TW201435488A - Coating liquid for forming inorganic oxide coating film, inorganic oxide coating film, and display device - Google Patents

Abstract

Provided are: a coating liquid for forming a metal oxide coating film, said coating liquid being suitable for forming a metal oxide coating film that can be patterned a metal oxide coating film that is formed using the coating liquid and a highly reliable display device that is provided with the metal oxide coating film. This coating liquid for forming a metal oxide coating film contains metal alkoxide having a double bond in the structure, and a photosensitive polymer containing a photopolymerization initiator.

Description

Coating liquid for forming an inorganic oxide film, inorganic oxide film, and display device

The present invention relates to a coating liquid for forming a metal oxide film suitable for forming a moldable metal oxide film, a metal oxide film obtained from the coating liquid, and a display device including the metal oxide film.

In recent years, with the popularization of smart phones, the display screen of mobile phones has been enlarged. Therefore, a touch panel that can perform an input operation using the display of the display is actively developed. According to the touch panel, since the input means such as the switch of the push type is not required, the display screen can be enlarged.

The touch panel detects a contact position of an operation area that is contacted by a finger or a pen. With this function, the touch panel is used as an input device.

The detection method of the contact position is, for example, a resistive film method or a capacitance method. The resistive film method uses two substrates that are opposed to each other, and the electrostatic capacitance method can use only one substrate. Therefore, according to the electrostatic capacity method, a thin touch panel can be constructed, and since it is suitable for mobile devices, etc., it has been Actively develop.

The touch panel is assembled in a display device of a liquid crystal display device, and can be used as a display device with a touch panel function capable of detecting a touch position. Since the touch panel is used to recognize the display device via the touch panel, the transparent electrode is made of a member having excellent light transmittance. For example, an inorganic material such as ITO (Indium Tin Oxide) is used. Further, the interlayer insulating film is made of an acrylic material which is patterned and insulative.

Usually, an insulating film layer (OC2) is disposed on the electrode, and an organic acrylic resin can also be used in this portion. When a film is formed using an organic acrylic resin, patterning is generally performed by lithography. The purpose of this OC2 is to protect the transparent electrode, but the organic material is a film, and the hardness as a protective film is insufficient. The adhesion to a transparent electrode such as ITO is poor, which causes one of the reasons why the reliability of the touch panel is lowered.

In this case, a metal oxide film containing an inorganic material as a component is reviewed. When a film containing an inorganic material is used as a component, the hardness is generally high, and it is expected to have high reliability as an electrode protective film for a touch panel. However, it is difficult to form a metal oxide film containing an inorganic material as a film by the above-described patterning.

[Advanced technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 2881847

[Summary of the Invention]

The present invention has been made in view of the above problems, and an object of the present invention is to provide a coating liquid for forming a metal oxide film which is suitable for forming a metal oxide film which can be patterned.

In addition, a metal oxide film which is formed by the above method and which is excellent in reliability, and a display element which is excellent in reliability of the metal oxide film are provided.

In order to solve the above-mentioned problems, the inventors have intensively studied the results, and found that a composition for adding a photosensitive polymer containing a photopolymerization initiator to a metal alkoxide containing a double bond is used for coating a metal oxide film. The cloth liquid can solve the problem and the present invention is completed. That is, the present invention is characterized by the following.

(1) A coating liquid for forming a metal oxide film, which comprises a metal alkoxide containing a double bond in a structure and a photosensitive polymer having a photopolymerization initiator.

(2) The coating liquid for forming a metal oxide film according to the above (1), wherein the photopolymerization initiator is introduced into the photosensitive polymer by a covalent bond.

(3) The coating liquid for forming a metal oxide film according to the above (1) or (2), which comprises the first metal represented by the following formula (I) The alkoxide, the second metal alkoxide represented by the following formula (II), the metal salt represented by the following formula (III), the organic solvent, water, the precipitation preventing agent, and the photosensitive agent containing the photopolymerization initiator Polymer.

M ¹ (OR ¹ ) _n (I)

(M ¹ represents at least one metal selected from the group consisting of ruthenium, titanium, osmium, zirconium, boron, aluminum, magnesium, and zinc. R ¹ represents an alkyl group having 1 to 5 carbon atoms or an ethoxy group. n represents an integer from 2 to 5.)

R ² _m Si(OR ³ ) _4-m (II)

(R ² is an organic group selected from an alkyl group having 1 to 30 carbon atoms which is substituted by a vinyl group, a styryl group, a phenyl group, a naphthyl group and an acryloyl group, a methacrylanyl group or an aryl group. R ³ is An alkyl group having 1 to 5 carbon atoms or an ethylene group. m is an integer of 1 to 3.)

M ² (X) _k or M ² oxalate (III)

(M ² represents at least one metal selected from the group consisting of aluminum, indium, zinc, zirconium, hafnium, tantalum, niobium, tantalum and niobium. X represents hydrochloric acid, nitric acid, sulfuric acid, acetic acid, aminosulfonic acid, sulfonic acid The residue of acetamidineacetic acid or acetylacetonate or such basic salt. k represents the valence of M ² ).

(4) The coating liquid for forming a metal oxide film according to any one of the above (1) to (3), further comprising a third metal alkoxide represented by the following formula (IV).

R ⁴ ₁ M ³ (OR ⁵ ) _p-1 (IV)

(M ³ represents at least one metal selected from the group consisting of ruthenium, titanium, osmium, zirconium, boron, aluminum, magnesium, and zinc. R ⁴ represents a hydrogen atom or a fluorine atom, and may be substituted by a halogen atom or ethylene. a group having a carbon number of 1 to 20 which is substituted with a glycidoxy group, a mercapto group, a methacryloxy group, an acryloxy group, an isocyanate group, an amine group or a ureido group, and may have a hetero atom. ⁵ represents an alkyl group having 1 to 5 carbon atoms. p is an integer of 2 to 5, and when l is 3, it is 1 or 2, and when p is 4, it is an integer of 1 to 3, and when p is 5, it is 1 An integer of ~4).

(5) The coating liquid for forming a metal oxide film according to any one of the above (1), wherein the content of the second metal alkoxide is 25 mol with respect to the total metal alkoxide. More than 8% of the ear.

(6) The coating liquid for forming a metal oxide film according to any one of the above (1), wherein the content of the photosensitive polymer containing the photopolymerization initiator is relative to the metal solid content. It is 20% by weight or more.

The coating liquid for forming a metal oxide film according to any one of the above aspects, wherein the precipitation preventing agent is N-methyl-pyrrolidone, ethylene glycol, or dimethyl group. At least one selected from the group consisting of methotrexate, dimethylacetamide, diethylene glycol, propylene glycol, hexanediol, and the like.

(8) The coating liquid for forming a metal oxide film according to any one of the above items (3) to (7), wherein the metal atom of the metal salt has a molar number (M ² ) and a metal alkoxide metal The ratio of the total number of moles (M) of atoms is 0.01 ≦ M ² / M ≦ 0.7.

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

The coating liquid for forming a metal oxide film according to any one of the above-mentioned items, wherein the metal salt is a metal nitrate, a metal sulfate, a metal acetate or a metal chloride. A metal oxalate, a metal amide sulfonate, a metal sulfonate, a metal acetoacetate, a metal acetyl acetonate or an alkaline salt thereof.

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

(12) A metal oxide film obtained by using the coating liquid for forming a metal oxide film according to any one of the above items (1) to (11).

