WO2004069740A1

WO2004069740A1 - Metal alkoxide hydrolyzate

Info

Publication number: WO2004069740A1
Application number: PCT/JP2004/001186
Authority: WO
Inventors: Toshimi Fukui; Junko Nakamoto; Kenji Yamada; Mitsuhisa WADA; Yoshitaka Fujita; Nobuo Kimura
Original assignee: Nippon Soda Co., Ltd.
Priority date: 2003-02-05
Filing date: 2004-02-05
Publication date: 2004-08-19
Also published as: JP4780764B2; JPWO2004069740A1

Abstract

A metal oxide sol comprised of a metal alkoxide hydrolyzate whose structure has been spectrally elucidated, which is used to obtain a film exhibiting highly satisfactory denseness and smoothness. The metal alkoxide hydrolyzate is a product obtained by hydrolysis of a metal alkoxide characterized in that 70 atomic% or more of the oxygen atoms brought in the product in water used for the hydrolysis are μ3-oxygen atoms.

Description

2004/001186

Specification

Metal alkoxide hydrolysis products

The present invention relates to a metal alkoxide hydrolysis product having a property of dispersing stably without aggregation in an organic solvent in the absence of an acid, a base, and / or a dispersion stabilizer. Background technology:

As a method for producing a transparent and homogeneous metal oxide sol, for example, a method for producing a metal oxide precursor sol by hydrolyzing and polymerizing one or more metal alkoxides, There is known a method for producing a metal oxide precursor sol, characterized in that the addition of water is carried out at a temperature of not more than 120 ° C. (Refer to Japanese Patent Application Laid-Open No. 10-29-87697)

In addition, organic solvent-soluble high molecular weight ladder-like polytitanoxane is obtained by hydrolyzing tetraalkoxytitanium at a temperature of 20 to 90 ° C using water of 1.0 to 1.7 times mol. Is known. The low molecular weight ladder-like polytinoxane is said to dissolve in the organic solvent even in the case of a high molecular weight that gels and becomes insoluble in the organic solvent with the conventional chain polytitanoxane, and provides a dense thin film. (Refer to Japanese Patent Application Laid-Open No. Hei 11-1990)

Also, an alcohol solution containing 0.1 to 2.0 moles of water is added to 1 mole of the metal salt partially hydrolyzed by adding water, and the mixture is heated to hydrolyze the metal salt. There is known a method for producing a metal oxide precursor solution by forming a metal hydroxide, condensing it after dehydration condensation, and then concentrating it. It is stated that the metal oxide precursor solution forms a complex to provide a homogeneous metal thin film having excellent storage stability and no cracks. (Refer to Japanese Patent Application Laid-Open No. 2001-33420)

DISCLOSURE OF THE INVENTION:

The metal thin film using the metal oxide sol obtained by any of the above methods has a problem that the film is insufficient to satisfy the denseness and smoothness of the film.

INDUSTRIAL APPLICABILITY The present invention is used to obtain a film that can sufficiently satisfy denseness and smoothness. It is an object of the present invention to provide a metal oxide sol comprising a metal alkoxide hydrolysis product whose structure has been clarified spectrally.

The present inventors have conducted intensive studies to solve the above problems, and as a result, by devising a mixing temperature, a mixing amount, and a mixing method of water with respect to a metal alkoxide, an acid, a base, and the like can be contained in an organic solvent. A metal oxide sol that can stably disperse even without the presence of a dispersion stabilizer and a dispersion stabilizer was found, and various spectra of the particles were measured. Led to.

That is, the present invention

(1) A product obtained by hydrolyzing a metal alkoxide, wherein at least 70 atomic% of oxygen atoms incorporated in the product in water used for hydrolysis are oxygen atoms. With respect to the metal alkoxide hydrolysis product,

(2) a product obtained by a metal alkoxide to hydrolyze more than 80 atomic% of incorporated into the product in water which need use in hydrolysis oxygen atom, a 2 ³ oxygen atoms A metal alkoxide hydrolysis product characterized by

(3) The metal alkoxide hydrolyzation product according to (1), wherein 30 atomic% or less of oxygen atoms incorporated into the product in the water used for hydrolysis is ² oxygen atoms. object,

(4) The metal alkoxide hydrolyzate according to (2), wherein less than 20 atomic% of oxygen atoms incorporated into the product in the water used for hydrolysis are // ² oxygen atoms. Decomposition products,

