JPH1024516A - Transparent conductive laminate and transparent tablet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make a transparent electrode substrate having good slidability and high light transmittance by laminating a surface roughening layer on the side on which a transparent conductive layer on a substrate the surface roughness of which is specified and specifying the surface roughness. SOLUTION: As for a transparent conductive laminate, in the transparent conductive laminate which is formed by laminating a transparent conductive layer on one surface of a substrate of an organic polymer molding, with regard to the surface roughness of the substrate, the average roughness of the central surface is made to be less than 0.003μm. A surface roughening layer is laminated on the side on which the transparent conductive layer on the substrate is laminated, and as the transparent conductive laminate, with regard to the surface roughness of the surface on the side on which the transparent conductive layer is laminated, the average roughness of the central surface is made to be 0.003-0.04μm. Concerning a transparent tablet, in a transparent tablet in which two transparent electrode substrates are arranged so that the electrode surfaces faces each other, the transparent conductive laminate is to be used as one transparent electrode substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive laminate in which a transparent conductive layer is laminated on one surface of a substrate made of an organic polymer molded product, and a method using the transparent conductive laminate. It is about the transparent tablet to be created.

[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.

Conventionally, transparent tablets have been arranged at regular intervals on a liquid crystal display. Recently, however, the upper part of the liquid crystal display has been used to reduce the weight and thickness, improve the transmittance, and reduce parallax. A tablet with an integrated input display, in which a tablet is inserted between a polarizing plate and a liquid crystal cell, is being studied.

[0004]

In the tablet integrated with input display, the tablet is sandwiched between two polarizing plates, so that the transparent electrode substrate used in the tablet is optically isotropic. There is a need. That is, when the optical isotropy of the transparent electrode substrate is inferior, there is a problem of a reduction in panel display performance such as a coloring phenomenon and a decrease in visibility due to the presence of retardation. In particular, an optically isotropic organic polymer film such as polycarbonate or polyarylate is preferably used because the transparent electrode substrate on the tablet needs flexibility. For the lower transparent electrode substrate, glass, the above-mentioned optically isotropic organic polymer film, organic polymer sheet, or the like is used.

[0005] Here, if the flatness of the conductive surface of these transparent electrode substrates is extremely high, there is a problem that an operation failure occurs such that the upper and lower transparent electrode substrates are in close contact with each other and difficult to separate during input. Also, regarding the surface opposite to the electrode surface,
When the flatness of the surface is extremely high, in various processes such as etching, printing, and heat sealing at the time of tablet production, it is difficult to separate the transparent electrode substrate from the line to be conveyed. Challenges arise.

Generally, in a transparent tablet of the resistive film type, when the distance between the upper and lower transparent electrode substrates is reduced, reflected light from both electrode surfaces interferes with each other, resulting in strong light interference fringes (Newton rings). May occur and visibility may be reduced. In order to prevent the light interference fringes, it is effective to roughen the electrode surface to an appropriate roughness to make the reflected light scattered. However, this method has a problem that the light transmittance and the visibility are reduced with an increase in the haze of the electrode substrate.

SUMMARY OF THE INVENTION The present invention has been made to solve these problems, and has as its object to obtain a transparent electrode substrate having excellent slipperiness and high light transmittance. It is an object of the present invention to obtain a transparent tablet having a high transmittance and a low haze, which is less likely to cause malfunction and optical interference fringes.

