JP3071843B2 - Liquid composition for forming metal oxide film, method for producing the same, and method for forming oxide film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid composition for forming a metal oxide film, a method for producing the same, and a method for forming a metal oxide film. The present invention relates to a liquid composition as a raw material for producing various metal oxide films over an oxide film, a method for producing the liquid composition, and a method for forming a metal oxide film using the composition.

[0002]

2. Description of the Related Art As a method of forming a metal oxide-based film, there are known a sputtering method, a vapor deposition method, an ion beam method, and the like which are performed in a vacuum or in an atmosphere of an inert gas such as argon.
There is known a method of vaporizing a metal oxide once and depositing it on a substrate, such as a CVD method. However, these methods are not only expensive in equipment cost, but also difficult to adjust the film components because the evaporation rate and the deposition rate of each component constituting the composite oxide are different. Not exclusively.

A doctor blade method of forming an oxide film by forming a fine powder of a composite metal oxide into a slurry, applying the slurry to a substrate, and then firing the same, is also known. Since the thickness is affected by the particle size of the oxide fine powder or the size of the particles as an aggregate thereof, it is difficult to obtain a uniform and desired film thickness.

On the other hand, if a method for producing an oxide film using a solvent-soluble organometallic compound as a raw material, two or more kinds of metal compounds can be compounded at an arbitrary ratio. Since an oxide film can be easily obtained and a single-crystal thin film can be formed as necessary, it is beginning to be used in the field of electronic devices such as diodes.

As one of the film forming techniques using such an organic metal compound, there is a sol-gel method using a metal alkoxide, and according to this method, a TiO ₂ film, a SiO ₂ film, a ZrO ₂ film are used.
Methods for producing several types of metal oxide films, such as films, have been developed. There is also known a thermal decomposition method in which a metal salt of an organic acid is used as a starting material, diluted with a solvent, coated on a substrate, and then heated to obtain an oxide film. For example, stearate and naphthenate are known. A method of obtaining a ZnO ₂ film, an In ₂ O ₃ film, a SnO ₂ film, or the like using octylate, octylate or the like has also been proposed.

However, the above-mentioned organometallic compounds
Of these, metal alkoxides are generally expensive and
Optimal solvent type and solubility depending on the type of alkoxide
Are different, so all metal alkoxides can be mixed
They cannot be combined by composition. Also, for example
SnO_TwoFilm, In_TwoO _ThreeMembrane, ZrO_TwoAs a raw material for forming films
Naphthenate, octylate, stearic acid used
Organic salts such as salt and caprate are available at relatively low cost
Can be used, but the storage stability as a liquid is poor
And it is difficult to obtain an oxide film with excellent smoothness.
That problem is pointed out. In addition, one of the organometallic compounds
Using a metal complex compound as a raw material for forming a metal oxide thin film
Although some attempts have been made, metal complex compounds are generally
Storage stability is poor and the resulting oxide film is smooth
And lacks practicality due to poor adhesion to the substrate.

On the other hand, as superconducting materials that have recently been receiving attention, there are Y-Ba-Cu-based and Bi-Sr-Ca-Cu-based composite metal oxides. Attempts have also been made to use soluble metal organic acid salts, or to add a chelating agent to a metal alkoxide and solubilize it in an organic solvent before use.

That is, these methods adjust a solvent-soluble organic acid salt or metal alkoxide containing the metal element,
These solutions are mixed so as to have an appropriate composition, coated on a substrate, dried, and then oxidized and thermally decomposed to obtain a metal oxide film.

However, in this method, the stability of the solution containing each organic acid salt or metal alkoxide or the mixture thereof is poor, and some metal compounds are precipitated in the mixed system. Is difficult to obtain. Even if obtained, there is a problem that the film is brittle or the adhesion to the substrate is poor. Moreover, only a limited number of organometallic compounds such as organic acid salts and metal alkoxides are available as commercial products, and many of them are difficult to synthesize themselves. The types of metal oxide films are significantly limited.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and has as its object to solve the above-mentioned problems pointed out in the prior art. A liquid composition which exhibits excellent adhesion even to a simple substrate and which can easily produce various metal oxide films ranging from a single element system to a composite system having excellent film forming ability, and a method for producing the same. It is assumed that. Another object of the present invention is to provide a method for forming a uniform and sound metal oxide film free from defects such as cracks using such a liquid composition.

