JPH0483704A - Liquid composition for forming metallic oxide film, its production and production of metallic oxide film - Google Patents

Abstract

PURPOSE:To improve coating and film-forming properties and obtain a homogeneous oxide film by converting a specific metallic compound (Ma), an organic compound (Lb), a monobasic acid (Ac), a resin acid (Rd) and an organic solvent (Se) into a solution under prescribed conditions. CONSTITUTION:A metallic compound (Ma) selected from inorganic metallic salts and organometallic compounds, an organic compound (Lb) having 1-6 nitrogen and/or oxygen atoms as ligand atoms, a monobasic acid (Ac) having 1-2 alcoholic hydroxyl groups as a substituent group, a resin acid (Rd) selected from rosin, abietic acid and pimaric acid and an organic solvent (Se) are mixed so as to provide 0.1-4mol (Lb) and/or (Ac) based on 1 gram-atom (expressed in terms of metal) of (Ma) and contents of the respective (Rd) and (Se) accounting for 5-80wt.% in the total weight of the composition. When the (Se) is contained in mixing, heating is carried out or ammonia gas is made to exist to provide the objective solution.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] 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.
A liquid composition that serves as a raw material for manufacturing various metal oxide films ranging from single-component metal oxide films to composite metal oxide films, a method for producing the same, and a method for forming a metal oxide film using the composition. It is related to.

[Prior Art] Methods for forming metal oxide films include sputtering, vapor deposition, ion beam method, and CVD, which are performed under vacuum or in an inert gas atmosphere such as argon. The mainstream method is to vaporize the material and then deposit it on the substrate.

However, these methods not only require high equipment costs, but also make it difficult to adjust the film components because the evaporation rate and precipitation rate of each component that makes up the composite oxide differs, and it is difficult to obtain the desired properties. is not limited. Another known method is the doctor blade method, in which fine composite metal oxide powder is made into a slurry, coated on a substrate, and fired. Since it is affected by the size of particles as aggregates, it is difficult to obtain a uniform film thickness as desired.

On the other hand, if a thin film manufacturing method uses solvent-soluble organometallic compounds as raw materials, it is possible to combine two or more metal compounds in any ratio, making it easier to obtain the desired thin film, and moreover, as needed. Since it is possible to form single-crystalline thin films, it has begun to be used in the field of electronic devices such as transistors and diodes.

One of the thin film forming techniques using such organometallic compounds is the sol-gel method using metal alkoxides, and this method can be used to produce several types of metal oxide thin films such as Tie, thin film, 5in2 thin film, and ZrO2 thin film. being developed. Also known is a thermal decomposition method that uses a metal salt of an organic acid as a starting material, dilutes it with a solvent, coats it on a substrate, and then heats it to obtain an oxide thin film. , octylate, etc.
Methods for obtaining a 2 thin film, an In2O3 thin film, a 5n02 thin film, etc. have been proposed.

However, among the organometallic compounds mentioned above, metal alkoxides are generally expensive, and the type of optimal solvent and solubility differ depending on the type of metal alkoxide.
Not all metal alkoxides can be combined in all formulations.

Also, for example, 5n02 film, In203 film, pb02 film,
Organic acid salts such as naphthenate, octylate, stearate, and caprylate, which are used as raw materials for forming ZrO2 films, can be produced manually at relatively low cost, but they have poor storage stability as liquid substances. Moreover, there is a problem that the smoothness of the film deteriorates in many cases. Furthermore, attempts have been made to use a metal complex compound, which is a type of organometallic compound, as a raw material for forming metal oxide thin films, but when this method is adopted, the smoothness of the film and the adhesion to the substrate are poor. Lacks practicality. On the other hand, Y-Ba-Cu and B i-3r-C are superconducting materials that have recently attracted attention.
There are a-Cu-based composite metal oxides, and to produce thin films made of such composite oxides, solvent-soluble metal organic acid salts are used, or chelating agents are added to metal alkoxides to produce thin films that are soluble in organic solvents. Attempts have also been made to use it by dissolving it. That is, these methods prepare solvent-soluble organic acid salts and metal alkoxides containing the metal element, mix them to an appropriate composition, and then apply the mixture onto a substrate.
After drying, it is oxidized and thermally decomposed to obtain a composite metal oxide film. However, with this method, the stability of solutions containing organic acid salts, metal alkoxides, etc. and the stability of the mixture obtained using them is poor, and some metal compounds precipitate, making it difficult to achieve the desired composition. It is difficult to obtain a metal oxide film having the following properties, and even if it is obtained, there are problems in that the film itself is fragile or has poor adhesion to the substrate. In addition, organic metal compounds such as organic acid salts and metal alkoxides are commercially available with only a limited number of elements, and many of them are difficult to synthesize. The types of metal oxide films are severely limited.

