TW201531577A - Transparent conductive film, method for producing the same, and electronic device using the same - Google Patents

Abstract

The present invention aims to provide a transparent conductive laminate having an excellent humidity/heat resistant property, a method for producing the same, and an electronic device using the same. The present invention is directed to a transparent conductive laminated body and the like, wherein a gas barrier layer and a transparent conductive layer are respectively formed on at least one surface of a resin substrate, the transparent conductive layer including a zinc oxide is a zinc oxide film which is doped with gallium and indium, and which contains indium in the range of 0.01 to 25 atom% and contains gallium in the range of 0.01 to 10 atom% with respect to the total weight(100 atom%) of zinc, gallium, oxygen and indium measured by XPS analysis, a proportion of [rho]1/[rho]0 is set to a value 1.5 or less, if [rho]0 is an initial resistivity, and [rho]1 is a resistivity after 500 hours under a condition at 60 DEG C, 95%RH, and a thickness of the zinc oxide film is set to a value within the range of 10 nm to 300 nm.

Description

Transparent conductive film, method for producing transparent conductive film, and electronic device using transparent conductive film

The present invention relates to a transparent conductive film, a method for producing a transparent conductive film, and an electronic device using the transparent conductive film, in particular, a transparent conductive film excellent in wet heat characteristics, a method for producing a transparent conductive film, and a transparent conductive film. Thin film electronic device.

Conventionally, a transparent conductive film in which tin-doped indium oxide is used as a material for forming a transparent conductive layer is widely used as an image display device including a liquid crystal device or an organic electroluminescence device (organic EL device).

Further, a tin-doped indium oxide containing a large amount of indium containing a high-priced and rare metal is used as an alternative to the transparent conductive layer, and a transparent conductive film using zinc oxide excellent in transparency or surface smoothness has been proposed.

More specifically, a transparent conductive film in which an Al ₂ O ₃ thin film is formed on an organic polymer laminate substrate and a Ga-doped ZnO GZO thin film is formed thereon (see, for example, Patent Document 1).

Further, there has been proposed a low-resistivity transparent conductor in which zinc oxide is used as a main component and a resistivity is lowered by a dopant which is easy to adjust in concentration.

In other words, a transparent conductor having a transparent conductor composed of zinc oxide, indium oxide, and gallium oxide, and a low-resistivity transparent conductor in which the element concentrations of indium and gallium are respectively within a specific range (for example, Patent Document 2) .

Further, there has been proposed a transparent conductive zinc oxide film doped with a specific element for the purpose of obtaining excellent moisture heat resistance even at an extremely thin film level.

In other words, it is proposed to add zinc oxide, a first element composed of Ga and/or Al, and at least one selected from the group consisting of In, Bi, Se, Ce, Cu, Er, and Eu. The transparent conductive zinc oxide film of the second element has a specific resistance within a specific range before and after the specific damp heat test, and a transparent conductivity of a ratio of the atomic ratio of zinc to the second element and a film thickness within a specific range. A zinc oxide film (for example, Patent Document 3).

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent No. 4917897 (Application Patent Range, etc.)

[Patent Document 2] Japanese Laid-Open Patent Publication No. 2006-147325 (Patent Patent Application, etc.)

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2013-147727 (Patent Patent Application, etc.)

However, in the transparent conductive film disclosed in Patent Document 1, it has been found that the gallium-doped zinc oxide film has insufficient heat and humidity resistance characteristics regardless of whether or not it is necessary to use an Al ₂ O ₃ film as an undercoat layer.

Further, in the low-resistivity transparent conductor disclosed in Patent Document 2, it has been found that although the resistivity is improved, there is no problem in consideration of the moist heat characteristics.

Further, the transparent conductive zinc oxide film disclosed in Patent Document 3 has been found to have a certain degree of moist heat characteristics, but the film formation conditions are too strict, and the film thickness must be 140 nm or less, and the use is limited to a relatively narrow problem. .

Therefore, the inventors of the present invention have diligently studied the results of such a problem and found that a transparent conductive film is formed by forming a transparent conductive film on at least one surface of a resin substrate, and the zinc oxide film contains oxidation. Zinc oxide film, which is doped with gallium and indium, and contains a specific amount of gallium and indium measured by XPS analysis, and has a specific range of specific resistance and film thickness, and is characterized by moist heat characteristics. The present invention is excellent in that it is completed.

In other words, the present invention provides a transparent conductive film or a transparent conductive film which is excellent in moist heat characteristics, for example, at 60 ° C and a relative humidity of 95%, and has a low rate of increase in specific resistance after storage for 500 hours. And an electronic device using such a transparent conductive film.

According to the present invention, there is provided a transparent conductive film which is a transparent conductive film formed by forming a gas barrier layer and a transparent conductive layer on at least one side of a resin substrate, characterized in that the transparent conductive layer is doped together with zinc oxide. A zinc oxide film made of gallium and indium, the transparent conductive layer is set to 0.01% of the total amount of zinc, the amount of gallium, the amount of oxygen, and the amount of indium measured by elemental analysis of XPS (100 atom%). At the same time as the value in the range of 25 atom%, the amount of gallium is set to a value in the range of 0.1 to 10 atom%, and the initial specific resistance is set to ρ ₀ , and the condition is kept at 500 ° C and a relative humidity of 95% for 500 hours. When the specific resistance is ρ ₁ , the ratio represented by ρ ₁ / ρ ₀ is 1.5 or less, and the film thickness of the zinc oxide film is in the range of 10 to 300 nm, which solves the above problems.

That is, the transparent conductive layer of the present invention can improve the moist heat characteristics of the transparent conductive layer by containing a specific amount of gallium and indium.

Further, the transparent conductive layer exhibits appropriate light transmittance and conductivity because of its specific film thickness and moist heat characteristics.

Further, since the transparent conductive film is provided with a gas barrier layer, a transparent conductive film excellent in gas barrier layer properties can be obtained.

Further, in the constitution of the present invention, the specific resistance at the initial stage of the transparent conductive film layer is set to ρ ₀ , and the specific resistance after storage for 1000 hours is preferably set to ρ under conditions of 60 ° C and a relative humidity of 95%. _{At 2} o'clock, the ratio expressed by ρ ₂ / ρ ₀ is set to a value of 2.0 or less.

With such a configuration, transparent conductive having superior wet heat characteristics can be obtained. film.