[0011]

Means for Solving the Problems The constitution of the liquid composition for forming a metal oxide film according to the present invention which can solve the above problems is one kind selected from the group consisting of metal rosinate and abietic acid salt. Or two or more resin salts (hereinafter referred to as Ma)
1) with nitrogen and / or oxygen as coordinating atoms
One or two or more organic compounds having up to 6
Rosin (hereinafter referred to as Ac) or one or more monobasic acids having 4 to 13 carbon atoms (hereinafter referred to as Ac)
d) organic solvent (hereinafter referred to as Se) Lb and / or Ac per gram atom in terms of metal of the above Ma
Is contained in a total amount of 0.1 to n mol (n is the average oxidation number of Ma), and the content of Rd in the total amount of the composition is 5 to 8
It has a gist in that it is blended so that the content of Se is 0% by weight and the content of Se is 5 to 80% by weight.

This liquid composition has a total of Lb and / or Ac per gram atom in terms of metal of Ma.
0.1 to nmol (n is the average oxidation number of Ma), and each content of Rd and Se in the total amount of the composition is 5 to 80, respectively.
The components can be mixed at the same time or in any order so as to obtain a weight percent, and at the time of mixing containing Se as a mixed component, it can be easily obtained by heating or refluxing to form a solution. When the liquid composition is applied and dried on an appropriate substrate and then oxidized and fired at 440 ° C. or higher, a metal oxide film having uniform and excellent physical properties can be obtained.

[0013]

As described above, the composition for forming a metal oxide film according to the present invention comprises a metal resinate (Ma) selected from the group consisting of a metal rosinate and an abietic acid salt, containing nitrogen and / or
Or one or more (Lb) organic compounds having 1 to 6 oxygen atoms as coordinating atoms, and 4 to 13 carbon atoms.
The organic solvent (Se) is solubilized by combining with one or more of the monobasic acids (Ac), and rosin (Rd) is further added as another component to form a metal-containing component. It is characterized by further promoting the solubilization, increasing the storage stability of the solution, and further enhancing the film forming ability and the adhesion to the substrate.

In the present invention, as the resin acid salt (Ma), various rosinates using rosin (rosin) as a raw material and various metal salts of abietic acid which is a main component of rosin (rosin) are used. These metal resinates may be commercially available products, or may be synthesized, for example, by the following method. That is, as a method for synthesizing a metal resinate, an aqueous solution of a metal halide, nitrate, formate, acetate or the like, rosin 1.1 times the stoichiometric amount, and / or abietic acid and ammonia water or diethylamine, After mixing one of the amines such as dimethylamine, triethylamine and trimethylamine with a solution obtained by dissolving or suspending the same in an organic solvent, the mixture is refluxed to extract the metal resinate into the organic solvent and separate the solvent phase. After that, a method of distilling off the solvent is exemplified. At this time, depending on the case, the solvent may be used without being distilled off.

As the organic solvent to be used, any solvent may be used as long as it has a high solubility in the formed metal resinate and can be separated from the aqueous phase. Preferred examples thereof include benzene, toluene, xylene and terpine. Oil and the like. The resin acid solution mixed with the metal salt aqueous solution can be used in the form of a Na salt or the like. However, when the existence of Na ions is disliked when used as an electronic material, the Na salt or the like is used. It is better not to use it for types. Further, as a simple method, a method of directly reacting a metal alkoxide with a resin acid in an organic solvent can also be used.

Next, examples of the organic compound (Lb) having 1 to 6 nitrogen and / or oxygen as ligands include amines such as ammonia, ethylenediamine and triethylenetetramine, monomethylamine, monoethylamine, dimethylamine, diethylamine, and the like. Alkylamines such as trimethylamine and triethylamine; monoethanolamine, diethanolamine, triethanolamine,
Ethanolamines such as N-methylethanolamine, N-methyldiethanolamine and N-propylethanolamine; β-diketone compounds such as acetylacetone: β-diketone esters such as methyl acetoacetate and ethyl acetoacetate: ethylene glycol, diethylene glycol , Glycerin, 2-ethylhexane-1,3-
Examples include polyhydric alcohols such as diols.

