JP6669083B2 - Polarizing plate integrated touch sensor and method of manufacturing the same - Google Patents

Description

  The present invention relates to a polarizing plate integrated touch sensor and a method for manufacturing the same. More specifically, even under high-temperature, high-humidity, and other environmental fluctuations, the deformation of the polarizing plate in the touch sensor is suppressed, and a reduction in the detection sensitivity and malfunction of the transparent conductive layer due to the deformation is suppressed. The present invention relates to an integrated touch sensor and a method for manufacturing the same.

  There are various types of touch panels that detect contact with a finger or the like, and a capacitance type is widely used as a device that requires multipoint detection, such as a smartphone. The capacitance type touch panel has, for example, a transparent conductive layer provided with a matrix-like electrode pattern on a detection surface, and detects a change in capacitance at a position touched by a finger or the like. .

  In recent years, in addition to smartphones, touch panels have been mounted on tablets, notebook computers, and the like, and accordingly, there has been a demand for larger, lighter, and thinner touch panels. In order to satisfy these demands, touch panels having a touch sensor called an in-cell type or a middle cell type, in which a touch sensor and a polarizing plate or the like are integrally formed, have come to be used.

  The polarizing plate has a zero retardation film or a 波長 wavelength film (also referred to as λ / 4 retardation film) adjacent to the polarizer, and is transparent on the zero retardation film or the １ ／ wavelength film. A touch panel on which a conductive layer and a glass plate are arranged has been proposed (for example, see Patent Document 1). In this touch panel, when polarized sunglasses are worn, a quarter-wave film is substantially used so that blackout does not occur depending on the viewing angle.

  However, the polarizer expands and contracts due to environmental fluctuations (high temperature, high humidity), the adjacent quarter-wave film is slightly deformed, and the capacitance of the film changes. This had adverse effects such as a decrease in detection sensitivity and malfunction.

Japanese Patent No. 5268005

  The present invention has been made in view of the above-described problems and circumstances, and a problem to be solved is that, even under environmental changes such as high temperature and high humidity, deformation of the polarizing plate in the touch sensor is suppressed, and the deformation is accompanied by the deformation. An object of the present invention is to provide a polarizing plate-integrated touch sensor and a method of manufacturing the same, which suppress a decrease in sensor detection sensitivity and a malfunction of the transparent conductive layer.

  The present inventor, in order to solve the above problems, in the process of examining the cause of the above problems, by a polarizer integrated touch sensor to arrange a specific substrate film between the polarizer and the transparent conductive layer, high temperature, Even under environmental changes such as high humidity, the deformation of the polarizing plate in the touch sensor is suppressed, and the reduction in sensor detection sensitivity and malfunction of the transparent conductive layer due to the deformation are suppressed. It has been found that a production method can be obtained.

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

1. At least a transparent conductive layer, a base film A, a polarizer, a base film B, and a polarizing plate integrated type touch sensor having an adhesive layer in this order,
The base film A contains a cycloolefin polymer as a main component and an additive different from the cycloolefin polymer,
An environment in which the concentration of the additive in the base film A is 1.1 times or more different between the polarizer side and the surface of the transparent conductive layer side, and the base film A is at a temperature of 23 ° C. and a relative humidity of 55%. A touch panel integrated with a polarizing plate, wherein an in-plane retardation value Ro measured at a light wavelength of 550 nm is in a range of 50 to 200 nm.

  2. The concentration of the additive in the base film A is different in a range of 1.1 to 1.6 times on the surface on the polarizer side and on the surface on the transparent conductive layer side, according to claim 1, characterized in that: Polarizer integrated touch sensor.

  3. (1) The additive according to (1) or (2), wherein the water absorption of the additive obtained from the following formula (1) in accordance with JIS K 7209 (Method A) is in the range of 0.05 to 3% by mass. 13. The polarizing plate-integrated touch sensor according to the item.

Formula (1) Water absorption = {(w ₂ −w ₁ ) / w ₁ } × 100 (%)
(Wherein, w ₁ is the dry mass (mg) of the additive before immersion in water, and w ₂ is the mass of the additive after immersion in water at 23.0 ± 1.0 ° C. for 24 ± 1 hour. (Mg).)
4. The polarizing plate integrated touch sensor according to any one of claims 1 to 3, wherein the additive has a molecular weight in a range of 50 to 5,000.

  5. The polarizing plate according to any one of claims 1 to 4, wherein the additive is at least one selected from the group consisting of a compound having a pyrrole ring and a compound having an indole ring. Body type touch sensor.

  6. 6. The method for manufacturing a touch sensor with integrated polarizing plate according to any one of items 1 to 5, wherein the base film A is manufactured by a solution casting method. Manufacturing method of touch sensor with integrated polarizing plate.

  By the above-described means of the present invention, even under environmental changes such as high temperature and high humidity, the deformation of the polarizing plate in the touch sensor is suppressed, and the decrease in sensor detection sensitivity and malfunction of the transparent conductive layer due to the deformation are suppressed. And a polarizing plate-integrated touch sensor and a method for manufacturing the same.

  Although the mechanism of manifesting or acting the effects of the present invention has not been clarified, it is speculated as follows.

  The touch panel integrated with a polarizing plate of the present invention has at least a transparent conductive layer, a base film A, a polarizer, a base film B, and an adhesive layer in this order. It is presumed that the expansion and contraction of the substrate and the deformation of the base film A changed the capacitance of the base film A constituting the polarizing plate, which lowered the detection sensitivity of the upper electrode sensor. You.

  Therefore, a base film having high resistance to expansion and contraction of the polarizer is required. To some extent, simply using a thick base film will solve the problem, but on the other hand, there is a strong demand for thinner displays.

  Therefore, in the present invention, with respect to the shrinkage of the polarizer, in the thickness direction of the base film, by providing a distribution of additives other than the resin as the main component, a film having a difference in shrinkage on the front and back surfaces of the film. It has been found that, by manufacturing, the contraction force of the polarizer can be canceled out and the deformation of the entire polarizing plate can be suppressed.

  In particular, in the melt casting film forming method, the additive is liable to precipitate and bleed during the film forming, and it is difficult to unevenly distribute the additive on the film surface side. The additive tends to be unevenly distributed on the Air surface and the Belt surface. As a result, the surface of the film having a large amount of the additive has a structure in which the additive is dense, and the other surface has a structure in which the additive is sparse. For this reason, it is presumed that a difference in water content occurs due to environmental changes such as wet heat, and a difference in shrinkage occurs in the film. In particular, by using a polar additive such as a compound having a pyrrole ring or a compound having an indole ring, the molecular weight according to the present invention is in the range of 50 to 5000, and the additive is used for solution casting film formation. It is presumed that the solvent having a polarity used in the method moves to the film surface as the solvent evaporates from the film surface, and the solvent tends to be unevenly distributed.

  As a result, it is presumed that the deformation of the polarizing plate is suppressed, and a decrease in sensor detection sensitivity and malfunction of the transparent conductive layer due to the deformation of the polarizing plate described above can be suppressed.

Schematic diagram showing the configuration of a polarizing plate integrated touch sensor of the present invention. Schematic diagram showing the configuration of a display device with a touch panel including the polarizing plate integrated touch sensor of the present invention. Schematic diagram for explaining the shrinkage ratio in oblique stretching of the base film Schematic diagram showing an example of a rail pattern of an oblique stretching machine applicable to the method for producing a base film of the present invention. Schematic diagram showing an example of a manufacturing method according to an embodiment of the present invention (an example in which the film is unwound from a long continuous film roll and then obliquely stretched). Schematic diagram showing another example of the manufacturing method according to the embodiment of the present invention (an example in which the film is unwound from a long continuous film roll and then obliquely stretched). Schematic diagram showing another example of the manufacturing method according to the embodiment of the present invention (an example in which the film is unwound from a long continuous film roll and then obliquely stretched). Schematic diagram showing an example of a manufacturing method according to an embodiment of the present invention (an example in which a long continuous film is continuously obliquely stretched without being wound up). Schematic diagram showing another example of a manufacturing method according to an embodiment of the present invention (an example in which a long continuous film is continuously obliquely stretched without being wound up).

  The polarizing plate integrated touch sensor of the present invention is a polarizing plate integrated touch sensor having at least a transparent conductive layer, a base film A, a polarizer, a base film B, and an adhesive layer in this order, Film A contains, as main components, a cycloolefin polymer and an additive different from the cycloolefin polymer, and the concentration of the additive in the base film A is such that the polarizer side and the transparent conductive layer In the environment of the substrate film A at a temperature of 23 ° C. and a relative humidity of 55%, the in-plane retardation value Ro measured at an optical wavelength of 550 nm is 50 to 200 nm. It is characterized by being within the range. This feature is a technical feature common to the inventions according to claims 1 to 6.

  As an embodiment of the present invention, from the viewpoint of exhibiting the effects of the present invention, the concentration of the additive in the base film A may be 1.1 to 1.0 on the polarizer side and the transparent conductive layer side. It is preferable that the difference be within a range of 6 times, since a difference in shrinkage can be exhibited between the front and back surfaces of the film.

  In addition, when the water absorption of the additive is in the range of 0.05 to 3% by mass, when the additive is unevenly distributed on the surface side of the base film A, the environment such as high temperature, high humidity, etc. This is a preferred embodiment from the viewpoint that a stable contraction difference under fluctuation can be exhibited.

  Further, the additive has a molecular weight in the range of 50 to 5,000, in particular, a compound having a pyrrole ring, and at least one selected from a group of compounds having an indole ring, the base film A in the base film A This is a preferred embodiment in that the additive is likely to be unevenly distributed due to the concentration distribution thereof and to exhibit a difference in shrinkage between the front and back surfaces of the film.

  In the manufacturing method of the polarizing plate-integrated touch sensor of the present invention, manufacturing the base film A by a solution casting film forming method controls the concentration distribution of the additive in the base film A. In addition, it is a suitable production method.

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

<< Outline of Polarizer Integrated Touch Sensor of the Present Invention >>
The polarizing plate integrated touch sensor of the present invention is a polarizing plate integrated touch sensor having at least a transparent conductive layer, a base film A, a polarizer, a base film B, and an adhesive layer in this order, Film A contains, as main components, a cycloolefin polymer and an additive different from the cycloolefin polymer, and the concentration of the additive in the base film A is such that the polarizer side and the transparent conductive layer The in-plane retardation value Ro measured at a light wavelength of 550 nm in an environment of a temperature of 23 ° C. and a relative humidity of 55% in the environment of the base film A at a temperature of 23 ° C. and a relative humidity of 55% is in the range of 50 to 200 nm. It is characterized by being within.

  The feature of the base film A is that the concentration of the additive contained therein is 1.1 times or more different between the surface of the polarizer side and the surface of the transparent conductive layer side. The difference is expressed. Whether the concentration of the additive on the polarizer side or the transparent conductive layer side is increased is determined by the direction of the curl due to the shrinkage of the polarizer, and the direction of the curl due to the shrinkage of the polarizer. What is necessary is just to adjust the uneven distribution of the additive concentration and the conditions for forming the transparent conductive layer on the front and back surfaces of the base film A so that the reverse curl is developed.

  In the present invention, the concentration of the additive on the polarizer side and the surface of the transparent conductive layer side means an average value of the concentration of the additive in a portion of 1 μm from the surface of the film. Here, “concentration” is a percentage of the mass of the additive in the total mass of the resin and the additive constituting the film, and the unit is mass%.

