JPS6150904B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for manufacturing an inorganic fired body. More specifically, the present invention relates to a method for producing inorganic fired bodies such as microspheres, coatings, films, and foams from polymetalloxane having phenoxy groups. In particular, the present invention relates to a method for producing an inorganic coating or film by forming a coating or film using a polymetalloxane having a phenoxy group in the side chain, subjecting it to infusible treatment as necessary, and then firing it. It is something. In recent years, as a result of technological developments in many industrial fields including the electronics industry, physical properties superior to those of conventional materials, such as heat resistance, insulation, conductivity, ferroelectricity, and strong There is a strong desire to develop materials that have magnetism, translucency, etc. Such materials include silica or alumina films for chemically and mechanically protecting glass, alumina for IC substrates, and PLZT for surface acoustic wave filters.
Films such as tin oxide or indium oxide films of transparent conductive films are well known. As described above, the applications of metal oxides, particularly in the form of coatings and films, to electronic materials are extremely wide-ranging, and various manufacturing methods have also been proposed for this purpose. Previously, the present inventors proposed a method for producing an inorganic film using polymetalloxane as a starting material (Japanese Patent Laid-Open Nos. 54-43241 and 1982-129894). The above method has a high metal oxide content in the precursor film, which results in a dense film after firing, resulting in high strength, and the coating solution has better coverage than other methods. It also has many advantages over other methods, such as good wettability and easy adhesion to the substrate. According to subsequent studies by the present inventors, it was found that the quality of coating and film formation largely depends on the type of organic group in the side chain of the polymetalloxane. In other words, organic residues with a large number of carbon atoms, such as higher acyloxy groups and higher alkoxy groups, are effective in improving film-forming properties and elongation during coating, and improve coating workability compared to lower organic residues. and the stability and strength of the film are improved. However, when a large amount of organic residues with a large number of carbon atoms are introduced into the side chain, the ratio of metal atoms in the precursor film decreases, resulting in a decrease in the strength of the film after firing, and a large amount of organic residues. The combustion and thermal decomposition of gas generate large amounts of a wide variety of gases, resulting in local differences in the atmosphere and, therefore, differences in the degree of combustion. This method is still unsatisfactory, as it has the disadvantages of uneven coating quality, localized foaming, and cracking. As a result of intensive research into these points, the present inventors found that polymetalloxane containing polymetalloxane with a phenoxy group introduced into the side chain has a significantly superior structure compared to the number of carbon atoms it contains. The present inventors have completed the method of the present invention by discovering that a film having excellent scratch strength and uniformity can be produced by imparting film properties and by firing a film precursor made from the polymetalloxane. That is, the present invention [A] General formula

[expression] and/or

[Formula] (In the formula, M is group a, group a, Cr, Mn, Fe,
Trivalent metal atoms of Co, Ni or rare earth elements or tetravalent metal atoms of group a, Zr, Hf, Cr, Mn, Fe, Co or Ce, Y is an organic residue, nitro group or halogen, m is 0 ~5 integer, X ₁ is

Indicates an organic residue, hydrogen atom, nitro group, or halogen that is the same as or different from [Formula]. ) Structural units represented by 0.1 to 95 mol% and [B] General formula

[expression] and/or

[Formula] (where M is the same as above, X ₂ and X ₃ are

Indicates organic residues excluding [Formula]. The present invention provides a method for producing an inorganic fired body, which comprises forming a molded article from an organic solvent solution containing a polymetalloxane containing 99.9 to 5 mol % of structural units represented by the following formula, and then firing the molded article. The method of the present invention will be explained in more detail below. The raw material polymetalloxane used in the method of the present invention has the general formula [A]

[expression] and/or

Contains 0.1 to 95 mol% of the structural unit represented by [Formula] (where M, Y, m and X are the same as above), and the balance is [B]

