboxylic acid residues present in the polyarylate resin is , Preferably from 35 to 100 mol%, more preferably 100 mol%.

  The polyarylate resin according to the present invention preferably contains a terminal group for closing the terminal of the molecule. When the terminal of the molecule is sealed, the acid value of the polyarylate resin is reduced, and the polyallylate resin is hardly decomposed by light. The terminal group is preferably a monohydric phenol residue, a monohydric acid chloride residue, a monohydric alcohol residue, and / or a monohydric carboxylic acid residue in that the acid value can be reduced. More preferably, they are a phenolic residue and a monohydric alcohol residue.

  In the present invention, a residue of an aliphatic diol, a residue of an alicyclic diol, a residue of an aliphatic dicarboxylic acid, and a residue of an alicyclic dicarboxylic acid are added to the polyarylate resin within a range that does not impair the effects of the present invention. It may contain a group. Examples of the aliphatic diol include ethylene glycol and propylene glycol. Examples of the alicyclic diol include 1,4-cyclohexanediol, 1,3-cyclohexanediol, and 1,2-cyclohexanediol. Examples of the aliphatic dicarboxylic acid include adipic acid and sebacic acid. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,2-cyclohexanedicarboxylic acid.

  Examples of the method for producing the polyarylate resin according to the present invention include a method of reacting in an organic solvent such as an interfacial polymerization method and a solution polymerization method, and a method of reacting in a molten state such as melt polymerization. From the viewpoint of the polymerizability and the appearance of the obtained resin, it is preferable to use an interfacial polymerization method which allows a reaction in an organic solvent, particularly a reaction at a low temperature.

  In order to obtain a high tensile elongation at break, the weight average molecular weight of the polyarylate resin is preferably 12,000 or more, more preferably 50,000 or more.

[2] Retardation raising agent The retardation raising agent referred to in the present application is a retardation value Rt (3) in the thickness direction of an optical compensation film containing 3 parts by mass of the compound with respect to 100 parts by mass of the resin used for the optical compensation film. (Measured at 23 ° C./55% RH, wavelength 590 nm)) is a compound having a function of exhibiting a value of 1.1 times or more as compared with an optical compensation film not added.

  The phase difference increasing agent according to the present invention is not particularly limited, and is, for example, a well-known disk having an aromatic ring described in JP-A-2006-113239, paragraphs [0143] to [0179]. Compounds (1,3,5-triazine-based compounds, etc.), rod-like compounds described in paragraphs [0106] to [0112] of JP-A-2006-113239, paragraphs [0118] to [0133] of JP-A-2012-214682. Use of the pyrimidine compounds described in paragraphs [0022] to [0028] of JP-A-2011-140637, and the polyester compounds described in paragraphs [0044] to [0058] of WO2012 / 014571. Can be.

  The properties required for the retardation enhancer according to the present invention include: excellent compatibility with the resin, excellent retardation manifestation when the film is thinned, excellent precipitation resistance, and high humidity. In the heat treatment, during the heat treatment, the orientation of the phase difference increasing agent itself is disturbed, and the phase difference derived from the compound is added. It is preferable that the fluctuation can offset the phase difference fluctuation derived from the polymer molecules constituting the film.

  From such a viewpoint, it is preferable to use the following nitrogen-containing heterocyclic compound as a retardation increasing agent.

(Nitrogen-containing heterocyclic compound)
The retardation increasing agent according to the present invention is preferably a nitrogen-containing heterocyclic compound having a structure represented by the following general formula (1).

  The nitrogen-containing heterocyclic compound according to the present invention is a nitrogen-containing heterocyclic compound having a pyrrole ring, a pyrazole ring, a triazole ring, or an imidazole ring, among nitrogen-containing heterocyclic compounds having a structure represented by the following general formula (1). A ring compound is preferable from the viewpoint of exerting a favorable interaction on the phase difference increasing function and the orientation of the resin molecules during the heat treatment.

<Compound having structure represented by general formula (1)>

In the general formula (1), A ₁ , A ₂ and B each independently represent an alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2- A cycloalkyl group (cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Among them, an aromatic hydrocarbon ring or an aromatic heterocyclic ring is preferable, and a 5- or 6-membered aromatic hydrocarbon ring or an aromatic heterocyclic ring is particularly preferable.

  The structure of the 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring is not limited, and examples thereof include a benzene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a 1,2,3-triazole ring, , 4-triazole ring, tetrazole ring, furan ring, oxazole ring, isoxazole ring, oxadiazole ring, isoxadiazole ring, thiophene ring, thiazole ring, isothiazole ring, thiadiazole ring, isothiadiazole ring and the like. .

The 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring represented by A ₁ , A ₂ and B may have a substituent. As the substituent, for example, a halogen atom ( Fluorine atom, chlorine atom, bromine atom, iodine atom, etc., alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group, etc.), cycloalkyl Group (cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), alkenyl group (vinyl group, allyl group, etc.), cycloalkenyl group (2-cyclopenten-1-yl, 2-cyclohexen-1-yl group, etc.) ), Alkynyl group (ethynyl group, propargyl group, etc.), aromatic hydrocarbon ring group (phenyl group, p-tolyl group, naphthyl group, etc.), aromatic heterocyclic group (2 Pyrrole, 2-furyl, 2-thienyl, pyrrole, imidazolyl, oxazolyl, thiazolyl, benzimidazolyl, benzoxazolyl, 2-benzothiazolyl, pyrazolinone, pyridyl, pyridinone, 2- Pyrimidinyl group, triazine group, pyrazole group, 1,2,3-triazole group, 1,2,4-triazole group, oxazole group, isoxazole group, 1,2,4-oxadiazole group, 1,3,4 -Oxadiazole group, thiazole group, isothiazole group, 1,2,4-thiodiazole group, 1,3,4-thiadiazole group, etc.), cyano group, hydroxy group, nitro group, carboxy group, alkoxy group (methoxy group) Ethoxy group, isopropoxy group, tert-butoxy group, n-octyloxy group, 2-meth An oxyoxy group, an aryloxy group (a phenoxy group, a 2-methylphenoxy group, a 4-tert-butylphenoxy group, a 3-nitrophenoxy group, a 2-tetradecanoylaminophenoxy group, etc.), an acyloxy group (a formyloxy group, Acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group, etc., amino group (amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenyl) Amino), acylamino (formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, etc.), alkyl and arylsulfonylamino (methylsulfonylamino, butylsulfonylamino, phenyl) Sulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group, etc., mercapto group, alkylthio group (methylthio group, ethylthio group, n-hexadecylthio group, etc.), arylthio group (phenylthio group) , P-chlorophenylthio group, m-methoxyphenylthio group, etc.), sulfamoyl group (N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N -Acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N'-phenylcarbamoyl) sulfamoyl group, etc.), sulfo group, acyl group (acetyl group, pivaloylbenzoyl group, etc.), carbamoyl group (carbamoyl group) Group, N-methylcarbamoyl group, N, N-di Chi-carbamoyl, N, N-di -n- octylcarbamoyl group, and each group such as N- (methylsulfonyl) carbamoyl group).

In the general formula (1), A ₁ , A ₂ and B may represent a benzene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a 1,2,3-triazole ring or a 1,2,4-triazole ring. It is preferable because an optical compensatory film having an excellent effect of changing optical characteristics and having excellent durability can be obtained.

In the general formula (1), T ₁ and T ₂ each independently represent a pyrrole ring, a pyrazole ring, an imidazole ring, a 1,2,3-triazole ring or a 1,2,4-triazole ring. Among these, a pyrazole ring, a triazole ring or an imidazole ring are particularly excellent in the effect of suppressing a change in retardation during heat treatment, and are preferable because a resin composition having excellent durability is obtained. It is particularly preferred that there is. The pyrazole ring, 1,2,3-triazole ring or 1,2,4-triazole ring or imidazole ring represented by T ₁ and T2 may be a tautomer. Specific structures of a pyrrole ring, a pyrazole ring, an imidazole ring, a 1,2,3-triazole ring or a 1,2,4-triazole ring are shown below.

In the formula, * represents a bonding position to L ₁ , L ₂ , L ₃ or L ₄ in the general formula (1). R ⁵ represents a hydrogen atom or a non-aromatic substituent. Examples of the non-aromatic substituent represented by R ⁵ include the same groups as the non-aromatic substituents among the substituents that A ₁ may have in the general formula (1). When the substituent represented by R ⁵ is a substituent having an aromatic group, A ₁ and T ₁ or B and T ₁ are easily twisted, and A ₁ , B and T ₁ can form an interaction with the resin. Therefore, it is difficult to suppress a change in optical characteristics. In order to enhance the effect of suppressing fluctuations in optical properties, R ⁵ is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom. .

In the general formula (1), T ₁ and T ₂ may have a substituent. Examples of the substituent include a substituent that A ₁ and A ₂ in the general formula (1) may have. Similar groups can be mentioned.

In the general formula (1), L ₁ , L ₂ , L _3, and L ₄ each independently represent a single bond or a divalent linking group, and are 5-membered or 6-membered via 2 or less atoms. Membered aromatic hydrocarbon rings or aromatic heterocycles are connected. The term “via two or less atoms” means the minimum number of atoms existing between the connected substituents among the atoms constituting the connecting group. The divalent linking group having 2 or less linking atoms is not particularly limited, but includes an alkylene group, an alkenylene group, an alkynylene group, O, (C = O), NR, S, and (O = S = O). A divalent linking group selected from the group consisting of: or a combination of two divalent linking groups. R represents a hydrogen atom or a substituent. Examples of the substituent represented by R include an alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group, etc.), a cycloalkyl group ( Cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), aromatic hydrocarbon ring group (phenyl group, p-tolyl group, naphthyl group, etc.), aromatic heterocyclic group (2-furyl group, 2-thienyl group) Group, 2-pyrimidinyl group, 2-benzothiazolyl group, 2-pyridyl group and the like), cyano group and the like. The divalent linking group represented by L ₁ , L ₂ , L ₃ and L ₄ may have a substituent, and the substituent is not particularly limited. For example, A in the general formula (1) Examples include the same groups as the substituents that ₁ and A ₂ may have.

In the general formula (1), L ₁ , L ₂ , L _3, and L ₄ have an increased interaction with the resin because the compound having the structure represented by the general formula (1) has higher planarity. Since it becomes stronger and fluctuations in optical characteristics are suppressed, a single bond or O, (C = O) -O, O- (C = O), (C = O) -NR or NR- (C = O ), And more preferably a single bond.

In the general formula (1), n represents an integer of 0 to 5. When n represents an integer of 2 or more, a plurality of A ₂ , T ₂ , L ₃ , and L ₄ in the general formula (1) may be the same or different. The larger the value of n, the stronger the interaction between the compound having the structure represented by the general formula (1) and the resin, and the better the effect of suppressing fluctuations in optical characteristics. The smaller the value of n, the more compatible the resin. Is excellent. For this reason, n is preferably an integer of 1 to 3, and more preferably 1 or 2.

<Compound having structure represented by general formula (2)>
The compound having a structure represented by the general formula (1) is preferably a compound having a structure represented by the general formula (2).

