JPS6150903B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a composition for producing an inorganic fired body. More specifically, the present invention relates to a composition suitable for producing inorganic fired bodies such as microspheres, coatings, films, and foams from polymetalloxane containing specific compounds. The present invention relates to a composition suitable for producing an inorganic coating or film by forming a coating or film using xane, subjecting it to treatments such as infusibility if necessary, and then firing. 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 for this reason, various manufacturing methods have also been proposed. 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. Due to the combustion and thermal decomposition of gases, a large amount of various gases are generated, resulting in local differences in the atmosphere and, therefore, differences in the degree of combustion. This method is still not satisfactory, as it may cause uneven quality of the inorganic film, localized foaming, or cracking. In view of these circumstances, the present inventors have conducted extensive research into ways to overcome the above-mentioned drawbacks, and have found that by adding a certain type of compound to an organic solvent solution of polymetalloxane, significantly superior film-forming properties can be achieved. The present inventors have discovered that it is possible to produce a coated molded article with extremely high scratch strength and uniformity when the film is formed and fired, and the present invention has been completed. That is, the present invention provides: [A] General formula

[expression] and/or

[Formula] (In the formula, M is a group, Va group, Cr, Mn, Co, Ni
or a trivalent metal atom of a rare earth element, or a
metal atoms of the group Zr, Hf, Cr, Mn, Fe, Co or Ce, Y ₁ and Y ₂ represent organic residues. ) A polymetalloxane having a structural unit represented by [B] General formula

[Formula] R ₁ −N=C= O,

[Formula] H ₂ N (−CH ₂ −) _o OH or

[Formula] (In the formula, R ₁ , R ₂ and R ₃ are alkyl groups or alkenyl groups having 1 to 18 carbon atoms, R ₄ is an alkyl group or alkenyl group having 1 to 18 carbon atoms or hydrogen, and R ₅ is An inorganic fired body comprising an organic solvent solution containing one or more of the compounds represented by (an alkyl group or alkenyl group having 2 to 18 carbon atoms, n is an integer of 2 to 18) The present invention provides a composition for manufacturing. The present invention will be explained in more detail below. The polymetalloxane used in the composition of the present invention has the general formula [A]

[expression] and/or teeth

[Formula] (wherein M, Y ₁ and Y ₂ are the same as above), and 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 the specific Examples include boron, aluminum, gallium, indium, arsenic, antimony, bismuth, silicon, germanium, tin, lead, yttrium, zirconium, rare earth elements, chromium, manguin, iron, cobalt, nickel, and the like.
Aluminum, silicon, indium, tin, etc. are particularly suitable for film or coating applications. Y ₁ and Y ₂ represent organic residues, specifically alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, methoxy group, ethoxy group, n- propoxy group, iso-propoxy group, n-butoxy group, iso-
Alkoxy groups such as butoxy groups, acyl groups such as acetyl groups, propionyl groups, benzoyl groups, alkoxycarbonyl groups such as methoxycarbonyl groups, ethoxycarbonyl groups, propoxycarbonyl groups,
phenoxycarbonyl group, cyano group, vinyl group,
Examples include alkenyl groups such as propenyl groups, phenyl groups or substituted phenyl groups, and phenoxy groups. Specifically, the polymetalloxane used in the present invention is, for example, trimethylaluminum, triethylaluminum, tripropylaluminum, triethoxyaluminum, triisopropoxyaluminum, diethylaluminium hydride, diisopropoxymonoethylaluminum, monoethoxydiethylaluminum, tetraethylzirconium , tetraisopropoxyzirconium, tetrabutylzirconium, trimethylzirconium hydride, diethyldiisopropoxyzirconium, tetraethylsilicon, tetrapropylsilicon, methylsilicate, ethylsilicate, trimethylindium, triethylindium, triethoxyindium, diethylisopropoxyindium, tetramethyl It can be obtained by partially hydrolyzing organometallic compounds such as tin, tetraethyltin, tetrapropyltin, tetramethoxytin, tetraethoxytin, and tetraisopropoxytin. Partial hydrolysis can be carried out under known conditions. The [B] compound used in the composition of the present invention has the general formula

[Formula] R ₁ −N=C=O, R ₁ −COCH ₂ COR ₅ , NH ₂ (−CH ₂ −) _o OH or
A compound represented by R ₄ CHOHCOOR ₁ (wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and n are the same as above) is used. general formula