Further, in the constitution of the invention, it is preferred that the resin substrate is selected from the group consisting of At least 1 of a group consisting of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, cycloolefin copolymer, cycloolefin polymer, polyether oxime, and polyamidiamine Kind.

According to this configuration, the transparent conductive film can be imparted with flexibility and transparency.

Further, in the constitution of the present invention, the gas barrier layer is preferably selected At least one of a free metal, an inorganic oxide, an inorganic nitride, an inorganic oxynitride, an inorganic carbide, an inorganic sulfide, an inorganic oxynitride carbide, a polymer compound, and a composite of these.

With such a configuration, the gas barrier layer can exhibit sufficient gas barrier layer properties.

Further, in the constitution of the present invention, it is preferred to set the water vapor transmission rate of the gas barrier layer to 0.1 g. m ^-2 . The value below day ^-1 .

By restricting the water vapor transmission rate as described above, it is prevented from further permeating the water vapor or the like even if it is immersed in water vapor or the like through the resin substrate, and as a result, deterioration of the transparent conductive layer can be prevented.

Moreover, another aspect of the present invention is an electronic device, It is characterized in that any of the above transparent conductive films is used for a transparent electrode.

As described above, by using a transparent conductive film having excellent wet heat characteristics and gas barrier properties on the transparent electrode, long-term stability of the electronic device can be suitably achieved.

Furthermore, still another aspect of the present invention provides a method for producing a transparent conductive film, which is characterized in that a transparent conductive film is formed by forming a gas barrier layer and a transparent conductive layer on at least one surface of a resin substrate, and is characterized in that it comprises The following steps (1) to (3); (1) a step of preparing a resin substrate and a sintered body, (2) a step of forming a gas barrier layer on at least one side of the resin substrate, and (3) forming a zinc oxide film In the step, the zinc oxide film is applied to the gas barrier layer by a sputtering method or a vapor deposition method, and the zinc oxide film formed by doping gallium and indium together with zinc oxide is used as a transparent material from the sintered body. The conductive layer and the transparent conductive layer are set to have a value in the range of 0.01 to 25 atom% with respect to the total amount of zinc, the amount of gallium, the amount of oxygen, and the amount of indium measured by elemental analysis of XPS (100 atom%). At the same time, the amount of gallium is set to be in the range of 0.1 to 10 atom%, and the specific resistance at the initial stage of the zinc oxide film is ρ ₀ , and the specific resistance after storage for 500 hours under conditions of 60 ° C and 95% relative humidity when defined as ρ _1, represented by the ratio ρ ₁ / ρ ₀ is a value of 1.5 or less, and Thickness value within the range of 10 ~ 300nm.

In other words, by performing such a production, a transparent conductive film excellent in wet heat characteristics and gas barrier properties can be stably produced.

Further, in the practice of the invention, it is preferred that the temperature of the resin substrate when the transparent conductive layer is formed on the resin substrate is set to a value in the range of 10 to 150 °C.

By carrying out such a production, it is advantageous not only to manufacture a transparent conductive film which can be used for many purposes, but also to economically improve the type of the resin substrate which can be used.

10, 10 ' ‧ ‧ transparent conductive layer

12‧‧‧Resin substrate

14‧‧‧ gas barrier

16‧‧‧Undercoat

18‧‧‧Other layers

20‧‧‧GZO film

50, 50 ' , 50 " , 50 ''' ‧‧‧ Transparent conductive film

Fig. 1 (a) to (d) are diagrams for explaining a state of a transparent conductive film comprising a transparent conductive layer of the present invention.

Fig. 2 is an X-ray diffraction diagram of the In Plane method of a zinc oxide film comprising zinc, gallium and oxygen of the present invention simultaneously doped with indium.

Fig. 3 is a X-ray diffraction diagram of the 002 plane by the Out of Plane method of the zinc oxide film of the present invention.

Fig. 4 is a photograph for explaining the crystal structure of the GZO film.

Fig. 5 is a view for explaining the relationship between the amount of indium of the present invention and the specific resistance of the transparent conductive layer.

Fig. 6 is a view for explaining the moist heat characteristics of the transparent conductive film of the present invention.

[First Embodiment]

The first embodiment is a transparent conductive film which is a transparent conductive film in which a gas barrier layer and a transparent conductive layer are formed on at least one surface of a resin substrate, and is characterized in that the transparent conductive layer is doped with gallium oxide and doped with gallium. And a zinc oxide film made of indium, the transparent conductive layer is set to 0.01 to 25 atom in terms of the total amount of zinc, the amount of gallium, the amount of oxygen, and the amount of indium measured by elemental analysis of XPS (100 atom%). At the same time as the value in the range of %, the amount of gallium is set to a value in the range of 0.1 to 10 atom%, and the initial specific resistance is set to ρ ₀ , and after 500 hours at 60 ° C and a relative humidity of 95%, it is stored for 500 hours. When the specific resistance is ρ ₁ , the ratio represented by ρ ₁ / ρ ₀ is 1.5 or less, and the film thickness of the zinc oxide film is in the range of 10 to 300 nm.

Hereinafter, the transparent conductive film of the first embodiment will be specifically described with reference to the appropriate drawings.

Transparent conductive layer

The transparent conductive layer is characterized by a zinc oxide film doped with gallium and indium together with zinc oxide, and a total amount of zinc, gallium, oxygen, and indium measured by elemental analysis by XPS ( 100 atom%), the amount of indium is set to a value in the range of 0.01 to 25 atom%, and the amount of gallium is set to a value in the range of 0.1 to 10 atom%.

In other words, the transparent conductive layer is a transparent conductive layer which is excellent in wet heat characteristics or transparency by including a specific element in a specific amount ratio by a transparent conductive layer.

(1) Crystal structure

It is known that a zinc oxide film already has a hexagonal crystal wurtzite type crystal structure, and a gallium-doped zinc oxide film (hereinafter referred to as a GZO film) is also shown in Fig. 4, and has a hexagonal wurtzite type. The crystal structure is a film with strong c-axis alignment.

Further, the transparent conductive layer of the present invention is a zinc oxide film (hereinafter sometimes referred to as an In-GZO film) doped with gallium and indium together with zinc oxide, and the amount of indium is As shown in Fig. 2 and Fig. 3, it can be understood that the columnar structure has a high c-axis alignment property.