[0008]

Means for Solving the Problems The transparent conductive laminate of the present invention is formed on one surface of a substrate made of an organic polymer molded product.
In the transparent conductive laminate in which the transparent conductive layers are laminated, the substrate has a surface roughness of 0. 0 in center plane average roughness (SRa).
003 μm or less, a surface roughening layer is laminated on at least the side on which the transparent conductive layer is laminated on the substrate, and the surface roughness of at least the surface on which the transparent conductive layer is laminated is a transparent conductive laminate. 0.003 in center plane average roughness (SRa)
０．０0.04 μm. Further, the transparent tablet of the present invention is characterized in that the transparent conductive laminate of the present invention is used as at least one transparent electrode substrate in a transparent tablet in which two transparent electrode substrates are arranged with their electrode surfaces facing each other. And

That is, the transparent conductive laminate of the present invention is characterized in that a slippery layer is laminated on at least the conductive surface on an organic polymer molded product having excellent smoothness. Although slipperiness is generally considered to be related to the surface roughness of the substrate,
According to the study of the present inventors, the surface roughness of the laminate is determined by the center plane average roughness (SRa) in order to develop good lubricity.
Is preferably 0.003 μm or more,
It was found that when the thickness was less than 3 μm, the slipperiness was low and the above-mentioned problems often occurred. The center plane average roughness (SR
As a) increases, the haze value increases. For this reason, in the laminate of the present invention, the center plane average roughness (SRa) needs to be 0.04 μm or less.

[0010] Here, the center plane average roughness (SRa) is defined as the center line average roughness (R) described in JIS B0601.
This is a three-dimensional extension of a), and is defined as follows. First, a portion having an area Sm is extracted from the roughness curved surface on the center surface thereof, and the X-axis and the Y-axis are placed on the center surface of the extracted portion as orthogonal coordinate axes. Further, when an axis perpendicular to the center plane is defined as a Z-axis and the roughness surface is represented by z = f (x, y),
The value SRa (μm) obtained by the following equation (a) is called the center plane average roughness. Note that Lx · Ly = Sm in the following equation (A).

[0011]

(Equation 1)

For this reason, the center plane average roughness is 0.003 μm.
m, a substrate made of an organic polymer molded product having a particle size of less than m, for example, when an amorphous organic polymer molded product such as a polycarbonate or a polyarylate is used as a substrate, in which a filler is rarely added, By providing a roughening layer on the
The center plane average roughness (SRa) of the surface of the laminate is set to 0.
003 to 0.04 μm. In the present invention, in order to solve the above-mentioned problem, it is necessary that the roughened layer is laminated on at least the side on which the transparent conductive layer is laminated on the substrate. Further, depending on the use as the transparent conductive laminate, the surface roughening layer is formed on both sides of the substrate, and the surface roughness of the surfaces on both sides of the transparent conductive laminate is the center plane average roughness (SRa). More preferably, it is 0.003 to 0.04 μm.

The roughened layer can be provided by smooth processing, that is, processing for forming minute projections at an appropriate density on the substrate surface. In particular,
Examples include a method of coating a coating film in which fine particles are dispersed as a filler, and a method of applying mechanical processing such as embossing or sand blasting to a base material, but from the viewpoint of simplicity of the process, A method of coating a coating film in which fine particles are dispersed is preferably used.

Here, when coating a coating film in which fine particles as a filler are dispersed, it is necessary to minimize a decrease in coating film strength due to the dispersion of the filler and an increase in haze due to light scattering. According to the study of the present inventors, when a filler having an average primary particle size smaller than the film thickness of the coating film is used, it is necessary to add a large amount of the filler in order to develop the lubricity, which increases the haze and the coating film. It was found that adverse effects such as a decrease in strength were observed. This is considered to be because if the primary particle size of the filler is small, the proportion of the filler which is completely buried in the coating film and does not contribute to the surface roughening becomes extremely large. For these reasons, it is preferable to use a filler having a primary particle size larger than the film thickness of the coating film. However, if the primary particle size of the filler exceeds three times the film thickness, the fixability of the filler tends to decrease. For this reason, it is preferable that the average primary particle size of the fine particles used as a filler is in a range of about 1.1 to 3 times the thickness of the coating film.