(5) The method according to any one of (1) to (4), wherein 10 atomic% or less of oxygen atoms incorporated into the product in the water used for the hydrolysis is ⁴ oxygen atoms. The metal alkoxide hydrolysis product described,

(6) Any of (1) to (4), wherein 5 atomic% or less of oxygen atoms incorporated into the product in the water used for hydrolysis is // ⁴ oxygen atoms. The metal alkoxide hydrolysis product according to the above,

(7) When the metal alkoxide has the formula (I)

M (OR) _η

(Wherein, M represents a metal atom, R represents a C1- (10 alkyl group, n represents 2004/001186

Represents child price. The present invention relates to the metal alkoxide hydrolysis product according to any one of (1) to (6), which is a compound represented by the formula:

(8) Equation (I)

M (OR) _η

(Wherein, M represents a metal atom, R represents a C 1 to (: 10 represents an alkyl group, and n represents a atomic value.) A product obtained by hydrolyzing a metal alkoxide represented by the following formula: The product has a functional group represented by R in the product, and a chemical shift of a hydrogen atom in the functional group in a proton nuclear magnetic resonance spectrum using tetramethylsilane as a standard of 0 ppm. A metal alkoxide represented by the formula (I), wherein the metal alkoxide has a hydrogen atom having the chemical shift value shifted to a lower magnetic field than the chemical shift value of the hydrogen atom in R. Regarding the product,

(9) Equation (I)

M (OR) _η

(Wherein, M represents a metal atom, R represents a C1-C10 alkyl group, and n represents a valence). A product obtained by hydrolyzing a metal alkoxide represented by Then, the product has a functional group represented by the aforementioned OR in the product, and the carbon atom at the α-position of the oxygen atom in the functional group is a carbon atom. The tetramethylsilane in the nuclear magnetic resonance spectrum is 0 p. The standard chemical shift value of pm is a carbon atom which is the chemical shift value shifted to a lower magnetic field than the chemical shift value of the position of the oxygen atom in R in the metal alkoxide represented by the formula (I). Wherein the chemical shift value of the carbon atom at the / 3 position of the oxygen atom in the functional group is greater than the chemical shift value of the position of the oxygen atom in R in the metal alkoxide represented by the formula (I). Having a carbon atom having the chemical shift value shifted to a high magnetic field. It relates the metal alkoxide hydrolysis product, wherein Rukoto,

(10) The metal alkoxide hydrolysis product according to (9), which has two kinds of carbon atoms having different relaxation times (Ί \),

(11) The relaxation time (Τ _χ ) of the carbon atom, which is the chemical shift value shifted to the low magnetic field, is the chemical shift value of the chemical shift region on the high magnetic field side higher than the chemical shift value shifted to the low magnetic field. Shorter than the relaxation time (Τ \) of a carbon atom 2004 / 00H86

A metal alkoxide hydrolysis product according to (9) or (10),

(12) The relaxation time (T,) of the carbon atom, which is the chemical shift value shifted to the high magnetic field, is the chemical shift value of the chemical shift region on the lower magnetic field side than the chemical shift value shifted to the high magnetic field. The metal alkoxide hydrolysis product according to any one of (9) to (11), wherein the hydrolysis time is shorter than the relaxation time (1 \) of the carbon atom.

(13) The metal alkoxide hydrolysis product has a property of being stably dispersed without aggregation in an organic solvent in the absence of an acid, a base, and / or a dispersion stabilizer. (1) The metal alkoxide hydrolysis product according to any one of (12) to (12),

(14) The metal according to any one of (1) to (13), wherein the metal alkoxide is metal tetraisopropoxide and has a nuclear magnetic resonance spectrum shown in FIGS. 1 and 2. Alkoxide hydrolysis products.

The metal alkoxide hydrolysis product having a spectral structural characteristic of the present invention can be stably dispersed without aggregation in an organic solvent in the absence of an acid, a base, and / or a dispersion stabilizer. Has properties.

