JP2001264505A - Antireflection transparent electrically conductive laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antireflection transparent electrically conductive laminated film which is excellent in antistatic performance, electromagnetic wave shielding property, antireflection performance, stain-proofing property, productivity and mechanical characteristics, is excellent further in adhesion and can be stuck to a face panel. SOLUTION: The antireflection transparent electrically conductive laminated film is obtained by laminating a transparent base (1), a hard coat layer (2), a transparent electyically conductive layer (3) with fine particles comprising at least one metal, at least one antireflection layer (4) having a refractive index different from that of the transparent electrically conductive layer and a stain- proofing layer (5) in this order. The hard coat layer (2) contains a binder polymer prepared by polymerizing and crosslinking a polyfunctional acrylate compound containing dispersed inorganic fine particles containing at least one selected from the group comprising aluminum oxide, silicon dioxide, titanium dioxide and zirconium oxide. The antireflection layer (4) is substantially formed from a product prepared by partially hydrolyzing and polymerizing an alkyl silicate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-reflective transparent conductive laminated film having an excellent antistatic effect, electromagnetic wave shielding effect, anti-reflective effect, mechanical properties and antifouling property, and having improved adhesion. To an image display device.

[0002]

2. Description of the Related Art In a cathode ray tube, a plasma display, and the like used as a TV cathode ray tube or a computer display, dust adheres due to static electricity generated on a face panel surface, thereby lowering visibility. It has problems such as adverse effects. Further, the flattening of the cathode ray tube or the like requires an antireflection function. Furthermore, when the face panel surface is touched by hands or wiped to remove dirt, there is a problem that scratches are likely to occur.

For the purpose of preventing static electricity, shielding electromagnetic waves and preventing reflection, a method has been proposed in which a conductive layer is formed directly on the face panel surface by vapor deposition or sputtering of a metal such as silver or a conductive metal oxide such as ITO. However, film formation requires vacuum processing and high-temperature processing, and has the disadvantage that manufacturing costs are high or productivity is low.

A method of forming a conductive thin film by a coating method by a sol-gel method has also been proposed (Hani et al., Nati.
onal Technical Report 40,
No. 1, (1994) 90), high-temperature treatment is required, and lamination on a plastic film or a hard coat, which is a transparent substrate, is subject to deterioration of the substrate, which limits the materials that can be used as the substrate. There was a problem.

[0005] A transparent conductive paint in which conductive oxide fine particles and colloids are dispersed has also been proposed (JP-A-6-34).
4489, JP-A-7-268251), which has a problem that the conductivity of the transparent conductive layer is low.

Therefore, in order to further increase the conductivity, a method of forming a transparent conductive film made of metal fine particles has been proposed (Japanese Patent Application Laid-Open Nos. 63-160140 and 9-551).
No. 75). Further, a method of forming a low-reflection transparent conductive film by applying an antireflection paint such as tetraethoxysilane on the transparent conductive film has been proposed (JP-A-10-14).
No. 2401). However, there is a problem that mechanical strength is weak only by coating metal fine particles on a transparent base material, and that an antireflection layer formed from an antireflection paint such as tetraethoxysilane has low adhesion to a transparent conductive layer. . Also, for curing of anti-reflective paint such as tetraethoxysilane, usually,
Long-time high-temperature heat treatment is required, and the lamination of the antireflection layer by the sol-gel method has a problem that the transparent substrate is limited. Therefore, the method of forming the low-reflection transparent conductive film has a problem that it can only be applied directly to the glass face panel.

On the other hand, silver fine particles are directly applied to a glass face panel by a spin coating method, and a sintering reaction is caused at around 150 ° C., and Ag ₂ O on the surface is also baked by causing a decomposition reaction, thereby obtaining a conductive material. Although an improvement has been proposed (Japanese Patent Application Laid-Open No. 10-66861), this method is also applicable only to heat-resistant substrates such as glass. Therefore, instead of a method of directly forming a coating film on the front surface of a face panel, which requires a large investment in equipment and requires high-temperature treatment, a method of attaching a thin film formed on a base material has been proposed (Taki et al.,
National Technical Report
t, 42, No. 3 (1996) 264-268).

However, even in these methods, a method of forming a thin film is based on ITO (indium titanium oxy).
This method is a method of forming a conductive layer by vapor deposition or sputtering of a conductive metal oxide such as de), and requires vacuum treatment for film formation, which is problematic in manufacturing cost and productivity.

In order to solve these problems, the present inventors have studied a film having a hard coat layer and a transparent conductive layer composed of metal fine particles on a transparent substrate, and further laminating an anti-reflective transparent conductive layer. However, the adhesion between the transparent conductive layer and other layers has not been sufficient.

