WO2015122392A1

WO2015122392A1 - Transparent conductor and method for producing same

Info

Publication number: WO2015122392A1
Application number: PCT/JP2015/053573
Authority: WO
Inventors: 仁一粕谷; 一成多田; 健一郎平田
Original assignee: コニカミノルタ株式会社
Priority date: 2014-02-13
Filing date: 2015-02-10
Publication date: 2015-08-20
Also published as: JPWO2015122392A1

Abstract

The objective of the present invention is to provide: a transparent conductor which has high light transmittance and achieves improved electrical connection between a transparent metal layer and a circuit board; and a method for producing the transparent conductor. A transparent conductor according to the present invention comprises at least a transparent substrate, a first high-refractive-index layer, a transparent metal layer and a second high-refractive-index layer in this order, and is characterized in that: the first high-refractive-index layer and/or the second high-refractive-index layer contains at least zinc sulfide; the transparent conductor is patterned; and the transparent metal layer is electrically connected to a circuit board via an anisotropic conductive member.

Description

Transparent conductor and method for producing the same

The present invention relates to a transparent conductor and a manufacturing method thereof. More specifically, the present invention relates to a transparent conductor improved in electrical connection between a transparent metal layer having a high light transmittance and a circuit board, and a method for manufacturing the transparent conductor.

In recent years, transparent conductors have been used in various devices such as liquid crystal displays, plasma displays, display devices such as inorganic and organic EL (electroluminescence) displays, touch panels, and solar cells.

In a touch panel type display device or the like, wiring including a transparent conductor is disposed on the image display surface of the display element. Therefore, the transparent conductor is required to have high light transmittance. In such various display devices, a transparent conductor using ITO having a high light transmittance is often used.

In recent years, a capacitive touch panel display device has been developed, and it is required to further reduce the surface electrical resistance of the transparent conductor. However, the conventional ITO film has a problem that the surface electric resistance cannot be sufficiently lowered.

Then, using the layer (henceforth Ag layer or a transparent metal layer) formed by vapor-depositing silver is examined for a transparent conductive layer (for example, refer patent document 1). In order to increase the light transmittance of the transparent conductor, the Ag layer is formed of a film having a high refractive index (for example, niobium oxide (Nb ₂ O ₅ ), IZO (indium / zinc oxide), ICO (indium / cerium oxide), a It has also been proposed to sandwich the film with GIO (a film made of gallium, indium, and oxygen) (see, for example, Patent Documents 2 to 4 and Non-Patent Document 1). Further, it has been proposed to sandwich the Ag layer with a layer containing zinc sulfide (hereinafter also referred to as a ZnS layer or a zinc sulfide-containing layer) (see, for example, Non-Patent Documents 2 and 3).

However, as shown in Patent Documents 2 to 4, a transparent conductor in which an Ag layer is sandwiched between dielectric layers such as niobium oxide and IZO has insufficient moisture resistance. As a result, when a transparent conductor is used in a high humidity environment, there is a problem that the Ag layer is easily corroded.

On the other hand, in the transparent conductor in which the Ag layer is sandwiched between the ZnS layers, although the moisture resistance of the transparent conductor is sufficiently high, silver is sulfided and sulfided when forming the Ag layer or forming the ZnS layer. Silver is likely to occur. As a result, there is a problem that the light transmittance of the transparent conductor is lowered.

In addition, since the insulating property of ZnS contained in the ZnS layer is high, there is a problem that the electrical connection with the Ag layer is not stable.

Special table 2011-508400 gazette JP 2006-184849 A JP 2002-15623 A JP 2008-226581 A

The present invention has been made in view of the above problems and situations. The problem to be solved is to provide a transparent conductor improved in electrical connection between a transparent metal layer having a high light transmittance and a circuit board, and a method for manufacturing the transparent conductor.

In order to solve the above problems, the present inventor is effective in that the transparent metal layer is electrically connected to the circuit substrate through the anisotropic conductive member in the process of examining the cause of the above problems. We found out that there was a present invention.
That is, the said subject which concerns on this invention is solved by the following means.

1. A transparent conductor having at least a transparent substrate, a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order;
At least one of the first high refractive index layer and the second high refractive index layer is a layer containing at least zinc sulfide,
The transparent conductor is patterned, and
A transparent conductor, wherein the transparent metal layer is electrically connected to a circuit board via an anisotropic conductive member.

2. A sulfurization preventing layer containing at least one compound selected from a metal oxide, a metal fluoride, and a metal nitride is provided between the zinc sulfide-containing layer and the transparent metal layer. The transparent conductor according to item.

3. It has a lead-out wiring part formed of the transparent conductor itself,
3. The transparent conductor according to

claim

1 or 2, wherein the lead-out wiring portion is electrically connected to the circuit board through the anisotropic conductive member.

4. The transparent conductor according to any one of claims 1 to 3, further comprising a lead wiring part and a touch sensor part.

5. It is a manufacturing method of the transparent conductor given in any 1 paragraph from the 1st term to the 4th term,
Forming a layer structure by laminating a first high refractive index layer, a transparent metal layer and a second high refractive index layer in this order on one surface of the transparent substrate;
Electrically connecting the layer structure to a circuit board through an anisotropic conductive member;
A method for producing a transparent conductor, comprising:

By the above means of the present invention, it is possible to provide a transparent conductor improved in electrical connection between a transparent metal layer having high light transmittance and a circuit board, and a method for manufacturing the transparent conductor.
The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

As described above, when the transparent metal layer and the layer containing ZnS are formed adjacent to each other, there is a problem that metal sulfide is easily generated and the light transmittance of the transparent conductor is likely to be lowered. The metal sulfide is presumed to be produced as follows.

When a transparent metal layer is formed on the first high refractive index layer as a layer containing at least zinc sulfide (hereinafter also referred to as a zinc sulfide-containing layer) by a vapor deposition method such as sputtering, the zinc sulfide-containing layer The unreacted sulfur component is expelled into the layer formation atmosphere by the transparent metal layer material (metal material). Then, the ejected sulfur component reacts with the metal, and metal sulfide is deposited on the zinc sulfide-containing layer. Moreover, when forming a zinc sulfide content layer and a transparent metal layer continuously, the sulfur component contained in the atmosphere of layer formation of a zinc sulfide content layer remains in a transparent metal layer atmosphere. And this sulfur component and the metal derived from a transparent metal layer react, and metal sulfide deposits on a zinc sulfide content layer.

On the other hand, when the second high refractive index layer (zinc sulfide-containing layer) is formed on the transparent metal layer, the metal in the transparent metal layer is expelled into the layer formation atmosphere by the material of the second high refractive index layer. . The ejected metal reacts with the sulfur component, and metal sulfide is deposited on the surface of the transparent metal layer. Furthermore, a metal sulfide is generated on the surface of the transparent metal layer also when the surface of the transparent metal layer comes into contact with the sulfur component in the layer forming atmosphere.

On the other hand, for example, as shown in FIG. 2, in the transparent conductive layer 10 according to the present invention, it is preferable that the first antisulfurization layer 5 a is laminated on the first high refractive index layer 2. In this configuration, since the first high refractive index layer 2 is protected by the first sulfidation preventing layer 5a, the sulfur component in the first high refractive index layer 2 is hardly ejected when the transparent metal layer 3 is formed. Further, even if the first high refractive index layer 2 and the transparent metal layer 3 are continuously formed, the sulfur component contained in the atmosphere of the first high refractive index layer 2 is formed in the first sulfurization preventing layer 5a. It reacts with the component and is adsorbed by the component of the first antisulfurization layer 5a. Therefore, the atmosphere in which the transparent metal layer 3 is formed does not easily contain sulfur, and the generation of metal sulfide is suppressed.

Further, in the transparent conductive layer 10 according to the present invention, the second sulfidation preventing layer 5 b is laminated on the transparent metal layer 3. In this configuration, since the transparent metal layer 3 is protected by the second antisulfurization layer 5b, the metal in the transparent metal layer 3 is hardly ejected when the second high refractive index layer 4 is formed. Further, the sulfur component in the atmosphere forming the second high refractive index layer 4 is difficult to come into contact with the surface of the transparent metal layer 3. Therefore, it is difficult for metal sulfides to be generated on the surface of the transparent metal layer 3.

Furthermore, since the resistance is low, the transparent conductive layer can be used as a lead-out wiring when adapted to a touch panel. Conventionally, the lead wiring is provided after patterning the transparent conductive layer in the touch panel. However, when the transparent conductive layer is patterned, the step of providing the lead wiring is reduced by creating the lead wiring with the transparent conductive layer. Can do.
In addition, the problem that the layer containing ZnS is highly insulating and difficult to conduct is that the conductive particles enter the transparent conductive layer by heating and pressurizing the conductive particle-containing layer, and the transparent metal layer in the transparent conductive layer I found that the problem is solved by the contact between the electrode and the conduction.

Schematic diagram showing the entire transparent conductor of the present invention The schematic diagram which shows the arrangement | positioning aspect of the connection of the transparent conductor of this invention, and a circuit board Schematic sectional view showing an example of a touch panel Schematic sectional view showing an example of the layer structure of a transparent conductor Schematic sectional view showing an example of conductive particles Schematic sectional view showing an example of conductive particles Schematic which shows the manufacturing method electrically connected with a circuit board through the anisotropic conductive member of the transparent conductor of this invention Schematic sectional view showing an example of the transparent conductor of the present invention Schematic sectional view showing an example of the transparent conductor of the present invention

The transparent conductor of the present invention is a transparent conductor having at least a transparent substrate, a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order, the first high refractive index layer and At least one layer of the second high refractive index layer is a layer containing at least zinc sulfide, the transparent conductor is patterned, and the transparent metal layer is a circuit through an anisotropic conductive member. It is electrically connected to the substrate. This feature is a technical feature common to the inventions according to claims 1 to 5.

As an embodiment of the present invention, at least one kind selected from a metal oxide, a metal fluoride, and a metal nitride is provided between the layer containing zinc sulfide and the transparent metal layer from the viewpoint of manifesting the effects of the present invention. It is preferable to have a sulfidation preventive layer containing the above compound.
This is because the atmosphere in which the transparent metal layer is formed does not easily contain sulfur, and the generation of metal sulfide is suppressed.

Further, it is preferable that a lead-out wiring portion formed of the transparent conductor itself is provided, and the lead-out wiring portion is electrically connected to the circuit board via the anisotropic conductive member. This is because it suitably functions as a touch panel sensor.

Further, it is preferable that the lead-out wiring part and the touch sensor part are provided, because the transparent conductive layer can be used as the lead-out wiring, so that the process of providing the lead-out wiring can be reduced by one.

Moreover, as a method for producing a transparent conductor, a step of forming a layer structure by laminating a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order on one surface of a transparent substrate; It is preferable that the method further includes a step of electrically connecting the layer structure to a circuit board through an anisotropic conductive member. Thereby, a transparent conductor can be manufactured suitably.

Hereinafter, the present invention, its constituent elements, and modes and modes for carrying out the present invention will be described in detail. In the present application, “˜” is used in the sense of including the numerical values described before and after it as lower and upper limits.

