KR20090092719A - Conductive multilayer film, polarizing plate and touch panel - Google Patents

Abstract

An object of the present invention is to provide a conductive laminated film, a polarizing plate, and a touch panel capable of obtaining a high contrast, high visibility touch panel.

According to the present invention, there is provided a film, a particle-containing resin layer and an indium oxide containing a cyclic olefin polymer and having a quarter wave plate function in an in-plane retardation with respect to transmitted light having a wavelength of 550 nm in a range of 128 to 148 nm. Provided are a conductive laminated film, a polarizing plate using the same, and a touch panel having the polarizing plate, which have a transparent conductive layer having a weight ratio of 95: 5 to 99: 1.

Description

Conductive Laminated Film, Polarizer and Touch Panel {CONDUCTIVE MULTILAYER FILM, POLARIZING PLATE AND TOUCH PANEL}

This invention relates to the electroconductive laminated | multilayer film, polarizing plate, and touch panel with high contrast and high visibility.

BACKGROUND ART In electronic devices such as personal digital assistants (PDAs), note PCs, OA devices, medical devices, or car navigation systems, touch panels having input means for these displays are widely used.

In the transparent conductive film type touch panel, a thin film of metal oxide such as indium tin oxide, tin antimony acid or metal such as gold, palladium, aluminum or silver is provided as a transparent conductive film on one side of the transparent base film. Since the metal thin film has a large reflection of light, the contrast of the liquid crystal display is remarkably lowered, resulting in a very hard to see screen.

As a method of solving such a problem, Patent Document 1 described below discloses two transparent conductive films (lamination films of glass and ITO) facing each other via a first quarter wave plate and a spacer from the liquid crystal display side in order. It is proposed to arrange | position a 1/4 wavelength plate and a polarizing plate of 2, and to improve visibility.

However, only by using the touch panel of the said structure, the contrast of a liquid crystal display is still inadequate, and since a touch panel becomes a multilayered structure, there exists a problem that optical characteristics, such as light transmittance and viewing angle compensation property, are inferior. In order to simplify a layer structure, what laminated | stacked ITO on the film which provided the quarter wave plate function as a transparent conductive film is proposed, but there existed a problem that a phase difference will fall when exposed to high temperature at the time of crystallization annealing or touch panel manufacture. In addition, when the weight ratio of indium oxide to tin oxide is 90:10, there is also a problem that crystallization does not occur even if high temperature annealing treatment is performed, and durability is poor.

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-48625

An object of the present invention is to provide a conductive laminated film, a polarizing plate, and a touch panel capable of obtaining a high contrast, high visibility touch panel.

The electroconductive laminated film of this invention contains the cyclic olefin type polymer obtained by (co) polymerizing the monomer containing the 1 or more types of compound represented by following formula (1), and also the in-plane phase difference with respect to the transmitted light of wavelength 550nm is 128- It is characterized by having a film having a quarter wave plate function in the range of 148 nm, a particle-containing resin layer and a transparent conductive layer having a weight ratio of indium oxide and tin oxide of 95: 5 to 99: 1.

(Wherein, R ¹ to R ⁴ each independently represent a hydrogen atom; a halogen atom; or a monovalent organic group that may contain oxygen, nitrogen, sulfur, or silicon,

R ¹ and R ² and R ³ and R ⁴ may be bonded to each other independently to form an alkylidene group,

R ¹ and R ² , R ³ and R ⁴ , and R ² and R ³ may be bonded to each other independently to form a monocyclic or polycyclic carbocyclic or heterocyclic ring,

x represents an integer of 0 to 3, y represents 0 or 1)

The polarizing plate of the present invention is characterized in that the conductive laminated film of the present invention is laminated on a polarizing film.

The touch panel of the present invention is characterized by having the polarizing plate of the present invention.

According to the present invention, it is possible to obtain a touch panel which does not generate projection due to reflection of light, has high contrast and is also excellent in visibility. Moreover, even if heat processing in a touch panel manufacturing process is carried out, a touch panel with a very small change in phase difference and a very small change in resistance value can be obtained.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure for demonstrating the angle of the absorption axis and the optical axis of each layer in the touchscreen of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.

The conductive laminated film of the present invention has a film having a quarter wave plate function, a particle containing resin layer and a transparent conductive layer, and preferably has a film / particle containing resin layer / transparent conductive layer having a quarter wave plate function. It has a laminated structure in order.

<Film with 1/4 wave plate function>

The film having a quarter wave plate function according to the present invention comprises a cyclic olefin polymer obtained by (co) polymerizing a monomer containing at least one compound represented by the following formula (1), and is applied to transmitted light having a wavelength of 550 nm. The phase difference with respect to the film is a film having a quarter wave plate function of 128 to 148 nm, preferably 133 to 143 nm. Here, the phase difference is defined as the product of the refractive index difference Δn of the birefringent light and the thickness d Δnd. By having the said phase difference, reflected light can be prevented in the polarizing plate of this invention, and the effect that a high contrast touch panel is obtained is exhibited.

The film having the 1/4 wavelength plate function is preferably obtained by stretching the film obtained from the cyclic olefin polymer.

(Cyclic olefin polymer)

As a cyclic olefin type polymer obtained by (co) polymerizing the monomer containing the 1 or more types of compound represented by the said General formula (1) which comprises the film which has a 1/4 wavelength plate function which concerns on this invention, it is represented by said General formula (1) Ring-opening (co) is used alone or in combination of two or more kinds of cyclic olefin compounds (hereinafter also referred to as "specific monomers") having a norbornene skeleton, or in combination with a copolymer monomer other than the cyclic olefin compounds. It is preferable to obtain superposition | polymerization or addition (co) polymerization, and to hydrogenate the double bond in a main chain after that.

In addition, the following general formula (1a) represents the structural unit derived from a specific monomer, and what is obtained by superposing | polymerizing or copolymerizing a specific monomer is also called "(co) polymer" hereafter.

(Wherein R ¹ to R ⁴ , x and y are the same as R ¹ to R ⁴ , x and y of Formula 1 above)

Specifically as a (co) polymer, the (co) polymer of following (i)-(iii) is preferable. Among these, the hydrogenated (co) polymer as described in (ii) is especially preferable.

(i) Ring-opening (co) polymers of specific monomers and copolymerizable monomers as necessary (hereinafter also referred to as "specific ring-opening (co) polymers").

(ii) Hydrogenated (co) polymers of certain ring-opening (co) polymers.

(iii) addition (co) polymers of specific monomers with copolymerizable monomers as necessary.

(Specific monomer)

Although the following compounds are mentioned as a specific example of the specific monomer used as a raw material of a cyclic olefin type polymer, It is 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 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-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-n-butoxycarbonyltetracyclo [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-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

5-ethylidenebicyclo [2.2.1] hept-2-ene,

8-ethylidenetetracyclo [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-fluorotetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-fluoromethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-difluoromethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-pentafluoroethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8-difluorotetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,9-difluorotetracyclo [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-trifluoromethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8,9-trifluorotetracyclo [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-tetrafluorotetracyclo [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-trifluoromethyltetracyclo [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-pentafluoropropoxytetracyclo [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-trifluoromethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-chloro-8,9,9-trifluorotetracyclo [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 ^7,10 ] -3-dodecene

Etc. can be mentioned. These may be used alone or in combination of two or more.

Preferred of these specific monomers, in the general formula (1), R ¹ and R ³ represent a hydrogen atom or a hydrocarbon group of 1 to 10, more preferably 1 to 4, still more preferably 1 to 2 carbon atoms, R ² and R ⁴ are hydrogen atoms; Or a monovalent organic group which may contain an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom, at least one of R ² and R ⁴ 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 to 4, still more preferably 0 to 2, particularly preferably x = 0, y = The specific monomer of 1 is preferable at the point that the glass transition temperature of the cyclic olefin polymer obtained is high, and it is excellent also in mechanical strength.

As a monovalent organic group which has the said polarity, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, a cyano group, etc. are mentioned, for example. The monovalent organic groups having these polarities may be bonded via a linking group such as a methylene group. Moreover, a hydrocarbon group etc. which the bivalent organic group which has polarity, such as a carbonyl group, an ether group, a silyl ether group, a thioether group, and an imino group, couple | bond and couple | bond are mentioned as a polar group. Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group and allyloxycarbonyl group are preferable, and an alkoxycarbonyl group and allyloxycarbonyl group are more preferable.