(13) A metal oxide film obtained by using the coating liquid for forming a metal oxide film according to any one of the above items (1) to (11), which has a refractive index in the range of 1.50 to 1.70. .

(14) A display device comprising the metal oxide film according to the above item (12) or (13).

The coating liquid for forming a metal oxide film of the present invention can produce a metal oxide film having high reliability. Moreover, by providing the obtained metal oxide film, it is possible to provide a display device with high reliability.

[Formation of the Invention] <Coating liquid for forming a metal oxide film>

The coating liquid for forming a metal oxide film of the present invention is characterized by comprising a metal alkoxide containing a double bond in a structure and a photosensitive polymer containing a photopolymerization initiator.

In particular, the coating liquid for forming a metal oxide film of the present invention contains a first metal alkoxide represented by the following formula (I), a second metal alkoxide represented by the following formula (II), and the following A metal salt represented by the formula (III), an organic solvent, water and a precipitation preventive agent, and a photosensitive polymer containing a photopolymerization initiator.

M ¹ (OR ¹ ) _n (I)

(M ¹ represents at least one metal selected from the group consisting of ruthenium, titanium, osmium, zirconium, boron, aluminum, magnesium, and zinc. R ¹ represents an alkyl group having 1 to 5 carbon atoms or an ethoxy group. n represents an integer from 2 to 5.)

R ² _m Si(OR ³ ) _4-m (II)

(R ² is an organic group selected from an alkyl group having 1 to 30 carbon atoms which is substituted by a vinyl group, a styryl group, a phenyl group, a naphthyl group and an acryloyl group, a methacrylanyl group or an aryl group. R ³ is An alkyl group having 1 to 5 carbon atoms or an acetyl group. m is an integer from 1 to 3.)

M ² (X) _k or M ² oxalate (III)

(M ² represents at least one metal selected from the group consisting of aluminum, indium, zinc, zirconium, hafnium, tantalum, niobium, tantalum and niobium. X represents hydrochloric acid, nitric acid, sulfuric acid, acetic acid, aminosulfonic acid, sulfonic acid The residue of acetamidineacetic acid or acetamidine or such basic salt. k represents the valence of M ² ).

The respective constituents contained in the coating liquid for forming a metal oxide film of the present invention and the coating liquid for forming the metal oxide film, and the preferred aspects thereof, will be described in detail below.

<First metal alkoxide>

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

M ¹ (OR ¹ ) _n (I)

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

When a metal alkoxide represented by the formula (I) is a decane oxide or a partial condensate thereof, one or a mixture of two or more compounds or a partial condensate (preferably 5) of the compound represented by the general formula (V) can be used. Polymer below).

Si(OR') ₄ (V)

In the formula (V), R' represents an alkyl group having 1 to 5 carbon atoms, preferably a carbon number. 1 to 3 alkyl or ethyl fluorenyl.

More specifically, as the decane oxide, for example, a tetraalkoxy decane such as tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, tetrabutoxy decane or tetraethoxy decane can be used.

In addition, when a titanium alkoxide or a partial condensate thereof is used as the metal alkoxide represented by the formula (I), one or a mixture of two or more compounds or a partial condensate of the compound represented by the general formula (VI) may be used. (preferably below the 5-mer).

Ti(OR") ₄ (VI)

(R" represents an alkyl group having 1 to 5 carbon atoms.)

The metal alkoxide represented by the formula (VI), specifically, a tetraalkoxy titanium compound such as titanium tetraethoxide, tetrapropoxy titanium or tetrabutoxy titanium can be used as the titanium alkoxide. Or a partial condensate such as Tetrabutyl Orthotitanate Tetramer or the like.

Other examples of the metal alkoxide represented by the formula (I) include, for example, a tetraalkoxy zirconium compound such as tetraethoxyzirconium, tetrapropoxyzirconium or zirconium tetrabutoxide; a trialkoxyaluminum compound such as a base aluminum, an aluminum triisopropoxide or a triethoxyaluminum; a pentamoxyquinone compound such as a pentapropyloxyanthracene or a pentabutoxyanthracene;

<2nd metal alkoxide>

The coating liquid for forming a metal oxide film of the present invention preferably contains a second metal alkoxide represented by the following formula (II).

R ² _m Si(OR ³ ) _4-m (II)

In the formula (II), R ² is an organic group selected from an alkyl group having 1 to 30 carbon atoms which is substituted by a vinyl group, a styryl group, a phenyl group, a naphthyl group and an acryloyl group, a methacrylanyl group or an aryl group. base. R ³ is an alkyl group having 1 to 5 carbon atoms or an ethylene group. m is an integer from 1 to 3. The phenyl group, the naphthyl group or the aryl group each have an aromatic ring, and the aromatic ring has a double bond in its structure, and thus is a group having a double bond.

Specific examples of the metal alkoxide represented by the formula (II) include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl triethoxy decane, styryl trimethoxy decane, and styrene. Triethoxy decane, styryl tripropoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl triethoxy decane, styryl trimethoxy decane, styrene Triethoxy decane, propylene methoxy propyl trimethoxy decane, propylene methoxy propyl triethoxy decane, methacryloxypropyl trimethoxy decane, methacryloxy methoxy propyl Triethoxy decane, allyl triethoxy decane, methacryloxypropyl methyl dimethoxy decane, methacryloxypropyl methyl diethoxy decane, methyl Vinyl dimethoxy decane, methyl vinyl diethoxy decane, diphenyl dimethoxy decane, diphenyl diethoxy decane, and the like. These may be used alone or in combination of two or more.

<3rd metal alkoxide>

In the coating liquid for forming a metal oxide film of the present invention, the third metal alkoxide represented by the following formula (IV) is preferably used together with the first metal alkoxide.

R ⁴ ₁ M ³ (OR ⁵ ) _p-1 (IV)

In the formula (IV), M ³ , R ² , R ³ and p are as defined above. Among them, M ^{3 is} preferably ruthenium, titanium, zirconium or aluminum, and particularly preferably ruthenium or titanium.

When the coating liquid for forming a metal oxide film of the present invention contains the second and third metal alkoxides and the metal oxide film is formed on a film made of an organic material such as an acrylic material, the coating can be relaxed. The difference in thermal stretchability between the film and the organic film. As a result, even if a metal oxide film is formed on the organic film, cracking of the metal oxide film can be prevented. For example, in the touch panel, an organic film made of an acrylic material is used for the interlayer insulating film or the like, and even if a metal oxide film is formed thereon, cracking of the metal oxide film on the interlayer insulating film can be prevented.

The content of the second metal alkoxide is preferably 25 mol% or more, and more preferably 30 mol% or more, based on the total amount of the metal alkoxide contained in the coating liquid for forming a metal oxide film.

When the content of the second metal alkoxide is less than 25 mol%, the compatibility with the photosensitive polymer containing the photopolymerization initiator added is inferior, and when the film is formed, the film is whitened or a sufficient image cannot be obtained. A phenomenon such as characterization.

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. ~20% by weight, more preferably 1~15% by weight. When the ratio is large, the storage stability of the coating liquid for forming a metal oxide film is deteriorated, and the film thickness control of the metal oxide film is difficult. Further, when the ratio is small, the thickness of the obtained metal oxide film is reduced, and in order to obtain a predetermined film thickness, it is necessary to apply a plurality of times.

When a preferred metal alkoxide represented by the formula (III), for example, M ³ is ruthenium, for example, the following compounds are mentioned.