[expression] and/or

It is a polymer consisting of the formula: (wherein M, X ₂ and X ₃ are the same as above). In the above general formula, M may be any metal of the above type that can be converted into a metal oxide by firing, but specific examples include boron, aluminum, gallium, indium, silicon, germanium, tin, lead, yttrium, zirconium, and rare earth metals. element, chromium,
Examples include manganese, iron, cobalt, and nickel. Aluminum, silicon, indium, tin, etc. are particularly suitable for film or coating applications. Y represents an organic residue, nitro group or halogen,
Specifically, alkyl groups such as methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, methoxy group, ethoxy group,
Alkoxy groups such as n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group,
Acyl groups such as acetyl group, propionyl group, benzoyl group, alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, alkenyl group such as phenoxycarbonyl group, cyano group, vinyl group, propenyl group, phenyl group or substituted phenyl groups, phenoxy groups, halogens such as chlorine and fluorine, and the like. When Y is substituted with a plurality of substituents, Y may be the same or different substituents, and m is an integer of 0 to 5, preferably an integer of 1 to 3. X ₁ is

[Formula] represents an organic residue, a nitro group, a halogen, or a hydrogen atom that is the same as or different from [Formula], specifically Y and m as described above.

[Formula] group, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, alkyl group such as iso-butyl group, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group , n-butoxy group, alkoxy group such as iso-butoxy group, acetyl group, propionyl group,
Examples include acyl groups such as benzoyl groups, halogens such as chlorine and fluorine, nitrile groups, and hydrogen atoms. X ₂ and X ₃ are

Indicates organic residues excluding [Formula], specifically methyl group, ethyl group, n
- Alkyl groups such as propyl group, iso-propyl group, n-butyl group, iso-butyl group, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, etc. alkoxy group, acetyl group, propionyl group,
Examples include acyl groups such as benzoyl group. The polymetalloxane used in the present invention can be prepared by the method described below. For example, dimethylphenoxyaluminum, diethylphenoxyaluminum, dipropylphenoxyaluminum, dimethoxyphenoxyaluminum, diethoxyphenoxyaluminum, dipropoxyphenoxyaluminum, dimethylacetylphenoxyaluminum, dimethyldiphenoxyaluminum silicone, di-(ethoxyphenoxy)-diethyl silicone, P-chlorophenoxy-trimethoxy silicone, P-nitrophenoxy-triethoxy silicone, P-ethylphenoxy-triisopropoxy zirconium, diethyldiphenoxy zirconium, di-(ethoxy carbonylphenoxy)-dimethoxyzirconium, diethylphenoxyindium, P-methoxycarbonylphenoxy-diethoxyindium, O-cyanophenoxy-diisopropoxyindium, dimethyldiphenoxytin, O-ethoxycarbonylphenoxy- Partial hydrolysis of organometallic compounds having phenoxy groups such as triisopropoxytin, or trimethylaluminum, triethylaluminum, tripropylaluminum, triethoxyaluminum, triisopropoxyaluminum, diethylaluminum hydride, diisopropoxymono Ethyl aluminum, monoethoxy diethyl aluminum, tetraethyl zirconium, tetraisopropoxy zirconium, tetrabutyl zirconium, trimethyl zirconium hydride, diethyl diisopropoxy zirconium, tetraethyl silicon, tetrapropyl silicon, methyl silicate, ethyl silicate, iso-propyl silicate, trimethyl indium Polymers obtained by partial hydrolysis of , triethyl indium, triethoxy indium, diethyl iso-propoxy indium, tetramethyl tin, tetraethyl tin, tetrapropyl tin, tetramethoxy tin, tetra ethoxy tin, tetra iso-propoxy tin, etc. Organic residues of metalloxane

[Formula] group, or by partially hydrolyzing a mixture of an organometallic compound having a phenoxy group and an organometallic compound not having a phenoxy group, or by partially hydrolyzing an organometallic compound having a phenoxy group. It can be produced by a method such as mixing a partial hydrolyzate of an organometallic compound that does not have a phenoxy group. Partial hydrolysis can be carried out under known conditions. Organic residues of polymetalloxane

