JP3521237B2 - Composition for forming metal oxide film, method for producing the same, and method for forming metal 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 composition for forming a metal oxide film, a method for producing the same, and a method for forming a metal oxide film.

In this specification, "%" means
It means "% by weight".

[0003]

2. Description of the Related Art Metal oxide films have been conventionally used as various functional films. The mainstream of these film forming methods is a physical method such as a sputtering method, a vapor deposition method or an ion beam method, or a chemical method such as a CVD method, which is performed under vacuum or in an atmosphere of an inert gas such as argon gas. Has become. However, these methods require expensive equipment. Further, in the case of obtaining a composite oxide, it is difficult to adjust the film components due to the difference in evaporation rate or precipitation rate of each component, and the film often fails to obtain desired characteristics. Further, it is often technically difficult to form a large-area film.

Also known is a doctor blade method in which a fine powder of a composite metal oxide is made into a slurry, which is applied onto a substrate and baked. However, in this method, the film thickness is affected by the particle size of the oxide powder and the size of the particles as an aggregate thereof, so that it is difficult to obtain an arbitrary film thickness.

There is a method of applying a solution of an organometallic compound soluble in a specific solvent onto a substrate. In this method, two or more kinds of organometallic compounds can be compounded in an arbitrary ratio even when forming a composite oxide film, and thus a target composition and film thickness can be easily obtained.

[0006] A typical example of the film forming technique using such an organic metal oxide is a sol-gel method using a metal alkoxide, and a metal salt of an organic acid as a raw material, which is diluted with a solvent. There is known a thermal decomposition method or the like in which a metal oxide is applied to a substrate and heated to obtain a metal oxide.

TiO ₂ film, SiO ₂ by sol-gel method
Methods have been developed for producing several types of metal oxide films such as films, ZrO ₂ films and the like. However, among the organic metal oxides, metal alkoxides are generally expensive and cannot be easily synthesized, so that they are not necessarily combined in various compounding compositions.

Further, in the thermal decomposition method, ZnO is prepared by using naphthenate, octylate, etc., which are relatively inexpensively available.
A method for obtaining a film and a SnO ₂ film has been proposed. However, these cannot be freely combined in various ways.

Further, there has been an attempt to use a metal complex which is a kind of organic acid as a raw material for forming a metal oxide. However, the metal complex is generally poor in storage stability as a liquid and poor in film-forming properties such as adhesion to the substrate and smoothness, so that it is not practical.

On the other hand, an organic acid metal salt soluble in a solvent is used to produce a thin film of a composite metal oxide of superconducting material or various dielectrics, or a chelating agent is added to a metal alkoxide to prepare an organic solvent. Has been attempted to be solubilized with respect to. However, if the solution containing each organic acid metal salt and metal alkoxide is unstable,
Alternatively, it may be difficult to obtain a metal oxide film having a desired composition due to the deposition of a part of the metal compound. Even if a metal oxide film is obtained, there are problems that the film is weak and the adhesion to the substrate is poor.
Moreover, organic metal compounds such as organic acid salts and metal alkoxides are not available as commercial products except limited ones, and it is often difficult to synthesize them. Therefore,
Since the type of composite metal oxide film that can be produced by this method is significantly limited, only relatively low-viscosity solutions are used in the dipping method, spraying method, etc. It is not common as a liquid composition.

[0011]

SUMMARY OF THE INVENTION Therefore, the present invention solves the problems of the prior art and shows a single or composite element metal which has excellent film-forming ability while exhibiting excellent adhesion to any substrate. An object of the present invention is to provide a composition for forming a metal oxide film, which can easily produce an oxide film.

Another object of the present invention is to provide a method for producing the above metal oxide film forming composition.

A further object of the present invention is to provide a method for forming a uniform and good metal oxide film free from defects by using the above composition for forming a metal oxide film.

[0014]

Means for Solving the Problems As a result of intensive studies in view of the current state of the art, the present inventor has (1) at least one kind of organic acid metal salt, and (2) 1 to 4 At least one organic compound having oxygen as a coordinating atom,
It has been found that the above object can be achieved by a composition obtained by mixing (3) at least one kind of organic polymer compound and rosin and (4) an organic solvent in a specific ratio. That is, when using this composition, by baking the coating film of the composition, while exhibiting excellent adhesion to the substrate, a metal oxide film of a single or composite element excellent in film forming ability is formed. It was found that it can be easily manufactured. Also,
It has been found that a composition capable of producing a uniform and good metal oxide film without defects can be formed by mixing these components simultaneously or in a specific order and heating and refluxing at a specific stage.