In addition, the monomer in which one or more of R <^2> and R <^4> shows the monovalent organic group which has a polarity represented by general _formula :-(CH2) nCOOR in the said General formula ( ₁ ) has the high glass transition temperature of the cyclic olefin type polymer obtained. And low hygroscopicity, and excellent adhesiveness with various materials is preferable. In the formula, R represents a hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 4, more preferably 1 to 2 carbon atoms, preferably an alkyl group. In addition, although n is an integer of 0-5 normally, since the value of n is small, since the glass transition temperature of the cyclic olefin polymer obtained becomes high, it is preferable, and the specific monomer which n is 0 is preferable at the point that the synthesis | combination is easy. Do.

In Formula 1, R ¹ or R ³ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and even more preferably a methyl group. In particular, the fact that such an alkyl group is bonded to the same carbon atom as the carbon atom to which the monovalent organic group having a polarity represented by the formula:-(CH ₂ ) _n COOR is bonded can lower the hygroscopicity of the resulting cyclic olefin polymer. It is preferable at the point.

(Copolymerizable monomer)

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

Moreover, as a copolymerizable monomer in an addition (co) polymer, the compound which has a reactive unsaturated double bond, for example is preferable, Specifically, olefin type compounds, such as ethylene, propylene, butene; Vinyl unsaturated hydrocarbon compounds, such as styrene, (alpha) -methylstyrene, and vinylcyclopentene; (Meth) acrylates, such as methyl methacrylate, etc. are mentioned.

(Opening polymerization catalyst)

The ring-opening (co) polymerization reaction is carried out in the presence of a metathesis catalyst. As this metathesis catalyst, a known one can be used, and for example, (a) at least one selected from the compounds of W, Mo, and Re, and (b) the periodic table of the Deming group IA element (for example, Li, Na , K, etc.), Group IIA elements (e.g., Mg, Ca, etc.), Group IIB elements (e.g., Zn, Cd, Hg, etc.), Group IIIA elements (e.g., B, Al, etc.), IVA From compounds having a group element (e.g., Si, Sn, Pb, etc.) or group IVB element (e.g., Ti, Zr, etc.) and having one or more of the above element-carbon bonds or the element-hydrogen bonds It is a catalyst which consists of a combination with 1 or more types chosen. In this case, alcohols, aldehydes, ketones, amines and the like can be preferably used in order to increase the activity of the catalyst. In the upper left column on page 9, the compound disclosed in line 17 may be used.

(Solvent for polymerization reaction)

As a solvent (solvent constituting a molecular weight regulator solution, a specific monomer and / or a metathesis catalyst) used in the ring-opening (co) polymerization reaction, for example, alkanes such as pentane, hexane, heptane, octane, nonane and decane ; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin and norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; Halogenated alkanes such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform, tetrachloroethylene, and halogenated aryl; Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate and dimethoxyethane; Ethers, such as dibutyl ether, tetrahydrofuran, and dimethoxyethane, etc. are mentioned, These may be used individually by 1 type, or may be used together 2 or more types. Among these, aromatic hydrocarbons are preferable.

As a usage-amount of a solvent, "a solvent: specific monomer (weight ratio)" is the quantity which is usually 1: 1-10: 1, Preferably it is the quantity which is 1: 1-5: 1.

The molecular weight of the obtained ring-opening (co) polymer can be controlled by the polymerization temperature, the kind of the catalyst and the kind of the solvent, but for example, ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene And-molecular weight modifiers, such as styrene and alpha-olefins, such as 1-octene, 1-nonene, and 1-decene, can also be performed.

Although the ring-opening (co) polymer obtained as mentioned above can be used as it is, the (iii) hydrogenated (co) polymer obtained by hydrogenating the olefinic unsaturated bond in the molecule | numerator of this (co) polymer is excellent in heat-coloring property and light resistance In addition, since durability of the film which has a quarter wave plate function can be improved, it is preferable.

(Hydrogenation catalyst)

The hydrogenation reaction can apply the method of hydrogenating a normal olefinic unsaturated bond. In other words, by adding a hydrogenation catalyst to the solution of the ring-opening (co) polymer, hydrogen gas at atmospheric pressure to 300 atm, preferably 3 to 200 atm is operated at 0 to 200 캜, preferably 20 to 180 캜. Is done.

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 heterogeneous catalysts and homogeneous catalysts.

As a heterogeneous catalyst, the solid catalyst which carried noble metal catalyst substances, such as palladium, platinum, nickel, rhodium, ruthenium, on support | carriers, such as carbon, a silica, alumina, titania, is mentioned. As the homogeneous catalyst, nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octate / n-butyllithium, titanocenedichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (tri Phenylphosphine) rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium and the like. The form of the catalyst may be powder or particulate.

The hydrogenation rate of the hydrogenated (co) polymer is 50% or more, preferably 90% or more, more preferably 98% or more, most preferably 99% or more, as measured by 500 MHz and ¹ H-NMR. The higher the hydrogenation rate, the better the stability to heat and light, and when used as the transparent film of the present invention, stable characteristics can be obtained over a long period of time.

Moreover, when an aromatic group is contained in a ring-opening (co) polymer molecule, such an aromatic group is less likely to lower heat colorability and light resistance, and conversely, has an advantageous effect on optical properties such as optical properties such as refractive index and wavelength dispersion or heat resistance. In some cases, it does not necessarily need to be hydrogenated.

In the ring-opening (co) polymer obtained as described above, 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, pentaerythritol tetra Keith [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like, and / or ultraviolet absorbents such as 2,4-dihydroxybenzophenone, 2-hydroxy Stabilization can be performed by adding -4-methoxybenzophenone and the like. Moreover, additives, such as a lubricant, can also be added for the purpose of improving workability.

Moreover, it is preferable that the gel content contained in the said hydrogenated (co) polymer is 5 weight% or less, and, as for the hydrogenated (co) polymer used as the said cyclic olefin type polymer, it is more preferable that it is 1 weight% or less.

As the cyclic olefin polymer, a hydrogenated (co) polymer is also used after the ring-opening (co) polymer is cyclized by a Friedelcraft reaction.

(Addition polymerization catalyst)

As a catalyst for synthesizing the addition (co) polymer, known ones can be used, and specifically, at least one selected from the group consisting of titanium compounds, zirconium compounds and vanadium compounds, and organoaluminum compounds as cocatalysts.

(Physical Properties of Cyclic Olefin Polymer)

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

When the intrinsic viscosity [η] _inh , the number average molecular weight and the weight average molecular weight are in the above ranges, the heat resistance, the water resistance, the chemical resistance, the mechanical properties of the cyclic olefin polymer, and the optical properties when used as the conductive laminated film of the present invention Balance with stability becomes good.

As glass transition temperature (Tg) of a cyclic olefin type polymer, it is 120 degreeC or more normally, Preferably it is 120-350 degreeC, More preferably, it is 130-250 degreeC, More preferably, it is 140-200 degreeC. This is because the change in optical properties of the obtained cyclic olefin polymer film is made stable, and the heat deterioration of the resin is prevented when it is heated and processed to near Tg 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, still more preferably 0.1 to 1% by weight. If the saturation absorption is within the above range, the optical properties are uniform, and the resulting cyclic olefin polymer film is excellent in adhesiveness with other optical members, adhesives and the like, no peeling or the like occurs during use, and also excellent compatibility with antioxidants and the like. It is also possible to add a large amount. In addition, a saturated water absorption is a value obtained by immersing in 23 degreeC water for 1 week and measuring an increase weight according to ASTMD570.

As the cyclic olefin polymer, its photoelastic coefficient (C _P ) is 0 to 100 (× 10 ^-12 Pa ^-1 ), and the stress optical coefficient (C _R ) is 1,500 to 4,000 (× 10 ^-12 Pa ^-1) ) Is desirable. Herein, the photoelastic coefficient (C _P ) and the stress optical coefficient (C _R ) are described in various documents, for example, the Polymer Journal, Vol. 27, No. 9, pp943-950 (1995), Japanese Rheological Society, Vol. 19, No. 2, p93-97 (1991)], and [Photoelastic test method, Nikkan Kogyo Shin-Bungsha, 7th edition, 1975]. Whereas the former indicates the degree of occurrence of the phase difference due to the stress in the glass state of the polymer, the latter indicates the degree of occurrence of the phase difference due to the stress in the flow state.

The large photoelastic coefficient (C _P ) indicates that the optical properties are sensitively changed in the external factors or the stresses generated by freezing distortion thereof when the cyclic olefin polymer film is bonded to another optical member or adhesive. For example, in the case of laminating a transparent conductive layer as in the present invention, or in the case of fixing it to another optical member, the microscopic stress generated by the shrinkage of the material due to residual distortion during bonding, temperature change, humidity change, or the like is used. This means that unnecessary phase difference is likely to occur. Accordingly, the smaller the photoelastic coefficient C _P as possible, the better.

