WO2016181756A1

WO2016181756A1 - Liquid crystal display device with touch panel and method for manufacturing such liquid crystal display device

Info

Publication number: WO2016181756A1
Application number: PCT/JP2016/062055
Authority: WO
Inventors: 里誌森井
Original assignee: コニカミノルタ株式会社
Priority date: 2015-05-13
Filing date: 2016-04-15
Publication date: 2016-11-17
Also published as: KR20190096444A; CN107533253B; JPWO2016181756A1; KR20170125098A; CN107533253A; KR102057017B1; KR102011587B1; JP6627869B2

Abstract

The problem to be solved by the present invention is to provide: a liquid crystal display device with a touch panel, equipped with a vertical alignment (VA) mode liquid crystal cell and having outstanding frontal contrast; and a method for manufacturing such display device. This liquid crystal display device with a touch panel is equipped, on the visible side of a VA mode liquid crystal cell, with a touch panel module with an integrated polarizing plate having a transparent conductive layer, and is characterized in that the touch panel module with the integrated polarizing plate having the transparent conductive layer comprises, in order from the VA mode liquid crystal cell to the visible side, an optical compensation film having a transparent conductive layer on at least one surface thereof, a polarizer, and a protective film, and in that the glass transition temperature Tg of the optical compensation film is in the range 155-250°C.

Description

Liquid crystal display device with touch panel and manufacturing method thereof

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

In recent years, liquid crystal display devices equipped with touch panels have become popular and are expected to increase in the future.

For example, in a capacitive 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 extending Y electrode pattern. The X electrode pattern and the Y electrode pattern come into contact with each other by touching with a finger on the surface of the touch panel, and a 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 diagram showing an example of a liquid crystal display device with a touch panel provided with a conventional out-cell touch panel module.

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

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

In the future, as the display devices become thinner, the touch panel, which is a main member, is required to be thinner.

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 touch panel module called a so-called mid-cell type or inner-cell type in contrast to an out-cell type (for example, Patent Document 1). And Patent Document 2). These polarizing plate integrated type touch panel modules correspond to the reduction in thickness of the member by forming the transparent electrode on an optical compensation film or a protective film that is a constituent element of the polarizing plate.

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

There are a plurality of types of liquid crystal cells depending on the liquid crystal molecules used, but at present, VA (vertical alignment) mode and IPS (in-plane switching) mode are mainstream. In general, the VA mode is said to be superior in front contrast as compared to the IPS mode. This is because the VA mode liquid crystal molecules are aligned vertically when the electric field is off, so that the backlight light can be further prevented from leaking to the viewer 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 type liquid crystal display cell, as expected for the case of using an IPS mode type liquid crystal display cell. The front contrast improvement effect 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 solution to the problem is to provide a liquid crystal display device with a touch panel having a VA mode liquid crystal cell excellent in front contrast and a method for manufacturing the same. is there.

In order to solve the above problems, the present inventor, in the process of examining the cause of the above problems, etc., a liquid crystal with a touch panel comprising 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 the viewing side. It has been found that the object of the present invention can be solved when the glass transition temperature Tg of the optical compensation film is not less than a specific value.

That is, the above-mentioned problem 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 the VA mode liquid crystal cell,
A polarizing plate integrated touch panel module having the transparent conductive layer,
From the VA mode type liquid crystal cell toward the viewer side, it has an optical compensation film having a transparent conductive layer on at least one surface, a polarizer and a protective film in this order, and
A liquid crystal display device with a touch panel, wherein the optical compensation film has a glass transition temperature Tg of 155 to 250 ° C.

2. 2. The liquid crystal display device with a touch panel as set forth in claim 1, wherein the optical compensation film contains any one of a cycloolefin resin, a polyimide resin and a polyarylate resin.

3. The fluctuation of the retardation value Ro in the in-plane direction when the optical compensation film is heat-treated at 150 ° C. for 1 hour is within ± 3.0%, and the fluctuation of the retardation value Rt in the thickness direction is 3. The liquid crystal display device with a touch panel according to

item

1 or 2, which is within a range of ± 4.0%.

4. Item 4. The liquid crystal display device with a touch panel according to any one of items 1 to 3, wherein a thickness of the optical compensation film is in a range of 10 to 40 μm.

5. 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 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 represents a hydrogen atom, an alkyl group, or an acyl group. Represents a sulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group, q represents 1 or 2, and n and m each represents an integer of 1 to 3.)
6). A method for manufacturing a liquid crystal display device with a touch panel, which manufactures the liquid crystal display device with a touch panel according to any one of items 1 to 5,
Forming the transparent conductive layer on at least one surface of the optical compensation film, and then performing a heat treatment at 150 ° C. or higher;
Bonding a polarizer so as to be sandwiched between an optical compensation film and a protective film on which the transparent conductive layer is formed, to produce a polarizing plate integrated touch panel module;
A step of bonding the optical compensation film side of the polarizing plate integrated touch panel module to the VA mode liquid crystal cell, and a method of manufacturing a liquid crystal display device with a touch panel.

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 type liquid crystal cell excellent in front contrast and a method for manufacturing the same.

The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

In general, in the case of an IPS mode type liquid crystal cell, a film having no retardation in the optical compensation film, that is, 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 do.

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

When a transparent conductive layer is provided on the optical compensation film in order to produce the polarizing plate-integrated touch panel module referred to as the so-called mid cell type or inner cell type, the transparent conductive layer is formed after the transparent conductive layer is formed. In order to reduce the resistance value, heat treatment (also referred to as annealing treatment) is required. For example, specifically, a heat treatment is performed at 150 ° C. for about 30 minutes, but this disturbs the orientation of the polymer molecules in the optical compensation film, resulting in insufficient optical compensation performance, and the front surface. It is presumed that the contrast is lowered.

According to the configuration of the present invention, in order to cope with the above phenomenon, by using an optical compensation film having a heat resistance having a glass transition point Tg of 155 ° C. or higher, the retardation value variation due to the heat treatment is suppressed, and the VA mode is achieved. It is presumed that excellent front contrast, which is a characteristic characteristic of the liquid crystal, can be achieved.

Also, as described above, there is a case where the optical compensation film is required to be thin with a thickness of 40 μm or less in order to reduce the thickness of the touch panel. At that time, since the phase difference value and the film thickness are in a contradictory relationship, in the case of a thin film having a thickness of 40 μm or less, an additive capable of increasing the phase difference value by addition (in this application, a phase difference increasing agent). It is effective to add it to the film. The present inventor has discovered a phase difference increasing agent having a specific structure capable of obtaining a more excellent effect while examining various phase difference increasing agents. By adding this additive, during the heat treatment, the orientation of the retardation increasing agent itself is disturbed, and the retardation variation derived from the compound occurs, thereby canceling the retardation variation derived from the polymer molecules constituting the film. It is speculated that even a thin film can realize an excellent retardation value and heat treatment fluctuation resistance.

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

The liquid crystal display device with a touch panel of the present invention is 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 the VA mode liquid crystal cell, and the polarization having the transparent conductive layer. The plate-integrated touch panel module has 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 type 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. This feature is a technical feature common to the claimed invention.

As an embodiment of the present invention, from the viewpoint of manifesting the effects of the present invention, it is preferable that the optical compensation film contains any of a cycloolefin resin, a polyimide resin, or a polyarylate resin. From the viewpoint of satisfying the glass transition temperature Tg, it is preferable.

In addition, the fluctuation of the retardation value Ro in the in-plane direction when the optical compensation film is heat-treated at 150 ° C. for 1 hour is within a range of ± 3.0%, and the retardation value Rt in the thickness direction is The fluctuation is within ± 4.0% of the range, so that the optical compensation function is sufficiently developed, the fluctuation of the phase difference due to the heat treatment is suppressed, and the excellent front contrast when the VA mode type liquid crystal cell is used. From a viewpoint that can be achieved, this is a preferable performance.

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

In the method for manufacturing a liquid crystal display device with a touch panel according to the present invention, the transparent conductive layer is formed on at least one surface of the optical compensation film, and then a heat treatment is performed at 150 ° C. or more, and a polarizer is formed on the transparent conductive layer. Bonding so as to be sandwiched between an optical compensation film and a protective film 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 It is preferable to provide the process of bonding.

Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In the present application, “˜” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

<< Outline of Liquid Crystal Display Device with Touch Panel of the Present Invention >>
The liquid crystal display device with a touch panel of the present invention is 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 the VA mode liquid crystal cell, and the polarization having the transparent conductive layer. The board-integrated touch panel module
From the VA mode type liquid crystal cell toward the viewer side, it has an optical compensation film having a transparent conductive layer on at least one surface, a polarizer and a protective film in this order, and
The optical compensation film has a glass transition temperature Tg in the range of 155 to 250 ° C.

As described above, the liquid crystal display device with a touch panel of the present invention is characterized by including a VA mode type liquid crystal display cell. By adopting the VA mode type liquid crystal display cell, a conventional IPS mode type liquid crystal display cell is obtained. Compared with the liquid crystal display device with a touch panel used, the front contrast is improved.

