KR102094049B1 - Method for producing coating solution for metal oxide coating, coating solution for metal oxide coating, and metal oxide coating - Google Patents

Abstract

A method for producing a coating solution for a metal oxide coating that does not involve a solvent replacement process, obtains sufficient hardness even at low-temperature firing, and has good printability and in-plane uniformity in the flexographic printing method, for the produced metal oxide coating A coating liquid and a metal oxide film are provided. The first metal alkoxide is hydrolyzed in the presence of a metal salt and an organic solvent to obtain a solution of the first process, and a second metal alkoxide having a lower reactivity than the first metal alkoxide in the solution of the first process. And a second step of adding, hydrolyzing and condensing to obtain a solution in the second step, and a third step of adding a precipitation inhibitor to the solution in the second step.

Description

METHOD FOR PRODUCING COATING SOLUTION FOR METAL OXIDE COATING, COATING SOLUTION FOR METAL OXIDE COATING, AND METAL OXIDE COATING}

The present invention relates to a coating solution for a metal oxide film and a method for manufacturing the same, and more specifically, to form a film having excellent mechanical strength and an arbitrary refractive index on a substrate such as glass, ceramic, metal, plastic, etc. Moreover, it is related with the coating liquid for metal oxide films which can obtain sufficient hardness also by low-temperature baking, and its manufacturing method.

Conventionally, it has been practiced to form inorganic coatings on various surfaces for substrates such as glass, ceramic, metal, and plastic. By forming the inorganic film on the surface of the substrate, it becomes possible to impart electrical properties, optical properties, chemical properties, mechanical properties, and the like to the substrate. Therefore, these inorganic films have been put into practical use as conductive films, insulating films, selective transmission or absorption of light, alkali elution prevention films, chemical resistant films, hard coat films, and the like.

As a method of forming such an inorganic film, vapor phase methods such as CVD (Chemical Vapor Deposition), PVD (Physical Vapor Deposition), sputtering, or a liquid phase method using an alkoxide compound or the like can be cited.

In general, vapor phase methods require expensive and large-scale devices such as vacuum deposition devices. In addition, there is also a problem that the size and shape of the substrate that can be formed are limited. On the other hand, a so-called sol-gel method is known as a liquid method using an alkoxide compound or the like. This method has the advantage of being capable of coping with patterning in the case of forming a film with a large-area coating or a flexographic printing method as a film forming method. For this reason, the inorganic coating by a liquid phase method is actively used as a coating film in an electronic device (for example, refer patent document 1). In the case of using the liquid phase method, particularly the flexographic printing method, in-plane uniformity of the coated film becomes important. In addition, the high refractive index component used in the sol-gel method has high reactivity, and it is common to form a complex with glycol, acetylacetone, etc. from the viewpoint of storage stability, and control the reactivity to perform polycondensation. However, when produced by the above method, in order to obtain sufficient hardness, 300 ° C or higher was required as the firing temperature.

In recent years, inorganic coatings have been used for new applications such as touch panels, and it has been required to fire at a temperature of 250 ° C. or lower from the influence on peripheral members and to obtain a high hardness of the resulting film. For example, at a firing temperature of 100 ° C, the pencil hardness is 3 H or more, and at 200 ° C, 7 H or more.

In the touch panel application, hardness is required not only from the viewpoint of device life, but also from the viewpoint of suppressing the increase in the defective rate due to scratches in the conveying process.

In order to obtain a film of sufficient hardness by low-temperature firing, a method of hydrolyzing a metal alkoxide with an alcohol-based solvent that does not involve complex formation with glycol or the like is known (for example, see Patent Document 2). However, in this method, there were problems such as difficulty in forming a film by the flexographic printing method.

Therefore, in order to obtain a film of sufficient hardness by low-temperature firing, and to obtain in-plane uniformity when applied by a flexographic printing method, after hydrolyzing and polycondensing the metal alkoxide with an alcohol-based solvent, the solvent is glycol, etc. A method of substituting with a desired solvent has been proposed (for example, see Patent Document 3). However, in this method, a solvent replacement process must be performed, and there is a problem that the manufacturing process becomes complicated.

From the above, it has been desired to achieve a high hardness coating at a low temperature without involving a solvent replacement step, and a film obtained by a flexographic printing method or the like having in-plane uniformity.

Japanese Patent Publication No. 2881847 Japanese Patent Publication No. Hei01-014258 WO 2007/020781 Publication

This invention is made | formed in view of such a point. That is, the object of the present invention is a method for producing a coating solution for a metal oxide coating having sufficient hardness and also having good printability and in-plane uniformity at low temperature firing, and for a metal oxide coating produced by the production method. It is to provide a coating liquid and a metal oxide film.

The present inventor has found that the above object can be achieved as a result of extensive research conducted in order to achieve the above object.

In this way, this invention makes the following a summary.

1. The first metal alkoxide is hydrolyzed in the presence of a metal salt and an organic solvent to obtain a solution in the first process, and a second metal in which the solution in the first process is less reactive than the first metal alkoxide A second step of adding alkoxide, hydrolyzing and condensing to obtain a solution in the first step, and a third step of adding a precipitation inhibitor to the solution in the second step, to prepare a coating solution for a metal oxide coating. Way.

2. The manufacturing method of the coating liquid for metal oxide films of said 1 whose 1st metal alkoxide is a metal alkoxide represented by following formula (I).

