JP2000301648A - Transparent conductive laminate and transparent tablet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain low reflectivity of a surface of a transparent conductive layer, small coloring of transmitted light and excellent visibility by setting sum of optical film thicknesses of the transparent layers of specific number to a specific value, and specifying chromaticness index b* values of L*a*b* table color of mean reflectivity of a laminated surface and transmitted light of a laminate. SOLUTION: A transparent conductive layer having a refractive index of 1.7 to + 0.3, a thickness of 20 to 90 nm, a layer having a refractive index of 1.35 to 1.5 and a thickness of 30 to 110 nm and a transparent conductive layer having a thickness of 12 to 30 nm are sequentially laminated from a substrate side. A sum of optical film thicknesses of the three layers is set to about 180 to 230 nm. Mean reflectivity of a laminated surface of the conductive layer at a wavelength of 450 to 650 nm is set to 5.5% or below, and chromaticness index b* values of L*a*b* table color decided according to the Japanese Industrial Standard Z 8729 of the transmitted light of the laminate are set to about 0 to 2. The conductive layer is made of a metal oxide, for example, tin oxide, indium oxide, zinc oxide, gallium oxide or the like and their mixtures are preferably used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a light transmittance of at least one surface of a substrate made of an organic polymer in which a layer having optical coherence and a transparent conductive layer are laminated in this order from the substrate side. The present invention relates to an extremely high transparent conductive laminate, and further relates to a transparent tablet using the transparent conductive laminate as at least one transparent electrode substrate.

[0002]

2. Description of the Related Art In recent years, portable information devices equipped with a liquid crystal display for displaying information and a transparent tablet for inputting information (also referred to as touch switches, touch panels, and flat switches) have begun to be widely used. The resistive film type transparent tablet, which is often used as a transparent tablet, is composed of two transparent electrode substrates with a transparent conductive layer formed facing each other at an interval of about 10 μm. The two electrodes contact each other to operate as a switch. For example, menu selection on a display screen or input of a figure or a handwritten document can be performed.

As such a transparent electrode substrate, for example, a transparent conductive material made of a metal oxide such as indium oxide (ITO) or zinc oxide containing tin oxide is formed on a substrate such as glass or various thermoplastic polymer films. Layered layers are widely used.

Here, the transparent tablet is often arranged on various displays such as a liquid crystal display device and a CRT. However, if the light has a high reflectance or absorptivity when the light passes through the transparent tablet, the display is difficult. This is not preferable because it causes a decrease in contrast and brightness of the display screen.

In the case where only a transparent conductive layer is laminated on the above-mentioned substrate, light interference of reflected light at two interfaces between the substrate and the transparent conductive layer and between the transparent conductive layer and the air, and the formation of the transparent conductive layer itself. Coloring is often observed in light transmitted through the transparent electrode substrate due to light absorption or the like. For example, at present, for transparent tablet applications, the thickness of the transparent conductive layer is about 20-30.
Those having a thickness of about nm are widely used, and the transmitted light often has a slightly brownish coloration. However, when the degree of such coloring is remarkable, the hue of the display screen is changed, which is not preferable.

[0006]

As a method for reducing the reflectance of the surface of the transparent electrode, a method of laminating a layer having an appropriate optical interference (hereinafter referred to as an optical interference layer) on the underlayer of the transparent conductive layer is proposed. Are patent applications filed by the present applicant, for example, Japanese Patent No. 1815750,
No. 27, JP-A-10-24516, etc., it cannot be said that the latter phenomenon of coloring of the transmitted light of the transparent conductive substrate was necessarily sufficiently suppressed.

[0007]

Means for Solving the Problems The present inventors have established that the optical interference layer and the transparent conductive layer satisfy a specific relationship,
It has been found that the above problems can be solved.

That is, the present invention firstly provides a transparent conductive laminate in which a transparent conductive layer is laminated on the outermost surface of at least one surface of an organic polymer substrate, in order from the substrate side, (A1) layers having a refractive index of the there thickness of 20~90nm range in the range of the refractive index +0.3 of the transparent conductive layer from 1.7 (H ₁ layer), is (B1) a refractive index from 1.35 to 1.5
A layer thickness in the range of in the range of 30~110nm (L ₁ layer), (C) a thickness in the range of 12~30nm transparent conductive layer, is laminated, (D) said third layer The sum of the optical film thicknesses of about 180 to 230 nm,
(F) a wavelength of 450 to 650 nm of the laminated surface of the transparent conductive layer
Is not more than 5.5%, and (G) the chromaticity index b ^* value of the L ^* a ^* b ^* color system of the transmitted light of the laminate specified in Japanese Industrial Standard Z8729 is approximately This is achieved by a transparent conductive laminate characterized by being in the range of 0 to 2.

The present invention also provides a transparent conductive laminate comprising a transparent conductive layer laminated on the outermost surface of at least one surface of an organic polymer substrate, wherein (A2) The refractive index is 1.7 to the refractive index of the transparent conductive layer +
Layers in the range of 0.3 (H ₂ layers), (B2) a layer having a refractive index in the range of 1.35 to 1.5 (L ₂ layers), the (C) the film thickness is 12~30nm range there transparent conductive layer, is laminated, the reflectivity of the (E) said L _2-layer surface wave 260 to
(F) an average reflectance at a wavelength of 450 to 650 nm of the laminated surface of the transparent conductive layer is 5.5% or less, and (G) transmitted light of the laminated body. The L ^* a ^* b ^* color system has a chromaticness index b ^* value defined in Japanese Industrial Standard No. Z8729, which is in the range of about 0 to 2, and is achieved by a transparent conductive laminate.

Further, the present invention provides, in a third aspect, a transparent conductive laminate in which a transparent conductive layer is laminated on the outermost surface of at least one surface of an organic polymer substrate, wherein the refractive index of the substrate is 1.7. be more than, in order from the least substrate side, and (A3) refractive index in the range of 1.35 to 1.5 layer thickness is in the range of 10 to 30 nm (L ₃ layer), (C
3) a transparent conductive layer having a thickness in the range of 12 to 30 nm is laminated, and (F) a wavelength 4
The average reflectance at 50 to 650 nm is 5.5% or less, and (G) Japanese Industrial Standard Z87 of the transmitted light of the laminate.
The transparent conductive laminate is characterized in that the chromaticity index b ^* value of the L ^* a ^* b ^* color system defined in No. 29 is in the range of approximately 0 to 2.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In order to reduce the reflectivity inside a transparent tablet and to obtain an achromatic color or a color of transmitted light similar to that described above, a transparent conductive layer of a transparent conductive laminate is laminated. Surface wavelength 450-650n
m is 5.5% or less, and Z8 of Japanese Industrial Standards (JIS) of the transmitted light of the transparent conductive laminate.
The chromaticity index b ^* value of the L ^* a ^* b ^* color system defined in 729 is in the range of about 0 to 2, preferably 0 to 2.
It is important to be in the range of 1.5. When the b ^* value of the transmitted light of the transparent conductive laminate exceeds 2.0, the transmitted light tends to have a yellowish coloring and the appearance tends to deteriorate, and when the value becomes a negative value less than 0 This is because the total light transmittance of the laminate tends to decrease significantly.

In the present invention, as this type of light used for color measurement of the transmitted light and those using standard light D ₆₅ prescribed in Z8720 of JIS, simple not subjected to visibility correction with respect to the average reflectance Average value shall be used.

The color and the reflectance of the surface of the transparent conductive layer indicate the reflected light generated at the interface between the transparent conductive layer and the optical interference layer when the transparency of the laminate is high, that is, when the laminate has little light absorption. Varies in accordance with the mutual interference conditions, that is, the film thickness and refractive index of each layer, the stacking order of each layer, and the like.