That is, the present invention provides the following.

1. A composition for forming a metal oxide film,
(1) at least one kind of organic acid metal salt, (2) at least one kind of organic compound having 1 to 4 oxygen as coordination atoms, (3) at least one kind of organic polymer compound and rosin, and (4) organic Contains at least one solvent,
(5) Component (1) is contained in an amount of 0.5 to 20% in terms of metal oxide, and (6) component (1) contains 1 gram atom of metal,
Component (2) in an amount of 0.1 to n mol (n is the average oxidation number of the metal in component (1), and is a weighted average oxidation number when two or more metals are used); 7) A composition for forming a metal oxide film, which contains 5 to 80% of the component (3) and 20 to 80% of the (8) component (4).

2. In the method for producing a composition for forming a metal oxide film, (1) at least one kind of organic acid metal salt,
(2) at least one organic compound having 1 to 4 oxygens as coordinating atoms, (3) at least one organic polymer compound and rosin, and (4) at least one organic solvent. In the composition, (5) component (1) is 0.5 to 20% in terms of metal oxide, and component (2) is 0.1 to n per 1 gram atom of metal in component (1). Mol (n is the average oxidation number of the metal in component (1), and is the weighted average oxidation number when two or more metals are used), (7) component (3) is 5-80%, And (8) a metal oxidation characterized by mixing and heating the component (1), the component (2), the component (3) and the component (4) in a proportion of 20 to 80% of the component (4). A method for producing a composition for forming a physical film.

3. In the method for producing a composition for forming a metal oxide film, (1) at least one kind of organic acid metal salt,
(2) at least one organic compound having 1 to 4 oxygens as coordinating atoms, (3) at least one organic polymer compound and rosin, and (4) at least one organic solvent. In the composition, (5) component (1) is 0.5 to 20% in terms of metal oxide, and component (2) is 0.1 to n per 1 gram atom of metal in component (1). Mol (n is the average oxidation number of the metal in component (1), and is the weighted average oxidation number when two or more metals are used), (7) component (3) is 5-80%, And (8) Component (1), Component (2) and Component (4) are mixed at a ratio of 20 to 80% of Component (4), and then Component (3) is mixed and heated. And a method for producing a composition for forming a metal oxide film.

4. In the method for producing a composition for forming a metal oxide film, (1) at least one kind of organic acid metal salt,
A composition formed by using (2) at least one organic compound having 1 to 4 oxygens as coordinating atoms, (3) at least one organic polymer compound and rosin, and (4) at least one organic solvent. In the product, the component (1) is 0.5 to 20% in terms of metal oxide, and the component (2) is 0.1 to nmole per 1 gram atom of the metal in the component (1). (N is the average oxidation number of the metal in component (1), and is the weighted average oxidation number when two or more metals are used),
(7) Component (3) is 5 to 80%, and (8) Component (4)
Is 20 to 80%, and component (1) and component (3)
And the component (4) are mixed and heated, and then the component (2) is mixed, the method for producing a composition for forming a metal oxide film.

5. A method for forming a metal oxide film, which comprises coating the composition for forming a metal oxide film of the above 1 on a substrate and baking the composition at 400 ° C. or higher.

The organic acid metal salt used in the present invention (hereinafter referred to as M
Examples of a) include metal salts of saturated monocarboxylic acids having 6 to 10 carbon atoms and metal salts of cyclic monocarboxylic acids.

6 to 10 carbon atoms as an organic acid component of Ma
Examples of the saturated monocarboxylic acid include hexanoic acid, enanthic acid, octylic acid, capric acid and the like.

Examples of the cyclic monocarboxylic acid include naphthenic acid which is a main component of petroleum acid and abietic acid and naphthoic acid which are main components of rosin.

The metal used as the metal component of Ma is
2A group; Mg, Ca, Sr, Ba, 3A group; Y, lanthanoids of La, Ce, Pr, Nd, Sm, Eu, Gd,
Dy, Er, Yb, 4A group; Ti, Zr, 5A group; V,
Nb, Ta, 6A group; Cr, 7A group; Mn, 8 group; F
e, Co, Ni, 1B group; Cu, 2B group; Zn, 3B
Group: B, Al, Ga, In, 4B group: Si, Ge, S
Examples include n, Pb, and 5B groups; Sb, Bi, and the like.