For example, methyltrimethoxydecane, methyltripropoxydecane, methyltriethoxydecane, methyltributoxydecane, methyltripentyloxydecane, methyltripentyloxydecane, Methyltriphenoxydecane, methyltribenzyloxydecane, methyltriphenylethoxydecane, glycidoxymethyltrimethoxydecane, glycidoxymethyltriethoxydecane, α- Glycidoxyethyl trimethoxy decane, α-glycidoxyethyl triethoxy decane, β-glycidoxyethyl trimethoxy decane, β-glycidoxyethyl triethoxy Decane, α-glycidoxypropyltrimethoxydecane, α-glycidoxypropyltriethoxydecane, β-glycidoxypropyltrimethoxydecane, β-glycidoxypropyl Triethoxy decane, γ-glycidoxypropyl trimethoxy decane, γ-glycidoxypropyl triethoxy decane, γ-glycidoxypropyl tripropoxy decane, γ-shrinkage Glycidoxypropyl tributoxy decane, γ-glycidoxypropyl triphenoxy decane, α-glycidoxy butyl Methoxy decane, α-glycidoxybutyl triethoxy decane, β-glycidoxy butyl triethoxy decane, γ-glycidoxy butyl trimethoxy decane, γ-glycidol Oxybutyl triethoxy decane, δ-glycidoxy butyl trimethoxy decane, δ-glycidoxy butyl triethoxy decane, (3,4-epoxycyclohexyl)methyl Trimethoxydecane, (3,4-epoxycyclohexyl)methyltriethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, β-(3,4 -Epoxycyclohexyl)ethyltriethoxydecane, β-(3,4-epoxycyclohexyl)ethyltripropoxydecane, β-(3,4-epoxycyclohexyl) Ethyl tributoxy decane, β-(3,4-epoxycyclohexyl)ethyltriphenoxydecane, γ-(3,4-epoxycyclohexyl)propyltrimethoxydecane, γ -(3,4-epoxycyclohexyl)propyltriethoxydecane, δ-(3,4-epoxycyclohexyl)butyltrimethoxydecane, δ-(3,4-epoxy Cyclohexyl)butyltriethoxydecane, glycidoxymethylmethyldimethoxydecane, glycidoxymethylmethyldiethoxydecane, α-glycidoxyethylmethyldi Methoxydecane, α-glycidoxyethylmethyldiethoxydecane, β-glycidoxyethylmethyldimethoxydecane, β-glycidoxyethylethyldimethoxy Baseline, α-glycidoxypropylmethyldimethoxydecane, α-glycidoxypropylmethyldiethoxydecane, β-glycidoxypropylmethyldimethoxydecane , β-glycidoxypropylethyldimethoxydecane, γ-glycidoxypropylmethyldimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, γ - glycidoxypropylmethyldipropoxydecane, γ-shrink Glyceroxypropylmethyldibutoxydecane, γ-glycidoxypropylmethyldiphenoxydecane, γ-glycidoxypropylethyldimethoxydecane, γ-glycidyloxy Propyl ethyl diethoxy decane, γ-glycidoxypropyl vinyl dimethoxy decane, γ-glycidoxypropyl vinyl diethoxy decane, ethyl trimethoxy decane, Ethyltriethoxydecane, γ-chloropropyltrimethoxydecane, γ-chloropropyltriethoxydecane, γ-chloropropyltriethoxydecane, 3,3,3-trifluoropropane Trimethoxy decane, γ-mercaptopropyltrimethoxydecane, γ-mercaptopropyltriethoxydecane, β-cyanoethyltriethoxydecane, chloromethyltrimethoxydecane, chloromethyl Triethoxydecane, N-(β-aminoethyl)γ-aminopropyltrimethoxydecane, N-(β-amino B Γ-aminopropylmethyldimethoxydecane, γ-aminopropylmethyldimethoxydecane, N-(β-aminoethyl)γ-aminopropyltriethoxy Decane, N-(β-aminoethyl)γ-aminopropylmethyldiethoxydecane, dimethyldimethoxydecane, phenylmethyldimethoxydecane, dimethyldiethyl Oxydecane, phenylmethyldiethoxydecane, γ-chloropropylmethyldimethoxydecane, γ-chloropropylmethyldiethoxydecane, dimethyldiethoxydecane, Γ-mercaptopropylmethyldimethoxydecane, γ-mercaptomethyldiethoxydecane, γ-ureidopropyltriethoxydecane, γ-ureidopropyltrimethoxydecane, γ-urea Propyltripropoxydecane, (R)-N-1-phenylethyl-N'-triethoxydecylpropylurea, (R)-N-1-phenylethyl-N' -trimethoxydecyl propyl urea, 3-isocyanate propyl triethoxy decane, trifluoropropyltrimethoxy decane, bromopropyltriethoxy decane, diethyldiethoxy decane, two Ethyldimethoxydecane, trimethylethoxysilane, trimethylmethoxydecane, and the like. These may be used alone or in combination of two or more.

Further, in the coating liquid for forming a metal oxide film of the present invention, in addition to the first metal alkoxide and the second metal alkoxide, other metal alkane may be contained within a range that does not impair the effects of the present invention. Oxide.

<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 formula (III).

M ² (X) _k or M ² oxalate (III)

In the formula (III), M ² , X and k are as defined above. Among them, M ² represents aluminum, indium, bismuth, and zirconium. X represents a residue of hydrochloric acid, nitric acid, acetic acid, sulfonic acid, acetamidineacetic acid or acetamidineacetone or such a basic salt is preferred. The residue of each acid in the above X, for example, nitric acid is also called nitrate, and sulfuric acid is also called sulfate, which contains an amount equivalent to the valence of M ² . Further, the basic salt means a case where an OH group is contained in the residue of each of the above acids.

Among the metal salts represented by the formula (III), a nitrate, a chloride salt, an oxalate or an alkali salt thereof is particularly preferred. In particular, from the viewpoint of ease of availability and storage stability of the coating liquid for forming a metal oxide film, it is more preferably a nitrate of aluminum, indium or bismuth.

The content of the metal salt contained in the coating liquid for forming a metal oxide film is the total number of moles (M) of metal atoms constituting the metal alkoxide and the number of moles (M ² ) of the metal atom of the above metal salt. The total content ratio is preferably one that satisfies the ratio (mol ratio) described below.

0.01≦M ² /M≦0.7

When the ratio is less than 0.01, the mechanical strength of the obtained film is insufficient, which is not preferable. Moreover, when it exceeds 0.7, the adhesiveness of the coating film to the base material, such as a glass substrate and a transparent electrode, will fall. Further, when firing at a low temperature of 450 ° C or lower, the chemical resistance of the obtained metal oxide film tends to be lowered. Among them, the ratio is preferably 0.01 to 0.6.

<organic solvent>

The coating liquid for forming a metal oxide film of the present invention contains an organic solvent. In the organic solvent, when a coating film is formed from a coating liquid for forming a metal oxide film to obtain a metal oxide film, the metal oxide film shape is adjusted. The viscosity of the coating liquid is used to improve the applicability.

The content of the organic solvent in the coating liquid for forming a metal oxide film is preferably from 80 to 99.5% by weight, more preferably from 85 to 99.5% by weight based on the total metal alkoxide contained in the coating liquid for forming a metal oxide film. 99% by weight. When the content of the organic solvent is small, the thickness of the obtained metal oxide film is reduced, and in order to obtain a predetermined film thickness, it is necessary to apply a plurality of times. When the content is large, the storage stability of the coating liquid for forming a metal oxide film is deteriorated, and the film thickness of the metal oxide film is difficult to control.

