JP2009202538A - Electrically-conductive laminated film, polarizing plate, and touch panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrically-conductive laminated film which is excellent in glare-proof properties and anti-Newton ring properties, has no irregularity of brightness, and to provide a polarizing plate using the film and a touch panel with the polarizing plate. <P>SOLUTION: The electrically-conductive laminated film having a layer consisting of a transparent resin film, a particle-containing resin layer and a transparent electrically-conductive layer, is characterized in that the particle-containing resin layer contains a profile polymer particle with a shape in which two approximately spherical particles, a particle (a) and a particle (b), are joined together, and the profile polymer particle has a number-average particle diameter of 0.8-10 μm. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a conductive laminated film, a polarizing plate using the film, and a touch panel having the polarizing plate. More specifically, the present invention includes a conductive laminated film having excellent antiglare property and anti-Newton ring property and having no luminance unevenness by containing irregularly shaped polymer particles, a polarizing plate using the film, and the polarizing plate. The present invention relates to a so-called polarizing plate integrated inner touch panel.

  Currently, liquid crystal display devices are used as display devices for televisions, personal computers, and the like. The liquid crystal display device includes a light source, a light guide plate disposed and irradiated in the vicinity of the light source, and a liquid crystal display panel such as a light diffusion plate, a prism sheet, and a touch panel sequentially disposed in front of the light guide plate. I have. The light diffusing plate disposed in front of the light guide plate is used for more uniformly diffusing the light that has passed through the light guide plate. Attempts have been made to improve the luminance of the liquid crystal display device by improving the characteristics of the light diffusion plate.

  As related art, a light diffusing plate using light diffusing resin particles in which a variation coefficient (CV value) of an average particle size and a particle size distribution is set within a predetermined range is disclosed (for example, Patent Document 1). reference).

  However, even when the light diffusing plate using the light diffusing resin particles described in Patent Document 1 is used, it cannot be said that the luminance of the liquid crystal display device is sufficiently improved, and further improvement is desired. It was. Specifically, there has been a demand for the development of a light diffusing plate having good light transmittance and light diffusibility and higher brightness. In order to satisfy such a demand, a light diffusion plate using synthetic resin particles having an average particle size and an average particle size distribution set within a predetermined range is disclosed (for example, see Patent Document 2).

  However, even with the light diffusing plate using the synthetic resin particles described in Patent Document 2, there is still room for improvement in light transmittance and light diffusibility. Development of a material capable of producing such a light diffusion molded product has been desired.

Further, in the above liquid crystal display device or the like, when transmitted light or reflected light is not properly diffused on the surface, the pixel looks distorted when viewed from the front, and further discomforts to the eyes (so-called “brightness” There was a problem of "unevenness"). In order to prevent the above problems, an antiglare film is usually provided on the surface of the liquid crystal display device, but there is room for improvement in the performance of the antiglare film.
JP-A-7-234304 JP 2004-226604 A

  The present invention has a conductive laminated film excellent in antiglare property (performance for preventing glare, the same shall apply hereinafter) and anti-Newton ring property and without uneven brightness, a polarizing plate using the film, and the polarizing plate. An object is to provide a touch panel.

As a result of intensive studies on the touch panel in order to solve the above problems, the inventors of the present invention have excellent antiglare property and anti-Newton ring property as well as luminance by incorporating irregular polymer particles in the conductive laminated film constituting the touch panel. The inventors have found that unevenness can be prevented and have completed the present invention.

That is, this invention is specified by the matter described below.
The conductive laminated film of the present invention is a conductive laminated film having a layer made of a transparent resin film, a particle-containing resin layer, and a transparent conductive layer, and the particle-containing resin layer is two substantially spherical particles ( a) shaped polymer particles having a shape in which the particles and (b) particles are combined, and the shaped polymer particles have a number average particle diameter of 0.8 to 10 [mu] m.

  The odd-shaped polymer particles are preferably composed of at least one polymer selected from (1) a polymer having an aromatic vinyl monomer unit and (2) a polymer having an acrylic monomer unit.

The deformed polymer particles are preferably composed of at least two types of polymers.
It is preferable that (a ′) particles, which are substantially spherical particles, are seed polymer particles, and the shape of the (b) particles is formed by seed polymerization.

It is preferable that the particle-containing resin layer and the transparent conductive layer are sequentially laminated on the surface of the transparent resin film.
The transparent resin film is preferably composed of a cyclic olefin polymer obtained by (co) polymerizing a monomer containing at least one compound represented by the following formula (I).

（式中、Ｒ¹〜Ｒ⁴は、それぞれ独立に、水素原子；ハロゲン原子；炭素原子数１〜１０の炭化水素基；または酸素原子、窒素原子、イオウ原子もしくはケイ素原子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または１〜３の整数を表し、ｙは、０または１を表す。）
上記異形ポリマー粒子は、上記粒子含有樹脂層中に０．５〜５０重量％で含有されることが好ましい。

(In the formula, each of R ^{1 to} R ⁴ independently contains a hydrogen atom; a halogen atom; a hydrocarbon group having 1 to 10 carbon atoms; or an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom. Represents a monovalent organic group, and R ¹ and R ² , 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, and x is 0 or 1 to 3 And y represents 0 or 1.)
The irregularly shaped polymer particles are preferably contained in the particle-containing resin layer at 0.5 to 50% by weight.

The particle-containing resin layer can contain the irregular shaped polymer particles and the active energy ray-curable resin composition.
Moreover, this invention is a touchscreen characterized by having the polarizing plate characterized by the said electroconductive laminated film being laminated | stacked on a polarizing film, and this polarizing plate.

The present invention provides a conductive laminated film that is excellent in antiglare property and anti-Newton ring property and does not have uneven brightness by containing one kind of irregularly shaped polymer particles without using a plurality of particles having different particle sizes, and the film The polarizing plate and touch panel which use this can be provided.

  The present invention is a conductive laminated film having a transparent resin film, a particle-containing resin layer, and a transparent conductive layer, wherein the particle-containing resin layer is two substantially spherical particles (a) particles and (b) particles And the modified polymer particles have a number average particle diameter of 0.8 to 10 μm.

Hereinafter, the present invention will be specifically described.
<Transparent resin film>
As the transparent resin film, a film made of a thermoplastic resin having transparency and heat resistance is preferable.

The thermoplastic resin preferably has a glass transition temperature of 120 ° C. or more and a linear expansion coefficient of 7.0 × 10 ⁻⁵ / ° C. or less. For example, a cyclic olefin polymer, polycarbonate (PC), polyarylate ( PAR), polysulfone (PSF), polyethersulfone (PES), polyparaphenylene (PPP), polyarylene ether phosphine oxide (PEPO), polyimide (PPI), polyetherimide (PEI), polyamideimide (PAI) Etc. Of these, cyclic olefin polymers and PES are preferred, and cyclic olefin polymers are more preferred.

(Cyclic olefin polymer)
As the cyclic olefin polymer, a cyclic olefin compound having a norbornene skeleton is used alone or in combination of two or more, or a copolymerization monomer other than the cyclic olefin compound is further used in combination with ring-opening (co) polymerization or addition. Those obtained by (co) polymerization and then hydrogenation of double bonds in the main chain are preferred.

  The cyclic olefin compound is preferably a monomer containing at least one compound represented by the following formula (I) (hereinafter also referred to as “specific monomer”). The following formula (I ′) represents a structural unit derived from a specific monomer, and what is obtained by polymerizing or copolymerizing the specific monomer is also referred to as “(co) polymer” hereinafter.

（式（１）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に、水素原子；ハロゲン原子；炭素原子数１〜１０の炭化水素基；または酸素原子、窒素原子、イオウ原子もしくはケイ素原子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または１〜３の整数を表し、ｙは、０または１を表す。）

(In Formula (1), R < ¹ > -R < ⁴ > respectively independently contains a hydrogen atom; a halogen atom; a C1-C10 hydrocarbon group; or an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom. R ¹ and R ² , R ³ and R ⁴ may be independently bonded to each other to form an alkylidene group, and R ¹ and R 2 may be 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, and x is 0 or Represents an integer of 1 to 3, and y represents 0 or 1.)

（式（Ｉ'）中、Ｒ¹〜Ｒ⁴、ｘおよびｙは、上記式（Ｉ）のＲ¹〜Ｒ⁴、ｘおよびｙと同様
である。）
（共）重合体としては、具体的には、下記（ｉ）〜（ｉｉｉ）の（共）重合体が好ましい。

(In the formula ^{(I '), R 1 ~R} 4, x and y are the same as R ¹ to R ^4, x and y of the above formula (I).)
Specifically, the (co) polymer is preferably the following (co) polymers (i) to (iii).

