TWI599624B - A method for producing a finely-coated inorganic oxide film-forming coating solution and a fine inorganic oxide film - Google Patents

Description

Coating liquid for forming inorganic oxide film which can be finely applied, and method for producing fine inorganic oxide film

The present invention relates to a coating liquid for forming a metal oxide film to be applied by a fine droplet discharge device, a metal oxide film obtained by using the coating liquid, and a method for producing the metal oxide film .

In recent years, the popularity of smart phones has increased, and the display screen of mobile phones has become larger. Therefore, the development of a touch panel capable of utilizing the input operation of the display of the display has become popular. According to the touch panel, an input means such as a push switch is not required, and therefore, the display screen is enlarged.

The touch panel detects a contact position of an operation area that is touched by a finger or a stylus pen. With this function, the touch panel is used as an input device. The detection method of the contact position is a resistive film method or a capacitance method. In the resistive film method, two substrates facing each other are used. On the other hand, in the capacitance mode, one substrate can be used. Therefore, according to the electrostatic capacitance method, a thin touch panel can be constructed, and It is suitable for carrying machines, etc., so it has been enthusiastically developed in recent years.

Touch panel, built in display of liquid crystal display device, etc. The device is used as a display device with a touch panel function capable of detecting a touch position. When the display panel is operated, since the display device is viewed through the touch panel, a member having excellent light transmission characteristics is used for the transparent electrode. For example, an inorganic material such as ITO (Indium Tin Oxide) is used. Further, in the case of the interlayer insulating film, an acrylic material which can be patterned and insulative is used.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 2881847

In the case of a capacitive touch panel, an electrode in two directions of the X-axis direction and the Y-axis direction perpendicular to the X-axis direction is required, and the change in electrostatic capacitance at the time of finger contact is detected, thereby detecting the coordinates. To identify the touch position or touch action. In this case, a bridge structure in which the electrode in the X-axis direction and the electrode in the Y-axis direction overlap each other to prevent the position detection from being erroneously operated by insulating the electrode in the X-axis direction from the electrode in the Y-axis direction (bridge structure) ) and make it cross.

An insulating film used in a portion of the bridge structure (hereinafter, the insulating film used herein is also referred to as an electrode insulating portion fine insulating layer) (0C1)), an organic acrylic resin is generally used. However, when an organic resin is used for the insulating film of a portion of the bridge structure and an interlayer insulating film of an inorganic material is used for the upper layer, the inorganic interlayer insulating film is cracked by the thermal stretchability of the organic resin. Further, when the bridging structure is made of an organic resin, there is a problem that the majority of the film is removed after the entire film is formed on the substrate, and thus there is a problem in terms of manufacturing efficiency.

In such a case, a metal oxide film containing an inorganic material as a component is discussed. In the case of a film having an inorganic material as a component, the hardness is generally high, and high reliability can be expected as an electrode protective film for a touch panel. Further, by making the insulating film of the bridge portion an inorganic material, cracking can be prevented even when an inorganic material is applied to the upper layer. However, in the metal oxide film containing an inorganic material as a component, it is difficult to form a film by the above-described patterning.

Therefore, it is proposed to use a Dot coating of a fine droplet discharge device such as an inkjet coating device or a nozzle dispensing device, in order to form a metal oxide film only in a portion where the bridge between the transparent electrodes is formed. In the coating liquid for forming a metal oxide film, the control of the droplet size and the wettability after the substrate is immersed is difficult, so that it is difficult to form a fine pattern.

The present invention has been completed in view of such a viewpoint. In other words, it is an object of the present invention to provide a coating liquid for forming a metal oxide film which is suitable for forming a fine metal oxide film using a fine droplet discharge device. In addition, it provides a method that is formed in such a way and has excellent reliability. A method of forming a metal oxide film and a metal oxide film using a nozzle dispenser.

The present invention has been made in order to achieve the above objects, and the following matters are intended.

(1) A coating liquid for forming a metal oxide film, which is used for coating by a fine droplet discharge device, and is characterized by containing a metal alkoxide represented by the following general formula (I), and the following The metal salt, the organic solvent, the water, and the precipitation inhibitor represented by the general formula (II) contain 30% by mass or more of ethylene glycol, propylene glycol, 1,2-butanediol, and 1,3- in all organic solvents. Butylene glycol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentane At least one selected from the group consisting of alcohol, 2,5-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and N-methylpyrrolidone, and having a surface tension of 28 mN/m or more .

M ¹ (OR ¹ ) _n (I) (M ¹ represents at least one metal selected from the group consisting of ruthenium, titanium, osmium, zirconium, boron, aluminum, magnesium, and zinc; and R ¹ represents a carbon number 1 to 5 alkyl or ethoxylated; n is an integer from 2 to 5.)

M ² (X) _k (II) (M ² represents at least one metal selected from the group consisting of aluminum, indium, zinc, zirconium, hafnium, tantalum, niobium, tantalum and niobium; X system represents hydrochloric acid, A residue of nitric acid, sulfuric acid, acetic acid, oxalic acid, aminesulfonic acid, sulfonic acid, acetoacetic acid or acetylpyruvate, or a basic salt thereof; k is a valence of M ² ).

(2) The coating liquid for forming a metal oxide film according to the above (1), further comprising a second metal alkoxide represented by the following general formula (III), R ² ₁ M ³ (OR ³ _M-1 (III) (M ³ represents at least one metal selected from the group consisting of ruthenium, titanium, osmium, zirconium, boron, aluminum, magnesium, and zinc; and R ² represents a hydrogen atom or a fluorine atom) Or may be substituted with a halogen atom, a vinyl group, a glycidoxy group, a decyl group, a methacryloxy group, an acryloxy group, an isocyanate group, an amine group or a urea group, and may have a carbon number of 1 to 20 of a hetero atom. a hydrocarbon group; R ³ represents an alkyl group having 1 to 5 carbon atoms; m represents an integer of 2 to 5; 1 is 1 or 2 when m is 3, and an integer of 1 to 3 when m is 4; When m is 5, it is an integer of 1 to 4).

(3) The coating liquid for forming a metal oxide film according to the above (2), wherein the content of the second metal alkoxide is 15 mol% or more based on the total metal alkoxide.

