KR101408013B1 - Electrically-conductive transparent film - Google Patents

Abstract

A transparent conductive film obtained by laminating a layer (A) and a layer (B) on a base film in this order, wherein the layer (A) comprises at least one kind of binder resin selected from a thermoplastic resin, a thermosetting resin and an active energy ray- And an optical adjustment layer comprising metal oxide particles having an average particle diameter of 200 nm or less, and the layer (B) is a conductive organic polymer layer. This transparent conductive film has electrical characteristics and transmittance equal to those of ITO without using ITO using indium, which is an expensive rare metal, and is preferable as a transparent electrode for displays, particularly, an electrode for a touch panel.

Description

ELECTRICALLY-CONDUCTIVE TRANSPARENT FILM

The present invention relates to a transparent conductive film, and more particularly, to a transparent conductive film having electrical characteristics and transmittance equal to those of ITO without using indium tin oxide (ITO) using indium, which is a rare metal, , A transparent electrode for display, and the like, particularly, a transparent conductive film preferable as an electrode for a touch panel.

BACKGROUND ART Conventionally, as an inorganic conductive material, tin-doped indium oxide (ITO), tin oxide, indium oxide, zinc oxide, zinc oxide doped with aluminum, and the like have been known. Among them, ITO BACKGROUND ART Transparent conductive films are widely used as liquid crystal displays, transparent electrodes such as transparent touch panels, and the like.

As such a transparent conductive film, it is well known that an ITO film is formed on the surface of a transparent film such as a polyethylene terephthalate film or a triacetyl cellulose film by a dry process such as a vacuum evaporation method, a sputtering method, or an ion plating method (for example, Patent Documents 1 and 2).

By the way, the touch panel adopts the resistance film method at present about 90%. The resistance film type touch panel generally includes a touch-side plastic substrate on which a transparent conductive thin film such as an ITO film is laminated on one surface of a transparent plastic substrate, and a transparent conductive thin film such as an ITO film on one surface of a transparent substrate such as glass Side transparent substrates are arranged opposite to each other with the transparent spacers facing each other with an insulating spacer interposed therebetween.

The input is performed by pressing a touch input surface (the surface opposite to the transparent conductive thin film side) of the touch-side plastic substrate with a pen or a finger to form a transparent conductive thin film of the touch- And the transparent conductive thin film is brought into contact with each other.

However, in such a resistive-type touch panel, the input operation is repeated, that is, the contact between the transparent conductive thin film of the touch-side plastic substrate and the transparent conductive thin film of the display-side transparent substrate is repeated, There arises a problem that the thin film is worn, cracked, or peeled off from the substrate. Therefore, in order to solve such a problem, generally, a hard coat layer made of a cured resin is formed between the transparent plastic substrate and the transparent conductive thin film. In addition, a hard coat layer is often formed on the surface of the transparent plastic substrate opposite to the transparent conductive thin film.

However, ITO used as a transparent conductive thin film on such a transparent conductive film or a transparent conductive plastic substrate is expensive because indium, which is a rare metal, is used, and a special process is required for forming a thin film. In addition, there is a problem that it is poor in handleability because it is hard and weak. Therefore, in order to solve these problems, it has been studied to use a conductive organic polymer compound (see, for example, Patent Documents 3 and 4).

However, although it is possible to obtain electric characteristics equivalent to those of ITO in the conductive organic polymer compound, it is practically impossible to reduce the transmittance of the obtained conductive film or the like so that it can not be put to practical use.

As described above, the conductive organic polymer compound has a lower transmittance than that of ITO in the case of obtaining an electric characteristic equivalent to that of ITO, and deteriorates in electrical characteristics when the transmittance is increased (electrical characteristics and transmittance depend on film thickness) . When the transmittance is low, there is a fear that the visibility as a display is lowered.

JP 2006-216266 A JP 2007-133839 A JP 2002-179954 A WO2006 / 082944A

The present invention has been made under such circumstances, and it is an object of the present invention to provide a transparent electrode for display, which is preferably used as an electrode for a touch panel, having an electric characteristic and a transmittance equal to that of the ITO without using ITO using an expensive rare metal indium It is an object of the present invention to provide a transparent conductive film.

DISCLOSURE OF THE INVENTION The inventors of the present invention have made intensive studies in order to achieve the above object and as a result have found that an optical adjusting layer having a high refractive index including a specific resin and metal oxide particles having an average particle diameter of a predetermined value or less is provided on the base film, , It is possible to improve the transmittance while suppressing the reflection of the surface and maintaining the electrical characteristics by providing the conductive organic polymer layer having a refractive index lower than that of the optical adjustment layer. Thus, it is possible to improve the electrical characteristics and transmittance Of the transparent conductive film. The present invention has been completed on the basis of such findings.