  In other words, it means that the average value of the concentration of the additive on at least one surface of the base film A according to the present invention is higher than the average value of the concentration of the internal additive, It is preferable that the concentration distribution of the additive has a gradient (also referred to as a concentration gradient in the present application). That is, it is preferable that the additive is not uniformly contained in the film, but that the additive is unevenly distributed in the film to create a portion where the concentration of the additive is high and a portion where the concentration of the additive is low.

  The substrate film A according to the present invention can be manufactured without complicated adjustment in manufacturing by selecting an additive and employing a solution casting film forming method described later.

  The above-mentioned “having a concentration gradient” refers to a form in which a concentration gradient of the additive exists along the thickness direction of the film. For example, as the simplest example, when the base film A according to the present invention is cut so as to be bisected in a plane perpendicular to its thickness direction (in a plane parallel to the plane direction of the film), Preferred embodiments are those in which the amount of additive present in the fragment containing the surface is greater than the amount of additive present in the other fragment. When this is generalized, when the base film A according to the present invention is cut so as to be equally divided by k in a plane perpendicular to its thickness direction (in a plane parallel to the plane direction of the film), each fragment is obtained. Also preferred is an embodiment wherein the amount of additive present at the surface gradually decreases from the surface-containing fragment to the other fragment. In the embodiment, the case where k = 2 is separately described above, but k is preferably 3 or more, more preferably 5 or more, further preferably 10 or more, and particularly preferably 20 or more. is there. The concentration gradient may be either a continuous gradient or a discontinuous gradient.

  The distribution measurement of the additive in the base film A can be quantified by the following Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) analysis method.

<Measurement method>
The TOF-SIMS analysis method here refers to a mass that can measure the chemical information of atoms and molecules on a solid sample with a sensitivity of one molecular layer or less, and can observe the distribution of specific atoms and molecules with a spatial resolution of 100 nm or less. It is an analytical method. TOF-SIMS analysis is a type of secondary ion mass spectrometry (SIMS) in which a primary sample is irradiated with a primary ion beam and ions (secondary ions) emitted from the outermost surface of the sample are detected. By doing so, an analysis is performed. Since a time-of-flight mass spectrometer (TOF-MS) is used as the mass spectrometer, it is called TOF-SIMS. According to the TOF-SIMS analysis method, a non-destructive sample measurement can be performed by irradiating a sample with an ion beam in a pulsed manner. It has been widely applied.

  As an apparatus, for example, TFS-2100 manufactured by Physical Electronics is used, and the measurement is performed at a temperature of 23 ° C. and a humidity of 55% RH.

  The concentration of a surface (for example, surface (A)) where the amount of the additive detected is large using the TOF-SIMS analysis method (for example, surface (A)) is dA, and the concentration of the surface where the amount of the additive is small (for example, surface (B)) is Is dB, since the concentration of the additive of the base film A according to the present invention needs to be 1.1 times or more different between the surface (A) and the surface (B), the ratio dA / dB value is It can be expressed as 1.1 or more.

  In the present invention, the dA / dB value is preferably in the range of 1.1 to 1.6, more preferably in the range of 1.1 to 1.5, and still more preferably 1. It is in the range of 2-1.4. When the dA / dB value is 1.1 or more, the effect of the difference in shrinkage between the front and back surfaces of the film of the present invention is exhibited. When the dA / dB value is 1.6 or less, the film physical properties of the front and back surfaces (for example, , Expansion ratio, etc.), curl during processing can be suppressed, and it is easy to handle.

<Structure of the polarizing plate integrated touch sensor of the present invention>
The polarizing plate integrated touch sensor of the present invention is a polarizing plate integrated touch sensor having at least a transparent conductive layer, a base film A, a polarizer, a base film B, and an adhesive layer in this order, Film A contains, as main components, a cycloolefin polymer and an additive different from the cycloolefin polymer, and the concentration of the additive in the base film A is such that the polarizer side and the transparent conductive layer In the environment of the substrate film A at a temperature of 23 ° C. and a relative humidity of 55%, the in-plane retardation value Ro measured at a light wavelength of 550 nm is in a range of 50 to 200 nm in an environment at a temperature of 23 ° C. and a relative humidity of 55%. It is characterized by being within.

  The structure of the polarizing plate integrated touch sensor of the present invention will be described with reference to the drawings.

  FIG. 1A is a schematic view illustrating a configuration of a polarizing plate integrated touch sensor of the present invention.

  The polarizing plate integrated touch sensor 1 of the present invention has at least a transparent conductive layer 2, a base film A4, a polarizer 6, a base film B7, and an adhesive layer 5 in this order. In the figure, the adhesive layer 5 is also disposed between the base film A4, the polarizer 6, and the base film B7, but can be omitted. The above is the minimum structure, and a functional layer (intermediate layer, antistatic layer, smoothing layer, ultraviolet absorbing layer, anti-curl layer, etc.) may be provided between each member. Among them, it is preferable to have a hard coat layer 3 described below between the transparent conductive layer 2 and the base film A.

  The total thickness of the polarizing plate-integrated touch sensor of the present invention is not particularly limited, but is preferably in the range of 7 to 80 μm, more preferably 10 from the viewpoint of prevention of bending, good resistance value, handleability, and the like. ６０60 μm.

  FIG. 1B is a schematic diagram illustrating a configuration of a touch panel member and a display device including the polarizing plate integrated touch sensor of the present invention.

  The display device 10 provided with the touch sensor 1 with a polarizing plate integrated type of the present invention includes a glass plate 11, a transparent conductive layer 2, an intermediate layer 12, a hard coat layer 3, a base film A4, a polarizer 6, and a base film from the top. It is preferable to have a structure in which B7 (hereinafter referred to as the touch panel member 9) and the liquid crystal display device 13 are laminated via the adhesive layer 5. In addition, a functional layer (an antistatic layer, a smoothing layer, an ultraviolet absorbing layer, an anti-curl layer, etc.) may be appropriately provided between the members.

  Hereinafter, each component constituting the polarizing plate integrated touch sensor of the present invention will be described in detail.

[1] Base film A
The base film A according to the present invention contains a cycloolefin polymer as a main component and an additive different from the cycloolefin polymer, and the concentration of the additive in the base film A is the polarizer. The in-plane retardation value Ro measured at a light wavelength of 550 nm under an environment of a temperature of 23 ° C. and a relative humidity of 55% of the base film A at a temperature of 23 ° C. and a relative humidity of 55% is different from that of the base film A by 1.1 times or more. , 50 to 200 nm.

  The base film A according to the present invention is characterized by containing a cycloolefin polymer as a main component and an additive different from the cycloolefin polymer.

  The cycloolefin polymer is excellent in transparency, mechanical strength, thermal stability, moisture shielding property, and the like, and therefore has high dimensional stability against environmental fluctuations of the polarizing plate integrated touch sensor.

  The thickness of the substrate film according to the present invention is preferably a thin film in order to cope with thinning and weight reduction of the touch sensor, preferably in the range of 5 to 40 μm, more preferably 10 to 30 μm. Within range. If the film thickness of the base film is 5 μm or more, workability can be ensured, and if it is 40 μm or less, disconnection of the transparent conductive layer hardly occurs.

[1-1] Cycloolefin polymer As the cycloolefin polymer, polymers of various cycloolefin monomers can be used, and a cycloolefin monomer having a norbornene skeleton is homopolymerized or copolymerized. It is preferable to use the obtained polymer.

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

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

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

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

(In the general formula (A-1), R ^{1 to} R ⁴ each independently represent a hydrogen atom or a halogen atom, or have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom. Represents a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms or a polar group; p represents a natural number of 0 to 2)
Examples of the polar group include a carboxy group, a hydroxy group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, and a cyano group.These polar groups are bonded via a linking group such as a methylene group. You may. In addition, a hydrocarbon group to which a divalent organic group having polarity such as a carbonyl group, an ether group, a silyl ether group, a thioether group, and an imino group is bonded as a linking group is also exemplified as the polar group. Among these, a carboxy group, a hydroxy group, an alkoxycarbonyl group or an allyloxycarbonyl group is preferable, and an alkoxycarbonyl group or an allyloxycarbonyl group is particularly preferable from the viewpoint of securing the solubility during solution film formation.

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

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

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

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

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

The cycloolefin polymer is a polymer obtained by homopolymerizing or copolymerizing a cycloolefin monomer having a structure represented by the general formulas (A-1) and (A-2) having a norbornene skeleton. There are, for example, the following.
(1) Ring-opening polymer of cycloolefin monomer (2) Ring-opening copolymer of cycloolefin monomer and copolymerizable monomer (3) Ring-opening polymer of the above (1) or (2) ( Hydrogenated (co) polymer of (co) polymer (4) The ring-opened (co) polymer of (1) or (2) is cyclized by Friedel-Crafts reaction and then hydrogenated (co) polymer (5) Saturated polymer of cycloolefin monomer and unsaturated double bond-containing compound (6) Addition (co) polymer of cycloolefin monomer and hydrogenated (co) polymer thereof (7) In the alternating copolymer of a cycloolefin-based monomer and methacrylate or acrylate, (1) to (3) are preferable, and (3) is more preferable.

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

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

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

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

(In the general formula (B-1), X is a group represented by —CH ＝ CH— or a group represented by the formula: —CH ₂ CH ₂ —. R ^{1 to} R ⁴ are each independently Represents a hydrogen atom or a halogen atom, or may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or Represents a polar group, and p represents a natural number of 0 to 2.)

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

[1-2] Additive The additive according to the present invention is an additive different from the cycloolefin polymer, and the concentration of the additive in the base film A is the same as that of the transparent conductive material. It is characterized by a difference of 1.1 times or more on the surface on the layer side.

  In addition, when the water absorption of the additive obtained from the following formula (1) in accordance with JIS K 7209 (Method A) is in the range of 0.05 to 3% by mass, the uneven distribution of the additive is reduced. It is preferable for accelerating. More preferably, it is in the range of 0.3 to 3% by mass.

Formula (1) Water absorption = {(w ₂ −w ₁ ) / w ₁ } × 100 (%)
(Wherein, w ₁ is the dry mass (mg) of the additive before immersion in water, and w ₂ is the mass of the additive after immersion in water at 23.0 ± 1.0 ° C. for 24 ± 1 hour. (Mg).)
The additive preferably has a molecular weight in the range of 50 to 5,000, and the additive is at least one selected from the group consisting of a compound having a pyrrole ring and a compound having an indole ring, It is preferable from the viewpoint of promoting uneven distribution as an additive.

  This is because a compound having a pyrrole ring or a compound having an indole ring is a polar compound. It is presumed that, together with the volatilization of ethanol during drying, the compound easily moves to the surface side of the web to promote uneven distribution. In particular, when the weight average molecular weight is within the above range, it is easy to move.

  Also, if the number of pyrrole rings and indole rings per molecule is 3 or more, the number of polar groups per molecule increases, and it becomes more susceptible to the uneven distribution of the solvent in the solution casting. It is easier and more preferable.