(In the formula, A ₁ , A ₂ , T ₁ , T ₂ , L ₁ , L ₂ , L ₃ and L ₄ are respectively A ₁ , A ₂ , T ₁ , T ₂ , L ₂ in the general formula (1). _{1, L} 2, _{L 3} and .A ₃ and _{T 3 L 4} as synonymous, the .L ₅ and _{L 6} represent the same group as _{a 1} and _{T 1,} respectively, in the general formula (1), the general Represents the same group as L ₁ in Formula (1), and m represents an integer of 0 to 4.)
m is preferably an integer of 0 to 2, and more preferably an integer of 0 to 1, since the smaller the value of m, the better the compatibility with the resin.

<Compound having structure represented by general formula (1.1)>
The compound having a structure represented by the general formula (1) is preferably a triazole compound having a structure represented by the following general formula (1.1).

_(Wherein, A 1, B, _{L 1} and _{L 2,} .k representing the _A 1, B, the same group as _{L 1} and _{L 2} in formula (1) represents an integer of 1 to 4 .T ₁ represents a 1,2,4-triazole ring.)
Further, the triazole compound having a structure represented by the general formula (1.1) is preferably a triazole compound having a structure represented by the following general formula (1.2).

(In the formula, Z represents a structure of the following general formula (1.2a). Q represents an integer of 2 to 3. At least two Zs represent at least one Z substituted with a benzene ring. Bonds to the ortho or meta position.)

(In the formula, R ¹⁰ represents a hydrogen atom, an alkyl group or an alkoxy group. P represents an integer of 1 to 5. * represents a bonding position with a benzene ring. T ₁ represents a 1,2,4-triazole ring. Represents.)
The compound having the structure represented by the general formula (1), (2), (1.1) or (1.2) may form a hydrate, a solvate or a salt. In the present invention, the hydrate may contain an organic solvent, and the solvate may contain water. That is, “hydrate” and “solvate” include mixed solvates containing both water and organic solvents. Salts include acid addition salts formed with inorganic or organic acids. Examples of inorganic acids include, but are not limited to, hydrohalic acids (such as hydrochloric acid, hydrobromic acid), sulfuric acid, phosphoric acid, and the like. Examples of organic acids include acetic acid, trifluoroacetic acid, propionic acid, butyric acid, oxalic acid, citric acid, benzoic acid, alkylsulfonic acid (such as methanesulfonic acid), and allylsulfonic acid (benzenesulfonic acid, 4-toluene). Sulfonic acid, 1,5-naphthalenedisulfonic acid, etc.), and the like, but is not limited thereto. Of these, hydrochloride, acetate, propionate and butyrate are preferred.

  Examples of salts include those in which the acidic moiety present in the parent compound is a metal ion (eg, an alkali metal salt, such as a sodium or potassium salt, an alkaline earth metal salt, such as a calcium or magnesium salt, an ammonium salt, an alkali metal ion, an alkaline earth metal salt). And salts formed when adjusted with an organic base (ethanolamine, diethanolamine, triethanolamine, morpholine, piperidine, etc.) by a metal ion or an aluminum ion, and the like. Not limited. Of these, sodium salts and potassium salts are preferred.

  Examples of the solvent contained in the solvate include any of common organic solvents. Specifically, alcohols (eg, methanol, ethanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, t-butanol), esters (eg, ethyl acetate), hydrocarbons (eg, toluene, hexane) , Heptane), ether (eg, tetrahydrofuran), nitrile (eg, acetonitrile), ketone (acetone) and the like. Preferably, it is a solvate of an alcohol (eg, methanol, ethanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, t-butanol). These solvents may be reaction solvents used in the synthesis of the compound, solvents used in crystallization purification after synthesis, or a mixture thereof.

  Further, two or more kinds of solvents may be simultaneously contained, or a form containing water and a solvent (for example, water and an alcohol (for example, methanol, ethanol, t-butanol, etc.)) may be used.

  In addition, even if the compound having the structure represented by the general formula (1), (2), (1.1) or (1.2) is added in a form not containing water, a solvent or a salt, Hydrates, solvates or salts may be formed in the optical compensation film of the invention.

  The molecular weight of the compound having the structure represented by the general formula (1), (2), (1.1) or (1.2) is not particularly limited, but the smaller the molecular weight, the better the compatibility with the resin and the larger. As the effect of suppressing the change of the optical value with respect to the change of the environmental humidity is higher, the range is preferably from 150 to 2,000, more preferably from 200 to 1500, and even more preferably from 300 to 1,000.

  Further, the nitrogen-containing heterocyclic compound according to the present invention is particularly preferably a compound having a structure represented by the following general formula (3).

（式中Ａはピラゾール環を表す。Ａｒ_１及びＡｒ_２はそれぞれ芳香族炭化水素環又は芳香族複素環を表し、置換基を有してもよい。Ｒ_１は水素原子、アルキル基、アシル基、スルホニル基、アルキルオキシカルボニル基、又はアリールオキシカルボニル基を表す。ｑは１又は２を表す。ｎ及びｍはそれぞれ１〜３の整数を表す。）
Ａｒ_１及びＡｒ_２で表される芳香族炭化水素環又は芳香族複素環は、それぞれ一般式（１）で挙げた５員若しくは６員の芳香族炭化水素環又は芳香族複素環であることが好ましい。また、Ａｒ_１及びＡｒ_２の置換基としては、前記一般式（１）で表される構造を有する化合物で示したのと同様な置換基が挙げられる。

(In the formula, A represents a pyrazole ring. Ar ₁ and Ar ₂ each represent an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and may have a substituent. R ₁ is a hydrogen atom, an alkyl group, or an acyl group. , A sulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. Q represents 1 or 2. n and m each represent an integer of 1 to 3.)
The aromatic hydrocarbon ring or aromatic heterocyclic ring represented by Ar ₁ and Ar ₂ may be the 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring described in the general formula (1), respectively. preferable. Examples of the substituent for Ar ₁ and Ar ₂ include the same substituents as those described for the compound having the structure represented by the general formula (1).

Specific examples of R ₁ include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), an alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl) Group, 2-ethylhexyl group, etc.), acyl group (acetyl group, pivaloylbenzoyl group, etc.), sulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, etc.), alkyloxycarbonyl group (eg, methoxycarbonyl group), And an aryloxycarbonyl group (for example, a phenoxycarbonyl group and the like).

  q represents 1 or 2, and n and m represent an integer of 1 to 3.

  The compound having a 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring used in the present invention is preferably a compound represented by the above general formula (1), (2), (1.1) or (1.2). A compound having a structure represented by the formula is preferable, and a compound having a structure represented by the general formula (3) is more preferable. The compound having a 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring that can be used in the present invention is a compound described in paragraphs [0140] to [0214] of WO 2014/109350. Can be mentioned as a specific example. Note that the present invention is not limited by the specific examples. Further, specific examples may be tautomers, and may form hydrates, solvates or salts.

  Similarly, for the method of synthesizing the compounds mentioned in the specific examples, paragraphs [0215] to [0239] of WO 2014/109350 can be referred to.

<How to Use Compounds Having Structures Represented by General Formulas (1) to (3)>
The compound having the structure represented by the general formulas (1) to (3) according to the present invention can be contained in the optical compensation film by appropriately adjusting the amount thereof. , Preferably 0.1 to 10% by mass, particularly preferably 1 to 5% by mass, particularly preferably 2 to 5% by mass. The addition amount varies depending on the type of the resin and the type of the compound, but the optimum value can be determined by the addition amount at which the optical compensation film of the present invention exhibits a desired retardation value. Within this range, the phase difference fluctuation can be reduced even during the heat treatment without impairing the mechanical strength of the optical compensation film of the present invention.

  As a method for adding the compound having the structure represented by the general formulas (1) to (3), the compound may be added as a powder to the resin forming the optical compensation film. You may add to the resin which forms a compensation film.

[3] Other additives In addition to the additives, the optical compensation film according to the present invention includes a plasticizer, an antioxidant, a matting agent, a light stabilizer, an optical anisotropy controlling agent, an antistatic agent, a release agent, and the like. May be included. The details of the main additives are described below.

[Plasticizer]
A plasticizer is an additive that generally has the effect of improving brittleness, lowering the melt viscosity, or imparting flexibility by being added to a polymer. In some cases, the glass transition temperature Tg of the optical compensation film may be lowered, so that the glass transition temperature Tg of the optical compensation film is preferably used within a range that is controlled within the range of the present invention.

  In the present invention, as the plasticizer, known plasticizers such as phthalate ester, fatty acid ester, trimellitate, phosphate, polyester, sugar ester, and acrylic polymers can be used.

  The amount of the plasticizer added is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 5% by mass, based on the resin.

[UV absorber]
The optical compensation film according to the present invention can contain an ultraviolet absorber.

  Examples of the ultraviolet absorber include, for example, oxybenzophenone-based compounds, benzotriazole-based compounds, salicylate-based compounds, benzophenone-based compounds, cyanoacrylate-based compounds, nickel complex-based compounds, etc. Compounds are preferred. Further, ultraviolet absorbers described in JP-A-10-182621 and JP-A-8-337574, and polymer ultraviolet absorbers described in JP-A-6-148430 are also preferably used.

  As the ultraviolet absorber used in the present invention, from the viewpoint of preventing deterioration of the polarizer and the liquid crystal display cell, it is excellent in the ability to absorb ultraviolet light having a wavelength of 370 nm or less, and from the viewpoint of displayability of the liquid crystal display cell, has a wavelength of 400 nm or more. It is preferable to have a characteristic of less absorption of visible light.

  The amount of the ultraviolet absorber added is preferably in the range of 0.1 to 5% by mass, more preferably in the range of 0.5 to 5% by mass, based on the resin.

  Examples of the benzotriazole-based ultraviolet absorber useful in the present invention include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-t. -Butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butyl Phenyl) -5-chlorobenzotriazole, 2- [2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2,2 -Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2'-hydroxy-3 -T-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol, octyl-3 -[3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- ( 5-chloro-2H-benzotriazol-2-yl) phenyl] propionate, but is not limited thereto.

  As commercial products, “Tinuvin (TINUVIN) 928”, “Tinuvin (TINUVIN) 171”, “Tinuvin (TINUVIN) 326”, and “Tinuvin (TINUVIN) 328” (all trade names, manufactured by BASF Japan) are preferable. Can be used.

[Antioxidant]
The antioxidant has a role of delaying or preventing the optical compensation film from being decomposed by, for example, a halogen in a residual solvent in the optical compensation film or phosphoric acid in a phosphoric acid-based plasticizer. Preferably.

  As such an antioxidant, a hindered phenol compound is preferably used. For example, 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octa Sil-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide) 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxy) Benzyl) -isocyanurate and the like.

  Particularly, 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3 -(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferred. Further, for example, a hydrazine-based metal deactivator such as N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine or tris (2,4-di- A phosphorus-based processing stabilizer such as (t-butylphenyl) phosphite may be used in combination.

  The amount of the antioxidant added is preferably in the range of 0.1 to 5% by mass, more preferably 0.5 to 3% by mass, based on the resin.

[Mat agent]
It is also preferable to add fine particles as a matting agent to the optical compensation film according to the present invention in order to prevent scratches and deterioration of transportability when the produced film is handled.

  Examples of the fine particles include fine particles of an inorganic compound and fine particles of a resin. Examples of inorganic compound fine particles include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, and silicate. Examples include magnesium and calcium phosphate. Fine particles containing silicon are preferred in that turbidity is reduced, and silicon dioxide is particularly preferred.

