JP3356968B2 - Transparent conductive film, method of manufacturing the same, and display device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is particularly useful for a display surface of a cathode ray tube or a plasma display, etc., and has a transparent and excellent antistatic effect and electromagnetic wave shielding effect, a large film strength, salt water resistance and oxidation resistance. TECHNICAL FIELD The present invention relates to a transparent conductive film having good transparency and durability such as ultraviolet resistance, a natural hue of a transmitted image, and good visibility, a method for manufacturing the same , and a display device having the transparent conductive film formed on a display surface.

[0002]

2. Description of the Related Art At present, a cathode ray tube used as a TV cathode ray tube or a computer display projects characters and images on a display surface by projecting an electron beam on a phosphor screen emitting red, green and blue light. Therefore, there is a fear that dust adheres to the display surface due to static electricity generated on the display surface to lower visibility, and that the environment is affected by radiating electromagnetic waves. Recently, it has been pointed out that a plasma display, which is being applied to a wall-mounted television or the like, may generate static electricity or emit electromagnetic waves.

[0003] In order to solve the problems of generation of static electricity and radiation of electromagnetic waves, conventionally, a transparent metal thin film is formed on a display surface of a display device by a sputtering method or a vapor deposition method, or fine particles such as silver and gold are used. Is applied to a display surface by dispersing the compound in a liquid, and a transparent conductive film is formed to achieve antistatic and / or electromagnetic wave shielding. In addition, when these thin films are formed on the display surface, interface reflection occurs and visibility is reduced. To prevent this, the upper and / or lower layers of the transparent conductive film have different refractive indices. Lamination of a transparent thin film is also performed.

For example, Japanese Patent Application Laid-Open No. 8-77832 discloses that
As a transparent conductive film excellent in an electromagnetic wave shielding effect and an antireflection effect, a transparent metal thin film made of a metal fine particle containing at least silver having an average particle diameter of 2 to 200 nm and a transparent film having a different refractive index from the transparent metal thin film have been proposed. I have.

[0005]

According to these methods, although antistatic and electromagnetic wave shielding effects can be expected, when silver is used as a metal, absorption at a specific wavelength of transmitted light depends on its light transmission spectrum. The problem is that the conductive film is colored and the hue of the transmitted image looks unnatural, the film is soft and scratches easily occur, and silver is deteriorated when exposed to salt water, and the surface of the conductive film is deteriorated. Since the resistance value is increased and the electromagnetic wave shielding effect is reduced, there has been a problem that durability is poor especially in a place exposed to salt fog, such as a beach, so that it has been difficult to put it to practical use. The present invention has been made in order to solve the above-described problems, and accordingly, has as its object a transparent and excellent antistatic effect and an electromagnetic wave shielding effect, and has a large film strength and is represented by salt water resistance. that durability is good, yet hue natural visibility of transmitted images and excellent transparent conductive film thereof
An object of the present invention is to provide a manufacturing method and a display device in which the transparent conductive film is formed on a display surface.

[0006]

In order to solve the above-mentioned problems , the present invention provides the following transparent conductive film, a method for manufacturing the same, and a method for manufacturing the same.
And a display device. That is, the transparent conductive film of the present invention
After applying and drying a paint containing ruthenium microparticles having an average particle size of 50 nm or less, a temperature of 300 ° C. to 1000 ° C.
In the baked form, a portion of the ruthenium oxide Rute
Characterized by having a transparent conductive layer converted to
I do. The transparent conductive layer is made of ruthenium and ruthenium oxide.
It is preferred which comprises 10 wt% or more combined and. It is preferable that one or more transparent thin films having a refractive index different from the refractive index of the transparent conductive layer are provided in the upper layer and / or the lower layer of the transparent conductive layer. It is preferable that a transparent thin film having irregularities is provided on the outermost layer of the transparent conductive film. At least one of the transparent conductive films
It is preferable that the layer contains a coloring material. Departure
The method for producing a bright transparent conductive film has an average particle size of 50 nm or less.
Apply and dry the paint containing the ruthenium particles of
Then, the paint is baked at a temperature of 300C to 1000C,
Converting part of the ruthenium to ruthenium oxide;
And features. The display device of the present invention is the transparent conductive material of the present invention.
Preferably, the electrode film is formed on the display surface.
No.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. The present inventors have conducted intensive research on a transparent conductive film that can be used on the display surface of a display device, is transparent, has an excellent antistatic effect and an electromagnetic wave shielding effect, and has excellent durability. Ruthenium fine particles with an average particle size of 50 nm or less
After applying the paint containing the particles to the substrate and drying,
It has been found that the above object can be achieved by baking at a baking temperature in the range of ~ 1000 ° C, and the present invention has been achieved.