The organic solvent used for the coating liquid for forming a metal oxide film of the present invention may, for example, be an alcohol such as methanol, ethanol, propanol, butanol, 2-methyl-1-propanol or 2-methyl-2-propanol. Ethyl esters such as ethyl acetate; glycols such as ethylene glycol or ester derivatives thereof; ethers such as diethyl ether; ketones such as acetone, methyl ethyl ketone and cyclohexanone; benzene, toluene, etc. Aromatic hydrocarbons, etc. These can be used singly or in combination.

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

When the diol or its monoether contained in the organic solvent used for the coating liquid for forming a metal oxide film of the present invention has a molar ratio of less than 1 to the alkoxide titanium, the stability of the titanium alkoxide The properties and effects are small, and the storage stability of the coating liquid for forming a metal oxide film is deteriorated. In addition, there is no problem in using a large amount of the glycol or its monoether. For example, all of the organic solvents used for the coating liquid for forming a metal oxide film are the above-mentioned glycols. Or its monoether is no problem. However, when the coating liquid for forming a metal oxide film does not contain titanium alkoxide, it is not necessary to particularly contain the above diol and/or its monoether.

<Precipitation inhibitor>

The coating liquid for forming a metal oxide film of the present invention preferably contains a precipitation preventing agent. The precipitation preventing agent in the present invention refers to an organic solvent having a function of preventing precipitation of a metal salt in the coating film when the coating film is formed from the coating liquid for forming a metal oxide film. The precipitation preventing agent is, for example, N-methyl-pyrrolidone, dimethylformamide, dimethylacetamide, ethylene glycol, diethylene glycol, propylene glycol or hexanediol or derivatives thereof. Among them, preferred are N-methyl-pyrrolidone, ethylene glycol, diethylene glycol, propylene glycol, hexanediol or derivatives thereof. At least one type of the precipitation inhibitor can be used.

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

(Precipitation inhibitor/metal oxide) ≧1.

When the ratio is less than 1, when the film is formed, the effect of preventing precipitation of the metal salt becomes small. Further, the use of a large amount of the precipitation preventing agent does not have any influence on the coating liquid for forming a metal oxide film, but is preferably 200 or less.

The precipitation inhibitor may be added during the hydrolysis or condensation reaction of the metal alkoxide, particularly the decane oxide, the titanium alkoxide or the decane oxide and the titanium alkoxide in the presence of the metal salt, or after the hydrolysis and condensation reaction Add to.

<Photosensitive polymer>

The photosensitive polymer contained in the coating liquid for forming a metal oxide film of the present invention contains a polymer soluble in an alkali group and a polymerizable group.

The polymer is, for example, a polymer obtained by copolymerization using a monomer having an unsaturated double bond such as acrylate, methacrylate, acrylamide, methacrylamide or styrene.

The alkali-soluble organic group is, for example, an organic group having a carboxyl group, a phenolic hydroxyl group, an acid anhydride group, a maleimide group, or the like.

An organic group having a carboxyl group such as acrylic acid, methacrylic acid, Crotonic acid, mono-(2-(acryloxy)ethyl)phthalate, mono-(2-(methacryl)醯oxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)propene oxime Amine, 4-vinylbenzoic acid, and the like.

An organic group having a phenolic hydroxyl group, for example, hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)butylene Imine and the like.

The organic group having an acid anhydride group is, for example, maleic anhydride, itaconic anhydride or the like.

An organic group having a maleimide group such as maleimide.

Specific examples of the polymerizable group include an acrylate group, a methacrylate group, a vinyl group, an allyl group, and the like, but are not limited thereto.

A specific example of such a compound is dipentaerythritol hexaacrylate, two seasons. Pentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylic acid Ester, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylol methane tetraacrylate, tetramethylol methane tetramethacrylate, three Hydroxymethylpropane triacrylate, trimethylolpropane trimethacrylate, 1,3,5-tripropylenesulfonylhexahydro-S-triazine, 1,3,5-trimethylpropenyl hexa Hydrogen-S-triazine, tris(hydroxyethylpropenyl)isocyanurate, tris(hydroxyethylmethacryloyl)isocyanurate, tripropylene fluorenylacetal ( Formal), trimethyl propylene fluorenyl acetal, 1,6-hexane diol acrylate, 1,6-hexane diol methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethyl Acrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 2-hydroxyl Diol diacrylate, 2-hydroxypropanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, isopropyl glycol diacrylate, isopropyl glycol dimethacrylate, triethyl Diol diacrylate, triethylene glycol dimethacrylate, N, N'-bis(acryloyl)cysteine, N,N'-bis(methacrylinyl) cysteine Amine acid, thiodiethylene glycol diacrylate, thiodiethylene glycol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F II Methacrylate, bisphenol S diacrylate, bisphenol S dimethacrylate, fluorene diacrylate, bisphenoxyethanol hydrazine dimethacrylate, diallyl ether Bisphenol A, o-Diallyl bisphenol A, maleic acid diallyl ester, triallyl trimellitate, etc., but not limited thereto.

<Photopolymerization initiator>

In the coating liquid for forming an inorganic oxide film of the present invention, the photopolymerization initiator contained in the photosensitive polymer is not particularly limited as long as it generates radicals by exposure. Specific examples are benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (milaxone), 4,4'-bis(ethylamino)benzol Ketone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethyl fluorene, phenanthrene and other aromatic ketones, benzoin methyl ether, benzoin ether, benzoin benzene a benzoin such as an ether such as a benzoin ether, a methyl benzene ene or an ethyl benzoate; a 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-( o-Chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triaryl imidazole dimer, 2-(o-chlorophenyl)-4,5-di (m-methylphenyl)imidazole dimer, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-trichloromethyl-5- Styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl- Halomethyloxadiazole compound of 5-(p-methoxystyryl)-1,3,4-oxadiazole, 2,4-bis(trichloromethyl)-6-p-methoxy Styryl-S-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl) -1,3-butadienyl)-S-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-S-triazine, 2-(naphthalene-1 -base)- 4,6-bis-trichloromethyl-S-triazine, 2-(4-ethoxy-naphthalen-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2- a halomethyl-S-triazine compound such as (4-butoxy-naphthalen-1-yl)-4,6-bis-trichloromethyl-S-triazine or the like, 2,2-dimethoxy -1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylacetone, 1,2-benzyl-2- Dimethylamino-1-(4-morpholinylphenyl)-butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, diphenylethylenedione (Benzil), benzhydrylbenzoic acid , methyl benzoyl benzoate, 4-benzylidene-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylamino benzoate, p-dimethyl Isoamyl benzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2, 4-dimethylthioxanthone, isopropylthioxanthone, 1-(4-phenylthiophenyl)-1,2-octanedione-2-(O-benzylidenehydrazine), ethyl ketone , 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-ethylindenyl), 4-benzylidenyl- Methyl diphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4- Morpholinyl)Phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholine) Phenyl]-1-butanone, α-dimethoxy-α-phenylethanone, phenylbis(2,4,6-trimethylbenzylidene)phosphorus oxide, diphenyl ( 2,4,6-trimethylbenzhydryl)phosphorus oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, etc. .