On the other hand, the larger the stress optical coefficient (C _R ) is, for example, when the retardation expression is imparted to the cyclic olefin polymer film, the desired phase difference can be obtained with a small draw ratio, or the film can be given a large phase difference. When it is easy to obtain or the same phase difference is desired, there is a big advantage that the film can be thinned as compared with a small stress optical coefficient (C _R ).

In view of the above, the photoelastic modulus (C _P ) is preferably 0 to 100 (× 10 ^-12 Pa ^-1 ), more preferably 0 to 80 (× 10 ^-12 Pa ^-1 ), even more preferably Is 0 to 50 (x10 ^-12 Pa ^-1 ), particularly preferably 0 to 30 (x10 ^-12 Pa ^-1 ), most preferably 0 to 20 (x10 ^-12 Pa ^-1 ). This is to minimize unnecessary phase differences due to stress generated when the transparent conductive layer is laminated, stress generated when the conductive laminated film is fixed to another optical member, phase difference caused by environmental changes when used, and the like.

(additive)

The cyclic olefin polymer can be further stabilized by adding known antioxidants, ultraviolet absorbers and the like. Moreover, in order to improve workability, you may add the additive used in conventional resin processing, such as a lubricant.

As said antioxidant, a pentaerythryl tetrakis [3- (3,5-di-t- butyl- 4-hydroxyphenyl) propionate], 2, 6- di-t- butyl-, for example 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, and the like. Examples of the ultraviolet absorbent include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and the like. Can be mentioned.

(Method for producing film having 1/4 wave plate function)

The film having a quarter wave plate function according to the present invention is obtained by molding the above-mentioned cyclic olefin polymer into a film or sheet by a known method such as melt molding method or solution casting method (solvent casting method). ) Can be produced by stretching treatment. As a shaping | molding method of a film, the solvent casting method is preferable at the point that the uniformity and surface smoothness of a film thickness become favorable. In addition, in view of manufacturing cost, the melt molding method is preferable. The disc film has a film thickness of 70 to 250 μm, preferably 80 to 200 μm, and a difference between the maximum thickness and the minimum thickness of the film is within 3 μm, preferably within 2 μm.

The film which has a quarter wave plate function which concerns on this invention can be extended | stretched by the well-known uniaxial stretching method or the biaxial stretching method specifically ,. That is, the uniaxial stretching method by the tenter method, the compression stretching method between rolls, the longitudinal uniaxial stretching method using a roll with a different main source, or the biaxial stretching method which combined the uniaxial and longitudinal uniaxial axes, and the inflation method Law, etc. may be used. Among them, longitudinal uniaxial stretching is preferable in terms of production cost.

In the case of the uniaxial stretching method, the stretching speed is usually 1 to 5,000% / min, preferably 50 to 1,000% / min, more preferably 100 to 1,000% / min, still more preferably 100 to 500% / Minutes. In the biaxial stretching method, stretching may be performed in two directions at the same time, or stretching may be performed in a direction different from the first stretching direction after uniaxial stretching. In these cases, the crossing 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, usually 1 to 5,000% / min, preferably 50 to 1,000% / min, more preferably 100 to 1,000% / min, and even more preferred. Preferably from 100 to 500% / min.

The stretching processing 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 polymer. Range. Since it is in the said range, since generation | occurrence | production of phase difference nonuniformity can be suppressed and control of a refractive index ellipsoid becomes easy, it is preferable.

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

Although the stretched film can be cooled as it is, it is left to stand for at least 10 seconds or more, preferably 30 seconds to 60 minutes, more preferably 1 minute to 60 minutes under a temperature atmosphere of Tg-20 ° C to Tg. As a result, a film having a stable quarter wave plate function with little change with time of retardation characteristics is obtained.

In addition, the coefficient of linear expansion of the film having a quarter wave plate function is preferably 1 × 10 ⁻⁴ (1 / ° C.) or less, more preferably 9 × 10 ⁻ , in a temperature range of 20 ° C. to 100 ° C. ^{It is 5} (1 / degreeC) or less, More preferably, it is 8 * 10 <^-5> (1 / degreeC) or less, Especially preferably, it is 7 * 10 <^-5> (1 / degrees C) or less. Further, the difference in linear expansion coefficient between the stretching direction and the vertical direction thereof is preferably 5 × 10 ⁻⁵ (1 / ° C.) or less, more preferably 3 × 10 ⁻⁵ (1 / ° C.) or less, still more preferably 1 It is ^x10-5 (1 / degreeC) or less. By using the coefficient of linear expansion in the said range, when the film which has the said 1/4 wavelength plate function is used for the electroconductive laminated | multilayer film of this invention, the change of phase difference which a stress change including influences, such as temperature and humidity at the time of use, and transparency are transparent When the resistance value change of a conductive film is suppressed and used as the electroconductive laminated film of this invention, stability of a long term characteristic can be obtained.

In the stretched film as described above, the molecules are oriented by stretching to provide a phase difference to the transmitted light, but the phase difference is controlled by the phase difference value of the film before stretching and the stretching ratio, the stretching temperature, and the thickness of the film after stretching orientation. can do.

Since the visibility of a touchscreen becomes favorable, the total light transmittance of the film which has a quarter wave plate function becomes like this. Preferably it is 85% or more, More preferably, it is 88% or more, More preferably, it is 90% or more.

In addition, since the thickness of the film which has a quarter wave plate function ensures favorable handling and makes winding in roll shape easy, it is usually 1-500 micrometers, Preferably it is 1-300 micrometers, More preferably, Preferably it is 10-250 micrometers, More preferably, it is 50-200 micrometers.

The thickness distribution of the film having a quarter wave plate function is usually within ± 20%, preferably within ± 10%, more preferably within ± 5%, still more preferably within ± 3% of the average value. . Further, the variation in thickness per cm is usually 10% or less, preferably 5% or less, more preferably 1% or less, and still more preferably 0.5% or less. By performing such thickness control, the nonuniformity in the electroconductive laminated film surface can be prevented.

Moreover, the film which has a 1/4 wavelength plate function which concerns on this invention may be surface-treated in order to improve adhesiveness with a particle containing resin layer. Examples of the surface treatment include plasma treatment, corona treatment, alkali treatment and coating treatment. In particular, by using corona treatment, the adhesion between the film having a quarter wave plate function and the particle-containing resin layer can be strengthened.

As corona treatment conditions, it is preferable that it is 1-1000 W / m <2> / min, and, as for the irradiation amount of corona discharge electrons, it is more preferable to set it as 10-100 W / m <2> / min. In the case where the irradiation amount is lower than this, a sufficient surface modification effect may not be obtained. In addition, when the irradiation amount is higher than this, the treatment effect may be extended to the inside of the film having a quarter wave plate function, and the film itself may be deteriorated. There is. This corona treatment can be performed not only on the surface in contact with the particle-containing resin layer, but also on the surface on the opposite side thereof.

In addition, the coating may be performed immediately after the corona treatment, or the coating may be carried out after static elimination. However, since the appearance of the particle-containing resin layer becomes good, it is preferable to apply the electrostatic charge after coating.

<Particle-containing resin layer>

The particle-containing resin layer is formed on one or more surfaces of the film having a quarter wave plate function, and protects damage of the film having a quarter wave plate function, and the surface of the conductive laminated film or 1/4 It has an anti-glare effect on the reflected light at the film interface having a wave plate function.

The particle-containing resin layer usually contains particles for expressing antiglare property and a binder. It is preferable that the said binder is formed from an active energy ray curable resin composition.

The particle-containing resin layer is a layer formed by curing or drying particles and active energy ray-curable resins after coating or drying a coating composition obtained by dispersing or dissolving them in an organic solvent capable of dispersing or dissolving them with various coaters. to be.

(particle)

Although the particle | grains used for a particle containing resin layer are not specifically limited, For example, it may be any of what is normally used as a filler, Acrylic resin, aromatic vinyl resin, carbon black, copper, nickel, silver, iron, or these Composite powder; Metals such as zinc oxide, tin oxide, titanium oxide, tin monoxide, calcium oxide, magnesium oxide, beryllium oxide, aluminum oxide, silica (fumed silica, fused silica, precipitated silica, ultrafine amorphous silica, crystalline silica, silicic anhydride, etc.) oxide; Metal carbonates such as calcium carbonate, potassium carbonate, sodium carbonate, magnesium carbonate and barium carbonate; Metal carbides such as metal nitrides such as boron nitride, silicon nitride, aluminum nitride, and SiC; Metal hydroxides such as aluminum hydroxide and magnesium hydroxide; Aluminum borate, barium titanate, calcium phosphate, calcium silicate, clay, gypsum, barium sulfate, miker, diatomaceous earth, clay, talc, zeolite, pigment and the like. Among them, acrylic resins, aromatic vinyl resins, and silicas are preferable in terms of production cost.