[0010]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and has an antistatic property,
An object of the present invention is to provide an anti-reflective transparent conductive laminated film which is excellent in electromagnetic wave shielding property, anti-reflection property, anti-fouling property, productivity, mechanical properties, excellent in adhesion, and can be attached to a face panel. Furthermore, the present invention has excellent electromagnetic wave shielding properties, antireflection properties, antifouling properties, and mechanical properties of the image display surface, and can be manufactured with high productivity by attaching a film to a face panel, and also prevents film peeling. It is an object of the present invention to provide a completed image display device.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above circumstances, and as a result, have found that a hard coat layer on a transparent support, a transparent conductive layer having fine particles of at least one or more metals, At least one layer formed on an outer layer of the transparent conductive layer and having a refractive index different from that of the transparent conductive layer;
In a laminated film comprising a transparent antireflection layer of the layer and an antifouling layer formed on the outermost layer, the hard coat layer is formed by polymerizing and crosslinking a polyfunctional acrylate compound in which specific inorganic fine particles are dispersed. It has been found that the above problem can be solved by forming the antireflection layer from a partially hydrolyzed polymer of an alkyl silicate substantially by forming the antireflection layer from a binder polymer. The reason is that the transparent conductive layer having fine metal particles interposed between the hard coat layer and the antireflection layer partially forms a kind of cohesive structure, so that the antireflection layer applied on the transparent conductive layer is hard. It is considered that the film is partly in contact with the coat layer, so that the adhesion between the hard coat layer and the antireflection layer can be improved and the problem of film peeling can be solved. The present invention has been made based on this finding.

That is, the present invention provides (1) a transparent support, a hard coat layer, a transparent conductive layer having fine particles made of at least one kind of metal, and reflection of at least one layer having a refractive index different from that of the transparent conductive layer. An antireflective transparent conductive laminated film in which an antireflection layer and an antifouling layer are laminated in this order, wherein the hard coat layer is at least one selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide and zirconium oxide. It comprises a binder polymer obtained by polymerizing and crosslinking a polyfunctional acrylate compound in which inorganic fine particles containing seeds are dispersed, and the antireflection layer is substantially formed of an alkyl silicate partially hydrolyzed polymer. (2) The hard coat layer contains 5-80% by mass of inorganic fine particles. (1) The antireflection transparent conductive laminated film according to the item (1), (3) that the antireflection layer is substantially formed of a partially hydrolyzed polymer of methyl silicate and / or ethyl silicate. (1) or (2), wherein the antireflection transparent conductive laminated film according to (1) or (2), (4) the antireflection layer contains a partially hydrolyzed polymer of methyl silicate and / or ethyl silicate, and an acid or alkali. The anti-reflection transparent conductive laminated film according to the item (3), wherein the laminated film is formed by a coating solution to be applied.

(5) The antireflection conductive laminated film according to the item (3) or (4), wherein the antireflection layer is substantially formed of a partially hydrolyzed polymer of methyl silicate. ) At least 10% by weight of antireflection
The anti-reflective transparent conductive laminated film according to any one of the above items (1) to (5), comprising:
(7) A binder obtained by polymerizing and crosslinking a polyfunctional acrylate compound containing at least one selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide, and zirconium oxide on a transparent support, in which inorganic fine particles are dispersed. After forming a hard coat layer containing a polymer and forming thereon a transparent conductive layer having fine particles made of at least one kind of metal, the film is washed with water, heated, and further treated with an alkyl silicate partially hydrolyzed polymer. (8) The method for producing an antireflection transparent conductive laminated film, wherein a cured antireflection layer is formed, and (8) the reflection according to any one of (1) to (6) on an image display surface. It is an object of the present invention to provide an image display device characterized by having a transparent conductive laminated film for prevention.

The anti-reflection transparent conductive laminated film of the present invention can be directly laminated on the surface of a cathode ray tube or a plasma display used as a TV cathode ray tube or a computer display. As a result, the equipment and process are much more remarkable than the conventional method of forming a conductive film using a physical vapor deposition (PVD) method or a chemical vapor deposition (CVD) method, or a method of directly applying a conductive film or the like to a face panel or the like. It can be simplified, and furthermore, the mechanical properties of the surface, particularly the scratch resistance, can be improved, and problems such as film peeling due to low adhesion do not occur. Also,
By directly laminating the film of the present invention to a liquid crystal display, it is possible to improve the mechanical properties and the reflection properties of the surface of the liquid crystal display.

