JP2509722B2 - Coating liquid for forming transparent conductive ceramics film, substrate with transparent conductive ceramics film and method for producing the same, and use of substrate with transparent conductive ceramics film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a coating liquid for forming a transparent conductive ceramics film and a method for producing the same. The present invention also relates to a substrate with a transparent conductive ceramics coating, a method for producing the same, and uses of the substrate with a transparent conductive ceramics coating. More specifically, the present invention has excellent adhesion to a substrate, such as glass and plastic, and has excellent durability such as alkali resistance, acid resistance, salt water resistance and scratch resistance, and a highly transparent conductive material. TECHNICAL FIELD The present invention relates to a coating liquid for forming a transparent conductive ceramics coating capable of continuously forming a conductive ceramics coating at a low temperature of about 120 ° C. and a method for producing the same.

The present invention also relates to a substrate with a transparent conductive ceramics coating formed using the above coating liquid for forming a transparent conductive ceramics coating, and a method for producing the same. Further, the present invention relates to a display device having the above-mentioned base material with a transparent conductive ceramics film as a front plate and a copier having the above-mentioned base material with a transparent conductive ceramics film as a top plate glass.

BACKGROUND ART Glass or plastic is a transparent substrate,
It is used for various purposes. However, since these base materials are insulators, static electricity is easily generated on the surface. If these glass or plastic base materials are used as they are as front panels for display devices such as cathode ray tubes (CRT), fluorescent display tubes (FIP), plasma displays (PDP), liquid crystal displays (LCD), etc., dust and dirt will adhere. And the image becomes difficult to see. In the case of LCD, static electricity may cause IC damage or malfunction. A copying machine 1 equipped with an automatic document feeder (ADF) 2 as shown in FIG.
In this case, static electricity generated on the top plate glass 3 during document feeding may cause a paper jam, which makes it impossible to continuously feed the document. Further, the surface hardness of a plastic substrate is low, so that it may be easily scratched and the transparency of the substrate may be deteriorated.

In order to solve the above problems, CVD method, PVD method,
A method of forming a metal thin film or a conductive inorganic oxide film on a base material by a vapor phase method such as a sputtering method has been proposed. However, although the coating film obtained by this method is excellent in transparency and conductivity, it has low acid resistance and alkali resistance and low scratch resistance, and is therefore easily scratched. Further, in order to form these coatings, a vacuum vapor deposition apparatus is required, and the area or shape of the substrate on which the coating can be formed is limited by the apparatus. In addition, the coating could not be formed at a low temperature, and since it was a batch method, continuous productivity was poor.

In addition, the top plate glass provided with the antistatic coating obtained by the above method may be scraped off by the document supplied to the ADF or the rubber belt attached to the ADF. In such a top plate glass, when the copy density is increased, that is, when a copy is made in gray scale, a new problem arises that the scraped off portion becomes a stain and is developed.

In addition, a conductive paint in which a conductive substance is dispersed in resin,
A method of applying conductivity to a substrate has also been proposed. However, although the coating film obtained by this method is excellent in conductivity, there is a problem that it is inferior in transparency, durability and scratch resistance.

On the other hand, in some cases, the front plate of the display device is desired to have not only the antistatic effect but also a regular reflectance reducing effect (hereinafter referred to as non-glare) in order to prevent glare.
The following methods, for example, are known for imparting antiglare and antistatic effects to the front plate of the display device. That is, after heating a front plate made of glass, plastic or the like in advance, a partially hydrolyzed colloidal solution of a silicon compound such as silicate ester, or a silicon compound such as silicon tetrachloride, or platinum, gold, palladium,
A method in which a solution in which a water-soluble compound of an inorganic metal such as tin is mixed is sprayed on the front plate to form a fine uneven coating of silicon oxide or its hydrate on the surface, followed by drying and firing is disclosed in JP-A-61-16452. It is disclosed in the publication.

Further, a method of forming a coating layer in which tin oxide or indium oxide and silicon oxide are mixed or laminated by a vacuum vapor deposition method or a dip method on a front plate of a CRT is disclosed in Japanese Utility Model Publication No. 59-168951.

However, in the front plate of the display device obtained by these methods, non-glare is insufficient, and the antistatic effect changes depending on the ambient temperature and humidity. Moreover, in some cases, the resolution of the display device may decrease. Further, the formed coating has weak adhesion to the front plate and is easily peeled off, or has low mechanical strength and is easily scratched,
Further, since it has low durability, it peeled off or started to flow, and it was not possible to maintain the non-glare and antistatic effects for a long time.

The applicant of the present invention is Japanese Patent Application No. 61-299686, in which a zirconium oxy salt, a silicon alkoxide or a derivative thereof,
An application is made for a coating liquid for forming a conductive film in which a conductive substance is uniformly dispersed in water and an organic solvent. Using these coating solutions, the coating film obtained by baking at a temperature of 250 ° C. or higher is excellent in performance such as transparency, conductivity, and scratch resistance, but baking at a temperature of less than 250 ° C. The obtained coating was inferior in durability and was difficult to apply to a plastic substrate. In addition, since the stability of this coating solution is not always sufficient, during coating, especially during continuous production by transfer printing, the coating solution may gel on the roll, which may cause difficulties in continuous production. . Furthermore, in order to store the coating solution for a long period of time, it had to be kept at 15 ° C or lower.

The present invention aims to solve the above-mentioned problems associated with the conventional technology. That is, firstly, the acetylacetonato chelate compound and the conductive substance are
It is an object of the present invention to provide a transparent conductive ceramics film-forming coating solution (hereinafter referred to as coating solution I) that is uniformly dissolved or dispersed in a mixed solvent composed of water and an organic solvent.

Second, acetylacetonato chelate compounds (excluding dialkoxy-bisacetylacetonatozirconium)
And a silicon compound and a conductive substance are uniformly dissolved or dispersed in a mixed solvent of water and an organic solvent to provide a coating liquid for forming a transparent conductive ceramics film (hereinafter referred to as coating liquid II). I am trying.

Thirdly, a coating for forming a transparent conductive ceramics film in which an acetylacetonato chelate compound, an alkoxide of a metal other than silicon, and a conductive substance are uniformly dissolved or dispersed in a mixed solvent composed of water and an organic solvent. The purpose is to provide a liquid (hereinafter referred to as coating liquid III).

Fourth, an acetylacetonato chelate compound, a silicon compound and an alkoxide of a metal other than silicon,
The purpose of the present invention is to provide a coating liquid for forming a transparent conductive ceramics film (hereinafter referred to as coating liquid IV) in which a conductive substance is uniformly dissolved or dispersed in a mixed solvent of water and an organic solvent.