[Formula] As a method for substitution with a group, mixing phenols with polymetalloxane obtained by partial hydrolysis of an organometallic compound at a temperature of usually 0 to 100°C causes an exchange reaction of side chain groups, which facilitates substitution. can do. In carrying out the present invention, the compounds used to introduce the above-mentioned substituted phenoxy groups include cresol, ethylphenol, propylphenol, butylphenol, dimethylphenol, methylethylphenol, diethylphenol, and methylpropylphenol. , ethylpropylphenol, dipropylphenol, trimethylphenol, triethylphenol, methoxyphenol, ethoxyphenol, propoxyphenol, butoxyphenol, dimethoxyphenol, methoxyethoxyphenol, diethoxyphenol, methoxypropoxyphenol, dipropoxyphenol, trimethoxyphenol, Triethoxyphenol, hydroxyacetophenone, propionylphenol, butyrylphenol, diacetylphenol, acetylpropionylphenol, dipropionylphenol, triacetylphenol, methyl hydroxybenzoate, ethyl hydroxybenzoate, propyl hydroxybenzoate, butyl hydroxybenzoate , di-(methoxycarbonyl)-phenol, di-(ethoxycarbonyl)-phenol, di-(propoxycarbonyl)-phenol, tri-(methoxycarbonyl)-phenol, tri-(ethoxycarbonyl)-phenol, cyanophenol,
Chlorphenol, chlorophenol, nitrophenol, dinitrophenol, picric acid, etc. are suitable. In carrying out the method of the present invention, any organic solvent that can dissolve the polymetalloxane can be used, specifically ethyl ether, tetrahydrofuran, dioxane, benzene, toluene,
Examples include xylene and hexane. In carrying out the method of the present invention, [A] general formula in the raw material polymetalloxane