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., the heat treatment after forming the transparent conductive layer causes a change in retardation value due to disturbance of polymer molecules in the optical compensation film, resulting in a decrease in the optical compensation function, which is a characteristic characteristic of VA mode liquid crystal. Excellent front contrast cannot be obtained.

In addition, 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 glass transition temperature range in a state of containing them. . For example, when a plasticizer or the like is added, the glass transition temperature may be lowered depending on the type and addition amount, which is a design consideration.

The glass transition temperature Tg can be determined by measuring, 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 20 ° C./min and held for 10 minutes under the condition of a nitrogen flow rate of 50 ml / min (first scan). Next, the temperature is lowered to 30 ° C. at a rate of 20 ° C./min and held for 10 minutes (second scan), and further raised to 250 ° C. at 20 ° C./min (third scan) to create a DSC curve. Then, the glass transition temperature Tg is obtained from the DSC curve of the obtained third scan.

Furthermore, 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 fluctuations in retardation value during heat treatment. .

As a result of various investigations of general-purpose resin films in the course of studying the present invention, diacetyl cellulose films have large dimensional fluctuations due to humidity, and when a transparent conductive layer is formed on the film, shrinkage and elongation occur during storage, and the electrode Cracking and the like occurred, making it difficult to use. Further, the PET film has a too large retardation, so that it is difficult to use it as an optical compensation film for a VA mode liquid crystal display device. Similarly, a 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. Furthermore, the acrylic resin film has a low glass transition temperature Tg and is not suitable 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 of the present invention is 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 the VA mode liquid crystal cell, and the polarization having the transparent conductive layer. The plate-integrated touch panel module has 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 type 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., and the optical compensation film contains any of cycloolefin resin, polyimide resin, or polyarylate resin. From the viewpoint of control of the property 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 configuration of the comparative example.

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

A liquid crystal display device 10 with a touch panel 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. The touch panel module T having the transparent conductive layer 5 and the protective layer 6 on both sides of 4 is bonded to the polarizing plate P1 through the adhesive layer 3, and the front plate 7 is bonded to the touch panel module T through 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. In general, the liquid crystal cell 1 is an IPS mode type.

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

The liquid crystal display device 20 with a touch panel 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 the liquid crystal cell 1, and the optical compensation film T2 has both sides thereof. A polarizing plate integrated touch panel module having a so-called mid cell type or inner cell type structure in which a transparent conductive layer 5 is formed. By adopting such a configuration, the liquid crystal display device with a touch panel can be thinned compared to the out-cell type. Adhesion between the respective films and layers is preferably performed by appropriately forming the adhesive layer 3.

Similarly, 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. Here, the liquid crystal cell 1 is a VA mode type.

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 absorption layer, an anti-curl layer, etc.) may be provided between the members as necessary. Forming a hard coat layer as a protective layer of the film or forming an antistatic layer is a preferred embodiment.

The total thickness of the 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 viewpoint 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 showing another example of the configuration of the liquid crystal display device with a touch panel provided with the polarizing plate integrated touch panel module of the present invention.

3 is a structure in which the transparent conductive layer 5 is formed as an upper layer of the protective film T1 and the optical compensation film T2, respectively.

FIG. 4 is a schematic diagram showing another example of the configuration of a liquid crystal display device with a touch panel provided with 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 provided with 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 disposed below the optical compensation film T2. In this case, the transparent conductive layer preferably has a configuration in which an X electrode pattern and a Y electrode pattern are interposed in an insulating layer.

FIG. 6 is a schematic diagram showing another example of the configuration of a liquid crystal display device with a touch panel provided with 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 disposed on the upper layer of the optical compensation film T2. Similarly, the transparent conductive layer in this case has an X electrode pattern and a Y electrode pattern in the layer through an insulating layer. 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 higher. The optical compensation film usually contains a resin, a plasticizer, various additives, a matting agent, and the like. In the present invention, the glass transition temperature Tg as a finished film is 155 ° C. or higher.

The glass transition temperature Tg needs to be 155 ° C. or higher from the viewpoint of suppressing phase difference variation 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. It is 250 degrees C or less. When Tg exceeds 250 ° C., the adhesion and crack resistance may decrease with an increase in internal stress. Therefore, the present invention is intended for 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 155 ° C. or more as a single resin, and in consideration of the retardation and stability, among them, a cellulose ester resin , Preferably containing any of cycloolefin resin, polyimide resin or polyarylate resin, more preferably containing any of cycloolefin resin, polyimide resin or polyarylate resin, cycloolefin It is particularly preferable to contain a resin.

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

Among the above, the lower fatty acid ester of cellulose 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 substitution degree of acetyl group is X, and the substitution degree of propionyl group or butyryl group is Y Those satisfying the following formulas (I) and (II) are preferred.

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 in the range of 1.8 to 2.0. It is preferable.

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

Solvent: dichloromethane Column: Shodex K806, K805, K803G
(Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (GL Science Co., Ltd.)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Co., Ltd.) A calibration curve with 13 samples from Mw = 500 to 1000000 was used. The 13 samples are preferably used at approximately equal intervals.

[1.2] Cycloolefin resin As the cycloolefin resin, polymers of various cycloolefin monomers can be used. A cycloolefin monomer having a norbornene skeleton is homopolymerized or copolymerized. It is preferable to use the resulting 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). .

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

(In General Formula (A-1), R ¹ to R ⁴ each independently represents a hydrogen atom or a halogen atom, or has a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom. And represents a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms or a polar group, and p represents a natural number of 0 to 2.
The polar group refers to a functional group that is polarized 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, and these polar groups are connected via a linking group such as a methylene group. It may be bonded. In addition, 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 Also, examples of the polar group include a hydrocarbon group having 1 to 30 carbon atoms in 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 ensuring solubility during solution film formation.

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

(In the general formula (A-2), ^{R 5} is independently a hydrogen atom, .R ⁶ represents an alkyl silyl group having a hydrocarbon group, or an alkyl group having 1 to 5 carbon atoms of 1 to 5 carbon atoms, 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 molecular symmetry is lost. It is preferable from the viewpoint of uneven distribution of the additive because the diffusion movement between the resin and the additive at the time of solvent volatilization is promoted and the movement of the additive to the film-forming film surface is promoted accordingly.

R ⁵ is preferably 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, particularly an alkoxycarbonyl group or an aryloxycarbonyl group. It is also preferable from the viewpoint of ensuring solubility during film formation.

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

The cycloolefin resin is a polymer obtained by homopolymerization or copolymerization of a cycloolefin monomer having a norbornene skeleton and having a structure represented by the general formulas (A-1) and (A-2). For example, the following can be mentioned.
(1) Ring-opening polymer of cycloolefin monomer (2) Ring-opening copolymer of cycloolefin monomer and copolymerizable monomer (3) Ring-opening of (1) or (2) above ( Hydrogenated (co) polymer of (co) polymer (4) (co) polymer hydrogenated after cyclization of the ring-opened (co) polymer of (1) or (2) above by Friedel-Craft reaction (5) Saturated polymer of cycloolefin monomer and unsaturated double bond-containing compound (6) Addition type (co) polymer of cycloolefin monomer and hydrogenated (co) polymer (7) Alternate copolymer of cycloolefin monomer and methacrylate or acrylate The polymers of (1) to (7) are all known methods, for example, JP-A-2008-107534 and JP-A-2005-227606. It can be obtained by the method described in the publication. For example, as the catalyst and solvent used in the ring-opening copolymerization (2) above, for example, those described in paragraphs 0019 to 0024 of JP-A-2008-107534 can be used. As the catalyst used for hydrogenation in the above (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 of (4) above, for example, those described in paragraph 0029 of JP-A-2008-107534 can be used. As the catalyst used in the above addition polymerization (5) to (7), for example, those described in paragraphs 0058 to 0063 of JP-A-2005-227606 can be used. The alternating copolymerization reaction (7) can be performed, for example, by the method described in paragraphs 0071 and 0072 of JP-A-2005-227606.

Of these, the polymers (1) to (3) and (5) are preferred, and the polymers (3) and (5) are more preferred.

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

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

(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 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, wherein R ⁶ represents a carboxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an amide; 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 the present specification, the description of JP-A-2008-107534 is used for the production method of the cycloolefin resin according to the present application, and the description thereof is omitted.

The cycloolefin resin 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 that the polystyrene-reduced number average molecular weight (Mn) measured by the gel permeation chromatography (GPC) is 8000 to 100,000, more preferably 10,000 to 80,000, particularly preferably 12000. The weight average molecular weight (Mw) is preferably 20,000 to 300,000, more preferably 30,000 to 250,000, and 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. The case where Tg is 110 ° C. or higher is preferred because deformation hardly occurs due to use under high temperature conditions or secondary processing such as coating or printing.
On the other hand, when Tg is 350 ° C. or lower, it is possible to avoid the case where the molding process becomes difficult, and it is possible to suppress the possibility that the resin is deteriorated by heat during the molding process.
The cycloolefin-based resin may be a specific hydrocarbon-based resin described in, for example, Japanese Patent Application Laid-Open No. 9-221577 and Japanese Patent Application Laid-Open No. 10-287732, or a known heat, as long as the effects of the present invention are not impaired. Plastic resins, thermoplastic elastomers, rubbery polymers, organic fine particles, inorganic fine particles, etc. may be blended, such as specific wavelength dispersants, plasticizers, antioxidants, release accelerators, rubber particles, UV absorbers, etc. An additive may be included.
As the cycloolefin resin, commercially available products can be preferably used. Examples of commercially available products include trade names of ARTON (registered trademark) G, ARTON F, ARTON R, and ARTON RX from JSR Corporation. These are available on the market 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 is shown below.

First, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (TFMB), which is 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 the temperature was −20 to 100 ° C. using a mechanical stirrer. The mixture is stirred in the range, preferably in the range of 20 to 60 ° C. for 1 to 72 hours. By using TFMB and 6FDA, visible light permeability and solubility are improved. The number of moles of diamine and the number of moles of tetracarboxylic dianhydride are charged at substantially equal moles. The total monomer concentration during the polymerization is 5 to 40% by mass, preferably 10 to 30% by mass. By carrying out polymerization in this monomer concentration range, a polyimide precursor solution having a uniform and high degree of polymerization can be obtained.重合 If the polymerization is carried out at a concentration lower than the above monomer concentration range, the degree of polymerization of the polyimide precursor is not sufficiently high, and the finally obtained polyimide resin film may be brittle, which is not preferable.

The polymerization solvent is not particularly limited, but 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, 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 in combination of two or more.

[Production method of polyimide resin]
The polyimide resin represented by the formula (P1) can be produced by a dehydration ring-closing reaction (imidation reaction) of the polyimide precursor obtained by the above method. For the imidization reaction, chemical imidization is used in which the resulting polyimide resin exhibits better dimensional stability. Chemical imidization can be performed using a dehydrating cyclization agent (chemical imidization agent) comprising an acid anhydride of an organic acid and an organic tertiary amine. For example, by using the polyimide precursor varnish as it is or after appropriately diluting with a solvent, a dehydration cyclization reagent is added thereto and stirred at 0 to 100 ° C., preferably 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, etc. can be used, but the cost and ease of post-treatment are not limited. In view of the above, 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.

In the chemical imidation 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 catalyst used is preferably in the range of 0.1 to 2 moles relative to the acid anhydride. If the chemical imidization is carried out outside these ranges, the imidation reaction may not be completed, or the imidization may not be completed in the reaction solution, resulting in insufficient imidization.

After the imidization is completed, the reaction solution can be used for coating as it is, or the reaction solution is dropped into a large amount of poor solvent, or a poor solvent is added to the reaction solution to precipitate and wash the polyimide resin. In the case of a reaction solvent or chemical imidization, excess chemical imidization agent is removed, and then dried under reduced pressure to obtain a polyimide resin powder. The poor solvent that can be used is not particularly limited as long as it does not dissolve the polyimide resin, but water, methanol, ethanol from the viewpoint of affinity with the reaction solvent and 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 5000 to 2000000, more preferably 10,000 to 1000000, and further preferably 50000 to 500000. When the weight average molecular weight is 5000 or more, sufficient strength can be obtained in the case of a film, and dimensional stability tends to be improved, so that sufficient dimensional stability can be obtained. On the other hand, if it is 2000000 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 polyethyleneglycol 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 general formula (P2), X must be a divalent group containing a fluorine atom. By making X in the general formula (P2) a divalent group containing a fluorine atom, it has excellent heat resistance and light transmittance in the visible light region and shorter wavelength region (ultraviolet region). Thus, a polyarylate resin having flame retardancy superior to that of the prior art and suppressing yellowing due to ultraviolet rays can be obtained. When X is a divalent group not containing a fluorine atom, the flame retardancy is lowered, yellowing occurs due to ultraviolet irradiation, and the light transmittance is lowered.

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

In general formula (P2a), R ^1a and R ^2a independently represent 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 these, it is preferable that R ^1a and R ^2a are trifluoromethyl groups.
R ¹ and R ² represent a substituent bonded to the benzene ring in the general formula (P2).

Since bisphenol giving the structure represented by the general formula (P2) is easily industrially available or easily synthesized, R ¹ and R ^{2 in} the general formula (P2) independently have 1 carbon atom. Or a hydrocarbon group, a halogenated alkyl group or a halogen atom. Among these, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a phenyl group, and a cyclohexyl group are preferable, and a bromine atom and a methyl group are more preferable.
p and q represent the number of substituents R ¹ and R ² bonded to the benzene ring, respectively, and are independently integers of 0 to 4. For example, if p and q is 0, all of the hydrogen atoms bonded to the benzene ring in the general formula (P2) represents that which is not substituted with R ¹ and R ^2. When p is 2 to 4, a plurality of R ¹ may be the same or different from each other. When q is 2 to 4, the plurality of R ² may be the same or different from each other. Since bisphenol giving the structure represented by the general formula (P2) is easily industrially available or easily synthesized, p and q are preferably 0.

Examples of the bisphenol that gives the structure represented by the general formula (P2) include 2,2-bis (4-hydroxyphenyl) hexafluoropropane [BisAF], 2,2-bis (3,5-dimethyl-4-). And hydroxyphenyl) hexafluoropropane and 2,2-bis (tetramethyl-4-hydroxyphenyl) hexafluoropropane. Among these, BisAF is preferable because it is easily available industrially. In the case of using BisAF, in the general formula (P2), p = 0, q = 0, and X = —C (CF ₃ ) ₂ —.

In the present invention, the bisphenol residue may contain a residue of bisphenol other than 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 give such residues 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, among the entire bisphenol residues 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) Area) and the suppression of yellowing by 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), the light transmittance in a short wavelength region (ultraviolet region) is lowered, or yellowing is easily caused by ultraviolet rays. For example, when only terephthalic acid that gives a structure not represented by the general formula (P3) is used for the aromatic dicarboxylic acid, the polyarylate resin has a reduced light transmittance in the short wavelength region (ultraviolet region) and is yellowed by ultraviolet rays. It becomes easy to do.

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

R ³ and R ⁴ are independently carbon atoms having 1 to 6 carbon atoms because aromatic dicarboxylic acids that give the structure represented by the general formula (P3) are industrially easily available or easily synthesized. A hydrogen group, a halogenated alkyl group or a halogen atom; Among these, chlorine, bromine, methyl group, ethyl group, phenyl group, and cyclohexyl group are preferable, and bromine and methyl group are more preferable.
r and s represent the number of substituents bonded to the benzene ring, and are independently an integer of 0 to 4. For example, when r and s are 0, it represents 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, the plurality of R ³ may be the same or different from each other. When s is 2 to 4, the plurality of R ⁴ may be the same or different from each other.

Examples of the aromatic dicarboxylic acid that gives 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. Diphenyl ether-3,3'-dicarboxylic acid, diphenyl ether-3,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid. Of these, diphenyl ether-4,4′-dicarboxylic acid is preferable because it is easily available industrially. 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 contain a residue of an aromatic dicarboxylic acid other than the aromatic dicarboxylic acid that gives 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 that gives such a residue include terephthalic acid, isophthalic acid, and orthophthalic acid. Of these, 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, among the aromatic dicarboxylic acid residues present in the polyarylate resin, aromatic dicarboxylic acid residues (isophthalic acid) having a structure represented by the general formula (P3) In the case of containing a residue, the ratio of 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%, It is more preferably 50 to 100 mol%, further preferably 80 to 100 mol%, and most preferably 100 mol%.

From the viewpoint of the tensile elongation at break of the polyarylate resin, the ratio of the aromatic dicarboxylic acid residue having the structure represented by the general formula (P3) to the total aromatic dicarboxylic acid residue present in the polyarylate resin is 35 to 100 mol% is preferable, and 100 mol% is more preferable.

The polyarylate resin according to the present invention preferably contains an end group for sealing the end of the molecule. When the end of the molecule is sealed, the acid value of the polyarylate resin is reduced and it is difficult to be 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 preferred are monohydric phenol residues and monohydric alcohol residues.

In the present invention, within the range that does not impair the effects of the present invention, the residue of the aliphatic diol, the residue of the alicyclic diol, the residue of the aliphatic dicarboxylic acid, the residue of the alicyclic dicarboxylic acid is added to the polyarylate resin. 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 or a solution polymerization method, or a method of reacting in a molten state such as melt polymerization. From the viewpoint of the polymerizability and the appearance of the resulting resin, it is preferable to use an interfacial polymerization method that allows a reaction in an organic solvent, particularly a reaction at a low temperature.

Since high tensile elongation at break can be obtained, the weight average molecular weight of the polyarylate-based resin is preferably 12000 or more, and more preferably 50000 or more.

[2] Retardation increasing agent In the present application, the retardation increasing agent is a retardation value Rt 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 1.1 times or more compared to an uncompensated optical compensation film.

The retardation increasing agent according to the present invention is not particularly limited. For example, a disk having an aromatic ring described in paragraphs [0143] to [0179] of JP-A-2006-113239, which is well known in the art, is known. -Like compounds (1,3,5-triazine 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 Pyrimidine compounds described in JP-A-2011-140637, epoxy ester compounds described in paragraphs [0022] to [0028], polyester compounds described in paragraphs [0044] to [0058] of international publication 2012/014571, etc. Can do.