(Equation 1)

M ¹ (OR ¹ ) _n (Ⅰ)

In formula (I), M ¹ is composed of titanium (Ti), tantalum (Ta), zirconium (Zr), boron (B), tin (Sn), indium (In), bismuth (Bi), and niobium (Nb) It is at least one species selected from the group. R ¹ is an alkyl group having 1 to 5 carbon atoms, and n is a valence 2 to 5 of M ¹ .

3. The manufacturing method of the coating liquid for metal oxide films as described in said 1 or 2 in which the organic solvent in 1st process is a solvent represented by following formula (T1), (T2), or (T3).

[Formula 1]

(In the formula, X ₁ , X ₃ , X ₅ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X ₂ , X ₄ and X ₆ are an alkyl group or phenyl group having 1 to 4 carbon atoms, and P is a hydrogen atom or carbon number. 1 to 3 alkyl groups, m, n are each independently an integer of 1 to 3, l, j, k, h, i are each independently an integer of 2 to 3)

4. The coating solution for metal oxide coating according to any one of 1 to 3, wherein the metal salt in the first step is a metal salt represented by the following formula (II) or a metal oxalate used in the following formula (II): Manufacturing method.

M ³ (X) _k (II)

(In formula (II), M ³ is aluminum (Al), indium (In), zinc (Zn), zirconium (Zr), bismuth (Bi), lanthanum (La), tantalum (Ta), yttrium (Y) And cerium (Ce), X is chlorine, nitric acid, sulfuric acid, acetic acid, sulfamic acid, sulfonic acid, acetoacetic acid, acetylacetonate or a basic salt thereof, k is M ³ Is a singer)

5. The manufacturing method of the coating liquid for metal oxide films in any one of said 1-4 whose 2nd metal alkoxide in a 2nd process is a metal alkoxide represented by the following general formula (III) or (IV).

(Equation 3)

M ² (OR ¹ ) _n (Ⅲ)

In Formula (III), M ² is at least one member selected from the group consisting of silicon (Si), magnesium (Mg), and zinc (Zn). R ¹ is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 2 to 5 carbon atoms.

(Equation 4)

R ² _l M ² (OR ³ ) _m-1 (IV)

In Formula (IV), M ² is at least one member selected from the group consisting of silicon (Si), magnesium (Mg), and zinc (Zn). R ² may be substituted with a hydrogen atom or a fluorine atom, and may also be substituted with a halogen atom, vinyl group, glycidoxy group, mercapto group, methacryloxy group, acryloxy group, isocyanate group, amino group or ureido group. Moreover, it is a C1-C20 hydrocarbon group which may have a hetero atom. R ³ is an alkyl group having 1 to 5 carbon atoms. m is an integer of 2-5. l is 1 or 2 when m is 3, 1 to 3 when m is 4, and 1 to 4 when m is 5;

6. The precipitation preventing agent in the third step is selected from the group consisting of N-methyl-pyrrolidone, ethylene glycol, dimethylformamide, dimethylacetamide, diethylene glycol, propylene glycol, hexylene glycol, and derivatives thereof. The manufacturing method of the coating liquid for metal oxide films in any one of said 1-5 which is at least 1 sort which is used.

7. The coating liquid for metal oxide coatings manufactured using the manufacturing method in any one of said 1-6.

8. The coating liquid for metal oxide coatings for flexographic printing according to 7 above, wherein the viscosity of the coating liquid is 8 to 80 mPa · s.

9. Metal oxide film obtained using the coating liquid for metal oxide films described in 7 or 8 above.

10. The metal oxide film obtained by baking the coating film of the coating liquid for metal oxide films described in 7 or 8 at a temperature of 100 to 250 ° C.

11. An electronic device comprising the metal oxide coating according to 9 or 10 above.

According to the manufacturing method of the present invention, it becomes possible to stably and efficiently obtain a coating solution for a metal oxide film. In addition, the coating solution for a metal oxide film produced by the production method of the present invention can obtain a metal oxide film having a sufficient hardness even in a baking process at a low temperature.

Although it is not always clear as to what reason the coating liquid from which such a metal oxide film can be produced by the manufacturing method of the present invention, the following are generally considered.

In the conventional manufacturing method, the metal component and the solvent component form a complex having low reactivity, and thus a film having sufficient hardness cannot be produced. On the other hand, in the production method of the present invention, it is considered that such a complex is not formed and the metal component reacts sufficiently, so that a film having a high hardness can be obtained even at a low temperature.

The method for producing a coating solution for coating a metal oxide according to the present invention, after the first metal alkoxide having high reactivity is hydrolyzed in the presence of a metal salt and a specific organic solvent 1, the second reactivity is lower than that of the first metal alkoxide Metal alkoxide is added to perform hydrolysis and polycondensation, and finally, a specific solvent 2 and a precipitation inhibitor are added.

Moreover, the coating liquid for metal oxide coatings of this invention is the coating liquid for metal oxide coatings produced by the said method.

<First process>

In the method for producing a coating solution for a metal oxide film of the present invention, first, a highly reactive first metal alkoxide is hydrolyzed and polycondensed in the presence of a metal salt and an organic solvent.

The first metal alkoxide contains at least one selected from metal alkoxides represented by the following formula (I).

(Equation 5)

M ¹ (OR ¹ ) _n (Ⅰ)

In formula (I), M ¹ is composed of titanium (Ti), tantalum (Ta), zirconium (Zr), boron (B), tin (Sn), indium (In), bismuth (Bi), and niobium (Nb) It is at least one species selected from the group. R ¹ is an alkyl group having 1 to 5 carbon atoms, preferably 2 to 4 carbon atoms, and n is an integer of 2 to 5 carbon atoms.