Specifically, in order to realize the above-mentioned preferred colors, it is preferable that the transmittance of the transparent conductive laminate in the visible region of the transmitted light has a maximum point in a wavelength range of about 450 to 530 nm. From the viewpoint of obtaining a high transmittance at the same time, it is more preferable to have a maximum point in the wavelength range of 470 to 530 nm.

In order to obtain such a spectrum of transmitted light, the reflectance of the surface of the transparent conductive layer must be 430 to 430.
510 nm, preferably 450-510 nm
It is more preferable to have a minimum point in the region of (1). In the first invention, the transparent conductive laminate of the present invention comprises an optical interference layer on a substrate made of an organic polymer, and a transparent conductive layer formed thereon. That is, at least from the substrate side, (A1) H ₁ layer: the refractive index is in the range of 1.7 or more and not more than about 0.3 larger than the refractive index of the transparent conductive layer, and the film thickness is 20 to in the range of 90nm, (B1) L ₁ layer: in the range of the refractive index is 1.35 to 1.5, and the thickness is in the range of 30～110Nm,
(C) Transparent conductive layer: the layer thickness is in the range of 12 to 30 nm. If the refractive indices of the H ₁ layer and the L ₁ layer are out of the above ranges, the effect of reducing the reflectance of the surface of the transparent conductive layer laminated on the L ₁ layer is undesirably reduced.

In the transparent conductive laminate, (D) the sum of the optical thicknesses of the three layers is about 180 to 230 nm. Here, the optical film thickness is a value obtained by multiplying the refractive index of the layer by the film thickness, and the sum of the optical film thicknesses of the H ₁ layer, the L ₁ layer, and the transparent conductive layer is about 180 to 230 nm. By laminating three layers in combination, a transparent conductive laminate having good color and low reflectance can be obtained.

[0017] reflectivity of L ₁ layer surface wave 260-3
It is preferable to have a minimum point in a region of 90 nm.

As the transparent conductive layer in the transparent conductive laminate of the present invention, a layer mainly composed of a metal oxide is preferably used. The surface resistance value is 100 to 2000 Ω / □, more preferably 15 to 30 nm.
It is preferable to use a transparent conductive layer having a range of 0 to 2000 Ω / □. When the thickness of the transparent conductive layer is less than 12 nm, the stability of the resistance value over time tends to be inferior.
Exceeding the ratio is not preferable because the reflectance of the transparent conductive layer is significantly increased even when the optical interference layer is laminated.

Specifically, for example, a layer made of tin oxide, indium oxide, zinc oxide, gallium oxide, or the like, and a layer made of a material obtained by mixing them in an appropriate ratio are preferably used. A layer made of a material to which one or more kinds of titanium oxide, aluminum oxide, zirconium oxide and the like are added at a ratio of about several weight% is preferably used.

These transparent conductive layers are formed by a sputtering method,
Lamination can be performed using a known vacuum film forming process such as an ion plating method, a vacuum deposition method, and a CVD method.
Among them, the sputtering method is preferable from the viewpoint of the film thickness uniformity and the composition uniformity in the width direction and the length direction.

The optical interference layer in the transparent conductive laminate comprises the H ₁ layer and the L ₁ layer.
Formed by stacking the _first layer and the L ₁ layer in this order. The H ₁ layer has a refractive index (A) of 1.7 to about 0.3 from the refractive index of the transparent conductive layer.
A There thickness 20~90nm the range of large refractive index, L ₁ layer, (B) the refractive index is located thickness in the range of 1.35 to 1.5 in the range of 30～110Nm. Such H
_In addition to the one obtained by laminating _one layer and the L ₁ layer, for example, in addition to the lamination of the H ₁ layer and the L ₁ layer, the substrate is in contact with the H ₁ layer and has a refractive index of about 1.5 or less, Is a layer having a thickness of 30 to 100 nm (L ′
Layer) and has a refractive index intermediate between H ₁ layer and the substrate (a layer underlying the optical interference layer), thickness approximately 30~100nm
An optical interference layer such as a layer (M layer) may be provided to form a three-layer structure.

The difference in the refractive index at the interface between the substrate made of an organic polymer serving as the base of the optical interference layer, the protective layer described below, and the layer of the optical interference layer used in contact with the base is preferable. Is preferably at least 0.1, more preferably at least 0.15, in order to exhibit a high optical interference effect of the optical interference layer and reduce the reflection of the transparent conductive layer surface.

These optical interference layers can be formed by various vacuum film forming processes such as a sputtering method, a vapor deposition method, an ion plating method and a CVD method, a micro gravure coating method, and the like.
It can be prepared by various roll coating methods typified by Meyer bar coating method, direct gravure coating method, etc., wet coating methods such as knife coating method, curtain coating method, spin coating method, spray coating method, and the combination thereof. is there.

More specifically, various inorganic dielectric layers formed by using a vacuum film forming process, for example, MgF ₂ , Si
O ₂ , CaF ₂ , NaF, Na ₃ AlF ₆ , LiF, Al ₂
O ₃ , CeF ₄ , LaF ₃ , NdF ₃ , TiO ₂ , MgO,
PbF ₃ , ThO ₂ , ZrO ₂ , ZnS, SnO ₂ , In ₂
A layer composed of O ₃ , Sb ₂ O ₃ , CeO 2, Nd ₂ O ₃ , La ₂ O _{3 and the} like, and a mixture thereof, and a resin cross-linked layer formed by a wet coating method, for example, silicon, titanium, zirconium, A resin crosslinked layer formed by hydrolysis and dehydration condensation of a simple substance or a mixture of metal alkoxides such as tin, tantalum, and indium;
Examples thereof include a resin crosslinked layer in which fine particles of various metal oxides having the following particle diameters are dispersed.

Regarding the various optical interference layers exemplified above,
From the viewpoint of obtaining high productivity among them, it is particularly preferable to use an optical interference layer formed of a resin cross-linked layer formed by the wet coating method, and further, among the resin cross-linked layers formed by the wet coating, mechanical strength and stability of the layer It is most preferable to use a crosslinked layer made of a metal alkoxide, particularly an alkoxide of titanium, zirconium or silicon, from the viewpoints of excellent properties and excellent adhesion to a transparent conductive layer and a substrate. Here, the crosslinked layer of titanium and zirconium alkoxide functions as a high refractive index layer having a refractive index of about 1.6 or more and, in some cases, about 1.7 or more in the optical interference layer. The crosslinked layer has a refractive index of about 1.10 in the optical interference layer.
It functions as a low refractive index layer having a refractive index of 5 or less.

Examples of the titanium alkoxide include titanium tetraisopropoxide, tetra-n-propyl orthotitanate, titanium tetra-n-butoxide, and tetrakis (2-ethylhexyloxy) titanate. Examples of the zirconium alkoxide include zirconium alkoxide. Tetraisopropoxide,
Zirconium tetra-n-butoxide is exemplified.

Examples of the silicon alkoxide include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4 epoxycyclohexyl) )
Examples include ethyltrimethoxysilane, vinyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, and γ-aminopropyltriethoxysilane. Is done.

It is often preferable to use a mixture of two or more of these silicon alkoxides, if necessary, from the viewpoints of the mechanical strength, adhesion and solvent resistance of the layer. The weight ratio is 0.
It is preferable that the silicon alkoxide having an amino group in the molecule is contained in the range of 5 to 60%.

These metal alkoxides may be used as a monomer or may be used after being subjected to hydrolysis and dehydration condensation beforehand and appropriately oligomerized. Usually, the coating solution dissolved and diluted in an appropriate organic solvent is used as a substrate. Apply on top. The coating film formed on the substrate undergoes hydrolysis due to moisture in the air or the like, and subsequently crosslinking proceeds by dehydration condensation.

In general, appropriate heat treatment is required to promote crosslinking, and 10 to 10 times is required in the wet coating process.
It is preferable to perform a heat treatment at a temperature of 0 ° C. or more for several minutes or more. In some cases, in parallel with the heat treatment,
By irradiating the coating film with actinic rays such as ultraviolet rays, the crosslinkability can be further improved.