That is,

(1) A transparent conductive film obtained by laminating a layer (A) and a layer (B) on a base film in this order, wherein the layer (A) is a thermoplastic resin, , And a metal oxide particle having an average particle diameter of 200 nm or less, wherein the layer (B) is a conductive organic polymer layer;

(2) The transparent conductive film as described in (1) above, wherein the surface resistivity is 300 to 800? / ?, and the total light transmittance is 86% or more;

(3) The transparent conductive film described in (1) or (2) above, wherein (B) the reflectance at a wavelength of 550 nm on the surface of the conductive organic polymer layer is 5% or less;

(4) The transparent conductive film according to any one of (1) to (3) above, wherein (B) the refractive index of the conductive organic polymer layer is lower than (A) the refractive index of the optical adjusting layer;

(5) The conductive polymer composition according to any one of (1) to (4) above, wherein the conductive organic polymer compound constituting the conductive organic polymer layer (B) is at least one selected from the group consisting of a polythiophene type, a polyaniline type, Transparent conductive film;

(6) The optical recording medium according to any one of the above items (1) to (5), wherein the optical adjustment layer (A) contains metal oxide particles having an average particle diameter of 200 nm or less in an amount of 1 to 700 A transparent conductive film according to any one of (1) to (5) above, wherein the transparent conductive film is contained at a ratio of the mass part to the transparent conductive film.

(7) The optical recording medium according to (7), wherein the optical adjustment layer (A) comprises a thermoplastic resin and / or an active energy ray-curable resin as the binder resin and further contains titanium oxide particles and / or antimony- , The transparent conductive film described in any one of (1) to (6) above;

(8) The transparent conductive film according to any one of (1) to (7) above, wherein a hard coat layer is provided on the back surface of the base film; And

(9) The transparent conductive film according to any one of (1) to (8), wherein a hard coat layer is provided between the base film and the optical adjustment layer.

.

According to the present invention, it is possible to provide a transparent conductive film having electrical characteristics and transmittance equal to those of the ITO, which is preferable as an electrode for a display panel, such as a transparent electrode for a display, without using ITO using an expensive rare metal indium .

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view showing an exemplary structure of a transparent conductive film of the present invention;
2 is a schematic cross-sectional view showing the structure of another example of the transparent conductive film of the present invention;
3 is a schematic cross-sectional view showing the structure of another example of the transparent conductive film of the present invention;
4 is a schematic cross-sectional view showing a structure of still another example of the transparent conductive film of the present invention.

The transparent conductive film of the present invention is characterized in that an optical adjustment layer (A) having the following characteristics and a conductive organic polymer layer (B) are sequentially laminated on a base film.

[Base film]

The base film used in the transparent conductive film of the present invention is not particularly limited and may be appropriately selected from known plastic films as a substrate of conventional optical films. Examples of such a plastic film include a polyester film such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, a polyethylene film, a polypropylene film, a cellophane, a diacetylcellulose film, a triacetylcellulose film, an acetylcellulose butyrate A polyvinyl chloride film, a polyvinyl alcohol film, an ethylene-vinyl acetate copolymer film, a polystyrene film, a polycarbonate film, a polymethylpentene film, a polysulfone film, a polyetheretherketone film, A polyetherimide film, a polyimide film, a fluorine resin film, a polyamide film, an acrylic resin film, a norbornene resin film, a cycloolefin resin film and the like. These base films may be either transparent or semitransparent, and may be colored or non-colored, and may be appropriately selected depending on the application.

The thickness of the base film is not particularly limited and may be appropriately selected according to the circumstances, but is usually in the range of about 15 to 300 mu m, preferably 30 to 200 mu m, more preferably 50 to 200 mu m. The base film may be surface-treated on one side or both sides by an oxidation method, an irregularity method or the like, if necessary, for the purpose of improving the adhesion with the layer provided on the surface of the base film. Examples of the oxidation method include a corona discharge treatment, a plasma treatment, a chromic acid treatment (wet), a flame treatment, a hot air treatment, an ozone / ultraviolet ray irradiation treatment and the like. a sand blast method, a solvent treatment method, and the like. These surface treatment methods are appropriately selected depending on the type of the substrate film, but generally, the corona discharge treatment method is preferably used from the viewpoints of effects and operability.

[(A) Optical adjustment layer]

In the transparent conductive film of the present invention, the optical adjustment layer is provided as the (A) layer on the base film described above. The optical adjustment layer is a layer containing at least one kind of binder resin selected from a thermoplastic resin, a thermosetting resin and an active energy ray-curable resin, and metal oxide particles having an average particle diameter of 200 nm or less.

The refractive index of the optical adjustment layer is made higher than the refractive index of the conductive organic polymer layer (B), which will be described later, provided on the layer to reduce the reflectance of the surface, thereby increasing the total light transmittance and improving the transparency Function.

(Binder resin)

In the optical adjustment layer, at least one resin selected from a thermoplastic resin, a thermosetting resin and an active energy ray-curable resin is used as the binder resin.

≪ Thermoplastic resin &

The thermoplastic resin preferably has transparency. Examples of the thermoplastic resin include aromatic polyester resins, aliphatic polyester resins, polyester urethane resins, polyolefin resins such as polyethylene, polypropylene, polymethylpentene and polycycloolefin, Cellulose resins such as acetyl cellulose, triacetyl cellulose and acetyl cellulose butyrate, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl alcohol resins, polystyrene resins, polycarbonate resins, acrylic resins, polyamide resins Resins and the like. These may be used singly or in combination of two or more kinds.

≪ Thermosetting resin &

The thermosetting resin refers to a cured product of a thermosetting compound which is polymerized, crosslinked and cured by application of heat. As the thermosetting resin, for example, a thermosetting addition reaction-type silicone resin can be used. As the addition reaction-type silicone resin, for example, at least one selected from polyorganosiloxanes having an alkenyl group as a functional group in the molecule may be mentioned. Preferable examples of the polyorganosiloxane having an alkenyl group as a functional group in the molecule include polydimethylsiloxane having a vinyl group as a functional group, polydimethylsiloxane having a hexenyl group as a functional group, and mixtures thereof.

