JPS5841720A - Composition forming metallic oxide film - Google Patents

Abstract

PURPOSE:To form a metallic oxide film of good quality in a wide range of substrate temperatures in forming the metallic oxide film on the surface of a substrate by the ultrasonic atomizing film-forming method, by using a solution containing an organometallic compound as a film-forming component in an organic solvent as a film-forming composition. CONSTITUTION:In forming a metallic oxide film on the surface of a substrate, e.g. glass, ceramic or metal, by the ultrasonic atomizing film-forming method, a solution containing one or two or more organometallic compounds selected from the group of monomers or polymers of organic compounds expressed by formula[I]and polycondensates, obtained by reacting alkoxides of a metallic atom (M) expressed by formula[II]with water, and having an average molecular weight <=5,000 as a metallic oxide film-forming component in an organic solvent, e.g. an alcohol or alkyl acetate, is used as a film-forming composition. A metallic oxide film of good quality is formed in a wide range of substrate temperatures.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition for forming a metal oxide film, particularly a composition suitable for forming a metal oxide film on a substrate by an ultrasonic atomization film forming method.

A metal oxide film (hereinafter referred to as "metal oxide film") formed on a heat-resistant substrate such as glass, ceramic, or metal.
have specific electrical, optical, chemical, and/or mechanical properties depending on their type, and can be used as conductive films, insulating films, alignment films, photomasks, alkali blocking films, heat ray reflective films, ultraviolet absorbing films, and mechanical , IIk films, etc., are used in a wide range of fields including the electronics field and the opto-mechanical field.

On the other hand, with the diversification of the fields in which metal oxide coatings are used, the coating composition, that is, the types of metal atoms used in oxide coatings and their combinations, have expanded and diversified. There is a strong demand for improvements in the denseness, homogeneity, and adhesion of the coating to the substrate, as well as flexibility in selecting the thickness depending on the purpose of the papermaking application.

In addition, although methods for forming metal oxide films are diversifying, there is no industrial method that simultaneously satisfies both film performance and economic efficiency, and the current situation is that each method has to sacrifice one of them. It is. As one of the methods for forming a high-quality metal oxide film, the ultrasonic atomization film formation method (4I Publication No. 1848-37786, Japanese Patent Publication No. 1848-155)
No. 45) is known. The coughing method involves preparing a solution of an inorganic or organic metal compound that forms an oxide film, alone or in a mixture, in water or an organic solvent (hereinafter referred to as a "film-forming composition"), By applying sound waves, this was made into extremely fine mist droplets, and the resulting mist droplets were entrained in a carrier gas and heated to a temperature higher than the decomposition temperature of the metal compound contained therein. This method involves contacting a heat-resistant substrate, causing oxidative decomposition and sintering to occur simultaneously on the substrate, and forming a gold-oxide film having various thicknesses on the substrate. This method uses relatively simple equipment and can form a homogeneous and dense metal oxide film in a relatively wide range of thickness through simple operations, so it can be used in a wide range of industrial applications. As expected, there are not many examples regarding this method, so there is much that is not known about what kind of solution of what kind of compound should be used as the film-forming composition.

For example, although the above-mentioned Japanese Patent Publication No. 48-37786 suggests that organic tin (for example, lower alkyl esters) can be used, it only describes an ethanol solution of tin chloride as an example. Furthermore, in Japanese Patent Publication No. 55-15545, although Mllk describes the types of metal oxide films, it only describes an aqueous solution of iron chloride as a film-forming composition.

As a result of intensive research regarding the formation of metal oxide films by the ultrasonic atomization film formation method, the present inventors have found that an organic solvent solution containing the following organic gold compound as a metal oxide film-forming component is used as a film-forming composition. The present invention was completed based on the discovery that a high-quality metal oxide film can be obtained over a wide range of substrate temperatures by using this method.

An object of the present invention is to provide a metal oxide coating-forming composition that is excellent in stability and can yield a high-quality metal oxide coating in the formation of a metal oxide coating by an ultrasonic atomization coating method.

The present invention is based on the general formula [! ] M-(OR)s-X(s-s) ・” (1
Monomers and/or multimers of organometallic compounds represented by 1, and the general formula [Seal] M・(on) false ・・
・A metal oxide film is formed by applying 91 types or 2 or more types of organometallic compounds selected from the group of condensation products with an average molecular weight of 5000 or less obtained by the reaction of the metal alkoxy P represented by [Seal] with water. This is a metal oxide film forming component for an ultrasonic atomized film forming method, characterized in that it is contained in an organic solvent as a forming component.

In the present invention, M in general formula (1) is Sc.