The organic compound (Lb) has the effect of increasing the stability in solution by coordinating nitrogen and / or oxygen contained in the molecule with the resin salt (Ma). In order to effectively exert such an effect, the molecule must have at least one nitrogen and / or oxygen as a coordinating atom. In addition, from the relation of the complex forming ability of the metal element, 4 to 6 coordination may be used as a normal complex compound. Therefore, even if the number of coordination atoms is 7 or more, it is not very effective. It is sufficient that the number of coordinating atoms is 1 or more and 6 or less. The atoms having coordination ability include P, As, S, Se and the like in addition to nitrogen and oxygen. In the present invention, nitrogen and oxygen are selected as those which can be easily eliminated by firing and have no toxicity.

Monobasic acid (Ac) having 4 to 13 carbon atoms
Glycolic acid, hydroacrylic acid, lactic acid, glyceric acid, α-oxyacetic acid, γ-oxybutyric acid, trimethylolacetic acid, oxytrimethylacetic acid, 2-hydroxy-
Monobasic acids having an alcoholic hydroxyl group such as 2-methylacetic acid, leucic acid, 2-ethyl-3-hydroxyhexanoic acid, and 2-hydroxyhexanoic acid; hexanoic acid, 2-ethylhexanoic acid, and naphthenic acid. Among these, particularly preferred are monobasic acid and 2-ethylhexanoic acid which can form a 5- or 6-membered ring together with the above-mentioned metal elements. These may be used alone or in combination with the organic compound (Lb). It is possible to obtain a solution which is uniform and has a storage stability of one year or more. If the monobasic acid has less than 4 carbon atoms, the solubility in a solvent may be poor or the storage stability may be poor, which is not preferred. Those having more than 13 carbon atoms are not preferred because they have poor solubility in a solvent and have a problem of carbonization during firing.

Both the metal compound (Lb) and the monobasic acid (Ac) have the effect of promoting the solubilization of the metal resinate (Ma) in the organic solvent (Se) and enhancing the storage stability. These can be used alone or, if necessary, in combination of two or more.

The amount of the metal compound (M)
(Lb) per gram atom in terms of metal of a) and / or
Alternatively, the total sum of (Ac) should be in the range of 0.1 to n mol (n is the average oxidation number of the metal): preferably in the range of 0.5 to n / 2 mol, and if less than 0.1 mol, the storage stability is poor,
On the other hand, if it exceeds n mol, the smoothness of the film at the time of film formation decreases, or the film foams at the time of firing, and the film-forming ability deteriorates.

Pine resin (rosin) (Rd) acts not only as a viscosity modifier for the solubilized liquid composition, but also as a film-forming agent and an agent for improving the adhesion to a substrate, and is used as a gum rosin or tall oil. Rosin, wood rosin, and the like are typical examples. The rosin contains abietic acid, neoabietic acid, dihydroabietic acid, tetrahydroabietic acid, etc. The composition of the pine resin varies depending on the type of rosin and the treatment method. May be used. It should be noted that rosin is widely marketed as a natural product and can be obtained at a low cost, so it can be said that it is the simplest material. Various commercially available rosins have been known in addition to natural products, such as those modified by adjusting the degree of unsaturation, and any of them can be used in the present invention.

The amount of the rosin (Rd) is in the range of 5 to 80% by weight, more preferably 10 to 60% by weight, based on the final liquid composition.
When the amount is less than 80% by weight, the film forming ability tends to be deteriorated. On the other hand, when the amount is more than 80% by weight, the storage stability of the liquid composition is deteriorated.

As the organic solvent (Se), any solvent may be used as long as it can solubilize each of the above-mentioned components, and the workability at the time of film formation (vaporization, large and small vapor pressure, etc.) and film formation method May be appropriately selected in consideration of the type (eg, immersion method, spray method, printing method, etc.).
Alcohols such as methyl alcohol and ethyl alcohol; methyl ether, ethyl ether; aromatic hydrocarbons such as toluene; ketones such as acetone and methyl ethyl ketone; terbineol; turpentine oil; glycols such as ethylene glycol and ethylene glycol monoethyl ether; These can be used alone, and can also be used as a mixed solvent of two or more.

The amount of the organic solvent (Se) used should be in the range of 5 to 80% by weight, preferably 10 to 60% by weight in the final liquid composition. If it is less than 5% by weight, the dissolution of the rosin (Rd) and the metal resinate (Ma) becomes insufficient, while if it exceeds 20% by weight, the solution concentration in terms of oxide becomes too low, which is not practical.