[0015] The amount of the filler particles added to the coating film is preferably in the range of 0.05 to 0.5% by weight. If the amount is less than 0.05%, sufficient lubricity cannot be obtained, and if it exceeds 0.5%, haze unnecessarily increases, which is not preferable. As the fine particles to be added as such a filler, it is preferable to use those that hardly cause aggregation and sedimentation of the fine particles in the coating solution, and specifically, commercially available organic silicon fine particles, crosslinked acrylic fine particles, crosslinked polystyrene fine particles, and the like are preferably used. Can be

By the way, the roughened coating film (hereinafter referred to as a roughened layer) is used to evaluate the solvent resistance to an acidic aqueous solution or an alkaline aqueous solution used at the time of etching the conductive layer. More preferably, it has sufficient solvent resistance. Examples of the coating film having such solvent resistance include various resin crosslinking such as a radiation crosslinking layer of an acrylic resin, a thermal crosslinking layer of a phenoxy resin, a thermal crosslinking layer of an epoxy resin, and a thermal crosslinking layer of a silicon alkoxide. 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.

A radiation cross-linkable resin is a resin that undergoes cross-linking when irradiated with radiation such as ultraviolet rays or electron beams. A polyfunctional acrylate component having two or more acryloyl groups in a unit structure is contained 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 crosslinking the resin layer by irradiating 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 general formula (1) with a polyfunctional isocyanate compound. .

[0020]

Embedded image

Here, R ^{1 to} R ⁶ are the same or different hydrogen or an 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 containing 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, it is possible to improve the crosslinking speed by adding an appropriate 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 general formula (2) is preferable. .

[0025]

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.

Known curing agents are used as such a curing agent for crosslinking the epoxy resin. 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 preferable 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.

In coating the crosslinked resin layer, the precursor composition of the crosslinked resin and filler are dissolved in various organic solvents, and the coating solution is adjusted in concentration and viscosity. After coating on the layer, the layer is cross-linked by irradiation of radiation, heat treatment or the like. As a coating method,
Various coating methods such as a microgravure coating method, a die coating method, a reverse roll coating method, a curtain coating method, and a spin coating method are used.

As described above, the substrate made of an organic polymer molded product used in the present invention has a surface roughness of not more than 0.003 μm in center plane average roughness. Regarding the thickness of the molded product, when the transparent conductive laminate of the present invention is used as an upper electrode substrate of a transparent tablet, 50 to 400
μm, and when it is used as a lower electrode substrate, it may be in a range of 50 to 1000 μm.
It is preferable from the viewpoint of the operating characteristics, lightness, and lightness of the transparent tablet. Further, the retardation of the molded product is preferably 20 nm or less from the viewpoint of optical isotropy. Here, the retardation is the product of the refractive index difference Δn of the birefringence Δn and the film thickness d, and here, a multi-wavelength birefringence measuring device manufactured by JASCO Corporation (trade name “M-15”)
0 ”) at a wavelength of 590 nm.

Examples of these optically isotropic organic polymer molded articles include molded articles such as polycarbonate, polyarylate, polyethersulfone, and triacetyl cellulose. From the viewpoint of properties and the like, polycarbonate and polyarylate are more preferred. Examples of the molding method of the molded body include known methods such as a melt extrusion method, a solution casting method, and an injection molding method.From the viewpoint of obtaining excellent optical isotropy, particularly, a solution casting method is used. Preferably, molding is performed.

The transparent conductive layer used in the present invention may be a known one such as a layer made of tin oxide (SnO ₂ ) and / or indium oxide (In ₂ O ₃ ),
In particular, both compounds, ITO, are preferably used.
When it is necessary to reduce the power consumption of the tablet, it is preferable to use a transparent conductive layer having a relatively large specific resistance, and it is preferable to use SiO ₂ , TiO ₂ , Al ₂ O ₃ , Z
A transparent conductive layer to which a small amount of a metal oxide selected from rO ₂ , MgO, and ZnO is added is preferably used.

The thickness of such a transparent conductive layer is 10 to 50.
The range of nm is preferable from the viewpoint of the resistance value, the stability of the resistance value with time, and the transparency. Alternatively, these transparent conductive layers can be laminated using a known vapor deposition method such as a sputtering method, an ion plating method, a vacuum evaporation 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.

