TWI408704B - Conductive transparent film and its use - Google Patents

Abstract

A transparent conductive film comprising a transparent film of cycloolefin resin and, sequentially superimposed on a surface thereof, a particle-containing protective layer resulting from photohardening of a composition for protective layer formation containing an actinic energy ray hardening resin composition and particles and a transparent conductive layer, wherein the actinic energy ray hardening resin composition contains a polyfunctional monomer and a polymer resulting from addition reaction of acrylic acid to a glycidyl (meth)acrylate polymer. Accordingly, through lamination of a transparent film of low birefringence, low moisture absorption, high transparency, high heat resistance, etc., a particle-containing protective layer having transparency, being capable of preventing Newton rings while preventing uneven display and excelling in image clarity and a transparent conductive layer, there is provided a conductive transparent film that is satisfactory with respect to these properties and that especially when used as a transparent electrode for touch panel, gives clear images.

Description

Conductive transparent film and use thereof

The present invention relates to a conductive transparent film and its use. More specifically, the present invention relates to a conductive transparent film containing a particle protective layer and a transparent conductive layer, and a touch panel using the same, and a transparent film formed of a cyclic olefin resin. The display device of this touch panel.

In the early days, polycarbonate (PC) and polymethyl methacrylate (PMMA) were widely used as molding materials for optical applications. PC has high birefringence, and PMMA has high water absorption and insufficient heat resistance. Development of novel molding materials of equal performance.

Therefore, in recent years, cyclic olefin-based resins have been attracting attention and have been widely used.

However, the cyclic olefin-based resin film has a problem of low birefringence, low moisture absorption, high transparency, and high heat resistance, and has a problem that the surface is slightly weak and easily damaged.

In general, in order to impart a hard coat property to various plastic materials, an active energy ray-curable resin is coated on the surface of the plastic material.

Therefore, the surface of the cyclic olefin-based resin film is also an active energy ray-curable resin, and a general-purpose resin has a problem that the adhesion to the cyclic olefin-based resin is insufficient.

In this case, there is a method of containing a polymer having a non-reactive component in an active energy ray-curable coating agent (for example, Patent Document 1); and a method of blending an alicyclic (meth)acrylic compound of a polymerizable compound (for example, a patent) Document 2); a proposal of a method using a specific photopolymerization initiator (for example, Patent Document 3). By such methods, the adhesion can be improved.

However, in these methods, the crosslinking density of the active energy ray-curable coating agent is lowered by the addition of such a polymer or the like, and the scratch resistance of the obtained cured film is lowered to cause curling, and further, the cyclic olefin system is used. The hardness of the hardened film on the resin film is insufficient.

Moreover, in the use of various materials such as a plasma display device or a liquid crystal display device such as a mobile phone, a PDA (mobile information terminal), or a video camera, the molding material for optical use is more vividly reflected, and at the same time, The illuminating of the displayed image caused by the reflection or scattering of the light incident on the screen or the light emitted from the screen; and the display image does not cause the iridescent ripple of the so-called Newton ring due to the interference of light, and the performance is more strictly required.

Further, the touch panel used as the input terminal disposed on the front surface of the display device does not impair the optical characteristics of the displayed image, and the above-described high performance is also required. Further, regarding the performance of the touch panel, the optical characteristics of the conductive transparent film are largely negative.

In addition, with respect to such high performance, various anti-reflection measures and anti-glare measures have been adopted, and the present situation has not been able to satisfy all the requirements.

Under such circumstances, the working colleagues of the present invention have conducted in-depth research on the characteristics of optical forming materials such as antireflection films and antiglare films, and have found that low birefringence, low moisture absorption, and high transparency are ensured. Basic characteristics such as high heat resistance, plus the need to eliminate the uneven display of the so-called whitish and/or blackened parts, or the uneven display of the background image, the uneven display such as glare and/or glare, and the light of Newton's ring. The three unsuitable conditions dominated by the interference effect make the balance of these good. In addition, it has been found that a particle-containing protective layer which exhibits an excellent anti-mite effect is formed on the surface of a transparent film made of a cyclic olefin resin having properties such as curability, scratch resistance, hardness, adhesion, and transparency. Further, the conductive transparent film in which the transparent conductive layer is laminated can be eliminated in a balanced manner, and the present invention is completed.

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei.

The present invention provides a basic characteristic of ensuring low birefringence, low moisture absorption, high transparency, high heat resistance, and a well-balanced display unevenness or background for removing the so-called whitish and/or blackened portions. Three types of unsuitable conductive transparent films, such as uneven display, glare and/or glare, and interference effects of Newton's ring light, and touch panels using the conductive transparent film, and having such a touch The display device of the panel is a problem. In other words, the present invention provides a surface of a transparent film made of a cyclic olefin resin having properties such as curability, scratch resistance, hardness, adhesion, and transparency, and exhibits an excellent antiglare effect. A conductive transparent film containing a particle protective layer, a transparent conductive layer, a touch panel using the conductive transparent film, and a display device having the touch panel are the subject matter.

The conductive transparent film of the present invention is characterized in that a conductive transparent film comprising a particle protective layer and a transparent conductive layer is laminated on the surface of the transparent film in this order; and the transparent film is made of a cyclic olefin resin. The particle-containing protective layer is a layer obtained by photo-curing a composition for forming a protective layer containing an active energy ray-curable resin composition and particles having an average particle diameter of 50 to 600 nm, and the active energy ray hardenability. The resin composition contains: (A) 40 to 60% by weight of a polyfunctional monomer having 3 or more acrylonitrile groups, and (B) in a (meth)acrylic acid glycidyl ester polymer, acrylic acid is added 10 to 60% by weight of the polymer formed by the reaction, and (0) 0 to 50% by weight of the other acrylic oligomers which are optional [however, the total of the components (A), (B) and (C) is 100% by weight. ].

In the present invention, the cyclic olefin-based resin is preferably obtained by subjecting a monomer containing at least one compound represented by the following formula (I) to (co)polymerization.

[In the formula (I), R ¹ to R ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a polar group, or another monovalent organic group; R ¹ and R ² or R ^{3 ;} An integral divalent hydrocarbon group may be formed with R ⁴ ; R ¹ or R ² , and R ³ or R ⁴ may be bonded to each other to form a monocyclic or polycyclic structure; m is 0 or a positive integer; p is 0 or a positive integer] .

The conductive transparent film of the present invention contains a particle protective layer and exhibits a haze value of 12% or less per layer.

In the conductive transparent film of the present invention, it is preferred to laminate the particle-containing protective layer on both surfaces of the transparent film.

In the conductive transparent film of the present invention, the protective layer preferably contains primary particles having a particle diameter of 1300 nm or more in an amount of 1.5 to 7% by weight based on the total particles.

The conductive transparent film of the present invention is composed of a laminated polarizing plate, and the polarizing plate is preferably laminated by a pressure-sensitive adhesive.

The touch panel of the present invention is characterized in that it has the conductive transparent film of the present invention as at least one transparent electrode. Moreover, the display device of the present invention is characterized in that the touch panel of the present invention is provided on the display surface side.

According to the present invention, by using a transparent film made of a cyclic olefin resin, it is possible to provide a conductive transparent film which ensures basic characteristics such as low birefringence, low moisture absorption, high transparency, and high heat resistance. Further, according to the present invention, by using a specific particle and a specific resin composition, a particle-containing protective layer is formed, and the above-mentioned transparent film is excellent in adhesion, and a conductive transparent film imparting a hard coating function can be provided. . Further, according to the present invention, by using particles having a specific average particle diameter, transparency can be ensured, display unevenness of a portion which is whitish and blackened can be prevented, and it is possible to effectively prevent occurrence of transparency due to improvement in transparency. The Newton's ring, which interferes with light, prevents the phenomenon of fading and glare of the image, and fully exhibits good imageability, and provides a conductive transparent film having a particle-containing protective layer having a good balance of all characteristics.

According to the present invention, by laminating the transparent conductive layer on the protective layer, it is possible to provide a conductive transparent film which satisfies all of the above characteristics, and in particular, when a transparent electrode for a touch panel is used, a clear image is obtained.

Further, according to the present invention, it is possible to provide low birefringence, low moisture absorption, high transparency, high heat resistance, and the like, and to ensure transparency, and to prevent uneven display of whitish and blackened portions, and at the same time, can effectively prevent Newton's ring prevents the appearance of the image from falling and shining, and fully exhibits good imageability. A touch panel and display device for obtaining vivid images.

[Embodiment of the Invention]

The invention will be specifically described below.

The conductive transparent film of the present invention is mainly composed of a transparent film, a particle-containing protective layer, and a transparent conductive layer, and is preferably used as an anti-glare film or an anti-reflection film.

[transparent film]

The transparent film of the present invention is mainly composed of a cyclic olefin resin. The cyclic olefin-based resin has the following (co)polymer or the like.

(1) A ring-opening polymer of a cyclic olefin (hereinafter referred to as "specific monomer") represented by the following formula (I).

(2) A ring-opening copolymer of the specific monomer and a copolymerizable monomer.

(3) A hydrogenated (co)polymer of the ring-opened (co)polymer of the above (1) or (2).

(4) A hydrogenated (co)polymer obtained by cyclizing a ring-opening (co)polymer of the above (1) or (2) by a Friedel-Crafts reaction.

(5) A specific monomer and a saturated copolymer containing an unsaturated double bond compound.

(6) A shaped (co)polymer selected from the group consisting of a specific monomer, a vinyl cyclic hydrocarbon monomer, and a cyclopentadiene monomer, and a hydrogenated (co)polymer thereof.

(7) An interactive copolymer of a specific monomer and an acrylate.