Moreover, when using a titanium alkoxide as a metal alkoxide represented by Formula (I), the mixture containing at least 1 type of compound represented by following formula (VIII) is used.

(Equation 7)

Ti (OR ") ₄ (Ｖ)

In formula (VII), R "is an alkyl group having 1 to 5 carbon atoms, preferably 2 to 4 carbon atoms.

More specifically, titanium tetraalkoxide compounds such as titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, or partial condensates such as titanium tetra-n-butoxide tetramer are used as titanium alkoxides. .

In addition, examples of the metal alkoxide represented by formula (I) include zirconium tetraalkoxide compounds such as zirconium tetraethoxide, zirconium tetrapropoxide, and zirconium tetrabutoxide, aluminum tributoxide, aluminum triisopropoxide, And aluminum trialkoxide compounds such as aluminum triethoxide, and tantalum pentaalkoxide compounds such as tantalum pentapropoxide and tantalum pentabutoxide.

As the metal salt, it is possible to use a metal salt represented by the following formula (II) or a metal oxalate used in the following formula (II).

(Equation 8)

M ³ (X) _k (II)

In formula (II), M ³ is a metal. As M ³ , aluminum (Al), indium (In), zinc (Zn), zirconium (Zr), bismuth (Bi), lanthanum (La), tantalum (Ta), yttrium (Y) or cerium (Ce), etc. And metals. X is chlorine, nitric acid, sulfuric acid, acetic acid, sulfamic acid, sulfonic acid, acetoacetic acid, acetylacetonate or basic salts thereof. k is a singer of M ³ .

Among the above compounds, metal nitrate, metal chloride salt, metal oxalate or a basic salt thereof is particularly preferable. Among them, nitrate of aluminum, indium or cerium is more preferable from the viewpoint of availability and storage stability of the coating composition.

As said specific organic solvent 1, the solvent represented by following formula (T1), (T2), or (T3) is contained.

[Formula 2]

(Wherein, X ₁ , X ₃ , X ₅ is a hydrogen atom or a C 1-4 alkyl group or a phenyl group, X ₂ , X ₄ , X ₆ is a C 1-4 alkyl group or a phenyl group, P is a hydrogen atom or It is a C1-C3 alkyl group, m and n are each independently an integer of 1-3, and l, j, k, h, and i are each independently an integer of 2-3.)

Examples of the formula (T1) include 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol di And ethyl ether, propylene glycol dipropyl ether, or propylene glycol dibutyl ether.

Examples of the formula (T2), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, di And propylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, or dipropylene glycol dibutyl ether.

Examples of the formula (T3), triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monophenyl ether, triethylene glycol dimethyl ether, And triethylene glycol diethyl ether, triethylene glycol dipropyl ether, and triethylene glycol dibutyl ether.

In addition, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and t-butanol, esters such as ethyl acetate, or aromatic hydrocarbons such as benzene and toluene. The organic solvent 1 may be mixed and reacted with at least one or more. The content of the other solvent is preferably about 1 to 90%, more preferably 10 to 80%.

As a reaction temperature of the hydrolysis and polycondensation in the first step, from the viewpoint of storage stability in the final solution, 0 to 50 ° C is preferable, and 5 to 40 ° C is more preferable. As reaction time, from a viewpoint of storage stability in a final solution, 5 minutes-5 hours are preferable, and 15 minutes-2 hours are more preferable.

<Second process>

In the second step, a second metal alkoxide having low reactivity is added to the solution obtained in the first step, followed by stirring.

The second metal alkoxide contains a metal alkoxide represented by the following general formula (III) or general formula (IV).

(Eq. 9)

M ² (OR ¹ ) _n (Ⅲ)

In formula (III), M ² is silicon (Si), magnesium (Mg) or zinc (Zn). R ¹ is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 2 to 5 carbon atoms.

(Equation 10)

R ² _l M ² (OR ³ ) _m-1 (IV)

In Formula (IV), M ² represents silicon (Si), magnesium (Mg), or zinc (Zn). R ² may be substituted with a hydrogen atom or a fluorine atom, and may also be substituted with a halogen atom, vinyl group, glycidoxy group, mercapto group, methacryloxy group, acryloxy group, isocyanate group, amino group or ureido group. Moreover, it is a C1-C20 hydrocarbon group which may have a hetero atom. R ³ is an alkyl group having 1 to 5 carbon atoms. m is an integer of 2-5. l is 1 or 2 when m is 3, 1 to 3 when m is 4, and 1 to 4 when m is 5;

When a silicon alkoxide or a partial condensate thereof is used as the metal alkoxide represented by formula (III), a mixture or a partial condensate (preferably not more than pentamer) containing at least one compound represented by the following formula (VI) Is used.

(Equation 11)

Si (OR ') ₄ (VI)

In formula (VI), R 'is a C1-C5 alkyl group or an acetyl group.

More specifically, tetraalkoxysilanes, such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and tetraacetoxysilane, etc. are used as a silicon alkoxide.

As a metal alkoxide represented by general formula (VI), the following compounds are mentioned, for example.