Fifth, glass, plastic, etc. formed with the coating liquid I, II, III or IV, on which a transparent conductive ceramic coating formed with excellent durability, transparency, scratch resistance, adhesion and antistatic effect is formed. The sixth purpose is to provide a base material (hereinafter referred to as a base material A), and sixthly, a base material such as glass or plastic (hereinafter, a base material) on which a transparent conductive ceramics coating having not only glare but also non-glare is formed. B)), and further to provide a method for producing the above-mentioned base material.

The seventh object is to provide a display device using the base material A as a front plate (hereinafter referred to as display device A).

The eighth object is to provide a display device (hereinafter referred to as display device B) using the base material B as a front plate.

The ninth object is to provide a copying machine using the base material A as a top plate glass.

DISCLOSURE OF THE INVENTION A coating liquid I according to the present invention is characterized in that an acetylacetonato chelate compound and a conductive substance are uniformly dissolved or dispersed in a mixed solvent of water and an organic solvent.

The coating liquid II according to the present invention comprises an acetylacetonato chelate compound (excluding dialkoxy-bisacetylacetonatozirconium), a silicon compound, and a conductive substance, which are uniformly mixed in a mixed solvent of water and an organic solvent. It is characterized by being dissolved or dispersed.

The coating liquid III according to the present invention is characterized in that an acetylacetonato chelate compound, an alkoxide of a metal other than silicon, and a conductive substance are uniformly dissolved or dispersed in a mixed solvent composed of water and an organic solvent. I am trying.

The coating liquid IV according to the present invention, an acetylacetonato chelate compound, a silicon compound and an alkoxide of a metal other than silicon, and a conductive substance are uniformly dissolved or dispersed in a mixed solvent consisting of water and an organic solvent. It is characterized by being.

The base material A according to the present invention comprises a base material and a transparent conductive ceramic coating formed on the base material by using the above coating liquid I, II, III or IV, and has a surface resistance of 10 ³ to. Ten
^{It is 11} Ω / □, the total light transmittance is 85% or less, and the haze is 10% or less.

The base material B according to the present invention comprises a base material and a transparent conductive ceramics coating formed on the base material by using the above coating liquids I, II, III or IV, and has a surface resistance of 10 ³ to. Ten
It is characterized by ¹¹ Ω / □ and glossiness of 30-100%.

The display device A according to the present invention comprises a base material and a transparent conductive ceramics coating formed on the base material by using the above coating liquid I, II, III or IV, and has a surface resistance of 10 ³
~ 10 ¹¹ Ω / □, total light transmittance of 85% or more,
It is characterized in that it has a substrate A having a haze of 10% or less and a resolution of 50 lines / cm or more as a front plate.

The display device B according to the present invention comprises a base material and a transparent conductive ceramics film formed on the base material by using the above coating liquid I, II, III or IV, and has a surface resistance of 10 ³
~10 ¹¹ Ω / □ and is, glossiness is 30% to 100%, the resolution is 50 lines / cm or more base B, and characterized by including a front plate.

The copying machine according to the present invention comprises a base material and a transparent conductive ceramic coating formed on the base material by using the above coating liquids I, II, III or IV, and has a surface resistance of 10 ³ to 10 ^3.
The base material A having a total light transmittance of ¹¹ Ω / □, a total light transmittance of 85% or more, and a haze of 10% or less is provided as a top plate glass.

A particularly preferred first method for producing a transparent conductive ceramics coated substrate according to the present invention is the coating liquids I, II and II described above.
The method is characterized in that I or IV is applied to a base material previously heated and maintained at 40 to 90 ° C., and then dried and / or baked.

A particularly preferred second production method of the transparent conductive ceramics coated substrate according to the present invention is the above coating liquids I, II and II.
Irradiating the coating film with an electromagnetic wave having a wavelength shorter than visible light after and / or during at least one of the step of coating I or IV on the substrate, the step of drying the coating, and the step of baking the coating. Is characterized by.

A particularly preferred third method for producing a transparent conductive ceramics film-coated substrate according to the present invention is to apply a transparent protective film-forming coating liquid onto the transparent conductive ceramics film-coated substrate obtained as described above. After coating, it is dried and / or baked, or the transparent conductive ceramics-coated substrate obtained as described above is heated and held in advance at 40 to 90 ° C. to further protect the substrate. The coating liquid for film formation is applied and then dried and / or fired.

A particularly preferred fourth manufacturing method of the transparent conductive ceramics film-coated substrate according to the present invention is the above-mentioned third transparent conductive ceramics film-coated substrate manufacturing method, which comprises the step of applying a coating liquid for forming a transparent protective film. After at least one of the steps of drying the transparent protective film, baking the transparent protective film, and / or
Alternatively, the transparent protective film is irradiated with an electromagnetic wave having a wavelength shorter than that of visible light during the process.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of a copying machine equipped with an automatic document feeder, FIG. 2 is an explanatory view of a bar chart used when measuring the resolution of a substrate, and FIG. The figure is an illustration of an apparatus used for measuring the resolution of a substrate.

DESCRIPTION OF SYMBOLS 1 ... Copier, 2 ... Automatic document feeder 3 ... Top plate, 4 ... Bar chart BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the coating liquid I according to the present invention will be specifically described.

The coating liquid I according to the present invention is formed by uniformly dissolving or dispersing an acetylacetonato chelate compound and a conductive substance in a mixed solution of water and an organic solvent. Each component will be described below. .

The acetylacetonato chelate compound is a chelate compound having an acetylacetone molecule as a ligand and is a compound or a condensate represented by the following formula (I), and in the present invention, one selected from these or Use in combination of two or more. In this coating liquid I, the acetylacetonato chelate compound plays a role of improving the dispersibility of the conductive substance and the thermal stability of the coating liquid, and acts as a protective colloid for the conductive substance. Inferred.

[Wherein, a + b is 2 to 4, a is 0 to 3, b is 1 to 4, R is —C _n H _{2n + 1} (n = 3 or 4), and X is Is CH ₃ −, CH ₃ O−, C ₂ H ₅ −, C ₂ H ₅ O−
Is. M ₁ is the IB group, IIA group, B group, or I group of the periodic table.
IIA, B group, IVA, B group, VA group, B group, VIA group, V group
An element selected from Group IIA and Group VIIIA or vanadyl (V
O). Among these, preferable combinations of these elements and the like and a and b are as shown in the following table. ] In the present invention, as the conductive substance, tin oxide, a conductive substance known as a conventional conductive substance such as antimony, tin oxide or indium oxide doped with fluorine or phosphorus, or indium oxide doped with tin or fluorine is used. A wide variety of substances are used.

These conductive materials are preferably fine particles having an average particle size of 0.4 μm or less. CRT, FIP, PDP, LCD
For applications requiring high transparency with low haze (cloudiness value) such as front plates of display devices or top plate glass for copying machines, it is preferable to use a conductive substance having an average particle diameter of 0.01 to 0.1 μm. preferable. However, the average particle size of the conductive material is
Even if the particle size is less than 0.1 μm, the transparency of the obtained transparent conductive ceramics coating decreases if many particles exceeding 0.1 μm are contained.
It is preferable that the particles have the following particle sizes.

