KR20140031809A - Transparent electrode substrate, method for producing same and image display device - Google Patents

Abstract

A transparent electrode substrate comprises a conductive layer formed on an insulating substrate and at least one side, in a thickness direction, of the insulating substrate. The conductive layer comprises: a transparent conductive layer formed on one side of the insulating substrate in the thickness direction; a low resistive layer which is formed on one side of the transparent conductive layer in the thickness direction and reduces electrical resistance of the conductive layer; and an adhesion layer which is interposed between the transparent layer and the low resistive layer and contains 8 wt% of phosphorous or more. [Reference numerals] (AA) Upper side; (BB) Left side; (CC) Thickness direction; (DD) Right side; (EE) Left and right direction; (FF) Lower side

Description

Transparent electrode substrate, its manufacturing method, and image display apparatus TECHNICAL FIELD

The present invention relates to a transparent electrode substrate, a method for producing the same, and an image display device, in particular, a method for producing a transparent electrode substrate, a transparent electrode substrate obtained thereby, and an image display device including the transparent electrode substrate.

Background Art Conventionally, it is known to use a transparent electrode substrate provided with a transparent electrode as a touch panel in an image display device such as a liquid crystal display device.

For example, a substrate for a display device obtained by performing nickel plating on a transparent electrode formed on the entire main surface of the substrate and further copper plating thereon has been proposed (for example, Japanese Patent Laid-Open No. 1994). See -148661.

In the substrate for display device of JP 1994-148661 A, the adhesion layer of a transparent electrode and a copper layer by a nickel layer (nickel plating layer), reducing the electrical resistance of these laminated bodies by a copper layer (copper plating layer). Is improving.

Japanese Patent Publication No. 1994-148661

However, it is desired to further improve the adhesion between the transparent electrode and the copper layer, depending on the use and purpose of the display device substrate.

An object of the present invention is to provide a transparent electrode substrate having a high adhesion between the transparent conductor layer and the low resistance layer, a manufacturing method thereof, and an image display device including the transparent electrode substrate.

The transparent electrode substrate of this invention is equipped with the insulated substrate and the conductor layer formed in the at least one thickness direction side of the said insulated substrate, The said conductor layer is the transparent conductor layer formed in the said thickness direction one side of the said insulated substrate. And a low resistance layer formed on one side of the thickness direction of the transparent conductor layer to reduce electrical resistance of the conductor layer, interposed between the transparent conductor layer and the low resistance layer, and having a phosphorus content ratio of 8 It is characterized by including the adhesion layer which is mass% or more.

In the transparent electrode substrate of the present invention, the transparent conductor layer is formed from indium tin oxide, and the low resistance layer is formed from one or more metals selected from the group consisting of copper, silver, and gold. It is suitable that the layer is formed from a composition containing nickel and phosphorus.

Moreover, in the transparent electrode board | substrate of this invention, it is suitable for the said conductor layer to further provide the protective layer formed from the easy etching material on one side of the said thickness direction of the said low resistance layer.

Moreover, in the transparent electrode substrate of this invention, it is suitable that the said easy etching material is 1 or more types of metals chosen from nickel, tin, and a nickel copper alloy.

Moreover, in the transparent electrode substrate of this invention, the said transparent conductor layer is formed in the whole surface of the said thickness direction one side of the said insulated substrate, and the said contact bonding layer is formed in the whole thickness direction one side surface of the said transparent conductor layer, It is suitable that the said low resistance layer is formed in the whole surface of the said thickness direction one side of the said contact | attachment layer.

Moreover, in the transparent electrode substrate of this invention, it is suitable that the said conductor layer is formed as a conductor pattern in the said insulated substrate.

Moreover, in the transparent electrode board | substrate of this invention, it is suitable that the said conductor pattern is provided continuously with the lead-out wiring which consists of the said conductor layer, and the said lead-out wiring, and is equipped with the transparent electrode which consists of the said transparent conductor layer.

Moreover, the manufacturing method of the transparent electrode board | substrate of this invention is a preparatory process of preparing the laminated board which consists of an insulated substrate and the transparent conductor layer laminated | stacked on at least one side of the said thickness direction, and an adhesive layer is the said transparent conductor layer. The adhesion layer lamination process of laminating | stacking so that the phosphorus content ratio in the said adhesion layer may be 8 mass% or more, and the low resistance layer which laminates a low-resistance layer on the said thickness direction one side of the said adhesion layer It is characterized by including a resistance process.

Moreover, the manufacturing method of the transparent electrode substrate of this invention adds the patterning process which forms a conductor pattern by etching the conductor layer provided with the said transparent conductor layer, the said contact | attachment layer, and the said low resistance layer after the said low resistance process. It is suitable to provide with.

Further, in the method for manufacturing a transparent electrode substrate of the present invention, a transparent electrode is formed from the transparent conductor layer by removing the low resistance layer and the adhesion layer from a part of the conductor pattern. It is suitable to further provide the process of making the said conductor layer corresponding to remainder into an outgoing wiring.