Ma is a known compound and can be easily synthesized. For example, an aqueous solution of metal halides, nitrates, sulfates, acetates and the like, and 1.1 times the stoichiometric amount of the above organic acid and ammonia water and water necessary to produce organic acid salts of the respective metals. After dissolving or suspending an alkaline solution such as sodium oxide solution in an organic solvent, the organic acid salt is extracted into the organic solvent by refluxing, the solvent phase is separated, and then the solvent is generally distilled off. Indicated.

Alternatively, with respect to the metal alkoxide, at least one kind of the organic acid having the above-mentioned carboxyl group is selected, and 1/3 to 1 times the stoichiometric amount necessary to generate the organic acid salt of each metal. It is also possible to synthesize an organic acid metal salt in which a part of the alkoxyl group of the metal alkoxide is substituted with an organic acid group by adding the above-mentioned compound in the range up to and refluxing in an organic solvent. This may optionally be used without distilling off the solvent. Further, even if unreacted metal alkoxide remains, it can be used as it is.

In the present invention, the organic compound having 1 to 4 oxygens as coordination atoms (hereinafter sometimes referred to as Lb) promotes the dissolution of Ma in Sd, and the coordination atom contained in the molecule. Coordinatively bonding oxygen and Ma, which is, has the effect of improving storage stability. In order to effectively exert the effect of enhancing the stabilization in the solution state,
Lb must have at least one oxygen atom in the molecule and must form a 5-membered ring or a 6-membered ring with the metal element. As a coordination element, N, P, As,
Although S and Se are conceivable, in the present invention, a compound having oxygen as a coordination atom is used because it easily disappears by firing and does not cause pollution. Examples of Lb used in the present invention include β-diketones, β-ketoesters, polyhydric alcohols and higher alcohols.

Examples of β-diketone include acetylacetone and dipivaloylmethane.

Examples of β-ketoesters include methyl acetoacetate and ethyl acetoacetate.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, glycerin, 2-ethylhexane-1,3-diol and the like.

As the higher alcohol, hexanol,
Heptanol, n-octanol, 2-ethylhexanol, decanol, etc. are illustrated.

These Lb can be used alone or in combination of two or more kinds. The amount of Lb used is
The metal conversion amount of Ma is 0.1-n (n
Is the average oxidation number of the metal or the weighted average oxidation number) moles when two or more metals are used. Lb amount is 0.1
If it is less than the molar amount, the storage stability is not improved, whereas n
If it exceeds the molar amount, the smoothness of the coating film at the time of film formation is lowered, or foaming occurs at the time of firing to lower the film forming ability. L
The amount of b is 0.25 to n per gram atom of metal in Ma.
The ratio is preferably / 2 mol.

In the present invention, at least one organic polymer compound and rosin (hereinafter sometimes referred to as Rc)
Has a function of acting as a viscosity modifier for the composition in which Ma is solubilized, and a function of enhancing the film-forming ability and the adhesion to the substrate.

Examples of the organic polymer compound include natural polymer compounds such as celluloses and polysaccharides and synthetic polymer compounds.

Examples of celluloses include methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose and the like.

Examples of the polysaccharides include xanthan gum and the like.

Examples of synthetic polymer compounds include polyvinyl alcohol, polyvinylpyrrolidone, polymethylmethacrylate and the like.

Examples of the rosin include gum rosin, tall rosin, wood rosin and the like.

When rosin is used alone as a viscosity modifier, if the viscosity of the composition exceeds 10,000 cps, the coating film often foams during firing. However, when used in combination with an organic polymer compound, foaming is suppressed and a smooth and uniform film is obtained.

The compounding ratio of the organic polymer compound and rosin is 100 parts by weight of the total of the two, the former: the latter = 10-9.
It is set to 0:10 to 90.

The content of Rc in the composition finally obtained is 5 to 80%. 5% content
If it is less than the above, the film forming ability is deteriorated. On the other hand, when it exceeds 80%, foaming may occur during firing, the film forming ability may be deteriorated, and the storage stability may be deteriorated to generate a precipitate. The content of Rc in the composition finally obtained is more preferably 10 to 70%,
10 to 60% is particularly preferable.

The organic solvent (hereinafter sometimes referred to as Sd) used in the present invention generally has high solubility in organic acid metal salts and organic compounds having oxygen as a coordination atom,
Any solvent that can be separated from the aqueous phase may be used, and among these, workability during film formation (vaporization, large or small vapor pressure, etc.), film formation method (immersion method, spray method, screen printing method, etc.)
It is appropriately selected in consideration of the above. Examples of Sd include turpentine oil, pine oil, ligroin, alcohol, ether, aromatic hydrocarbon, ketone and the like.