[In the formula (I), R ¹ to R ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a polar group, or another monovalent organic group; R ¹ and R ² or R ^{3 ;} and R ⁴ may form a divalent hydrocarbon group of integration; ^{R. 1} or R ^2, or R ³ and R ⁴ may be bonded to each other to form a monocyclic or polycyclic junction configured; m is 0 or a positive integer; p is 0 or a positive integer] .

[specific monomer]

Specific examples of the specific monomer used as a raw material of the cyclic olefin resin include the following compounds and the like; and the present invention is not limited to such specific examples.

Bicyclo[2.2.1]hept-2-ene, tricyclo[4.3.0.1 ^2,5 ]-8-nonene, tricyclo[4.4.0.1 ^2,5 ]-3-(unde)ene, tetracyclic [4.4.0.1 ^2,5 .1 ^7,10] -3- (XII) ene, pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- ( XV) alkenyl , 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-methoxycarbonylbicyclo[2.2.1]heptane- 2-ene, 5-methyl-5-methoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyanobicyclo[2.2.1]hept-2-ene, 8-methoxy Carbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-(dodecene), 8-ethoxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-( Twelf) alkene, 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-(12) Alkene, 8-methyl-8-n-butoxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-(dodecene), 5-ethylenebicyclo[2.2.1] Hept-2-ene, 8-ethylenetetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-(dodecene), 5-phenylbicyclo[2.2.1]heptan-2- Alkene, 8-phenyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-(dodecene), 5-fluorobicyclo[2.2.1]hept-2-ene, 5-fluoromethyl Bicyclo[2.2.1]hept-2-ene, 5-trifluoromethylbicyclo[2.2.1]hept-2-ene, 5-pentafluoroethylbicyclo[2.2.1]hept-2- Alkene, 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-trifluoromethyl Ring [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-tetra(trifluoromethyl)bicyclo[2.2 .1] Geng-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-five Fluoroethyl-6,6-bis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene, 5,6-difluoro-5-pentafluoroisopropyl-6-trifluoromethyl Ring [2.2.1]hept-2-ene, 5-chloro-5,6,6-trifluorobicyclo[2.2.1]hept-2-ene, 5,6-difluoro-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-pentafluoro-propoxy bicyclo [2.2.1] hept-2-ene, 8-fluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- (twelve Alkenyl, 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-pentafluoroethyltetracyclic [4.4.0.1 ^2,5 .1 ^7,10 ]-3-(dodecene), 8,8-difluorotetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-(12) Alkene, 8,9- Fluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- (XII) alkylene, 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-tetra(trifluoromethyl)tetracyclic [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- (XII) hexene, 8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- (12) alkene, 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-pentafluoropropoxy yl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- (XII) alkenyl, 8-pentafluoro-fluoro-8- Yl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- (XII) hexene, 8,9-difluoro-8-isopropyl-pentafluoro -9-trifluoromethyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-(dodecene), 8-chloro-8,9,9-trifluorotetracycline [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), and the like.

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

Preferably, in the above formula (I), R ¹ and R ³ are a hydrogen atom or a hydrocarbon number of from 1 to 10, more preferably from 1 to 4, most preferably from 1 to 2; and R ² and R ⁴ is a hydrogen atom or a monovalent organic group, and at least one of R ² and R ⁴ is a hydrogen atom or a polar group other than a hydrocarbon group; m is an integer of 0 to 3; p is an integer of 0 to 3, preferably m + p =0~4, more preferably 0~2, and most preferably m=1, p=0. The specific monomer having m=1 and p=0 has a high glass transition temperature and excellent mechanical strength, and is suitable.

The polar group of a specific monomer has a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amine group, a decylamino group, a cyano group or the like; and these polar groups may be bonded via a linking group such as a methylene group. Further, a hydrocarbon group having a divalent organic group having a polar group such as a carbonyl group, an ether group, a methyl sulfonyl group, a thioether group or an imine group, which is bonded to a linking group, is also a polar group. Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group or an aryloxycarbonyl group is preferred, and an alkoxycarbonyl group or an aryloxycarbonyl group is more preferred.

Further, at least one of R ² and R ⁴ is a monomer having a polar group represented by the formula -(CH ₂ ) _n COOR, and the obtained cyclic olefin resin has high glass transition temperature, low hygroscopicity, and superiority to various materials. Adhesive, very suitable. In the above formula of the specific polar group, R is a hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and the alkyl group is most suitable. Further, n is usually from 0 to 5, and the smaller the value of n, the higher the glass transition temperature of the cyclic olefin-based resin, which is suitable. Further, n is a specific monomer of 0, which is easy to synthesize and is very suitable.

Further, 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 of 1 to 2, most preferably a methyl group; in particular, the alkyl group is a bond. When it is bonded to the same carbon atom to which a specific polar group represented by the above formula -(CH ₂ ) _n COOR is bonded, the hygroscopicity of the obtained cyclic olefin resin can be lowered, which is suitable.

[copolymerizable monomer]

Specific examples of the copolymerizable monomer include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene. The carbon number of the cyclic olefin is preferably 4 to 20, more preferably 5 to 12. These may be used alone or in combination of two or more.

The preferred range of use of the specific monomer/copolymerizable monomer is from 100/0 to 50/50, more preferably from 100/0 to 60/40, by weight.

[Open-loop polymerization catalyst]

In the present invention, in order to obtain (1) a ring-opening polymer of a specific monomer, and (2) a ring-opening polymerization reaction of a ring-opening copolymer of a specific monomer and a copolymerizable monomer, in the presence of a metathesis catalyst get on.

The metathesis catalyst is composed of: (a) at least one selected from the group consisting of W, Mo, and Re, and (b) selected from elements having a periodic group IA (eg, Li, Na, K, etc.), Group IIA (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 Group IVB elements (eg, Ti) a catalyst obtained by combining at least one of the elements of the compound of Zr, etc., a carbon bond or at least one of the element-hydrogen bond. Further, in this case, in order to increase the activity of the catalyst, the additive (c) described later may be added.

(a) Representative examples of suitable W, Mo or Re compounds are WCl ₆ , MoCl ₆ , ReOCl _{3 ,} etc., JP-A-1-132626, page 8 left lower column, sixth line, eighth page, upper right column Compounds recorded in line 17 and so on.

Specific examples of the component (b) include n-C ₄ H ₉ Li, (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , (C ₂ H ₅ )AlCl ₂ , methyl arumomic acid, LiH, etc., JP-A-1-132626, page 8 of the upper right column, line 18 to page 8, the compound described in the third row of the lower right column, and the like. As a representative example of the component (c) of the additive, an alcohol, an aldehyde, a ketone, an amine or the like can be used; and further, it can be used in the upper left column of the lower right column, the 16th line to the 9th page, on page 8 of the Japanese Patent Publication No. 1-132626. The compound shown on line 17.

The amount of the metathesis catalyst used is, in the range of the molar ratio of the above component (a) to the specific monomer, "(a) component: specific monomer" is usually in the range of 1:500 to 1:50,000, preferably 1: The range of 1,000~1:10,000. (a) The ratio of the component to the component (b), in terms of metal atomic ratio, (a): (b) is in the range of 1:1 to 1:50, preferably 1:2 to 1:30. (a) The ratio of the component to the component (c), in terms of molar ratio, (c): (a) is in the range of 0.005 to 15:1, preferably 0.05:1 to 7:1.

[Solvent for polymerization]

The solvent used in the ring-opening polymerization reaction (the solvent constituting the molecular weight modifier solution, the solvent of the specific monomer and/or the metathesis catalyst), for example, pentane, hexane, heptane, octane, decane, decane Alkane; cyclohexane such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromine Halogenated alkane such as hexane, dichloromethane, dichloroethane, dibromohexane, chlorobenzene, chloroform or tetrachloroethylene; halogenated aryl; ethyl acetate, n-butyl acetate, isobutyl acetate, C A saturated carboxylic acid ester such as methyl ester or dimethoxyethane; an ether such as dibutyl ether, tetrahydrofuran or dimethoxyethane. These may be used singly or in combination, and among these, aromatic hydrocarbons are preferred.

The amount of the solvent used, "solvent: specific monomer (weight ratio)" is usually 1:1 to 10:1, preferably 1:1 to 5:1.

[Molecular weight regulator]

The molecular weight of the obtained ring-opening (co)polymer can be adjusted depending on the polymerization temperature, the type of the catalyst, and the type of the solvent. In the present invention, the molecular weight modifier is allowed to coexist in the reaction system to be adjusted.

Here, suitable molecular weight modifiers include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-decene, and the like. Α-olefins, styrene, etc.; among these, 1-butene and 1-hexene are most suitable. These molecular weight modifiers may be used alone or in combination of two or more.

The amount of the molecular weight modifier used is 0.005 to 0.6 mol, preferably 0.02 to 0.5 mol, based on 1 mol of the specific monomer supplied to the ring-opening polymerization.

In order to obtain (2) a ring-opening copolymer, in a ring-opening polymerization step, a specific monomer and a copolymerizable monomer may be subjected to ring-opening copolymerization; further, in polybutadiene or polyisoprene. An unsaturated hydrocarbon polymerization having a carbon-carbon double bond of 2 or more in a main chain of a conjugated diene compound, a styrene-butadiene copolymer, an ethylene-nonconjugated diene copolymer, a polybornene or the like A specific monomer is subjected to ring-opening polymerization in the presence of a substance or the like.

The ring-opening (co)polymer obtained as described above can be used as it is; the olefin in the molecule of the (co)polymer is unsaturatedly bonded and hydrogenated to obtain (3) hydrogenated (co)polymer, which is heat resistant It is excellent in coloring property or light resistance, and can improve the durability of the phase difference film.