Moreover, the manufacturing method of the transparent electrode board | substrate of this invention further includes the process of laminating | stacking the protective layer which consists of an easy etching material on the said thickness direction one surface of the said low resistance layer, In the said patterning process, the said transparent conductor It is suitable to form a conductor pattern by etching the conductor layer including the layer, the adhesion layer, the low resistance layer and the protective layer.

Moreover, the manufacturing method of the transparent electrode board | substrate of this invention forms a transparent electrode from the said transparent conductor layer by removing the said protective layer, the said low resistance layer, and the said contact | attachment layer from a part of the said conductor pattern, It is suitable to further provide the process of making the said conductor layer corresponding to the remainder of the said conductor pattern into outgoing wiring.

Moreover, the image display apparatus of this invention is equipped with said transparent electrode board | substrate, The said transparent electrode board | substrate is equipped with the insulated substrate and the conductor layer formed in the at least one thickness direction side of the said insulated substrate, The said conductor layer The transparent conductor layer formed in the said thickness direction one side of the said insulated substrate, the low resistance layer formed in the said thickness direction one side of the said transparent conductor layer, and reducing the electrical resistance of the said conductor layer, and the said transparent conductor It is interposed between a layer and the said low resistance layer, It is characterized by including the adhesive layer whose phosphorus content rate is 8 mass% or more.

Moreover, in the image display apparatus of this invention, it is suitable that the said transparent electrode substrate is a touch panel.

Moreover, it is suitable that the image display apparatus of this invention is a liquid crystal display device.

Since the transparent electrode substrate of this invention obtained by the manufacturing method of the transparent electrode substrate of this invention is interposed between a transparent conductor layer and a low resistance layer, and is provided with the adhesion layer whose phosphorus content rate is 8 mass% or more, it is transparent. The adhesion between the conductor layer and the low resistance layer can be sufficiently increased. Therefore, reliability can be improved.

Therefore, since the image display apparatus of this invention is equipped with the transparent electrode substrate which improved reliability, it is excellent in reliability.

1 is a process chart showing a first embodiment of a method for manufacturing a transparent electrode substrate of the present invention,
1A is a step of preparing an insulating substrate and laminating an optical adjustment film;
1 (b) is a step of laminating the transparent conductor layer on the upper surface of the optical adjustment film,
1 (c) is a step of laminating an adhesive layer on the upper surface of the transparent conductor layer,
1 (d) is a step of laminating a low resistance layer on the upper surface of the adhesion layer,
1 (e) shows a step of laminating a protective layer on the upper surface of the low resistance layer.
FIG. 2 is a process chart for forming a conductor pattern from the conductor layer of the transparent electrode substrate shown in FIG. 1E,
2 (a) is a step of laminating the first etching resist on the upper surface of the protective layer,
2 (b) is a step of etching the conductor layer and subsequently removing the first etching resist;
2C is a step of laminating a second etching resist on an insulating substrate so as to cover a portion corresponding to the lead wiring in the conductor pattern;
FIG.2 (d) shows the process of etching the protective layer, the low resistance layer, and the contact bonding layer exposed from a 2nd etching resist, and then removing a 2nd etching resist.
FIG. 3: shows sectional drawing of the liquid crystal display device in which the transparent electrode substrate shown to FIG. 2 (d) is provided as a touch panel.
4 is an enlarged cross-sectional view when the touch panel of the liquid crystal display shown in FIG. 3 is disassembled.
FIG. 5: shows sectional drawing of the modification of the transparent electrode board | substrate of 1st Embodiment (the aspect in which a conductor layer is provided in the both sides of an insulated substrate).
FIG. 6: shows sectional drawing of the modification (the aspect in which a protective layer is not provided) of the transparent electrode substrate of 1st Embodiment.
FIG. 7: shows sectional drawing of the modification (the aspect in which an optical adjustment film is not provided) of the transparent electrode substrate of 1st Embodiment.
FIG. 8: shows sectional drawing of the modification (the aspect in which an optical adjustment film is not provided) of the transparent electrode substrate of 1st Embodiment.

≪ First Embodiment >

<Transparent electrode substrate>

In each figure, the paper vertical direction (thickness direction) is made into a 1st direction, the paper left-right direction is made into a 2nd direction, and the paper depth direction (rear direction) may be made into a 3rd direction.

In FIG. 1E, the transparent electrode substrate 1 as an embodiment of the present invention has a flat plate shape, and is formed on the insulating substrate 2 and the insulating substrate 2 (one side in the thickness direction). The conductor layer 3 is provided.

The insulating board | substrate 2 is formed in the film form (or thin plate shape) corresponding to the external shape of the transparent electrode substrate 1 in planar view. As a material which forms the insulated substrate 2, a transparent material is mentioned, for example. Examples of the transparent material include inorganic transparent materials such as glass, such as polyethylene terephthalate (PET), polymethacrylate (PMMA), polycarbonate (PC), polyethylene (PE), and cycloolefin polymer (COP). A transparent material is mentioned. Preferably, an organic transparent material, more preferably PET is mentioned from a light thinning viewpoint. The glass transition temperature of the above-mentioned material is 180 degreeC or more, for example, and 220 degrees C or less, for example. The thickness of the insulating substrate 2 is, for example, 10 μm or more, preferably 25 μm or more, and for example, 300 μm or less, preferably 200 μm or less.