[0015]

Embodiments of the present invention will be described below in detail. FIG. 1 is a schematic cross-sectional view showing a layer structure of an antireflection transparent conductive laminated film according to a preferred embodiment of the present invention. A hard coat layer 2, a transparent conductive layer 3 formed of fine particles made of at least one metal, and an antireflection layer 4 having a refractive index different from that of the transparent conductive layer 3 on its outer layer are substantially formed from the side of the transparent support 1. It is formed from a partially hydrolyzed polymer of alkyl silicate, and has an antifouling layer 5 as the outermost layer. FIG. 1 shows an example in which the antireflection layer is a single layer, but may have two or more antireflection layers each having a refractive index different from that of the transparent conductive layer.

The laminated film of the present invention prevents the film from being damaged due to the provision of the hard coat layer. Further, since a transparent conductive layer having fine particles made of at least one kind of metal is laminated, it has sufficient conductivity, can prevent charging, and effectively blocks electromagnetic waves radiated from a cathode ray tube or the like. be able to. Further, by having an antireflection layer, reflected light from the outside can be reduced, and the film can be prevented from being stained by an antifouling layer provided on the outermost layer.

The transparent support used in the present invention includes:
It is preferable to use a plastic film. Examples of the polymer forming the plastic film include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene Naphthalate, poly-1,4-cyclohexane dimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin ( For example, polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, poly Includes ether imides, polymethyl methacrylate and polyether ketone. Triacetyl cellulose, polycarbonate and polyethylene terephthalate are preferred. The light transmittance of the transparent support is 80.
%, More preferably 86% or more. The haze of the transparent support is preferably 2.0% or less, more preferably 1.0% or less. The refractive index of the transparent support is 1.4 to 1.7.
It is preferred that

The thickness of the transparent support film is not particularly limited and may be appropriately selected according to the purpose of use, but is preferably 20 to 500 μm. If the thickness is too small, the film strength is weak, and if the thickness is too large, the stiffness may be large and it may be difficult to attach the film. The transparent support film may be colored or vapor-deposited as desired, and may contain an ultraviolet absorber. Further, for the purpose of improving the adhesion to a layer provided on the surface, one or both surfaces can be subjected to a surface treatment by an oxidation method, a roughening method, or the like, if desired. Examples of the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet method), flame treatment, hot air treatment, and ozone / ultraviolet irradiation treatment. Further, one or more undercoat layers can be provided. Examples of the material for the undercoat layer include copolymers such as vinyl chloride, vinylidene chloride, butadiene, (meth) acrylate, and vinyl ester, and water-soluble polymers such as latex and gelatin.

In the present invention, the hard coat layer has a function of imparting scratch resistance to the transparent support. The hard coat layer includes a cross-linked polymer of an acrylate compound,
It can be formed by applying a coating solution containing a polyfunctional acrylate compound and a polymerization initiator on a transparent support and polymerizing the polyfunctional acrylate compound. As the functional group, an ethylenically unsaturated group is preferable. In the present invention, the acrylate compound also includes a methacrylate compound. The polyfunctional acrylate compound is preferably an ester of a polyhydric alcohol and acrylic acid or methacrylic acid. Examples of polyhydric alcohols include ethylene glycol, 1,4-cyclohexanol, pentaerythritol, trimethylolpropane, trimethylolethane, dipentaerythritol, 1,2,4-cyclohexanol, polyurethane polyol and polyester polyol. . Trimethylolpropane, pentaerythritol, dipentaerythritol and polyurethane polyols are preferred. Two or more polyfunctional acrylate compounds may be used in combination.

In the present invention, by adding and dispersing inorganic fine particles in the hard coat layer, the crosslinking shrinkage as a film can be improved and the flatness of the coating film can be improved. The inorganic fine particles can further enhance the adhesion at the contact portion between the hard coat layer and the antireflection layer as described above. As the inorganic fine particles, those having an affinity for silicon contained in the antireflection layer are preferable. In the present invention, any one of silicon dioxide particles, titanium dioxide particles, zirconium oxide particles, and aluminum oxide particles is used. The average particle diameter of the inorganic fine particles is 1 to 200.
It is preferably 0 nm, more preferably 2 to 1000 nm, still more preferably 5 to 500 nm, and most preferably 10 to 200 nm. The addition amount of the inorganic fine particles is preferably 1 to 99% by mass of the total amount of the hard coat layer, and is preferably 3 to 99% by mass.
And more preferably 90 to 90% by mass.
Most preferably, it is% by mass. In the present invention, inorganic fine particles other than those described above may be further added.