[Problems to be Solved by the Invention] The present invention has been made paying attention to such circumstances, and its purpose is pointed out in the prior art. Easily produces various metal oxide films ranging from single element systems to composite systems, which solves the above problems and exhibits excellent adhesion to any substrate and excellent film formation ability. The purpose of the present invention is to provide a liquid composition and a method for producing the same. Another object of the present invention is to provide a method for forming a homogeneous and sound metal oxide film free of defects such as cracks using such a liquid composition.

[Means for Solving the Problems] The composition of the liquid composition for forming a metal oxide film according to the present invention that can solve the above problems is as follows: (1) selected from the group consisting of inorganic metal salts and organic metal compounds; species or two or more metal compounds (hereinafter referred to as Ma), ■ one or more organic compounds having 1 to 6 nitrogen and/or oxygen as coordinating atoms (hereinafter referred to as Lb), ■ substituents One or more monobasic acids having one or two alcoholic hydroxyl groups (hereinafter referred to as Ac)
, ■ One or more resin acids selected from the group consisting of pine resin, abietic acid, and pimaric acid (hereinafter referred to as Rd); ■ 1 gram of an organic solvent (hereinafter referred to as Se) in terms of the metal of the above Ma. Contains 0.1 to 4 moles of Lb and/or Ac in total per atom, and the content of Rd in the total composition is 5 to 80% by weight.
The gist is that the content of Se is 5 to 80% by weight.

In this liquid composition, the total amount of Lb and/or Ac is 0.1 to 4 per 1 gram atom of Ma in terms of metal.
The components are mixed simultaneously or in any order so that the respective contents of Rd and Se in the total amount of the composition are 5 to 80% by weight, and S is added as a mixed component.
When mixing containing e, it can be easily obtained by heating or making a solution in the presence of ammonia gas, and after coating and drying this liquid composition on a suitable substrate, it can be heated at 440°C or higher. When oxidized and fired, a metal oxide film that is homogeneous and has excellent physical properties can be obtained.

[Function] As mentioned above, the metal oxide film forming composition according to the present invention has the following effects:
A metal compound (Ma) selected from the group consisting of inorganic metal salts and organic metal compounds, and one or two organic compounds having 1 to 6 nitrogen and/or oxygen coordinating atoms.
(Lb) and one or more monobasic acids having one or two alcoholic hydroxyl groups as a substituent (Ac).
The solubilization of metal-containing components is further enhanced by further blending one or more resin acids (Rd) selected from the group consisting of pine resin, abietic acid, and pimaric acid as other components. It is characterized by the fact that it accelerates the process, improves the storage stability of the solution, and furthermore improves film-forming ability and adhesion to the substrate.

In the present invention, the metal compound (Ma) includes (a) metal halides, nitrates, carboxylic acids having 1 to 8 carbon atoms, monocarboxylic acids having 1 to 8 carbon atoms having 1 or 2 alcoholic hydroxyl groups, and naphthenes; Inorganic metal salts such as metal carbhonates having a cyclopentane ring or cyclohexane ring such as acid salts, (b) 1 to 6 nitrogen and/or oxygen coordinating atoms;
Organometallic compounds, such as β-diketone compounds represented by acetylacetone; Alkylamines represented by monomethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, etc.; monoethanolamine, jetanolamine, triethanolamine, Ethanolamines represented by N-methylethanolamine, N-methyljetanolamine, N-propylethanolamine, etc.; Methyl acetoacetate,
β-ketonic acid esters represented by ethyl acetoacetate, etc., amine compounds represented by ammonia, ethylenediamine, triethylenetetramine, etc. are used as ligands.
(8) Organometallic compounds such as metal alkoxides having alkyl groups such as methyl, ethyl, propyl, and butyl groups; (d) Pine resin, abietic acid, pimaric acid, etc. Examples include metal salts of resin acids.

