JP4340144B2 - Method for producing metal-metal oxide composite - Google Patents

Description

  The present invention relates to a method for producing a composite of a metal and a metal oxide. Specifically, the present invention relates to a method for producing a metal-metal oxide composite in which a metal composed of a specific metal element is dissolved in a metal oxide at an atomic level or contained in a state close thereto.

Metal oxides are known to have a variety of excellent functions depending on the type of metal atom and whether they are single or composite. It's being used. Furthermore, it has been proposed that these metal oxides deposited on the surface of a substrate to be formed as a film or obtained as particles are useful for various functional applications and are actually used in various application fields. ing.
On the other hand, in a metal oxide, a metal composed of another metal atom is dissolved at an atomic level or contained in a state close to that (hereinafter referred to as “solid solution or the like in this specification”). In recent years, various functional devices such as metal-metal oxide composites have been developed as functional materials that exhibit various functions as metal oxides and have predetermined metal properties. In the field of application, it is frequently used and applied as the film and particles described above.

Such metal-metal oxide composites (particularly, particles) can be prepared by co-precipitation of a hydroxide or carbonate from an inorganic salt or metal alkoxide of different metals (main metal or different metal) with an aqueous solution or alcohol. A method of firing the product in a high temperature and firing the product at a high temperature, a method of mixing powders of different metals (main metal and different metal) and firing at a high temperature are well known. However, since the reaction is mainly based on thermal equilibrium, it has been difficult to obtain a metal-metal oxide composite in which a dissimilar metal is dissolved in a high concentration.
As another manufacturing method for this, the present inventor has proposed a method capable of directly obtaining a metal-metal oxide composite (particularly, particles) in which different metals are dissolved in a solid solution at a relatively low temperature (for example, Patent Documents 1 and 2).
JP 2000-185916 A JP 2002-020107 A

However, in the above-mentioned another production method, as a metal (dissimilar metal) to be dissolved in a metal oxide or the like, a particularly easily reducible metal (specifically, Pt, Pd, Ru, Rh, Ir, Ni, Cu, Ag ( In particular, when using Pt, Pd, Ru, Rh, Ir)), segregation of different metals is likely to occur, and it is difficult to obtain a metal-metal oxide composite in which different metals are dissolved. There was a problem.
Therefore, the problem to be solved by the present invention is to disperse a composite formed by dissolving a metal composed of a specific metal element (reducible metal) in a metal oxide, for example, in a solvent. Another object of the present invention is to provide a method for producing a metal-metal oxide composite which can be easily obtained as a particle or as a film formed on the surface of a substrate.

The present inventor has intensively studied to solve the above problems. In the process, it was found that the above problems could be solved at once by selecting a specific combination of compounds as a starting material and generating a metal-metal oxide composite in the presence of an acidic substance. The invention has been completed.
That is, the method for producing a metal-metal oxide composite according to the present invention includes at least one metal element selected from the metal element group (1) consisting of Pt, Pd, Ru, Rh, Ir, Ni, Cu, and Ag. Or a metal carboxylate containing at least one metal element selected from the metal element group (2) consisting of Zn, Ti and Sn and an alcohol, or the metal element group A compound containing at least one metal element selected from (1) and a metal alkoxy group-containing compound and a carboxyl group-containing compound containing at least one metal element selected from the metal element group (2) And a mixture obtained by mixing the raw materials essential for the starting material and / or a pre-reacted material obtained from the raw materials essential for the starting raw material. The composite system of a metal and a metal oxide is produced | generated by making a mixed system into the high temperature state of 100 degreeC or more in presence of an acidic substance.

  According to the present invention, a composite formed by dissolving a metal composed of a specific metal element (easily reducible metal) in a metal oxide, for example, as particles dispersed in a solvent, or A method for producing a metal-metal oxide composite that can be easily obtained as a film formed on the surface of a substrate can be provided.

Hereinafter, the present invention will be described in detail. However, the scope of the present invention is not limited to these descriptions, and modifications other than the following examples can be made as appropriate without departing from the spirit of the present invention.
The method for producing a metal-metal oxide composite according to the present invention (hereinafter sometimes referred to as the production method of the present invention) is a specific method comprising Pt, Pd, Ru, Rh, Ir, Ni, Cu and Ag. A metal element composed of at least one metal element selected from the metal element group (1) (hereinafter sometimes referred to as a specific metal) is composed of a metal element not included in the metal element group (1). A metal-metal oxide composite (hereinafter referred to as a metal-metal oxide composite) formed by being dissolved in the metal oxide containing at least one metal element selected from the group (2) or contained in a state close to it. , Sometimes referred to simply as a composite).

  In the production method of the present invention, a metal element group (2) comprising a compound (1A) containing at least one metal element selected from the metal element group (1) and a metal element not contained in the metal element group (1). ) Or a metal carboxylate containing at least one metal element selected from the above and an alcohol to form a starting material (hereinafter, this starting material combination may be referred to as “combination A”), or A compound (1B) containing at least one metal element selected from the metal element group (1), a metal alkoxy group-containing compound containing at least one metal element selected from the metal element group (2), and a carboxyl group-containing compound Are used as starting materials (hereinafter, this combination of starting materials may be referred to as “combination B”).

As described above, the metal element (that is, the easily reducible metal element) included in the metal element group (1) includes Pt, Pd, Ru, Rh, Ir, Ni, Cu, and Ag. Pt, Pd, Ru, Rh, and Ir are particularly preferable because they are highly easily reducible and the production method of the present invention can be applied more effectively.
As described above, the metal element included in the metal element group (2) includes metal elements not included in the metal atom group (1). Specifically, In, Sn, Zn, Ti, and the like are included. It can be illustrated.
The compound (1A) in the combination A is not limited as long as it contains any one metal element selected from the metal element group (1) or a compound containing two or more metal elements. Inorganic salts such as sulfates, nitrates, halides and carbonates and basic salts thereof; inorganic complexes such as ammonia complexes; organic acid salts such as carboxylates and sulfonates and basic salts thereof; Preferred examples include metal alkoxides; organometallic complexes such as amine complexes, glycol complexes, and β-diketone complexes; among others, (basic) nitrates, (basic) carboxylates, metal alkoxides, and glycol complexes. However, it is more preferable in that the metal of the metal element group (1) is likely to be complexed with the metal oxide, and the ligand hardly remains in the complex. Only one type of compound (1A) may be used, or two or more types may be used in combination.