  The average primary particle size of the fine particles is preferably in the range of 5 to 400 nm, and more preferably in the range of 10 to 300 nm. These may be mainly contained as secondary aggregates having a particle size in the range of 0.05 to 0.3 μm, and as primary particles without aggregating as long as the particles have an average particle size in the range of 80 to 400 nm. It is also preferred that they are included.

  The content of these fine particles in the film is preferably in the range of 0.01 to 1% by mass, and particularly preferably in the range of 0.05 to 0.5% by mass.

  For example, fine particles of silicon dioxide are commercially available under the trade names of Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (all manufactured by Nippon Aerosil Co., Ltd.) and used. Can be.

  Fine particles of zirconium oxide are commercially available under the trade name of Aerosil R976 and R811 (all manufactured by Nippon Aerosil Co., Ltd.) and can be used.

  Examples of resin fine particles include silicone resin, fluorine resin and acrylic resin. Silicone resins are preferred, and those having a three-dimensional network structure are particularly preferred. For example, trade names of Tospearl 103, 105, 108, 120, 145, 3120 and 240 (all manufactured by Toshiba Silicone Co., Ltd.) And can be used.

  Of these, Aerosil 812 and Aerosil R972V are particularly preferably used because they have a large effect of lowering the coefficient of friction while keeping the haze of the film low.

  In the optical compensation film according to the present invention, the dynamic friction coefficient of at least one surface is preferably in the range of 0.2 to 1.0.

[4] Production method of optical compensation film The production method of the optical compensation film according to the present invention will be described by way of an example using a cycloolefin-based resin.

[4.1] Solution casting film production method The method for producing the optical compensation film of the present invention is preferably carried out by a solution casting film production method (hereinafter, also referred to as a solution casting method), and a known method is appropriately employed. Can be adopted.

  As the solvent used in the solution casting method, for example, a chlorinated solvent such as chloroform and dichloromethane; an aromatic solvent such as toluene, xylene, benzene, and a mixed solvent thereof; methanol, ethanol, isopropanol, n-butanol, Alcohol solvents such as 2-butanol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethyl sulfoxide, dioxane, cyclohexanone, tetrahydrofuran, acetone, methyl ethyl ketone (MEK), ethyl acetate, diethyl ether; These solvents may be used alone or in combination of two or more.

  The solvent used in the present invention is preferably a mixed solvent of a good solvent and a poor solvent, and the good solvent is, for example, dichloromethane as a chlorinated organic solvent, methyl acetate or acetic acid as a non-chlorinated organic solvent. Ethyl, amyl acetate, acetone, methyl ethyl ketone, tetrahydrofuran, 1,3-dioxolan, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1 -Propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro -2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, methanol, ethanol, n- Propanol, iso- propanol, n- butanol, sec- butanol, tert- butanol and the like, it is preferable among them is dichloromethane.

  The poor solvent is preferably an alcohol-based solvent, and the alcohol-based solvent is preferably selected from methanol, ethanol, and butanol from the viewpoint of improving peelability and enabling high-speed casting.

  In the present invention, if it is a mixed solvent, the good solvent is preferably used in an amount of 55% by mass or more based on the total amount of the solvent, more preferably 70% by mass or more, and further preferably 80% by mass or more.

  When the optical compensation film is formed by the solution casting method, for example, a dope containing the cycloolefin-based resin and the compound having the structure represented by the general formula (3) and a solvent is prepared, and the dope is used as a support. Cast on top.

  That is, a step of preparing a dope by dissolving at least a cycloolefin resin and a compound having a structure represented by the general formula (3), a step of casting the dope on a belt-shaped or drum-shaped metal support, It is preferable to include a step of drying the stretched dope as a web, a step of peeling the dope from the metal support, a step of stretching or maintaining the width, a step of drying, and a step of winding the finished film.

  In the solution casting method, the concentration of the cycloolefin-based resin in the dope is preferably such that the higher the concentration, the lower the drying load after casting on the metal support is, but the higher the concentration of the cycloolefin-based resin is. The load at the time of filtration increases, and filtration accuracy deteriorates. The concentration for satisfying both is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass. The metal support in the casting step is preferably one whose surface is mirror-finished. As the metal support, a stainless steel belt or a drum whose surface is plated with a casting is preferably used.

  The width of the cast can be 1-4 m. The surface temperature of the metal support in the casting step is appropriately determined at 0 to 100 ° C, more preferably 5 to 30 ° C, and is set to a temperature at which the solvent does not boil and foam. A higher temperature is preferred because the drying speed of the web can be increased. However, if the temperature is too high, the web may foam or the flatness may deteriorate.

  Alternatively, it is also a preferable method to gel the web by cooling and to peel the web from the drum in a state containing a large amount of residual solvent. The method of controlling the temperature of the metal support is not particularly limited, and includes a method of blowing hot air or cold air, and a method of bringing hot water into contact with the back side of the metal support. It is preferable to use hot water since the time required for the temperature of the metal support to become constant is short because heat is transferred more efficiently.

  When using hot air, in consideration of the temperature drop of the web due to the latent heat of evaporation of the solvent, while using hot air above the boiling point of the solvent, air may be used at a temperature higher than the target temperature while preventing foaming. .

  In particular, it is preferable to change the temperature of the support and the temperature of the drying air during the period from the casting to the peeling to efficiently perform the drying.

  In order for the optical compensation film to show good flatness, the amount of the residual solvent when the web is peeled off from the metal support is preferably from 10 to 150% by mass, more preferably from 20 to 40% by mass or from 60 to 130% by mass. And particularly preferably 20 to 30% by mass or 70 to 120% by mass.

  The residual solvent amount is defined by the following equation.

Residual solvent amount (% by mass) = {(M−N) / N} × 100
Here, M is the mass of the sample collected at any time during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.

  Further, in the drying step of the optical film, the web is peeled off from the metal support, and further dried, so that the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less, particularly preferably 0.1% by mass or less. Preferably it is 0 to 0.01% by mass or less.

  In the film drying process, a roller drying method (a method in which the web is alternately passed through a number of rollers arranged vertically and drying) or a method in which the web is dried while being conveyed by a tenter method is employed.

  The optical compensation film according to the present invention is preferably stretched from the viewpoint of adjusting the smoothness and retardation of the film.

  In the method for producing an optical film according to the present invention, it is preferable that the film is stretched in the longitudinal direction and / or the width direction or the oblique direction.

  The stretching operation may be performed in multiple stages. When performing biaxial stretching, simultaneous biaxial stretching may be performed or stepwise may be performed. In this case, stepwise means, for example, that stretching in different stretching directions can be performed sequentially, or that stretching in the same direction is divided into multiple stages and stretching in different directions is added to any of the stages. Is also possible.

Thus, for example, the following stretching steps are also possible:
・ Stretching in the longitudinal direction → stretching in the width direction → stretching in the longitudinal direction → stretching in the longitudinal direction ・ Stretching in the width direction → stretching in the width direction → stretching in the longitudinal direction → stretching in the longitudinal direction This includes the case where the film is stretched in one direction and the other is contracted by relaxing the tension.

  The residual solvent amount at the start of stretching is preferably in the range of 2 to 50% by mass.

  When the amount of the residual solvent is 2% by mass or more, the film thickness deviation is small, and it is preferable from the viewpoint of flatness. When the amount is 50% by mass or less, the unevenness on the surface is reduced and the flatness is improved.

  In the method for producing an optical compensation film according to the present invention, the film may be stretched in the longitudinal direction and / or the width direction, preferably in the width direction, so that the film thickness after stretching is in a desired range. Although it depends on the type of resin, when the lowest Tg of the glass transition point Tg of the film is TgL and the highest Tg is TgH, the film can be stretched in a temperature range of (TgL−200 ° C.) to (TgH + 50 ° C.). preferable. When the film is stretched in the above temperature range, the haze is reduced because the stretching stress can be reduced. Further, an optical compensation film containing a cycloolefin-based resin which suppresses the occurrence of breakage and is excellent in flatness and coloring property of the film itself can be obtained. The stretching temperature is more preferably in the range of (TgL-150 ° C) to (TgH + 40 ° C).

  In the method for producing an optical compensation film according to the present invention, the self-supporting film peeled from the support can be stretched in the longitudinal direction by regulating the running speed with a stretching roller. The stretching ratio in the longitudinal direction is preferably from 1.03 to 2.00 times, more preferably from 1.10 to 1.80 times, still more preferably from 1.20 to 1.60 times in a temperature range of 30 to 250 ° C. is there.

  In order to stretch in the width direction, for example, the entire drying process or a part of the process as described in JP-A-62-46625 is carried out by holding both ends of the film width in the width direction with clips or pins. A method of drying while drying (referred to as a tenter method), in particular, a tenter method using a clip is preferably used.

  It is preferable that the film stretched in the longitudinal direction or the unstretched film is introduced into the tenter with both ends in the width direction being gripped by the clip, and is stretched in the width direction while traveling with the tenter clip. The stretching ratio in the width direction is not particularly limited, but is preferably 1.03 to 2.00 times, more preferably 1.10 to 1.80 times, and further preferably 1.20 to 20 times in a temperature range of 30 to 300 ° C. It is 1.60 times.

  In stretching in the width direction, it is preferable to stretch the film in the width direction at a stretching speed of 50 to 1000% / min from the viewpoint of improving the flatness of the film.

  When the stretching speed is 50% / min or more, the flatness is improved, and the film can be processed at a high speed. Therefore, it is preferable from the viewpoint of production suitability. It can be processed without any problem, which is preferable.

  A more preferred stretching speed is in the range of 100 to 500% / min. The stretching speed is defined by the following equation.

Stretching speed (% / min) = [(d ₁ / d ₂ ) −1] × 100 (%) / t
(In the above formula, d ₁ is the width of the resin film after stretching in the stretching direction, d ₂ is the width of the resin film before stretching in the stretching direction, and t is the time required for stretching (min). Is.)
In the stretching step, holding and relaxing are usually performed after stretching. That is, in this step, it is preferable to perform a stretching step of stretching the film, a holding step of holding the film in a stretched state, and a relaxation step of relaxing the film in the stretching direction in this order. In the holding step, the stretching at the stretching ratio achieved in the stretching step is held at the stretching temperature in the stretching step. In the relaxation stage, after the stretching in the stretching stage is held in the holding stage, the stretching is released by releasing the tension for stretching. The relaxation step may be performed at a stretching temperature or lower in the stretching step.

  When the film is stretched in an oblique direction, JP-A-2005-321543 and JP-A-2013-120208 can be referred to.

  Next, the stretched film is dried by heating. When the film is heated by hot air or the like, a means for preventing used hot air from being mixed is preferably used by installing a nozzle capable of exhausting used hot air (air containing a solvent or wetting air). The hot air temperature is more preferably in the range of 40 to 350 ° C. The drying time is preferably about 5 seconds to 30 minutes, more preferably 10 seconds to 15 minutes.

  The heating and drying means is not limited to hot air, and for example, an infrared ray, a heating roller, a microwave, or the like can be used. From the viewpoint of simplicity, it is preferable to perform drying with hot air or the like while transporting the film with the rollers arranged in a staggered manner. The drying temperature is more preferably in the range of 40 to 350 ° C. in consideration of the amount of the residual solvent, the expansion and contraction rate in conveyance, and the like.

  In the drying step, the film is preferably dried until the amount of the residual solvent becomes 0.5% by mass or less.

