JPH05319958A - Coating solution for forming coating film of compound metal oxide - Google Patents

Abstract

PURPOSE:To obtain a coating solution having high utility, providing a thick film by coating treatment one time. CONSTITUTION:A coating solution for forming a coating film of compound metal oxide comprises a solution consisting of (a) at least one selected from a reaction product of at least one selected from a metal of general formula M1An(A:OR or halogen) such as Ti compound and a beta-diketone compound, a partial hydrolyzate of the reaction product and a partially acylated substance of the reaction product, (b) a polyhydric alcohol and (c) at least one selected from among a metal carboxylic acid salt compound of the general formula M2(OCOR)m, a nitrate compound of the formula M2(NO3)m of a metal such as Pb and a nitrite compound of the formula M3(NO2)l of a metal such as Sr. A coating solution comprises a solution consisting of the components (a), (b) and (C) and (d) an alcohol-soluble polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating solution for forming a composite metal oxide film, and more particularly to a coating solution having excellent storage stability and forming a thick ferroelectric film.

[0002]

2. Description of the Related Art PbTiO ₃ --PbZrO ₃ , PbTi
_{O 3, PbTiO 3 -PbZrO 3 -La} 2 O 3, Li
A composite metal oxide film such as NbO ₃ is used as a ferroelectric film. This ferroelectric film has piezoelectricity, pyroelectricity,
It exhibits electrostriction and electro-optic effects, and is widely used as an electronic element such as ultrasonic cleaning, condenser pick-up vibrator, communication filter, sonic delay circuit, high voltage generating transformer, infrared sensor, and other ignition elements and various types. It is also used as an electro-optical material.

By the way, as a method of forming a ferroelectric film on a substrate, a method of applying a solution containing a compound such as Pb, Zr, or Ti on the substrate, drying and baking it is easy to operate. It is often used because of its advantages such as forming a ferroelectric film on a substrate having a complicated shape.

However, conventional coating liquids for forming a ferroelectric film usually use alkoxide compounds as compounds such as Pb, Zr and Ti, and these alkoxide compounds are easily hydrolyzed. When prepared and stored as a coating solution, there is a problem that precipitates are likely to occur in the coating solution and the storage stability is not excellent. Then, in order to solve such a problem, Japanese Patent Laid-Open No.
Japanese Unexamined Patent Publication No. 1-97159 proposes to use a part of alkoxy groups of an alkoxide compound by substituting it with a β-diketone group. Further, Japanese Patent Laid-Open No. 2-6335 proposes a coating solution with less generation of precipitates by adopting a solution containing a mixture of lead alkoxide or lead salt, zirconium alkoxide, titanium alkoxide, ethanolamine and alcohol. However, none of them has practical storage stability, and there is a strong demand for the development of a coating liquid having more excellent storage stability. Further, in the case of the conventionally known coating liquid, in the coating process, the limit film thickness of the ferroelectric film formed by one coating operation is about 1000 A or less. Is required
There is also a problem that the coating process is complicated.

[0005]

DISCLOSURE OF THE INVENTION The inventors of the present invention have excellent storage stability as a coating solution for forming a composite metal oxide film acting as a ferroelectric film, as compared with conventional coating solutions, and As a result of repeated studies for the purpose of providing a highly practical coating solution capable of obtaining a thick film by a single coating treatment,
By the coating liquid obtained by combining specific compounds,
The inventors have found that the object can be achieved and completed the present invention.

[0006]