In the present invention, by laminating an optical interference layer as a base of the transparent conductive layer, it is possible to reduce the reflection on the conductive surface and increase the light transmittance of the laminate. Here, the optical interference layer is a layer formed by laminating one or two or more thin films having different refractive indexes from the adjacent layers. As a result of reflected light from each interface interfering with each other, the transparent conductive layer surface Is defined as a layer in which the film thickness and the refractive index of each layer are set so that the reflectance in particular, particularly the reflectance at a wavelength of 450 to 600 nm, is effectively reduced.

As such an optical interference layer, a single layer of a low refractive index layer having a refractive index of 1.5 or less or a high refractive index layer having a refractive index of 1.6 or more from the substrate side may be used. A laminate having a low refractive index layer having a refractive index of 1.5 or less is preferably used, and a laminate having three or more layers may be used as necessary.

These layers are formed by various vacuum film forming processes such as sputtering, vapor deposition, ion plating and CVD, wet coating such as roll coating, curtain coating and spin coating, and a combination thereof. Can be created.

Specifically, various inorganic dielectric layers such as MgF, SiO ₂ , and the like formed by using a vacuum film forming process.
CaF ₂ , NaF, Na ₃ AlF ₆ , LiF, Al ₂ O ₃ ,
CeF ₃ , LaF ₃ , NdF ₃ , TiO ₂ , MgO, PbF
₃ , ThO ₂ , ZrO ₂ , ZnS, SnO ₂ , In ₂ O ₃ , S
Examples include layers composed of b ₂ O ₃ , CeO ₂ , Nd ₂ O ₃ , Ln ₂ O _{3 and the} like, and a mixture thereof, and further, a resin cross-linked layer formed by using a wet coating method, for example,
Silicone, titanium, zirconium, tin, tantalum, indium and other simple metal alkoxides or a mixture thereof, a resin crosslinked layer formed by hydrolysis and dehydration condensation, and fine particles of various metal oxides having a particle size of several tens nm or less. And a resin crosslinked layer in which is dispersed.

Among these, from the viewpoint of manufacturing cost, it is preferable to use an optical interference layer formed of a resin cross-linked layer formed by the above-mentioned wet coating method. From the viewpoint of adhesion and stability, it is most preferable to use a crosslinked layer of titanium, zirconium and silicon alkoxide. Here, the crosslinked layer of alkoxide of titanium and zirconium mainly functions as a layer having a high refractive index in the optical interference layer, and the crosslinked layer of silicon alkoxide is mainly a layer having a low refractive index in the optical interference layer. It works.

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, for example, 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.

These silicon alkoxides are preferably used as a mixture of two or more kinds from the viewpoint of the mechanical strength, adhesion and solvent resistance of the layer. In particular, from the viewpoint of solvent resistance, all of the silicon alkoxides are used. The weight ratio of 0.1 in the composition.
It is preferable that the silicon alkoxide having an amino group in the molecule is contained in the range of 5 to 40%.

These metal alkoxides may be used as a monomer, or may be used after being subjected to hydrolysis and dehydration condensation in advance to be 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 and 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.

As described above, when the optical interference layer is laminated on the substrate side in contact with the transparent conductive layer, the light transmittance of the transparent conductive laminate is improved by several percent or more as compared with the case where the optical interference layer is not laminated. I do. When the transparent conductive laminate is used as the upper and lower electrode substrates of the transparent tablet, the light transmittance of the tablet is improved, and the occurrence of optical interference fringes (Newton rings) of the tablet is reduced. all right. This is presumed to be due to a synergistic effect between the reduction effect of the light interference intensity due to the decrease in the light reflectance of the upper and lower electrode surfaces and the scattering effect of the reflected light due to the fine unevenness of the roughened layer of the present invention. You. Here, the degree of surface roughening of the electrode surface in the present invention is very small, as compared with the conventional method using only the scattering effect of reflected light due to surface roughening, so that an increase in haze due to surface roughening is suppressed. , A highly visible transparent tablet can be obtained.