As alcohol, methyl alcohol,
Examples include ethyl alcohol, terpineol, ethylene glycol and the like.

Examples of the ether include methyl ether, ethyl ether, ethylene glycol monoethyl ether and the like.

Examples of aromatic hydrocarbons include benzene, toluene, xylene and the like.

Examples of ketones include acetone and methyl ethyl ketone.

These solvents may be used alone or in combination of two or more. The amount of Sd used is 20 to 80% based on the amount of the composition finally obtained. 20
If it is less than%, the dissolution of Ma and Lb becomes insufficient, which adversely affects the storage stability. On the other hand, if it exceeds 80%, the concentration becomes too low to be practical. The amount of Sd used is more preferably 20 to 70% in the finally obtained composition, and particularly preferably 10 to 60%.

The method for producing the composition of the present invention includes:
(A) A method of mixing Ma, Lb, Rc and Sd and heating and dissolving, (b) adding Ma and Lb to Sd, and then Rc
Method of adding and dissolving by heating (c) Ma and Rc to S
There is a method in which Lb is mixed after being added to d and heated and dissolved. At least at the stage of mixing Sd, the system was adjusted to 60
A uniform composition can be obtained by heating under reflux at a temperature of ℃ to 110 ℃, preferably 80 ℃ to 110 ℃.

The composition for forming a metal oxide film thus obtained is stable even when left in the air, and no alteration or generation of impurities is observed for a long period of time. Further, the composition has, for example, 10 cps at 25 ° C.
~ Viscosity can be adjusted in the range of about 20,000 cps, dipping method,
The viscosity can be adjusted to be suitable for various film forming methods from the spinner method to the screen printing method.

To the composition of the present invention, a cationic, nonionic or anionic surfactant or a defoaming agent may be added as a leveling agent for improving coatability, if necessary. You can also

When the composition of the present invention is used, it may be diluted with a suitable solvent if necessary, and a heat-resistant substrate such as silica, alumina, magnesia or zirconia, a metal substrate such as stainless steel, aluminum or copper, glass, various materials, etc. A metal oxide film is obtained by applying it to the surface of a ceramics or the like by an arbitrary method, predrying it at 50 ° C. to 120 ° C., or baking as it is at a temperature of 400 ° C. to 1200 ° C., preferably 450 ° C. to 850 ° C. be able to.

In coating, it is preferable that the concentration of metal oxide in the composition is 0.5 to 20%.
When the content of metal oxide in the composition is less than 0.5%, it is 1
Since the film thickness formed by the single coating is too thin, repeated coating is required to increase the film thickness, which is not practical. On the other hand, if it exceeds 20%, the adhesion of the oxide film to the substrate may be lowered, or the film may be cracked. The metal oxide equivalent content is preferably 1 to 10%. When the metal oxide conversion concentration in the composition exceeds 10% or the viscosity is 100 cps or more, a smoother and more uniform oxide film can be easily obtained by performing preliminary drying.

The thickness of the thin film formed by the composition varies depending on the type of composition. Oxide conversion content 5%,
When the viscosity is 50 to 80 cps, the film thickness is usually 0.1 to 0.3 μm by one application by the dipping method. Since the film is more uniform and smooth, the film thickness is preferably 0.1 to 0.2 μm.

[0054]

Industrial Applicability According to the present invention, a metal oxide film having excellent adhesion to any substrate and capable of easily forming a metal oxide film of a single element or a composite element having excellent film forming ability. A forming composition is obtained. By using this composition, a uniform and good metal oxide film having no defects can be formed. In addition, this composition has excellent stability.
Therefore, the composition for forming a metal oxide film obtained by the present invention includes various forming materials such as an ultraviolet absorbing film, a heat ray reflecting film, a dielectric film, a superconductor film, a conductive film and an insulating film or an inorganic pigment. It is useful as a binder for various fine particle powders such as, and has a wide application range as a sensor material, a superconducting material, a conductive material, various coating materials, and the like.

[0055]

【Example】

Example 1 A solution in which 40 g of octylic acid and 54 g of tantalum ethoxide were heated and refluxed, and a portion of the ethoxyl group was replaced with octyl acid was dissolved in advance in 75 g of gum rosin and 10 g of polyvinyl alcohol having a polymerization degree of 1500 in 200 g of terpineol. In addition, 15 g of ethyl acetoacetate was added, and the mixture was stirred well. 130 g of terpine oil was added to this liquid to obtain about 500 g of a composition. The oxide of this composition (Ta
₂ O ₅ ) conversion content is 5.2%, viscosity is 80 cps (2
It was 5 ° C) and could be stably stored for more than one year.