For example, methyltrimethoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripentoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxy Silane, methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β -Glycidoxyethyl trimethoxysilane, β-glycidoxyethyl triethoxysilane, α-glycidoxypropyl trimethoxysilane, α-glycidoxypropyl triethoxysilane, β-glycidoxypropyltri Methoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ- Glycidoxypropyl tributoxysilane, γ-glycidoxypropyl Triphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ -Glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3, 4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- ( 3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxy cycle Hexyl) butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β- Glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane Methoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ- Glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyl Dimethoxysilane, γ-glycidoxypropyl ratio Nildiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetyl Methoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, β-cyanoethyl Triethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, N- (β-aminoethyl) γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) γ-aminopropylmethyldime Methoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) γ-aminopropyltriethoxysilane, N- (β-aminoethyl) γ-aminopropylmethyldiethoxysilane, dimethyldimethoxysilane , Phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane Silane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ- Mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripro Foxysilane, (R) -N-1-phenylethyl-N'-triethoxysilylpropylurea, (R) -N-1-phenylethyl-N'-trimethoxysilylpropylurea, allyltriethoxysilane , 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-isocyanatepropyltriethoxysilane Silane, trifluoropropyl trimethoxysilane, bromopropyl Liethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, p-styryltrimethoxysilane, p-sty And reel triethoxysilane, p-styryl tripropoxysilane, and methyl vinyl diethoxysilane. These may be used alone or in combination of two or more.

As a reaction temperature of the hydrolysis and polycondensation in the second step, from the viewpoint of storage stability in the final solution, 0 to 50 ° C is preferable, and 5 to 40 ° C is more preferable.

As reaction time, from a viewpoint of storage stability in a final solution, 5 minutes-5 hours are preferable, and 15 minutes-2 hours are more preferable.

<The third process>

In the third step, a precipitation inhibitor is added to the solution obtained in the second step.

The precipitation preventing agent contained in the coating liquid for metal oxide coatings of the present invention prevents metal salts from depositing in the coating film when forming the coating film. Examples of the precipitation inhibitor include N-methyl-pyrrolidone, dimethylformamide, dimethylacetamide, ethylene glycol, diethylene glycol, propylene glycol or hexylene glycol, or derivatives thereof. One or more of these can be used.

The precipitation inhibitor converts the metal of the metal salt into a metal oxide, and the ratio (weight ratio) of (prevention agent) / (metal oxide) is preferably 1 or more. When the ratio is less than 1, the effect of preventing the precipitation of metal salts at the time of forming the coated film becomes small. On the other hand, the use of a large amount of the precipitation preventing agent does not affect the coating composition, but since it inhibits the in-plane uniformity when applied, the ratio is more preferably 200 or less.

A metal alkoxide, especially silicon alkoxide, titanium alkoxide, or silicon alkoxide and titanium alkoxide may be added to the precipitation inhibitor during hydrolysis and polycondensation reaction in the presence of a metal salt, and after completion of the hydrolysis and polycondensation reaction It may be added.

Among the precipitation inhibitors, N-methyl-pyrrolidone, or ethylene glycol, propylene glycol, hexylene glycol, diethylene glycol, or monomethyl, monoethyl, monopropyl, monobutyl, or monophenyl ether thereof is more preferable. .

Moreover, as specific solvent 2 added in a 3rd process, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, hexylene glycol (2-methyl- Glycols such as 2,4-pentanediol), 1,6-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, or diketones such as acetylacetone and 2,4-hexanedione. , These can be used at least 1 type.

Among them, from the viewpoint of in-plane uniformity when forming a film, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, hexylene glycol (2-methyl- Glycols, such as 2,4-pentanediol), 1,6-hexanediol, diethylene glycol, dipropylene glycol, or triethylene glycol are preferable.

Moreover, since ethylene glycol, propylene glycol, hexylene glycol, and diethylene glycol exemplified as the precipitation preventing agent can also be used as a specific solvent 2, when they are used as a precipitation preventing agent, specific organic solvent 2 is separately added. There is no need to use it.

The content ratio of the metal atom (M ¹ and M ² ) of the metal alkoxide and the metal atom (M ³ ) of the metal salt contained in the coating solution for metal oxide coating is in terms of molar ratio,

0.01 ≤ M ³ / (M ¹ + M ² + M ³ ) ≤ 0.7

It is desirable to satisfy the relationship. If this ratio is less than 0.01, it is not preferable because the mechanical strength of the resulting coating is not sufficient. On the other hand, when it exceeds 0.7, the adhesion of the coat film to a substrate such as a glass substrate or a transparent electrode decreases. The ratio is more preferably 0.01 to 0.6.

<Other ingredients>

In the coating solution for forming a metal oxide film of the present invention, as long as the effects of the present invention are not inhibited, other components other than the above-mentioned components, for example, inorganic fine particles, metallox oligomers, metalloxane polymers, leveling Ingredients, such as a surfactant and surfactant, 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 colloidal solutions of these inorganic fine particles are particularly preferable. The colloidal solution may be one in which inorganic fine particles are dispersed in a dispersion medium, or a commercially available colloidal solution.

In the present invention, it is possible to impart the surface shape and other functions of the formed cured film by containing the inorganic fine particles. As the inorganic fine particles, the average particle diameter is preferably 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 decrease.

Water and an organic solvent are mentioned as a dispersion medium of an inorganic fine particle. As a colloidal solution, it is preferable that pH or pKa is adjusted to 1-10 from a viewpoint of the stability of the coating liquid for film formation, More preferably, it is 2-7.

Examples of the organic solvent used as a dispersion medium for a colloidal solution include methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, 2-methyl-2,4-pentanediol, diethylene glycol, dipropylene 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 γ-butyrolactone; Or ethers, such as tetrahydrofuran and 1,4-dioxane, are mentioned. Of these, alcohols and ketones are preferred. These organic solvents can be used alone or as a dispersion medium by mixing two or more.