Examples of the diluting solvent include alcohol and hydrocarbon solvents such as ethanol, isopropyl alcohol, butanol, 1-methoxy-2-propanol, and the like.
Hexane, cyclohexane, ligroin and the like are preferred, but other polar solvents such as xylene, toluene, cyclohexanone, methyl isobutyl ketone, and isobutyl acetate can also be used. These can be used alone or as a mixture of two or more solvents.

The substrate made of the organic polymer constituting the transparent conductive laminate of the present invention is not particularly limited, but it is preferable that the substrate has high transparency, and specifically, a substrate having a wavelength of 450 to 650 nm. The average value of the transmittance of the region is preferably at least 80% or more, more preferably 85% or more.

When the transparent conductive laminate of the present invention is used as an input-side transparent electrode substrate (movable electrode substrate) of a pair of transparent electrode substrates constituting a transparent tablet, the transparent conductive laminate is appropriately applied to an external input such as a pen. Organic polymers that provide a substrate with some flexibility to deform are preferred. Therefore, a film-shaped molded substrate made of a thermoplastic polymer is suitably used as such a substrate. Specifically, for example, polyethylene terephthalate, polyethylene naphthalate,
Preferable examples include polycarbonate, polyarylate, polyethersulfone, triacetylcellulose, diacetylcellulose, various polyolefins, modified products thereof, and copolymers thereof with other materials. These film-shaped molded substrates are suitably molded by a general melt extrusion method or a solution casting method, but if necessary, the molded film-shaped substrate is subjected to uniaxial stretching or biaxial stretching to obtain a mechanical strength. It is also preferable to increase the optical function and the optical function.

The thickness of the substrate obtained in this manner and suitable as a movable electrode substrate is in the range of about 10 to 400 μm, more preferably 20 to 200 μm. It is preferable from a viewpoint or the like.

In the case where the transparent conductive laminate of the present invention is used for a transparent electrode substrate (fixed electrode substrate) used in opposition to the movable electrode substrate, it is not always necessary to have high flexibility. Depending on the form, a property (high rigidity) of less deformation due to external force may be required. Therefore, in addition to the film-shaped molded substrate made of the thermoplastic polymer, a similar thermoplastic polymer is used. Alternatively, a sheet-shaped molded substrate made of a thermosetting product of various materials such as an epoxy-based or acrylic-based material and / or an ultraviolet-cured product can also be suitably used. As a method for forming such a sheet-shaped molded substrate, a melt extrusion method, a solution casting method, an injection molding method, a cast polymerization molding method and the like can be mentioned.

In some cases, a film-shaped or sheet-shaped molded substrate on which a transparent electrode is not formed is adhered to the surface of the film-shaped molded substrate opposite to the transparent electrode surface by backing. An electrode substrate having such a configuration is also preferably used.

The thickness of the thus obtained electrode substrate suitable as a fixed electrode substrate is about 10 to 2000 μm.
m, more preferably 50 to 1000 μm, and most preferably 70 to 700 μm.

Recently, the input side (user side) of the tablet
A new type of transparent tablet having a configuration in which a polarizing plate is laminated on a surface has been developed. The advantage of this configuration is that the reflectance of extraneous light inside the tablet can be reduced by half or less mainly due to the optical action of the polarizing plate.

When the above substrate is used in a tablet of this type, since polarized light passes through the transparent electrode substrate, it is preferable to use a substrate having more excellent optical isotropy as the substrate. When the refractive index of the substrate in the slow axis direction is nx, the refractive index in the fast axis direction is ny, and the thickness of the substrate is d (nm), Re = (nx−ny) × d
It is further preferable that the in-plane retardation Re represented by (nm) is at least 30 nm or less, more preferably 20 nm or less. Here, the value of the in-plane retardation of the substrate is represented by a measured value at a wavelength of 590 nm using a multi-wavelength birefringence index measuring device (trade name “M-150”) manufactured by JASCO Corporation.

Examples of the organic polymer having excellent optical isotropy include polycarbonate, amorphous polyarylate, polyether sulfone, triacetyl cellulose, diacetyl cellulose, amorphous polyolefin and modified products thereof. Or a copolymer with another kind of material, such as a thermosetting molded product or an ultraviolet curable molded product of an organic material such as an epoxy-based or acrylic-based material is preferable, but from the viewpoint of moldability, manufacturing cost, thermal stability, and the like, polycarbonate is preferred. ,
Most preferred are amorphous polyarylate, amorphous polyolefin and modified products thereof or copolymers with other materials.

More specifically, examples of the polycarbonate include bisphenol A, 3,3,5-1,1-di (4-phenol) cyclohexylidene and / or 3,3,5-trimethyl-1,1- Di (4-phenol) cyclohexylidene, fluorene-9,9-di (4
-Phenol), fluorene-9,9-di (3-methyl-4-phenol), etc., having an average molecular weight of about 30,000 to 1 consisting of a homo- or copolymerized bisphenol component.
Polycarbonate in the range of 00000 (“Panlite” manufactured by Teijin Chemicals and “Apec H” manufactured by Bayer
T "and the like are exemplified).

Examples of the amorphous polyarylate include, as commercial products, "Elmec" manufactured by Kaneka Corporation, "U-Polymer" manufactured by Unitika, "Isalil" manufactured by Isonova, and the like.

Examples of the amorphous polyolefin include "ZEONEX" manufactured by Zeon Corporation and "ARTON" manufactured by Japan Synthetic Rubber Co., Ltd. as commercial products.

Examples of the method of forming a substrate made of these organic polymer materials include a melt extrusion method, a solution casting method, and an injection molding method. From the viewpoint of obtaining excellent optical isotropy. In particular, it is preferable to perform molding using a solution casting method.

In the use of a tablet through which polarized light passes, the value of the in-plane retardation of the substrate is very important. In addition, the three-dimensional refractive index characteristics of the substrate, that is, the thickness direction of the substrate, K = {(nx + ny) / 2−nz} × d, where nz is the refractive index of
It is preferable that the value be in the range of at least -250 to +150 nm, more preferably -200 to +100 nm, in order to obtain a viewing angle characteristic with high visibility of the tablet.

When the solvent resistance and / or hard coat property of the substrate made of the above organic polymer is insufficient for the performance required for the intended use, the above-mentioned properties are improved on one or both sides of the substrate. It is preferable to laminate a protective layer having a function. Here, when the optical interference layer and the transparent conductive layer are laminated on the protective layer, the refractive index difference of the protective layer may be at least 0.1 or more at the interface where the optical interference layer contacts as described above. It is preferable from the viewpoint of obtaining low reflectivity.

Here, the solvent resistance is required mainly in the tablet manufacturing process. Therefore, the criteria for the required characteristics are slightly different depending on the method of manufacturing the tablet, but the following solvent resistance is required. Become. That is, when a protective layer is laminated on a substrate as described above, it is preferable to laminate a protective layer exhibiting such solvent resistance on the substrate.

Organic solvent resistance: A few drops of toluene (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) typified as a solvent for a silver paste which is printed on the transparent conductive layer when a tablet is prepared, are dropped at 25 ° C. After visual observation of changes in appearance such as cloudiness, swelling and dissolution of the surface after standing for 3 minutes, and when no change is confirmed, it is determined that the composition has organic solvent resistance.

Alkali-resistant aqueous solution resistance: A few drops of a 3.5 wt% aqueous sodium hydroxide solution used for dissolving the resist during patterning of the transparent conductive layer is dropped on the sample surface,
After standing for 3 minutes, changes in the appearance such as cloudiness, swelling, and dissolution of the surface are visually observed, and if no change is confirmed, it is determined to have alkali-resistant aqueous solution resistance.