More specifically, FIG. 2 shows an X-ray diffraction pattern by the In plane method when the amount of indium is changed. Here, the characteristic curve A is an X-ray diffraction pattern of an In-GZO film obtained from a sintered body having a weight ratio of ZnO:Ga ₂ O ₃ :In ₂ O ₃ =94.0:5.7:0.3, and the characteristic curve B is by weight. The X-ray diffraction pattern of the In-GZO film obtained by the sintered body of ZnO:Ga ₂ O ₃ :In ₂ O ₃ =93.5:5.7:1.0, and the characteristic curve C is a weight ratio of ZnO:Ga ₂ O ₃ : X-ray diffraction pattern of the In-GZO film obtained from the sintered body of In ₂ O ₃ = 89.3: 5.7: 5.0, and the characteristic curve D is a weight ratio of ZnO:Ga ₂ O ₃ :In ₂ O ₃ =84.3:5.7: The X-ray diffraction pattern of the In-GZO film obtained from the sintered body of 10.0, the characteristic curve E does not contain indium, that is, the X-ray diffraction pattern of the GZO film.

Further, Fig. 3 shows an X-ray diffraction pattern by the Out of Plane method at 002 plane. Here, as in FIG. 2, the characteristic curve A is an X-ray diffraction pattern of an In-GZO film obtained from a sintered body having a weight ratio of ZnO:Ga ₂ O ₃ :In ₂ O ₃ =94.0:5.7:0.3, characteristics Curve B is an X-ray diffraction pattern of an In-GZO film obtained from a sintered body having a weight ratio of ZnO:Ga ₂ O ₃ :In ₂ O ₃ =93.5:5.7:1.0, and the characteristic curve C is a weight ratio of ZnO: X-ray diffraction pattern of the In-GZO film obtained by the sintered body of Ga ₂ O ₃ :In ₂ O ₃ =89.3:5.7:5.0, the characteristic curve D is a weight ratio of ZnO:Ga ₂ O ₃ :In ₂ O ₃ =84.3: X-ray diffraction pattern of the In-GZO film obtained from the sintered body of 5.7:10.0, the characteristic curve E does not contain indium, that is, the X-ray diffraction pattern of the GZO film.

That is, it is understood from FIGS. 2 to 3 that the crystal structure is similar because the In-GZO film exhibits the same diffraction peak as the GZO film.

(2) Composition

Further, in the present invention, the transparent conductive layer is characterized by a total amount of zinc (100 atom%) measured by elemental analysis by XPS, and the amount of indium is set to 0.01 to 25 atom. The value in the range of %, and the amount of gallium is set to a value in the range of 0.1 to 10 atom%.

The reason for this is that if the amount of indium in the transparent conductive layer is a value within the above range, good moist heat characteristics and conductivity can be exhibited.

Further, when the amount of indium in the transparent conductive layer exceeds 25 atom%, the specific resistance becomes a value which is remarkably increased, and the electrical characteristics of the transparent conductive film are lowered.

According to this, from the viewpoint of having good wet heat characteristics, the total amount of zinc, the amount of gallium, the amount of oxygen, and the amount of indium measured by elemental analysis by XPS in the transparent conductive layer are 100% by weight. Preferably, the indium concentration is set to a value in the range of 0.02 to 7 atom%, and the gallium concentration is set to a value in the range of 0.5 to 10 atom%.

Further, the amount of each element measured by elemental analysis of XPS means the average value of the element amounts at respective depths measured by XPS analysis in the depth direction of the entire transparent conductive layer.

(3) Film thickness

Further, in the present invention, the film thickness of the transparent conductive layer is a value in the range of 10 to 300 nm.

This reason is because when the film thickness of the transparent conductive layer is less than 10 nm, it is difficult to form a stable formation of the transparent conductive layer, or the wet heat characteristics and the like may be remarkably lowered.

In addition, when the film thickness of the transparent conductive layer is a value exceeding 300 nm, it takes a long time to form the transparent conductive layer, and productivity may be lowered.

Accordingly, the film thickness of the transparent conductive layer is preferably in the range of 20 to 250 nm, more preferably in the range of 30 to 200 nm.

Further, the film thickness (d) of the transparent conductive layer can be measured using a spectroscopic ellipsometer as specifically described in Example 1.

(4) specific resistance

Further, it is preferable that the initial specific resistance ( ρ ₀ ) of the transparent conductive layers 10 and 10 ' illustrated in Figs. 1(a) to (d) is more than 5 × 10 ^-4 Ω. Cm, 1 × 10 ^-1 Ω. The value below cm.

This reason is because the initial specific resistance of the transparent conductive layer is 5 × 10 ^-4 Ω. When the value is less than cm, the film formation conditions may become complicated.

In addition, because the initial specific resistance of the transparent conductive layer exceeds 1 × 10 ^-1 Ω. When the value of cm is obtained, there is a case where appropriate conductivity is not obtained.

Accordingly, it is more preferable that the initial specific resistance of the transparent conductive film layer is 5.5 × 10 ^-4 Ω. Cm~1×10 ^-2 Ω. The value in the range of cm is more preferably 6 × 10 ^-4 Ω. Cm~5×10 ^-3 Ω. The value in the range of cm.

Further, the specific resistance (ρ) of the transparent conductive layer was calculated in the first embodiment by the film thickness (d) of the transparent conductive film and the measured surface resistivity (R).

Here, the relationship between the amount of indium of the zinc oxide film constituting the transparent conductive layer of the present invention and the specific resistance of the transparent conductive layer will be described with reference to FIG.

That is, the horizontal axis of Fig. 5 shows the amount of indium in the zinc oxide film, and the vertical axis shows the specific resistance of the zinc oxide film.

It is understood that the specific resistance is accompanied by an increase in the amount of indium in the zinc oxide film, the specific resistance is remarkably increased, and the electrical characteristics are lowered.

Accordingly, it is understood that the amount of indium in the zinc oxide film is a total amount (100 atom%) of the amount of zinc, the amount of gallium, the amount of oxygen, and the amount of indium measured by elemental analysis by XPS, and the amount of indium is 0.01 to 25 atom%. In the range of values, the zinc oxide film maintains a value within a specific specific resistance range to obtain appropriate electrical characteristics.