This composition was dipped by a dipping method (pulling speed: 10 mm
/ Min) on the MgO substrate and then at 100 ° C for 3
It was dried for 0 minutes and immediately baked at 500 ° C. for 30 minutes to obtain a transparent thin film of tantalum oxide with a slight bluish tint. The dielectric breakdown voltage of this film (film thickness 0.3 μm) was 70V.
In addition, the test was performed in accordance with the cross cut test method defined in JIS-K-5400. However, when the squares of the test piece were prepared using a diamond glass cutting tool and a peeling test with cellophane tape was conducted, no peeling was observed at all.

Example 2 40 g of octylic acid and 54 g of tantalum ethoxide were heated under reflux and a part of the ethoxyl group was replaced with octyl acid, which was previously mixed with 50 g of gum rosin and 100 g of xanthan gum.
Was added to the solution dissolved in terpineol and stirred well.
To this, 15 g of ethyl acetoacetate was added to obtain about 500 g of a composition. The oxide (Ta ₂ O ₅ ) conversion content of this composition was 5.3%, and the viscosity was 6000 cps (25 ° C.).

This composition was printed on a glass substrate with a 300 mesh screen, dried at a temperature of 100 ° C. for 30 minutes, and then baked at 500 ° C. for 30 minutes to obtain a smooth tantalum oxide thin film.

Comparative Example 1 40 g of octylic acid and 54 g of tantalum ethoxide were heated to reflux, and part of the ethoxyl group was replaced with an octyl group. In advance, 310 g of gum rosin was added to terpineol 80.
It was added to the solution heated and dissolved in g and stirred well. Further, 15 g of ethyl acetoacetate was added to obtain about 500 g of the composition. The oxide (Ta ₂ O ₅ ) equivalent content of this composition is
The viscosity was 5.1% and the viscosity was 8000 cps (25 ° C.).

This composition was printed on a glass substrate with a 320 mesh screen and then dried at a temperature of 100 ° C. for 30 minutes. Then, it was baked at 500 ° C. for 30 minutes to obtain a film having a trace of foaming.

Example 3 210 g of caprylic acid was added to 76 g of methyl borate to give 1
Heated to reflux for hours. 50 g of gum rosin, 30 g of ethyl cellulose and 20 g of ethylene glycol were dissolved in advance in 80 g of terpineol and 57 g of methanol,
The boron solution prepared above was mixed to obtain about 500 g of the composition. The oxide (B ₂ O ₃ ) conversion content of this composition was 4.7% and the viscosity was 60 cps (25 ° C.).

This composition was applied to a glass substrate by a dipping method (pulling speed: 10 mm / min) and baked at 400 ° C. for 1 hour to obtain a smooth boron oxide thin film.

Example 4 300 g of copper naphthenate was added to a solution prepared by previously dissolving 40 g of gum rosin and 10 g of polyvinylpyrrolidone in 90 g of terpine oil, and mixed well. Further, 30 g of ethyl acetoacetate was added, and the mixture was refluxed for 3 hours. Then, the total amount was adjusted to 500 g with toluene. The oxide of this composition (Cu
The converted content of O) is 4.5% and the viscosity is 80 cps (25
℃). This composition was applied to a stainless steel substrate of SUS316 by a dipping method (pulling speed 10 mm / min),
It was dried at 100 ° C. for 15 minutes. Then, it was baked at 700 ° C. for 15 minutes to obtain a slightly bluish brown transparent CuO film.

Example 5 23 g of titanium tetra-n-butoxide, 19 g of 2-ethylhexanoic acid and 10 g of 2-ethylhexanol were mixed and then refluxed for 2 hours. 70 g of barium abietic acid was added to this solution, and the mixture was further refluxed for 1 hour.

In advance, 20 g of gum rosin, 10 g of polyvinylpyrrolidone and 10 g of xanthan gum were dissolved in 30 g of terpineol. This solution was added to the previously prepared Ba, T
After mixing the liquid containing i, add terpine oil to a total volume of 5
It was set to 00 g. The oxide of this composition (BaO + Ti
O ₂ ) converted content is 4.8%, viscosity is 100 cps
(25 ° C).

This composition was applied to a stainless steel substrate by a dipping method (pulling speed: 10 mm / min) and then 700
Baking for 15 minutes at ° C. Obtained (BaO + TiO ₂ ).
The composite film was slightly white and transparent with a film thickness of about 0.2 μm.