Properties required for the retardation increasing agent according to the present invention include excellent compatibility with a resin, excellent retardation when a film is thinned, excellent precipitation resistance, and high humidity. In the present invention, it is excellent in resistance to fluctuations in retardation value due to the entry and exit of moisture, but by adding the retardation increasing agent, the orientation of the retardation increasing agent itself is disturbed during the heat treatment, and the retardation derived from the compound. It is preferable that the fluctuation in phase difference can be offset by the polymer molecules constituting the film.

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

[Nitrogen-containing heterocyclic compounds]
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 having a favorable interaction on the retardation increasing function and the orientation of the resin molecules during the heat treatment.

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

The structure of the 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring is not limited, but for example, benzene ring, pyrrole ring, pyrazole ring, imidazole ring, 1,2,3-triazole ring, 1,2 , 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, etc. .

The 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring represented by A ₁ , A ₂ and B may have a substituent. Examples of the substituent include 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 Groups (cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), alkenyl groups (vinyl group, allyl group, etc.), cycloalkenyl groups (2-cyclopenten-1-yl, 2-cyclohexen-1-yl group, etc.) ), Alkynyl groups (ethynyl group, propargyl group, etc.), aromatic hydrocarbon ring groups (phenyl group, p-tolyl group, naphthyl group, etc.), aromatic heterocyclic groups (2 Pyrrole group, 2-furyl group, 2-thienyl group, pyrrole group, imidazolyl group, oxazolyl group, thiazolyl group, benzimidazolyl group, benzoxazolyl group, 2-benzothiazolyl group, pyrazolinone group, pyridyl group, pyridinone group, 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-methyl Xyloxy group, etc.), aryloxy groups (phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group, etc.), acyloxy groups (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 groups, etc.), acylamino groups (formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, etc.), alkyl and arylsulfonylamino groups (methylsulfonylamino group, butylsulfonylamino group, 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 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 compensation film having excellent optical property fluctuation effects and excellent durability can be obtained.

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

In the formula, * represents a bonding position with 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 substituent among the substituents that A ₁ in the general formula (1) may have. 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 fluctuations 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, and 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 or 6 via 2 or less atoms. Membered aromatic hydrocarbon rings or aromatic heterocycles are linked. The term “via two or less atoms” refers to the minimum number of atoms existing between the connected substituents among the atoms constituting the linking 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). It is a divalent linking group selected from the group consisting of or a linking group in which two of them are combined. 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.), 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, etc.) Group, 2-pyrimidinyl group, 2-benzothiazolyl group, 2-pyridyl group, etc.), 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) and ₁ and a ₂ have include the same groups as also substituents.

In the general formula (1), L ₁ , L ₂ , L ₃ and L ₄ can interact with the resin by increasing the planarity of the compound having the structure represented by the general formula (1). Since it becomes stronger and fluctuations in optical properties 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, the plurality of A ₂ , T ₂ , L ₃ , and L ₄ in the general formula (1) may be the same or different. The larger n is, the stronger the interaction between the compound having the structure represented by the general formula (1) and the resin is, and the better the effect of suppressing fluctuations in optical properties is. The smaller n is the compatibility with the resin. Is excellent. For this reason, n is preferably an integer of 1 to 3, more preferably an integer of 1 or 2.

<Compound having a structure represented by the 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 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 And represents the same group as L ₁ in Formula (1), m represents an integer of 0 to 4.)
A smaller m is superior in compatibility with the resin, and therefore m is preferably an integer of 0 to 2, more preferably an integer of 0 to 1.

<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 1-4 T ₁ represents a 1,2,4-triazole ring.)
Furthermore, 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 the 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 on a benzene ring. Bonded to 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 (hydrochloric acid, hydrobromic acid, etc.), 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 (methanesulfonic acid, etc.), allylsulfonic acid (benzenesulfonic acid, 4-toluene) Sulfonic acid, 1,5-naphthalenedisulfonic acid, and the like), but are not limited thereto. Of these, hydrochloride, acetate, propionate and butyrate are preferable.

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

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

Further, two or more kinds of solvents may be included at the same time, or a form containing water and a solvent (for example, water and alcohol (for example, methanol, ethanol, t-butanol, etc.)) may be used.

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, solvent or 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 compound, the better the compatibility with the resin and the greater As the effect of suppressing fluctuations in the optical value with respect to changes in environmental humidity is higher, the range of 150 to 2000 is preferable, 200 to 1500 is more preferable, and 300 to 1000 is more preferable.

Furthermore, 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).

(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 represents a hydrogen atom, an alkyl group, or an acyl group. Represents a sulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group, q represents 1 or 2, and n and m each represents 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-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring mentioned in the general formula (1), respectively. preferable. Examples of the substituent for Ar ₁ and Ar ₂ include the same substituents as those shown for the compound having the structure represented by the general formula (1).

Specific examples of R ₁ include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkyl groups (methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group). 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), An aryloxycarbonyl group (for example, phenoxycarbonyl group etc.) etc. are mentioned.

Q represents 1 or 2, and n and m represent integers of 1 to 3.

The compounds having a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle used in the present invention are, among others, those represented by the general formulas (1), (2), (1.1) and (1.2). A compound having the structure represented is preferable, and a compound having a structure represented by the general formula (3) is more preferable. The compound having a 5-membered 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 International Publication No. 2014/109350. Can be given as a specific example. In addition, this invention is not limited at all by the said specific example. Further, specific examples may be tautomers, and may form hydrates, solvates or salts.

For the synthesis methods of the compounds mentioned in the specific examples, paragraphs [0215] to [0239] of International Publication No. 2014/109350 can be similarly referred.

<About the method of using the compound having the structure represented by the 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. 0.1 to 10% by mass, preferably 1 to 5% by mass, particularly preferably 2 to 5% by mass. The addition amount varies depending on the type of 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), it may be added as a powder to the resin forming the optical compensation film. You may add to 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 control agent, an antistatic agent, a release agent, and the like. May be included. Details of the main additives are described below.

[Plasticizer]
A plasticizer is generally an additive that has the effect of improving brittleness, decreasing melt viscosity, or imparting flexibility by adding it to a polymer. Therefore, the glass transition temperature Tg of the optical compensation film may be lowered. Therefore, the glass transition temperature Tg of the optical compensation film is preferably used within the range of the present invention.

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

The addition amount of the plasticizer is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 5% by mass with respect to the resin.

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

Examples of ultraviolet absorbers include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like, but less benzotriazole compounds 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 preferably used.

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

The addition amount of the ultraviolet absorber is preferably in the range of 0.1 to 5% by mass, more preferably in the range of 0.5 to 5% by mass with respect to the resin.

Examples of the benzotriazole-based ultraviolet absorber useful in the present invention include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 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- '-T-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -6- (straight 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 A mixture of (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate can be mentioned, but is not limited thereto.

Further, as a commercial product, “TINUVIN 928”, “TINUVIN 171”, “TINUVIN 326”, “TINUVIN 328” (above, trade name, manufactured by BASF Japan Ltd.) are preferable. Can be used.

[Antioxidant]
Antioxidants, for example, have a role of delaying or preventing the optical compensation film from being decomposed by halogen as a residual solvent in the optical compensation film or phosphoric acid as a phosphoric acid plasticizer. It is preferable to make it.

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], oct Decyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxy Benzyl) -isocyanurate and the like.

In particular, 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferred. Further, for example, hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di- A phosphorus processing stabilizer such as t-butylphenyl) phosphite may be used in combination.

The addition amount of the antioxidant is preferably in the range of 0.1 to 5% by mass, more preferably in the range of 0.5 to 3% by mass with respect to the resin.

[Matting agent]
In the optical compensation film according to the present invention, it is also preferable to add fine particles as a matting agent in order to prevent the produced film from being scratched or having poor transportability when handled.

Fine particles include inorganic compound fine particles and resin fine particles. Examples of fine particles of inorganic compounds 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, silicic acid Examples thereof include magnesium and calcium phosphate. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.

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. If the particles have an average particle size in the range of 80 to 400 nm, the primary particles are not aggregated. It is also preferable that it is contained.

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, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.). Can do.

Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.

Examples of resin fine particles include silicone resin, fluororesin and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) Are commercially available and can be used.

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

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

[4] Method for Producing Optical Compensation Film An example using a cycloolefin resin will be described as a method for producing an optical compensation film according to the present invention.

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

Examples of the solvent used in the solution casting method include chlorinated solvents such as chloroform and dichloromethane; aromatic solvents such as toluene, xylene, benzene, and mixed solvents thereof; methanol, ethanol, isopropanol, n-butanol, Examples thereof include 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, and 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. Examples of the good solvent include dichloromethane as a chlorinated organic solvent, and methyl acetate and acetic acid as a non-chlorine organic solvent. Ethyl, amyl acetate, acetone, methyl ethyl ketone, tetrahydrofuran, 1,3-dioxolane, 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 solvent, and the alcohol 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 the solvent is a mixed solvent, the good solvent is preferably used in an amount of 55% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more based on the total amount of the solvent.