The above photopolymerization initiator can be easily obtained from commercially available products, and specific examples thereof include IRGACURE 173, IRGACURE 500, IRGACURE 2959, IRGACURE 754, IRGACURE 907, and IRGACURE. 369, IRGACURE 1300, IRGACURE 819, IRGACURE 819DW, IRGACURE 1880, IRGACURE 1870, DAROCURE TPO, DAROCURE 4265, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE 250 (above, BASF), KAYACURE DETX-S, KAYACURE CTX, KAYACURE BMS, KAYACURE 2-EAQ (above is made by Nippon Kayaku Co., Ltd.), TAZ-101, TAZ-102, TAZ-103, TAZ-104, TAZ-106, TAZ-107, TAZ-108, TAZ-110, TAZ -113, TAZ-114, TAZ-118, TAZ-122, TAZ-123, TAZ-140, TAZ-204 (manufactured by Green Chemical Co., Ltd.) and the like.

These photopolymerization initiators may be used singly or in combination of two or more kinds.

In addition, when the photopolymerization initiator and the photosensitive polymer are respectively present in the coating liquid for forming an inorganic oxide film of the present invention, the inorganic substance of the present invention may be present depending on the type and amount of the photopolymerization initiator. The coating liquid for forming an oxide film causes a problem of preservation stability. Therefore, such a photopolymerization initiator is preferably a covalent bond and is preferably introduced into a photosensitive polymer.

When the photosensitive polymer contains a skeleton of a photopolymerization initiator (hereinafter, the photosensitive polymer is also referred to as a polymer having an initial function), and the polymer having an initial function added is relative to the metal solid component. It is preferably contained in an amount of 20% by weight or more, and more preferably 30% by mass or more. When it is less than 20% by mass, sufficient patterning property cannot be obtained.

<Other ingredients>

The coating liquid for forming a metal oxide film of the present invention may contain other components such as inorganic fine particles, metalloxanes oligomers, or metal oxyalkylene polymers as long as the effects of the present invention are not impaired. , components such as flat agents and surfactants.

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

In the present invention, by containing inorganic fine particles, the surface shape or other functions of the formed cured film can be imparted. The average particle diameter of the inorganic fine particles 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 be lowered.

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

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

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

In the coating liquid for forming a metal oxide film of the present invention, a metal alkoxide containing the first metal alkoxide and the second metal alkoxide is hydrolyzed in the presence of the metal salt to obtain a condensate. Contains water. The amount of the water is preferably 2 to 24 moles per mole of the total moles of the first and second metal alkoxides. When the ratio of the amount of water (mole) / (the total number of moles of the metal alkoxide) is 2 or less, the hydrolysis of the metal alkoxide is insufficient, the film formability is lowered, or the obtained metal oxide film is obtained. Further, when the ratio is more than 24, it is not preferable because the polycondensation is continued to lower the storage stability, and the molar ratio is preferably 2 to 20.

In addition, when the metal salt contained in the coating liquid for forming a metal oxide film is a water-containing salt, since the water content is involved in the hydrolysis reaction, the amount of water contained in the coating liquid for forming a metal oxide film must be considered. The moisture content of the salt. For example, when the coexisting metal salt is an aqueous salt of an aluminum salt, the moisture component participates in the reaction, and therefore, for the amount of water used for hydrolysis, the content of the aluminum salt must be considered. Moisture.

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

Further, since the metal oxide film of the present invention has almost no heat-expandability, even if an inorganic material is used for the electrode protective layer of the upper layer, cracking does not occur.

The metal oxide film obtained by using the coating liquid for a metal oxide film of the present invention can be applied to a bridge portion of an X-axis and a Y-axis used for a capacitive touch panel, in addition to a protective film which can be used for a transparent electrode. Insulation layer, etc.

The control of the refractive index of the metal oxide film of the present invention can be achieved by controlling the composition of the coating liquid for forming a metal oxide film. In other words, the metal oxide film of the present invention is produced by hydrolyzing and condensing the metal alkoxide contained in the coating liquid for forming a metal oxide film, and by forming the composition of the metal alkoxide, it can be formed. The refractive index of the metal oxide film is adjusted within a predetermined range. For example, when a metal alkoxide is selected from a decane oxide and a titanium alkoxide, the metal oxidization can be adjusted within a range as described later, specifically, in the range of 1.45 to 2.1, by adjusting the mixing ratio thereof. The refractive index of the film. The refractive index of the metal oxide film is preferably 1.50 to 1.70.

In other words, the coating liquid for forming a metal oxide film is applied to form a film, and it is preferably a metal oxide film formed after drying and baking. When the desired refractive index has been determined, the metal alkoxide, such as the compositional molar ratio of the decane oxide to the titanium alkoxide, can be determined to achieve the refractive index.

For example, the refractive index of the metal oxide film of the coating liquid for forming a metal oxide film obtained by hydrolysis of the decane oxide is about 1.45. In addition, the refractive index of the metal oxide film of the coating liquid for forming a metal oxide film obtained by hydrolyzing only the titanium alkoxide is about 2.1. Therefore, when the refractive index of the metal oxide film is set to a specific value between about 1.45 and 2.1, a coating liquid for forming a metal oxide film can be produced by using a decane oxide and a titanium alkoxide at a predetermined ratio. The refractive index value.

Further, the refractive index of the obtained metal oxide film can also be adjusted by using another metal alkoxide. Further, the refractive index of the metal oxide film in the present invention can be adjusted by selecting film formation conditions in addition to the composition conditions. Thus, the high hardness of the metal oxide film can be achieved, and the desired refractive index value can be achieved.

In the metal oxide film of the present invention, particularly in order to suppress the phenomenon in which the transparent electrode pattern is recognized, the refractive index is preferably controlled in the range of 1.50 to 1.70, more preferably in the range of 1.52 to 1.70. As described above, the refractive index control method can be realized by controlling the film formation method in addition to the composition of the coating liquid for forming a metal oxide film.

In the coating liquid for forming a metal oxide film, particularly when the titanium alkoxide component is contained, the viscosity is gradually increased when stored at room temperature. Although there is no doubt that it is a big problem in practical use, when the thickness of the metal oxide film is precisely controlled, it is preferable to carefully manage the temperature and the like. Such a viscosity rises as a titanium in the coating liquid for forming a metal oxide film The composition ratio of the alkoxide is more and more obvious. This is because the titanium alkoxide has a higher hydrolysis rate and a faster condensation reaction than the decane oxide.

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

Process (1) Titanium alkoxide is sufficiently mixed with a titanium alkoxide in advance in the presence of a metal salt, and if necessary, mixed with a decane oxide in an organic solvent Hydrolysis is carried out in the presence of it. Thus, a coating liquid for forming a metal oxide film having a small change in viscosity can be obtained. This method is more effective because it is heated when the titanium alkoxide is mixed with a glycol. Therefore, a transesterification reaction occurs between the alkoxy group of the titanium alkoxide and the glycol, and the hydrolysis and condensation reaction are stabilized. The reason.

In the production method (2), the decane oxide is subjected to a hydrolysis reaction in the presence of a metal salt, and then mixed with a titanium alkoxide solution mixed with a glycol to carry out a condensation reaction to obtain a coating liquid for forming a metal oxide film. Thereby, a coating liquid for forming a metal oxide film having a small change in viscosity can be obtained.