The transparent conductor of the present invention is a transparent conductor having at least a transparent substrate, a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order. (2) At least one of the high refractive index layers is a layer containing at least zinc sulfide, the transparent conductor is patterned, and the transparent metal layer is electrically connected to the circuit board via the anisotropic conductive member. Connected.
An example of the outline of the patterned transparent conductor 100 of this invention is shown to FIG. 1A. An example of the layer configuration of the transparent conductor 100 is shown in FIG. 2 (the lead wiring portion is not shown). As shown in FIG. 1A, a conductive region a and an insulating region b are formed in the transparent conductive layer 10 of the transparent conductor 100 by patterning.
As shown in FIG. 2, the transparent conductor of the present invention contains at least one compound selected from a metal oxide, a metal fluoride, and a metal nitride between a layer containing zinc sulfide and a transparent metal layer. It is preferable to have a sulfidation preventing layer.
Moreover, it is preferable to have the lead-out wiring part 12 pulled out from the conduction | electrical_connection area a. The lead wiring part 12 is preferably formed of the transparent conductor 100 itself.

The transparent conductor of the present invention preferably has a lead-out wiring portion formed of the transparent conductor itself, and the lead-out wiring portion is preferably electrically connected to the circuit board via an anisotropic conductive member. .
Specifically, the lead-out wiring portion includes a conductive particle containing layer 6 / electrode 7 / flexible substrate 8 (circuit board, flexible printed circuit board, and FPC) on the opposite surface of the transparent conductive layer 10 that the transparent substrate 1 contacts. Also referred to as a substrate).
That is, the region of the lead-out wiring portion 12 that is connected to the circuit board serving as the connection terminal 11 has the conductive particle-containing layer 6, the electrode 7, and the flexible substrate 8 in the lead-out wiring portion formed of the transparent conductor itself. It is formed by pressure bonding (see FIG. 1B, the electrode 7 is not shown). In FIG. 1B, illustration of the transparent conductive layer 10 patterned in the X-axis direction is omitted for the sake of simplicity.

From the state shown in FIG. 1B, the conductive particle-containing layer 6, the electrode 7 and the flexible substrate 8 are pressure-bonded, and the display panel 16 is bonded to the transparent conductive layer 10 (transparent conductor 100) with an adhesive 15. Can be manufactured (see FIG. 1C).
When a display panel 16 is bonded to the transparent conductive layer 10 (transparent conductor 100) to form a touch panel, a region surrounded by a broken line illustrated in FIG. 1A functions as the touch sensor unit 13.
As a method for manufacturing the touch panel by bonding the display panel 16 to the transparent conductive layer 10 (transparent conductor 100), a known method can be appropriately used.

As shown in FIG. 2, the transparent conductor 100 of the present invention is provided with a transparent substrate 1 and a transparent conductive layer 10. The transparent conductive layer 10 is provided with at least a first high refractive index layer 2, a transparent metal layer 3, and a second high refractive index layer 4.
In the transparent conductor 100 of the present invention, either one or both of the first high refractive index layer 2 and the second high refractive index layer 4 are zinc sulfide-containing layers containing ZnS.
Further, between the zinc sulfide-containing layer (the first high refractive index layer 2 and the second high refractive index layer 4) and the transparent metal layer 3, the sulfide prevention layer 5 (the first sulfide prevention layer 5a and the second sulfide). A prevention layer 5b) is preferably provided.
Further, as described above, the transparent conductive layer 10 is patterned. A known method can be used as a patterning method and shape, and the patterning method and shape can be appropriately changed according to the purpose of use of the transparent conductor.

Hereinafter, the transparent substrate 1 and the transparent conductive layer 10 will be described, and further, the conductive particle-containing layer 6 provided in the lead-out wiring portion will be described. The electrode generally used in the range which does not inhibit the effect of this invention can be used for the electrode used by this invention. Similarly, a flexible substrate can be used as long as it is a flexible printed circuit board that can be greatly deformed.

The transparent conductive layer 10 may be provided with a layer other than the first high refractive index layer 2, the transparent metal layer 3, the second high refractive index layer 4, and the antisulfurization layer 5. For example, an underlayer that can become a growth nucleus when forming the transparent metal layer 3 may be provided adjacent to the transparent metal layer 3 between the transparent metal layer 3 and the first high refractive index layer 2. However, the layers constituting the transparent conductive layer 10 according to the present invention are all layers made of an inorganic material. For example, even if an adhesive layer made of an organic resin is laminated on the second high refractive index layer 4, the laminated body from the first high refractive index layer 2 to the second high refractive index layer 4 is made of the transparent conductive layer 10. It is.

The transparent conductor 100 of the present invention has a transparent substrate 1 in addition to the transparent conductive layer 10 including a first high refractive index layer, a transparent metal layer, and a second high refractive index layer. Furthermore, the transparent metal layer is electrically connected to the circuit board via an anisotropic conductive member.
After describing the layer structure of the transparent conductive layer first, the other parts will be described.

1. 1. Layer structure of transparent conductive layer (1-1) First high refractive index layer The first high refractive index layer 2 is a light transmitting property of the conductive region a of the transparent conductor, that is, the region where the transparent metal layer 3 is formed. And is formed at least in the conduction region a of the transparent conductor 100. The first high-refractive index layer 2 may be formed also in the insulating region b of the transparent conductor 100, but from the viewpoint of making it difficult to visually recognize the pattern formed of the conductive region a and the insulating region b, only the conductive region a. It is preferable to be formed.

The first high refractive index layer 2 includes a dielectric material or an oxide semiconductor material having a refractive index higher than that of the transparent substrate 1 described later. The refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material is preferably 0.1 to 1.1 larger than the refractive index of light having a wavelength of 570 nm of the transparent substrate 1, and is preferably 0.4 to 1.0. Larger is more preferable.
On the other hand, the specific refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the first high refractive index layer 2 is preferably larger than 1.5, and is 1.7 to 2.5. More preferably, it is 1.8 to 2.5. When the refractive index of the dielectric material or the oxide semiconductor material is larger than 1.5, the first high refractive index layer 2 sufficiently adjusts the light transmittance of the conduction region a of the transparent conductor 100.
The refractive index of the first high refractive index layer 2 is adjusted by the refractive index of the material included in the first high refractive index layer 2 and the density of the material included in the first high refractive index layer 2.

The dielectric material or oxide semiconductor material contained in the first high refractive index layer 2 may be an insulating material or a conductive material. The dielectric material or oxide semiconductor material can be a metal oxide. _TiO 2 Examples of metal oxides, ITO (indium tin _{_{_{_{oxide), ZnO, Nb 2 O 5}}}} , ZrO 2, CeO 2, Ta 2 O 5, Ti 3 O 5, Ti 4 O 7, Ti 2 O 3 , TiO, SnO ₂ , La ₂ Ti ₂ O ₇ , IZO (indium oxide / zinc oxide), AZO (Al doped ZnO), GZO (Ga doped ZnO), ATO (Sb doped SnO), ICO (indium cerium oxide) , Bi ₂ O ₃ , Ga ₂ O ₃ , GeO ₂ , WO ₃ , HfO ₂ , a-GIO (amorphous oxide composed of gallium, indium, and oxygen) and the like. The first high refractive index layer 2 may contain only one kind of the metal oxide or two or more kinds.

Further, the dielectric material or the oxide semiconductor material included in the first high refractive index layer 2 may be ZnS. When ZnS is contained in the first high refractive index layer 2, moisture hardly penetrates from the transparent substrate 1 side, and corrosion of the transparent metal layer 3 is suppressed. The first high refractive index layer 2 may contain only ZnS, and may contain other materials together with ZnS. Materials included with ZnS is a metal oxide or SiO ₂ or the like, which may be the dielectric material or an oxide semiconductor material, particularly preferably SiO _2. When SiO ₂ is contained together with ZnS, the first high refractive index layer is likely to be amorphous, and the flexibility of the transparent conductor is likely to be enhanced.

When the first high refractive index layer 2 contains other materials together with ZnS, the amount of ZnS is 0.1 to 95% by mass or less with respect to the total number of moles of the materials constituting the first high refractive index layer 2. It is preferably 50 to 90% by mass or less, and more preferably 60 to 85% by mass or less.
When the ratio of ZnS is high, the sputtering rate is increased, and the formation rate of the first high refractive index layer 2 is increased. On the other hand, when many components other than ZnS are contained, the amorphous nature of the first high refractive index layer 2 is increased, and cracking of the first high refractive index layer 2 is suppressed.

The thickness of the first high refractive index layer 2 is preferably 15 to 150 nm, more preferably 20 to 80 nm. When the thickness of the first high refractive index layer 2 is 15 nm or more, the first high refractive index layer 2 sufficiently adjusts the light transmittance of the conductive region a of the transparent conductor 100. On the other hand, if the thickness of the first high refractive index layer 2 is 150 nm or less, the light transmittance of the region including the first high refractive index layer 2 is unlikely to decrease. The thickness of the first high refractive index layer 2 is measured with an ellipsometer.

The first high refractive index layer 2 can be a layer formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method and a thermal CVD method. From the standpoint that the refractive index (density) of the first high refractive index layer 2 is increased, the first high refractive index layer 2 is preferably a layer formed by an electron beam evaporation method or a sputtering method. In the case of the electron beam evaporation method, in order to increase the film density, it is desirable that there is an assist by an ion assist method (ION Assisted Deposition: IAD).

Further, when the first high refractive index layer 2 is a layer patterned into a desired shape, the patterning method is not particularly limited. The first high refractive index layer 2 may be, for example, a layer formed in a pattern by a vapor deposition method by arranging a mask having a desired pattern on the surface to be formed. It may be a layer patterned by.

(1-2) First Antisulfuration Layer When ZnS is contained in the first high refractive index layer, that is, when the first high refractive index layer 2 is a zinc sulfide-containing layer, as shown in FIG. It is preferable that a first antisulfurization layer 5 a is provided between the high refractive index layer 2 and the transparent metal layer 3. Although the first sulfidation preventing layer 5a may be formed also in the insulating region b of the transparent conductor 100, as shown in FIG. 4 from the viewpoint of making it difficult to visually recognize the pattern composed of the conductive region a and the insulating region b. In addition, it is preferably formed only in the conduction region a.

The first sulfidation preventing layer 5a may be a metal oxide, metal nitride, metal fluoride, or the like, or a layer containing Zn. The first sulfidation preventing layer 5a may contain only one kind or two or more kinds. However, when the first high refractive index layer 2, the first sulfidation preventing layer 5a, and the transparent metal layer 3 are continuously formed, the metal oxide can react with sulfur or adsorb sulfur. A compound is preferred. In the case where the metal oxide is a compound that reacts with sulfur, the reaction product of the metal oxide and sulfur preferably has high visible light permeability.

Examples of metal oxides include TiO ₂ , ITO, ZnO, Nb ₂ O ₅ , ZrO ₂ , CeO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , Ti ₄ O ₇ , Ti ₂ O ₃ , TiO, SnO _2. , La ₂ Ti ₂ O ₇ , IZO, AZO, GZO, ATO, ICO, Bi ₂ O ₃ , a-GIO, Ga ₂ O ₃ , GeO ₂ , SiO ₂ , Al ₂ O ₃ , HfO ₂ , SiO, MgO, Y ₂ O ₃ , WO _{3 and the} like are included.
Examples of metal fluorides include LaF ₃ , BaF ₂ , Na ₅ Al ₃ F ₁₄ , Na ₃ AlF ₆ , AlF ₃ , MgF ₂ , CaF ₂ , BaF ₂ , CeF ₃ , NdF ₃ , YF _{3 and the} like. .
Examples of the metal nitride include Si ₃ N ₄ , AlN, and the like.