(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.
(Specific monomer)
Specific examples of the specific monomer used as the raw material for the cyclic olefin polymer include the following compounds, but are not limited to these specific examples.
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-trifluoromethoxytetracyclo [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-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene,
8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.
4.0.1, ² , ^5.1,10 ] -3-dodecene and the like. These may be used alone or in combination of two or more.

Among these specific monomers, in the above formula (I), R ¹ and R ³ are hydrogen atoms or 1 to 10 carbon atoms, more preferably 1 to 4, more preferably 1 to 2. 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 monovalent organic group having a polarity other than a hydrogen atom or a hydrocarbon group, x represents an integer of 0 to 3, y represents an integer of 0 to 3, more preferably x + y = 0-4, more preferably 0-2, particularly preferably x = 0, y = 1, the cyclic olefin polymer obtained has a high glass transition temperature and mechanical strength. It is preferable at the point which becomes excellent.

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.

Furthermore, in the above formula (I), a monomer in which at least one of R ² and R ⁴ represents a monovalent organic group having a polarity represented by the formula: — (CH ₂ ) _n COOR is a cyclic product. The olefin polymer 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 polymer, which is preferable, and the specific unit amount where n is 0. The body is preferred because it is easy to synthesize.

In the above formula (I), 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 polymer can be lowered.

(Copolymerizable 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 this 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 (the solvent constituting the molecular weight regulator solution, the solvent for the specific monomer and / or the metathesis catalyst) include, for example, pentane, hexane,
Alkanes such as heptane, octane, nonane, decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, Halogenated alkanes such as methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform, and tetrachloroethylene, aryl halides; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, and dimethoxyethane And ethers such as dibutyl ether, tetrahydrofuran, and dimethoxyethane. These may be used alone or in combination of two or more. 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- By adding (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and / or UV absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, etc. Can be stabilized. Further, additives such as a lubricant can be added for the purpose of improving processability.

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

Further, as the cyclic olefin polymer, a (co) polymer obtained by cyclization of the ring-opened (co) polymer by 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 polymers)
The molecular weight of the cyclic olefin polymer is intrinsic viscosity [η] _inh , preferably 0.2 to
Number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) of 5 dl / g, more preferably 0.3 to 3 dl / g, still more preferably 0.4 to 1.5 dl / g. 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 polymer, and the conductive laminated film of the present invention As a result, the balance with the stability of the optical properties when used as a good is obtained.

  The glass transition temperature (Tg) of the cyclic olefin polymer is usually 120 ° C. or higher, preferably 120 to 350 ° C., more preferably 130 to 250 ° C., and further preferably 140 to 200 ° C. This is to stabilize the change in optical properties of the obtained cyclic olefin polymer 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 polymer 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 resulting cyclic olefin polymer film is excellent in adhesiveness with other optical members and adhesives, and peeling occurs during use. In addition, 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 polymer 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 (× Those satisfying 10 ⁻¹² Pa ⁻¹ ) are preferred. 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), photoelasticity experiment method, Nikkan Kogyo Shimbun,
It is described in the 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 ) is generated from an external factor or a strain generated from its own frozen strain when the cyclic olefin polymer film is used in combination with another optical member or an adhesive. Represents that the optical characteristics change sensitively due to stress, etc. For example, when a transparent conductive layer is laminated as in the present invention, and when used by being fixed to another optical member, the residual at the time of bonding It means that an unnecessary phase difference is likely to be generated due to a minute stress generated by distortion, shrinkage of a material due to temperature change, humidity change, and the like. 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 draw ratio when imparting the retardation to a cyclic olefin polymer film, or a large amount. There is a great merit that it is easy to obtain a film capable of imparting a phase difference, and 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. To 50 (× 10 ⁻¹² Pa ⁻¹ ), particularly preferably 0 to 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 polymer can be further stabilized by adding known antioxidants, ultraviolet absorbers and 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] And methane, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] and the like. Examples thereof include 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone.

(Transparent resin film)
When a cyclic olefin polymer film is used as the transparent resin film, the cyclic olefin polymer is molded into a film or sheet by a known method such as a melt molding method or a solution casting method (solvent casting method). Can be used. Of these, the 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 retardation of the transparent resin film is preferably 0 to 50 nm, more preferably 0 to 20 nm, and still more preferably 0 to 10 nm because a polarizing plate integrated inner touch panel with high contrast and high visibility can be obtained. Have.

The total light transmittance of the transparent resin 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.
The thickness of the transparent resin film is generally 1 to 500 μm, preferably 1 to 300 μm, more preferably 10 to 250 μm, and more preferably, because it ensures good handling and facilitates winding into a roll. Is 50 to 200 μm.

  The thickness distribution of the transparent resin 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.

  The transparent resin film may be stretched as necessary, and specifically can be produced 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.

  In the case of using a cyclic olefin polymer film, 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 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. 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. Is 100 to 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 to Tg + 10 ° C., based on the glass transition temperature (Tg) of the transparent resin. Range. 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 not particularly limited because it is determined by the type of resin and desired properties, but when using a cyclic olefin polymer film, it is usually 1.01 to 10 times, preferably 1.1 to 5 times. More preferably, it is 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.

Further, the linear expansion coefficient of the transparent resin 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. In the case of a retardation film, 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, more 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. Here, the phase difference is defined by the product (Δnd) of the refractive index difference (Δn) of birefringent light and the thickness (d). Such a stretched film preferably has a high contrast and a polarizing plate-integrated inner touch panel with high visibility. Therefore, the stretched film preferably has Δnd of ¼ of the wavelength λ of transmitted light.

  Further, the transparent resin film may be subjected to a surface treatment for the purpose of enhancing the adhesiveness with the particle-containing protective layer. Examples of the surface treatment include plasma treatment, corona treatment, alkali treatment, and coating treatment. In particular, the use of corona treatment can strengthen the adhesion between the transparent resin film and the particle-containing protective layer.

When the cyclic olefin polymer film is used, the corona treatment condition is preferably 1 to 1,000 W / m ² / min as the irradiation amount of corona discharge electrons.
More preferably, it is 0 W / m ² / min. 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 transparent resin 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 particle-containing protective layer but also on the opposite surface.

Further, it may be applied immediately after the corona treatment, or may be applied after neutralizing. Since the appearance of the particle-containing protective layer is good, it is preferable to coat after removing the charge.
<Particle-containing resin layer>
The particle-containing resin layer is generally composed of two substantially spherical particles (a) particles and (b) deformed polymer particles having a shape in which the particles are combined, and a base resin portion. The base resin part is preferably formed from an active energy ray-curable resin composition.

(Atypical polymer particles)
The irregularly shaped polymer particles have a shape in which (a) particles and (b) particles are bonded. Here, “(a) particles” and “(b) particles” describe two substantially spherical shapes present in the irregular polymer particles as particles. Typical shapes of the irregularly shaped polymer particles include a spherical shape having a spherical protrusion as shown in FIG. 1A, a rugby ball shape as shown in FIG. 1B, a twin sphere shape as shown in FIG. However, the modified polymer particles are not limited to these. A preferable shape in the present invention includes a sphere having a spherical protrusion as shown in FIG. As used herein, the term “deformed” refers to (a) particles in a cross section obtained by cutting the deformed polymer particles according to an embodiment of the present invention along a plane passing through the center of the particles (a) and (b) the center of the particles ( b) A shape in which the center-to-center distance exceeds 0 and is equal to or less than the sum of (a) particle radius and (b) particle radius.

  The odd-shaped polymer particles preferably have a ratio of the number average value (L) of the major axis to the number average value (D) of the minor axis (L) / (D) = 1.1 to 1.9. 1.2-1.8 is more preferable.

  Here, “major axis” and “minor axis” in the case where the irregularly shaped polymer particles have a spherical shape having spherical protrusions as shown in FIG. As shown in FIG. 2, the major axis (L) is represented by the distance from the end of (a) particle 1 to the end of (b) particle 2. The short diameter (D) is represented by the diameter of the larger one of the particles ((a) particle 1 in FIG. 2).