In addition, an optical adjusting film 24 is formed on the entire upper surface of the insulating substrate 2. The optical adjusting film 24 is made of, for example, an inorganic optical material such as a SiO ₂ based material, an organic optical material, or the like, 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, for example, 1000 nm or less, preferably 500 nm or less.

The conductor layer 3 is provided on the insulating board 2 with the space | interval of the optical adjustment film 24 interposed. That is, the conductor layer 3 is laminated | stacked on the whole upper surface of the optical adjustment film 24. As shown in FIG. The conductor layer 3 consists of a some layer, and is specifically, on the transparent conductor layer 4 formed in the upper surface (one side of thickness direction) of the optical adjustment film 24, and the transparent conductor layer 4 upper surface. The low resistance layer 5 formed in one side of the thickness direction, and the adhesion layer 6 interposed between the transparent conductor layer 4 and the low resistance layer 5 are provided. Moreover, the conductor layer 3 is equipped with the protective layer 7 formed in the upper surface (one side of thickness direction) of the low resistance layer 5. FIG. That is, as the conductor layer 3, the transparent conductor layer 4, the adhesion layer 6, the low resistance layer 5, and the protective layer 7 are formed on the optical adjustment film 24 (one side in the thickness direction). Laminated sequentially.

The transparent conductor layer 4 is a layer for touch input in the transparent electrode 10 (refer to FIG. 2 (d)) which will be described later, and is located at the lowest layer in the conductor layer 3, and has an optical adjustment film 24. It is formed on the front of the upper surface of the). As a transparent conductor which forms the transparent conductor layer 4, oxides, such as indium tin oxide (ITO), are mentioned, for example. The thickness of the transparent conductor layer 4 is, for example, 5 nm or more, preferably 10 nm or more, and for example, 200 nm or less, preferably 30 nm or less.

The low resistance layer 5 is a layer which reduces the electrical resistance of the conductor layer 3, and is laminated on the transparent conductor layer 4 with the adhesive layer 6 interposed therebetween. Examples of the material for forming the low resistance layer 5 include conductive materials (specifically, metals) such as copper, silver, gold, and alloys thereof. Preferably, copper, silver, and gold are mentioned. The thickness of the low resistance layer 5 of these materials is appropriately set by the electric resistance value required for the conductor layer 3, and specifically, is 50 nm or more, preferably 100 nm or more, and for example, 3000 nm or less, Preferably it is 1000 nm or less.

The adhesion layer 6 is a layer which improves the adhesion between the transparent conductor layer 4 and the low resistance layer 5, and is formed on the entire upper surface of the upper surface of the transparent conductor layer 4 and the lower surface of the lower resistance layer 5. have. As a material which forms the adhesion layer 6, the composition etc. which contain nickel and phosphorus as an essential component are mentioned, for example.

Nickel is contained as a main component in a composition, and the content rate is remainder of the content rate of phosphorus.

Phosphorus is contained as a subcomponent in the composition, and the content ratio (phosphorus content ratio) is 8 mass% or more, Preferably it is 9 mass% or more, More preferably, it is 10 mass% or more, For example, 15 mass It is% or less, Preferably it is 13 mass% or less.

If the content ratio of phosphorus is below the said minimum, the adhesive force of the transparent conductor layer 4 and the contact bonding layer 6 cannot fully be improved. On the other hand, when the content rate of phosphorus exceeds the said upper limit, stable plating may not be possible.

In addition, a composition contains catalysts, such as noble metals, such as palladium and rhodium, as an optional component in an appropriate ratio as needed.

The thickness of the adhesive layer 6 is, for example, 50 nm or more, preferably 100 nm or more, and, for example, 3000 nm or less, preferably 500 nm or less.

The protective layer 7 is a layer which protects the low resistance layer 5, is located in the uppermost layer in the conductor layer 3, and is formed in the whole upper surface of the low resistance layer 5. As shown in FIG. The protective layer 7 is formed from protective materials, such as nickel, tin, a nickel copper alloy, and gold, for example. Preferably, the protective layer 7 is formed from the easy etching material. The easy etching material is a material which is easily etched (removed) in the etching described later (see FIGS. 2 (b) and 2 (d)), and specific examples include metals such as nickel, tin, and nickel copper alloys. Can be. In addition, each said material may be prepared as a composition containing the additive (for example, phosphorus etc.) mixed in the formation process of the protective layer 7, etc. The protective layer 7 is formed as a single layer or a plurality of layers having different materials. Preferably, it is formed as a single layer. The thickness of the protective layer 7 is 20 nm or more, for example, and considering the etching time in 2nd etching mentioned later, it is 100 nm or less, for example.

