JP2010055944A - Conductive laminate film, and touch panel using the same - Google Patents

Abstract

An object of the present invention is to provide a conductive laminated film and a touch panel that can suppress generation of interference fringes, have high contrast, have less glare, have excellent durability, and have high visibility.
The conductive laminated film (A) of the present invention has a ridge shape formed at a predetermined pitch with a UV curable resin composition on at least one surface of a transparent resin film (I). The shape resin layer (II) and the transparent conductive layer (III) are laminated in this order. The touch panel of the present invention has the conductive laminated film of the present invention.
[Selection] Figure 1

Description

  The present invention relates to a conductive laminated film and a touch panel using the same. Specifically, the present invention relates to a conductive laminated film suitable for use in a touch panel that is provided on a liquid crystal display and can be used as an input means, and a touch panel using the same.

  In an electronic device such as a personal digital assistant (PDA), a notebook PC, an OA device, a medical device, or a car navigation system, a touch panel having an input means on these displays is widely used.

  The transparent conductive film type touch panel has a transparent base film provided with a thin film of metal oxide such as indium tin oxide or tin antimonic acid or metal such as gold, palladium, aluminum or silver as a transparent conductive film on one side of the transparent base film. These metal oxides or metal thin films have a large light reflection, so that the contrast of the liquid crystal display is remarkably lowered and the screen becomes extremely difficult to see.

  As a method for solving such a problem, in Patent Document 1, two transparent conductive films (a laminated film of glass and ITO) facing each other through a first quarter-wave plate and a spacer in order from the liquid crystal display side. It has been proposed to arrange a second quarter-wave plate and a polarizing plate to increase visibility.

  However, the contrast of the liquid crystal display is still insufficient only by using the touch panel having the above configuration, and the optical characteristics such as light transmittance and viewing angle compensation are inferior because the touch panel has a multilayer structure. There is a problem.

  On the other hand, in Patent Document 2, there is an attempt to suppress the generation of interference fringes by making the transparent resistive film a special shape. However, this method cannot suppress the surface reflected light, and high contrast, visibility, and durability cannot be obtained.

For this reason, there has been a strong demand for the appearance of a touch panel that has excellent optical characteristics, high visibility, suppresses interference fringes, and has excellent durability.
Japanese Patent Laid-Open No. 10-48625 JP 2005-18726 A

  An object of the present invention is to provide a conductive laminated film and a touch panel, in which generation of interference fringes is suppressed, contrast is high, glare is small, durability is high, and visibility is high.

The conductive laminated film (A) of the present invention is a cocoon-shaped resin layer in which a cocoon shape is formed at a predetermined pitch with a UV curable resin composition on at least one surface of a film (I) made of a transparent resin. II) and the transparent conductive layer (III) are laminated in this order.

In such a conductive laminated film (A) of the present invention, the bowl-shaped resin layer (II) is 100 to
It is preferable that the protrusion has a polygonal cross section with a pitch in the range of 5000 μm, and the height of the protrusion is 0.1 to 10 μm.

  In the conductive laminated film (A) of the present invention, the film (I) made of a transparent resin is preferably a retardation film having an in-plane retardation in the range of 128 to 148 nm with respect to transmitted light having a wavelength of 550 nm.

In the conductive laminated film (A) of the present invention, the film (I) made of a transparent resin preferably contains a cyclic olefin resin and / or a polycarbonate resin.
The conductive laminated film (A) of the present invention is a cyclic product obtained by (co) polymerizing a monomer (co) comprising at least one compound represented by the following formula (1) with a film (I) made of a transparent resin. It is preferable that an olefin resin is included.

（式（１）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に、水素原子；ハロゲン原子；または酸素、窒素、イオウもしくはケイ素を含有していてもよい１価の有機基を表し、
Ｒ¹とＲ²と、Ｒ³とＲ⁴とが、それぞれ独立に、相互に結合してアルキリデン基を形成していてもよく、
Ｒ¹とＲ²と、Ｒ³とＲ⁴と、Ｒ²とＲ³とが、それぞれ独立に、相互に結合して単環または多環の炭素環もしくは複素環を形成してもよく、
ｘは０〜３の整数を表し、ｙは０または１を表す。）
本発明の導電性積層フィルム（Ａ）は、透明導電性層（III）が、結晶性ＩＴＯからな
ることが好ましい。

(In the formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom; a halogen atom; or a monovalent organic group that may contain oxygen, nitrogen, sulfur or silicon;
R ¹ and R ² and R ³ and R ⁴ may be independently bonded to each other to form an alkylidene group,
R ¹ and R ² , R ³ and R ⁴ , and R ² and R ³ may be independently bonded to each other to form a monocyclic or polycyclic carbocyclic or heterocyclic ring,
x represents an integer of 0 to 3, and y represents 0 or 1. )
In the conductive laminated film (A) of the present invention, the transparent conductive layer (III) is preferably made of crystalline ITO.

The touch panel of the present invention preferably has the conductive laminated film (A) of the present invention.
The touch panel of the present invention comprises the conductive laminated film (A) of the present invention,
A conductive laminate film (B) in which a transparent conductive layer, a retardation film, and a polarizing plate are laminated in this order, and
Both the film (I) made of a transparent resin constituting the conductive laminated film (A) and the retardation film constituting the conductive laminated film (B) have an in-plane retardation of 128 with respect to transmitted light having a wavelength of 550 nm. The retardation film is preferably in the range of ˜148 nm.

The touch panel of the present invention has a transparent conductive layer (III) constituting the conductive laminated film (A).
And the transparent conductive layer constituting the conductive laminated film (B) are preferably made of crystalline ITO.

According to the present invention, there is no reflection due to reflection of light, generation of interference fringes is suppressed, high contrast, less glare, a clear display can be achieved, durability is excellent, and conductivity is high. A laminated film and a touch panel can be provided.

Hereinafter, the present invention will be specifically described.
Conductive laminated film (A)
In the conductive laminated film (A) of the present invention, a bowl-shaped resin layer (II) and a transparent conductive layer (III) are laminated in this order on at least one surface of the transparent resin film (I). Become.

<Film made of transparent resin (I)>
The film (I) made of a transparent resin may be any film that has transparency and can be used as a base film for the conductive laminated film (A), and a film containing a known transparent resin can be used. In the present invention, it is preferable to use a film containing a cyclic olefin resin and / or a polycarbonate resin as the film (I) made of a transparent resin. When the film (I) made of a transparent resin contains a cyclic olefin resin and / or a polycarbonate resin, the film (I) may be formed of one kind of cyclic olefin resin or polycarbonate resin. You may form from the resin composition which combined 2 or more types, or the resin composition which contains another resin component further. In the present invention, the film (I) made of a transparent resin is more preferably a film made of a resin or a resin composition in which the resin component is only one or more cyclic olefin resins, or only one or more polycarbonate resins. A film made of a cyclic olefin resin is more preferable. When the film (I) made of a transparent resin is a film made of a cyclic olefin resin or a polycarbonate resin, in addition to being excellent in transparency, it can be suitably used as a retardation film, suppressing reflected light and improving visibility. Improvement can be achieved.

The film (I) made of the transparent resin according to the present invention may be a film that does not exhibit retardation, or may be a retardation film. When the film (I) is a retardation film, it is desirable that the in-plane retardation with respect to transmitted light having a wavelength of 550 nm is 128 to 148 nm, preferably 133 to 143 nm, and preferably a 1 / 4λ retardation film. Particularly preferred. Here, the phase difference is defined by the product (Δnd) of the refractive index difference (Δn) of birefringent light and the thickness (d). When the film (I) made of a transparent resin has such a phase difference, reflected light can be effectively prevented, and a high-contrast touch panel is obtained, which is preferable.

  The retardation film is preferably obtained by stretching a film obtained from a cyclic olefin resin or polycarbonate resin, and obtained by stretching a film obtained from a cyclic olefin resin. More preferably.

-Cyclic olefin resin As the cyclic olefin resin that can constitute the transparent resin film (I), a copolymer containing at least one cyclic olefin compound having a norbornene skeleton, or a copolymer with a cyclic olefin compound is further copolymerized. The monomer composition containing a polymerizable monomer is preferably obtained by ring-opening (co) polymerization or addition (co) polymerization, and a double bond in the main chain of the obtained (co) polymer is present. What was hydrogenated is used more suitably.

  The cyclic olefin resin is a resin obtained by (co) polymerizing a monomer containing at least one compound represented by the following formula (1) (hereinafter also referred to as “specific monomer”). Is preferred.