Acid-resistant aqueous solution resistance: Several drops of an etching solution (a mixture of 35 wt% ferric chloride aqueous solution, 35 wt% hydrochloric acid, and water in a ratio of 1: 1: 10) used for patterning the transparent conductive layer are applied to the sample surface. After dripping and leaving at 25 ° C. for 3 minutes, changes in the appearance such as cloudiness, swelling, and dissolution of the surface are visually observed. If no change is observed, it is determined that the composition has acid-resistant aqueous solution resistance.

In the use of the transparent tablet, the hard coat property is not an essential characteristic item. However, the purpose is to increase the durability against repeated input to the tablet, in particular, to change the resistance and linearity of the transparent conductive layer, and to stabilize the tablet. In order to increase the input load value (ON load value) and to prevent the substrate surface from being damaged or deformed due to input to the tablet by a pen or the like, it is often preferable that the hard coat property is high.

From the viewpoint of enhancing the durability, the hard coat property is such that the pencil hardness as defined in Japanese Industrial Standard K5400 is at least 2B or more, more preferably F or more.
Most preferably, it is 2H or more. That is, when a protective layer is laminated on a substrate as described above, it is preferable to laminate a protective layer exhibiting such a hard coat property on the substrate.

Examples of the protective layer having such properties include a resin crosslinked layer, for example, a radiation crosslinked layer of an acrylic resin, a thermally crosslinked layer of a phenoxy resin, a thermal crosslinked layer of an epoxy resin, and a thermal crosslinked layer of a silicon alkoxide. And various resin cross-linked layers. Among them, the radiation-crosslinked layer of an acrylic resin is most preferably used because it has a feature that a layer having a high degree of cross-linking can be obtained in a relatively short time by irradiation with radiation, so that the load on the production process is small.

The radiation-crosslinkable resin refers to a resin that undergoes crosslinking upon irradiation with radiation such as ultraviolet rays or electron beams, and contains a polyfunctional acrylate component having two or more acryloyl groups in a unit structure in the resin composition. Acrylic resin contained. For example, trimethylolpropane triacrylate, trimethylolpropane ethylene oxide modified triacrylate, trimethylolpropane propylene oxide modified triacrylate, isocyanuric acid ethylene oxide modified triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Various acrylate monomers such as dimethylol tricyclodecane diacrylate, and polyester-modified, urethane-modified, and epoxy-modified polyfunctional acrylate oligomers are preferably used for this purpose. These resins may be used in a single composition or in a mixture of several kinds. In some cases, it is also preferable to add appropriate amounts of hydrolysates of various silicon alkoxides to the composition.

When the resin layer is crosslinked by irradiation with ultraviolet rays, a known photoreaction initiator is added in an appropriate amount. Examples of the photoreaction initiator include diethoxyacetophenone and 2-methyl-1- {4- (methylthio) phenyl}.
Acetophenone compounds such as -2-morpholinopropane, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-hydroxycyclohexylphenyl ketone; benzoin compounds such as benzoin and benzyldimethylketal; benzophenone and benzoyl Benzophenone compounds such as benzoic acid; thioxanthone, 2,
And thioxanthone compounds such as 4-dichlorothioxanthone.

The thermally crosslinked layer of the phenoxy resin includes a layer obtained by thermally crosslinking a phenoxy resin, a phenoxyether resin, or a phenoxyester resin represented by the following formula (1) with a polyfunctional isocyanate compound.

[0057]

Embedded image

Here, R ^{1 to} R ⁶ are the same or different hydrogen or alkyl group having 1 to 3 carbon atoms, and R ⁷ is 2 to 5 carbon atoms.
X is an ether group, an ester group, and m is 0
An integer of 3 to 3, and n means an integer of 20 to 300, respectively. Among them, particularly, R ¹ and R ² are methyl groups, R ^{3 to} R ⁶
Is preferably hydrogen, and R ⁷ is preferably a pentylene group, from the viewpoint of easy synthesis and productivity.

The polyfunctional isocyanate compound may be any compound having two or more isocyanate groups in one molecule, and examples thereof include the following. 2,6-
Tolylene diisocyanate, 2,4-tolylene diisocyanate, tolylene diisocyanate-trimethylolpropane adduct, t-cyclohexane-1,4-diisocyanate, m-phenylene diisocyanate, p
Phenylene diisocyanate, hexamethylene diisocyanate, 1,3,6-hexamethylene triisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate −
Hydrogenated diphenylmethane-4,4'-diisocyanate, lysine diisocyanate, lysine ester triisocyanate, triphenylmethane triisocyanate,
Tris (isocyanatephenyl) thiophosphate,
m-tetramethylxylylene diisocyanate, p-tetramethyl xylylene diisocyanate, 1,6,11
Polyisocyanates such as undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, bicycloheptane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like; Mixtures or adducts of polyhydric alcohols. Among them, from the viewpoint of versatility and reactivity,
6-tolylene diisocyanate, 2,4-tolylene diisocyanate, tolylene diisocyanate-trimethylolpropane adduct, and hexamethylene diisocyanate are preferred.

In addition, the crosslinking rate can be improved by adding a suitable amount of a known tertiary amine such as triethylenediamine or an organic tin compound such as dibutyltin dilaurate as a reaction accelerator.

As the thermally crosslinked layer of the epoxy resin, various types can be used. Among them, a layer obtained by thermally crosslinking a novolak type epoxy resin represented by the following formula (2) is preferable.

[0062]

Embedded image

Here, R ⁸ represents hydrogen or a methyl group, and R ⁹ represents hydrogen or a glycidyl phenyl ether group. In addition, q represents an integer from 1 to 50. In practice, the value of q generally has a distribution and is difficult to specify, but a larger average number is preferable, and a value of 3 or more, and more preferably 5 or more Is preferred.

As the curing agent for crosslinking such an epoxy resin, a known curing agent is applied. For example, curing agents such as amine-based polyaminoamides, acids and acid anhydrides, imidazole, mercaptan, and phenol resins are used. Among these, acid anhydrides and alicyclic amines are preferably used, and more preferably acid anhydrides. Examples of the acid anhydride include alicyclic acid anhydrides such as methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, aromatic acid anhydrides such as phthalic anhydride, and aliphatic acid anhydrides such as dodecenyl phthalic anhydride. Among them, methylhexahydrophthalic anhydride is particularly preferred. Incidentally, as the alicyclic amine, bis (4-amino-3-methyldicyclohexyl) methane, diaminocyclohexylmethane,
Examples include isophorone diamine, and bis (4-amino-3-methyldicyclohexyl) methane is particularly preferable.

When an acid anhydride is used as a curing agent, a reaction accelerator for accelerating the curing reaction between the epoxy and the acid anhydride may be added. Examples of the reaction accelerator include known second and third known compounds such as bendimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, pyridine and 1,8-diazabicyclo (5,4,0) undecene-1. Curing catalysts such as amines and imidazoles are exemplified.

As the thermally crosslinked layer of silicon alkoxide, it is preferred to use a mixture of two or more silicon alkoxides having 2 to 4 functionalities, more preferably 3 to 4 functionalities. Those which are appropriately hydrolyzed and dehydrated and condensed to suitably oligomerize are also preferably used.

Examples of usable silicon alkoxides include, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3 4, epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-
Examples include aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, and the like.

These silicon alkoxide layers are:
Crosslinking proceeds thermally, but the degree of crosslinking can be further increased by irradiating the coating film with actinic rays such as ultraviolet rays as necessary.