Examples of the crosslinking agent include a polyorganosiloxane having at least two silicon-bonded hydrogen atoms in a molecule, specifically, a dimethylhydrogensiloxy end-blocked dimethylsiloxane-methylhydrogensiloxane copolymer, End-blocked dimethylsiloxane-methylhydrogensiloxane copolymer, trimethylsiloxy-terminated poly (methylhydrogensiloxane), poly (hydrogenosilsesquioxane), and the like. The amount of the crosslinking agent to be used is generally selected in the range of 0.1 to 100 parts by mass, preferably 0.3 to 50 parts by mass, based on 100 parts by mass of the addition reaction type silicone resin.

As the catalyst, a platinum compound is generally used. Examples of the platinum-based compound include particulate platinum, particulate platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complex of chloroplatinic acid, palladium, rhodium catalyst and the like. The amount of the catalyst to be used is about 1 to 1000 ppm as the platinum-group metal with respect to the total amount of the addition reaction type silicone resin and the crosslinking agent.

The reaction-type silicone resin can be cured by heating at a temperature of about 70 to 160 ° C.

≪ Active energy ray curable resin &

The active energy ray curable resin refers to a cured product of an active energy ray curable compound which has both energy in an electromagnetic wave or a charged particle beam, that is, an energy ray such as ultraviolet rays or electron rays is irradiated to polymerize, crosslink and cure.

Examples of such active energy ray-curable compounds include radical polymerization type photopolymerizable prepolymers and / or photopolymerizable monomers. Examples of the radical polymerization type photopolymerizable prepolymer include polyester acrylate, epoxy acrylate, urethane acrylate, and polyol acrylate. These photopolymerizable prepolymers may be used alone or in combination of two or more.

Examples of the photopolymerizable monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentylglycol di (meth) acrylate (Meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalic neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, (Meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane di (meth) acrylate, dicyclohexylmethane di (meth) acrylate, (Meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, (Meth) acrylates such as pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylol propane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta And polyfunctional acrylates such as erythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate. These photopolymerizable monomers may be used alone, or two or more of them may be used in combination, or may be used in combination with the photopolymerizable prepolymer.

In the present invention, the photopolymerizable prepolymer and / or the photopolymerizable monomer may be used in combination with various conventionally known photopolymerization initiators, if necessary.

The blending amount thereof is usually in the range of 0.2 to 10 parts by mass based on 100 parts by mass of the photopolymerizable prepolymer and / or the photopolymerizable monomer.

The active energy ray-curable compound containing such a photopolymerizable prepolymer and / or photopolymerizable monomer and, if necessary, a photopolymerization initiator can be cured by irradiation with active energy rays, for example, ultraviolet rays. When an electron beam is irradiated as an active energy ray, a photopolymerization initiator is not required.

In the present invention, as the binder resin constituting the optical adjustment layer of the layer (A), a thermoplastic resin and an active energy ray-curable resin are preferable among those exemplified above. The thermosetting resin using the addition reaction type silicone resin is disadvantageous in that the cost is increased and the adhesion with the conductive organic polymer layer of the layer (B) provided thereon is increased. Since the optical adjustment layer is coated with a thin film, the active energy ray (ultraviolet ray) curable resin is particularly preferably a thermoplastic resin because it may be affected by oxygen inhibition during curing.

(Metal oxide particles)

For the optical adjustment layer, metal oxide particles are used for adjusting the refractive index. Examples of the metal oxide particles include high refractive index metal oxide particles such as titanium oxide, tantalum oxide, zirconium oxide, niobium oxide, hafnium oxide, tin oxide, and antimony doped tin oxide (ATO). Since the metal oxide is used for adjusting the refractive index, the amount of the metal oxide to be used is very small as compared with the conventional one used as a conductive thin film on the film in order to obtain conductivity.

This metal oxide particle needs to have an average particle diameter of 200 nm or less. When the average particle diameter exceeds 200 nm, the haze value is increased and the transparency is lowered. The preferred average particle diameter is 150 nm or less. The lower limit value is about 2 nm from the viewpoint of manufacturability.

The average particle diameter of the metal oxide particles is a value measured by a dynamic scattering method.

The blending amount of the metal oxide particles is preferably about 1 to 700 parts by mass with respect to 100 parts by mass of the binder resin. When the blending amount is less than 1 part by mass, it is difficult to improve the refractive index. When the blending amount exceeds 700 parts by mass, the amount of the metal oxide is large and the coating film is weakened. A more preferable blending amount is 10 to 600 parts by mass, more preferably 100 to 400 parts by mass.

When the refractive index of the optical adjusting layer is not higher than the refractive index of the conductive organic polymer layer of the layer (B) provided thereon, a sufficient antireflection effect can not be obtained and improvement of the total light transmittance can not be expected. The metal oxide particles may be appropriately selected in consideration of the refractive index, transparency and price, and are preferably titanium oxide particles, tin oxide particles, and antimony-doped tin oxide particles, and particularly titanium oxide particles and / or antimony- Tin particles are preferred.