Ga, 81, Ge, SunS PbS Wb,
Ta, M8, 81), Bi, MOLW,
8e, represents a metal atom selected from the group of To%Mn%Co and Ml, R represents the same or different alkyl group having 1 to 8 carbon atoms, and X forms a chelate ring with the metal atom M. The general formula X, Ijt (where,
t represents 1 or 2. ) represents the same or different residues of the organic compound, where the negative value represents the valence of the metal atom M,
Tsuru is an integer from 0 or 1 to Taku. In addition, the general formula [
[M, R and Kamo therein represent the same meanings as above.

The organic compound represented by the general formula [general formula Propionic acid, butyric acid, lauric acid, stearic acid, acrylic acid, methacrylic acid, croton, acid, malate/11% fumaric acid, hydroxycal d7rlt such as lactic acid,
Glyceric acid, phosphorus ft1, etc., glycols such as ethylene glycol, propylene glycol, octyle/
These are organic compounds that can be formed with a metal atom M, such as glycols and amines such as triethanolane.

In the present invention 1ji, the organometallic compound represented by the general formula (1) is a methoxide, ethoxide, isopropoxide, butoxide, bentoxide, hexyl oxide, etc. of the metal atom M represented by the general formula (31), and these two.
The alkoxy groups O1@*9 of the alkoxy groups having more than one species of different alkoxy groups and the flukoxides of the metal atom M were all substituted with the organic compound O*ll5X represented by the general formula X-Ht. These are monomers and/or polymers of organometallic compounds. These organometallic compounds exist as monomers or polymers depending on the manufacturing method, type of slag agent, etc. Another metal oxide film-forming component is obtained by a reaction between a flukoxide of the metal atom M and water.

The repeating constituent unit is the general formula [gate] (MCOR><*-wh>・0.] ...(
IilJ (here M, R and negative have the same meaning as above t-
where the vortex represents an integer of 1 or %-1). ) is a polycondensation product in which the number of repeats of the constituent units of the metal atom MO oxyalkoxides is 2 to 20, and the average precharge is 5000 or less. Original F! In A, the film-forming components in the 11% composition are organic solvent-soluble compounds among the organometallic compounds. The organic solvent that is one of the compositions includes alcohols having 1 to 4 carbon atoms such as methanol, ethanol, isopronol, butanol, methyl acetate, alkyl acetate esters having 3 to 60 carbon atoms such as ethyl acetate, and methyl acetoacetate. , alkyl acetoacetates having 5 to 6 carbon atoms such as ethyl acetoacetate, and acetylacetone, or a mixed solvent of two or more thereof.

Film-forming composition of the present invention, 111 of the organometallic compound
Alternatively, it is an organic solvent solution in which two or more of the metal oxide film-forming components have a solubility of less than or equal to 10, preferably 10 or less, and more preferably 3' to 61, the solubility in the solvent used as the metal oxide film forming component. When containing two or more types of organometallic compounds, organometallic compounds containing the same or different substituents of the four metals can be included, and organometallic compounds containing different substituents of the same metal can be included. I can do it. Furthermore, an organometallic compound having the same or different substituents of a metal other than the metal M can also be contained as a dopant.

In the film-forming composition of the present invention, the organometallic compounds that are metal oxide film-forming components are present in an oxygen-containing air stream.
It is stable up to temperatures of 200° C. or higher,69 and rapidly decomposes at temperatures specific to scissors compounds, and is formed on a film substrate containing gold six compound as the main component. therefore,
The organometallic compounds that are the components for forming the metal oxide film undergo oxidative decomposition (hydrolysis and dehydration condensation occur simultaneously) on a heat-resistant substrate maintained at a temperature of 300°C or higher in the ultrasonic atomization film formation method. (including cases in which the same applies hereinafter) and sintering of the decomposed products are performed simultaneously, or sintering is performed separately, and the conditions are satisfied to perform oxidative decomposition primarily. On the other hand, the organic solvent, which is another component of the composition, depends on the atomization conditions in the ultrasonic atomization film formation method, especially the density of the composition, which is a factor that affects the average particle size of the mist droplets produced by applying ultrasonic waves. and adjust surface tension. Therefore, although it varies depending on the type and concentration of the organometallic compound that is one of the composition components, a composition with a desired average particle size can be obtained by using one or a mixed solvent of two or more of the above-mentioned organic decomposition solvents. You can get mist droplets.

In order to form a multimetal oxide film using the film-forming composition of the present invention by the ultrasonic atomization film-forming method, the film-forming composition flowing out from the container or container of the ultrasonic atomization device is used. applying ultrasonic sound to generate mist droplets, entraining the mist droplets with an appropriate carrier gas, and bringing them into contact with a heat-resistant substrate maintained at a temperature of 300°C or higher in the film forming apparatus. 200mm thick on the skeleton base
A dense metal oxide film of ~1oooo

The metal oxide film forming composition of the present invention has the following characteristics when forming a metal oxide film on a heat-resistant substrate by an ultrasonic atomization film forming method.