In the present invention, a structure is generally used in which an appropriate roughening layer is provided on an organic polymer molded product, and then an optical interference layer is laminated between the roughening layer and the transparent conductive layer. However, when using various resin crosslinked layers such as the above-mentioned metal alkoxide crosslinked layer as the optical interference layer, the optical interference layer can also serve as the roughened layer. That is, as at least one layer of the optical interference layer, fine particles having an average primary particle size in a range of from 0.05 to 0.5% by weight in the above-mentioned resin crosslinked layer in a range of 1.1 to 3 times the layer thickness. When a roughened layer in which is dispersed is used, the object of the present invention can be achieved with a simpler layer structure.

In the following Examples and Comparative Examples, various characteristics were evaluated in the following manner.

Organic solvent resistance: A few drops of toluene (special grade, manufactured by Wako Pure Chemical Industries, Ltd.), which is a solvent of a silver paste used for printing on the transparent conductive layer at the time of tablet preparation, is dropped on the sample surface, and the temperature is 25 ° C. After 3 minutes, the surface was visually observed for changes in appearance such as cloudiness, swelling, and dissolution. When no change was observed, it was determined that the composition had organic solvent resistance.

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

Acid-resistant aqueous solution: Several drops of an etchant (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 were visually observed. If no change was observed, it was determined that the composition had acid-resistant aqueous solution resistance.

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

Center plane average roughness (SRa): A three-dimensional surface roughness measuring instrument manufactured by Kosaka Laboratory Co., Ltd. (trade name "Surfcoder SE")
−30 KS ”), measuring width 200 μm, measuring length 1
The measurement was performed under the condition of mm.

[0056]

Example 1 Using a polycarbonate resin having an average molecular weight of 37,000 and comprising bisphenol A alone, a thickness of 98 μm, a center plane average roughness (SRa) of 0.0012 μm, and a retardation of 7 ± 2 nm by a solution casting method. Was obtained.

As a coating liquid for forming a roughened layer, trimethylolpropane ethylene oxide-modified acrylate (trade name “Aronix M-3” manufactured by Toa Gosei Chemical Co., Ltd.)
50 ") 100 parts by weight, 7 parts by weight of photoinitiator 1-hydroxycyclohexyl phenyl ketone (trade name" Irgacure 184 "manufactured by Ciba Geigy), average particle diameter 4.
A liquid obtained by mixing 0.1 parts by weight of 5 μm silicon resin fine particles (trade name “Tospearl 145” manufactured by Toshiba Silicone Co., Ltd.) and 200 parts by weight of 1-methoxy-2-propanol was used.

This coating solution was roll-coated on the above-mentioned polycarbonate film, dried at 60 ° C. for 1 minute, and then integrated with a high-pressure mercury lamp of 120 W / cm ² to obtain an integrated light amount of about 8%.
Curing is performed under the conditions of 00 mJ / cm ² and the film thickness is about 3.5.
A μm roughened layer was formed, followed by a similar roughened layer on the opposite side of the film.

When the above-mentioned various solvent resistance tests were performed on the surface on which the roughened layer was formed, no change in the appearance was observed, and the surface was excellent in solvent resistance.

Next, an indium-tin oxide layer was formed on one surface of the roughened layer by a sputtering method to produce a transparent conductive film. The sputtering target has a composition of indium and tin in a weight ratio of 9: 1 and a packing density of 90%.
Was used. After setting the film in the sputtering apparatus, the film was evacuated to a pressure of 1.3 mPa, and then the volume ratio of Ar to O ₂ was 98.5: 1.5.
Was introduced, and the atmospheric pressure was adjusted to 0.27 Pa. Then, the film temperature is 50 ° C. and the input power density is 1 W
DC sputtering was performed under the condition of / cm ² to laminate a transparent conductive layer. The thickness of this transparent conductive layer was about 19 nm, and the surface resistance was about 280 Ω / □.