(Formation of optical adjustment layer)

In the transparent conductive film of the present invention, the optical adjustment layer is provided as the layer (A) on the above-mentioned base film. For this purpose, first, a coating solution for forming an optical adjustment layer is prepared.

A method for producing an optical recording medium which comprises an appropriate medium containing at least one selected from a thermoplastic resin as a binder resin, a thermosetting resin and an active energy ray-curable resin, and metal oxide particles dissolved or dispersed at a predetermined ratio and having a solid content of about 0.1 to 10 mass% To prepare a coating solution for forming an adjustment layer.

The coating liquid for forming an optical adjustment layer is then coated on the base film by a conventionally known method such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method To a predetermined dry thickness, and dried at about 70 to 110 DEG C for about 30 seconds to about 2 minutes. In addition, if necessary, curing treatment is carried out by thermal curing or irradiation of active energy rays. When only the thermoplastic resin is used as the binder resin, it is sufficient that the drying treatment is sufficient, and the curing treatment by irradiation of the thermosetting or active energy ray does not need to be performed, which is preferable because the operation is simple.

In this way, an optical adjustment layer having a thickness of about 50 to 500 nm, preferably 100 to 200 nm, can be formed. The refractive index of the optical adjusting layer is usually about 1.60 to 2.00, preferably 1.65 to 1.90.

[(B) Conductive Organic Polymer Layer]

In the transparent conductive film of the present invention, a conductive organic polymer layer is provided as the (B) layer on the optical adjustment layer of the layer (A) formed as described above.

(Conductive organic polymer compound)

The conductive organic polymer compound constituting the conductive organic polymer layer of the layer (B) is not particularly limited and may be any polymeric compound having conductivity and dissolvable or dispersible in a suitable solvent. Examples thereof include trans-type polyacetylene, Polyacetylene type such as sheath type polyacetylene and polydiacetylene; Poly (phenylene) based materials such as poly (p-phenylene) and poly (m-phenylene); Polythiophene series such as polythiophene, poly (3-alkylthiophene), poly (3-thiophene-beta-ethane sulfonic acid), complex of polyalkylene dioxythiophene and polystyrene sulfonate; Polyaniline series such as polyaniline, polymethylaniline and polymethoxyaniline; Polypyrroles such as polypyrrole, poly 3-methylpyrrole and poly 3-octylpyrrole; Poly (phenylene vinylene) based polymers such as poly (p-phenylenevinylene); Poly (vinylsulfide) system; Poly (p-phenylene sulfide) system; And poly (thienylenevinylene) -based compounds. Of these, polythiophene-based, polyaniline-based, and polypyrrole-based compounds are preferable from the standpoints of performance and ease of availability, and polythiophene-based compounds are more preferable from the viewpoints of colorability and conductivity. The complex of the polyalkylene dioxythiophene and polystyrene sulfonate can be obtained by, for example, oxidizing and polymerizing polystyrene sulfonic acid or its salt and an aqueous medium using an oxidizing agent of peroxosulfuric acid in the presence of a trivalent iron ion, (See, for example, [Non-Patent Document 1] and [Non-Patent Document 2]).

[Formula 1]

[Poly (3,4-ethylenedioxythiophene) poly (styrene sulfonic acid) aqueous dispersion]

Examples of commercially available products of the polyalkylene dioxythiophene / polystyrene sulfonate complex or a product thereof include "SEPLEGYDA" (trade name, product of Shin-Etsu Polymer Co., Ltd.), "CLEVIOS P" Products].

These conductive organic polymer compounds may be used singly or in combination of two or more.

Non-Patent Document 1: Stephan Kirchmeyer & Knud Reuter, J. Mater . Chem . , 2005, 15, 2077-2088

Non-Patent Document 2: H. C. Starck Pamphlet, Product Information

If the conductive organic polymer compound itself has good film-forming properties, it is not necessary to use a binder resin, but when the film-forming property is poor, it can be used in combination with a binder resin.

The binder resin is preferably a thermoplastic resin. Examples of the binder resin include aromatic polyester resins, aliphatic polyester resins, polyester urethane resins, polyolefin resins such as polyethylene, polypropylene, polymethylpentene and polycycloolefin, Based resin, polyvinyl alcohol-based resin, polyvinyl alcohol-based resin, polystyrene-based resin, polycarbonate-based resin, acrylic-based resin, polyamide-based resin, etc. . These may be used singly or in combination of two or more kinds.

(Formation of Conductive Organic Polymer Layer)

To form the conductive organic polymer layer, a coating solution for forming a conductive organic polymer layer is first prepared.

The conductive organic polymer compound, preferably at least one selected from the group consisting of polythiophene-based, polyaniline-based and polypyrrole-based compounds, and a binder resin to be used as required, preferably the aforementioned thermoplastic resin and the above- , An antioxidant, an ultraviolet absorber, a light stabilizer, and the like, and then applying a coating solution on the optical adjustment layer by a conventionally known method such as a bar coating method, a knife coating method, a roll coating method, The conductive organic polymer layer can be formed by applying the coating solution so as to have a predetermined dry thickness using a blade coating method, a die coating method, a gravure coating method, or the like, and drying at about 70 to 130 DEG C for about 30 seconds to 2 minutes.