  When the compound (1A) is a metal carboxylate, as the metal carboxylate, specifically, in the molecule, a hydrogen atom of a carboxyl group is selected from a specific metal atom (metal element group (1)) Any compound having at least a structure substituted with at least one metal element atom) may be used, and more specifically, for example, saturated monocarboxylic acid, unsaturated monocarboxylic acid, saturated polyvalent carboxylic acid, and unsaturated A salt composed of a chain carboxylic acid such as a polyvalent carboxylic acid and the metal atom; a salt composed of a cyclic saturated carboxylic acid and the metal atom; an aromatic such as an aromatic monocarboxylic acid and an aromatic unsaturated polyvalent carboxylic acid A salt composed of a group carboxylic acid and the metal atom; and in the molecule of the various carboxylic acids, a hydroxyl group, amino group, nitro group, alkoxy group, sulfone group, cyano group, Salts comprising a compound having a functional group or atomic group, such as androgenic atom and the metal atom; and the like, which may be a hydrate containing water of crystallization. Only 1 type may be used for the metal carboxylate as a compound (1A), and it may use 2 or more types together.

  As the metal carboxylate in the combination A, specifically, the hydrogen atom of the carboxyl group is substituted in the molecule with a metal atom (at least one metal atom selected from the metal element group (2)). And more specifically, for example, a chain carboxylic acid such as a saturated monocarboxylic acid, an unsaturated monocarboxylic acid, a saturated polycarboxylic acid and an unsaturated polycarboxylic acid, and the above-mentioned A salt composed of a metal atom; a salt composed of a cyclic saturated carboxylic acid and the metal atom; a salt composed of an aromatic carboxylic acid such as an aromatic monocarboxylic acid and an aromatic unsaturated polyvalent carboxylic acid; and the metal atom; Furthermore, functional groups such as hydroxyl group, amino group, nitro group, alkoxy group, sulfone group, cyano group and halogen atom in the molecule of various carboxylic acids Salts composed of a compound having a Dan said metal atom; and the like, which may be a hydrate containing water of crystallization, but is preferably anhydrous. Only 1 type may be used for the metal carboxylate in the combination A, and 2 or more types may be used together.

  Examples of the alcohol in the combination A include aliphatic monohydric alcohols (methanol, ethanol, isopropyl alcohol, n-butanol, t-butyl alcohol, stearyl alcohol, etc.), and aliphatic unsaturated monohydric alcohols (allyl alcohol, crotyl alcohol). And propargyl alcohol), alicyclic monohydric alcohols (cyclopentanol, cyclohexanol, etc.), aromatic monohydric alcohols (benzyl alcohol, cinnamyl alcohol, methylphenyl carbitol, etc.), phenols (ethylphenol, octylphenol) , Catechol, xylenol, guaiacol, p-cumylphenol, cresol, m-cresol, o-cresol, p-cresol, dodecylphenol, naphthol, nonylph And monohydric alcohols such as heterocyclic monohydric alcohols (furfuryl alcohol, etc.); alkylene glycols (ethylene glycol, propylene glycol, trimethylene glycol, 1, 4) -Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, pinacol, diethylene glycol, triethylene glycol, etc.), alicyclic glycol (cyclopentane- 1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, etc.) and polyoxyalkylene glycols (polyethylene glycol, polypropylene glycol, etc.) Cole: propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, triethylene glycol monomethyl Derivatives such as ethers and ethylene glycol monoacetates such as monoethers or monoesters of the above glycols; trivalent alcohols such as glycerin and trimethylolethane; tetravalent alcohols such as erythritol and pentaerythritol; pentavalents such as lipitol and xylitol Trihydric or higher polyhydric alcohols such as alcohol and hexahydric alcohols such as sorbitol, In polyhydric aromatic alcohols such as drobenzoin, benzpinacol and phthalyl alcohol, dihydric phenols such as catechol, resorcin and hydroquinone, polyhydric phenols such as trihydric phenols such as pyrogallol and phloroglucin, and these polyhydric alcohols And a derivative in which a part of OH groups (1 to (n-1) (where n is the number of OH groups per molecule)) is an ester bond or an ether bond; Of these, alcohols having tertiary, secondary, and especially primary hydroxyl groups are particularly preferred for alcoholic hydroxyl groups because the metal can be obtained at a lower temperature. For similar reasons, aliphatic alcohols are also preferred. Only 1 type may be used for the alcohol in the combination A, and 2 or more types may be used together.

The amount of the compound (1A) used in the combination A is not limited, and the ratio of the total number of metal atoms in the entire compound (1A) to the total number of metal atoms in the entire metal carboxylate in the combination A is 1 It is preferable to be set to ˜20 atomic%, more preferably 1 to 10 atomic%. If the ratio is less than 1 atomic%, the composite effect of the metal of the metal element group (1) may not be sufficiently exhibited. If the ratio exceeds 20 atomic%, the segregated product of the metal of the metal element group (1) In addition to the formation of a large amount, the intended function / physical properties of the composite may be reduced or inhibited, and other functions / physical properties may also be reduced or inhibited.
The ratio of the amount of metal carboxylate and alcohol used in combination A is not limited, but the ratio of the total number of hydroxyl groups (derived from alcohol) to the total number of carboxyl groups possessed by the metal carboxylate (hydroxyl group / The carboxyl group) is preferably 0.8 / 1 to 1000/1, and more preferably 1.2 / 1 to 100/1.

  The compound (1B) in the combination B contains any one metal element selected from the metal element group (1), or a compound containing two or more metal elements, like the compound (1A). The inorganic salt such as sulfate, nitrate, halide and carbonate, and basic salts thereof; inorganic complex such as ammonia complex; organic such as carboxylate and sulfonate Preferred examples include acid salts and basic salts thereof; metal alkoxides; organometallic complexes such as amine complexes, glycol complexes, and β-diketone complexes; among them, (basic) nitrates, (basic) Carboxylic acid salts, metal alkoxides, and glycol complexes make it easier for the metal of the metal element group (1) to be complexed with the metal oxide, and the ligand remains in the complex. Hard and more preferable in view. Only 1 type may be used for a compound (1B) and it may use 2 or more types together.

About the case where a compound (1B) is a metal carboxylate, the description in case the said compound (1A) is a metal carboxylate is applicable similarly. Only 1 type may be used for the metal carboxylate as a compound (1B), and it may use 2 or more types together.
Although it does not limit as a metal alkoxy group containing compound in the combination B, For example, following General formula (1):
M (OR ^a ) _nm R ^b _m (1)
Where M is a metal atom (at least one metal atom selected from the metal element group (1)); R ^a is a hydrogen atom and an optionally substituted alkyl group, cycloalkyl group, acyl group; , At least one selected from the group consisting of an aralkyl group and an aryl group; R ^b is a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an acyl group, an aralkyl group, an aryl group and an unsaturated aliphatic residue. And at least one selected from the group consisting of a group and an organic group containing a functional group other than the OR ^a group; n is the valence of the metal atom M ′; m is an integer in the range of 0 to n−1.)
Or a condensate obtained by subjecting this compound to (partial) hydrolysis / condensation. Only 1 type may be used for the metal alkoxy group containing compound in the combination B, and 2 or more types may be used together.