The present invention provides: (a) General formula (I) M ₁ An ... (I) (wherein M ₁ represents Ti, Zr, Nb, Hf or Ta, and A is − Represents an OR or a halogen atom, wherein R is a saturated or unsaturated hydrocarbon having 1 to 6 carbon atoms, and n is an integer of 2 to 5). At least one selected from a reaction product of one kind with a β-diketone compound, a partial hydrolyzate of the reaction product and a partial acylated product of the reaction product, (b) a polyhydric alcohol compound, and C) General formulas (II), (III) and (IV) M ₂ (OCOR) m ... (II) (In the formula, M ₂ is Pb, Sr, Ba, Mg, Zn, La,
Y or Li is shown, and R is a saturated or unsaturated hydrocarbon having 1 to 6 carbon atoms. Further, a metal carboxylate compound represented by m is an integer of 1 to 4, M ₂ (NO ₃ ) m ... (III) (In the formula, M ₂ is Pb, Sr, Ba, Mg, Zn, La,
Indicates Y or Li. Further, a metal nitrate compound represented by m is an integer of 1 to 4, and M ₃ (NO ₂ ) 1 ... (IV) (In the formula, M ₃ represents Sr, Ba or Li. Also, 1 is 1
A metal nitrite compound represented by the formula:
A coating solution for forming a composite metal oxide film, which comprises a solution containing at least one selected from the group consisting of: (a) General formula (I) M ₁ An ... (I) (wherein M ₁ is Ti, Zr , Nb, Hf or Ta, A represents —OR or a halogen atom, wherein R is a saturated or unsaturated hydrocarbon having 1 to 6 carbon atoms, and n is an integer of 2 to 5). At least one selected from a reaction product of at least one selected from the metal compounds represented by and a β-diketone compound, a partial hydrolyzate of the reaction product, and a partial acylated product of the reaction product. 1 type, (b) polyhydric alcohol compound (c) general formulas (II), (III) and (IV) M ₂ (OCOR) m ... (II) (In the formula, M ₂ is Pb, Sr, Ba, Mg. , Zn, La,
Y or Li is shown, and R is a saturated or unsaturated hydrocarbon having 1 to 6 carbon atoms. Further, a metal carboxylate compound represented by m is an integer of 1 to 4, M ₂ (NO ₃ ) m ... (III) (In the formula, M ₂ is Pb, Sr, Ba, Mg, Zn, La,
Indicates Y or Li. Further, a metal nitrate compound represented by m is an integer of 1 to 4, and M ₃ (NO ₂ ) 1 ... (IV) (In the formula, M ₃ represents Sr, Ba or Li. Also, 1 is 1
A metal nitrite compound represented by the formula:
The present invention provides a coating solution for forming a composite metal oxide film, which comprises a solution containing at least one kind selected from the above and (d) an alcohol-soluble polymer.

The present invention will be described in detail below. The component (a) used in the coating liquid of the present invention is a metal compound represented by the general formula (I) and a β-diketone compound, a partial hydrolyzate of the reaction product and a partial acylated product of the reaction product. is there. Specifically, examples of the compound represented by the general formula (I) include metal alkoxide compounds and metal halogen compounds, and examples of the metal alkoxide compound include Ti.
(OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₃
H ₇ ) ₄ , Ti (OC ₄ H ₉ ) ₄ , Ti (OC
₅ H ₁₁ ) ₄ , Ti (OC ₆ H ₁₃ ) ₄ , Zr (OCH
₃ ) ₄ , Zr (OC ₂ H ₅ ) ₄ , Zr (OC
₃ H ₇ ) ₄ , Zr (OC ₄ H ₉ ) ₄ , Zr (OC ₅ H
₁₁ ) ₄ , Zr (OC ₆ H ₁₃ ) ₄ , Nb (OCH ₃ ).
₄ , Nb (OC ₂ H ₅ ) ₄ , Nb (OC ₃ H ₇ ) ₄ , N
b (OC ₄ H ₉ ) ₄ , Nb (OC ₅ H ₁₁ ) ₄ , Nb
(OC ₆ H ₁₃ ) ₄ , Ta (OCH ₃ ) ₄ , Ta (OC
₂ H ₅ ) ₄ , Ta (OC ₃ H ₇ ) ₄ , Ta (OC
₄ H ₉ ) ₄ , Ta (OC ₅ H ₁₁ ) ₄ , Ta (OC ₆ H
₁₃ ) ₄ , Hf (OCH ₃ ) ₄ , Hf (OC
₂ H ₅ ) ₄ , Hf (OC ₃ H ₇ ) ₄ , Hf (OC
_{4 H 9) 4, Hf (} OC 5 H 11) 4, Hf (OC 6 H
₁₃ ) _{4 and the} like. These metal alkoxide compounds may be used alone or in combination of two or more.

TiC is used as the metal halide compound.
l ₄ , TiBr ₄ , TiI ₄ , ZrCl ₄ , ZrB
r ₄ , ZrI ₄ , NbCI ₄ , NbBr ₄ , NbI ₄ ,
_{TaCl 4, TaBr 4, TaI 4} , HfCl 4, Hf
Br _{4 and the} like can be exemplified. These metal halogen compounds may be used alone or in combination of two or more.