The center surface average roughness (SRa) of the conductive layer surface of the transparent conductive film thus produced was 0.0045 μm, and the non-conductive surface side was 0.0043 μm.
The haze was 0.8% and the light transmittance was 87.4%.
In addition, even when the film surface opposite to the surface on which the conductive layer is laminated (hereinafter referred to as a non-conductive surface) is placed on a flat glass plate or the like, the film surface may not adhere to and be separated from the glass surface. Without any trouble, it was excellent in slipperiness.

Further, using the transparent conductive films thus produced as upper and lower electrode substrates, analog transparent tablets were produced by a known method. When an input test was performed on the tablet using a plastic input pen, no operation failure was observed in which the upper and lower electrode surfaces were in close contact with each other and did not separate.

[0063]

EXAMPLE 2 Tetrabutoxy titanate (trade name "B-4" manufactured by Nippon Soda Co., Ltd.) was applied on one side of a roughened layer laminated on both sides of the film in Example 1 by ligroin (manufactured by Wako Pure Chemical Industries, Ltd.). Roll coating using a coating solution diluted with a mixed solvent of butanol (a grade of a special grade manufactured by Wako Pure Chemical Industries, Ltd.) and butanol (a grade of a special grade), and heat-treated at 130 ° C. for 2 minutes to obtain a film thickness of about 70 nm. A layer having a refractive index of about 1.82 was formed.

Further, the layer was roll-coated with a coating liquid having the following composition and heat-treated at 130 ° C. for 2 minutes to form a layer having a thickness of about 45 nm and a refractive index of about 1.45. That is, γ-glycidoxypropyltrimethoxysilane (trade name “KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) and methyltrimethoxysilane (trade name “K” manufactured by Shin-Etsu Chemical Co., Ltd.)
BM13 ”) was mixed at a molar ratio of 1: 1 and the silane was hydrolyzed by a known method using an aqueous acetic acid solution (pH 3.0). For the silane hydrolyzate thus obtained,
N-β (aminoethyl) γ-aminopropyltrimethoxysilane (trade name “KBM603” manufactured by Shin-Etsu Chemical Co., Ltd.) was added at a weight ratio of the solid content of 20: 1, and isopropyl alcohol (Wako Pure Chemical Industries, Ltd.) was added. Was diluted with a mixed solvent of n-butanol (special grade manufactured by Wako Pure Chemical Industries, Ltd.) and n-butanol (special grade manufactured by Wako Pure Chemical Industries, Ltd.) to obtain a coating liquid for forming the layer.

When a solvent resistance test was performed on the surface on which the two layers were laminated, no change in appearance was observed, and the surface was excellent in solvent resistance.

Further, an indium-tin oxide layer having a thickness of about 19 nm and a surface resistance of about 280 Ω / □ was formed on the same surface in the same manner as in Example 1 to produce a transparent conductive film. The center plane average roughness (SRa) of the conductive layer surface of the transparent conductive film thus prepared is 0.0041 n.
m, haze was 0.8%, and light transmittance was 92.4%.

Next, in the same manner as in Example 1, the transparent conductive film was used as the upper and lower electrode substrates to produce an analog type transparent tablet. This tablet did not exhibit any malfunctions such that the upper and lower electrode surfaces were in close contact during input and did not separate. When the tablet was observed under a three-wavelength fluorescent lamp, light interference fringes (Newton rings) were almost observed. Did not.