In General Formula (1), R ^a is preferably an optionally substituted alkyl group such as an alkoxyalkyl group and / or a hydrogen atom, and more preferably an optionally substituted alkyl group. R ^b represents an optionally substituted alkyl group, cycloalkyl group, acyl group, aralkyl group, aryl group, unsaturated aliphatic residue, and functional group other than the OR ^a group such as a β-diketone compound. At least one selected from the group consisting of organic groups is preferred.
The metal alkoxy group-containing compound may be other than those described above, and may be a heterometallic alkoxy group-containing compound in addition to a single metal alkoxy group-containing compound. The heterometal alkoxy group-containing compound is a metal alkoxy group-containing compound having two or more different metal atoms and connected via an alkoxy group or an oxygen atom, or by a metal-metal bond.

In the case of obtaining a crystalline metal, it is most preferable to use a compound in which m is 0 in the general formula (1) as a main component, and examples thereof include single metal alkoxy group-containing compounds and heterometal alkoxy group-containing compounds. It is done.
Specifically, the carboxyl group-containing compound in the combination B may be a compound having at least a carboxyl group in the molecule, and more specifically, for example, formic acid, acetic acid, propionic acid, isobutyric acid, caproic acid. , Saturated fatty acids such as caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid (saturated monocarboxylic acids), unsaturated fatty acids such as acrylic acid, methacrylic acid, crotonic acid, oleic acid, linolenic acid (unsaturated monocarboxylic acids) Acid), oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, saturated polycarboxylic acid such as β, β-dimethylglutaric acid, and unsaturated polycarboxylic acid such as maleic acid and fumaric acid. Carboxylic acids; Cyclic saturated carboxylic acids such as cyclohexanecarboxylic acid; Fragrances such as benzoic acid, phenylacetic acid, and toluic acid Aromatic carboxylic acids such as unsaturated polycarboxylic acids such as aromatic monocarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid; acetic anhydride, maleic anhydride, pyromellitic anhydride, etc. Carboxylic anhydride: trifluoroacetic acid, o-chlorobenzoic acid, o-nitrobenzoic acid, anthranilic acid, p-aminobenzoic acid, anisic acid (p-methoxybenzoic acid), toluic acid, lactic acid, salicylic acid (o-hydroxy) A compound having a functional group or atomic group such as a hydroxyl group other than a carboxyl group, an amino group, a nitro group, an alkoxy group, a sulfonic acid group, a cyano group, or a halogen atom in a molecule such as benzoic acid); acrylic acid homopolymer, acrylic (Co) polymers of the above unsaturated carboxylic acids such as acid-methyl methacrylate copolymer; Saturated carboxylic acid in order to obtain particles having excellent dispersibility are preferred. Only 1 type may be used for the carboxyl group-containing compound in the combination B, and 2 or more types may be used together. Further, when the carboxyl group-containing compound is a liquid, it can also be used as a reaction solvent as described later.

  The amount of the compound (1B) used in the combination B is not limited, and the ratio of the total number of metal atoms in the entire compound (1B) to the total number of metal atoms in the entire metal alkoxy group-containing compound in the combination B is as follows. It is preferable to be 1 to 20 atomic%, and more preferably 1 to 10 atomic%. If the ratio is less than 1 atomic%, the composite effect of the metal of the metal element group (1) may not be sufficiently exhibited. If the ratio exceeds 20 atomic%, the segregated product of the metal of the metal element group (1) In addition to the formation of a large amount, the intended function / physical properties of the composite may be reduced or inhibited, and other functions / physical properties may also be reduced or inhibited.

The ratio of the amount used of the metal alkoxy group-containing compound and the carboxyl group-containing compound in the combination B is not limited, but the molar ratio of the carboxyl group-containing compound to the metal alkoxy group-containing compound is contained in the metal alkoxy group-containing compound. Preferably, the lower limit is a value exceeding 0.8 Nav, more preferably a value exceeding 1.2 Nav, and the upper limit is preferably less than 10 Nav. . Here, the average valence number Nav is a p-type metal alkoxy group-containing compound having different metal elements as the metal alkoxy group-containing compound (containing metal elements are M ₁ , M ₂ , M ₃ ,. _When the p-type metal alkoxy group-containing compound (2 ≦ p), which is _p , is used in combination, the following formula:

(In the formula, Ni represents the valence (valence) of the metal Mi. Further, Xi represents the number of moles of the metal element Mi used as the metal alkoxy group-containing compound. P is an integer of 2 or more. )
It can be calculated from Further, the number of carboxyl groups contained in the total amount of the carboxyl group-containing compound may be a value exceeding 0.8 N ′ with respect to the number N ′ of alkoxy groups contained in the total amount of the metal alkoxy group-containing compound. 1N ′ to 10N ′ are particularly preferable.
In the production method of the present invention, the combination A is used as a starting material, or the combination B is used as a starting material, and a metal-metal oxide composite is formed in the presence of an acidic substance. It is important to. By generating the above in the presence of an acidic substance, even a readily reducible metal can be easily and efficiently dissolved in the metal oxide at the atomic level. Specifically, by bringing the mixed system of the starting materials of combination A into a high temperature state in the presence of an acidic substance, or bringing the mixed system of starting materials of combination B into a high temperature state in the presence of an acidic substance, A metal-metal oxide composite is produced. Here, the mixed system means a mixture containing raw materials essential to the starting material and / or a pre-reaction product obtained from the raw materials essential to the starting material. A part of the mixed system may be a preliminary reaction product, and the other may be a mixture.

Although it does not limit as said acidic substance, For example, nitric acid, a sulfuric acid, hydrohalic acid, a sulfonic acid, carboxylic acid etc. can be mentioned preferably, Among these, carboxylic acid is more preferable.
Although it does not limit as carboxylic acid used as said acidic substance, if the above-mentioned combination A is used as a starting material, it has a carboxyl group whose value of pKa (dissociation constant) is larger than the carboxyl group of metal carboxylate Carboxylic acid is preferred. For example, when the metal carboxylate is an acetate, the carboxylic acid is preferably formic acid, glycolic acid, glyoxylic acid, oxalic acid, fluoroacetic acid, etc., and the metal carboxylate is a carboxylate having an alkyl group having 3 or more carbon atoms. In the case of acid salts, preferred examples of the carboxylic acid include acetic acid, formic acid, glycolic acid, glyoxylic acid, oxalic acid and fluoroacetic acid.

The amount of the acidic substance used is not limited, and is a molar ratio with respect to the metal atom in the entire metal carboxylate in combination A or the metal atom in the entire metal alkoxy group-containing compound in combination B. Therefore, it is preferably 0.01 to 20, more preferably 0.1 to 10. When the molar ratio is less than 0.01, a metal segregation product of the metal element group (1) is likely to be generated, and when it exceeds 20, the metal oxide of the metal element group (1) may not be generated. .
In the production method of the present invention, the acidic material is a metal - it is sufficient be present in the reaction system in forming the metal oxide composite, timing and method of addition and the like of the addition is not limited. Specifically, the acidic substance is preferably added to the mixed system when the mixed system of the starting materials of combination A or the mixed system of starting materials of combination B is brought to a high temperature state. More preferably, the pre-reacted material, which will be described later, is added before being produced.