Examples of β-diketone compounds include acetylacetone, trifluoroacetylacetone,
Hexafluoroacetylacetone, benzoylacetone, benzoyltrifluoroacetone, dibenzoylmethane, acetoacetic acid methyl ester, acetoacetic acid ethyl ester, acetoacetic acid butyl ester and the like can be mentioned.
These may be used alone or in combination of two or more. Preferred as the β-diketone compound are acetoacetic acid methyl ester, acetoacetic acid ethyl ester,
Acetoacetic acid butyl ester.

As the reaction conditions for preparing the component (a), one obtained by reacting the β-diketone compound in a ratio of 1 to 6 mols with respect to 1 mol of the above-mentioned metal compound can be preferably used. This reaction may be carried out in an organic solvent, or the β-diketone compound may be added to the solution obtained by dissolving the metal compound in the organic solvent to cause the reaction. Further, a partial hydrolyzate or a partial acylate of the reaction product is also included as the component (a) of the present invention.

The polyhydric alcohol compound as the component (b) used in the coating liquid of the present invention is an essential component for enhancing the solubility of the component (c) and the storage stability of the coating liquid. Mention may be made of ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, hexylene glycol, octylene glycol, glycerin, glyceryl monoacetate, glyceryl monobutyrate, trimethylolpropane, glyceryl monoacrylate, glyceryl monomethacrylate. You can These polyhydric alcohol compounds may be used alone or in combination of two or more.

Among these polyhydric alcohol compounds, particularly preferred are propylene glycol, glyceryl monoacetate, glyceryl monobutyrate, glyceryl monoacrylate, glyceryl monomethacrylate and the like.

Further, the polyhydric alcohol compound of the component (b) used in the present invention is preferably reacted with the above-mentioned component (a), and the polyhydric alcohol is contained per mol of the metal compound of the component (a). By using the reaction product obtained by reacting 1 to 6 mol, a coating solution having extremely excellent storage stability can be prepared, and the reaction product is that the component (b) is added to the component (a). It can be confirmed by the change in color of the reaction solution obtained as described above, and the component (b) is completely different from the organic solvent for obtaining the coating property as the coating liquid described later as its function.

Examples of the metal carboxylate compound, metal nitrate compound and metal nitrite compound represented by the above general formulas (II), (III) and (IV) of the component (c) used in the coating liquid of the present invention are: Specifically, as the metal carboxylate compound, Ba (CH ₃ COO) ₂ nH ₂ O, L
_{a (CH 3 COO) 3 nH} 2 O, Pb (CH 3 COO)
₂ nH ₂ O, Li (CH ₃ COO) nH ₂ O, Zn (C
H ₃ COO) ₂ nH ₂ O, Sr (CH ₃ COO) ₂ nH
₂ O, Y (CH ₃ COO) ₃ nH ₂ O, Mg (CH ₃ C
OO) ₂ nH ₂ O and the like, and as the metal nitrate compound, Ba (NO ₃ ) ₂ nH ₂ O, La (NO
₃ ) ₃ nH ₂ O, Pb (NO ₃ ) ₂ nH ₂ O, Li (N
O ₃ ) nH ₂ O, Mg (NO ₃ ) ₂ nH ₂ O, Sr (N
O ₃ ) ₂ nH ₂ O, Zn (NO ₃ ) ₂ nH ₂ O, Y (N
O ₃ ) ₃ nH ₂ O and the like, and as the metal nitrite compound, Sr (NO ₂ ) ₂ nH ₂ O, Ba (N
_{O 2) 2 nH 2 O,} Li (NO 2) nH 2 O , and the like. These can be used alone or in combination of two or more.

The coating solution of the present invention comprises the above-mentioned component (a),
In addition to those containing the component (b) and the component (c),
By blending an alcohol-soluble polymer as the component (d), it is possible to prepare a coating solution for forming a film having particularly improved thick film properties.

The alcohol-soluble polymer which is the component (d) is not particularly limited as long as it is a polymer which can be dissolved in alcohol, but a polymer having a hydroxyl group in the polymer structure is preferable. Specifically, polyvinyl acetate partially saponified polyvinyl alcohol, formal resin, butyral resin, polyglycerin, 2-hydroxymethyl acrylate, 2-hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl. Mention may be made of homopolymers and copolymers such as acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate and 2-hydroxybutyl methacrylate.

