TW201411662A - Transparent electrode substrate, its manufacturing method and image display device - Google Patents

Abstract

A transparent electrode substrate includes: an insulation substrate; and a conductive layer formed at least on one side of the insulation substrate in the thickness direction. The conductive layer includes: a transparent conductive layer formed on one side of the insulation substrate in the thickness direction; a low-resistance layer formed on one side of the transparent conductive layer in the thickness direction for lowering the resistance of the conductive layer; and a protection layer formed with etching-friendly material on one surface of the low-resistance layer in the thickness direction. The etching friendly material is selected from at least one metal consisting of nickel, tin and nickel-copper alloy. The transparent conductive layer is formed with indium tin oxide. The low-resistance layer is formed with at least one metal selected from the group consisting of copper, silver and gold.

Description

Transparent electrode substrate, manufacturing method thereof and image display device

The present invention relates to a transparent electrode substrate, a method for producing the same, and an image display device, and more particularly to a method for producing a transparent electrode substrate, a transparent electrode substrate obtained by the method for producing the transparent electrode substrate, and the transparent substrate An image display device for an electrode substrate.

It is known that a transparent electrode substrate provided with a transparent electrode is used as a touch panel in an image display device such as a liquid crystal display device.

For example, a transparent electrode obtained by sequentially depositing a pattern of indium tin oxide (ITO, Indium Tin Oxides), a copper layer (copper single layer gold plating), and a gold layer (electrolytic gold plating layer) on a glass substrate is proposed. A substrate (for example, see Japanese Patent Laid-Open No. Hei 6-148661).

In the Japanese Patent Publication No. Hei 6-148661, the copper layer is protected by corrosion of the gold layer (electrolytic gold plating layer) on the outermost surface of the transparent electrode substrate.

However, depending on the use of the transparent electrode substrate, it is necessary to sequentially deposit an ITO layer, a copper layer, and a gold layer on the entire upper surface of the glass substrate, and then pattern these laminated portions into a desired shape by etching.

However, since the gold layer is difficult to etch due to high chemical stability, there is a problem that the layered portion cannot be patterned into a desired shape.

An object of the present invention is to provide a transparent electrode substrate including a conductor layer which can be easily patterned, a method for producing the same, and an image display device.

The transparent electrode substrate of the present invention includes: an insulating substrate; and a conductor layer formed on one side of at least one of thickness directions of the insulating substrate; and the conductor layer includes: a transparent conductor layer formed on the insulating substrate One side in the thickness direction; a low resistance layer formed on one side of the thickness direction of the transparent conductor layer for reducing the resistance of the conductor layer; and a protective layer formed of the easy-etching material at the low resistance One of the above thickness directions of the layer.

Further, in the transparent electrode substrate of the present invention, it is preferable that the easily etchable material is at least one selected from the group consisting of nickel, tin, and nickel-copper alloy.

Further, in the transparent electrode substrate of the present invention, it is preferable that the transparent conductor layer is formed of indium tin oxide, and the low resistance layer is formed of at least one metal selected from the group consisting of copper, silver, and gold. .

Further, in the transparent electrode substrate of the present invention, it is preferable that the transparent conductor layer is formed on one surface of the insulating substrate on one side in the thickness direction, and the low resistance layer is formed in the thickness direction of the transparent conductor layer. One of the entire surfaces is formed, and the protective layer is formed on one surface of the low-resistance layer in the thickness direction.

Further, in the transparent electrode substrate of the present invention, it is preferable that the conductor layer is formed as a conductor pattern on the insulating substrate.

Further, in the transparent electrode substrate of the present invention, preferably, the conductor pattern includes: a lead wire including the conductor layer; and a transparent electrode formed continuously with the lead wire and including the transparent conductor layer.

Moreover, the method for producing a transparent electrode substrate of the present invention includes the steps of: preparing a laminate comprising an insulating substrate and a transparent conductor layer laminated on at least one of the thickness directions of the insulating substrate; Step, which will be low The resist layer is laminated on one side of the thickness direction of the transparent conductor layer, and a protective step is formed by forming a protective layer on the surface of the low-resistance layer in one of the thickness directions.

Moreover, it is preferable that the method for producing a transparent electrode substrate of the present invention further includes a patterning step of performing the protective layer on the conductor layer including the transparent conductor layer, the low resistance layer, and the protective layer. Etching forms a conductor pattern.

Further, the method for producing a transparent electrode substrate of the present invention further includes the step of forming a transparent electrode from the transparent conductor layer by partially removing the protective layer and the low resistance layer from one of the conductor patterns, and The conductor layer corresponding to the remaining portion of the conductor pattern serves as a lead wiring.

Moreover, the image display device of the present invention includes a transparent electrode substrate; the transparent electrode substrate includes: an insulating substrate; and a conductor layer formed on one side of at least one of thickness directions of the insulating substrate; and the conductor layer includes: a transparent conductor layer formed on one side of the thickness direction of the insulating substrate; and a low resistance layer formed on one side of the thickness direction of the transparent conductor layer for reducing resistance of the conductor layer; and a protective layer It is formed on one surface of the low-resistance layer in the thickness direction by an easily etchable material.

Further, in the image display device of the present invention, it is preferable that the transparent electrode substrate is a touch panel.

Moreover, it is preferable that the image display device of the present invention is a liquid crystal display device.

The transparent electrode substrate of the present invention obtained by the method for producing a transparent electrode substrate of the present invention can be easily included in the thickness direction because it includes a protective layer formed on one surface in the thickness direction of the low-resistance layer by an etchable material. A conductor layer of a low resistance layer on which a protective layer is formed is etched and patterned into a desired shape.