When X-ray diffraction of this film was measured, patterns having peaks at diffraction angles of 22 °, 31.5 ° and 38.5 ° were obtained, and it was found that BaTiO ₃ was produced.

Example 6 78 g of zirconium tetra-n-butoxide, 25 g of caprylic acid and 10 g of n-octanol were added, and the mixture was refluxed for 2 hours. 30 g of gum rosin and 30 g of polyvinyl alcohol having a polymerization degree of 1500 were dissolved in 50 g of terpine oil in advance, and then the previously prepared Zr solution was added and mixed well. Further, 19 g of ethyl acetoacetate was added to make the total amount to 300 g with pine oil. This composition is an oxide (Zr
It had an O ₂ -converted content of 6.2% and a viscosity of 70 cps (25 ° C.).

When this composition was applied to a glass substrate heated to 500 ° C. with a spray gun, a ZrO ₂ film was instantaneously formed.

This film is eraser (No. 6 made by Lion)
When a wear test was performed with a pressing force of 50 g,
There was no change during the round trip. JIS as in Example 1
When a peeling test was performed according to K-5400, no peeling was observed.

Example 7 An average particle size of 0.1 was added to the Zr-containing composition prepared in Example 6.
After adding 20 μm of silica having a thickness of 20 μm, it was applied to a white tile by spraying and baked at 600 ° C. to obtain a film having a white color tone.

Example 8 The Zr-containing composition prepared in Example 6 had an average particle size of 0.1.
After adding red iron oxide of 20 μm to 20%, it was applied to a white tile by spraying and baked at 600 ° C. to obtain a film having a red color tone.

Comparative Example 2 A composition was obtained in exactly the same manner as Example 1 except that 162 g of tantalum ethoxide and 100 g of terpineol were used. The oxide (Ta ₂ O ₅ ) equivalent content of this composition is 1
The viscosity was 5% and the viscosity was 70 cps (25 ° C.).

This composition was dipped by a dipping method (pulling speed: 10 mm
/ Min) was applied to the MgO substrate and fired in the same manner as in Example 1. When the film was partially peeled off.

Example 9 71 g of indium caprate and 5 g of tin 2-ethylhexanoate (weight ratio In ₂ O ₃ : SnO ₂ = 95: 5) were added to 30 g of gum rosin, 10 g of methylcellulose, 50 g of n-octanol, 30 g of acetylacetone and 1 of toluene.
00 g was added to the heated solution, and the mixture was refluxed for 1 hour.
Then, 20 g of terpineol was added to obtain about 300 g of the composition. The oxide of this composition (In ₂ O ₃ + Sn
O ₂ ) converted content 4.8%, viscosity 70 cps (25 ° C.)
Met.

This composition was applied to a glass substrate heated to 500 ° C. with a spray gun to give an almost transparent (In ₂ O ₃ +
A SnO ₂ ) composite film was obtained. The resistance of this membrane sheet is about 2
It was × 10 ⁴ Ω / sq. Furthermore, after leaving at 400 ° C. for 5 minutes in a nitrogen gas atmosphere containing 5% hydrogen gas,
The resistance of the membrane sheet was 3 × 10 ² Ω / sq.

Example 10 A composition was obtained in the same manner except that 300 g of cobalt octylate was used instead of the copper naphthenate of Example 4. The oxide (CoO) conversion content of this composition was 7.4% and the viscosity was 75 cps (25 ° C.).

This composition was applied to a glass substrate heated to 500 ° C. by a spray gun to obtain a brown and transparent CoO thin film which can be used as a heat ray reflective film.

Example 11 20 g of zinc oxide was refluxed with 35 g of 2-ethylhexanoic acid and 74 g of abietic acid in 100 g of toluene for 2 hours. After the reflux, 30 g of methyl acetoacetate was added, and 15 g of tall rosin and polyvinyl alcohol 2 having a degree of polymerization of 500
0 g was added and further dissolved by heating. After dissolving, add ethylene glycol monoethyl ether to about 400
g of composition was obtained. The oxide (ZnO) equivalent content of this composition was 4.7% and the viscosity was 60 cps (25 ° C.). This composition was applied to quartz glass (pulling speed: 10
mm / min), and baked at 500 ° C. for 15 minutes to obtain a transparent ZnO thin film that can be used as an ultraviolet absorbing film. The ultraviolet-visible spectrum of this film showed a transmittance of 95% or more in the visible region and absorbed ultraviolet rays having a wavelength of 380 nm or less.