Next, the manufacturing method of the transparent electrode substrate 1 is demonstrated with reference to FIGS. 1 (a) -1 (e).

In this method, first, as shown to Fig.1 (a), the insulating substrate 2 is prepared. Subsequently, the optical adjusting film 24 is formed (laminated) on the entire upper surface of the insulating substrate 2.

Subsequently, as shown in FIGS. 1B to 1E, 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, first, as shown in FIG. 1 (b), the transparent conductor layer 4 is 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, sputtering or the like is used. Preferably, sputtering is used.

Thereby, the laminated board 19 provided with the insulating substrate 2, the optical adjustment film 24, and the transparent conductor layer 4 laminated | stacked on the upper surface (one side of thickness direction) of the optical adjustment film 24 is prepared. (Preparation process)

Next, as shown in FIG.1 (c), the adhesion layer 6 is formed in the upper surface of the transparent conductor layer 4 (adhesion layer lamination process).

Specifically, the adhesion layer 6 is formed on the upper surface of the transparent conductor layer 4 by, for example, plating, physical vapor deposition, or the like. Preferably, plating is used.

As plating, electroless plating and electrolytic plating are mentioned, for example, Preferably electroless plating is mentioned.

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 upper surface of the adhesion layer 6 is pretreated as needed.

As pretreatment, degreasing, soft etching, pickling, etc. are mentioned, for example. In degreasing, the laminated board 19 is immersed in neutral degreasing liquid. In soft etching, the laminated board 19 is immersed in aqueous solution of persulfates, such as sodium persulfate, for example.

After the pretreatment, a catalyst film (not shown) is laminated on the upper surface (surface) of the transparent conductor layer 4 as necessary. A catalyst film (not shown) is formed by immersing the laminated board 19 in catalyst liquid. As a catalyst liquid, the liquid (dispersion liquid or solution) containing a catalyst or the catalyst compound containing it as a composition is mentioned, for example. As a catalyst, noble metals, such as palladium and rhodium, are mentioned, for example. As a catalyst compound, a noble metal compound (noble metal salt) etc. are mentioned, for example. The content rate of the catalyst and / or catalyst compound in aqueous solution is set suitably.

Immersion temperature is 15 degreeC or more, Preferably it is 20 degreeC or more, and also 50 degrees C or less, Preferably it is 40 degrees C or less, for example.

Immersion time is 0.5 minutes or more, for example, preferably 1 minute or more, and also 10 minutes or less, Preferably it is 5 minutes or less, for example.

Subsequently, the laminated board 19 in which the catalyst film (not shown) was laminated | stacked on the surface is immersed in an electroless plating liquid.

An electroless plating liquid is prepared by mix | blending a nickel compound, a phosphorus compound, and water.

As a nickel compound, nickel salts, such as nickel sulfate and nickel nitrate, etc. are mentioned, for example. Nickel salts, when combined with water, form nickel cations (Ni ²⁺ ).

As a phosphorus compound, phosphorus reducing agents, such as hypophosphorous acid and hypophosphite (for example, sodium hypophosphite etc.), are mentioned, for example. When the phosphorus-based reducing agent is blended with water, it forms a phosphorus anion (specifically, hypophosphite anion: HPO ₂ ⁻ ).

The electroless plating solution may also contain additives such as complexing agents, oxycarboxylic acids, ammonium chloride and the like in an appropriate ratio.

The pH of the electroless plating solution is, for example, 2 or more, preferably 3 or more, and for example, 7 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 for example, 90 ° C or lower, preferably 80 ° C or lower. When the immersion temperature is outside the above range, the thickness of the adhesion layer 6 may not be set in a desired range.

When the laminated plate 19 is immersed in the electroless plating solution, the reduction action of the phosphorus anion (specifically, hypophosphite anion: HPO ₂ ⁻ ) on the surface of the adhesion layer 6 (specifically, the catalyst film), Nickel cations (Ni ²⁺ ) are reduced to form nickel (Ni), and the adhesion layer 6 is formed while containing phosphorus (P) therein.

Thereafter, the adhesion layer 6 is heated (baked) as necessary.

Heating temperature is below the glass transition temperature of the insulated substrate 2 and the optical adjustment film 24, and is 100 degreeC or more, for example, Preferably it is 120 degreeC or more. The heating time is, for example, 1 minute or more, preferably 5 minutes or more, and for example, 90 minutes or less, preferably 60 minutes or less.

Furthermore, after that, the upper surface (surface) of the contact bonding layer 6 is washed with water as needed.

Subsequently, as shown in FIG.1 (d), the low resistance layer 5 is formed in the upper surface of the adhesion layer 6 (low resistance process).

Specifically, the low resistance layer 5 is formed on the upper surface of the adhesion layer 6 by, for example, plating, physical vapor deposition, or the like. Preferably, from the viewpoint of improving the adhesiveness to the adhesion layer 6, plating, More preferably, the low resistance layer 5 is formed by electrolytic plating.