（式（１）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に、水素原子；ハロゲン原子；または酸素、窒素、イオウもしくはケイ素を含有していてもよい１価の有機基を表し、
Ｒ¹とＲ²と、Ｒ³とＲ⁴とが、それぞれ独立に、相互に結合してアルキリデン基を形成していてもよく、
Ｒ¹とＲ²と、Ｒ³とＲ⁴と、Ｒ²とＲ³とが、それぞれ独立に、相互に結合して単環または多環の炭素環もしくは複素環を形成してもよく、
ｘは０〜３の整数を表し、ｙは０または１を表す。）
本発明において好適に用いられる環状オレフィン系樹脂としては、下記（ｉ）〜（ｉｉｉ）の（共）重合体が好ましい。
（ｉ）特定単量体と、必要に応じて共重合性単量体との開環（共）重合体（以下「特定の開環（共）重合体」ともいう。）。
（ｉｉ）特定の開環（共）重合体の水素添加（共）重合体。
（ｉｉｉ）特定単量体と、必要に応じて共重合性単量体との付加（共）重合体。

(In the formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom; a halogen atom; or a monovalent organic group that may contain oxygen, nitrogen, sulfur or silicon;
R ¹ and R ² and R ³ and R ⁴ may be independently bonded to each other to form an alkylidene group,
R ¹ and R ² , R ³ and R ⁴ , and R ² and R ³ may be independently bonded to each other to form a monocyclic or polycyclic carbocyclic or heterocyclic ring,
x represents an integer of 0 to 3, and y represents 0 or 1. )
As the cyclic olefin-based resin suitably used in the present invention, the following (i) to (iii) (co) polymers are preferable.
(I) A ring-opening (co) polymer of a specific monomer and, if necessary, a copolymerizable monomer (hereinafter also referred to as “specific ring-opening (co) polymer”).
(Ii) Hydrogenated (co) polymers of specific ring-opening (co) polymers.
(Iii) Addition (co) polymer of a specific monomer and, if necessary, a copolymerizable monomer.

  Among these, in the present invention, among the (co) polymers of (ii) above, that is, in the main chain of the (co) polymer obtained by ring-opening (co) polymerizing a monomer containing a specific monomer. A resin in which the double bond is hydrogenated is preferable. Examples of such a cyclic olefin-based resin include resins having a structural unit represented by the following formula (1 ′).

（式（１’）中、Ｒ¹〜Ｒ⁴、ｘおよびｙは、上記式（１）のＲ¹〜Ｒ⁴、ｘおよびｙと同様である。）
（特定単量体）
このような環状オレフィン系樹脂の原料として用いられる特定単量体の具体例としては、特に限定されるものではないが、たとえば次のような化合物が挙げられる。
ビシクロ［２.２.１］ヘプト−２−エン、
トリシクロ［４.３.０.１^2,5］−８−デセン、
トリシクロ［４.４.０.１^2,5］−３−ウンデセン、
テトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、
ペンタシクロ［６.５.１.１^3,6.０^2,7.０^9,13］−４−ペンタデセン、
５−メチルビシクロ［２.２.１］ヘプト−２−エン、
５−エチルビシクロ［２.２.１］ヘプト−２−エン、
５−メトキシカルボニルビシクロ［２.２.１］ヘプト−２−エン、
５−メチル−５−メトキシカルボニルビシクロ［２.２.１］ヘプト−２−エン、
５−シアノビシクロ［２.２.１］ヘプト−２−エン、
８−メトキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、
８−エトキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、
８−ｎ−プロポキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン
、
８−イソプロポキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン
、
８−ｎ−ブトキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、
８−メチル−８−メトキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ド
デセン、
８−メチル−８−エトキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ド
デセン、
８−メチル−８−ｎ−プロポキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−
３−ドデセン、
８−メチル−８−イソプロポキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−
３−ドデセン、
８−メチル−８−ｎ−ブトキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３
−ドデセン、

(Wherein (1 '), R ¹ to R ^4, x and y are the same as R ¹ to R ^4, x and y of the above formula (1).)
(Specific monomer)
Specific examples of the specific monomer used as a raw material for such a cyclic olefin resin are not particularly limited, and examples thereof include the following compounds.
Bicyclo [2.2.1] hept-2-ene,
Tricyclo [4.3.0.1 ^2,5 ] -8-decene,
Tricyclo [4.4.0.1 ^2,5 ] -3-undecene,
Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
Pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- pentadecene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-cyanobicyclo [2.2.1] hept-2-ene,
8 methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl -8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -
3-dodecene,
8-methyl-8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -
3-dodecene,
8-methyl -8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3
-Dodecene,

5-ethylidenebicyclo [2.2.1] hept-2-ene,
8 ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
5-phenylbicyclo [2.2.1] hept-2-ene,
8-phenyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
5-fluorobicyclo [2.2.1] hept-2-ene,
5-fluoromethylbicyclo [2.2.1] hept-2-ene,
5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-pentafluoroethylbicyclo [2.2.1] hept-2-ene,
5,5-difluorobicyclo [2.2.1] hept-2-ene,
5,6-difluorobicyclo [2.2.1] hept-2-ene,
5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,5,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5-heptafluoro-iso-propyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene,
8-fluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-fluoro-methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 difluoromethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 pentafluoroethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8-difluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-difluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- trifluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3
-Dodecene,
8,8,9,9- tetrafluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8,8,9,9- tetrakis (trifluoromethyl) tetracyclo [ 4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- trifluoro-9-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- trifluoro-9-trifluoromethoxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- trifluoro-9-pentafluoro propoxy tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-Fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-difluoro-8-heptafluoro-iso- propyl-9-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-Chloro -8,9,9- trifluoro tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-Dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene,
8- (2,2,2-trifluoroethoxy-carbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8- (2,2,2-trifluoroethoxy-carbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene These can be used either alone Two or more kinds may be used in combination.

Among these specific monomers, R ¹ and R ^{3 in} the above formula (1) are preferably hydrogen atoms or 1 to 10 carbon atoms, more preferably 1 to 4, more preferably 1 to 4. 2 represents a hydrocarbon group, R ² and R ⁴ represent a hydrogen atom; or a monovalent organic group which may contain an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom, and R ² and R ⁴ At least one represents a hydrogen atom or a monovalent organic group having a polarity other than a hydrocarbon group, x represents an integer of 0 to 3, y represents an integer of 0 to 3, more preferably x + y = 0 to 4, more preferably 0 to 2, particularly preferably x = 0 and y = 1. Use of a monomer containing such a specific monomer is preferable in that the obtained cyclic olefin-based resin has a high glass transition temperature and excellent mechanical strength.

  Examples of the monovalent organic group having the polarity include a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, and a cyano group. These monovalent organic groups having polarity may be bonded via a linking group such as a methylene group. In addition, a hydrocarbon group or the like in which a divalent organic group having polarity such as a carbonyl group, an ether group, a silyl ether group, a thioether group, or an imino group is bonded as a linking group is also exemplified. Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, and an allyloxycarbonyl group are preferable, and an alkoxycarbonyl group and an allyloxycarbonyl group are more preferable.

Further, in the above formula (1), when at least one of R ² and R ⁴ contains a monomer representing a monovalent organic group having a polarity represented by the formula: — (CH ₂ ) _n COOR The obtained cyclic olefin-based resin is preferable in that it has a high glass transition temperature, low hygroscopicity, and excellent adhesion to various materials. In the formula, R represents a hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, desirably an alkyl group. In addition, n is usually an integer of 0 to 5, but the smaller the value of n, the higher the glass transition temperature of the resulting cyclic olefin resin, which is preferable, and the specific monomer where n is 0. Is preferred because of its easy synthesis.

In the above formula (1), R ¹ or R ³ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and further preferably a methyl group. In particular, it is obtained that such an alkyl group is bonded to the same carbon atom as the carbon atom to which the monovalent organic group having the polarity represented by the above formula: — (CH ₂ ) _n COOR is bonded. This is preferable in that the hygroscopicity of the cyclic olefin resin can be lowered.

(Copolymerizable monomer)
The cyclic olefin resin used in the present invention may be obtained by copolymerizing a copolymerizable monomer together with a cyclic olefin compound such as a specific monomer.

  Specific examples of the copolymerizable monomer in the ring-opening (co) polymer include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene. As a carbon atom number of a cycloolefin, 4-20 are preferable and 5-12 are more preferable. These may be used alone or in combination of two or more.

  The copolymerizable monomer in the addition (co) polymer is preferably a compound having a reactive unsaturated double bond, specifically, an olefinic compound such as ethylene, propylene, and butene; And vinyl unsaturated hydrocarbon compounds such as α-methylstyrene and vinylcyclopentene; and (meth) acrylates such as methyl methacrylate.

(Ring-opening polymerization catalyst)
The ring-opening (co) polymerization reaction is performed in the presence of a metathesis catalyst. As the metathesis catalyst, a known catalyst can be used. For example, (a) at least one selected from W, Mo and Re compounds, and (b) a Deaming periodic table group IA element (for example, Li, Na, K, etc.), Group IIA elements (eg, Mg, Ca, etc.), Group IIB elements (eg, Zn, Cd, Hg, etc.), Group IIIA elements (eg, B, Al, etc.), Group IVA elements (eg, Si, Sn, Pb, etc.) or a compound of group IVB elements (for example, Ti, Zr, etc.), and at least one selected from those having at least one of the element-carbon bond or the element-hydrogen bond A catalyst composed of a combination. In this case, alcohols, aldehydes, ketones, amines and the like can be suitably used to increase the activity of the catalyst, but further, JP-A-1-132626, page 8, lower right column, page 16. It is also possible to use the compounds shown in line 17 to page 17, upper left column, line 17.

(Solvent for polymerization reaction)
Examples of the solvent used in the ring-opening (co) polymerization reaction (solvent constituting the molecular weight modifier solution, solvent for the specific monomer and / or metathesis catalyst) include pentane, hexane, heptane, octane, nonane, decane, etc. Alkanes; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylenedi Halogenated alkanes and aryl halides such as bromide, chlorobenzene, chloroform and tetrachloroethylene; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate and dimethoxyethane; Ether, tetrahydrofuran, include such ethers such as dimethoxyethane, they may be used in combination of two or more types may be used alone. Of these, aromatic hydrocarbons are preferred.