Among them, a particularly preferable conductive substance is the “method for producing conductive powder” previously filed by the applicant (Japanese Patent Laid-Open No. 63-11519).
JP-A-62-230617) or "Tin oxide sol and method for producing the same" (JP-A-62-230617).

In the present invention, as the organic solvent, methanol, ethanol, propanol, butanol, diacetone alcohol, furfuryl alcohol, ethylene glycol, alcohols such as hexylene glycol, acetic acid methyl ester, esters such as acetic acid ethyl ester, diethyl ether, Ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether, and ketones such as acetone and methyl ethyl ketone are used alone or in combination.

In the coating liquid I formed by the above components,
The mixing ratio of the acetylacetonato chelate compound and the conductive substance is 0.5 ≦ E in terms of the weight ratio of each oxide.
As _{O x / M 1 O x ≦} 5 (EO x oxide conductive material, M ₁ O _x
Is preferably an acetylacetonato chelate compound represented as an oxide). If this value is less than 0.5, the conductivity is not sufficient, while if this value exceeds 5, the dispersibility of the conductive material and the thermal stability of the coating solution are reduced, and the transparency and adhesion of the resulting coating are The abrasion resistance tends to be poor, and the storage stability and continuous productivity of the coating solution tend to be poor.

The solid content concentration in the coating liquid I according to the present invention is (EO _x + M
₁ O _x ), and it may be 15% by weight or less. If this value exceeds 15% by weight, the storage stability of the coating liquid tends to deteriorate, while if the solid content concentration is too low,
Since it is necessary to repeat the coating operation several times in order to obtain the target film thickness, the solid content concentration is practically 0.1% by weight or more.

The water concentration in the coating liquid I according to the present invention is preferably in the range of 0.1 to 50% by weight. If this value is less than 0.1% by weight, the acetylacetonato chelate compound is not sufficiently hydrolyzed, and the unreacted product of the acetylacetonato chelate compound remains in the obtained coating film, and the resulting coating film and the substrate Adhesion is reduced, and the resulting coating tends to be low in scratch resistance and durability. On the other hand, this value is 50
When the content is more than the weight%, the coating material is repelled from the base material and it becomes difficult to form a coating film.

The coating liquid II according to the present invention comprises an acetylacetonato chelate compound (excluding dialkoxy-bisacetylacetonatozirconium), a silicon compound, and a conductive substance, which are uniformly mixed in a mixed solvent of water and an organic solvent. It is dissolved or dispersed.

In the coating liquid III according to the present invention, an acetylacetonato chelate compound, an alkoxide of a metal other than silicon, and a conductive substance are uniformly dissolved or dispersed in a mixed solvent of water and an organic solvent.

Furthermore, the coating liquid IV according to the present invention, an acetylacetonato chelate compound, a silicon compound and an alkoxide of a metal other than silicon, and a conductive substance are uniformly dissolved or dispersed in a mixed solvent composed of water and an organic solvent. Has been done.

As the acetylacetonato chelate compound, the conductive substance, water and the organic solvent, the same ones as in the above coating liquid I are used. Therefore, here, a silicon compound and an alkoxide of a metal other than silicon will be described.

Regarding the acetylacetonato chelate compound,
All the compounds represented by the above formula (I) are used,
In the above formula (I), the compound in which M ₁ is Zr and a = 2 and b = 2 corresponds to dialkoxybisacetylacetonato zirconium, and the applicant previously filed another application for this compound. Therefore, in the coating liquid II, the dialkoxybisacetylacetonato zirconium is excluded from the acetylacetonato chelate compound.

In the coating liquids II, III and IV, the acetylacetonato chelate compound plays a role of improving the dispersibility of the conductive material and the thermal stability of the coating liquid, and acts as a protective colloid for the conductive material. It is inferred that

As the silicon compound, one kind or a combination of two or more kinds selected from the compound represented by the following formula (II) or a condensate thereof is used.

R _a —Si (OR ′) _4-a (II) (In the formula, R is C _n H _{2n + 1} − (n = 1 to 4), a hydrogen atom or a halogen atom, and a is 0. ~ 3,
R ′ is C _n H _{2n + 1} − (n = 1 to 4), hydrogen atom or C _n H
_{2n + 1} OC ₂ H ₄ − (n = 1 to 4)).

These silicon compounds may be used as they are or after being partially hydrolyzed. The conditions for the partial hydrolysis include general methods for partially hydrolyzing a silicon compound, such as mixing the silicon compound with methanol or ethanol, and adding water and an acid to the resulting mixture to partially hydrolyze. Although the conditions can be adopted, the following conditions are particularly preferable. Hydrochloric acid, nitric acid, phosphoric acid, acetic acid, or acetic anhydride is used as the acid, and the mixing ratio of the acid and the silicon compound is 0.01 ≦ acid / SiO ₂ ≦ 0.5 (weight ratio when the silicon compound is converted to SiO ₂ ). It is preferable. If this value is less than 0.01, unreacted silicon compounds are multiply present and the conductivity of the resulting coating tends to be impaired. On the other hand, when this value exceeds 0.5, the partial hydrolysis rate becomes too fast, and the continuous productivity and the storage stability of the coating liquid tend to be deteriorated. The mixing ratio of water and the silicon compound is preferably water / silicon compound ≧ 2 (molar ratio when the silicon compound is converted into SiO ₂ ). If this value is less than 2, unreacted silicon compound remains in the coating, so that the adhesion between the obtained coating and the substrate is lowered, and the scratch resistance and durability of the coating tend to be lowered. . The partial hydrolysis temperature is preferably in the range of 30-80 ° C.

As a metal alkoxide other than silicon, the following formula:
M ₂ (OR) _n (wherein, M ₂ is a metal other than silicon, R is an alkyl group or C _n H _{2n + 1} O ₂ — (n = 3 to 10)
And n is the same integer as the valence of M ₂ . 1) or a combination of 2 or more kinds selected from the compounds represented by the formula) or their condensates. M in the above formula
₂ is not particularly limited as long as it is a metal other than silicon, and is preferably Group IB, Group IIA or Group B of the periodic table,
Group IIIA, B, IVA, B, VA, B, VIA, B
A metal selected from Group VIII and Group VIII elements, more preferably Cu, Be, Ba, Zn, Al, B, In, Ga, Ti, Zr, Hf,
Ge, Sn, Pb, V, Nb, Ta, Bi, Sb, Cr, W, Fe, Ni, S
c, Y, Ce, Te. Further, hanadyl (VO) is also a preferable group, and it is assumed here that it is contained in a metal other than silicon.

Alkoxides other than these silicon alkoxides are used as they are without partial hydrolysis.