  When the starting material of combination A is used, the preliminary reaction product is a reaction product obtained by reacting a metal carboxylate with an alcohol, or when the starting material of combination B is used, a metal alkoxy group-containing compound and a carboxyl group. The state of any stage until a metal-metal oxide composite (especially metal oxide) is produced as a reactant by reaction with the contained compound (production of a metal-metal oxide composite (especially metal oxide)) Is a reaction intermediate in a state before being recognized, and a precursor (a metal-metal oxide composite precursor (especially a metal oxide precursor) to a metal-metal oxide composite (especially a metal oxide) produced. )). That is, the pre-reacted material is a precursor that is not one of the above-described starting materials and is not a metal-metal oxide composite (particularly metal oxide) to be generated. Such a pre-reactant can be obtained, for example, by simply mixing (preferably mixing under pressure) each starting material, or the mixture of each starting material in a moderately high temperature state (preferably a metal-metal oxide). And a composite (particularly a metal oxide) is obtained at a temperature lower than the temperature at which the composite is obtained.

The mixed system is preferably a fluid liquid such as a paste, a suspension, or a solution. If necessary, a reaction solvent may be used in addition to the starting materials. Specifically, when mixing a part or all of the starting materials of the combination A or B, or when bringing the mixed system composed of these starting materials to a high temperature state, the reaction is further performed after adding a reaction solvent. You can do it.
When a reaction solvent is also used, the amount used thereof is not limited. However, in consideration of economically obtaining a metal-metal oxide composite, the amount of metal carboxylate or metal alkoxy group-containing compound used is It is preferable to be 0.1 to 50% by weight based on the total weight including the reaction solvent.

  As the reaction solvent, a solvent other than water, that is, a non-aqueous solvent is preferable. Examples of the non-aqueous solvent include ethylbenzene, octane, xylenes, cyclohexane, cyclohexylbenzene, dimethylnaphthalene, styrene, solvent naphtha, decalin, decane, tetralin, dodecylbenzene, toluene, methylcyclohexane, methylcyclopentane, and liquid paraffin. Hydrocarbon solvents; various halogenated hydrocarbon solvents; alcohols such as alcohols in the combination A described above (including phenols, polyhydric alcohols and derivatives thereof having a hydroxyl group, etc.) solvents; anisole, epi Chlorohydrin, epoxybutane, crown ethers, diisoamyl ether, diethyl acetate, dioxane, diglycidyl ether, diphenyl ether, dibutyl ether, dibenzyl ether Ether or acetal solvents such as dimethyl ether and methyl-t-butyl ether; acetylacetone, acetaldehyde, acetophenone, acetone, isophorone, ethyl-n-butylketone, diacetone alcohol, diisobutylketone, cyclohexanone, di-n-propylketone, phorone, mesi Ketone or aldehyde solvents such as tiloxide, methyl-n-amyl ketone, methyl isobutyl ketone, methyl ethyl ketone, methylcyclohexanone and methyl-n-heptyl ketone; diethyl adipate, triethyl acetylcitrate, ethyl acetoacetate, methyl abietic acid, benzoic acid Benzyl acid, methyl benzoate, isoamyl isovalerate, ethyl isovalerate, propyl formate, tributyl citrate, methyl cinnamate 2-ethylhexyl acetate, cyclohexyl acetate, n-butyl acetate, benzyl acetate, methyl acetate, methyl cyclohexyl acetate, benzyl salicylate, methyl salicylate, dibutyl oxalate, diethyl tartrate, ethyl stearate, butyl stearate, dioctyl sebacate, sebacic acid Dibutyl, diphenyl carbonate, dimethyl carbonate, butyl lactate, methyl lactate, dioctyl phthalate, dimethyl phthalate, γ-butyrolactone, butyl propionate, benzyl propionate, methyl propionate, borate esters, dioctyl maleate, dimethyl malonate , Ester solvents such as isoamyl butyrate, methyl butyrate and phosphates; ethylene carbonate, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol Coal diglycidyl ether, ethylene glycol dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, diethylene glycol diacetate, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol dibenzoate , Diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol di-2-ethyl butyrate, triethylene glycol dimethyl ether, polyethylene glycol fatty acid diester and water at both ends Derivative compounds in which the active hydrogens of all hydroxyl groups of polyhydric alcohols are substituted with alkyl groups or acetoxy groups, such as poly (oxyethylene-oxypropylene) derivatives having no group; carboxylic acids and their anhydrides; silicone oils and Mineral oil; and the like. In particular, as a reaction solvent in the case of the combination A, it is preferable to use an alcohol used as an essential starting material as a solvent.

  In producing the metal-metal oxide composite, it is preferably produced in the presence of a specific polyhydric alcohol or a derivative compound thereof. Thereby, a metal-metal oxide composite can be produced with good yield. Specific polyhydric alcohols or derivative compounds thereof include 1) β-diols or hydroxyl groups bonded to adjacent carbon atoms, and 2) at least one hydroxyl group of the polyhydric alcohol substituted with an alkoxy group having 4 or more carbon atoms. A compound having at least one OH group, 3) a compound having at least one hydroxyl group of a polyhydric alcohol substituted with a carboxyl group having 4 or more carbon atoms, and having at least one OH group, Etc. These specific polyhydric alcohols or derivative compounds thereof may be used as the reaction solvent described above, or may be used as any of the starting materials, or separately added and used separately from the reaction solvent and the starting materials. May be.

  In producing the metal-metal oxide composite, it is preferable that the mixed system contains less water because defects in the resulting metal-metal oxide composite are reduced. Specifically, when the starting material of combination A is used, the molar ratio “moisture / metal atom in metal carboxylate” of water in the mixed system and metal atom in metal carboxylate is less than 4. The molar ratio is more preferably less than 1, and particularly preferably less than 0.5. On the other hand, when the starting material of combination B is used, the molar ratio of the moisture in the mixed system and the metal atom in the metal alkoxy group-containing compound “the metal atom in the water / metal alkoxy group-containing compound” is less than 1. It is preferable that only a small amount of water is contained, the molar ratio is more preferably less than 0.2, and particularly preferably less than 0.1.