Next, as organic compounds (Lb) having 1 to 6 nitrogen and/or oxygen as coordinating atoms, amines such as ammonia, ethylenediamine, triethylenetetramine: monomethylamine, monomethylamine, monoethylamine, dimethylamine, diethylamine Alkylamines such as , trimethylamine, and triethylamine; Ethanolamines such as monoethanolamine, jetanolamine, triethanolamine, N-methylethanolamine, N-methylgetanolamine, and N-propylethanolamine; β such as acetylacetone - Diketone compounds: β-diketonate dimethyls such as methyl acetoacetate and ethyl acetoacetate, ethylene glycol,
Examples include polyhydric alcohols such as diethylene glycol and glycerin. In addition to nitrogen and oxygen, atoms having coordinating ability include P, As% S, Se, etc. In the present invention, nitrogen and oxygen were selected because they are easily eliminated by firing and are non-toxic.

Examples of monobasic acids (Ac) include monobasic acids having one or two alcoholic hydroxyl groups as substituents, such as glycolic acid, hydroacrylic acid, lactic acid, glyceric acid, α-
Examples include oxybutyric acid, γ-oxybutyric acid, trimethyloleacetic acid, oxytrimethylacetic acid, 2-hydroxy-2-methylacetic acid, and leucinic acid. Particularly preferred among these are monobasic acids that can form a 5- or 6-membered ring with the metal element, such as glycolic acid, hydroxyacrylic acid, lactic acid, α-oxybutyric acid, β-oxybutyric acid, and leucinic acid. When these are used alone or in combination with an organic compound (Lb), it is possible to obtain a solution that is uniform and has storage stability for one year or more.

The above metal compound (Lb) and monobasic acid (Ac) are
Both have the effect of promoting solubilization of metal compounds (Ma) in organic solvents (Se) and increasing storage stability.
These can be used alone or in combination of two or more types if necessary.

The amount used is (Lb) and/or (Ac) per gram atom of the metal compound (Ma) in terms of metal.
The total amount is in the range of 0.1 to 4 moles, preferably 0.5 to 3
If the amount is less than 0.1 mol, solubility in organic solvents and storage stability will deteriorate, making it impossible to obtain a homogeneous solution.

On the other hand, if the amount exceeds 4 mol, the storage stability may deteriorate or foaming may occur during baking during film formation, resulting in poor film forming ability.

These organic compounds (Lb) and monobasic acids (Ac) correspond to metal complex compounds or monobasic acid salts that may be used as metal compounds, if similar compounds are included in them. It is better to subtract only the quantity.

Resin acids (Rd) act as viscosity modifiers and improve film-forming ability. Among these, pine resin is a type of natural resin, and includes gum rosin, wood rosin,
Typical examples include tall rosin and the like. Pine resin contains abietic acid, neoabietic acid, dihydroabietic acid, tetrahydroabietic acid, etc., and the component composition varies depending on the type of pine resin or processing method, but any type of resin can be used in the present invention. Of course, it is also possible to use abietic acid, pimaric acid, etc. as JEIm. Furthermore, rosin esters such as methyl abietate and diethylene glycol abietate, which are esterified abietic acid, can also be used, but if the entire amount is replaced with rosin ester, it becomes difficult to solubilize when obtaining a liquid composition and it becomes difficult to preserve the composition. Stability also deteriorates, so even if they are used together, they should be used only to partially replace the resin acids.

Among the resin acids (Rd), pine resin is widely available on the market as a natural product and can be obtained at low cost, so it can be said to be the most convenient material. In addition, there are a variety of commercially available pine resins, including natural products as well as those modified by adjusting the degree of unsaturation, and any of them can be used in the present invention.

The blending amount of the resin acids (Rd) is in the range of 5 to 80% by weight, more preferably 1% by weight in the finally obtained solution.
The content ranges from 0 to 60%, and if it is less than 5%, the film forming ability tends to deteriorate, while if it exceeds 80% by weight, the storage stability will deteriorate.