[Formula] (In the formula, R ₁ , R ₂ and R ₃ are the same as above) Examples of specific examples include N, N-
Dimethylacetamide, N,N-methylethylacetamide, N,N-dimethylpropionamide, N,N-diethylpropionamide, N,N
-Amides having an alkyl group and/or alkenyl group having 1 to 18 carbon atoms as a substituent, such as diethylbutyramide, N,N-dimethyloctylamide, N,N-diethyllauramide; General formula R ₁ -N= Specific examples of the compound represented by C=O (in the formula, R ₁ is the same as above) include ethyl isocyanate, propyl isocyanate, butyl isocyanate, pentyl isocyanate, octyl isocyanate, lauryl isocyanate, and isocyanate. Isocyanate esters such as stearyl: Compounds represented by the general formula R ₁ COCH ₂ COR ₅ (wherein R ₁ and R ₅ are the same as above) include, for example, propionylacetone, butyrylacetone, and pentalylacetone. β-diketones such as noylacetone, octanoylacetone, lauroylacetone, stearoylacetone, dipropionylmethane; Compounds represented by the general formula NH ₂ (-CH ₂ -) _o OH (where n is the same as above) Specifically, amino alcohols such as 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 8-aminooctanol, and 12-aminolauryl alcohol; general formula R ₄ CHOHCOOR ₁ (in the formula R ₁ , R ₄ are the same as above), specifically, for example, methyl glycolate, ethyl lactate, ethyl α-hydroxybutyrate, ethyl α-hydroxycaprylate, methyl α-hydroxystearate, α-
Examples include α-hydroxycarboxylic acid esters such as ethyl hydroxyoleate and octyl α-hydroxypropionate. In the composition of the present invention, the proportion of the compound [B] to the polymetalloxane [A] is generally 60% by weight or less, preferably 0.01 to 40% by weight, particularly preferably 0.1 to 20% by weight. If the ratio of the [B] compound to the polymetalloxane [A] is less than 0.01% by weight, the effect of improving film-forming properties, moldability, and physical properties will be slight, and if it exceeds 40% by weight, the film-forming property will decrease. , the moldability becomes poor. The organic solvent constituting the composition of the present invention includes:
Any substance that dissolves polymetalloxane can be used, specifically ethers such as ethyl ether, tetrahydrofuran, and dioxane, alcohols such as ethanol and isopropyl alcohol, and aromatic carbonization such as benzene, toluene, and xylene. Examples include hydrogen. The ratio of polymetalloxane to the solvent varies depending on the shape of the fired product to be produced; for example, in the case of a film, the ratio is 0.1 in terms of the oxide after firing.
It is preferably about 10% by weight. By using an organic solvent solution of polymetalloxane prepared by adding the compound [B] defined in the method of the present invention as a raw material for forming, film forming properties and formability are improved, and when the film is formed and fired, it is possible to prevent scratches. The effect is that a coated molded article with extremely high strength and uniformity can be manufactured. It is sufficient that the degree of polymerization of the polymetalloxane used in the composition of the present invention is 2 or more, and although there is no particular upper limit, a degree of polymerization of 1000 or less is generally used from the viewpoint of ease of polymerization reaction. Polymetalloxane is soluble in organic solvents such as ethyl ether, tetrahydrofuran, benzene, toluene, and isopropyl alcohol, and at an appropriate concentration becomes a viscous liquid with excellent stringiness. 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 A solution having a viscosity of 1 centipoise or more and 5000 centipoise or less is suitable for film formation. Therefore, the coating solution is prepared to provide a viscosity within this range. In addition, 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, small amounts of lithium, beryllium, boron, sodium, magnesium, silicon, phosphorus,
It is desirable to add one or more compounds containing potassium, calcium, titanium, chromium, manganese, yttrium, zirconium, lanthanum, tungsten, etc. to improve the physical properties of the resulting inorganic coating. be. 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.). 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, but 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. can. 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. The inorganic film precursor in 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. That is, for example, in the context of manufacturing an alumina film, if the precursor film is fired in an oxygen-containing atmosphere, for example in air, it will substantially transform into an alumina film at about 500°C. In addition, in order to obtain these various alumina films, the precursor film may be fired in an inert atmosphere such as nitrogen or in vacuum, and then exposed to an atmosphere containing oxygen to remove organic or carbonaceous materials. . Further, the obtained alumina film may be further fired in a reducing atmosphere such as hydrogen. In the above explanation, the production of inorganic coatings from polymetalloxane has been detailed, but the composition of the present invention can be used for purposes other than the production of inorganic coatings, such as molded bodies, films, etc. made from the polymetalloxane of the present invention.
It is also useful for producing inorganic fired bodies such as foams and microspheres. When producing molded bodies, films, etc., the polymetalloxane solution of the present invention has little viscosity unevenness, so it is easy to mold into films etc. to a constant thickness, and it has chemical and physical properties. In addition, the polymetalloxane solution is relatively stable, and its properties change less over time. According to the composition of the present invention described in detail above, when producing fired bodies such as metal oxide coatings, molded bodies, and films from polymetalloxane, film forming properties and moldability are significantly improved, and metal oxide It exhibits the effect of significantly improving the scratch strength etc. of the material coating. Furthermore, since the polymetalloxane of the composition of the present invention has extremely high solubility in solvents, it is difficult to cause gelation. Molded bodies, films, etc. of oxides also have the advantage of being uniformly transparent bodies. 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 monoisoproboxydiethylaluminum 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. Then isostearic acid
Add 0.3 mol and 24 g of N,N dimethylacetamide, stir under reflux, further dissolve this polyaluminoxane solution in benzene, remove the ether by distillation, and add the structural formula to it. 0.07 mol of ethyl silicate given by was dissolved. This was concentrated so that the polyaluminoxane concentration was 5% by weight, and the viscosity was 10 centipoise, and it was transparent and homogeneous 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, left in air at room temperature for one hour, and then heated to 500°C at a heating rate of 100°C/hour in air. The temperature is raised 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 monoisopropoxydiethylaluminum 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. Adding ethyl lactate in the amount shown in Table 1 to the isopropoxyaluminoxane,
After stirring under reflux and further adding 0.5 mol of acetic acid, the alumina concentration was adjusted to 3% by weight 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 50 mol% of organic residues are stearoyloxy groups and 50 mol% are isopropoxy groups, degree of polymerization 40
A solution prepared by adding butyl isocyanate to a 3% by weight xylene solution of polystanoxane to give a concentration of 1% by weight relative to the polystaxane, a 3% by weight xylene solution was applied onto a slide glass, and heated at 450°C for 30 minutes.
A tin oxide film having a thickness of 900 Å was formed by baking for a minute. This film is amorphous according to X-rays, and when observed with an optical microscope, there were no cracks.
It was also optically uniform. Comparative Example 3 3% by weight of polystanoxane shown in Example 11
When a xylene solution was coated on a slide glass without adding butyl isocyanate and dried, cracks appeared in the coating film. Example 7 1 mole of triethyl indium was added to 600 c.c. of toluene.
After partial hydrolysis with 1 mol of water, N,N
Add 40g of diethylpropionamide and raise the temperature to 80
℃ and stirred for about 3 hours. After diluting the polymer solution with toluene to a concentration of 5 wt% in terms of indium oxide, it was applied onto a slide glass and baked at 450°C for 30 minutes to form an indium oxide film with a thickness of 800 Å. Formed. This film was transparent, even, and uniform.