[0068]

Example 3 On the polycarbonate film of Example 1, tetrabutoxy titanate (trade name "B" manufactured by Nippon Soda Co., Ltd.)
-4 ") The average primary particle size is 120 n with respect to 100 parts by weight.
0.45 parts by weight of silicon oxide fine particles of m. and further mixed with ligroin (a grade of first grade manufactured by Wako Pure Chemical Industries, Ltd.)
Roll coating with a coating solution diluted with a mixed solvent of butanol (a grade manufactured by Wako Pure Chemical Industries, Ltd.)
Heat treatment was performed at 130 ° C. for 5 minutes to form a layer having a thickness of about 64 nm and a refractive index of about 1.87.

Further, the layer was roll-coated with a coating solution having the following composition and heat-treated at 130 ° C. for 7 minutes to form a layer having a thickness of about 50 nm and a refractive index of about 1.45. That is, γ-glycidoxypropyltrimethoxysilane (trade name “KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) and methyltrimethoxysilane (trade name “KB manufactured by Shin-Etsu Chemical Co., Ltd.”
M13 ") in a molar ratio of 1: 1 and an aqueous solution of acetic acid (P
H about 3.0), and the silane was hydrolyzed by a known method. To the hydrolyzate of the silane thus obtained, N-β (aminoethyl) γ-aminopropyltrimethoxysilane (trade name “KBM603” manufactured by Shin-Etsu Chemical Co., Ltd.) was added at a weight ratio of solids of 20: 1. Further, the mixture is diluted with a mixed solvent of isopropyl alcohol (a grade manufactured by Wako Pure Chemical Industries, Ltd.) and n-butanol (a grade manufactured by Wako Pure Chemical Industries, Ltd.) to form a coating liquid for forming the layer. And

Here, when a solvent resistance test was performed on the surface on which the two layers were laminated, no change in appearance was observed, and the surface was excellent in solvent resistance.

Subsequently, an indium film having a thickness of about 19 nm and a surface resistance of about 280 Ω / □ was formed on the same surface in the same manner as in Example 1.
A tin oxide layer was formed to produce a transparent conductive film.
The center plane average roughness (SRa) of the conductive layer surface of the transparent conductive film thus prepared was 0.0061 nm, the haze was 0.7%, and the light transmittance was 91.4%.

Next, in the same manner as in Example 1, an analog type transparent tablet was produced using the transparent conductive film as the upper and lower electrode substrates. This tablet did not exhibit any malfunctions such that the upper and lower electrode surfaces were in close contact during input and did not separate. When the tablet was observed under a three-wavelength fluorescent lamp, light interference fringes (Newton rings) were almost observed. Did not.

[0073]

Comparative Example 1 A transparent conductive film was prepared in exactly the same manner as in Example 1, except that the silicone resin particles were not mixed in the coating solution used for forming the roughened layer. . The center plane average roughness (SRa) of the conductive layer surface of the transparent conductive film thus prepared was 0.001.
8 μm, 0.002 μm on the non-conductive surface side, and 0.3 haze
%, And the light transmittance was 87.8%. When the non-conductive surface of this transparent conductive film was placed on a flat glass plate, a phenomenon that the film was stuck to the glass surface and did not separate frequently occurred.

Further, using this transparent conductive film,
When an analog type transparent tablet was prepared and subjected to an input test in the same manner as in Example 1, operation failures such that the upper and lower electrode substrates were in close contact with each other and did not come apart frequently occurred, and light interference fringes (Newton rings) were generated. Occurrence was clearly observed.

[0075]

Comparative Example 2 Trimethylolpropane ethylene oxide-modified acrylate (trade name “Aronix M-3 manufactured by Toa Gosei Chemical Co., Ltd.) was used as a coating liquid for forming a roughened layer.
50 ") 100 parts by weight, 7 parts by weight of photoinitiator 1-hydroxycyclohexylphenyl ketone (trade name" Irgacure 184 "manufactured by Ciba Geigy), 0.5 part by weight of silica having an average primary particle size of about 100 nm, 1- Methoxy-2
-A transparent conductive film was prepared in exactly the same manner as in Example 1 except that a coating solution mixed with 130 parts by weight of propanol was used.