As the amount of the solvent used, “solvent: specific monomer (weight ratio)” is usually in an amount of 1: 1 to 10: 1, preferably in an amount of 1: 1 to 5: 1. The
The molecular weight of the resulting ring-opening (co) polymer can be adjusted depending on the polymerization temperature, the type of catalyst, and the type of solvent. For example, ethylene, propene, 1-butene, 1-pentene, 1-hexene. Further, α-olefins such as 1-heptene, 1-octene, 1-nonene, and 1-decene, and a molecular weight regulator such as styrene may be added.

  The ring-opening (co) polymer obtained as described above can be used as it is, but (iii) hydrogen obtained by hydrogenating an olefinically unsaturated bond in the molecule of this (co) polymer. The additive (co) polymer is preferable because it is excellent in heat-resistant coloring and light resistance and can improve the durability of the retardation film.

(Hydrogenation catalyst)
For the hydrogenation reaction, a method of hydrogenating a normal olefinically unsaturated bond can be applied. That is, a hydrogenation catalyst is added to a ring-opening (co) polymer solution, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, acts at 0 to 200 ° C., preferably 20 to 180 ° C. Is done by letting

  As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. Examples of the hydrogenation catalyst include a heterogeneous catalyst and a homogeneous catalyst.

  Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania. In addition, homogeneous catalysts include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium. Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, and the like. The form of the catalyst may be powder or granular.

The hydrogenation rate of the hydrogenated (co) polymer is 500 MHz and the value measured by ¹ H-NMR is 5
It is 0% or more, preferably 90% or more, more preferably 98% or more, and most preferably 99% or more. The higher the hydrogenation rate, the better the stability to heat and light. When used as the transparent film of the present invention, stable characteristics can be obtained over a long period of time.

  In addition, when the ring-opening (co) polymer molecule has an aromatic group, the aromatic group is less likely to deteriorate the heat resistance coloring property and light resistance, and conversely, optical characteristics such as refractive index and wavelength dispersion. The optical properties such as the above or heat resistance may be brought about, and hydrogenation is not necessarily required.

The ring-opening (co) polymer obtained as described above includes known antioxidants such as 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3, 3′-di-t-butyl-5,5′-dimethyldiphenylmethane, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and / or UV absorbers such as 2,4-dihydroxybenzophenone, 2
It can be stabilized by adding -hydroxy-4-methoxybenzophenone or the like. Further, additives such as a lubricant can be added for the purpose of improving processability.

  The hydrogenated (co) polymer used as the cyclic olefin resin preferably has a gel content contained in the hydrogenated (co) polymer of 5% by weight or less, preferably 1% by weight or less. It is more preferable that

Further, as the cyclic olefin-based resin, a (co) polymer obtained by cyclization of the ring-opened (co) polymer by a Friedel-Craft reaction and then hydrogenation is also used.
(Addition polymerization catalyst)
As the catalyst for synthesizing the addition (co) polymer, a known catalyst can be used, specifically, at least one selected from the group consisting of a titanium compound, a zirconium compound and a vanadium compound, and an assistant. It is an organoaluminum compound as a catalyst.

(Physical properties of cyclic olefin resin)
The molecular weight of the cyclic olefin resin is intrinsic viscosity [η] _inh , preferably 0.2-5.
dl / g, more preferably 0.3 to 3 dl / g, still more preferably 0.4 to 1.5 dl / g, and number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC). Is preferably 8,000 to 100,000, more preferably 10,000 to 80,000, still more preferably 12,000 to 50,000, and the weight average molecular weight (Mw) is preferably 20,000 to 300,000, more preferably 30,000 to 250,000, and still more preferably 40,000 to 200,000 are suitable.

When the intrinsic viscosity [η] _inh , number average molecular weight and weight average molecular weight are within the above ranges, the heat resistance, water resistance, chemical resistance, mechanical properties of the cyclic olefin resin, and the conductive laminated film of the present invention The balance with the stability of optical characteristics when used is good.

  As glass transition temperature (Tg) of cyclic olefin resin, it is 120 degreeC or more normally, Preferably it is 120-350 degreeC, More preferably, it is 130-250 degreeC, More preferably, it is 140-200 degreeC. This is to stabilize the change in optical properties of the obtained cyclic olefin resin film and prevent thermal deterioration of the resin when heated to near Tg and processed, such as stretching.

  The saturated water absorption at 23 ° C. of the cyclic olefin resin is preferably 2% by weight or less, more preferably 0.01 to 2% by weight, and still more preferably 0.1 to 1% by weight. If the saturated water absorption is within this range, the optical characteristics are uniform, the adhesiveness between the obtained cyclic olefin resin film and other optical members and adhesives is excellent, and peeling does not occur during use. Moreover, it is excellent in compatibility with an antioxidant and the like, and can be added in a large amount. The saturated water absorption is a value obtained by immersing in 23 ° C. water for 1 week and measuring the increased weight according to ASTM D570.

The cyclic olefin-based resin has a photoelastic coefficient (C _P ) of 0 to 100 (× 10 ⁻¹² Pa ⁻¹ ) and a stress optical coefficient (C _R ) of 1,500 to 4,000 (× 10 Those satisfying ⁻¹² Pa ⁻¹ ) are preferable. Here, with respect to the photoelastic coefficient (C _P ) and the stress optical coefficient (C _R ), various documents such as Polymer Journal, Vol. 27, No, 9pp 943-950 (1995), Journal of the Japanese Society of Rheology, Vol. .19, No. 2, p93-97 (1991), photoelastic experiment method, Nikkan Kogyo Shimbun, 7th edition of 1975. The former represents the degree of occurrence of phase difference due to stress in the glass state of the polymer, while the latter represents the degree of occurrence of phase difference due to stress in the flow state.

The large photoelastic coefficient (C _P ) means that stress generated from external factors or strain generated from its own frozen strain when a cyclic olefin resin film is used in combination with another optical member or adhesive. For example, when a transparent conductive layer is laminated as in the present invention or when it is used fixed to another optical member, residual strain at the time of bonding is expressed. It means that an unnecessary phase difference is likely to be generated due to a minute stress generated by shrinkage of a material accompanying a temperature change or a humidity change. Therefore, it is better that the photoelastic coefficient (C _P ) is as small as possible.

On the other hand, a large stress optical coefficient (C _R ) means that, for example, a desired retardation can be obtained with a small stretch ratio when imparting retardation to a cyclic olefin-based resin film. There is a great merit that it is easy to obtain a film capable of imparting a phase difference, and that when the same phase difference is desired, the film can be thinned as compared with a film having a small stress optical coefficient (C _R ).

From the above viewpoint, the photoelastic coefficient (C _P ) is preferably 0 to 100 (× 10 ⁻¹² Pa ⁻¹ ), more preferably 0 to 80 (× 10 ⁻¹² Pa ⁻¹ ), and still more preferably 0. ^{~50 (× 10 -12 Pa -1)} , particularly preferably ^{0~30 (× 10 -12 Pa -1)} , most preferably 0 to 20 (
× 10 ⁻¹² Pa ⁻¹ ). Minimizes unnecessary phase difference due to stress generated when the transparent conductive layer is laminated, stress generated when the conductive laminated film is fixed to other optical members, and phase change caused by environmental changes during use This is to limit it to the limit.

(Additive)
The cyclic olefin-based resin can be further stabilized by adding a known antioxidant, ultraviolet absorber, or the like. Moreover, in order to improve workability, the additive used in conventional resin processings, such as a lubricant, can also be added.

  Examples of the antioxidant include pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone.

Polycarbonate resin The polycarbonate resin that can form the transparent resin film (I) is not particularly limited, and any aromatic homopolycarbonate or copolycarbonate known in the art can be used. . The polycarbonate component may be produced according to any method generally known in the art, such as an interfacial polycondensation method, a polycondensation method in a homogeneous phase, or a transesterification method. These methods and associated reactants, polymers, catalysts, solvents and conditions are well known in the art and are described in U.S. Pat. Nos. 2,964,974, 2,970,137, 2,999,835. No. 2,999,846, No. 3,028,365, No. 3,153,008, No. 3,187,065, No. 3,215,668, No. 3,258,414 and No. No. 5,010,162. Suitable polycarbonates are based, for example, on one or more of the following bisphenols: dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (Hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfoxides, bis (hydroxyphenyl) sulfones, alkylcyclohexylidene bisphenols, α, α-bis (hydroxyphenyl) diisopropylbenzenes Derivatives whose nuclei are alkylated or derivatives whose nuclei are halogenated, and mixtures thereof.

  Specific examples of these bisphenols include 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1- Bis (4-hydroxyphenyl) cyclohexane, α, α-bis (4-hydroxyphenyl) diisopropylbenzene, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro- 4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4) -Hydroxyphenyl) sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, α, α-bis (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis (3 5-dichloro-4-hydroxyphenyl) propane and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane. A particularly preferred bisphenol is 2,2-bis (4-hydroxyphenyl) propane, more commonly known as bisphenol A. The above bisphenols can be reacted with phosgene to produce an aromatic polycarbonate. Suitable polycarbonates are also described in US Pat. No. 4,677,162.

Other resin When the film made of the transparent resin according to the present invention is made of a resin other than the cyclic olefin resin and the polycarbonate resin, examples of the transparent resin include polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, and triacetyl cellulose. , Polyethersulfone, polyimide and the like.