In the coating liquids II, III and IV formed by the above components, an acetylacetonato chelate compound,
The mixing ratio with the conductive substance is preferably 0.001 ≦ M ₁ O _x / EO _x ≦ 1 in terms of weight ratio of each oxide. If this value is less than 0.001, the dispersibility of the conductive substance and the thermal stability of the coating solution are reduced, the transparency and adhesion of the resulting coating are deteriorated, and the storage stability and continuous productivity of the coating solution are reduced. It tends to get worse. On the other hand, when this value exceeds 1, the transparency and adhesion of the obtained coating film may deteriorate,
There is a tendency for the conductivity to decrease.

The acetylacetonato chelate compound and the silicon compound and / or the alkoxide of the metal other than silicon are 0.001 ≦ M ₁ O _x / A in the weight ratio of each oxide.
It is preferable that ≦ 10. In this formula, M ₁ O _x is the weight of the acetylacetonato chelate compound converted to oxide, A is SiO ₂ in the case of the coating liquid II,
In the case of coating liquid III, it is M ₂ O _x , and in the case of coating liquid IV, it is SiO ₂
+ M ₂ O _x . However, M ₂ O _x represents an alkoxide of a metal other than silicon as an oxide. If this value is less than 0.001, the alkali resistance, acid resistance, salt water resistance, water resistance, and solvent resistance of the coating are not sufficient, while if it exceeds 10, the adhesion and transparency of the resulting coating tend to decrease. .

In the coating liquid IV, the mixing ratio of the silicon compound and the alkoxide of the metal other than silicon is 0.001 ≦ M ₂ O _x / (M ₂ O
It is preferable that _x + SiO ₂ ) ≦ 0.99 (weight ratio).

Furthermore, the conductive substance is 0.5 ≦ E in terms of weight ratio in terms of oxide.
It is preferable that O _x / (A + M ₁ O _x ) ≦ 5. This value is
If it is less than 0.5, the conductivity of the resulting coating is not sufficient, while if it exceeds 5, the adhesion and scratch resistance of the coating tend to decrease.

The solid content concentration in the coating liquids II, III and IV according to the present invention may be 15% by weight or less, calculated as EO _x + A + M ₁ O _x . If this value exceeds 15% by weight, the storage stability of the coating solution tends to deteriorate, while if the solid content concentration is too low, the coating operation is repeated several times to obtain the target film thickness. Therefore, the solid concentration is practically 0.1% by weight or more.

The water concentration in the coating liquids II, III and IV according to the present invention is preferably in the range of 0.1 to 50% by weight. If this value is less than 0.1% by weight, the acetylacetonato chelate compound, the silicon compound, and the alkoxide of a metal other than silicon are not sufficiently hydrolyzed, and unreacted substances remain in the obtained film, and the film and the substrate There is a tendency that the adhesiveness with and the scratch resistance and durability of the obtained coating film are reduced. On the other hand, when this value exceeds 50% by weight, repelling with the base material occurs during coating and it becomes difficult to form a film.

Next, a method for producing coating liquids I, II, III and IV according to the present invention will be described. The coating liquid I is a conductive substance, water,
It can be produced by mixing the organic solvent and the acetylacetonato chelate compound by an appropriate method.
Coating liquids II, III, and IV were prepared by adding one or more acetylacetonato chelate compounds to water and an organic solvent in which a conductive substance was dispersed to improve the dispersibility and stability of the conductive substance, and then further adding a silicon compound. And / or by adding an alkoxide of a metal other than silicon. Alternatively, it can also be produced by previously mixing a silicon compound and / or an alkoxide of a metal other than silicon with the acetylacetonato chelate compound, and then mixing the obtained mixed liquid with a conductive substance. It is not preferable to contact the silicon compound and / or the alkoxide of a metal other than silicon with the conductive substance before adding the acetylacetonato chelate compound, because the conductive substance aggregates.

The coating liquids I and I according to the present invention thus produced
With I, III, and IV, the conductive substance in the coating solution is kept in a monodispersed state by the protective colloidal action of the acetylacetonato chelate compound, and therefore a film with excellent transparency and conductivity can be obtained. Moreover, since the thermal stability of the coating liquid is improved, the gel ratio of the coating liquid does not occur during continuous production, and it can be stored for a long time even at about 40 ° C.

In the present invention, the coating solutions I, II, III and I as described above are used.
As the base material to which V is applied, a transparent base material such as glass or plastic can be used, and these base materials can have any shape such as a flat plate shape or a curved surface shape. In the present invention, a base material having a roughened surface (for example, ground glass) may be used. This is because when the coating liquid is applied to the surface of the roughened base material, the coating liquid penetrates into the surface of the roughened base material to form a coating, so that the surface becomes flat and the base material becomes transparent. . Further, when a substrate having such a roughened surface is used, the adhesion between the coating and the substrate is significantly improved.

 Next, the base material A will be described.

The base material A comprises a base material and the above coating liquids I, I on the base material.
Consisting of a transparent conductive ceramic coating formed by using I, III or IV, surface resistance of 10 ³ -10 ¹¹ Ω / □, total light transmittance of 85% or more, haze of 10% or less Is.

Such a base material A has the coating liquids I, II, II as described above.
I or IV is applied to the substrate at room temperature by a coating method such as a dipping method, a spinner method, a spray method, a roll coater method, and a flexographic printing method to form a flat film,
It can be produced by drying and / or firing. After coating, if it is dried and cured at a temperature of room temperature to 110 ° C., a substrate A having excellent adhesion, scratch resistance and transparency can be obtained. If this coating is further baked at a temperature of 120 ° C. or higher and at a temperature not higher than the glass transition temperature of the base material, the base material A having improved durability can be obtained. At this time, it may be fired any number of times as long as the temperature is not higher than the glass transition point of the substrate.

Further, in the present invention, if manufactured by the following method,
Further, the coated substrate A having a remarkable effect is obtained.

In the first manufacturing method, in the manufacturing process of the base material A as described above, any one or more of a coating liquid application process on the base material, a coating film drying process, and a coating film baking process. After and / or during the process, the coating film is irradiated with an electromagnetic wave having a shorter wavelength than visible light. By irradiating the coating film with electromagnetic waves, the baking temperature of the coating film can be lowered. For example, if the coating film is irradiated with electromagnetic waves, the baking temperature of the coating film will be 300 ° C.
Even in this case, a coating film having the same performance as that obtained by firing at 400 ° C. without irradiation with electromagnetic waves can be obtained.

As an electromagnetic wave having a shorter wavelength than visible light, specifically,
There are ultraviolet rays, electron beams, X-rays, γ rays, etc., but ultraviolet rays are practical. As an ultraviolet ray source, it has a maximum emission around 250 nm and 360 nm, and its irradiation intensity is 10 mW / cm ² or more, preferably 100 m.
It is desirable to use a W / cm ² high pressure mercury lamp. 100 mJ / cm ² or more, preferably 1 using such an ultraviolet source.
By irradiating the coating film with irradiation energy of 000 mJ / cm ² or more, a highly durable film can be obtained at low temperature.