(5) Humid heat characteristics

Further, the specific resistance of the transparent conductive layers 10 and 10 ' illustrated in Figs. 1(a) to 1(d) is ρ ₀ at the initial stage, and is stored for 500 hours under conditions of 60 ° C and a relative humidity of 95%. When the subsequent specific resistance is ρ ₁ , it is preferable to set the ratio represented by ρ ₁ / ρ ₀ to a value of 1.5 or less.

Further, when the specific resistance after storage for 1000 hours at 60 ° C and a relative humidity of 95% is preferably ρ ₂ , the ratio represented by ρ ₂ / ρ ₀ is 2.0 or less.

Further, the specific resistance ( ρ ₀ , ρ ₁ , ρ ₂ ) of the transparent conductive layer can be measured by using a surface resistance measuring device as described in detail in the first embodiment.

Here, the relationship between the configuration of the transparent conductive layer of the transparent conductive film and the change in specific resistance before and after the environmental test will be described with reference to FIG. 6 .

That is, on the horizontal axis of Fig. 6, the storage elapsed time under the condition of 60 ° C and a relative humidity of 95% is shown, and on the vertical axis, the ratio expressed by ρ ₁ / ρ ₀ and ρ ₂ / ρ ₀ is shown.

Further, the characteristic curve A shows a wet heat characteristic curve of the In-GZO film obtained from a sintered body having a weight ratio of ZnO:Ga ₂ O ₃ :In ₂ O ₃ =94.0:5.7:0.3, and the characteristic curve B shows the weight by weight. The ratio of the wet heat characteristics of the In-GZO film obtained by the sintered body of ZnO:Ga ₂ O ₃ :In ₂ O ₃ =93.5:5.7:1.0, the characteristic curve C shows the weight ratio of ZnO:Ga ₂ O ₃ : The wet heat characteristic curve of the In-GZO film obtained from the sintered body of In ₂ O ₃ = 89.3: 5.7: 5.0, and the characteristic curve D is shown by the weight ratio of ZnO:Ga ₂ O ₃ :In ₂ O ₃ =84.3:5.7: The curve of the moist heat characteristics of the In-GZO film obtained from the sintered body of 10.0, the characteristic curve E shows a curve which does not contain indium, that is, the wet heat characteristics of the GZO film.

Thus, the characteristic curves A to E can be understood as the transparent conductive layer of the GZO film, and the moist heat characteristics are dramatically improved by adding a small amount of indium.

Further, it has been found that the increase in the amount of indium blending tends to further improve the moist heat characteristics.

Further, it is understood that the in-GZO film further doped with the indium of the present invention has a low increase rate of the value of ρ ₂ / ρ ₀ after 1000 hours, and maintains a value of 2.0 or less.

That is, it is understood that the ratio of the change in specific resistance of the In-GZO film in a hot and humid environment has been low for a long time as compared with the GZO film, and the wet heat characteristics are excellent in elapsed time.

Accordingly, as described above, the ratio represented by ρ ₁ / ρ ₀ is preferably a value of 1.4 or less, more preferably 1.3 or less, still more preferably 1.2 or less.

Further, the ratio represented by ρ ₂ / ρ ₀ is preferably a value of 1.8 or less, more preferably a value of 1.6 or less, and still more preferably a value of 1.4 or less.

2. Gas barrier layer (1) Aspect

Further, in the present invention, the gas barrier layers 14 and 14 ' are formed on at least one surface of the resin substrate 12 as shown in Figs. 1(a) to 1(d).

More specifically, as illustrated in FIG. 1 , the gas barrier layer 14 is formed between the resin substrate 12 and the transparent conductive layer 10 and penetrates the resin substrate 12 to prevent further penetration of the water vapor or the like even if it is immersed in water vapor or the like. As a result, it is a layer for preventing deterioration of the transparent conductive layer 10.

Accordingly, the specific gas barrier layer properties are not particularly limited, and examples thereof include metals such as aluminum, magnesium, zirconium, titanium, zinc, and tin; cerium oxide and oxidation. Inorganic oxides of aluminum, magnesium oxide, zirconium oxide, titanium oxide, zinc oxide, indium oxide, tin oxide, etc.; inorganic nitrides such as tantalum nitride; inorganic carbides; inorganic sulfides; oxygen nitrogen of such composites An inorganic oxidized carbide such as bismuth oxide; an inorganic carbide carbide; an inorganic oxynitride carbide; a polymer compound or the like, alone or in combination of two or more.

Further, the gas barrier layer may contain other synthetic components such as various polymer resins, hardeners, anti-aging agents, light stabilizers, flame retardants, and the like.

Further, as shown in Fig. 1(c), the gas barrier layer can form a plurality of layers on the resin substrate to form a gas barrier layer after forming the transparent conductive layer (not shown).

(2) Film thickness

Further, the film thickness of the gas barrier layer 14 illustrated in Fig. 1 is preferably in the range of 20 nm to 50 μm.

The reason for this is that by providing the gas barrier layer having such a specific film thickness, it is possible to further obtain excellent gas barrier properties or adhesion, and to impart flexibility and film strength.

Accordingly, the film thickness of the gas barrier layer is more preferably in the range of 30 nm to 1,000 nm, and more preferably in the range of 40 nm to 500 nm.

(3) Water vapor transmission rate (WVTR)

Further, it is preferred that the water vapor transmission rate measured in an atmosphere of a gas barrier layer of 40 ° C and a relative humidity of 90% is set to 0.1 g. m ^-2 . The value below day ^-1 , more preferably 0.05g. m ^-2 . The value below day ^-1 , and more preferably 0.01g. m ^-2 . The value below day ^-1 .

For this reason, by setting the value of the water vapor transmission rate as described above, deterioration of the transparent conductive layer can be prevented, and gas barrier properties excellent in moist heat resistance can be obtained.

Further, as the water vapor transmission rate of the gas barrier layer, a known method can be used. The measurement can be measured, for example, as shown in Example 1, using a commercially available water vapor transmission rate measuring device.

3. Resin substrate (1) Category

The resin used for the resin base material 12 illustrated in FIG. 1 is not particularly limited as long as it is excellent in flexibility and transparency, and examples thereof include polyimine, polyamine, polyamidimide, and poly Polyphenylene ether, polyether ketone, polyetheretherketone, polyolefin, polyester, polycarbonate, polyfluorene, polyether oxime, polyphenylene sulfide, polyarylate, acrylic resin, ring An olefin-based copolymer, a cycloolefin-based polymer, an aromatic polymer, a polyurethane-based polymer, or the like.