[Formula] and/ma Taha

The proportion of the structural unit represented by the formula (hereinafter referred to as the amount of substitution) is generally 0.1 to 95 mol%, preferably 1 to 80 mol%, most preferably 3 to 60 mol%, based on the metal atoms in the total polymetalloxane. It is mole%. If the amount of substitution in the polymetalloxane is less than 0.1 mol%, the effect of improving film forming properties, moldability and physical properties will be slight, while if it exceeds 95 mol%, film forming properties and moldability will become poor. Undesirable. Furthermore, if we describe the effect on formability mainly from the viewpoint of film-forming property, the effect is considerably more pronounced when the amount of substitution is 1 mol% or more compared to the unsubstituted product, and furthermore, this film-forming property is It improves in proportion to the amount, but 3
At more than mol %, the degree of improvement in film-forming properties relative to the amount of substitution becomes less noticeable. The degree of improvement in film-forming properties also depends on the types of coexisting side chain substituents. In general, those substituted in a ratio of 1 to 80 mol% exhibit the most stable and high film-forming properties, and when the ratio exceeds 80 mol%, this effect gradually decreases until 95 mol%.
If it exceeds this, the solubility of polymetalloxane in organic solvents decreases, resulting in film-forming properties and formability that are equal to or lower than those without additives, and solid content precipitates when concentrated to obtain a viscous liquid. Because of this, the replacement effect disappears. Therefore, the polymetalloxane having a phenoxy group in the side chain defined in the method of the present invention,
By using it as a molding raw material, film forming properties and moldability are improved, and when fired from polymetalloxane, it is possible to produce a coated molded product with extremely high scratch strength and uniformity. Although it is not clear why the above-mentioned effects are produced by having a phenoxy group in the side chain of polymetalloxane, the inclusion of the phenoxy group in the side chain causes polymetalloxane to have lubricity.
As a result, film-forming properties and formability are improved, and when an organic residue with a carbon number similar to that of a phenoxy group is introduced into the side chain, the side chain group burns within the precursor film, causing local heating, which occurs during firing. This is undesirable because it causes local differences in the degree of firing of the film, reducing the homogeneity and density of the film, and ultimately reducing the strength of the film.However, in the case of phenoxy groups, the firing temperature is It is thought that local heating is avoided because a considerable amount of phenoxy groups are decomposed and eliminated, resulting in the effect that there is no decrease in scratch strength or non-uniformity due to firing. The substrate to which the film forming method of the present invention can be applied may be any material such as glass, metal, ceramics, etc. as long as it can withstand the heat treatment temperature during film formation. The film forming method consists of a step of applying the polymetalloxane solution and a step of forming a film by decomposing the polymetalloxane, and existing coating methods such as dipping, spraying, and casting can be used as the coating method. Conversion of the film into a metal oxide by decomposition can be achieved by heat treatment at 400°C or higher and 2000°C or lower, or by heat treatment at 400°C or higher after hydrolysis with atmospheric moisture, steam, or water. . Alternatively, it is also possible to use a method in which the polymetalloxane solution is applied to the surface of a substrate heated to 400° C. or higher, and simultaneously thermally decomposed on the surface of the substrate to form a metal oxide film. It is sufficient that the degree of polymerization of the polymetalloxane used in the method of the present invention is 2 or more, and there is no particular upper limit, but the degree of polymerization is generally
1000 or less are used. Polymetalloxane is soluble in organic solvents such as ethyl ether, tetrahydrofuran, benzene, toluene, and hexane, and at an appropriate concentration becomes a viscous liquid with excellent film-forming properties. The relationship between the concentration of polymetalloxane and the film-forming properties of its solution varies depending on the desired film thickness, the type of polymetalloxane used, its degree of polymerization, and the solvent, and cannot be unambiguously determined, but in general, it has a viscosity of 1 centipoise or more
Solutions below 5000 centipoise are suitable for film formation. Therefore, the coating solution is prepared to provide a viscosity within this range. It is desirable to add organic polymers such as polyethylene glycol, polyvinyl formal, polyvinyl acetate, and other suitable organic substances to the coating solution in order to improve film-forming properties. In addition, the coating solution contains one or more compounds containing small amounts of lithium, beryllium, boron, sodium, magnesium, silicon, phosphorus, potassium, calcium, titanium, chromium, manganese, yttrium, zirconium, lanthanum, tungsten, etc. It is desirable to add it in order to improve various physical properties of the resulting inorganic coating. In addition, by mixing two or more types of polymetalloxanes made of different metal atoms, molding, and firing, composite oxides [e.g., spinel-type oxides (MgAl ₂ O ₄ , Al-si spinel, etc.), perovskite-type oxides] It is also possible to produce coatings, films, etc. that have excellent properties in molds (LaAlO ₃ , etc.). According to the method of the present invention, a polymetalloxane having a phenoxy group is used as a raw material, a compound containing silicon is mixed therein, and a precursor film having a high silica-alumina content is formed by forming a film from this and firing the precursor film. As a result, a uniform silica-alumina coating having extremely high mechanical strength and heat resistance can be produced. Among these polymetalloxanes containing phenoxy groups, in the present invention, the alumina content is 10%.
Above, preferably 20% or more is used.
The alumina content referred to here is given by [51/(molecular weight of structural unit)] x 100 (%). When the alumina content is less than 10%, it is difficult to obtain a silica-alumina coating with practical strength. On the other hand, as a compound containing silicon to be mixed with