In the second production method of the base material A, a coating solution for forming a transparent protective film is further applied to the surface of the base material A obtained as described above on which the coating film is formed, by a dipping method, a spinner method, or a spray method. , A roll coater method, a flexographic printing method, and the like to form a flat film, and then dry and / or
Or bake. The transparent protective film-forming coating liquid used at this time may be one in which the coating film obtained by this coating liquid contains SiO ₂ and / or ZrO ₂ as the main components. Examples thereof include a solution containing a partial hydrolyzate of silicon or zirconium alkoxide, a chelate compound of silicon or zirconium, or an oxyzirconium salt. Alternatively, a coating liquid obtained by removing all or part of the conductive substance from the coating liquid I, II, III or IV according to the present invention can also be used.

In the third method for producing the base material A, in the second method for producing the base material A as described above, the step of applying the coating liquid for forming the transparent protective film, the step of drying the transparent protective film, and the step of baking the transparent protective film. After and / or during any one or more of the steps, the transparent protective film is irradiated with an electromagnetic wave having a shorter wavelength than visible light.

The substrate A thus obtained has a surface resistance of 10 ³ to 10 ¹¹ Ω / □, a total light transmittance of 85% or more, and a haze of 10% or less, as described above. When the surface resistance of the base material A exceeds 10 ¹¹ Ω / □, a sufficient antistatic effect cannot be obtained. If the total light transmittance and haze are worse than the above values, the transparency is poor.

Surface device A using the substrate A according to the present invention as a front plate
Then, it is preferable that the substrate A as the front plate has a resolution of 50 lines / cm or more in addition to the above performance. This resolution was measured as follows. That is, the bar chart 4 as shown in FIG. 2 is pasted on the side 7 of the base material A on which the coating is not formed, and the base material A is the outside with the side on which the coating is formed as shown in FIG. 50 cm wide, 30 vertical
It is placed in a box 9 of cm, and it is confirmed how many bars are separated and visible per cm by 30 cm from the base A, and the resolution of the base A is determined by the number of separated and visible bars per cm. And At this time, the inner wall of the box body was white, and 20 W fluorescent lamps 8 were provided on both sides of the inner wall of the box with respect to the base material A. The bar chart was prepared by increasing the number of bars every 5 bars / cm, for example, 10 bars / cm, 15 bars / cm, 20 bars / cm, 25 bars / cm. In the bar chart of FIG. 2, 5
Is a linear printing portion, and 6 is a gap. The width a of the linear print portion and the width b of the gap were equal.

In a copying machine using the base material A according to the present invention as a top plate glass, the base material A as a top plate glass has a light transmittance at a wavelength of 550 nm of ± 5 with respect to the light transmittance of the base material before forming the coating. It is preferable not to exceed%.

Since the coating of the base material A is made of ceramics, it is very difficult to scrape it. However, a part of the coating is scraped by a document supplied to the ADF or a rubber belt attached to the ADF, so that the coating is formed. It may become thin, or the base material before film formation may be exposed to cause a kind of scratch.

When the difference between the light transmittance of the scratched portion at the wavelength of 550 nm and the light transmittance of the substrate before film formation exceeds ± 5%, when the gray scale is copied, the scratches appear on the copy as spots.

Therefore, when the base material A is used as a top plate glass,
550n for each of substrate A, scratches and before film formation
The light transmittance at the wavelength of m is Tt ₁ (%), Tt ₂ (%), T
When t ₀ (%) is set, it is desirable that both Tt ₁ −Tt ₀ and Tt ₂ −Tt ₀ do not exceed ± 5%, preferably ± 3%.

In the present invention, the base material for forming a coating film when the base material A is used as a top plate glass can be a base material for a top plate glass used in an ordinary copying machine.

 Next, the base material B will be described.

The base material B comprises a base material and the above coating liquids I, I on the base material.
A transparent conductive ceramic coating formed by using I, III or IV, and has a surface resistance of 10 ³ to 10 ¹¹ Ω / □ and a glossiness of 30 to 100%.

In the first method for producing the base material B, the coating liquid I, II, III or IV as described above is applied to the base material which is previously heated and maintained at 40 to 90 ° C, preferably 50 to 70 ° C. It is applied to form an uneven film piece, and then dried and / or baked.

If the heating temperature of the base material is lower than 40 ° C., the liquid components cannot be sufficiently dried at the time of application to cause leveling to form a flat film, which tends to prevent non-glare. on the other hand
When the temperature exceeds 90 ° C, the liquid components are rapidly dried, and the adhesion, transparency and durability of the coating tend to be significantly reduced. In this way, when the coating liquid is applied to the substrate, it is preferable to adjust the amount of the coating liquid and the coating speed so that the substrate does not deviate from this temperature. After coating, if dried and cured at a temperature of room temperature to 110 ° C., a base material B having a film having excellent adhesion to the base material, scratch resistance, and transparency is obtained. If this coating is further baked at a temperature of 120 ° C. or higher and at a temperature not higher than the glass transition point of the base material, the base material B having the coating with improved durability can be obtained. At this time, it may be fired any number of times as long as the temperature is not higher than the glass transition point of the substrate.

In the second manufacturing method of the base material B, any one of the coating step of the coating liquid on the base material, the drying step of the coating film, and the baking step of the coating film in the first manufacturing method of the base material B as described above. After one or more steps and / or during the steps, the coating film is irradiated with an electromagnetic wave having a wavelength shorter than visible light. By irradiating the coating film with electromagnetic waves, the baking temperature of the coating film can be lowered. For example, if the coating film is irradiated with electromagnetic waves, even if the coating film is baked at a temperature of 300 ° C., it will be 400 A film with the same performance as that obtained by firing at ℃ is obtained.

In the third production method of the base material B, the base material A on which the transparent protective film is not formed or the base material B obtained by the above-mentioned first and second methods is further heated and held at 40 to 90 ° C. Then, a coating solution for forming a transparent protective film is applied to form an uneven film piece, and then dried and / or baked. At this time, as the transparent protective film forming coating liquid, the same coating liquid as the coating liquid used in the second manufacturing method of the substrate A can be used.

In the fourth manufacturing method of the base material B, in the third manufacturing method of the base material B as described above, the step of applying the coating liquid for forming the transparent protective film, the step of drying the transparent protective film, and the step of baking the transparent protective film. After and / or during any one or more of the steps, the transparent protective film is irradiated with an electromagnetic wave having a shorter wavelength than visible light.

The electromagnetic wave having a shorter wavelength than visible light used in the second and fourth manufacturing methods of the base material B is the same as the electromagnetic wave used in the manufacturing method of the base material A.