The deformed polymer particles preferably have a shape in which the particle diameters of (a) particles and (b) particles are different, and when the particle diameter is (a) particles> (b) particles, the particle diameter of (a) particles (L _a ) and (b
) The ratio of the particle diameter to the particle diameter (L _b ) is preferably (L _a ) / (L _b ) = 1.05-20, more preferably 1.1-10, 1.2 More preferably, it is ~ 3.

If the value of (L _a ) / (L _b ) exceeds 20, the balance between light transmittance and light diffusibility may be inferior. On the other hand, if the value of (L _a ) / (L _b ) is less than 1.05, the balance between light transmittance and light diffusibility may be deteriorated, and the anti-Newton ring property may be deteriorated.

(Polymer constituting particles)
The deformed polymer particles are preferably composed of at least one polymer selected from (1) a polymer having an aromatic vinyl monomer unit, and (2) a polymer having an acrylic monomer unit. More preferably, the irregularly shaped polymer particles are composed of at least two types of polymers.

  The two types of polymers are (a ′) a polymer constituting the seed polymer particles (hereinafter also referred to as “first polymer”) and seed polymerization in the method for producing deformed polymer particles described later. By making the polymer constituting the (b) particles formed (hereinafter also referred to as “second polymer”) different, it can be introduced into the deformed polymer particles.

The first polymer is preferably a polymer capable of absorbing an oil-soluble polymerization initiator containing an organic compound having a water solubility of 10 ⁻² wt% or less. Specific examples include styrene polymers such as styrene polymers and styrene-butadiene copolymers, and styrene- (meth) acrylic acid ester polymers.

  The first polymer and the second polymer include, for example, (1) an aromatic vinyl monomer unit (hereinafter also referred to as “constituent unit (1)”), and (2) an acrylic unit as a constituent unit. At least one component selected from the group consisting of a monomer unit (hereinafter also referred to as “structural unit (2)”) and (3) other monomer units (hereinafter also referred to as “structural unit (3)”). It is preferable that it contains a unit, and it is preferable that the types of constituent units, the content ratio, and the like are different as described below.

(1) Aromatic vinyl monomer unit The aromatic vinyl monomer used to constitute the structural unit (1) includes, for example, styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-tert-butylstyrene, 3,4-dimethylstyrene, 4-methoxystyrene, 4-ethoxystyrene, 2-chlorostyrene, 3 -Chlorostyrene, 4-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene, 4-chloro-3-methylstyrene, divinylbenzene, 1-vinylnaphthalene, 2-vinylpyridine, 4-vinylpyridine, Monobromostyrene, dibromostyrene, tribromostyrene, hydroxystyrene, styrenes Sulfonic acid, styrene sulfonic acid Natorumu salts. Of these, styrene,
Divinylbenzene and α-methylstyrene are preferred. These aromatic vinyl monomers can be used singly or in combination of two or more.

(2) Acrylic monomer unit The acrylic monomer used for constituting the structural unit (2) is a monomer having a polar functional group in its molecule. Preferred examples of the polar functional group include a carboxyl group, a cyano group, a hydroxyl group, a glycidyl group, and an ester group. Specific examples of the acrylic monomer include monomers shown in the following <1> to <5>. In addition, the monomer illustrated below can be used individually by 1 type or in combination of 2 or more types.

  <1> Carboxyl group-containing monomer: (meth) acrylic acid, crotonic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, monomethyl maleate, monoethyl maleate, itaconic acid Carboxyl group-containing unsaturated monomers such as monomethyl, monoethyl itaconate, and mono-2- (meth) acryloyloxyethyl hexahydrophthalate, and anhydrides thereof. Of these, (meth) acrylic acid is preferred.

  <2> Monomers containing cyano groups: vinyl cyanide monomers such as (meth) acrylonitrile, crotonnitrile, cinnamate nitrile; 2-cyanoethyl (meth) acrylate, 2-cyanopropyl (meth) acrylate, 3 -Cyanopropyl (meth) acrylate and the like. Of these, (meth) acrylonitrile is preferable.

  <3> Hydroxyl group-containing monomer: hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) Hydroxy (cyclo) alkyl mono (meth) acrylates such as acrylate; substituted hydroxy (cyclo) alkyl mono (3-chloro-2-hydroxypropyl (meth) acrylate, 3-amino-2-hydroxypropyl (meth) acrylate and the like ( (Meth) acrylates and the like. Of these, hydroxymethyl (meth) acrylate is preferable.

  <4> Glycidyl group-containing monomers: allyl glycidyl ether, glycidyl (meth) acrylate, methyl glycidyl methyl acrylate, epoxidized cyclohexyl (meth) acrylate, and the like. Of these, glycidyl (meth) acrylate is preferable.

  <5> Ester group-containing monomer: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate (Cyclo) alkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate, alkoxy (cyclo) alkyl (meth) acrylates such as p-methoxycyclohexyl (meth) acrylate; trimethylolpropane tri (meth) acrylate Polyvalent (meth) acrylates such as vinyl esters such as vinyl acetate, vinyl propionate and vinyl versatate. Of these, methyl (meth) acrylate is preferable.

(3) Other monomer units Examples of the other monomers constituting the structural unit (3) include those shown below.
N-methylol unsaturated carboxylic acid amides such as N-methylol (meth) acrylamide and N, N-dimethylol (meth) acrylamide; aminoalkyl group-containing acrylamides such as 2-dimethylaminoethylacrylamide; (meth) acrylamide; Amides or imides of unsaturated carboxylic acids such as N-methoxymethyl (meth) acrylamide, N, N-ethylenebis (meth) acrylamide, maleic acid amide, maleimide; N-methylacrylamide, N, N-dimethylacrylamide, etc. N-monoalkyl (meth) acrylamides, N, N-dialkylacrylamides; aminoalkyl group-containing (meth) acrylates such as 2-dimethylaminoethyl (meth) acrylate; 2- (dimethylaminoethoxy) ethyl (meth) Ak Aminoalkoxyalkyl group-containing (meth) acrylates such as rate; vinyl halides such as vinyl chloride, vinylidene chloride and fatty acid vinyl ester; 1,3-butadiene, 2-methyl-1,3-butadiene, 2- Conjugated diene compounds such as chloro-1,3-butadiene and 2,3-dimethyl-1,3-butadiene.

(Configuration of first and second polymers)
There may be various combinations of the first polymer and the second polymer, but the following two embodiments are preferable. In any embodiment, the ratio of each structural unit is described as the sum of the structural unit (1), the structural unit (2), and the structural unit (3) being 100% by weight.

<Aspect I>
First polymer: 60 to 98% by weight of the structural unit (1), 2 to 40% by weight of the structural unit (2), and 0 to 38% by weight of the structural unit (3). If the proportion of the structural unit (1) is less than 60% by weight, the light diffusibility may be inferior. On the other hand, if it exceeds 98% by weight, it tends to be difficult to obtain irregularly shaped polymer particles.

  Second polymer: The structural unit (1) is 0 to 25% by weight, the structural unit (2) is 75 to 100% by weight, and the structural unit (3) is 0 to 25% by weight. If the proportion of the structural unit (2) is less than 75% by weight, the light transmittance may be inferior.

<Aspect II>
First polymer: The structural unit (1) is 60 to 100% by weight, and the structural unit (3) is 0 to 40% by weight. If the proportion of the structural unit (1) is less than 60% by weight, the light diffusibility may be inferior.

Second polymer: the structural unit (1) is 60 to 98% by weight, the structural unit (2) is 2 to 40% by weight, and the structural unit (3) is 0 to 40% by weight.
The irregular polymer particles have a ratio of (a ′) particle refractive index (R _a ) to (b) particle refractive index (R _b ): (R _a ) / (R _b ) = 0.7 to 1. 4, more preferably 0.8 to 1.3, and even more preferably 0.85 to 1.25. When the value of (R _a ) / (R _b ) is less than 0.7, it tends to be difficult to obtain irregularly shaped polymer particles. On the other hand, (R _a
) / (R _b ) exceeding 1.4 tends to make it difficult to obtain irregularly shaped polymer particles. The refractive index is a value measured by the following method.

  Refractive index measurement: <1> Particles to be measured are dried at 80 ° C. for 24 hours, crushed, and filtered through a 60 mesh wire net to prepare dried primary particles. <2> A primary particle dispersion is prepared by mixing dry primary particles and a refractive index standard solution (manufactured by Cargille) having an appropriate refractive index. <3> The primary particle dispersion is observed with a microscope to confirm whether or not the outline of the primary particle is visible, and the refractive index of the refractive index standard solution when the primary particle dispersion is not visible is the “refractive index” of the particle. It was.