[hydrogenation catalyst]

For the hydrogenation reaction, a method of hydrogenating a usual olefinic unsaturated bond can be employed. That is, a hydrogenation catalyst is added to the solution of the ring-opening polymer, and a hydrogen gas having a normal pressure of -300 atmospheres, preferably 3 to 200 atmospheres, is applied thereto at a temperature of 0 to 200 ° C, preferably 20 to 180 ° C. Hydrogenation is carried out.

As the hydrogenation catalyst, a hydrogenation reaction of a usual olefinic compound can be used. The hydrogenation catalyst has an uneven catalyst and a uniform catalyst.

The heterogeneous catalyst may be a solid catalyst in which a noble metal catalyst such as palladium, platinum, nickel, rhodium or ruthenium is supported on a carrier such as carbon, cerium oxide, alumina or titania. Further, the homogeneous catalyst is, nickel naphthenate/triethylaluminum, acetonitrile acetone/triethylaluminum, cobalt octylate/n-butyllithium, titanyl dichloride/diethylaluminum Chloride, barium acetate, chlorotris(triphenylphosphine) ruthenium, dichlorotris(triphenylphosphine) ruthenium, chlorohydrocarbonyltris(triphenylphosphine) ruthenium, dichlorocarbonyltris(triphenylphosphine) ruthenium Wait. The form of the catalyst may be in the form of powder or granules.

These hydrogenation catalysts are used in a ratio of open-loop (copolymer: hydrogenation catalyst (weight ratio) of 1:1 × 10 ^-6 to 1:2).

Hydrogenation ratio of the hydrogenated (co) polymer, the determination of at 500MHz, ¹ H NMR is 50% or more, preferably 90% or more, more preferably 98% or more, more preferred 99%. The higher the hydrogenation rate, the more excellent the stability with respect to heat or light. When the transparent film of the present invention is used, it is possible to obtain a specific stability over a long period of time.

Further, when an aromatic group is contained in the ring-opening (co)polymer molecule, the heat-resistant coloring property and light resistance of the aromatic group are extremely reduced. Conversely, optical properties such as refractive index and wavelength dispersion property or heat resistance are also exhibited. The advantageous effects of optical properties do not require hydrogenation.

The ring-opened (co)polymer obtained above can be obtained by adding a well-known antioxidant such as 2,6-di-tert-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di Tert-butyl-5,5'-dimethyldiphenylmethane, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane; ultraviolet absorber For example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, or the like can be stabilized. Further, an additive such as a slip agent may be added for the purpose of improving workability.

In addition, as the hydrogenated (co)polymer used in the cyclic olefin resin used in the present invention, the gel content of the hydrogenated (co)polymer is preferably 5% by weight or less, and preferably 1% by weight. The following is best.

Further, in the cyclic olefin resin used in the present invention, (4) the ring-opening (co)polymer of the above (1) can be cyclized by a Friedel-Crafts reaction and then hydrogenated ( Co)polymer.

[cyclization by the Friedel-Crafts reaction]

The method of cyclizing the ring-opening (co)polymer of the above (1) or (2) by a Friedel-Crafts reaction is not particularly limited, and it can be described in JP-A-50-154399. A well-known method of using acidic compounds. Specific examples of the acidic compound include Lewis acid such as AlCl ₃ , BF ₃ , FeCl ₃ , Al ₂ O ₃ , HCl, CH ₃ ClCOOH, zeolite, activated clay, and Bronsted acid.

The cyclized ring-opened (co)polymer can be hydrogenated in the same manner as the ring-opened (co)polymer of (1) or (2) above.

Further, as the cyclic olefin resin used in the present invention, (5) a saturated copolymer of the above specific monomer and a compound containing an unsaturated double bond may be used.

[Compound containing unsaturated double bond]

The compound containing an unsaturated double bond may, for example, be ethylene, propylene or butylene, and is preferably an olefin compound having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms.

The preferred range of use of the specific monomer/unsaturated double bond compound is 90/10 to 40/60, more preferably 85/5 to 50/50 by weight.

In the present invention, in order to obtain (5) a specific monomer and a saturated copolymer containing an unsaturated double bond compound, a usual addition polymerization method can be used.

[Addition Polymerization Catalyst]

In order to synthesize the catalyst of the above (5) saturated copolymer, at least one selected from the group consisting of a titanium compound, a zirconium compound and a vanadium compound, and an organoaluminum compound as a catalyst can be used.

Here, the titanium compound may be titanium tetrachloride or titanium trichloride; and the zirconium compound may be bis(cyclopentadienyl)zirconium chloride or bis(cyclopentadienyl)zirconium dichloride.

Further, as the vanadium compound, a vanadium compound represented by a general formula VO(OR) _a X _b or V(OR) _c X _d or an electron-donating additive may be used.

[However, R is a hydroxyl group; X is a halogen atom; 0≦a≦3, 0≦b≦3, 2≦(a+b)≦3, 0≦c≦4, 0≦d≦4, 3≦(c+d)≦ 4].

The electron donor is an oxygen-containing electron donor such as an alcohol, a phenol, a ketone, an aldehyde, a carboxylic acid, an ester of an organic acid or an inorganic acid, an ether, a decylamine, an acid anhydride or an alkoxysilane; ammonia, an amine, a nitrile a nitrogen-containing electron donor such as an isocyanate or the like.

Further, the organoaluminum compound of the promoter may be at least one selected from the group consisting of at least one aluminum-carbon bond or aluminum-hydrogen bond.

In the above, for example, when a vanadium compound is used, the ratio of the ratio of the vanadium compound to the organoaluminum compound to the aluminum atom of the vanadium atom (Al/V) is 2 or more, preferably 2 to 50, and most preferably 3 to 20. range.

The solvent for the polymerization reaction used in the addition polymerization can be the same as the solvent used in the ring-opening polymerization reaction. Further, the adjustment of the molecular weight of the obtained (5) saturated copolymer is usually carried out using hydrogen.

Further, the cyclic olefin resin used in the present invention may be one selected from the group consisting of (6) the specific monomer, and one or more monomers of a vinyl cyclic olefin monomer or a cyclopentadiene monomer. Molded copolymers and hydrogenated copolymers thereof.

[Ethylene-based cyclic hydrocarbon monomer]

Examples of the vinyl cyclic hydrocarbon-based monomer include vinylcyclopentene monomers such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene; 4-vinylcyclopentane; a vinylated hydrocarbon monomer such as a vinyl cyclopentane monomer such as 4-isopropenylcyclopentane; 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl- a vinylcyclohexene monomer such as 4-isopropenylcyclohexene, 2-methyl-4-vinylcyclohexene or 2-methyl-4-isopropenylcyclohexene; 4-vinyl ring Vinylcyclohexane monomer such as hexane or 2-methyl-4-isopropenylcyclohexane; styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, Styrene monomer such as 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-phenylstyrene, p-methoxystyrene; d-pinene, 1-decene, Terpene monomers such as biguanide, d-decadiene, 1-decadiene, and dipentene; vinylcycloheptene monomers such as 4-vinylcycloheptene and 4-isopropenylcycloheptene Ethylene such as 4-vinylcycloheptane or 4-isopropenylcycloheptane Cycloheptane based monomer. Preferred is styrene or α-methylstyrene. These may be used alone or in combination of two or more.

[cyclopentadiene monomer]

(6) The cyclopentadiene monomer used in the monomer of the addition copolymer is, for example, cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-B Cyclopentadiene, 5-methylcyclopentadiene, 5,5-dimethylcyclopentadiene, and the like. Preferred is cyclopentadiene. These may be used alone or in combination of two or more.

An additive (co)polymer selected from the group consisting of a specific monomer, a vinyl-based cyclic hydrocarbon monomer, and a cyclopentadiene monomer, and the above-mentioned (5) specific monomer can be used. It is obtained by the same addition polymerization method as a saturated copolymer containing an unsaturated double bond compound.

Further, the hydrogenated (co)polymer of the addition (co)polymer can be obtained by the same hydrogenation method as the hydrogenated (co)polymer of the (3) ring-opened (co)polymer.

Further, as the cyclic olefin resin used in the present invention, (7) an interactive copolymer of the specific monomer and the acrylate may be used.

[Acrylate]

(7) The acrylate used in the production of the cross-linking copolymer of the specific monomer and the acrylate is, for example, methyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate or the like having a carbon number of 1 to 20 a chain-like, branched or cyclic alkyl acrylate; a glycidyl group-containing acrylate having 2 to 20 carbon atoms such as a glycidyl acrylate or a 2-tetrahydrofurfuryl acrylate; a benzyl acrylate or the like An acrylate having an aromatic ring group having 6 to 20 carbon atoms; an acrylate having a polycyclic structure having 7 to 30 carbon atoms such as isobornyl acrylate or dicyclopentyl acrylate.

In the present invention, in order to obtain (7) a cross-copolymer of the specific monomer and the acrylate, in the presence of a Lewis acid, when the total of the specific monomer and the acrylate is 100 mol, usually the specific monomer is 30 to 70 moles, acrylate is 70 to 30 moles; preferably 40 to 60 moles of the specific monomer, 60 to 40 moles of acrylate; more preferably with the specific single The radical polymerization is carried out at a ratio of 45 to 55 moles and an acrylate of 55 to 45 moles.

The amount of Lewis acid used to obtain (7) the copolymer of the specific monomer and the acrylate is 0.001 to 1 mole per 100 moles of the acrylate. Further, a well-known radical generating organic peroxide or an azobis system radical polymerization initiator can be used. The polymerization temperature is usually -20 to 80 ° C, preferably 5 to 60 ° C. Further, the polymerization solvent may be the same as the solvent used in the ring-opening polymerization reaction.

Further, the term "interactive copolymer" as used in the present invention means that it is not adjacent to a structural unit derived from the specific monomer, that is, a neighboring structural unit derived from the specific monomer, and must have a structural unit derived from the acrylate. The meaning of the constructed copolymer; it is not to negate the constructor from which the structural units of the acrylate are adjacent to each other.