The number average particle diameter of the particle | grains used at the time of formation of a particle containing resin layer is not specifically limited, For example, 0.8-10 micrometers, Preferably it is 0.9-7 micrometers, More preferably, it is 1-5 micrometers. By having such an average particle diameter, transparency of a resin composition can be ensured and a haze value can be adjusted to an appropriate value. Thereby, there exists no luminance nonuniformity and the electroconductive laminated film with favorable anti-glare property is obtained. In addition, two or more kinds of particles having different particle diameters may be used.

Moreover, even if the release polymer particle which has a shape which two or more substantially spherical particles couple | bonded is used, since anti-Newtoning property becomes favorable, it is preferable. As the release polymer particles, polymer particles containing styrene resins, acrylic resins, and the like are preferable, and one substantially spherical particle is used as seed polymer particles, and is formed in a shape in which two or more particles are bonded by seed polymerization. It is preferable.

(Active energy ray curable resin composition)

It is preferable that the binder of a particle containing resin layer is formed from an active energy ray curable resin composition. The active energy ray-curable resin composition is preferably a polyfunctional monomer having three or more (A) acryloyl groups (hereinafter also referred to as "(A) component") and (B) glycidyl (meth) acrylate-based polymer. A polymer formed by addition reaction of acrylic acid (hereinafter also referred to as "(B) component") and (C) optionally other acrylic oligomers (hereinafter also referred to as "(C) component") are formulated in a specific amount. In particular, (A) component is a component which can provide the hardness of the transparent conductive layer tracked from an active energy ray curable resin composition, adhesiveness to a transparent resin film, etc. (B) A component is a component which can provide the further improvement of the hardness of a transparent conductive layer, curability, the reduction of the curling occurrence at the time of hardening, etc .. By mix | blending (B) component, (B) component is high molecular weight and has a large number of hydroxyl groups in a molecule | numerator, compatibility with the high hydrophobicity (A) component falls, and the surface from which (B) component is obtained It is considered that it is because it transfers to the surface of a protective film. (C) component is an arbitrary component which can provide toughness etc.

From the viewpoint of obtaining sufficient hardness and adhesiveness, the surface tension of the component (A) is preferably in the range of 37 mN / m or less, and preferably 30 mN / m or more. The measurement of surface tension is by the wilhemy method using the Kyowa CBVP type surface tension meter.

Specific examples of the component (A) include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, triacrylate of glycerin propylene glycol adduct, and triacrylate of trimethylolpropane propylene glycol adduct. In these, since a hardened coating film becomes high hardness, trimethylol propane triacrylate and ditrimethylol propane tetraacrylate are preferable.

It is preferable that the compounding quantity of (A) component in an active energy ray curable resin composition is 40-60 weight% (however, the sum total of (A)-(C) component is 100 weight%), and 50-60 weight% is preferable. Do.

Component (B) is a polymer acrylate formed by adding acrylic acid to a glycidyl (meth) acrylate-based polymer as described above. The amount of acrylic acid added to the epoxy group is preferably about 1: 1 to 1: 0.8, and preferably about 1: 1 to 1: 0.9 because unreacted epoxy adversely affects the stability of the composition.

As glycidyl (meth) acrylate type polymer, the homopolymer of glycidyl (meth) acrylate, the copolymer of glycidyl (meth) acrylate, and the various (alpha), (beta)-unsaturated monomer which does not contain a carboxyl group Etc. can be mentioned. As (alpha), (beta)-unsaturated monomer which does not contain the said carboxyl group, various (meth) acrylic acid ester, styrene, vinyl acetate, an acrylonitrile, etc. can be illustrated. In addition, when a glycidyl (meth) acrylate and an alpha, beta -unsaturated monomer containing no carboxyl group are copolymerized to obtain a glycidyl (meth) acrylate polymer, no crosslinking occurs during the reaction. High viscosity and gelation can be effectively prevented. The molecular weight of the glycidyl (meth) acrylate-based polymer is about 5,000 to 100,000 weight average molecular weight, and preferably about 10,000 to 50,000, from the viewpoints of reduction of curling property during curing and prevention of gelation during acrylic addition reaction. The use ratio of glycidyl (meth) acrylate in the component (B) is preferably 70% by weight or more and preferably 75% by weight or more in consideration of the hardness of the transparent conductive layer, the transferability of the polymer and the like.

The well-known copolymerization method can be applied to manufacture of (B) component. The glycidyl (meth) acrylate polymer is prepared by introducing a monomer, a polymerization initiator, a chain transfer agent and a solvent, if necessary, into a reaction vessel under conditions of 80 to 90 ° C. for 3 to 6 hours under a nitrogen stream. It is appropriate to do. Although the (B) component can be obtained by ring-opening-esterifying the glycidyl (meth) acrylate type polymer and acrylic acid obtained in this way, in order to prevent superposition | polymerization of acrylic acid itself normally, it is good to carry out under oxygen stream, As for reaction temperature, 100 to 120 degreeC, and reaction time are about 5 to 8 hours are suitable.

It is preferable that the compounding quantity of (B) component in an active energy ray curable resin composition is 10-60 weight% (however, the sum total of (A)-(C) component is 100 weight%), and 20-50 weight% is preferable. Do.

As a specific example of (C) component, polyfunctional polyester acrylate, polyfunctional urethane acrylate, and epoxy acrylate are mentioned. Especially, polyfunctional urethane acrylate is preferable from a viewpoint of the scratch resistance, toughness, etc. of a cured coating film. For example, (a) a urethane reaction product of a (meth) acrylate having a hydroxyl group with an isocyanate compound having two or more isocyanate groups in a molecule, (b) a polyol, a polyol in an isocyanate compound having two or more isocyanate groups in a molecule The reaction product etc. which add the (meth) acrylate which has a hydroxyl group to the remaining isocyanate group after synthesize | combining an adduct by making ester or polyamide diol react (for example, Unexamined-Japanese-Patent No. 2002) -275392).

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

As for the compounding quantity of (C) component in an active energy ray curable resin composition, 0-50 weight% (however, the sum total of (A)-(C) component is 100 weight%) is suitable.

Active energy ray curable resin composition can mix | blend the organic solvent in order to adjust the viscosity according to an individual use. It is suitable that the organic solvent does not melt | dissolve the cyclic olefin polymer film which is a transparent film, For example, an ester solvent, an alcohol solvent, and a ketone solvent are preferable.

As an active energy ray used in order to harden an active energy ray curable resin composition, any of ultraviolet-ray, an electron beam, etc. may be sufficient, for example. When hardening a resin composition with an electron beam etc., a photoinitiator is unnecessary, but when hardening with an ultraviolet-ray, about 1-15 weight part of photoinitiators can be normally contained with respect to 100 weight part of resin compositions. As a photoinitiator, various well-known things, such as Darocure 1173, Irgacure 651, Irgacure 184, Irgacure 907, Irgacure 754 (all are the Ciba Specialty Chemicals make), benzophenone, can be used. As needed, various additives other than the above, for example, a polymerization inhibitor, antioxidant, an ultraviolet absorber, an antistatic agent, an optical stabilizer, a solvent, an antifoamer, a leveling agent, etc. can also be mix | blended.

(Other ingredients)

In addition to the particle | grains and active energy ray curable resin composition, a coating composition can be made to contain other components, such as a hardening | curing agent, a dispersing agent, and dye as needed.

It is preferable that the content rate of another component is 0-10 weight part with respect to particle | grain + active energy ray curable resin composition = 100 weight part, It is more preferable that it is 0-5 weight part, It is especially preferable that it is 0-3 weight part.

(Organic solvent)

The organic solvent contained in the coating composition may disperse or dissolve particles and the active energy ray-curable resin composition, and the coating composition may be in the form of a slurry. Specific examples of such organic solvents include water, toluene, cyclohexane, Methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), N-methyl- 2-pyrrolidone (NMP), etc. are mentioned.

It is preferable that it is 10-2000 weight part with respect to particle | grains + active energy ray curable resin composition = 100 weight part, and, as for the content rate of the organic solvent with respect to a coating composition, it is more preferable that it is 20-1000 weight part.

(Method for Producing Coating Composition)

The coating composition can be obtained by uniformly dispersing or dissolving the particles and the active energy ray-curable resin composition and the above-mentioned other components added as necessary. In addition, the other components may be dispersed or dissolved later. Although it does not specifically limit about a stirring method, For example, it can stir using various kneading machine, bead mill, a high pressure homogenizer, etc.