  In the production method of the present invention, to bring the mixed system to a high temperature state, the temperature of the mixed system is increased to a temperature higher than room temperature (a temperature at which a metal-metal oxide composite (particularly metal oxide) is generated). It is to warm up. The temperature of the high temperature state varies depending on the type of composite to be obtained, etc., but is usually 50 ° C. or higher, and preferably 100 ° C. or higher in order to increase the crystallinity of the metal oxide in the composite. It is preferable that it is the range of 100-300 degreeC. In particular, as will be described later, when a metal-metal oxide composite is to be obtained as a film, and an organic substrate such as a polymer film is used as the substrate, the temperature of 100 to 200 ° C. It is preferable that it is a range, More preferably, it is the range of 100-150 degreeC.

As specific temperature raising means for bringing the mixed system into a high temperature state (including a temperature raising means for bringing the preliminary reaction product into a moderately high temperature state), heating by a heater, warm air or hot air is possible. Although it is general, it is not limited to this, For example, means, such as a heating by ultraviolet irradiation, can also be employ | adopted.
When the mixed system is brought into a high temperature state, when the mixed system is in contact with a gas, it can be performed in any atmosphere of an oxidizing gas or a non-oxidizing gas. Examples of the oxidizing gas include air and oxygen-nitrogen mixed gas. Examples of the non-oxidizing gas include nitrogen gas, inert gas such as helium and argon, hydrogen gas, and mixed gas thereof. It is done.

  In a preferred form of the production method of the present invention, the metal-metal oxide composite is preferably generated by heating under pressure. The heating when the mixed system is brought into a high temperature state (including heating when the preliminary reaction product is brought into a moderately high temperature state) may be performed under normal pressure, under pressure, or under reduced pressure. Although it is good, a metal-metal oxide composite can be produced in a solvent having a lower boiling point by heating under pressure. In particular, when the metal-metal oxide composite is obtained as particles, the metal-metal oxide composite is obtained in a state of being dispersed in the dispersion, but the dispersion can be achieved by heating under pressure. It can be obtained as a highly dispersible dispersion with little or no agent.

In the production method of the present invention, the metal-metal oxide composite may be produced by heating in the presence of inorganic fine particles having an average particle size of 100 nm or less. In the case of obtaining a metal-metal oxide composite as particles, it is particularly preferable to do so, and the coarsening of particles due to aggregation and fusion between the generated particles is suppressed, and particles having a fine particle diameter are high. The yield can be obtained.
The inorganic fine particles are not limited, and for example, metals, alloys, metal oxides, metal sulfides, metal selenides, metal tellurides, metal nitrides, metal carbides, metal oxynitrides, and the like can be used. . Among them, particles of metal-metal oxide composites obtained separately by the production method of the present invention, or metal oxide particles (preferably starting from metal carboxylate and alcohol, or metal alkoxy Particles obtained by heating using a group-containing compound and a carboxyl group-containing compound as starting materials are preferred. In addition, as an inorganic fine particle, only 1 type may be used and 2 or more types may be used.

  In the production method of the present invention, the mixing performed to obtain the mixed system of the starting materials (the mixture and / or the pre-reacted material) and the temperature rise performed to bring the obtained mixed system to a high temperature state (the above-mentioned In the case where the pre-reacted material is obtained by mixing each starting raw material and gradually raising the temperature to a high temperature, including the temperature rise to bring the temperature to a moderately high temperature) It is possible to go to the same part), and there is no limitation. Also, in the mixing performed to obtain the above mixed system, there is no limitation on how to mix each starting material. For example, all the starting materials to be used may be mixed at the same time, For example, in order to suppress the formation of segregated metal of the metal element group (1), the compound (1A) is produced when the metal oxide of the metal element group (2) is generated. ) And the compound (1B) are preferably mixed (for example, the following 2) to 5). ).

For specific embodiments of the mixing and heating, for example,
1) A mode in which the temperature of the mixture is raised to a predetermined temperature after mixing each starting material,
2) The alcohol or the carboxyl group-containing compound is heated to a predetermined temperature, and while maintaining the predetermined temperature, other starting materials (compound (1A) and metal carboxylate, or compound (1B) and A mode of mixing a metal alkoxy group-containing compound),
3) A reaction solvent and a metal carboxylate are mixed, or a metal alkoxy group-containing compound is mixed and heated to a predetermined temperature, and the other starting materials ( Embodiment in which compound (1A) and alcohol, or compound (1B) and carboxyl group-containing compound) are mixed,
4) A metal carboxylate and an alcohol are mixed, or a metal alkoxy group-containing compound and a carboxyl group-containing compound are mixed and heated to a predetermined temperature, and the compound (1A) or the compound (1B) A mode of mixing,
5) An embodiment in which each starting material is separately heated to a predetermined temperature and then mixed is preferred.

In the production method of the present invention, the produced metal-metal oxide composite may be obtained as particles, or the produced metal-metal oxide composite may be fixed on the surface of the substrate as a film. It may be. When obtained as particles, composite particles of a metal (metal atom) composed of the metal element of the metal element group (1) and a metal oxide containing the metal element of the metal element group (2) are obtained. When obtained as a film, a composite film of a metal (metal atom) composed of the metal element of the metal element group (1) and a metal oxide containing the metal element of the metal element group (2) is obtained.
When the metal-metal oxide composite is obtained as particles, the average particle size is preferably 1 to 100 nm, and more preferably 1 to 20 nm. When the average particle diameter exceeds 100 nm, the dispersion stability of the obtained particle dispersion becomes insufficient, and when used as a paint, the film formability and the like may be easily deteriorated.

  In the production method of the present invention, the metal-metal oxide composite is produced as particles in a reaction liquid (dispersion) obtained by bringing the mixed system to a high temperature state. Specifically, according to the production method of the present invention, as a reaction liquid (dispersion liquid) in which particles of a metal-metal oxide composite controlled to have the above average particle diameter are dispersed at 0.1 to 50% by weight. It is preferable to be obtained, and more preferably 1 to 20% by weight. Therefore, when it is intended to obtain a metal-metal oxide composite as particles (powder), the obtained reaction liquid (dispersion) should be subjected to normal separation means such as centrifugation or filtration. Good. Further, the obtained reaction liquid (dispersion liquid) is used as a concentrated liquid of a desired concentration by using an ultrafiltration membrane or by removing a part of the solvent by heating, or processed into a paste form and used. You can also Further, the reaction liquid (dispersion), the concentrated liquid, or the paste-like processed product is heated in the presence of a desired solvent to obtain the reaction liquid (dispersion), the concentrated liquid, or the paste-like processed material. The solvent initially contained in the product may be removed and replaced with a desired solvent. Such a reaction liquid (dispersion liquid), concentrated liquid, or paste-like processed product can be suitably used as a film forming material or a paint as it is or by mixing a binder component or the like as necessary.