The preferred molecular weight of the cyclic olefin resin used in the present invention is an intrinsic viscosity [η] _inh ; 0.2 to 5 dl/g, more preferably 0.3 to 3 dl/g, most preferably 0.4 to 1.5 dl/g; The polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 8,000 to 100,000, more preferably 10,000 to 80,000, most preferably 12,000 to 50,000, and a weight average molecular weight (Mw) of 20,000 to 300,000. More preferably, it is 30,000 to 250,000, and most preferably is in the range of 40,000 to 200,000.

When the intrinsic viscosity [η] _inh , the number average molecular weight, and the weight average molecular weight are in this range, the heat resistance, water resistance, chemical resistance, and mechanical properties of the cyclic olefin resin are used as the anti-caries film of the present invention. The balance of stability of optical properties is good.

The glass transition temperature (Tg) of the cyclic olefin resin used in the present invention is usually 120 ° C or higher, preferably 120 to 350 ° C, more preferably 130 to 250 ° C, and most preferably 140 to 200 ° C. The optical characteristics of the obtained cyclic olefin-based resin film can be stabilized, and the thermal deterioration of the resin during heat processing in the vicinity of Tg can be prevented.

The cyclic olefin resin used in the present invention has a saturated water absorption at 23 ° C of preferably 2% by weight or less, more preferably 0.01 to 2% by weight, most preferably 0.1 to 1% by weight. When the saturated water absorption ratio is in this range, the optical characteristics are uniform, and the obtained cyclic olefin-based resin film is excellent in adhesion to other optical members or adhesives, and does not cause peeling or the like in use; It is also excellent in solubility and can be added in large quantities. The saturated water absorption is a value obtained by measuring the weight added by immersing it in water at 23 ° C for one week in accordance with ASTM D570.

The cyclic olefin resin used in the present invention has a photoelastic coefficient (C _P ) of 0 to 100 (×10 ^-12 Pa ^-1 ) and a stress optical coefficient (C _R ) of 1,500 to 4,000 (×). 10 ^-12 Pa ^-1 ). Here, in terms of photoelastic coefficient (C _P ) and stress optical coefficient (C _R ), various literatures (polymer Journal, vol. 27, No. 9 pp 943 to 950, 1995; Nippon Rheology Society, vol. 19 , No. 2, p 93~97, 1991; photoelasticity test method, published by the Nikkan Kogyo Shimbun, and the 7th edition of the 50th year. Compared with the former, the phase of the stress in the glass state of the polymer The degree of production, which is the degree of phase difference due to stress in the fluid state.

The photoelastic coefficient (C _P ) is large, and when a cyclic olefin resin film is used in combination with other optical members or adhesives, sensitive optical characteristics are caused by external factors or stress generated by self-freezing strain. For example, when the protective layer of the present invention is laminated and fixed to other optical members, it is easy to generate minute stress due to shrinkage of the bonded residual strain or temperature change or humidity change. Produces an unnecessary phase difference. Therefore, it is preferable to reduce the photoelastic coefficient (C _P ) as much as possible.

On the other hand, when the stress optical coefficient (C _R ) is large, for example, when a phase difference is imparted to the cyclic olefin-based resin film, a desired phase difference is obtained with a very small stretching ratio, and it is easy to obtain a large distribution. When the phase difference film is expected to have the same phase difference, it has a large advantage of being able to make the film thinner than the application optical coefficient (C _R ).

From the above viewpoints, the photoelastic coefficient (C _P ) is preferably 0 to 100 (×10 ^-12 Pa ^-1 ), more preferably 0 to 80 (×10 ^-12 Pa ^-1 ), more preferably 0. ~50 (×10 ^-12 Pa ^-1 ), preferably 0 to 30 (×10 ^-12 Pa ^-1 ), and most preferably 0 to 20 (×10 ^-12 Pa ^-1 ). An unnecessary phase difference such as a stress generated when the protective layer is laminated, a stress generated when the anti-smear film is fixed to another optical member, a change in phase difference due to an environmental change during use, and the like is minimized. The reason.

The cyclic olefin-based resin used in the present invention is composed of (1) to (2) ring-opened (co)polymers, (3) to (4) hydrogenated (co)polymers, and (5). a saturated copolymer, (6) an addition (co)polymer or a hydrogenated (co)polymer thereof, or (7) an interpolymer; wherein a well-known antioxidant, an ultraviolet absorber, etc. are added, which is more stable Chemical. Further, in order to improve the workability, an additive used in conventional resin processing such as a slip agent may be added.

The cyclic olefin resin used in the present invention can be added by adding a well-known antioxidant such as 2,6-di-tert-butyl-4-methylphenol or 2,2'-dioxy-3,3'-. Di-tert-butyl-5,5'-dimethyldiphenylmethane, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane; ultraviolet absorption Agents such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone and the like are more stable. Further, an additive such as a slip agent may be added for the purpose of improving workability.

The cyclic olefin-based resin film used in the ruthenium-proof film of the present invention can be formed into a film or a known method by a known method such as a melt molding method or a solution casting method (solvent casting method). Flaky. Among them, from the viewpoint of uniformity of film thickness and surface smoothness, a solvent casting method is preferred. Further, from the viewpoint of production cost, a melt molding method is preferred.

The thickness of the transparent olefin resin film used in the present invention, that is, the cyclic olefin resin film is usually 1 to 500 μm, preferably 1 to 300 μm, more preferably 10 to 250 μm, most preferably 50 to 200 μm. It ensures good handling and is easy to take up in a roll shape.

The thickness distribution of the transparent film (cyclic olefin-based resin film) used in the present invention is usually within ±20%, preferably within ±10%, more preferably within ±5%, and most preferably within ±5%. Within ±3%. Further, the change in thickness per 1 cm is usually 10% or less, preferably 5% or less, more preferably 1% or less, and most preferably 0.5% or less. By performing the thickness control, unevenness can be prevented in the surface of the conductive transparent film such as a tamper-proof film.

Specifically, there is a product name "A Frozen" manufactured by JSR Co., Ltd.

The transparent film used in the conductive transparent film of the present invention can be used for stretching as required. Specifically, it can be produced by a well-known uniaxial stretching method or a biaxial stretching method. That is, a transverse uniaxial stretching method by a tenter method, a compression stretching method between rollers, a longitudinal uniaxial stretching method using a drum having a different circumferential diameter, or the like, or a combination of a horizontal single axis and a single axis can be used. Axial stretching method, stretching method by a blow molding method, or the like.

In the case of uniaxial stretching, the stretching speed is usually from 1 to 5,000%/min, preferably from 50 to 1,000%/min, more preferably from 100 to 1,000%/min, most preferably from 100 to 500%/min.

In the biaxial stretching, the film may be stretched in two directions at the same time, or may be stretched in a direction different from the initial stretching direction after the uniaxial stretching. In these cases, the intersection angle of the two stretching axes is usually in the range of 120 to 60 degrees. Further, the stretching speed may be the same or different in each stretching direction, and is usually 1 to 5,000%/min, preferably 50 to 1,000%/min, more preferably 100 to 1,000%/min, and most preferably 100~500%/min.

The stretching temperature is not particularly limited. The glass transition temperature (Tg) of the cyclic olefin resin of the present invention is usually Tg ± 30 ° C, preferably Tg ± 10 ° C, more preferably Tg - 5 . ~Tg+10 °C range. When it is within this range, it is possible to suppress the occurrence of unevenness in the phase difference, and it is easy to control the refractive index ellipsoid, which is suitable.

The draw ratio is not particularly limited, and is usually 1.01 to 10 times, preferably 1.1 to 5 times, more preferably 1.1 to 3.5 times. When the draw ratio exceeds 10 times, it is difficult to control the phase difference.

The stretched film can be directly cooled and allowed to stand at a temperature of Tg-20 ° C to Tg for at least 10 seconds, preferably from 30 seconds to 60 minutes, more preferably from 1 to 60 minutes. Thereby, a retardation film made of a stable cyclic olefin-based resin film having a phase change characteristic with little change with time can be obtained.

Further, the linear expansion coefficient of the cyclic olefin resin film used in the present invention is preferably 1 × 10 ^-4 (1/°C) or less, more preferably 9 × 10 ^{-5 in} the range of 20 to 100 °C. (1/°C) or less, more preferably 8 × 10 ^-5 (1/°C) or less, and most preferably 7 × 10 ^-5 (1/°C) or less. Further, in the case of the retardation film, the difference between the stretching direction and the linear expansion coefficient perpendicular to the direction is preferably 5 × 10 ^-5 (1/°C) or less, more preferably 3 × 10 ^-5 (1). /°C) is preferably 1 × 10 ^-5 (1/°C) or less. When the linear expansion coefficient of the cyclic olefin-based resin film is used as the anti-glare film of the present invention, the stress caused by the influence of temperature and humidity during use can be suppressed. The change and the change in the phase difference or the change in the tamper resistance; when used as the anti-glare film of the present invention, the stability of the long-term characteristics can be obtained.

The stretched film as described above imparts a phase difference in the molecularly aligned transmitted light by stretching; the phase difference can be obtained by the phase difference, the stretching ratio, the stretching temperature, and the stretching of the film before stretching. The thickness of the film after alignment is controlled. Here, the phase difference is defined by the product of the refractive index difference (Δn) and the thickness (d) of the birefringent light (Δnd).

[protective layer containing particles]

The particle-containing protective layer of the present invention (hereinafter simply referred to as a protective layer) is a composition for forming a protective layer containing an active energy ray-curable resin composition and particles having an average particle diameter of 50 to 600 nm, and is photocured. Get the layer.