(Formation method of a particle containing resin layer)

The particle-containing resin layer is formed by curing and coating the particles, the active energy ray-curable resin, and the coating composition obtained by dispersing or dissolving them in an organic solvent that can be dispersed or dissolved in a slurry form after coating and drying with various coaters. do.

The particle is preferably 0.5 to 50% by weight, more preferably 0.5 to 10% by weight, still more preferably 1 to 5% by weight in the particle-containing resin layer. If the content ratio of particle | grains is in the said range, it is preferable from an anti-glare viewpoint.

As the coating method of the particle-containing resin layer, various methods such as bar coater coating, air knife coating, gravure coating, gravure reverse coating, reverse roll coating, lip coating, die coating, dip coating, offset printing, flexographic printing, and screen printing can be used. It can be adopted. Gravure reverse coating and die coating are preferable at the point which the external appearance of a particle containing resin layer becomes favorable.

Particles contained in the particle-containing resin layer are integrated on the film having a quarter wave plate function by the cured resin. In addition, some of the particles may be in a state in which some of the particles protrude from the surface of the resin. Further, the protruding portions of the particles may be entirely covered by the resin, or only a part of them may be covered. Further, the particles may be in a state where all of the particles are completely embedded in the resin.

Although it does not specifically limit about the thickness of a particle containing resin layer, Usually, it is 1-20 micrometers, Preferably it is about 1-7 micrometers.

(Physical Properties of Laminated Films Containing Film / Particle-Containing Resin Layers Having a 1/4 Wavelength Plate Function)

(1) Haze is also referred to as cloudiness, and indicates the degree of cloudiness and the degree of diffusion. For example, haze (%) in accordance with JIS K-7136, using a commercially available Suga Shizuki Co., Ltd. HGM-2DP and the like. Can be measured. 30% or less is preferable, 20% or less is more preferable, and 10% or less of the haze of a notation film is more preferable. If the haze is outside the above range, cloudiness occurs and the visibility of the touch panel is lowered.

 (2) Since the total light transmittance (%) is measured according to JIS K-7361 using, for example, commercially available Suga Shikenki Co., Ltd. HGM-2DP, the visibility of the touch panel is improved. 80% or more is preferable, 83% or more is more preferable, and 85% or more is more preferable.

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

(4) When pencil hardness is measured by JISK5600-5-4 using NPK manufactured by Toyo Seiki Co., Ltd., it is preferable that it is HB or more. If it is below HB, a scratch may arise in a transparent conductive film at the time of ITO film-forming.

(5) It is preferable that the outline of a fluorescent lamp cannot be recognized at all when an anti-glare property shines a fluorescent lamp (3520 lm) on a notation film, and evaluates the degree of blur of the outline of a fluorescent lamp by visual observation.

(6) In the case of luminance nonuniformity, when the screen of Sharp's mobile tool SL-6000N is displayed in green, and the marking film is placed and visually evaluated, it is preferable that the luminance nonuniformity of the pixel is hardly recognized.

(7) When anti-Newton ring property puts a notation film on the smooth glass plate (thickness 3mm, material: soda glass) so that a particle-containing resin layer may stick, press it with a finger, and visually evaluate whether a Newton ring occurs, It is preferable that a Newton ring does not occur.

(8) The heat shrinkage percentage (%) was allowed to stand for 60 minutes in the forced film dryer in a forced circulation dryer heated at 150 ° C, and measured the dimensional change of the film before and after heating using Mitsutoyo manufactured dimensional measurement microscope 176-812, When calculating a thermal contraction rate, 1.5% or less is preferable, 1.3% or less is more preferable, 1.0% or less is still more preferable. When thermal contraction rate exceeds 1.5%, deformation of a touch panel may arise.

(9) The residual solvent (%) is left to stand in the forced circulation dryer heated at 160 ° C. for 30 minutes, the mass change before and after heating is investigated, and the mass increase rate (%) is set as the residual solvent (%). , 2% or less is preferable, 1.5% or less is more preferable, and 1% or less is further more preferable. When the residual solvent exceeds 2%, the amount of volatile solvent at the time of ITO film formation increases, and the defect of an ITO film may arise.

(10) The phase difference is preferably 128 to 148 nm when measuring the phase difference (nm) with respect to light having a wavelength of 550 nm using "KOBRA-21ADH / PR" manufactured by Oji Keisoku Kiki Co., Ltd., 133 143 nm is more preferable. When the phase difference deviates from the above, the contrast and visibility of the liquid crystal display are lowered.

<Transparent conductive layer>

In the electroconductive laminated film of this invention, a transparent conductive layer is further laminated | stacked on the film in which the particle | grain containing resin layer was laminated | stacked on the surface of the film which has a 1/4 wavelength plate function mentioned above.

The transparent conductive layer may have a weight ratio of indium oxide and tin oxide of 95: 5 to 99: 1, and may further include a layer containing polythiophene, inorganic nanoparticles, metal elements, etc. in a range that does not impair the effects of the present application. And a layer having transmittance in the visible light region and having conductivity.

As a target at the time of forming a transparent conductive film, a conventionally well-known ITO target is used. As a target agent used for forming the ITO film, the weight ratio of indium oxide and tin oxide is preferably 95: 5 to 99: 1, more preferably 96: 4 to 98: 2, still more preferably 97: 3 to 98 It is preferable to use: 2. If the weight ratio is outside the above range, an increase in the resistance value occurs. In addition, when the weight ratio is within the above range, when combined with a film having a quarter wave plate function including a cyclic olefin polymer having a structure derived from the formula (1) and a particle-containing resin layer, projection by light reflection It does not generate | occur | produce, it is high contrast, the change of the phase difference after heat processing is small, and the electrically conductive laminated film excellent in durability can be obtained.

"Tg of room temperature-a film" is preferable, and, as for the substrate temperature at the time of ITO film-forming, "Tg-20 degreeC of room temperature-a film" is more preferable. If it is more than Tg, deterioration of the film may occur.

In addition, with respect to the total amount of oxygen, preferably Ar and O ₂ in Ar as an atmosphere gas at the time of film formation, preferably 0.05 to 20% by volume, more preferably 0.01 to 10% by volume, still more preferably 0.1 By introducing 3% by volume of O ₂ , the transparency and conductivity of the ITO thin film can be improved.

As a method of forming the transparent conductive layer, any conventionally known techniques such as vacuum deposition, sputtering, and ion plating can be used. From the standpoint of film uniformity and adhesion of a thin film to a transparent substrate, the thin film by sputtering Formation is preferred. In addition, the thin film material to be used also includes gold, silver, platinum, palladium, copper, aluminum, nickel, chromium, titanium, cobalt, tin, alloys thereof, and the like, in addition to metal oxides such as tin oxide containing antimony, for example. Can also be used. It is preferable that the thickness of this electroconductive thin film shall be 30 GPa or more, and when it is thinner than this, it may be difficult to become the continuous film which has favorable electroconductivity that surface resistance becomes 1000 ohms / square or less. On the other hand, when too thick, the fall of transparency may be caused, and as a preferable thickness, it is about 50-2000 GPa.

<Easy Adhesive Layer>

An easy adhesive layer can also be laminated | stacked for the purpose of improving the adhesiveness of a particle containing resin layer and a transparent conductive layer, and providing a gas barrier property. The easily adhesive layer may or may not contain metal oxide fine particles, but containing metal oxide fine particles is preferable because of improved adhesiveness. Usually, a preferable easy adhesive layer is obtained by manufacturing the coating liquid containing the composition containing a metal oxide fine particle and polysiloxane, and coating and drying this coating liquid on a transparent resin film.

(Metal oxide fine particles)

The metal oxide fine particles used for the easy adhesion layer are not particularly limited as long as the metal oxide fine particles are oxide fine particles of a metal element. For example, antimony oxide, zirconium oxide, anatase titanium oxide, rutile titanium oxide, brookite titanium oxide, and 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, terbinium oxide, Dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, rhodium oxide, calcium oxide, gallium oxide, lithium oxide, strontium oxide, tungsten oxide, barium oxide, magnesium oxide and complexes thereof, and indium-tin composite oxide And oxides of complexes of two or more of the above metals.

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, particularly preferably 0.1 to 50 nm. When the primary average particle diameter of metal oxide fine particles exists in the said range, the laminated | multilayer film excellent in light transmittance can be obtained.

(Polysiloxane)

It is preferable that the polysiloxane used for an easily bonding layer is a polyfunctional polysiloxane.