This method is more effective for the following reasons. In other words, although the hydrolysis reaction of the decane oxide proceeds at a relatively fast rate, the subsequent condensation reaction is slower than that of the titanium alkoxide. Therefore, after the completion of the hydrolysis reaction, when the titanium alkoxide is rapidly added, the stanol group of the decane oxide after the hydrolysis reaction is uniformly reacted with the titanium alkoxide. Thereby, the condensation reactivity of the titanium alkoxide stabilizes the hydrolyzed decane oxide.

A method of mixing a prehydrolyzed decane oxide with a titanium alkoxide has been attempted. However, when the organic solvent used for the reaction does not contain a glycol, a coating liquid for forming a metal oxide film which is excellent in storage stability cannot be obtained. Further, the method shown in (2) is also a case where a coating liquid for forming a metal oxide film is obtained from another metal alkoxide and a decane oxide having a faster hydrolysis rate.

<film making>

The coating liquid for a metal oxide film of the present invention can be applied to a metal oxide film of the present invention after a coating film is formed by a coating method which is generally applied. The coating method can be, for example, a dip coating method, a spin coating method, a spray coating method, a flow coating method, a brush coating method, a bar coating method, a gravure coating method, a roll transfer method, or a blade coating method. Method, air knife coating method, slit coating method, screen printing method, inkjet method, letterpress printing method, and the like. Among them, a spin coating method, a slit coating method, a blade coating method, and a spray coating method are preferably used.

<dry>

The metal oxide film of the present invention is obtained by drying and baking a coating film formed on a substrate.

The drying step is preferably in the range of room temperature to 150 ° C, more preferably in the range of 40 to 120 ° C. The time is preferably from about 30 seconds to about 10 minutes, more preferably from about 1 to 8 minutes. The drying method is preferably a heating plate or a hot air circulating oven or the like.

<graphical step>

In the present invention, when the dried film is exposed to light containing an ultraviolet region within a range in which solubility is maintained in the developing solution, the polymer having the initial function generates radicals, promotes and introduces into the polymer and the inorganic film. The substituent is subjected to a polymerization reaction to selectively insolubilize the dried film of the exposed portion. Light including an ultraviolet region, for example, a light source including a wavelength of 180 nm or more and 400 nm or less is commercially available, and is preferable.

The light source is, for example, a mercury lamp, a metal halide lamp, a xenon lamp, an excimer laser lamp, or the like.

The irradiation amount can be appropriately selected as needed, and is preferably 100 to 10,000 mJ/cm ² , more preferably 150 to 8,000 mJ/cm ² in terms of wavelength 365 nm.

The developing liquid used in the present invention is an etched metal oxide film. Therefore, it is preferred to use a basic compound solution or an acidic compound solution.

As the alkaline compound solution (alkaline developing solution), for example, an aqueous solution of an alkali metal, a quaternary ammonium hydroxide, a cerium salt, a phosphate, an acetate, an amine or the like can be used. Specific examples are sodium hydroxide, potassium hydroxide, ammonium hydroxide, trimethylbenzylammonium hydroxide, tetramethylammonium hydroxide, sodium citrate, sodium phosphate, sodium acetate, monoethanolamine, diethanolamine, triethanolamine, etc. Aqueous solution.

The acidic compound solution (acidic developing solution) is preferably an aqueous solution of an organic acid such as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid or phosphoric acid, or an organic acid such as formic acid or acetic acid. However, the amount of the basic compound or the acidic compound is preferably such that the exposed portion and the unexposed portion are sufficiently produced with respect to the amount of water. The amount of solubility is poor.

<burning>

The firing step considers the heat resistance of other constituent members of the touch panel, and is preferably in the range of 100 ° C to 300 ° C, more preferably in the range of 150 ° C to 250 ° C. The time is preferably 5 minutes or longer, more preferably 15 minutes or longer. The firing method is preferably a heating plate, a heat cycle oven, an infrared oven or the like.

Further, in order to control the refractive index and increase the hardness, an ultraviolet irradiation step may be additionally performed between the patterning step and the firing step. When ultraviolet irradiation is performed, the refractive index of the metal oxide film can be adjusted by selecting the amount of irradiation. In the metal oxide film, in order to obtain a desired refractive index, when ultraviolet irradiation is required, for example, a high pressure mercury lamp can be used. When a high-pressure mercury lamp is used, the irradiation amount of 1000 mJ/cm ² or more for total light irradiation is preferably 365 nm, and the irradiation amount of 3000 mJ/cm ² to 10000 mJ/cm ² is more preferable.

In addition to high-pressure mercury lamps, ultraviolet light sources can use low-pressure mercury lamps, metal halide lamps, xenon lamps, and excimer laser lamps. When a light source other than a high-pressure mercury lamp is used, the same amount of accumulated light amount as that used in the above-described high-pressure mercury lamp may be used. When ultraviolet irradiation is performed, an ultraviolet irradiation step can be performed between the drying step and the firing step.

[Examples]

The following is more specifically illustrated by the embodiments of the present invention, but Not limited to this.

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

TEOS: tetraethoxy decane

ACPS: propylene methoxy propyl trimethoxy decane

MPMS: methacryloxypropyltrimethoxydecane

StTMS: Styryltrimethoxydecane

TTE: tetraethoxy titanium

TIPT: Titanium tetraisopropoxide

AN: Aluminum nitrate hexahydrate

EG: ethylene glycol

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

BCS: 2-butoxyethanol (alias: butyl cellosolve)

PGME: propylene glycol monomethyl ether

EtOH: ethanol

<Synthesis Example 1> <A1 liquid>

12.7 g of AN and 3.0 g of water were placed in a 200 mL flask, and the mixture was stirred to dissolve AN. Thereto were added 13.4 g of EG, 38.3 g of HG, 36.4 g of BCS, 15.5 g of TEOS, and 18.5 g of MPMS, and the mixture was stirred at room temperature for 30 minutes.

<A2 liquid>

TIPT 4.7g and HG 57.5g were added to a 300 mL flask, and the mixture was stirred at room temperature for 30 minutes.

The <A1 liquid> was mixed with the <A2 liquid>, and stirred at room temperature for 30 minutes to obtain a solution (K1).

50.0 g of this solution K1 was weighed, and 99.3 g of PGME and 0.9 g of a polymer UV-H4000 (manufactured by KSM Co., Ltd.) having a starting function were added to obtain a solution (KL1).

<Synthesis Example 2>

In a 300 mL flask, 3.3 g of AN, 3.0 g of water, and 76.1 g of EtOH were placed, and the mixture was stirred to dissolve AN. To the solution were added 8.6 g of TEOS and 10.2 g of MPMS, and the mixture was stirred at room temperature for 30 minutes. Then, 18.8 g of TTE was added, and the mixture was further stirred at room temperature for 30 minutes.

HG 109.3g and BCS 46.8g were added to this solution, and the pressure was gradually reduced to 80 mmHg (10.7 kPa) at 60 ° C by a rotary vacuum evaporator (manufactured by Tokyo Chemical Industry Co., Ltd., N-1000S-WD), and distilled off at the same time. The solvent gave 200 g of solution (K2).

50.0 g of this solution K2 was weighed, and 97.0 g of PGME and 3.0 g of a polymer UV-H4000 (manufactured by KSM Co., Ltd.) having a starting function were added to obtain a solution (KL2).