The essential components constituting the liquid composition according to the present invention are as described above. In the present invention, the metal resinate (Ma), the organic compound (Lb) and / or the monobasic acid (Ac) pine resin are used. The reactants or mixtures of (Rd) have a favorable effect on each other and are solubilized in the organic solvent (Se);
A uniform and stable liquid composition can be obtained.

Furthermore, the presence of rosin (Rd) significantly improves the film-forming properties and the adhesion to the substrate, and the organic compound (Lb) and / or monobasic acid (Ac) makes the storage stability as a liquid composition. Thus, a liquid composition containing various metal elements can be produced, and a liquid composition having a composite composition can be obtained by appropriately mixing these.

The method of producing the liquid composition of the present invention includes (1) a method of simultaneously mixing and mixing Ma and Lb and / or Ac, Rd and Se, and (2) a method of mixing Ma and Lb and / or
Or a method of adding and mixing Ac to Se and then adding and mixing Rd; (3) a method of adding and mixing Ma and Rd to Se and then adding and mixing Lb and / or Ac thereto; Is adopted. When the system is heated to about 60 to 90 ° C. or refluxed in a blending or mixing stage containing at least Se as a blending component, a uniform liquid composition can be obtained.

The liquid composition for forming a metal oxide film thus obtained is stable even in the state of being left in the air, and shows no alteration or generation of insolubles for one year or more. The liquid composition has a viscosity of, for example, 1 at 25 ° C.
The viscosity can be arbitrarily adjusted in a range from 0 centipoise to about 20,000 centipoise, and can be adjusted to a viscosity suitable for various film forming methods such as an immersion method, a spinner method, and a screen printing method.

If necessary, it is effective to add a cationic, nonionic, anionic or other surfactant as a leveling agent for improving the coating property, or to add an antifoaming agent to the liquid composition. is there.

The liquid composition thus obtained may be used as it is or, if necessary, further diluted with an appropriate organic solvent, for example, a heat-resistant substrate such as silica, magnesia, alumina, zirconia, glass or various ceramics, stainless steel, It is applied to a surface of a metal substrate such as copper or aluminum by any method such as a dipping method, a spinner method, a screen printing method, and dried at about 50 to 120 ° C., and then 440
When firing at a temperature of at least 450 ° C, preferably at least 450 ° C,
A metal oxide film can be obtained.

If the heating and sintering temperature is lower than 440 ° C., even if the sintering is performed for a long time, a part of the sintering tends to remain as a carbide. Therefore, the sintering is preferably performed at 450 ° C. or more.

The concentration in terms of metal oxide in the liquid composition is 1
If the amount exceeds 0% by weight or the viscosity is 100 centipoise or more, pre-drying is performed before firing, so that a smoother and more uniform oxide film is easily obtained. The content in terms of metal oxide in the liquid composition is 0.5 to 20% by weight,
It is preferably 1 to 10% by weight, and if it is less than 0.5% by weight, the film thickness that can be formed by one coating is too thin. . On the other hand, if it exceeds 20% by weight, the adhesion of the oxide film to the substrate may be reduced, or the film may be cracked.

The liquid composition for forming a metal oxide film obtained by the present invention is used for various films such as an ultraviolet absorbing film, a heat ray reflecting film, a superconductor film, various dielectric films, a conductive film and an insulating film. It can be used for manufacturing.

[0034]

EXAMPLES Next, the structure, operation and effects of the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.

Example 1 15 g (0.046 mol) of lanthanum oxide was suspended in 100 ml of water.
Add 14 g of nitric acid (61%) and dissolve. 45 g of rosin (gum rosin) and 9 g of aqueous ammonia are added to 150 g of turpentine oil while stirring and gradually added thereto while stirring. 6.6 g of 2-ethylhexanoic acid (0.046
Mol) and 3.4 g (0.023 mol) of triethanolamine and kept at 50-60 ° C. for 30 minutes. Further, 60 g of rosin (gum rosin) is added and dissolved by refluxing to give a liquid composition of 3 g.
00g was obtained. The metal oxide (La ₂ O ₃ ) content in this solution was 4.3% by weight, and the viscosity at 25 ° C. was 580 cp.
s. This composition was stable even in the air, and no deterioration was observed even after being left for one year or more.