The organic solvent (Se) may be any solvent as long as it can solubilize each of the above components, depending on the workability during film formation (evaporability, vapor pressure, etc.) and the type of film formation method. They may be selected appropriately with consideration, and specific examples include alcohols such as methyl alcohol and ethyl alcohol; ethers such as methyl ether and ethyl ether; aromatic hydrocarbons such as toluene; ketones such as acetone and methyl ethyl ketone; and terpineol: Examples include glycols such as turpentine oil, ethylene glycol, and ethylene glycol monoethyl ether, which can be used alone or as a mixed solvent of two or more.

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

The essential components constituting the liquid composition according to the present invention are as described above, but in the present invention, resin acids (Rd), metal compounds (Ma), organic compounds (Lb), and/or monobasic acids (Ac) The reactants or mixtures have a favorable influence on each other, so that solubilization in the organic solvent (Se) is promoted, and a uniform and stable liquid composition can be obtained.

Moreover, the presence of resin acids (Rd) significantly improves the film formation properties and adhesion to the substrate, and by applying this onto any substrate, drying and firing, it is possible to form a homogeneous metal. An oxide film can be obtained. Note that organic compounds (Lb
) and/or monobasic acid (Ac) is a metal compound (M
This improves the solubilization of a) in the organic solvent (Se) and the storage stability in the solution state, but if the amount of these is too large, carbides will remain in the oxide film after firing, which will affect the film performance. It is better to reduce the contents of the organic compound (Lb) and monobasic acid (Ac) as much as possible since they may have an adverse effect. Therefore, when selecting the type of organic compound (Lb) and/or monobasic acid (Ac), it is desirable to select one that can minimize the amount added while taking into consideration the stability of the final solution. .

The method for producing the composition of the present invention includes (1) Ma, L
(2) A method of adding and mixing Ma, Lb and/or Ac to Se, and then adding and mixing Rd thereto; (3) After adding and mixing Ma and Rd to Se, L
A method of adding and mixing B and/or Ac is adopted, but at each blending or mixing step, the system is heated to 60%
Solubilization is significantly promoted by heating to about 90°C or by blowing in ammonia gas, and a uniform liquid composition with excellent storage stability can be obtained in a short period of time.

Depending on the type of raw materials used, ammonium chloride, chloride ions, nitrate ions, etc. may be mixed in during the reaction process and have an adverse effect such as corrosion on metal substrates. After solubilization, insoluble matter may be removed by filtration or the like, and ionic impurities may be removed by treatment with an ion exchange resin or the like.

The thus obtained liquid composition for forming a metal oxide film is stable even when left in the air, and shows no deterioration or formation of insoluble matter for more than one year. In addition, this liquid composition can be arbitrarily adjusted to have a viscosity of, for example, 25° C. over a range of 10-odd centimeters to about 20,000 centimeters, and can be used with various film-forming methods such as dipping, spinner, and screen printing. The viscosity is suitable for use. It is also effective to add to this liquid composition, if necessary, a cationic, nonionic, or anionic surfactant as a leveling agent for improving coating properties, or an antifoaming agent.

The liquid composition obtained in this way can be used as it is, or in some cases further diluted with a suitable organic solvent, for use on heat-resistant substrates such as silica, magnesia, alumina, zirconia, glass, various ceramics, stainless steel, copper, etc. It is coated on the surface of a metal substrate such as aluminum by any method such as dipping, spinner, screen printing, etc., preferably dried at about 50 to 120°C, and then heated to a temperature of 440°C or higher, preferably 450°C or higher. By firing with , a metal oxide film can be obtained.

If the heating and firing temperature is lower than 440°C, a portion tends to remain as carbide even if fired for a long time, so it is preferable to perform the firing at a temperature of 450°C or higher.

If the metal oxide concentration in the liquid composition exceeds 10% by weight or the viscosity exceeds 100 centipoise, pre-drying prior to firing will produce a smooth and uniform oxide film. is easy to obtain. The content in terms of metal oxide in the liquid composition is preferably 0.5 to 30% by weight, preferably 1 to 20%. If it is less than 0.5% by weight, the film thickness that can be formed by one coat will be reduced. Since it is too thin, it is not practical because it would be necessary to recoat it many times to increase the film thickness. On the other hand, if it exceeds 30% by weight, the adhesion of the oxide film to the substrate may decrease or cracks may occur in the film.