When the metal-metal oxide composite is fixed on the surface of the base material as a film, the mixed system is brought into contact with the base material, and the contact system is brought to a high temperature state to thereby form the metal-metal oxide composite. A method of forming a film (hereinafter referred to as “Method I”), or while applying the mixed system to the surface of the substrate while keeping the mixed system in a high temperature state or in a high temperature state, It can be easily obtained by a method of forming a metal-metal oxide composite film (hereinafter referred to as “Method II”).
When adopting Method I, more specifically, the contact system is brought into a high temperature state, and the mixed system is applied to the surface of the base material to bring the base material into a high temperature state (hereinafter, “ It may be carried out by any one of the methods (hereinafter referred to as “Method I ₁ ”) and the method in which the substrate is immersed in the mixed system to bring it into a high temperature state (hereinafter referred to as “Method I ₂ ”). Method I ₁ and Method II are methods in which the mixed system is applied to the surface of a substrate. In Method I ₁ , after the application, in Method II, the mixed system is brought to a high temperature state before or during application. The metal-metal oxide composite is fixed on the surface of the substrate to form a metal-metal oxide composite film. In Method I ₁ and Method II, the mixed system may be applied while the substrate is heated to a high temperature state. On the other hand, Method I ₂ is to deposit and grow a metal-metal oxide composite on the surface of the substrate by bringing the mixed system into a high temperature state while the substrate is immersed in the mixed system. This is a method of fixing and forming a metal-metal oxide composite film. Hereinafter, method I ₁ and method II will be described as coating methods, and method I ₂ will be described as immersion methods.

In the coating method, after application to the method I ₁ In the mixed system of the substrate, in the coating before or coating to a substrate of the mixed system In method II, be it a mixed system in which a high temperature condition, the mixed system There are no limitations on the mixing at the time of obtaining, the temperature rise at the high temperature, and the timing of application to the substrate. However, when the mixed system contains a pre-reacted material, the pre-reacted material may not exist in a dissolved state at room temperature for a long time. It is preferable to apply. Further, a mode in which the method II and the method I ₁ are combined is also preferable, and it is preferable that the temperature of the base material is further increased after the mixed system whose temperature is increased before or during the application is applied to the base material.

In Method II, as a specific example of a mode in which the mixed system is brought into a high temperature state during application to the mixed system substrate, for example, the mixed system is passed through a heated pipe directly connected to the coated portion of the substrate. However, the present invention is not limited to these. Examples include, but are not limited to, a mode in which the mixture is heated and applied, and a mode in which the mixed system is heated in a pan of a roll coater and applied to the substrate while being heated. As a specific example of a mode in which the mixed system is brought to a high temperature state before application to the mixed system substrate in Method II, for example, the mixed system is heated using a (pressure-resistant) batch reactor or the like. However, the form applied to the substrate is not limited.
When the coating method is employed and the mixed system contains a reaction solvent, the reaction solvent has a boiling point at normal pressure at which the metal-metal oxide composite is formed (temperature at which a high temperature state is reached). It is preferable to select a higher reaction solvent than Thereby, the film | membrane of the metal-metal oxide composite excellent in transparency and the film | membrane of the metal-metal oxide composite with high metal content are obtained easily. Further, in this case, the content of the reaction solvent is preferably equimolar or more, more preferably twice or more molar in terms of molar ratio to the metal contained in the mixed system. When the coating method is employed and the reaction system contains a reaction solvent, it is preferable to select a non-aqueous solvent that can be azeotroped with water as the reaction solvent. Thereby, a dense metal-metal oxide composite film can be easily formed at a lower temperature. In this case, the content of the reaction solvent is preferably equimolar or more, more preferably 2 times mol or more, and further preferably 5 times or more, in terms of the molar ratio to the metal contained in the mixed system. In the coating method, a film of the metal-metal oxide composite is formed by heating, and the reaction solvent and the like can be volatilized and removed.

In the coating method, the method for applying the mixed system to the substrate is not limited. Specifically, for example, a bar coater method, a roll coater method, a knife coater method, a die coater method, and a spin coat method. Conventionally known methods such as a spray method and a dipping method may be employed.
In the coating method, when a high temperature state is set, only the base material may be heated by heating from the base material side, or only the coating surface is heated by heating from the coating surface side. However, the temperature of both the base material and the coated surface may be raised by combining these, and there is no limitation.

In the coating method, the case of adopting a configuration of combining method II and methods I _1, the temperature at the time of a high temperature state in the coating prior to or coating, a temperature at which to produce a preliminary reaction product is preferable, specifically, It is preferably 50 ° C. or higher and a temperature equal to or lower than a temperature when a high temperature state is applied after coating.
In the coating method, the heating time when the high temperature state is set is not limited, and specifically, 10 seconds to 1 hour is preferable, but the crystallinity is increased or the adhesion to the substrate is increased. For the purpose, it may be further aged by heating. The temperature, time, and temperature raising means during aging are not limited and may be appropriately selected.

The coating method is suitable for obtaining a metal-metal oxide composite film in the form of a continuous layer, particularly a dense continuous layer having a high surface smoothness.
In the immersion method, the substrate is immersed in the mixed system until the formation of the metal-metal oxide composite is completed, preferably until the formation reaction of the metal-metal oxide composite is started. There is no limitation on the timing of mixing when obtaining a mixed system, the temperature rise when making a high temperature state, and the immersion timing of the substrate. However, when the mixed system contains a pre-reacted material, the pre-reacted material may not exist in a dissolved state for a long time at room temperature. It is preferable to immerse.

In the immersion method, a commonly used apparatus can be used, but a device having a function of fixing the substrate is preferable. For example, a batch reaction apparatus in which a substrate (base material) holder is installed can be used. The presence or absence of stirring and the stirring conditions are not limited, and may be selected as appropriate.
In the immersion method, when the high temperature state is set, the temperature of the entire mixed system may be increased while the base material is immersed, or only the base material may be selectively selected while the base material is immersed. Although the temperature may be raised, the metal-metal oxide composite having high adhesion to the substrate surface is more likely to occur when the temperature of the substrate alone is selectively raised. It is preferable because a film is easily formed.

The immersion method is suitable for obtaining a metal-metal oxide composite film having a discontinuous layer or a continuous layer having a porous structure. However, depending on the temperature at the time of high temperature and the type of raw material, the macro structure of the metal-metal oxide composite film (continuous layer or discontinuous layer, or whether it is excellent in denseness or porous, etc. ) And crystal structure (crystallite size, shape, etc.) can be controlled.
The material of the base material obtained by fixing the metal-metal oxide composite as a film on the surface of the base material is not limited. Specifically, for example, oxide, nitride, carbide, etc. Inorganic materials such as ceramics and glass; polyester resins such as PET, PBT and PEN, polycarbonate resins, polyphenylene sulfide resins, polyethersulfone resins, polyetherimide resins, polyimide resins, amorphous polyolefin resins, polyarylate resins, aramid resins, Polyetheretherketone resin, (meth) acrylic resin, PVC resin, PVDC resin, PVA resin, EVOH resin, polyimide resin, polyamideimide resin, PTFE, PVF, PGF, ETFE and other fluororesins, epoxy resin and polyolefin resin, etc. And seed resin, aluminum in these various resins, processed products of organic matter, such as vapor deposition of alumina and silica; various metals; and the like preferably. In the production method of the present invention, a film can be formed at a lower temperature than in the prior art, so that a polymer film or a polymer plate can be selected as the substrate, and the industrial value is extremely high.