In the active energy ray-curable resin composition, it is preferred to blend (A) a polyfunctional monomer having 3 or more acryl fluorenyl groups (hereinafter referred to as (A) component), (B) in (methyl group). a polymer obtained by subjecting acrylic acid to an addition reaction in a glycidyl acrylate-based polymer [hereinafter referred to as (B) component], and (C) an optional other acrylic oligomer [hereinafter referred to as (C) ) ingredients], made. In particular, the component (A) is a component which imparts hardness to the protective layer obtained by the active energy ray-curable resin composition, adhesion to a transparent film, and the like. (B) The composition is a component which can increase the hardness of the protective layer and impart a reduction in the hardenability and the occurrence of curling at the time of hardening. By blending the component (B), the component (B) has a high molecular weight and is caused by a hydroxyl group having a large amount in the molecule, and the compatibility with the highly hydrophobic (A) component is lowered, and the component (B) is obtained in the obtained surface protective film. The surface moves for the sake of it. (C) Ingredients are optional ingredients that impart strength and toughness.

The surface tension of the component (A) is preferably 37 mN/m or less, more preferably 30 mN/m or more from the viewpoint of obtaining sufficient hardness and adhesion. The surface tension was measured by the vertical plate method using the Concord CBVP type surface tension meter.

Specific examples of the component (A) include trimethylolpropane triacrylate, bis(trimethylolpropane) tetraacrylate, glycerin propylene glycol adduct triacrylate, and trimethylolpropane propylene glycol adduct. The triacrylate or the like is preferably trimethylolpropane triacrylate or di(trimethylolpropane) tetraacrylate from the viewpoint of making the cured coating film high in hardness.

The amount of the component (A) in the active energy ray-curable resin composition is preferably 40 to 60% by weight (however, the total of the components (A), (B), and (C) is 100% by weight). 50~60% by weight is more suitable.

The component (B) is a polymer acrylate obtained by subjecting acrylic acid to an addition reaction in a (meth)acrylic acid glycidyl ester polymer as described above. The amount of acrylic acid added to the epoxy group is preferably 1:1~1:0.8, 1:1~1:0.9 because the unreacted epoxy has an adverse effect on the stability of the composition. More suitable.

(meth)acrylic acid propyl propyl ester polymer, a single polymer of (meth)acrylic acid propyl propyl ester; (meth)acrylic acid propyl propyl ester, and various carboxyl groups without α, β a copolymer of an unsaturated monomer or the like. The carboxyl group-free α,β-unsaturated monomer may be various (meth) acrylate, styrene, vinyl acetate, acrylonitrile or the like. Further, when the (meth)acrylic acid glycidyl ester is copolymerized with a carboxyl group-free α,β-unsaturated monomer to obtain a (meth)acrylic acid glycidyl ester-based polymer, the reaction time is not Crosslinking is produced to effectively prevent high viscosity or gelation. The molecular weight of the (meth)acrylic acid propyl propyl ester polymer is from 5,000 to 100,000 in terms of the weight reduction at the time of curing and the prevention of gelation in the acrylic acid addition reaction. A degree of 10,000 to 50,000 is preferred. The ratio of use of the (meth)acrylic acid glycidyl ester in the component (B) is preferably 70% by weight or more, more preferably 75% by weight or more, in consideration of the hardness of the protective layer and the mobility of the polymer.

(B) For the production of the components, a well-known copolymerization method can be used. The production of a (meth)acrylic acid propyl propyl ester polymer is carried out by adding the monomer, a polymerization initiator, a chain transfer agent and a solvent according to requirements to a reaction vessel at a temperature of 80 to 90 ° C under a nitrogen gas stream. The condition of ~6 hours is more suitable. The (meth)acrylic acid glycidyl acrylate polymer thus obtained is subjected to a ring-opening esterification reaction with acrylic acid to obtain a component (B); generally, the polymerization of the acrylic acid itself is prevented to be carried out under an oxygen gas stream. Preferably, the reaction temperature is 100~120 ° C, and the reaction time is suitable for 5-8 hours.

The amount of the component (B) in the active energy ray-curable resin composition is preferably 10 to 60% by weight (however, the total of the components (A), (B), and (C) is 100% by weight). 20~50% by weight is more suitable.

Specific examples of the component (C) include polyfunctional polyester acrylate, polyfunctional urethane acrylate, epoxy acrylate, and the like. Among them, polyfunctional urethane acrylate is preferred from the viewpoints of scratch resistance, toughness, and the like of the cured coating film. For example, (a) a urethane reaction product having a hydroxyl group (meth) acrylate and an isocyanate compound having two or more isocyanate groups in the molecule; (b) having two or more isocyanate groups in the molecule; In the isocyanate compound, a reaction product in which a polyhydric alcohol, a polyester or a polyamidoamine-based diol is reacted and synthesized, and a (meth) acrylate having a hydroxyl group is added to a residual isocyanate group Etc. (for example, refer to JP-A-2002-275392).

The polyfunctional urethane acrylate is a urethane reaction product obtained from a (meth) acrylate having a hydroxyl group and a polyvalent isocyanate compound having two or more isocyanate groups. The (meth) acrylate having a hydroxyl group is preferably pentaerythritol tri(meth)acrylate or dipentaerythritol penta(meth)acrylate.

The amount of the component (C) in the active energy ray-curable resin composition is preferably from 0 to 50% by weight (however, the total of the components (A), (B), and (C) is 100% by weight).

The active energy ray-curable resin composition can be adjusted to its viscosity depending on the application, and can be blended with an organic solvent. The organic solvent is preferably one in which a cyclic olefin-based resin film of a transparent film cannot be dissolved; for example, an ester solvent, an alcohol solvent, or a ketone solvent is preferred.

The active energy ray used for curing the active energy ray-curable resin composition is preferably, for example, an ultraviolet ray or an electron ray. When the resin composition is cured by an electron beam or the like, the photopolymerization initiator is not required, and when it is cured by ultraviolet rays, it is usually contained in an amount of from 1 to 15 parts by weight based on 100 parts by weight of the resin composition. Photopolymerization initiators can be used in Dalogues-1173, Iruga Chul-651, Iruga Chul-184, Iruga Chul-907, Iruga Chul-754 (even Giba special chemistry Various companies, such as the company, benzophenone and other well-known people. Additives other than the above may be blended according to requirements, such as a polymerization inhibitor, an antioxidant, an ultraviolet absorber, an antistatic agent, a light stabilizer, a solvent, an antifoaming agent, a planarizing agent, and the like.

The particles contained in the protective layer are not particularly limited. For example, it may be any one which is generally used as a filler, and has carbon black, copper, nickel, silver, iron or a composite powder thereof; zinc oxide, tin oxide, titanium oxide, tin oxide, calcium oxide, magnesium oxide, cerium oxide. Metal oxides such as alumina, cerium oxide (smoked cerium oxide, molten cerium oxide, precipitated cerium oxide, ultrafine powder amorphous cerium oxide, crystalline cerium oxide, anhydrous citric acid, etc.); calcium carbonate , metal carbonates such as potassium carbonate, sodium carbonate, magnesium carbonate, barium carbonate; metal nitrides such as boron nitride, tantalum nitride, aluminum nitride; metal carbides such as SiC; metal hydroxides such as aluminum hydroxide and magnesium hydroxide Aluminium borate, barium titanate, calcium phosphate, calcium citrate, clay, gypsum, barium sulfate, mica, diatomaceous earth, clay, talc, zeolite, pigment, etc., of which cerium oxide is preferred.

Specifically, the particles used in the preparation of the protective layer forming composition are Ayello Gyro 50, 90G, 130, 200, 200V, 200CF, 300, 380 manufactured by Ayello Gyro Co., Ltd., Japan. , R972, R972V, R974, RX200, R202, R805, R812S, OX50; Jerbosta MX020W, MX030W, MX050W, MX100W, MX-150, MX-180, MX-300, MA1002, West Persian, manufactured by Nippon Shokubai Co., Ltd. KE-E10, KE-E30, KE-E40, KE-E50, KE-E70; MX-series, MR-series, MP-series, etc., manufactured by the company.

When the composition for forming a protective layer is prepared, it is added to the active energy ray-curable resin composition as a raw material. The mixed particles are not particularly limited; and the average particle diameter (primary average particle diameter) is preferably as a main component in the range of about 1 to 100 nm, about 1 to 50 nm, and further 1 to 25 nm. In addition, it is also suitable to adjust the composition for forming a protective layer by using particles of a group having a particle diameter different from that of the particles to be added as a main component, and having an average particle diameter of about 50 to 800 nm and a range of 100 nm to 3 μm. Specifically, for example, a small amount of particles having a particle diameter of about 1300 nm or more, preferably about 1300 nm to 3 μm, is added together with particles having an average particle diameter of about 1 to 100 nm, and it is suitable to prepare a composition for forming a protective layer. In the preparation of the protective layer-forming composition, the particle component may be added after the preparation of the active energy-curable resin composition, or may be simultaneously or sequentially mixed with each component of the active energy ray-curable resin composition.

In the protective layer after formation, the primary particles added during the preparation of the protective layer forming composition may be in a form of being dispersed; the primary particles added during the preparation may be agglomerated, or may be secondary or tertiary aggregated particles. The form of dispersion; it may be a form in which the primary particles and the agglomerated particles of the secondary particles or more are mixed. In any case, in the protective layer formed, the average particle diameter of the particles is preferably from 50 to 600 nm, preferably from 50 to 400 nm, more preferably from 50 to 200 nm. By having such an average particle diameter, the transparency of the resin composition can be ensured, and the haze value can be adjusted to an appropriate value. Therefore, when the anti-glare film of the present invention is disposed on the surface of the black background image, it is possible to effectively prevent the occurrence of a blush on a black background and to clearly reflect the background image.