<Synthesis Example 3>

AN 300 g of AN, 3.0 g of water, and 75.4 g of EtOH were placed in a 300 mL flask, and the mixture was stirred to dissolve AN. To the solution were added 5.2 g of TEOS and 14.3 g of MPMS, and the mixture was stirred at room temperature for 30 minutes. Then, 18.8 g of TTE was added, and the mixture was further stirred at room temperature for 30 minutes.

HG 108.8g and BCS 46.6g were added to this solution, and the pressure was gradually reduced to 80 mmHg (10.7 kPa) at 60 ° C by a rotary vacuum evaporator (manufactured by Tokyo Chemical Industry Co., Ltd., N-1000S-WD), and distilled off simultaneously. The solvent gave 200 g of solution (K3).

50.0 g of this solution K3 was weighed, and 98.5 g of PGME and 1.5 g of a polymer UV-H4000 (manufactured by KSM Co., Ltd.) having a starting function were added to obtain a solution (KL3).

<Synthesis Example 4> <B1 liquid>

12.7 g of AN and 3.0 g of water were placed in a 200 mL flask, and the mixture was stirred to dissolve AN. Thereto were added EG 13.5 g, HG 38.6 g, BCS 36.7 g, TEOS 15.5 g, and ACPS 17.5 g, and the mixture was stirred at room temperature for 30 minutes.

<B2 liquid>

TIPT 4.7g and HG 57.9g were added to a 300 mL flask, and stirred at room temperature for 30 minutes.

The <B1 liquid> was mixed with the <B2 liquid>, and stirred at room temperature for 30 minutes to obtain a solution (K4).

50.0 g of this solution K4 was weighed, and 98.5 g of PGME and 1.5 g of a polymer UV-H4000 (manufactured by KSM Co., Ltd.) having a starting function were added to obtain a solution (KL4).

<Synthesis Example 5> <C1 liquid>

12.7 g of AN and 3.0 g of water were placed in a 200 mL flask, and the mixture was stirred to dissolve AN. Thereto were added EG 13.6 g, HG 38.8 g, BCS 36.8 g, TEOS 15.5 g, and StTMS 16.8 g, and the mixture was stirred at room temperature for 30 minutes.

<C2 liquid>

TIPT 4.7g and HG 58.2g were added to a 300 mL flask, and stirred at room temperature for 30 minutes.

The <C1 liquid> was mixed with <C2 liquid>, and stirred at room temperature for 30 minutes to obtain a solution (K5).

50.0 g of this solution K5 was weighed, and 98.5 g of PGME and 1.5 g of a polymer UV-H4000 (manufactured by KSM Corporation) having a starting function were added to obtain a solution (KL5).

<Synthesis Example 6>

AN 300 g of AN, 3.0 g of water, and 75.4 g of EtOH were placed in a 300 mL flask, and the mixture was stirred to dissolve AN. 11.7 g of MPMS was added to this solution, and the mixture was stirred at room temperature for 30 minutes. Then, 25.0 g of TTE was added, and the mixture was further stirred at room temperature for 30 minutes.

To this solution, 110.2 g of HG and 47.2 g of BCS were added, and the pressure was gradually reduced to 80 mmHg (10.7 kPa) at 60 ° C by a rotary vacuum evaporator (manufactured by Tokyo Chemical Industry Co., Ltd., N-1000S-WD), and distilled off simultaneously. The solvent gave 200 g of solution (K6).

This solution K6 is weighed 50.0g, and PGME 97.0g is added and attached The polymer of the initial function, UV-H4000 (manufactured by KSM Co., Ltd.), 3.0 g, gave a solution (KL6).

<Synthesis Example 7>

The solution K6 obtained in Synthesis Example 6 was weighed to 50.0 g, and 100 g of PGME was added thereto to obtain a solution (KM1).

<Synthesis Example 8> <D1 liquid>

12.7 g of AN and 3.0 g of water were placed in a 200 mL flask, and the mixture was stirred to dissolve AN. Thereto were added EG 13.7 g, HG 39.1 g, BCS 37.1 g, and TEOS 31.1 g, and the mixture was stirred at room temperature for 30 minutes.

<D2 liquid>

TIPT 4.7g and HG 58.6g were added to a 300 mL flask, and the mixture was stirred at room temperature for 30 minutes.

The <D1 liquid> was mixed with the <D2 liquid>, and stirred at room temperature for 30 minutes to obtain a solution (K7).

50.0 g of this solution K7 was weighed, and 97.0 g of PGME and 3.0 g of a polymer UV-H4000 (manufactured by KSM Co., Ltd.) having a starting function were added to obtain a solution (KM2).

<Synthesis Example 9> <E1 liquid>

Add 12.7 g of AN and 3.0 g of water to a 200 mL flask and stir. The AN is dissolved. EG 13.6 g, HG 38.9 g, BCS 37.0 g, TEOS 28.0 g, and MPMS 3.7 g were added, and the mixture was stirred at room temperature for 30 minutes.

<E2 liquid>

TIPT 4.7g and HG 58.4g were added to a 300 mL flask, and the mixture was stirred at room temperature for 30 minutes.

The <E1 liquid> was mixed with the <E2 liquid>, and stirred at room temperature for 30 minutes to obtain a solution (K8).

50.0 g of this solution K8 was weighed, and 97.0 g of PGME and 3.0 g of a polymer UV-H4000 (manufactured by KSM Co., Ltd.) having a starting function were added to obtain a solution (KM3).

<Synthesis Example 10> <F1 liquid>

12.7 g of AN and 3.0 g of water were placed in a 200 mL flask, and the mixture was stirred to dissolve AN. Thereto were added 13.5 g of EG, 38.6 g of HG, 36.7 g of BCS, 21.7 g of TEOS, and 11.1 g of MPMS, and the mixture was stirred at room temperature for 30 minutes.

<F2 liquid>

TIPT 4.7g and HG 57.9g were added to a 300 mL flask, and stirred at room temperature for 30 minutes.

The <F1 liquid> was mixed with the <F2 liquid>, and stirred at room temperature for 30 minutes to obtain a solution (K9).

50.0 g of this solution K9 was weighed, and 99.7 g of PGME and 0.3 g of a polymer UV-H4000 (manufactured by KSM Co., Ltd.) having a starting function were added to obtain a solution. (KM4).

<Synthesis Example 11>

50.0 g of the solution K3 was weighed, and 97.0 g of PGME and 3.0 g of polymethyl methacrylate (manufactured by Junsei Chemical Co., Ltd.) were added to obtain a solution (KM5).

The composition of each solution is shown in Table 1.

<film forming method>

The solution of the example was filtered under pressure with a membrane filter having a pore size of 0.5 μm, and coated on a substrate by spin coating to form a film. The substrate was dried on a hot plate at 80 ° C for 3 minutes.

<Graphation test>

A film was formed on the glass substrate on which Cr was vapor-deposited by the above-described film formation method. Next, the Cr-deposited glass is placed on one of the substrates to form an ultraviolet-exposed portion and an unexposed portion. Then, a high-pressure mercury lamp (input power supply 1000 W) was used for irradiation for 2 seconds at 50 mW/cm ² (wavelength: 365 nm) by an ultraviolet irradiation device (manufactured by Eyegraphics Co., Ltd., UB 011-3A) (the cumulative irradiation light amount was 100 mJ/cm). ² ).

Then, it was immersed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide for 30 seconds, and then the remaining water was blown off with a blower to visually observe the film surface.