Example 12 Yttrium octylate 100 g and gum rosin 50 g,
5 g of ethyl cellulose was refluxed with 50 g of terpine oil for 2 hours. At the time of heating, 10 g of acetylacetone was added, and the amount was adjusted to 300 g with toluene. The oxide of this composition (Y ₂ O
₃ ) Converted content is 4.8%, viscosity 85cps (25 ℃)
Met.

This composition and the Zr-containing composition of Example 6 were prepared in a weight ratio of ZrO ₂ : Y ₂ O ₃ = 95: 5 to prepare a composition.

This composition was applied to quartz glass by a dipping method (pulling rate: 10 mm / min) and baked at 1100 ° C. for 2 hours. A weak white film that can be used as a yttria-stabilized zirconia film was obtained.

Example 13 A composition was obtained in the same manner as in Example 12 except that yttrium octylate was replaced with 50 g of barium octylate and 10 g of acetylacetone was replaced with 20 g of n-octanol. The oxide (BaO) equivalent content of this composition was 5.1%, and the viscosity was 50.
It was cps (25 ° C).

Then, the Cu-containing composition of Example 4, the Y-containing composition of Example 12 and the Ba-containing composition of this Example were divided so that the molar ratio was Y: Ba: Cu = 1: 2: 3. It was taken and mixed to obtain a solution.

This composition was applied to quartz glass by a dipping method (pulling speed: 10 mm / min) and baked at 850 ° C. to obtain a black film. When X-ray diffraction of this film was measured, a pattern of perovskite type YBa ₂ Cu ₃ O _7-X (orthorhombic system) was obtained. Further, when the temperature dependence of the resistance value was measured, the resistance value was 0 at 105K. It was found that a superconductor was formed.

Example 14 100 g of ethyl silicate, 122 of 2-ethylhexanol
g and 68 g of octyl acid were mixed, 0.1 g of p-toluenesulfonic acid was added, and the mixture was refluxed for 2 hours. After refluxing, 30 g of gum rosin and 30 g of xanthan gum were added and dissolved by heating, and then ethyl alcohol: ethylene glycol = 1: 1.
150 g of 1 mixed solution was added to obtain about 550 g of the composition. The oxide (SiO ₂ ) equivalent content of this composition is 5.
The viscosity was 1% and the viscosity was 50 cps (25 ° C.).

This composition and the boron-containing composition obtained in Example 3 were mixed in a weight ratio of SiO ₂ : B ₂ O ₃ = 1: 1 and immersed in a stainless steel substrate by a dipping method (pulling speed: 10 m
m / min) and baked at 500 ° C. to obtain a transparent film. Then, it was immersed in water for 24 hours. After drying, it was confirmed by an electron microscope that the SiO ₂ film had pores.

Example 15 100 g of europium naphthenate and gum rosin 30
g and polyvinyl alcohol 20 g were added to toluene: ethanol = 1: 1 mixed solution 60 g, and the mixture was refluxed for 1 hour.
Then, 30 g of ethyl acetoacetate was added, and the mixture was made up to 300 g with toluene. The oxide (Eu ₂ O ₃ ) equivalent content of this composition was 4.2% and the viscosity was 50 cps (25 ° C.).

This composition was applied to a stainless steel substrate by a dipping method (pulling rate: 10 mm / min) and baked at 500 ° C. to obtain a weak pink film applicable to a phosphor.

Example 16 83 g of tin octylate, 1.5 g of antimony ethoxide and 3 g of octyl acid were added to 30 g of a ligroin: acetone = 1: 1 mixed solution, and the mixture was refluxed for 2 hours.

Next, 50 g of gum rosin and 100 g of hydroxypropyl cellulose were added and dissolved by heating. Further, add 20 g of glycerin, and add 30 g of terpineol.
It was set to 0 g. The oxide of this composition (SnO ₂ + Sb ₂ O
₃ ) Converted content 5.1%, viscosity 13,000 cps (25 ° C)
Met.