(Method for producing irregularly shaped polymer particles)
The irregularly shaped polymer particles can be produced, for example, according to the following method. First, the (a ′) particles comprising the first polymer can be obtained by a usual emulsion polymerization method using an aqueous medium. The “aqueous medium” means a medium mainly composed of water. Specifically, the water content in the aqueous medium is preferably 40% by weight or more, and more preferably 50% by weight or more. Other media that can be used in combination with water include compounds such as esters, ketones, phenols, and alcohols.

  The conditions for emulsion polymerization may be in accordance with known methods. For example, when the total amount of monomers used is 100 parts, usually 100 to 500 parts of water is used, and the polymerization temperature is -10 to 100 ° C (preferably -5 to 100 ° C, more preferably 0 to 90 ° C). C.) and a polymerization time of 0.1 to 30 hours (preferably 2 to 25 hours). As a method of emulsion polymerization, a batch method in which monomers are charged at once, a method in which monomers are divided or continuously supplied, a method in which a monomer pre-emulsion is divided or continuously added, or these A method that combines methods in stages can be adopted. Moreover, the molecular weight regulator used for normal emulsion polymerization, a chelating agent, an inorganic electrolyte, etc. can be used 1 type, or 2 or more types as needed.

When an initiator is used in emulsion polymerization, examples of the initiator include persulfates such as potassium persulfate and ammonium persulfate; benzoyl peroxide, lauroyl peroxide, tert-butylperoxy-2-ethylhexano Organic peroxides such as ate; azo compounds such as azobisisobutyronitrile, dimethyl-2,2′-azobisisobutyrate, 2-carbamoylazaisobutyronitrile; radical emulsifying compounds having a peroxide group A redox system in which a reducing agent such as a radical emulsifier containing sodium, sodium hydrogen sulfite, and ferrous sulfate is combined can be used. Moreover, when using an emulsifier, 1 or more types selected from the group which consists of a well-known anionic emulsifier, a nonionic emulsifier, and an amphoteric emulsifier can be used as this emulsifier. In addition, you may use the reactive emulsifier etc. which have an unsaturated double bond in a molecule | numerator.

  There is no restriction | limiting in particular in the molecular weight modifier used for emulsion polymerization. Specific examples of molecular weight regulators include n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, thioglycolic acid Mercaptans such as dimethyl xanthogen disulfide, diethyl xanthogen disulfide, diisopropyl xanthogen disulfide, etc .; Xanthogen disulfides such as tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide; chloroform, carbon tetrachloride, tetrabromide Halogenated hydrocarbons such as carbon and ethylene bromide; hydrocarbons such as pentaphenylethane and α-methylstyrene dimer; Kurorein, methacrolein, allyl alcohol, 2-ethylhexyl thioglycolate, terpinolene, alpha-Terunepin, .gamma. Terunepin, dipentene, etc. 1,1-diphenyl ethylene. These molecular weight regulators may be used alone or in combination of two or more. Of these, mercaptans, xanthogen disulfides, thiuram disulfides, 1,1-diphenylethylene and α-methylstyrene dimer are preferred.

  The polymerization conversion rate of the monomer at the end of the emulsion polymerization is preferably 80% by weight or more, more preferably 90% by weight or more, and further preferably 95% by weight or more. When the monomer for the second polymer is added in a state where the polymerization addition ratio of the first polymer is less than 80% by weight, the particles (a ′) and (b) formed are clearly separated. It becomes difficult to do. The obtained particles (a ′) comprising the first polymer are usually spherical particles. (A ′) The number average particle diameter of the particles is preferably 0.1 to 10 μm, and more preferably 0.2 to 10 μm. (A ') If the number average particle diameter of the particles is outside this range, it may be difficult to produce by emulsion polymerization.

In the presence of the obtained particles (a ′), the monomer for the second polymer is polymerized. More specifically, (b) particles can be formed by seed polymerizing the monomer for the second polymer in a state where the obtained (a ′) particles are used as seed polymer particles. . For example, (a ′) the second polymer monomer or its pre-emulsion may be added all at once, in a divided manner, or continuously in an aqueous medium in which particles are dispersed. The amount of the particles (a ′) used at this time is preferably 1 to 10,000 parts by weight, and 2 to 9,000 parts by weight with respect to 100 parts by weight of the monomer for the second polymer. More preferably. When an initiator or an emulsifier is used in the polymerization, the same one as used in the production of (a ′) particles can be used. Also, the conditions such as the polymerization time may be the same as in the production of (a ′) particles.

  (A ′) When the second polymer monomer is introduced into the aqueous medium in which the particles are dispersed, as shown in FIG. The part is usually occluded once (a ′) by the particles, and polymerization is initiated in or at the surface of the (a ′) particles. As the polymerization proceeds, the compatibility of the second polymer monomer with the first polymer decreases, and the second polymer monomer phase separates from the first polymer. For this reason, at the initial stage of polymerization, (a ′) the polymerization can proceed at a plurality of positions of the particle. However, when the monomer units constituting each polymer satisfy the relationship described so far, the second weight The coalescence of (a ′) particles polymerized at various points tends to gather together to form a single (b) particle (FIG. 3B). When (b) particles grow to a certain size, the subsequent polymerization proceeds mainly with the (b) particles (FIG. 3 (c)). In this way, deformed polymer particles in which (a) particles and (b) particles are asymmetrically separated are formed.

  The number average particle diameter of the irregular shaped polymer particles obtained as described above is 0.8 to 10 μm, preferably 0.9 to 7 μm, more preferably 1 to 5 μm. When the number average particle diameter is larger than 10 μm, it may be difficult to produce by an emulsion polymerization method. Moreover, when it is smaller than 0.8 μm, sufficient light diffusibility may not be obtained. In addition, the “number average particle diameter” in the irregularly shaped polymer particles refers to the length of the irregularly shaped polymer particles with respect to the longest direction, and can be measured by, for example, a light scattering method.

  The ratio (area ratio = (a) / (b)) between the exposed surface formed by the particles (a) and the exposed surface formed by the particles (area ratio = (a) / (b)) is 5 / It is preferable that it is 95-45 / 55 or 55 / 45-95 / 5, and it is more preferable that it is 10 / 90-40 / 60 or 60 / 40-90 / 10. Note that (a) + (b) = 100. When the proportion of either one of (a) particles and (b) particles is less than the above range, the effect due to the irregular polymer particles being “abnormal” may not be sufficiently obtained. In addition, the ratio of the exposed surface of each primary particle which occupies for the total surface area of a deformed polymer particle can be measured from an electron micrograph, for example.

The shape of the irregular polymer particles depends on the weight ratio of (a) particles to (b) particles, the separability between (a) particles and (b) particles, (b) the polymerization conditions when forming the particles, etc. Various changes.
(Method for forming particle-containing resin layer)
The particle-containing resin layer formed on at least one surface of the transparent resin film is a coating obtained by dispersing or dissolving a deformed polymer particle, an active energy ray-curable resin, and an organic solvent in which these particles can be dispersed or dissolved. The composition is a layer formed by coating and drying the composition with various coaters and then curing the resin.

  The deformed polymer particles are preferably contained in the particle-containing resin layer in an amount of 0.5 to 50% by weight, more preferably 0.5 to 10% by weight, and further preferably 1 to 5% by weight. It is suitable from a viewpoint of anti-glare property that the content rate of a deformed polymer particle is in the said range.

Coating methods for particle-containing protective layers include bar coater coating, air knife coating, gravure coating, gravure reverse coating, reverse roll coating, lip coating, die coating, dip coating, offset printing, flexographic printing Various methods such as printing and screen printing can be employed. Gravure reverse coating or die coating is preferable because the appearance of the particle-containing protective layer is improved.

  The irregular polymer particles contained in the particle-containing resin layer are integrated on the cyclic olefin polymer film by the cured resin. Note that some of the irregularly shaped polymer particles may be in a state in which a part thereof protrudes from the surface of the resin. Further, the protruding portion of the irregularly shaped polymer particles may be entirely covered with the resin or may be only partially covered. Note that all of the irregular polymer particles may be completely buried in the resin.

Although it does not specifically limit about the thickness of a particle-containing resin layer, Usually, 1-20 micrometers, Preferably it is about 1-7 micrometers.
(Active energy ray-curable resin composition)
The base resin portion of the particle-containing resin layer is preferably formed from an active energy ray-curable resin composition. The active energy ray-curable resin composition preferably comprises (A) a polyfunctional monomer having three or more acryloyl groups (hereinafter also referred to as “component (A)”), (B) glycidyl (meth) acrylate polymer and acrylic. A polymer obtained by addition reaction of an acid (hereinafter also referred to as “component (B)”) and (C) optionally other acrylic oligomer (hereinafter also referred to as “component (C)”) in a specific amount. . In particular, the component (A) is a component that can impart the hardness of the transparent conductive layer followed by the active energy ray-curable resin composition, the adhesion to the transparent resin film, 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 during 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 active energy ray-curable resin composition is suitably 40 to 60% by weight (however, the total of the components (A) to (C) is 100% by weight). And is preferably 50 to 60% by weight.

  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. Α, β not containing the carboxyl group
Examples of the unsaturated monomer 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 active energy ray-curable resin composition is suitably 10 to 60% by weight (however, the total of the components (A) to (C) is 100% by weight). 20 to 50% by weight is preferable.

  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 active energy ray-curable resin composition is suitably 0 to 50% by weight (however, the total of the components (A) to (C) is 100% by weight).
The active energy ray-curable resin composition can be blended with an organic solvent in order to adjust the viscosity according to the individual application. As the organic solvent, those which do not dissolve the cyclic olefin polymer film, which is a transparent film, are suitable. For example, ester solvents, alcohol solvents, and ketone solvents are preferable.

As the active energy ray used for curing the active energy ray-curable resin composition, for example, any of ultraviolet rays, electron beams and the like may be used. 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.

(Other ingredients)
In addition to the irregularly shaped polymer particles and the active energy ray-curable resin composition, the coating composition can contain other components such as a curing agent, a dispersing agent, and a dye as necessary.

  The content ratio of the other components is preferably 0 to 10 parts by weight, more preferably 0 to 5 parts by weight with respect to the irregularly shaped polymer particles + active energy ray-curable resin composition = 100 parts by weight. 0 to 3 parts by weight is particularly preferable.

(Organic solvent)
The organic solvent contained in the coating composition only needs to disperse or dissolve the irregularly shaped polymer particles and the active energy ray-curable resin composition to form the coating composition in a slurry state. Specific examples thereof include water, toluene, cyclohexane, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), N-methyl-2-pyrrolidone (NMP) and the like.

  The content ratio of the organic solvent to the coating composition is preferably 10 to 2,000 parts by weight with respect to the irregularly shaped polymer particles + active energy ray-curable resin composition = 100 parts by weight, and 20 to 1,000 parts by weight. More preferably, it is a part.

(Manufacturing method of coating composition)
In order to produce the coating composition, first, the solvent is removed from the emulsion containing the deformed polymer particles obtained according to the method for producing the deformed polymer particles described above to obtain dried deformed polymer particles (step <1>). . In this step <1>, the method for removing the solvent from the emulsion is not particularly limited, but a freeze-drying method and a spray-drying method are preferable because they can be easily dried.

  In addition, it is preferable to dry until the content rate of a solvent will be 5.0 weight% or less, and it is more preferable to dry until it will be 3.0 weight% or less. When the solvent content is more than 5.0% by weight, dispersibility in the active energy ray-curable resin composition is lowered, and it tends to be difficult to produce a molded product having a uniform light diffusion function. is there.

  Next, the obtained deformed polymer particles in the dried state, the active energy ray-curable resin composition, and the organic solvent are dispersed or dissolved (step <2>). In this step <2>, the coating composition can be obtained by uniformly dispersing or dissolving the irregularly shaped polymer particles, the active energy ray-curable resin composition, and the above-described other components added as necessary. . Other components may be dispersed or dissolved later. Although it does not specifically limit about the stirring method, For example, it can stir using various kneaders, a bead mill, a high-pressure homogenizer, etc.

(Physical properties of laminated film consisting of transparent resin film / particle-containing resin layer)
The haze is also referred to as haze value and represents the degree of haze and the degree of diffusion. For example, haze (in accordance with JIS K-7136 is used, using commercially available Suga Test Instruments Co., Ltd. HGM-2DP). %) Can be measured. The haze of the title film is preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less. When the haze is outside the above range, white blur occurs and the visibility of the touch panel decreases.

When the total light transmittance (%) is measured in accordance with JIS K-7361 using, for example, a commercially available Suga Test Instruments Co., Ltd. HGM-2DP, the visibility of the touch panel is improved. 80% or more, more preferably 83% or more, and still more preferably 85% or more.

  For example, when the transmitted light b * is measured according to JIS Z-8722 using a commercially available color difference meter RETS-1200VA manufactured by Otsuka Electronics Co., Ltd., the visibility of the touch panel is improved. -10 are preferred, 0-5 are more preferred, and 0-2 are even more preferred.

  The 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 or equal to HB, the transparent conductive film may be damaged during ITO film formation.

The antiglare property is preferably such that the fluorescent lamp (total luminous flux 3520 lm) is projected on the title film and the outline of the fluorescent lamp is visually evaluated for the degree of blurring of the fluorescent lamp.
The luminance unevenness is preferably such that the luminance unevenness of the pixels is hardly recognized when the screen of the Sharp mobile tool SL-6000N is displayed in green, and then the mark film is placed and visually evaluated.

  Anti-Newton ring property is a visual observation of whether or not Newton rings are generated by placing the title film on a smooth glass plate (thickness 3 mm, material: soda glass) so that the particle-containing resin layer is in close contact and pressing with a finger. When evaluating, it is preferable that a Newton ring does not generate | occur | produce.

  The thermal shrinkage rate (%) is determined by allowing the title film to stand for 60 minutes in a forced circulation dryer heated to 150 ° C., and measuring the dimensional change of the film before and after heating using a Mitutoyo dimensional measuring microscope 176-812. And when calculating a thermal contraction rate, 1.5% or less is preferable, 1.3% or less is more preferable, and 1.0% or less is further more preferable. If the heat shrinkage rate exceeds 1.5%, the touch panel may be deformed.

  For the residual solvent (%), the title film was allowed to stand for 30 minutes in a forced circulation dryer heated to 160 ° C., the mass change before and after heating was examined, and the mass increase rate (%) was determined as the residual solvent (%). When it does, 2% or less is preferable, 1.5% or less is more preferable, and 1% or less is further more preferable. If the residual solvent exceeds 2%, the amount of the volatile solvent at the time of ITO film formation increases and a defect of the ITO film may occur.

  When the phase difference is measured using “KOBRA-21ADH / PR” manufactured by Oji Scientific Instruments, 0 nm to 50 nm is preferable, 0 nm to 20 nm is more preferable, and 0 to 10 nm is more preferable. When the phase difference deviates from the above, the visibility of the liquid crystal display is lowered.

<Transparent conductive layer>
The conductive laminated film of the present invention is obtained by further laminating a transparent conductive layer on a film obtained by laminating a particle-containing resin layer on the surface of the transparent resin film described above.

The transparent conductive layer is a layer obtained from an inorganic / organic composite material in which indium oxide containing tin oxide, indium oxide containing titanium oxide, tin oxide, titanium oxide, polythiophene, inorganic nanoparticles, etc. are dispersed, It is a layer having transparency in the visible light region and having conductivity.

  A conventionally well-known ITO target is used as a target at the time of forming a transparent conductive film. 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 substrate temperature during ITO film formation is preferably “room temperature to film Tg”, more preferably “room temperature to film Tg−20 ° C.”. If it is Tg or more, film deterioration may occur.

Further, Ar is a trace amount of oxygen as an atmospheric gas during film formation, preferably 0.05 to 20% by volume, more preferably 0.01 to 10% by volume, and still more preferably based on the total of Ar and O _2. When 0.1 to 3% by volume of O ₂ is introduced, the transparency and conductivity of the ITO thin film can be improved.

  As a method for forming the transparent conductive layer, any of the conventionally known techniques such as a vacuum deposition method, a sputtering method, and an ion plating method can be used, but the uniformity of the film and the adhesion of the thin film to the transparent substrate can be used. From the viewpoint, thin film formation by sputtering is preferable. 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 1,000 Ω / □ or less. On the other hand, if the thickness is too large, the transparency may be lowered, and the preferred thickness is about 50 to 2,000 mm.