Among these, since it is excellent in transparency, flexibility, and versatility, it is preferably selected from the group consisting of polyester, polycarbonate, polyimine, polydecylamine or cycloolefin polymer, and polyether oxime. At least one of them is more preferably a polyester or a cycloolefin polymer.

More specifically, examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyarylate.

Further, examples of the polyamines include wholly aromatic polyamines, nylon 6, nylon 66, and nylon copolymers.

In addition, examples of the cycloolefin polymer include a norbornene-based polymer, a monocyclic cyclic olefin polymer, a cyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer, and the like. Hydride. For example, Appel (Ethylene-cycloolefin copolymer manufactured by Mitsui Chemicals Co., Ltd.), Arton (northene-based polymer manufactured by JSR Corporation), ZEONOR (northene-based polymer manufactured by Zeon Corporation of Japan), and the like.

(2) Film thickness

In addition, the film thickness of the resin base material 12 illustrated in FIG. 1 may be determined depending on the purpose of use, etc., but it is preferably in the range of 1 to 1000 μm from the viewpoint of flexibility and ease of handling, and more preferably It is a value in the range of 5 to 250 μm, and more preferably in the range of 10 to 200 μm.

(3) Additives

In addition, the resin base material may contain various additives such as an antioxidant, a flame retardant, and a lubricant, in addition to the above-described resin component, without impairing transparency and the like.

4. Other layers

Further, in the transparent conductive film of the present invention, various other layers may be provided if necessary.

Examples of such other layers include an undercoat layer (primer layer), a planarization layer, a hard coat layer, a protective layer, an antistatic layer, an antifouling layer, an antiglare layer, a color filter, an adhesive layer, Decorative layer, printed layer, etc.

Here, as shown in FIG. 1(d), the undercoat layer 16 is used to lift the adhesion layer provided between the resin substrate and the transparent conductive layer, and as the material, for example, an amino formate resin may be used. Acrylic resin, decane coupling A known person such as a solvent, an epoxy resin, a polyester resin, or an ultraviolet curable resin.

Further, as shown in Fig. 1(d), it is preferable to provide a layer 18 (anti-glare layer, antistatic layer, anti-reflection layer) for each application in a surface opposite to the transparent conductive layer 10 of the resin substrate 12. , antifouling layer, etc.).

5. Transparent conductive film (1) Aspect

The transparent conductive films 50, 50 ' , 50 " , 50 ''' illustrated in Figs. 1(a) to (d) are formed on the resin substrate 12 on one or both sides to form gas barrier layers 14, 14 ' and transparent. a transparent conductive film formed by the conductive layers 10, 10 ' , and a transparent conductive layer is a zinc oxide film formed by doping gallium and indium together with zinc oxide, the transparent conductive layer being compared with zinc determined by elemental analysis by XPS The total amount of the amount, the amount of gallium, the amount of oxygen, and the amount of indium (100 atom%), the amount of indium is set to a value in the range of 0.01 to 25 atom%, and the amount of gallium is set to a value in the range of 0.1 to 10 atom%, which is specific Humid heat characteristics and film thickness.

Further, in the present invention, the transparent conductive layer has a specific thickness of, for example, any of 20 to 600 nm, preferably a light transmittance of 70% or more, more preferably 80% or more. More preferably, it is more than 90%.

Further, the transparency of the transparent conductive film is, for example, any one of 10 μm to 1 mm, and preferably has a light transmittance of 50% or more, more preferably 60% or more, more preferably 60% or more. For 70% The value above.

(2) specific resistance

The specific resistance (ρ) of the transparent conductive films 50, 50 ' , 50 " , 50 ''' illustrated in Figs. 1(a) to (d) is, in fact, the same as the specific resistance of the transparent conductive layers 10, 10 ' , Therefore, the explanation is omitted.

[Second Embodiment]

The second embodiment is a method for producing a transparent conductive film, which is a method for producing a transparent conductive film in which a gas barrier layer and a transparent conductive layer are formed on at least one surface of a resin substrate, and the method comprises the following steps (1) )~(3);

(1) Step of preparing a resin substrate and a sintered body

(2) a step of forming a gas barrier layer on at least one side of the resin substrate

(3) a step of forming a zinc oxide film, wherein the zinc oxide film is on the gas barrier layer, and the sintered body is doped with gallium and indium together with zinc oxide by using a sputtering method or a vapor deposition method. The zinc oxide film is used as a transparent conductive layer, and the transparent conductive layer is set to 0.01% of the total amount of zinc, the amount of gallium, the amount of oxygen, and the amount of indium measured by elemental analysis by XPS (100 atom%). At the same time as the value in the range of 25 atom%, and the value of gallium is set to be in the range of 0.1 to 10 atom%, the initial specific resistance of the zinc oxide film is set to ρ ₀ at 60 ° C and a relative humidity of 95%. When the specific resistance after storage for 500 hours is ρ ₁ , the ratio represented by ρ ₁ / ρ ₀ is 1.5 or less, and the film thickness is a value in the range of 10 to 300 nm.

Hereinafter, a method of producing the transparent conductive film of the second embodiment will be specifically described.

1. Step (1): Step of preparing a resin substrate and a sintered body

The step (1) is a step of preparing a resin substrate and a sintered body.

That is, the transparent conductive layer exemplified in FIGS. 1(a) to 1(d) preferably has a zinc oxide as a main component and a film formed of a sintered body further containing gallium oxide and indium oxide.

Further, in the sintered body in which the transparent conductive layer is formed, it is preferable to set the blending amount of zinc oxide to a value in the range of 15 to 99.98% by weight with respect to the total amount of the sintered body, and to determine the blending amount of gallium oxide. It is a value in the range of 0.01 to 15% by weight, and the blending amount of indium oxide is set to a value in the range of 0.01 to 70% by weight.

For this reason, it is possible to efficiently form a transparent conductive layer having excellent wet heat characteristics by using a ternary sintered body of zinc oxide-gallium oxide-indium oxide which adjusts the blending amount, and finally, the production efficiency can be improved.

More specifically, when the blending amount of indium oxide is less than 0.01% by weight with respect to the entire amount of the sintered body, the amount of indium contained in the transparent conductive layer after film formation is remarkably reduced, and sufficient moist heat is not obtained. The case of characteristics.