About the solid content concentration in the coating liquid for metal oxide coating, when a metal alkoxide and a metal salt are converted into a metal oxide, it is preferable that it is the range of 0.5 wt%-20 wt% as solid content. When the solid content exceeds 20 wt%, the storage stability of the coating solution for metal oxide coating deteriorates, and it becomes difficult to control the film thickness of the coating film. On the other hand, when the solid content is less than 0.5 wt%, the thickness of the resulting coat film becomes thin, and multiple coatings are required to obtain a predetermined film thickness.

The amount of water used for the hydrolysis of the metal alkoxide is preferably 2 to 24 in terms of molar ratio, and more preferably 2 to 20 in terms of the total number of moles of the metal alkoxide. When the molar ratio (amount of water (molar) / (total number of moles of metal alkoxide)) is 2 or less, hydrolysis of the metal alkoxide is insufficient, thereby reducing the film-forming properties or decreasing the strength of the resulting metal oxide film. Do not. Moreover, when the molar ratio is more than 24, since polycondensation continues to progress, storage stability is lowered, which is not preferable.

Further, for example, when silicon alkoxide, titanium alkoxide, or silicon alkoxide and titanium alkoxide are used as the metal alkoxide, the amount of water used for their hydrolysis is, in the same way, silicon alkoxide, titanium alkoxide, or silicon alkoxide and titanium It is preferable to make it more than 2 in terms of molar ratio with respect to the total number of moles of the alkoxide.

In the hydrolysis process when preparing the coating solution for metal oxide coating, when the coexisting metal salt is a hydrous salt, the water content used for hydrolysis is related to the water content of the hydrolyzed water. It is necessary to consider the water content of the metal salt. For example, when the coexisting metal salt is an aluminum salt, and the aluminum salt is a hydrous salt, it is necessary to consider the water content of the aluminum salt with respect to the amount of water used for hydrolysis because the water content is involved in the reaction.

The coating liquid for a metal oxide film described above can be formed into a coating film by applying a generally applied coating method, and thereafter it can be used as a metal oxide film. As the coating method, for example, a dip coating method, a spin coating method, a spray coating method, a brush coating method, a roll transfer method, a screen printing method, an inkjet method or a flexo printing method is used. Among them, the inkjet method and the flexo printing method preferred for pattern printing are particularly preferred.

Among them, in the case of forming a film by flexographic printing, in order to obtain in-plane uniformity when forming a film, the viscosity range is generally 8 to 80 mPa · s, more preferably 9 to 70 mPa · s, More preferably, it is 9-60 mPa * s.

In order to obtain a desired viscosity range, glycols such as butanediol, pentanediol, dipropylene glycol, or triethylene glycol, alkyl alcohols having 6 or more carbons, etc. may be added to the coating liquid obtained up to the third step.

Moreover, as another film forming method, the viscosity range in the case of using the spin coat method, for example, is preferably 1 to 40 mPa · s, and when using the dip coat method, 1 to 10 mPa · s is preferable. When the inkjet method is used, 1.8 to 18 mPa · s is preferable.

When using these coating methods, the coating liquid in the flexographic printing method may be diluted with alcohols, glycol ethers, glycol ether acetates or ketones to a desired viscosity range.

<Metal oxide film>

When a metal oxide film is produced by firing a coating film of a coating solution for a metal oxide film, the refractive index of the metal oxide film varies depending on the firing temperature. In this case, the higher the firing temperature, the higher the refractive index of the metal oxide film. Therefore, it is possible to adjust the refractive index of the metal oxide film obtained by selecting the firing temperature at an appropriate value. Specifically, in consideration of the heat resistance of other touch panel components, the firing temperature is preferably in the range of 100 ° C to 300 ° C, more preferably in the range of 150 ° C to 250 ° C.

Moreover, when irradiating ultraviolet rays (UV) to the coating film before firing, since the polycondensation reaction is promoted, sufficient hardness is likely to be obtained. In the coating film, when the desired hardness can be achieved by selecting conditions such as composition, ultraviolet irradiation need not be performed.

When ultraviolet irradiation is required to obtain a desired hardness, a high pressure mercury lamp can be used, for example. When a high-pressure mercury lamp is used, an irradiation amount of 1000 mJ / cm 2 or more in total light irradiation is preferable in terms of 365 nm, and an irradiation amount of 3000 mJ / cm 2 to 10000 mJ / cm 2 is more preferable. Further, there is no particular designation for the UV light source, and other UV light sources may be used. In the case of using another light source, it is sufficient to irradiate the same amount of accumulated light amount as when using the high-pressure mercury lamp.

The metal oxide film produced as described above can be widely used as a sensor protective film or insulating film in various electronic devices such as touch panels, liquid crystal display elements, and electronic paper.

Example

Hereinafter, the present invention will be described in more detail by examples, but is not limited to these.

The abbreviations in the compounds used in this example are as follows.

TEOS: Tetraethoxysilane

UPS: γ-ureidopropyl triethoxysilane

MPMS: Methacrylic oxypropyl trimethoxysilane

MTES: methyltriethoxysilane

TTE: Tetraethoxy titanium

TIPT: Tetraisopropoxytitanium

AN: Aluminum nitrate hexahydrate

EG: ethylene glycol

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

BCS: 2-butoxyethanol (alias: butyl cellosolve)

PGME: Propylene glycol monomethyl ether

EtOH: ethanol

InN: Indium nitrate trihydrate

ZTB: zirconium tetra-n-butoxide

<Synthesis Example 1>

In a 300 ml flask, 11.9 g of AN and 2.8 g of water were added and stirred, and the AN was dissolved. There, 25.8 g of BCS and 12.4 g of TTE were added and stirred at room temperature for 30 minutes. Then, 14.7 g of TEOS and 7.5 g of MPMS were added, and the mixture was further stirred at room temperature for 30 minutes. HG 120.5 g and BCS 4.4 g were mixed with this solution to obtain a solution (K1).