The in-plane film was evaluated as 0 in the case where the in-plane film was completely left, and the film was evaluated as 1 only in the edge portion, and the film was evaluated as 2 in the in-plane, and the film was evaluated as 2 in the in-plane. Those with some deterioration on the surface were evaluated as 4, and those with no change at all were evaluated as 5.

<film state>

On the glass substrate on which Cr was vapor-deposited, a film was produced by the above-described film formation method. The substrate was visually observed, and the film was uniformly evaluated as ○, and the whitened person was evaluated as ×.

<refractive index>

The substrate was used as a substrate (100), and the solution of the example was filtered under pressure with a membrane filter having a pore size of 0.5 μm, and coated on a substrate by spin coating to form a film. The substrate was dried on a hot plate at 80 ° C for 3 minutes.

Then, a high-pressure mercury lamp (input power supply 1000 W) was used for irradiation for 2 seconds at 50 mW/cm ² (wavelength: 365 nm) by an ultraviolet irradiation device (manufactured by Eyegraphics Co., Ltd., UB 011-3A) (the cumulative irradiation light amount was 100 mJ/cm). ² ), the film was formed by firing in a hot air circulating oven at 230 ° C for 30 minutes.

Using this substrate, the refractive index at a wavelength of 633 nm was measured with an Ellipsometer (DVA-FLVW, manufactured by Gully Optical Co., Ltd.).

The results of the patterning test, film state and refractive index are shown in Table 2.

It is understood from Table 1 that the film states of the patterning property and stability can be obtained in Examples 1 to 6.

In Comparative Example 1, since the acrylic polymer (photosensitive polymer containing a photopolymerization initiator) having an initial function was not added, patterning property could not be obtained.

In Comparative Example 2, since the substituent component having a double bond (metal alkoxide having a double bond) was not contained, the compatibility with the acrylic polymer having an initial function was lacking, and the film was whitened.

Comparative Example 3 cannot be obtained because it does not have an initiator and an initial function. To the patterning.

As in the examples in Table 2, the coating liquid for a metal oxide film is a solid component with respect to the metal, and 20% by weight or more of an acrylic polymer having an initial function is added, and the inorganic polymer of the main polymer has a double Since the substituent of the bond contains 25 mol% or more, a metal oxide film having a stable film state and having good patterning property can be obtained.

[Industrial availability]

The coating liquid for forming a metal oxide film of the present invention can be used for forming a metal oxide film having high reliability, and can be used for a display element, an insulating layer, etc., even if it is formed in a pattern, and the film state can be maintained in stability.

The entire contents of the specification, the scope of the application, and the abstract of the Japanese Patent Application No. 2012-226156, filed on Jan.

Claims (14)

A coating liquid for forming a metal oxide film, which comprises a metal alkoxide containing a double bond in a structure and a photosensitive polymer having a photopolymerization initiator. The coating liquid for forming a metal oxide film according to the first aspect of the invention, wherein the photopolymerization initiator is introduced into the photosensitive polymer by a covalent bond. The coating liquid for forming a metal oxide film according to the first or second aspect of the invention, wherein the metal alkoxide is a first metal alkoxide represented by the following formula (I), and the following formula (II) And a composition comprising a second metal alkoxide (alkoxide) and a metal salt represented by the following formula (III), and an organic solvent, water, and a precipitation preventive agent, M ¹ (OR ¹ ) _n (I) (M ¹ represents at least one metal selected from the group consisting of ruthenium, titanium, osmium, zirconium, boron, aluminum, magnesium, and zinc, and R ¹ represents an alkyl group having 1 to 5 carbon atoms or an ethoxylated group. n represents an integer of 2 to 5) R ² _m Si(OR ³ ) _4-m (II) (R ² is a vinyl group, a styryl group, a phenyl group, a naphthyl group and an acryloyl group, a methacryloyl group or An organic group selected from an alkyl group having 1 to 30 carbon atoms substituted by an aryl group, R ³ is an alkyl group having 1 to 5 carbon atoms or an ethylene group, and m is an integer of 1 to 3) M ² (X) _k or M ² oxalate (III) (M ² represents at least one metal selected from the group consisting of aluminum, indium, zinc, zirconium, hafnium, tantalum, niobium, tantalum and niobium, and X represents hydrochloric acid, nitric acid, sulfuric acid, Residue of acetic acid, aminosulfonic acid, sulfonic acid, ethyl acetate or acetonitrile or this Basic salts, k represents the valence of M is ^2). The coating liquid for forming a metal oxide film according to any one of claims 1 to 3, further comprising a third metal alkoxide represented by the following formula (IV). R ⁴ ₁ M ³ (OR ⁵ ) _p-1 (IV) (M ³ represents at least one metal selected from the group consisting of ruthenium, titanium, osmium, zirconium, boron, aluminum, magnesium, and zinc, and R ⁴ represents Substituted by a hydrogen atom or a fluorine atom, and may be substituted by a halogen atom, a vinyl group, a glycidoxy group, a fluorenyl group, a methacryloxy group, an acryloxy group, an isocyanate group, an amine group or a urea group. Further, it may have a hydrocarbon group having 1 to 20 carbon atoms of a hetero atom, R ⁵ represents an alkyl group having 1 to 5 carbon atoms, p is an integer of 2 to 5, and when 1 is p, it is 1 or 2, and when p is 4 , is an integer from 1 to 3, and when p is 5, it is an integer from 1 to 4.) The coating liquid for forming a metal oxide film according to any one of claims 1 to 4, wherein the content of the second metal alkoxide is 25 mol% or more based on the total metal alkoxide. The coating liquid for forming a metal oxide film according to any one of claims 1 to 5, wherein the content of the photosensitive polymer containing the photopolymerization initiator is 20% by weight based on the solid content of the metal. the above. For example, the metal oxide of any one of the claims 1 to 6 is a coating liquid for forming a film, wherein the precipitation preventing agent is N-methyl-pyrrolidone, ethylene glycol, dimethylformamide, dimethylacetamide, diethylene glycol, propylene glycol, hexanediol, and At least one selected from the group consisting of such derivatives. The coating liquid for forming a metal oxide film according to any one of claims 3 to 7, wherein the molar number of the metal atom of the metal salt (M ² ) and the metal atom of the metal alkoxide are the same The molar ratio (M) is 0.01 ≦ M ² /M ≦ 0.7. The coating liquid for forming a metal oxide film according to any one of claims 1 to 8, wherein the first metal alkoxide-based decane oxide or a partial condensate thereof is mixed with a titanium alkoxide. The coating liquid for forming a metal oxide film according to any one of claims 3 to 9, wherein the metal salt is a metal nitrate, a metal sulfate, a metal acetate, a metal chloride, a metal oxalate, a metal amine sulfonate, a metal sulfonate, a metal acetoacetate, a metal acetyl acetonate or an alkaline salt thereof. The coating liquid for forming a metal oxide film according to any one of the above claims, wherein the first metal alkoxide-based decane oxide or a mixture of a partial condensate thereof and a titanium alkoxide is the aforementioned The organic solvent contains an alkanediol or a monoether derivative thereof. A metal oxide film, which is characterized by using a coating liquid for forming a metal oxide film according to any one of claims 1 to 11. And got it. A metal oxide film obtained by using a coating liquid for forming a metal oxide film according to any one of claims 1 to 11 which has a refractive index in the range of 1.50 to 1.70. A display device characterized by having a metal oxide film as disclosed in claim 12 or 13.