In addition, in the method for producing these base materials B, the coating liquid is
It is preferably applied onto the substrate by a spray method.

The substrate B thus obtained has a surface resistance of 10 ³ to 10 ¹¹ Ω / □ as described above, and the glossiness when measured at a measurement angle of 60 ° C. in the glossiness measurement method of JIS K7105-81. But
It is 30 to 100%.

Surface device B using the base material B according to the present invention as a front plate
Then, it is preferable that the base material B as the front plate has a resolution of 50 lines / cm or more in addition to the above performance. This resolution is measured by the same method as for the base material A as the front plate.

The glossiness of the base material B is a value measured at a measurement angle of 60 ° C. in the glossiness measuring method of JIS K7105-81 as described above, and when the value is less than 30%, the transparency of the base material B is Tends to decrease, while the upper limit of this value is not particularly limited,
When it exceeds 0%, non-glare does not occur, so 100% or less is preferable.

In the substrate B, the surface average roughness R _Z (10-point average roughness measured according to JIS B0601-82) is preferably 0.2 to 5.0 μm. If the average roughness is less than 0.2 μm,
Although the resolution and transparency are excellent, non-glare decreases, and there is a tendency that a sufficient antistatic effect cannot be obtained.
On the other hand, when it exceeds 5.0 μm, resolution and transparency tend to be lowered.

EFFECTS OF THE INVENTION The coating solution according to the present invention has the acetylacetonato chelate compound and the conductive substance uniformly dissolved or dispersed in a mixed solvent composed of water and an organic solvent as described above, or further acetylacetonato. It is formed by uniformly dissolving or dispersing a chelate compound, a silicon compound and / or an alkoxide of a metal other than silicon, and a conductive substance in a mixed solvent of water and an organic solvent.

Therefore, the coating liquid according to the present invention can maintain a conductive substance in a monodispersed state in the coating liquid by the action of a protective colloid of an acetylacetonato chelate compound and form a film excellent in transparency and conductivity. You can Moreover, since the thermal stability of the coating liquid is improved, the coating liquid does not gel during continuous production, and it can be stored for a long time even at about 40 ° C.

The base materials A and B according to the present invention have a coating film composed of a metal oxide such as zirconia and silica, and a conductive substance on a substrate, and are excellent in scratch resistance, adhesion and durability. .

Further, the substrate A according to the present invention has a surface resistance of 10 ³ to 10 ^3.
11 Ω / □, the total light transmittance is 85% or more, the haze is 10% or less, and the substrate B according to the present invention has a surface resistance of 10 ³ to 10 ¹¹ Ω / □, The glossiness when measured at a measurement angle of 60 ° C in the glossiness measurement method of JIS K7105-81
Since it is 30 to 100%, it is excellent in transparency, antistatic effect and non-glare.

Display device A using the substrate A according to the present invention as a front plate
Then, the resolution of the substrate A as the front plate is 50 lines / cm or more, and in the display device B using the substrate B as the front plate, the resolution of the substrate B as the front plate is 50 lines / cm. That is all.

In a copying machine using the base material A according to the present invention as a top plate glass, the base material A has a light transmittance at a wavelength of 550 nm of ± 5% with respect to the light transmittance of the base material before the coating is formed, even as the top glass. Since it does not exceed the range, even if a part of the film is shaved and thinned or a part is completely shaved off, the shaved part does not appear as a stain when copying in gray scale.

Therefore, the transparent conductive ceramics coated substrate according to the present invention is used to prevent static electricity such as front plates of display devices such as CRTs, FIPs, PDPs or LCDs, top glass for copiers, instrument panels, telewriting terminals and lenses. It can be used in fields requiring functionality and non-glare.

Further, this front plate may constitute the display device itself, or may be disposed on the front surface of the display device. Specifically, in the case of an LCD, for example, the transparent conductive ceramics coating of the present invention may be formed directly on the outer surface of one of the substrates with electrodes for sandwiching the liquid crystal and located in front of the substrate. However, the base material on which the transparent conductive ceramics coating of the present invention is formed may be arranged further on the front surface of the substrate with electrodes on the front surface side. In the case of CRT, the transparent conductive ceramics coating of the present invention may be formed directly on the outer surface of the display panel of the CRT, or the substrate on which the transparent conductive ceramics coating of the present invention is formed further on the front surface of the display panel. May be arranged.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 6 [Coating liquid I] An acetylacetonato chelate compound shown below, a conductive substance and an organic solvent were mixed and stirred to form a coating liquid for forming a transparent conductive ceramics coating as shown in Table 1 (coating liquid 1
~ 6) was obtained.

Acetylacetonato chelate compound (M ₁ O _x ) (1) A butanol solution of dibutoxy-bisacetylacetonato zirconium containing 13% by weight of ZAB 1 ZrO ₂ .

(2) TAP1 dibutoxy containing 10 wt% as TiO ₂ - bis acetylacetonato titanium butanol solution.

Conductive substance (EO _x ) (1) TL93 Antimony-doped tin oxide sol (ELCOM TL-93, manufactured by Catalysts & Chemicals Industries, Ltd., solid content concentration 20% by weight, average particle size 0.07 μm, particles of 0.1 μm or less (87% of all particles) (2) TL30 Antimony-doped tin oxide fine powder in water dispersion (Catalyst Chemical Co., Ltd. ELCOM TL-30, solid content concentration 20% by weight, average particle size 0.2 μm) Organic Solvent Ethanol (Et OH), Isopropanol (IPA) Examples 7 to 21 [Coating liquid II] After mixing the acetylacetonato chelate compound shown below, a conductive substance and an organic solvent, the silicon liquid shown below was added to this mixed liquid to give a transparent liquid as shown in the third. Coating liquids (coating liquids 7 to 21) for forming a conductive ceramics film were obtained.

Acetylacetonato chelate compound (M ₁ O _x ) (1) ZAB1 (same as Examples 1 to 6) (2) ZAB2 ZrO ₂ containing 10 wt% Zr (OC ₄ H ₉ ) _1.5 · (Ac) _2.5 ( A
c: acetylacetone ion) butanol solution.

(3) ZAB3 A butanol solution of tributoxymonoacetylacetonato zirconium containing 10% by weight as ZrO ₂ .

(4) TAP1 (same as Examples 1 to 6) (5) TAP2 An IPA solution of triisopropoxymonoacetylacetonato titanium containing 10% by weight as TiO ₂ .

(6) A butanol solution of dibutoxybis acetylacetonato hafnium containing 10% by weight of HFAB HfO ₂ .