(4) The coating liquid for forming a metal oxide film according to any one of the above aspects, wherein the precipitation inhibitor is N-methyl-pyrrolidone, ethylene glycol, or the like. At least one selected from the group consisting of methylformamide, dimethylacetamide, diethylene glycol, propylene glycol, hexanediol, and derivatives thereof.

(5) The coating liquid for forming a metal oxide film according to any one of the above (1), wherein the metal atom (M ² ) of the metal salt and the metal atom of the metal alkoxide are combined. The molar ratio of (M) is 0.01 ≦M ² /M≦0.7.

(6) The coating liquid for forming a metal oxide film according to any one of the above-mentioned, wherein the first metal alkoxide-based decane oxide or a partial condensate thereof and the titanium alkoxide are oxidized. a mixture of things.

(7) The coating liquid for forming a metal oxide film according to any one of the above-mentioned items, wherein the metal salt is a metal nitrate, a metal sulfate, a metal acetate, a metal chloride or a metal. An oxalate, a metal amine sulfonate, a metal sulfonate, a metal acetoacetate, a metal acetoacetate or an alkaline salt thereof.

The coating liquid for forming a metal oxide film according to any one of the above-mentioned, wherein the first metal alkoxide-based decane oxide or a partial condensate thereof and the titanium alkane are oxidized. A mixture of substances, the organic solvent comprising an alkanediol or a monoether derivative thereof.

(9) A metal oxide film which is obtained by coating a coating liquid for forming a metal oxide film according to any one of the above (1) to (8) by a fine droplet discharge device.

(10) A metal oxide film which is obtained by coating a coating liquid for forming a metal oxide film according to any one of the above (1) to (8) by a nozzle dispenser.

(11) A metal oxide film which is obtained by coating a coating liquid for forming a metal oxide film according to any one of the above (1) to (8) by a piezoelectric nozzle dispenser. .

(12) A method for forming a metal oxide film, which is used for forming a metal oxide film according to any one of the above (1) to (8) The coating liquid was formed using a nozzle dispenser to form a fine insulating layer at the electrode intersection.

(13) A method for forming a metal oxide film, which is a coating liquid for forming a metal oxide film according to any one of the above (1) to (8), using a piezoelectric nozzle dispenser. A fine insulating layer at the intersection of the electrodes is formed.

By using the coating liquid for forming a metal oxide film of the present invention, a metal oxide film having a fine pattern of a small Dot diameter can be formed. Further, the obtained metal oxide film has a feature of high reliability.

<Coating liquid for forming a metal oxide film>

The coating liquid for forming a metal oxide film of the present invention contains the first metal alkoxide represented by the above general formula (I), the metal salt represented by the above general formula (II), an organic solvent, water, and And a precipitation inhibitor.

<First metal alkoxide>

The coating liquid for forming a metal oxide film of the present invention contains a first metal alkoxide having a structure represented by the following general formula (I).

M ¹ (OR ¹ ) _n (I)

In the formula (I), M ¹ , R ¹ and n are as defined above. Among them, M ¹ is preferably ruthenium, titanium, zirconium or aluminum, and particularly preferably ruthenium or titanium. Further, n is preferably 3 or 4.

When a decane oxide or a partial condensate thereof is used as the metal alkoxide represented by the formula (I), one or a mixture of two or more compounds or a partial condensate of the compound represented by the general formula (IV) is used. (preferably below the pentamer).

Si(OR') ₄ (IV)

In the formula (IV), R' represents an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms or an ethoxy group.

More specifically, as the decane oxide, a tetraalkoxy decane such as tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, tetrabutoxy decane or tetraethoxy decane is used. Wait.

Further, when a titanium alkoxide or a partial condensate is used as the metal alkoxide represented by the formula (I), one or a mixture of two or more kinds of compounds represented by the general formula (V) or a partial condensation is used. (preferably below the pentamer).

Ti(OR") ₄ (V)

In the formula (V), R" represents an alkyl group having 1 to 5 carbon atoms.

The metal alkoxide represented by the formula (I), specifically, a tetraalkane oxide compound such as tetraethylene titania, tetrapropylene titania or tetrabutyltitanate or tetra-n-butyl is used as the titanium alkoxide. A partial condensate or the like of a titanium oxide tetramer or the like.

Other examples of metal alkoxides represented by formula (I) Examples thereof include a tetraalkyl zirconia compound such as tetraethoxy zirconia, tetrapropoxide zirconia, and tetrabutyl zirconia; a trialkyl alumina compound such as tributyl aluminate, triisopropylaluminate or triethylaluminum oxide; A pentadecane ruthenium oxide compound such as arsenic trioxide or pentabutyl ruthenium oxide.

<2nd metal alkoxide>

In the coating liquid for forming a metal oxide film of the present invention, a second metal alkoxide represented by the following formula (III) may be further used together with the first metal alkoxide.

R ² ₁ M ³ (OR ³ ) _m-1 (III)

In the formula (III), M ³ , R ² , R ³ and m are as defined above. Among them, M ³ is preferably bismuth (Si), titanium (Ti), zirconium (Zr), or aluminum (Al), and particularly preferably bismuth (Si) or titanium (Ti).

In the coating liquid for forming a metal oxide film of the present invention, when a metal oxide film is formed on a film made of an organic material such as an acrylic material by containing a second metal alkoxide, the coating can be relaxed. The difference in thermal stretchability between the film and the organic film. As a result, even if a metal oxide film is formed on the organic film, cracking of the metal oxide film can be prevented. For example, in the touch panel, even if an organic film made of an acrylic material is used for the interlayer insulating film or the like, and a metal oxide film is formed thereon, the metal oxide film on the interlayer insulating film can be prevented from being turtle-produced. crack.

When the second metal alkoxide is used in the coating liquid for forming a metal oxide film of the present invention, the content of the first metal alkoxide is The total amount of the metal alkoxide contained in the coating liquid for forming a metal oxide film is preferably 20 mol% to 85 mol%, more preferably 30 mol% to 70 mol%.