In the case of forming an optical compensation film by a solution casting method, for example, a dope containing a compound having a structure represented by the cycloolefin resin and the general formula (3) and a solvent is prepared, and the dope is supported on the 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 have a step of drying the stretched dope as a web, a step of peeling from the metal support, a step of stretching or maintaining the width, a step of drying, and a step of winding up the finished film.

In the solution casting method, the concentration of the cycloolefin resin in the dope is preferably higher because the drying load after casting on the metal support can be reduced, but the concentration of the cycloolefin resin is too high. The load at the time of filtration increases, resulting in poor filtration accuracy. The concentration that achieves both of these is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass. The metal support in the casting (casting) step preferably has a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support.

The cast width can be 1 ~ 4m. 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. Higher temperatures are preferable because the web can be dried faster, but if the temperature is too high, the web may foam or flatness may deteriorate.

Alternatively, it is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent. The method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing warm air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short.

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

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

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

Residual solvent amount is defined by the following formula.

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

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. The content is preferably 0 to 0.01% by mass or less.

In the film drying process, generally, a roller drying method (a method in which webs are alternately passed through a plurality of upper and lower rollers) and a tenter method for drying while transporting the web are 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, the film is preferably stretched in the longitudinal direction and / or the lateral direction or the oblique direction.

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

Thus, for example, the following stretching steps are possible:
-Stretch in the longitudinal direction-> Stretch in the width direction-> Stretch in the longitudinal direction-> Stretch in the longitudinal direction-Stretch in the width direction-> Stretch in the width direction-> Stretch in the longitudinal direction-> Stretch in the longitudinal direction Includes stretching in one direction and contracting the other while relaxing the tension.

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

If the residual solvent amount is 2% by mass or more, the film thickness deviation is small and preferable from the viewpoint of flatness, and if it is within 50% by mass, the surface unevenness 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 lateral direction, preferably in the lateral direction so that the film thickness after stretching is in a desired range. Depending 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. If it extends in the said temperature range, since a extending | stretching stress can be reduced, haze will become low. Moreover, the optical compensation film containing the cycloolefin resin which suppressed generation | occurrence | production of a fracture | rupture and was excellent in planarity and the coloring property of the film itself is 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, a self-supporting film peeled from a support can be stretched in the longitudinal direction by regulating the running speed with a stretching roller. The draw ratio in the longitudinal direction is preferably 1.03 to 2.00 times, more preferably 1.10 to 1.80 times, still more preferably 1.20 to 1.60 times in the 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 processing as described in JP-A-62-46625 is carried out by holding the both ends of the film with a clip or a pin in the width direction. A method of drying while drying (referred to as a tenter method), among which a tenter method using a clip is preferably used.

The film stretched in the longitudinal direction or the unstretched film is preferably introduced into the tenter in a state where both ends in the width direction are held by the clip, and stretched in the width direction while running 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 still more preferably 1.20 to 1.0 times in a temperature range of 30 to 300 ° C. 1.60 times.

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

If the stretching speed is 50% / min or more, the planarity is improved and the film can be processed at high speed, which is preferable from the viewpoint of production aptitude, and if it is within 1000% / min, the film is broken. Can be processed without any problem.

More preferable stretching speed is in the range of 100 to 500% / min. The stretching speed is defined by the following formula.

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

Moreover, when extending | stretching in the diagonal direction, Unexamined-Japanese-Patent No. 2005-321543 and Unexamined-Japanese-Patent No. 2013-120208 can be referred.

Next, the stretched film is heated and dried. When the film is heated with hot air or the like, a means for preventing the mixing of used hot air by installing a nozzle that can exhaust used hot air (air containing solvent or wet air) is also preferably used. 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.

Further, the heating and drying means is not limited to hot air, and for example, infrared rays, heating rollers, microwaves, etc. can be used. From the viewpoint of simplicity, it is preferable to dry with hot air or the like while transporting the film with rollers arranged in a staggered manner. The drying temperature is more preferably in the range of 40 to 350 ° C. in consideration of the residual solvent amount, the stretching ratio during conveyance, and the like.

In the drying step, it is preferable to dry the film until the residual solvent amount is 0.5% by mass or less.

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

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 in the range of 10 to 150 μm, and preferably 10 to 80 μm for a liquid crystal display device, In view of recent thinning, the range of 10 to 40 μm is particularly preferable.

In order to reduce 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 it becomes a problem, since the compound having the structure represented by the general formula (3) according to the present invention is excellent in bleed-out resistance, it can be thinned.

The thickness of the film may be adjusted by adjusting the solid content concentration contained in the dope, the slit gap of the die base, the extrusion pressure from the die, the metal support speed, and the like. The width of the 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 still more preferably in the range of 0.8 to 2.5 m. The length is preferably wound in the range of 100 to 10000 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 kind and amount of additives, the draw ratio, 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 by containing a retardation increasing agent. The in-plane retardation value Ro and the thickness direction retardation value Rt were measured using an automatic birefringence meter Axoscan (Axo Scan Mueller Matrix Polarimeter: manufactured by Axometrics) in 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. The phase difference value Rt is preferably in the range of 110 to 140 nm from the viewpoint of improving the visibility such as viewing angle and contrast when the VA liquid crystal display device is provided. The optical compensation film can be adjusted within the range of the 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, the optical compensation film according to the present invention has a variation in the in-plane retardation value Ro of ± 3.0% when heat-treated at 150 ° C. for 1 hour, and the retardation in the thickness direction It is preferable that the variation of the value Rt is within a range of ± 4.0%.

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

Variation in retardation 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 due to the heat treatment of the optical compensation film within the above range, the selection of the resin according to the present invention and the addition (type and addition amount) of the retardation increasing agent are combined. Is an effective method, and can be achieved by appropriately adjusting and adjusting.

[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 produced by the melt casting method will be described.

[Melted pellet manufacturing process]
The composition containing a resin used for melt extrusion is usually preferably kneaded in advance and pelletized.

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

It is important to dry the raw material before extruding to prevent the raw material from being decomposed. In particular, since the resin may easily absorb moisture, it is preferable to dry it at 70 to 140 ° C. for 3 hours or more with a dehumidifying hot air dryer or a vacuum dryer so that the moisture content is 200 ppm or less, and further 100 ppm or less.

Additives may be fed into the extruder and fed into the extruder, or may be fed through individual feeders. In order to mix a small amount of additives such as an antioxidant uniformly, it is preferable to mix them in advance.

Mixing of the antioxidants may be performed by mixing solids, and if necessary, the antioxidant may be dissolved in a solvent, impregnated with a thermoplastic resin and mixed, or mixed by spraying. May be.

A vacuum nauter mixer or the like is preferable because drying and mixing can be performed simultaneously. Further, if the contact with air, such as the exit from the feeder unit or die, it is preferable that the atmosphere such as dehumidified air and dehumidified N ₂ gas.

The extruder is preferably processed at as low a temperature as possible so as to be able to be pelletized so that the shear force is suppressed and the resin does not 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. From the uniformity of kneading, the meshing type is preferable.

Film formation is performed using the pellets obtained as described above. It is also possible to feed the raw material powder directly to the extruder with a feeder and form a film as it is without pelletization.

[Process for extruding molten mixture from die to cooling roller]
First, the pellets produced are extruded using a single-screw or twin-screw extruder, the melting temperature Tm during extrusion is set to about 200 to 300 ° C., filtered through a leaf disk type filter or the like to remove foreign matter, and then the T-die Are coextruded into a film, solidified on a cooling roller, and cast while pressing with an elastic touch roller.

When introducing into the extruder from the supply hopper, it is preferable to prevent oxidative decomposition or the like under vacuum, reduced pressure, or inert gas atmosphere. Tm is the temperature of the die exit portion of the extruder.

∙ If foreign matter such as scratches or plasticizer aggregates adheres to the die, streaky defects may occur. Such defects are also referred to as die lines, but in order to reduce surface defects such as die lines, it is preferable to have a structure in which the resin retention portion is minimized in the piping from the extruder to the die. . It is preferable to use a die that has as few scratches as possible inside the lip.

The inner surface that comes into contact with the molten resin, such as an extruder or a die, is preferably subjected to surface treatment that makes it difficult for the molten resin to adhere to the surface by reducing the surface roughness or using a material with low surface energy. Specifically, a hard chrome plated or ceramic sprayed material is polished so that the surface roughness is 0.2 S or less.

There is no particular limitation on the cooling roller, but it is a roller having a structure in which a heat medium or a cooling medium whose temperature can be controlled flows with a highly rigid metal roller, and the size is not limited, but the film is melt extruded. The diameter of the cooling roller is usually about 100 mm to 1 m.

The surface material of the cooling roller includes carbon steel, stainless steel, aluminum, titanium and the like. Further, in order to increase the hardness of the surface or improve the releasability from the resin, it is preferable to perform a surface treatment such as hard chrome plating, nickel plating, amorphous chrome plating, or ceramic spraying.

The surface roughness of the cooling roller surface is preferably 0.1 μm or less in terms of 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 to further polish the surface that has been subjected to surface processing so as to have the above-described surface roughness.