Claims (1)

[Claims] 1 [A] General formula [Formula] and/or [Formula] (wherein M is a group, a group, Cr, Mn, Fe,
A trivalent metal atom of Co, Ni or a rare earth element or a tetravalent metal atom of group a, Zr, Hf, Cr, Mn, Fe, Co or Ce, Y ₁ and Y ₂ represent organic residues. ) and [B] general formula [formula] R ₁ -N=C=O, [formula] NH ₂ (-CH ₂ -) _o OH or [formula] (in the formula , R ₁ , R ₂ and R ₃ are an alkyl group or alkenyl group having 1 to 18 carbon atoms, R ₄ is an alkyl group or alkenyl group having 1 to 18 carbon atoms or hydrogen, and R ₅ is an alkyl group or alkenyl group having 1 to 18 carbon atoms. 1. A composition for producing an inorganic fired body, comprising an organic solvent solution containing one or more of the following alkyl or alkenyl groups, n being an integer of 2 to 18. 2. Inorganic firing according to claim 1, characterized in that a polymetalloxane in which M in the general formula [A] is one or more of aluminum, indium, silicon, tin, or zirconium is used. Composition for body manufacturing. 3. The composition for producing an inorganic fired body according to claim 1, wherein the ratio of the compound [B] to the polymetalloxane is in the range of 0.01 to 60% by weight. 4. The composition for producing an inorganic fired body according to claim 1, wherein the organic solvent is an ether, an alcohol, or an aromatic hydrocarbon.