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

Next, the configuration and effects of the present invention will be specifically explained with reference to examples, but the present invention is not limited by the following examples.

[Example] Hereinafter, the configuration and effects of the present invention will be specifically explained using examples, but the present invention is not limited by the following examples.

Example 1 Anhydrous tantalum pentachloride TaCl5 0.1 mol (35,8
g) was dissolved in a mixed solvent of 0.5 mol (23 g) of ethyl alcohol and 500 ml of hexane, and 0.05 mol (3.1 g) of ethanolamine was added.
The reaction was carried out by blowing ammonia gas at a flow rate of 0.2j2/min for 4 hours. After the reaction was completed, ammonium chloride as a by-product was filtered off, and volatile components such as hexane were distilled off from the filtrate using a rotary evaporator in a water bath at 60° C. under reduced pressure of 100 mmHg. When this was added with stirring to a solution in which 100 g of gum rosin had been dissolved in 450 g of terpineol in advance, 500 g of a liquid composition for forming a metal oxide film containing tantalum was obtained.

The content of this composition in terms of metal oxide was 5.3% by weight. This composition was also stable in the air, and no deterioration was observed for more than one year. The viscosity of this composition was 6° cps at 25°C.

The composition obtained above was soaked using the dipping method (pulling speed 10 mm/w).
in) on a glass substrate, then at 100°C for 30
After drying for a minute and immediately baking at 450° C. for 1 hour, a transparent thin film with a slightly bluish tint was obtained. Further, a similar thin film was formed on an SO5304 stainless steel substrate to obtain a transparent thin film, and then a 90 degree bending test was performed, and no cracking or peeling occurred.

Example 2 25 g of gum rosin was heated and dissolved in a mixed solvent of 100 g of terpineol and 50 g of toluene, and 50 g of aluminum tri-5ec-butoxide was added to the resulting homogeneous solution with stirring, and then 13 g of ethyl acetoacetate was added, and the mixture was heated at 100°C. Heated for an additional 15 minutes.

230 g of the obtained homogeneous solution was used as a liquid composition for forming an aluminum-containing thin film. The content of aluminum oxide in this composition was 4.3% by weight. Further, the viscosity was 35 cps at 25°C, and it could be stored stably for more than one year.

Using this composition, the dipping method (pulling speed 20 mm/m)
1n) on a quartz substrate, and then dried at 100° C. for 1 hour. When this was baked at 500° C. for 1 hour, a transparent thin film was obtained. When this thin film was analyzed by X-ray diffraction, it was found to be amorphous.
Similar X-ray diffraction analysis after re-baking for a time revealed that α-A
It was confirmed that it was 1203.

Comparative Example 1 An aluminum-containing composition was obtained in exactly the same manner as in Example 2 except that ethyl acetoacetate was not added, and its stability was examined. As a result, a white precipitate was formed within one week.

In addition, an aluminum-containing composition obtained in exactly the same manner as in Example 2 except that the amount of gum rosin added was changed to 2.5 g was applied onto a glass substrate by the dipping method under the same conditions, and baked at 500°C for 1 hour. As a result, a membrane containing a crank was obtained.

Example 3 0.1 mol (13.7 g) of metallic barium Ba was gradually added and dissolved in 100 g of a methyl alcohol solution in which 0.1 mol (6.1 g) of monoethanolamine was dissolved under a nitrogen stream. This solution was filtered using 5C3 filter paper under a nitrogen stream, and the filtrate was mixed with terpineol 4.
It was added to a solution heated and dissolved in a mixed solvent of 5 g and 33 g of toluene while stirring to obtain a homogeneous solution. If a small amount of precipitate formed immediately after the addition was completed, it was completely dissolved by heating.

The viscosity of the liquid composition thus obtained is 50 at 25°C.
cps, and the concentration in terms of oxide (Bad) is 5% by weight.
It was dead.

Using this composition, the dipping method (pulling speed 10 mm/w)
In) was applied onto a quartz substrate, dried at 100° C. for 1 hour, and then fired at 500° C. for 1 hour, resulting in an almost transparent oxide film.