Examples of the elastic touch roller include JP-A-03-124425, JP-A-08-224772, JP-A-07-1000096, JP-A-10-272676, WO97 / 028950, and JP-A-11-235747. As described in JP-A-2002-36332, JP-A-2005-172940 and JP-A-2005-280217, a thin-film metal sleeve-covered silicon rubber roller can be used.

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 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. The shape of the transparent electrode pattern is a touch panel module (for example, a capacitance type). The pattern is not particularly limited as long as it is a pattern that operates satisfactorily as a touch panel module. For example, JP 2011-511357 A, JP 2010-164938 A, JP 2008-310550 A, and JP 2003-511799 A. Examples include patterns described in Japanese Patent 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 Y-axis formed on the optical compensation film, and Y formed on the optical compensation film or other protective film. A transparent conductive layer patterned on the axis or the X-axis is superposed, a polarizer, a protective film or the like is laminated using an adhesive layer as appropriate, and a cover glass is provided on the outermost surface if necessary. Furthermore, the liquid crystal display device with a touch panel of the present invention can be manufactured by combining the touch panel with a VA mode type liquid crystal display device.

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

[Transparent conductive material]
The transparent conductive layer according to the present invention is not particularly limited as long as it satisfies the above resistance value, but a transparent conductive material such as ITO (indium-tin oxide) or IZO (indium-zinc oxide) is used. In particular, ITO is preferably used from the viewpoints of conductivity and transparency. The transparent conductive layer using ITO uses a wet process such as a coating method, an inkjet method, a coating method, or a dip method, or a dry process such as a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, or a CVD method. The method may be mentioned, but it is preferable to form by a vapor deposition method.

After forming the transparent conductive layer, it is preferable to perform heat treatment (also referred to as annealing) in order to reduce the resistance value of the transparent conductive layer. The heating temperature is in the range of 150 to 250 ° C., 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 base material that supports the transparent conductive layer. However, when a cycloolefin resin is used as the base material, the heating temperature is in the range of 150 to 180 ° C., and the heating time is 5 to 30. It is preferably in the range of minutes.

[Metal nanowires]
Moreover, it is also preferable to use the transparent conductive layer which consists of a metal fine wire (metal nanowire, metal mesh).

Metal nanowire refers to a conductive substance whose material is metal, the shape is needle-like or thread-like, and the diameter is nanometer size. The metal nanowire may be linear or curved. If a transparent conductive layer composed of metal nanowires is used, the metal nanowires can be shaped like a mesh, so that a good electrical conduction path can be formed even with a small amount of metal nanowires. A transparent conductive layer having a small thickness can be obtained. Furthermore, when the metal nanowire has a mesh shape, a transparent conductive film having a high light transmittance can be obtained by forming openings in the mesh space.

The ratio between the thickness d and the length L of the metal nanowire (aspect ratio: L / d) is preferably in the range of 10 to 100,000, more preferably in the range of 50 to 100,000, particularly preferably. Is in the range of 100 to 10,000. Thus, if metal nanowire with a large aspect ratio is used, metal nanowire cross | intersects favorably and high electroconductivity can be expressed with a small amount of metal nanowire. As a result, a transparent conductive film having a 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 the short diameter when the cross section of the metal nanowire is elliptical. 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. If it is such a range, a transparent conductive layer with 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. If it is such a range, a highly conductive transparent conductive layer can be obtained.

Any appropriate metal can be used as the metal constituting the metal nanowire as long as it is a highly conductive metal. As a metal which comprises the said metal nanowire, silver, gold | metal | money, copper, nickel etc. are mentioned, for example. Moreover, you may use the material which performed the plating process (for example, gold plating process) to these metals. Among these, 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 in which an applied voltage or current is applied to the precursor surface from the tip of the probe, a metal nanowire is pulled out at the probe tip, and the metal nanowire is continuously formed. Can be mentioned. In the method of reducing silver nitrate in a solution, silver nanowires can be synthesized by liquid phase reduction of a silver salt such as silver nitrate in the presence of a polyol such as ethylene glycol and polyvinylpyrrolidone.

Uniform sized silver nanowires are, for example, Xia, Y. et al. etal. , Chem. Mater. (2002), 14, 4736-4745, Xia, Y. et al. etal. , Nano letters (2003) 3 (7), 955-960, mass production is possible.

The transparent conductive layer can be formed by coating the composition for forming a transparent conductive layer containing the metal nanowire on the optical compensation film or protective film according to the present invention. More specifically, after applying the dispersion liquid (composition for forming a transparent conductive layer) in which the metal nanowires are dispersed in a solvent on the optical compensation film or the protective film, the coating 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 the 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. If it is such a range, the transparent conductive layer excellent in electroconductivity and light transmittance can be formed.

The transparent conductive layer forming composition containing the metal nanowire may further contain any appropriate additive depending on the purpose. Examples of the additive include a corrosion inhibitor that prevents corrosion of metal nanowires, and a surfactant that prevents aggregation of metal nanowires. The kind, number, and amount of additives used can be appropriately set according to the purpose. Moreover, the said composition for transparent conductive layer formation may contain arbitrary appropriate binder resins as needed, as long as the effect of this invention is acquired.

Any appropriate method can be adopted as a method for 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 method, intaglio printing method, and gravure printing method.

Any appropriate drying method (for example, natural drying, air drying, heat drying) can be adopted as a method for drying the coating layer. 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, it is preferable to perform a heat treatment (also referred to as annealing) in order to similarly reduce the resistance value of the transparent conductive layer. The heating temperature is in the range of 150 to 250 ° C., 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 base material that supports the transparent conductive layer. However, when a cycloolefin resin is used as the base material, the heating temperature is in the range of 150 to 180 ° C., and the heating time is 5 to 30. It is preferably in the range of 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. If it is such a range, the transparent conductive layer excellent in electroconductivity and light transmittance can be obtained.

When the transparent conductive layer contains 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 a 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 it is a highly conductive metal. As a metal which comprises the said metal mesh, silver, gold | metal | money, copper, nickel etc. are mentioned, for example. Moreover, you may use the material which performed the plating process (for example, gold plating process) to these metals. Among these, copper is preferable, and a migration phenomenon is unlikely to occur, which is preferable from the viewpoint of suppressing disconnection during keystroke.

The transparent conductive layer containing a metal mesh can be formed by any appropriate method. For example, the transparent conductive layer is formed by applying a photosensitive composition containing silver salt (a composition for forming a transparent conductive layer) onto the laminate, and then performing an exposure process and a development process to form a fine metal wire in a predetermined pattern. It can obtain by forming. The transparent conductive layer can also be obtained by printing a paste containing metal fine particles (a composition for forming a transparent conductive layer) in a predetermined pattern.

Details of such a transparent conductive layer and a method for forming the transparent conductive layer are described in, for example, Japanese Patent Application Laid-Open No. 2012-18634, and the description thereof is incorporated herein by reference. As another example of the transparent conductive layer composed of a metal mesh and a method for forming the transparent conductive layer, a transparent conductive layer and a method for forming the transparent conductive layer described in JP-A-2003-331654 can be given.

When the transparent conductive layer contains a metal mesh, the thickness of the transparent conductive layer is preferably in the range of 0.1 to 30 μm, 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] Adhesive layer The adhesive layer used in the present invention contains an adhesive, and the adhesive contains a thermosetting resin, an ultraviolet (UV) curable resin, or a chemically curable resin, and is optical. In addition to being transparent, those showing moderate viscoelasticity and adhesive properties are preferred.

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

The above-mentioned 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 an aqueous system such as an emulsion type, a colloidal dispersion type, or an aqueous solution type that 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, 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, particularly preferably 0.5 to 30 μm. When coating, the pressure-sensitive adhesive generally has a viscosity at 25 ° C. of 1000 to 6000 mPa / sec, preferably 2000 to 4000 mPa / sec, for example 3000 to 4000 mPa / sec. Here, the viscosity is, for example, a value read by using a B-type viscometer BH II manufactured by Tokimec (Tokyo Keiki) and rotating the rotor for 30 seconds after standing. The Young's modulus (E) of the adhesive resin after being completely cured is preferably 1 to 100 MPa, for example 5 to 20 MPa.

Acrylic adhesives include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, (meth)

acrylic

1 or 2 or more kinds of alkyl esters of 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 monomers such as (meth) acrylic acid, itaconic acid, maleic acid, maleic anhydride, 2-hydroxyethyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate that can be copolymerized with esters In combination, isocyanate crosslinker, epoxy crosslinker, aziridine crosslinker, metal chelate crosslinker It includes a crosslinking agent that is reacted.

Examples of the epoxy resin 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, “NORLANDD optical adhesion” by Edmund Optics is available. Agent NOA68 "or" Super Elastic Resin "manufactured by Sony Chemical & Information Device Corporation can be used.

In order to accelerate photocuring of the pressure-sensitive adhesive, it is preferable to further contain a photopolymerization initiator. The blending amount of the photopolymerization initiator is preferably contained in a mass ratio of photopolymerization initiator: adhesive = 20: 100 to 0.01: 100.

Specific examples of the photopolymerization initiator include alkylphenone series, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto. It is not a thing. Commercially available products may be used, and preferred examples include Irgacure 184, Irgacure 907, and Irgacure 651 manufactured by BASF Japan.