The state in which the metal alkoxide hydrolysis product is stably dispersed without agglomeration is a state in which the metal alkoxide hydrolysis product is not coagulated and is not separated inhomogeneously, preferably a transparent and homogeneous state. In this case, “transparent” refers to a state in which the transmittance of visible light is high. Specifically, the concentration of the dispersoid is 0.5% by weight in terms of oxide, and the optical path length of the quartz cell is 1 cm. It refers to a state in which the target sample is an organic solvent, and preferably exhibits a transmittance of 80 to 100% as represented by a spectral transmittance measured under the condition of a light wavelength of 550 nm. The average particle size of the metal alkoxide is preferably in the range of 1 to 50 nm, more preferably in the range of 1 to 20 nm, and more preferably monodisperse in the particle size distribution of 0 to 50 nm.

As used herein, the organic solvent is not particularly limited as long as the organic solvent is an organic substance capable of dispersing the dispersoid. Specifically, alcohol solvents such as methanol, ethanol, and isopropyl alcohol; methylene chloride; Chlorinated solvents such as chloroform, hexane, cyclohexane, benzene, toluene, xylene, benzene, etc. Hydrocarbon solvents, ether solvents such as tetrahydrofuran, getyl ether and dioxane; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. Aprotic polar solvents, and silicones such as methylpolysiloxane and ethylphenylpolysiloxane used as a dispersion medium of a titanium dioxide dispersion described in JP-A-9-120838. As will be described later, in order to carry out the hydrolysis reaction using water at a low temperature, a solvent having high water solubility and not coagulating at a low temperature is preferable. Specifically, a lower alcohol solvent is used. And ether-based solvents. These solvents can be used alone or in combination of two or more.

The acid or base in this case is used as a deflocculant to re-disperse the precipitate formed by coagulation, or as a catalyst for producing dispersoids such as colloid particles by hydrolyzing and dehydrating and condensing metal alkoxides and the like. The acid is not particularly limited as long as it functions as a dispersant for the generated dispersoid, and specific examples of the acid include mineral acids such as hydrochloric acid, nitric acid, boric acid, and boric hydrofluoric acid, acetic acid, formic acid, and the like. Examples thereof include organic acids such as oxalic acid, carbonic acid, trifluoroacetic acid, P-toluenesulfonic acid, and methanesulfonic acid. Further, a photoacid generator that generates an acid by light irradiation, specifically, Examples thereof include diphenyldoniumhexafluorophosphate, triphenylphosphoniumhexafluorophosphate and the like. Examples of the base include triethanolamine, triethylamine, 1,8-diazapicyclo [5,4,0] -7-decene, ammonia, dimethylformamide, and phosphine.

In this case, the dispersion stabilizer refers to a component added to disperse the dispersoid in the dispersion medium as stably as possible, and includes an anticoagulant such as a deflocculant, a protective colloid, and a surfactant. Show. Specific examples of the compound having such an action include chelating compounds. The compound has at least one carboxyl group in the molecular skeleton and has a strong chelating effect on metals. Preferably, such compounds include glycolic acid, dalconic acid, lactic acid, tartaric acid, citric acid, Examples thereof include polycarboxylic acids such as malic acid and succinic acid, and hydroxycarboxylic acids, and further include pyrophosphoric acid and tripolyphosphoric acid. Similarly, polydentate ligand compounds having strong chelating ability for metal atoms include acetylacetone, methyl acetoacetate, ethyl acetate, ethyl acetate-n-propyl, and acetate acetate-i-one. Propyl, acetoacetate-n-butyl, acetoacetate-sec-butyl, acetoacetate-t-butyl, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2, 4 one octane one dione,

Examples thereof include 2,4-nonanedione and 5-methyl-hexanedione. In addition, as aliphatic amines, hydrostearic acids, and polyesteramines, Sulpers 3000, 9000, 17000, 20000, 24 000 (all manufactured by Zeneca), Disperbyk—161, —162, —1 6

3, -164 (above, manufactured by Big Chemical Co., Ltd.) and the like. Examples thereof include dimethylpolysiloxane methyl (poly) described in JP-A-9-208438, JP-A-2000-53421, and the like. Examples thereof include silicone compounds such as (siloxyalkylene) siloxane copolymer, trimethylsiloxycyanic acid, carboxy-modified silicone oil, and amine-modified silicone.

As a method for producing a metal alkoxide hydrolysis product having a spectral structural characteristic according to the present invention, specifically, a solution containing a metal alkoxide is added to a metal alkoxide by adding 1 to 2 moles or more to 2 moles or more of a metal alkoxide. A step of adding less than one mole of water in a plurality of times, wherein at least one of the steps of adding the water in a plurality of times is at least モル times the mole number of the metal alkoxide. For example, a production method in which less than twice the amount of water is added can be exemplified.