As polyfunctional polysiloxane, the polysiloxane obtained by carrying out the de-alcoholization of polyfunctional polysiloxane which has a dimethylsiloxane chain, and polydimethylsiloxane is mentioned as a preferable thing. It is preferable that a terminal functional group is an alkoxyl group or a hydroxyl group with polyfunctional polysiloxane and polydimethylsiloxane, and the polyfunctional polysiloxane is obtained by de-alcohol-reacting dimethylsiloxane and polydimethylsiloxane which respectively have a different terminal functional group.

<Anti-reflective layer>

It is also preferable that the electroconductive laminated | multilayer film of this invention has an antireflection layer between a transparent conductive layer and a particle containing resin layer for the purpose of improving the transmittance | permeability of visible region. The antireflection layer usually consists of a laminated structure of two or more layers including a low refractive index layer such as silicon oxide and magnesium fluoride and a high refractive index layer such as titanium oxide, niobium oxide, and tantalum oxide.

As a method of forming a low and high refractive index layer containing these inorganic oxides, a coating liquid containing ultra-fine particles of inorganic oxides such as metal alkoxides and zirconium oxides can be formed by vacuum evaporation, sputtering, ion plating (drying). A well-known method, such as a coating method (wet process), can be employ | adopted.

Moreover, it is also preferable to coat the organic material which has a fluoropolymer as a main component as a low refractive layer.

<Conductive Laminated Film>

The following <1>-<3> is mentioned as a preferable aspect of the electroconductive laminated film of this invention.

The surface in which the particle containing resin layer and the transparent conductive layer are laminated | stacked in order on the film surface which has a <1> wavelength plate function, and the particle containing resin layer of the film which has the said 1/4 wavelength plate function is formed, and The electroconductive laminated | multilayer film by which particle | grain containing resin layer is further laminated | stacked on the opposite surface.

That is, it is an electroconductive laminated film laminated | stacked in order of the film / particle containing resin layer which has a transparent conductive layer / particle containing resin layer / 1/4 wavelength plate function.

The surface in which the particle containing resin layer and the transparent conductive layer are laminated | stacked in order on the film surface which has a <2> quarter wave plate function, and the particle containing resin layer of the film which has the said quarter wave plate function is formed, and The electroconductive laminated | multilayer film which a hard coat layer is further laminated | stacked on the opposite surface.

That is, it is an electroconductive laminated | multilayer film laminated | stacked in order of the film / hard coat layer which has a transparent conductive layer / particle containing resin layer / 1/4 wavelength plate function.

Particles are further contained on the surface opposite to the surface on which the hard coating layer and the transparent conductive layer are laminated | stacked on the <3> transparent resin film surface in order, and the hard coating layer of the film which has the said 1/4 wavelength plate function is formed. A conductive laminated film in which a resin layer is laminated.

That is, it is an electroconductive laminated | multilayer film laminated | stacked in order of the film / particle containing resin layer which has a transparent conductive layer / hard coating layer / 1/4 wavelength plate function.

The conductive laminated film is a coating composition containing no particles (hereinafter referred to as a "hard coating agent"), that is, active on the surface opposite to the surface on which the particle-containing resin layer of the film having a quarter wave plate function is formed. It is preferable that the hard coat layer containing an energy ray curable resin composition 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, bending of a film can be prevented by providing a resin layer on both surfaces.

Moreover, it is preferable that a conductive laminated film laminates an antireflection layer between a transparent conductive layer and a particle containing resin layer, or between a transparent conductive layer and a hard coating layer. By providing the antireflection layer in this manner, the transmittance in the visible light region is further improved, which is preferable.

About each physical property measured by the above-mentioned method of an electroconductive laminated film, a preferable aspect is shown below.

(1) About 5 to 12% is preferable and, as for haze, about 5 to 10% is more preferable. If the haze falls within the above range, cloudiness can be prevented and the background image can be more clearly reflected. In addition, haze correlates with the average particle diameter, particle size distribution, content rate, etc. of the release polymer particle contained in a particle containing resin layer, and the electroconductive particle contained in a transparent conductive layer.

(2) Since the visibility of a touch panel improves the total light transmittance, 80% or more is preferable, 83% or more is more preferable, and 85% or more is more preferable.

(3) Since the visibility of a touch panel improves the transmitted light b *, 0-12 are preferable, 0-7 are more preferable, and 0-4 are more preferable.

(4) As for pencil hardness, HB or more is preferable. If the pencil hardness is less than HB, scratches may occur in the transparent conductive film during ITO film formation.

(5) It is preferable that anti-glare property cannot recognize the outline of a fluorescent lamp at all.

(6) It is preferable that luminance unevenness hardly recognizes luminance unevenness of a pixel.

(7) It is preferable that a Newton ring does not produce a Newton ring.

(8) The heat shrinkage rate is preferably 1.5% or less, more preferably 1.3% or less, and even more preferably 1.0% or less. When thermal contraction rate exceeds 1.5%, deformation of a touch panel may arise.

(9) 2% or less is preferable and, as for a residual solvent, 1% or less is more preferable.

(10) When phase difference (nm) with respect to the light of wavelength 550nm is measured using "KOBRA-21ADH / PR" by Oji Keisokukiki Co., Ltd., the phase difference is preferably 128 to 148 nm, 133 143 nm is more preferable. When the phase difference deviates from the above, the contrast and visibility of the liquid crystal display are lowered. Moreover, it is preferable that the change of the phase difference before and after heat-processing a conductive laminated film at 150 degreeC for 2 hours is 7% or less, Preferably it is 5% or less.

(11) When the surface resistance (Ω / □) is measured using, for example, a commercially available low-resistance meter "Loresta GP" manufactured by Mitsubishi Chemical Corporation, 200 to 1500 Ω / □ is preferable. , 250 to 1000 Ω / square is more preferable, and 300 to 500 Ω / square is more preferable. When surface resistance exceeds 1500 ohms / square, it may become difficult to become the continuous film which has favorable electroconductivity. On the other hand, when it is less than 200 ohms / square, it may become easy to cause the fall of transparency and malfunction of a touchscreen.

<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. As such a polarizing plate, the thing in which the electroconductive laminated film was formed in one side of a polarizing film, etc. are mentioned.

Although it does not specifically limit as said polarizing film, It will specifically limit if it is a film which has a function as a polarizing film, ie, the function which divides incident light into two polarization components which run directly to each other, passes only one of them, and absorbs or disperse another component. Although not mentioned, For example, polyvinyl alcohol (henceforth "PVA") iodine type polarizing film; PVA dye-based polarizing film which adsorbed and oriented dichroic dye to PVA system film; Polyene type polarizing film which formed polyene by dehydration reaction of a PVA system film, dehydrochloric acid reaction of a polyvinyl chloride film, etc .; The polarizing film etc. which have a dichroic dye in the surface and / or inside of the PVA system film containing modified PVA containing a cationic group in a molecule | numerator are mentioned. Among these, a PVA iodine polarizing film is preferable.

The manufacturing method of a polarizing film is not specifically limited, A conventionally well-known method is applicable. For example, the method of adsorbing iodine ion after extending | stretching a PVA system film; A method of stretching a PVA film after dyeing with a dichroic dye; A method of dyeing with a dichroic dye after stretching the PVA film; A method of stretching the dichroic dye after printing the PVA film; After extending | stretching a PVA system film, the method of printing a dichroic dye, etc. are mentioned. More specifically, iodine is dissolved in a potassium iodide solution to form higher order iodine ions, which are adsorbed onto a PVA film and stretched, and then immersed in an aqueous solution of 1 to 5 wt% boric acid at a bath temperature of 30 to 40 ° C. A method of manufacturing a polarizing film; Alternatively, the PVA film is treated with boric acid in the same manner as described above, stretched in the uniaxial direction by 3 to 7 times, and then immersed in a 0.05 to 5% by weight aqueous solution of dichroic dye at a bath temperature of 30 to 40 ° C to adsorb the dye, and then 80 And a method of manufacturing a polarizing film by drying at 100 ° C. and heat fixing.

Although the thickness of a polarizing film is not specifically limited, 10-50 micrometers is preferable and 15-45 micrometers is more preferable.

Although these polarizing films can also be used for manufacture of the polarizing plate of this invention as it is, they can also be used by giving a corona discharge process and a plasma process to the surface which contact | connects an adhesive bond layer.

The polarizing plate of this invention adhere | attaches a polarizing film with a pressure sensitive adhesive on the surface on the opposite side to the transparent conductive layer of the electroconductive laminated film in which the cyclic olefin type polymer film, the particle containing resin layer, and the transparent conductive layer were laminated | stacked, and comprises a polarizing plate. desirable.