The coating solution of the present invention comprises the above-mentioned (a),
Those containing each component of (b) and (c), and (b),
In addition to each of the components (b) and (c), the above component (d) is blended, but in order to improve the coating properties as a coating liquid, each component is used in a form dissolved in an organic solvent. Preferably. Examples of such an organic solvent include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol,
Ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, octylene glycol, diethylene glycol, dipropylene glycol, dihexylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene Glycol monophenyl ether, ethylene glycol monobenzyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol dipropyl Ether, ethylene glycol dibenzyl ether, ethylene glycol methyl ethyl diether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, methyl carbitol, ethyl carbitol, butyl carbitol, phenyl carbitol, benzyl carbitol, Dimethyl carbitol,
Examples thereof include diethyl carbitol, dibutyl carbitol, diphenyl carbitol, dibenzyl carbitol, methyl ethyl carbitol, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol dibutyl ether. These organic solvents may be used alone or in combination of two or more.

Next, a method for producing the coating liquid of the present invention will be described. The coating liquid of the present invention comprises the above-mentioned components (a), (b) and (c), and (d) is added to each of the components (a), (b) and (c). It is obtained by dissolving the product in an organic solvent. The method for producing the product is to prepare a reaction product of the component (a) and the polyhydric alcohol compound (b), and then prepare the component (c). It is important to add at least one selected from the above-mentioned metal carboxylate compound, metal nitrate compound and metal nitrite compound, and if this order is changed, a coating solution excellent in solubility and storage stability can be obtained. Cannot be prepared. Further, the component (d) is preferably added to the coating liquid prepared from the components (i), (b) and (c) as described above.

The proportion of each component is 1 mol or more, preferably 1 to 6 mol, of the polyhydric alcohol compound of the component (b), relative to 1 mol of the metal compound of the component (a). Various metal compounds of component (c) 0.5 to 5
The amount is preferably in the range of 0.8 to 3 mol.
If the blending range deviates from these ranges, a coating solution having excellent storage stability cannot be prepared, which is not preferable. Further, the alcohol-soluble polymer of the component (d) is 1 to 100 parts by weight, preferably 3 to 40 parts by weight, based on 100 parts by weight of the solid content of the coating liquid obtained from each of the components (a), (b) and (c). It is mixed in the range of. If the component (d) deviates from this range, a thick coating film having excellent uniformity cannot be obtained, which is not preferable.

The coating solution of the present invention is applied to a substrate obtained by firing powder of plastics, glass, ceramics, metal nitride, metal carbonate, etc., metal, semiconductor substrate, etc. It is possible to form a composite metal oxide film that is an excellent ferroelectric film. In this case, as a coating means, any of a dipping and pulling method, a spray method, a spin coating method, a brush coating method, a roll coating method and a printing method can be used. Examples of heating means include hot plate heating, hot air heating, burner heating, infrared heating, laser heating, and high frequency heating. A heating temperature of 250 ° C. or higher, preferably 350 ° C. or higher, can form a chemically stable film, but it is limited by the material of the substrate, etc., so it must be appropriately selected within a temperature that the substrate can withstand. ..

[0021]

The coating liquid of the present invention has the above-mentioned (a),
By combining the components (b) and (c), it is possible to easily prepare a coating liquid with extremely excellent storage stability compared to conventional coating liquids, and to easily form a ferroelectric film with excellent characteristics. It is extremely practical because it can be formed and a thick film can be obtained by a single coating process. Further, by adding the component (d) to the coating liquid obtained by combining the respective components (a), (b) and (c), it is possible to improve the thick film property by a single coating treatment. A highly practical coating liquid can be obtained.

[0022]

【Example】

Example 1 28.4 g (0.1 mol) of tetrapropoxy titanium was mixed with 23.2 g (0.2 mol) of methyl acetoacetate, and 8
After reacting with stirring at 0 ° C. for 30 minutes, 6.1 g (0.1 mol) of glacial acetic acid was added and reacted at 80 ° C. for 30 minutes, and then returned to room temperature, and 13.4 g of glyceryl monoacetate (0.1. 2 mol) and added at 80 ° C for 3
After reacting for 0 minutes, return to room temperature, 50 g of ethylene glycol monomethyl ether and strontium acetate 2
A coating liquid was prepared by adding 1.4 g (0.1 mol) and heating to 40 ° C. to mix and dissolve.