These protective layers are laminated directly on a substrate made of an organic polymer or via an appropriate intermediate layer. As such an intermediate layer, for example, a layer having a function of improving the adhesion between the protective layer and the substrate, or a K layer described later.
Various phase compensation layers such as a layer having a negative three-dimensional refractive index characteristic, a layer having a viscoelastic property to relieve stress (vertical stress, horizontal stress) applied to a substrate, for example, a storage elastic modulus near room temperature. A layer having a thickness of about 1 kg / mm ² or less, a layer having a function of preventing moisture or air from permeating or absorbing moisture or air, a layer having a function of absorbing ultraviolet rays or infrared rays, A layer having a function of reducing the concentration is preferably used.

The actual method of coating the protective layer on the substrate is as follows. The precursor composition of the resin cross-linked product and the filler are dissolved in various organic solvents, and a coating liquid whose concentration and viscosity are adjusted is used. After coating on the object, the layer is cross-linked by radiation irradiation, heat treatment or the like. Examples of the coating method include a microgravure coating method, a Meyer bar coating method, a direct gravure coating method, a reverse roll coating method, a curtain coating method, a spray coating method, a comma coating method, a die coating method, a knife coating method, a spin coating method, and the like. Various coating methods are used.

In the present invention, if necessary, the surface of the substrate made of an organic polymer or the surface of various coating layers coated on the substrate is preferably made to have an appropriate unevenness.

One of the purposes is to improve the slipperiness of the substrate or the laminated substrate on which the various coating layers and the transparent conductive layer are laminated, and to prevent the substrate from moving in close contact with the substrate surface or the substrate surface or a flat plate. Prevention of blocking phenomenon, prevention of seizure of electrodes, improvement of unwinding and winding of substrate in roll-to-roll process, and handling on worktable (flat plate) in single wafer process Can be increased.

Another object is to appropriately scatter light reflected on the surface of the transparent conductive layer.
That is, when the flatness of the surface of the transparent conductive layer is high, light interference fringes (Newton rings) resulting from mutual interference of the reflected lights on the transparent conductive layer surfaces of the pair of transparent electrode substrates disposed as a transparent tablet relative to each other. May be observed with the naked eye, and the visibility of the tablet may be reduced.However, if the surface of the transparent conductive layer has moderate irregularities, the optical interference fringes become unclear and the visibility is reduced. Can be suppressed.

When the reflectance of the surface of the transparent conductive layer is reduced by laminating the optical interference layer as in the present invention, the optical interference fringes are generated even if the degree of the unevenness is relatively weak. There is a feature that is effectively suppressed.

Here, in the case of the transparent conductive laminate of the present invention, the surface roughness of the surface of the transparent conductive layer suitable for the above requirements is approximately 0.02 to 0.04 in center line surface roughness SRa.
A range of 5 μm is preferred. When the SRa value is less than 0.02 μm, the effect of obscuring the optical interference fringes tends to be insufficient. Conversely, when the SRa value exceeds 0.05 μm, light scattering on the surface of the transparent conductive layer is caused. The resilience is significantly increased, and disadvantages such as blurring of the displayed image and reduction in the transmittance of the laminate are likely to occur.

Still another object is to provide an anti-glare property by appropriately scattering extraneous light (sunlight, indoor illumination light, etc.) reflected on the surface of the substrate on which input is made with a pen or the like. No. That is, when the surface of the substrate on which this input is made is flat and high, extraneous light is specularly reflected on the surface, so that a so-called reflection phenomenon is likely to occur, and the visibility of the tablet may be reduced. Many. On the other hand, when the surface has moderate unevenness, extraneous light is appropriately scattered and reflected on the surface, and the reflection phenomenon is suppressed, that is, antiglare property is exhibited.

Note that the surface of the substrate on which this input is made is
The reflection phenomenon can also be reduced by laminating an optical interference layer having a function of reducing the reflectance mainly in the wavelength region of 450 to 650 nm. In some cases, such an optical interference layer is laminated on the surface. This is also preferably performed. In this case, the surface may be somewhat flat, but more preferably the surface has relatively weak irregularities. As a material and a forming method for forming such an optical interference layer, the same material and a forming method as those of the optical interference layer to be laminated as a base of the above-described transparent conductive layer are preferably used.

There are various methods for making the surface of the substrate made of an organic polymer or the surface of the protective layer or the optical interference layer coated on the substrate moderately uneven, and for example, there are various methods. A method of forming and shaping the substrate and various coating layers using a mold, a method of applying mechanical processing such as embossing and sandblasting, and dispersing an appropriate amount of fine particles (filler) in the substrate and various coating layers. And the like.

In particular, a method of mixing an appropriate amount of fine particles in a dispersed state in a protective layer or an optical interference layer coated on a substrate is most preferable from the viewpoint of simplicity of the process, stability and the like.

In this case, it is necessary to minimize a decrease in coating strength, an increase in light scattering, and a deterioration in appearance of the coating due to the dispersion of the fine particles. About 1.0 to 2.0 times, more preferably about 1.0 to 1.5 times, most preferably 1.1 to 1.3 times the film thickness of A method using a combination of a resin component and a fine particle which has an average particle diameter of 0.3 μm or less and in which the fine particles are aggregated with an aggregate diameter of about 5 μm or less, more preferably 3 μm or less in a coating film, may be mentioned.

In the former method, the mixing amount of the fine particles is preferably in the range of about 0.05 to 5.0%, more preferably 0.1 to 3.0% by weight. If the mixing amount is less than 0.05%, sufficient slip properties cannot be obtained in many cases, and if it exceeds 5.0%, the light scattering property is remarkably increased, and the visibility of the tablet may be reduced. It is not preferable because there are many.

In the latter method, the mixing ratio of the fine particles is about 0.5 to 30% by weight, more preferably 0.5 to 30%.
It is preferably in the range of 範 囲 20%. 0.5% mixture
If less than 30%, sufficient slip properties cannot be obtained in many cases, and if it exceeds 30%, light scattering properties often increase remarkably, and cracks and the like of the coating film may occur, which is not preferable.

As the type of the fine particles, it is preferable to use those which hardly cause sedimentation of the fine particles in the coating liquid, and specifically, commercially available organic silicon fine particles, crosslinked acrylic fine particles, crosslinked polystyrene fine particles and the like are preferably used.

According to the present invention, by using the above-mentioned transparent conductive laminate as at least one electrode substrate, it is possible to provide a tablet having little reflection and coloring and good transparency. Here, when the transparent conductive laminate of the present invention is used for a pair of electrode substrates of a tablet, that is, both a movable electrode substrate and a fixed electrode substrate, the effect intended by the present invention becomes particularly remarkable. The effect can be obtained even if it is used for only one of the fixed electrode substrate and the fixed electrode substrate. For example, it is possible to obtain good visibility even in a tablet configuration using a transparent electrode laminate of the present invention for a movable electrode substrate and a glass electrode substrate having a transparent electrode formed on a conventional glass plate for a fixed electrode substrate. it can.

According to the present invention, it is clear that the above problems can be solved by using a specific optical interference layer so as to exhibit the same performance as the transparent conductive laminate of the present invention. Was.

That is, second, in a transparent conductive laminate in which a transparent conductive layer is laminated on the outermost surface of at least one surface of a substrate made of an organic polymer, in order from the substrate side,
(A2) The refractive index of 1.7 to the refractive index of the transparent conductive layer +0.
3 layer (H ₂ layer), (B2) a refractive index of 1.3
Layers in the range of 5 to 1.5 (L ₂ layers), is (C) a thickness of 1
A transparent conductive layer having a thickness in the range of _{2 to} 30 nm;
(F) the average reflectance of the laminated surface of the transparent conductive layer at a wavelength of 450 to 650 nm is 5.5%.
And (G) the L ^* a ^* b ^* color system chromaticity index b ^* value of the transmitted light of the laminate specified in Japanese Industrial Standard Z8729 is approximately in the range of 0 to 2. Achieved by the transparent conductive laminate featured.