Polyorganosilol having the structural unit of [formula] Kisan,

A polysilicate ester having the structural unit of [Formula] (R ₁ and R ₂ are organic atomic groups) is suitable, but an organosilane having the structure R _o SiX _4-o (X is OH, OR, etc.) is suitable. (R is an organic atomic group, n is an integer of 4 or less), a silicate ester having a structure of Si(OR) ₄ (R is an organic atomic group), and other silicon-containing compounds in general can be used. It is desirable that the silicon-containing compound to be mixed has a high silica content, but one with a low silica content may also be used. In particular, when producing a silica-alumina coating with a low silica content, the silica content of the silicon-containing compound to be mixed may be small. Further, it is desirable that the silicon-containing compound to be mixed is uniformly dissolved and mixed in the polyaluminoxane solution, but it may be dispersed and mixed without being dissolved. Further, it is preferable that the silicon-containing compound to be mixed has film-forming properties by dissolving itself in the polyaluminoxane solution, but this is not an essential condition. The maximum amount of silicon-containing compounds that can be mixed is:
Although it depends on the film-forming properties of the silicon-containing compound itself, even silicon-containing compounds that do not have film-forming properties can have a silica content of 60% by weight in the silica-alumina coating after firing. Even if the amounts are mixed, the mixed polyaluminoxane solution maintains sufficient film-forming properties to form a film. In some cases, it may be effective to mix two or more silicon-containing compounds into the polyaluminoxane solution. For manufacturing silica alumina coating
The ratio of SiO ₂ :Al ₂ O ₃ is preferably adjusted to 1 to 30% by weight: 99 to 70% by weight. Since the inorganic coating precursor thus obtained is formed into a uniform and continuous film, it is extremely convenient for improving the physical properties of the inorganic coating after firing. The inorganic film precursor used in the method of the present invention is infusible with respect to heat, and can be easily formed into an inorganic film by firing it in an atmosphere containing oxygen such as air. Embodiments of the present invention will be described below with reference to Examples, but the present invention is not limited to the following Examples. Example 1 1 mole of monoisopropoxy diethylaluminum was dissolved in 600 c.c. of ethyl ether and hydrolyzed with 1 mole of water to obtain polyisopropoxyaluminoxane with a degree of polymerization of 130. Next, 0.1 mol of ethyl O-hydroxybenzoate was added and stirred under reflux to dissolve 0.1 mol of the isopropoxy groups in the polyisopropoxyaluminoxane.

Substituted with [Formula] group. Dissolve this polyaluminoxane in benzene,
After distilling off the ether, the structural formula is 0.07 mol of ethyl silicate given by was dissolved. This was prepared so that the concentration of polyaluminoxane was 2% by weight to obtain a transparent homogeneous liquid with no uneven viscosity. After immersing the glass plate in this solution, the glass plate was slowly pulled up to prevent flow marks from forming, and left in air at room temperature for one hour. Raise the temperature to ℃,
It was baked at 500°C for 1 hour. The film thickness was measured using a surface roughness meter and was approximately 500 Å. Examples 2 to 5, Comparative Examples 1 and 2 1 mol of monoisopropoxy diethylaluminum was dissolved in 600 c.c. of ethyl ether and hydrolyzed with 1 mol of water to obtain polyisopropoxyaluminoxane with a degree of polymerization of 130. O-hydroxyacetophenone was added to the polyisopropoxyaluminoxane in the amount shown in Table 1 and stirred under reflux to separate each of the isopropoxy groups in the polyisopropoxyaluminoxane.

Substituted with [Formula] group. Isopropoxy groups are almost 100% substituted with acetophenoxy groups. In order to improve stability, 0.2 mol of stearic acid was further added to this and refluxed to obtain a stock solution. A film of these was formed on a glass plate and fired in the same manner as in Example 1. The results are shown in Table 1.