Next, the coating solution was coated on a silicon wafer by a spinner method at 3000 rpm for 30 seconds, and
After drying at 0 ° C. for 20 minutes and baking at 400 ° C. for 30 minutes in air, a transparent and uniform film of SrTiO ₃ of about 1000 A was formed. Further, even when the above-mentioned coating liquid was allowed to stand at room temperature for 3 months, no precipitation of impurities and the like was observed in the coating liquid and no change in properties was observed.

Example 2 29.48 g (0.09) tetrapropoxyzirconium
Mol) and 3.40 g (0.01 mol) of tetrabutoxytitanium while mixing at 80 ° C. for 30 minutes while stirring,
26 g (0.1 mol) of acetoacetic acid ethyl ester was added, and the reaction was continued while stirring at 80 ° C. for 30 minutes, whereupon 1.8 g (0.1 mol) of water, 5 μl of concentrated hydrochloric acid,
After adding a mixture of 10 g of ethylene glycol monoethyl ether and reacting at 60 ° C. for 60 minutes, 15.2 g (0.2 mol) of propylene glycol was added,
After heating at 60 ° C. for 30 minutes, 37.9 g of lead acetate was added and dissolved while heating at 50 to 70 ° C. to prepare a coating solution.

Next, the coating solution is coated on a silicon wafer by a spinner method at 4000 rpm for 30 seconds, and then 80
After drying at 50 ° C. for 15 minutes and baking at 500 ° C. for 40 minutes in air, a transparent and uniform film of about 2000 A was formed. Further, even when the above-mentioned coating liquid was allowed to stand at room temperature for 3 months, no precipitation of impurities and the like was observed in the coating liquid and no change in properties was observed.

Example 3 29.48 g (0.09) tetrapropoxyzirconium
Mol) and 3.40 g (0.01 mol) of tetrabutoxytitanium while mixing at 80 ° C. for 30 minutes while stirring,
26 g (0.1 mol) of acetoacetic acid ethyl ester was added, and the mixture was further stirred at 80 ° C. for 30 minutes for reaction, and then 15.2 g (0.2 mol) of propylene glycol.
Was added and heated at 60 ° C. for 30 minutes, and then lead acetate 37.
A coating liquid was prepared by adding 9 g and dissolving it while heating at 50 to 70 ° C. Next, the coating solution was applied onto a silicon wafer by a spinner method at 4000 rpm for 30 seconds, dried at 80 ° C. for 15 minutes, and then at 500 ° C. for 4 minutes.
When baked in air for 0 minutes, a transparent and uniform film of about 1500 A was formed. Further, even when the above-mentioned coating liquid was allowed to stand at room temperature for 3 months, no precipitation of impurities and the like was observed in the coating liquid and no change in properties was observed.

Example 4 A coating solution obtained by adding 15 g of a 20% by weight ethylene glycol monomethyl ether solution of 2-hydroxypropyl methacrylate to 10 g of the coating solution obtained in Example 3 was used. As a result of forming a film by the operation of 1., a transparent and uniform film of about 5000 A was formed.
Further, even when the coating solution was allowed to stand at room temperature for 3 months, no precipitation of impurities and the like was observed in the coating solution, and no change in characteristics was observed.

Example 5 10 g of the coating solution obtained in Example 3 was mixed with 30 parts of butyral resin.
00-2 (manufactured by Denka Kagaku Kogyo Co., Ltd.) was used to obtain a coating solution obtained by adding 10 g of a 20 wt% ethylene glycol monomethyl ether solution, and a coating was formed in the same manner as in Example 3. As a result, about 5000 A was obtained. A transparent and uniform film was formed. Further, this coating solution was allowed to stand at room temperature for 3 months, precipitation of impurities and the like in the coating solution was not observed at all, and no change in properties was observed.