Here, it is preferable that the thickness of the first sulfidation preventing layer 5a is a thickness capable of protecting the surface of the first high refractive index layer 2 from an impact when the transparent metal layer 3 is formed. On the other hand, ZnS that can be contained in the first high refractive index layer has a high affinity with the metal contained in the transparent metal layer 3. Therefore, if the thickness of the first antisulfurization layer 5a is very thin and a part of the first high refractive index layer 2 is slightly exposed, a transparent metal layer grows around the exposed part, and the transparent metal Layer 3 tends to be dense. That is, the first antisulfurization layer 5a is preferably relatively thin, preferably 0.1 to 10 nm, more preferably 0.5 to 5 nm, and further preferably 1 to 3 nm. The thickness of the first sulfurization preventing layer 5a is measured with an ellipsometer.

The first sulfidation preventing layer 5a may be a layer formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, or a thermal CVD method.

When the first antisulfurization layer 5a is a layer patterned into a desired shape, the patterning method is not particularly limited. The first sulfidation preventing layer 5a may be a layer formed in a pattern by a vapor deposition method, for example, by placing a mask having a desired pattern on the surface to be formed, by a known etching method. It may be a patterned layer.

(1-3) Transparent Metal Layer The transparent metal layer 3 is a layer for conducting electricity in the transparent conductor 100. In the transparent conductive layer 10 provided in the transparent conductor of the present invention, as shown in FIG. 1A, the transparent metal layer 3 may be laminated on the entire surface of the transparent substrate 1, according to the intended use of the device. It may be patterned into a desired shape. In the transparent conductor of the present invention, the region a where the transparent metal layer 3 is laminated is a region where electricity is conducted (hereinafter also referred to as “conduction region”). On the other hand, the region b not including the transparent metal layer 3 is an insulating region (see FIGS. 2 and 4).

The pattern composed of the conductive region a and the insulating region b is appropriately selected according to the use of the transparent conductor 100. For example, when the transparent conductor 100 is applied to an electrostatic touch panel, as shown in FIG. 1A, a pattern including a plurality of conductive regions a and a line-shaped insulating region b that divides the conductive regions a. sell.

The metal contained in the transparent metal layer 3 is not particularly limited as long as it is a highly conductive metal, and can be, for example, silver, copper, gold, platinum, titanium, chromium, or the like. The transparent metal layer 3 may contain only one kind of these metals or two or more kinds. From the viewpoint of high conductivity, the transparent metal layer is preferably made of silver or an alloy containing 90 at% or more of silver. The metal combined with silver can be zinc, gold, copper, palladium, aluminum, manganese, bismuth, neodymium, molybdenum, and the like. For example, when silver and zinc are combined, the sulfidation resistance of the transparent metal layer is increased. When silver and gold are combined, salt resistance (NaCl) resistance increases. Furthermore, when silver and copper are combined, the oxidation resistance increases.

The plasmon absorption rate of the transparent metal layer 3 is preferably 10% or less (over the entire range) over a wavelength range of 400 to 800 nm, more preferably 7% or less, and even more preferably 5% or less. If there is a region having a large plasmon absorption rate in a part of the wavelength of 400 to 800 nm, the transmitted light of the conductive region a of the transparent conductor 100 is likely to be colored.

The plasmon absorption rate at a wavelength of 400 to 800 nm of the transparent metal layer 3 is measured by the following procedure.
(I) A platinum palladium film is formed to a thickness of 0.1 nm on a glass substrate using a magnetron sputtering apparatus. The average thickness of platinum-palladium is calculated from the film formation rate of the manufacturer's nominal value of the sputtering apparatus. After that, a 20 nm thick metal film is formed by sputtering on the substrate to which platinum palladium is attached.

(Ii) Then, measurement light is incident from an angle inclined by 5 ° with respect to the normal of the surface of the obtained metal film, and the light transmittance and light reflectance of the metal film are measured. Then, light absorptivity = 100− (light transmittance + light reflectance) is calculated from the light transmittance and light reflectance at each wavelength, and this is used as reference data. The light transmittance and light reflectance are measured with a spectrophotometer.

(Iii) Subsequently, a transparent metal layer to be measured is formed on the same glass substrate. And about the said transparent metal layer, light transmittance and light reflectance are measured similarly. The reference data is subtracted from the obtained light absorption rate, and the calculated value is defined as the plasmon absorption rate.

The thickness of the transparent metal layer 3 is 10 nm or less, preferably 3 to 9 nm, and more preferably 5 to 8 nm. In the transparent conductor 100 of the present invention, since the thickness of the transparent metal layer 3 is 10 nm or less, the metal inherent reflection hardly occurs in the transparent metal layer 3. Furthermore, when the thickness of the transparent metal layer 3 is 10 nm or less, the light transmittance of the transparent conductor 100 can be easily adjusted by the first high refractive index layer 2 and the second high refractive index layer 4, and the surface of the conductive region a Reflection of light at the surface is easy to be suppressed. The thickness of the transparent metal layer 3 is measured with an ellipsometer.

The transparent metal layer 3 can be a layer formed by any of the forming methods. However, in order to change the average transmittance of the transparent metal layer, it is formed on a layer formed by a sputtering method or an underlayer described later. It is preferred that the layer be a layer.

In the sputtering method, since the material collides with the formed body at a high speed at the time of formation, a dense and smooth layer can be easily obtained, and the light transmittance of the transparent metal layer 3 is easily increased. Further, when the transparent metal layer 3 is a layer formed by sputtering, the transparent metal layer 3 is hardly corroded even in an environment of high temperature and low humidity. The type of the sputtering method is not particularly limited, and may be an ion beam sputtering method, a magnetron sputtering method, a reactive sputtering method, a bipolar sputtering method, a bias sputtering method, a counter sputtering method, or the like. The transparent metal layer 3 is particularly preferably a layer formed by a counter sputtering method. That is, when the transparent metal layer 3 is a layer formed by the facing sputtering method, the transparent metal layer 3 becomes dense and the surface smoothness is likely to increase. As a result, the surface electrical resistance of the transparent metal layer 3 becomes lower and the light transmittance is likely to increase.

On the other hand, when the transparent metal layer 3 is a layer formed on the underlayer described later, the underlayer becomes a growth nucleus when the transparent metal layer 3 is formed, so that the transparent metal layer 3 tends to be a smooth layer. As a result, even if the transparent metal layer 3 is thin, plasmon absorption hardly occurs. In this case, the method for forming the transparent metal layer 3 is not particularly limited, and may be a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, or a thermal CVD method.

Further, when the transparent metal layer 3 is a layer patterned into a desired shape, the patterning method is not particularly limited. For example, the transparent metal layer 3 may be a layer formed by arranging a mask having a desired pattern, or may be a layer patterned by a known etching method.

(1-4) Second anti-sulfurization layer When the second high-refractive index layer described later is a zinc sulfide-containing layer, as shown in FIG. 2, the gap between the transparent metal layer 3 and the second high-refractive index layer 4 is It is preferable that the second antisulfurization layer 5b is formed. The second sulfidation preventing layer 5b may be formed also in the insulating region b of the transparent conductor 100, but from the viewpoint of making it difficult to visually recognize the pattern composed of the conductive region a and the insulating region b, only the conductive region a. Preferably it is formed.

The second sulfidation preventing layer 5b is a layer containing metal oxide, metal nitride, metal fluoride, etc., or Zn. Only one of these may be included in the second sulfurization prevention layer 5b, or two or more thereof may be included. The metal oxide, metal nitride, and metal fluoride may be the same as the metal oxide, metal nitride, and metal fluoride contained in the first high refractive index layer 2.

On the other hand, the thickness of the second antisulfurization layer 5b is preferably a thickness capable of protecting the surface of the transparent metal layer 3 from an impact when the second high refractive index layer 4 is formed. On the other hand, the metal contained in the transparent metal layer 3 and the ZnS contained in the second high refractive index layer 4 have high affinity. Therefore, if the thickness of the second antisulfuration layer 5b is very thin and a part of the transparent metal layer 3 is slightly exposed, the transparent metal layer 3, the second antisulfurization layer 5b, and the second high refractive index layer. Adhesion with 4 tends to increase. Accordingly, the specific thickness of the second antisulfurization layer 5b is preferably 0.1 to 10 nm, more preferably 0.5 to 5 nm, and further preferably 1 to 3 nm. The thickness of the second sulfurization preventing layer 5b is measured with an ellipsometer.

The second antisulfurization layer 5b may be a layer formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, or the like.

When the second antisulfurization layer 5b is a layer patterned into a desired shape, the patterning method is not particularly limited. The second antisulfurization layer 5b may be a layer formed in a pattern by a vapor deposition method, for example, by placing a mask having a desired pattern on the surface to be formed, and by a known etching method. It may be a patterned layer.

(1-5) Second High Refractive Index Layer The second high refractive index layer 4 is a layer for adjusting the light transmittance of the conductive region a of the transparent conductor 100, that is, the region where the transparent metal layer 3 is formed. And formed at least in the conductive region a of the transparent conductor 100. The second high-refractive index layer 4 may be formed in the insulating region b of the transparent conductor 100, but is formed only in the conductive region a from the viewpoint of making it difficult to visually recognize the pattern composed of the conductive region a and the insulating region b. It is preferable that

The second high refractive index layer 4 includes a dielectric material or an oxide semiconductor material having a refractive index higher than that of the transparent substrate 1. The refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material is preferably 0.1 to 1.1 larger than the refractive index of light having a wavelength of 570 nm of the transparent substrate 1, and is preferably 0.4 to 1.0. Larger is more preferable. On the other hand, the specific refractive index of light having a wavelength of 570 nm of the dielectric material or the oxide semiconductor material contained in the second high refractive index layer 4 is preferably larger than 1.5 and is 1.7 to 2.5. More preferably, it is 1.8 to 2.5. When the refractive index of the dielectric material or the oxide semiconductor material is larger than 1.5, the light transmittance of the conductive region a of the transparent conductor 100 is sufficiently adjusted by the second high refractive index layer 4. The refractive index of the second high refractive index layer 4 is adjusted by the refractive index of the material included in the second high refractive index layer 4 and the density of the material included in the second high refractive index layer 4.

The dielectric material or oxide semiconductor material included in the second high refractive index layer 4 may be an insulating material or a conductive material. The dielectric material or oxide semiconductor material can be a metal oxide. The metal oxide may be the same as the metal oxide included in the first high refractive index layer. The second high refractive index layer 4 may include only one kind of the metal oxide or two or more kinds.

Further, the dielectric material or the oxide semiconductor material included in the second high refractive index layer 4 may be ZnS. When ZnS is contained in the second high refractive index layer 4, it becomes difficult for moisture to permeate from the second high refractive index layer 4 side, and corrosion of the transparent metal layer 3 is suppressed. The second high refractive index layer 4 may contain only ZnS or may contain other materials together with ZnS. The material included together with ZnS is a metal oxide that can be the dielectric material or the oxide semiconductor material, or SiO ₂ , and particularly preferably SiO ₂ . When SiO ₂ is contained together with ZnS, the second high refractive index layer 4 is likely to be amorphous, and the flexibility of the transparent conductor is likely to be enhanced.