-Manufacture of the film (I) which consists of transparent resins The film (I) which consists of transparent resins used by this invention can be obtained by shape | molding transparent resins, such as cyclic olefin resin or polycarbonate resin, in a film or sheet form. The method of forming the transparent resin into a film can be appropriately selected according to the type of the transparent resin or the desired properties of the film. For example, a method such as a melt molding method or a solution casting method is adopted. Can do. As a method for forming the film, a solvent casting method is preferable from the viewpoint of good film thickness uniformity and surface smoothness. From the viewpoint of production cost, the melt molding method is preferable. The film thus formed is not particularly limited, but usually the film thickness is 70 to 250 μm, preferably 80 to 200 μm, and the difference between the maximum thickness and the minimum thickness of the film is within 3 μm, preferably Is preferably within 2 μm.

  When the film (I) made of a transparent resin is a film having a retardation (retardation film), the film-like product formed of the transparent resin as described above is used as a raw film, and this film is formed in a desired position. It can manufacture by extending | stretching so that it may become a phase difference. The film thickness of the raw film is 70 to 250 μm, preferably 80 to 200 μm, and the difference between the maximum thickness and the minimum thickness of the film is within 3 μm, preferably within 2 μm.

Specifically, the retardation film can be produced by stretching a raw film by a known uniaxial stretching method or biaxial stretching method. That is, a horizontal uniaxial stretching method by a tenter method, a compression stretching method between rolls, a longitudinal uniaxial stretching method using rolls with different circumferences, a biaxial stretching method in which horizontal uniaxial and longitudinal uniaxial are combined, a stretching method by an inflation method Etc. can be used.
Of these, longitudinal uniaxial stretching is preferred from the viewpoint of production cost.

In the case of the uniaxial stretching method, the stretching speed is usually 1 to 5,000% / min, preferably 50 to 1,000% / min, more preferably 100 to 1,000% / min, More preferably, it is 100 to 500% / min. In the case of the biaxial stretching method, stretching may be performed in two directions at the same time, or the stretching may be performed in a direction different from the first stretching direction after uniaxial stretching. In these cases, the intersection angle of the two stretching axes is usually in the range of 120 to 60 degrees. Further, the stretching speed may be the same or different in each stretching direction, and is usually 1 to 5,000% / min, preferably 50 to 1,000% / min, more preferably. 100-1,000
% / Min, more preferably 100 to 500% / min.

  The stretching temperature is not particularly limited, but is usually Tg ± 30 ° C., preferably Tg ± 10 ° C., more preferably Tg-5 based on the glass transition temperature (Tg) of the resin constituting the film. It is the range of -Tg + 10 degreeC. Since it is within the above range, it is possible to suppress the occurrence of phase difference unevenness, and it is preferable because the refractive index ellipsoid can be easily controlled.

  The draw ratio is usually 1.01 to 10 times, preferably 1.1 to 5 times, more preferably 1.1 to 3.5 times. When the draw ratio exceeds 10 times, it may be difficult to control the phase difference.

  The stretched film may be cooled as it is, but it is allowed to stand in a temperature atmosphere of Tg-20 ° C. to Tg for at least 10 seconds, preferably 30 seconds to 60 minutes, more preferably 1 minute to 60 minutes. As a result, a stable retardation film with little change in retardation characteristics with time can be obtained.

The linear expansion coefficient of the retardation film is preferably 1 × 10 ⁻⁴ (1 / ° C.) or less, more preferably 9 × 10 ⁻⁵ (1 / ° C.) in the temperature range of 20 ° C. to 100 ° C. Or less, more preferably 8 × 10 ⁻⁵ (1 / ° C.) or less, and particularly preferably 7 × 10 ⁻⁵ (1 / ° C.) or less. Further, the difference in linear expansion coefficient between the stretching direction and the direction perpendicular thereto is preferably 5 × 10 ⁻⁵ (1 / ° C.) or less, more preferably 3 × 10 ⁻⁵ (1 / ° C.) or less, and further preferably 1 × 10 ⁻⁵ (1 / ° C.) or less. By setting the linear expansion coefficient within the above range, when the retardation film is used in the conductive laminated film of the present invention, the change in retardation exerted by stress changes including the effects of temperature and humidity during use, Changes in the resistance value of the transparent conductive film are suppressed, and long-term stability can be obtained when used as the conductive laminated film of the present invention.

  The film stretched as described above is oriented with molecules due to stretching and gives a phase difference to transmitted light. This phase difference is the retardation value of the film before stretching, the stretching ratio, the stretching temperature, the stretching orientation. It can be controlled by the thickness of the later film.

The total light transmittance of the retardation film is preferably 85% or more, more preferably 88% or more, and still more preferably 90% or more, since the visibility of the touch panel is improved.
In addition, the thickness of the retardation film ensures good handling and facilitates winding into a roll shape, and is usually 1 to 500 μm, preferably 1 to 300 μm, more preferably 10 to 250 μm, More preferably, it is 50-200 micrometers.

The thickness distribution of the retardation film is usually within ± 20% of the average value, preferably within ± 10%, more preferably within ± 5%, and further preferably within ± 3%. The variation in thickness per 1 cm is usually 10% or less, preferably 5% or less, more preferably 1% or less, and further preferably 0.5% or less. By performing such thickness control, unevenness in the surface of the conductive laminated film can be prevented.

-Surface Treatment The film (I) made of the transparent resin according to the present invention may be subjected to a surface treatment for the purpose of improving the adhesiveness with the ridge-shaped resin layer (II). Examples of the surface treatment include plasma treatment, corona treatment, alkali treatment, and coating treatment. In particular, by using corona treatment, the adhesion between the film (I) made of a transparent resin and the bowl-shaped resin layer (II) can be strengthened.

As corona treatment conditions, the irradiation dose of corona discharge electrons is 1-1000 W / m ² / mi.
n is preferable, and 10 to 100 W / m ² / min is more preferable. If the irradiation amount is lower than this, a sufficient surface modification effect may not be obtained, and if the irradiation amount is higher than this, the treatment effect reaches the inside of the retardation film, and the film itself is There is a risk of deterioration. This corona treatment may be performed not only on the surface in contact with the bowl-shaped resin layer (II) but also on the opposite surface.

  In addition, when the ridge-shaped resin layer (II) is formed on the film (I) made of the transparent resin subjected to the corona treatment, the film (I) immediately after the corona treatment may be used. It is preferable to use it.

<Saddle-shaped resin layer (II)>
The ridge-shaped resin layer (II) is formed of a UV curable resin composition on at least one surface of the film (I) made of the transparent resin. Since the conductive laminated film (A) of the present invention has the bowl-shaped resin layer (II), the anti-Newton ring property can be secured, the clear feeling can be improved, and the glare can be prevented.

  The ridge-shaped resin layer (II) has a ridge shape formed at a predetermined pitch, and preferably the ridge shape is a shape having protrusions having a polygonal cross section at a predetermined pitch. The formation pitch of the ridge shape (the protrusion having a polygonal cross section) is preferably in the range of 100 to 5000 μm, and more preferably in the range of 200 to 1000 μm. If the formation pitch of the ridge shape (protrusion pitch) is less than 100 μm, glare may occur, and if it exceeds 5000 μm, the anti-Newton ring property may not be sufficiently exhibited. Further, the height of the ridge is usually set in the range of 0.1 to 10 μm, preferably 0.5 to 3 μm. If it is 0.1 μm, the anti-Newton ring property is not expressed, and if it is 10 μm or more, a bumpy feeling can be felt at the time of input when assembled as a touch panel. The saddle-shaped cross section preferably has a triangular shape, and is preferably formed by continuously transferring the same shape onto a film (I) made of a transparent resin using a transfer roll or the like. For example, when the liquid crystal is used in the lower display device, the ridge shape angle is formed at an angle of 10 to 45 ° with respect to the polarization axis as a countermeasure against moire. Therefore, when a ¼λ retardation film is used as the base film, it is desirable that the base film is formed at an angle of 10 to 80 ° with respect to the slow axis.

(UV curable resin composition)
The UV curable resin composition for forming the bowl-shaped resin layer is preferably (A) a polyfunctional monomer having three or more acryloyl groups (hereinafter also referred to as “component (A)”), (B) glycidyl (meth) acrylate. A specific amount of a polymer (hereinafter also referred to as “component (B)”) obtained by addition reaction of acrylic acid to a system polymer and (C) any other acrylic oligomer (hereinafter also referred to as “component (C)”). It mixes with. In particular, the component (A) is a component that can impart the hardness of the transparent conductive layer (III) followed by the bowl-shaped resin layer (II), the adhesion to the film (I) made of the transparent resin, and the like. The component (B) is a component that can impart further improvement in the hardness of the transparent conductive layer, curability, reduction of curling at the time of curing, and the like. By blending the component (B), the component (B) has a high molecular weight and has many hydroxyl groups in the molecule, so the compatibility with the highly hydrophobic component (A) decreases. (B) It is thought that it is because it transfers to the surface of the surface protective film from which a component is obtained. (C) component is an arbitrary component which can provide toughness etc.

  The surface tension of the component (A) is suitably in the range of 37 mN / m or less, more preferably 30 mN / m or more, from the viewpoint that sufficient hardness and adhesion can be obtained. The surface tension is measured by a vertical plate method (wilhemy method) using a Kyowa CBVP surface tension meter.

  Specific examples of the component (A) include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, triacrylate of glycerol propylene glycol adduct, and triacrylate of trimethylolpropane propylene glycol adduct. Trimethylolpropane triacrylate and ditrimethylolpropane tetraacrylate are preferable because the cured coating film has high hardness.