Example 4 0.1 mol (20.0 g) of copper acetate [Cu(C)1sC00)z.H20 was suspended in 60 ml of ethyl alcohol, and 0.2 mol (15 g) of diethylamine was added and dissolved therein. Ta. After filtering off undissolved substances using No. 5C filter paper, 20 g of abietic acid was previously dissolved in a mixed solvent of 60 g of terpineol and 30 g of ethyl alcohol by heating, and the mixture was added with stirring. 60~ after addition
The mixture was maintained at a temperature of 70° C. for 15 minutes to dissolve some of the precipitate generated during the addition to obtain a homogeneous solution. The resulting film-forming liquid composition had an oxide (Cub) equivalent concentration of 4.5 weight and a viscosity of 70 cps at 25°C.

Using this composition, the dipping method (pulling speed 10 mm
/mln) on a glass substrate, dried at 100°C for 1 hour, and then baked at 500°C for 1 hour, to obtain a black uniform film.

Example 5 Tin octylate (0.18gSn027g) 69 g
and 0.6 g of ethanolamine were added with stirring to a solution in which 40 g of rosin (Harima Kasei Co., Ltd. "Harimac T-80") was dissolved in a mixed solvent of 120 g of terpineol and 20 g of toluene by heating. The thus obtained composition had an oxide (SnO□) concentration of 5.5% by weight and a viscosity of 40 cps at 25°C.

Using this composition, the dipping method (pulling speed 10 mm/m
1n) on a glass substrate, dried at 100°C for 30 minutes, and then baked at 500°C for 1 hour to obtain a transparent film.

Comparative Example 2 A liquid composition was obtained in exactly the same manner as in Example 5, except that an extra amount of terpineol was added instead of adding rosin, and the composition was subjected to a dipping method (pulling speed 10 mm/m1n). When it was coated on a glass substrate and baked under the same conditions as in Example 5, a non-uniform film with a citron skin shape was obtained.

Example 6 Zinc acetate [Zn(CH3COO)2'2H20] 33
．． 7g (0,154 mol) in 70ml of ethyl alcohol
After adding 18 g of methyl acetoacetate, ammonia gas was blown into the solution until it became clear. When a clear liquid is obtained, excess ammonia gas is expelled by heating, and rosin (Harima Kasei Co., Ltd. "R-WWJ"
) was gradually added to a heated solution of 80 g of terpineol and 30 g of isopropyl alcohol in a mixed solvent with stirring. Then 70 on the hot plate
A liquid composition was obtained by heating at ~80°C for 15 minutes. This composition was a homogeneous solution with a concentration of 5% by weight in terms of oxide (2nO), and a viscosity of 40 cps at 25°C.

Using this composition, the dipping method (pulling speed 20 mm
/m1n) on a glass substrate, dried at 100°C for 10 minutes, and then baked at 450°C for 1 hour.
(350r+m wavelength), X-ray diffraction analysis confirmed the pattern of ZnO, although it was a little broad.

Comparative Example 3 A liquid composition was obtained in the same manner as in Example 6 except that terpineol was added in place of rosin, and a thin film was formed under the same conditions as in Example 6. Although the film was transparent, it had cracks.

Example 7 7.4 g of metallic barium Ba (0,0
54 mol) was added and dissolved, and insoluble matter was filtered through 5C3 filter paper to obtain a filtrate. This filtrate and telorhabdoxy titanate [Tl(OBu)4] (content 0.232g・Ti(h)
/g) 18.4g and triethanolamine 1.0
g in advance using rosin (Harima Kasei Co., Ltd. "Harimak T-80").
J) 50g was heated and dissolved in a mixed solvent of 70g of terpineol and 70g of isopropyl alcohol,
Additions were made according to the order listed above.

The partially formed precipitate was completely dissolved by heating at 70 to 80° C. for 15 minutes to obtain a liquid composition.

The viscosity of this composition was 180 cps at 28°C.

Using this liquid composition, the immersion method (pulling speed 5 mm)
/m1n) on a quartz substrate, dried at 100°C for 15 minutes, and then baked at 850°C for 3 hours to obtain a transparent film. When this film was subjected to X-ray diffraction analysis, a BaTiO3 diffraction chart was obtained.