Thereafter, as shown in FIG. 1E, the protective layer 7 is formed on the upper surface of the low resistance layer 5.

The protective layer 7 can be formed by the same method as the above-mentioned adhesion layer 6. On the other hand, as plating, in view of the uniformity of the thickness of the protective layer 7 and the corrosion prevention of the low resistance layer 5, electroless plating is preferably employed.

Thereby, the transparent electrode substrate 1 is obtained.

As shown in FIG. 1E, the transparent electrode substrate 1 forms 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), it may be formed as the conductor pattern 8.

That is, as shown to Fig.2 (a)-(d), in the transparent electrode substrate 1, the conductor pattern 8 is obtained by pattern-processing the conductor layer 3 by etching.

As shown in FIG. 2 (d), the conductor pattern 8 includes the lead wiring 9 and the transparent electrode 10 that is formed (not shown) in succession to the lead wiring 9.

The lead wires 9 are arranged in plural on the main end of the transparent electrode substrate 1 with a gap therebetween. The lead wires 9 are formed on the upper surface of the optical adjustment film 24 (on the insulating substrate 2), and the conductor layer 3 (specifically, the transparent conductor layer 4, the adhesion layer 6, and the low layer). Resistive layer 5 and protective layer 7).

In the liquid crystal display device 30 (refer FIG. 3) mentioned later, the transparent electrode 10 comprises the detection part (sensor), and is arrange | positioned in multiple numbers at the center of the transparent electrode board | substrate 1 with mutually spaced apart. It is. As the pattern of the transparent electrode 10, it extends in the front-back direction, for example, and is formed in the left-right direction at intervals mutually. The transparent electrode 10 is on the optical adjustment film 24 and consists of the transparent conductor layer 4.

Next, a method (patterning step) of etching the conductor layer 3 to form the conductor pattern 8 in the transparent electrode substrate 1 will be described with reference to FIGS. 2A to 2D. do.

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

Specifically, first, the dry film resist is laminated on the entire upper surface of the protective layer 7, and then the first etching resist 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 1st etching resist 17 is etched. In this etching, the etching liquid which melt | dissolves the conductor layer 3 and does not dissolve the transparent conductor layer 4 and the optical adjustment film 24 is used.

Thereby, the conductor pattern 8 which consists of the transparent conductor layer 4, the contact bonding layer 6, the low resistance layer 5, and the protective layer 7 is formed.

Thereafter, the first etching resist 17 is removed by peeling.

Next, in this method, as shown in FIG. 2C, the second etching resist 18 corresponds to the lead wiring 9 (see FIG. 2D) on the optical adjustment film 24. The conductor layer 3 is covered and formed so as to expose the conductor layer 3 corresponding to the transparent electrode 10 (see FIG. 2 (d)).

Specifically, first, the 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, secondly, by exposure and development. The etching resist 18 is formed in the above pattern.

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

In etching, the etching solution which dissolves the protective layer 7, the low resistance layer 5, and the adhesion layer 6 while not dissolving the transparent conductor layer 4 and the optical adjustment film 24 is used.

Thereafter, the second etching resist 18 is removed by peeling.

Thereby, the transparent electrode 10 is formed from the transparent conductor layer 4 by removing the protective layer 7, the low resistance layer 5, and the adhesion layer 6 from a part of the conductor pattern 8. In addition, the conductor layer 3 corresponding to the remainder of the conductor pattern 8 is used as the lead wire 9.

On the other hand, in the conductor layer 3 other than the pattern of the transparent electrode 10 and the lead-out wiring 9, by the etching shown in FIG.2 (b), the protective layer 7, the low resistance layer 5, The adhesion layer 6 and the transparent conductor layer 4 are etched.

Thereby, as shown in FIG.2 (d), the transparent electrode board | substrate 1 in which the conductor pattern 8 provided with the drawing wiring 9 and the transparent electrode 10 is formed in the upper surface of the optical adjustment film 24. As shown in FIG. Get)

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

And since the transparent electrode board | substrate 1 obtained by this manufacturing method is interposed between the transparent conductor layer 4 and the low resistance layer 5, and is provided with the adhesion layer whose phosphorus content rate is 8 mass% or more, The adhesion between the transparent conductor layer 4 and the low resistance layer 5 can be sufficiently increased. Therefore, reliability can be improved.

<Touch panel>

Next, the liquid crystal display device 30 including the touch panel 20 in which the transparent electrode substrate 1 shown in FIG. 2 (d) is used 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 mobile phone, and has a plate-shaped LCD module 14 and a polarizing plate 12 provided on the LCD module 14 with a gap therebetween. The touch panel 20 provided in the upper surface of the polarizing plate 12, and the protective glass layer 11 provided in the upper surface of the touch panel 20 are provided.

Although not shown, a circuit board, a housing, and the like are provided below the LCD module 14.

Moreover, in the center part of the left-right direction and the front-back direction of the liquid crystal display device 30, between the LCD module 14 and the polarizing plate 12 is the gap layer 13 as an air layer. On the other hand, the gap layer 13 is partitioned by the spacer 21 arrange | positioned at frame shape in the principal end part.