When the second high refractive index layer 4 contains other materials together with ZnS, the amount of ZnS is 0.1% by mass or more and 95% by mass with respect to the total number of moles of components constituting the second high refractive index layer 4. % Is preferably 50% by mass or more and 90% by mass or less, and more preferably 60% by mass or more and 85% by mass or less. When the ratio of ZnS is high, the sputtering rate increases and the formation rate of the second high refractive index layer 4 increases. On the other hand, when the amount of components other than ZnS increases, the amorphousness of the second high refractive index layer 4 increases, and cracking of the second high refractive index layer 4 is suppressed.

The thickness of the second high refractive index layer 4 is preferably 15 to 150 nm, and more preferably 20 to 80 nm. When the thickness of the second high refractive index layer 4 is 15 nm or more, the light transmittance of the conduction region a of the transparent conductor 100 is sufficiently adjusted by the second high refractive index layer 4. On the other hand, if the thickness of the second high refractive index layer 4 is 150 nm or less, the light transmittance of the region including the second high refractive index layer 4 is unlikely to decrease. The thickness of the second high refractive index layer 4 is measured with an ellipsometer.

The formation method of the second high refractive index layer 4 is not particularly limited, and is a layer formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, or the like. It can be. From the standpoint that the moisture permeability of the second high refractive index layer 4 is lowered, the second high refractive index layer 4 is particularly preferably a layer formed by a sputtering method.

Further, when the second high refractive index layer 4 is a layer patterned into a desired shape, the patterning method is not particularly limited. The second high refractive index layer 4 may be, for example, a layer formed in a pattern by a vapor deposition method by arranging a mask having a desired pattern on the surface to be formed. Moreover, the layer patterned by the well-known etching method may be sufficient.

When either one of the first high refractive index layer 2 and the second high refractive index layer 4 is a zinc sulfide-containing layer, the first high refractive index layer 2 or the second high refractive index layer 2 that is the zinc sulfide-containing layer. An antisulfurization layer 5 is provided between the refractive index layer 4 and the transparent metal layer 3. On the other hand, when both the first high refractive index layer 2 and the second high refractive index layer 4 are zinc sulfide-containing layers, either the first high refractive index layer 2 or the second high refractive index layer 4 and the transparent metal The sulfidation prevention layer 5 may be provided between the layer 3 and the first high refractive index layer 2 that is each zinc sulfide-containing layer, and from the viewpoint of sufficiently increasing the light transmittance of the transparent conductor 100 and It is preferable that an antisulfurization layer 5 is provided between the second high refractive index layer 4 and the transparent metal layer 3. In other words, it is preferable that the antisulfurization layer 5 is provided between the first high refractive index layer 2 and the transparent metal layer 3 and between the transparent metal layer 3 and the second high refractive index layer 4.

(1-6) Underlayer As described above, the transparent conductor 100 may be provided with an underlayer serving as a growth nucleus when the transparent metal layer 3 is formed. The underlayer is a layer formed on the transparent substrate 1 side of the transparent metal layer 3 and adjacent to the transparent metal layer 3, that is, between the first high refractive index layer 2 and the transparent metal layer 3, or the first sulfide. It may be a layer formed between the prevention layer 5a and the transparent metal layer 3. The underlayer is preferably formed at least in the conductive region a of the transparent conductor, and may be formed in the insulating region b of the transparent conductor 100.

When the transparent conductor 100 is provided with a base layer, the smoothness of the surface of the transparent metal layer 3 is increased even if the transparent metal layer 3 is thin. The reason is as follows.

When the material of the transparent metal layer 3 is deposited, for example, on the first high refractive index layer 2 by a general vapor deposition method, atoms attached to the first high refractive index layer 2 are initially deposited at the initial stage of formation. It moves (move) and atoms gather together to form a lump (island structure). And a film grows clinging to this lump. Therefore, in the layer at the initial stage of formation, there is a gap between the lumps and it does not conduct. When a lump further grows from this state, a part of the lump is connected and barely conducted. However, since there is still a gap between the lumps, plasmon absorption occurs. As the formation proceeds further, the lumps are completely connected and plasmon absorption is reduced. However, on the other hand, the intrinsic reflection of the metal occurs and the light transmittance of the layer is reduced.

On the other hand, when a base layer made of a metal that is difficult to migrate is formed on the first high refractive index layer 2, the transparent metal layer 3 grows using the base layer as a growth nucleus. That is, the material of the transparent metal layer 3 is difficult to migrate, and the film grows without forming the island-like structure described above. As a result, a smooth transparent metal layer 3 can be easily obtained even if the thickness is small.

Here, the base layer contains palladium, molybdenum, zinc, germanium, niobium or indium, an alloy of these metals with another metal, an oxide or a sulfide of these metals (for example, ZnS). Is preferred. The underlayer may contain only one kind, or two or more kinds.

The amount of palladium, molybdenum, zinc, germanium, niobium or indium contained in the underlayer is preferably 20% by mass or more, more preferably 40% by mass or more, and further preferably 60% by mass or more. When the metal is contained in the base layer in an amount of 20% by mass or more, the affinity between the base layer and the transparent metal layer 3 is increased, and the adhesion between the base layer and the transparent metal layer 3 is likely to be increased. It is particularly preferable that the underlayer contains palladium or molybdenum.

On the other hand, the metal that forms an alloy with palladium, molybdenum, zinc, germanium, niobium, or indium is not particularly limited, but may be a platinum group other than palladium, gold, cobalt, nickel, titanium, aluminum, chromium, or the like.

The thickness of the underlayer is 3 nm or less, preferably 0.5 nm or less, and more preferably a monoatomic film. The underlayer can also be a film in which metal atoms adhere to the transparent substrate 1 with a distance therebetween. When the adhesion amount of the underlayer is 3 nm or less, the underlayer hardly affects the light transmission property and optical admittance of the transparent conductor 100. The presence or absence of the underlayer is confirmed by the ICP-MS method. Further, the thickness of the underlayer is calculated from the product of the formation speed and the formation time.

The underlayer can be a layer formed by sputtering or vapor deposition. Examples of the sputtering method include an ion beam sputtering method, a magnetron sputtering method, a reactive sputtering method, a bipolar sputtering method, and a bias sputtering method. The sputtering time for forming the underlayer is appropriately selected according to the desired average thickness and formation rate of the underlayer. The sputter formation rate is preferably 0.1 to 15 Å / second, more preferably 0.1 to 7 Å / second.

On the other hand, examples of the vapor deposition method include vacuum vapor deposition method, electron beam vapor deposition method, ion plating method, ion beam vapor deposition method and the like. The deposition time is appropriately selected according to the desired thickness and formation rate of the underlayer. The deposition rate is preferably 0.1 to 15 Å / second, more preferably 0.1 to 7 Å / second.

When the ground layer is a layer patterned into a desired shape, the patterning method is not particularly limited. The underlayer may be, for example, a layer formed in a pattern by a vapor deposition method by placing a mask having a desired pattern on the surface to be formed, or a layer patterned by a known etching method It may be.

(1-7) Low Refractive Index Layer The transparent conductor 100 of the present invention has a low refractive index layer (not shown) for adjusting the light transmittance of the conductive region a of the transparent conductor on the second high refractive index layer 4. May be provided. The low refractive index layer may be formed only in the conductive region a of the transparent conductor 100, or may be formed in both the conductive region a and the insulating region b of the transparent conductor 100.

In the low refractive index layer, the refractive index of light having a wavelength of 570 nm is higher than the refractive index of light having a wavelength of 570 nm of the dielectric material or the oxide semiconductor material included in the first high refractive index layer 2 and the second high refractive index layer 4. A dielectric material or oxide semiconductor material having a low rate is included. The refractive index of the light of wavelength 570 nm of the dielectric material or oxide semiconductor material contained in the low refractive index layer is the light of wavelength 570 nm of the material contained in the first high refractive index layer 2 and the second high refractive index layer 4. The refractive index is preferably 0.2 or more lower and more preferably 0.4 or more lower.

The specific refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the low refractive index layer is preferably less than 1.8, more preferably 1.30 to 1.6, Particularly preferred is 1.35 to 1.5. The refractive index of the low refractive index layer is mainly adjusted by the refractive index of the material included in the low refractive index layer and the density of the material included in the low refractive index layer.

The dielectric material or the oxide semiconductor material included in the low refractive index layer is MgF ₂ , SiO ₂ , AlF ₃ , CaF ₂ , CeF ₃ , CdF ₃ , LaF ₃ , LiF, NaF, NdF ₃ , YF ₃ , YbF _3. , Ga ₂ O ₃ , LaAlO ₃ , Na ₃ AlF ₆ , Al ₂ O ₃ , MgO, and ThO ₂ . Dielectric material or oxide semiconductor materials among _{_{_{_{others, MgF 2, SiO 2, CaF}}}} 2, CeF 3, LaF 3, LiF, NaF, NdF 3, Na 3 AlF 6, Al 2 O 3, MgO, or is ThO ₂ In view of low refractive index, MgF ₂ and SiO ₂ are particularly preferable. The low refractive index layer may contain only one kind of these materials or two or more kinds.

The thickness of the low refractive index layer is preferably 10 to 150 nm, more preferably 20 to 100 nm. When the thickness of the low refractive index layer is 10 nm or more, the light transmittance on the surface of the transparent conductor is easily finely adjusted. On the other hand, if the thickness of the low refractive index layer is 150 nm or less, the thickness of the transparent conductor is reduced. The thickness of the low refractive index layer is measured with an ellipsometer.

The low refractive index layer may be a layer formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, or a thermal CVD method. From the viewpoint of ease of formation and the like, the low refractive index layer is preferably a layer formed by electron beam evaporation or sputtering.

Further, when the low refractive index layer is a patterned layer, the patterning method is not particularly limited. The low refractive index layer may be a layer formed in a pattern by a vapor deposition method, for example, by placing a mask having a desired pattern on the surface to be formed, and is patterned by a known etching method. It may be a layer.

(1-8) Third High Refractive Index Layer As described above, the transparent conductor 100 of the present invention further includes a third that adjusts the light transmittance of the conductive region a of the transparent conductor on the low refractive index layer. A high refractive index layer may be provided. The third high refractive index layer may be formed only in the conductive region a of the transparent conductor 100, or may be formed in both the conductive region a and the insulating region b of the transparent conductor 100.

The third high refractive index layer preferably includes a dielectric material or an oxide semiconductor material having a refractive index higher than the refractive index of the transparent substrate 1 and the refractive index of the low refractive index layer.
The specific refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the third high refractive index layer is preferably larger than 1.5, more preferably 1.7 to 2.5. Preferably, it is 1.8 to 2.5. When the refractive index of the dielectric material or the oxide semiconductor material is larger than 1.5, the light transmittance of the conductive region a of the transparent conductor 100 is sufficiently adjusted by the third high refractive index layer. The refractive index of the third high refractive index layer is adjusted by the refractive index of the material included in the third high refractive index layer and the density of the material included in the third high refractive index layer.