The composition obtained above was diluted twice with toluene, applied to a glass substrate by a dipping method (pulling speed: 10 mm / min), dried at 100 ° C. for 30 minutes, and immediately dried at 550 ° C.
When heated and baked at 20 ° C. for 20 minutes, a transparent lanthanum oxide thin film was obtained. A similar thin film was formed on a SUS304 stainless steel substrate to obtain a transparent thin film, and a 90-degree bending test was performed. As a result, no crack or peeling was observed.

Example 2 25 g (0.052 mol) of tantalum ethoxide was added to a solution prepared by heating and dissolving 40 g of rosin (gum rosin) and 3.8 g of diethylamine in 200 g of terpineol before stirring.
15 g of 2-ethylhexanoic acid and 20 g of toluene
Was added to give about 300 g of a liquid composition. The metal oxide (Ta ₂ O ₅ ) content in this composition was 3.7% by weight, and the viscosity was 85 cps at 25 ° C., so that the composition can be stably stored for one year or more.

This composition was immersed in a dipping method (with a lifting speed of 10 mm
/ min) on a quartz substrate.
After drying for an hour and immediately baking at 500 ° C. for 30 minutes, a transparent bluish tantalum oxide thin film was obtained.

Example 3 A resinate solution obtained by adding 17 g (0.1 mol) of barium hydroxide and 60 g (0.2 mol) of abiethyl acid to a mixture of 150 g of toluene and 150 g of terpineol was heated and refluxed for 3 hours. When 13 g of ethyl acetoacetate is added, and 25 g of rosin (gum rosin) is further added and dissolved by heating, a liquid composition is obtained.

This composition had a viscosity of 50 cps at 25 ° C. and a metal oxide equivalent (BaO) concentration of 4.5% by weight.

This composition was immersed in a dipping method (with a pulling speed of 10 mm / m
After coating on a quartz substrate according to (in), drying at 100 ° C. for 1 hour and then baking at 850 ° C. for 1 hour, a nearly transparent barium oxide thin film was obtained.

Example 4 155 g (0.5 mol) of lithium abietic acid was added to turpentine oil 50
Then, 12 g (0.1 mol) of ethyl acetoacetate is added, and 20 g of gum rosin is further added. This is heated and stirred to obtain a liquid composition comprising a homogeneous solution. By adding 4 g of triethanolamine to the above reaction system, the dissolution rate of lithium abietate in turpentine oil can be increased.

The metal oxide (Li ₂
O) The converted content is 3.0% by weight, and the viscosity at 25 ° C. is 6200 cp.
s. This solution is stable for at least 6 months. When this composition is used, it is printed on a glass substrate using a 295 mesh screen, dried at 100 ° C., and baked at 500 ° C. for 30 minutes. A transparent lithium oxide film was obtained.

Comparative Example 1 A liquid composition was obtained in the same manner as in Example 4 except that ethyl acetoacetate and triethanolamine were not added. This liquid composition was unstable, with one part sediment occurring in about one week.

Example 5 Lactic acid was used instead of 2-ethylhexanoic acid in Example 1.
A liquid composition was obtained in exactly the same manner except that 1 g (0.046 mol) was used. The composition is dipped in the immersion method (pulling speed 10 mm / mi
The composition was applied on a glass substrate according to n) and dried and fired under the same conditions as in Example 1 to obtain a transparent lanthanum oxide film.

Example 6 28 g (0.1 mol) of indium oxide In ₂ O ₃ was suspended in 200 ml of water, and 30 g of nitric acid (61%) was added thereto and dissolved. 90 g of rosin (gum rosin) is previously dissolved in 200 g of toluene, and this solution is gradually added to a solution to which 22 g of diethylamine has been added. Then, the mixture is heated under reflux for 1 hour, cooled, and the organic phase is separated. The solvent is removed to obtain a viscous solution. Then add 50 g of turpentine oil to this viscous liquid.
, 2-ethylhexanoic acid 28g, acetylacetone 5g
, 120 g of gum rosin and heating under reflux for about 30 minutes to obtain a liquid composition. The composition had a metal oxide equivalent (In ₂ O ₃ ) content of 5.8% by weight and a viscosity at 25 ° C. of 850%.
It was 0cps. The composition was stable in air and did not show any alteration for at least 6 months.

The composition obtained above was printed on a glass substrate using a 275 mesh screen, dried at 100 ° C. and baked at 550 ° C. for 20 minutes to obtain a transparent indium oxide film.