  The winding step is a step of winding the obtained film and cooling it to room temperature. The winding machine may be a generally used one, and can be wound by a winding method such as a constant tension method, a constant torque method, a taper tension method, and a program tension control method with constant internal stress.

  The thickness of the optical compensation film according to the present invention varies depending on the purpose of use, but is usually in the range of 5 to 500 μm, preferably 10 to 150 μm, and more preferably 10 to 80 μm for a liquid crystal display device. In consideration of recent thinning, the thickness is particularly preferably in the range of 10 to 40 μm.

  In reducing the thickness of the optical compensation film to 40 μm or less, it is generally necessary to increase the content of an additive such as a retardation increasing agent in order to maintain the performance of the retardation film. Although there is a problem, the compound having a structure represented by the general formula (3) according to the present invention is excellent in bleed-out resistance and can be formed into a thin film.

  The thickness of the film may be adjusted by adjusting the concentration of the solids contained in the dope, the slit gap between the die caps, the extrusion pressure from the die, the speed of the metal support, and the like so as to obtain the desired thickness. The width of the transparent resin film obtained as described above is preferably in the range of 0.5 to 4 m, more preferably in the range of 0.6 to 3 m, and even more preferably 0.8 to 2.5 m. The length is preferably wound in the range of 100 to 10,000 m per roll, more preferably in the range of 500 to 9000 m, and still more preferably in the range of 1000 to 8000 m.

  The optical compensation film according to the present invention can realize desired optical characteristics by appropriately adjusting the process conditions such as the polymer structure to be used, the type and amount of the additive, the stretching ratio, and the residual volatile content at the time of peeling. .

The optical compensation film according to the present invention has a desired retardation value by performing a stretching treatment or preferably a stretching treatment in which a retardation increasing agent is contained. The in-plane retardation value Ro and the retardation value Rt in the thickness direction were measured using an automatic birefringence meter Axoscan (Axo Scan Mueller Matrix Polarimeter: manufactured by Axometrics) under an environment of 23 ° C. and 55% RH. at a wavelength of 590 nm, subjected to three-dimensional refractive index measured, resulting refractive indices _{n x,} n y, it can be calculated from _{n z.}

  In the optical compensation film according to the present invention, the retardation value Ro in the in-plane direction of the optical compensation film represented by the following formulas (i) and (ii) is in the range of 40 to 60 nm, It is preferable that the retardation value Rt be in the range of 110 to 140 nm from the viewpoint of improving the visibility such as the viewing angle and the contrast when the VA type liquid crystal display device is provided. The optical compensation film can be adjusted within the range of the above retardation value by stretching while adjusting the stretching ratio at least in the width direction.

Formula _{(i): Ro = (n} x -n y) × d (nm)
Formula _{(ii): Rt = {(} n x + n y) / 2-n z} × d (nm)
In [Equation (i) and Formula (ii), n _x represents a refractive index in the direction x in which the refractive index is maximized in the plane direction of the film. n _y, in-plane direction of the film, the refractive index in the direction y perpendicular to the direction x. _nz represents the refractive index in the thickness direction z of the film. d represents the thickness (nm) of the film. ]
Further, in the optical compensation film according to the present invention, the fluctuation of the in-plane retardation value Ro when heat-treated at 150 ° C. for one hour is within ± 3.0%, and the retardation in the thickness direction is within ± 3.0%. It is preferable that the variation of the value Rt be within a range of ± 4.0%.

  In the heat treatment, the change in the phase difference value before and after the film sample is left at 150 ° C. for 1 hour in a thermostat such as an oven can be obtained by the following equation.

Fluctuation of phase difference value Ro or Rt = {(Ro value or Rt value after heat treatment-Ro value or Rt value before heat treatment) / (Ro value or Rt value before heat treatment)} × 100 (%)
In order to control the fluctuation of the Ro value and the fluctuation of the Rt value of the optical compensation film due to the above-mentioned heat treatment within the above-mentioned ranges, a combination of the selection of the resin according to the present invention and the addition (type and amount) of the phase difference increasing agent is used. Is an effective method, and can be achieved by appropriately adjusting the combination.

[4.2] Melt casting film forming method The method for producing the optical compensation film of the present invention can also be performed by a melt casting film forming method (hereinafter, also referred to as a melt casting method).

  The case where the optical compensation film according to the present invention is manufactured by a melt casting method will be described.

[Molten pellet production process]
It is preferable that the resin-containing composition used for melt extrusion is usually kneaded and pelletized in advance.

  Pelletization may be performed by a known method. For example, a dried resin and an additive are supplied to an extruder by a feeder, kneaded using a single-screw or twin-screw extruder, extruded from a die into a strand, water-cooled or It can be done by air cooling and cutting.

  It is important that the raw materials are dried before extrusion in order to prevent decomposition of the raw materials. In particular, since the resin may easily absorb moisture, it is preferable to dry the resin at 70 to 140 ° C. for 3 hours or more with a dehumidifying hot air drier or a vacuum drier to keep the water content to 200 ppm or less, further 100 ppm or less.

  The additives may be supplied to an extruder in a feed extruder or may be supplied by individual feeders. A small amount of an additive such as an antioxidant is preferably mixed beforehand in order to mix uniformly.

  The mixing of the antioxidant may be performed by mixing the solids together, or, if necessary, dissolving the antioxidant in a solvent and impregnating and mixing the thermoplastic resin, or by spraying and mixing. You may.

A vacuum Nauta mixer or the like is preferable because drying and mixing can be performed simultaneously. In addition, when contacting air such as a feeder portion or an outlet from a die, it is preferable to use an atmosphere such as dehumidified air or dehumidified N ₂ gas.

  The extruder is preferably processed at a temperature as low as possible so that the extruder can suppress the shearing force and pelletize the resin so as not to deteriorate (molecular weight reduction, coloring, gel formation, etc.). For example, in the case of a twin-screw extruder, it is preferable to rotate in the same direction using a deep groove type screw. The meshing type is preferable from the viewpoint of uniformity of kneading.

  Film formation is performed using the pellets obtained as described above. Instead of pelletizing, the raw material powder can be directly supplied to an extruder by a feeder, and a film can be formed as it is.

[Step of extruding molten mixture from die to cooling roller]
First, the prepared pellets are extruded using a single-screw or twin-screw extruder to a melting temperature Tm of about 200 to 300 ° C., and are filtered with a leaf disk type filter or the like to remove foreign substances. From the film, solidified on a cooling roller, and cast while pressing against an elastic touch roller.

  When introducing into the extruder from the supply hopper, it is preferable to prevent the oxidative decomposition and the like under a vacuum or reduced pressure or in an inert gas atmosphere. In addition, Tm is the temperature of the die exit part of the extruder.

  When a foreign matter such as a scratch or a condensate of a plasticizer adheres to the die, a streak-like defect may occur. Such a defect is also referred to as a die line, but in order to reduce surface defects such as a die line, it is preferable that the piping from the extruder to the die has a structure in which the stagnation portion of the resin is as small as possible. . It is preferable to use a die or a lip with as little scratches as possible.

  It is preferable that the inner surface of the extruder, the die, or the like that comes into contact with the molten resin is subjected to a surface treatment such that the molten resin does not easily adhere to the surface by reducing the surface roughness or using a material having a low surface energy. Concretely, hard chromium plating or ceramic sprayed is polished to a surface roughness of 0.2 S or less.

  Although there is no particular limitation on the cooling roller, it is a roller having a structure in which a heat medium or a coolant capable of controlling the temperature flows inside with a high-rigidity metal roller, and the size is not limited, but a melt-extruded film. It is sufficient that the cooling roller has a size sufficient to cool the roller, and the diameter of the cooling roller is usually about 100 mm to 1 m.

  Examples of the surface material of the cooling roller include carbon steel, stainless steel, aluminum, and titanium. In order to further increase the hardness of the surface and improve the releasability from the resin, it is preferable to apply a surface treatment such as hard chrome plating, nickel plating, amorphous chromium plating, or ceramic spraying.

  The surface roughness of the cooling roller surface is preferably 0.1 μm or less in Ra, and more preferably 0.05 μm or less. The smoother the roller surface, the smoother the surface of the resulting film. Of course, it is preferable that the surface processed surface is further polished to have the above-described surface roughness.

  Examples of the elastic touch roller include JP-A-03-124425, JP-A-08-224772, JP-A-07-100960, JP-A-10-272676, WO97 / 028950, and JP-A-11-235747. And a silicone rubber roller coated with a thin film metal sleeve as described in JP-A-2002-36332, JP-A-2005-172940 and JP-A-2005-280217.

  When peeling the film from the cooling roller, it is preferable to control the tension to prevent deformation of the film.

  The steps after the peeling are the same as those in the solution casting method.

[5] Touch Panel Module The touch panel module according to the present invention is characterized in that a transparent conductive layer is formed on the optical compensation film according to the present invention. There is no particular limitation as long as it is a pattern that operates well as a touch panel module. For example, JP-A-2011-511357, JP-A-2010-164938, JP-A-2008-310550, and JP-A-2003-511799. And Japanese Patent Application Publication No. 2010-541109.

  The touch panel module according to the present invention basically includes a transparent conductive layer patterned on the X axis or the Y axis formed on the optical compensation film, and a Y layer formed on the optical compensation film or another protective film. The transparent conductive layer patterned on the axis or the X axis is laminated, a polarizer, a protective film, and the like are laminated using an appropriate adhesive layer, and a cover glass is provided on the outermost surface if necessary. Further, by combining the touch panel with a VA mode liquid crystal display device, a liquid crystal display device with a touch panel of the present invention can be manufactured.

[5.1] Transparent conductive layer The transparent conductive layer according to the present invention preferably has a sheet resistance of the transparent conductive layer in the range of 0.01 to 150 Ω / □. More preferably, the resistance value of the transparent conductive layer is in the range of 0.1 to 100 Ω / □. When the resistance value of the transparent conductive layer is 0.01 Ω / □ or more, durability against environmental changes such as high temperature and high humidity is obtained, and when the resistance value is 150 Ω / □ or less, it is preferable from the viewpoint of curling suppression. .

[Transparent conductive material]
The material of the transparent conductive layer according to the present invention is not particularly limited as long as the material satisfies the above-mentioned resistance value, but a transparent conductive material such as ITO (indium-tin oxide) or IZO (indium-zinc oxide) is used. It is particularly preferable to use ITO from the viewpoint of conductivity and transparency. For the transparent conductive layer using ITO, a method using a wet process such as a coating method, an inkjet method, a coating method, or a dip method, or a dry process such as an evaporation method (resistance heating, an EB method), a sputtering method, or a CVD method is used. Although a method is mentioned, it is preferable to form by an evaporation method.

  After the formation of the transparent conductive layer, heat treatment (also referred to as annealing) is preferably performed to reduce the resistance value of the transparent conductive layer. The heating temperature is in the range of 150 to 250C, and the heating time is in the range of 1 to 60 minutes. Conditions may be optimized depending on the configuration and characteristics of the substrate that supports the transparent conductive layer. However, when a cycloolefin-based resin is used as the substrate, the heating temperature is in the range of 150 to 180 ° C., and the heating time is 5 to 30. Minutes.

[Metal nanowire]
It is also preferable to use a transparent conductive layer made of a thin metal wire (metal nanowire, metal mesh).