As the metal alkoxide used in the above method, specifically, a compound represented by the formula (I) can be preferably exemplified. In the formula (I), M represents a metal atom. Specifically, the metal atom used in the present invention is an alkali metal element or an alkaline earth metal element from the second period to the sixth period of the periodic table. And elements from the group consisting of Group 3B elements, Group 4B elements and Group 5B elements from Periods 3 to 6 of the Periodic Table, transition metal elements, and Lanthanide Node elements. One or a combination of two or more metals can be exemplified, such as titanium, zirconium, and aluminum. Particularly preferred is one selected from the group consisting of silicon, germanium, germanium, indium, tin, tantalum, zinc, tungsten and lead.

In the formula (I), R represents a C1-C10 alkyl group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group Group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n_decanyl group and the like.

Specific examples of the metal alkoxide used in the present invention include: methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, tetramethoxysilane, tetramethoxysilane. Ethoxysilane, tetrapropoxysilane, germanium tetramethoxide, germanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, zirconium tetrapropoxide, zirconium tetrabutoxide, aluminum triethoxy, aluminum triplobox Oxide, aluminum tryptoxide, tetrachlorosilane, tetrabromosilane, dimethyldichlorosilane, tetrakis (getylamino) silane, 4-amino Butyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, benzyltrichlorosilane, benzyltriethoxysilane, t-butylphenyldichlorosilane, 2-chloroethyltriethoxysilane, 3-cloth Propyltrichlorosilane, 8-bromooctyltrichlorosilane, 3-bromopropyltrichlorosilane, (3,3,3-trifluoromethyl) dichlorosilane, (3,3,3-trifluoropropyl) trichlorosilane, chloro Methyltrichlorosilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, (3-glycidoxypropyl) methyljetoxysilane, 3-glycidoxypropyltrimethoxysilane, aryltrichloromouth silane, Aryltriethoxy Silane, pinylmethyldiacetoxysilane, pinylmethylbis (methylethylketoximine) silane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrichlorosilane , 3-acryloxypropyltrimethoxy 04 001186

Silanes and the like can be exemplified, and particularly preferred are tetramethoxysilane, tetraethoxysilane, titanium tetraisopropoxide, titanium tetrabutoxide, zirconium tetraisopropoxide, zirconium tetrabutoxide and the like.

These metal alkoxides can be used alone or in combination of two or more.

In the method for producing a metal alkoxide hydrolysis product having a spectral structural feature of the present invention, in performing the above-described step, at least one of the following (1) to (3) It is preferably carried out under

(1) the temperature of at least one of the steps of mixing water is equal to or lower than the hydrolysis start temperature of the metal alkoxide;

(2) After the step of adding water, the temperature is raised to a temperature not lower than the hydrolysis start temperature of the metal alkoxide,

(3) After the step of adding water in an amount of 1 to 2 moles or more and less than 1 mole per mole of the metal alkoxide, the remaining required amount of water is added at a temperature equal to or lower than the hydrolysis start temperature of the metal alkoxide. To do.

By adding these conditions, a metal alkoxide hydrolysis product that can be stably dispersed without aggregation in an organic solvent can be obtained more stably.

The method of mixing the solution containing the metal alkoxide with water is not particularly limited, and water may be added to the metal alkoxide solution, or the metal alkoxide may be added to the solution containing water. It is preferred to add it later.

As the water to be mixed, general tap water, distilled water, ion-exchanged water and the like can be used. Among them, distilled water or ion-exchanged water is preferable, and ion-exchanged water having an electric conductivity of 2 as Zcm or less is particularly preferable.

The water is preferably used after being diluted with an organic solvent. As such an organic solvent, those having a freezing point below the temperature at which the metal alkoxide does not react with water and hydrolyze, that is, those having a freezing point of 0 ° C or less, particularly 110 ° C or less are preferred. . As such an organic solvent, those having no reactivity with the metal alkoxide are preferable, and specifically, alcohols, aliphatic hydrocarbons, and aromatic hydrocarbons 2004/001186