Accordingly, it is more preferable to set the amount of zinc oxide to be in the range of 27 to 99.4% by weight based on the total amount of the sintered body, and to set the blending amount of gallium oxide to be in the range of 0.5 to 8% by weight. And the amount of indium oxide is determined as A value in the range of 0.1 to 65 wt%.

Further, it is more preferable to set the blending amount of zinc oxide to a value in the range of 33 to 98.7 wt% with respect to the total amount of the sintered body, and to set the blending amount of gallium oxide to a value in the range of 1 to 7 wt%. And the blending amount of indium oxide is set to a value within a range of 0.3 to 60% by weight.

Further, the details of the resin substrate are omitted as described above.

2. Step (2): Step of forming a gas barrier layer

The step (2) is a step of forming the gas barrier layers 14 and 14 ' of the transparent conductive film, preparing the resin substrate 12 having a desired gas barrier layer, and forming the gas barrier layers 14, 14 ' on the resin substrate.

Further, the method for forming the gas barrier layer is not particularly limited, and examples thereof include a method in which the material is formed on the substrate by a vapor deposition method, a sputtering method, an ion plating method, a thermal CVD method, or a plasma CVD method. Or a method in which a solution in which the above materials are dissolved or dispersed in an organic solvent is applied onto a resin substrate by a known coating method, the resulting coating film is appropriately dried, or the obtained coating film is subjected to atmospheric piezoelectric slurry treatment. A method of forming a reforming process such as an ion implantation process or a lamp annealing process.

For example, the gas barrier layer 14 described above is a layer containing a polyazide compound and can be formed by performing a plasma ion implantation treatment.

As such a plasma ion implantation treatment, an ion present in a plasma generated using an external electric field, a method of injecting a layer containing a polyazide compound, or an external electric field, may be present in the plasma. In the middle Ion, a method of injecting a layer containing a polyazide compound, which is generated only by an electric field of a negative high voltage pulse of a layer formed of a material for forming a gas barrier layer.

Further, examples of the ions to be implanted include hydrogen, nitrogen, oxygen, argon, helium, neon, krypton, and xenon.

3. Step (3): Step of forming a transparent conductive layer

The step (3) is a method of forming a transparent conductive layer on at least one side of the resin substrate.

Examples of the method of forming the transparent conductive layer include a physical production method represented by a sputtering method or a vapor deposition method, and a chemical production method represented by a chemical vapor deposition method.

Among these, since a transparent conductor layer can be formed easily, a sputtering method or a vapor deposition method is preferable. That is, by forming by sputtering or vapor deposition, since the composition of the formed transparent conductive layer can be easily regulated, the transparent conductive layer can be efficiently formed.

As more specific sputtering methods, DC sputtering, DC magnetron sputtering, RF sputtering, RF magnetron sputtering, DC+RF overlap sputtering, DC+RF overlap magnetron Tube sputtering, counter target sputtering, ECR sputtering, dual magnetron sputtering, etc.

Moreover, as a more specific vapor deposition method, a resistance heating method, an electron beam heating method, a laser heating method, an arc vapor deposition method, an induction heating method, etc. are mentioned.

Further, the conditions for sputtering or vapor deposition are not particularly limited, but the back pressure is preferably 1 × 10 ^-2 Pa or less, more preferably 1 × 10 ^-3 Pa or less.

Further, when the method of forming the argon gas into the system is selected, the pressure in the system is preferably 0.1 to 5 Pa, more preferably 0.2 to 1 Pa.

Further, by introducing a gas species in the system by a sputtering method or a vapor deposition method, it is preferable to use a mixed gas of argon (Ar) or argon (Ar) and oxygen (O ₂ ), but it is also possible to use a gas other than Ar. Diluted gas, nitrogen (N ₂ ), and the like. When a mixed gas is used, the mixing ratio (O ₂ /(Ar + O ₂ )) is preferably set to a value in the range of 0.01 to 20, more preferably in the range of 0.1 to 10.

The reason for this is that if the mixing ratio of argon and oxygen is in the above range, a conductive layer having a lower specific resistance and a lower reflectance can be formed into a film.

Further, it is preferable that the temperature of the resin substrate when the transparent conductive layer is formed on the resin substrate is set to a value in the range of 10 to 150 °C.

For this reason, if the temperature of the resin substrate is in the range of 10 to 150 ° C, a suitable transparent conductive layer can be formed even if the resin substrate has a relatively low softening point.

[Third embodiment]

The third embodiment is an electronic device characterized in that any one of the above transparent conductive films is used for a transparent electrode.

More specifically, a liquid crystal display, an organic EL display, an inorganic EL display, an electronic paper, a solar cell, an organic transistor, an organic EL illumination, an inorganic EL illumination, and a thermoelectric conversion including a transparent electrode having a specific transparent conductive film can be used. Devices, gas sensors, etc.

In other words, the electronic device of the present invention has the transparent conductive film described in the first embodiment, and therefore has a very small specific resistance and can suppress the increase in specific resistance over a long period of time.

[Examples]

Hereinafter, the present invention will be described in further detail by way of examples. However, the following description is illustrative of the invention, and the invention is not limited thereto.

[Example 1] 1. Manufacture of transparent conductive film (1) Step (1): Step of preparing a resin substrate and a sintered body

A polyethylene terephthalate film (A4100, manufactured by Toyobo Co., Ltd., thickness: 100 μm) was prepared as a resin substrate.

Further, a ternary sintered body of zinc oxide-gallium oxide-indium oxide (ZnO:Ga ₂ O ₃ :In ₂ O ₃ =94.0% by weight: 5.7% by weight: 0.3% by weight) was prepared.

(2) Step (2): Step of forming a gas barrier layer

Next, a solution of a primer layer made of a photocurable resin was applied onto a resin substrate, and then heat-treated at 120 ° C for 1 minute, and dried.

Secondly, use UV light ray and use high pressure mercury lamp, line speed: 20m/min, cumulative light quantity: 100mJ, peak intensity: 1.466W, pass Number of times: UV irradiation was performed under conditions of 2 times to form an undercoat layer.

Next, AQUAMICANL 110-20 (manufactured by Clariant Japan Co., Ltd.) as a polyazide compound was applied onto the formed undercoat layer, and then heat-treated at 120 ° C for 1 minute, and dried to obtain a poly-containing polymer. A layer of a decazane compound (film thickness: 150 nm). Thereafter, it was air-dried at 23 ° C in a 50% RH atmosphere.