When the second metal alkoxide is used in the coating liquid for forming a metal oxide film of the present invention, the content of the second metal alkoxide is related to the metal alkane contained in the coating liquid for forming a metal oxide film. The total amount of oxides is preferably from 80 mol% to 15 mol%, more preferably from 70 mol% to 30 mol%. When the carbon number of R ² is 3 or less, when the content of the metal alkoxide represented by the formula (III) is 30% or more, the carbon number of R ² is 4 or more, or when the sulfhydryl group is contained in R ² , The content of the second metal alkoxide is preferably 15% or more, more preferably 75 mol% or less.

When the content of the second metal alkoxide is less than 15 mol%, There is a case where the coating film obtained on the above organic film is cracked. In addition, when it is 80 mol% or more, cracks do not occur, but there is a case where a uniform metal oxide film cannot be obtained. By setting it as such content, it can suppress that the crack of the said metal oxide film generate|occur|produces.

When the second metal alkoxide is used in the coating liquid for forming a metal oxide film of the present invention, the total content of the metal alkoxide contained in the coating liquid for forming a metal oxide film of the present invention is preferably It is 0.5% by weight to 20% by weight, more preferably 1% by weight to 15% by weight. In the case where the ratio is large, the storage stability of the coating liquid for forming a metal oxide film is deteriorated, and the thickness of the coating film becomes difficult to control. On the other hand, in the case of a small amount, the thickness of the obtained coating film becomes thin, and in order to obtain It needs to be coated several times for a specific film thickness.

A preferred metal alkoxide represented by the formula (III), for example, when M ³ is hydrazine, the following compounds can be mentioned.

For example, methyl trimethoxy decane, methyl tripropoxy decane, methyl triethoxy decane, methyl tributoxy decane, methyl tripentoxysilane, methyl Methyl triamyloxysilane, methyltriphenyloxydecane, methyltribenzyloxydecane, methyltriphenylethoxydecane, glycidoxymethyltrimethoxydecane, propylene oxide Oxymethyltriethoxydecane, α-glycidoxyethyltrimethoxydecane, α-glycidoxyethyltriethoxydecane, β-glycidoxyethyltrimethoxy Baseline, β-glycidoxyethyltriethoxydecane, α-glycidoxypropyltrimethoxydecane, α-glycidoxypropyltriethoxydecane, β-ring Oxypropoxypropyltrimethoxydecane, β-glycidoxypropyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyl III Ethoxy decane, γ-glycidoxypropyl tripropoxy decane, γ-glycidoxypropyl tributoxy decane, γ-glycidoxypropyl triphenoxy decane, --glycidyl Butyl trimethoxy decane, α-glycidoxybutyl triethoxy decane, β-glycidoxy butyl triethoxy decane, γ-glycidoxy butyl trimethoxy Decane, γ-glycidoxybutyltriethoxydecane, δ-glycidoxybutyltrimethoxydecane, δ-glycidoxybutyltriethoxydecane, (3,4 -Epoxycyclohexyl)methyltrimethoxydecane, (3,4-epoxycyclohexyl)methyltriethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, --(3,4-epoxycyclohexyl)B Triethoxy decane, β-(3,4-epoxycyclohexyl)ethyltripropoxydecane, β-(3,4-epoxycyclohexyl)ethyl tributoxy decane, β-( 3,4-epoxycyclohexyl)ethyltriphenoxydecane, γ-(3,4-epoxycyclohexyl)propyltrimethoxydecane, γ-(3,4-epoxycyclohexyl)propyl Triethoxy decane, δ-(3,4-epoxycyclohexyl)butyltrimethoxydecane, δ-(3,4-epoxycyclohexyl)butyltriethoxydecane, glycidoxy Methyl methyl dimethoxy decane, glycidoxymethyl methyl diethoxy decane, α-glycidoxyethyl methyl dimethoxy decane, α-glycidoxy B Methyldiethoxydecane, β-glycidoxyethylmethyldimethoxydecane, β-glycidoxyethylethyldimethoxydecane, α-glycidoxy Propylmethyldimethoxydecane, α-glycidoxypropylmethyldiethoxydecane, β-glycidoxypropylmethyldimethoxydecane, β-glycidoxy Propyl propyl dimethoxy decane, γ-glycidoxypropyl methyl dimethoxy decane, γ-glycidoxypropyl methyl diethoxy decane, γ-glycidyl Propylmethyldipropoxydecane, γ-glycidoxypropylmethyldibutoxydecane, γ-glycidoxypropylmethyldiphenoxydecane, γ-glycidyl Oxypropylethyldimethoxydecane, γ-glycidoxypropylethyldiethoxydecane, γ-glycidoxypropylvinyldimethoxydecane, γ-epoxy Propoxypropyl vinyl diethoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl triethoxy methoxy Decane, phenyltrimethoxydecane, phenyltriethoxydecane, phenyltriethoxydecane, γ-chloropropyltrimethoxydecane, γ-chloropropyltriethoxydecane, γ-chloride Propyltriethoxydecane, 3,3,3-trichloropropyltrimethoxy Baseline, γ-methacryloxypropyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-mercaptopropyltriethoxydecane, β-cyanoethyltriethoxydecane , chloromethyltrimethoxydecane, chloromethyltriethoxydecane, N-(β-aminoethyl)γ-aminopropyltrimethoxydecane, N-(β-aminoethyl)γ -Aminopropylmethyldimethoxydecane, γ-aminopropylmethyldimethoxydecane, N-(β-aminoethyl)γ-aminopropyltriethoxydecane, N -(β-aminoethyl)γ-aminopropylmethyldiethoxydecane, dimethyldimethoxydecane, phenylmethyldimethoxydecane, dimethyldiethoxydecane , phenylmethyldiethoxydecane, γ-chloropropylmethyldimethoxydecane, γ-chloropropylmethyldiethoxydecane, dimethyldiethoxydecane, γ-甲Propylene methoxy propyl methyl dimethoxy decane, γ-methyl propylene methoxy propyl methyl diethoxy decane, γ-mercaptopropyl methyl dimethoxy decane, γ-fluorenyl Diethoxy decane, methyl vinyl dimethoxy decane, methyl vinyl diethoxy fluorene Alkane, γ-ureidopropyltriethoxydecane, γ-ureidopropyltrimethoxydecane, γ-ureidopropyltripropoxydecane, (R)-N-1-phenylethyl- N'-triethoxydecyl propyl urea, (R)-N-1-phenylethyl-N'-trimethoxydecyl propyl urea, allyl triethoxy decane, 3-methyl Acryloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-propenyloxypropyltri Ethoxy decane, 3-isocyanate propyl triethoxy decane, trifluoropropyl trimethoxy decane, bromopropyl triethoxy decane, diethyl diethoxy decane, diethyl dimethoxy Decane, diphenyldimethoxydecane, diphenyldiethoxydecane, trimethylethoxydecane, trimethylmethoxy Decane, p-styryltrimethoxydecane, p-styryltriethoxydecane, p-styryltripropoxydecane, and the like. These may be used alone or in combination of two or more.