In general, inorganic fine particles have a poor affinity for a binder polymer. Therefore, simply mixing the two easily breaks the interface, cracks the film, and makes it difficult to improve the scratch resistance. By treating the inorganic fine particles with a surface treating agent containing an organic segment, the affinity between the inorganic fine particles and the polymer binder is improved, and this problem can be solved. The surface treatment agent must be able to form bonds with the metal particles on the one hand and have a high affinity for the binder polymer on the other hand. As the functional group capable of forming a bond with a metal, a metal alkoxide is preferable, and specific examples thereof include metal alkoxide compounds such as aluminum and titanium. Alternatively, a compound having an anionic group is preferable, and a compound having a phosphoric acid group, a sulfonic acid group, or a carboxylic acid group as a functional group is more preferable. Further, it is preferable that the polymer is chemically bonded to the binder polymer, and a polymer having a vinyl polymer group introduced at the terminal is preferable. For example, when synthesizing a binder polymer from a monomer having an ethylenically unsaturated group as a polymerizable group and a crosslinkable group,
It is preferable that the metal alkoxide compound or the anionic compound has an ethylenically unsaturated group at a terminal. In this surface treatment method, it is preferable that the inorganic fine particles are coated with the above-mentioned surface treatment agent, and after the addition to the binder polymer, the coated surface treatment agent is cured and crosslinked simultaneously with the crosslinking of the binder polymer.

For the synthesis reaction of the crosslinked binder polymer (polymerization reaction of the polyfunctional monomer), it is preferable to use a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenones, benzophenones, benzoylbenzoate of Michler, α-amyloxime ester, tetramethylthiuram monosulfide and thioxanthone. A photosensitizer may be used in addition to the photopolymerization initiator. Examples of photosensitizers include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone. The photopolymerization initiator is preferably used in an amount of 0.1 to 15 parts by mass based on 100 parts by mass of the polyfunctional monomer.
More preferably, it is used in the range of 0 parts by mass. The photopolymerization reaction is preferably carried out by irradiating ultraviolet rays after applying and drying the hard coat layer.

The transparent conductive layer of the present invention contains fine particles made of at least one kind of metal (hereinafter also referred to as metal fine particles). Fine particles composed of one or more metals include gold,
Fine particles of metals such as silver, copper, aluminum, iron, nickel, palladium and platinum, or alloys of these metals. Particularly, fine particles containing silver are preferable, and fine particles of an alloy of palladium and silver are more preferable from the viewpoint of weather resistance. The content of palladium is preferably 5 to 30% by weight. When the amount of palladium is small, the weather resistance may be deteriorated. When the amount of palladium is large, the conductivity may be reduced. Examples of the method for producing metal fine particles include a method for producing fine particles by a low-vacuum evaporation method and an aqueous solution of a metal salt containing iron (I
I), a method of preparing a metal colloid which is reduced with a reducing agent such as an amine such as hydrazine, boron hydride or hydroxyethylamine.

The average particle diameter of these metal fine particles is 1 to 100.
nm is preferred. When it exceeds 100 nm, the light absorption by the metal fine particles becomes large, so that the light transmittance of the particle layer is reduced and the haze is increased, and when the average particle size of these metal fine particles is less than 1 nm, In some cases, it becomes difficult to disperse the fine particles and the surface resistance of the fine particle layer rapidly increases, so that a film having a low resistance value that can achieve the object of the present invention cannot be obtained. The transparent conductive layer is preferably substantially composed of only metal fine particles, and preferably does not contain a nonconductive material such as a binder from the viewpoint of conductivity.

The transparent conductive layer is formed by applying a coating material in which metal fine particles are dispersed in a solution mainly composed of water or an organic solvent or the like on the hard coat layer. For the purpose of stabilizing the dispersion of the metal fine particles, a solution mainly composed of water is preferable. Examples of the solvent that can be mixed with water include ethyl alcohol, n-propyl alcohol, i-propyl alcohol, butyl alcohol, methylcellosolve, butylcellosolve and the like. Are preferred. The coating amount of the metal fine particles is 50 to 1
50 mg / m ² is preferred. If the coating amount is small, sufficient conductivity cannot be obtained, and if the coating amount is large, the transmittance may be too low.

The surface resistivity of the transparent conductive layer is required to be 1000 Ω / □ or less in order to meet the TCO guidelines established by the Swedish Central Workers' Council, and the transmittance is preferably 50% or more. The surface resistivity is a resistance value when electrodes are installed on two parallel sides of a square area.
Although the unit is Ω, it is represented by Ω / □ for convenience. In the present invention, the surface resistivity is represented by Ω / □.

In the present invention, the transparent conductive layer can be subjected to heat treatment or water treatment in order to improve conductivity and permeability. The heat treatment depends on the heat resistance of the transparent support.
The following is preferable, and 100 to 150 ° C is more preferable.
If the temperature is too high, the transparent support is likely to be deformed by heat. If the temperature is too low, it is difficult to obtain the effect of the heat treatment, so that a long-time treatment may be required.

The heat treatment is preferably performed in a wet state while passing through a heating zone, since uniform treatment can be achieved. The stay time can be adjusted by the length of the heating zone and the transport speed. It is also possible to heat the roll-shaped film in a high-temperature bath, but it is necessary to set a time in consideration of variations in heat conduction.