  The metal nanowire refers to a conductive material having a material of metal, a needle-like or thread-like shape, and a nanometer-size diameter. The metal nanowire may be straight or curved. If a transparent conductive layer composed of metal nanowires is used, the metal nanowires form a mesh, so that even a small amount of metal nanowires can form a good electric conduction path, and the electric resistance can be improved. A transparent conductive layer having a small particle size can be obtained. Furthermore, since the metal nanowires have a mesh shape, an opening is formed in a gap between the meshes, so that a transparent conductive film having high light transmittance can be obtained.

  The ratio (aspect ratio: L / d) of the thickness d to the length L of the metal nanowire is preferably in the range of 10 to 100,000, more preferably in the range of 50 to 100,000, and particularly preferably. Is in the range of 100 to 10,000. When the metal nanowires having a large aspect ratio are used, the metal nanowires can intersect favorably, and a small amount of the metal nanowires can exhibit high conductivity. As a result, a transparent conductive film having high light transmittance can be obtained.

  In the present specification, the “thickness of the metal nanowire” means the diameter when the cross section of the metal nanowire is circular, and means the minor axis when the cross section is elliptical, and If it is square, it means the longest diagonal. The thickness and length of the metal nanowire can be confirmed by a scanning electron microscope or a transmission electron microscope.

  The thickness of the metal nanowire is preferably less than 500 nm, more preferably less than 200 nm, particularly preferably in the range of 10 to 100 nm, and most preferably in the range of 10 to 50 nm. Within such a range, a transparent conductive layer having high light transmittance can be formed.

  The length of the metal nanowire is preferably in the range of 2.5 to 1000 μm, more preferably in the range of 10 to 500 μm, and particularly preferably in the range of 20 to 100 μm. Within such a range, a transparent conductive layer having high conductivity can be obtained.

  Any appropriate metal can be used as the metal constituting the metal nanowire as long as the metal has high conductivity. Examples of the metal constituting the metal nanowire include silver, gold, copper, and nickel. Further, a material obtained by plating (for example, gold plating) on these metals may be used. Among them, silver or copper is preferable from the viewpoint of conductivity.

  Any appropriate method can be adopted as a method for producing the metal nanowire. For example, a method of reducing silver nitrate in a solution, a method of applying an applied voltage or current to the precursor surface from the tip of the probe, extracting a metal nanowire at the tip of the probe, and continuously forming the metal nanowire, etc. No. In the method of reducing silver nitrate in a solution, a silver nanowire can be synthesized by performing a liquid phase reduction of a silver salt such as silver nitrate in the presence of a polyol such as ethylene glycol and polyvinylpyrrolidone.

  Silver nanowires of uniform size are described, for example, in Xia, Y .; et al. Chem. Mater. (2002), 14, 4736-4745, Xia, Y .; et al. , Nano letters (2003) 3 (7), 955-960.

  The transparent conductive layer can be formed by applying the composition for forming a transparent conductive layer containing the metal nanowires on the optical compensation film or the protective film according to the present invention. More specifically, after applying the dispersion liquid (the composition for forming a transparent conductive layer) obtained by dispersing the metal nanowires in a solvent on the optical compensation film or the protective film, the applied layer is dried, A transparent conductive layer can be formed.

  Examples of the solvent include water, alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents, aromatic solvents, and the like. From the viewpoint of reducing environmental load, it is preferable to use water.

  The dispersion concentration of the metal nanowires in the composition for forming a transparent conductive layer containing the metal nanowires is preferably in the range of 0.1 to 1% by mass. Within such a range, a transparent conductive layer having excellent conductivity and light transmittance can be formed.

  The composition for forming a transparent conductive layer including the metal nanowires may further contain any appropriate additive depending on the purpose. Examples of the additive include a corrosion inhibitor for preventing corrosion of the metal nanowire, a surfactant for preventing aggregation of the metal nanowire, and the like. The type, number and amount of the additives used can be appropriately set according to the purpose. In addition, the composition for forming a transparent conductive layer may include any appropriate binder resin, if necessary, as long as the effects of the present invention can be obtained.

  Any appropriate method can be adopted as a method of applying the composition for forming a transparent conductive layer containing the metal nanowires. Examples of the coating method include spray coating, bar coating, roll coating, die coating, inkjet coating, screen coating, dip coating, letterpress printing, intaglio printing, and gravure printing.

  As a method for drying the coating layer, any appropriate drying method (for example, natural drying, blast drying, and heat drying) can be adopted. For example, in the case of heat drying, the drying temperature is typically in the range of 100 to 200 ° C., and the drying time is typically in the range of 1 to 10 minutes.

  After drying, heat treatment (also referred to as annealing) is preferably performed in order to lower the resistance value of the transparent conductive layer. The heating temperature is in the range of 150 to 250C, and the heating time is in the range of 1 to 60 minutes. Conditions may be optimized depending on the configuration and characteristics of the substrate that supports the transparent conductive layer. However, when a cycloolefin-based resin is used as the substrate, the heating temperature is in the range of 150 to 180 ° C., and the heating time is 5 to 30. Minutes.

  When the transparent conductive layer contains metal nanowires, the thickness of the transparent conductive layer is preferably in the range of 0.01 to 10 μm, more preferably in the range of 0.05 to 3 μm, and particularly preferably. Is in the range of 0.1 to 1 μm. Within such a range, a transparent conductive layer having excellent conductivity and light transmittance can be obtained.

  When the transparent conductive layer includes metal nanowires, the total light transmittance of the transparent conductive layer is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more.

[Metal mesh]
The transparent conductive layer including the metal mesh is formed by forming fine metal wires in a lattice pattern on the transparent substrate. Any appropriate metal can be used as the metal constituting the metal mesh as long as the metal has high conductivity. Examples of the metal constituting the metal mesh include silver, gold, copper, nickel and the like. Further, a material obtained by plating (for example, gold plating) on these metals may be used. Among them, copper is preferable, and the migration phenomenon does not easily occur, and is also preferable from the viewpoint of suppressing disconnection at the time of keying.

  The transparent conductive layer including the metal mesh can be formed by any appropriate method. For the transparent conductive layer, for example, a photosensitive composition containing silver salt (a composition for forming a transparent conductive layer) is applied on the laminate, and thereafter, an exposure treatment and a development treatment are performed to form a thin metal wire into a predetermined pattern. Can be obtained. Further, the transparent conductive layer can also be obtained by printing a paste containing fine metal particles (composition for forming a transparent conductive layer) in a predetermined pattern.

  The details of such a transparent conductive layer and a method for forming the same are described in, for example, JP-A-2012-18634, and the description is incorporated herein by reference. Another example of a transparent conductive layer formed of a metal mesh and a method of forming the same include the transparent conductive layer described in JP-A-2003-331654 and a method of forming the same.

  When the transparent conductive layer includes a metal mesh, the thickness of the transparent conductive layer is preferably in the range of 0.1 to 30 μm, and more preferably in the range of 0.1 to 9 μm.

  When the transparent conductive layer includes a metal mesh, the transmittance of the transparent conductive layer is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.

[5.2] Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer used in the present invention contains a pressure-sensitive adhesive, and the pressure-sensitive adhesive contains a thermosetting resin, an ultraviolet (UV) curable resin, or a chemically curable resin. In addition to those that are not only transparent, but also exhibit appropriate viscoelasticity and adhesive properties.

  Specific adhesives include adhesives or adhesives such as acrylic copolymers, epoxy resins, polyurethanes, silicone polymers, polyethers, butyral resins, polyamide resins, polyvinyl alcohol resins, and synthetic rubbers. Can be mentioned. In the present invention, a thermosetting method, a photocuring method, a film formed by a chemical reaction, etc., is preferably an adhesive which is cured, and among them, an acrylic copolymer and an epoxy resin most control adhesive properties. It is easy to use and excellent in transparency, weather resistance, durability and the like, and can be preferably used.

  The pressure-sensitive adhesive may be a one-component type or a type in which two or more components are mixed before use. The pressure-sensitive adhesive may be a solvent system using an organic solvent as a medium, or may be a water system such as an emulsion type, a colloid dispersion liquid type, or an aqueous solution type, which is a medium containing water as a main component. It may be a solvent type. The concentration of the pressure-sensitive adhesive liquid may be appropriately determined depending on the film thickness after adhesion, a coating machine, coating conditions, and the like, and is usually 0.1 to 50% by mass.

  The thickness of the adhesive layer can be appropriately formed in the range of 0.1 to 100 μm, preferably 0.5 to 50 μm, and particularly preferably 0.5 to 30 μm. When applying, the adhesive has a viscosity at 25 ° C. of generally 1000 to 6000 mPa / sec, preferably 2000 to 4000 mPa / sec, for example 3000 to 4000 mPa / sec. Here, the viscosity is a value obtained by, for example, using a B-type viscometer BH II manufactured by Tokimec (Tokyo Keiki) Co., Ltd. and rotating the rotor for 30 seconds after standing still. The Young's modulus (E) of the adhesive resin after completely cured is preferably 1 to 100 MPa, for example, 5 to 20 MPa.

  Examples of the acrylic adhesive include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, and (meth) acrylic. One or more alkyl acrylates having 1 to 20 carbon atoms such as 2-ethylbutyl acid, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, and the alkyl acrylate Copolymerization with functional group monomers such as (meth) acrylic acid, itaconic acid, maleic acid, maleic anhydride, 2-hydroxyethyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate copolymerizable with esters. In combination, isocyanate-based crosslinking agent, epoxy-based crosslinking agent, aziridine-based crosslinking agent, metal chelate-based crosslinking agent, etc. Include those obtained by reacting a crosslinking agent.

  Examples of the epoxy resin pressure-sensitive adhesive include a resin composition obtained by modifying an ultraviolet light-curable epoxy resin with a silicone elastomer and adding precipitated silica as an inorganic filler. For example, "Norland Optical Bonding" manufactured by Edmund Optics Inc. Agent NOA68 "or" Optical elastic resin (Super View Resin) "manufactured by Sony Chemical & Information Device Co., Ltd. can be used.

  In order to promote the photocuring of the pressure-sensitive adhesive, it is preferable to further include a photopolymerization initiator. As the compounding amount of the photopolymerization initiator, it is preferable to include the photopolymerization initiator: adhesive = 20: 100 to 0.01: 100 in mass ratio.

  Specific examples of the photopolymerization initiator include, but are not limited to, alkylphenones, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. Not something. These may be commercially available ones, and preferred examples include Irgacure 184, Irgacure 907, and Irgacure 651 manufactured by BASF Japan K.K.

  As a method for forming the adhesive layer, it is preferable to apply the above-mentioned adhesive-containing composition by coating, for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, a curtain coating method And a conventionally known method such as an ink jet method.

  In the case of heat curing, it is preferable to apply heating at 80 ° C. or higher in a dryer, and the heating time is appropriately set.

  As the light source for the UV curing treatment, any light source that generates ultraviolet light can be used without limitation. For example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, and the like can be used.

Irradiation conditions vary depending on each lamp, but the irradiation amount of the active ray is usually 50 to 1000 mJ / cm ² , preferably 50 to 300 mJ / cm ² . The heat treatment temperature after UV curing is preferably 80 ° C. or higher.

  Further, after the adhesive layer is provided, it is preferable that a release sheet is laminated on the surface until the adhesive sheet is bonded to another member.