Further, in the coating liquid for forming a metal oxide film of the present invention, in addition to the first metal alkoxide and the second metal alkoxide, other metal alkoxide may be contained as long as the effects of the present invention are not impaired. Things.

<metal salt>

The metal salt contained in the coating liquid for forming a metal oxide film of the present invention is represented by the following general formula (II).

M ² (X) _k (II)

In the formula (II), M ² , X, and k are as defined above. Among them, M ² is preferably aluminum, indium, antimony or zirconium. Further, X is preferably a residue of hydrochloric acid, nitric acid, acetic acid, sulfonic acid, acetoacetic acid or acetylpyruvate or an alkaline salt thereof. The residue of each acid in the above X, for example, nitric acid is also called nitrate, and sulfuric acid is also called sulfate, and the amount thereof is contained in an equivalent amount to the valence of M ² . Further, the basic salt means a case where an OH group is contained in the residue of each of the above acids.

Among the metal salts represented by the formula (II), a nitrate, a chloride salt, an oxalate or a basic salt thereof is particularly preferred. Among them, from the viewpoint of easiness of obtaining and storage stability of the coating liquid for forming a metal oxide film, it is more preferable to use a nitrate of aluminum, indium or bismuth.

<organic solvent>

The coating liquid for forming a metal oxide film of the present invention contains an organic solvent. When the metal oxide film is formed by forming a coating film of the coating liquid for forming a metal oxide film, the organic solvent is used to adjust the viscosity of the coating liquid for forming a metal oxide film to improve the coating property. The content of the organic solvent in the coating liquid for forming a metal oxide film is preferably 80% by weight to 99.5% by weight based on the total amount of the metal alkoxide contained in the coating liquid for forming a metal oxide film. More preferably, it is 85% by weight to 99% by weight. When the content of the organic solvent is small, the thickness of the obtained metal oxide film is reduced, and coating is required several times in order to obtain a specific film thickness. On the other hand, in the case where the content is large, the storage stability of the coating liquid for forming a metal oxide film is deteriorated, and the film thickness of the metal oxide film is difficult to control.

In the coating liquid for forming a metal oxide film of the present invention The organic solvent to be used may, for example, be methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol or 2-methyl-2-propane. Alcohols such as alcohols; esters such as ethyl acetate; glycols such as ethylene glycol; or ester derivatives thereof; ethers such as diethyl ether; acetone, methyl ethyl ketone, ring A ketone such as ketone or the like; an aromatic hydrocarbon such as benzene or toluene. These systems can be used alone or in combination.

In the coating liquid for forming a metal oxide film of the present invention, the organic solvent contains 30% by mass or more of ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butylene glycol, and 1, 4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,5- Hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and N-methylpyrrolidone At least one selected from the group (hereinafter, also referred to as a specific organic solvent). Further, the coating liquid for forming a metal oxide film of the present invention has a surface tension of 28 mN/m or more. Thereby, the coating of the fine pattern by the nozzle dispenser can be performed.

When the titanium alkoxide component is contained in the coating liquid for forming a metal oxide film, the alkanediol contained in the organic solvent or the monoether thereof may, for example, be ethylene glycol, diethylene glycol or propylene glycol. , hexanediol, or such monomethyl, monoethyl, monopropyl, monobutyl or monophenyl ether.

The diol or a monoether thereof contained in the organic solvent used for the coating liquid for forming a metal oxide film of the present invention, if the molar ratio is less than 1 with respect to the titanium alkoxide, the titanium alkoxide The stability effect is reduced, and the storage stability of the coating liquid for forming a metal oxide film is deteriorated. On the other hand, a large amount of a glycol or a monoether thereof is used without any problem. For example, all of the organic solvents used in the coating liquid for forming a metal oxide film may be the above-mentioned glycols or monoethers thereof. However, in the case where the coating liquid for forming a metal oxide film does not contain a titanium alkoxide, it is not necessary to particularly contain the above-mentioned diol and/or its monoether.

<precipitation inhibitor>

The coating liquid for forming a metal oxide film of the present invention contains a precipitation inhibitor. The precipitation inhibitor of the present invention is an organic solvent which has an effect of preventing precipitation of a metal salt into a coating film when a coating film is formed from a coating liquid for forming a metal oxide film. a precipitation inhibitor, preferably N-methyl- At least one selected from the group consisting of pyrrolidone, ethylene glycol, dimethylformamide, dimethylacetamide, diethylene glycol, propylene glycol, hexanediol, and the like. Among them, N-methyl-pyrrolidone, ethylene glycol, diethylene glycol, propylene glycol, hexanediol or the like are more preferred. At least one type of the precipitation inhibitor may be used.

The content of the precipitation inhibitor in the coating liquid for forming a metal oxide film is preferably such that the metal of the metal salt is converted into a metal oxide to satisfy the ratio (weight ratio) described below.

(precipitation inhibitor / metal oxide) ≧ 1

When the ratio is less than 1, the effect of suppressing precipitation of the metal salt at the time of film formation becomes small. On the other hand, when a precipitation inhibitor is used in a large amount, it does not have any influence on the coating liquid for forming a metal oxide film, but it is preferably 200 or less.

The precipitation inhibitor may be added to the metal alkoxide, in particular, a decane oxide, a titanium alkoxide, or a decane oxide and a titanium alkoxide, in the presence of a metal salt for hydrolysis or condensation reaction, or After the hydrolysis and condensation reactions are completed, they are added.