The refractive index of the conductive organic polymer layer of the layer (B) thus formed is required to be lower than the refractive index of the optical adjustment layer of the layer (A) for the reasons described above, and its thickness is usually about 50 to 500 nm , Preferably 180 to 250 nm. In addition, the reflectance at a wavelength of 550 nm on the surface thereof is preferably 5% or less, more preferably 3% or less.

When the reflectance exceeds 5%, the reflected light increases, the total light transmittance of the transparent conductive film decreases, and transparency deteriorates.

In the transparent conductive film of the present invention, it is preferable that the surface resistivity is 300 to 800? / ?, and the total light transmittance is 86% or more. There is a correlation between the thickness of the conductive organic polymer layer and the surface resistivity, and as the thickness of the layer increases, the surface resistivity tends to decrease. When the surface resistivity is less than 300? / ?, the visible light transmittance is low and the visibility may deteriorate, so that it is not suitable as a display. When the surface resistivity exceeds 800 OMEGA / & squ &, it is difficult to drive the touch panel because it is insufficient as an electrode. In addition, when the total light transmittance is less than 86%, the visibility is deteriorated, so that it is not suitable as a display. A more preferable surface resistivity is 400 to 700? / ?, more preferably 500 to 600? / ?. More preferably, the total light transmittance is 87% or more, and more preferably 88% or more.

The method of measuring the reflectance, total light transmittance and surface resistivity will be described in detail later.

[Hard coat layer]

In order to impart scratch resistance to the transparent conductive film of the invention, a hard coat layer may be formed on the back surface of the base film or between the base film and the optical adjustment layer, if necessary. The hard coat layer provided on the back surface of the substrate film may be provided with an antiglare function.

In order to form the hard coat layer, a coating solution for forming a hard coat layer is first prepared.

(Coating liquid for hard-cord layer formation)

In the present invention, as the coating solution for forming a hard coat layer having an antiglare function provided on the back surface of the base film, for example, an active energy ray curable compound and inorganic fine particles or organic fine particles may be used.

Examples of the active energy ray-curable compound include a radical polymerizable type photopolymerizable prepolymer and / or a photopolymerizable monomer. As for these, the same ones as exemplified in the description of the above-mentioned (A) active energy ray-curable compound in the optical adjustment layer can be used.

As the inorganic fine particles, silica-based fine particles are preferable from the viewpoint of transparency. Examples of the organic fine particles include silicone fine particles, maleic acid resin fine particles, acrylic resin fine particles, acryl-styrene copolymer fine particles, polycarbonate fine particles, polyethylene fine particles, polystyrene fine particles, benzoguanamine based resin fine particles .

The shapes of the inorganic fine particles and the organic fine particles are not particularly limited, but spherical, needle-like, amorphous or the like is used. From the viewpoint of the anti-glare performance, it is preferable that the shape is irregular.

The average particle diameter is preferably 6 to 10 μm from the viewpoint of the anti-glare performance, and the particle size distribution is preferably 70% or more in the weight fraction within the average particle diameter ± 2 μm. The average particle diameter and the particle size distribution of the fine particles refer to values measured by the Coulter counter method.

In the present invention, the inorganic fine particles and the organic fine particles may be used singly or in combination of two or more kinds. In addition, from the viewpoint of the anti-glare performance, the compounding amount of the active energy ray- Is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, per 100 parts by mass.

The coating solution for forming a hard coat layer used in the present invention may contain, if necessary, the above-mentioned active energy ray-curable compound, inorganic fine particles and organic fine particles, and a photopolymerization initiator and various additive components, For example, an antioxidant, an ultraviolet absorber, a silane coupling agent, a light stabilizer, a leveling agent, a defoaming agent and the like may be added at predetermined ratios, respectively, and dissolved or dispersed.

Examples of the solvent include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, alcohols such as methanol, ethanol, propanol and butanol, Ketones such as ethyl ketone, 2-pentanone, isophorone and cyclohexanone, esters such as ethyl acetate and butyl acetate, ether solvents such as ethyl cellosolve and propylene glycol monomethyl ether, and the like .

The concentration and viscosity of the coating solution for forming a hard coat layer prepared as described above are not particularly limited and may be suitably selected in accordance with the circumstances.

The coating solution for forming a hard coat layer prepared as described above is applied to the back surface of a base film by a conventionally known method such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, A hard coat layer having an antiglare function is formed by coating a coating film using a coating method, drying, and then irradiating an active energy ray to cure the coating film.

Examples of the active energy ray include ultraviolet rays and electron beams. The ultraviolet ray is obtained by a high-pressure mercury lamp, an electrodeless lamp, a metal halide lamp, a xenon lamp, etc., and the irradiation amount is usually 100 to 500 mJ / cm 2, while the electron beam is obtained by an electron beam accelerator or the like, 350kV. Among these active energy rays, ultraviolet rays are particularly preferable. When an electron beam is used, a cured film can be obtained without adding a photopolymerization initiator.

The thickness of the hard coat layer thus formed is preferably larger than the average particle diameter of the organic fine particles used in the present invention. Therefore, the lower limit is about 2 탆, and the upper limit is set by hardening and shrinking of the hard coat layer, Which is about 20 mu m from the viewpoint of preventing curling of the film. A preferable thickness is in the range of 5 to 15 占 퐉, and a particularly preferable thickness is 8 to 12 占 퐉.