<Synthesis Example 2>

In a 300 ml flask, 11.9 g of AN and 2.8 g of water were added and stirred, and the AN was dissolved. There, 28.2 g of BCS and 12.4 g of TTE were added and stirred at room temperature for 30 minutes. Thereafter, 12.6 g of TEOS and 7.2 g of MTES were added, and the mixture was further stirred at room temperature for 30 minutes. 122.5 g of HG and 2.4 g of BCS were mixed with this solution to obtain a solution (K2).

<Synthesis Example 3>

In a 300 ml flask, 11.9 g of AN and 2.8 g of water were added and stirred, and the AN was dissolved. There, 25.9 g of BCS and 12.4 g of TTE were added and stirred at room temperature for 30 minutes. Thereafter, 15.7 g of TEOS, 5.0 g of MPMS, and 1.3 g of UPS were added, followed by stirring at room temperature for 30 minutes. 120.7 g of HG and 4.3 g of BCS were mixed with this solution to obtain a solution (K3).

<Synthesis Example 4>

In a 300 ml flask, 11.9 g of AN and 2.8 g of water were added and stirred, and the AN was dissolved. There, 25.8 g of PGME and 12.4 g of TTE were added and stirred at room temperature for 30 minutes. Then, 14.7 g of TEOS and 7.5 g of MPMS were added, and the mixture was further stirred at room temperature for 30 minutes. HG 120.5 g and PGME 4.4 g were mixed with this solution to obtain a solution (K4).

<Synthesis Example 5>

In a 300 ml flask, 11.9 g of AN and 2.8 g of water were added and stirred, and the AN was dissolved. There, 26.8 g of BCS and 12.4 g of TTE were added and stirred at room temperature for 30 minutes. Thereafter, 21.0 g of TEOS was added, and the mixture was further stirred at room temperature for 30 minutes. 121.6 g of HG and 3.5 g of BCS were mixed with this solution to obtain a solution (K5).

<Synthesis Example 6>

<A1 liquid>

In a 200 ml flask, 11.9 g of AN and 2.8 g of water were added and stirred, and the AN was dissolved. There, 13.6 g of EG, 38.8 g of HG, 37.0 g of BCS, 14.7 g of TEOS, and 7.5 g of MPMS were added and stirred at room temperature for 30 minutes.

<A2 liquid>

In a 300 ml flask, 15.4 g of TIPT and 58.3 g of HG were added and stirred at room temperature for 30 minutes.

<A1 liquid> and <A2 liquid> were mixed and stirred at room temperature for 30 minutes to obtain a solution (K6).

<Synthesis Example 7>

In a 300 ml flask, 3.4 g of AN, 3.1 g of water, and 75.1 g of EtOH were added and stirred, and the AN was dissolved. To this solution, 16.3 g of TEOS and 8.33 g of MPMS were added and stirred at room temperature for 30 minutes. Thereafter, 13.8 g of TTE was added, and the mixture was stirred for 30 minutes at room temperature.

To this solution, 124.1 g of HG and 31.0 g of BCS were added, and the solvent was distilled off under reduced pressure at 60 ° C to 80 mmHg (10.7 ㎪) at 60 ° C by a rotary vacuum evaporator (N-1000S-WD manufactured by Tokyo Ewha Machine Co., Ltd.). Removed to obtain 200 g of solution (K7).

<Synthesis Example 8>

In a 300 ml flask, 11.9 g of AN and 2.8 g of water were added and stirred, and the AN was dissolved. There, 120.6 g of HG, 30.2 g of BCS, 14.7 g of TEOS, and 7.5 g of MPMS were added and stirred at room temperature for 30 minutes. Thereafter, 12.4 g of TTE was added, and further stirred at room temperature for 30 minutes to obtain a solution (K8).

<Synthesis Example 9>

<B1 liquid>

In a 200 ml flask, 11.9 g of AN and 2.8 g of water were added and stirred, and the AN was dissolved. There, 13.7 g of EG, 39.2 g of HG, 37.2 g of BCS, and 21.0 g of TEOS were added and stirred at room temperature for 30 minutes.

<B2 liquid>

In a 300 ml flask, 15.4 g of TIPT and 58.8 g of HG were added and stirred at room temperature for 30 minutes.

<B1 liquid> and <B2 liquid> were mixed, and stirred at room temperature for 30 minutes to obtain a solution (K9).

<Synthesis Example 10>

In a 300 ml flask, 3.4 g of AN, 3.1 g of water, and 76.4 g of EtOH were added and stirred, and the AN was dissolved. 23.3 g of TEOS was added to this solution, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 13.8 g of TTE was added, and the mixture was stirred for 30 minutes at room temperature.

80.0 g of EtOH was added to the solution obtained in Synthesis Example 10 to obtain a solution (K10).

Similarly, to the solution obtained in Synthesis Example 10, 125.1 g of HG and 31.3 g of BCS were added, and 80 mmHg (10.7 mm 2) at 60 ° C. by a rotary vacuum evaporator (N-1000S-WD manufactured by Tokyo Ewha Machine Co., Ltd.). ), The solvent was distilled off under reduced pressure until 200 g of a solution (K11) was obtained.