The transparent conductive laminate has a specific optical interference layer on a substrate made of an organic polymer, and a transparent conductive layer formed thereon. That is, at least from the substrate side, (A2) H ₂ layer: refractive index is in the range of approximately 0.3 refractive index larger than the refractive index of 1.7 or more transparent conductive layer, (B2) L ₂ layer: refractive index (C) transparent conductive layer: film thickness of 12 to 30 nm
Are stacked in this order. If the refractive indices of the H ₂ layer and the L ₂ layer are out of the above range, the effect of reducing the reflectance of the surface of the transparent conductive layer laminated on the L ₂ layer is undesirably reduced.

Then, in the above transparent conductive laminate,
(E) reflectance of the L ₂ layer surface wavelength 260-390
By having the minimum point in the region of nm, a transparent conductive laminate having good color and low reflectance can be obtained.

Further, the above-mentioned transparent conductive laminate is provided with (D)
It is desirable that the sum of the optical thicknesses of the three layers is approximately 180 to 230 nm. Here, the optical film thickness is a value obtained by multiplying the refractive index of the layer by the film thickness as described above, and the sum of the optical film thicknesses of the H ₂ layer, the L ₂ layer, and the transparent conductive layer is approximately 180 to 230 n.
By laminating the three layers in a combination that gives m, a transparent conductive laminate having good color and low reflectance can be obtained.

The thickness of the H ₂ layer is preferably in the range of 20 to 90 nm. The L ₂ layer preferably has a thickness in the range of 30 to 110 nm.

The transparent conductive layer, the substrate made of an organic polymer, and the protective layer constituting the transparent conductive laminate are the same as those described above.

Further, according to the present invention, the above problems can be solved by using a single layer of a specific optical interference layer so as to exhibit the same performance as the transparent conductive laminate of the present invention. It became clear.

That is, the present invention thirdly provides a transparent conductive laminate in which a transparent conductive layer is laminated on the outermost surface of at least one surface of an organic polymer substrate, wherein the refractive index of the substrate is 1.7. be more than, in order from the least substrate side, and (A3) refractive index in the range of 1.35 to 1.5 layer thickness is in the range of 10 to 30 nm (L ₃ layer), (C
3) a transparent conductive layer having a thickness in the range of 12 to 30 nm is laminated, and (F) a wavelength 4
The average reflectance at 50 to 650 nm is 5.5% or less, and (G) Japanese Industrial Standard Z87 of the transmitted light of the laminate.
The transparent conductive laminate is characterized in that the chromaticity index b ^* value of the L ^* a ^* b ^* color system defined in No. 29 is in the range of approximately 0 to 2.

The transparent conductive laminate has a single layer of a specific optical interference layer on a substrate made of an organic polymer, and a transparent conductive layer is further formed thereon. That is, (A3) the refractive index is 1.35 to 1.5 at least from the substrate side.
Layer (L) having a film thickness in the range of 10 to 30 nm.
( ₃ layers) and (C3) a transparent conductive layer having a thickness in the range of 12 to 30 nm are laminated in this order. If the refractive index of the L ₃ layer is outside the above range, the effect of reducing the reflectance of the surface of the transparent conductive layer laminated on the L ₃ layer on decreases undesirably.

In the transparent conductive laminate,
When the refractive index of the substrate (layer serving as a base of the optical interference layer) is 1.7 or more, for example, a substrate such as a biaxially stretched polyethylene naphthalate film (in-plane refractive index of about 1.76), The optical interference layer has a single layer structure having a refractive index of 1.35 to 1.5 and a film thickness in the range of about 10 to 30 nm, so that the transmittance is high and the hue is good. Here, when the refractive index of the substrate is less than 1.7, it is difficult to keep the b ^* value of the transmitted light of the laminated body in the range of 0 to 2 when the optical interference layer having the single-layer structure is laminated. However, only when the refractive index of the substrate is 1.7 or more, the b ^* value is set to 0 to 2
And the reflectance of the transparent conductive layer surface is 5.5%.
In some cases, it may be possible to:

In the transparent conductive laminate, the L ₃ layer preferably has a surface reflectance of 260 to 39 wavelengths.
By having the minimum point in the region of 0 nm, a transparent conductive laminate having good color and low reflectance can be obtained.

As the transparent conductive layer, the organic polymer substrate, and the protective layer constituting the transparent conductive laminate, the same as those described above are used.

Hereinafter, embodiments of the present invention will be described. The evaluation of various characteristics in the following examples and comparative examples was performed in the following manner.

Total light transmittance and haze value: Measurement was performed using a measuring instrument (trade name “COH-300A”) manufactured by Nippon Denshoku Industries Co., Ltd.

Measurement of transmission spectrum, reflection spectrum, reflectance, and calculation of color (b ^* value): Measurement of each spectrum and calculation of color were performed using an integrating sphere measurement mode and a calculation program of Hitachi U3500 spectrophotometer. went. The angle of incidence of the measurement light on the sample was 0 degree in the transmission mode and 10 degrees in the reflection mode. In the measurement in the reflection mode, a light-shielding layer was formed on the back side of the sample using a commercially available black spray, The measurement was performed in a state where there was almost no reflection of light from the back surface or incidence of light from the back surface side. In calculating the reflection color, the light source is Japanese Industrial Standard Z.
The measurement was carried out under the condition of a 2-degree visual field, employing the standard light D ₆₅ specified in 8720.

Evaluation of solvent resistance: The evaluation was performed according to the method described in the specification.

Evaluation of hard coat property: Japanese Industrial Standard K5
The pencil hardness was measured under a load of 1 kg according to the standard 400.

Refractive index and thickness of each layer: The optical interference layer and the transparent conductive layer are laminated as a single layer on a suitable thermoplastic film substrate having a different refractive index from these layers under the same coating conditions. It was calculated by an optical simulation using the wavelength of the maximum peak or the minimum peak of the reflectivity, which appears on the light reflection spectrum of the laminated surface based on the light interference effect, and the value of the peak reflectivity. The refractive index of the protective layer was measured using an Abbe refractometer, and the thickness of the protective layer was determined by calculation using the same optical interference method as that for the optical interference layer.

Example 1 Biaxially stretched polyethylene terephthalate (PET) film having a thickness of about 75 μm (HSL-75 manufactured by Teijin Limited, in-plane refractive index: about 1.64, pencil hardness F)
An optical interference layer consisting of two layers was laminated on one side of the above.

That is, first, tetrabutoxy titanate (trade name “B-4” manufactured by Nippon Soda Co., Ltd.) was converted into ligroin (a first-grade product manufactured by Wako Pure Chemical Industries) and butanol (a special grade manufactured by Wako Pure Chemical Industries) Roll coating was performed using a coating solution diluted with the mixed solvent of (Product) and heat-treated at 130 ° C. for 2 minutes to form a layer having a thickness of about 41 nm and a refractive index of about 1.82.

Next, the layer was roll-coated with a coating solution having the following composition and heat-treated at 130 ° C. for 5 minutes to form a layer having a thickness of about 51 nm and a refractive index of about 1.47. That is, 720 parts by weight of water and 2-propanol 108
After mixing 0 parts by weight and 46 parts by weight of acetic acid, 480 parts by weight of γ-glycidoxypropyltrimethoxysilane (trade name “KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) and methyltrimethoxysilane (trade name manufactured by Shin-Etsu Chemical Co., Ltd.) "KBM13") 2
40 parts by weight and N-β (aminoethyl) γ-aminopropyltrimethoxysilane (trade name “KBM manufactured by Shin-Etsu Chemical Co., Ltd.
603 ") 120 parts by weight are sequentially mixed and stirred for 3 hours to carry out hydrolysis and partial condensation of the alkoxysilane mixture, and further dilute with a mixed solvent of isopropyl alcohol and 1methoxy-2-propanol at a weight ratio of 1: 1. To form a coating liquid for forming the layer. The surface of the film on which the optical interference layer was laminated had good solvent resistance.