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

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

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

Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays 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.

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

Although various release sheets can be used as the release sheet, it is typically composed of a base sheet having peelability on the surface. Examples of the base sheet include films such as polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, and polycarbonate resin, films in which fillers such as fillers are blended with these films, and synthetic paper. Moreover, paper base materials, such as glassine paper, clay coat paper, and quality paper, are mentioned.

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

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

Polyvinyl alcohol polarizing films include those obtained by dyeing iodine on polyvinyl alcohol films and those obtained by dyeing dichroic dyes.

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

The film 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, a degree of saponification of 99.0 to 99 described in JP2003-248123A, JP2003-342322A, and the like. 99 mol% ethylene-modified polyvinyl alcohol is preferably used. In addition, it is preferable to prepare a polarizing plate by preparing a polarizer by the method described in JP-A 2011-1000016, Japanese Patent No. 4691205, and Japanese Patent No. 4804589, and laminating it with the base film of the present invention. .

[6.2] Protective film It is preferable that the film arrange | positioned on the opposite side to the surface which bonded the optical compensation film of the polarizer is a film which functions as a protective film of a polarizer.

As such a protective film, the above-mentioned optical compensation film may be used. KC4KR, KC8UY, KC6UY, KC4UY, KC4UE, KC8UE, KC8UY-HA, KC2UA, KC4UA, KC6UAKC, 2UAH, KC4UAH, KC6UAH, TZ, 40 FUJI TAC TD40UL, FUJI TAC R02, FUJI TAC R06, or more from FUJIFILM Corporation) is preferably used. Door can be.

Also, resin films such as polyethylene terephthalate, polyethylene naphthalate, and polycarbonate, polyarylate, polyethersulfone, polysulfone, fluorene ring-modified polycarbonate, alicyclic modified polycarbonate, acryloyl compound, and the like can be given. Among these resin substrates, films such as polyethylene terephthalate (abbreviation: PET), polybutylene terephthalate, polyethylene naphthalate (abbreviation: PEN), polycarbonate (abbreviation: PC) are flexible in terms of cost and availability. It is preferably used as a resin 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, more preferably in the range of 10 to 70 μm.

[6.3] Manufacturing method of polarizing plate The polarizing plate is manufactured by bonding the optical compensation film and the protective film according to the present invention to a polarizer using a completely saponified polyvinyl alcohol aqueous solution (water glue) or the above-mentioned adhesive. It is preferable. 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 the pretreatment step for bonding, it is preferable to perform an easy adhesion treatment on the adhesive surface of the optical compensation film or the protective film with the polarizer. Examples of the easy adhesion treatment include saponification treatment, corona treatment, and plasma treatment. Is mentioned.

[7] Other Layers The polarizing plate integrated touch panel module according to the present invention can 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 in order to improve 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 resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, an ultraviolet curable epoxy resin, or the like. Among them, it is preferable to contain an ultraviolet curable acrylate resin.

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

[8] Liquid Crystal Display Device The liquid crystal display device with a touch panel according to 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 excellent in front contrast, which is an advantage of the VA mode. can do. As the VA mode type liquid crystal, known ones can be used without limitation.

In a liquid crystal display device, normally two polarizing plates, a polarizing plate on the viewing side and a polarizing plate on the backlight side, are bonded to a liquid crystal cell via an adhesive layer, and the optical compensation film according to the present invention is used. The polarizing plate provided is disposed 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 of the present invention or other It is preferable to use an optical compensation film. As another optical compensation film, it can be preferably selected from the above-mentioned commercially available cellulose ester films. Similarly, the protective film can be preferably selected from the above-mentioned commercially available cellulose ester films, and further a polyester film, an acrylic film, a polycarbonate film, or the like can be used.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.

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

[resin]
Cycloolefin resin (COP): ARTON G7810, manufactured by JSR Corporation Cellulose acetate propionate (CAP): 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 the formula (P1)>
(Polymerization of polyimide precursor)
Using a reactor equipped with a stainless 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 A polyamic acid was produced. During the polymerization reaction, in order to prevent moisture from being mixed, the polymerization reaction was carried out by flowing nitrogen gas dehydrated by passing through silica gel at 0.05 L / min.

In the above separable flask, 223.5 g of N, N-dimethylformamide (DMF) is charged as a polymerization solvent, and 40.0 g (0.125 mol) of trifluoromethylbenzene (TFMB) is dissolved therein. To this solution, 55.5 g (0.125 mol) of 1,1,1,3,3,3-hexafluoro-2,2-di (3,4-dicarboxyphenyl) propane dianhydride (6FDA) Added and stirred to dissolve completely. 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 rotational speed of 4 rpm. In addition, the preparation density | concentration of the aromatic diamine compound and aromatic tetracarboxylic dianhydride in this reaction solution is 30 mass% with respect to all the reaction liquids.

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

(Extraction of polyimide resin)
The polyimide resin solution was placed in a funnel having a hole diameter of about 5 mm and extracted by dropping in 5 L of methanol. 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 polyimide in the solution was hung in the methanol solution so that the diameter of the dripped polyimide solution was 1 mm or less near the methanol interface while adjusting the height between the funnel and the liquid surface of the methanol so as to form a fiber. The resin may be in a fibrous form, but by continuing stirring, what once becomes a fibrous form in the solution is decomposed and divided into fibers of 5 mm or less in the solution.

Further, 5 L of methanol was added to the divided resin solid solution, and the solid content was completely extracted and taken out. 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 the bisphenol component and p-tert-butylphenol [PTBP] as the end-capping agent 1.34 parts by weight of sodium hydroxide [NaOH] as an alkali, 1.28 parts by weight of a 50% by weight aqueous solution of tri-n-butylbenzylammonium chloride [TBBAC] as a polymerization catalyst, As an antioxidant, 0.5 part by mass of sodium hydrosulfite was 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 agitated in advance, and the organic phase was added to the aqueous phase under strong agitation and allowed to undergo an interfacial polymerization reaction at 15 ° C. for 2 hours. The molar ratio was BisAF: DEDC: PTBP: TBBBAC: NaOH = 98.5: 100.0: 3.0: 0.68: 210.

Thereafter, 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 10 times with pure water, and the organic phase was added into methanol to precipitate the 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): degree of acetyl group substitution 2.85, weight average molecular weight 250,000)
Acrylic resin (Ac): Dianal BR85 (Mitsubishi Rayon Co., Ltd., weight average molecular weight: 280,000)
[Additive]
As additives, the following compounds were used as the retardation increasing compounds A1 to 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 charged into a 2 L four-necked flask equipped with a thermometer, a stirrer, and a quick cooling tube. The temperature is gradually raised with stirring until reaching 230 ° C. in a nitrogen stream. The dehydration condensation reaction was carried out while observing the degree of polymerization. After completion of the reaction, 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 according to the following procedure.

In a SUS polymerization reactor with an internal volume of 40 liters equipped with a stirrer, 24 liters of deionized water was added, and 30 g of an anionic polymer compound aqueous solution was added as a dispersion stabilizer, and 36 g of sodium sulfate was added as a dispersion stabilizer, and stirred and dissolved. I let you. In a container equipped with another stirrer, methyl methacrylate (MMA) and acryloylmorpholine (ACMO) are added so that MMA is 73.1% by mass and ACMO is 22.4% by mass (total charged moles). The monomer mixture was charged with 12 g of 2,2′-azobisisobutyronitrile as a polymerization initiator, 24 g of n-octyl mercaptan as a chain transfer agent, As a mold, 24 g of stearyl alcohol was added and stirred and dissolved. The monomer mixture in which the polymerization initiator, the chain transfer agent and the release agent thus obtained were dissolved was converted into a 40-liter SUS polymerization reactor (deionized water, dispersed) equipped with the stirrer described above. Stabilizer and dispersion stabilizing aid are housed) and stirred at 175 rpm for 15 minutes while purging with nitrogen. Thereafter, the polymerization was started by heating to 80 ° C., and after completion of the polymerization exothermic peak, 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 additive solution)
Fine particles (Aerosil R812: manufactured by Nippon Aerosil Co., Ltd., primary average particle diameter: 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, dispersed with Manton Gorin Went.

Furthermore, dispersion was performed with an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution.

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, cycloolefin-based resin (COP) was added to the pressurized dissolution tank with stirring at a flow rate of 200 kg / min. Next, 5 minutes after the start of solvent addition, the fine particle additive solution was added, and this was heated to 80 ° C. and completely dissolved while stirring. The heating temperature was raised from room temperature at 5 ° C./min, dissolved in 30 minutes, and then lowered at 3 ° C./min.

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

<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 Particulate additive solution 3 parts by mass Next, using an endless belt casting apparatus, the dope was uniformly cast on a stainless steel belt support at a temperature of 33 ° C. and a width of 1500 mm. did. The temperature of the stainless steel belt was controlled at 30 ° C.

On the stainless steel belt support, the solvent was evaporated until the amount of residual solvent in the cast (cast) film reached 75%, and then peeled off from the stainless steel belt support with a peeling tension of 130 N / m.