Further, by performing a water treatment such as washing with water on the transparent conductive layer prior to the heat treatment, the heat treatment can be performed more efficiently. Water treatment such as washing is performed by applying only water by a normal coating method, specifically, dip coating,
There is a method of applying water to the transparent conductive layer by spraying or showering, for example, by applying water with a wire bar. After watering the transparent conductive layer, excess water can be
It can be scraped with a wire bar or rod bar, or scraped with an air knife.

These water treatments can further reduce the surface resistance of the transparent conductive layer after the heat treatment, increase the transmittance, flatten the transmission spectrum, and reflectivity after the antireflection layer is laminated. The effect on the reduction of the amount becomes significant.

In the present invention, the antireflection layer has a refractive index different from that of the transparent conductive layer and is preferably smaller than 2. The difference in the refractive index means that the difference in the refractive index is at least 0.01 or more, but when the refractive index is a complex number because the transparent conductive layer or the antireflection layer has absorption, the imaginary number When the portions are different by 0.01 or more, it can be considered that the refractive indexes are different. Here, the product of the refractive index and the thickness (nm) of the antireflection layer is more preferably in the range of 100 to 200. The antireflective layer is formed substantially from an alkyl silicate partially hydrolyzed polymer. Here, “substantially formed from an alkyl silicate partially hydrolyzed polymer” means that the alkyl silicate partially hydrolyzed polymer is formed in 60% by mass or more of the whole. Further, in the present invention, the antireflection layer preferably comprises 1
It contains 0% by mass or more, more preferably 20 to 70% by mass of silicon. The alkyl silicate partially hydrolyzed polymer that can be used in the present invention has 1 to 3 carbon atoms.
Those having a lower alkyl group are preferred, ethyl silicate and methyl silicate are more preferred, and methyl silicate is particularly preferred. Examples of the alkyl silicate partially hydrolyzed polymer include those in which orthoalkyl silicate is hydrolyzed and dehydration condensation polymerization is advanced to some extent. As the orthoalkyl silicate, for example, orthomethyl silicate (Si (OCH
₃ ) ₄ ), ortho-ethyl silicate (Si (OC
₂ H ₅ ) ₄ ) Orthopropyl silicate (Si (OC
₃ H _{7) 4),} ortho-butyl silicate (Si (OC
₄ H _{9) 4),} or the like can be used. Orthoalkyl silicate having two or more alkyl groups in the same molecule may be used. Further, two or more kinds of alkyl orthosilicates may be used as a mixture.

The orthoalkyl silicate is easily hydrolyzed in the presence of water, and the alkoxyl group becomes a hydroxyl group, and is polymerized by dehydration polycondensation. The partially hydrolyzed alkyl silicate polymer in the present invention also includes such a polymer that has undergone a certain degree of polycondensation. In order to promote the dehydration-condensation polymerization reaction, a small amount of water or an acid such as hydrochloric acid or sulfuric acid, or an alkali such as sodium hydroxide or ammonia can be coexisted as a reaction catalyst. The antireflection layer can be preferably formed from a coating solution containing an alkyl silicate partially hydrolyzed polymer and the above-mentioned acid or alkali. The concentration of the alkyl silicate partially hydrolyzed polymer in the coating solution is appropriately set,
% By mass is preferred. The amount of the acid or alkali is not particularly limited, and is usually a so-called catalytic amount. As the solvent, for example, methanol, ethanol, propanol, acetone,
MEK (methyl ethyl ketone) or the like is used.

The alkyl silicate partially hydrolyzed polymer can be prepared using orthoalkyl silicate as a starting material as described above. However, if the same alkyl silicate partially hydrolyzed polymer is obtained, the raw material is not necessarily orthoalkyl. Not limited to silicate. As commercially available products, for example, ethyl silicate 40 and methyl silicate 51 (both are trade names, manufactured by Tama Chemical Industry Co., Ltd.) are marketed, but such compounds can be used as they are or after further hydrolytic condensation polymerization. It can be used after being diluted to a predetermined amount. Further, for example, a hydrolyzate of an alkoxide such as titanium, zirconium, or aluminum can be added as needed.

Further, MS51 and MSH1 (both trade names, manufactured by Mitsubishi Chemical Industries, Ltd.), etc., which are commercially available as the coating liquid, can also be suitably used. Since these have a methyl silicate-based reactive group and exhibit high reactivity, they are characterized in that sufficient curing can be obtained under relatively mild heating conditions, like the TMOS monomer.

After the formation of the above antireflection layer, preferably 80
Heat treatment at a temperature of from 150 to 150 ° C, more preferably from 100 to 140 ° C, can promote the curing of the coating film. The heat treatment time is not particularly limited, but is preferably about 1 day or less in consideration of suitability for production and the like.