  The blending amount of the component (A) in the UV curable resin composition is suitably 40 to 60% by weight (however, the total of the components (A) to (C) is 100% by weight). 50 to 60% by weight is preferable.

  As described above, the component (B) is a polymer acrylate obtained by addition reaction of acrylic acid to a glycidyl (meth) acrylate polymer. The addition amount of acrylic acid to the epoxy group is suitably about 1: 1 to 1: 0.8 because unreacted epoxy adversely affects the stability of the composition, and 1: 1 to 1: 0.9. The degree is preferred.

  Examples of the glycidyl (meth) acrylate polymer include homopolymers of glycidyl (meth) acrylate, copolymers of glycidyl (meth) acrylate and various α, β-unsaturated monomers not containing a carboxyl group, and the like. Can be mentioned. Examples of the α, β-unsaturated monomer not containing the carboxyl group include various (meth) acrylic acid esters, styrene, vinyl acetate, acrylonitrile and the like. When glycidyl (meth) acrylate and an α, β-unsaturated monomer not containing a carboxyl group are copolymerized to obtain a glycidyl (meth) acrylate polymer, crosslinking occurs during the reaction. Therefore, high viscosity and gelation can be effectively prevented. The molecular weight of the glycidyl (meth) acrylate polymer is a weight average molecular weight of about 5,000 to 100,000 from the viewpoint of curling reduction during curing and prevention of gelation during the acrylic addition reaction, and 10,000 to 50 About 1,000 is preferable. (B) 70 weight% or more is suitable for the usage-amount of the glycidyl (meth) acrylate in a component in consideration of the hardness of a transparent conductive layer, the transferability of a polymer, etc., and 75 weight% or more is preferable.

  A known copolymerization method can be applied to the production of the component (B). The glycidyl (meth) acrylate polymer is produced by charging this monomer, a polymerization initiator, and, if necessary, a chain transfer agent and a solvent into a reaction vessel, under conditions of 80 to 90 ° C. for about 3 to 6 hours under a nitrogen stream. It is appropriate to do in The resulting glycidyl (meth) acrylate polymer and acrylic acid can be subjected to a ring-opening esterification reaction to obtain the component (B). Usually, in order to prevent polymerization of acrylic acid itself, The reaction temperature is suitably 100 to 120 ° C., and the reaction time is suitably about 5 to 8 hours.

  The blending amount of the component (B) in the UV curable resin composition is suitably 10 to 60% by weight (however, the sum of the components (A) to (C) is 100% by weight), 20 to 50% by weight is preferred.

  Specific examples of the component (C) include polyfunctional polyester acrylate, polyfunctional urethane acrylate, and epoxy acrylate. Of these, polyfunctional urethane acrylates are preferred from the viewpoints of scratch resistance and toughness of the cured coating film. For example, (a) a urethane reaction product of (meth) acrylate having a hydroxyl group and an isocyanate compound having two or more isocyanate groups in the molecule, and (b) an isocyanate compound having two or more isocyanate groups in the molecule. Examples include a reaction product obtained by reacting a polyol, polyester or polyamide-based diol to synthesize an adduct and then adding a (meth) acrylate having a hydroxyl group to the remaining isocyanate group (for example, JP-A-2002-275392). Issue).

  The polyfunctional urethane acrylate is a urethane reaction product composed of a (meth) acrylate having a hydroxyl group and a polyvalent isocyanate compound having two or more isocyanate groups. As the (meth) acrylate having a hydroxyl group, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like are preferable.

The blending amount of the component (C) in the UV curable resin composition is suitably 0 to 50% by weight (however, the sum of the components (A) to (C) is 100% by weight).
The active energy ray used for curing the UV curable resin composition may be, for example, any of ultraviolet rays and electron beams. When the resin composition is cured with an electron beam or the like, a photopolymerization initiator is not required, but when cured with ultraviolet rays, the photopolymerization initiator is usually 1 to 15 weights per 100 parts by weight of the resin composition. About parts can be contained. As the photopolymerization initiator, various known ones such as Darocur 1173, Irgacure 651, Irgacure 184, Irgacure 907, Irgacure 754 (all manufactured by Ciba Specialty Chemicals), benzophenone, and the like can be used. If necessary, various additives other than those described above, for example, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, an antistatic agent, a light stabilizer, a solvent, an antifoaming agent, and a leveling agent may be blended.

(Physical properties of film (I) / laminated film composed of bowl-shaped resin layer (II))
The conductive laminated film (A) of the present invention has a film (I) made of a transparent resin, a bowl-shaped resin layer (II) and a transparent conductive layer (III), but forms a transparent conductive layer (III). When the ridge-shaped resin layer (II) is formed on one side of the film (I) in the laminated film in which the ridge-shaped resin layer (II) is formed on the previous film, that is, the film (I) made of a transparent resin, Preferably, it has the following physical properties.

  (1) Haze is also referred to as haze value and represents the degree of haze and the degree of diffusion. The haze (%) can be measured. The haze of the title film is preferably 1% or less. When the haze is outside the above range, white blur occurs and the visibility of the touch panel decreases.

(2) Total light transmittance (%) is, for example, commercially available Suga Test Instruments Co., Ltd. HGM-2D
When using P or the like and measuring according to JIS K-7361, the visibility of the touch panel is improved, so 80% or more is preferable, 83% or more is more preferable, and 85% or more is more preferable.

  (3) When the transmitted light b * (%) is measured according to JIS Z-8722 using, for example, a commercially available color difference meter RETS-1200VA manufactured by Otsuka Electronics Co., Ltd., the visibility of the touch panel is improved. Since it improves, 0 to 10% is preferable, 0 to 5% is more preferable, and 0 to 2% is more preferable.

  (4) Pencil hardness is preferably HB or higher when measured according to JIS K5600-5-4 using NP manufactured by Toyo Seiki Co., Ltd. If it is less than HB, the transparent conductive film may be damaged during ITO film formation.

  (5) For anti-glare properties, when a fluorescent lamp (total luminous flux 3520 lm) is projected on the title film and the degree of blur of the fluorescent lamp outline is visually evaluated, it is preferable that the outline of the fluorescent lamp is not known at all.

  (6) It is preferable that the luminance unevenness of the pixel is hardly recognized when the screen of the mobile tool SL-6000N manufactured by Sharp is displayed in green and then evaluated by visual observation after placing the title film thereon.

  (7) Anti-Newton ring property is whether the Newton ring is generated by placing the title film on a smooth glass plate (thickness 3 mm, material: soda glass) so that the bowl-shaped resin layer is in close contact with the finger and pressing it with a finger. When visually evaluating, it is preferable that Newton rings do not occur.

  (8) The heat shrinkage rate (%) is determined by allowing the title film to stand for 60 minutes in a forced circulation dryer heated to 150 ° C., and using a dimension measurement microscope 176-812 made by Mitutoyo before and after heating. When measuring the change and calculating the heat shrinkage rate, it is preferably 1.5% or less, more preferably 1.3% or less, and even more preferably 1.0% or less. If the heat shrinkage rate exceeds 1.5%, the touch panel may be deformed.

  (9) The retardation is not particularly limited, but when the film (I) made of transparent resin is a retardation film, “KOBRA-21ADH / PR” manufactured by Oji Scientific Instruments Co., Ltd. The phase difference (nm) measured for transmitted light having a wavelength of 550 nm is preferably 128 to 148 nm, and more preferably 133 to 143 nm. If the phase difference deviates from the above, the contrast and visibility of the liquid crystal display may be lowered.

<Transparent conductive layer (III)>
In the conductive laminated film (A) of the present invention, the above-described ridge-shaped resin layer (II) is formed on a film (I) made of a transparent resin, and the transparent conductive layer is further formed on the ridge-shaped resin layer (II). (III) is laminated.

The transparent conductive layer (III) constituting the conductive laminated film (A) of the present invention is not particularly limited as long as it has a transparency in the visible light region and has conductivity. Inorganic / organic composite materials in which indium oxide containing tin oxide (indium tin oxide, hereinafter also referred to as ITO), indium oxide containing titanium oxide, tin oxide, titanium oxide, polythiophene, inorganic nanoparticles, etc. are dispersed The layer obtained from is mentioned. In the present invention, the transparent conductive layer (III) is preferably a layer made of ITO, and more specifically, a layer made of crystalline ITO.

(Formation of transparent conductive layer (III))
When forming the transparent conductive layer (III) made of ITO, a conventionally known ITO target is used as a target. As a target agent used for forming the ITO film, the weight ratio of indium oxide to tin oxide is preferably 99: 0.5 to 99:20, more preferably 99: 1 to 90:15, and still more preferably 99: 1. It is desirable to use the one of ˜90: 10. When the weight ratio is out of the above range, the resistance value increases.

The temperature during the ITO film formation is preferably not higher than the glass transition temperature (Tg) of the film (I) made of transparent resin, more preferably “room temperature to Tg of transparent resin”, and “room temperature to Tg− of transparent resin”. “20 ° C.” is more preferable. When the Tg of the transparent resin constituting the film (I) is exceeded, the film may be deteriorated. In addition, when the Tg of the bowl-shaped resin layer (II) is lower than the Tg of the transparent resin, it is desirable to perform film formation at a temperature equal to or lower than the Tg of the bowl-shaped resin layer (II).

In addition, a small amount of oxygen in Ar as an atmosphere gas during ITO film formation, preferably 0.05 to 20% by volume, more preferably 0.01 to 10% by volume, and more preferably 0.01 to 10% by volume with respect to the total of Ar and O ₂ When 0.1 to 3% by volume of O ₂ is preferably introduced, the transparency and conductivity of the ITO thin film can be improved.