Next, a transparent conductive layer was laminated on the surface of the film on which the optical interference layer was laminated, to produce a transparent conductive film. As the transparent conductive layer, an indium-tin oxide (ITO) was used, and the layer was formed to have a thickness of about 22 nm by a DC magnetron sputtering method. That is, an ITO target having a composition of indium oxide and tin oxide in a weight ratio of 95: 5 and a packing density of 98% was used as a target, the film was set in a sputtering apparatus, and then exhausted to a pressure of 1.3 mPa. A mixed gas of Ar and O _{2 at} a volume ratio of 98.5: 1.5 was introduced, and the atmospheric pressure was adjusted to 0.27 Pa. Then, sputtering was performed under the conditions of a film temperature of 50 ° C. and an input power density of 1 W / cm ² , and a transparent conductive layer of ITO was laminated on the optical interference layer. The surface resistance of this transparent conductive layer is about 230
Ω / □, and the refractive index was about 2.0. Table 1 shows the optical characteristics of this transparent conductive film.

Example 2 A biaxially stretched polyethylene terephthalate film having a thickness of about 188 μm (OFW manufactured by Teijin Limited)
Example 1 except that protective layers were laminated on both surfaces of -188, an in-plane refractive index of about 1.65, and a pencil hardness of F) as follows.
A transparent conductive film was prepared in the same manner as described above.

That is, 50 parts by weight of polyester acrylate (M8560 manufactured by Toagosei Chemical) and dipentaerythritol hexaacrylate (DPH manufactured by Nippon Kayaku Co., Ltd.) were provided on the film surface on the side where the optical interference layer and the transparent conductive layer were laminated.
A) 50 parts by weight, 7 parts by weight of a photoinitiator (Irgacure 184 manufactured by Ciba Geigy), 0.03 part by weight of silicone oil (SH28PA manufactured by Dow Chemical Toray), 200 parts by weight of 1 methoxy-2-propanol as a diluting solvent Perform roll coating using the coating liquid,
After drying the solvent at 60 ° C. for 1 minute, the lamp intensity is 16
Using a high-pressure mercury lamp of 0 W / cm, the integrated light amount is about 600 mJ.
The coating layer was cured by irradiating ultraviolet rays under the condition of / cm ² , and a protective layer having a thickness of about 4.3 μm and having a smooth surface was laminated.

On the other side of the film, the average particle diameter of the coating liquid composition was about 4.5 μm as a filler.
Is coated in the same manner as described above using a coating liquid containing 2.0 parts by weight of silicone cross-linked fine particles (Tospearl 145 manufactured by Toshiba Silicone Co., Ltd.), and has a film thickness of about 4.1 μm and a uniform fine surface. A protective layer having irregularities was laminated.

The refractive index of these protective layers was about 1.53 according to Abbe refractometer, the pencil hardness on the film was 2H, and the solvent resistance was good. The surface of the protective layer on which the fine irregularities were formed had good antiglare properties.

Further, Example 1 was formed on the protective layer having a smooth surface.
An optical interference layer and a transparent conductive layer were laminated in exactly the same manner as in the above to prepare a transparent conductive film. Table 1 shows the optical characteristics of the film.

[Example 3] A biaxially stretched polyethylene terephthalate film having a thickness of about 75 µm (OFW-
A transparent conductive film was produced in exactly the same manner as in Example 1 except that protective layers were laminated on both surfaces of 75, a refractive index of 1.64, and a pencil hardness of F) as follows.

That is, on the film surface on which the optical interference layer and the transparent conductive layer are laminated, 50 parts by weight of polyester acrylate (M8560, manufactured by Toagosei Chemical) and dipentaerythritol hexaacrylate (DPH, manufactured by Nippon Kayaku)
A) 50 parts by weight, average particle size of about 3.0 μm as a filler
1.0 parts by weight of silicone cross-linked fine particles (Tospearl 130 manufactured by Toshiba Silicone), 7 parts by weight of a photoinitiator (Irgacure 184 manufactured by Ciba Geigy), and silicone oil (SH28PA manufactured by Dow Chemical Toray) as a leveling agent
Roll coating was performed using a coating solution consisting of 0.03 parts by weight and 200 parts by weight of 1-methoxy-2-propanol as a diluting solvent. After drying the solvent at 60 ° C. for 1 minute, a high-pressure mercury lamp having a lamp intensity of 160 W / cm was used. The coating layer was cured by irradiating ultraviolet rays under the conditions of an integrated light quantity of about 600 mJ / cm ² , and a protective layer having a thickness of about 2.7 μm and having fine irregularities uniformly formed on the surface was laminated.

On the other side of the film, coating was carried out in the same manner as described above, using a coating liquid having a composition not containing the silicone crosslinked fine particles of the coating liquid composition, and a film thickness of about 2.7 μm. A protective layer having a smooth surface was laminated.

The pencil hardness of the protective layer on the film was H or 2H, and the solvent resistance was good.

Further, the optical interference layer and the transparent conductive layer were laminated on the protective layer having the above-mentioned uneven surface uniformly formed in the same manner as in Example 1 to form a transparent conductive film. Table 1 shows the optical characteristics of this film.

A transparent tablet prepared by a known method using this transparent conductive film as a movable electrode substrate, and using a glass plate having a thickness of 1.1 mm and a transparent conductive layer of ITO laminated on one side as a fixed electrode substrate. Was observed under a commercially available three-wavelength fluorescent lamp, and no occurrence of light interference fringes (Newton's ring) was observed, and the visibility was excellent.

Example 4 The same procedure as in Example 1 was repeated except that the thickness of the cured layer of titanium alkoxide was 47 nm and the thickness of the cured layer of silicon alkoxide was 57 nm. A functional film was prepared. Table 1 shows the optical characteristics of this film.

Example 5 A transparent conductive film was formed in the same manner as in Example 1 except that the thickness of the cured layer of titanium alkoxide laminated in Example 3 was changed to 74 nm, and the thickness of the cured layer of silicon alkoxide was changed to 30 nm. A functional film was prepared. Table 1 shows the optical characteristics of this film.

Example 6 The same procedure as in Example 1 was carried out except that the thickness of the hardened layer of titanium alkoxide was 38 nm and the thickness of the hardened layer of silicon alkoxide was 47 nm. A functional film was prepared. Table 1 shows the optical characteristics of this film.

[Example 7] A cured layer of titanium alkoxide laminated in Example 3 had a thickness of 53 nm, a cured layer of silicon alkoxide had a thickness of 65 nm, and a transparent conductive layer had a thickness of 15 nm. A transparent conductive film was produced in exactly the same manner as in Example 1. Table 1 shows the optical characteristics of this film.

[Embodiment 8] A film having a thickness of about 34 nm and a refractive index of about 2.
2 zirconium oxide layers were formed. That is, after using a titanium oxide target having a packing density of 90% as a target and setting the film in a sputtering apparatus,
The gas was evacuated to a pressure of mPa, and a mixed gas of Ar and O2 in a volume ratio of 98: 2 was introduced.
Pa. Then, sputtering was performed under the conditions of a film temperature of 50 ° C. and an input power density of 1 W / cm ² , and a zirconium oxide layer was laminated.

Next, a silicon oxide layer having a thickness of 51 nm and a refractive index of about 1.46 was formed by DC magnetron sputtering. That is, using a silicon target as a target, setting the film in a sputtering apparatus, evacuating to a pressure of 1 mPa, and then Ar and O ₂
Was introduced at a volume ratio of 70:30, and the atmospheric pressure was set to 0.27 Pa. Then, sputtering was performed at a film temperature of 50 ° C. and an input power density of 1 W / cm ² , and a silicon oxide layer was laminated.

Thereafter, a transparent conductive film of indium oxide having a thickness of 22 nm and a refractive index of 2.0 was laminated in the same manner as in Example 1 to form a transparent conductive film. Table 1 shows the optical characteristics of this film.