  The number of compounds having a pyrrole ring as a partial structure in the molecule is very large and is not particularly limited. Examples of the compound having a pyrrole ring in the present invention include 1H-pyrrole and its isomers (2H-pyrrole, 3H-pyrrole). -Pyrrole) and pyrrole derivatives having a substituent introduced into pyrrole, for example, N-butyl-2,5-dimethylpyrrole, N-phenyl-2,5-dimethylpyrrole, N-phenyl-3-formyl-2 , 5-dimethylpyrrole, N-phenyl-3,4-diformyl-2,5-dimethylpyrrole and the like, or a mixture thereof.

Further, as a compound having a plurality of pyrrole rings, bilirubin having an open chain structure having four pyrrole rings, or a ring structure in which four pyrrole rings are bonded to each other with one carbon atom interposed therebetween And corrinoids, phorbins, porphyrinogens, porphyrins, chlorins, florins, porhydimetenes, porhometins, cholines, bacteriochlorins, isobacteriochlorins and the like. Among them, 1H-pyrrole and its isomer, vinyl bin and porphyrin (21H, 23H-porphine) can be preferably used.
In addition, many derivatives and metal complexes of porphyrin are known and can be appropriately selected and used.

  Examples of the compound having an indole ring include indole alone, and indole derivatives such as 2-methyl-1H-indole, 2-methyl-1-methyl-1H-indole, 2-methyl-1-isopropyl-1H-indole, -Methyl-1-phenyl-1H-indole, 2-ethyl-1H-indole, 2-ethyl-1-methyl-1H-indole, 2-ethyl-1-phenyl-1H-indole, 2-phenyl-1H-indole 2-phenyl-1-methyl-1H-indole, 2-phenyl-1-phenyl-1H-indole, 3-methyl-1H-indole, 3-methyl-1-methyl-1H-indole, 3-methyl-1 -Isopropyl-1H-indole, 3-methyl-1-phenyl-1H-indole, 3-ethyl-1H- And 3-ethyl-1-methyl-1H-indole, 3-ethyl-1-phenyl-1H-indole, 3-phenyl-1H-indole, 3-phenyl-1-methyl-1H-indole, 3-phenyl- 1-phenyl-1H-indole, 3- (4-fluorophenyl) -1-isopropyl-1H-indole, 2-amino-3- (indolyl) propionic acid (tryptophan), indole-3-acetic acid, 3- [3 Methyl-(4-fluorophenyl) -1-isopropyl-1H-indol-2-yl] acrylate, 3- [3- (4-fluorophenyl) -1-isopropyl-1H-indol-2-yl] acrylic acid Ethyl, 3- [3- (4-fluorophenyl) -1-isopropyl-1H-indol-2-yl] acrylic acid n- Ropyr, isopropyl 3- [3- (4-fluorophenyl) -1-isopropyl-1H-indol-2-yl] acrylate, 3- [3- (4-fluorophenyl) -1-isopropyl-1H-indole- N-butyl 2-yl] acrylate, isobutyl 3- [3- (4-fluorophenyl) -1-isopropyl-1H-indol-2-yl] acrylate, 3- [3- (4-fluorophenyl)- Tert-butyl 1-isopropyl-1H-indol-2-yl] acrylate, phenyl 3- [3- (4-fluorophenyl) -1-isopropyl-1H-indol-2-yl] acrylate, 3- [3 -(4-Fluorophenyl) -1-isopropyl-1H-indol-2-yl] benzyl acrylate, 3- [3- (4-fluorophenyl 1) -Isopropyl-1H-indol-2-yl] acrylonitrile, methyl 3- (1-methyl-2-phenyl-1H-indol-3-yl) acrylate, 3- (1-methyl-2-phenyl) Ethyl -1H-indol-3-yl) acrylate, n-propyl 3- (1-methyl-2-phenyl-1H-indol-3-yl) acrylate, 3- (1-methyl-2-phenyl-1H) -Indol-3-yl) acrylate, n-butyl 3- (1-methyl-2-phenyl-1H-indol-3-yl) acrylate, 3- (1-methyl-2-phenyl-1H-indole -3-yl) isobutyl acrylate, tert-butyl 3- (1-methyl-2-phenyl-1H-indol-3-yl) acrylate, 3- (1-methyl-2) Phenyl-1H-indol-3-yl) acrylate, phenyl 3- (1-methyl-2-phenyl-1H-indol-3-yl) acrylate, 3- (1-methyl-2-phenyl-1H-) Indole-3-yl) acrylonitrile, 4- [3- (4-fluorophenyl) -1-isopropyl-1H-indol-2-yl] -3-buten-2-one, 4- (1-methyl-2- Phenyl-1H-indol-3-yl) -3-buten-2-one, 3- [3- (4-fluorophenyl) -1-isopropyl-1H-indol-2-yl] -1-phenylpropenone, 3- (1-methyl-2-phenyl-1H-indol-3-yl) -1-phenylpropenone and the like. Among them, it is preferable to use indole, 2-amino-3- (indolyl) propionic acid (tryptophan) and the like.

[1-3] Other additives In the base film A according to the present invention, in addition to the additives, a plasticizer, an antioxidant, a matting agent, a light stabilizer, an optical anisotropy controlling agent, an antistatic agent, It may contain a release agent and the like, and if it can be unevenly distributed on the film surface, it can be used as an additive according to the present invention. The details of the main additives are described below.

[Plasticizer]
A plasticizer is an additive that generally has the effect of improving fragility, reducing melt viscosity, or imparting flexibility by being added to a polymer. In the case of the resin of the preferred embodiment, the resin is added in order to improve the moisture permeability with respect to the fluctuation of the humidity of the external environment, and thus has a function as a moisture permeability preventing agent.

  In the present invention, it is preferable to use a polyester resin as the plasticizer. The polyester resin is obtained by polymerizing a dicarboxylic acid and a diol, and 70% or more of the dicarboxylic acid structural units (the structural units derived from dicarboxylic acid) are aromatic. 70% or more of the diol structural unit (the structural unit derived from a diol) is derived from an aliphatic diol.

  The ratio of the structural unit derived from the aromatic dicarboxylic acid is 70% or more, preferably 80% or more, and more preferably 90% or more.

  The proportion of the structural unit derived from the aliphatic diol is at least 70%, preferably at least 80%, more preferably at least 90%. Two or more polyester resins may be used in combination.

  Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, naphthalenedicarboxylic acid such as 2,7-naphthalenedicarboxylic acid, and 4,4′-biphenyldicarboxylic acid , 3,4'-biphenyldicarboxylic acid and the like and ester-forming derivatives thereof.

  As the polyester resin, an aliphatic dicarboxylic acid such as adipic acid, azelaic acid, and sebacic acid and a monocarboxylic acid such as benzoic acid, propionic acid, and butyric acid can be used as long as the object of the present invention is not impaired.

  Examples of the aliphatic diol include ethylene glycol, 1,3-propylene diol, 1,4-butane diol, 1,4-cyclohexane dimethanol, 1,6-hexane diol, and ester-forming derivatives thereof.

  As the polyester resin, monoalcohols such as butyl alcohol, hexyl alcohol, and octyl alcohol, and polyhydric alcohols such as trimethylolpropane, glycerin, and pentaerythritol can be used without impairing the object of the present invention.

  For the production of the polyester resin, a known method such as direct esterification or transesterification can be applied. Examples of the polycondensation catalyst used in the production of the polyester resin include known antimony compounds such as antimony trioxide and antimony pentoxide, germanium compounds such as germanium oxide, titanium compounds such as titanium acetate, and aluminum compounds such as aluminum chloride. Can, but is not limited to.

  Preferred polyester resins include polyethylene terephthalate resin, polyethylene terephthalate-isophthalate copolymer resin, polyethylene-1,4-cyclohexane dimethylene-terephthalate copolymer resin, polyethylene-2,6-naphthalenedicarboxylate resin, polyethylene-2, 6-naphthalenedicarboxylate-terephthalate copolymer resin, polyethylene-terephthalate-4,4'-biphenyldicarboxylate resin, poly-1,3-propylene-terephthalate resin, polybutylene terephthalate resin, polybutylene-2,6-naphthalene And dicarboxylate resins.

  More preferred polyester resins include polyethylene terephthalate resin, polyethylene terephthalate-isophthalate copolymer resin, polyethylene-1,4-cyclohexane dimethylene-terephthalate copolymer resin, polybutylene terephthalate resin, and polyethylene-2,6-naphthalene dicarboxylate. Resins.

The intrinsic viscosity of the polyester resin (value measured at 25 ° C. in a phenol / 1,1,2,2-tetrachloroethane = 60/40 mass ratio mixed solvent) is in the range of 0.7 to 2.0 cm ³ / g. Is more preferable, and more preferably in the range of 0.8 to 1.5 cm < ³ > / g. When the intrinsic viscosity is 0.7 cm ³ / g or more, the molecular weight of the polyester resin is sufficiently high, so that a molded product of the polyester resin composition obtained by using the polyester resin has the necessary mechanical properties as a molded product. At the same time, the transparency becomes good. When the intrinsic viscosity is 2.0 cm ³ / g or less, the moldability is good. As other plasticizers, compounds described in general formulas (PEI) and (PEII) in paragraphs 0056 to 0080 of JP-A-2013-97279 may be used.

[UV absorber]
The base film of the present invention may contain an ultraviolet absorber.

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

  When the base film of the present invention is used as a protective film for a polarizing plate in addition to a retardation film, the ultraviolet absorber absorbs ultraviolet light having a wavelength of 370 nm or less from the viewpoint of preventing deterioration of a polarizer or an organic EL element. From the viewpoint of excellent performance and display properties of the organic EL element, the organic EL element preferably has a characteristic of absorbing less visible light having a wavelength of 400 nm or more.

  The amount of the ultraviolet absorber added is preferably in the range of 0.1 to 5.0% by mass, more preferably in the range of 0.5 to 5.0% by mass, based on the polymer composition. preferable.

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

  As commercial products, “Tinuvin (TINUVIN) 109”, “Tinuvin (TINUVIN) 171”, “Tinuvin (TINUVIN) 326”, and “Tinuvin (TINUVIN) 328” (all trade names, manufactured by BASF Japan) are preferable. Can be used.

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

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

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

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

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

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

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

  In the case of a λ / 4 retardation film having a multilayer structure by a co-casting method, it is preferable to contain the added amount of fine particles on the surface. Fine particles of silicon dioxide are commercially available under the trade names of Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (all manufactured by Nippon Aerosil Co., Ltd.) and used. Can be.

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

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

  Among these, Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large effect of lowering the friction coefficient while keeping the haze of the base film low.

  In the substrate 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.

[1-4] Production Method of Base Film A The base film A according to the present invention is preferably a film produced by a solution casting method.

  The concentration of the additive in the base film A according to the present invention is characterized in that the surface of the polarizer side and the surface of the transparent conductive layer side differ by 1.1 times or more.

  This is because, in a solution casting film forming method, when a dope is cast on a casting support (a metal belt-like support or a drum-like support), the solvent contained in the dope is dried during the drying process. The additive that is not compatible with the resin as the main component moves to the surface side of the film as the solvent dries. In particular, when the dope is spread on the casting support during film formation, the solvent does not dry and volatilize from the casting support surface side (Belt surface). Therefore, the additive is first added to the air interface side of the web (Air). Surface) with solvent.

  Then, in the state of raw dry, the whole is not yet dried, the film is peeled off from the casting support, the Belt surface in contact with the casting support is released to the air interface, and the solvent is dried from both surfaces. Volatilized.