Conductive substance (1) TL93, TL30 (same as Examples 1 to 6) (2) TL130 Tin-doped indium oxide fine powder in water dispersion (Catalyst Chemical Co., Ltd. ELCOM TL-130, solid content) Concentration 25
% By weight, average particle size 0.25 μm) Silicon liquid (1) Silicon liquids A to D and F As shown in Table 2, an ethanol solution of tetraethoxysilane containing 28 wt% as SiO ₂ (ethyl silicate manufactured by Tama Chemical Industry Co., Ltd.). 28, abbreviated as ES-28) or tetraethoxysilane containing 40% by weight of SiO ₂ in ethanol (abbreviated as ES-40 above), ethanol was added, and a nitric acid aqueous solution was further added. After heating this mixture for a certain period of time,
It cooled to room temperature and obtained the silicon liquid.

(2) Silicone solution E A sodium silicate aqueous solution containing 5% by weight as SiO ₂ (Si
1000 g of O ₂ / Na ₂ O = 3 mol / mol) was passed through a cation exchange resin column while keeping it at 15 ° C. 445 g of methyl cellosolve was added to this liquid and sufficiently dispersed, and then heated to 70 ° C. under reduced pressure with a rotary evaporator to distill 945 g of water to obtain a silicon liquid E.

Examples 22 to 26 [Coating Liquid III] After mixing the following acetylacetonato chelate compound, a conductive substance and an organic solvent, a metal alkoxide was added and mixed to form a transparent conductive ceramic film as shown in Table 4. Coating liquids (coating liquids 22 to 26) were obtained.

Acetylacetonato chelate compound (1) A trisacetylacetonato aluminum containing 5% by weight of AAC Al ₂ O ₃ dissolved in an ethanol / triene mixed solvent (weight ratio 1/1).

Conductive substance (1) TL94 Phosphorus-doped tin oxide sol (ELCOM TL-94 manufactured by Catalysts & Chemicals Co., Ltd., solid content concentration 20% by weight, average particle size)
87% of all particles are 0.07 μm and 0.1 μm or less).

Metal alkoxide (M ₂ O _x ) (1) A butanol solution of tetrabutoxy zirconium containing 10% by weight of TBZR ZrO ₂ .

(2) An IPA solution of tetraisopropoxy titanium containing 10% by weight of TPTI TiO ₂ .

Examples 27 to 32 [Coating Liquid IV] After mixing the following acetylacetonato chelate compound, conductive substance and organic solvent, silicon liquid and metal alkoxide were added to this mixed liquid and mixed, as shown in Table 5. Coating liquid for forming transparent conductive ceramics coating (coating liquid 27
~ 32) was obtained.

Acetylacetonato chelate compound (1) Bisacetylacetonal cobalt containing 10% by weight of COA CoO was dissolved in a toluene / acetone mixed solvent (weight ratio 1/1).

Metal alkoxide (1) An ethanol solution of pentaethoxytantalum containing 5% by weight of PETA Ta ₂ O ₅ .

In addition, Example 30 (coating solution 30) was prepared as follows.

A mixed solution of a predetermined amount of TAP1, TL30 and ethanol was prepared. Separately, 10% by weight of monomethyltrimethoxysilane as SiO ₂ IPA solution (TMS) 250 g, TPTI 250 g, acetic anhydride
A mixed liquid of 2.5 g and 60 g of water was prepared, added to the above mixed liquid and sufficiently stirred to obtain a coating liquid 30.

Examples 33-1 to 33-32 Using the coating liquid for forming a transparent conductive ceramics coating obtained in the above Examples 1 to 32, it was applied to a 14-inch cathode ray tube panel glass under the conditions shown in Table 6. Then
A film was formed. The following evaluations were performed on these examples.

 The results are shown in Tables 7 and 8.

Transparency: Light transmittance (Tt) at wavelength 550 nm and haze (H) were measured by a haze computer (manufactured by Suga Test Instruments Co., Ltd.).

Display resistance (Rs): Measured with a high star (measurement voltage 500V) or a low star (measurement voltage 10 to 90V) (manufactured by Mitsubishi Yuka).

Resolution: A bar chart as shown in FIG. 2 is pasted on the non-coated side of the base material, and this base material is placed in a box so that the coated side is on the outside as shown in FIG. The resolution of the substrate was defined as the number of bars that were placed on the body and were separated from the substrate by 30 cm and could be visually recognized separately per cm. At this time, bar charts were produced every 5 lines / cm (10, 15, 20, 25, etc.) and used.

Glossiness (G): The glossiness (G) was evaluated at a measuring angle of 60 ° in the glossiness measuring method of JIS K7105-81. In addition, in order to avoid the influence of reflected light from the back surface of the measurement base material, the back surface was coated with black or a black tape was applied, and then the measurement was performed.

Adhesion: First, a piece of commercially available 12 nm wide cellophane tape is attached to the coating. The rest was kept perpendicular to the coating and was peeled off momentarily to visually inspect for any coating left on the panel glass.

Membrane strength: Fix the panel glass on the platform scale, put an office eraser (LION No.50-50 equivalent) on the cover, and
After sliding 150 times back and forth under a load of kg, the surface resistance (R
s) and gloss (G) were measured.

Average roughness (Rz): In the measurement method of Rz of JIS B0601-82, a stylus type film thickness meter (Rank Taylor Hobson Co.,
It was measured using the product name Talystep).

Durability: After soaking in the following 7 kinds of liquids, the adhesiveness was evaluated. Further, the glossiness and the surface resistance before and after the test were compared.

1) 120% of 15% by weight ammonia water at room temperature.

2) 120 wt% salt water at room temperature for 120 hours.

3) 30 minutes in boiling water.

4) 120 hours at room temperature in 50 wt% acetic acid water.

5) Acetone for 1 week at room temperature.

6) Ethanol for 1 week at room temperature.

7) 1 week in n-propanol at room temperature.

Examples 34-1 to 34-31 Using the coating liquid for forming the transparent conductive ceramics coating obtained in Examples 1 to 31, 450 × 300 under the conditions shown in Table 9.
It was applied to a soda glass for top glass of 4 mm to prepare a top glass with a coating.

In addition to the above, the following evaluations were performed on these examples.

Paper passing test: The coated top glass was installed in the copier of the ADF machine, and A4 size copy paper was supplied to the ADF to check the number of sheets until paper jam occurred.

Stain test: ADF until spots appear on gray scale
The number of A4 size copy sheets supplied to the company was checked. Furthermore, the light transmittance (T
t) was measured. However, the Tt after the paper passing test was measured for those with no stain.

For comparison, the top glass before the coating was formed and the ITO glass having the ITO film formed on the surface by the sputtering method were also incorporated in a copying machine and evaluated in the same manner.

 The results are shown in Table 10.

Coating method: Roll coater method. UV irradiation condition: 210mW / c
Irradiate a high-pressure mercury lamp of m ² and 2kW for 3 minutes.