Ruthenium fine particles having an average particle size of 50 nm or less
Applying a paint containing child on the substrate, 300 ° C. after drying to 1
If you deposited and baked at a temperature of 000 ℃, ruthenium fine
Since the particle size of the particles is small, the total surface area of the fine particles is sufficiently large, and at the above-mentioned baking temperature, part of the ruthenium becomes acidic.
To ruthenium iodide . Ruthenium oxide, not chemical stability typified by salt water is just higher than ruthenium, will not be impaired conductivity of the transparent conductive film be generated ruthenium oxide. Baking temperature is 300 ℃
If less than 100%, the formation of ruthenium oxide is insufficient, and
If the temperature exceeds 0 ° C., troubles such as damage to the base material and deterioration of the film components occur.

At the same time as the formation of ruthenium oxide, in the transparent conductive film obtained by baking in the above-mentioned temperature range, at least a part of the ruthenium fine particles fuse with each other to form an at least partially continuous metal thin film and / or metal oxide. An object thin film is formed. For this reason, in the transparent conductive film of the present invention, much higher conductivity than that obtained by simply contacting the metal fine particles is obtained, and as a result, the antistatic effect and the electromagnetic wave shielding effect are excellent. Instead, a highly transparent and durable transparent conductive film can be obtained. When the average particle size of the ruthenium fine particles exceeds 50 nm, the formation of ruthenium oxide and the fusion of the particles become insufficient, and the light absorbency becomes large, and if sufficient conductivity is obtained, the transparency is lost. Decrease.

[0010] The transparent conductive film comprises ruthenium and ruthenium oxide.
It is preferred that the content be 10% by weight or more in total with ruthenium . In general, the conductive performance of a transparent conductive film required to exhibit an electromagnetic wave shielding effect in addition to an antistatic function is represented by the following equation 1. S = 50 + 10 log (1 / ρf) + 1.7t√ (f / ρ) Formula 1 In the formula, S (dB): Electromagnetic wave shielding effect ρ (Ω-cm); Volume resistivity of conductive film f (MHz); Electromagnetic wave Frequency t (cm): film thickness of conductive film. Here, the thickness t is 1 μm from the viewpoint of securing transparency.
(1 × 10 ⁻⁴ cm) or less, the electromagnetic wave shielding effect S can be approximately expressed by the following equation 2 if the term including the film thickness t is ignored in the equation 1. S = 50 + 10log (1 / ρf) Equation 2

Here, as the value of S (dB) increases, the electromagnetic wave shielding effect increases. Generally, the electromagnetic wave shielding effect is S>
If it is 30 dB, it is considered to be effective, and if S> 60 dB, it is considered to be excellent. In addition, since the frequency of the electromagnetic wave to be regulated is generally in the range of 10 kHz to 1000 MHz, the conductivity of the transparent conductive film requires a volume resistivity (ρ) of 10 ³ Ω-cm or less. That is, the lower the volume specific resistance value (ρ) of the transparent conductive film, the more effectively electromagnetic waves of a wider range of frequencies can be shielded. To satisfy this condition, the transparent conductive film must contain ruthenium and acid.
It is necessary that the total content of ruthenium and ruthenium be 10% by weight or more. If the content is less than 10% by weight, the conductivity is reduced, and it is difficult to obtain a substantial electromagnetic wave shielding effect.

After satisfying the above conditions, the thickness of the transparent conductive film should be 200 in consideration of transparency and antireflection properties.
nm or less is preferable. The obtained transparent conductive film may be a smooth film or a film having an uneven network structure.

The metal used for the transparent conductive film of the present invention is ruthenium.
Um is preferred. Among the platinum group metals, ruthenium is relatively inexpensive, has high conductivity, has high chemical stability, and easily integrates ruthenium fine particles at the time of film formation, thereby further improving conductivity while maintaining high transparency. be able to. Further, ruthenium is 300 ° C to 1000 ° C.
Of ruthenium oxide (Ru)
O ₂ ) . This ruthenium oxide has extremely high chemical stability and electrical conductivity typified by salt water resistance, and does not have a light absorption peak of a specific wavelength in the visible light region of 400 nm to 700 nm even in hue. It has the advantage of not coloring. Further, the transparent conductive film converted into at least ruthenium oxide has an optimized refractive index, and is preferable in terms of antireflection performance. The state of ruthenium and ruthenium oxide present in the transparent conductive film may be in the form of fine particles, or may be in a state where the particles are fused with each other and are at least partially continuous.