When the transparent conductive film of the present invention is required to have further improved flame retardance, the 60 占 specular gloss measured according to JIS K 5600 is preferably 100 or less, more preferably 80 or less. If it exceeds 100, the antiglare effect is not sufficiently exhibited.

On the other hand, when a hard coat layer is provided between the base film and the optical adjustment layer, for example, a coating liquid for forming a hard coat layer having the above-mentioned anti-scattering function, a coating liquid excluding fine silica particles and organic fine particles And the coating solution is coated on the base film in the same manner as described above to form a coating film. After drying, the coating film is irradiated with an active energy ray to cure the coating film to form a hard coat layer. Subsequently, the optical adjustment layer of the layer (A) may be formed on the hard coat layer in the same manner as described above.

In the transparent conductive film of the present invention, an antifouling coat layer can be formed on the hard coat layer provided on the back surface of the base film, if necessary. The antifouling coat layer can be formed by applying a coating liquid containing a fluorine resin to the antireflection coating layer by a known method such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, To form a coating film on the hard coat layer, followed by drying treatment.

The thickness of the antifouling coat layer is usually in the range of 1 to 10 nm, preferably 3 to 8 nm.

Next, another example of the constitution of the transparent conductive film of the present invention will be described with reference to Figs. 1 to 4. Fig.

1 to 4 are sectional schematic views showing another example of the constitution of the transparent conductive film of the present invention. Fig. 1 is a cross-sectional view of the transparent conductive film of the present invention, 2 shows a structure in which the hard coat layer 4-a is further formed on the back surface of the base film 1 in FIG. 1, and the hard coat layer 4-a is formed on the back surface of the base film 1 And a transparent conductive film 20 having a laminated structure.

3 shows a transparent conductive film 30 having a configuration in which a hard coat layer 4-b is further provided between the base film 1 and the optical adjustment layer 2 in FIG. 1, 4 is a schematic view showing the hard coat layers 4-a and 4-b between the back surface of the base film 1 and the substrate film 1 and the optical adjustment layer 2, respectively, (4-b).

The transparent conductive film of the present invention has electric characteristics and transmittance equal to those of the ITO without using tin-doped indium oxide (ITO) using indium, which is an expensive rare metal, It is preferably used as an electrode for use.

Example

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited in any way by these examples.

In addition, various characteristics in each example were measured according to the following methods.

(1) Surface resistivity of transparent conductive film

A test piece was prepared in accordance with JIS K 7194 and a test piece was prepared so that the surface of the conductive organic polymer layer was measured using a surface resistivity meter " Rollester (EP) probe (4 probe probe) " manufactured by Mitsubishi Chemical Corporation And the surface resistivity was measured.

(2) Total light transmittance of the transparent conductive film

Was measured in accordance with JIS K 7361-1 using a haze meter " NDH2000 " manufactured by Nippon Denshoku Kogyo Co., Ltd. (Nippon Denshoku Industries Co., Ltd.).

(3) Reflectance of the transparent conductive film

The test piece was fixed on a black acrylic plate so that the conductive organic polymer layer surface was on the incident light side using a spectrophotometer "UV-3101PC" manufactured by Shimadzu Corporation (Shimazu Seisakusho Co., Ltd.) Was measured.

(4) The refractive index of the layer (A) and the layer (B)

Was measured using a thin film measuring apparatus "F20" manufactured by Phil Matrix Co., Ltd.

(5) 60 ° specular gloss of transparent conductive film

VG2000 "manufactured by Nippon Denshoku Kogyo Co., Ltd., and the test piece was placed so that the opposite surface of the conductive organic polymer layer was on the side of the incident light, and measured according to JIS K 5600.

(6) Average particle diameter of metal oxide particles

Was measured by a dynamic scattering method.

Example  One

(1) (A) Formation of optical adjustment layer

100 parts by mass of a polyester resin ("Vylonal MD1245", a solid content concentration of 30% by mass, water dilution, manufactured by Toyo Boseki Co., Ltd.) and 100 parts by mass of a titanium oxide water dispersion 240 parts by mass of "ND146", average particle diameter of 10 nm, solid content concentration of 25% by mass) and 566 parts by mass of purified water were uniformly mixed to prepare a coating liquid for forming an optical adjusting layer having a solid content concentration of 1.5% by mass.

Next, a polyethylene terephthalate film ("A4300" manufactured by Toyo Boseki Co., Ltd.) having a thickness of 188 μm was coated with a Meyer Bar, and then dried at 100 ° C. for 1 minute to obtain an optical adjustment Layer.

(2) Formation of conductive organic polymer layer (B)

100 parts by mass of polythiophene coat (SEPLEGYDA, a product of Shin-Etsu Polymer Co., Ltd., solid content concentration: 2.4% by mass) were coated on the surface of the optical adjustment layer formed in (1) And dried for 1 minute to form a conductive organic polymer layer having a thickness of 200 nm to obtain a transparent conductive film. The measurement results of various characteristics are shown in Table 1 below.