The shape / form of the substrate is not limited, and examples thereof include a film shape, a sheet shape, a plate shape, a fiber shape, a laminated body shape, a block shape, and a honeycomb shape. It may have a structure or a porous structure. In particular, when a porous body having a porous structure having a block shape or a honeycomb shape is used and a porous body formed by forming a metal-metal oxide composite film on the surface thereof, various catalysts, etc. Useful for.
The base material is not limited in terms of function, specifically, optically transparent and opaque; electrically, an insulator, a conductor, a p-type or n-type semiconductor or a dielectric; Magnetically, it is selected according to the purpose, such as a magnetic material or a non-magnetic material.

When the resulting metal-metal oxide composite is fixed on the surface of the substrate as a film, the thickness of the film (thickness in the direction perpendicular to the surface of the substrate) is not limited, but is usually 1 nm. It is preferable that it is -1000 micrometers, More preferably, it is 1 nm-1 micrometer.
In the metal-metal oxide composite (metal-metal oxide composite particles, metal-metal oxide composite film) obtained by the production method of the present invention, a specific metal is present at the atomic level in the metal oxide (that is, It is either in solid solution (as atoms or ions) or contained in a state close to that. For details on the form of the resulting metal-metal oxide composite, (1) when the metal oxide is amorphous, the specific metal is atomized in the metal oxide particles or metal oxide film. It is preferable that it is dissolved at a level or contained (dispersed) in a state close to that (that is, with a particle size of 1 nm or less). On the other hand, (2) when the metal oxide is crystalline, (2-1) when it consists of a single crystal, a specific metal is dissolved in the metal oxide particles or metal oxide film at the atomic level. (2-2) When it is made of a polycrystal, the specific metal is dissolved in the metal oxide particles or metal oxide film at the atomic level, or It is preferably contained (dispersed) in a close state (that is, with a particle size of 1 nm or less).

The metal-metal oxide composite obtained by the production method of the present invention contains a specific metal element, but since the metal is solid-solved at the atomic level, the metal alone particles or films Compared with transparency and the like. Therefore, it is very useful for various optical devices as a functional material having the transparency, for example, a functional material in the optical field.
Specifically, the metal-metal oxide composite particles can be used as a good film-forming material (paint, etc.) by adding a binder or the like to the dispersion liquid as necessary. In particular, the composite particles are average particles. In the case of ultrafine particles having a diameter of 100 nm or less, it is a preferable material for ink for ink jet drawing.

The metal-metal oxide composite film is useful as, for example, a transparent conductive film, a transparent electromagnetic shielding film, a nonlinear optical film, a (dilute) magnetic semiconductor film, a magneto-optical film, and a photocatalytic film.
In addition, the metal-metal oxide composite obtained by the production method of the present invention is obtained by dissolving a specific metal in the metal oxide at the atomic level, and the specific metal has catalytic ability. In some cases, as a catalyst for various reactions, even more excellent performance can be exhibited compared to the case of a single metal or the like. Furthermore, also in terms of physicality, when a specific metal is supported on a carrier as it is, the specific metal supported by use peels off or the metal melts and aggregates due to heat during use. However, when a metal-metal oxide composite obtained by the production method of the present invention is used, a specific metal that can exhibit catalytic ability is a metal. Since it is dissolved in the oxide at the atomic level, the above-mentioned problems do not occur, and the long-term stability of the catalytic ability can be effectively achieved. When used for a catalyst, as described above, a porous body having a block-like or honeycomb-like shape as a base material and having a metal-metal oxide composite film formed on the surface thereof is used. You can get it.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited at all by these. In the following, “parts by weight” may be simply referred to as “parts” for convenience. “Metal element (1)” means the “metal element contained in the metal element group (1)”, and “metal element (2)” means the metal contained in the “metal element group (2)”. It shall mean “element”.
Evaluation methods and measurement methods in Examples and Comparative Examples are shown below.
<Crystallinity of metal-metal oxide composite film>
A metal-metal oxide composite film formed on the surface of a substrate or the like is measured by a thin film X-ray diffraction measurement method. From the obtained diffraction pattern, the crystallinity of the film (metal oxide which is a component of the film) Of crystallinity). The measurement apparatus and measurement conditions (scanning conditions) are as follows.

Measuring device: RAD-rX (using attachment for thin film measurement) (manufactured by Rigaku Corporation)
Output: 55kV, 180mA
X-ray incident angle: normally fixed at 0.5 ° (fixed appropriately within the range of 0.2 to 0.5 ° as necessary)
2θ: 3 to 100 °
Scanning speed: Scanning at 2 ° / min as 2θ <Composition analysis of metal-metal oxide composite film>
A part of the surface of the metal-metal oxide composite film formed on the surface of a substrate or the like was scraped and thinned by an ion milling method was used as a sample. While observing the surface of this sample with an FE-TEM (electrolytic emission transmission electron microscope, manufactured by Hitachi, product name: HF-2000), XMA (energy dispersive X-ray microanalyzer, manufactured by Kevex, product name) : Elemental analysis using Sigma type, beam diameter (= spatial resolution): 10 ： Φ), composition ratio of metal components (composition ratio of metal elements (1) and (2)), and metal element (1) The presence / absence of segregated metal (particulate metal), the dispersion state of the metal component of the metal element (1), and the like were measured and evaluated. Such measurement / evaluation was performed at arbitrary plural locations on the film surface.

[Example 1]
A pressure-resistant glass reactor equipped with a stirrer, an addition port, a thermometer, a nitrogen gas introduction port and a distillate gas outlet, which can be heated from the outside, an addition tank connected to the addition port, and the distillate gas outlet A reactor equipped with a connected cooler (directly connected to the trap) was prepared.
In the reactor, a mixture of 18 parts of copper (II) acetate as a compound of the metal element (1) and 200 parts of methanol was charged, and the gas phase part was purged with nitrogen gas. The temperature was raised from 20 ° C. to 100 ° C. (0.4 MPa) with stirring, and then cooled to obtain a solution (1a).