  As a result, when the film is cast, drying of the solvent on the Air surface occurs preferentially, so that a large amount of the additive is present on the Air surface side, and thereafter, when the film is peeled from the casting support, the Belt surface is removed. Since the solvent can be dried and volatilized on the side as well, the additive similarly moves to the Belt side together with the solvent, causing uneven distribution and concentration gradient on both sides of the base film A. Therefore, the concentration of the additive increases in the order of the inside of the film <the Belt surface side <the Air surface side, and a sparse portion and a dense portion of the additive are formed, which may affect the shrinkage of the film. it can.

  Therefore, a proper time is required for transporting and drying the film on the casting support after casting the dope, and the peeling time from casting to peeling is in the range of about 30 seconds to 5 minutes. Is preferably within the range of 30 seconds to 2 minutes, more preferably for stabilizing the uneven distribution of the additive.

  In addition, since the movement of the additive due to the volatilization of the solvent occurs, the drying temperature during casting film formation is also an influential factor, and varies depending on the type of the solvent used, but is in the range of 10 to 50 ° C. Is preferred. More preferably. It is in the range of 20-40 ° C.

  Further, the temperature of the casting support is usually appropriately determined within the range of 0 to 100 ° C. However, in the present invention, the temperature of the casting support also affects the volatilization of the solvent. Is preferably adjusted in the range of 5 to 60 ° C, more preferably in the range of 10 to 55 ° C, and particularly preferably in the range of 20 to 40 ° C.

  The method of controlling the temperature of the casting support is not particularly limited, and includes a method of blowing hot or cold air, and a method of bringing hot water into contact with the back side of the casting support. It is preferable to use hot water since the time required for the temperature of the casting support to become constant is short because heat is transferred more efficiently.

  In the solution casting method according to the present invention, a step of preparing a dope by dissolving a resin and an additive in a solvent, a step of casting the dope on a belt-shaped or drum-shaped casting support, It is carried out by a step of drying as a web, a step of peeling off from a casting support, a step of stretching or maintaining a width, a step of further drying, and a step of winding up a finished film.

  Also, JP-A-2000-301555, JP-A-2000-301558, JP-A-7-032391, JP-A-3-193316, JP-A-5-086212, and JP-A-62-037131 JP-A-2-276607, JP-A-55-014201, JP-A-2-111511, and JP-A-2-208650. Applicable to the invention.

  As for the concentration of the cycloolefin polymer in the dope, a higher concentration is preferable because the drying load after casting on the casting support can be reduced, but if the concentration of the cycloolefin polymer is too high, the load at the time of filtration is increased. And the accuracy of filtration decreases. The concentration satisfying these requirements is preferably in the range of 10 to 35% by mass, and more preferably in the range of 15 to 25% by mass. The viscosity of the dope before casting (casting step) is preferably in the range of 500 to 50,000, more preferably in the range of 1000 to 12,000.

  The casting support in the casting step is preferably made of metal whose surface is mirror-finished, and as the casting support, a stainless steel belt or a drum whose surface is plated with a casting is preferably used. The width of the cast can be in the range of 1-4 m.

  In order for the base film A to exhibit good flatness, the amount of residual solvent when the web is peeled from the casting support is preferably in the range of 10 to 150% by mass, and more preferably 20 to 40% by mass. Or in the range of 60 to 130% by mass, particularly preferably in the range of 20 to 30% by mass or in the range of 70 to 120% by mass.

  The residual solvent amount is defined by the following equation.

Residual solvent amount (% by mass) = {(M−N) / N} × 100
In addition, M is the mass of the sample collected at any time during or after production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour. In the step of drying the film using the cycloolefin polymer, the web is preferably peeled off from the casting support, and further dried to reduce the residual solvent amount to 1% by mass or less, more preferably 0.1% by mass or less. %, Particularly preferably within a range of 0 to 0.01% by mass.

  In the present invention, the temperature at the peeling position on the casting support is preferably in the range of −50 to 40 ° C., more preferably in the range of 10 to 40 ° C., and in the range of 15 to 30 ° C. Most preferably.

  An organic solvent useful for forming a dope when the substrate film A according to the present invention is produced by a solution casting method is used without limitation as long as it can simultaneously dissolve a cycloolefin polymer and other additives. be able to.

  For example, as a chlorine-based organic solvent, methylene chloride, as a non-chlorine-based organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolan, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- Examples include 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, and the like. Preferably, methylene chloride, methyl acetate, ethyl acetate and acetone can be preferably used.

  The dope preferably contains, in addition to the above organic solvent, a linear or branched aliphatic alcohol having 1 to 4 carbon atoms in the range of 1 to 40% by mass. When the ratio of the alcohol in the dope is high, the web gels and the peeling from the casting support becomes easy.

  Particularly, a dope composition in which a cycloolefin polymer is dissolved in a solvent containing methylene chloride and a linear or branched aliphatic alcohol having 1 to 4 carbon atoms in a range of at least 15 to 45% by mass in total. It is preferably an object.

  Examples of the linear or branched aliphatic alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol. Of these, ethanol is preferred because of the stability of the dope, the relatively low boiling point and the good drying property.

  After the film is peeled, the film is dried in a film drying step. In the film drying step, the web is generally transported by a roll drying method (a method in which the web is alternately passed through a number of rolls arranged vertically and dried) or a tenter method. A drying method is adopted.

  The film is preferably stretched during or after drying in order to improve flatness or impart a retardation.

  As a method for stretching the base film A, a known roll stretching machine or tenter can be preferably used. The stretching temperature is usually preferably in the temperature range of Tg to Tg of the resin constituting the film + 60 ° C.

  The stretching method is not particularly limited. For example, a method in which a circumferential speed difference is applied to a plurality of rolls, and a longitudinal stretching is performed using the circumferential speed difference between the rolls, and both ends of the web are fixed with clips or pins, and the intervals between the clips and pins are widened in the traveling direction. And a method in which the film is spread in the horizontal direction and stretched in the horizontal direction, or a method in which the film is simultaneously spread vertically and horizontally and stretched in both the vertical and horizontal directions. Of course, these methods may be used in combination. That is, the film may be stretched in the transverse direction, in the longitudinal direction, or in both directions with respect to the film forming direction. In the case of stretching in both directions, simultaneous stretching or sequential stretching may be performed. You may. In the case of the so-called tenter method, it is preferable to drive the clip portion by a linear drive method, since smooth stretching can be performed and the risk of breakage can be reduced.

  In the present invention, in particular, the stretching is performed in the transport direction using the peripheral speed difference of the film transport rolls, or both ends of the web are perpendicularly intersected with the transport direction (also referred to as the width direction or the TD direction) by clips or the like. It is preferable to use a tenter method for holding, and further to form a λ / 4 retardation film using a tenter capable of independently controlling the holding length (distance from the start to the end of holding) of the web by the left and right holding means. preferable.

  The substrate film A according to the present invention has an in-plane retardation value Ro measured at an optical wavelength of 550 nm in an environment of a temperature of 23 ° C. and a relative humidity of 55% within a range of 50 to 200 nm, and has a λ / 4 position. It is a phase difference film. The in-plane retardation value Ro is more preferably in the range of 100 to 160 nm.

  The in-plane retardation value Ro was measured by using an automatic birefringence meter Axoscan (Axo Scan Mueller Matrix Polarimeter: manufactured by Axometrics) at a light wavelength of 590 nm under an environment of 23 ° C. and 55% RH at a light wavelength of 590 nm. The refractive index is measured, and the refractive index can be calculated from the obtained refractive indexes nx, ny, and nz by the following equation (i).

Formula _{(i): Ro = (n} x -n y) × d (nm)
In [Equation (i), 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. d represents the thickness (nm) of the film. ]
In order to control the in-plane retardation value in the above range, it is preferable that the film is stretched in the direction of 45 ° with respect to the film transport direction in the stretching step. When the orientation angle θ with respect to the film longitudinal direction is 35 to 55 °, a roll-shaped polarizing film (polarizer) whose slow axis has a transmission axis in a direction parallel to the longitudinal direction and a roll-to-roll by aligning the longitudinal direction. By laminating, a roll-shaped long circularly polarizing plate can be easily produced, so that there is little cut loss of the film, which is advantageous in production.

[Diagonal stretching step]
As described above, the base film A of the present invention has an in-plane retardation value Ro measured at a light wavelength of 550 nm in the range of 50 to 200 nm, and particularly in the range of 100 to 160 nm. It is preferable in terms of exhibiting the function as above, and its characteristics can be imparted by stretching the formed base film A in an oblique direction.

  The stretching method applicable to the present invention is not particularly limited. For example, a method in which a plurality of rollers are provided with a peripheral speed difference, and between them, a method of stretching in a longitudinal direction using a peripheral speed difference between a plurality of rollers. A method in which both ends of the web are fixed with clips or pins, and the interval between the clips or pins is expanded in the direction of travel and stretched in the vertical direction. Similarly, a method in which the web is stretched in the horizontal direction and stretched in the horizontal direction. The method of stretching in both directions can be employed alone or in combination.

  FIG. 2 is a schematic diagram illustrating the shrinkage ratio in oblique stretching.

In Figure 2, when the oblique stretching the base film A in the direction of the reference numerals 22, substrate film A shrinks to M ₂ by being obliquely bent. That is, when the gripper holding the base film A advances without bending at the bending angle θ, it should advance by the length M ₁ ′ in a predetermined time. However, in reality, it bends at the bending angle θ and advances by M ₁ (where M ₁ = M ₁ ′). At this time, the direction enters the film (the direction perpendicular to the stretching direction (TD direction) 21), since the gripper is proceeding by M _2, the base film A has a length M _{3 (although,} M ₃ = M ₁ −M ₂ ).

At this time, the shrinkage (%)
Shrinkage (%) = (M ₁ −M ₂ ) / M ₁ × 100. When the bending angle is θ, M ₂ = M ₁ × sin (π−θ), and the contraction rate is
Shrinkage (%) = (1−sin (π−θ)) × 100.

  In FIG. 2, reference numeral 21 indicates a stretching direction (TD direction), reference numeral 23 indicates a transport direction (MD direction), and reference numeral 24 indicates a slow axis.

[Stretching by oblique stretching device]
Next, the oblique stretching method of stretching in the 45 ° direction will be further described.

  In the method for producing the base film A according to the present invention, it is preferable to use an oblique stretching device as a method for giving the base film A an orientation in an oblique direction.

  As the oblique stretching device applicable to the present invention, by changing the rail pattern in various ways, the orientation angle of the film can be freely set, and the orientation axis of the film can be uniformly oriented with high precision in the lateral direction across the film width direction. It is preferable to use a film stretching apparatus capable of controlling the film thickness and retardation with high precision.

  FIG. 3 is a schematic diagram showing an example of a rail pattern of an oblique stretching device applicable to the production of the base film A of the present invention. FIG. 3 shown here is an example, and the stretching apparatus applicable in the present invention is not limited to this.

  In general, in the oblique stretching apparatus, as shown in FIG. 3, the unwinding direction D2 of the long stretched film is different from the winding direction D2 of the stretched stretched film, and the unwinding angle θi is formed. ing. The dispensing angle θi can be arbitrarily set to a desired angle within a range of more than 0 ° and less than 90 °.

  In the present specification, the term “long” refers to a film having a length at least about 5 times or more, preferably 10 times or more the width of the film.