Next, the following plasma ion implantation apparatus is used to inject a plasma ion of argon into a layer containing a polyazide compound to form a gas barrier layer as a plasma ion implantation membrane (hereinafter referred to as a gas barrier layer). PHPS layer).

(plasma ion device)

RF power supply: Japan Electronics Co., Ltd., model "RF" 56000

High-voltage pulse power supply: Kurita Manufacturing Co., Ltd., model "PV-3-HSHV-0835"

(plasma ion implantation conditions)

Plasma generated gas: argon (Ar)

Gas flow: 100sccm

Duty ratio: 0.5%

Repeat frequency: 1000Hz

Applied voltage: -6kV

RF power supply: frequency 13.56MHz, applied power 1000W

Intracavity pressure: 0.2Pa

Pulse width: 5μsec

Processing time (ion injection time): 5 minutes

Conveying speed: 0.2m/min

In the resin substrate of the gas barrier layer obtained by lamination, a water vapor transmission rate measuring apparatus (manufactured by MOCON Co., Ltd., AQUATRAN) was used to measure the water vapor transmission rate at 40 ° C and a relative humidity of 90%. , for 0.02g. m ^-2 . Day ^-1 .

(3) Step (3): Step of forming a transparent conductive layer

Next, for the resin substrate of the gas barrier layer obtained by lamination, a transparent conductive layer (film thickness: 100 nm) was formed by the DC magnetron sputtering method using the above-described ternary sintered body under the following sputtering conditions. And become a transparent conductive film.

Resin substrate temperature: 20 ° C

DC output: 500W

Carrier gas: argon (Ar)

Film formation pressure: 0.6Pa

Film formation time: 35sec.

2. Evaluation of transparent conductive film

The obtained transparent conductive film was subjected to the following measurement and evaluation.

(1) Elemental analysis in XPS analysis

XPS measurement and analysis device (manufactured by ULVAC-PHI, Quantum 2000), elemental analysis of zinc, gallium, indium and oxygen in the transparent conductive layer of the obtained transparent conductive film. The amount of each element measured by the obtained XPS is shown in Table 1.

(2) Film thickness of transparent conductive layer (d)

The film thickness (d) of the transparent conductive layer of the obtained transparent conductive film was measured using a spectroscopic ellipsometer M-2000U (manufactured by J.A. Woollam. Japan Co., Ltd.).

(3) Calculation of ρ ₂ / ρ ₀ and ρ ₁ / ρ ₀

The initial surface resistivity (R ₀ ) of the transparent conductive layer of the obtained transparent conductive film was used as a surface resistance measuring device, as LORESTA-GP MCP-T600 (manufactured by Mitsubishi Chemical Corporation) and a probe, and PROBE TYPE was used. ASP (manufactured by Mitsubishi Chemical Analytic Co., Ltd.) was measured under ambient conditions of a temperature of 23 ° C and 50% RH.

Next, the obtained transparent conductive film was allowed to stand in an environment of 60 ° C and 95% RH for 500 hours, and after taking out, the temperature was adjusted for 1 day in a 23 ° C 50% RH environment. The humidity was measured, and the surface resistivity (R ₁ ) after the damp heat test was measured.

Further, the obtained transparent conductive film was allowed to stand in an environment of 60 ° C and 95% RH for 1000 hours, and after taking out, the temperature was adjusted for 1 day in a 23 ° C 50% RH environment. The humidity was measured, and the surface resistivity (R ₂ ) after the damp heat test was measured.

That is, the initial surface resistivity (R ₀ ) of the transparent conductive layer and the surface resistivity (R ₁ and R ₂ ) after the damp heat test are measured, and the film thickness (d) of the transparent conductive film is further determined by Equations (1) to (3) calculate the specific resistance ( ρ ₀ ) and the specific resistance ( ρ ₁ , ρ ₂ ) after the damp heat test, and obtain the ratio of ρ ₂ / ρ ₀ and ρ ₁ / ρ ₀ . The results obtained are shown in Table 1.

Further, Fig. 5 shows the relationship between the blending amount of indium in Example 1 and the specific resistance, and Fig. 6 shows the elapsed time of the damp heat test in Example 1 and the specific resistance before and after the damp heat test. The relationship of the ratios ( ρ ₁ / ρ ₀ and ρ ₁ / ρ ₀ ).

R ₀ = ρ ₀ /d (1)

R ₁ = ρ ₁ /d (2)

R ₂ = ρ ₂ /d (3)

[Example 2]

In the second embodiment, a transparent conductive film was produced and evaluated in the same manner as in Example 1 except that a PHP layer was formed, that is, a PHPS layer was formed, and a PHPS layer was formed thereon, followed by formation of a transparent conductive layer. The results obtained are shown in Table 1.

Further, the resin substrate having a two-layer gas barrier layer has a water vapor transmission rate of 0.005 g. m ^-2 . Day ^-1 .

[Example 3]

In Example 3, except that a three-layer PHPS layer was formed, that is, a PHPS layer was formed, and two layers of PHPS layers were formed thereon, a total of three layers were formed, and then a transparent conductive layer was formed, and other fabrications and evaluations were carried out in the same manner as in Example 1. Transparent conductive film. The results obtained are shown in Table 1.

Further, the water vapor transmission rate of the resin substrate having the gas barrier layer of 3 layers is 0.0005 g. m ^-2 . Day ^-1 .

[Examples 4 to 6]

In Examples 4 to 6, except that the weight ratio of the ternary sintered body used for sputtering was changed to ZnO:Ga ₂ O ₃ :In ₂ O ₃ =93.3:5.7:1.0, and Example 1~ 3 A transparent conductive film was produced and evaluated in the same manner. The results obtained are shown in Table 1.

[Examples 7 to 9]

In Examples 7 to 9, except that the weight ratio of the ternary sintered body used for sputtering was changed to ZnO:Ga ₂ O ₃ :In ₂ O ₃ =89.3:5.7:5.0, the same as Example 1~ 3 A transparent conductive film was produced and evaluated in the same manner. The results obtained are shown in Table 1.

[Comparative Example 1]

In Comparative Example 1, a transparent conductive film was produced and evaluated in the same manner as in Example 1 except that the gas barrier layer was not formed after the undercoat layer was formed on the resin substrate. The results obtained are shown in Table 1.