  Although various release sheets can be used as the release sheet, it is typically composed of a substrate sheet having a releasable surface. Examples of the base sheet include films of polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polycarbonate resin, and the like, and films and synthetic paper in which a filler such as a filler is blended with these films. Further, paper base materials such as glassine paper, clay-coated paper, and high-quality paper can be used.

[6] Polarizing plate The polarizing plate according to the present invention has an optical compensation film, a polarizer, and a protective film having the transparent conductive layer on at least one surface in this order from the VA mode liquid crystal cell toward the viewing side. ing.

[6.1] Polarizer The polarizer is an element that transmits only light having a polarization plane in a certain direction, and examples thereof include a polyvinyl alcohol-based polarizing film.

  Polyvinyl alcohol-based polarizing films include those obtained by dyeing a polyvinyl alcohol-based film with iodine and those obtained by dyeing a dichroic dye.

  The polarizer can be obtained by uniaxially stretching the polyvinyl alcohol film and then dyeing, or dyeing the polyvinyl alcohol film and then uniaxially stretching, and preferably further performing a durability treatment with a boron compound.

  The thickness of the polarizer is preferably in the range of 5 to 30 μm, and more preferably in the range of 5 to 15 μm.

  Examples of the polyvinyl alcohol film include an ethylene unit content of 1 to 4 mol%, a degree of polymerization of 2000 to 4000, and a degree of saponification of 99.0 to 99 described in JP-A-2003-248123 and JP-A-2003-342322. .99 mol% of ethylene-modified polyvinyl alcohol is preferably used. In addition, it is preferable to produce a polarizer and bond it to the base film of the present invention to produce a polarizing plate by the methods described in JP-A-2011-100161, JP-A-46991205, and JP-A-4804589. .

[6.2] Protective film It is preferable that the film disposed on the side of the polarizer opposite to the surface where the optical compensation film is bonded is a film that functions as a protective film for the polarizer.

  As such a protective film, the above-mentioned optical compensation film may be used. KC4UZT, Fujitsu UZT80 FUJITAC TD40UL, FUJITAC R02, FUJITAC R06, manufactured by FUJIFILM Corporation. Can.

  In addition, resin films such as polyethylene terephthalate, polyethylene naphthalate, and polycarbonate, and resin films such as polyarylate, polyether sulfone, polysulfone, fluorene ring-modified polycarbonate, alicyclic modified polycarbonate, and acryloyl compound can be given. Among these resin substrates, films such as polyethylene terephthalate (abbreviation: PET), polybutylene terephthalate, polyethylene naphthalate (abbreviation: PEN), and polycarbonate (abbreviation: PC) are flexible in terms of cost and availability. It is preferably used as a resinous base material.

  The thickness of the protective film is not particularly limited, but can be about 10 to 200 μm, preferably in the range of 10 to 100 μm, and more preferably in the range of 10 to 70 μm.

[6.3] Manufacturing method of polarizing plate For manufacturing a polarizing plate, the optical compensation film and the protective film according to the present invention are bonded to a polarizer using a completely saponified polyvinyl alcohol aqueous solution (water glue) or the adhesive. Is preferred. In the liquid crystal display device, the optical compensation film according to the present invention is preferably provided on the liquid crystal cell side of the polarizer.

  As a pretreatment step for bonding, it is preferable to perform an easy-adhesion treatment on the surface of the optical compensation film or the protective film that adheres to the polarizer, such as a saponification treatment, a corona treatment, and a plasma treatment. Is mentioned.

[7] Other Layers The polarizing plate-integrated touch panel module according to the present invention may optionally include other layers as necessary. Examples of the other layers include a hard coat layer, an antistatic layer, an antiglare layer, an antireflection layer, and a color filter layer.

  The hard coat layer may be formed on the protective layer on the viewing side to improve the scratch resistance, or may be formed on the surface of the optical compensation film as a protective layer when forming the transparent conductive layer. The hard coat layer may contain an ultraviolet-curable urethane acrylate resin, an ultraviolet-curable polyester acrylate-based resin, an ultraviolet-curable epoxy acrylate-based resin, an ultraviolet-curable polyol acrylate-based resin, or an ultraviolet-curable epoxy resin. It is particularly preferable to contain an ultraviolet curable acrylate resin.

The antistatic layer has a sheet resistance of 1 × 10 ¹¹ Ω / □ or less, preferably 1 × 10 ¹⁰ Ω / □ or less, more preferably 1 × 10 ⁹ Ω / □ or less when the antistatic layer is formed. A layer containing a material that can be Examples of the antistatic agent include metal oxides, surfactant-type antistatic agents, silicone-based antistatic agents, organic boric acid-based antistatic agents, polymer-based antistatic agents, and antistatic polymer materials. Conjugated polymers, ionic polymers, conductive polymers, and the like can be used.

[8] Liquid crystal display device The liquid crystal display device with a touch panel of the present invention is characterized by using a VA mode (MVA, PVA) type liquid crystal, and provides a liquid crystal display device with a touch panel that is superior in front contrast, which is an advantage of the VA mode. can do. As the VA mode liquid crystal, a known liquid crystal can be used without limitation.

  In a liquid crystal display device, usually, two polarizing plates, a polarizing plate on a viewing side and a polarizing plate on a backlight side, are used by being bonded to a liquid crystal cell via an adhesive layer, and the optical compensation film according to the present invention is used. The provided polarizing plate is arranged on the viewing side and functions as a polarizing plate integrated touch panel module.

  On the other hand, the polarizing plate on the backlight side is preferably a polarizing plate in which an optical compensation film, a polarizer and a protective film are laminated in this order from the liquid crystal cell side, and the optical compensation film is the optical compensation film of the present invention or another. It is preferable to use an optical compensation film. As other optical compensation films, those selected from the above-mentioned commercially available cellulose ester films can be preferably used. Similarly, the protective film is similarly selected from the above-mentioned commercially available cellulose ester films and can be preferably used. Further, a polyester film, an acrylic film, a polycarbonate film, or the like can be used.

  Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. In the examples, “parts” or “%” is used, but “parts by weight” or “% by weight” is used unless otherwise specified.

Example 1
The following resins were used as the cellulose ester resin, cycloolefin resin, polyimide resin, polyarylate resin and acrylic resin used in the examples.

[resin]
Cycloolefin resin (COP): ARTON G7810, cellulose acetate propionate (CAP) manufactured by JSR Corporation: acetyl group substitution degree 1.5, propionyl group substitution degree 1.0, total acyl group substitution degree 2.5, Weight average molecular weight 250,000)
Polyimide resin (PI): A polyimide resin was synthesized by the following method.

<Polyimide resin A: polyimide having a structure represented by formula (P1)>
(Polymerization of polyimide precursor)
Using a reaction apparatus equipped with a stainless steel separable flask as a reaction vessel, two paddle blades as a stirring device in the separable flask, and a device having a cooling capacity of 20.9 kJ / min as a cooling device. Polyamic acid was produced. During the polymerization reaction, a nitrogen gas which had been dehydrated by passing through silica gel was flowed at 0.05 L / min in order to prevent water from being mixed, thereby performing the polymerization reaction.

  223.5 g of N, N-dimethylformamide (DMF) as a polymerization solvent is charged into the separable flask, and 40.0 g (0.125 mol) of trifluoromethylbenzene (TFMB) is dissolved therein. 55.5 g (0.125 mol) of 1,1,1,3,3,3-hexafluoro-2,2-di (3,4-dicarboxyphenyl) propane dianhydride (6FDA) was added to this solution. The mixture was added and stirred to completely dissolve. After complete dissolution, the mixture was stirred to increase the polymerization viscosity to 80 Pa · s. The viscosity of the polyamic acid solution was kept for 1 hour in an aqueous solution kept at 23 ° C., and the viscosity at that time was measured with a B-type viscometer. 7 was measured at a rotation speed of 4 rpm. The concentration of the aromatic diamine compound and the aromatic tetracarboxylic dianhydride in the reaction solution was 30% by mass based on the total reaction solution.

(Chemical imidization to polyimide resin)
DMF was added to the above solution to a solid content concentration of 15% by mass, and 60 g of pyridine (pkBH +; 5.17) was added as an imidization accelerator (molar ratio of imidization accelerator / amide group in polyamic acid = 3). Disperse completely. 30.6 g of acetic anhydride (molar ratio of dehydrating agent / amide group in polyamic acid = 1.2) was added to the dispersed solution at a rate of 1 g per minute, and the mixture was further stirred for 30 minutes. After the stirring, the internal temperature was raised to 100 ° C., and the mixture was heated and stirred for 5 hours.

(Extraction of polyimide resin)
The solution of the polyimide resin was put into a funnel having a hole diameter of about 5 mm, and was dropped in 5 L of methanol for extraction. At the time of extraction, extraction was performed while stirring methanol at high speed with a stirring blade rotated at 1500 rpm or more. The diameter of the suspended polyimide solution is 1 mm or less near the methanol interface, and the height is adjusted between the funnel and the liquid surface of methanol. The resin may be in a fibrous form, but by continuing stirring, the fibrous once in the solution is decomposed and cut into fibers of 5 mm or less in the solution.

  Further, 5 L of methanol was added to the separated resin solid content solution to completely extract and take out the solid content, and the solid content was washed with isopropanol in a Soxhlet extractor, and then 100 ° C. in a vacuum dryer. And dried as a polyimide resin. The weight average molecular weight was 100,000.

  Polyarylate resin (PA): A polyarylate resin was synthesized by the following method.

  In a reaction vessel equipped with a stirrer, 100 parts by mass of 2,2-bis (4-hydroxyphenyl) hexafluoropropane [BisAF] as a bisphenol component and p-tert-butylphenol [PTBP] as a terminal blocking agent 1.34 parts by weight of sodium hydroxide, 25.4 parts by weight of sodium hydroxide [NaOH] as an alkali, and 1.28 parts by weight of a 50% by weight aqueous solution of tri-n-butylbenzylammonium chloride [TBBAC] as a polymerization catalyst. And 0.5 parts by mass of sodium hydrosulfite as an antioxidant were dissolved in 1750 parts by mass of water (aqueous phase).

  Separately, 89.1 parts by mass of diphenyl ether-4,4'-dicarboxylic acid chloride [DEDC] as an aromatic dicarboxylic acid component was dissolved in 1200 parts by mass of dichloromethane (organic phase).

  The aqueous phase was previously stirred, and the organic phase was added to the aqueous phase with vigorous stirring, and an interfacial polymerization reaction was performed at 15 ° C. for 2 hours. The molar ratio was BisAF: DEDC: PTBP: TBBAC: NaOH = 98.5: 100.0: 3.0: 0.68: 210.

  Thereafter, the stirring was stopped, and the aqueous phase and the organic phase were decanted and separated. After removing the aqueous phase, 500 parts by mass of dichloromethane, 2000 parts by mass of pure water, and 2 parts by mass of acetic acid were added to the organic phase to stop the reaction, followed by stirring at 15 ° C. for 30 minutes. Thereafter, the organic phase was washed ten times with pure water, and the organic phase was added to methanol to precipitate a polymer. The precipitated polymer was filtered and dried to obtain a polyarylate resin having a weight average molecular weight of 110,000.

Triacetyl cellulose (TAC): acetyl group substitution degree 2.85, weight average molecular weight 250,000)
Acrylic resin (Ac): Diamond BR85 (manufactured by Mitsubishi Rayon Co., weight average molecular weight: 280,000)
[Additive]
As the additives, the following compounds were used as the retardation increasing compounds Compound A1 to Compound A5, polyester plasticizer B1 and acrylic resin B2.