The outermost antifouling layer preferably contains a known organic compound having a low surface energy containing a fluorine atom, specifically, a silicon compound containing a fluorohydrocarbon group, Examples include a hydrogen group-containing polymer, a fluorocarbon, a graft of a silicon-containing monomer, and a block copolymer. These are preferably thermosetting or crosslinkable resins containing a radiation-curable group. The surface of the antifouling layer preferably has a contact angle with water of 80 ° or more, more preferably 90 ° or more.

The production of the laminated film of the present invention is carried out by dipping a coating of each layer on a base film (transparent support),
It can be performed by sequentially forming and drying each layer by a known thin film forming method such as a spinner method, a spray method, a roll coater method, a gravure method, and a wire bar method. In the present invention, after the formation of the transparent conductive layer, it is preferable to wash the film with water, and then form a sufficiently cured antireflection layer after heating.
The heat treatment is as described above.

The anti-reflection transparent conductive laminated film of the present invention is applied to an image display device such as a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), and a cathode ray tube display (CRT). Applicable. The image display device of the present invention can be manufactured by bonding the transparent support side of the antireflection transparent conductive laminated film to the image display surface of the image display device.

[0039]

The present invention will be described more specifically with reference to the following examples. Example 1 (Preparation of Inorganic Particle Dispersion M-1) The following amounts of each reagent were measured in a ceramic-coated vessel. Cyclohexanone 337 g PM-2 (phosphate group-containing methacrylate manufactured by Nippon Kayaku Co., Ltd.) 31 g AKP-G015 (Alumina manufactured by Sumitomo Chemical Co., Ltd.) 92 g The above mixture was subjected to 1600 rpm for 10 hours by a sand mill (1/4 G sand mill). Finely dispersed. Media is 1
1400 g of mmφ zirconia beads were used. The particle size of the obtained surface-treated alumina was 93 nm.

(Preparation of Coating Liquid for Hard Coat Layer) 43% by mass methanol dispersion of surface-treated alumina fine particles 1
To 16 g, 97 g of methanol and 163 of isopropanol
g and 163 g of butyl acetate were added. To the mixture, 200 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd.)) was added and dissolved. To the obtained solution, 7.5 g of a photopolymerization initiator (Irgacure 907 (trade name, manufactured by Ciba Geigy)) and a photosensitizer (Kayacure DETX (trade name, manufactured by Nippon Kayaku Co., Ltd.))
5.0 g of 4 was added and dissolved. After stirring the mixture for 30 minutes, the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a hard coat layer.

(Preparation of Silver-Palladium Colloid Dispersion) 3
Preparation 0% iron sulfate _{(II) FeSO 4 · 7H 2} O, 40% citric acid, mixed, mixed holding, stirring thereto while 10% of the silver nitrate and palladium nitrate (molar ratio 9/1 to 20 ° C. The solution was added and mixed at a speed of 200 ml / min, and thereafter, washing with water was repeated by centrifugation, which was generated.
Pure water was added so that the final concentration was 3% by mass to prepare a silver-palladium colloidal dispersion. As a result of TEM observation, the particle diameter of the obtained silver colloid particles was about 9 to 12 nm. As a result of measurement by ICP, the ratio of silver to palladium was the same as the charging ratio of 9/1.

(Preparation of Silver Colloid Coating Liquid) To 100 g of the above silver colloid dispersion liquid, i-propyl alcohol was added, ultrasonically dispersed, and filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating liquid.

(Preparation of Antireflection Layer Coating Solution L-1) To 50 g of tetramethoxysilane, 15 g of 0.01 N nitric acid was added dropwise over 30 minutes, and the mixture was vigorously stirred for 3 hours. After confirming that the solution became homogeneous, it was left at room temperature for 12 hours and further
Stirred for minutes. This solution was filtered through a polypropylene filter having a pore size of 1 μm, and then diluted with 450 g of methanol to prepare a coating solution for a low antireflection layer.

(Preparation of Coating Solution for Antifouling Layer) To a thermally crosslinkable fluoropolymer (JN-7214 (trade name, manufactured by Nippon Synthetic Rubber Co., Ltd.)) was added isopropyl alcohol, and a 0.2% by mass crude dispersion was prepared. Was prepared. The coarse dispersion was further ultrasonically dispersed to prepare a coating solution for an antifouling layer.