  At the entrance of the oblique stretching device (position A in the figure), both ends of the long film web are gripped by left and right grippers (tenters), and are run with the grippers. The left and right grippers are left and right at the entrance of the oblique stretching device (position A in the drawing), and the right and left grippers Ci and Co, which are opposed to each other in a direction substantially perpendicular to the film traveling direction (extending direction D1), are left and right. The film runs on the asymmetric rails Ri and Ro, and releases the film gripped by the tenter at the position at the end of the stretching (the position B in the drawing).

  At this time, as the left and right gripping tools facing each other at the oblique stretching device entrance (position A in the drawing) travel on the left and right asymmetric rails Ri and Ro, the gripping tools Ci traveling on the Ri side become the Ro side. Is a positional relationship that advances with respect to the gripper Co that travels.

  That is, at the entrance of the oblique stretching device (starting position of gripping of the film by the gripper) A, the grippers Ci and Co, which have been opposed in a direction substantially perpendicular to the film feeding direction D1, are positioned at the end of the stretching of the film. In the state B, the straight line connecting the grippers Ci and Co is inclined by an angle θL with respect to a direction substantially perpendicular to the film winding direction D2.

  According to the above-mentioned method, the raw film is obliquely stretched. Here, “substantially perpendicular” means that the angle is in a range of 90 ± 1 °.

  More specifically, in the method for producing the base film A according to the present invention, it is preferable to perform the oblique stretching using the above-described obliquely stretchable tenter.

  This stretching apparatus is an apparatus for heating a raw film to an arbitrary temperature at which stretching can be performed, and for stretching the film obliquely.

  This stretching apparatus includes a heating zone, a pair of right and left rails on which grippers for transporting a film travel, and a number of grippers traveling on the rails.

  Both ends of the film sequentially supplied to the inlet of the stretching device are gripped by a gripper, the film is guided into the heating zone, and the film is released from the gripper at the outlet of the stretching device. The film released from the gripper is wound on a core. Each of the pair of rails has an endless continuous track, and the gripper, which has released the gripping of the film at the outlet of the stretching device, travels outside and is sequentially returned to the inlet.

  In addition, the rail pattern of the stretching device has an asymmetric shape on the left and right, depending on the orientation angle given to the elongated stretched film to be manufactured, the stretching ratio, etc., the rail pattern can be adjusted manually or automatically. It has become.

  In the oblique stretching device used in the present invention, it is preferable that the position of each rail section and rail connection section can be freely set and the rail pattern can be arbitrarily changed (circle section in FIG. 3 shows an example of the connection section). ).

  In the present invention, the gripping device of the stretching device travels at a constant speed while maintaining a constant interval with the gripping devices before and after. The traveling speed of the gripper can be appropriately selected, but is usually in the range of 1 to 100 m / min.

  The difference between the traveling speeds of the pair of right and left grippers is usually 1% or less, preferably 0.5% or less, more preferably 0.1% or less of the traveling speed. This is because if there is a difference in the traveling speed between the left and right of the film at the exit of the stretching process, wrinkles and shifts occur at the exit of the stretching process, so that the speed difference between the left and right grippers is required to be substantially the same speed. That's why.

  In a general stretching device, etc., there is a speed unevenness that occurs on the order of seconds or less depending on the cycle of the teeth of the sprocket driving the chain, the frequency of the drive motor, and the like, and often causes unevenness of several percent. It does not correspond to the speed difference described in the invention.

  In a stretching apparatus applicable to the present invention, a rail that regulates the trajectory of a gripping tool often requires a large bending rate, particularly at a position where film conveyance is oblique. In order to avoid interference between the gripping tools due to sharp bending or local stress concentration, it is preferable that the locus of the gripping tool draws a curve at the bent portion.

  In the present invention, the raw long film is sequentially gripped by the left and right grippers at the entrance of the oblique stretching device (position A in the drawing), and travels with the travel of the grippers. At the entrance of the oblique stretching device (position A in the figure), the left and right gripping tools facing in a direction substantially perpendicular to the film advancing direction (unwinding direction D1) run on rails that are asymmetrical in the left and right directions, and are preheated. , A heating zone having a stretching zone and a heat setting zone.

  The preheating zone refers to a section at the entrance of the heating zone, in which the travel is performed with the gap between the grippers gripping both ends kept constant.

  The stretching zone refers to a section in which the gap between the grippers holding both ends starts to open and reaches a predetermined interval. In the stretching zone, the above-described oblique stretching is performed, but if necessary, the film may be stretched in the longitudinal direction or the transverse direction before and after the oblique stretching. In the case of oblique stretching, shrinkage is accompanied by bending in the MD direction (fast axis direction) which is a direction perpendicular to the slow axis during bending.

  The heat setting zone refers to a section in which the gripping tools at both ends run parallel to each other during a period in which the distance between the gripping tools after the stretching zone becomes constant again. After passing through the heat setting zone, it may pass through a section (cooling zone) in which the temperature in the zone is set to be equal to or lower than the glass transition temperature Tg of the thermoplastic resin constituting the film. At this time, in consideration of shrinkage of the film due to cooling, a rail pattern may be used in which the gap between the grippers opposed to each other is narrowed in advance.

  The temperature of each zone is the glass transition temperature Tg of the thermoplastic resin, the temperature of the preheating zone is in the range of Tg to (Tg + 30) ° C, and the temperature of the stretching zone is in the range of Tg to (Tg + 30) ° C. The temperature of the zone is preferably set in the range of (Tg−30) ° C. to Tg.

  In addition, in order to control thickness unevenness in the width direction, a temperature difference may be provided in the width direction in the stretching zone. In order to make the temperature difference in the width direction in the stretching zone, there are known methods such as adjusting the opening degree of the nozzle for sending hot air into the constant temperature chamber so as to make a difference in the width direction, and controlling the heating by arranging the heaters in the width direction. Can be used.

  The lengths of the preheating zone, the stretching zone, the shrinking zone, and the cooling zone can be appropriately selected, and the length of the preheating zone is usually in the range of 100 to 150% with respect to the length of the stretching zone. Is usually in the range of 50 to 100%.

  The stretching ratio (W / Wo) in the stretching step is preferably in the range of 1.3 to 3.0, and more preferably in the range of 1.5 to 2.8. When the stretching ratio is within this range, thickness unevenness in the width direction can be reduced.

  In the stretching zone of the oblique stretching device, if the stretching temperature is made different in the width direction, the thickness unevenness in the width direction can be further improved. Wo represents the width of the film before stretching, and W represents the width of the film after stretching.

  As the oblique stretching method applicable in the present invention, in addition to the method shown in FIG. 3, the stretching methods shown in FIGS. 4A to 4C and FIGS.

  FIG. 3 is a schematic view showing an example of a production method applicable to the present invention (an example in which the film is unwound from a long film material roller and then obliquely stretched), and the long film material once wound up in a roll shape. Is shown and a pattern of oblique stretching is shown.

  FIG. 4 is a schematic view showing an example of another manufacturing method applicable to the present invention (an example of continuous oblique stretching without winding a long film raw material), and winding a long film raw material. 2 shows a pattern in which an oblique stretching step is continuously performed without any step.

  4 and 5, reference numeral 25 denotes an oblique stretching device, reference numeral 26 denotes a film feeding device, reference numeral 27 denotes a transport direction changing device, reference numeral 28 denotes a winding device, and reference numeral 29 denotes a film forming device. In each of the drawings, the same reference numerals may be omitted.

  The film feeding device 26 is slidable and pivotable or slidable so that the film can be sent out at a predetermined angle with respect to the oblique stretching device entrance. Is preferably sent out.

  4A to 4C show patterns in which the arrangements of the film feeding device 26 and the transport direction changing device 27 are respectively changed.

  FIGS. 5A and 5B show a pattern in which a film formed by the film forming apparatus 29 is directly fed to the stretching apparatus 25.

  With such a configuration of the film feeding device 26 and the transport direction changing device 27, it is possible to further reduce the width of the entire manufacturing apparatus, and to finely control the film feeding position and angle. It is possible to obtain a long stretched film having small variations in thickness, optical value and optical value. Further, by making the film feeding device 26 and the transport direction changing device 27 movable, it is possible to effectively prevent the right and left clips from biting into the film.

  By arranging the winding device 28 so that the film can be pulled at a predetermined angle with respect to the outlet of the oblique stretching device, it is possible to finely control the position and angle at which the film is taken, and the film thickness and optical values vary. It is possible to obtain a long stretched film having a small value. Therefore, wrinkles of the film can be effectively prevented, and the film can be wound up in a long length because the winding property of the film is improved.

  In the present invention, the drawing tension T (N / m) of the stretched film is preferably adjusted within the range of 100 N / m <T <300 N / m, preferably 150 N / m <T <250 N / m. .

  In consideration of the productivity of the long circularly polarizing plate, the base film A (λ / 4 retardation film) according to the present invention has an orientation angle of 45 ± 2 ° with respect to the transport direction, which indicates a roll with the polarizing film. Bonding with a to-roll is possible, which is preferable.

[2] Hard coat layer The hard coat layer, which is a preferred embodiment of the present invention, is preferably formed on at least one surface of the base film A. Preferably, by providing a hard coat layer on the transparent conductive side of the substrate film A, it is possible to suppress the occurrence of scratches on the surface layer due to transportation before processing the transparent conductive layer, and it is possible to improve the adhesion with the transparent conductive layer Becomes Further, it is preferable that the surface of the base film A on which the hard coat layer is provided is selected depending on the direction in which the base film A is contracted to cope with the contraction of the polarizer.

  Examples of the curable resin used for forming the hard coat layer used in the present invention include a thermosetting resin and an active energy ray-curable resin. It can be preferably used.

[2-1] Thermosetting resin The thermosetting resin is not particularly limited. Specifically, epoxy resin, cyanate ester resin, phenol resin, bismaleimide-triazine resin, polyimide resin, acrylic resin, vinylbenzyl resin And various thermosetting resins.

  The epoxy resin may be any resin having an average of two or more epoxy groups per molecule. Specifically, bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol type epoxy resin Resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, aromatic glycidylamine type epoxy resin (specifically, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, Diglycidyl toluidine, diglycidyl aniline, etc.), alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A novolak epoxy resin Epoxy resin having a butadiene structure, phenol aralkyl type epoxy resin, epoxy resin having a dicyclopentadiene structure, diglycidyl ether of bisphenol, diglycidyl ether of naphthalene diol, glycidyl ether of phenol, and diglycidyl of alcohol Examples include etherified products, and alkyl-substituted, halogenated, and hydrogenated products of these epoxy resins. These may be used alone or in combination of two or more.

[2-2] Active energy ray-curable resin The active energy ray-curable resin that can be suitably used in the present invention refers to a resin that cures through a cross-linking reaction or the like by irradiation with an active ray such as an ultraviolet ray or an electron beam. . As the active energy ray-curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used. The active energy ray-curable resin is cured by irradiation with an actinic ray such as an ultraviolet ray or an electron beam. A resin layer is formed. Typical examples of the active energy ray-curable resin include an ultraviolet ray-curable resin and an electron beam-curable resin, but an ultraviolet ray-curable resin that is cured by irradiation with ultraviolet rays is preferable.

[Ultraviolet curable resin]
Hereinafter, an ultraviolet curable resin suitable for forming the hard coat layer used in the present invention will be described.