However, the water vapor transmission rate of the resin substrate having only the undercoat layer is 6.8 g. m ^-2 . Day ^-1 .

[Comparative Example 2]

In Comparative Example 2, after the undercoat layer was formed on the resin substrate, a yttrium oxide (SiOx) layer was formed to have a film thickness of 100 nm by the following conditions of the sputtering method.

Next, a transparent conductive film was produced and evaluated in the same manner as in Example 1 on the formed SiOx layer. The results obtained are shown in Table 1.

Further, the water vapor transmission rate of the resin substrate having the SiOx layer and the undercoat layer is 0.5 g. m ^-2 . Day ^-1 .

[Comparative Example 3, Comparative Example 4]

In Comparative Example 3 and Comparative Example 4, the weight ratio of the ternary sintered body used for sputtering was changed to ZnO:Ga ₂ O ₃ :In ₂ O ₃ =93.3:5.7:1.0, and other comparative examples. The transparent conductive film was also manufactured and evaluated in the same manner as in 1 to 2. The results obtained are shown in Table 1.

[Comparative Example 5, Comparative Example 6]

In Comparative Example 5 and Comparative Example 6, except that the weight ratio of the ternary sintered body used for sputtering was changed to ZnO:Ga ₂ O ₃ :In ₂ O ₃ =89.3:5.7:5.0, other and comparative examples were used. The transparent conductive film was also manufactured and evaluated in the same manner as in 1 to 2. The results obtained are shown in Table 1.

In Examples 1 to 9, after obtaining 500 hours, The rate of change of the specific resistance is 1.5 or less, and the transparent conductive film having a long-term specific resistance change rate of 2.0 or less even after 1000 hours is obtained.

Further, in Comparative Examples 1, 3, and 5 which did not have a gas barrier layer, the specific resistance after the environmental test was remarkably increased, and after 500 hours, the rate of change of the specific resistance was 100 times or more.

Further, in Comparative Examples 2, 4, and 6 having a gas barrier layer having a low water vapor transmission rate, the specific resistance after the environmental test was increased, and the rate of change in the specific resistance was 5 times or more after 500 hours.

[Industrial Applicability]

Above, as detailed, transparent conductive thin film according to the present invention a film, which is a transparent conductive film formed by forming a gas barrier layer and a transparent conductive layer on at least one side of a resin substrate, and the amount of zinc, the amount of gallium, the amount of oxygen, and the amount of the transparent conductive layer measured by elemental analysis of XPS The amount of indium includes a zinc oxide film having a specific amount of indium and a gallium amount, and the zinc oxide film can efficiently obtain wet heat characteristics and gas barrier properties by using specific wet heat characteristics and film thickness. Transparent conductive film.

Therefore, the transparent conductive film of the present invention is an electric product, an electronic component, an image display device (organic electroluminescence device, an inorganic electroluminescence device, a liquid crystal display device, an electronic paper, etc.), which is desired to have specific moist heat characteristics, and the like. Among various uses, it is expected to be effectively used as a transparent electrode or the like.

Claims (8)

A transparent conductive film which is formed by forming a gas barrier layer and a transparent conductive layer on at least one side of a resin substrate, wherein the transparent conductive layer is formed by doping gallium and indium together with zinc oxide. In the zinc oxide film, the amount of indium is set to be in the range of 0.01 to 25 atom% with respect to the total amount of zinc, the amount of gallium, the amount of oxygen, and the amount of indium measured by elemental analysis by XPS (100 atom%). At the same time, the amount of gallium is set to a value in the range of 0.1 to 10 atom%, and the initial specific resistance is set to ρ ₀ , and the specific resistance after storage for 500 hours under conditions of 60 ° C and 95% relative humidity When ρ ₁ is determined, the ratio represented by ρ ₁ / ρ ₀ is 1.5 or less, and the film thickness of the transparent conductive layer is a value in the range of 10 to 300 nm. The transparent conductive film of claim 1, wherein the specific resistance at the initial stage of the transparent conductive film layer is ρ ₀ , and the specific resistance after storage for 1000 hours is set at 60 ° C and a relative humidity of 95%. When ρ ₂ , the ratio represented by ρ ₂ / ρ ₀ becomes a value of 2.0 or less. The transparent conductive film of claim 1, wherein the resin substrate is selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, cycloolefin copolymer, and cycloolefin polymer. At least one of the group consisting of polyether oxime and polyamidimide. The transparent conductive film of claim 1, wherein the gas barrier is The barrier layer is selected from the group consisting of a metal, an inorganic oxide, an inorganic nitride, an inorganic oxynitride, an inorganic carbide, an inorganic sulfide, an inorganic oxycarbide carbide, a polymer compound, and at least one of these composites. Composition. The transparent conductive film of claim 1, wherein the gas barrier layer of the gas barrier layer is set to 0.1 g. m ^-2 . The value below day ^-1 . An electronic device obtained by using the transparent conductive film of claim 1 on a transparent electrode. A method for producing a transparent conductive film, which is a method for producing a transparent conductive film formed by forming a gas barrier layer and a transparent conductive layer on at least one side of a resin substrate, comprising the following steps (1) to (3); (1) a step of preparing the resin substrate and the sintered body, (2) a step of forming a gas barrier layer on at least one surface of the resin substrate, and (3) a step of forming a zinc oxide film, wherein the zinc oxide film is as described above On the gas barrier layer, a zinc oxide film doped with gallium and indium, together with zinc oxide, is used as the transparent conductive layer from the sintered body by a sputtering method or a vapor deposition method, and the transparent conductive layer is opposed to The total amount of zinc, gallium, oxygen, and indium measured by elemental analysis of XPS (100 atom%), the amount of indium is set to a value in the range of 0.01 to 25 atom%, and the amount of gallium is set to 0.1~ In the range of 10 atom%, the specific resistance at the initial stage of the zinc oxide film is ρ ₀ , and the specific resistance after storage for 500 hours is ρ ₁ at 60 ° C and a relative humidity of 95%, ρ ₁ / ρ ₀ ratio of 1.5 or less represented by the values, and having a thickness in the range of 10 ~ 300nm Value. The method for producing a transparent conductive film according to claim 7, wherein the temperature of the resin substrate when the transparent conductive layer is formed on the resin substrate is set to a value within a range of 10 to 150 °C.