Continuation of the front page (56) References JP-A-56-165202 (JP, A) JP-A-63-152675 (JP, A)

Claims (20)

(57) [Claims] 1. A coating liquid for forming a transparent conductive ceramics film, wherein an acetylacetonato chelate compound and a conductive substance are uniformly dissolved or dispersed in a mixed solvent of water and an organic solvent. . 2. An acetylacetonato chelate compound (excluding dialkoxy-bisacetylacetonatozirconium), a silicon compound, and a conductive substance are uniformly dissolved or dispersed in a mixed solvent consisting of water and an organic solvent. A coating liquid for forming a transparent conductive ceramics film, which is characterized in that 3. An acetylacetonato chelate compound, an alkoxide of a metal other than silicon, and a conductive substance,
A coating liquid for forming a transparent conductive ceramics film, which is uniformly dissolved or dispersed in a mixed solvent of water and an organic solvent. 4. An acetylacetonato chelate compound, a silicon compound and an alkoxide of a metal other than silicon, and a conductive substance are uniformly dissolved or dispersed in a mixed solvent consisting of water and an organic solvent. A coating liquid for forming a transparent conductive ceramics film. 5. The acetylacetonato chelate compound according to any one of claims 1 to 4, wherein the acetylacetonato chelate compound is at least one compound represented by the following formula (I) and / or a condensate thereof. The coating liquid for forming the transparent conductive ceramics film as described in 1. (Wherein in a + b is 2 to 4, a is 0 to 3, b is 1 to 4, R is C _n H _{2n +} 1 - a (n = 3, 4), X is CH ₃ −, CH ₃ O−, C ₂ H ₅ − or C ₂ H ₅ O−,
M ₁ is Group IB, Group IIA, Group B, Group IIIA, Group B, Group I of the periodic table
It is an element or vanadyl (VO) selected from VA, B group, VA, B group, VIA group, VIIIA group, and VIII group. ). 6. The method according to claim 2 or 4, wherein the silicon compound is at least one compound represented by the following formula (II) and / or a condensate thereof. Coating liquid for forming the transparent conductive ceramics film of. R _a —Si (OR ′) _4-a (II) (wherein R is C _n H _{2n + 1} − (n = 1 to 4), a hydrogen atom or a halogen atom, and R ′ is C _n H _{2n + 1} − (n
= 1 to 4), hydrogen atom or _{C n H 2n + 1 OC 2} H 4 - (n = 1~
4) and a = 0 to 3). 7. The alkoxide of a metal other than silicon is at least one kind of a compound represented by the following formula (III) and / or a condensate thereof: The coating liquid for forming the transparent conductive ceramics film as described in any one of the above. M ₂ (OR) _n (III) (wherein n is the same integer as the valence of M ₂ and R
Is an alkyl group or C _n H _2n O _2- (n = 3 to 10), and M
₂ is a metal other than silicon. ) 8. The conductive material is tin oxide, antimony or tin oxide doped with fluorine or phosphorus, indium oxide, indium oxide doped with tin or fluorine, and any one of claims 1 to 7. A coating liquid for forming a transparent conductive ceramics film as described in 1. 9. A base material, and claims 1 to 8 on the base material.
Which comprises a transparent conductive ceramics film formed by using the coating liquid for forming a transparent conductive ceramics film according to any one of 1 to ³ , and has a surface resistance of 10 ³ to 10 ¹¹ Ω / □ and a total light transmittance of A substrate with a transparent conductive ceramics coating, which is 85% or more and has a haze of 10% or less. 10. A substrate, and a transparent conductive ceramics film formed on the substrate using the coating liquid for forming a transparent conductive ceramics film according to any one of claims 1 to 8. And has a surface resistance of 10 ³ to 10 ¹¹ Ω / □,
A substrate with a transparent conductive ceramics coating, which has a glossiness of 30 to 100%. 11. The transparent conductive ceramic coating according to claim 9 or 10, wherein a transparent protective film is formed on the transparent conductive ceramic coating. Base material with ceramic coating. 12. The coating liquid for forming a transparent conductive ceramics coating according to claim 1, which is 40 times in advance.
A method for producing a substrate with a transparent conductive ceramics coating, which comprises drying and / or firing after applying to a substrate heated and maintained at a temperature of up to 90 ° C. 13. When forming a transparent conductive ceramics film on a substrate using the coating liquid for forming a transparent conductive ceramics film according to any one of claims 1 to 8, A transparent conductive ceramic coating film, characterized in that the coating film is irradiated with an electromagnetic wave having a wavelength shorter than visible light after and / or at least one of the coating process, the coating film drying process and the coating film baking process. Of manufacturing a coated substrate. 14. A transparent conductive ceramics film is formed on a base material using the coating liquid for forming a transparent conductive ceramics film according to claim 1, and then at least the base material is formed. A substrate having a transparent conductive ceramics coating, characterized in that the coating surface is preliminarily heated and maintained at 40 to 90 ° C., a coating solution for forming a transparent protective film is applied on the coating, and then dried and / or baked. Production method. 15. A transparent conductive ceramics coating film is formed on a substrate by using the coating liquid for forming a transparent conductive ceramics coating film according to any one of claims 1 to 8, and then on this coating film. When forming the transparent protective film, the step of applying the coating liquid for forming the transparent protective film, the step of drying the transparent protective film,
A method for producing a substrate with a transparent conductive ceramic coating, comprising irradiating the transparent protective film with an electromagnetic wave having a wavelength shorter than visible light after and / or during at least one step of baking the transparent protective film. 16. A base material, and a transparent conductive ceramics film formed on the base material by using the coating liquid for forming the transparent conductive ceramics film according to any one of claims 1 to 8. And has a surface resistance of 10 ³ to 10 ¹¹ Ω / □,
A front plate for a display device, which comprises a transparent conductive ceramics-coated substrate having a total light transmittance of 85% or more, a haze of 10% or less, and a resolution of 50 lines / cm or more. 17. A base material, and a transparent conductive ceramics film formed on the base material by using the coating liquid for forming a transparent conductive ceramics film according to any one of claims 1 to 8. And has a surface resistance of 10 ³ to 10 ¹¹ Ω / □,
A front plate for a display device, which is made of a substrate having a transparent conductive ceramics coating and having a glossiness of 30 to 100% and a resolution of 50 lines / cm or more. 18. The base material with a transparent conductive ceramics film according to claim 16 or 17, wherein the base material has a transparent protective film formed on the transparent conductive ceramics film. Front plate for display device. 19. A substrate, and a transparent conductive ceramics film formed on the substrate using the coating liquid for forming a transparent conductive ceramics film according to any one of claims 1 to 8. And has a surface resistance of 10 ³ to 10 ¹¹ Ω / □,
A top glass for a copying machine, which is made of a transparent conductive ceramics coated substrate having a total light transmittance of 85% or more and a haze of 10% or less. 20. The copying machine according to claim 19, which comprises a substrate having a transparent protective film formed on the transparent conductive ceramics film. Top glass for use.