[Table] Example 6 A 3% by weight xylene solution of polyaluminoxane with a degree of polymerization of 40, in which 80 mol% of the organic residues are nitrophenoxy groups and 20 mol% are stearoyloxy groups, was applied onto a slide glass. C. for 30 minutes to form an aluminum oxide film having a thickness of 1000 Å. This film was amorphous when viewed by X-rays, and was optically uniform with no cracks when observed using an optical microscope. Comparative Example 3 A 3% by weight xylene solution of polyaluminoxane with a degree of polymerization of 40, in which 80 mol% of the organic residues are ethoxy groups and 20 mol% are stearoyloxy groups, was applied onto a slide glass and dried. , cracks occurred in the paint film. Example 7 P-cyanophenol corresponding to 30 mol% of the organic residues was added to a dioxane solution of polyaluminoxane with a degree of polymerization of 40, in which 80 mol% of the organic residues were isopropoxy groups and 20 mol% were ethyl groups. The silica content after firing the film is 30%.
% of ethyl silicate. The mixed liquid was concentrated to obtain a liquid with a viscosity of 7500 cp, and this was
Push it out into the air through a μm x 50mm slit,
A transparent film was obtained. This was left in the air for one day and then fired at 1000°C to obtain a transparent silica alumina film with a thickness of 20 μm. Example 8 1 mole of triethyl indium was added to 600 c.c. of toluene.
After partial hydrolysis with 1 mol of water, 0.3 mol of ethyl salicylate was added, the temperature was raised to 80°C, and the mixture was stirred for about 3 hours. The polymer solution was further diluted with toluene to a concentration of 5 wt% in terms of indium oxide, and then applied onto a slide glass.
Firing was performed at 450°C for 30 minutes to form an indium oxide film with a thickness of 800 Å. This film was transparent and uniform, and was found to be amorphous by X-ray analysis. Example 9 0.1 mole of triisopropoxy-p-methylphenoxytin was dissolved in 800 c.c. of isopropyl alcohol, hydrolyzed with 0.1 mole of water, applied on a slide glass, and baked at 500°C for 30 minutes. Then, a tin oxide film having a thickness of 700 Å was formed. Visually, this film was transparent, smooth, and uniform. Example 10 1 mole of tetraethoxyzirconium and 0.05 mole of triisopropoxyyttrium were dissolved in 600 c.c. of tetrahydrofuran, and after hydrolysis with 1 mole of water, 0.2 mole of methyl salicylate was added and stirred, and then concentrated to reduce the viscosity. It was concentrated to 7000 cp and used as a stock solution. The stock solution was extruded through a 100 μm x 500 mm slit and then calcined in air to 1300°C, yielding a zirconia film with a film thickness of 25 μm and a tensile strength of 5 t/cm ² .

Claims (1)

[Claims] 1 [A] General formula [Formula] and/or [Formula] (wherein M is a group, Va group, Cr, Mn, Fe,
Co, Ni, or trivalent metal atoms of rare earth elements or 4 of group a, Zr, Hf, Cr, Mn, Fe, Co, or Ce
Valid metal atom, Y is an organic residue, nitro group or halogen, m is an integer from 0 to 5, X ₁
represents an organic residue, a hydrogen atom, a nitro group, or a halogen, which is the same as or different from [Formula]. ) 0.1 to 95 mol% of structural units represented by [B] General formula [Formula] and/or [Formula] (where M is the same as above, and X _{2 and} A method for producing an inorganic fired body, which comprises forming a molded article from an organic solvent solution containing a polymetalloxane containing 99.9 to 5 mol % of the structural unit represented by the following formula, and then firing the molded article. 2 M in the general formula is aluminum, indium,
2. The method for producing an inorganic fired body according to claim 1, characterized in that polymetalloxane, which is one or more of silicon, tin, and zirconium, is used. 3. The method for producing an inorganic fired body according to claim 1 or 2, wherein m in the general formula is an integer of 1 to 3. 4 [A] General formula [Formula] and/or [Formula] (where M is aluminum, indium, silicon, tin or zirconium, Y is an organic residue,
nitro group or halogen; m is an integer of 1 to ₂ ; 4. A method for producing an inorganic fired body according to claim 1, 2 or 3, characterized in that a polymetalloxane having 1 to 80 mol% of the structural unit represented by the following formula is used. 5. Claim 1, characterized in that the inorganic fired body is a film or a coating.
The method for producing an inorganic fired body according to item 2, 3 or 4.