The dielectric material or oxide semiconductor material contained in the third high refractive index layer may be an insulating material or a conductive material. The dielectric material or oxide semiconductor material is preferably a metal oxide or ZnS. Examples of the metal oxide include the metal oxide contained in the first high refractive index layer 2 or the second high refractive index layer 4 described above. The third high refractive index layer may contain only one kind of the metal oxide or ZnS, or two or more kinds. A dielectric material such as SiO ₂ may be included together with the metal oxide and ZnS.

The thickness of the third high refractive index layer is not particularly limited, and is preferably 1 to 40 nm, and more preferably 5 to 20 nm. When the thickness of the third high refractive index layer is in the above range, the light transmittance of the conductive region a of the transparent conductor 100 is sufficiently adjusted. The thickness of the third high refractive index layer is measured with an ellipsometer.

The formation method of the third high refractive index layer is not particularly limited, and may be a layer formed by the same method as the first high refractive index layer 2 and the second high refractive index layer 4.

2. About other structure of a transparent conductor The other structure provided in a transparent conductor is demonstrated.

(2-1) Transparent substrate The transparent substrate 1 included in the transparent conductor 100 can be the same as the transparent substrate of various display devices. The transparent substrate 1 includes a glass substrate, a cellulose ester resin (for example, triacetylcellulose, diacetylcellulose, acetylpropionylcellulose, etc.), a polycarbonate resin (for example, Panlite, Multilon (both manufactured by Teijin Limited)), a cycloolefin resin (for example, ZEONOR (manufactured by Nippon Zeon), Arton (manufactured by JSR), APPEL (manufactured by Mitsui Chemicals)), acrylic resin (for example, polymethyl methacrylate, "Acrylite (manufactured by Mitsubishi Rayon), Sumipex (manufactured by Sumitomo Chemical)) , Polyimide, phenol resin, epoxy resin, polyphenylene ether (PPE) resin, polyester resin (eg, polyethylene terephthalate (PET), polyethylene naphthalate), polyethersulfone, ABS / AS resin, MBS resin, police It may be a transparent resin film made of len, methacrylic resin, polyvinyl alcohol / EVOH (ethylene vinyl alcohol resin), styrene block copolymer resin, etc. When the transparent substrate 1 is a transparent resin film, the film includes two or more kinds. Resin may be included.

From the viewpoint of transparency, the transparent substrate 1 is a glass substrate, or a cellulose ester resin, a polycarbonate resin, a polyester resin (particularly polyethylene terephthalate), a triacetyl cellulose, a cycloolefin resin, a phenol resin, an epoxy resin, a polyphenylene ether (PPE) resin, A film made of polyethersulfone, ABS / AS resin, MBS resin, polystyrene, methacrylic resin, polyvinyl alcohol / EVOH (ethylene vinyl alcohol resin), or styrene block copolymer resin is preferable.

The transparent substrate 1 preferably has high transparency to visible light, and the average transmittance of light having a wavelength of 450 to 800 nm is preferably 70% or more, more preferably 80% or more, and 85% or more. More preferably it is. When the average light transmittance of the transparent substrate 1 is 70% or more, the light transmittance of the transparent conductor 100 is likely to be increased. Further, the average absorptance of light having a wavelength of 450 to 800 nm of the transparent substrate 1 is preferably 10% or less, more preferably 5% or less, and further preferably 3% or less.

The average transmittance is measured by making light incident from an angle inclined by 5 ° with respect to the normal line of the surface of the transparent substrate 1. On the other hand, the average absorptance is calculated as the average absorptivity = 100− (average transmissivity + average reflectivity) by making light incident from the same angle as the average transmissivity and measuring the average reflectivity of the transparent substrate 1. . Average transmittance and average reflectance are measured with a spectrophotometer.

The refractive index of light having a wavelength of 570 nm of the transparent substrate 1 is preferably 1.40 to 1.95, more preferably 1.45 to 1.75, and still more preferably 1.45 to 1.70. . The refractive index of the transparent substrate is usually determined by the material of the transparent substrate. The refractive index of the transparent substrate is measured with an ellipsometer.

The haze value of the transparent substrate 1 is preferably 0.01 to 2.5, more preferably 0.1 to 1.2. When the haze value of the transparent substrate is 2.5 or less, the haze value of the transparent conductor is suppressed. The haze value is measured with a haze meter.

The thickness of the transparent substrate 1 is preferably 1 μm to 20 mm, more preferably 10 μm to 2 mm. When the thickness of the transparent substrate is 1 μm or more, the strength of the transparent substrate 1 is increased, and it is difficult to crack or tear the first high refractive index layer 2. On the other hand, if the thickness of the transparent substrate 1 is 20 mm or less, the flexibility of the transparent conductor 100 is sufficient. Furthermore, the thickness of the apparatus using the transparent conductor 100 can be reduced. Moreover, the apparatus using the transparent conductor 100 can also be reduced in weight.

(2-2) Anisotropic Conductive Member The anisotropic conductive member is used to electrically connect the transparent metal layer and the circuit board. Examples of the anisotropic conductive member include fine conductive particles having conductivity mixed with a thermosetting resin. For example, as shown in FIG. 4, the conductive particles that are anisotropic conductive members included in the anisotropic conductive material are positioned between the electrodes arranged at a predetermined interval and the transparent conductive layer 10. When pressurized, the conductive particles are pressed.
Thereby, for example, the conductive layer P3 included in the conductive particles P1 shown in FIG. 3A is in contact with the electrode 7 and the transparent metal layer 3, thereby providing a conductive path.
On the other hand, since the conductive particles P1 located in the portion where no pressure is applied hold the insulating layer, the insulating property between the electrodes arranged side by side is held. That is, a conductive path is formed in the conduction direction 9 shown in FIG. 4, and anisotropy that maintains insulation is formed in a direction orthogonal to the conduction direction 9.
Note that FIG. 4 schematically shows a case where there is one particle between the electrode and the transparent conductive layer, but a conduction path may be formed in the conduction direction 9 by having a plurality of particles.
As an anisotropic conductive material containing an anisotropic conductive member, an anisotropic conductive film (hereinafter also referred to as ACF), an anisotropic conductive paste, or the like can be used.
These anisotropic conductive members will be described separately for conductive particles and conductive particle-containing layers.

(2-2-1) Conductive particle-containing layer The conductive particle-containing layer that can be used in the present invention is not particularly limited as long as it is a layer containing conductive particles as an anisotropic conductive member. It can be appropriately selected according to the purpose. For example, it contains at least conductive particles, a layer-forming resin, a radical polymerizable compound, a polymerization initiator, and, if necessary, other components such as a silane coupling agent. The layer to contain is mentioned.

The layer forming resin is not particularly limited and can be appropriately selected depending on the purpose. For example, phenoxy resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, urethane resin, butadiene resin, polyimide resin, polyamide resin, Examples thereof include polyolefin resins. Layer forming resin may be used individually by 1 type, and may use 2 or more types together. Among these, phenoxy resin is particularly preferable from the viewpoints of film formability, processability, and connection reliability.
The phenoxy resin is a resin synthesized from bisphenol A and epichlorohydrin, and an appropriately synthesized resin or a commercially available product may be used.
There is no restriction | limiting in particular as content of layer forming resin in an electroconductive particle content layer, According to the objective, it can select suitably.

The radical polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include acrylic compounds and liquid acrylates. Specific examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, and isobutyl. Acrylate, phosphate group-containing acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, trimethylolpropane triacrylate, dimethyloltricyclodecane diacrylate, tetramethylene glycol tetraacrylate, 2-hydroxy-1,3-diaacryloxypropane, 2,2-bis [4- (acryloxymethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, dicyclopentenyl acrylate, Li tricyclodecanyl acrylate, tris (acryloxyethyl) isocyanurate, urethane acrylate, epoxy acrylate. In addition, what made the said acrylate the methacrylate can also be used. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as content of the said radically polymerizable compound in an electroconductive particle content layer, According to the objective, it can select suitably.

The polymerization initiator is not particularly limited as long as it can polymerize a radical polymerizable compound, and can be appropriately selected according to the purpose. However, the polymerization initiator generates a free radical by heat or light. Is preferred.
As a polymerization initiator that generates free radicals by heat or light, an organic peroxide is preferable, and a half-life temperature of 1 minute is 90 to 180 ° C. from the viewpoint of reactivity and storage stability, and a 10-hour half-life temperature. An organic peroxide having a temperature of 40 ° C. or higher is more preferable.
In order to perform bonding in 10 seconds or less, the half-life temperature for 1 minute is preferably 180 ° C. or less. When the 10-hour half-life temperature is 40 ° C. or lower, it may be difficult to store at 5 ° C. or lower.
Examples of the polymerization initiator that generates free radicals by heat include organic peroxides and azo compounds. Examples of the organic peroxide include benzoyl peroxide and tertiary butyl peroxide. Examples of the azo compound include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65), 2 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis (2-methylbutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis [ 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide], dimethyl-2,2′-azobis (2-methoxypropionate) and the like. These may be used individually by 1 type and may use 2 or more types together.
Examples of the polymerization initiator that generates free radicals by light include alkylphenone, benzoin, benzophenone, dicarbonyl compounds, thioxanthone, acylphosphine oxide, and derivatives thereof. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as content of the polymerization initiator in an electroconductive particle content layer, According to the objective, it can select suitably.

There is no restriction | limiting in particular as a silane coupling agent, According to the objective, it can select suitably, For example, an epoxy-type silane coupling agent, an acrylic-type silane coupling agent, a thiol-type silane coupling agent, an amine-type silane cup A ring agent etc. are mentioned.
There is no restriction | limiting in particular as content of the silane coupling agent in an electroconductive particle content layer, According to the objective, it can select suitably.

The average thickness of the conductive particle-containing layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 100 μm, and more preferably 4 to 30 μm. When the average thickness is less than 1 μm, the conductive particle-containing layer may not be sufficiently filled between the circuits. When the average thickness exceeds 100 μm, the conductive particle-containing layer cannot be sufficiently eliminated, resulting in poor conduction. There is. When the average thickness is within the particularly preferable range, the conductive particle-containing layer is appropriately filled, which is advantageous in terms of adhesion and conduction reliability.
Here, the average thickness is an average value when arbitrarily measuring five locations.

(2-2-2) Conductive Particles The conductive particles that can be used as the anisotropic conductive member according to the present invention are not particularly limited and may be appropriately selected depending on the intended purpose. For example, metal particles And metal-coated resin particles.
Examples of the metal particles include nickel, cobalt, silver, copper, gold, and palladium. These may be used individually by 1 type and may use 2 or more types together. Among these, nickel, silver, and copper are preferable. In order to prevent these surface oxidations, particles having gold or palladium on the surface may be used. Furthermore, you may use what gave the metal film and the insulating film with the organic substance on the surface.
Examples of the metal-coated resin particles include particles in which the surface of the resin core is coated with any metal of nickel, copper, gold, and palladium. Similarly, particles obtained by applying gold or palladium to the outermost surface of the resin core may be used. Further, a resin core whose surface is coated with a metal protrusion or an organic material may be used.
In the case of particles coated with nickel, the curing temperature is as high as 200 ° C., but the hardness is high and it is easy to break through.
In the case of particles coated with gold, the hardness is low, but the curing temperature is preferably as low as 140 ° C.