<Anchor coat layer>
An anchor coat layer may be laminated between the transparent resin film layer and the transparent conductive layer for the purpose of improving the adhesion between the transparent resin film layer and the transparent conductive layer and providing gas barrier properties. The anchor coat layer may or may not contain metal oxide fine particles, but it is preferable to contain metal oxide fine particles because adhesion is improved. A preferred anchor coat layer is obtained by preparing a coating liquid comprising 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 anchor coat layer is not particularly limited as long as it is a metal element oxide fine particle. 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 , Barium oxide, 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 anchor coat 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. Polysiloxane is obtained.

<Antireflection layer>
The conductive laminated film of the present invention preferably has an antireflection layer between the transparent conductive layer and the particle-containing resin layer for the purpose of improving the transmittance in the visible light region. The antireflection layer is usually composed of a laminated film having a low refractive index layer and a high refractive index layer. Preferred examples include a low refractive index layer made of silicon oxide, magnesium fluoride, etc., titanium oxide, niobium oxide, and the like. And a laminated structure of two or more layers including a high refractive index layer made of tantalum oxide or the like. Generally, it becomes a laminated structure in the order of transparent conductive layer / low refractive index layer / high refractive index layer / particle-containing resin layer.

  Examples of the method for forming the low refractive index layer and the high refractive index layer include known methods such as vacuum deposition, sputtering, ion plating (dry process), and inorganic oxides such as metal alkoxides and zirconium oxide. A coating method (wet process) of a coating solution containing the ultrafine particles can also be employed.

It is also preferable to apply an organic material mainly composed of a fluoropolymer as the low refractive index layer.
<Conductive laminated film>
As preferred embodiments of the conductive laminated film of the present invention, the following <1> to <3> may be mentioned.

  <1> A particle-containing resin layer and a transparent conductive layer are sequentially laminated on the surface of the transparent resin film, and a particle-containing resin layer is further provided on the surface opposite to the surface on which the particle-containing resin layer of the transparent resin film is formed. A laminated conductive film.

That is, the conductive laminated film is laminated in the order of transparent conductive layer / particle-containing resin layer / transparent resin film / particle-containing resin layer.
<2> A particle-containing resin layer and a transparent conductive layer are sequentially laminated on the surface of the transparent resin film, and a hard coat layer is further laminated on the surface of the transparent resin film opposite to the surface on which the particle-containing resin layer is formed. Conductive laminated film.

That is, the conductive laminated film is laminated in the order of transparent conductive layer / particle-containing resin layer / transparent resin film / hard coat layer.
<3> A hard coat layer and a transparent conductive layer are sequentially laminated on the surface of the transparent resin film, and a particle-containing resin layer is further laminated on the surface of the transparent resin film opposite to the surface on which the hard coat layer is formed. A conductive laminated film.

That is, the conductive laminated film is laminated in the order of transparent conductive layer / hard coat layer / transparent resin film / particle-containing resin layer.
The conductive laminated film has a coding composition (hereinafter also referred to as “hard coat treatment agent”) that does not contain irregular polymer particles on the surface opposite to the surface on which the particle-containing resin layer of the transparent resin film is formed. It is preferable that a hard coat layer made of an active energy ray-curable resin composition (which may optionally contain the filler described above) is formed. In this case, the film thickness of a hard-coat layer is not specifically limited, The film thickness similar to the particle-containing resin layer mentioned above is mentioned. Thus, by providing a particle-containing resin layer on both sides, warping of the film can be prevented.

  The conductive laminated film preferably has an anchor coat layer and / or an antireflection layer laminated between the transparent conductive layer and the particle-containing resin layer, or between the transparent conductive layer and the hard coat layer. Thus, it is preferable to provide the anchor coat layer and / or the antireflection layer because the gas barrier property and the adhesiveness are excellent and the transmittance in the visible light region is improved.

A preferable aspect is shown below about each physical property measured according to the method mentioned above of an electroconductive laminated film.
The haze is preferably about 5 to 12%, more preferably about 5 to 10%. When the haze is within the above range, white blur can be prevented and the background image can be projected more clearly. The haze correlates with the average particle diameter, particle size distribution, content ratio, and the like of the deformed polymer particles contained in the particle-containing resin layer and the conductive particles contained in the transparent conductive layer.

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.
The transmitted light b * is preferably from 0 to 12, more preferably from 0 to 7, and even more preferably from 0 to 4, since the visibility of the touch panel is improved.

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.
For the antiglare property, it is preferable that the outline of the fluorescent lamp is not known at all.

It is preferable that the luminance unevenness hardly recognizes the luminance unevenness of the pixel.
The anti-Newton ring property is preferably such that no Newton ring is generated.
The heat shrinkage rate 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.

The residual solvent is preferably 2% or less, and more preferably 1% or less.
The phase difference is preferably 0 to 50 nm, more preferably 0 to 20 nm, and further preferably 0 nm to 10 nm.

  When the surface resistance (Ω / □) is measured using, for example, a commercially available low resistivity meter “Loresta-GP” manufactured by Mitsubishi Chemical Corporation, 200 to 1500Ω / □ is preferable, and 250 to 1000Ω / □ is more preferable, and 300 to 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.

<Polarizing plate>
The polarizing plate of the present invention is characterized in that the above-mentioned conductive laminated film of the present invention is laminated on a polarizing film. Examples of such a polarizing plate include those in which a conductive laminated film is formed on one side of a polarizing film.

  The polarizing film is not particularly limited, but functions as a polarizing film, that is, incident light is divided into two polarization components orthogonal to each other, only one of them is allowed to pass, and the other component is absorbed or dispersed. The polarizing film is not particularly limited as long as it has a function of allowing the dichroic dye to adsorb on the PVA film, for example, polyvinyl alcohol (hereinafter also referred to as “PVA”) / iodine polarizing film. Oriented PVA / dye polarizing film; polyene polarizing film in which polyene is formed by dehydration reaction of PVA film, dehydrochlorination reaction of polyvinyl chloride film, etc .; from modified PVA containing cationic groups in the molecule And a polarizing film having a dichroic dye on the surface and / or inside of the PVA-based film. 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.

  The polarizing plate of the present invention is bonded to the polarizing film with a pressure sensitive adhesive on the surface opposite to the transparent conductive layer of the conductive laminated film in which the cyclic olefin polymer film, the particle-containing resin layer and the transparent conductive layer are laminated. It is preferable to constitute a polarizing plate.

  As the pressure sensitive adhesive, polyvinyl alcohol pressure sensitive adhesive, polyurethane pressure sensitive adhesive, acrylic pressure sensitive adhesive, rubber pressure sensitive adhesive, silicone pressure sensitive adhesive, and the like are suitable. From the viewpoint of enhancing the adhesion between the transparent resin film and the polarizing film, a polyvinyl alcohol pressure sensitive adhesive, a polyurethane pressure sensitive adhesive, and a mixed adhesive thereof are preferred.

  The polarizing plate 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 described later, and is particularly suitable for a touch panel application, particularly a touch panel application for a display device.

<Touch panel>
The touch panel of the present invention is characterized in that a transparent conductive layer and a polarizing plate are integrated, and is called a so-called polarizing plate integrated inner touch panel. Specifically, the polarizing plate of the present invention is suitably used as an upper electrode and / or a lower electrode of a touch panel such as a 4-wire resistive film system or a 5-wire resistive film system. The upper electrode and the lower electrode are bonded via a spacer so that the respective transparent conductive layers are opposed to each other via a gap. As the spacer, for example, spherical particles having a uniform size, a dot pattern of a cured resin formed by screen printing, patterning of a photosensitive composition, or the like is preferable. 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.

  When the visibility when the display screen of the touch panel thus obtained is touched by hand is visually evaluated, it is preferable that there is no coloring or white blur and the visibility is good.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. Hereinafter, “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.

○: The outline of the fluorescent lamp is not known at all.
Δ: The outline of the fluorescent lamp is slightly known.
X: The outline of the fluorescent lamp can be clearly seen.

(6) Luminance unevenness The screen of the mobile tool SL-6000N manufactured by Sharp was displayed in green, and then a film was placed thereon, and visually evaluated according to the following criteria.

○: Pixel luminance unevenness is hardly recognized.
Δ: Pixel luminance unevenness can be recognized but is not noticeable.
X: Pixel brightness unevenness can be clearly recognized.

(7) Anti-Newton ring property The film is placed on a smooth glass plate (thickness 3 mm, material: soda glass) so that the particle-containing resin layer is in close contact, and pressed with a finger to see if Newton rings occur. evaluated.