As a method for forming the transparent conductive layer (III), any of the conventionally known techniques such as a vacuum deposition method, a sputtering method, and an ion plating method can be used. From the viewpoint of adhesion, it is preferable to form a thin film by a sputtering method. In addition to the above, the thin film material to be used is, for example, metal oxide such as tin oxide containing antimony, gold, silver, platinum, palladium, copper, aluminum, nickel, chromium, titanium, cobalt, tin, or these An alloy or the like may be used. The thickness of the conductive thin film is preferably 30 mm or more, and if it is thinner than this, it may be difficult to form a continuous film having good conductivity with a surface resistance of 1000 Ω / □ or less. On the other hand, if it is too thick, it may cause a decrease in transparency and the like, and a suitable thickness is about 50 to 2000 mm.

When forming an ITO thin film as the transparent conductive layer (III), it is preferable to form crystalline ITO. The film formation method of the crystalline ITO thin film includes a pulse sputtering method in which the power applied to the target electrode (cathode) is intermittently changed, and a dual cathode pulse sputtering method in which a plurality of cathodes are arranged as a basic configuration in this pulse sputtering method. Is used. These sputtering methods preferably use a magnetron sputtering method in order to cope with a plasma discharge at a better degree of vacuum. Also, in order to have a stable generation of pulse current and freedom of condition setting, a pulse generation unit is used. It is preferable to use a bipolar type or a unipolar type. Alternatively, it can be obtained by a method of crystallization by annealing at a temperature level of about 150 ° C. after film formation. The durability is remarkably improved by using a crystallized ITO film.

<Easily adhesive layer>
The conductive laminated film (A) of the present invention has a bowl-shaped resin layer (II) for the purpose of improving the adhesion between the bowl-shaped resin layer (II) and the transparent conductive layer (III) and imparting gas barrier properties. It is also preferable to have an easy-adhesion layer between the transparent conductive layer (III). The easy-adhesion layer may or may not contain metal oxide fine particles, but it is preferable to contain metal oxide fine particles because adhesion is improved. Usually, a preferable easy-adhesion layer is obtained by preparing a coating liquid composed of a composition containing metal oxide fine particles and polysiloxane, and coating and drying the coating liquid on a transparent resin film.

(Metal oxide fine particles)
The type of metal oxide fine particles used in the easy adhesion layer is not particularly limited as long as it is an oxide fine particle of a metal element. For example, antimony oxide, zirconium oxide, anatase type titanium oxide, rutile type titanium oxide, brookite type oxidation Titanium, zinc oxide, tantalum oxide, indium oxide, hafnium oxide, tin oxide, niobium oxide, aluminum oxide, cerium oxide, scandium oxide, yttrium oxide, lanthanum oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide, Terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, lutetium oxide, calcium oxide, gallium oxide, lithium oxide, strontium oxide, tungsten oxide, oxide Potassium, magnesium oxide, and complexes thereof, and indium - such as oxides of the metal 2 or more complex such as tin composite oxides.

  The primary average particle diameter of the metal oxide fine particles is preferably 0.1 to 100 nm, more preferably 0.1 to 70 nm, and particularly preferably 0.1 to 50 nm. When the primary average particle diameter of the metal oxide fine particles is in the above range, a laminated film having excellent light transmittance can be obtained.

(Polysiloxane)
The polysiloxane used for the easy-adhesion layer is preferably a polyfunctional polysiloxane.

  As the polyfunctional polysiloxane, a polysiloxane obtained by subjecting a polyfunctional polysiloxane having a dimethylsiloxane chain and a polydimethylsiloxane to a dealcoholization reaction is preferable. The polyfunctional polysiloxane and the polydimethylsiloxane preferably have an alkoxyl group or a hydroxyl group at the terminal functional group. The polyfunctional polysiloxane and the polydimethylsiloxane are obtained by subjecting dimethylsiloxane and polydimethylsiloxane having different terminal functional groups to a dealcoholization reaction. Polysiloxane is obtained.

<Antireflection layer>
The conductive laminated film (A) of the present invention may have an antireflection layer between the ridge-shaped resin layer (II) and the transparent conductive layer (III) for the purpose of improving the transmittance in the visible light region. preferable. The antireflection layer usually has a laminated structure of two or more layers including a low refractive index layer such as silicon oxide and magnesium fluoride and a high refractive index layer such as titanium oxide, niobium oxide and tantalum oxide.

  As a method for forming a low and high refractive index layer composed of these inorganic oxides, vacuum deposition, sputtering, ion plating (dry process) or ultrafine particles of inorganic oxides such as metal alkoxides and zirconium oxide are used. A publicly known method such as a coating method (wet process) of the coating liquid containing it can be employed.

It is also preferable to apply an organic material mainly composed of a fluoropolymer as the low refractive layer.
<Characteristics of conductive laminated film (A)>
The conductive laminated film (A) of the present invention preferably has the following physical properties. In addition, the measurement method of each following physical-property value is as having mentioned above in the physical property of the laminated film which consists of a film (I) / bowl-shaped resin layer (II) unless there is particular notice.

(1) The haze is preferably 1% or less. When the haze is 1% or less, white blurring can be prevented and the background image can be projected more clearly.
(2) The total light transmittance is preferably 80% or more, more preferably 83% or more, and even more preferably 85% or more because the visibility of the touch panel is improved.

(3) The transmitted light b * is preferably 0 to 12%, more preferably 0 to 7%, and still more preferably 0 to 4% because the visibility of the touch panel is improved.
(4) The pencil hardness is preferably HB or higher. If the pencil hardness is less than HB, the transparent conductive film may be damaged during ITO film formation.

(5) It is preferable that the antiglare property does not reveal the outline of the fluorescent lamp.
(6) It is preferable that the luminance unevenness hardly recognizes the luminance unevenness of the pixel.
(7) It is preferable that anti-Newton ring property does not generate Newton ring.

  (8) The heat shrinkage rate is preferably 1.5% or less, more preferably 1.3% or less, and further preferably 1.0% or less. If the heat shrinkage rate exceeds 1.5%, the touch panel may be deformed.

  (9) The phase difference is preferably 128 to 148 nm, preferably 133 to 143 nm when measuring the phase difference (nm) for light having a wavelength of 550 nm using “KOBRA-21ADH / PR” manufactured by Oji Scientific Instruments. Is more preferable. When the phase difference deviates from the above, the contrast and visibility of the liquid crystal display are lowered.

  (10) The surface resistance (Ω / □) is preferably 200 to 1500 Ω / □, for example, when measured using a commercially available low resistivity meter “Loresta-GP” manufactured by Mitsubishi Chemical Corporation. -1000Ω / □ is more preferable, and 300-500Ω / □ is more preferable. If the surface resistance exceeds 1500 Ω / □, it may be difficult to form a continuous film having good conductivity. On the other hand, if it is less than 200 Ω / □, transparency may be lowered and a touch panel may malfunction.

Touch panel In the touch panel of the present invention, the conductive laminated film (A) of the present invention is suitably used as an upper electrode and / or a lower electrode of a 4-wire resistive film type touch panel or the like. And the display apparatus which has a touch-panel function is obtained by arrange | positioning this touch panel in the front surface of a liquid crystal display.

  The touch panel of the present invention has the conductive laminated film (A) provided with the above-described saddle-shaped resin layer (II), and preferably the conductive laminated film (A) as the lower electrode and the conductive as the upper electrode. It is the structure which used the combination laminated film (B). The conductive laminated film (A) and the conductive laminated film (B) are preferably combined through a spacer as necessary so that the respective transparent conductive layers face each other.

  The conductive laminated film (B) used as the upper electrode of the touch panel is preferably formed by laminating a transparent conductive layer, a transparent resin film, and, if necessary, a polarizing plate in this order. The transparent resin film constituting the conductive laminated film (B) used as the upper electrode may be a retardation film or a film that does not exhibit retardation, such as a normal PET film. Moreover, the thing similar to an electroconductive laminated film (A) can also be used as an electroconductive laminated film (B).

As a transparent conductive layer which comprises a conductive laminated film (B), the thing similar to the transparent conductive layer (III) which comprises the conductive laminated film (A) mentioned above is mentioned, Especially the transparent conductive layer which consists of ITO. The transparent layer is preferable, and the transparent conductive layer made of crystalline ITO is more preferable. The transparent conductive layer is formed on the transparent resin film via an easy adhesion layer, an antireflection layer, or the like as necessary.

When the transparent resin film constituting the conductive laminated film (B) is a retardation film, it is desirable that the in-plane retardation with respect to transmitted light having a wavelength of 550 nm is 128 to 148 nm, preferably 133 to 143 nm. A / 4λ retardation film is particularly preferable.

The conductive laminated film (B) used in the present invention preferably has a polarizing plate on the side opposite to the transparent conductive layer of the transparent resin film. The polarizing plate constituting the conductive laminated film (B) has a function of polarizing film, that is, splitting incident light into two polarizing components orthogonal to each other, allowing only one of them to pass, and absorbing or dispersing the other components. If it has a film | membrane, it will not specifically limit. As such a polarizing film, for example, polyvinyl alcohol (hereinafter also referred to as “PVA”) / iodine polarizing film; PVA / dye polarizing film obtained by adsorbing and orienting a dichroic dye on a PVA film; PVA film A polyene-based polarizing film in which a polyene is formed by a dehydration reaction of a polyvinyl chloride film, a dehydrochlorination reaction of a polyvinyl chloride film, etc .; two colors on the surface and / or inside of a PVA-based film composed of a modified PVA containing a cationic group in the molecule And a polarizing film having a functional dye. Of these, PVA / iodine polarizing films are preferred.