There is no restriction | limiting in particular as a metal coating method to a resin core, According to the objective, it can select suitably, For example, an electroless-plating method, sputtering method, etc. are mentioned.
The material for the resin core is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include styrene-divinylbenzene copolymer, benzoguanamine resin, cross-linked polystyrene resin, acrylic resin, and styrene-silica composite resin. Can be mentioned.
There is no restriction | limiting in particular as content of the electroconductive particle in an electroconductive particle content layer, According to the wiring pitch of a circuit member, a connection area, etc., it can adjust suitably.

The structure of the conductive particles will be described.
In FIG. 3, an example of the electroconductive particle contained in the electroconductive particle content layer used for this invention is shown with sectional drawing.

As shown in FIG. 3A, the conductive particles P1 have resin particles P2 and a conductive layer P3 covering the surface P2a of the resin particles P2. The conductive particles P1 are coated particles in which the surface P2a of the resin particles P2 is coated with the conductive layer P3. Therefore, the conductive particles P1 have the conductive layer P3 on the surface P1a.

The conductive layer P3 includes a first conductive layer P4 covering the surface P2a of the resin particle P2, and a solder layer P5 (second conductive layer) covering the surface P4a of the first conductive layer P4. Have The outer surface layer of the conductive layer P3 is a solder layer P5. Thus, the conductive layer P3 may have a multilayer structure, or may have a multilayer structure of two layers or three or more layers.

As described above, the conductive layer P3 has a two-layer structure. As in the modification shown in FIG. 3B, the conductive particles P11 may have a solder layer P12 as a single conductive layer. The surface layer on the outer side of the conductive layer in the conductive particles may be a solder layer. However, conductive particles P1 are preferable among the conductive particles P1 and the conductive particles P11 because the production of the conductive particles is easy.

The method for forming the conductive layer P3 on the surface P2a of the resin particle P2 and the method for forming the solder layers P5 and P12 on the surface P2a of the resin particle P2 are not particularly limited. Examples of the method for forming the conductive layer P3 and the solder layers P5 and P12 include a method by electroless plating, a method by electroplating, a method by physical collision, a method by physical vapor deposition, and metal powder or metal powder and a binder. And the like, and a method of coating the surface of the resin particles. Of these, electroless plating or electroplating is preferable. Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering. Further, in the method based on the physical collision, for example, a theta composer or the like is used.

The method of forming the solder layers P5 and P12 is preferably a method by physical collision. The solder layers P5 and P12 are preferably formed by physical impact.

Conventionally, the particle diameter of conductive particles having a solder layer on the outer surface layer of the conductive layer has been about several hundred μm. This is because the solder layer could not be formed uniformly even if conductive particles having a particle size of several tens of μm and the surface layer being a solder layer were obtained. On the other hand, by using a theta composer, even when conductive particles having a particle size of several tens of μm, particularly a particle size of 0.1 μm or more and a particle size of 50 μm or less are obtained, A solder layer can be uniformly formed on the surface of the conductive layer.

The conductive layer P3 other than the solder layer is preferably made of metal. The metal constituting the conductive layer P3 other than the solder layer is not particularly limited. Examples of the metal include gold, silver, copper, platinum, palladium, zinc, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and alloys thereof. In addition, tin-doped indium oxide (ITO) can also be used as the metal. As for the said metal, only 1 type may be used and 2 or more types may be used together.

The first conductive layer P4 is preferably a nickel layer, a palladium layer, a copper layer, or a gold layer, more preferably a nickel layer, a copper layer, or a gold layer, and even more preferably a copper layer. The conductive particles preferably have a nickel layer, a palladium layer, a copper layer, or a gold layer, more preferably have a nickel layer, a copper layer, or a gold layer, and still more preferably have a copper layer. By using the conductive particles having these preferable conductive layers for the connection between the electrodes, the connection resistance between the electrodes can be further reduced. In addition, a solder layer can be more easily formed on the surface of these preferable conductive layers. Note that the first conductive layer P4 may be a solder layer. The conductive particles may have a plurality of solder layers.

The thickness of the solder layers P5 and P12 is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 20 nm or more, preferably 70 μm or less, more preferably 40 μm or less, still more preferably 10 μm or less, and particularly preferably 5 μm or less. is there. When the thickness of the solder layers P5 and P12 is equal to or greater than the above lower limit, the conductivity is sufficiently high. If the thickness of the solder layers P5 and P12 is equal to or less than the above upper limit, the difference in thermal expansion coefficient between the resin particles P2 and the solder layers P5 and P12 becomes small, and peeling of the solder layers P5 and P12 hardly occurs.

When the conductive layer has a multilayer structure, the total thickness of the conductive layer is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 30 nm or more, preferably 70 μm or less, more preferably 40 μm or less, still more preferably It is 10 μm or less, particularly preferably 5 μm or less.

Examples of the resin for forming the resin particles P2 include polyolefin resin, acrylic resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polysulfone, and polyphenylene. Examples thereof include oxides, polyacetals, polyimides, polyamideimides, polyetheretherketones, and polyethersulfones. Since the hardness of the resin particle P2 can be easily controlled within a suitable range, the resin for forming the resin particle P2 is a polymer obtained by polymerizing one or more polymerizable monomers having an ethylenically unsaturated group. It is preferable that

The average particle diameter of the conductive particles P1 and P11 is preferably 0.1 μm or more, more preferably 1 μm or more, preferably 100 μm or less, more preferably 80 μm or less, still more preferably 50 μm or less, and particularly preferably 40 μm or less. When the average particle diameter of the conductive particles P1, P11 is not less than the above lower limit and not more than the above upper limit, the contact area between the conductive particles P1, P11 and the electrode can be sufficiently increased, and a conductive layer is formed. It is difficult to form the conductive particles P1 and P11 aggregated together. Further, the distance between the electrodes connected via the conductive particles P1 and P11 does not become too large, and the conductive layer is difficult to peel from the surface P2a of the resin particle P2.

When the anisotropic conductive paste is used, the size is suitable as the conductive particles, and the distance between the electrodes can be further reduced. Therefore, the average particle diameter of the conductive particles P1 and P11 is 0.1 μm. As mentioned above, it is especially preferable that it is 50 micrometers or less.

The “average particle diameter” of the conductive particles P1 and P11 indicates a number average particle diameter. The average particle diameter of the conductive particles P1 and P11 can be obtained by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope and calculating an average value.

The CV value (coefficient of variation of particle size distribution) of the conductive particles is preferably 10% or less, and more preferably 3% or less. When the CV value exceeds 10%, it is difficult to cause variations in the distance between the electrodes connected by the conductive particles.

The CV value is represented by the following formula.
CV value (%) = (ρ / Dn) × 100
ρ: standard deviation of diameter of conductive particles Dn: average particle diameter

3. Method for Producing Transparent Conductor The method for producing a transparent conductor of the present invention includes at least a film forming step and a joining step, and further includes other steps such as a patterning step as necessary.
The transparent conductor of the present invention is produced by the method for producing a transparent conductor of the present invention. As an example of a specific method for producing a transparent conductor, a layer structure is formed by laminating a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order on one surface of a transparent substrate. A transparent conductor is manufactured by providing a step, a step of patterning the transparent conductive layer, and a step of electrically connecting a predetermined region of the layer structure to the circuit board via an anisotropic conductive member. Is done.
Below, the manufacturing method of a transparent conductor is demonstrated in detail. Details of the patterning will be described later.

<Film formation process>
The film forming step is not particularly limited as long as it is a step of forming a layer structure by laminating the first high refractive index layer, the transparent metal layer, and the second high refractive index layer in this order on one surface of the transparent substrate. It can be appropriately selected depending on the purpose. For example, it is preferable to provide an antisulfurization layer between at least one of the transparent metal layer and the first high refractive index layer and between the transparent metal layer and the second high refractive index layer.

<Connection process>
The connecting step is not particularly limited as long as the predetermined region of the layer structure is electrically connected to the circuit board via the anisotropic conductive member, and can be appropriately selected according to the purpose. However, it is preferable because the conductive particle-containing layer can be more appropriately flowed at the portion of the connection terminal which is a predetermined region by heating and pressing the circuit board with the heating pressing member.
As a heating press member, the press member which has a heating mechanism is mentioned, for example. Examples of the pressing member having a heating mechanism include heat sealing.
The heating temperature is not particularly limited as long as it is a temperature at which the conductive particle-containing layer and the insulating adhesive layer are cured, and can be appropriately selected according to the purpose, but is preferably 140 to 200 ° C.
The pressing pressure is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 to 10 MPa.
The heating and pressing time is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 0.5 to 120 seconds.

Here, an example of the manufacturing method of the transparent conductor of this invention is shown using FIG. FIG. 4 is a schematic cross-sectional view showing before and after pressure-bonding an anisotropic conductive member of a transparent conductor.
First, the first high refractive index layer 2, the first antisulfurization layer 5a, the transparent metal layer 3, the second antisulfurization layer 5b, and the second high refractive index layer 4 are laminated in this order on one surface of the transparent substrate 1. To form a layered structure.

Subsequently, as a connection step, the circuit board is heated and pressed by a heating and pressing member (not shown) to join the conductive particle-containing layer containing conductive particles and the connection terminal as a predetermined region of the layer structure. As a result, the wiring material of the circuit board and the wiring material of the layer structure composed of the transparent conductive layer and the transparent substrate are electrically connected via the conductive particles contained in the conductive particle-containing layer, and transparent conductive A body is obtained (FIG. 4). An arrow shown along the direction in which the transparent conductive layer is laminated on the transparent substrate represents the conduction direction 9.

4). Regarding the physical properties of the transparent conductor The average transmittance of light having a wavelength of 450 to 800 nm of the transparent conductor of the present invention is preferably 83% or more, more preferably 85% in both the conduction region a and the insulation region b. Or more, more preferably 88% or more. When the average transmittance in the above wavelength range is 83% or more, the transparent conductor can be applied to applications requiring high transparency to visible light.

On the other hand, the average transmittance of light having a wavelength of 400 to 1000 nm of the transparent conductor is preferably 80% or more in both the conduction region a and the insulation region b, more preferably 83% or more, and still more preferably 85%. That's it. When the average transmittance of light having a wavelength of 400 to 1000 nm is 80% or more, the transparent conductor can also be applied to applications requiring transparency with respect to light in a wide wavelength range, for example, solar cells.

On the other hand, the average absorptance of light having a wavelength of 400 to 800 nm of the transparent conductor is preferably 10% or less, more preferably 8% or less, and even more preferably in both the conduction region a and the insulation region b. 7% or less. In addition, the maximum value of the light absorptance of the transparent conductor having a wavelength of 450 to 800 nm is preferably 15% or less, more preferably 10% or less, both in the conduction region a and the insulation region b. Preferably it is 9% or less. On the other hand, the average reflectance of light having a wavelength of 500 to 700 nm of the transparent conductor is preferably 20% or less, more preferably 15% or less, and even more preferably in both the conduction region a and the insulation region b. Is 10% or less. The lower the average absorptance and average reflectance of the transparent conductor, the higher the aforementioned average transmittance.