<Synthesis Example 11>

In a 300 ml flask, 10.7 g of AN and 2.5 g of water were added and stirred, and the AN was dissolved. To this, 39.6 g of BCS and 25.3 g of TTE were added and stirred at room temperature for 30 minutes. Thereafter, 2.9 g of TEOS and 3.4 g of MPMS were added, and the mixture was further stirred at room temperature for 30 minutes. HG 124.1 g and BCS 7.0 g were mixed with this solution to obtain a solution (K12).

<Synthesis Example 12>

In a 300 ml flask, 12.7 g of AN and 3.0 g of water were added and stirred, and the AN was dissolved. There, 25.1 g of BCS and 3.8 g of TTE were added and stirred at room temperature for 30 minutes. Thereafter, 21.7 g of TEOS and 11.1 g of MPMS were added, and the mixture was further stirred at room temperature for 30 minutes. HG 118.2 g and BCS 4.4 g were mixed with this solution to obtain a solution (K13).

<Synthesis Example 13>

In a 300 ml flask, 3.4 g of AN and 3.1 g of water were added and stirred, and the AN was dissolved. There, 26.4 g of BCS and 13.8 g of TTE were added and stirred at room temperature for 30 minutes. Thereafter, 16.3 g of TEOS and 8.3 g of MPMS were added, and further stirred at room temperature for 30 minutes. 124.1 g of HG and 4.7 g of BCS were mixed with this solution to obtain a solution (K14).

<Synthesis Example 14>

In a 300 ml flask, 9.3 g of InN and 2.3 g of water were added and stirred, and AN was dissolved. There, 27.1 g of BCS and 10.3 g of TTE were added and stirred at room temperature for 30 minutes. Thereafter, 12.2 g of TEOS and 6.2 g of MPMS were added, and the mixture was further stirred at room temperature for 30 minutes. 127.8 g of HG and 4.8 g of BCS were mixed with this solution to obtain a solution (K15).

<Synthesis Example 15>

In a 300 ml flask, 9.6 g of AN and 2.3 g of water were added and stirred, and the AN was dissolved. 38.8 g of BCS and 19.2 g of ZTB were added thereto, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 11.0 g of TEOS and 5.6 g of MPMS were added, and the mixture was further stirred at room temperature for 30 minutes. 106.6 g of HG and 6.9 g of BCS were mixed with this solution to obtain a solution (K16).

<Production method Ⅰ>

The solution prepared in Synthesis Example was pressure-filtered with a membrane filter having a pore diameter of 0.5 µm, and deposited on a glass substrate on which ITO (Indium-Tin-Oxide) was formed by spin coating. The substrate was dried on a hot plate at 60 ° C for 3 minutes, and then fired in a hot air circulation oven at 180 ° C for 30 minutes to form a metal oxide film.

<Production method Ⅱ>

The solution prepared in the above Synthesis Example was pressure-filtered with a membrane filter having a pore diameter of 0.5 µm, and deposited on a glass substrate on which ITO was formed by spin coating. After drying this substrate for 3 minutes on a hot plate at 60 ° C., 50 mW / cm 2 (wavelength 365 nm) using an ultraviolet irradiation device (manufactured by iGraphics, UB011-3A type) and a high pressure mercury lamp (input power 1000 W). (Converted) for 2 minutes (accumulated 6000 mJ / cm 2), and baked in a hot air circulation oven at 230 ° C. for 30 minutes to form a film.

The metal oxide films (KL1 to KL5) obtained by forming the solutions K1 to K5 into the film forming methods I or II were used as Examples 1 to 5.

The metal oxide films (KM1 to KM6) obtained by forming the solutions K6 to K11 into the above film forming methods I or II were used as Comparative Examples 1 to 6.

The metal oxide films (KL6 to KL10) obtained by forming the solutions K12 to K16 into the film forming method I or II were used as Examples 6 to 10.

〔Pencil hardness〕

A metal oxide film was formed by the above-mentioned film forming method I or film forming method II using a transparent conductive film substrate for the substrate. The obtained film was measured according to the test method JIS K 5400.

〔Printability〕

The coating solution for film formation of the example and the coating solution of the comparative example were pressure-filtered with a membrane filter having a pore diameter of 0.5 µm, and thereafter, an S-15 type printing machine (manufactured by Inuma Gauge, Anilox roll (300 mm 3), convex plate) A coating film was formed on a glass substrate on which ITO was formed (thickness of the substrate was 0.7 mm) by using (net point 400 L 30% 70 °). This coating film was dried on a hot plate at a temperature of 60 ° C. for 3 minutes to obtain a cured film. The obtained cured film was observed with the naked eye, and a good case in which the cured film was free of pinholes and stains was ○, where pinholes and stains were generated, or cratering was generated to form a state where the film was not sufficiently formed on the substrate.

Table 1 shows the pencil hardness of the obtained film.

It was found that Examples 1 to 5 had good printability and high hardness even without a solvent distillation removal step. In Comparative Examples 1, 3 and 4, sufficient hardness was not obtained, and in Comparative Examples 2 and 5, sufficient hardness was obtained, but a solvent distillation removal process was required for Comparative Example 2, and Comparative Example 5 was flexo. In printing, application was difficult.

Specifically, for example, when Example 1 is compared with Comparative Example 2, Comparative Example 5 and Comparative Example 6, the hardness is equivalent. However, since Comparative Example 2 and Comparative Example 6 require a solvent distillation removal process, the process becomes complicated.