Example  2

(1) (A) Formation of optical adjustment layer

100 parts by mass of a polyester resin ("Vylon 20SS", a solid content 30% by mass, diluted with toluene / methyl ethyl ketone), and an antimony-doped tin oxide dispersion [Ishihara Sangyo 200 parts by mass of "SNS-10T", average particle diameter 90 nm, solid content 30% by mass) and 270 parts by mass of toluene were uniformly mixed to obtain a coating liquid for forming an optical adjusting layer having a solid content concentration of 3% Lt; / RTI >

Next, a Maya bar was coated on the surface of a polyethylene terephthalate film ("A4300" manufactured by Toyo Boseki Co., Ltd.) having a thickness of 188 μm and dried at 100 ° C. for 1 minute to form an optical adjustment layer having a thickness of 200 nm.

(2) Formation of conductive organic polymer layer (B)

A transparent conductive film was obtained by forming a conductive organic polymer layer on the surface of the optical adjustment layer formed in (1) above, in the same manner as in (2) of Example 1. Table 1 shows the measurement results of various characteristics.

Example  3

(1) (A) Formation of optical adjustment layer

, 100 parts by mass of a UV curable coating agent ("Seika Beam EXF-01L (NS)", 100% by solid content, manufactured by Daiichi Seika Kogyo Co., Ltd.) and an antimony doped tin oxide toluene dispersion "SNS- , 400 parts by mass of 10T (described above) and 450 parts by mass of toluene were uniformly mixed to prepare a coating liquid for forming an optical adjusting layer having a solid content concentration of 3% by mass.

Then, the coating was applied to a surface of a polyethylene terephthalate film ("A4300" manufactured by Toyo Boseki Co., Ltd.) having a thickness of 188 μm and dried at 80 ° C. for 1 minute. Ultraviolet rays of 500 mJ / To thereby form an optical adjustment layer having a thickness of 200 nm.

(2) Formation of conductive organic polymer layer (B)

A transparent conductive film was obtained by forming a conductive organic polymer layer on the surface of the optical adjustment layer formed in (1) above, in the same manner as in (2) of Example 1. Table 1 shows the measurement results of various characteristics.

Example  4

100 parts by mass of "100 parts by mass" of "SEIKA BAY EXF-01L (NS)", a product of Daiichi Seika Kogyo Co., Ltd., solid content: 100%) was placed on the back surface of the base PET film of the transparent conductive film obtained in Example 1 And 100 parts by mass of toluene were uniformly mixed to obtain a hard coat agent having a solid content concentration of 50% by mass, which was then dried at 80 ° C for 1 minute, irradiated with ultraviolet rays of 250 mJ / A transparent conductive film having a 탆 hard coat layer was obtained. Table 1 shows the measurement results of various characteristics.

Example  5

(1) Formation of a flash-resistant hard coat layer

100 parts by mass of a solid content of 100% by mass of a hard coat type ultraviolet curable hard coat ("Seika Beam EXF-01L (NS)", a product of Daiichi Seika Corporation) and amorphous silicon beads [manufactured by Momentive Performance Japan Co., Quot; Pearl 240 "), 75 parts by mass of ethyl cellosolve and 75 parts by mass of isobutanol were uniformly mixed to prepare a water-repellent hard coat agent having a solid content concentration of 40% by mass. This hard coat agent was coated on the back side of the PET film of the base material of the transparent conductive film obtained in Example 1, followed by drying at 80 DEG C for 1 minute, and then irradiated with ultraviolet rays of 250 mJ / Thereby obtaining a transparent conductive film having a light-scattering hard coat layer having a thickness of 4 占 퐉. Table 1 shows the measurement results of various characteristics.

Example  6

(1) Formation of clear hard coat layer

, 100 parts by mass of a solid content of 100%] and 100 parts by mass of toluene were mixed uniformly to prepare a hard coat layer having a solid content concentration of 50% by mass (trade name, manufactured by Nippon Kayaku Co., A coating agent was prepared.

Next, after coating the surface of a polyethylene terephthalate film ("A4300" manufactured by Toyo Boseki Co., Ltd.) having a thickness of 188 μm with Maiya Bar, drying at 80 ° C. for 1 minute, ultraviolet rays of 250 mJ / And a hard coat layer having a thickness of 5 탆 was formed.

(2) (A) Formation of optical adjustment layer

In the same manner as in Example 1, an optical adjustment layer was formed on the surface of the hard coat layer formed in (1) above.

(3) (B) Formation of Conductive Organic Polymer Layer

On the surface of the optical adjustment layer obtained in (2) above, a conductive organic polymer layer was formed in the same manner as in (2) of Example 1.

(4) Formation of clear hard coat layer

A hard coat layer was formed on the back surface of the base PET film in the same manner as in the above (1) to obtain a transparent conductive film provided with hard coat layers on both sides of the base film. Table 1 shows the evaluation results of various characteristics.

Comparative Example  One

100 parts by mass of "polythiophene coat" (described above) was applied to the surface of a polyethylene terephthalate film ("A4300" manufactured by Toyo Boseki Co., Ltd.) having a thickness of 188 μm and dried at 130 ° C. for 1 minute To form a conductive organic polymer layer having a thickness of 200 nm to obtain a transparent conductive film. Table 1 shows the measurement results of various characteristics.

Comparative Example  2

(1) Formation of a polyester resin layer

, 100 parts by mass of a polyester resin (Vylon 20SS, solid content 30% by mass, toluene / methyl ethyl ketone dilution), 720 parts by mass of toluene and 180 parts by mass of methyl ethyl ketone were mixed uniformly, To prepare a coating solution for forming a polyester resin layer having a solid content concentration of 3% by mass.