(Preparation of Antireflective Transparent Conductive Laminated Film) A coating liquid for a hard coat layer was applied to a 188 μm polyethylene terephthalate film using a wire bar to a thickness of 8 μm, dried, and irradiated with ultraviolet rays to hard coat layer. Was prepared. After the corona treatment, the silver colloid coating solution was coated with a wire bar at a coating amount of 70 mg / m ^2.
And dried at 40 ° C. Water fed by a pump was sprayed on the silver colloid-coated surface, excess water was removed with an air knife, and a treatment was carried out for 5 minutes while transporting in a heating zone at 120 ° C. Next, an antireflection layer coating liquid L-1 was applied to a thickness of 80 nm, dried, and heat-treated at 120 ° C. for 2 hours. Further, the coating solution for the antifouling layer was similarly applied at 5 mg / m ² with a wire bar, and dried and heat-treated at 120 ° C.

Example 2 A hard coat coating solution was prepared using the following M-2 solution in which silica fine particles were dispersed in an inorganic particle dispersion, and the following L-2 solution was used as an antireflection layer coating solution. An anti-reflective transparent conductive laminated film was formed in exactly the same manner as in Example 1 except for the difference.

(Preparation of Inorganic Particle Dispersion M-2) The following reagents were weighed in a ceramic-coated vessel. Cyclohexanone 337 g 3-methacryloyloxypropyltrimethoxysilane 10 g Silica fine particles (average particle diameter: 14 nm) 92 g The above mixture was finely dispersed at 1600 rpm for 10 hours by a sand mill (1/4 G sand mill). Media is 1
1400 g of mmφ zirconia beads were used.

(Preparation of Coating Solution L-2 for Antireflection Layer) MS
50 g of H1 (trade name, manufactured by Mitsubishi Chemical Corporation) was filtered through a polypropylene filter having a pore size of 1 μm, and then diluted with 450 g of methanol to prepare an antireflection layer coating solution.

Comparative Example 1 Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd.))
125 g and urethane acrylate oligomer (UV
-6300B (trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)) 12
5 g was dissolved in 450 g of industrial denatured ethanol.
A photopolymerization initiator (Irgacure 907) was added to the obtained solution.
7.5 g (trade name, manufactured by Ciba Geigy) and a photosensitizer (Kayacure DETX (trade name, manufactured by Nippon Kayaku))
A solution of 5.0 g dissolved in 47.5 g of methyl ethyl ketone was added. After stirring the mixture, the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for the hard coat layer. A laminated film was produced in the same manner as in Example 1 except that the coating liquid for a hard coat layer prepared as described above was used.

Comparative Example 2 (Preparation of Coating Solution L-3 for Antireflection Layer) 15 g of 0.01 N nitric acid was added dropwise to 50 g of tetrabutoxysilane over 30 minutes, and the mixture was vigorously stirred for 3 hours. After confirming that the solution became homogeneous, the solution was allowed to stand at room temperature for 12 hours and further stirred for 30 minutes. This solution was filtered through a polypropylene filter having a pore size of 1 μm, and then diluted with 450 g of methanol to prepare a coating solution for an antireflection layer. A laminated film was prepared in the same manner as in Example 1, except that the antireflection layer coating solution L-3 prepared as described above was used.

The characteristics of each of the produced laminated films were measured by the following methods. (Evaluation of antireflection film) (1) Surface resistivity Measured by a four-terminal method surface resistivity meter (Loresta GP (trade name, manufactured by Mitsubishi Chemical Corporation)). (2) Reflectance 450-650 using a spectrophotometer (manufactured by JASCO Corporation)
The average reflectance of specular reflection in the incident light 5 ° in the wavelength region of nm was measured. (3) Antifouling property A fingerprint was adhered to the film surface, and a state of wiping off the film using Toraysee (trade name, manufactured by Toray Industries, Inc.) was observed and evaluated according to the following criteria. ：: The fingerprint was completely wiped off. ×: A part of the fingerprint remained without being wiped off. (4) Hardness of Pencil Scratch Test After the film was conditioned for 2 hours at a temperature of 25 ° C. and a relative humidity of 60%, Using a pencil for test defined by JIS-S-6006, the hardness of a pencil with no scratch was measured at a load of 1 kg according to the pencil hardness evaluation method specified by JIS-K-5400. (5) Scratch resistance test using steel wool After the film was conditioned for 2 hours at a temperature of 25 ° C. and a relative humidity of 60%, the steel wool of # 0000 was grounded with a contact area of 1 mm.
cm ^2, to observe the scratches after 50 reciprocating in weighting 200 g, were evaluated by the following criteria. ：: No scratches △: Weak scratches found ×: Clear scratches found (6) Adhesion test The film was conditioned for 2 hours at a temperature of 25 ° C and a relative humidity of 60%, and then a cutter knife Were cut so as to form 10 × 10 pieces, and observed after peeling with a polyester tape, and evaluated according to the following criteria. ：: No peeling Δ: Slight peeling at the end ×: Clear peeling is observed

Table 1 shows the measurement results. Each film has a surface electrical resistivity of 200Ω / □ and an average reflectance of 0.8%.
And the antifouling property was ○.