In addition, when Example 5 and Comparative Example 5 were compared, the hardness was better in Comparative Example. However, in Comparative Example 5, film formation in flexographic printing was difficult, and even when applied by spin coating, strong striation was generated compared to other solutions.

From the above, it was found that, in order to satisfy all of the characteristics of fairness, printability, and hardness, only Examples 1 to 10 obtained using the production method were used.

In addition, when the device obtained by using the films obtained in Examples 1 to 10 as, for example, an electrode protective film for a touch panel, an element is produced, defects occurring in the process can be reduced, and pattern printing is also performed in flexographic printing. By carrying out, improvement in productivity is expected. Moreover, since a film baked at a low temperature and having a high hardness can be obtained, a touch panel element having good reliability can be obtained.

Industrial availability

When the coating solution for metal oxide coating obtained in the production method of the present invention is used, mechanical strength is excellent on substrates such as glass, ceramics, metals, plastics, etc., it has an arbitrary refractive index and sufficient hardness even at a low-temperature firing process. It becomes possible to manufacture a metal oxide film having a. Moreover, the metal oxide film obtained by coating the coating liquid is useful as a sensor protective film or an insulating film among various electronic devices such as touch panels, liquid crystal display elements, and electronic paper.

In addition, the entire content of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2011-239371, filed on October 31, 2011, is cited herein, and accepted as the disclosure of the present invention.

Claims (11)

The first metal alkoxide is hydrolyzed in the presence of a metal salt and an organic solvent to obtain a solution of the first process, and a second metal alkoxide having a lower reactivity than the first metal alkoxide in the solution of the first process. A method for producing a coating solution for a metal oxide coating, comprising a second step of adding, hydrolyzing and condensing to obtain a solution in the second step, and a third step of adding a precipitation inhibitor to the solution in the second step. ,
The organic solvent in the first step is a solvent represented by the following formulas (T1), (T2) or (T3),
[Formula 1]

(In the formula, X ₁ , X ₃ , X ₅ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X ₂ , X ₄ and X ₆ are an alkyl group or phenyl group having 1 to 4 carbon atoms, and P is a hydrogen atom or carbon number. 1 to 3 alkyl groups, m, n are each independently an integer of 1 to 3, l, j, k, h, i are each independently an integer of 2 to 3)
The precipitation inhibitor in the third step is at least selected from the group consisting of N-methyl-pyrrolidone, ethylene glycol, dimethylformamide, dimethylacetamide, diethylene glycol, propylene glycol, hexylene glycol, and derivatives thereof. The manufacturing method of the coating liquid for 1 type metal oxide film. According to claim 1,
The manufacturing method of the coating liquid for metal oxide films in which a 1st metal alkoxide is a metal alkoxide represented by following formula (I).
(Equation 1)
M ¹ (OR ¹ ) _n (Ⅰ)
In formula (I), M ¹ is composed of titanium (Ti), tantalum (Ta), zirconium (Zr), boron (B), tin (Sn), indium (In), bismuth (Bi), and niobium (Nb) It is at least one species selected from the group. R ¹ is an alkyl group having 1 to 5 carbon atoms, and n is a valence 2 to 5 of M ¹ . delete According to claim 1,
The manufacturing method of the coating liquid for metal oxide films in which the metal salt in 1st process is a metal salt represented by following formula (II) or a metal oxalate used in following formula (II).
M ³ (X) _k (II)
(In formula (II), M ³ is aluminum (Al), indium (In), zinc (Zn), zirconium (Zr), bismuth (Bi), lanthanum (La), tantalum (Ta), yttrium (Y) And cerium (Ce), X is chlorine, nitric acid, sulfuric acid, acetic acid, sulfamic acid, sulfonic acid, acetoacetic acid, acetylacetonate or a basic salt thereof, k is M ³ Is a singer) According to claim 1,
The manufacturing method of the coating liquid for metal oxide films in which the 2nd metal alkoxide in 2nd process is a metal alkoxide represented by following formula (III) or (IV).
M ² (OR ¹ ) _n (Ⅲ)
In Formula (III), M ² is at least one member selected from the group consisting of silicon (Si), magnesium (Mg), and zinc (Zn). R ¹ is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 2 to 5 carbon atoms.
(Equation 4)
R ² _l M ² (OR ³ ) _m-1 (IV)
In Formula (IV), M ² is at least one member selected from the group consisting of silicon (Si), magnesium (Mg), and zinc (Zn). R ² may be substituted with a hydrogen atom or a fluorine atom, and may also be substituted with a halogen atom, vinyl group, glycidoxy group, mercapto group, methacryloxy group, acryloxy group, isocyanate group, amino group or ureido group. Moreover, it is a C1-C20 hydrocarbon group which may have a hetero atom. R ³ is an alkyl group having 1 to 5 carbon atoms. m is an integer of 2-5. l is 1 or 2 when m is 3, 1 to 3 when m is 4, and 1 to 4 when m is 5; delete The coating liquid for metal oxide coatings manufactured using the manufacturing method in any one of Claims 1, 2, 4, and 5. The method of claim 7,
Coating solution for metal oxide coatings for flexographic printing with a viscosity of coating solution of 8 to 80 mPa · s A metal oxide film obtained by using the coating liquid for metal oxide film according to claim 7. The metal oxide film obtained by baking the coating film of the coating liquid for metal oxide films of Claim 7 at a temperature of 100-250 degreeC. An electronic device comprising the metal oxide film according to claim 9.