Next, the coating solution was applied to the surface of a polyethylene terephthalate film ("A4300" manufactured by Toyo Boseki Co., Ltd.) having a thickness of 188 μm and dried at 100 ° C. for 1 minute to obtain a polyester having a thickness of 200 nm Thereby forming a resin layer.

(2) Formation of Conductive Organic Polymer Layer

100 parts by mass of "polythiophene coat" (described above) were laminated on the surface of the polyester resin layer formed in the above (1) using a Maya bar, and then dried at 130 ° C for 1 minute to obtain a A transparent conductive film was obtained by forming a conductive organic polymer layer. Table 1 shows the measurement results of various characteristics.

Reference example  One

(1) Formation of optical adjusting layer

Polyester resin ("VYLON 20SS" manufactured by Toyoboseki Co., Ltd., solid content 30% by mass). , 900 parts by mass of an antimony-doped tin oxide dispersion ("SNS-10T" manufactured by Ishihara Sangyo Co., Ltd .; average particle diameter 90 nm, solid content 30% by mass)] and 100 parts by mass of toluene 9000 parts by mass were uniformly mixed to prepare a coating liquid for forming an optical adjusting layer having a solid content concentration of 3% by mass.

Next, the coating solution was applied to the surface of a polyethylene terephthalate film ("A4300" manufactured by Toyo Boseki Co., Ltd.) having a thickness of 188 μm and dried at 100 ° C. for 1 minute to obtain an optical adjustment Layer.

(2) Formation of conductive organic polymer layer (B)

The transparent conductive film was formed by forming the conductive organic polymer layer on the surface of the optical adjustment layer formed in (1) above in the same manner as in (2) of Example 1, but in the case of laminating the conductive organic polymer layer, It is difficult to form a conductive organic polymer layer having a good surface state because metal oxides in the adjustment layer are often removed. The refractive index of the optical adjusting layer formed in (1) was 1.78.

INDUSTRIAL APPLICABILITY The transparent conductive film of the present invention has electrical characteristics and transmittance equal to those of ITO without using tin-doped indium oxide (ITO) using indium, which is an expensive rare metal, It can be preferably used as an electrode.

1: base film 2: optical adjusting layer
3: conductive organic polymer layer 4-a and 4-b: hard coat layer
10, 20, 30 and 40: transparent conductive film

Claims (10)

A transparent conductive film comprising a base film on which a layer (A) and a layer (B) are laminated in order,
Wherein the layer (A) is an optical control layer comprising at least one binder resin selected from a thermoplastic resin and an active energy ray-curable resin and metal oxide particles having an average particle diameter of 200 nm or less, and the layer (B) As the organic polymer layer,
Wherein the metal oxide particles are titanium oxide and antimony-doped tin oxide, or titanium oxide or antimony-doped tin oxide,
100 to 400 parts by mass of the metal oxide particles are contained in 100 parts by mass of the binder resin,
Wherein the refractive index of the layer (A) is 1.65 to 1.90 and the refractive index of the layer (B) is lower than the refractive index of the layer (A). The transparent conductive film according to claim 1, which has a surface resistivity of 300 to 800? / ?, and a total light transmittance of 86% or more. The transparent conductive film according to claim 1 or 2, wherein the (B) surface of the conductive organic polymer layer has a reflectance of 550 nm or less at 5% or less. The transparent conductive film according to claim 1 or 2, wherein the conductive organic polymer compound (B) constituting the conductive organic polymer layer is at least one selected from a polythiophene-based, polyaniline-based, and polypyrrole-based compound. The transparent conductive film according to claim 1 or 2, wherein a hard coat layer is provided on the back surface of the base film. The transparent conductive film according to claim 1 or 2, wherein a hard coat layer is provided between the base film and the optical adjustment layer (A). The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is selected from the group consisting of an aromatic polyester resin, an aliphatic polyester resin, a polyester urethane resin, polyethylene, polypropylene, polymethylpentene, polycycloolefin, diacetylcellulose, At least one selected from the group consisting of a cellulose-based resin such as polyvinyl chloride-based resin, a cellulose-based resin and a cellulose butyrate, a polyvinyl chloride resin, a polyvinylidene chloride resin, a polyvinyl alcohol resin, a polystyrene resin, a polycarbonate resin, Wherein the transparent conductive film is a transparent conductive film. The transparent conductive film according to claim 1, wherein the active energy ray-curable resin is at least one selected from the group consisting of a photopolymerizable prepolymer and a photopolymerizable monomer. The photopolymerizable prepolymer according to claim 8, wherein the photopolymerizable prepolymer is at least one selected from the group consisting of a polyester acrylate prepolymer, an epoxy acrylate prepolymer, a urethane acrylate prepolymer and a polyol acrylate prepolymer A transparent conductive film characterized by: The method of claim 8, wherein the photopolymerizable monomer is selected from the group consisting of 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentylglycol di (Meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalic neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, Acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, allylcyclohexyldi (meth) acrylate, isocyanurate di (meth) (Meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, (Meth) acrylate, propylene oxide-modified dipentaerythritol penta (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid-modified dipentaerythritol penta Is at least one polyfunctional acrylate selected from the group consisting of dipentaerythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (metha) acrylate.

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