(b) Fine droplets of the film-forming composition with an average particle size of several pm and a narrow and stable particle size distribution can be obtained.

It exists stably in the mist droplets below the oxidative decomposition temperature, and can be completely decomposed to form a metal oxide film on a substrate kept at a high temperature, or can be sintered at an even higher temperature to form a high-performance metal. An oxidative decomposition film tube is formed that gives an oxidation film l[t-.

)) The resulting metal oxide film is dense, dense, and chemically and mechanically homogeneous.

By using a film-forming composition containing two or more desired organic compounds of different metals, a metal oxide composition film having a desired composition can be obtained.

The film forming composition of the present invention can be applied not only to ultrasonic atomization film forming methods but also to dipping methods, spray methods, spinner methods, etc.
It can also be used in a metal oxide film forming method using a solution-like film forming composition such as a roll coating method, and a high quality metal oxide film can be obtained.

The present invention provides a metal oxide film forming composition capable of forming a dense and homogeneous metal oxide film on a substrate by an ultrasonic atomization film forming method. By using the composition, it has become possible to obtain high-performance oxide films of various metals that could not be obtained conventionally by ultrasonic atomization film formation methods.

Hereinafter, the present invention will be explained in more detail using examples. However, the scope of the present invention is not limited to the following examples.

Example 1 f ) 5 , Z ) * Shishira 7 [81(00,
it,),] 7.3 ti, t-containing acetylacetate);/-S-! An ultrasonic atomization film forming apparatus with an oscillation frequency of 9.13 MH was used, using a mixed agent solution of tanol as a film forming composition.

A silicon oxide film was formed on the glass. By ultrasonic atomization, mist droplets of the film-forming composition with an average particle size of 5 to 6 μm were obtained, and the entire air of the mist droplets was introduced into a film-forming device as a carrier gas, and was preheated to a temperature of 300°C. 9. Contact with the glass substrate. Then, the temperature of the glass substrate was gradually raised to 500° C. to completely sinter it.

A transparent silicon oxide film with a thickness of 1000× was formed on a glass substrate. The resulting silicon nine oxide coating was homogeneous, hard, and had strong adhesion to the substrate), and had a high transmittance for visible light mI. Furthermore, the etching rate (11, R) is 5
! /sea and showed superior chemical resistance compared to the silicon oxide coating obtained by the Ippin method.

Super Example 2 A metal surface coating was formed on a substrate using the same ultrasonic self-forming coating device as used in Example 1 and the coating composition shown in attached Table 1. Table 1 shows the properties of the conversion-forming composition and the metal surface coating obtained.

Procedural amendment (method) @ 1a57-J/, P8 Haruki Shimada, Commissioner of the Japan Patent Office, 1, Indication of the case Showa Kanto Patent Office No. 138134 λ We name Metal oxide wave film formation Relatives 5 Amendment case Relationship with Applicant: No. 291, Otemachi 2-chome, Chiyoda-ku, Tokyo 100 (430
) ＠Yokoyama Kai (712B), 9291 Otemachi 2-chome, Chiyoda-ku, Tokyo, Yokoyama Kai (712B), 2-9291 Otemachi, Chiyoda-ku, Tokyo Month, 26th (shipment date) & revised statement 2 contents of amendment (no change in contents)

Claims (1)

[Claims] 1. General formula (1) % formula % and a metal atom of tin 1 m from the group of N(, R
is the same or different alkyl group X#i having 1 to 8 carbon atoms;
The residue of the same or different type of organic compound represented by H1 (where Kt is 1 or 2) is the valence of the metal atom M and represents Ol or an integer from 1 to 0. ) Monomers and/or polymers of organic compounds represented by the following formula and the general formula M·(OR)s...(1) (ζ where Ml, R and % have the same meanings as above. ) One or more organometallic compounds separated from the group of condensation products having an average molecular weight of 5000 or less obtained by the reaction of an alkoxide of a metal atom y represented by y with water, as a metal oxide film forming component, 1. A metal oxide film-forming composition for use in an ultrasonic atomization film-forming method, characterized by containing a metal oxide film in an organic solvent. 2. The organic compound represented by the general formula
The film-forming composition according to claim 1, which is 11!1 or 2 or more selected from the group of 8 saturated or unsaturated carunic acids, human tetrahedroxylic acids, glycols, and eye groups. thing. 3. Organic solvent is alcohol with 1 to 4 carbon atoms, 3 carbon atoms
Formation of a film according to claim 1, which is a solvent selected from the group of alkyl acetate esters having 6 to 6 carbon atoms, alkyl acetoacetate esters having 5 to 6 carbon atoms, and acetylacetone alone or in a mixture of two or more of them. Composition.