The protective layer is usually in a liquid or suspended active energy ray-curable resin composition, and the particles are mixed and stirred to uniformly disperse the particles. In this case, the distribution of the particles or the state of aggregation can be controlled by adjusting the stirring method, the stirring speed, the stirring force, the stirring time, etc., and the primary particles used as the raw material can be almost completely dispersed by the primary particles and simultaneously formed and used as a raw material. The agglomerated particles such as secondary particles of a predetermined particle diameter having different primary particles may be partially collapsed or agglomerated to form tertiary particles. In the present invention, before the formation of the protective layer and in the forming step, the average particle diameter is preferably in the above range regardless of the particle diameter of the particles in the state in which the protective layer is completed. However, here, the average particle diameter in the active energy ray-curable resin composition is regarded as the average particle diameter in the state in which the protective layer is completed. At this time, the average particle diameter (d: the diameter of the hydrodynamics) is the value obtained by the Gum blue method from the autocorrelation function obtained by the photon correlation method. The autocorrelation function can be directly determined by the time change of the scattering intensity. ([Tau]) represented by the following formula G ₂ of the secondary autocorrelation function. G ₂ (τ)=1+β|G ₁ (τ)| ²

[wherein, G ₁ (τ) is an autocorrelation function of one time, and β is a constant].

When the particles are monodisperse, G ₁ (τ) becomes a single exponential decay curve, and the decay constant Γ is used as shown in the following equation.

G ₁ (τ)=exp(-Γ τ) ln(G ₁ (τ))=-Γ τ

Also, Γ, using the diffusion coefficient D, as shown in the following equation, Γ = q ² D q = (4πn ₀ / λ ₀ ). Sin(θ/2)

(where q is the scattering vector; n ₀ is the refractive index of the solvent, and λ ₀ is the wavelength of the laser light).

The average particle size d can be used by Einstein. The style of Stokus is determined by the diffusion coefficient D.

d=kT/3π η ₀ D

(Wherein, d is the average particle diameter; K is Boltzmann's constant; T is the absolute temperature; η ₀ is the viscosity of the solvent).

The average particle diameter can be measured by, for example, FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.

Further, any method known in the art can be used for the dispersion/stirring of the particles; the primary particle diameter of the dispersed/stirred particles can be appropriately selected by the strength of the dispersion/stirring force and the length of the dispersion/stirring time. In particular, in the case of particles in a form in which the primary particles are mixed with the agglomerated particles of the secondary particles or more, on the one hand, the particle size of the so-called nanoparticles which is not agitated and stirred while being agitated is selected to be small; It is preferable that the particle diameter of the so-called macroscopic particles of the particle dispersion/stirring is large to mix the two.

Moreover, the particles, in terms of the protective layer after formation, ensure the transparency of the protective layer by the small average particle size; on the other hand, by dispersing the larger particles, the Newton's ring can be effectively prevented, and at the same time, it can shine. Suppressed to a minimum. In particular, when used in a display device such as a touch panel, when a film or the like is laminated on the surface of the transparent conductive film of the present invention, the Newton's ring due to contact with the film can be more effectively prevented.

The particles, in the protective layer, are preferably contained in an amount of 10 to 30%, more preferably 17 to 22%, based on the total weight of the protective layer. Thereby, unevenness such as whitishness and blackening can be prevented, and the background image can be clearly displayed. In addition, anti-Newtonian ringing, to prevent sparkling, can properly adjust the balance of the three kinds.

The maximum height roughness Ry (μm) of the protective layer is preferably set to a level of 1.8 to 3.2, more preferably 2.0 to 3.2, and most preferably 2.0 to 2.6. By adjusting the maximum height roughness as described above, it is possible to effectively exhibit the anti-Newtonian ring property and the surface height roughness Ry in accordance with the average particle diameter of the particles and/or the ratio of the particles having a large particle size as described above. In the reference length specified in JIS B0601 '94, the sum of the maximum value of the mountain height of the contour curve and the maximum value of the valley depth. The maximum height roughness can be measured using, for example, a surface roughness shape measuring machine Hantel Safir E-35A (manufactured by Tokyo Seimitsu Co., Ltd.).

In order to achieve the surface height roughness (Ry) as described above, the maximum particle diameter (Rm) in the protective film after formation is usually 30 μm or less, preferably 20 μm or less, and more preferably 10 μm or less. Further, from another viewpoint, the particles having a particle diameter of 1300 nm or more account for 1.5 to 7% by weight of the total particles, more preferably 1.5 to 5% by weight, and most preferably 2.0 to 5% by weight. good. In particular, particles having a particle diameter of 2000 nm or more are preferably 1.5 to 6% by weight in the total particles, more preferably 1.5 to 5.5% by weight. Thus, by including a specific larger particle size within this range, the above-described generation of Newton's rings can be more reliably prevented. Further, the particles having a larger particle size can also effectively prevent the glare described later; when a large amount of particles are contained, the glare is reversed in the opposite direction, and the anti-Newton ring can be prevented and prevented within the range of the above particles. The effect of the sparkle is balanced to the maximum.

Further, the image forming property of the protective layer is preferably 5% or more, more preferably 20% or more, and most preferably 40% or more. Here, the imageability refers to an index indicating the degree of discomfort caused by light scattering due to light scattering, and when the value is large, the image is excellent in imageability, and it is difficult to cause glare. Specifically, in the optical comb having a predetermined width interval, the ratio of the light passing through the interval is displayed. For example, it can be measured by the image measuring machine ICM-1T (manufactured by Scarlet Tester Co., Ltd.). In the present invention, the interval between the optical combs is set to 0.5 mm. Also, this glare is usually liable to occur in the case of forming particles having a uniform particle diameter, which are protected by particles having a larger particle diameter. Therefore, in order to prevent the occurrence thereof, particles having a large particle diameter are not contained, and particles having a small particle diameter are uniformly dispersed. However, in this case, it is easy to generate a Newton's ring. Therefore, it is necessary to limit the occurrence of both to the minimum of the parametric variables; in the present invention, the average particle diameter of the particles and the maximum height roughness (Ry) of the protective layer can be satisfied by adjusting the imageability at the same time. The cause of the balance between each other.

Further, the protective layer has a haze value of preferably 12% or less, more preferably 10% or less, and most preferably 5% or less. The haze value is also expressed by turbidity, turbidity, and diffusivity. By setting this value within the above range, so-called blushing can be prevented. Further, the haze value is related to the average particle diameter, particle size distribution, and the like of the particles contained in the protective layer. Therefore, in addition to the above-described average particle diameter and/or the content ratio of the larger particles, the background image can be more clearly reflected.

As described above, the protective layer of the present invention is prepared by mixing particles in a resin composition, preparing a liquid or suspension using a suitable organic solvent, and applying it to a transparent film to be dried, by irradiating an active energy ray. Can be formed. The coating method of the active energy ray-curable resin composition can be applied by bar coating, blade coating, gravure coating, gravure reverse coating, reverse roller coating, lip coating, die coating, Various methods such as dip coating, offset printing, flexographic printing, screen printing, and the like. The irradiation of the active energy ray is not particularly limited, and can be appropriately adjusted by a well-known method in the field depending on the composition of the resin composition, the type of the active energy ray, the thickness of the resin composition, and the like. The film thickness of the protective layer is not particularly limited, and is usually preferably from 1 to 20 μm, more preferably from 1 to 10 μm, and most preferably from 1 to 5 μm.

The conductive transparent film of the present invention is formed on the opposite side of the surface of the transparent film-containing protective layer containing the particle, and further formed of the active energy ray-curable resin composition (which may contain the above-mentioned filler) The back protective layer is preferred. In this case, the film thickness of the back surface protective layer is not particularly limited, and may be the same thickness as the above protective layer. The warpage of the film can be prevented by providing the protective layer on both sides.

Further, the surface of the protective layer has a pencil hardness of HB or more, preferably F or more, and most preferably H or more, and the surface hardness required as a protective layer can be maintained. Further, the surface of the protective layer is subjected to a load of 450 g, and the abrasion caused by the use of steel wool for 10 round-back wiping is preferably 10 or less; from the viewpoint of surface hardness, no flaw is optimal at all.

[Transparent Conductive Layer]

The conductive transparent film of the present invention is formed by laminating a film containing a particle protective layer on the surface of the transparent film, and further laminating a transparent conductive layer.

The transparent conductive layer of the present invention is a layer having conductivity and having conductivity in a visible light region.

As a method of forming the transparent conductive layer, any conventionally known technique such as a vacuum deposition method, a sputtering method, or an ion plating method can be used. From the viewpoint of the uniformity of the film or the adhesion of the film to the transparent substrate, It is preferred to form a film by sputtering. Further, the film material to be used is not particularly limited; for example, indium oxide containing tin oxide, metal oxide such as tin oxide containing antimony, and the like, gold, silver, platinum, palladium, copper, aluminum, nickel, chromium, titanium are suitably used. , cobalt, tin or alloys of these. The thickness of the conductive film is 30 When it is thinner than this, it is difficult to form a continuous film having a good electrical conductivity with a surface resistance of 1,000 Ω/□ or less. On the other hand, when the thickness is too thick, the transparency is reduced, and the suitable thickness is 50 to 2000. The extent of it.

[anti-reflection layer]

The conductive transparent film of the present invention preferably has an antireflection layer between the transparent conductive layer and the protective layer for the purpose of improving the transmittance in the visible light region. The antireflection layer is usually composed of a low refractive index layer such as cerium oxide or magnesium fluoride, and a single layer or a two or more laminated structure of a high refractive index layer such as titanium oxide, cerium oxide or cerium oxide.

The inorganic oxide is thus low. The method for forming the high refractive index layer may be a vacuum evaporation method, a sputtering method, an ion plating method (dry process, or a coating method containing a coating solution of various metal alkoxides or inorganic oxide ultrafine particles (wet) Well-known methods such as the type process.