  Polyester plasticizer B1: A polyester plasticizer was synthesized by the following procedure.

  180 g of ethylene glycol, 278 g of phthalic anhydride, 91 g of adipic acid, 610 g of benzoic acid, and 0.191 g of tetraisopropyl titanate as an esterification catalyst were placed in a 2 L four-necked flask equipped with a thermometer, a stirrer, and a cooling tube for cooling. The temperature is gradually increased while stirring in a nitrogen stream until the temperature reaches 230 ° C. A dehydration condensation reaction was performed while observing the degree of polymerization. After the reaction was completed, unreacted ethylene glycol was distilled off under reduced pressure at 200 ° C. to obtain a polyester plasticizer B1. The acid value was 0.20 and the number average molecular weight was 450.

  Acrylic resin B2: An acrylic resin was synthesized by the following procedure.

  24 liters of deionized water is placed in a 40 liter polymerization reactor made of SUS equipped with a stirrer, and 30 g of an aqueous solution of an anionic polymer compound as a dispersion stabilizer and 36 g of sodium sulfate as a dispersion stabilizing aid are added and stirred and dissolved. I let it. In a vessel equipped with another stirrer, methyl methacrylate (MMA) and acryloyl morpholine (ACMO) were added so that MMA was 73.1% by mass and ACMO was 22.4% by mass (total charged moles). (MMA / ACMO = 70/30), and 12 g of 2,2'-azobisisobutyronitrile as a polymerization initiator, 24 g of n-octyl mercaptan as a chain transfer agent, and 24 g of stearyl alcohol was added as a mold agent and stirred and dissolved. The thus obtained monomer mixture in which the polymerization initiator, the chain transfer agent and the release agent are dissolved is mixed with a 40-liter SUS polymerization reactor (deionized water, dispersion (Containing a stabilizer and a dispersion stabilizing assistant), and stirred at 175 rpm for 15 minutes while replacing with nitrogen. Thereafter, the mixture was heated to 80 ° C. to start polymerization, and after the peak of the exothermic polymerization was completed, a heat treatment was performed at 115 ° C. for 10 minutes to complete the polymerization. The obtained bead polymer was filtered, washed with water, and dried at 80 ° C. for 24 hours to obtain an acrylic resin B2 of methyl methacrylate (MMA) and acryloylmorpholine (ACMO) having a weight average molecular weight of 60,000.

Example 1
<Preparation of optical compensation film 101>
(Preparation of fine particle addition liquid)
Fine particles (Aerosil R812: manufactured by Nippon Aerosil Co., Ltd., primary average particle size: 7 nm, apparent specific gravity 50 g / L) 4 parts by mass Dichloromethane 48 parts by mass Ethanol 48 parts by mass After stirring and mixing with a dissolver for 50 minutes, and then dispersing with Manton-Gaulin. Was done.

  Further, dispersion was performed with an attritor so that the particle size of the secondary particles became a predetermined size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a liquid containing fine particles.

  Next, a main dope 1 having the following composition was prepared. First, dichloromethane was added to the pressure dissolution tank at a flow rate of 400 kg / min and ethanol at a flow rate of 20 kg / min. Three minutes after the start of the addition of the solvent, the cycloolefin-based resin (COP) was charged into the pressure dissolution tank with stirring at a flow rate of 200 kg / min. Next, 5 minutes after the start of the introduction of the solvent, the liquid for adding fine particles was introduced, heated to 80 ° C., and completely dissolved while stirring. The heating temperature was increased from room temperature at 5 ° C./min, dissolved for 30 minutes, and then decreased at 3 ° C./min.

The dope viscosity was 10,000 CP, and the water content was 0.50%. This is Azumi Filter Paper No. Using 244 (filtration accuracy 0.005 mm) at a filtration flow rate of 300 L / m ² · h and a filtration pressure of 1.0 × 10 ⁶ Pa, main dope 1 was prepared.

<Composition of main dope 1>
Cycloolefin resin (COP): ARTON G7810, JSR (
Co., Ltd. 100 parts by mass Dichloromethane 200 parts by mass Ethanol 10 parts by mass Fine particle additive liquid 3 parts by mass Then, using an endless belt casting device, the above dope is uniformly cast on a stainless steel belt support at a temperature of 33 ° C. and 1500 mm width. did. The temperature of the stainless steel belt was controlled at 30 ° C.

  The solvent was evaporated on the stainless belt support until the residual solvent amount in the cast film became 75%, and then the film was peeled off from the stainless belt support at a peel tension of 130 N / m.

  The peeled cycloolefin-based resin film was stretched 20% in the width direction using a tenter while applying heat at 160 ° C. The residual solvent at the start of stretching was 15%. Next, the drying was completed while being conveyed by a number of rollers in the drying zone. The drying temperature was 130 ° C., and the transport tension was 100 N / m. After drying, the film was slit to a width of 1.5 m, knurling was applied to both ends of the film at a width of 10 mm and a height of 10 μm, and the film was wound into a roll to obtain an optical compensation film 101 having a dry film thickness of 45 μm.

<Preparation of optical compensation film 102>
In the production of the optical compensation film 101, the following main dope 2 was prepared and used, and an optical compensation film 102 was produced in the same manner except that the film thickness was 10 μm.

<Composition of main dope 2>
Cycloolefin resin (COP): ARTON G7810, JSR (
Co., Ltd. 100 parts by mass Dichloromethane 200 parts by mass Ethanol 10 parts by mass Additive A1 4 parts by mass Fine particle additive liquid 3 parts by mass The stretching ratio was adjusted so that the optical compensation film had the retardation value shown in Table 1.

<Preparation of base film A103 to 108>
The optical compensation films 103 to 108 were produced in the same manner as in the production of the optical compensation film 102 except that the type, amount, and thickness of the additive were changed as shown in Table 1.

<Preparation of optical compensation film 109>
An optical compensation film 109 was produced in the same manner as in the production of the optical compensation film 101, except that the following main dope 3 was prepared and used.

<Composition of main dope 3>
Cellulose acetate propionate (CAP) 100 parts by mass Dichloromethane 200 parts by mass Ethanol 10 parts by mass Fine particle additive liquid 3 parts by mass <Preparation of optical compensation film 110>
In the production of the optical compensation film 109, 5 parts by mass of the additive A2 was added, the stretching ratio was adjusted to have the retardation value shown in Table 1, and the optical compensation film 110 was prepared in the same manner except that the film thickness was changed. Was prepared.

<Preparation of optical compensation film 111>
An optical compensation film 110 was produced in the same manner as in the production of the optical compensation film 101, except that the following main dope 4 was prepared and used.

<Composition of main dope 4>
Polyimide resin (PI) 100 parts by mass Dichloromethane 200 parts by mass Ethanol 10 parts by mass Fine particle additive liquid 3 parts by mass <Preparation of optical compensation film 112>
In the production of the optical compensation film 111, 2 parts by mass of the additive A2 was added, the stretching ratio was adjusted so that the optical compensation film had the retardation value shown in Table 1, and the film thickness was changed in the same manner. An optical compensation film 112 was produced.

<Preparation of optical compensation film 113>
An optical compensation film 113 was produced in the same manner as in the production of the optical compensation film 101, except that the following main dope 5 was prepared and used.

<Composition of main dope 5>
Polyarylate resin (PA) 100 parts by mass Dichloromethane 200 parts by mass Ethanol 10 parts by mass Fine particle additive liquid 3 parts by mass <Preparation of optical compensation film 114>
In the production of the optical compensation film 113, 2 parts by mass of the additive A2 was added, the stretching ratio was adjusted so that the optical compensation film had the retardation value shown in Table 1, and the film thickness was changed in the same manner. An optical compensation film 114 was produced.

<Preparation of optical compensation film 115>
In the production of the optical compensation film 102, an optical compensation film 115 was produced in the same manner except that the following main dope 6 was prepared and used, and the film thickness was 45 μm.

<Composition of main dope 6>
Cycloolefin resin (COP): ARTON G7810, JSR (
Co., Ltd. 100 parts by mass Dichloromethane 200 parts by mass Ethanol 10 parts by mass Additive B1 6 parts by mass Fine particle additive liquid 3 parts by mass The stretching ratio was adjusted to the retardation value shown in Table 1.

<Preparation of optical compensation film 116>
In the production of the optical compensation film 110, the following main dope 7 was prepared and used, and an optical compensation film 116 was produced in the same manner except that the film thickness was 45 μm.

<Composition of main dope 7>
Cellulose acetate propionate (CAP) 100 parts by mass Dichloromethane 200 parts by mass Ethanol 10 parts by mass Additive B1 6.5 parts by mass Fine particle additive liquid 3 parts by mass <Preparation of optical compensation film 117>
In the production of the optical compensation film 101, an optical compensation film 117 was produced in the same manner except that the film was stretched by 5% in the longitudinal direction and the width direction and the film thickness was 45 μm.

<Preparation of optical compensation film 118>
In the production of the optical compensation film 116, the following main dope 8 was prepared and used, and an optical compensation film 118 was produced in the same manner except that the film was stretched by 5% in the longitudinal direction and the width direction and the film thickness was 45 μm.

<Composition of main dope 8>
Triacetyl cellulose (TAC) 100 parts by mass Dichloromethane 200 parts by mass Ethanol 10 parts by mass Additive B2 10 parts by mass Fine particle additive liquid 3 parts by mass <Preparation of optical compensation film 119>
In the production of the optical compensation film 116, the following main dope 9 was prepared and used, and an optical compensation film 118 was produced in the same manner except that the film thickness was 45 μm.

<Composition of main dope 9>
Acrylic resin (Ac): Diamond BR85 (Mitsubishi Rayon)
100 parts by mass Dichloromethane 200 parts by mass Ethanol 10 parts by mass Fine particle additive liquid 3 parts by mass <Preparation of transparent conductive layer>
The silver nanowire used was manufactured by Y. Sun, B .; Gates, B .; Mayers, & Y. Xia, "Crystalline silver nanowires by soft solution processing", Nano Letters, (2002), 2 (2) After the method using a polyol, in the presence of polyvinylpyrrolidone (PVP) in the presence of polyvinylpyrrolidone (PVP). This is a silver nanowire that was synthesized by dissolving silver sulfate in water and reducing it. That is, the present invention used nanowires synthesized by the modified polyol method described in Cambrios Technologies Corporation, US Provisional Application No. 60 / 815,627.

As a metal nanowire forming a transparent conductive layer, silver nanowire water containing 0.5 wt% / v of silver nanowire synthesized in the above manner and having a minor axis diameter of about 70 to 80 nm and an aspect ratio of 100 or more in an aqueous medium is used. The thickness of the dispersion composition (ClearOhmTM, Ink-A AQ, manufactured by Cambrios Technologies Corporation) is dried on one surface of the optical compensation films 101 to 119 using a slot die coating machine to a thickness of 1.5 μm. After coating and drying as described above, a pressure treatment was performed at a pressure of 2000 kN / m ² to form a transparent conductive layer.

  Next, a transparent conductive layer was formed on the other surface of the optical compensation film in the same manner as described above, and then heat treatment (annealing) was performed at 150 ° C. for 30 minutes to reduce the resistance.