  Examples of the UV-curable resin include a UV-curable urethane acrylate resin, a UV-curable polyester acrylate resin, a UV-curable epoxy acrylate resin, a UV-curable polyol acrylate resin, and a UV-curable epoxy resin. be able to.

  UV-curable acrylic urethane-based resins are generally obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and further, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, or the like. It can be easily obtained by reacting an acrylate monomer having a hydroxy group. For example, a resin described in JP-A-59-151110 can be used.

  Examples of the UV-curable polyester acrylate resin include those easily formed by reacting a polyester polyol with a 2-hydroxyethyl acrylate or 2-hydroxy acrylate monomer, and JP-A-59-151112. Resins described in the gazette can be used.

  Specific examples of the ultraviolet-curable epoxy acrylate-based resin include those formed by making epoxy acrylate an oligomer, adding a reactive diluent and a photoreaction initiator thereto, and reacting the oligomer. No. 105738 can be used.

  In the present invention, it is preferable to use an ultraviolet-curable polyol acrylate-based resin, and examples of such a compound include a polyfunctional acrylate resin. Here, the polyfunctional acrylate resin is a compound having two or more acryloyloxy groups or methacryloyloxy groups in the molecule.

  Examples of the monomer of the polyfunctional acrylate resin include, for example, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, tetramethylolmethane Triacrylate tetramethylol methane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Dipenta Risritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, Tetramethylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerin trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetra Methacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate. These compounds are used alone or in combination of two or more. Further, oligomers such as dimers and trimers of the above monomers may be used.

Commercially available UV-curable resins applicable in the present invention include, for example, ADEKA OPTOMER KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B ( As described above, manufactured by ADEKA Corporation; Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D -102, NS-101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (all manufactured by Koei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHCX-9 (K-3 ), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR90 (Manufactured by Dainichiseika Color & Chemicals Mfg. (Ltd.)); KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201,
UVECRYL29202 (all manufactured by Daicel UCB); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120, RC-5122, RC-5152, Aurex No. RC-5171, RC-5180, RC-5181 (all manufactured by DIC Corporation); 340 Clear (all made by China Paint Co., Ltd.); Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (all made by Sanyo Chemical Industries, Ltd.) SP-1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.); RCC-15C (manufactured by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by: Toagosei Co., Ltd.) can be appropriately selected and used.

[Photopolymerization initiator]
Further, in order to promote the curing of the ultraviolet-curable resin, it is preferable that the photopolymerization initiator is contained in the range of 2 to 30% by mass based on the ultraviolet-curable resin. As the photopolymerization initiator, a group of double salts of an onium salt that releases a Lewis acid that initiates cationic polymerization by light irradiation is particularly preferable.

  As such an onium salt, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator. In particular, aromatic onium salts described in JP-A Nos. 50-151996 and 50-158680 are useful. Group VIA aromatic onium salts described in JP-A-50-151997, JP-A-52-30899, JP-A-59-55420, JP-A-55-125105, and JP-A-56-8428. Oxosulfonium salts described in JP-A-56-149402, JP-A-57-192429 and the like, aromatic diazonium salts described in JP-B-49-17040 and the like, described in US Pat. No. 4,139,655 and the like. And the like are preferred. In addition, examples thereof include an aluminum complex and a photodecomposable silicon compound-based polymerization initiator. The cationic polymerization initiator can be used in combination with a photosensitizer such as benzophenone, benzoin isopropyl ether, and thioxanthone.

[Various additives]
Further, the hard coat layer may contain fine particles of an inorganic compound or an organic compound in order to adjust the scratch resistance, the slipperiness and the refractive index.

  Examples of the inorganic fine particles used in the hard coat layer include silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, indium tin oxide (ITO), zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, and carbonate. Mention may be made of calcium, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. In particular, silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used.

  The organic particles include polymethacrylate methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicone resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, and melamine resin. An ultraviolet curable resin composition such as powder, polyolefin-based resin powder, polyester-based resin powder, polyamide-based resin powder, polyimide-based resin powder, or polyfluoroethylene-based resin powder can be added. Particularly preferably, cross-linked polystyrene particles (for example, SX-130H, SX-200H, SX-350H, manufactured by Soken Chemical), polymethyl methacrylate-based particles (for example, MX150, MX300, manufactured by Soken Chemical), and fluorine-containing acrylic resin fine particles are exemplified. . Examples of the fluorine-containing acrylic resin fine particles include commercially available products such as Nippon Paint FS-701. Examples of the acrylic particles include S-4000 manufactured by Nippon Paint, and examples of the acryl-styrene particles include S-1200 and MG-251 manufactured by Nippon Paint.

  In order to enhance the heat resistance of the hard coat layer, an antioxidant that does not suppress the photocuring reaction may be selected and used, or a known ultraviolet absorber may be contained.

  The coating liquid for forming a hard coat layer used for forming the hard coat layer may contain a solvent, or may contain and dilute as necessary, if necessary. Examples of the organic solvent contained in the coating solution for forming the hard coat layer include hydrocarbons (eg, toluene, xylene, etc.), alcohols (eg, methanol, ethanol, isopropanol, butanol, cyclohexanol, etc.), ketones (E.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (e.g., methyl acetate, ethyl acetate, methyl lactate, etc.), glycol ethers, and other organic solvents, or a mixture thereof for use. it can. 5% by mass or more, more preferably 5 to 80%, of propylene glycol monoalkyl ether (1 to 4 carbon atoms in the alkyl group) or propylene glycol monoalkyl ether acetate (1 to 4 carbon atoms in the alkyl group). It is preferable to use the above-mentioned organic solvent contained in the range of mass%.

  As a method for producing the hard coat layer, using a coating liquid for forming a hard coat layer, for example, a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and a known wet coating method such as an ink jet method are used. be able to.

  The coating amount of the coating liquid for forming a hard coat layer is appropriately in the range of 0.1 to 40 μm as a wet layer thickness, and preferably 0.5 to 30 μm. Further, the layer thickness is in the range of 0.1 to 30 μm, preferably in the range of 1 to 10 μm.

  As a method of curing the hard coat layer, after forming the hard coat layer, the hard coat layer is irradiated with an active energy ray, preferably ultraviolet ray, to finally cure the hard coat layer.

The light source used to cure the ultraviolet-curable resin by a photocuring reaction to form a cured hard coat layer can be used without limitation as long as it is a light source that generates ultraviolet light. For example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, and the like can be used. Irradiation conditions vary depending on each lamp, but the irradiation amount of the active energy ray is preferably in the range of 5 to 350 mJ / cm ² , and particularly preferably in the range of 250 to 300 mJ / cm ² .

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

  Further, the transparent conductive layer according to the present invention may be any material as long as it satisfies the above-mentioned resistance value, but preferably contains a copper mesh, and copper is less likely to cause a migration phenomenon than other metals and suppresses disconnection during keying. It is preferable from a viewpoint.

[3-1] Metal nanowire The metal nanowire is a conductive material having a material of metal, a needle-like or thread-like shape, and a diameter of nanometer size. The metal nanowire may be straight or curved. If a transparent conductive layer composed of metal nanowires is used, the metal nanowires form a mesh, so that even a small amount of metal nanowires can form a good electric conduction path, and the electric resistance can be improved. Can be obtained. Furthermore, since the metal nanowires have a mesh shape, an opening is formed in a gap between the meshes, so that a transparent conductive film having high light transmittance can be obtained.

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

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

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

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

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

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

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

  The transparent conductive layer can be formed by applying a composition for forming a transparent conductive layer containing the metal nanowires on the transparent substrate. More specifically, after applying the dispersion liquid (the composition for forming a transparent conductive layer) in which the metal nanowires are dispersed in a solvent to the transparent substrate, the applied layer is dried to form a transparent conductive layer. Can be formed.

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

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

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

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

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

  When the transparent conductive layer contains metal nanowires, the thickness of the transparent conductive layer is preferably in the range of 0.01 to 10 μm, more preferably in the range of 0.05 to 3 μm, and particularly preferably. Is in the range of 0.1 to 1 μm. Within such a range, a transparent conductive film having excellent conductivity 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 even more preferably 95% or more.

[3-2] Metal mesh The transparent conductive layer including the metal mesh is formed by forming fine metal wires in a lattice pattern on the transparent substrate. Any appropriate metal can be used as the metal constituting the metal mesh as long as the metal has high conductivity. Examples of the metal constituting the metal mesh include silver, gold, copper, and nickel. Further, a material obtained by plating (for example, gold plating) on these metals may be used. Among them, copper is preferable, and the migration phenomenon does not easily occur, and is also preferable from the viewpoint of suppressing disconnection at the time of keying.

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

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

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

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

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

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

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

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

  Examples of the polyvinyl alcohol film include a content of ethylene units of 1 to 4 mol%, a degree of polymerization of 2,000 to 4,000, and a degree of saponification of 99.0 to 99 described in JP-A-2003-248123, JP-A-2003-342322, and the like. .99 mol% of ethylene-modified polyvinyl alcohol is preferably used. In addition, it is preferable to produce a polarizer and bond it with the base film of the present invention to produce a polarizing plate by the methods described in JP 2011-100161 A, JP 4691205 A, and JP 4804589 A. .

[5] Base film B
The base film B disposed on the side opposite to the base film A of the polarizer is preferably a film that functions as a protective film for the polarizer.

  As such a protective film, a base film A may be used. For example, commercially available cellulose ester films (for example, Konica Minoltack KC8UX, KC5UX, KC4UX, KC8UCR3, KC4SR, KC4BR, KC4CR, KC4DR, KC4FR, KC4U, Z60UZU, ZC60UZU, ZC60UZU, ZC60UZU, ZC60UZU, ZC80UZU, KC4UTA, KC4UTA , FUJITAC TD40UL, FUJITAC R02, FUJITAC R06, manufactured by FUJIFILM Corporation. That.

  Further, for example, resin films such as polyethylene terephthalate, polyethylene naphthalate, and polycarbonate, alicyclic polyolefins (for example, ZEONOR (registered trademark), polyarylate, polyether sulfone, polysulfone, cycloolefin copolymer, polyimide (manufactured by Nippon Zeon Co., Ltd.) Examples thereof include resin films such as Neoprim (registered trademark) manufactured by Mitsubishi Gas Chemical Company, Inc., fluorene ring-modified polycarbonate, alicyclic-modified polycarbonate, and acryloyl compounds (the parentheses indicate the glass transition temperature Tg). Among materials, in terms of cost and availability, polyethylene terephthalate (abbreviation: PET), polybutylene terephthalate, polyethylene naphthalate (abbreviation: PEN), polycarbonate (abbreviation: PC), etc. Film preferably used as the resin base material flexibility.

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

[6] Other Layers The polarizer-integrated touch sensor of the present invention may include any appropriate other layers as necessary. Examples of the other layers include an antistatic layer, an antiglare layer, an antireflection layer, and a color filter layer.

  Hereinafter, other layers than the above other layers will be described.

[6-1] Adhesive Layer The adhesive layer is formed by appropriately bonding members constituting the polarizer-integrated touch sensor of the present invention to form a laminate, or by joining the polarizer-integrated touch sensor of the present invention to a display device. And constituent layers for forming a touch panel display device.

  The adhesive layer is not particularly limited, and for example, any of a dry laminating agent, a wet laminating agent, a pressure-sensitive adhesive, a heat sealing agent, a hot melt agent and the like are used.