○: Newton ring does not occur.
Δ: Newton ring slightly occurs.
X: Newton ring clearly occurs.

(8) Heat shrinkage rate The film was allowed to stand in a forced circulation dryer heated to 150 ° C for 60 minutes, and the dimensional change of the film before and after heating was measured using a dimensional measurement microscope 176-812 made by Mitutoyo. Shrinkage rate (%) was calculated. The vertical direction of the film is MD, and the horizontal direction is TD.

(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) 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) Visibility evaluation of touch panel The visibility when the touch screen display screen was touched by hand was visually evaluated.
○: Visibility is good without coloring or white blurring.

×: Visibility is poor due to coloring and white blurring.
[Synthesis Example 1] Cyclic Olefin Polymer A
8-methyl-8-methoxycarbonyltetracyclo represented by the following formula (2) [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 227.5 parts, bicyclo [6] represented by the following formula (3)
2.2.1] 22.5 parts of hept-2-ene, 18 parts of 1-hexene (molecular weight regulator) and 750 parts of toluene (solvent for ring-opening polymerization reaction) were charged into a nitrogen-substituted reaction vessel. 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 this system was heated and stirred at 80 ° C. for 3 hours to cause ring-opening polymerization reaction. Thus, a ring-opening copolymer solution was obtained. The polymerization conversion rate in this polymerization reaction was 97%.

このようにして得られた開環共重合体溶液４，０００部をオートクレーブに仕込み、この開環共重合体溶液に、ＲｕＨＣｌ（ＣＯ）［Ｐ（Ｃ₆Ｈ₅）₃］₃ ０．４８部を添加し、水素ガス圧力１００ｋｇ／ｃｍ²、反応温度１６０℃の条件下で、３時間加熱攪拌して水
素添加反応を行った。

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] Cyclic olefin polymer film A-1
The obtained cyclic olefin polymer A was dissolved in toluene so that the solid concentration would be 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] Cyclic olefin polymer film A-2
Using a twin screw extruder, 100 parts of cyclic olefin polymer A, 0.3 part of pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] as an antioxidant, and Melting 1.5 parts of 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] as an antioxidant at 270 ° C. After kneading, it was extruded onto a strand, and after cooling with water, a pellet was obtained through a feeder ruder. The obtained pellets were circulated and dehumidified and dried at 100 ° C. for 3 hours under nitrogen, then sent to a hopper and melted at a resin temperature of 270 ° C. using a single screw extruder having a screw diameter of 75 mmφ.

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

  The lip opening was set to 0.5 mm in the width direction, and fine adjustment was performed by measuring thickness unevenness with an on-line thickness gauge installed on the downstream side of melt extrusion. The resin coming out of the die was dropped in the lead direct wire direction of a 250 mmφ cast roll (surface roughness: 0.1 μm) and crimped, and then pressed in order with two cooling rolls installed horizontally to the cast roll axis, and then peeled off. The tension was controlled at 4 kgf and the film was taken up to obtain a cyclic olefin polymer film A-2 having a thickness of 80 μm.

[Production Example 3] Polarizing film Pre-stretching of PVA at a stretching ratio of 3 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. Processed, followed by post-stretching at a draw ratio of 2 in a crosslinking bath consisting of an aqueous solution having a boric acid concentration of 5% by weight and a potassium iodide concentration of 8% by weight, followed by drying treatment Thus, a polarizing film was obtained.

[Preparation Example 1] Mixed adhesive PWA resin 163-030545 (molecular weight: 22,000, degree of saponification: 88 mol%) manufactured by Wako Pure Chemical Industries, Ltd. is added with water to obtain a solid content concentration. A 7 wt% aqueous solution was prepared. 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.

  Polyvinyl alcohol-based resin aqueous solution and polyurethane-based resin aqueous solution are mixed at a weight ratio of 1: 1 (solid content weight ratio of 80:20), and the solid content concentration is 15% by weight. An agent was prepared.

[Preparation Example 2] Polymer particles (A)
Stir 2 parts of 3,5,5-trimethylhexanoyl peroxyside (trade name “Perroyl 355”, manufactured by NOF Corporation, water solubility: 0.01%), 0.1 part of sodium lauryl sulfate, and 20 parts of water. After emulsification, the mixture was further microparticulated with an ultrasonic homogenizer to obtain an aqueous dispersion. To the obtained aqueous dispersion, 15 parts of monodispersed polystyrene particles having a number average particle diameter of 1.0 μm were added and stirred for 16 hours. Next, 70 parts of styrene (ST), 20 parts of divinylbenzene (DVB) and 10 parts of glycidyl methacrylate (GMA) are added, and the mixture is slowly stirred at 40 ° C. for 3 hours to monodisperse the monomer components (ST, DVB, and GMA). Absorbed in polystyrene particles. Then, it heated up at 75 degreeC and performed the polymerization reaction for 3 hours, and obtained the emulsion containing the (a) particle | grains which consist of a 1st polymer. The number average particle diameter of (a) particles was 1.8 μm, and almost no coagulum was generated.

  22.1 parts of the same aqueous dispersion as the above-mentioned aqueous dispersion and 20 parts of the emulsion containing the above-mentioned (a) particles (but as a solid content) were mixed and stirred for 16 hours. Next, 90 parts of methyl (meth) acrylate (MMA) and 10 parts of trimethylolpropane trimethacrylate (TMPMA) are added and stirred slowly at 40 ° C. for 3 hours to add monomer components (MMA and TMPMA) to the particles (a). Absorbed. Thereafter, the temperature is raised to 75 ° C., and a polymerization reaction is carried out for 3 hours to form (b) particles comprising the second polymer, and polymer particles (A) comprising (a) particles and (b) particles. An emulsion containing was obtained. The shape of the polymer particles (A) was irregular (dharma shape), the number average particle size of (b) particles was 2.5 μm, and the number average particle size of the polymer particles (A) was 4.5 μm.

[Preparation Example 3] Hard coat treatment agent A, coating composition B
An ultraviolet curable resin composition (Desolite Z-7524 manufactured by JSR Corporation: the composition is shown in Table 1. The solid content concentration is 53.2%) is converted to 45% by weight with methyl ethyl ketone. Thus, a hard coat treatment agent A comprising a coating composition containing no deformed polymer particles was obtained.

  To the obtained hard coat treatment agent A, 1% by weight of the polymer particles (A) is diluted with methyl ethyl ketone so that the solid content concentration becomes 40% by weight and stirred. Coating composition B was prepared by

［調製例４］アンカーコート層形成用塗布液
攪拌機および還流冷却器を備えた反応器に、Ｍｗ＝２０，０００のアルコキシ末端ポリシロキサン（ＧＥ東芝シリコーン（株）製、商品名：ＸＲ３１−Ｂ２７３３）６０重量部と、Ｍｗ＝４０００のヒドロキシ末端ポリジメチルシロキサン（ＧＥ東芝シリコーン（株）製、商品名：ＹＦ−３８００）４０重量部と、トルエン４２重量部と、ジ−ｉ−プロポキシ・エチルアセトアセテートアルミニウムのイソプロピルアルコール７５％希釈液０．２重量部とを入れて混合し、攪拌しながら８０℃で３時間脱アルコール反応を行った。次いで、メチルイソブチルケトン２８８重量部、メタノール７０重量部、水８０重量部およびトリエチルアミン１２重量部を添加して、６０℃で３時間加水分解・縮合反応を行った。その後、得られた反応液をシュウ酸で中和し、水相（下層）を除去した後に、水洗と水相除去を３回実施後、溶媒を留去してＭｗ＝３０，０００の多官能ポリシロキサンを得た。この多官能ポリシロキサンにメチルイソブチルケトン１００重量部を添加し、固形分濃度５０重量％のポリシロキサン溶液（Ｉ）を得た。

[Preparation Example 4] Coating solution for forming an anchor coat layer In a reactor equipped with a stirrer and a reflux condenser, an alkoxy-terminated polysiloxane with Mw = 20,000 (manufactured by GE Toshiba Silicone Co., Ltd., trade name: XR31-B2733) 60 parts by weight, 40 parts by weight of Mw = 4000 hydroxy-terminated polydimethylsiloxane (manufactured by GE Toshiba Silicone Co., Ltd., trade name: YF-3800), 42 parts by weight of toluene, and di-i-propoxyethyl acetoacetate An aluminum isopropyl alcohol 75% diluted solution 0.2 part by weight was added and mixed, and a dealcoholization reaction was performed at 80 ° C. for 3 hours while stirring. Subsequently, 288 parts by weight of methyl isobutyl ketone, 70 parts by weight of methanol, 80 parts by weight of water and 12 parts by weight of triethylamine were added, and a hydrolysis / condensation reaction was performed at 60 ° C. for 3 hours. Thereafter, the reaction solution obtained was neutralized with oxalic acid, and after removing the aqueous phase (lower layer), washing with water and removal of the aqueous phase were carried out three times, and then the solvent was distilled off to obtain a polyfunctional compound with Mw = 30,000. Polysiloxane was obtained. 100 parts by weight of methyl isobutyl ketone was added to this polyfunctional polysiloxane to obtain a polysiloxane solution (I) having a solid concentration of 50% by weight.