The center plane average roughness (SR) of the conductive surface and the non-conductive surface of the transparent conductive film thus prepared was
a) was 0.0023 μm, the haze was 0.5%, and the light transmittance was 87.6%. When the non-conductive surface of the transparent conductive film was placed on a flat glass plate or the like, a phenomenon often occurred in which the transparent conductive film was stuck to the glass surface and could not be separated.

Further, using this transparent conductive film,
An analog type transparent tablet was prepared in the same manner as in Example 1, and an input test was conducted. As a result, there were frequent operation failures in which the upper and lower electrode substrates came into close contact and did not separate.

[0078]

Comparative Example 3 Trimethylolpropane ethylene oxide-modified acrylate (trade name “Aronix M-3 manufactured by Toa Gosei Chemical Co., Ltd.”) was used as a coating liquid for forming a roughened layer.
50 ") 100 parts by weight, 7 parts by weight of a photoinitiator 1-hydroxycyclohexylphenyl ketone (trade name" Irgacure 184 "manufactured by Ciba Geigy Co., Ltd.), 3 parts by weight of silica having an average primary particle size of about 100 nm, 1-methoxy Other than using a coating liquid obtained by mixing 130 parts by weight of -2-propanol,
A transparent conductive film was produced in exactly the same manner as in Example 1.

The conductive surface and non-conductive surface of the transparent conductive film thus prepared have a center plane average roughness (SR
a) was 0.027 μm. Even when the non-conductive surface of this transparent conductive film was placed on a flat glass plate or the like, it did not stick to the glass surface and did not separate, and was excellent in slipperiness. Using this transparent conductive film, an analog-type transparent tablet was produced in the same manner as in Example 1, and an input test was performed. Did not.

However, the haze of this transparent conductive film was 4.1%, which was higher than that of Example 1, and the visibility of the tablet was lowered.

[0081]

The transparent conductive laminate of the present invention has excellent slipperiness on the conductive and non-conductive surfaces and low haze, and is extremely high by reducing surface reflection on the conductive surface. Light transmittance can be obtained. When this transparent conductive laminate is used as the upper and lower electrode substrates of the transparent tablet, a transparent tablet having less visibility and less occurrence of optical interference fringes and having excellent visibility can be obtained.

Claims (7)

[Claims] 1. A transparent conductive laminate having a transparent conductive layer laminated on one surface of a substrate made of an organic polymer molded product, wherein the substrate has a surface roughness having a center plane average roughness (SRa).
Is less than 0.003 μm, and a surface roughening layer is laminated on at least the side on which the transparent conductive layer is laminated on the substrate, and as a transparent conductive laminate, at least the surface of the surface on which the transparent conductive layer is laminated The roughness is 0.1 in terms of center plane average roughness (SRa).
003 to 0.04 μm. 2. The roughening layer is formed on both sides of the substrate, and the transparent conductive laminate has a surface roughness on both sides of 0.003 to 0.04 μm in center plane average roughness (SRa). The transparent conductive laminate according to claim 1, wherein: 3. A weight ratio of 0.05 to 0.05 in the roughened layer.
3. Fine particles having an average primary particle size in the range of 1.1 to 3 times the average thickness of the roughened layer are dispersed at a ratio of 0.5%. The transparent conductive laminate according to any one of the above. 4. The transparent conductive laminate according to claim 1, wherein an optical interference layer is laminated in contact with the transparent conductive layer on the substrate side of the transparent conductive layer. 5. The optical interference layer is formed by laminating one or more resin crosslinked layers, and the resin crosslinked layer is any one of silicon alkoxide, titanium alkoxide, zirconium alkoxide or a mixture selected from these alkoxides. The transparent conductive laminate according to claim 4, wherein the transparent conductive laminate comprises: 6. The optical interference layer according to claim 5, wherein at least one layer in the optical interference layer is laminated also as a roughening layer.
The transparent conductive laminate according to the above. 7. A transparent tablet in which two transparent electrode substrates are arranged 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 fact that