  As the adhesive, for example, a polyester resin, a urethane resin, a polyvinyl acetate resin, an acrylic resin, a silicone resin, a nitrile rubber, or the like is used. The lamination method is not particularly limited, and for example, it is preferable to perform the lamination continuously by a roll method from the viewpoint of economy and productivity. The thickness of the adhesive layer is usually preferably in the range of about 1 to 100 μm from the viewpoint of the adhesive effect, the drying speed, and the like.

  Note that the polarizing plate integrated touch sensor may include a release sheet on the other surface.

  The release sheet may be any as long as it can protect the adhesiveness of the adhesive layer. For example, an acrylic film or sheet, a polycarbonate film or sheet, a polyarylate film or sheet, a polyethylene naphthalate film or sheet, a polyethylene terephthalate film Or a sheet, a plastic film or sheet such as a fluorine film, or a resin film or sheet into which titanium oxide, silica, aluminum powder, copper powder, or the like has been kneaded, or coating a resin into which these have been kneaded, or applying a metal such as aluminum to a metal. A resin film or sheet subjected to surface processing such as vapor deposition is used.

  The thickness of the release sheet is not particularly limited, but is preferably in the range of usually 12 to 250 μm.

[7] Touch Panel Display Device As shown in FIG. 1B, the touch sensor with integrated polarizing plate of the present invention can be manufactured as a touch panel display device by being bonded to a liquid crystal display panel via an adhesive layer.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The touch sensor integrated with a polarizing plate of this embodiment is obtained by adding a hard coat layer 3 to the embodiment shown in FIG. 1A.

  The present invention will be described specifically with reference to examples, but the present invention is not limited to these. In the examples, unless otherwise specified, the operation was performed at room temperature (25 ° C.). Unless otherwise specified, “%” or “parts” means “% by mass” or “parts by mass”, respectively.

<Compounds used in Examples>
1H-pyrrole: molecular weight 67, water absorption 0.05%
Indole 1 (indole): molecular weight 117, water absorption 0.05%
Indole 2 (indole-3-acetoaldoxime N-oxide)
: Molecular weight 190, water absorption 0.06%
Bilirubin: molecular weight 585, water absorption 0.30%
Porphyrin 1 (21H, 23H-porphine)
: Molecular weight 310, water absorption 1.0%
Porphyrin 2 (protoporphyrin)
: Molecular weight 2738, water absorption 0.06%
Tryptophan: molecular weight 204, water absorption 3.00
Polypropylene: weight average molecular weight 200,000, water absorption 0.01%
66 nylon: weight average molecular weight 25,000, water absorption 3.5%
The water absorption was determined by the following formula (1) according to the method (A) of JIS K 7209 of the additive.

Formula (1) Water absorption = {(w ₂ −w ₁ ) / w ₁ } × 100 (%)
(Wherein, w ₁ is the dry mass (mg) of the additive before immersion in water, and w ₂ is the mass of the additive after immersion in water at 23.0 ± 1.0 ° C. for 24 ± 1 hour. (Mg).)
Example 1
<Preparation of base film A (cycloolefin polymer film) 101>
(Synthesis of cycloolefin polymer 1)
100 parts by mass of Exemplified Compound 11 of a cycloolefin monomer (general formula (A-1)), 3.6 parts by mass of 1-hexene as a molecular weight regulator and 200 parts by mass of toluene were charged into a reaction vessel purged with nitrogen. , Heated to 80 ° C. Thereto, and triethylaluminum _{((C 2 H 5) 3} Al) solution in toluene 0.17 parts by mass of 1.5 mol / L as a polymerization catalyst, tungsten hexachloride modified with t- butanol and methanol (WCl ₆₎ Then, 1.0 part by mass of a modified WCl ₆ solution (concentration: 0.05 mol / L) having a molar ratio of t-butanol to methanol and tungsten of 0.35: 0.3: 1 was added. A ring-opening polymerization reaction was carried out by heating and stirring for an hour to obtain a polymer solution. The polymerization conversion in this polymerization reaction was 96%.

4000 parts by mass of the obtained polymer solution was put into an autoclave, and 0.48 parts of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the polymer solution, and the reaction was carried out at a hydrogen gas pressure of 10 MPa. The mixture was heated and stirred at a temperature of 160 ° C. for 3 hours to perform a hydrogenation reaction.

After cooling the obtained reaction solution, the pressure of hydrogen gas was released, and the reaction solution was poured into a large amount of methanol to separate and collect a coagulated product. The collected coagulated product was dried to obtain cycloolefin polymer 1.
(Preparation of fine particle addition liquid)
Fine particles (Aerosil R812: manufactured by Nippon Aerosil Co., Ltd., primary average particle size: 7 nm, apparent specific gravity 50 g / L) 4 parts by mass Dichloromethane 48 parts by mass Ethanol 48 parts by mass After stirring and mixing with a dissolver for 50 minutes, and then dispersing with Manton-Gaulin. Was done.

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

  Next, a main dope 1 having the following composition was prepared. First, methylene chloride was added to the pressure dissolution tank at a flow rate of 400 kg / min and ethanol at a flow rate of 20 kg / min. Three minutes after the start of the addition of the solvent, the cycloolefin polymer 1 was charged into the pressure dissolution tank while stirring at a flow rate of 200 kg / min. Next, 5 minutes after the start of the introduction of the solvent, 1H-pyrrole was introduced, and further, 15 minutes after the start of the introduction of the solvent, the liquid for adding fine particles was introduced, and the mixture was heated to 80 ° C. and completely dissolved while stirring. did. The heating temperature was increased from room temperature at 5 ° C./min, dissolved for 30 minutes, and then decreased at 3 ° C./min.

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

<Composition of main dope 1>
Cycloolefin polymer 1 100 parts by mass 1H-pyrrole 3 parts by mass Methylene chloride 200 parts by mass Ethanol 10 parts by mass Fine particle additive liquid 3 parts by mass The above is charged into a closed main dissolving vessel, and dissolved with stirring to obtain a dope. Prepared.

  The prepared dope was cast on a stainless steel endless support (belt) at a flow rate of 710 L / hr. At that time, casting was performed while dropping dichloromethane at the casting end.

  At a drying temperature of 30 ° C., the solvent was evaporated until the amount of the residual solvent in the cast web became 30% by mass, and then peeled off from the stainless steel endless support at a peeling tension of 130 N / m. The residual solvent amount was adjusted to 5% by mass while drying the peeled web, and then the tenter drying zone was dried while being transported at a temperature of 140 ° C. for 20 minutes at a transport tension of 100 N / m with a number of rollers, An original film having a thickness of 43 μm was produced.

  The raw film is transported, stretched 1.5 times in the direction of 45 ° with respect to the film transport direction while applying heat of 175 ° C. using the apparatus of FIG. (Combined film) 101 was obtained. The thickness of the base film 101 was 25 μm.

<Preparation of base film A102>
A base film A102 of the present invention was obtained in the same manner as the base film A101, except that indole 1 was used for the pyrrole of the main dope 1 prepared with the base film A101.

<Preparation of base film A103>
The base film A103 of the present invention was prepared in the same manner as the base film A102 except that the indole 1 of the main dope 1 prepared in the base film A102 was changed to the indole 2, and the drying temperature of the casting support was changed to 35 ° C. Obtained.

<Preparation of base film A104>
The base film A104 of the present invention was obtained in the same manner as the base film A102 except that the indole 1 of the main dope 1 prepared in the base film A102 was changed to bilirubin, and the drying temperature of the casting support was changed to 35 ° C. Was.

<Preparation of base film A105>
The base film A105 of the present invention was prepared in the same manner as the base film A102 except that the indole 1 of the main dope 1 prepared with the base film A102 was changed to porphyrin 1 and the drying temperature of the casting support was set to 40 ° C. Obtained.

<Preparation of base film A106>
The base film A106 of the present invention was prepared in the same manner as the base film A102 except that the indole 1 of the main dope 1 prepared in the base film A102 was changed to porphyrin 2 and the drying temperature of the casting support was set to 40 ° C. Obtained.

<Preparation of base film A107>
The base film A107 of the present invention was obtained in the same manner as the base film A102, except that the indole 1 of the main dope 1 prepared with the base film A102 was changed to tryptophan, and the drying temperature of the casting support was changed to 45 ° C. Was.

<Preparation of base film A108>
A base film A108 of a comparative example was obtained in the same manner as the base film A102 except that the indole 1 of the main dope 1 made of the base film A102 was made of polypropylene and the drying temperature of the casting support was set at 30 ° C. Was.

<Preparation of base film A109>
The base film A109 of Comparative Example was prepared in the same manner as the base film A102 except that the indole 1 of the main dope 1 made of the base film A102 was made of 66 nylon and the drying temperature of the casting support was set at 50 ° C. Obtained.

<Preparation of base film A110-114>
In the production of the base film A105, the stretch ratio was changed as shown in Table 1, and the in-plane retardation value Ro was changed to the value shown in Table 1, to obtain base films A110 to 114.

<Coating of Hard Coat Layer on Base Films A101 to A114>
Then, on one side of the base films A101 to 114, using a microgravure, an ultraviolet-curing resin (OPSTAR Z7527 manufactured by JSR Corporation) and a surfactant (Surflon manufactured by AGC Seimi Chemical Co., Ltd.) containing acrylate and amorphous silica as main components. The coating liquid for forming a hard coat layer containing S-651) was applied to a thickness of 0.7 μm after drying, and dried.

Next, the coating film was irradiated with ultraviolet light at a light intensity of 270 mJ / cm ² in the atmosphere using a high-pressure mercury lamp and cured to form a hard coat layer on one side.

<Preparation of transparent conductive layer>
Silver nanowires are available from Y. Sun, B .; Gates, B .; Mayers, & Y. Xia, "Crystalline silver nanowires by solution processing", Nano Letters, (2002), 2 (2) After the method using a polyol, in the presence of glycol in the presence of polyvinylpyrrolidone (PVP). This is a nanowire synthesized by dissolving silver sulfate in water and reducing it. That is, the present invention used nanowires synthesized by the modified polyol method described in Cambrios Technologies Corporation, US Provisional Application No. 60 / 815,627.

As a metal nanowire forming a transparent conductive layer, a silver nanowire water containing a silver nanowire synthesized by the above method and having a minor axis diameter of about 70 to 80 nm and an aspect ratio of 100 or more in an aqueous medium is 0.5 w% / v. The thickness of the dispersion composition (ClearOhmTM, Ink-A AQ manufactured by Cambrios Technologies Corporation) is dried to 1.5 μm on a hard coat layer of the base films A101 to 106 using a slot die coater using a slot die coater. After coating and drying as described above, a pressure treatment was performed at a pressure of 2000 kN / m ² to form a transparent conductive layer.

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

  Next, the above-prepared polarizer was used as the base film A101-114, and the surface opposite to the side on which the transparent conductive layer was provided, and the base film B as Konica Minolta Tack KC4UA (manufactured by Konica Minolta Co., Ltd.) And bonded together via the following ultraviolet-curable adhesive solution to produce the polarizing plate integrated touch sensors 101 to 114.

  At that time, lamination was performed so that the absorption axis of the polarizer and the slow axis of the base film A were at 45 ° to form a circularly polarizing plate.