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

Specifically, the touch panel 20 includes a plurality (two) of transparent electrode substrates 1 disposed in a thickness direction with a gap therebetween, a transparent insulating film 22 interposed therebetween, and a plurality ( Three pressure-sensitive adhesive layers 15 are provided.

In each of the two transparent electrode substrates 1, the conductor layer 3 is disposed so as to face upward (thickness direction). In addition, in the two transparent electrode substrates 1, the direction in which the transparent electrodes 10 extend is set to cross each other (specifically, orthogonally) when projected in the thickness direction, for example, upper transparent The electrodes 10 extend in the front-rear direction and are disposed with a distance from each other in the left-right direction, while the lower transparent electrodes 10 extend in the left-right direction, and are disposed with a distance from each other in the front-rear direction. do.

The transparent insulating film 22 is formed with the same material and dimensions as the insulating substrate 2 in the above-mentioned transparent electrode substrate 1.

The pressure-sensitive adhesive layer 15 is disposed 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 the upper transparent electrode substrate 1. It is installed on the upper surface of.

In the liquid crystal display device 30, when a finger or the like touches or approaches the upper surface of the protective glass layer 11, a difference in capacitance is generated as compared with the case where the finger or the like does not touch, and it is extracted as a detection signal. Through the wiring 9, it is transmitted to a circuit board not shown.

On the other hand, the input signal is input from the circuit board to the LCD module 14, and the LCD module 14 displays an image. The image is visually recognized by the operator (or viewer) through the polarizing plate 12, the touch panel 20, and the protective glass layer 11.

And since this liquid crystal display device 30 is equipped with the transparent electrode substrate 1 with improved reliability, it is excellent in reliability.

<Modifications>

Although the image display apparatus of this invention is demonstrated as the liquid crystal display device 30 in the description of FIG. 3 and FIG. 4, although not shown, it can also be used as an organic electroluminescent device (organic EL device) etc., for example.

In addition, in each subsequent figure, the same code | symbol is attached | subjected about the member similar to FIGS. 1-4, and the detailed description is abbreviate | omitted.

In the embodiment of FIG. 1E, the conductor layer 3 is provided only on the upper side (one side in the thickness direction) of the insulating substrate 2. However, as shown in FIG. 5, for example, It can also be provided in both sides (upper and lower side, the thickness direction one side, and the other side).

That is, in FIG. 5, the transparent electrode substrate 1 is formed on the surface of the insulating substrate 2, the optical adjustment film 24 formed on the upper and lower surfaces thereof, and the two optical adjustment films 24, respectively. A conductor layer 3 is provided.

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

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

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

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

When using such a transparent electrode substrate 1 as the touch panel 20, the touch panel 20 can be comprised from one transparent electrode substrate 1. FIG. The transparent electrodes 10 in the upper and lower conductive patterns 8 are formed in a pattern intersecting with each other (specifically, orthogonal) when projected in the thickness direction.

In addition, although the protective layer 7 is provided in the conductor layer 3 in embodiment of FIG. 1 (e), for example, as shown to FIG. 1 (d), without providing the protective layer 7, The conductor layer 3 can also be comprised.

In FIG. 1D, the conductor layer 3 is formed from the transparent conductor layer 4, the adhesion layer 6, and the low resistance layer 5.

In addition, as shown in FIG. 6, the conductor layer 3 of the transparent electrode board | substrate 1 shown to FIG. It may be formed.

In FIG. 6, the lead wire 9 includes the transparent conductor layer 4, the adhesion layer 6, and the low resistance layer 5.

In order to obtain the transparent electrode substrate 1 shown in FIG. 6, as shown in FIGS. 2A to 2D, first, the first etching resist 17 is placed on the upper surface of the low resistance layer 5. Next, the conductor layer 3 (transparent conductor layer 4, adhesion layer 6 and low resistance layer 5) exposed from the first etching resist 17 is subsequently etched (patterned), and then The first etching resist 17 is peeled off. Thereafter, the second etching resist 18 is coated on the optical adjustment film 24 with the conductor layer 3 corresponding to the lead wiring 9, and the conductor layer 3 corresponding to the transparent electrode 10. ), The low resistance layer 5 and the adhesion layer 6 exposed from the second etching resist 18 are then removed by etching. Thereafter, the second etching resist 18 is removed.

Preferably, as shown in FIG. 1 (e), the protective layer 7 is provided in the conductor layer 3, and as shown in FIG. 2 (d), the protective layer 7 is drawn out from the wiring ( 9) to be installed. Thereby, damage and corrosion of the low resistance layer 5 in the conductor layer 3 shown in FIG. 1 (e), and the low resistance layer in the lead-out wiring 9 shown in FIG. 2 (d) ( 5) Damage or corrosion can be effectively prevented.