In another reactor, a mixture of 18 parts of zinc acetate anhydride containing metal element (2), 194 parts of 2-butoxyethanol and 6 parts of ethylene glycol was charged, and the gas phase part was purged with nitrogen gas. Thereafter, in a sealed state, the temperature was raised from 20 ° C. to 100 ° C. with stirring, followed by cooling to obtain a solution (1b).
A coating solution (1) was prepared by mixing 5 parts of the solution (1a) and 0.5 part of formic acid with 100 parts of the solution (1b).
A porous alumina substrate having a honeycomb shape is immersed in the coating liquid (1), taken out, put into a heating furnace, and heated at a rate of temperature increase of 10 ° C./min from normal temperature while flowing air. The temperature was raised to 180 ° C. and held for 60 minutes. Then, the film was formed on the surface of the alumina substrate by taking out from the heating furnace and cooling.

The film formed on the surface of the alumina substrate was evaluated for crystallinity by the method described above. As a result, a diffraction peak attributed to ZnO was confirmed, but a diffraction peak attributed to metal Cu was not confirmed. It was. In addition, as a result of performing composition analysis by the above-described method for the above film, the presence of fine segregated metal Cu was not recognized, and it was recognized that Cu was uniformly dispersed in each part of the film. The composition ratio (average value) of the metal element (1) and the metal element (2) was Cu / Zn = 5 atomic%.
Therefore, the film formed on the surface of the alumina base material is a metal-metal oxide composite film (Cu-ZnO film) in which ZnO crystals are the main constituent elements and Cu is contained at the atomic level. I can judge.

[Example 2]
In the same reactor as in Example 1, 0.23 parts of palladium (II) acetate anhydride as a compound of metal element (1), 0.05 part of oxalic acid, and titanium element containing metal element (2) -A mixture comprising 34 parts of butoxide, 34 parts of acetic acid and 150 parts of diethylene glycol dimethyl ether was charged, and a porous alumina substrate having a honeycomb shape was immersed in this mixture. Thereafter, the gas phase in the reactor was purged with oxygen-containing nitrogen gas (oxygen concentration: 2%), and the temperature was raised from 20 ° C. to 180 ° C. with stirring in a sealed state, and 180 ° C. ± 1 ° C. for 2 hours. After holding, the film was formed on the surface of the alumina substrate by cooling.

As a result of evaluating the crystallinity of the film formed on the surface of the alumina base material by the method described above, a diffraction peak attributed to anatase TiO ₂ was confirmed, but a diffraction peak attributed to metal Pd was It was not confirmed. In addition, as a result of performing composition analysis by the above-described method for the film, the presence of segregated fine particle metal Pd is not recognized, and it is recognized that Pd is uniformly dispersed in each part of the film. The composition ratio (average value) of the metal element (1) and the metal element (2) was Pd / Ti = 1 atomic%.
Therefore, the film formed on the surface of the alumina base material has an anatase type TiO ₂ crystal as a main component, and a metal-metal oxide composite film (Pd—TiO ₂ film) containing Pd at an atomic level. ).

Example 3
In the same reactor as in Example 1, 0.164 parts of rhodium (II) trifluoroacetate dimer as a compound of metal element (1), 0.02 part of p-toluenesulfonic acid hydrate, metal element (2 ) Containing stannic acetate (35.5 parts), zinc acetate (18.4 parts) and propylene glycol mono-n-butyl ether (200 parts), and the gas phase part is nitrogen gas. The solution (3) was obtained by raising the temperature from 20 ° C. to 100 ° C. with stirring and then cooling in a sealed state.
After spraying the solution (3) as a coating solution (3) on a glass substrate, it is put in a heating furnace, heated at a heating rate of 10 ° C./min from room temperature under a helium gas pressurization, and raised to 250 ° C. Hold for 60 minutes after warming. Then, the film was formed on the surface of the glass substrate by taking out from the heating furnace and cooling.

The film formed on the surface of the glass substrate was evaluated for crystallinity by the method described above. As a result, a diffraction peak attributed to ZnSnO ₃ was confirmed, but a diffraction peak attributed to metal Rh was confirmed. There wasn't. Moreover, as a result of performing composition analysis by the above-described method for the above film, the presence of segregated fine particle metal Rh was not recognized, and it was recognized that Rh was uniformly dispersed in each part of the film. The composition ratio (average value) of the metal element (1) and the metal element (2) was Rh / Sn = 0.5 atomic%.
Therefore, the film formed on the surface of the glass substrate is a metal-metal oxide composite film (Rh-ZnSnO ₃ film) containing ZnSnO ₃ crystal as a main component and containing Rh at an atomic level. It can be judged that there is.

[Comparative Example 1]
In Example 1, a film was formed on the surface of the alumina base material in the same manner except that formic acid was not used.
As a result of evaluating the crystallinity of the film formed on the surface of the alumina substrate by the method described above, a diffraction peak attributed to ZnO was confirmed, and a diffraction peak attributed to metal Cu was also confirmed. Further, as a result of the composition analysis performed on the film by the method described above, the presence of finely divided segregated metal Cu was observed.
[Comparative Example 2]
In Example 2, a film was formed on the surface of the alumina base material in the same manner except that oxalic acid and acetic acid were not used.

As a result of evaluating the crystallinity of the film formed on the surface of the alumina substrate by the method described above, a diffraction peak attributed to anatase TiO ₂ was confirmed, and a diffraction peak attributed to metal Pd was also confirmed. It was done. The film was subjected to composition analysis by the method described above, and as a result, the presence of finely divided metal Pd segregated material was observed.

  The production method of the present invention is, for example, a method for obtaining a metal-metal oxide composite film useful as a transparent conductive film, a transparent electromagnetic shielding film, a nonlinear optical film, a (dilute) magnetic semiconductor film, a magneto-optical film, a photocatalytic film, and the like. It is suitable as.

Claims (4)

A compound containing at least one metal element selected from the metal element group (1) consisting of Pt, Pd, Ru, Rh, Ir, Ni, Cu and Ag , and a metal element group (2) consisting of Zn, Ti and Sn A metal carboxylate containing at least one metal element selected from the group consisting of an alcohol and an alcohol, or
A compound containing at least one metal element selected from the metal element group (1); a metal alkoxy group-containing compound and a carboxyl group-containing compound containing at least one metal element selected from the metal element group (2); Starting material,
A mixture comprising a raw material essential for the starting material and / or a mixed system containing a pre-reacted material obtained from the raw material essential for the starting material is brought to a high temperature state of 100 ° C. or higher in the presence of an acidic substance. A method for producing a metal-metal oxide composite, wherein a composite of a metal and a metal oxide is produced. By bringing the mixed system into contact with the substrate and bringing the contact system into the high temperature state, or by applying the mixed system to the surface of the substrate while keeping the mixed system in the high temperature state or in the high temperature state. The method for producing a metal-metal oxide composite according to claim 1 , wherein the composite is produced as a film fixed on the surface of a substrate.   The method for producing a metal-metal oxide composite according to claim 2, wherein the substrate is porous. The metal-metal oxide composite according to claim 1, wherein the mixed system includes a reaction solvent, and the composite is generated as particles dispersed in the solvent by bringing the mixed system to the high temperature state. Manufacturing method.