The average transmittance, average reflectance, and average reflectance are preferably the average transmittance, average reflectance, and average reflectance under the usage environment of the transparent conductor. Specifically, when the transparent conductor is used by being bonded to an organic resin, it is preferable to prepare a layer made of the organic resin on the transparent conductor and measure the average transmittance and the average reflectance. On the other hand, when the transparent conductor is used in the air, it is preferable to measure the average transmittance and the average reflectance in the air. The transmittance and the reflectance are measured with a spectrophotometer by allowing measurement light to enter from an angle inclined by 5 ° with respect to the normal of the surface of the transparent conductor. The absorptance is calculated from a calculation formula of 100− (transmittance + reflectance).

Further, when the transparent conductor 100 has the conduction region a and the insulation region b, it is preferable that the reflectance of the conduction region a and the reflectance of the insulation region b are approximated. Specifically, the difference ΔR between the luminous reflectance of the conduction region a and the luminous reflectance of the insulating region b is preferably 5% or less, more preferably 3% or less, and still more preferably It is 1% or less, particularly preferably 0.3% or less. On the other hand, the luminous reflectances of the conductive region a and the insulating region b are each preferably 5% or less, more preferably 3% or less, and further preferably 1% or less. The luminous reflectance is a Y value measured with a spectrophotometer (U4100; manufactured by Hitachi High-Technologies Corporation).

Further, when the transparent conductor 100 has the conduction region a and the insulation region b, the a ^* value and the b ^* value in the L ^* a ^* b ^* color system are preferably within ± 30 in any region. More preferably, it is within ± 5, more preferably within ± 3.0, and particularly preferably within ± 2.0. If the a ^* value and the b ^* value in the L ^* a ^* b ^* color system are within ± 30, both the conduction region a and the insulation region b are observed as colorless and transparent. The a ^* value and b ^* value in the L ^* a ^* b ^* color system are measured with a spectrophotometer.

The surface electric resistance of the conductive region a of the transparent conductor is preferably 50Ω / □ or less, more preferably 30Ω / □ or less. A transparent conductor having a surface electric resistance value of 50 Ω / □ or less in the conduction region can be applied to a transparent conductive panel for a capacitive touch panel. The surface electrical resistance value of the conduction region a is adjusted by the thickness of the transparent metal layer and the like. The surface electrical resistance value of the conduction region a is measured in accordance with, for example, JIS K7194-1994, ASTM D257, and the like. It is also measured by a commercially available surface electrical resistivity meter.

5. Application to Touch Panel The transparent conductor of the present invention can be applied as a touch sensor part (hereinafter also referred to as “touch sensor electrode part”) of various types of touch panels. For example, it can be used in a surface capacitive touch panel, a projected capacitive touch panel, a resistive touch panel, and the like.
The layer structure of the touch sensor unit is a bonding method in which two transparent conductors are bonded as a transparent electrode, a method in which a transparent conductor is provided as a transparent electrode on both surfaces of a single substrate, a single-sided jumper or a through-hole method Or it is preferable that it is either a one area layer system.
In addition, the projected capacitive touch sensor is preferably AC driven rather than DC driven, and more preferably is a drive system that requires less time to apply voltage to the electrodes.
For example, when the transparent conductor of the present invention is applied to a touch sensor, as shown in FIG. 1A, it has a pattern including a plurality of conductive regions a and line-shaped insulating regions b that divide the conductive regions a. It can be molded and used as a transparent electrode.

6). Method for Forming Transparent Conductor Having Electrode Pattern A method for forming a pattern comprising a conductive region a and an insulating region b as shown in FIG. 1A will be described for the transparent conductor of the present invention.
In the transparent conductor of the present invention, at least the first high refractive index layer, the transparent metal layer, and the second high refractive index layer are laminated in this order on the transparent substrate 1 by the method described above. After the production, it is preferable to form a metal pattern electrode by patterning the transparent metal layer into a predetermined shape.
Specifically, for example, an electrode pattern as shown in FIG. 4 is preferably formed by photolithography using an etching solution. The line width of the electrode to be formed is preferably 50 μm or less, and particularly preferably 20 μm or less.

(Manufacturing process)
Hereinafter, a method for forming an electrode pattern by photolithography will be described.
The photolithographic method applied to the present invention includes resist coating such as curable resin, preheating, exposure, development (removal of uncured resin), rinsing, etching treatment with an etching solution, and resist stripping. The silver thin film layer can be processed into a pattern as shown in FIG. 1A, for example, and the shape of the pattern can be changed as appropriate.
In the present invention, a conventionally known general photolithography method can be appropriately used. For example, as the resist, either positive or negative resist can be used. In addition, after applying the resist, preheating or prebaking can be performed as necessary. At the time of exposure, a pattern mask having a predetermined pattern may be disposed, and light having a wavelength suitable for the resist used, generally ultraviolet rays, electron beams, or the like may be irradiated thereon. After the exposure, development is performed with a developer suitable for the resist used. After the development, the resist pattern is formed by stopping the development with a rinse solution such as water and washing. Next, the formed resist pattern is pretreated or post-baked as necessary, and then is etched with an etching solution containing an organic solvent to dissolve the intermediate layer in a region not protected by the resist and to form a silver thin film electrode Remove. After etching, the remaining resist is peeled to obtain a transparent electrode having a predetermined pattern. As described above, the photolithography method applied to the present invention is a method generally recognized by those skilled in the art, and a specific application mode thereof can be easily selected by a person skilled in the art according to a predetermined purpose. Can do.
Next, an electrode pattern forming method applicable to the present invention will be described with reference to the drawings.

As a first step, the first high refractive index layer 2, the first antisulfurization layer 5a, the transparent metal layer 3, the second antisulfurization layer 5b, and the second high refractive index layer 4 are laminated on the transparent substrate 1 in this order. The transparent conductive layer 10 thus prepared is prepared.
Next, in the resist film forming step, a resist film composed of a photosensitive resin composition or the like is uniformly coated on the transparent conductive layer 10. As the photosensitive resin composition, a negative photosensitive resin composition or a positive photosensitive resin composition can be used.
As a coating method, it is applied on the transparent conductive layer 10 by a known method such as micro gravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, etc., and heated by a hot plate, an oven or the like. It can be pre-baked in the apparatus. Pre-baking can be performed, for example, using a hot plate or the like within a range of 50 to 150 ° C. for 30 seconds to 30 minutes.

Then, in the exposure step, through a mask manufactured by predetermined electrode patterns, a stepper, a mirror projection mask aligner (MPA), using an exposure apparatus, such as a parallel light mask aligner, 10 ~ 4000J / ^{m 2} approximately (wavelength 365nm The resist film to be removed in the next step is irradiated with light in terms of exposure amount. The exposure light source is not limited, and ultraviolet rays, electron beams, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like can be used.

Next, in the developing step, the exposed transparent conductor is immersed in a developing solution to dissolve the resist film in the region irradiated with light.
As a developing method, it is preferable to immerse in a developing solution for 5 seconds to 10 minutes by a method such as showering, dipping or paddle. As the developer, a known alkali developer can be used. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, tetramethylammonium hydroxide. Examples thereof include aqueous solutions containing one or more quaternary ammonium salts such as side and choline. After the development, it is preferable to rinse with water, followed by dry baking within a range of 50 to 150 ° C.

Next, an etching process using an etching solution is performed.
As the etching solution applicable to the present invention, a solution containing an inorganic acid or an organic acid is preferable, and oxalic acid, hydrochloric acid, acetic acid, and phosphoric acid can be mentioned, and oxalic acid, acetic acid, and phosphoric acid are particularly preferable.
Specifically, for example, the transparent conductive layer 10 having a resist film is immersed in an etching solution containing an organic acid, and the transparent conductive layer 10 in the insulating region b not protected by the resist film is dissolved. The transparent conductive layer 10 in the protected conductive region a is formed as a predetermined electrode pattern.

Finally, the resist film is removed by immersing in a resist film stripping solution, for example, N-300 manufactured by Nagase ChemteX Corporation, so that a transparent conductor having an electrode pattern can be produced.
The image display device used for the touch sensor according to the present invention is not particularly limited, and a liquid crystal display device or an organic EL device that is usually used for a small electronic terminal can be used.

7). Applications of transparent conductors The above-mentioned transparent conductors include various types of displays such as liquid crystal, plasma, organic electroluminescence, field emission, touch panels, mobile phones, electronic paper, various solar cells, various electroluminescent dimming elements, etc. It can be preferably used for a substrate of an optoelectronic device.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.
In the production of the transparent conductors 101 to 103 of Examples 1 to 3, a transparent conductive layer having at least a first high refractive index layer, a transparent metal layer, and a second high refractive index layer is formed on a transparent substrate, and patterning is performed. Since the steps up to the formation are common, an example of a manufacturing method is given below.

As a transparent substrate, a PET film with a clear hard coat (G1SBF, referred to as “HCPET”, thickness: 125 μm) manufactured by Kimoto Co., Ltd. is used. ZnS—SiO ₂ ) / first antisulfation layer (ZnO) / transparent metal layer (Ag) / second antisulfation layer (ZnO) / second high refractive index layer (ZnS—SiO ₂ ) were laminated in this order. Next, the laminate was patterned by the following method to produce a transparent conductor 101 having wiring in a batch method. The thickness of each layer is J. A. Woollam Co. Inc. The measurement was made with a VB-250 VASE ellipsometer manufactured by the manufacturer.

(Formation of First High Refractive Index Layer (ZnS—SiO ₂ ))
As a vacuum sputtering apparatus, a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., Ltd. is used. Ar 20 sccm, O 2 0 sccm, sputtering pressure 0.1 Pa, room temperature, target side power 150 W, film formation rate 3.8 Å / sec. ₂ ) was RF sputtered. The target-substrate distance was 90 mm. The film thickness was 40 nm.

The volume ratio of ZnS to SiO ₂ in the first high refractive index layer was measured using X-ray photoelectron spectroscopy (XPS). As a result, the volume ratio of ZnS to SiO ₂ was 80:20. It was confirmed that.

(Formation of first antisulfurization layer (ZnO))
Next, ZnO was RF-sputtered at Ar 20 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 150 W, and deposition rate 1.1 liters / second. The target-substrate distance was 90 mm. The thickness of the ZnO layer was 1 nm.

(Formation of transparent metal layer (Ag))
Next, Ag was RF-sputtered at Ar 20 sccm, sputtering pressure 0.5 Pa, room temperature, target-side power 150 W, and deposition rate 14 Å / sec. The target-substrate distance was 90 mm. The layer thickness of the Ag layer was 7 nm.

(Formation of second anti-sulfurization layer (ZnO))
Next, ZnO was RF-sputtered at Ar 20 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 150 W, and deposition rate 1.1 liters / second. The target-substrate distance was 90 mm. The thickness of the ZnO layer was 1 nm.

(Formation of Second High Refractive Index Layer (ZnS—SiO ₂ ))
Next, the target (ZnS—SiO ₂ fired body) was RF-sputtered at Ar 20 sccm, O 2 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 150 W, and deposition rate 3.8 Å / sec. The target-substrate distance was 90 mm. The film thickness was 40 nm.

The volume ratio of ZnS to SiO ₂ in the second high refractive index layer was measured using X-ray photoelectron spectroscopy (XPS). As a result, the volume ratio of ZnS to SiO ₂ was 80:20. It was confirmed that.