Example 9 A substrate having a thickness of about 100 μm
m polycarbonate film (Teijin Pure Ace,
(Refractive index: 1.586, pencil hardness: 6B or less, in-plane retardation: 10 nm or less) On both surfaces, a protective layer is laminated in exactly the same manner as in Example 3, and an optical interference layer is formed on one surface of the protective layer in exactly the same manner as in Example 3. And a transparent conductive layer were laminated to form a transparent conductive film. The pencil hardness of these protective layers on the film was B, and the solvent resistance was also good. Table 1 shows the optical characteristics of this film.

Comparative Example 1 The procedure of Example 3 was repeated except that the cured layer of titanium alkoxide and the cured layer of silicon alkoxide were not laminated, and the transparent conductive layer was laminated directly on the PET film. A conductive film was created. Table 1 shows the optical characteristics of this film.

Comparative Example 2 The same procedure as in Example 3 was repeated except that the thickness of the cured layer of titanium alkoxide was 55 nm and the thickness of the cured layer of silicon alkoxide was 66 nm. A functional film was prepared. Table 1 shows the optical characteristics of this film.

Comparative Example 3 A transparent conductive film was formed in the same manner as in Example 3 except that the thickness of the cured layer of titanium alkoxide was 34 nm and the thickness of the cured layer of silicon alkoxide was 42 nm. A functional film was prepared. Table 1 shows the optical characteristics of this film.

[Comparative Example 4] As in Comparative Example 1, a transparent conductive layer was directly laminated on a PET film without laminating a cured layer of titanium alkoxide and a cured layer of silicon alkoxide. A transparent conductive film was produced in the same manner as in Comparative Example 1 except that the thickness was changed to 15 nm. Table 1 shows the optical characteristics of this film.

Example 10 A single-layer optical interference layer was laminated on one side of a biaxially stretched polyethylene naphthalate (PEN) film having a thickness of about 100 μm (in-plane refractive index: about 1.76, pencil hardness F). . That is, roll coating was performed using the same coating liquid with silicon alkoxide as used in Example 1, and heat treatment was performed at 130 ° C. for 5 minutes to obtain a film thickness of about 2
A layer having a thickness of 5 nm and a refractive index of about 1.47 was formed.

Next, as in Example 7, a transparent conductive layer made of ITO having a thickness of about 15 nm was laminated to produce a transparent conductive film. Table 1 shows the optical characteristics of this film.

[0133]

[Table 1]

Note: The measured value of the reflectivity tends to show a value slightly larger than the actual value due to the influence of stray light, back reflection of the sample, and the like. (Measurement error is within about 0.3%)

[0135]

The transparent conductive laminate of the present invention has the features that the reflectance of the surface of the transparent conductive layer is low and the transmitted light of the laminate is less colored. Very good visibility can be obtained with the created transparent tablet.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) H01B 5/14 H01B 5/14 A F term (Reference) 2H092 GA62 HA03 NA25 NA28 PA01 PA10 4F100 AA20B AA20C AA21B AA21C AK01A AK42A AR00B AR00C AR00D BA04 BA07 BA25 EJ38A GB41 JG01B JG01C JG01D JN01B JN01C JN01D JN06B JN06C JN06D JN18C JN30B JN30C JN30D YY00B YY00C YY00D 4K029AA11 BC02 AA13 BC

Claims (12)

[Claims] 1. A transparent conductive laminate having a transparent conductive layer laminated on the outermost surface of at least one surface of a substrate made of an organic polymer, wherein in order from the substrate side, (A1) a refractive index of 1.7 a layer thickness in the range of the refractive index +0.3 of the transparent conductive layer is in the range of 20 to 90 nm (H ₁ layer), (B
1) The refractive index is in the range of 1.35 to 1.5 and the film thickness is 30
Layers in the range of ~110nm (L ₁ layer), (C) a thickness transparent conductive layer in the range of 12～30Nm, is laminated, (D) sum of the optical thickness of said third layer is approximately 180-2
(F) the average reflectance of the laminated surface of the transparent conductive layer at a wavelength of 450 to 650 nm is 5.5%.
And (G) the L ^* a ^* b ^* color system chromaticity index b ^* value of the transmitted light of the laminate specified in Japanese Industrial Standard Z8729 is in the range of approximately 0 to 2. Characteristic transparent conductive laminate. 2. The transparent conductive laminate according to claim 1, wherein the H ₁ layer and / or the L ₁ layer is a layer obtained by mainly hydrolyzing and condensing a metal alkoxide. 3. The L ₁ layer is a layer mainly formed by hydrolyzing and condensing silicon alkoxide, and the H ₁ layer is a layer mainly formed by hydrolyzing and condensing titanium alkoxide and / or zirconium alkoxide. The transparent conductive laminate according to claim 1. (E) The reflectance of the surface of the L ₁ layer is 26 wavelengths.
A minimum point in a range of 0 to 390 nm.
The transparent conductive laminate according to any one of the above. 5. A transparent conductive laminate in which a transparent conductive layer is laminated on the outermost surface of at least one surface of a substrate made of an organic polymer, wherein (A2) a refractive index from 1.7 in order from the substrate side. layers in the range of the refractive index +0.3 of the transparent conductive layer (H ₂ layer), a layer (B2) refractive index is in the range of 1.35-1.5 (L ₂ layers), is (C) a thickness transparent conductive layer in the range of 12～30Nm, is laminated, (E) said L ₂
The reflectance of the layer surface has a minimum point in the wavelength range of 260 to 390 nm, and (F) the wavelength 450 of the laminated surface of the transparent conductive layer
(G) L ^* a ^* b ^* chromaticity index b ^* value of L ^* a ^* b ^* color system defined by Japanese Industrial Standard Z8729 for the average reflectance at 体 650 nm of not more than 5.5%. Is in the range of approximately 0 to 2. 6. The transparent conductive laminate according to claim 5, wherein the H ₂ layer and / or the L ₂ layer is a layer mainly formed by hydrolyzing and condensing a metal alkoxide. 7. The L ₂ layer is a layer mainly formed by hydrolysis and condensation of silicon alkoxide, and the H ₂ layer is a layer mainly formed by hydrolysis and condensation of titanium alkoxide and / or zirconium alkoxide. The transparent conductive laminate according to claim 5 or 6, wherein (D) The sum of the optical thicknesses of the three layers is about 1
The transparent conductive laminate according to any one of claims 5 to 7, which has a range of 80 to 230 nm. 9. The transparent conductive laminate according to claim 1, wherein a protective layer composed of a resin crosslinked layer is laminated on one or both sides of a substrate composed of an organic polymer. 10. A transparent conductive laminate in which a transparent conductive layer is laminated on the outermost surface of at least one surface of an organic polymer substrate, wherein the substrate has a refractive index of 1.7 or more, and in order from the substrate side, and (A3) a layer having a refractive index There are thickness in the range of 1.35 to 1.5 in the range of 10 to 30 nm (L ₃ layer) is (C3) thickness 12 to 30
and a transparent conductive layer in the range of nm.
(F) a wavelength of 450 to 650 nm of the laminated surface of the transparent conductive layer
Has an average reflectance of 5.5% or less, and (G) L ^* defined by Japanese Industrial Standard Z8729 for light transmitted through the laminate.
a ^* b ^* Chromaticness index b ^* value of color system is about 0
A transparent conductive laminate characterized by being in the range of 1 to 2. 11. The transparent conductive laminate according to claim 10, wherein the L ₃ layer is a layer mainly formed by hydrolyzing and condensing silicon alkoxide. 12. A transparent tablet in which two transparent electrode substrates are disposed with their electrode surfaces facing each other, wherein the transparent conductive laminate according to claim 1 is used as at least one of the transparent electrode substrates. A transparent tablet characterized by the following.