Comparative Example 2 A liquid composition was obtained in exactly the same manner as in Example 6 except that 2-ethylhexanoic acid and acetylacetone were not added. This composition is unstable, and in about one month
Partial precipitation occurred.

Example 7 30 g of rosin (gum rosin) and 28 of 2-ethylhexanoic acid
was dissolved in 60 g of turpentine oil by heating, and 33 g (0.095 mol) of titanium-tetra-n-butoxy was further added.
Keep at 0-60 ° C for 30 minutes. This solution contains oxide (Ti
O ₂ ) was 4.8% by weight, and the viscosity was 110 cps at 25 ° C. This liquid composition and the barium-containing liquid composition obtained in Example 3 were mixed at a weight ratio of 1: 1 and then SUS3
Immersion method on 16 stainless steel substrates (pulling speed 10mm / mi
The composition was applied in n), dried at 100 ° C. for 15 minutes, and baked at 700 ° C. for 30 minutes. As a result, a transparent film was obtained although it was slightly yellowed.

Example 8 2 g in 33 g (0.11 mol) of aluminum tri-n-butoxy
16 g of ethylhexane-1,3-diol and 14 g of ethyl acetoacetate are added, and the mixture is refluxed for 2 hours. After reflux, 30 g of abietic acid, 40 g of turpentine oil and toluene 2
Add 0 g and continue refluxing for another 2 hours. When a substantially uniform solution is obtained, 20 g of rosin (rosin) is added and dissolved by heating. 20 g of an ethanol solution of lithium ethoxide (0.1 mol in terms of Li) is added to this solution, and 7 g of triethanolamine is further added. When kept at 50-60 ° C. for 30 minutes, a liquid composition was obtained. The content in terms of oxide in this composition was 3.1% by weight, and the viscosity was 95 cps at 25 ° C.
Met. This composition is applied to a glass substrate by a dipping method (pulling speed: 10 mm / min), dried at 100 ° C., and then dried at 500 ° C.
For 20 minutes, a uniform and transparent film was obtained.

[0051]

The present invention is constituted as described above, and its effects are summarized as follows. (1) The liquid composition of the present invention has excellent coating properties and film forming properties, and forms a uniform film on various substrates such as glass, metal, ceramics, and ceramics. (2) The composition is uniform and very stable, and its viscosity can be easily adjusted, and can be adjusted to any viscosity according to the type of coating method. (3) Since this composition forms a homogeneous oxide film only by being oxidized and fired at a temperature of 440 ° C. or more after being applied to a substrate, it can be widely used as a sensor material, a superconductive material, various coating materials, and the like. it can.

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Claims (3)

(57) [Claims] 1. One or two or more resinates (hereinafter referred to as Ma) selected from the group consisting of metal rosinates and abietic acid salts having 1 to 6 nitrogen and / or oxygen as coordination atoms. One or more organic compounds (hereinafter referred to as Lb) One or more (hereinafter referred to as Ac) rosin (hereinafter referred to as Rd) organic solvent (hereinafter referred to as Se) of monobasic acid having 4 to 13 carbon atoms Is blended, and Lb is equivalent to 1 gram atom in terms of the metal of Ma.
And / or Ac in a total amount of 0.1 to n mol (n is the average oxidation number of Ma), and R accounts for the total amount of the composition.
A liquid composition for forming a metal oxide, which is blended so that the contents of d and Se are 5 to 80% by weight, respectively. 2. One or more resinates (hereinafter referred to as Ma) selected from the group consisting of metal rosinates and abietic acid salts having 1 to 6 nitrogen and / or oxygen as coordination atoms. One or more organic compounds (hereinafter referred to as Lb), one or more monobasic acids having 4 to 13 carbon atoms (hereinafter referred to as Ac), rosin (rosin) (hereinafter referred to as Rd), and an organic solvent (hereinafter referred to as Rd) Se)
Is expressed as Lb and / or A with respect to the metal conversion of Ma.
c is 0.1 to nmol in total (n is the average oxidation number of Ma), and each content of Rd and Se in the total amount of the composition is 5
The metal oxide is mixed at the same time or in an arbitrary order so that the content thereof becomes about 80% by weight, and at the time of mixing containing Se as a mixed component, the mixed system is heated to form a solution. Production method of liquid material for forming film. 3. A liquid composition for forming a metal oxide film according to claim 1, which is applied on a substrate, dried and then oxidized at 440 ° C. or higher.
A method for forming a metal oxide film, characterized by firing.