[0014] The transparent conductive film of the present invention comprises the above ruthenium.
In addition to and ruthenium oxide, for the purpose of further improving film strength, conductivity, transparency, and the like, if necessary, other components such as silicon, aluminum, zirconium, cerium,
Fine particles of oxides or composite oxides such as titanium, yttrium, zinc, magnesium, indium, tin, antimony, and gallium; metal fine particles such as silver, gold, copper, and nickel; and metal alkoxides such as silicon, titanium, and zirconium. It may appropriately contain an inorganic binder component such as a hydrolyzate, a silicone monomer, and a silicone oligomer.

The above-mentioned paint containing at least ruthenium fine particles is prepared by mixing the above-mentioned aqueous sol of ruthenium and, if necessary, an aqueous sol of other components, preferably with alcohol, and then using an ultrasonic disperser or the like to obtain the resulting mixture. It can be easily prepared by dispersing. In order to apply this paint on a substrate, any of ordinary thin film application techniques such as spin coating, roll coating, spraying, bar coating, dipping, meniscus coating, and gravure printing can be used. is there. Of these, spin coating is a particularly preferred coating method because a thin film having a uniform thickness can be formed in a short time. After application, the coating film is dried,
By baking at a firing temperature in the range of ~ 1000 ° C, at least a part of ruthenium is
A transparent conductive film converted to ruthenium can be formed.

In the transparent conductive film of the present invention, the transparent conductive film is used as a transparent conductive layer, and at least one transparent thin film having a refractive index different from the refractive index of the transparent conductive layer is formed on the upper and / or lower layers. Preferably, it is provided. Thus, external light reflection at the interface of the transparent conductive film can be removed or reduced.

This transparent thin film is expected to not only prevent the interface reflection in the multilayer thin film but also protect the surface from external force when used for the display surface of a display device.
It is preferable to provide a transparent thin film having practically sufficient strength on the transparent conductive layer.

Preferred materials for the transparent thin film include silicon,
An oxide, a complex oxide, or a nitride of aluminum, zirconium, cerium, titanium, yttrium, zinc, magnesium, indium, tin, antimony, gallium, or the like can be given. In particular, the following formula: M (OR) _m R _n (where M is Si, Ti or Zr, and R is C _1-
An alkyl group of C _4, m is an integer from 1 to 4, and n is formed from 4-m a is) a compound represented by, or one or more of a mixture of a partial hydrolyzate thereof Transparent thin films are preferred. More specifically, as a material capable of forming a transparent thin film of SiO ₂ having a high surface hardness and a relatively low refractive index, tetraethoxysilane (Si (O
C ₂ H ₅ ) ₄ ) is suitably used from the viewpoints of thin film forming property, transparency, bonding property with the transparent conductive layer, film strength and antireflection performance.

The transparent thin film is formed by a method in which a coating solution containing the above-mentioned components (a coating material for a transparent thin film) is uniformly applied to a base material to form a film, similarly to the method used for forming the transparent conductive film. be able to. For coating, any of ordinary thin film coating techniques such as spin coating, roll coating, spraying, bar coating, dipping, meniscus coating, and gravure printing can be used. Of these, spin coating is a particularly preferred coating method because a thin film having a uniform thickness can be formed in a short time. After coating, the coating film is dried and baked to obtain a transparent thin film.

In general, the antireflection ability of an interface in a multilayer thin film is determined by the refractive index and thickness of the thin film and the number of laminated thin films. By appropriately designing the thickness of the film and the transparent thin film, an effective antireflection effect can be obtained. In a multilayer film having antireflection ability, when the wavelength of reflected light to be prevented is λ, if the antireflection film has a two-layer structure, the high refractive index layer and the low refractive index layer are respectively λ from the substrate side. /
By setting the optical film thickness to 4, λ / 4, or λ / 2, λ / 4, reflection can be effectively prevented. In the case of a three-layer antireflection film, λ / 4 and λ / are used in order of the medium refractive index layer, the high refractive index layer, and the low refractive index layer from the substrate side.
An optical film thickness of 2, λ / 4 is effective.

In particular, considering the ease of manufacture and economy, an SiO ₂ film (refractive index: 1.46) having a relatively low refractive index and having a hard coat property is formed on the upper layer of the transparent conductive layer at λ / 4. It is preferable that the film is formed to have a film thickness.