On the other hand, the content of the metal salt contained in the coating liquid for forming a metal oxide film is the total number of moles (M) of the metal atoms constituting the metal alkoxide and the metal atom of the metal salt. The total content ratio of the number of ears (M ² ) satisfies the ratio (mol ratio) described below.

0.01≦M ² /M≦0.7

If the ratio is less than 0.01, the mechanical properties of the obtained film are strong. Not enough. On the other hand, when it exceeds 0.7, the adhesiveness of the coating film to the base material, such as a glass substrate and a transparent electrode, will fall. Further, after the low-temperature firing at 450 ° C or lower, the chemical resistance of the obtained metal oxide film tends to be lowered. Among them, the ratio is preferably 0.01 to 0.6.

Coating liquid for forming a metal oxide film of the present invention Other components other than the above components may be contained as long as the effects of the present invention are not impaired, for example, inorganic fine particles, metalloxane oligomers, metalloxane polymers, leveling agents, and interfacial activity. Ingredients such as agents.

The inorganic fine particles are preferably fine particles such as cerium oxide fine particles, alumina fine particles, titanium oxide fine particles, and magnesium fluoride fine particles, and the colloidal solution of the inorganic fine particles is particularly preferable. The colloidal solution may be one in which the inorganic fine particle powder is dispersed in a dispersion medium, or may be a colloidal solution of a commercially available product.

In the present invention, the surface shape or other functions of the formed cured film can be imparted by containing inorganic fine particles. The inorganic fine particle system preferably has an average particle diameter of 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm. When the average particle diameter of the inorganic fine particles exceeds 0.2 μm, the transparency of the cured film formed using the prepared coating liquid may be lowered.

Examples of the dispersion medium of the inorganic fine particles include water and an organic solvent. The colloidal solution is preferably adjusted to have a pH or pKa of from 1 to 10, preferably from 2 to 7, from the viewpoint of the stability of the coating liquid for film formation.

Examples of the organic solvent used in the dispersion medium of the colloidal solution include methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, and dibutyl. Alcohols, pentanediol, 2-methyl-2,4-pentanediol, diethylene glycol, dipropylene glycol, ethylene glycol monopropyl ether, etc.; methyl ethyl ketone, methyl isobutyl Ketones such as ketones; aromatic hydrocarbons such as toluene and xylene; decylamines such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; ethyl acetate and butyl acetate An ester such as an ester or γ-butyrolactone; an ether such as tetrahydrofuran or 1,4-dioxane. Among these, alcohols or ketones are preferred. These organic solvents may be used singly or in combination of two or more kinds as a dispersion medium.

In the coating liquid for forming a metal oxide film of the present invention The solid content concentration is preferably in the range of 0.5% by weight to 20% by weight based on the metal alkoxide and the metal salt. When the solid content exceeds 20% by weight, the storage stability of the coating liquid for forming a metal oxide film is deteriorated, and the film thickness of the metal oxide film is difficult to control. On the other hand, when the solid content is less than 0.5% by weight, the thickness of the obtained metal oxide film is reduced, so that it is necessary to apply a plurality of times in order to obtain a specific film thickness. Among them, the solid content concentration is preferably from 1% by weight to 15% by weight.

In the coating liquid for forming a metal oxide film of the present invention, in order to obtain a condensate, a metal alkoxide containing the first and second metal alkoxides is hydrolyzed in the presence of the metal salt. Contains water. The amount of water is preferably 2 to 24 moles based on the total moles of the first and second metal alkoxides. When the ratio of the amount of water (mole) / (the total number of moles of the metal alkoxide) is 2 or less, the hydrolysis of the metal alkoxide is insufficient, and the film formability is lowered, or the obtained coating is obtained. The strength of the film is lowered, so it is not good. In addition, when the above ratio is higher than 24, due to the aggregation Condensation continues, and storage stability is lowered, which is not preferable. Among them, the molar ratio is preferably 2 to 20.

Further, in the coating liquid for forming a metal oxide film When the metal salt is a water-containing salt, since the water content thereof participates in the hydrolysis reaction, it is necessary to consider the water content of the metal salt in terms of the amount of water contained in the coating liquid for forming a metal oxide film. For example, when the coexisting metal salt is an aqueous salt of an aluminum salt, since the water content thereof participates in the reaction, the water content of the aluminum salt needs to be considered in terms of the amount of water used for the hydrolysis.

The coating liquid for forming a metal oxide film of the present invention can form a metal oxide film suitable for a touch panel. The metal oxide film is a metal oxide film containing a metal oxide of an inorganic material as a main component, and has a high strength compared to a film of an organic material such as an acrylic material.

Further, since the metal oxide film hardly has thermal stretchability, even if an inorganic material is applied to the electrode protective layer of the upper layer, cracking does not occur.

The control of the refractive index of the metal oxide film can be achieved by controlling the composition of the coating liquid for forming a metal oxide film. In other words, the metal oxide film of the present invention is produced by hydrolyzing and condensing a metal alkoxide contained in the coating liquid for forming a metal oxide film, by selecting a composition of a metal alkoxide. The refractive index of the formed metal oxide film can be adjusted within a specific range. For example, when a decane oxide and a titanium alkoxide are selected as the metal alkoxide, by adjusting the mixing ratio thereof, it is possible to adjust the range within a specific range to be described later, specifically, in the range of about 1.45 to 2.1. Metal oxygen obtained The refractive index of the film.

That is, coating a coating liquid for forming a metal oxide film It is preferable to form a film, preferably after drying, and determine the desired refractive index in the metal oxide film formed after firing, in order to achieve the refractive index, a metal alkoxide, for example, a decane oxide and The composition of the titanium alkoxide is the molar ratio. For example, the refractive index of the metal oxide film derived from the coating liquid for forming a metal oxide film obtained by hydrolyzing only the decane oxide is about 1.45. In addition, the refractive index of the metal oxide film derived from the coating liquid for forming a metal oxide film obtained by hydrolyzing only the titanium alkoxide is about 2.1. Therefore, when the refractive index of the metal oxide film is to be set to a specific value of about 1.45 to 2.1, in order to realize the refractive index value, a metal oxide can be produced by using a decane oxide and a titanium alkoxide in a specific ratio. A coating liquid for forming a film.

In addition, even by using other metal alkoxides, The refractive index of the obtained metal oxide film can also be adjusted. Further, the refractive index of the metal oxide film of the present invention can be adjusted by selecting film formation conditions in addition to the composition conditions. In this way, the high hardness of the metal oxide film can be achieved, and the desired refractive index value can be achieved.

When the metal oxide film is obtained from the coating liquid for forming a metal oxide film of the present invention, as described above, it is preferred to dry the coating film of the coating liquid for forming a metal oxide film, followed by baking. Drying is preferably carried out at room temperature to 150 ° C, more preferably 40 to 120 ° C. In addition, the drying time is preferably from about 30 seconds to about 10 minutes, more preferably from 1 to 8 minutes. about. The drying method is preferably a heating plate or a hot air circulating oven or the like.

The firing is preferably carried out at 100 ° C to 300 ° C, more preferably at 150 ° C to 250 ° C, in consideration of heat resistance of the constituent members other than the touch panel. Further, the firing time is preferably 5 minutes or longer, more preferably 15 minutes or longer. The firing method is preferably a heating plate, a heat cycle oven, an infrared oven or the like.

The coating film of the coating liquid for forming a metal oxide film is used When the metal oxide film is produced by firing, the refractive index of the obtained metal oxide film varies depending on the firing temperature. At this time, the higher the firing temperature, the higher the refractive index of the metal oxide film. Therefore, the refractive index of the obtained metal oxide film can be adjusted by selecting the firing temperature to an appropriate value.

When the metal oxide film is obtained from the coating liquid for forming a metal oxide film, if the coating film is irradiated with ultraviolet rays (UV) before firing, the refractive index of the obtained metal oxide film is changed. Specifically, the more the amount of ultraviolet irradiation, the higher the refractive index of the metal oxide film. Therefore, the presence or absence of ultraviolet irradiation can be selected in order to achieve a desired refractive index. In particular, when the metal alkoxide contained in the coating liquid for forming a metal oxide film contains a titanium alkoxide, a zirconium alkoxide or a decane oxide, the coating film before firing is irradiated with ultraviolet rays ( UV) changes the refractive index of the obtained metal oxide film, and the higher the amount of ultraviolet irradiation, the higher the refractive index of the metal oxide film. Further, in the metal oxide film, the desired folding can be achieved by the selection conditions of the composition and the like. At the rate of exposure, ultraviolet radiation may not be applied.

When ultraviolet irradiation is performed, the refractive index of the metal oxide film can be adjusted by selecting the amount of irradiation. For the metal oxide film, in order to obtain a desired refractive index, when ultraviolet irradiation is required, for example, a high pressure mercury lamp can be used. When a high-pressure mercury lamp is used, it is preferable to irradiate an amount of irradiation of 1000 mJ/cm ² or more with all-optical light, and more preferably an irradiation amount of 3,000 mJ/cm ² to 10000 mJ/cm ² in terms of 365 nm. In addition to high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, xenon lamps, and excimer lamps can be used as the light source for ultraviolet rays. In the case of using a light source other than when a high-pressure mercury lamp is used, it is only necessary to irradiate the same amount of accumulated light as in the case of using the above-described high-pressure mercury lamp. When ultraviolet irradiation is performed, an ultraviolet irradiation step may be performed between the drying step and the baking step.

In the coating liquid for forming a metal oxide film, in particular When the titanium alkoxide component is contained, it has a property that the viscosity gradually rises at room temperature. In view of the fact that there is no serious problem in practical use, in the case of precisely controlling the thickness of the metal oxide film, it is preferable to carefully manage the temperature or the like. In addition, the increase in the viscosity is remarkable as the composition ratio of the titanium alkoxide in the coating liquid for forming a metal oxide film becomes large. It is generally believed that this is a faster hydrolysis rate of titanium alkoxide than decane oxide, and the condensation reaction is fast.

In the case where the coating liquid for forming a metal oxide film contains a titanium alkoxide, in order to reduce the viscosity change, the following two methods (1) or (2) are preferred.

(1) in the presence of a titanium alkoxide in the presence of a metal salt In the case of hydrolysis, the glycol is sufficiently mixed with the titanium alkoxide in advance, and if necessary, it is mixed with the decane oxide and hydrolyzed in the presence of an organic solvent. Thereby, a coating composition having a small change in viscosity is obtained. It is generally believed that this method is effective because it will generate heat after mixing titanium alkoxide with glycol, so it will cause transesterification reaction between alkoxy group of titanium alkoxide and glycol, and hydrolysis and condensation reaction. It was stabilized.

(2) After the hydrolysis reaction of the titanium hydride in the presence of a metal salt, the titanium alkoxide solution mixed with the diol is mixed and subjected to a condensation reaction to obtain a coating liquid for forming a metal oxide film. As a result, a coating liquid for forming a metal oxide film having a small change in viscosity is obtained.

It is generally believed that this method of production is valid for the following reasons. That is, although the hydrolysis reaction of the decane oxide proceeds at a relatively fast rate, the subsequent condensation reaction is slower than the titanium alkoxide. Therefore, when the titanium alkoxide is rapidly added after the completion of the hydrolysis reaction, the sterol group of the hydrolyzed decane oxide and the titanium alkoxide are uniformly reacted. Thereby, it is considered that the hydrolyzed decane oxide stabilizes the condensation reactivity of the titanium alkoxide.

Attempts have been made to mix pre-hydrolyzed decane oxides with titanium alkoxides. However, when the diol is not contained in the organic solvent used for the reaction, the coating liquid for forming a metal oxide film which is excellent in storage stability cannot be obtained. Further, the method shown in (2) is also useful in the case of obtaining a coating liquid for forming a metal oxide film from another metal alkoxide having a high hydrolysis rate and a decane oxide.

<Metal oxide film>

The coating liquid for forming a metal oxide film of the present invention is applied to a fine droplet coating apparatus, and is applied and formed into a film to form a metal oxide film. Although the fine droplet coating apparatus is carried out by an inkjet coating method or a dispenser coating method, the coating liquid for metal oxide coating of the present invention can be preferably used for coating with a dispenser. Coating by a fine droplet coating device by a cloth method.

In the dispenser coating method, there are a dispenser of the air method, the valve method, the spiral method, the volume method, and the spray method, but in terms of the fine pattern coating, the nozzle is used. The dispenser is better.

Further, in the nozzle dispenser, there are a gas valve method, a spiral tube method, and a piezoelectric method, and in terms of finer pattern coating, piezoelectric means is preferable.

The size of the droplet of the coating liquid for forming a metal oxide film to be discharged by the fine droplet discharge device is 250 μm or less depending on the relationship between the electrode in the X-axis direction of the touch panel and the distance between the electrodes in the Y-axis direction. It is better. More preferably, it is 230 μm or less.

[Examples]

Hereinafter, the present invention will be further specifically described, but it is not limited to those explained above.

The compounds used in this example are abbreviated as follows.

TEOS: tetraethoxy decane

MPS: γ-mercaptopropyltrimethoxydecane

UPS: γ-ureidopropyl triethoxy decane

ACPS: propylene methoxy propyl trimethoxy decane

TIPT: titanium tetraisopropoxide

AN: Aluminum nitrate hexahydrate

EG: ethylene glycol

HG: 2-methyl-2,4-pentanediol (alias: hexanediol)

NMP: N-methyl-2-pyrrolidone

1,3BDO: 1,3-butanediol

BCS: 2-butoxyethanol (alias: butyl 赛路苏)

EtOH: ethanol

<Synthesis Example 1> <A1 liquid>

12.7 g of AN and 3.0 g of water were added to a 200 mL flask, and the mixture was stirred to dissolve AN. EG 73.1 g, HG 14.6 g, BCS 36.6 g, TEOS 15.5 g, ACPS 10.5 g, MPS 1.5 g, and UPS 5.9 g were added thereto, and stirred at room temperature for 30 minutes.

<A2 liquid>

TIPT 4.7 g and HG 21.9 g were added to a 300 mL flask, and the mixture was stirred at room temperature for 30 minutes. The <A1 liquid> was mixed with the <A2 liquid>, and stirred at room temperature for 30 minutes to obtain a solution (K1).

<Synthesis Example 2> <B1 liquid>

12.7 g of AN and 3.0 g of water were added to a 200 mL flask, and the mixture was stirred to dissolve AN. EG 73.1 g, BCS 29.2 g, 1,3 BDO 29.2 g, TEOS 15.5 g, ACPS 10.5 g, MPS 1.5 g, and UPS 5.9 g were added thereto, and stirred at room temperature for 30 minutes.

<B2 liquid>

TIPT 4.7g and HG 14.6g were added to a 300 mL flask, and it stirred at room temperature for 30 minutes. The <B1 liquid> was mixed with the <B2 liquid>, and stirred at room temperature for 30 minutes to obtain a solution (K2).

<Synthesis Example 3> <C1 liquid>

12.7 g of AN and 3.0 g of water were added to a 200 mL flask, and the mixture was stirred to dissolve AN. EG 7.3 g, HG 32.2 g, NMP 58.5 g, TEOS 15.5 g, ACPS 10.5 g, MPS 1.5 g, and UPS 5.9 g were added thereto, and stirred at room temperature for 30 minutes.

<C2 liquid>

TIPT 4.7 g and HG 48.3 g were added to a 300 mL flask, and the mixture was stirred at room temperature for 30 minutes. The <C1 liquid> was mixed with the <C2 liquid>, and stirred at room temperature for 30 minutes to obtain a solution (K3).

<Synthesis Example 4> <D1 liquid>

12.7 g of AN and 3.0 g of water were added to a 200 mL flask, and the mixture was stirred to dissolve AN. EG 73.1 g, HG 17.6 g, NMP 29.2 g, TEOS 15.5 g, ACPS 10.5 g, MPS 1.5 g, and UPS 5.9 g were added thereto, and stirred at room temperature for 30 minutes.

<D2 liquid>

TIPT 4.7 g and HG 26.3 g were added to a 300 mL flask, and the mixture was stirred at room temperature for 30 minutes. The <D1 liquid> was mixed with the <D2 liquid>, and stirred at room temperature for 30 minutes to obtain a solution (K4).

<Synthesis Example 5> <E1 liquid>

12.7 g of AN and 3.0 g of water were added to a 200 mL flask, and the mixture was stirred to dissolve AN. HG 29.2 g, BCS 73.1 g, TEOS 15.5 g, ACPS 10.5 g, MPS 1.5 g, and UPS 5.9 g were added thereto, and stirred at room temperature for 30 minutes.

<E2 liquid>

TIPT 4.7 g and HG 43.9 g were added to a 300 mL flask, and the mixture was stirred at room temperature for 30 minutes. The <E1 liquid> was mixed with the <E2 liquid>, and stirred at room temperature for 30 minutes to obtain a solution (K5).

<Synthesis Example 6> <F1 liquid>

12.7 g of AN and 3.0 g of water were added to a 200 mL flask, and the mixture was stirred to dissolve AN. EG 29.2 g, EtOH 73.1 g, TEOS 15.5 g, ACPS 10.5 g, MPS 1.5 g, UPS 5.9 g were added thereto, and stirred at room temperature for 30 minutes.

<F2 liquid>

TIPT 4.7 g and EG 43.9 g were added to a 300 mL flask, and the mixture was stirred at room temperature for 30 minutes. The <F1 liquid> was mixed with the <F2 liquid>, and stirred at room temperature for 30 minutes to obtain a solution (K6).

<Synthesis Example 7> <G1 liquid>

12.7 g of AN and 3.0 g of water were added to a 200 mL flask, and the mixture was stirred to dissolve AN. EG 7.3 g, HG 43.9 g, NMP 29.2 g, TEOS 15.5 g, ACPS 10.5 g, MPS 1.5 g, and UPS 5.9 g were added thereto, and stirred at room temperature for 30 minutes.

<G2 liquid>

TIPT 4.7 g and HG 65.8 g were added to a 300 mL flask, and the mixture was stirred at room temperature for 30 minutes. The <G1 liquid> was mixed with the <G2 liquid>, and stirred at room temperature for 30 minutes to obtain a solution (K7).

[Surface Tension]

The AUTO DISPENCER AD-3 manufactured by Kyowa Interface Science Co., Ltd. was used to measure at a solution temperature of 25 °C.

[spit test]

The discharge test was performed using a nozzle dispenser coating apparatus Quspa-JET (manufactured by Jinhe Co., Ltd.). The discharge conditions are shown in Table 1 below.

[spit sex]

The case where the expected amount of liquid is discharged stably is regarded as ○, and the case where the amount of liquid is expected to be less than the expected amount of liquid or not to be discharged at all is regarded as ×.

[Dot Trail]

The above droplets were applied to an alkali-free glass, and then dried at 80 ° C for 5 minutes in a hot air circulating oven, and then fired at 230 ° C for 30 minutes in another hot air circulating oven. The diameter of the film to be completed was measured.

The obtained solutions K1 to K4 were used as the solutions of Examples 1 to 4, respectively. K5~K7 were used as comparative examples 1 to 3 to evaluate the above items.

The results obtained are shown in Table 2.

According to Table 2, in Examples 1 to 4, the discharge property was obtained, and the Dot diameter was controlled to be small.

In Comparative Example 1, since the specific organic solvent was not contained, the discharge property could not be obtained, and the Dot diameter could not be controlled.

In Comparative Example 2, although the specific organic solvent was contained in an amount of 30% by mass or more, the surface tension was less than 28 mN/m, so that the discharge property could not be obtained and the Dot diameter could not be controlled.

In Comparative Example 3, although the surface tension was 28 mN/m or more, since the specific organic solvent was not contained in an amount of 30% by mass or more, the discharge property was not obtained, but the Dot diameter could not be controlled.

From this, it is understood that the solvent composition of the coating liquid for a metal oxide film is 30% by mass or more of a specific organic solvent, and the surface tension is 28 mN/m, whereby discharge property can be obtained, and a fine pattern can be applied. .

[Industrial availability]

The coating liquid for forming a metal oxide film of the present invention can be used for forming a fine metal oxide film having a small Dot diameter.

In addition, the entire contents of the specification, the patent application, and the abstract of Japanese Patent Application No. 2012-221607, filed on Jan.

Claims (11)

A coating liquid for forming a metal oxide film, which is used for coating by a fine droplet discharge device, and is characterized by containing a first metal alkoxide represented by the following general formula (I), and the following a second metal alkoxide represented by the general formula (III), a metal salt represented by the following general formula (II), an organic solvent, water, and a precipitation inhibitor, and the content of the second metal alkoxide is relative to all The metal alkoxide is 15 mol% or more, and is contained in all organic solvents in an amount of 45 mass% or more from ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Alcohol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,5-hexanediol, At least one selected from the group consisting of diethylene glycol, dipropylene glycol, triethylene glycol, and N-methylpyrrolidone, and the surface tension of the coating liquid is 28 mN/m or more; M ¹ (OR ¹ ) _n (I) (M ¹ represents at least one metal selected from the group consisting of ruthenium, titanium, iridium, zirconium, boron, aluminum, magnesium, and zinc; and R ¹ represents an alkyl group having 1 to 5 carbon atoms; Or ethoxylated; n is an integer from 2 to 5) M ² (X) _k (II (M ² represents at least one metal selected from the group consisting of aluminum, indium, zinc, zirconium, hafnium, tantalum, niobium, tantalum, and niobium; and X system represents hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, a residue of an amine sulfonic acid, a sulfonic acid, an acetamidine acetic acid or an acetylpyruvate, or a basic salt thereof; k is a valence of M ² ) R ² ₁ M ³ (OR ³ ) _m-1 (III (M ³ represents at least one metal selected from the group consisting of ruthenium, titanium, iridium, zirconium, boron, aluminum, magnesium, and zinc; R ² represents a hydrogen atom or a fluorine atom, or may be a halogen atom, a vinyl group, a glycidoxy group, a decyl group, a methacryloxy group, an acryloxy group, an isocyanate group, an amine group or a ureido group, and may have a hydrocarbon atom having 1 to 20 carbon atoms; R ³ system An alkyl group having a carbon number of 1 to 5; m is an integer of 2 to 5; l is 1 or 2 when m is 3, an integer of 1 to 3 when m is 4, and 1 when m is 5. An integer of ~4). The coating liquid for forming a metal oxide film according to claim 1, wherein the precipitation inhibitor is N-methyl-pyrrolidone, ethylene glycol, dimethylformamide, dimethylacetamide. At least one selected from the group consisting of diethylene glycol, propylene glycol, hexanediol, and derivatives thereof. The coating liquid for forming a metal oxide film according to claim 1 or 2, wherein the molar number (M ² ) of the metal atom of the metal salt and the molar number of the metal atom of the metal alkoxide ( The molar ratio of M) is 0.01 ≦ M ² / M ≦ 0.7. The coating liquid for forming a metal oxide film according to claim 1 or 2, wherein the first metal alkoxide is a decane oxide or a partial condensate thereof and a mixture with a titanium alkoxide. The coating liquid for forming a metal oxide film according to claim 1 or 2, wherein the metal salt is a metal nitrate, a metal sulfate, a metal acetate, a metal chloride, a metal oxalate, a metal amine sulfonate, a metal sulfonate, a metal acetoacetate, a metal acetoacetate or an alkaline salt thereof. The coating for forming a metal oxide film as described in claim 1 or 2 The cloth liquid, wherein the first metal alkoxide is a decane oxide or a partial condensate thereof, and a mixture with a titanium alkoxide, and the organic solvent contains an alkanediol or a monoether derivative thereof. A metal oxide film obtained by coating a coating liquid for forming a metal oxide film according to any one of claims 1 to 6 by a fine droplet discharge device. A metal oxide film obtained by coating a coating liquid for forming a metal oxide film according to any one of claims 1 to 6 by a nozzle dispenser. A metal oxide film obtained by coating a coating liquid for forming a metal oxide film according to any one of claims 1 to 6 by a piezoelectric nozzle dispenser. A method for forming a metal oxide film, which is a coating liquid for forming a metal oxide film according to any one of claims 1 to 6, which uses a nozzle dispenser to form a fine insulating layer at the electrode intersection portion. A method for forming a metal oxide film, which is a coating liquid for forming a metal oxide film according to any one of claims 1 to 6, which uses a piezoelectric nozzle dispenser to form a fine insulation of an electrode intersection portion. Floor.