In the embodiment of FIGS. 1E and 2D, the optical adjustment film 24 is provided on the upper surface of the insulating substrate 2, but as shown in FIGS. 7 and 8, for example, the optical adjustment film. The transparent conductor layer 4 can also be directly formed in the upper surface of the insulated substrate 2, without providing 24.

Preferably, from the viewpoint of improving the optical characteristics, as shown in Fig. 1 (e) and Fig. 2 (d), the optical adjusting film 24 is provided on the upper surface of the insulating substrate 2.

Example

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, this invention is not limited to an Example and a comparative example at all.

<Production of Transparent Electrode Substrate>

Example 1

An insulating substrate having a thickness of 50 μm made of PET (glass transition temperature: 180 ° C. or more) was prepared (see FIG. 1 (a)). Subsequently, an optical adjusting film having a thickness of 25 nm made of SiO ₂ system (glass transition temperature: 200 ° C. or more) was laminated on the entire upper surface of the insulating substrate.

Next, the conductor layer was formed on the insulated substrate (optical adjustment film) (refer FIG. 1 (b)-FIG. 1 (e)).

Specifically, first, the transparent conductor layer made of ITO was formed on the upper surface of the optical adjustment film by sputtering. The thickness of the transparent conductor layer was 25 nm. Thereby, the laminated board provided with the insulated substrate, the optical adjustment film, and the transparent conductor layer was prepared.

Then, the adhesion layer was formed in the upper surface of the transparent conductor layer (refer FIG. 1 (c)).

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

Subsequently, the catalyst film was laminated | stacked on the surface of the transparent conductor layer by immersing a laminated board for 5 minutes in 25 degreeC catalyst liquid containing palladium.

Separately, an electroless plating solution containing nickel sulfate and hypophosphorous acid (reducing agent) was prepared. In the electroless plating solution, the mass ratio of nickel cations (Ni ²⁺ ) was adjusted to 2.5 mass%, and the mass ratio of hypophosphite anion (HPO ₂ ⁻ ) to 2 mass%. In addition, the pH of the electroless plating solution was 4.6.

And the laminated board in which the catalyst film was laminated | stacked on the surface of the transparent conductor layer was immersed for 5 minutes in 70 degreeC electroless plating liquid. Thereby, the adhesion layer of thickness 500nm which consists of a composition containing nickel and phosphorus was formed (through a catalyst film) on the whole upper surface of a transparent conductor layer.

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

Next, the low resistance layer was formed on the upper surface of the adhesion layer (see FIG. 1 (d)).

Subsequently, the laminated plate in which the adhesion layer was formed was immersed in the copper sulfate plating solution containing an additive, and it electrolytic-copper-plated for 1 minute and 20 ^second with the average current density of 1 A / dm <^2> . Thereby, the low-resistance layer of thickness 200nm which consists of copper was formed in the whole upper surface of an adhesion layer.

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

The low resistance layer was formed in accordance with the formation of the adhesion layer.

This obtained the transparent electrode substrate in which the transparent conductor layer, the contact bonding layer, the low resistance layer, and the protective layer were laminated | stacked sequentially on the optical adjustment film.

Examples 2-5 and Comparative Examples 1-5

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, the protective layer, and the like were changed in accordance with Table 1 and Table 2.

The detail of the change point from Example 1 is described below.

In Example 3, the protective layer was formed of electrolytic nickel. Detailed conditions of the electrolytic nickel are shown below.

Electrolytic Nickel Plating Solution: It consists of nickel sulfate, nickel chloride, boric acid and additives.

Electrolytic Condition: 0.5A / dm ²

Time: 30 seconds

Temperature: 40 ° C

In Example 4, the low resistance layer was formed by electroless copper plating. The detailed conditions of electroless copper plating are shown below.

Electrolytic Copper Plating Solution: Contains copper sulfate and formalin.

Time: 15 seconds

Temperature 40 ° C

For Example 5 and Comparative Example 1, no protective layer was formed.

About the comparative example 1, the contact bonding layer was formed from copper by sputtering.

For Comparative Examples 3 to 5, an adhesion layer was formed from a composition composed of nickel and boron using an electroless plating solution containing nickel sulfate and boron.

The boron concentration in each of the films of Comparative Examples 3 to 5 was appropriately adjusted by the ratio of the dimethylamine borane concentration and the nickel sulfate concentration, the pH, and the additives in the plating solution.

<Production of image display device>

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

<Evaluation>

Adhesion

Adhesion test (tape cross-cut test) was performed with respect to the transparent electrode board | substrate before forming a protective layer (transparent electrode board | substrate obtained in Example 5).

That is, the sheath which followed the front-back direction and the left-right direction in the 1 cm square area | region of the conductor layer of the said transparent electrode board | substrate was put in space | interval 1mm using a cutter knife. Then, when an adhesive tape is adhered to a conductor layer and the adhesive tape is peeled from a conductor layer, the thing which low resistance layer did not peel from a transparent conductor layer is evaluated as "(circle)", and a low resistance layer peels from a transparent conductor layer. What was evaluated was evaluated as "x".