Further, the low refractive index layer is also suitable for coating an organic material mainly composed of a fluoropolymer.

[Polarizer]

In the conductive transparent film of the present invention, in addition to the transparent film, the particle-containing protective layer, and the transparent conductive layer, a polarizing plate may be laminated.

As the polarizing plate constituting the conductive transparent film of the present invention, any of polarizing plates having a polarizing effect used in optical applications can be used. Such a polarizing plate includes a single-layer polarizing plate, a protective layer formed on both sides of the polarizing plate, and a protective layer formed on one side of the polarizing film.

The polarizing plate used in the present invention is not particularly limited; and as a function of the polarizing film, the incident light is divided into two polarizing components which are parallel to each other, and only one of them is passed, and the other components are absorbed or dispersed. There is no particular limitation on the film of the action, and any of the polarizing films can be used.

The polarizing film which can be used in the present invention is, for example, polyvinyl alcohol (hereinafter referred to as "PVA"). Iodine-based polarizing film; PVA film in the PVA film is adsorbed by dichroic dyeing. A dye-based polarizing film; a polyene-based polarizing film formed by a dehydration reaction of a PVA-based film or a dehydrochlorination reaction of a polyvinyl chloride film; and a PVA system formed by a modified PVA containing a cationic group in the molecule; A polarizing film of a dichroic dye or the like is formed on the surface and/or the inside of the film. Among these are PVA. An iodine-based polarizing film is preferred.

The method for producing the polarizing film used in the present invention is not particularly limited, and a conventionally known method can be used. For example, a method of adsorbing an IVA ion after stretching a PVA film; a method of stretching a PVA film by a dichroic dye; and stretching the PVA film and dyeing with a dichroic dye; A method in which a dichroic dye is printed on a PVA-based film and then stretched; a method in which a PVA-based film is stretched, and a dichroic dye is printed. More specifically, the iodine is dissolved in a potassium iodide solution, and the ion is adsorbed on the PVA film for stretching as a higher-order iodide ion; and then immersed in a 1 to 5 wt% aqueous solution of boric acid at a bath temperature of 30 to 40 ° C to A method of producing a polarizing film; or subjecting the PVA film to the same boric acid treatment as described above, and stretching it in a uniaxial direction by 3 to 7 times, and immersing it in a bath temperature of 30 to 40 ° C of 0.05 to 5% by weight of two colors An aqueous dye solution, which adsorbs a dye, and then is dried at 80 to 100 ° C to be thermally fixed to produce a polarizing film.

The thickness of the polarizing film used in the present invention is not particularly limited, and is preferably 10 to 50 μm and preferably 15 to 45 μm.

These polarizing films can be used as they are in the production of the polarizing plate of the present invention, or can be used by performing corona discharge treatment or plasma treatment on the surface in contact with the adhesive layer.

In the polarizing plate of the present invention, the conductive layer is adhered by a pressure-sensitive adhesive on the surface opposite to the transparent conductive layer of the laminate of the laminated transparent film, the particle-containing protective layer and the transparent conductive layer. A transparent film is preferred.

As the pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, or a polyoxygen-based pressure-sensitive adhesive can be used.

The conductive transparent film of the present invention is suitably used as a transparent electrode for a display such as a liquid crystal display or a touch panel, and is particularly suitable for use in a touch panel for a display device used in a touch panel.

The touch panel of the present invention is characterized in that it has the above-described conductive transparent film of the present invention as a transparent electrode. A display device of the present invention is characterized in that the touch panel is provided on a display surface side.

Specifically, the conductive transparent film of the present invention is preferably a touch panel upper electrode and/or a lower electrode which is a 4-wire resistive film method or a 5-wire resistive film method. Further, by disposing the touch panel on the front surface of the liquid crystal display, a display device having a touch panel function can be obtained.

[Examples]

The invention is more specifically illustrated by the following examples. The invention is not limited to the embodiments. In addition, the following "parts" are based on weight.

<Production of component (B)> In a reaction apparatus equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, 250 parts by weight of glycidyl methacrylate (hereinafter referred to as GMA) was added. 1.3 parts by weight of alkyl mercaptan, 1,000 parts by weight of butyl acetate, and 7.5 parts by weight of 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN), and then dropped in an atmosphere for about 1 hour under a nitrogen gas stream. The temperature was raised to 90 ° C and held for 1 hour. Next, a mixture of 750 parts by weight of GMA, 3.7 parts by weight of (d-)alkylsulfate and 22.5 parts by weight of AIBN was dropped into the system by a dropping funnel under a nitrogen gas stream for about 2 hours. After incubating at the same temperature for 3 hours, 10 parts by weight of AIBN was added and kept for 1 hour. Thereafter, the temperature was raised to 120 ° C and the temperature was kept for 2 hours. The weight average molecular weight of the obtained acrylic polymer was 19,000 (in terms of polystyrene of GPC). After cooling to 60 ° C, the nitrogen gas introduction tube was changed to an air introduction tube, and 507 parts by weight of acrylic acid (hereinafter referred to as AA), 2.0 parts by weight of methoxyquinone, and 5.4 parts by weight of triphenylphosphine were added, and then air-bubble. The temperature was raised to 110 °C. After 8 hours of incubation at the same temperature, 1.4 parts by weight of methoxy hydrazine was added, and after cooling, ethyl acetate was added until the nonvolatile content became 50%, that is, varnish B1 was obtained.

Further, the component (B) was used in the above-mentioned production example, and the amount of the monomer used for the initial feeding was 175 parts by weight of GMA, and 75 parts by weight of methyl methacrylate (hereinafter referred to as MMA), and the amount of the monomer used for the post-feeding was changed to The reaction was carried out in the same manner as in the above production example except that 525 parts by weight of GMA, 225 parts by weight of MMA, and the amount of AA were changed to 355 parts by weight; that is, varnish B2 having a nonvolatile content of 50% was obtained. The weight average molecular weight of the acrylic polymer before the AA reaction was 20,000.

Further, the component (B) was used in the above-mentioned production example, and the amount of the monomer used for the initial feeding was 125 parts by weight of GMA and 125 parts by weight of methyl methacrylate MMA, and the amount of the post-feeding monomer was changed to 375 parts by weight of GMA, MMA. The reaction was carried out in the same manner as in the above production example except that 375 parts by weight and the amount of AA used was changed to 254 parts by weight; that is, varnish B3 having a nonvolatile content of 50% was obtained. The weight average molecular weight of the acrylic polymer before the AA reaction was 23,000.

<Preparation of active energy ray-curable resin composition> (A) 50 parts by weight of trimethylolpropane triacrylate (surface tension: 36.2 mN/m), (B) 25 parts by weight of the above varnish (B1), and (C) 25 parts by weight of a polyfunctional urethane acrylate, adjusted to a solid content of 50% by ethyl acetate; and a photopolymerization initiator 1 to which a complex of 5% relative to the solid content is added Hydroxy-cyclohexyl phenyl ketone (manufactured by Jiba Specialty Chemicals Co., Ltd., trade name "Erugachuer 184") was prepared by dissolving to prepare an ultraviolet curable composition.

Further, the blending amount of the component (B) is converted in terms of solid content. The surface tension of the component (A) was determined by the vertical plate method using a Concord CBVP type surface tension meter. The polyfunctional urethane acrylate of the component (C) is manufactured by Arakawa Chemical Industries Co., Ltd. under the trade name "Bimsedo 557").

[Example 1]

UV curable composition (80% solid content adjusted with ethyl acetate, 70% solid content adjusted by MEK) 65.1 parts by weight of methyl ethyl ketone (hereinafter referred to as MEK) 10.0 parts by weight of cerium oxide (average particle size of about 12 mm, Japan Ayellojiru company) 9.17 parts by weight

The above ingredients were passed through a roller mill for 3 times. Thereafter, it was diluted with MEK to obtain a coating A for a protective layer of 48% solid content.

Further, the ultraviolet curable composition (80% solid content adjusted with ethyl acetate and 70% solid content adjusted by MEK) 57.1 parts by weight of acrylic particles (MX-180, average particle diameter: about 1.8 μm, manufactured by Amika Chemical Co., Ltd. 1.25 parts by weight of acrylic particles (MA-1002, average particle diameter of about 2.5 μm, manufactured by Nippon Shokubai Co., Ltd.) 0.25 parts by weight

The above components were blended in a stirring open cylinder (inner diameter of about 40 cm, inner side height of 58 cm), and dispersed and stirred for 150 minutes with a wing having a diameter of about 11 cm. Thereafter, it was diluted with MEK to obtain a coating B for a protective layer of 48% solid content.

95 parts by weight of the obtained coating material A and 25 parts by weight of the coating material B were mixed and applied to a film made of a cyclic olefin resin by a gravure reverse method (registered trademark, manufactured by JSR Co., Ltd., film thickness). 100 μm). After drying at 70 ° C for 40 seconds and irradiating ultraviolet rays of 300 mJ/cm ² for curing, a film having a protective layer having a film thickness of 1.7 μm was obtained.

On the opposite side to the surface of the protective layer of the film having the protective layer, a protective layer was formed in the same manner to form a film having a protective layer having a film thickness of 1.7 μm on both sides.

On the surface of the protective layer formed later, a slurry having an Ar flow rate of 200 sccm and an output of 1040 V/0.02 A was applied, and under the argon gas and oxygen gas flow, the target was In ₂ O ₃ /SnO ₂ = 90/10 (weight). Alloy, by sputtering, laminate thickness 200 The transparent conductive layer formed of ITO obtains the conductive transparent film 1.

[Embodiment 2]

In addition to the plasma treatment of Example 1, the thickness of the laminate is 600 by sputtering in sequence. Titanium oxide layer, thickness 600 After the ruthenium oxide, the conductive transparent film 2 was obtained in the same manner as in Example 1 except that ITO was sputtered.