Therefore, since the image display device of the present invention has a transparent electrode substrate including a conductor layer which is patterned with high precision, reliability can be improved.

1‧‧‧Transparent electrode substrate

2‧‧‧Insert substrate

3‧‧‧Conductor layer

4‧‧‧Transparent conductor layer

5‧‧‧Low-resisting layer

6‧‧ ‧ close layer

7‧‧‧Protective layer

8‧‧‧Conductor pattern

9‧‧‧Leading wiring

10‧‧‧Transparent electrode

11‧‧‧protective glass layer

12‧‧‧Polar plate

13‧‧‧ gap layer

14‧‧‧LCD module

15‧‧‧Adhesive layer

17‧‧‧1st resist layer

18‧‧‧2nd resist layer

19‧‧‧Laminated boards

20‧‧‧Touch panel

21‧‧‧ spacers

22‧‧‧Transparent insulating film

24‧‧‧Optical adjustment film

30‧‧‧Liquid crystal display device

Fig. 1 is a view showing a first embodiment of a method for producing a transparent electrode substrate of the present invention, wherein Fig. 1(a) shows a step of preparing an insulating substrate to laminate an optical adjustment film, and Fig. 1(b) shows a transparent conductor. The step of laminating the layer on the upper surface of the optical adjustment film, FIG. 1(c) shows the step of laminating the adhesion layer on the upper surface of the transparent conductor layer, and FIG. 1(d) shows the layer of the low resistance layer laminated on the adhesion layer. The step of the upper surface, FIG. 1(e) shows the step of laminating the protective layer on the upper surface of the low-resistance layer.

2 is a view showing a step of forming a conductor pattern by a conductor layer of the transparent electrode substrate shown in FIG. 1(e), and FIG. 2(a) shows a step of laminating a first resist on the upper surface of the protective layer. 2(b) shows a step of etching the conductor layer and then removing the first resist layer, and FIG. 2(c) shows that the second resist is applied so as to cover the portion corresponding to the lead wiring in the conductor pattern. The step of laminating the layer on the insulating substrate, and FIG. 2(d) shows the step of etching the protective layer, the low-resistance layer and the adhesion layer exposed from the second resist layer, and then removing the second resist layer.

3 is a cross-sectional view showing a liquid crystal display device in which a transparent electrode substrate shown in FIG. 2(d) is provided as a touch panel.

4 is an enlarged cross-sectional view showing the touch panel of the liquid crystal display device shown in FIG. 3 in an exploded manner.

Fig. 5 is a cross-sectional view showing a modification of the transparent electrode substrate of the first embodiment (a state in which conductor layers are provided on both sides of the insulating substrate).

6 is a cross-sectional view showing a modification of the transparent electrode substrate of the first embodiment (a state in which an adhesion layer is not provided), and FIG. 6(a) shows a state in which a conductor layer is formed on the entire upper surface of the insulating substrate.

Fig. 6(b) shows a state in which a conductor layer is represented as a conductor pattern.

Fig. 7 is a cross-sectional view showing a modification of the transparent electrode substrate of the first embodiment (the aspect in which the optical adjustment film is not provided).

Fig. 8 is a cross-sectional view showing a modification of the transparent electrode substrate of the first embodiment (the aspect in which the optical adjustment film is not provided).

<First embodiment> <Transparent electrode substrate>

In each of the drawings, the paper surface direction (thickness direction) is referred to as a first direction, the paper surface left and right direction is referred to as a second direction, and the paper surface depth direction (front and rear direction) is referred to as a third direction.

1(e), a transparent electrode substrate 1 according to an embodiment of the present invention has a flat plate shape and includes: an insulating substrate 2; and a conductor layer 3 formed on the insulating substrate 2 (one side in the thickness direction) ).

The insulating substrate 2 is formed into a film shape (or a thin plate shape) corresponding to the shape of the transparent electrode substrate 1 in plan view. The material for forming the insulating substrate 2 is, for example, a transparent material. Examples of the transparent material include inorganic transparent materials such as glass, and polyethylene terephthalate (PET), polymethacrylate (PMMA, Polymethacrylate), polycarbonate (PC, Polycarbonate), and polyethylene (Polyethylene Terephthalate). Organic transparent materials such as PE, Polyethylene, and Cycloolefin Polymer. From the viewpoint of lightness and thinness, an organic transparent material is preferable, and PET is more preferable. The glass transition temperature of the above material is, for example, 180 ° C or higher, and is, for example, 220 ° C or lower. The thickness of the insulating substrate 2 is, for example, 10 μm or more, preferably 25 μm or more, and is, for example, 300 μm or less, or preferably 200 μm or less.

Further, an optical adjustment film 24 is formed on the entire upper surface of the insulating substrate 2. The optical adjustment film 24 contains, for example, an inorganic optical material such as an SiO ₂ -based material or an organic optical material, and has a glass transition temperature of 180° C. or higher and a thickness of, for example, 1 nm or more, preferably 5 nm or more, and more preferably, for example, 1000 nm or less. Below 500 nm.