As said pressure sensitive adhesive, a polyvinyl alcohol-type pressure sensitive adhesive, an acryl-type pressure sensitive adhesive, a rubber type pressure sensitive adhesive, a silicone type pressure sensitive adhesive, etc. are preferable.

The polarizing plate of this invention can be used suitably as a transparent electrode of displays, such as a liquid crystal display and a touch panel mentioned later, and it is especially preferable for a touch panel use, especially the touch panel use for display apparatuses.

<Touch panel>

The touch panel of the present invention is characterized in that the transparent conductive layer and the polarizing plate are integrated, and is called a polarizing plate-integrated inner touch panel. Specifically, the polarizing plate of the present invention is preferably used as an upper electrode and / or a lower electrode of a touch panel such as a 4-wire resistive film method or a 5-wire resistive film method. And by arrange | positioning this touch panel in the front surface of a liquid crystal display, the display apparatus which has a touch panel function is obtained.

<Example>

Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In addition, all "parts" show a "weight part" hereafter.

Various physical properties were measured or evaluated as follows.

(1) haze

Haze (%) was measured based on JISK-7136 using Suga Shikeki Co., Ltd. HGM-2DP.

(2) total light transmittance

The total light transmittance (%) was measured based on JISK-7361 using Suga Shikeki HGM-2DP.

(3) transmitted light b *

The transmitted light b * was measured based on JIS Z-8722 using Otsuka Denshi Co., Ltd. color difference meter RETS-1200VA.

(4) pencil hardness

Pencil hardness was measured based on JISK-5600-5-4 using the Toyo Seiki Co., Ltd. pencil scraping coating film hardness tester NP.

(5) anti-glare

A fluorescent lamp (total luminous flux 3520 lm) was illuminated on the film, and the degree of blurring of the outline of the fluorescent lamp was evaluated visually on the following criteria.

(Circle): The outline of a fluorescent lamp is not known at all.

Δ: The outline of the fluorescent lamp is slightly understood.

X: The outline of a fluorescent lamp can be seen clearly.

(6) luminance unevenness

After making the screen of Sharp's mobile tool SL-6000N into a green display, the film was put and evaluated visually on the following references | standards.

(Circle): A brightness unevenness of a pixel can hardly be recognized.

(DELTA): Although the luminance nonuniformity of a pixel can be recognized, it is not outstanding.

X: The luminance nonuniformity of a pixel can be recognized clearly.

(7) anti-Newton ring

The film was placed on a smooth glass plate (thickness 3 mm, material: soda glass) so that the particle-containing resin layer was brought into close contact with the finger, and pressed with a finger to visually evaluate whether a Newton ring occurred.

(Circle): A Newton ring does not generate | occur | produce.

Δ: Newton ring slightly occurs.

X: Newton ring arises clearly.

(8) heat shrinkage

The film was allowed to stand for 60 minutes in a forced circulation dryer heated at 150 ° C, and the dimensional change of the film before and after heating was measured using a Mitsutoyo Dimension Measurement Microscope 176-812, followed by the longitudinal direction (MD) and width direction (TD) of the film. ) Was respectively measured and the heat shrinkage percentage (%) was calculated.

(9) residual solvent

The film was left still for 30 minutes in the forced circulation dryer heated at 160 ° C, and the mass change before and after the heating was examined to determine the mass increase rate (%) as the residual solvent (%).

(10) phase difference

The phase difference (nm) in wavelength 550nm of the transparent conductive laminated film before and after 150 degreeC and 2 hours treatment was measured using "KOBRA-21ADH / PR" by Oji Keisoku Kiki Co., Ltd.

(11) surface resistance

The surface resistance value (ohm / square) of the transparent conductive layer was measured using the low resistivity meter "Loresta GP" by Mitsubishi Chemical Corporation.

(12) Contrast evaluation of touch panel

In the dark room, the black display screen of the touch panel was viewed in the front direction, and the color change was visually observed to evaluate the following criteria.

(Circle): There is no color change of a touchscreen.

Δ: The color change of the touch panel is somewhat observed.

X: The color change of a touch panel is large.

(13) evaluation of visibility of the touch panel

The color change of the screen when the viewing angle was changed was visually observed.

(Circle): There is no color change of a touchscreen.

Δ: The color change of the touch panel is somewhat observed.

X: The color change of a touch panel is large.

Synthesis Example Cyclic Olefin Polymer A

227.5 parts of 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene, 22.5 parts of bicyclo [2.2.1] hept-2-ene, 1- 18 parts of hexene (molecular weight regulator) and 750 parts of toluene (solvent for ring-opening polymerization reaction) were put into the reaction container which carried out the nitrogen substitution, and this solution was heated at 60 degreeC. Then, 0.62 parts of triethylaluminum toluene solution (1.5 mol / L) and tungsten chloride (t-butanol: methanol: methanol: tungsten = 0.35 mol: 0.3 mol: 1) modified with t-butanol / methanol were added to the solution in the reaction vessel. 3.7 parts of toluene solution (concentration 0.05 mol / L) was added, and the ring-opening polymerization reaction was performed by heating and stirring this system at 80 degreeC for 3 hours, and the ring-opening copolymer solution was obtained. The polymerization conversion rate in this polymerization reaction was 97%.

4,000 parts of the ring-opening copolymer solution thus obtained were put into an autoclave, and 0.48 parts of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening copolymer solution, and the hydrogen gas pressure was 100 kg / cm 2, The hydrogenation reaction was performed by heat-stirring for 3 hours on conditions of reaction temperature 160 degreeC.

After cooling the obtained reaction solution (hydrogenated polymer solution), hydrogen gas was discharged. The reaction solution was poured into a large amount of methanol, the coagulum was separated and recovered, and dried to obtain a hydrogenated cyclic olefin polymer A.

Production Example 1 Cyclic Olefin Polymer Film A-1

The cyclic olefin polymer A obtained in the synthesis example was dissolved in toluene so that the solid content concentration was 30%. The solution viscosity at room temperature of the obtained solution was 30,000 mPa * s. 0.1 weight part of pentaerythryl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] as 100 weight part of cyclic olefin type polymer A to this solution as antioxidant. Part was added, and the resultant solution was filtered using a metal fiber sintered filter having a pore diameter of 5 µm manufactured by Nippon Pole while controlling the flow rate of the solution so that the pressure difference was within 0.4 MPa, and then installed in a Class 1000 clean room. Application | coating to 100-micrometer-thick PET film ("Lumier U94" by Toray Corporation) processed using the high grade "INVEX LABO coater" and hydrophilized (easy adhesive) by the acrylic acid type surface treating agent. It was. Subsequently, the obtained liquid layer was subjected to the primary drying treatment at 50 ° C., further subjected to the secondary drying treatment at 90 ° C., and then peeled from the PET film to form a cyclic olefin polymer film A-1 having a thickness of 188 μm. . The amount of residual solvent of obtained cyclic olefin polymer film A-1 was 0.5 weight%, and the light transmittance was 93% or more.

Production Example 2 Cyclic Olefin Polymer Film A-2

Film A-1 obtained in Production Example 1 was heated to 148 ° C. in a longitudinal drawing furnace provided with a wind direction control panel, and film was filmed at a furnace speed of 4.0 m / min in a layer in which the temperature distribution in the drawing machine was controlled to be within 148 ± 0.2 ° C. Cyclic olefin polymer film A-2 having an optical axis of 0 ± 2 degrees with respect to the film longitudinal direction with R0 of 138 nm, R0 of fluctuation of ± 5 nm with 1.2 times in the longitudinal direction and unfixed film width direction. Got.

Production Example 3 Polarizing Film

PVA is pre-stretched at a draw ratio of 3 times in a dyeing bath at a temperature of 30 ° C., which is composed of an aqueous solution having an iodine concentration of 0.03% by weight and a potassium iodide concentration of 0.5% by weight, followed by a boric acid concentration of 5% by weight and potassium iodide concentration of 8 The polarizing film was obtained by carrying out the post-extension process by extending | stretching 2 times the draw ratio twice in the crosslinking bath of 55 degreeC which consists of a weight% aqueous solution, and drying.