This composition was applied to a glass substrate by a dipping method (pulling rate: 10 mm / min) and baked at 550 ° C. for 15 minutes. This operation was repeated 3 times to obtain a slightly bluish film having a film thickness of about 0.8 μm. The sheet resistance of this film is 4 ×
It was 10 ³ Ω / sq.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C01G 3/02 C01G 3/02 9/02 9/02 A 15/00 15/00 B 19/00 19/00 A 23/00 23/00 C 25/00 25/00 51/04 51/04 C04B 35/49 C04B 35/49 Z C23C 18/12 C23C 18/12 (58) Fields investigated (Int.Cl. ⁷ , DB name) C01G 1/00-23/08 C01G 25/00-57/00 C01B 13/32

Claims (5)

(57) [Claims] 1. A composition for forming a metal oxide film, comprising: (1) at least one kind of organic acid metal salt, (2) at least one kind of organic compound having 1 to 4 oxygens as coordination atoms, 3) Methylcellulose, ethylcellulose, ethylhi
Droxyethyl cellulose, hydroxypropyl cellulose
Glucose, hydroxyethyl cellulose, xanthan gum,
Polyvinyl alcohol, polyvinyl pyrrolidone and poly
Contains at least one organic polymer compound selected from methyl methacrylate and rosin, and (4) at least one organic solvent, and contains (5) component (1) in an amount of 0.5 to 20% in terms of metal oxide, (6) 0.1 g of the component (2) is added to 1 gram atom of the metal in the component (1) (n is the average oxidation number of the metal in the component (1), and two or more metals are (7) component (3) is contained in 5 to 80%, and (8) component (4) is contained in 20 to 80%. Oxide film forming composition. 2. A method for producing a composition for forming a metal oxide film, comprising: (1) at least one kind of organic acid metal salt, (2) at least one kind of organic compound having 1 to 4 oxygens as coordination atoms, (3) Methylcellulose, ethylcellulose, ethylhi
Droxyethyl cellulose, hydroxypropyl cellulose
Glucose, hydroxyethyl cellulose, xanthan gum,
Polyvinyl alcohol, polyvinyl pyrrolidone and poly
At least one organic polymer compound selected from methyl methacrylate , rosin, and at least one organic solvent (4) are used, and the component (5) (1) is 0 in terms of metal oxide in the composition to be formed. 0.5 to 20%, (6) 0.1 nmol of the component (2) to 1 gram atom of the metal in the component (1) (n is the average oxidation number of the metal in the component (1), When two or more metals are used, it is a weighted average oxidation number), (7) component (3) is 5 to 80%, and (8) component (4)
Of the component (1), the component (2), the component (3) and the component (4) are mixed and heated at a ratio of 20 to 80%. Method. 3. A method for producing a composition for forming a metal oxide film, comprising: (1) at least one kind of organic acid metal salt; (2) at least one kind of organic compound having 1 to 4 oxygens as coordination atoms; (3) Methylcellulose, ethylcellulose, ethylhi
Droxyethyl cellulose, hydroxypropyl cellulose
Glucose, hydroxyethyl cellulose, xanthan gum,
Polyvinyl alcohol, polyvinyl pyrrolidone and poly
At least one organic polymer compound selected from methyl methacrylate , rosin, and (4) at least one organic solvent are used, and the component (5) component (1) is 0 in terms of metal oxide in the composition to be formed. 0.5 to 20%, (6) 0.1 nmol of the component (2) to 1 gram atom of the metal in the component (1) (n is the average oxidation number of the metal in the component (1), When two or more metals are used, it is a weighted average oxidation number), (7) component (3) is 5 to 80%, and (8) component (4)
Is 20 to 80%, and component (1) and component (2)
After mixing the component (4) and the component (4), the component (3) is mixed and heated, which is a method for producing a composition for forming a metal oxide film. 4. A method for producing a composition for forming a metal oxide film, comprising: (1) at least one kind of organic acid metal salt; (2) at least one kind of organic compound having 1 to 4 oxygens as coordination atoms; (3) Methylcellulose, ethylcellulose, ethylhi
Droxyethyl cellulose, hydroxypropyl cellulose
Glucose, hydroxyethyl cellulose, xanthan gum,
Polyvinyl alcohol, polyvinyl pyrrolidone and poly
At least one organic polymer compound selected from methyl methacrylate , rosin, and at least one organic solvent (4) are used, and the component (5) (1) is 0 in terms of metal oxide in the composition to be formed. 0.5 to 20%, (6) 0.1 nmol of the component (2) to 1 gram atom of the metal in the component (1) (n is the average oxidation number of the metal in the component (1), When two or more metals are used, it is a weighted average oxidation number), (7) component (3) is 5 to 80%, and (8) component (4)
Is 20 to 80%, and component (1) and component (3)
And the component (4) are mixed and heated, and then the component (2) is mixed, the method for producing a composition for forming a metal oxide film. 5. A method for forming a metal oxide film, which comprises coating the composition for forming a metal oxide film according to claim 1 on a substrate and baking at 400 ° C. to 1200 ° C.