The conductor layer 3 is provided on the insulating substrate 2 at intervals of the optical adjustment film 24. That is, the conductor layer 3 is laminated on the entire upper surface of the optical adjustment film 24. The conductor layer 3 includes a plurality of layers, specifically including a transparent conductor layer 4 formed on the upper surface (one surface in the thickness direction) of the optical adjustment film 24, and a low resistance layer 5 formed on the transparent conductor layer 4 (thickness direction) One side); and an adhesion layer 6 between the transparent conductor layer 4 and the low resistance layer 5. Further, the conductor layer 3 includes a protective layer 7 which is formed on the upper surface (one surface in the thickness direction) of the low-resistance layer 5. In other words, in the conductor layer 3, the transparent conductor layer 4, the adhesion layer 6, the low resistance layer 5, and the protective layer 7 are sequentially laminated on the optical adjustment film 24 (one side in the thickness direction).

The transparent conductor layer 4 is a layer for touch input in the transparent electrode 10 (see FIG. 2(d)) described below, and is located at the lowermost layer in the conductor layer 3, and is formed on the entire upper surface of the optical adjustment film 24. Examples of the transparent conductor forming the transparent conductor layer 4 include oxides such as indium tin oxide (ITO). The thickness of the transparent conductor layer 4 is, for example, 5 nm or more, preferably 10 nm or more, and is, for example, 200 nm or less, preferably 30 nm or less.

The adhesion layer 6 is a layer for improving the adhesion between the transparent conductor layer 4 and the low resistance layer 5, and is formed on the entire upper surface of the transparent conductor layer 4. Examples of the material for forming the adhesion layer 6 include alloys of nickel, copper, and the like (including a composition containing components other than the metal). From the viewpoint of obtaining a higher adhesion, a composition containing nickel, phosphorus or boron as an essential component is preferable.

Nickel is contained as a main component in the composition, and the content thereof is the remainder other than the content ratio of phosphorus or boron.

Phosphorus or boron is contained in the composition as a subcomponent, and the phosphorus content ratio is, for example, 8% by mass or more, preferably 9% by mass or more, more preferably 10% by mass or more, and further, for example, 15% by mass or less. Good is 13% by mass or less. Further, the content ratio of boron is, for example, 0.1% by mass or more, preferably 1% by mass or more, and further, for example, 5% by mass based on the composition. Hereinafter, it is preferably 3% by mass or less.

When the content ratio of phosphorus or boron is less than the above lower limit, the adhesion between the transparent conductor layer 4 and the adhesion layer 6 may not be sufficiently improved. On the other hand, when the content ratio of phosphorus or boron exceeds the above upper limit, stable plating cannot be performed.

Further, the composition contains a catalyst such as a noble metal such as palladium or rhodium as an optional component in an appropriate ratio.

The thickness of the adhesion layer 6 is, for example, 50 nm or more, preferably 100 nm or more, and is, for example, 3,000 nm or less, preferably 500 nm or less.

The low-resistance layer 5 is a layer for lowering the electric resistance of the conductor layer 3, and is laminated on the transparent conductor layer 4 via the (intervening) adhesion layer 6. Specifically, the low resistance layer 5 is formed on the entire upper surface of the adhesion layer 6. Examples of the material for forming the low-resistance layer 5 include conductive materials (specifically, metals) such as copper, silver, gold, and the like. Preferably, copper, silver, and gold are mentioned. The thickness of the low-resistance layer 5 of these materials is appropriately set according to the resistance value required for the conductor layer 3, and specifically, for example, 50 nm or more, preferably 100 nm or more, and further, for example, 3000 nm or less, preferably Below 1000nm.

The protective layer 7 protects the layer of the low-resistance layer 5, is located in the uppermost layer of the conductor layer 3, and is formed on the entire upper surface of the low-resistance layer 5. The protective layer 7 is formed of an easily etchable material. The easily etchable material is a material which is easily removed by etching (see FIGS. 2(b) and 2(d)), and specific examples thereof include metals such as nickel, tin, and nickel-copper alloy. Further, each of the above materials may be prepared as a composition containing an additive (for example, phosphorus or the like) mixed in the step of forming the protective layer 7.

The etchable material preferably contains a composition containing nickel, phosphorus or boron as an essential component, and more preferably a composition containing nickel and phosphorus as essential components. The content ratio of the essential components is the same as the content ratio of the adhesive layer 6.

The protective layer 7 is formed as a single layer or a plurality of layers different in material. It is preferably formed as a single layer. The thickness of the protective layer 7 is, for example, 20 nm or more, and is, for example, 100 nm or less in consideration of the etching time described below.

Next, a method of manufacturing the transparent electrode substrate 1 will be described with reference to FIGS. 1(a) to 1(e).

In this method, as shown in FIG. 1(a), the insulating substrate 2 is first prepared. Then, the optical adjustment film 24 is formed (laminated) on the entire upper surface of the insulating substrate 2.

Then, as shown in FIGS. 1(b) to 1(e), the conductor layer 3 is formed on the optical adjustment film 24.

That is, in order to form the conductor layer 3 on the optical adjustment film 24, as shown in FIG. 1(b), the transparent conductor layer 4 is first laminated on the upper surface of the optical adjustment film 24.

Specifically, in order to form the transparent conductor layer 4, for example, physical vapor deposition such as vacuum deposition, ion plating, or sputtering is used. It is preferred to use sputtering.

Thereby, the laminated board 19 including the insulating substrate 2, the optical adjustment film 24, and the transparent conductor layer 4 laminated on the upper surface (one surface in the thickness direction) of the optical adjustment film 24 is prepared (preparation step).

Then, as shown in FIG. 1(c), the adhesion layer 6 is formed on the upper surface of the transparent conductor layer 4 (the adhesion layer deposition step).

Specifically, the adhesion layer 6 is formed on the upper surface of the transparent conductor layer 4 by, for example, electroplating, physical vapor deposition, or the like. It is preferred to use electroplating.

Examples of the plating include electroless plating and electrolytic plating, and electroless plating is preferred.

In order to form the adhesion layer 6 on the upper surface of the transparent conductor layer 4 by electroless plating, first, for example, the surface of the upper surface of the adhesion layer 6 is pretreated as needed.

Examples of the pretreatment include degreasing, soft etching, pickling, and the like. Degreasing is performed by impregnating the laminated board 19 in a neutral degreasing liquid. The soft etching is performed by, for example, immersing the laminate 19 in an aqueous solution of persulfate such as sodium persulfate.

After the pretreatment, a catalyst film (not shown) is laminated on the upper surface (surface) of the transparent conductor layer 4 as needed. The catalyst film (not shown) is formed by immersing the laminate 19 in the catalyst liquid. to make. Examples of the catalyst liquid include a liquid (dispersion or solution) containing a catalyst or a catalyst compound containing a catalyst as a composition. Examples of the catalyst include noble metals such as palladium and rhodium. Examples of the catalyst compound include a noble metal compound (precious metal salt) and the like. The content ratio of the catalyst and/or the catalyst compound in the aqueous solution is appropriately set.

The immersion temperature is, for example, 15 ° C or higher, preferably 20 ° C or higher, and is, for example, 50 ° C or lower, preferably 40 ° C or lower.

The immersion time is, for example, 0.5 minutes or longer, preferably 1 minute or longer, and for example, 10 minutes or shorter, preferably 5 minutes or shorter.

Then, a laminate 19 having a catalyst film (not shown) on the surface layer is immersed in the electroless plating solution.

The electroless plating solution is prepared by blending a nickel compound and a phosphorus compound or a boron compound with water.

Examples of the nickel compound include nickel salts such as nickel sulfate and nickel nitrate. When a nickel salt is formulated in water, a nickel cation (Ni ²⁺ ) is formed.

Examples of the phosphorus compound include phosphorus-based reducing agents such as hypophosphorous acid and hypophosphite (for example, sodium hypophosphite). When a phosphorus-based reducing agent is formulated in water, a phosphorus-based anion (specifically, a hypophosphorous anion: HPO ₂ ^- ) is formed.

Examples of the boron compound include a boron hydride compound such as potassium borohydride or sodium borohydride, and an amine borane compound such as dimethylamine borane, trimethylamine borane or triethylamine borane. When the boride is formulated in water, a boron anion (specifically, a boric acid anion, BO ₃ ^3- ) is formed.

Further, the pH of the electroless plating solution is adjusted to, for example, 2 or more, preferably 4 or more, and for example, 6 or less, preferably 5 or less.

The immersion temperature, that is, the temperature of the electroless plating solution is, for example, 40 ° C or higher, preferably 60 ° C or higher, and further, for example, 90 ° C or lower, preferably 80 ° C or lower. When the immersion temperature is outside the above range, there is a case where the thickness of the adhesion layer 6 cannot be set to a desired range.

When the laminated plate 19 is immersed in the electroless plating solution, the nickel cation (Ni ²⁺ ) is reduced by the reduction of the phosphorus anion or the boron anion on the surface of the adhesion layer 6 (specifically, the catalyst film). Thus, nickel (Ni) is formed, and phosphorus (P) or boron (B) is contained inside to form the adhesion layer 6 on one side.

Then, the adhesion layer 6 is heated (baked) as needed.

The heating temperature is equal to or lower than the glass transition temperature of the insulating substrate 2 and the optical adjustment film 24, and is, for example, 100 ° C or higher, preferably 120 ° C or higher. The heating time is, for example, 1 minute or longer, preferably 5 minutes or longer, and for example, 90 minutes or shorter, preferably 60 minutes or shorter.

Further, the upper surface (surface) of the adhesion layer 6 is then washed with water as needed.

Then, as shown in FIG. 1(d), the low-resistance layer 5 is formed on the upper surface of the adhesion layer 6 (low resistance step).

Specifically, the low-resistance layer 5 is formed on the upper surface of the adhesion layer 6 by, for example, electroplating, physical vapor deposition, or the like. It is preferable to electroplate, and it is more preferable to form the low-resistance layer 5 by electrolytic plating from the viewpoint of improving the adhesion to the adhesion layer 6.

Then, as shown in FIG. 1(e), a protective layer 7 is formed on the upper surface of the low-resistance layer 5 (protection step).

The protective layer 7 is formed of an easily etchable material by the same method as the above-described adhesion layer 6.

Further, from the viewpoint of the uniformity of the thickness of the protective layer 7 and the corrosion prevention of the low-resistance layer 5, electroplating is preferably performed by electroless plating. Further, the time for immersing the laminated plate 19 in the electroless plating solution can be, for example, 1 second or longer, preferably 10 seconds or longer, and for example, 100 seconds or shorter, preferably 50 seconds or shorter.

Thereby, the transparent electrode substrate 1 is obtained.

As shown in FIG. 1(e), the transparent electrode substrate 1 is formed with the conductor layer 3 on the entire upper surface of the optical adjustment film 24 (the entire upper side of the transparent conductor layer 4), for example, as shown in FIG. 2(d). The conductor layer 3 can also be formed as a conductor pattern 8.

That is, as shown in FIGS. 2(a) to 2(d), in the transparent electrode substrate 1, the conductor pattern 8 is used by The conductor layer 3 is patterned by etching.

As shown in FIG. 2(d), the conductor pattern 8 includes a lead-out wiring 9 and a transparent electrode 10 which is formed continuously (not shown) with the lead-out wiring 9.

The lead wires 9 are disposed at a plurality of circumferential end portions of the transparent electrode substrate 1 at intervals. The lead wiring 9 includes a conductor layer 3 (specifically, a transparent conductor layer 4, an adhesion layer 6, a low resistance layer 5, and a protective layer 7) on the upper surface (on the insulating substrate 2) of the optical adjustment film 24.

The transparent electrode 10 constitutes a detecting portion (sensor) in the liquid crystal display device 30 (see FIG. 3) described below, and a plurality of the electrodes are disposed at intervals in the center of the transparent electrode substrate 1. The pattern of the transparent electrode 10 is formed, for example, in the front-rear direction, and is formed at intervals in the left-right direction. The transparent electrode 10 includes a transparent conductor layer 4 on the optical adjustment film 24.

Next, a method (patterning step) of forming the conductor pattern 8 by etching the conductor layer 3 on the transparent electrode substrate 1 will be described with reference to FIGS. 2(a) to 2(d).

First, in this method, as shown in FIG. 2(a), the first resist layer 17 is formed on the upper surface of the conductor layer 3.

Specifically, first, a dry film resist is laminated on the entire upper surface of the protective layer 7, and then the first resist layer 17 is formed in the same pattern as the conductor pattern 8 by exposure and development.

Then, in this method, as shown in FIG. 2(b), the conductor layer 3 exposed from the first resist layer 17 is etched. In the etching, an etching liquid which dissolves the conductor layer 3 without dissolving the transparent conductor layer 4 and the optical adjustment film 24 is used.

Thereby, the conductor pattern 8 including the transparent conductor layer 4, the adhesion layer 6, the low resistance layer 5, and the protective layer 7 is formed.

Then, the first resist layer 17 is removed by lift-off.

Then, in this method, as shown in FIG. 2(c), the conductor layer 3 corresponding to the lead wiring 9 (see FIG. 2(d)) is covered and exposed to the transparent electrode 10 (see FIG. 2(d)). In the manner of the conductor layer 3, the second resist layer 18 is formed on the optical adjustment film 24.

Specifically, first, a dry film resist is laminated on the entire upper surface of the optical adjustment film 24 including the conductor layer 3 (conductor pattern 8), and then the second resist layer 18 is formed in accordance with the above pattern by exposure and development. .

Then, in this method, as shown in FIG. 2(d), a portion of the conductor layer 3 exposed from the second resist layer 18, that is, the protective layer 7, the low-resistance layer 5, and the adhesion layer are removed by etching. 6.

An etching liquid which dissolves the protective layer 7, the low-resistance layer 5, and the adhesion layer 6 without dissolving the transparent conductor layer 4 and the optical adjustment film 24 is used for etching.

Then, the second resist layer 18 is removed by lift-off.

Thereby, the transparent electrode 10 is formed of the transparent conductor layer 4 by removing the protective layer 7, the low-resistance layer 5, and the adhesion layer 6 which are a part of the conductor pattern 8, and corresponds to the remaining portion of the conductor pattern 8. The conductor layer 3 serves as the lead wiring 9.

Further, in the conductor layer 3 other than the patterns of the transparent electrode 10 and the lead wiring 9, the protective layer 7, the low-resistance layer 5, the adhesion layer 6, and the transparent conductor layer have been etched by the etching shown in FIG. 2(b). 4 etching.

Thereby, as shown in FIG. 2(d), the transparent electrode substrate 1 including the lead pattern 9 and the conductor pattern 8 of the transparent electrode 10 is formed on the upper surface of the optical adjustment film 24.

Further, since the transparent electrode substrate 1 includes the protective layer 7 formed on the upper surface of the low-resistance layer 5 with an easily etchable material, the conductor layer of the low-resistance layer 5 including the protective layer 7 on the upper surface can be easily formed. 3 etching is performed to pattern into a desired shape.

The transparent electrode substrate 1 shown in FIG. 2(d) can be used, for example, as a touch panel.

<Touch Panel>

Next, a liquid crystal display device 30 including the touch panel 20 using the transparent electrode substrate 1 shown in FIG. 2(d) will be described with reference to FIGS. 3 and 4.

In FIG. 3, the liquid crystal display device 30 is, for example, a touch panel type mobile phone, and includes: a liquid crystal display (LCD) module 14; a polarizing plate. 12, which is disposed on the LCD module 14 at intervals; the touch panel 20 is disposed on the upper surface of the polarizing plate 12; and the protective glass layer 11 is disposed on the upper surface of the touch panel 20.

Further, although not shown, a circuit board, a casing, and the like are provided on the lower side of the LCD module 14.

Further, in the center portion of the liquid crystal display device 30 in the left-right direction and the front-rear direction, the gap between the LCD module 14 and the polarizing plate 12 is a gap layer 13 as an air layer. Further, the gap layer 13 is divided by the spacer 21 in which the circumferential end portion is arranged in a frame shape.

As shown in FIG. 4, the touch panel 20 includes two transparent electrode substrates 1 (in detail, the conductive layer 3 is formed as a transparent electrode substrate 1 of the conductor pattern 8).

Specifically, the touch panel 20 includes a plurality of (two) transparent electrode substrates 1 disposed at intervals in the thickness direction, a transparent insulating film 22 interposed between the transparent electrode substrates 1 , and a plurality of (3) Adhesive layer 15.

In each of the two transparent electrode substrates 1, the conductor layer 3 is disposed toward the upper side (thickness direction). Further, in the two transparent electrode substrates 1, the extending direction of the transparent electrodes 10 is set so as to intersect each other when intersecting in the thickness direction (specifically, orthogonal), and for example, the upper transparent electrode 10 extends in the front-rear direction. Further, the transparent electrodes 10 on the lower side are arranged in the left-right direction on the left and right sides, and are arranged at intervals in the front-rear direction.

The transparent insulating film 22 is formed using the same material and size as the insulating substrate 2 in the transparent electrode substrate 1.

The adhesive layer 15 is provided between the lower transparent electrode substrate 1 and the transparent insulating film 22, between the transparent insulating film 22 and the upper transparent electrode substrate 1, and on the upper surface of the upper transparent electrode substrate 1.

In the liquid crystal display device 30, when a finger or the like contacts or approaches the upper surface of the cover glass layer 11, a difference in electrostatic capacitance occurs as compared with the case where it is not in contact or close to each other, and the electrostatic capacitance difference is used as a detection signal through the lead wiring 9. It is transferred to a circuit board (not shown).

On the other hand, the input signal is input to the LCD module 14 from the circuit substrate, thereby The LCD module 14 displays an image. The operator (or the viewer) views the image through the polarizing plate 12, the touch panel 20, and the cover glass layer 11.

Further, since the liquid crystal display device 30 has the transparent electrode substrate 1 including the conductor pattern 8, the conductor pattern 8 is formed of the conductor layer 3 which is patterned with high precision, so that reliability can be improved.

<variation>

Although the image display device of the present invention has been described as the liquid crystal display device 30 in the description of FIGS. 3 and 4, the image display device of the present invention can be used as an organic electro-electric image, for example. A light-emitting device (Organic Electroluminescence Device) or the like.

In the following drawings, the same components as those in FIGS. 1 to 4 are denoted by the same reference numerals, and detailed description thereof will be omitted.

In the embodiment of FIG. 1(e), the conductor layer 3 is provided only on the upper side (one side in the thickness direction) of the insulating substrate 2. However, for example, as shown in FIG. 5, it may be provided on the insulating substrate 2 Side (upper side and lower side, one side in the thickness direction and the other side).

That is, in FIG. 5, the transparent electrode substrate 1 includes: an insulating substrate 2; optical adjustment films 24 respectively formed on the upper surface and the lower surface of the insulating substrate 2; and a conductor layer 3 formed on the two optical adjustment films The surface of 24.

The insulating substrate 2 is sandwiched by two optical adjustment films 24 in the thickness direction.

The two conductor layers 3 are formed on the upper surface of the optical adjustment film 24 on the upper surface, and are formed on the lower surface of the optical adjustment film 24 on the lower side.

The conductor layer 3 on the lower side is laminated on the entire lower surface of the optical adjustment film 24. In the lower conductor layer 3, the transparent conductor layer 4, the adhesion layer 6, the low resistance layer 5, and the protective layer 7 are sequentially laminated under the optical adjustment film 24 (the other side in the thickness direction).

Further, in the transparent electrode substrate 1 shown in FIG. 5, the conductor layer 3 can be formed as the conductor pattern 8 although not shown.

When such a transparent electrode substrate 1 is used as the touch panel 20, the touch panel 20 can be constituted by one transparent electrode substrate 1. The transparent electrodes 10 in the conductor patterns 8 on the upper and lower sides are formed in a pattern intersecting each other (specifically, orthogonal) when projected in the thickness direction.

Further, in the embodiment of Fig. 1(e), the adhesion layer 6 is provided on the conductor layer 3. However, as shown in Fig. 6(a), for example, the conductor layer 3 may be formed without providing the adhesion layer 6.

In FIG. 6(a), the conductor layer 3 is formed of a transparent conductor layer 4, a low-resistance layer 5, and a protective layer 7.

The low resistance layer 5 is formed directly on the entire upper surface of the transparent conductor layer 4.

Further, as shown in FIG. 6(b), the conductor layer 3 of the transparent electrode substrate 1 shown in FIG. 6(a) may be formed as a conductor pattern 8 including the lead wiring 9 and the transparent electrode 10.

In FIG. 6(b), the lead wiring 9 includes a transparent conductor layer 4, a low resistance layer 5, and a protective layer 7.

In order to obtain the transparent electrode substrate 1 shown in FIG. 6(b), as shown in FIGS. 2(a) to 2(d), first, the first resist layer 17 is formed on the upper surface of the protective layer 7, and then, The conductor layer 3 (the transparent conductor layer 4, the low resistance layer 5, and the protective layer 7) exposed from the first resist layer 17 is etched (patterned), and then the first resist layer 17 is peeled off. Then, the second resist layer 18 is formed on the optical adjustment film 24 so as to cover the conductor layer 3 corresponding to the lead wiring 9 and expose the conductor layer 3 corresponding to the transparent electrode 10, and then removed by etching. The protective layer 7 and the low-resistance layer 5 in which the second resist layer 18 is exposed. Then, the second resist layer 18 is removed.

Preferably, as shown in FIG. 1(e), the adhesion layer 6 is interposed between the transparent conductor layer 4 and the low resistance layer 5 in the conductor layer 3, and further, as shown in FIG. 2(d), The adhesion layer 6 is interposed between the transparent conductor layer 4 and the low resistance layer 5 in the lead wiring 9. Thereby, the adhesion between the transparent conductor layer 4 and the low-resistance layer 5 in the conductor layer 3 shown in FIG. 1(e) can be improved, and the transparent conductor in the lead-out wiring 9 shown in FIG. 2(d) can be improved. The adhesion between the layer 4 and the low-resistance layer 5 is good.

In the embodiment of FIGS. 1(e) and 2(d), the optical adjustment film 24 is provided on the upper surface of the insulating substrate 2. However, for example, as shown in FIGS. 7 and 8, the optical adjustment film may not be provided. 24, a transparent conductor layer 4 is directly formed on the upper surface of the insulating substrate 2.

From the viewpoint of improving the optical characteristics, it is preferable to provide the optical adjustment film 24 on the upper surface of the insulating substrate 2 as shown in Figs. 1(e) and 2(d).

Example

The present invention will be more specifically described below by showing examples and comparative examples. Further, the present invention is not limited by any examples and comparative examples.

<Production of Transparent Electrode Substrate> Example 1

An insulating substrate having a thickness of 50 μm including PET (glass transition temperature: 180 ° C or higher) was prepared (see FIG. 1( a )). Then, an optical adjustment film having a thickness of 25 nm including a SiO ₂ -based material (glass transition temperature: 200 ° C or higher) was laminated on the entire upper surface of the insulating substrate.

Then, the conductor layer is formed on an insulating substrate (optical adjustment film) (see FIGS. 1(b) to 1(e)).

Specifically, a transparent conductor layer containing ITO is first formed on the upper surface of the optical adjustment film by sputtering. The thickness of the transparent conductor layer was 25 nm. Thereby, a laminate including an insulating substrate, an optical adjustment film, and a transparent conductor layer is prepared.

Then, an adhesion layer is formed on the upper surface of the transparent conductor layer (refer to FIG. 1(c)).

Specifically, first, the laminate was immersed in a neutral degreasing liquid at 45 ° C for 5 minutes, and then immersed in a sodium persulfate aqueous solution at 25 ° C for 5 minutes to perform soft etching.

Then, the laminate was immersed in a contact liquid containing palladium at 25 ° C for 5 minutes to form a catalyst film on the surface layer of the transparent conductor layer.

An electroless plating solution containing nickel sulfate and hypophosphorous acid (reducing agent) is separately prepared. In the electroless plating solution, the mass ratio of nickel cation (Ni ²⁺ ) was adjusted to 2.5% by mass, and the mass ratio of hypophosphorous anion (HPO ₂ ^- ) was adjusted to 2% by mass. Further, the pH of the electroless plating solution was 4.6.

Then, a laminate having a catalyst film on the surface layer of the transparent conductor layer is at 70 ° C Immersion in electroless plating bath for 5 minutes. Thereby, an adhesive layer (intervening catalyst film) having a thickness of 500 nm containing a composition containing nickel and phosphorus was formed on the entire upper surface of the transparent conductor layer.

Then, the adhesive layer was washed with water for 1 minute.

Then, a low-resistance layer is formed on the upper surface of the adhesion layer (see FIG. 1(d)).

That is, the laminated plate on which the adhesion layer was formed was immersed in a copper sulfate plating solution containing an additive, and electrolytic copper plating was performed for 1 minute and 20 seconds at an average current density of 1 A/dm ² . Thereby, a low-resistance layer containing copper having a thickness of 200 nm was formed on the entire upper surface of the adhesion layer.

Then, a protective layer having a thickness of 30 nm containing a composition containing nickel and phosphorus was formed on the upper surface of the low-resistance layer (refer to FIG. 1(e)).

A low resistance layer is formed according to the formation method of the adhesion layer.

Thereby, a transparent electrode substrate in which a transparent conductor layer, an adhesion layer, a low resistance layer, and a protective layer are sequentially laminated on the optical adjustment film is obtained.

Examples 2 to 9 and Comparative Examples 1, 2

The transparent electrode substrate was obtained in the same manner as in Example 1 except that the conditions for forming the adhesion layer, the low resistance layer, and the protective layer were changed as described in Tables 1 and 2.

Details of the change point compared with the first embodiment will be described below.

In Example 3, a protective layer was formed of nickel by electrolytic nickel. The detailed conditions for electrolytic nickel are as follows.

Electrolytic nickel plating solution: comprising nickel sulfate, nickel chloride, boric acid and additives.

Electrolysis conditions: 0.5A/dm ²

Time: 30 seconds

Temperature: 40 ° C

In the fourth embodiment, a low-resistance layer was formed of copper by electroless copper plating. The detailed conditions of electroless copper plating are as follows.

Electrolytic copper plating solution: contains copper sulfate and formalin.

Time: 15 seconds

Temperature 40 ° C

In Example 5, an adhesion layer was formed by copper for sputtering.

In Examples 7 to 9, an electroless plating solution containing nickel sulfate and boron was used, and an adhesive layer was formed using a composition containing nickel and boron. The boron concentration in the film of each of Examples 7 to 9 was appropriately adjusted depending on the ratio of the concentration of dimethylamine borane to the concentration of nickel sulfate in the plating solution, pH, additives, and the like.

In Comparative Example 1, a protective layer was formed by gold electroless gold plating. The detailed conditions for electroless gold plating are as follows.

Plating solution containing potassium cyanide, potassium cyanide and additives

Temperature: 80 ° C

Time: 3 minutes

Thickness: 30nm

Comparative Example 2 did not form a protective layer.

<Production of Image Display Device>

In the transparent electrode substrates of Examples 1 to 5 and Comparative Examples 2 and 5, the conductor layer was processed into a conductor pattern (see FIGS. 2( a ) to 2 ( d )), and then a transparent electrode was produced according to the above embodiment. The substrate is used as a liquid crystal display device of a touch panel.

On the other hand, in the transparent electrode substrate of Comparative Example 1, etching was attempted in order to process the conductor layer into a conductor pattern. However, the conductor layer could not be etched (patterned).

<evaluation> ‧Intimate

The adhesion test (Tape Cross Cut test) was performed on the transparent electrode substrate before the formation of the protective layer (the transparent electrode substrate obtained in Comparative Example 2).

That is, using a cutting blade, the 1 cm square of the conductor layer of the transparent electrode substrate In the field, slits in the front-rear direction and the left-right direction are placed at intervals of 1 mm. Then, the tape was attached to the conductor layer, and the case where the low-resistance layer was not peeled off from the transparent conductor layer when the tape was peeled off from the conductor layer was evaluated as "○", and the case where the low-resistance layer was peeled off from the transparent conductor layer was evaluated. It is "X".

‧ resistance value (surface resistance)

The surface resistance of the conductor layers of the transparent electrode substrates of Examples 1 to 5 and 9 and Comparative Examples 1 and 2 was measured using a resistivity meter (LORESTA AX MCP-370 type manufactured by Mitsubishi Chemical Corporation).

‧Anti-rust (corrosive)

The image display device including the transparent electrode substrates of Examples 1 to 5 and 9 and Comparative Examples 1 and 2 was placed in an 85 ° C, 85% thermostat humidifier for 500 hours. Then, the lead wire was evaluated as "○" in the case of no discoloration corrosion, and the "x" was evaluated as the discoloration corrosion.

‧ Phosphorus content ratio and boron content ratio

The phosphorus content ratio or the boron content ratio in the adhesion layer and the protective layer is calculated by dissolving the film and measuring it by inductively coupled plasma (ICP).

The results are shown in the column of the close layer and the column of the protective layer.

"%" in the table indicates "% by mass".

In addition, the above description is provided as an exemplified embodiment of the present invention, and is merely illustrative and is not to be construed as limiting. Variations of the invention that are apparent to those skilled in the art are included in the scope of the following patent applications.

1‧‧‧Transparent electrode substrate

2‧‧‧Insert substrate

3‧‧‧Conductor layer

4‧‧‧Transparent conductor layer

5‧‧‧Low-resisting layer

6‧‧ ‧ close layer

7‧‧‧Protective layer

19‧‧‧Laminated boards

24‧‧‧Optical adjustment film

Claims (12)

A transparent electrode substrate, comprising: an insulating substrate; and a conductor layer formed on one side of at least one of thickness directions of the insulating substrate; and the conductor layer includes: a transparent conductor layer formed on the thickness of the insulating substrate One side of the direction; a low-resistance layer formed on one side of the thickness direction of the transparent conductor layer for reducing the electric resistance of the conductor layer; and a protective layer formed of an easily etchable material in the low resistance One of the above thickness directions of the layer. The transparent electrode substrate of claim 1, wherein the etchable material is at least one metal selected from the group consisting of nickel, tin, and nickel-copper alloy. The transparent electrode substrate according to claim 1, wherein the transparent conductor layer is formed of indium tin oxide, and the low resistance layer is formed of at least one metal selected from the group consisting of copper, silver, and gold. The transparent electrode substrate according to claim 1, wherein the transparent conductor layer is formed on one surface of the insulating substrate on one side in the thickness direction, and the low resistance layer is formed on one side of the thickness direction of the transparent conductor layer. The surface is formed on the entire surface of the low-resistance layer in one of the thickness directions. The transparent electrode substrate of claim 1, wherein The conductor layer is formed as a conductor pattern on the insulating substrate. The transparent electrode substrate of claim 5, wherein the conductor pattern comprises: a lead wire including the conductor layer; and a transparent electrode formed continuously with the lead wire and including the transparent conductor layer. A method for producing a transparent electrode substrate, comprising the steps of: preparing a laminate comprising an insulating substrate and a transparent conductor layer laminated on at least one of thickness directions of the insulating substrate; and a step of reducing resistance The low-resistance layer is laminated on one side of the thickness direction of the transparent conductor layer, and the protective step is to form a protective layer on one surface of the low-resistance layer in the thickness direction by an easy-etching material. The method for manufacturing a transparent electrode substrate according to claim 7, further comprising a patterning step of etching the conductor layer including the transparent conductor layer, the low resistance layer and the protective layer after the protecting step A conductor pattern is formed. The method for producing a transparent electrode substrate according to claim 8, further comprising the step of forming a transparent electrode from the transparent conductor layer by partially removing the protective layer and the low resistance layer from one of the conductor patterns, and The conductor layer corresponding to the remaining portion of the conductor pattern serves as the lead wiring. An image display device comprising: a transparent electrode substrate, wherein the transparent electrode substrate comprises: an insulating substrate; and a conductor layer formed on one side of at least one of thickness directions of the insulating substrate; and the conductor layer comprises: a transparent conductor layer formed on one side of the thickness direction of the insulating substrate; and a low resistance layer formed on one side of the thickness direction of the transparent conductor layer for reducing resistance of the conductor layer; and a protective layer It is formed of an easily etchable material on one surface of the low-resistance layer in the thickness direction. The image display device of claim 10, wherein the transparent electrode substrate is a touch panel. An image display device according to claim 10, which is a liquid crystal display device.