(Patterning of transparent conductive layer)
Next, a pattern having a conductive region a and an insulating region b is formed in accordance with the patterning method described above on the transparent conductive layer having at least the first high refractive index layer, the transparent metal layer, and the second high refractive index layer produced above. did.

A resist layer is formed in a pattern on the transparent conductive layer by a photolithography method, and a first high refractive index layer, a first antisulfurization layer, a transparent metal layer, a second antisulfurization layer, and a second high refractive index layer are formed. Etching was used to etch into a pattern including a plurality of conductive regions a and line-shaped insulating regions b separating the conductive regions a.

As an etching solution, “mixed liquid SEA-5” (phosphoric acid: 55 mass%, acetic acid: 30 mass%, water and other components: 15 mass%) manufactured by Kanto Chemical Co., Ltd. was used. The insulating region b includes only a transparent substrate. The width of the line-shaped insulating region b was 16 μm.

Further, transparent conductors 101 to 103 were produced through the following steps. A specific manufacturing method will be described.

[Example 1]
A case of the transparent conductor 101 in which conductive particles are contained by pressure bonding up to the transparent metal layer will be described (see FIG. 5A).
Using an ACF thermocompression bonding machine TCW-125C (manufactured by Nippon Avionics Co., Ltd.), an anisotropic conductive film is sandwiched between the transparent conductive layer and the transparent conductive layer formed on one surface. Pressure bonding was performed at 140 ° C. for 5 seconds at 3 N / MPa. On top of that, an electrode and a flexible substrate were provided.
An anisotropic conductive film (CP920CM-25AC manufactured by Dexerials Co., Ltd.) containing gold / nickel plated resin particles as conductive particles was used.

The conduction resistance after 10 seconds under the conditions of a temperature of 24 ° C. and a humidity of 30% RH was measured by a two-terminal method using CDM-20 manufactured by Custom. Specifically, it was confirmed that there is continuity by applying CDM-20 to the

connection terminals

11a and 11b shown in FIG. 1A among the plurality of connection terminals.

Moreover, the touch panel 201 as shown to FIG. 1C was produced by combining a display panel with the transparent conductor 101. FIG.
Specifically, a touch panel was manufactured by attaching a display panel including a substrate, a metal layer, an insulating layer, an indium tin oxide (ITO) layer, and a protective layer to a touch sensor using an adhesive. In the case of a touch panel, as shown in FIG. 1A, a region surrounded by a broken line is the touch sensor unit 13.
For the touch panel 201 including the transparent conductor 101, the conduction resistance after 10 seconds under the conditions of a temperature of 24 ° C. and a humidity of 30% RH is obtained by using the CDM-20 manufactured by Custom Co. It measured similarly and it confirmed that there was conduction.

[Example 2]
The case of the transparent conductor 102 in which conductive particles are contained by pressure bonding up to the base layer (ZnS—SiO ₂ ) is shown (see FIG. 5B).
Using an ACF thermocompression bonding machine TCW-125C (manufactured by Nippon Avionics Co., Ltd.), an anisotropic conductive film is sandwiched between the transparent conductive layer and the transparent conductive layer formed on one surface. Crimping was performed at 140 ° C. for 5 seconds at 4 N / MPa. On top of that, an electrode and a flexible substrate were provided.
As the anisotropic conductive film, a film containing gold-plated (CP920CM-25AC manufactured by Dexerials Corporation) resin particles as conductive particles was used.

connection terminals

11a and 11b shown in FIG. 1A among the plurality of connection terminals.

Moreover, the touch panel 202 as shown to FIG. 1C was produced by combining a display panel with the transparent conductor 102. FIG.
Specifically, a touch panel was manufactured by attaching a display panel including a substrate, a metal layer, an insulating layer, an indium tin oxide (ITO) layer, and a protective layer to a touch sensor using an adhesive. In the case of a touch panel, as shown in FIG. 1A, a region surrounded by a broken line is the touch sensor unit 13.
For the touch panel 202 including the transparent conductor 102, the conduction resistance after 10 seconds under the conditions of a temperature of 24 ° C. and a humidity of 30% RH is measured with the transparent conductor 102 by a two-terminal method using CDM-20 manufactured by Custom. It measured similarly and it confirmed that there was conduction.

[Example 3]
The case of the transparent conductor 103 containing conductive particles up to the transparent metal layer by pressure bonding will be described (see FIG. 5A).
Using an ACF thermocompression bonding machine TCW-125C (manufactured by Nippon Avionics Co., Ltd.), an anisotropic conductive film is sandwiched between the transparent conductive layer and the transparent conductive layer formed on one surface. Crimping was performed at 180 ° C. for 5 seconds at 4 N / MPa. On top of that, an electrode and a flexible substrate were provided.
As the anisotropic conductive film, a film containing gold-plated resin particles (CP920CM-25AC manufactured by Dexerials Corporation) as conductive particles was used.

connection terminals

11a and 11b shown in FIG. 1A among the plurality of connection terminals.

Moreover, the touch panel 203 as shown to FIG. 1C was produced by combining a transparent conductor 103 with a display panel.
Specifically, a touch panel was manufactured by bonding a display panel including a substrate, a metal layer, an insulating layer, an indium tin oxide (ITO) layer, and a protective layer to a transparent conductor using an adhesive. In the case of a touch panel, as shown in FIG. 1A, a region surrounded by a broken line is the touch sensor unit 13.
As for the touch panel 203 including the transparent conductor 103, the conduction resistance after 10 seconds under the conditions of a temperature of 24 ° C. and a humidity of 30% RH is obtained by using the CDM-20 manufactured by Custom Co. It measured similarly and it confirmed that there was conduction.

As shown in Examples 1 to 3, the transparent conductor according to the present invention is confirmed to be electrically conductive because the transparent metal layer is electrically connected to the circuit board via an anisotropic conductive member. We were able to.
Further, the light transmittance of the transparent conductor of the present invention produced in Examples 1 to 3 was measured using a spectrophotometer (U-3300 manufactured by Hitachi High-Technologies Corporation). Specifically, measurement light is incident from an angle inclined by 5 ° with respect to the normal line of the surface of the metal film of each transparent conductor, and the light transmittance and light reflectance of the metal film are measured. Then, light absorptivity = 100− (light transmittance + light reflectance) is calculated from the light transmittance and light reflectance at each wavelength, and this is used as reference data. And it preserve | saved in temperature 80 degreeC / relative humidity 90% RH atmosphere, measures the light transmittance (%) in the measurement light wavelength 550nm, and evaluates the light transmittance change after progress of 500 hours compared with the test start. did. It was confirmed that all the transparent conductors of Examples 1 to 3 were 85% or more.

In the production of the transparent conductors 101 to 103 of Examples 1 to 3, a transparent conductive layer having at least a first high refractive index layer, a transparent metal layer, and a second high refractive index layer on a transparent substrate, which is a common process. About the process of forming and patterning, you may produce by the following preparation methods. The composition of the ZnS compound 1 is as shown in Table 1.

(Formation of First High Refractive Index Layer (ZnS Compound 1))
As a vacuum sputtering apparatus, a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., Ltd. was used, and the target (ZnS compound) was prepared at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target side power 150 W, and deposition rate 3.8 Å / sec. 1) was DC sputtered. The target-substrate distance was 90 mm. The film thickness was 40 nm.

(Formation of first antisulfurization layer (GZO))
Next, GZO was DC sputtered at Ar 20 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 150 W, and deposition rate 1.1 liters / second. The target-substrate distance was 90 mm. The thickness of the GZO layer was 1 nm.

(Formation of transparent metal layer (Ag))
Next, Ag was DC sputtered at Ar 20 sccm, sputtering pressure 0.5 Pa, room temperature, target-side power 150 W, and deposition rate 14 Å / sec. The target-substrate distance was 90 mm. The layer thickness of the Ag layer was 7 nm.

(Formation of second anti-sulfurization layer (GZO))
Next, GZO was DC sputtered at Ar 20 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 150 W, and deposition rate 1.1 liters / second. The target-substrate distance was 90 mm. The thickness of the GZO layer was 1 nm.

(Formation of Second High Refractive Index Layer (ZnS Compound 1))
Next, the target (ZnS compound 1 fired body) was DC-sputtered at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 150 W, and deposition rate 3.8 Å / sec. The target-substrate distance was 90 mm. The film thickness was 40 nm.

Further, in the production of the transparent conductors 101 to 103 of Examples 1 to 3, the transparent conductive material having at least the first high refractive index layer, the transparent metal layer, and the second high refractive index layer on the transparent substrate, which is a common process. About the process of forming a layer and forming patterning, you may change the ZnS compound 1 of said preparation method into the ZnS compound 2, and may produce it. The composition of the ZnS compound 2 is as shown in Table 1.

As described above, for the transparent conductive layer prepared using ZnS compound 1 or ZnS compound 2, a transparent conductor can be prepared by the same method as in Examples 1 to 3, and the performance is also equivalent. I was able to confirm.

The present invention is used in the field of various optoelectronic devices such as liquid crystal, plasma, organic electroluminescence, field emission display, touch panel, mobile phone, electronic paper, various solar cells, various electroluminescence dimming elements there is a possibility.

100, 101, 102, 103 Transparent conductor 10 Transparent conductive layer 1 Transparent substrate 2 First high refractive index layer 3 Transparent metal layer 4 Second high refractive index layer 5 Antisulfuration layer 5a First antisulfuration layer 5b Second antisulfation Layer 6 Conductive particle-containing layer 7 Electrode 8 Flexible substrate (circuit board)
9

Conduction direction

11, 11a, 11b Connection terminal 12 Drawer wiring part 13 Touch sensor part 14 Wiring pattern 15 Adhesive 16 Display panel 200, 201, 202, 203 Touch panel a Conductive area b Insulating area P1 Conductive particles (anisotropic conductivity) Element)
P1a surface P2 resin particle P2a surface P3 conductive layer P4 first conductive layer P4a surface P5 solder layer (second conductive layer)
P11 Conductive particle P12 Solder layer

Claims

A transparent conductor having at least a transparent substrate, a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order;
At least one of the first high refractive index layer and the second high refractive index layer is a layer containing at least zinc sulfide,
The transparent conductor is patterned, and
A transparent conductor, wherein the transparent metal layer is electrically connected to a circuit board via an anisotropic conductive member.
The antisulfurization layer containing at least one compound selected from a metal oxide, a metal fluoride, and a metal nitride is provided between the layer containing zinc sulfide and the transparent metal layer. The transparent conductor according to 1.
It has a lead-out wiring part formed of the transparent conductor itself,
The transparent conductor according to claim 1, wherein the lead-out wiring part is electrically connected to the circuit board through the anisotropic conductive member.
The transparent conductor according to any one of claims 1 to 3, further comprising the lead-out wiring portion and a touch sensor portion.
It is a manufacturing method of the transparent conductor according to any one of claims 1 to 4,
Forming a layer structure by laminating a first high refractive index layer, a transparent metal layer and a second high refractive index layer in this order on one surface of the transparent substrate;
Electrically connecting the layer structure to a circuit board through an anisotropic conductive member;
A method for producing a transparent conductor, comprising: