KR20150064152A - Application liquid capable of fine application, for forming inorganic oxide coating film, and method for manufacturing fine inorganic oxide coating film - Google Patents

Abstract

There is provided a coating liquid for forming a metal oxide film suitable for forming a fine metal oxide coating.
A process for producing a polyurethane foam, which comprises a specific metal alkoxide, a specific metal salt, an organic solvent, water, and an anti-precipitation agent and is selected from the group consisting of ethylene glycol, propylene glycol, 1,2-butanediol, - 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 in an amount of 30 mass% or more in the total organic solvent and having a surface tension of 28 mN / m or more, Coating liquid for forming a film.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a coating solution for forming an inorganic oxide film capable of being finely applied, and a method for producing a coating film for a fine inorganic oxide film. BACKGROUND ART < RTI ID = 0.0 >

TECHNICAL FIELD The present invention relates to a coating liquid for forming a metal oxide film to be used for coating with a fine droplet discharging device, a metal oxide film obtained by using the coating liquid, and a method for producing the metal oxide film.

Recently, with the spread of smart phones, the display screen of cellular phones has become larger. For this reason, a touch panel capable of performing an input operation using a display on a display is actively developed. According to the touch panel, since input means such as a push-down switch is not required, the display screen can be enlarged.

The touch panel detects the contact position of the operation area that the finger or the pen touches. Using this function, the touch panel is used as an input device. The contact position detection method includes a resistance film method and a capacitance method. In the resistive film type, two opposing substrates are used, whereas in the electrostatic capacity type, one substrate can be used. For this reason, according to the electrostatic capacity method, a thin touch panel can be constructed, and therefore, development has been actively under progress since it is preferable for a portable device and the like.

The touch panel is mounted on a display device such as a liquid crystal display device and is used as a display device having a touch panel function capable of detecting a touch position. A member operating the touch panel visually observes the display device through the touch panel, and therefore, a member having excellent light transmission characteristics is used for the transparent electrode. For example, inorganic materials such as indium tin oxide (ITO) have been used. As the interlayer insulating film, an acrylic material which can be patterned and is insulating is used.

Japanese Patent No. 2881847

In the case of a capacitive touch panel, two directions of electrodes in the X-axis direction and the Y-direction perpendicular to the X-axis direction are required. By detecting a change in capacitance when a finger touches the touch panel, its coordinates are detected, And the touch operation is recognized. At this time, in order to prevent the position detection malfunction at the point where the electrode in the X-axis direction overlaps the electrode in the Y-axis direction, a cross-linking structure for insulating the electrode in the X- I have to.

An organic acrylic resin is generally used as an insulating film used in the cross-linked structure portion (hereinafter, the insulating film used herein is also referred to as an electrode intersection portion fine insulating layer OC1). However, when an organic resin is used for the insulating film of the crosslinked structure portion and an interlayer insulating film of an inorganic material is used for the upper layer, cracks are generated in the inorganic interlayer insulating film due to the thermal stretchability of the organic resin. When a crosslinked structure is formed with an organic resin, there is a problem in terms of production efficiency because a film is formed on the entire surface of the substrate once, and most of the film is removed.

Under such circumstances, studies have been made on metal oxide films containing inorganic materials as components. In the case of a film made of an inorganic material as a component, since the hardness is generally high, high reliability can be expected as an electrode protective film of a touch panel. In addition, by using the insulating film of the cross-linked portion as the inorganic material, occurrence of cracks can be prevented even when an inorganic material is applied to the upper layer. However, in a metal oxide film containing an inorganic material as a component, it is difficult to form the film by the above patterning.

Therefore, in order to deposit a metal oxide film only on the cross-linked portion between the transparent electrodes, Dot coating using a fine droplet discharging device such as an ink jet coating device or a jet dispensing coating device is proposed and examined. However, In the coating liquid, it is difficult to control the size of the droplet and the widening property after being immersed in the substrate, so that it is difficult to form a fine pattern.

The present invention has been made in view of this point. That is, an object of the present invention is to provide a coating liquid for forming a metal oxide film suitable for formation of a fine metal oxide coating using a fine droplet discharging apparatus. Another object of the present invention is to provide a metal oxide film formed by such a method and having high reliability and a method for forming a metal oxide film using the jet dispenser.

In order to achieve the above object, the present invention provides the following.

(1) A process for producing a metal alkoxide, which comprises reacting a metal alkoxide represented by the following general formula (I), a metal salt represented by the following general formula (II), an organic solvent, water, Butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, , At least one member selected from the group consisting of 5-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and N-methylpyrrolidone is contained in the total organic solvent in an amount of 30 mass% or more, m < 2 > / m < 2 > / m < 2 > or more.

M ¹ (OR ¹ ) _n (I)

Wherein M ¹ represents at least one metal selected from the group consisting of silicon, titanium, tantalum, zirconium, boron, aluminum, magnesium and zinc, R ¹ represents an alkyl group having 1 to 5 carbon atoms or an acetoxy group and n represents an integer of 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, bismuth, lanthanum, tantalum, yttrium and cerium.) X is at least one metal selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, A residue of a carboxylic acid, a carboxylic acid, a sulfonic acid, acetoacetic acid or acetylacetonate, or a basic salt thereof, and k represents a mantissa of M ² .

(2) The coating liquid for forming a metal oxide film according to (1), further comprising a second metal alkoxide represented by the following general formula (III).

R ² ₁ M ³ (OR ³ ) _ml (III)

Wherein M ³ represents at least one metal selected from the group consisting of silicon, titanium, tantalum, zirconium, boron, aluminum, magnesium and zinc, R ² represents a hydrogen atom or a fluorine atom, Which may be substituted with an atom, a vinyl group, a glycidoxy group, a mercapto group, a methacryloxy group, an acryloxy group, an isocyanate group, an amino group or a ureide group, M is an integer of 2 to 5, 1 is 1 or 2 when m is 3, and is an integer of 1 to 3 when m is 4, and R ³ is an alkyl group having 1 to 5 carbon atoms, When m is 5, it is an integer of 1 to 4.)

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

(4) The process according to any one of (1) to (4), wherein the precipitation inhibitor is at least one substance selected from the group consisting of N-methyl-pyrrolidone, ethylene glycol, dimethylformamide, dimethylacetamide, diethylene glycol, propylene glycol, hexylene glycol, The coating liquid for forming a metal oxide film according to any one of (1) to (3) above.

(5) The positive resist composition as described in any one of (1) to (4) above, wherein the molar ratio of the metal atom (M ² ) of the metal salt to the total amount (M) of the metal atom of the metal alkoxide is 0.01 ≦ M ² / A coating liquid for forming a metal oxide film described above.

(6) The coating liquid for forming a metal oxide film according to any one of (1) to (5), wherein the first metal alkoxide is a mixture of a silicon alkoxide or a partial condensate thereof and a titanium alkoxide.

(7) The process according to the above (1), wherein the metal salt is at least one selected from the group consisting of metal nitrate, metal sulfate, metal acetate, metal chloride, metal oxalate, metal spanate, metal sulfonate, metal acetoacetate, metal acetylacetonate, To (6) above. ≪ EMI ID = 1.0 >

(8) The process for producing a polymerizable composition according to any one of (1) to (7), wherein the first metal alkoxide is a mixture of a silicon alkoxide or a partial condensate thereof and a titanium alkoxide and the organic solvent comprises an alkylene glycol or a monoether derivative thereof A coating liquid for forming a metal oxide film according to any one of claims 1 to 6.

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

(10) A metal oxide film obtained by applying the coating liquid for forming a metal oxide film according to any one of (1) to (8) by means of a jet dispenser.

(11) A metal oxide film obtained by applying the coating liquid for forming a metal oxide film according to any one of (1) to (8) by means of a piezo jet dispenser.

(12) A method for forming a metal oxide film coating liquid as described in any one of (1) to (8) above, wherein the electrode intersection micro-insulating layer is formed using a jet dispenser.

(13) A method for forming a metal oxide film coating liquid as described in any one of (1) to (8) above, wherein an electrode intersection micro-insulating layer is formed using a piezo system jet dispenser.

By using the coating liquid for forming a metal oxide film of the present invention, it is possible to form a metal oxide film of a fine pattern with a small Dot diameter. Moreover, 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 a first metal alkoxide represented by the general formula (I), a metal salt represented by the general formula (II), an organic solvent, water, and an 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^One(OR^One)_n (I)

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

When a silicon alkoxide or a partial condensate thereof is used as the metal alkoxide represented by the formula (I), one or a mixture or partial condensate of the compound represented by the general formula (IV) ) Is used.

Si (OR ') ₄ (IV)

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

More specifically, examples of the silicon alkoxide include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and tetraacetoxysilane.

When a titanium alkoxide or a partial condensate is used as the metal alkoxide represented by the formula (I), one or a mixture or partial condensate of the compound represented by the general formula (V) (preferably 5 Or less) is used.

Ti (OR ") ₄ (V)

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

Specific examples of the metal alkoxide represented by the formula (I) include titanium alkoxide such as titanium tetraethoxide, titanium tetra propoxide, titanium tetraalkoxide compound such as titanium tetrabutoxide, or titanium tetra-n-butoxide And partial condensates such as tetramer.

Other examples of the metal alkoxide represented by the formula (I) include zirconium tetraalkoxide compounds such as zirconium tetraethoxide, zirconium tetrapropoxide and zirconium tetrabutoxide; Aluminum trialkoxide compounds such as aluminum tri-butoxide, aluminum triisopropoxide and aluminum triethoxide; And tantalum pentaalkoxide compounds such as tantalum pentapropoxide and tantalum pentabutoxide.

&Lt; Second 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 used together with the first metal alkoxide.

R ² ₁ M ³ (OR ³ ) _ml (III)

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

In the coating solution for forming a metal oxide film of the present invention, when the metal oxide film is formed on a film made of an organic material such as an acrylic material by containing the second metal alkoxide, the heat elasticity between the coat film and the organic film The difference is relaxed. As a result, even if a metal oxide film is formed on the organic film, cracking of the metal oxide film is prevented. For example, in the touch panel, cracks can be prevented from occurring in the metal oxide film on the interlayer insulating film even if an organic film made of an acrylic material is used for the above-described interlayer insulating film and a metal oxide film is formed thereon .

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 preferably from 20 mol% to 20 mol% based on the total amount of the metal alkoxide contained in the coating liquid for forming a metal oxide film, Is preferably 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 preferably 80 mol% or more, more preferably 80 mol% or less, To 15 mol%, and more preferably 70% to 30 mol%. When the carbon number of R ² is 3 or less and the content of the metal alkoxide represented by the formula (III) is 30% or more and the number of carbon atoms of R ² is 4 or more, or when a mercapto group is contained in R ² , The content of the alkoxide is more preferably 15% or more, and still more preferably 75 mol% or less.

When the content of the second metal alkoxide is less than 15 mol%, cracks may be generated in the coat film obtained on the organic film. On the other hand, when it is 80 mol% or more, cracks do not occur, but a phenomenon that a uniform metal oxide film can not be obtained may occur. With such a content, cracking in the metal oxide film can be suppressed.

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 0.5 wt% 20% by weight, and more preferably 1% by weight to 15% by weight. When the ratio is large, the storage stability of the coating liquid for forming a metal oxide film deteriorates, and it becomes difficult to control the thickness of the coat film. On the other hand, when the thickness is small, the thickness of the obtained coat film becomes thin, and coating is required several times in order to obtain a predetermined film thickness.

The preferable metal alkoxide represented by the formula (III) includes, for example, the following compounds when M ³ is silicon.

For example, there can be mentioned methyltrimethoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripentoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxy Silane, methyltriphenetyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane,? -Glycidoxyethyltrimethoxysilane,? -Glycidoxyethyltriethoxysilane,? -Glycidoxyethyltrimethoxysilane,? -Glycidoxyethyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? -Glycidoxypropyl tri Glycidoxypropyltrimethoxysilane, gamma -glycidoxypropyltriethoxysilane, gamma -glycidoxypropyltripropoxysilane, gamma -glycidoxypropyltrimethoxysilane, gamma -glycidoxypropyltrimethoxysilane, gamma -glycidoxypropyltrimethoxysilane, gamma- Glycidoxypropyltributoxysilane,? -Glycidoxypropyl Glycidoxybutyltrimethoxysilane,? -Glycidoxybutyltrimethoxysilane,? -Glycidoxybutyltrimethoxysilane,? -Glycidoxybutyltrimethoxysilane,? -Glycidoxybutyltrimethoxysilane,? -Glycidoxybutyltrimethoxysilane, -Glycidoxybutyltriethoxysilane,? -Glycidoxybutyltrimethoxysilane,? -Glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3, ? - (3,4-epoxycyclohexyl) ethyltriethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltripropoxysilane,? - (3,4-epoxycyclohexyl) ethyltripropoxysilane, (3,4-epoxycyclohexyl) propyltrimethoxysilane,? - (3,4-epoxycyclohexyl) propyltriethoxysilane,? - (3,4-epoxycycles Hexyl) butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane,? -Glycidoxyethylmethyldimethoxysilane,? -Glycidoxyethylmethyldiethoxysilane,? - Glycidoxyethylmethyldimethoxysilane,? -Glycidoxyethylethyldimethoxysilane,? -Glycidoxypropylmethyldimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane,? -Glycidoxypropylmethyldimethacrylate, Glycidoxypropylethyldimethoxysilane, gamma -glycidoxypropylmethyldimethoxysilane, gamma -glycidoxypropylmethyldiethoxysilane, gamma -glycidoxypropylmethyldipropoxysilane, gamma -glycidoxypropylmethyldimethoxysilane, gamma -glycidoxypropylethyldimethoxysilane, gamma- Glycidoxypropylmethyldibutoxysilane,? -Glycidoxypropylmethyldiphenoxysilane,? -Glycidoxypropylethyldimethoxysilane,? -Glycidoxypropylethyldiethoxysilane,? -Glycidoxypropylvinyl Dimethoxysilane, gamma -glycidoxypropylbis Vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, gamma -chloropropyltrimethoxysilane, gamma -chloropropyltriethoxysilane, gamma -chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, gamma-methacryloxy Propyltrimethoxysilane,? -Mercaptopropyltrimethoxysilane,? -Mercaptopropyltriethoxysilane,? -Cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, Aminopropyltrimethoxysilane, N- (? -Aminoethyl)? -Aminopropyltrimethoxysilane, N- (? -Aminoethyl)? -Aminopropylmethyldimethoxysilane,? -Aminopropylmethyldimethoxysilane, N- )? -aminopropyltriethoxysilane, N- (? -aminoethyl)? - amino Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane,? -Chloropropylmethyldimethoxysilane,? -Chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, dimethyldiethoxysilane, Silane,? -Methacryloxypropylmethyldimethoxysilane,? -Methacryloxypropylmethyldiethoxysilane,? -Mercaptopropylmethyldimethoxysilane,? -Mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methyl (R) -N-1-phenylethyl-N'-tri (meth) acrylate such as vinyldiethoxysilane,? -Ureidopropyltriethoxysilane,? -Ureidopropyltrimethoxysilane,? -Ureidopropyltripropoxysilane, (R) -N-1-phenylethyl-N'-trimethoxysilylpropylurea, allyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Triethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, trifluoropropyltrimethoxysilane, bromopropyltriethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, diphenyl Trimethyl methoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, p-styryltripropoxysilane, and the like. have. These may be used alone or in combination of two or more.

In addition to the first metal alkoxide and the second metal alkoxide, the coating liquid for forming a metal oxide film of the present invention may contain other metal alkoxides as long as the effect of the present invention is not impaired .

<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, cerium, or zirconium. X is preferably a residue of hydrochloric acid, nitric acid, acetic acid, sulfonic acid, acetoacetic acid or acetylacetonate, or a basic salt thereof. The residue of each acid in X is also referred to as, for example, silver nitrate and nitrate, and sulfuric acid is also referred to as sulfate, and the amount thereof is included so as to be equivalent to the valence of M ² . Further, the basic salt means a case in which OH groups are contained in the residues of the respective acids.

Of the metal salts represented by the formula (II), nitrates, chloride salts, oxalates or basic salts thereof are particularly preferable. Of these, aluminum, indium or cerium nitrates are more preferable from the viewpoints of availability and storage stability of the coating liquid for forming a metal oxide film.

<Organic solvent>

An organic solvent is contained in the coating liquid for forming a metal oxide film of the present invention. The organic solvent is used for adjusting the viscosity of the coating liquid for forming a metal oxide film and improving the coating property when the coating film is formed from the coating liquid for forming a metal oxide film to obtain a metal oxide film. The content of the organic solvent in the coating liquid is preferably 80 wt% to 99.5 wt%, more preferably 85 wt% to 99 wt% with respect to the total metal alkoxide contained in the coating liquid for forming a metal oxide film. When the content of the organic solvent is small, the thickness of the obtained metal oxide coating becomes thin, and a plurality of coatings are required to obtain a predetermined film thickness. On the other hand, in many cases, the storage stability of the coating solution for forming a metal oxide film is deteriorated, and it becomes difficult to control the film thickness of the metal oxide film.

Examples of the organic solvent used in the coating liquid for forming a metal oxide film of the present invention include organic solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, Alcohols such as 2-propanol; Esters such as acetic acid ethyl ester; Glycols such as ethylene glycol, and ester derivatives thereof; Ethers such as diethyl ether; Ketones such as acetone, methyl ethyl ketone, and cyclohexanone; And aromatic hydrocarbons such as benzene and toluene. These are used alone or in combination.

The coating liquid for forming a metal oxide film of the present invention may contain at least one selected from the group consisting of ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, A group consisting of 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,5-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, (Hereinafter, also referred to as a specific organic solvent) is contained in the organic solvent in an amount of 30 mass% or more. The surface tension of the coating liquid for forming a metal oxide film of the present invention is 28 mN / m or more. This makes it possible to apply a fine pattern by the jet dispenser.

Examples of the alkylene glycols or monoethers contained in the organic solvent when the coating liquid for forming a metal oxide film contains a titanium alkoxide component include ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol , Or monomethyl, monoethyl, monopropyl, monobutyl or monophenyl ether thereof.

When the molar ratio of the glycol or its monoether contained in the organic solvent used in the coating liquid for forming a metal oxide film of the present invention to the titanium alkoxide is less than 1, the effect on the stability of the titanium alkoxide is small and the formation of the metal oxide film The storage stability of the application liquid is deteriorated. On the other hand, the use of a large amount of glycols or monoethers thereof is not a problem at all. 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, when the coating solution for forming a metal oxide film does not contain a titanium alkoxide, it is not necessary to specifically contain the above-mentioned glycol and / or monoether thereof.

<Precipitation inhibitor>

The coating liquid for forming a metal oxide film of the present invention contains a precipitation inhibitor. The anti-precipitation agent in the present invention refers to an organic solvent having a function of preventing the metal salt from precipitating in the coating film when the coating film is formed from the coating solution for forming a metal oxide film. The precipitation inhibitor is preferably at least one selected from the group consisting of N-methyl-pyrrolidone, ethylene glycol, dimethylformamide, dimethylacetamide, diethylene glycol, propylene glycol, hexylene glycol and derivatives thereof . Among them, N-methyl-pyrrolidone, ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol or derivatives thereof are more preferable. At least one kind of 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 and the following ratio (weight ratio) is satisfied.

(Precipitation inhibitor / metal oxide) ≥ 1

If the ratio is less than 1, the effect of preventing deposition of the metal salt at the time of film formation becomes small. On the other hand, the use of a large amount of the precipitation inhibitor does not affect the coating liquid for forming a metal oxide film at all, but it is preferably 200 or less.

The precipitation inhibitor may be added when the metal alkoxide, particularly, the silicon alkoxide, the titanium alkoxide or the silicon alkoxide and the titanium alkoxide are subjected to the hydrolysis / condensation reaction in the presence of the metal salt, or may be added after the completion of the hydrolysis and condensation reaction do.

On the other hand, the content of the metal salt contained in the coating solution for forming a metal oxide film is such that the total content of the total number of moles (M) of the metal atoms constituting the metal alkoxide and the number of moles (M ² ) (Molar ratio) satisfying the following conditions.

0.01? M ² / M? 0.7

If the ratio is less than 0.01, the mechanical strength of the obtained film is not sufficient, which is not preferable. On the other hand, if it exceeds 0.7, adhesion of the coat film to a substrate such as a glass substrate or a transparent electrode is deteriorated. Further, when baking is performed at a low temperature of 450 DEG C or less, the chemical resistance of the obtained metal oxide film tends to be lowered. Among them, the ratio is more preferably 0.01 to 0.6.

In the coating liquid for forming a metal oxide film of the present invention, as long as the effect of the present invention is not impaired, other components other than the above-mentioned components, for example, an inorganic fine particle, a metal oxo acid oligomer, A surfactant, and the like may be contained.

As the inorganic fine particles, fine particles such as silica fine particles, alumina fine particles, titania fine particles, and magnesium fluoride fine particles are preferable, and a colloid solution of these inorganic fine particles is particularly preferable. The colloidal solution may be a dispersion of the inorganic fine particle powder in a dispersion medium, or a colloid solution of a commercially available product.

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

The dispersion medium of the inorganic fine particles includes water and an organic solvent. The colloid solution preferably has a pH or pKa adjusted to 1 to 10, more preferably 2 to 7, from the viewpoint of stability of the coating liquid for forming a film.

Examples of the organic solvent used in the dispersion medium of the colloid solution include organic solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, 2-methyl-2,4-pentanediol, diethylene glycol, Alcohols such as ethylene glycol monopropyl ether; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Aromatic hydrocarbons such as toluene and xylene; Amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate and? -Butyrolactone; And ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols or ketones are preferred. These organic solvents may be used alone or as a dispersion medium by mixing two or more kinds thereof.

The solid content concentration in the coating liquid for forming a metal oxide film of the present invention is preferably in the range of 0.5 wt% to 20 wt% when the metal alkoxide and the metal salt are converted into the metal oxide. If the solid content exceeds 20% by weight, the storage stability of the coating solution for forming a metal oxide film is deteriorated and it becomes difficult to control the film thickness of the metal oxide film. On the other hand, when the solid content is less than 0.5% by weight, the thickness of the obtained metal oxide coating becomes thin, and a plurality of coatings are required to obtain a predetermined film thickness. Among them, the solid concentration is more preferably 1 wt% to 15 wt%.

The coating liquid for forming a metal oxide film of the present invention contains water in order to hydrolyze the metal alkoxide containing the first and second metal alkoxides in the presence of the metal salt to obtain a condensate. The amount of such water is preferably 2 to 24 moles with respect to the total moles of the first and second metal alkoxides. When the ratio of the amount of water (mol) / (total number of moles of metal alkoxide) is 2 or less, the hydrolysis of the metal alkoxide becomes insufficient, and the film forming property is lowered or the strength of the obtained coat film is lowered When the above ratio is more than 24, the polycondensation proceeds continuously, and therefore, the storage stability is lowered, and therefore, the molar ratio is more preferably 2 to 20.

When the metal salt contained in the coating liquid for forming a metal oxide film is a hydrated salt, the water content is involved in the hydrolysis reaction. Therefore, the amount of water to be contained in the coating liquid for forming a metal oxide film is not particularly limited, . For example, when the coexisting metal salt is a hydrated salt of an aluminum salt, since the water content of the hydrated salt participates in the reaction, it is necessary to consider the water content of the aluminum salt with respect to 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 coating is a metal oxide coating mainly composed of a metal oxide, which is an inorganic material, and has a higher strength than a film of an organic material such as an acrylic material.

In addition, since this metal oxide film has almost no heat stretchability, even when an inorganic material is applied to the upper electrode protection layer, cracks do not occur.

The control of the refractive index of the metal oxide film can be realized by controlling the composition of the coating liquid for forming a metal oxide film. That is, the metal oxide coating in the present invention is produced by hydrolysis / condensation of a metal alkoxide contained in the coating solution for forming a metal oxide film. By selecting the composition of the metal alkoxide, the metal oxide coating It is possible to adjust the refractive index within a predetermined range. For example, when the silicon alkoxide and the titanium alkoxide are selected as the metal alkoxide, by adjusting the mixing ratio thereof, it is possible to obtain the metal oxide film of the present invention within the predetermined range described later, specifically within the range of about 1.45 to 2.1 It is possible to adjust the refractive index of the liquid crystal layer.

That is, when the desired refractive index is determined in the metal oxide film formed after the coating liquid for forming a metal oxide film is applied to form a film, and preferably after drying and firing, the refractive index of the metal alkoxide , For example, it is possible to determine the compositional molar ratio of the silicon alkoxide and the titanium alkoxide. For example, the refractive index of a metal oxide film from a coating liquid for forming a metal oxide film obtained by hydrolyzing only a silicon alkoxide is a value of about 1.45. The refractive index of the metal oxide film from the coating liquid for forming a metal oxide film obtained by hydrolyzing only titanium alkoxide is a value of about 2.1. Therefore, when it is desired to set the refractive index of the metal oxide film to a specific value between about 1.45 and about 2.1, a silicon oxide and a titanium alkoxide are used at a predetermined ratio so as to realize the refractive index, It is possible to prepare a liquid.

Also, by using another metal alkoxide, the refractive index of the resulting metal oxide film can be adjusted. The refractive index of the metal oxide film in the present invention can be adjusted by selecting film forming conditions other than the composition conditions. By doing so, it is possible to realize a high hardness of the metal oxide coating and realize a desired refractive index value.

When the metal oxide film is obtained from the coating liquid for forming a metal oxide film of the present invention, the coating film of the coating liquid for forming a metal oxide film is preferably dried and then fired. The drying is preferably carried out at room temperature to 150 ° C, more preferably at 40 to 120 ° C. The drying time is preferably about 30 seconds to 10 minutes, more preferably about 1 to 8 minutes. As the drying method, it is preferable to use a hot plate, a hot-air circulating oven, or the like.

The firing is preferably carried out at 100 캜 to 300 캜, preferably at 150 캜 to 250 캜, in consideration of the heat resistance of the components other than the touch panel. The baking time is preferably 5 minutes or more, more preferably 15 minutes or more. As the firing method, it is preferable to use a hot plate, a thermocycling oven, an infrared oven, or the like.

In the case of producing a metal oxide film by firing a coating film of a coating liquid for forming a metal oxide film, the refractive index of the metal oxide film obtained by the firing temperature varies. In this case, the higher the firing temperature, the higher the refractive index of the metal oxide film. Therefore, by selecting the firing temperature to an appropriate value, it is possible to adjust the refractive index of the resulting metal oxide coating.

In the case of obtaining a metal oxide film from a coating liquid for forming a metal oxide film, if the ultraviolet (UV) film is irradiated onto the film before firing, the refractive index of the resulting metal oxide film is changed. Specifically, the refractive index of the metal oxide film can be increased as the ultraviolet ray irradiation amount is increased. Therefore, in order to realize a desired refractive index, it is possible to select the presence or absence of ultraviolet irradiation. Particularly, when the metal alkoxide is contained in the coating liquid for forming a metal oxide film and contains a titanium alkoxide, a zirconium alkoxide or a tantalum alkoxide, the refractive index of the metal oxide film obtained by ultraviolet (UV) And the refractive index of the metal oxide film can be increased as the ultraviolet ray irradiation amount is increased. Further, in the case where a desired refractive index can be realized in the metal oxide film by selecting conditions such as composition, ultraviolet irradiation may not be performed.

In the case of ultraviolet ray irradiation, it is possible to adjust the refractive index of the metal oxide film by selecting the irradiation amount. For example, a high-pressure mercury lamp may be used when ultraviolet irradiation is required to obtain a desired refractive index in a metal oxide coating. In the case of using a high-pressure mercury lamp, an irradiation amount of 1000 mJ / cm 2 or more is preferable, and a dose of 3000 mJ / cm 2 to 10000 mJ / cm 2 is more preferable in terms of 365 nm. As a light source of ultraviolet rays, a low-pressure mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp, etc. may be used in addition to a high-pressure mercury lamp. In the case of using a light source other than the case of using a high-pressure mercury lamp, the same amount of integrated light as that in the case of using the high-pressure mercury lamp may be irradiated. When ultraviolet ray irradiation is performed, an ultraviolet ray irradiation step may be performed between the drying step and the baking step.

When the coating liquid for forming a metal oxide film contains a titanium alkoxide component in particular, it has a property that the viscosity is gradually increased under room temperature storage. There is no fear that this will be a big problem in practical use. However, in the case of precisely controlling the thickness of the metal oxide film, it is preferable to carefully manage temperature and the like. Such an increase in viscosity becomes remarkable as the composition ratio of the titanium alkoxide in the coating solution for forming a metal oxide film is increased. This is presumably because the hydrolysis rate of the titanium alkoxide is higher than that of the silicon alkoxide and the condensation reaction is faster.

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

(1) When the titanium alkoxide is hydrolyzed in the presence of the metal salt, the glycols and the titanium alkoxide are thoroughly mixed in advance, and if necessary mixed with the silicon alkoxide and hydrolyzed in the presence of the organic solvent. By doing so, a coating composition having a small change in viscosity is obtained. This production method is effective because it has an exothermic heat when the titanium alkoxide is mixed with the glycol, so that the transesterification reaction takes place between the alkoxy group of the titanium alkoxide and the glycol, and is stabilized by the hydrolysis / condensation reaction do.

(2) A silicon alkoxide is subjected to a hydrolysis reaction in advance in the presence of a metal salt, followed by mixing with a titanium alkoxide solution mixed with glycols to carry out a condensation reaction to obtain a coating liquid for forming a metal oxide film. By doing so, a coating liquid for forming a metal oxide film with a small change in viscosity is obtained.

It is considered that this method is effective for the following reasons. That is, the hydrolysis reaction of the silicon alkoxide is carried out at a high speed, but the subsequent condensation reaction is slow compared to the titanium alkoxide. Therefore, when the titanium alkoxide is rapidly added after the hydrolysis reaction is completed, the silanol group of the silicon alkoxide subjected to the hydrolysis reaction reacts uniformly with the titanium alkoxide. As a result, it is considered that the condensation reactivity of the titanium alkoxide stabilizes the hydrolyzed silicon alkoxide.

A method of mixing a previously hydrolyzed silicon alkoxide with a titanium alkoxide has already been attempted. However, when the organic solvent used for the reaction does not contain glycols, a coating solution for forming a metal oxide film having excellent storage stability can not be obtained. The method shown in (2) is also useful for obtaining a coating liquid for forming a metal oxide film from another metal alkoxide having a large hydrolysis rate and a silicon alkoxide.

&Lt; Metal oxide film &

The coating liquid for forming a metal oxide film of the present invention is applied and film-formed by applying a fine liquid droplet applying apparatus to form a metal oxide film. The fine liquid droplet applying device may be an ink jet applying method or a dispenser applying method. However, the coating liquid for a metal oxide coating of the present invention can be suitably used for application by a fine droplet applying device by a dispenser applying method.

The dispenser application method includes an air system, a valve system, a screw system, a volumetric system and a jet system dispenser, but a jet dispenser is preferable from the viewpoint of fine pattern application.

The jet dispenser includes an air valve system, a solenoid system, and a piezo system. Of these, the piezo system is preferable from the viewpoint of fine pattern coating.

The droplet size of the coating liquid for forming a metal oxide film to be discharged by the fine droplet discharging device is preferably 250 占 퐉 or less from the viewpoint of the distance between the electrode in the X axis direction and the electrode in the Y axis direction of the touch panel. More preferably not more than 230 mu m.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

The abbreviations of the compounds used in this embodiment are as follows.

TEOS: tetraethoxysilane

MPS:? -Mercaptopropyltrimethoxysilane

UPS:? - ureidopropyltriethoxysilane

ACPS: Acryloxypropyltrimethoxysilane

TIPT: Tetraisopropoxytitanium

AN: aluminum nitrate hydrate

EG: ethylene glycol

HG: 2-methyl-2,4-pentanediol (alias: hexylene glycol)

NMP: N-methyl-2-pyrrolidone

1,3BDO: 1,3-butanediol

BCS: 2-butoxyethanol (alias: butyl cellosolve)

EtOH: ethanol

&Lt; Synthesis Example 1 &

<A1>

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

&Lt; A2 liquid &

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

&Lt; Synthesis Example 2 &

&Lt; B1 liquid &

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

<B2 Liquid>

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

&Lt; Synthesis Example 3 &

<C1 liquid>

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

&Lt; C2 liquid &

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

&Lt; Synthesis Example 4 &

<D1 amount>

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

<D2 liquid>

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

&Lt; Synthesis Example 5 &

<E1 liquid>

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

<E2 liquid>

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

&Lt; Synthesis Example 6 &

<F1 sum>

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

<F2 liquid>

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

&Lt; Synthesis Example 7 &

<G1 liquid>

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

<G2 liquid>

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

[Surface tension]

And the solution temperature was measured at 25 캜 using AUTO DISPENCER AD-3 manufactured by Kyowa Interface Science Co.,

[Discharge test]

The jetting test was carried out using a jet dispenser application device Quspa-JET (manufactured by Shinwa Co., Ltd.). The discharge conditions are shown in Table 1 below.

[Dischargeability]

A case where the assumed liquid amount was stably discharged was rated &quot; Good &quot;, and a case where the estimated amount was less than the assumed liquid amount or not discharged at all was evaluated as &quot; x &quot;.

[Dot diameter]

The droplets were coated on alkali-free glass and then dried in a hot-air circulating oven at 80 DEG C for 5 minutes and then fired in a different hot-air circulating oven at 230 DEG C for 30 minutes. The diameter of the resulting coating was measured.

The obtained solutions K1 to K4 were respectively used in Examples 1 to 4 and the solutions K5 to K7 were used in Comparative Examples 1 to 3, and the above items were evaluated.

The obtained results are shown in Table 2.

From Table 2, it can be seen that in Examples 1 to 4, ejection properties were obtained and the Dot diameter could be controlled to be small.

In Comparative Example 1, since no specific organic solvent was contained, dischargeability was not obtained and the Dot diameter was not controlled.

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

In Comparative Example 3, although the surface tension was 28 mN / m or more, the dischargeability was obtained because the specific organic solvent was not contained in 30 mass% or more, but the Dot diameter could not be controlled.

Thereby, the solvent composition of the coating liquid for a metal oxide coating contains 30 mass% or more of a specific organic solvent and the surface tension is 28 mN / m, whereby the discharge property is obtained and a fine pattern can be coated I could.

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.

The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2012-221607 filed on October 3, 2012 are incorporated herein by reference and the disclosure of the specification of the present invention is hereby incorporated by reference.

Claims (13)

A process for producing an organic electroluminescent device, which comprises reacting a first metal alkoxide represented by the following general formula (I), a metal salt represented by the following general formula (II), an organic solvent, water and an precipitation inhibitor and reacting with ethylene glycol, propylene glycol, Butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, At least one member selected from the group consisting of 5-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and N-methylpyrrolidone is contained in an amount of 30 mass% or more in the total organic solvent, m &lt; 2 &gt; / m &lt; 2 &gt; / m &lt; 2 &gt; or more.
M ¹ (OR ¹ ) _n (I)
Wherein M ¹ represents at least one metal selected from the group consisting of silicon, titanium, tantalum, zirconium, boron, aluminum, magnesium and zinc, R ¹ represents an alkyl group having 1 to 5 carbon atoms or an acetoxy group and n represents an integer of 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, bismuth, lanthanum, tantalum, yttrium and cerium.) X is at least one metal selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, A residue of a carboxylic acid, a carboxylic acid, a sulfonic acid, acetoacetic acid or acetylacetonate, or a basic salt thereof, and k represents a valence of M ² . The method according to claim 1,
Further, a coating liquid for forming a metal oxide film containing a second metal alkoxide represented by the following general formula (III).
R ² ₁ M ³ (OR ³ ) _ml (III)
Wherein M ³ represents at least one metal selected from the group consisting of silicon, titanium, tantalum, zirconium, boron, aluminum, magnesium and zinc, R ² represents a hydrogen atom or a fluorine atom or a halogen atom, , A glycidoxy group, a mercapto group, a methacryloxy group, an acryloxy group, an isocyanate group, an amino group or a ureide group, and also a hydrocarbon group of 1 to 20 carbon atoms which may have a hetero atom. R ³ represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 2 to 5, 1 represents 1 or 2 when m is 3, and an integer of 1 to 3 when m is 4, Case is an integer from 1 to 4.) 3. The method of claim 2,
Wherein the content of the second metal alkoxide is 15 mol% or more based on the total metal alkoxide. 4. The method according to any one of claims 1 to 3,
Wherein the precipitation inhibitor is at least one selected from the group consisting of N-methyl-pyrrolidone, ethylene glycol, dimethylformamide, dimethylacetamide, diethylene glycol, propylene glycol, hexylene glycol and derivatives thereof Application liquid. 5. The method according to any one of claims 1 to 4,
Wherein the molar ratio of the number of moles of metal atoms (M ² ) of the metal salt to the total number of moles (M) of metal atoms of the metal alkoxide is 0.01 ≦ M ² / M ≦ 0.7. 6. The method according to any one of claims 1 to 5,
Wherein the first metal alkoxide is a mixture of a silicon alkoxide or a partial condensate thereof and a titanium alkoxide. 7. The method according to any one of claims 1 to 6,
Wherein the metal salt is a coating liquid for forming a metal oxide film which is a metal nitrate, a metal sulfate, a metal acetic acid salt, a metal chloride, a metal oxalate, a metal spanate, a metal sulfonate, a metal acetoacetate, a metal acetylacetonate or a basic salt thereof . 8. The method according to any one of claims 1 to 7,
Wherein the first metal alkoxide is a mixture of a silicon alkoxide or a partial condensate thereof and a titanium alkoxide, and the organic solvent contains an alkylene glycol or a monoether derivative thereof. A metal oxide film obtained by coating the coating solution for forming a metal oxide film according to any one of claims 1 to 8 with a fine droplet discharging device. A metal oxide film obtained by coating the coating liquid for forming a metal oxide film according to any one of claims 1 to 8 with a jet dispenser. A metal oxide film obtained by applying the coating liquid for forming a metal oxide film according to any one of claims 1 to 8 by means of a piezo system jet dispenser. 9. A method for forming a metal oxide film coating liquid according to any one of claims 1 to 8, wherein the electrode intersection micro-insulating layer is formed using a jet dispenser. 9. A method for forming a metal oxide film coating liquid according to any one of claims 1 to 8, wherein an electrode intersection micro-insulating layer is formed by using a piezo system jet dispenser.