  The manufacturing method of a polarizing film is not specifically limited, A conventionally well-known method is applicable. For example, a method of adsorbing iodine ions after stretching a PVA-based film; a method of stretching a PVA-based film after dyeing with a dichroic dye; a method of stretching a PVA-based film and then dyeing with a dichroic dye; And a method of stretching a chromogenic dye on a PVA-based film; a method of stretching a PVA-based film and then printing a dichroic dye. More specifically, iodine is dissolved in a potassium iodide solution to form higher-order iodine ions, the ions are adsorbed on a PVA film and stretched, and then a 1 to 5% by weight boric acid aqueous solution has a bath temperature of 30. A method for producing a polarizing film by immersing at -40 ° C; or a PVA film treated with boric acid in the same manner as described above and stretched about 3 to 7 times in a uniaxial direction, and then 0.05 to 5 wt% dichroism Examples include a method for producing a polarizing film by immersing the dye in an aqueous dye solution at a bath temperature of 30 to 40 ° C. to adsorb the dye, then drying at 80 to 100 ° C. and heat setting.

Although the thickness of a polarizing film is not specifically limited, 10-50 micrometers is preferable and 15-45 micrometers is more preferable.
These polarizing films may be used as they are for the production of the polarizing plate of the present invention, but can also be used after the corona discharge treatment or plasma treatment is applied to the surface in contact with the adhesive layer.

Although the polarizing plate used by this invention may be comprised only from the polarizing film, it may have a protective film for the purpose of providing moisture absorption resistance etc. to a polarizing film.
When the conductive laminated film (B) according to the present invention has a polarizing plate, the transparent conductive layer, the retardation film, and the polarizing plate are preferably laminated in this order, specifically, the retardation film, It is preferable that the polarizing plate is constituted by adhering to the polarizing film with a pressure-sensitive adhesive on the surface opposite to the transparent conductive layer of the conductive laminated film on which the transparent conductive layer is laminated.

As the pressure sensitive adhesive, a polyvinyl alcohol pressure sensitive adhesive, an acrylic pressure sensitive adhesive, a rubber pressure sensitive adhesive, a silicone pressure sensitive adhesive, and the like are suitable.
In the touch panel of the present invention, a conductive laminated film (B) in which a transparent conductive layer, a 1 / 4λ retardation film and a polarizing plate are integrally laminated in this order is used as an upper electrode, and a 1 / 4λ position is used as a corresponding lower electrode. By using the conductive laminated film (A) in which the bowl-shaped resin layer (II) and the transparent conductive layer (III) are laminated on the film (I) which is a phase difference film, reflected light is suitably suppressed, and visual recognition is performed. It is preferable because the properties are particularly improved.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following, “part” means “part by weight”.
Various physical properties were measured or evaluated as follows.

(1) Haze Using a Suga Test Instruments Co., Ltd. HGM-2DP, haze (%) was measured based on JIS K-7136.

(2) Total light transmittance Total light transmittance (%) was measured based on JIS K-7361 using Suga Test Instruments Co., Ltd. HGM-2DP.

(3) Transmitted light b *
Using a color difference meter RETS-1200VA manufactured by Otsuka Electronics Co., Ltd., the transmitted light b * (%) was measured according to JIS Z-8722.

(4) Pencil hardness Pencil hardness was measured based on JIS K-5600-5-4 using a pencil scratch coating film hardness tester NP manufactured by Toyo Seiki Co., Ltd.

(5) Antiglare property A fluorescent lamp (total light flux: 3520 lm) was projected on the film, and the degree of blurring of the outline of the fluorescent lamp was visually evaluated according to the following criteria.

A: The outline of the fluorescent lamp is not known at all. B: The outline of the fluorescent lamp is slightly understood. C: The outline of the fluorescent lamp is clearly understood. (6) Brightness unevenness After the screen of Sharp mobile tool SL-6000N is displayed in green, the film And visually evaluated according to the following criteria.

A: Pixel brightness unevenness is hardly recognized B: Pixel brightness unevenness is recognizable, but not noticeable C: Pixel brightness unevenness is clearly recognizable (7) Anti-Newton ring property A film is a smooth glass plate (thickness 3 mm, The material-containing resin layer was placed on top of the material (soda glass) and pressed with a finger, and it was visually evaluated whether Newton rings would occur.

A: Newton ring does not occur B: Newton ring slightly occurs C: Newton ring clearly occurs (8) Heat shrinkage rate The film is allowed to stand for 60 minutes in a forced circulation dryer heated to 150 ° C. Then, the dimensional change of the film before and after heating was measured for each of the longitudinal direction (MD) and the width direction (TD) of the film using a dimensional measurement microscope 176-812 manufactured by Mitutoyo, and the thermal shrinkage rate (%) was calculated.

(9) Residual solvent The film was allowed to stand in a forced circulation dryer heated to 160 ° C. for 30 minutes, the mass change before and after heating was examined, and the mass increase rate (%) was defined as the residual solvent (%).

(10) Phase difference (nm) at a wavelength of 550 nm was measured using “KOBRA-21ADH / PR” manufactured by Oji Scientific Instruments.

(11) Surface resistance The surface resistance value (Ω / □) of the transparent conductive layer was measured using a low resistivity meter “Loresta-GP” manufactured by Mitsubishi Chemical Corporation.

(12) Contrast evaluation of touch panel In a dark room, the black display screen of the touch panel was viewed from the front, and the color change was visually observed and evaluated according to the following criteria.

A: There is no color change of the touch panel and there is a clear feeling B: No color change of the touch panel C: Some color change of the touch panel is observed D: Color change of the touch panel is large (13) Visual recognition of the touch panel Evaluation of color The color change of the screen when the viewing angle was changed was visually observed.

A: There is no change in the color of the touch panel and there is a clear feeling B: There is no change in the color of the touch panel C: A slight change in the color of the touch panel is observed D: A large change in the color of the touch panel [Synthesis Example 1] Synthesis of cyclic olefin polymer A)
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
227.5 parts of 3-dodecene, 22.5 parts of bicyclo [2.2.1] hept-2-ene, 18 parts of 1-hexene (molecular weight regulator), 750 parts of toluene (solvent for ring-opening polymerization reaction) The solution was charged in a reaction vessel purged with nitrogen, and the solution was heated to 60 ° C. Next, 0.62 part of a toluene solution of triethylaluminum (1.5 mol / L) and tungsten hexachloride modified with t-butanol / methanol (t-butanol: methanol: tungsten) were added to the solution in the reaction vessel. 37 parts of a toluene solution (concentration 0.05 mol / L) of 35 mol: 0.3 mol: 1 mol) was added, and the system was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction. Thus, a ring-opening copolymer solution was obtained. The polymerization conversion rate in this polymerization reaction was 97%.

The autoclave was charged with 4,000 parts of the ring-opening copolymer solution thus obtained, and 0.48 part of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening copolymer solution. And a hydrogenation reaction was performed by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 160 ° C.

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

[Production Example 1] (Production of Cyclic Olefin Polymer Film A-1)
The cyclic olefin polymer A obtained in Synthesis Example 1 was dissolved in toluene so that the solid content concentration was 30%. The solution viscosity at room temperature of the obtained solution was 30,000 mPa · s. In this solution, pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] as an antioxidant was added in an amount of 0.1 weight with respect to 100 parts by weight of the cyclic olefin polymer A. The resulting solution was filtered using a metal fiber sintered filter made by Nippon Pole with a pore diameter of 5 μm while controlling the flow rate of the solution so that the differential pressure was within 0.4 MPa. Using an “INVEX Lab Coater” manufactured by Inoue Metal Industry installed in a clean room, a PET film having a thickness of 100 μm (made by Toray Industries, Inc.) treated with an acrylic acid-based surface treatment agent to make it hydrophilic (easy to adhere). Lumirror U94 "). Next, the obtained liquid layer was subjected to a primary drying treatment at 50 ° C., and further subjected to a secondary drying treatment at 90 ° C., and then peeled off from the PET film, whereby a 188 μm-thick cyclic olefin-based weight was obtained. Combined film A-1 was formed. The obtained cyclic olefin polymer film A-1 had a residual solvent amount of 0.5% by weight and a light transmittance of 93% or more.

[Production Example 2] (Production of Cyclic Olefin Polymer Film A-2)
The cyclic olefin polymer film A-1 obtained in Production Example 1 is heated to 148 ° C. in a longitudinal stretching furnace provided with a wind direction control plate, and the temperature distribution in the stretching machine furnace is within 148 ± 0.2 ° C. In the controlled layer, the furnace speed was 1.2 m in the longitudinal direction of the film at 4.0 m / min, uniaxial stretching without fixing the film width direction, R0 was 138 nm, R0 variation was ± 5 nm and light Cyclic olefin polymer film A-2 whose axis was 0 ± 2 degrees with respect to the film longitudinal direction was obtained.

[Production Example 3] (Production of polarizing film)
PVA was pre-stretched at a stretch ratio of 3 times in a dyeing bath at a temperature of 30 ° C. consisting of an aqueous solution having an iodine concentration of 0.03% by weight and a potassium iodide concentration of 0.5% by weight, and then boric acid A polarizing film is obtained by post-stretching at a stretch ratio of 2 in a cross-linking bath having a temperature of 55 ° C. consisting of an aqueous solution having a concentration of 5% by weight and a potassium iodide concentration of 8% by weight, followed by drying. It was.