Example 6 Tetrapropoxy zirconium 170.40 g (0.5
2 mol) and tetrabutoxy titanium 160.37 g (0.
(48 mol) was stirred at 80 ° C. for 30 minutes while mixing, and 13.2 g of the resulting solution was added to acetoacetic acid ethyl ester 1
0.4g (0.04mol) was added, and the mixture was further added at 100 ° C for 3
To the place where the reaction was stirred for 0 minutes, water 0.72
g (0.04 mol), concentrated hydrochloric acid 10 μl, and ethylene glycol monoethyl ether 4 g were added,
After reacting at 80 ° C. for 30 minutes, 6 g (0.08 mol) of propylene glycol was added, and after heating at 80 ° C. for 30 minutes, 15.7 g of lead acetate was added and dissolved while heating at 50 to 70 ° C. 36% by weight of 2-
A coating solution was prepared by adding 10 g of an ethylene glycol monomethyl ether solution of hydroxypropyl methacrylate.

Then, the coating solution is coated on a silicon wafer by a spinner method at 4000 rpm for 30 seconds,
After drying at 50 ° C. for 15 minutes and baking at 500 ° C. for 40 minutes in air, a transparent and uniform film of about 5000 A was formed. Further, even when the above-mentioned coating liquid was allowed to stand at room temperature for 3 months, no precipitation of impurities and the like was observed in the coating liquid and no change in properties was observed.

Claims (3)

[Claims] (A) General formula (I) M ₁ An ... (I) (In the formula, M ₁ represents Ti, Zr, Nb, Hf, or Ta, and A represents —OR or a halogen atom. And R is a saturated or unsaturated hydrocarbon having 1 to 6 carbon atoms, and n is an integer of 2 to 5), and at least one selected from the group consisting of β-diketone compounds. At least one selected from the reaction product of, the partial hydrolyzate of the reaction product, and the partially acylated product of the reaction product, (b) a polyhydric alcohol compound, and (c) a general formula (II), (III) and (IV) M ₂ (OCOR) m ... (II) (In the formula, M ₂ is Pb, Sr, Ba, Mg, Zn, La,
Y or Li is shown, and R is a saturated or unsaturated hydrocarbon having 1 to 6 carbon atoms. Further, a metal carboxylate compound represented by m is an integer of 1 to 4, M ₂ (NO ₃ ) m ... (III) (In the formula, M ₂ is Pb, Sr, Ba, Mg, Zn, La,
Indicates Y or Li. Further, a metal nitrate compound represented by m is an integer of 1 to 4, and M ₃ (NO ₂ ) 1 ... (IV) (In the formula, M ₃ represents Sr, Ba or Li. Also, 1 is 1
A metal nitrite compound represented by the formula:
A coating liquid for forming a composite metal oxide film, which comprises a solution containing at least one selected from the group consisting of: 2. (a) General formula (I) M ₁ An ... (I) (In the formula, M ₁ represents Ti, Zr, Nb, Hf or Ta, and A represents —OR or a halogen atom. Wherein R is a saturated or unsaturated hydrocarbon having 1 to 6 carbon atoms, and n is an integer of 2 to 5), and at least one selected from the metal compounds and a β-diketone compound. At least one selected from a reaction product, a partial hydrolyzate of the reaction product, and a partially acylated product of the reaction product.
Species, (b) polyhydric alcohol compound, (c) general formulas (II), (III) and (IV) M ₂ (OCOR) m ... (II) (wherein M ₂ is Pb, Sr, Ba, Mg) , Zn, La,
Y or Li is shown, and R is a saturated or unsaturated hydrocarbon having 1 to 6 carbon atoms. Further, a metal carboxylate compound represented by m is an integer of 1 to 4, M ₂ (NO ₃ ) m ... (III) (In the formula, M ₂ is Pb, Sr, Ba, Mg, Zn, La,
Indicates Y or Li. Further, a metal nitrate compound represented by m is an integer of 1 to 4, and M ₃ (NO ₂ ) 1 ... (IV) (In the formula, M ₃ represents Sr, Ba or Li. Also, 1 is 1
A metal nitrite compound represented by the formula:
A coating solution for forming a composite metal oxide film, which comprises a solution containing at least one selected from the group (d) and (d) an alcohol-soluble polymer. 3. The coating liquid according to claim 1, wherein the polyhydric alcohol is at least one selected from propylene glycol, glyceryl monoacetate, glyceryl monobutyrate, glyceryl monoacrylate and glyceryl monomethacrylate.