The peeled cycloolefin 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, drying was completed while the drying zone was conveyed by a number of rollers. The drying temperature was 130 ° C. and the transport tension was 100 N / m. After drying, it was slit into a width of 1.5 m, a knurling process having a width of 10 mm and a height of 10 μm was applied to both ends of the film, wound up into a roll, and an optical compensation film 101 having a dry film thickness of 45 μm was obtained.

<Preparation of optical compensation film 102>
In the production of the optical compensation film 101, an optical compensation film 102 was produced in the same manner except that the following main dope 2 was prepared and used, and the film thickness was changed to 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 solution 3 parts by mass The draw ratio was adjusted so that the optical compensation film had the retardation value shown in Table 1.

<Preparation of base film A103-108>
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>
In the production of the optical compensation film 101, an optical compensation film 109 was produced in the same manner 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 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 draw ratio was adjusted to the retardation value shown in Table 1, and the optical compensation film 110 was similarly changed except that the film thickness was changed. Was made.

<Preparation of optical compensation film 111>
In the production of the optical compensation film 101, an optical compensation film 110 was produced in the same manner 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 solution 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 draw 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>
In the production of the optical compensation film 101, an optical compensation film 113 was produced in the same manner 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 3 parts by mass <Preparation of optical compensation film 114>
In the production of the optical compensation film 113, 2 parts by mass of additive A2 was added, the draw 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 changed to 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 solution 3 parts by mass The draw ratio was adjusted to be 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 changed to 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 solution 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 optical compensation film 101 was stretched by 5% in the longitudinal direction and the width direction and the film thickness was changed to 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 the 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 to have a film thickness of 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 solution 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 changed to 45 μm.

<Composition of main dope 9>
Acrylic resin (Ac): Dianal BR85 (manufactured by Mitsubishi Rayon Co., Ltd.)
100 parts by mass Dichloromethane 200 parts by mass Ethanol 10 parts by mass Fine particle additive solution 3 parts by mass <Preparation of transparent conductive layer>
The silver nanowires used were Y. Sun, B.M. Gates, B.B. Mayers, & Y. Xia, “Crystalline silver nanobe by soft solution processing”, Nano letters, (2002), 2 (2) 165-168, followed by a method using a polyol in the presence of polyvinyl pyrrolidone (PVP). It is a silver nanowire synthesized by dissolving silver sulfate and reducing it. That is, in the present invention, nanowires synthesized by the modified polyol method described in Cambrios Technologies Corporation US Provisional Application No. 60 / 815,627 were used.

Silver nanowire water containing 0.5 wt% / v of silver nanowires having a minor axis diameter of about 70 to 80 nm and an aspect ratio of 100 or more synthesized by the above method as metal nanowires forming a transparent conductive layer The dispersion composition (ClearOmTM, 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 coater, so that the film thickness becomes 1.5 μm. After coating and drying as described above, 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 treatment) was performed at 150 ° C. for 30 minutes in order to reduce the resistance value.

<Preparation of polarizing plate and polarizing plate integrated touch panel module: 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 produced polarizer is sandwiched between one side of the produced optical compensation films 101 to 119 provided with a transparent conductive layer and Konica Minolta Tack KC4UA (manufactured by Konica Minolta Co., Ltd.) as a protective film. Then, the polarizing plate integrated touch panel modules 101 to 119 were manufactured by bonding with each other through the following ultraviolet curable adhesive solution.

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

3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 45 parts by mass Epolide GT-301 (Daicel's alicyclic epoxy resin)
40 parts by mass 1,4-butanediol diglycidyl ether 15 parts by mass Triarylsulfonium hexafluorophosphate 2.3 parts by mass 9,10-dibutoxyanthracene 0.1 parts by mass 1,4-diethoxynaphthalene 2.0 parts by mass In the preparation of the polarizing plate, the surface of the optical compensation film and the protective film was subjected to corona discharge treatment at a corona output intensity of 2.0 kW and a line speed of 18 m / min, and the above prepared UV curable adhesive was applied to the corona discharge treatment surface. 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 using an ultraviolet irradiation device with a belt conveyor (the lamp uses a D bulb manufactured by Fusion UV Systems) so that the integrated light amount becomes 750 mJ / cm ² , The UV curable adhesive layer was cured.

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

In addition, the polarizing plate integrated touch panel module including the optical compensation films 117 to 119 produced above is carefully peeled off from the commercially available IPS mode liquid crystal display device with a touch panel, and the polarizing plate is placed on the IPS mode liquid crystal cell. The optical compensation film side was bonded to prepare liquid crystal display devices 117 to 119 with a touch panel.

A polarizing plate having a configuration of an optical compensation film (Konica Minolta Tack KC8UCR3) / polarizer / protective film (Konica Minolta KC4UA, both manufactured by Konica Minolta Co., Ltd.) It bonded through the adhesive layer so that the compensation film side might become a 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 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 ( Calculated according to 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] Phase Compensation Variation of Optical Compensation Film The optical compensation film sample was left in an oven at 150 ° C. for 1 hour for heat treatment, and the variation in retardation value before and after that was determined by the following equation.

Variation in retardation 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 using a differential scanning calorimeter DSC220 manufactured by Seiko Instruments Inc. according to JIS K-7121. About 10 mg of the optical compensation film sample is set, and the temperature is raised from room temperature to 250 ° C. at 20 ° C./min for 10 minutes under the condition of a nitrogen flow rate of 50 ml / min (first scan), then 20 ° C./min. The temperature was lowered to 30 ° C. at a speed of 10 ° C. and held for 10 minutes (second scan), further raised to 20 ° C./250° C. (third scan), a DSC curve was created, and the obtained third scan 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 front contrast was measured by a front contrast measuring device (EZ-contrast) manufactured by ELDIM, and the amount of light during white display and black display was measured to obtain the ratio.

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

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

In addition, the optical compensation films 115 and 116 having an optical compensation film having a glass transition temperature Tg of less than 155 ° C. have large phase difference fluctuations, inferior front contrast, and lower contrast than IPS mode type liquid crystal display devices. It was.

Example 2
<Production of touch panel module>
An ITO film having a thickness of 20 nm was formed as a transparent conductive layer on one side of the optical compensation films 104, 110, 112 and 114 according to the present invention produced in Example 1 by sputtering, and etching was performed in the X direction. A first electrode pattern was formed.

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

<Preparation of polarizing plate and polarizing plate integrated touch panel module: see FIG. 6>
The polarizer produced in Example 1 was sandwiched between the side of the optical compensation films 201 to 204 provided with the transparent conductive layer and Konica Minolta Tack KC4UA (manufactured by Konica Minolta Co., Ltd.) as a protective film. The polarizing plate integrated touch panel modules 201 to 204 were manufactured by bonding with each other through the ultraviolet curable adhesive solution 1 of FIG.

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

On the opposite side of the liquid crystal cell, a polarizing plate having a configuration of an optical compensation film (Konica Minolta Tack KC8UCR3) / polarizer / protective film (Konica Minolta KC4UA, both manufactured by Konica Minolta Co., Ltd.) is used for optical compensation. It bonded through the adhesive layer so that the film side might become a liquid crystal cell side.

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

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

DESCRIPTION OF SYMBOLS 1 Liquid crystal cell 2 Polarizer T1 Protective film T2 Optical compensation film P1 Polarizing plate (viewing side)
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

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 the VA mode liquid crystal cell,
A polarizing plate integrated touch panel module having the transparent conductive layer,
From the VA mode type liquid crystal cell toward the viewer side, it has an optical compensation film having a transparent conductive layer on at least one surface, a polarizer and a protective film in this order, and
A liquid crystal display device with a touch panel, wherein the optical compensation film has a glass transition temperature Tg 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 resin, a polyimide resin, and a polyarylate resin.
The fluctuation of the retardation value Ro in the in-plane direction when the optical compensation film is heat-treated at 150 ° C. for 1 hour is within ± 3.0%, and the fluctuation of the retardation value Rt in the thickness direction is The liquid crystal display device with a touch panel according to claim 1 or 2, wherein the content is within a range of ± 4.0%.
The liquid crystal display device with a touch panel according to any one of claims 1 to 3, wherein a thickness of the optical compensation film is in a range of 10 to 40 µm.
The said optical compensation film contains the nitrogen-containing heterocyclic compound which has a structure represented by following General formula (3) as a phase difference raising agent, Any one of Claim 1- Claim 4 characterized by the above-mentioned. A liquid crystal display device with a touch panel according to 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 represents a hydrogen atom, an alkyl group, or an acyl group. Represents a sulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group, q represents 1 or 2, and n and m each represents an integer of 1 to 3.)
It is a manufacturing method of the liquid crystal display with a touch panel which manufactures the liquid crystal display with a touch panel as described in any one of Claims 1-5,
A step of heat-treating at least 150 ° C. after forming the transparent conductive layer on at least one surface of the optical compensation film;
Bonding a polarizer so as to be sandwiched between an optical compensation film and a protective film on which the transparent conductive layer is formed, to produce a polarizing plate integrated touch panel module;
A step of bonding the optical compensation film side of the polarizing plate integrated touch panel module to the VA mode liquid crystal cell, and a method of manufacturing a liquid crystal display device with a touch panel.