[Preparation Example 1] (Preparation of mixed adhesive)
Water was added to 163-030545 (molecular weight: 22,000, saponification degree: 88 mol%) manufactured by Wako Pure Chemical Industries, Ltd., which is a PVA resin, to prepare an aqueous solution having a solid content concentration of 7% by weight. . On the other hand, 100 parts of WLS-201 (solid concentration 35% by weight) manufactured by Dainippon Ink and Chemicals, which is a polyurethane resin, is added to CR- manufactured by Dainippon Ink & Co., which is a polyepoxy curing agent. 5 L (100% active ingredient product) 5 parts was blended and diluted with water to prepare an aqueous solution with a solid content of 20% by weight. The obtained polyurethane resin aqueous solution and polyvinyl alcohol resin aqueous solution were mixed at a weight ratio of 1: 1 (solid content weight ratio of 80:20), and a mixed adhesive having a solid content concentration of 15% by weight was obtained. Prepared.

[Production Example 1] (Production of laminated film B-1)
A UV curable resin (Desolite KZ-9136 manufactured by JSR Corporation) was applied to one side of the cyclic olefin polymer film A-2 by a gravure reverse method, and then adhered to a roll on which a bowl shape was formed. / ultraviolet cm ² was irradiated to obtain a thickness 5μ of triangular cross section height 1μ on the foundation, a film having a ridge shape of the pitch 400 [mu].

The results of measuring or evaluating various physical properties of the obtained laminated film B-1 are shown in Table 1, the appearance of the film is shown in FIG. 1, and the cross-sectional shape is shown in FIG.
[Production Example 2] (Production of laminated film B-2)
A laminated film B-2 was obtained in the same manner as in Production Example 1 except that the cyclic olefin polymer film A-1 was used instead of the cyclic olefin polymer film A-2. The results of measuring or evaluating various physical properties of the obtained laminated film B-2 are also shown in Table 1.

［実施例１］（導電性積層フィルムＣ−１の製造）
積層フィルムＢ−１における畝形状樹脂層の面に、大気中で５０Ｗ・ｍｉｎ／ｍ²のコ
ロナ放電処理を行なった。

[Example 1] (Production of conductive laminated film C-1)
The surface of the bowl-shaped resin layer in the laminated film B-1 was subjected to a corona discharge treatment of 50 W · min / m ² in the air.

  A transparent conductive layer was formed on the surface by sputtering using a target containing indium and tin under an argon gas inflow to obtain a conductive laminated film C-1. It was 550 ohms / square when the surface resistance value in the transparent conductive layer of the obtained electroconductive laminated film C-1 was measured. The results of measuring and evaluating various physical properties are shown in Table 2.

(conditions)
Substrate temperature: 50 ° C. or less Target: In ₂ O ₃ / SnO ₂ = 90/10 (weight ratio) oxide Atmosphere: Under argon flow Argon flow rate: 100 to 500 sccm
Output: 1 ~ 1.5Kw
[Example 2] (Production of conductive laminated film C-2)
Instead of the laminated film B-1, a conductive laminated film C-2 was obtained in the same manner as in Example 1 except that the laminated film B-2 was used. The results of measuring and evaluating various physical properties are also shown in Table 2.

[Comparative Example 1] (Production of conductive laminated film C-3)
Example 1 with the exception of using the cyclic olefin polymer film A-2 in place of the laminated film B-1 and using one side of the cyclic olefin polymer film A-1 instead of the surface of the bowl-shaped resin layer. Similarly, a conductive laminated film C-3 was obtained. The results of measuring and evaluating various physical properties are shown in Table 2.

［実施例３］（タッチパネルの作製）
実施例２で得られた導電性積層フィルムＣ−２を下部電極として、１８８μのＰＥＴフィルムに実施例１と同様の方法でＩＴＯをスパッタリングしたフィルムを上部電極とした。この２枚を、透明導電膜面が対向するように、スペーサーを介して重ね合わせ、液晶表示素子上に配置して、本発明のタッチパネルを得た。その構成を図３に示す。得られたタッチパネルについて、コントラストとアンチニュートンリング性と視認性を評価した。結果を表３に示す。

[Example 3] (Production of touch panel)
The conductive laminated film C-2 obtained in Example 2 was used as the lower electrode, and a film obtained by sputtering ITO on a 188 μm PET film in the same manner as in Example 1 was used as the upper electrode. The two sheets were overlapped with a spacer so that the transparent conductive film surfaces face each other and placed on the liquid crystal display element to obtain the touch panel of the present invention. The configuration is shown in FIG. About the obtained touch panel, contrast, anti-Newton ring property, and visibility were evaluated. The results are shown in Table 3.

[Example 4] (Production of polarizing plate and touch panel)
The mixed adhesive obtained in Preparation Example 1 was applied to the opposite side of the transparent conductive film of the conductive retardation film obtained by sputtering ITO on the cyclic olefin polymer film A-2 in the same manner as in Example 1. The upper electrode was laminated so as to be in contact with the polarizing film. In addition, it bonded together so that the absorption axis of a polarizing film and the optical axis of the phase-difference film in an electroconductive laminated film may make an angle of 45 degrees in that case.

  Using the conductive laminated film C-1 obtained in Example 1 as a lower electrode, these two sheets are overlapped via a spacer so that the transparent conductive film faces each other, and placed on the liquid crystal display element. A touch panel of the present invention was obtained. The configuration is shown in FIG.

  At this time, the polarization axis of the liquid crystal display element is set to 45 ° direction, the optical axis of the retardation film of the lower electrode is set to 0 ° direction, the axis of the bowl shape is set to 35 ° direction, and the optical axis of the retardation film of the upper electrode is set to The orientation was 90 ° and the optical axis of the polarizing plate was 45 °.

About the obtained touch panel, contrast, anti-Newton ring property, and visibility were evaluated. The results are shown in Table 3.
[Comparative Example 2] (Production of touch panel)
A touch panel was obtained in the same manner as in Example 2 except that the conductive laminated film C-3 was used instead of the conductive laminated film C-1. The contrast and anti-Newton ring visibility of the obtained touch panel were evaluated. The results are also shown in Table 3.

  The conductive laminated film of the present invention can be suitably used as a transparent electrode for a display such as a liquid crystal display or a touch panel, and is particularly suitable for a touch panel application, particularly a touch panel application for a display device. The touch panel of the present invention is useful as a touch panel for various display devices such as liquid crystal display elements. For example, personal digital assistant (PDA), notebook PC, OA equipment, medical equipment, or electronic equipment such as a car navigation system. It can be suitably used as a touch panel.

FIG. 1 shows the appearance of the conductive laminated film obtained in Production Example 1. FIG. 2 shows a cross-sectional shape of the conductive laminated film obtained in Production Example 1. FIG. 3 shows the configuration of the touch panel obtained in Example 3. FIG. 4 shows the configuration of the touch panel obtained in Example 4.

Claims (9)

A wrinkle-shaped resin layer (II) in which a wrinkle shape is formed at a predetermined pitch with a UV curable resin composition on at least one surface of a film (I) made of a transparent resin, and a transparent conductive layer (III)
Are laminated | stacked in this order, The electroconductive laminated film (A) characterized by the above-mentioned.   The ridge-shaped resin layer (II) has ridges having a polygonal cross section at a pitch in the range of 100 to 5000 μm, and the height of the ridges is 0.1 to 10 μm. The conductive laminated film (A) described.   The conductive laminated film according to claim 1 or 2, wherein the film (I) made of a transparent resin is a retardation film having an in-plane retardation in a range of 128 to 148 nm with respect to transmitted light having a wavelength of 550 nm. (A).   The conductive laminated film (A) according to any one of claims 1 to 3, wherein the film (I) made of a transparent resin contains a cyclic olefin-based resin and / or a polycarbonate resin. The film (I) made of a transparent resin contains a cyclic olefin-based resin obtained by (co) polymerizing a monomer containing at least one compound represented by the following formula (1): The electroconductive laminated film (A) in any one of 1-4.

(In the formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom; a halogen atom; or a monovalent organic group that may contain oxygen, nitrogen, sulfur or silicon;
R ¹ and R ² and R ³ and R ⁴ may be independently bonded to each other to form an alkylidene group,
R ¹ and R ² , R ³ and R ⁴ , and R ² and R ³ may be independently bonded to each other to form a monocyclic or polycyclic carbocyclic or heterocyclic ring,
x represents an integer of 0 to 3, and y represents 0 or 1. ) The conductive laminated film (A) according to any one of claims 1 to 5, wherein the transparent conductive layer (III) is made of crystalline ITO.   A touch panel comprising the conductive laminated film (A) according to claim 1. The conductive laminated film (A) according to any one of claims 1 to 6,
A conductive laminate film (B) in which a transparent conductive layer, a retardation film, and a polarizing plate are laminated in this order, and
Both the film (I) made of a transparent resin constituting the conductive laminated film (A) and the retardation film constituting the conductive laminated film (B) have an in-plane retardation of 128 with respect to transmitted light having a wavelength of 550 nm. A touch panel, which is a retardation film in a range of ˜148 nm. The transparent conductive layer (III) constituting the conductive laminated film (A) and the conductive laminated film (
The touch panel according to claim 8, wherein both of the transparent conductive layers constituting B) are made of crystalline ITO.

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