<Preparation of polarizing plate and touch panel module with integrated polarizing plate: see FIG. 2>
A roll-shaped polyvinyl alcohol film having a thickness of 80 µm was continuously stretched 5 times in an aqueous iodine solution and dried to obtain a polarizer having a thickness of 20 µm.

  Next, the above-prepared polarizer was sandwiched between one side of the above-prepared optical compensation films 101 to 119 provided with the transparent conductive layer and Konica Minolta Tack KC4UA (manufactured by Konica Minolta Co., Ltd.) as a protective film. Then, they were bonded via the following ultraviolet-curable adhesive liquid to produce polarizing plate integrated touch panel modules 101 to 119.

[Preparation of UV-curable adhesive liquid 1]
After mixing the following components, the mixture was defoamed to prepare an ultraviolet-curable adhesive liquid 1. The triarylsulfonium hexafluorophosphate was blended as a 50% propylene carbonate solution, and the solid content of the triarylsulfonium hexafluorophosphate is shown below.

3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 45 parts by mass Epolide GT-301 (alicyclic epoxy resin manufactured by Daicel)
40 parts by mass 1,4-butanediol diglycidyl ether 15 parts by mass Triarylsulfonium hexafluorophosphate 2.3 parts by mass 0.1 part by mass 9,10-dibutoxyanthracene 0.1 part by mass 2.0 parts by mass 1,4-diethoxynaphthalene The polarizing plate was prepared by subjecting the surfaces of the optical compensation film and the protective film to a corona discharge treatment at a corona output intensity of 2.0 kW and a line speed of 18 m / min. The liquid 1 was coated with a bar coater so that the film thickness after curing was about 3 μm to form an ultraviolet-curable adhesive layer.

The polarizing plate is irradiated with ultraviolet rays from the protective film side by using an ultraviolet irradiation apparatus with a belt conveyor (the lamp uses a D bulb manufactured by Fusion UV Systems Co., Ltd.) so that the integrated light amount becomes 750 mJ / cm ² . The ultraviolet curable adhesive layer was cured.

<Production of a liquid crystal display device with a touch panel equipped with a touch panel module integrated with a polarizing plate: see FIG. 2>
The polarizing plate integrated type touch panel module having the optical compensation films 101 to 116 produced above is bonded to a self-made VA mode type liquid crystal cell with the optical compensation film side of the polarizing plate to produce liquid crystal display devices 101 to 116 with a touch panel. did.

  In addition, the polarizing plate integrated type touch panel module including the optical compensation films 117 to 119 prepared above is carefully peeled off the touch panel module from a commercially available IPS mode type liquid crystal display device with a touch panel, and the polarizing plate is attached to the IPS mode type liquid crystal cell. The optical compensation films were bonded together to produce liquid crystal display devices 117 to 119 with a touch panel.

  On the opposite surface of the liquid crystal cell, a polarizing plate having the structure of an optical compensation film (Konica Minolta Tac KC8UCR3) / polarizer / protective film (Konica Minolta Tak KC4UA, all manufactured by Konica Minolta Co., Ltd.) is provided. The films were bonded via an adhesive layer such that the compensation film side was on the liquid crystal cell side.

≪Evaluation≫
[1] Retardation Value of Optical Compensation Film The in-plane retardation value Ro and the retardation value Rt in the thickness direction of the optical compensation film are measured by an automatic birefringence meter Axoscan (Axo Scan Mueller Matrix Polarimeter: manufactured by Axometrics). using, an environment of 23 ℃ · 55% RH, the optical wavelength of 590 nm, subjected to three-dimensional refractive index measured, resulting refractive indices _{n x,} n y, from _{n z,} the following formula (i) and ( ii).

Formula _{(i): Ro = (n} x -n y) × d (nm)
Formula _{(ii): Rt = {(} n x + n y) / 2-n z} × d (nm)
In [Equation (i) and Formula (ii), n _x represents a refractive index in the direction x in which the refractive index is maximized in the plane direction of the film. n _y, in-plane direction of the film, the refractive index in the direction y perpendicular to the direction x. _nz represents the refractive index in the thickness direction z of the film. d represents the thickness (nm) of the film. ]
[2] Variation in retardation value of optical compensation film The optical compensation film sample was left in an oven at 150 ° C for 1 hour to perform heat treatment, and the variation in retardation value before and after the heat treatment was determined by the following equation.

Fluctuation of phase difference value Ro or Rt = {(Ro value or Rt value after heat treatment-Ro value or Rt value before heat treatment) / (Ro value or Rt value before heat treatment)} × 100 (%)
[3] Glass transition temperature of optical compensation film The glass transition temperature Tg was determined by measuring with a differential scanning calorimeter DSC220 manufactured by Seiko Instruments Inc. according to JIS K-7121. About 10 mg of the optical compensation film sample was set, and the temperature was raised from room temperature to 250 ° C. at a rate of 20 ° C./min from the room temperature under a nitrogen flow rate of 50 ml / min, held for 10 minutes (first scan), and then 20 ° C./min. Then, the temperature was lowered to 30 ° C. at the speed described above, held for 10 minutes (second scan), and further raised to 250 ° C. at 20 ° C./min (third scan), and a DSC curve was created. The glass transition temperature Tg was determined from the DSC curve.

[4] Front contrast The front contrast of each of the manufactured liquid crystal display devices 101 to 119 with a touch panel was measured. The measurement of the front contrast was performed by a front contrast measuring device (EZ-contrast) manufactured by ELDIM, and the amount of light during white display and during black display was measured, and the ratio was obtained.

  The composition of the optical compensation film and the above evaluation results are shown in Table 1 below.

  Table 1 shows that the VA mode liquid crystal display device with the touch panel using the optical compensation films 101 to 114 according to the present invention is superior in the front contrast as compared with the IPS mode liquid crystal display devices 117 to 119.

  In addition, the optical compensation films 115 and 116 in which the glass transition temperature Tg of the optical compensation film is less than 155 ° C. have large fluctuation in retardation value, poor frontal contrast, and lower contrast than the IPS mode liquid crystal display device. Was.

Example 2
<Preparation of touch panel module>
On one surface of the optical compensation films 104, 110, 112, and 114 according to the present invention prepared in Example 1, an ITO film was formed as a transparent conductive layer so as to have a thickness of 20 nm by a sputtering method. A first electrode pattern was formed.

Next, as an insulating layer disposed between the electrode patterns, SiO ₂ is formed to a thickness of 200 nm by a sputtering method, and an ITO film is formed thereon by sputtering to a thickness of 20 nm. The film was formed, and a second electrode pattern was formed in the Y direction by etching. Further thereon, SiO ₂ was formed as an insulating layer to a thickness of 200 nm by a sputtering method. Next, a heat treatment (annealing treatment) is performed at 150 ° C. for 30 minutes to reduce the resistance, and the optical compensation films 201 to 201 having a transparent conductive layer corresponding to the optical compensation films 104, 110, 112, and 114 respectively. 204 were produced.

<Preparation of polarizing plate and touch panel module with integrated polarizing plate: see FIG. 6>
The polarizer produced in Example 1 was sandwiched between the side on which the transparent conductive layer of the optical compensation films 201 to 204 was provided, and Konica Minolta Tack KC4UA (manufactured by Konica Minolta, Inc.) as a protective film. Bonding was performed via the ultraviolet curable adhesive liquid 1 of Example 1 to produce the polarizing plate integrated touch panel modules 201 to 204.

<Production of a liquid crystal display device with a touch panel equipped with a touch panel module integrated with a polarizing plate: see FIG. 6>
A polarizing plate-integrated touch panel module 201 to 204 including the optical compensation films 201 to 204 prepared above is attached to a self-made VA mode type liquid crystal cell on the optical compensation film side where a transparent conductive layer is not formed, and a touch panel is provided. Liquid crystal display devices 201 to 204 were produced.

  On the surface on the opposite side of the liquid crystal cell, a polarizing plate having a configuration of an optical compensation film (Konica Minolta Tak KC8UCR3) / polarizer / protective film (Konica Minolta Tak KC4UA, all manufactured by Konica Minolta Co., Ltd.) is provided. The films were bonded via an adhesive layer so that the film side was on the liquid crystal cell side.

  When the front contrasts of the liquid crystal display devices 201 to 204 having the touch panel equipped with the manufactured polarizing plate integrated type touch panel module were measured in the same manner as in Example 1, the contrast ratio was 7500: 1, and Example 1 was reproduced. It was found that a VA mode type liquid crystal display device with a touch panel having excellent contrast was obtained.

  The liquid crystal display device with a touch panel according to the present invention has a thin film and excellent front contrast by having an optical compensation film, a polarizer, and a protective film having a transparent conductive layer on at least one surface according to the present invention in this order. A liquid crystal display device with a touch panel having a liquid crystal cell can be provided.

Reference Signs List 1 liquid crystal cell 2 polarizer T1 protective film T2 optical compensation film P1 polarizing plate (viewing side)
Reference Signs List 3 adhesive layer 4 conductive layer base film 5 transparent conductive layer 6 protective layer 7 front plate T touch panel module T3 optical compensation film T4 protective film P2 polarizing plate (backlight side)
10 Liquid crystal display device with touch panel of comparative example 20 Liquid crystal display device with touch panel of the present invention

Claims (6)

A liquid crystal display device with a touch panel, comprising a polarizing plate-integrated touch panel module having a transparent conductive layer on the viewing side of a VA mode liquid crystal cell,
A polarizing plate integrated touch panel module having the transparent conductive layer,
An optical compensation film having a transparent conductive layer on at least one surface, a polarizer, and a protective film in this order from the VA mode liquid crystal cell toward the viewing side, and
A liquid crystal display device with a touch panel, wherein the glass transition temperature Tg of the optical compensation film is in the range of 155 to 250 ° C.   The liquid crystal display device with a touch panel according to claim 1, wherein the optical compensation film contains any one of a cycloolefin-based resin, a polyimide-based resin, and a polyarylate-based resin.   When the optical compensation film is heat-treated at 150 ° C. for 1 hour, the variation of the in-plane retardation value Ro is within ± 3.0%, and the variation of the thickness direction retardation value Rt is less than ± 3.0%. 3. The liquid crystal display device with a touch panel according to claim 1, wherein the range is within ± 4.0%. 4.   4. The liquid crystal display device with a touch panel according to claim 1, wherein a thickness of the optical compensation film is in a range of 10 to 40 μm. 5. 5. The optical compensation film according to claim 1, further comprising a nitrogen-containing heterocyclic compound having a structure represented by the following general formula (3) as a retardation increasing agent. 6. A liquid crystal display device with a touch panel according to the item.

(In the formula, A represents a pyrazole ring. Ar ₁ and Ar ₂ each represent an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and may have a substituent. R ₁ is a hydrogen atom, an alkyl group, or an acyl group. , A sulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. Q represents 1 or 2. n and m each represent an integer of 1 to 3.) A method for manufacturing a liquid crystal display device with a touch panel, for manufacturing the liquid crystal display device with a touch panel according to claim 1,
After forming the transparent conductive layer on at least one surface of the optical compensation film, a step of heat treatment at 150 ° C. or more,
Laminating the polarizer so as to be sandwiched between the optically compensatory film and the protective film on which the transparent conductive layer is formed, and a step of producing a polarizing plate integrated type touch panel module,
Laminating the optical compensation film side of the polarizing plate-integrated touch panel module to the VA mode liquid crystal cell.

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