In the transparent conductive film of the present invention comprising two or more layers including a transparent conductive layer, the baking of the transparent conductive layer and the transparent thin film may be performed sequentially or simultaneously. For example, a paint for a transparent conductive film is applied to the display surface of a display device, a paint for a transparent thin film is applied thereon, and after drying, 30
The transparent conductive layer and the transparent thin film may be simultaneously formed by baking at a temperature of 0 ° C. to 1000 ° C. to form a low-reflection transparent conductive film.

It is preferable to provide a transparent thin film having irregularities on the outermost layer of the transparent conductive film. The transparent thin film having the irregularities scatters light reflected on the surface of the transparent conductive film, and has an effect of giving excellent antiglare properties to the display surface.

At least one of the transparent conductive films of the present invention
The layer may contain a coloring material. This coloring material is used for improving the contrast of a transmitted image and adjusting the color of transmitted light and reflected light. As this coloring material,
For example, monoazo pigment, quinacridone, iron oxide yellow, disazo pigment, phthalocyanine green, phthalocyanine blue, cyanine blue,
Flavanthrone yellow, dianthraquinolyl red, indanthrone blue, thioindigo bordeaux, perinone orange, perylene scarlet, perylene red 17
8, perylene maroon, dioxazine violet, isoindoline yellow, nickel nitroso yellow, madder lake, copper azomethine yellow, aniline black, alkali blue, zinc white, titanium oxide, red iron oxide, chrome oxide,
Iron black, titanium yellow, cobalt blue, cerulean blue, cobalt green, alumina white, viridian, cadmium yellow, cadmium red, vermilion, lithopone, graphite, molybdate orange, zinc chromate, calcium sulfate, barium sulfate, calcium carbonate, lead Organic and inorganic pigments such as white, ultramarine, manganese violet, cobalt violet, emerald green, navy blue, and carbon black, as well as azo dyes, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, quinoline dyes, and nitro dyes Dyes such as dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes, naphthalimide dyes and perinone dyes can be mentioned. These coloring materials can be used alone or in combination of two or more.

The type and amount of the coloring material to be used should be appropriately selected according to the optical film characteristics of the corresponding transparent conductive film. The absorbance A of the transparent thin film is generally represented by the following equation. A = log ₁₀ (I ₀ / I) = εCD where I _{0 is} incident light, I is transmitted light, C is color density, D is light distance, and ε is molar extinction coefficient.

In the transparent conductive film of the present invention, a coloring material having a molar extinction coefficient ε> 10 is generally used. The amount of the coloring material varies depending on the molar extinction coefficient of the coloring material used. Generally, the absorbance A of the laminated film and the single-layer film containing the coloring material is in the range of 0.0004 to 3 abs. Preferably, the amount is such that If these conditions are not satisfied, the transparency and / or the antireflection effect will decrease. When the coloring material is blended in the transparent conductive layer, the blending amount is 20% by weight or less, particularly 10% by weight, based on the metal content.
% By weight or less. If it exceeds 10% by weight, a decrease in conductivity is observed.
This will hinder the electromagnetic wave shielding effect.

In the display device of the present invention, any one of the transparent conductive films described above is formed on a display surface. This display device prevents the charging of the display surface, so that dust and the like do not adhere to the image display surface, shields electromagnetic waves, prevents various types of electromagnetic wave interference, and is excellent in light transmissivity. It is bright, the hue of the transmitted image is natural, the film thickness is uniform, the appearance of the display surface is good, the scratch resistance is good, and the salt water resistance is high, so it is suitable for environments exposed to salt fog. Even high durability. If the transparent thin film and / or the transparent thin film having irregularities are formed in addition to the transparent conductive layer, an antireflection effect and / or an antiglare effect for external light can be obtained.

[0028]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. The following were prepared as stock solutions common to Examples and Comparative Examples. (Ruthenium aqueous sol) An aqueous solution containing 0.15 mmol / l ruthenium chloride and a 0.024 mmol / l aqueous sodium borohydride solution were mixed, and the obtained colloidal dispersion was concentrated to 0.198 mmol / l. An aqueous sol containing mol / l of ruthenium fine particles was obtained. The average particle size of the ruthenium fine particles was 20 nm. (Silver aqueous sol) sodium citrate dihydrate (14
g) and an aqueous solution (6 g) in which ferrous sulfate (7.5 g) is dissolved.
0 g) was kept at 5 ° C., and silver nitrate (2.5 g) was added thereto.
An aqueous solution (25 g) in which g) was dissolved was added to obtain a red-brown silver sol. The silver sol was washed with water by centrifugation to remove impurity ions, and then added with pure water to obtain 0.185 mol / l.
An aqueous sol containing silver fine particles was obtained. The average particle size of the silver fine particles was 10 nm. (Transparent thin film paint A) Tetraethoxysilane (0.8 g)
And 0.1 N hydrochloric acid (0.8 g) and ethyl alcohol (9
8.4 g) to obtain a uniform solution.