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

3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 45 parts by mass Eporide GT-301 (alicyclic epoxy resin manufactured by Daicel) 40 parts by mass 1,4-butanediol diglycidyl ether 15 parts by mass Tria Reel sulfonium hexafluorophosphate 2.3 parts by mass 9,10-dibutoxyanthracene 0.1 parts by mass 2.0 parts by mass 1,4-diethoxynaphthalene 2.0 parts by mass A corona discharge treatment is performed at a corona output intensity of 2.0 kW and a line speed of 18 m / min. The ultraviolet curable adhesive liquid 1 prepared above is coated on the corona discharge treated surface so that the film thickness after curing becomes about 3 μm. Coating was performed with a bar coater to form an ultraviolet-curable adhesive layer.

The polarizing plate is irradiated with ultraviolet light from the base film B 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. Then, the ultraviolet curable adhesive layer was cured.

≪Evaluation≫
[1] Distribution Measurement of Additives of Base Film A The distribution of additives in the base film A is measured by the following time-of-flight secondary ion mass spectrometry (TOF-SIMS). The concentration of the additive from the film surface to the inside of 1 μm in the thickness direction was quantified by an analytical method.

<Measurement method>
As the device, TFS-2100 manufactured by Physical Electronics was used, and the measurement was performed at a temperature of 23 ° C. and a humidity of 55% RH.

  The concentration of a surface (for example, surface (A: Air surface)) where the amount of the additive detected is large using the TOF-SIMS analysis method (for example, the surface (A: Air surface)) is dA, and the surface where the amount of the additive detected is small (for example, the surface (B: Belt surface)) was defined as the density, and the ratio dA / dB value was determined.

  In the case of the base film A, when the dope is cast on a casting support, the concentration of the additive on the surface on the Air surface side is higher than the concentration of the additive on the surface on the Belt surface side. Confirmed that it is also high.

[2] Measurement of in-plane retardation value Ro The in-plane retardation value Ro of the base film A was measured at 23 ° C. using an automatic birefringence meter Axoscan (Axo Scan Mueller Matrix Polarimeter: manufactured by Axometrics). In an environment of 55% RH, a three-dimensional refractive index was measured at a light wavelength of 590 nm, and calculated from the obtained refractive indices nx, ny, and nz by the following equation (i).

Formula _{(i): Ro = (n} x -n y) × d (nm)
In [Equation (i), 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. d represents the thickness (nm) of the film. ]
[3] Measurement of Touch Sensor Sensitivity Each of the above-prepared touch sensors 101 to 114 with a polarizing plate was left at room temperature and in an environment of 80 ° C. and 90% RH for 1 hour, and was repeated 100 times.

  Thereafter, the sensitivity of the touch sensor was evaluated and evaluated according to the following criteria.

：: Touch of 0.1 sec was performed 100 times and detected 100 times ×: Touch of 0.1 sec was performed 100 times and detected 99 times or less Table 1 shows the configuration of the base film A and the evaluation results for each item.

  From the results in Table 1, the base films A101 to 107 and 111 to 113 of the present invention exhibit the effect of the difference in shrinkage between the front and back surfaces of the film of the present invention, and suppress deformation of the polarizing plate. It can be seen that the sensor sensitivity after the test is excellent.

Example 2
In the base film A105 produced in Example 1, the following cycloolefin polymer 2 was used in place of the cycloolefin polymer 1, and the drying temperature of the casting support was changed to the temperature shown in Table 2, and the air was dried. Base films A201 to 206 were prepared in the same manner except that the additive concentration ratio (dA / dB) of the surface (dA) / Belt surface (dB) was changed as shown in Table 2.

(Synthesis of cycloolefin polymer 2)
100 parts of Exemplified Compound 28 of a cycloolefin monomer (general formula (A-2)), 3.6 parts of 1-hexene as a molecular weight regulator and 200 parts of toluene were charged into a nitrogen-purged reaction vessel, and the mixture was heated at 80 ° C. Heated. Modified to, triethylaluminum _{((C 2 H 5) 3} Al) 1.5 mol / toluene solution 0.17 parts of L as a polymerization catalyst, tungsten hexachloride modified with t- butanol and methanol (WCl ₆₎ Then, 1.0 part of a WCl ₆ solution (concentration: 0.05 mol / L) having a molar ratio of t-butanol to methanol and tungsten of 0.35: 0.3: 1 was added, and the mixture was heated at 80 ° C. for 3 hours. A ring-opening polymerization reaction was performed by stirring to obtain a polymer solution. The polymerization conversion in this polymerization reaction was 98%.

4000 parts of the obtained polymer solution was put into an autoclave, 0.48 parts of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the polymer solution, the hydrogen gas pressure was increased to 10 MPa, and the reaction temperature was increased. The mixture was heated and stirred at 160 ° C. for 3 hours to carry out a hydrogenation reaction.

  After cooling the obtained reaction solution, the pressure of the hydrogen gas was released, and the reaction solution was poured into a large amount of methanol to separate and collect a coagulated product. The collected coagulated product was dried to obtain a cycloolefin polymer 2.

  Next, a polarizing plate integrated touch sensor was produced in the same manner as in Example 1 using the produced base films A201 to 206, and the same evaluation as in Example 1 was performed.

  The evaluation results are shown in Table 2 below.

  From the results in Table 2, it can be seen that the base films A202 to 206 of the present invention have excellent sensor sensitivity after the forced degradation test.

Example 3
In the base film A105 produced in Example 1, the following cycloolefin polymer 3 was used in place of the cycloolefin polymer 1, and the amount of porphyrin 1 was changed in the same manner except that the amount of porphyrin 1 was changed to the amount shown in Table 3. Thus, base films A301 to A307 were produced.

(Synthesis of cycloolefin polymer 3)
50 parts of Exemplified Compound 5 of cycloolefin monomer (general formula (A-1)), 200 parts of Exemplified Compound 28 of cycloolefin monomer (general formula (A-2)), and as a molecular weight regulator A reaction vessel in which 18 parts of 1-hexene and 750 parts of toluene had been replaced with nitrogen was charged and heated to 60 ° C. Modified to, triethylaluminum _{((C 2 H 5) 3} Al) 1.5 mol / toluene solution 0.62 parts of L as a polymerization catalyst, tungsten hexachloride modified with t- butanol and methanol (WCl ₆₎ Then, 5.1 parts of a WCl ₆ solution (concentration: 0.05 mol / L) having a molar ratio of t-butanol, methanol and tungsten of 0.35: 0.3: 1 was added, and heated at 80 ° C. for 3 hours. The ring-opening copolymerization reaction was performed by stirring to obtain a ring-opening copolymer solution. The polymerization conversion in this polymerization reaction was 97%.

4000 parts of the obtained ring-opening copolymer solution was put into an autoclave, 0.48 parts of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the copolymer solution, and the reaction was conducted under a hydrogen gas pressure of 10 MPa. The mixture was heated and stirred at a temperature of 165 ° C. for 3 hours to carry out a hydrogenation reaction.

  After cooling the obtained reaction solution, the pressure of the hydrogen gas was released, and the reaction solution was poured into a large amount of methanol to separate and collect a coagulated product. The collected coagulated product was dried to obtain cycloolefin polymer 3.

  Next, a polarizing plate integrated touch sensor was manufactured in the same manner as in Example 1 using the manufactured base films A301 to 307, and the same evaluation as in Example 1 was performed.

  The evaluation results are shown in Table 3 below.

  From the results in Table 3, it is understood that the base films A303 to 305 of the present invention in which the amount of porphyrin added is 3.0 to 5.0% by mass are particularly excellent in sensor sensitivity after the forced inferiority test.

Example 4
<Production of touch panel display device>
Using the base film A303 produced in Example 3, a transparent conductive layer was formed as a patterned transparent conductive layer as described in JP-T-2010-541109, to produce a polarizing plate integrated touch sensor. . Using this, a touch panel having an embodiment shown in FIG. 1B was produced.

  The touch panel previously bonded to the SONY 21.5 type VAIO Tap21 (SVT21219DJB) was peeled off, and the touch panel manufactured above was bonded to obtain a touch panel display device.

  The prepared touch panel had excellent visibility without any irregular reflection of the transparent conductive layer in visual observation from the surface side and observation in a state where polarized sunglasses were worn.

  In addition, the touch panel display device thus manufactured was left to stand for 1 hour each in an environment of room temperature and a temperature of 60 ° C./80% RH 1,000 times, and the touch sensor sensitivity after the forced inferiority test was measured. It was found that the durability of the touch panel with a polarizing plate of the present invention against environmental fluctuations was high.

  The polarizing plate-integrated touch sensor of the present invention suppresses the deformation of the polarizing plate in the touch sensor even under environmental changes such as high temperature and high humidity, and lowers or incorrectly detects the sensor sensitivity of the transparent conductive layer due to the deformation. Since the operation can be suppressed, it is suitable for a touch sensor of a smartphone or a touch panel.

DESCRIPTION OF SYMBOLS 1 Polarizer integrated touch sensor 2 Transparent conductive layer 3 Hard coat layer 4 Base film A
5 adhesive layer 6 polarizer 7 base film B
Reference Signs List 8 adhesive layer 9 touch panel member 10 touch panel display device 11 glass 12 intermediate layer 13 liquid crystal display device A base film A
21 Stretching direction (TD direction)
22 Stretching direction 23 Transfer direction (MD direction)
Reference Signs List 24 Slow axis 25 Oblique stretching device 26 Film unwinding device 27 Transport direction changing device 28 Winding device 29 Film forming device

Claims (6)

At least a transparent conductive layer, a base film A, a polarizer, a base film B, and a polarizing plate integrated type touch sensor having an adhesive layer in this order,
The base film A contains a cycloolefin polymer as a main component and an additive different from the cycloolefin polymer,
An environment in which the concentration of the additive in the base film A is 1.1 times or more different between the polarizer side and the surface of the transparent conductive layer side, and the base film A is at a temperature of 23 ° C. and a relative humidity of 55%. A touch panel integrated with a polarizing plate, wherein an in-plane retardation value Ro measured at a light wavelength of 550 nm is in a range of 50 to 200 nm.   The concentration of the additive in the base film A is different in a range of 1.1 to 1.6 times between the surface of the polarizer and the surface of the transparent conductive layer on the side of the transparent conductive layer. Polarizer integrated touch sensor. The water absorption of the additive obtained from the following formula (1) according to JIS K 7209 (Method A) is in the range of 0.05 to 3% by mass. 3. The touch sensor integrated with a polarizing plate according to 2.
Formula (1) Water absorption = {(w ₂ −w ₁ ) / w ₁ } × 100 (%)
(Wherein, w ₁ is the dry mass (mg) of the additive before immersion in water, and w ₂ is the mass of the additive after immersion in water at 23.0 ± 1.0 ° C. for 24 ± 1 hour. (Mg).)   The polarizing plate integrated touch sensor according to any one of claims 1 to 3, wherein the additive has a molecular weight within a range of 50 to 5000.   The polarizing plate according to any one of claims 1 to 4, wherein the additive is at least one selected from the group consisting of a compound having a pyrrole ring and a compound having an indole ring. Body type touch sensor.   6. The method of manufacturing a touch sensor with integrated polarizing plate according to claim 1, wherein the base film A is manufactured by a solution casting method. 7. Manufacturing method of touch sensor with integrated polarizing plate.

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