[Example 3]

The conductive transparent film obtained in Example 1 was cut into a square of 50 × 70 mm, and the conductive transparent film was used as the upper and lower electrodes, and the result of manufacturing a 4-wire resistive film type touch panel using the conductive paste was shown, and the linear upper and lower electrodes were displayed. Both are good linear responsiveness of 0.5%.

[Example 4]

The touch panel obtained in Example 3 was attached to a display having a resolution of 1,280 dots and a vertical line of 1024 lines using a pressure-sensitive adhesive, and the result of visual observation of the brilliance of the image was almost completely absent.

[Example 5]

UV curable composition (80% solid content adjusted with ethyl acetate, 70% solid content adjusted by MEK) 50 parts by weight MEK 10 parts by weight of cerium oxide (average particle size of about 2.0 μm, Tosoh cerium oxide Co., Ltd., K-500) 10 parts by weight

The above components were passed through a barrel mill for 3 times, and then diluted with MEK to obtain a coating C for a protective layer of 48% solid content.

95 parts by weight of the coating material A obtained in Example 1 and 5 parts by weight of the coating material C were mixed and applied to a film made of a cyclic olefin resin by a gravure inverse method (registered trademark, JSR Co., Ltd.). The film thickness is 100 μm). After drying at 70 ° C for 40 seconds, the film was cured by irradiation with ultraviolet rays of 300 mJ/cm ² to obtain a film having a protective layer having a film thickness of 3.0 μm.

On the opposite side to the surface of the protective layer of the film having the protective layer, a protective layer was formed in the same manner to form a film having a protective layer having a thickness of 3 μm on both sides.

On the surface of the protective layer formed later, a slurry having an Ar flow rate of 200 sccm and an output of 1040 V/0.02 A was applied, and under the argon gas and oxygen gas flow, the target was In ₂ O ₃ /SnO ₂ = 90/10 (weight). Alloy, by sputtering, laminate thickness 200 The transparent conductive layer formed of ITO, that is, the conductive transparent film 3 is obtained.

[Embodiment 6]

UV curable composition (80% solid content adjusted with ethyl acetate) 65.1 parts by weight MEK 25.8 parts by weight of cerium oxide (average particle diameter of about 12 μm, manufactured by Ayello Gyro, Japan) 9.17 parts by weight

The above components were blended in a stirring open cylinder (inner diameter: about 40 cm, inner side height: 58 cm), and dispersed and stirred for 150 minutes with a wing having a diameter of about 11 cm. Thereafter, it was diluted with MEK to obtain a coating for 40% of the protective layer.

The obtained coating material was applied by reverse gravitation to a transparent film made of a cyclic olefin resin (A-frozen (registered trademark, manufactured by JSR Co., Ltd., film thickness: 100 μm). After drying at 80 ° C for 60 seconds, the film was cured by irradiation with ultraviolet rays of 150 mJ/cm ² to obtain a film having a protective layer having a film thickness of 4 μm.

On the opposite side to the surface of the protective layer of the film having the protective layer, a protective layer was formed in the same manner to form a film having a protective layer having a film thickness of 4 μm on both sides.

On the surface of the protective layer formed later, an Ar flow rate of 200 sccm was applied, and after 1048 V/0.02 A of plasma treatment, the target was In ₂ O ₃ /SnO ₂ = 90/10 (under weight) under argon and oxygen inflow. Alloy, by sputtering, laminate thickness 200 The transparent conductive layer formed of ITO, that is, the conductive transparent film 4.

A conductive transparent film was obtained in the same manner as described above except that the protective layer was not formed on the opposite side to the surface having the protective layer. Further, the haze value, total light transmittance, and imageability of the conductive transparent film were measured, and the results are shown in Table 1.

[Embodiment 7]

In addition to the plasma treatment of Example 6, the thickness of the laminate is 600 by sputtering in sequence. Titanium oxide layer, thickness 600 After the ruthenium oxide, the conductive transparent film 5 was obtained in the same manner as in Example 6 except that ITO was sputtered.

[Embodiment 8]

The conductive transparent film 4 obtained in Example 6 was cut into a square of 50 × 70 mm, and the conductive transparent film was used as the upper and lower electrodes, and the result of manufacturing a 4-screen resistive film type touch panel using a conductive paste was shown, and the upper and lower electrodes were displayed. The linearity is 0.5% good linear response.

[Embodiment 9]

The touch panel obtained in Example 8 was attached to a display having a resolution of 1,280 dots and a vertical line of 1024 lines using a pressure-sensitive adhesive, and the result of the glare of the image was visually observed, and almost no glare was observed.

[Comparative Example 1]

A coating material was obtained in the same manner as in Example 6 except that the compounding component of Example 6 was dispersed and stirred for 30 to 45 minutes, and a conductive transparent film having a protective layer having a thickness of 4 μm was formed on both surfaces of the transparent film.

[Comparative Example 2]

A coating material was obtained in the same manner as in Example 6 except that the compounding component of Example 6 was stirred and stirred for 210 minutes, and a conductive transparent film having a protective layer having a thickness of 4 μm was formed on both surfaces of the transparent film.

The following evaluations were carried out on the conductive transparent films obtained in the above respective Examples and Comparative Examples. The results are shown in Table 1.

The (average particle diameter) was measured by FPAR-1000 manufactured by Otsuka Electronics Co., Ltd., and the average particle diameter was calculated by Gum Blue analysis.

(Maximum particle diameter) The maximum particle diameter was calculated by Gum Blue analysis using FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.

(Measurement of total light transmittance and haze value) The measurement was carried out according to JIS-K7361-1 (ISO 13468-1) using a haze meter manufactured by Nippon Denshoku Industries Co., Ltd., NDH 2000.

Fog value (%) = diffuse transmittance (%) / total light transmittance (%)

(White evaluation) Adhesive black tape on the back of the protective layer, with a 3-wavelength fluorescent lamp, by visual observation, "A" is white with no surface, "B" is white with a slight surface, practical No problem on the top, "C" is a clear white surface.

(Measurement of the maximum height roughness Ry) The measurement was carried out using a maximum height roughness shape measuring machine (HANDYSURF E-35A, manufactured by Tokyo Seimitsu Co., Ltd.) based on JIS B0601'94.

(Evaluation of anti-Newtonian ringing) Under a 3-wavelength fluorescent lamp, the glass plate was loaded on a black cardboard, and the coated surface was pressed with a finger to visually observe the unevenness of the interference during the contact, and "A" was completely absent. Uneven disturbance, "B" is slightly disturbed, and "C" is uneven.

(Evaluation of the imageability), which is used as an optical measuring machine with a gap of 0.5 mm, is used for the image measuring machine ICM-1T (manufactured by Saga Test Instruments Co., Ltd.), and the transmitted light from the interval of the optical comb is measured (%) ).

(Sparking Assessment) Sparkling assessment is to use the resolution, level 1280 dots, vertical 1024 line display to visually observe the brilliance of the painting; "A" is no shine, "B" is slightly shining, "C" is There is shine.

(Adhesion evaluation) According to the JIS square tape method (25 squares), a protective layer having a transparent conductive layer was used to form 25 squares of 2 mm square; the area was peeled off with a cellophane tape. The number of remaining squares is evaluated. "Good" is 25/25 and "bad" is 23/25 or less.

(Surface Resistance) The surface resistance of the transparent conductive layer was measured using a low resistivity meter "Loresda-GP" manufactured by Mitsubishi Chemical Corporation.

The present invention can be used in various optical devices, specifically, various types of displays such as a word processor, a computer, a television, a display panel, and a mobile phone, a liquid crystal display device, etc., and a conductive transparent film when the touch panel is used in combination. .

Claims (5)

A conductive transparent film which is formed by sequentially laminating a conductive transparent film comprising a particle protective layer and a transparent conductive layer on a surface of a transparent film, and the particle-containing protective layer is laminated on both surfaces of the transparent film; The transparent film is a cyclic olefin resin obtained by (co)polymerizing a monomer containing a compound of at least one compound represented by the following formula (I). Made into, [In the formula (I), R ¹ to R ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a polar group, or another monovalent organic group; R ¹ and R ² or R ^{3 ;} An integral divalent hydrocarbon group may be formed with R ⁴ ; R ¹ or R ² , and R ³ or R ⁴ may be bonded to each other to form a monocyclic or polycyclic structure; m is 0 or a positive integer; p is 0 or a positive integer, In the case where m and p are different from each other, the particle-containing protective layer is a composition for forming a protective layer containing an active energy ray-curable resin composition and particles having an average particle diameter of 50 to 600 nm, and is photocured. In the layer, the particles are 10 to 30% by weight of the entire particle protective layer, and the protective layer contains 1.5 to 7% by weight of particles having a particle diameter of 1,300 nm or more in the entire particles, and the active energy ray hardenability The resin composition contains: (A) 40 to 60% by weight of a polyfunctional monomer having 3 or more acrylonitrile groups, and (B) in a (meth)acrylic acid glycidyl ester polymer, acrylic acid is added 10 to 60% by weight of the polymer formed by the reaction, and (0) 0 to 50% by weight of the other acrylic oligomers which are optional [however, the total of the components (A), (B) and (C) is 100% by weight. ]. The conductive transparent film of claim 1, wherein the particles having a particle diameter of 1,300 nm or more include primary particles. The conductive transparent film according to claim 1 or 2, which is composed of a laminated polarizing plate which is formed by laminating a pressure-sensitive adhesive. A touch panel characterized by having a conductive transparent film according to any one of claims 1 to 3 as a 4-wire resistive film method or a 5-wire resistive film type upper electrode and/or lower portion of a touch panel electrode. A display device characterized in that a touch panel having the fourth application of the patent application is placed on the front side of the liquid crystal display to obtain a touch panel function.