Example 8 Tetrabutoxy titanate [Ti(OBu)4] (
65 g (content 0.2384i027 g) and 4.0 g of triethanolamine were gradually added and mixed to a solution in which 180 g of gum rosin had been heated and dissolved in 53 g of terpineol. When the reaction was accelerated by heating at 60 to 70°C for about 15 minutes, a liquid composition for forming a thin film was obtained. The viscosity of this composition was 6100 cps at 29°C, and this composition was coated on a glass substrate using a 1010 x 20 square screen with a 275 mesh, dried at 100°C for 30 minutes, and further baked at 500°C. , a transparent and uniform film was obtained.

Example 9 144 g of gum rosin was heated and dissolved in a mixed solvent of 80 g of toluene, 30 g of terpineol, and 20 g of ethyl alcohol, and ethyl acetoacetate aluminum di 5e was dissolved.
c-butyrate 7.2g, ethyl silicate 40
24.0g and lead naphthylate (30% pb solution) 2
Add 2.0 g in sequence and dissolve. Add 2g of N-methyljetanolamine to the colander and heat at 60-70℃ for 20 minutes.
Refluxed for minutes. The resulting composition had an oxide concentration of 5.
3% by weight, and the viscosity was 60 cps at 25°C.

Using this composition, apply it on a white tile with a brush.
After drying at 00° C. for 10 minutes and baking at 750 t for 1 hour, a transparent and uniform film was obtained. Moreover, no change was observed in this liquid composition for more than 6 months, and a similar film could be formed.

Example 10 After mixing 12.5 g of yttrium oxide [Y2O3] with 100 g of ammonium chloride, the mixture was heated to 350'C1 in an electric furnace.
It was held for 10 hours. After that, a portion was taken out and after confirming that it dissolved in water, 21 g of ethyl alcohol and n
- The mixture was suspended or dissolved in a mixed solvent of 600 ml of hexane, 6.5 g of monoethanolamine was added, and then ammonia gas was blown in at a rate of 0.2j2/min for 6 hours to advance the reaction. After the reaction, the precipitate was filtered off and the filtrate was evaporated using a rotary evaporator.
The solvent was removed under 100 m[11 Hg] at 0°C. The remaining liquid was prepared by adding 60 g of abietic acid and 10 g of pimaric acid to 60 g of isopropyl alcohol and 70 g of terpineol.
Add while stirring to a solution heated and dissolved in a mixed solvent of g,
A homogeneous solution was obtained. Oxide (Y2) of the obtained liquid composition
C13) The content calculated by tJk was 4.3% by weight, and the viscosity was 180 cps at 25°C.

Add 30 g of toluene to 50 g of this composition to make a uniform solution, apply it on a glass substrate by dipping method (pulling speed 10 mm/ml), dry at 100 ° C. for 10 minutes,
When baked at 550° C. for 30 minutes, a uniform and transparent film was obtained.

Comparative Example 4 A liquid composition was prepared in exactly the same manner as in Example 10 except that abietic acid and pimaric acid were not added, and this was applied onto a glass substrate by the dipping method (pulling speed 10 mm/m1n). After drying for 10 minutes at 550 °C
When baked at ℃ for 30 minutes, the film became non-uniform with a citron skin shape.

Example 11 4.1 g of bismuth Bi was mixed with 40 ml of acetic acid and 16 ml of 30% hydrogen peroxide solution, and heated to give a white to
A pale yellow precipitate was obtained. After adding and dissolving 20a+1 acetic acid to this precipitate, impurities were filtered off. This filtrate was concentrated on a water bath to obtain bismuth acetate containing 3.6 g in terms of B1□03. After this bismuth acetate was dissolved or dispersed in 40 ml of ethyl alcohol together with 2.2 g of triethanolamine and 2.1 g of lactic acid, ammonia gas was blown in at a rate of 0.2 fl 7% by weight for 1 hour to promote the reaction. After the reaction was completed, impurities were filtered off, and the filtrate was added to a solution prepared by heating and dissolving 30 g of gum rosin in 100 g of terpineol, and 20 g of tetrabutyl titanate was added thereto, followed by refluxing at 60 to 70° C. for 30 minutes.