Example 1 Preparation of transparent conductive film paint : Ruthenium aqueous sol 40 g Isopropyl alcohol 10 g Ethyl alcohol 50 g 45
0 ") to prepare a transparent conductive film paint.

Film formation : The above-mentioned transparent conductive film paint is applied to the display surface of a cathode ray tube using a spin coater, and after drying, the above-mentioned transparent thin film paint A is applied to the application surface similarly using a spin coater. , Put this CRT in the dryer,
The cathode ray tube of Example 1 having an anti-reflection and high conductive film was formed by baking at 450 ° C. for 1 hour to form a low-reflection transparent conductive film.

(Example 2) Preparation of transparent conductive film paint : Ruthenium aqueous sol 40 g isopropyl alcohol 10 g ethyl alcohol 50 g The above components were mixed and treated in the same manner as in Example 1 to prepare a transparent conductive film paint.

Film formation : A cathode ray tube of Example 2 having an anti-reflection and high conductive film was prepared by using the above transparent conductive film paint and treating it in the same manner as in Example 1 except that the baking temperature was 600 ° C. did.

(Comparative Example 1)Preparation of transparent conductive film paint : Aqueous ruthenium sol 40 g isopropyl alcohol 10 g ethyl alcohol 50 g
An electrocoat was prepared. Film formation : Using the above transparent conductive film paint, baking temperature of 15
Except that the temperature was set to 0 ° C., the same treatment as in Example 1 was performed to prevent reflection,
A cathode ray tube of Comparative Example 1 having a high conductive film was prepared.

(Comparative Example 2)Preparation of transparent conductive film paint : Aqueous silver sol 40 g isopropyl alcohol 10 g ethyl alcohol 50 g
An electrocoat was prepared. Film formation : Using the above transparent conductive film paint, as in Comparative Example 1.
Cathode ray of Comparative Example 2 having anti-reflection and high conductive film by processing
A tube was created.

(Evaluation Measurement) The performance of the low-reflection transparent conductive film formed on the cathode ray tube was measured by the following apparatus or method.
The appearance was visually evaluated. X-ray diffraction analysis: "PW1710" manufactured by Philips Co., Ltd. Surface resistance: "Loresta AP" manufactured by Mitsubishi Yuka Co., Ltd. (4-terminal method) Electromagnetic wave shielding property: Calculated by the above formula 1 based on 0.5 MHz Salt water resistance: 3 days after salt water immersion 0.5 MHz electromagnetic wave shielding property Scratch test: Under a load of 1 kg, the film surface was rubbed with a metal part at the tip of a mechanical pencil, and the degree of scratching was visually evaluated. ○: no scratch △: slightly scratched ×: scratched Transmittance: “Automatic Haze Meter H” manufactured by Tokyo Denshoku
III DP "Haze:" Automatic Haze meter HII manufactured by Tokyo Denshoku Co., Ltd. "
IDP ”Transmittance difference: The difference between the maximum transmittance and the minimum transmittance in the visible light region was determined using a“ U-3500 ”type self-recording spectrophotometer manufactured by Hitachi, Ltd. (The smaller the maximum-minimum transmittance difference in the visible light region, the flatter the transmittance and the sharper the hue of the transmitted image. Particularly, when the difference is 10% or less, the color of the transmitted image approaches black, and the higher the sharpness. Luminous reflectance: "MODEL C-11" manufactured by EG & G GAMMASCIENTIFIC Co., Ltd. Reflection color: "CR-300" manufactured by Minolta Camera Co. (White using CIE color system and CIE chromaticity diagram Point (x =
0.3137, y = 0.3198), and Δ (Δx ² + Δy ² ) using Δx and Δy. Thus, the closer the value of √ (Δx ² + Δy ² ) is to “0”, the whiter the reflection color becomes, that is, the closer to the natural light that is easy on the eyes. ) Visibility: Comprehensive evaluation including low reflection performance, reflection color, and transmission color ○: good ○ △; somewhat good △: acceptable △ ×; somewhat poor ×: poor Among the above evaluation tests, the physicochemical test results are shown. Table 1 shows the optical test results.

[0036]

[Table 1]

[Table 2]

From the results shown in Table 1, the cathode ray tubes of Examples 1 and 2 which were coated with a coating material containing ruthenium microparticles according to the present invention and baked at 450 ° C. or 600 ° C. were analyzed by X-ray diffraction. The presence of ruthenium oxide was confirmed in the film, and the presence of ruthenium oxide was not recognized in Comparative Example 1 in which the firing temperature was 150 ° C. Comparing Example 1 and Example 2 with Comparative Example 1, it can be seen that the surface resistance is not much different from the physicochemical characteristics (Table 1), and that the electromagnetic wave shielding property, salt water resistance and scratch resistance are greatly improved. . In the optical characteristics (Table 2), the luminous reflectance was reduced, the visibility was excellent, and the reflected color was close to the white point, and the transmitted image was improved so as to look natural. As a whole of these optical characteristics, the visibility evaluation of Examples 1 and 2 was clearly superior to Comparative Example 1. In Comparative Example 2, silver was used as the conductive material. However, not only the salt water resistance was poor and the durability was poor, but also the luminous reflectance was large and the reflection color was largely biased.

[0038]

The transparent conductive film of the present invention has an average particle size of 50.
After applying and drying a paint containing ruthenium fine particles having a particle size of not more than 300 nm, it is formed by baking at a temperature of 300 ° C. to 1000 ° C., and has a transparent conductive layer in which part of the ruthenium is converted to ruthenium oxide . It has excellent antistatic effect and electromagnetic wave shielding effect, and has high salt water resistance and scratch resistance. Further, the display device on which the transparent conductive film is formed has high transparency of the display surface, and the hue of the transmitted image is natural and clear. Further, ruthenium contained in the transparent conductive layer
Some of the ruthenium oxide is readily available at the baking temperature.
In spite of being relatively inexpensive, the salt water resistance, chemical stability, and scratch resistance are further improved, and there is an advantage that a transmission image becomes more natural also on a hue surface. If at least one transparent thin film having a refractive index different from the refractive index of the transparent conductive layer is provided on the upper layer and / or the lower layer of the transparent conductive layer, a transparent conductive film having low reflection can be obtained. Since the display device of the present invention is one in which the transparent conductive film is formed on a display surface, the display device has an excellent antistatic effect and an electromagnetic wave shielding effect, has good salt water resistance, has durability, A highly practical display device having high scratch resistance, high transparency of the display surface, and a natural and clear hue of the transmitted image is provided.

Continuation of front page (56) References JP-A-8-77832 (JP, A) JP-A-9-286936 (JP, A) JP-A-7-235220 (JP, A) JP-A-5-120921 (JP) JP-A-9-161561 (JP, A) JP-A-61-118931 (JP, A) JP-A-6-119816 (JP, A) JP-A-6-49394 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) H01B 5/14 H01B 13/00 B05D 5/12 C09D 5/24

Claims (7)

(57) [Claims] A ruthenium fine particle having an average particle size of 50 nm or less.
After applying and drying paint containing particles , 300 ° C ~ 100
Formed by baking at a temperature of 0 ° C., and a part of the ruthenium
Has a transparent conductive layer converted into ruthenium oxide . 2. The method according to claim 1, wherein the transparent conductive layer is made of ruthenium and ruthenium oxide.
The transparent conductive film according to claim 1 , wherein the total content of the transparent conductive film is 10% by weight or more. 3. An upper layer and / or a lower layer of the transparent conductive layer.
The layer has a refractive index different from that of the transparent conductive layer.
Characterized in that at least one transparent thin film is provided.
Item 3. The transparent conductive film according to Item 1 or 2. 4. An outermost layer of said transparent conductive film has irregularities.
Wherein a transparent thin film is provided.
4. The transparent conductive film according to 1, 2, or 3. 5. At least one layer of the transparent conductive film includes:
2. The method according to claim 1, wherein a coloring material is contained.
5. The transparent conductive film according to claim 4. 6. A combination of ruthenium and ruthenium oxide
Having a transparent conductive layer containing at least 10% by weight
A method for producing a conductive film, comprising a coating material containing ruthenium fine particles having an average particle size of 50 nm or less.
Is applied and dried, and then at a temperature of 300 ° C. to 1000 ° C.
Bake and convert part of the ruthenium to ruthenium oxide
A method for producing a transparent conductive film, comprising: 7. The method according to claim 1, wherein
A transparent conductive film is formed on a display surface.
Display device.