  120 parts by weight of powdered zirconium oxide fine particles (primary average particle size: 20 nm), 160 parts by weight of the polysiloxane solution (I) (80 parts by weight in terms of solid content) as a polysiloxane component, and 0.1 parts by weight of triethylamine And 720 parts by weight of diisobutyl ketone are added to a container, 2000 parts by weight of 0.1 mm diameter zirconia beads are added to the mixture, and the fine particles are dispersed for 6 hours using a paint shaker, and the solid content concentration is 20% by weight. A coating solution for forming an anchor coat layer comprising a polysiloxane composition containing metal oxide fine particles was obtained.

[Production Example 1] Laminated film B-1
Coating composition B was applied to one side of cyclic olefin polymer film A-1 by a gravure reverse method. The coated surface was dried at 80 ° C. for 60 seconds and irradiated with 150 mJ / cm ² ultraviolet rays to obtain a film having a particle-containing resin layer having a thickness of 1.7 μm.

  Next, a hard coat treatment agent A was used to form a hard coat layer on the opposite side of the film in the same manner, thereby forming a laminated film B-1 having a resin layer with a film thickness of 1.7 μm on both sides. Table 2 shows the results of measuring or evaluating various physical properties of the obtained laminated film B-1.

[Production Example 2] Laminated film B-2
In Production Example 1, a laminated film B-2 was obtained in the same manner as in Production Example 1 except that acrylic particles having a number average particle size of 4.3 μm were used instead of the polymer particles (A). Table 2 shows the results of measuring or evaluating various physical properties of the obtained laminated film B-2.

[Production Example 3] Laminated film B-3
In Production Example 1, acrylic particles having a number average particle size of 4.3 μm were used instead of the polymer particles (A), and the content of the hard coat treatment agent A was 25% by weight with respect to the total solid content. Except for having carried out, it carried out similarly to manufacture example 1, and obtained laminated | multilayer film B-3. Table 2 shows the results of measurement or evaluation of various physical properties of the obtained laminated film B-3.

製造例１では、防眩性、輝度ムラ、アンチニュートンリング性および位相差が良好であった。製造例２では、ニュートンリングが確認された。製造例３では、ニュートンリングは確認されないもののヘイズが高く、輝度ムラが劣っていた。製造例４では、位相差が大幅に上昇した。

In Production Example 1, the antiglare property, luminance unevenness, anti-Newton ring property and phase difference were good. In Production Example 2, Newton rings were confirmed. In Production Example 3, Newton's ring was not confirmed, but haze was high and luminance unevenness was inferior. In Production Example 4, the phase difference increased significantly.

[Example 1] Conductive laminated film C-1
The surface of the particle-containing resin layer in the laminated film B-1 is subjected to a corona discharge treatment of 50 W · min / m ² in the atmosphere, and the anchor coating layer forming coating solution is applied with a wire bar having a wet film thickness of 6 μm. And dried at 110 ° C. for 3 minutes to form an anchor coat layer.

  On the surface of the formed anchor coat layer, a transparent conductive layer was formed by sputtering under the following conditions using a target containing indium and tin under an argon gas inflow to obtain a conductive laminated film C-1. . Table 3 shows the results of measuring or evaluating various physical properties of the obtained conductive laminated film C-1.

(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
[Comparative Examples 1 and 2]
In Example 1, except that laminated films B-2 and B-3 were used instead of laminated film B-1, conductive laminated films D-1 and D-2 (comparative examples) were obtained in the same manner as in Example 1. 1, 2) was obtained. Results obtained by measuring or evaluating various physical properties of each of the obtained conductive laminated films in the same manner as in Example 1 are also shown in Table 3.

［実施例２］偏光板およびタッチパネル
偏光膜の両面に、混合接着剤を介して、積層フィルムＢ−１と導電性積層フィルムＣ−１とを用い、導電性積層フィルムＣ−１（ＩＴＯ層は偏光膜と反対側）の表面に順に、偏光膜、積層フィルムＢ−１を積層して、本発明の偏光板を得た。

[Example 2] Polarizing plate and touch panel A laminated film B-1 and a conductive laminated film C-1 are used on both sides of a polarizing film via a mixed adhesive, and the conductive laminated film C-1 (ITO layer is A polarizing film and a laminated film B-1 were laminated in this order on the surface opposite to the polarizing film to obtain a polarizing plate of the present invention.

  An ITO film transparent substrate for a touch panel is superimposed on the liquid crystal display element so that the ITO film is on top, and further, a spacer (micropearl SI, silica particles, average particle diameter 30 μm) is obtained thereon. The obtained polarizing plates were overlapped with the transparent conductive layer side down to obtain the touch panel of the present invention. Table 4 shows the results of evaluating the visibility of the touch panel.

[Comparative Examples 3 and 4]
In Example 2, the laminated films B-2 and B-3 were used instead of the laminated film B-1, and the conductive laminated films D-1 and D-2 were used instead of the conductive laminated film C-1. In the same manner as in Example 2, a polarizing plate and a touch panel (Comparative Examples 3 and 4) were obtained. Table 4 shows the results of evaluating the visibility of the touch panel.

Fig.1 (a)-(c) is a schematic diagram which shows one Embodiment of the irregular-shaped polymer particle | grain used for this invention, respectively. FIG. 2 is a schematic diagram for explaining the major axis and minor axis of the irregularly shaped polymer particles. FIG. 3 (a) is a schematic diagram showing an initial stage in which particles are grown (b), and FIG. 3 (b) is a schematic diagram showing an intermediate stage in which particles are grown (b). FIG.3 (c) is a schematic diagram which shows the last stage of a mode that (b) particle | grains grow.

Explanation of symbols

1 ... (a) Particle 2 ... (b) Particle D ... minor axis L ... major axis

Claims (10)

A conductive laminated film having a layer made of a transparent resin film, a particle-containing resin layer, and a transparent conductive layer,
The particle-containing resin layer contains irregularly shaped polymer particles having a shape in which two substantially spherical particles (a) particles and (b) particles are combined,
The electroconductive laminated film, wherein the irregularly shaped polymer particles have a number average particle diameter of 0.8 to 10 μm.   The irregularly shaped polymer particles are composed of at least one polymer selected from (1) a polymer having an aromatic vinyl monomer unit and (2) a polymer having an acrylic monomer unit. The conductive laminated film according to claim 1.   The conductive laminated film according to claim 1, wherein the deformed polymer particles are composed of at least two types of polymers.   The deformed polymer particle is a substantially spherical particle (a ′), wherein the particle is a seed polymer particle, and the shape of the (b) particle is formed by seed polymerization. The conductive laminated film described in 1.   The conductive laminated film according to claim 1, wherein the particle-containing resin layer and the transparent conductive layer are sequentially laminated on the surface of the transparent resin film. The said transparent resin film consists of a cyclic olefin type polymer obtained by (co) polymerizing the monomer containing the at least 1 sort (s) of compound represented by following formula (I), The conductive laminated film according to any one of 5.

(In the formula, each of R ^{1 to} R ⁴ independently contains a hydrogen atom; a halogen atom; a hydrocarbon group having 1 to 10 carbon atoms; or an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom. Represents a good monovalent organic group,
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 0 or an integer of 1 to 3, and y represents 0 or 1. )   The conductive laminated film according to any one of claims 1 to 6, wherein the deformed polymer particles are contained in the particle-containing resin layer in an amount of 0.5 to 50% by weight. The conductive laminated film according to any one of claims 1 to 7, wherein the particle-containing resin layer contains the irregularly shaped polymer particles and the active energy ray-curable resin composition.   A conductive polarizing film according to claim 1, which is laminated on a polarizing film.   A touch panel comprising the polarizing plate according to claim 9.

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