Resistance value (surface resistance)

The surface resistance of the conductor layer of the transparent electrode substrate of Examples 2-5 and Comparative Examples 1-5 was measured with the resistivity meter (made by Lorestar AX MCP-370 type Mitsubishi Chemical Analyst).

Antirust (corrosive)

The image display apparatus provided with the transparent electrode board | substrate of Examples 1-5 and Comparative Examples 1-5 was thrown into 85 degreeC and 85% of constant temperature high humidity for 500 hours. Then, the thing with no discoloration corrosion in the lead-out wiring was evaluated as "(circle)", and the thing with discoloration corrosion was evaluated as "x".

Phosphorus content and boron content

The phosphorus content ratio or boron content ratio in an adhesion layer and a protective layer was computed by melt | dissolving a film and measuring ICP.

The results are shown in the adhesion layer column and the protective layer column, respectively.

"%" In a table | surface shows that it is "mass%."

In addition, although the said description was provided as embodiment of an illustration of this invention, this is only a mere illustration and it must not interpret it limitedly. Modifications of the present invention apparent to those skilled in the art are included in the following claims.

Claims (15)

An insulating substrate and a conductor layer formed on at least one side of the insulating substrate in a thickness direction;
Wherein the conductor layer comprises:
A transparent conductor layer formed on one side of the insulating substrate in the thickness direction;
A low resistance layer formed on one side of the thickness direction of the transparent conductor layer to reduce electrical resistance of the conductor layer;
A transparent electrode substrate, which is interposed between the transparent conductor layer and the low resistance layer, and has an adhesion layer having a phosphorus content ratio of 8% by mass or more. The method of claim 1,
The transparent conductor layer is formed from indium tin oxide,
The low resistance layer is formed from at least one metal selected from the group consisting of copper, silver and gold,
The adhesion layer is formed from a composition containing nickel and phosphorus. The method of claim 1,
The transparent electrode substrate, wherein the conductor layer further includes a protective layer formed from an easy etching material on one side of the thickness direction of the low resistance layer. The method of claim 3, wherein
The easy-etching material is at least one metal selected from nickel, tin and nickel copper alloys. The method of claim 1,
The said transparent conductor layer is formed in the whole surface in the said thickness direction one side of the said insulated substrate,
The adhesion layer is formed on the entire surface of the thickness direction one side of the transparent conductor layer,
The low resistance layer is formed on an entire surface of the one side in the thickness direction of the adhesion layer. The method of claim 1,
The said conductor layer is formed as a conductor pattern in the said insulated substrate, The transparent electrode substrate characterized by the above-mentioned. The method according to claim 6,
The conductor pattern is,
A lead wire formed of the conductor layer;
A transparent electrode substrate, formed in succession to said lead-out wiring, comprising a transparent electrode made of said transparent conductor layer. A preparatory step of preparing a laminated plate having an insulated substrate and a transparent conductor layer laminated on at least one side in the thickness direction of the insulated substrate,
An adhesion layer lamination step of laminating an adhesion layer on one side of the thickness direction of the transparent conductor layer so that the phosphorus content ratio in the adhesion layer is 8% by mass or more, and
A low-resistance step of laminating a low-resistance layer on one side in the thickness direction of the adhesion layer is provided. The method of manufacturing a transparent electrode substrate. The method of claim 8,
And a patterning step of etching the conductor layer including the transparent conductor layer, the adhesion layer, and the low resistance layer after the low resistance step to form a conductor pattern. . The method of claim 9,
Removing the low resistance layer and the adhesion layer from a part of the conductor pattern to form a transparent electrode from the transparent conductor layer and to use the conductor layer corresponding to the remainder of the conductor pattern as lead wires; Method for producing a transparent electrode substrate characterized in that it further comprises. The method of claim 9,
A step of laminating a protective layer made of an easy etching material on one side of the thickness direction of the low resistance layer is further provided.
In the patterning step, a conductor pattern comprising the transparent conductor layer, the adhesion layer, the low resistance layer and the protective layer is etched to form a conductor pattern. The method of claim 11,
By removing the protective layer, the low resistance layer and the adhesion layer from a part of the conductor pattern, a transparent electrode is formed from the transparent conductor layer and the conductor layer corresponding to the remainder of the conductor pattern is drawn out. A process for producing a transparent electrode substrate, further comprising a step of forming a wiring. A transparent electrode substrate,
The transparent electrode substrate,
An insulating substrate and a conductor layer formed on at least one side in the thickness direction of the insulating substrate,
Wherein the conductor layer comprises:
A transparent conductor layer formed on one side of the insulating substrate in the thickness direction;
A low resistance layer formed on one side of the thickness direction of the transparent conductor layer to reduce electrical resistance of the conductor layer;
An image display device, comprising an adhesion layer interposed between the transparent conductor layer and the low resistance layer and having a phosphorus content ratio of 8% by mass or more. 14. The method of claim 13,
And the transparent electrode substrate is a touch panel. 14. The method of claim 13,
It is a liquid crystal display device, The image display apparatus characterized by the above-mentioned.

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