Preparation Example 1 Mixed Adhesive

Water was added to 163-03045 (molecular weight: 22,000, saponification degree: 88 mol%) manufactured by Wako Junyaku Kogyo Co., Ltd., a PVA-based resin, to prepare an aqueous solution having a solid content concentration of 7% by weight. On the other hand, CR-5L (an active ingredient) of Dainippon Ink Kogyo Co., Ltd. which is a polyepoxy clock hardening | curing agent in 100 parts of WLS-201 (solid content concentration 35weight%) made by Dainippon Ink & Chemical Co., Ltd. which is polyurethane-type resin 5 parts of 100% products) were mix | blended, and it diluted with water, and prepared the aqueous solution which is 20 weight% of solid content concentration. The obtained polyurethane-based resin aqueous solution and polyvinyl alcohol-based resin aqueous solution were mixed in a weight ratio of 1: 1 (80:20 in solid content weight ratio) to prepare a mixed adhesive having a solid content concentration of 15% by weight.

Production Example 2 Hard Coating Agent a, Coating Composition b

The ultraviolet curable resin composition (JSR Co., Ltd. make Desolite Z-7524: The composition is shown in following Table 1. Solid content concentration is 53.2%), It diluted with methyl ethyl ketone so that solid content concentration might be 45 weight%, and particle | grains were made into A hard coating treatment agent a containing a coating composition not included was obtained.

To the obtained hard coat treatment agent a, 1 wt% of the release polymer particles (JSR Co., Ltd. SX8707C-04, number average particle diameter of 4.5 µm) was diluted with methyl ethyl ketone so that the solid content concentration was 40% by weight. And stirring to prepare a coating composition b.

Production Example 1 Laminated Film B-1

Coating composition b was apply | coated to one side of cyclic olefin type polymer film A-2 by the gravure reverse method. The coated surface was dried at 80 ° C. for 60 seconds and irradiated with 150 mJ / cm 2 ultraviolet ray to obtain a film having a particle-containing resin layer having a thickness of 1.7 μm.

Subsequently, the hard coat layer was similarly formed on the opposite surface of the said film using the hard-coating agent a, and the laminated film B-1 which has the resin layer of 1.7 micrometers in thickness on both surfaces was formed. The results obtained by measuring or evaluating various physical properties of the obtained laminated film B-1 are shown in Table 2 below.

Production Example 2 Laminated Film B-2

Laminated film B-2 was obtained like manufacture example 1 except having used cyclic olefin polymer film A-1 instead of cyclic olefin polymer film A-2. The result of having measured or evaluated the various physical properties of obtained laminated | multilayer film B-2 is shown together in following Table 2.

Preparation Example 3 Coating Solution for Forming Easy Adhesive Layer

60 parts by weight of an alkoxy terminated polysiloxane (manufactured by GE Toshiba Silicone Co., Ltd., trade name: XR31-B2733) of Mw = 20,000 and a hydroxy terminated polydimethylsiloxane (GE Toshiba silicone of Mw = 4000) in a reactor equipped with a stirrer and a reflux cooler. 40 weight part of toluene, 42 weight part of toluene, and 0.2 weight part of isopropyl alcohol 75% diluents of di-i-propoxy ethyl acetoacetate aluminum were mixed, and it stirred, 80 The dealcoholization reaction was carried out at 占 폚 for 3 hours. Subsequently, 288 weight part of methyl isobutyl ketones, 70 weight part of methanol, 80 weight part of water, and 12 weight part of triethylamine were added, and the hydrolysis and condensation reaction was performed at 60 degreeC for 3 hours. Then, after neutralizing the obtained reaction liquid with oxalic acid and removing the water phase (lower layer), after performing water washing and water phase removal 3 times, the solvent was distilled off and the polyfunctional polysiloxane of Mw = 30,000 was obtained. 100 weight part of methyl isobutyl ketones were added to this polyfunctional polysiloxane, and the polysiloxane solution (I) of 50 weight% of solid content concentration was obtained.

120 parts by weight of powdered zirconium oxide fine particles (primary average particle diameter: 20 nm), 160 parts by weight of the polysiloxane solution (I) (80 parts by weight in terms of solid content) as a polysiloxane component, 0.1 parts by weight of triethylamine, and diiso 720 parts by weight of butyl ketone were placed in a container, and 2000 parts by weight of 0.1 mm diameter zirconia beads were added to the mixture to disperse the fine particles for 6 hours using a paint shaker, and the polysiloxane composition containing the metal oxide fine particles having a solid concentration of 20% by weight was prepared. The coating liquid for easy adhesion layer formation was obtained.

Example 1 Conductive Laminated Film C-1

After performing a corona discharge treatment of 50 W · min / m2 in the air on the surface of the particle-containing resin layer in the laminated film B-1, the coating liquid for easy adhesion layer formation was coated with a wire bar having a thickness of 6 μm. , And dried at 110 ° C. for 3 minutes to form an easy adhesive layer.

Using the target containing indium and tin on the surface of the easily formed adhesive layer under inflow of argon gas, the transparent conductive layer was formed by the sputtering method on condition of the following, and the electroconductive laminated film C-1 was obtained. It was 550 ohms / square when the surface resistance value in the transparent conductive layer of obtained electroconductive laminated film C-1 was measured. The results obtained by measuring and evaluating various physical properties are shown in Table 3 below.

(Condition)

Base material temperature: 50 degrees C or less

Target: oxide of In ₂ O ₃ / SnO ₂ = 90/10 (weight ratio)

Atmosphere: Argon Inflow

Argon flow rate: 100 to 500 sccm

Power: 1 to 1.5 Kw

Comparative Example 1

Conductive laminated film C-2 was obtained like Example 1 except having used laminated film B-2 instead of laminated film B-1. Table 3 shows the results of measuring and evaluating various physical properties.

Comparative Example 2

It carried out similarly to Example 1 except having used cyclic olefin type polymer film A-2 instead of laminated | multilayer film B-1, and using one side of cyclic olefin type polymer film A-2 instead of the surface of a particle containing resin layer. Laminated film C-3 was obtained. Table 3 shows the results of measuring and evaluating various physical properties.

Example 2 Production of Polarizing Plate and Touch Panel

On one side of the polarizing film obtained in Production Example 3, the mixed adhesive obtained in Production Example 1 is coated, and the conductive laminated film C-1 is laminated so that the surface opposite to the transparent conductive film contacts the polarizing film, and the polarizing plate D of the present invention. -1 was obtained. Moreover, it bonded together so that the absorption axis of a polarizing film and the optical axis of the film which has a quarter wave plate function in a conductive laminated film may form an angle of 45 degrees.

Two polarizing plates D-1 were superposed | superposed on the liquid crystal display element so that the transparent conductive film surface could face each other at the angle orthogonal to the absorption axis of each polarizing film, and was arrange | positioned on the liquid crystal display element, and the touchscreen of this invention was obtained. At this time, in FIG. 1 centering on a display screen, the absorption axis of the polarizing film in the polarizing plate near a display screen is 45 degrees, and the optical axis of the film which has a 1/4 wavelength plate function in this polarizing plate is 0. It was arrange | positioned so that the absorption axis of the polarizing film in the other polarizing plate which may be in a ° direction, and the downward navigation was 135 °, and the optical axis of the film having the 1/4 wavelength plate function in the polarizing plate was in the 90 ° direction.

Contrast and visibility were evaluated about the obtained touch panel. The results are shown in Table 4 below.

Comparative Example 3

A touch panel was obtained in the same manner as in Example 2, except that the conductive laminated film C-2 was used instead of the conductive laminated film C-1. Contrast and visibility were evaluated about the obtained touch panel. The results are shown in Table 4 together.

[Comparative Example 4]

A touch panel was obtained in the same manner as in Example 2, except that the conductive laminated film C-3 was used instead of the conductive laminated film C-1. Contrast and visibility were evaluated about the obtained touch panel. The results are shown in Table 4 together.

Claims (3)

1 / including a cyclic olefin polymer obtained by (co) polymerizing a monomer containing at least one compound represented by the following formula (1), and having an in-plane retardation with respect to transmitted light having a wavelength of 550 nm in a range of 128 to 148 nm. 4. A conductive laminated film comprising a film having a wave plate function, a particle-containing resin layer, and a transparent conductive layer having a weight ratio of indium oxide and tin oxide of 95: 5 to 99: 1. <Formula 1> (Wherein, R ¹ to R ⁴ each independently represent a hydrogen atom; a halogen atom; or a monovalent organic group that may contain oxygen, nitrogen, sulfur, or silicon, R ¹ and R ² and R ³ and R ⁴ may be bonded to each other independently to form an alkylidene group, R ¹ and R ² , R ³ and R ⁴ , and R ² and R ³ may be bonded to each other independently to form a monocyclic or polycyclic carbocyclic or heterocyclic ring, x represents an integer of 0 to 3, y represents 0 or 1) The conductive laminated film of Claim 1 is laminated | stacked on the polarizing film, The polarizing plate characterized by the above-mentioned. It has a polarizing plate of Claim 2, The touch panel characterized by the above-mentioned.