The resulting liquid composition had an oxide (Bi2(h) equivalent concentration of 3.2% by weight and a viscosity of 125 cps at 25°C.) This composition was also processed by dipping method (pulling speed 10 m).
m/m1n) on a white tile, then apply it as it is at 7
When baked at 50° C. for 1 hour, a homogeneous and nearly transparent film was obtained.

Example 12 18.4 g of zinc acetate was suspended in 70 ml of ethyl alcohol, 13.2 g of leucinic acid was added thereto, and then ammonia gas was blown in at a rate of 0.2 fl/min for 2 hours. After removing excess ammonia gas by heating, rosin (Harima Kasei Co., Ltd. "Harimac T-
80J) was added to a solution prepared by heating and dissolving 50 g of terpineol in 60 g of terpineol, and the mixture was stirred.

If a precipitate was generated during mixing, it was heated to 60 to 70° C. to dissolve it (if it is mixed with sufficient stirring when hot, there is no need to heat it again).

The viscosity of the liquid composition thus obtained was 85 cp at 25°C.
s, and the concentration in terms of oxide (ZnO2) is 4.3% by weight
Met.

Using this composition, the dipping method (pulling speed 10 mm/m
1n) on a quartz substrate, dried at 100t for 10 minutes, and then fired at 500°C for 30 minutes. When this operation was repeated five times, a transparent oxide film with a thickness of about 0.8 μm was obtained.

When the absorption spectrum of this film in the visible and ultraviolet regions was measured, the transmittance in the wavelength region larger than 400 nm was 85.
%, and the transmittance decreases rapidly from around 380 nm,
The transmittance near 340 nm was 15%.

[Effects of the Invention] The present invention is constructed as described above, and its effects are summarized as follows.

(1) The liquid composition of the present invention has excellent paintability and film-forming properties, and forms homogeneous films on various substrates such as glass, metal, ceramics, and ceramics.

(2) This composition is uniform and very stable, and its viscosity can be adjusted extremely easily, so that it can be adjusted to any viscosity depending on the type of coating method.

(3) This composition forms a homogeneous oxide film simply by oxidizing and baking at a temperature of 440°C or higher after being applied to a substrate, so it can be widely used as a sensor material, superconducting material, various coating materials, etc. I can do it.

Claims (3)

[Claims] (1) (a) One or more metal compounds selected from the group consisting of inorganic metal salts and organic metal compounds (hereinafter referred to as M
(referred to as a), (b) 1 to 6 with nitrogen and/or oxygen as coordinating atoms
One or more organic compounds (hereinafter referred to as Lb
(c) one or more monobasic acids having one or two alcoholic hydroxyl groups as substituents (hereinafter referred to as Ac); (d) selected from the group consisting of pine resin, abietic acid and pimaric acid. one or more resin acids (hereinafter referred to as R
d), (e) contains an organic solvent (hereinafter referred to as Se) with a total of 0.1 to 4 moles of Lb and/or Ac per 1 gram atom of Ma in terms of metal, and the total amount of the composition. The content of Rd in it is 5 to 80% by weight.
, a liquid composition for forming a metal oxide film, characterized in that the content of Se is 5 to 80% by weight. (2) (a) One or more metal compounds selected from the group consisting of inorganic metal salts and organic metal compounds (hereinafter referred to as M
(referred to as a), (b) 1 to 6 with nitrogen and/or oxygen as coordinating atoms
(c) one or more monobasic acids having one or two alcoholic hydroxyl groups as substituents (hereinafter referred to as Ac); (d) One or more resin acids selected from the group consisting of pine resin, abietic acid, and pimaric acid (hereinafter referred to as R
(referred to as d), (e) Organic solvent (hereinafter referred to as Se) to 1 gram atom of the above-mentioned Ma in terms of metal, Lb and/or Ac occupy a total of 0.1 to 4 mol in the total amount of the composition. Each content of Rd and Se is 5 to 80
A metal characterized in that each component is mixed simultaneously or in any order so as to achieve the same weight percentage, and when Se is included as a mixed component, it is heated or ammonia gas is present to turn it into a solution. A method for producing a liquid composition for forming an oxide film. (3) A method for forming a metal oxide film, which comprises applying the liquid composition for forming a metal oxide film according to claim (1) onto a substrate, drying it, and then oxidizing and baking it at 440°C or higher.