Table 1 Adhesion by Steel Wool Pencil Hardness Scratch Resistance Test Remarks ----------------------------------------------------------------------------------------------------- -Example 1 ○ 4H ○ Good surface condition Example 2 ○ 4H ○ Good surface condition Comparative Example 1 △ 2H △ Large curl of coating film Comparative Example 2 △ 2H × surface whitening --------------- −−−−−−−−−−−−−−−−−−−−−−−−−−−

As shown in Table 1, in Examples 1 and 2, a hard coat layer comprising a crosslinked polyfunctional acrylate containing specific inorganic fine particles and an antireflection layer formed from a partially hydrolyzed polymer of an alkyl silicate compound were used. It can be seen that the use of the laminated film provided improved the adhesiveness of the film while maintaining the surface hardness. However, when the reactivity of the antireflection layer liquid is low as in Comparative Example 2, curing may not be sufficient and sufficient performance may not be obtained.

[0055]

The antireflective transparent conductive laminated film of the present invention has high antistatic properties and electromagnetic wave shielding properties even with a simple layer structure, sufficiently prevents surface reflection, and has excellent surface mechanical strength. Therefore, the production of this anti-reflection transparent conductive laminated film has high productivity and can be produced at low cost, and since the anti-reflection layer is formed in close contact with other layers, peeling of the film is also prevented. ing. Further, by laminating the laminated film of the present invention on the surface of a cathode ray tube, a plasma display, or the like, it is possible to provide each function of shielding electromagnetic waves, preventing reflection, and preventing contamination of the surface. Excellent mechanical strength can be added.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of a layer configuration of an antireflection conductive laminated film of the present invention.

[Explanation of symbols]

 Reference Signs List 1 transparent support 2 hard coat layer 3 transparent conductive layer 4 antireflection layer 5 antifouling layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01B 5/14 G02B 1/10 A H04N 5/72 Z F term (Reference) 2H091 FA37X FB02 FB06 FB13 GA02 LA02 LA07 LA12 2K009 AA07 BB13 BB24 BB28 CC02 CC09 CC21 CC42 DD02 DD05 DD06 EE03 4F100 AA19B AA20B AA21B AA27B AB01C AK25B AK41 AK52E AR00B AR00C AR00D AR00E AT00A BA05 BA07 BA10A BA10E BA26 CC00B DE01B DE01C EJ05B EJ55 GB41 JG01C JK12B JL06E JN01A JN01C JN06D JN18D 5C058 AA01 AA06 AA11 BA35 DA01 DA08 DA10 5G307 FA02 FB02 FC05 FC08

Claims (8)

[Claims] 1. A transparent support, a hard coat layer, a transparent conductive layer having fine particles of at least one metal, at least one antireflection layer having a refractive index different from that of the transparent conductive layer, and antifouling. The layer is an anti-reflective transparent conductive laminated film laminated in this order, wherein the hard coat layer contains inorganic fine particles containing at least one selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide and zirconium oxide. An antireflective transparent conductive material comprising a binder polymer obtained by polymerizing and cross-linking a dispersed polyfunctional acrylate compound, wherein the antireflective layer is substantially formed from an alkyl silicate partially hydrolyzed polymer. Laminated film. 2. The antireflection transparent conductive laminated film according to claim 1, wherein the hard coat layer contains 5 to 80% by mass of inorganic fine particles. 3. The method according to claim 1, wherein the antireflection layer is substantially formed of a partially hydrolyzed polymer of methyl silicate and / or ethyl silicate.
4. The anti-reflective transparent conductive laminated film according to item 1. 4. The anti-reflection layer according to claim 3, wherein the anti-reflection layer is formed of a coating solution containing a partially hydrolyzed polymer of methyl silicate and / or ethyl silicate and an acid or alkali. Transparent conductive laminated film. 5. The anti-reflective conductive laminated film according to claim 3, wherein the anti-reflective layer is substantially formed of a partially hydrolyzed polymer of methyl silicate. 6. The method according to claim 1, wherein the antireflection layer contains at least 10% by weight of silicon.
Item 8. The antireflection transparent conductive laminated film according to item 8. 7. A polyfunctional acrylate compound containing at least one selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide and zirconium oxide and having inorganic fine particles dispersed thereon is polymerized and crosslinked on a transparent support. A hard coat layer containing a binder polymer is formed, and a transparent conductive layer having fine particles of at least one kind of metal is formed thereon. Then, the film is washed with water, heated, and further partially hydrolyzed with alkyl silicate. A method for producing an anti-reflective transparent conductive laminated film, comprising forming a cured anti-reflective layer from a product. 8. An image display device comprising the anti-reflective transparent conductive laminated film according to claim 1 on an image display surface.