, Halogenated hydrocarbons, ketones, esters, ethers, ketone ethers, ketone esters, ester ethers, and the like. More specific examples of these organic solvents include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, benzyl alcohol, methylcyclohexanol, ethanediol. , Propanediol, butanediol, pentanediol, hexylene glycol, octylendalicol, hexanetriol, 3,5,5-trimethyl-1-hexanol, butyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate , Butyl acetate, pentyl acetate, hexyl acetate, benzyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, methyl propionate, ethyl propionate, petit propionate , Pentyl propionate, dimethyl ketone, methyl ethyl ketone, pentanone, hexanone, methyl isobutyl ketone, heptanone, diisobutyl ketone, acetate nitrile, getyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, Dihexyl ether, anisol, tetrahydrofuran, tetrahydropyran, dimethoxyethane, dietoxetane, dibutoxetane, diethylene glycol dimethyl ether, diethylene glycol-diethyl ether, diethylene glycol dibutyl ether, methylal, acetal, pentane, hexane, Heptane, octane, nonane, decane, dodecane, toluene, xylene, ethylbenzene, cumene, mysitylene, tetralin, Tylbenzene, cymene, getylbenzene, pentylbenzene, dipentylbenzene, cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, decalin, chloromethane, dichloromethane, trichloromethane, tetrachloromethane, chloroethane, dichloroethane, trichloroethane Lichloroethane, tetrachloroethane, pentachloroethane, chloropropane, dichloropropane, trichloropropane, chlorobutane, chloropentane, chlorobenzene, dichlorobenzene, chlorotoluene, bromomethane, promoethane, bromopropane, promobenzene Bromomethane, etc. can be mentioned. Of these, alcohols, esters and hydrocarbons are preferred, and isopropanol, butanol, and pen are particularly preferred. 4 001186

Ethanol, hexanol, trimethylhexanol, ethyl acetate, propyl acetate, butyl acetate, pentane, hexane, xylene and the like are preferred. Further, the organic solvents can be used alone or in combination of two or more. When water and the organic solvent are uniformly dissolved and mixed, they can be used as they are. When water and the organic solvent are not mixed uniformly, they can be uniformly dispersed and used by a method such as stirring treatment or ultrasonic treatment. The amount of the organic solvent to be diluted is preferably in the range of 2 to 100 parts by weight with respect to 1 part by weight of water.

The amount of water used is preferably in the range of 12 moles or more and less than 2 moles relative to the number of moles of the metal compound. If the molar ratio is less than 1/2 times, hydrolysis and depolymerization do not proceed uniformly, and the metal compound represented by the formula (I) or the like may remain unreacted, and a homogeneous and dense film cannot be formed. .

On the other hand, if the molar ratio is more than 2 times, gelation or aggregation of particles occurs during the hydrolysis and polycondensation processes, so that a homogeneous and dense film cannot be formed.

The hydrolysis start temperature is the lowest temperature at which hydrolysis proceeds when the metal alkoxide comes into contact with water. Specifically, the hydrolysis initiation temperature described in Japanese Patent Application Laid-Open No. Hei 1-23407 can be exemplified. The temperature below the hydrolysis initiation temperature is not particularly limited as long as the solution does not solidify, but is preferably a temperature in the range of −50 to −100 ° C. After mixing with water at a temperature equal to or lower than the hydrolysis start temperature, it is preferable to carry out the reaction by raising the temperature to a temperature equal to or higher than the hydrolysis start temperature.

The hydrolysis and polycondensation process of the metal alkoxide under the above conditions is preferably performed in an organic solvent. Specific examples of such an organic solvent include those similar to the organic solvents used by mixing with water. Preferred examples are hydrocarbon solvents such as benzene and toluene, and ether solvents such as tetrahydrofuran and getyl ether.

The amount of the organic solvent to be used is 100 to 100,000 parts by weight, preferably 100 to 3,000 parts by weight, and preferably less than 100 parts by weight, based on 100 parts by weight of the metal alkoxide. In some cases, the generated fine particles grow in a bonded state, making it difficult to control the particle size. On the other hand, when the content exceeds 10,000,000 parts by weight, the solution is too dilute to produce fine particles. There is.

It is also preferable to carry out the reaction in the absence of the above-mentioned acid, base, and Z or a dispersion stabilizer. This is because these compounds are often difficult to remove after the reaction, and may be an obstacle in a later step.

The metal alkoxide hydrolyzate obtained by the above method is dissolved or uniformly dispersed in the used organic solvent without aggregation without using an acid, a base, or a dispersion stabilizer. And forms a clear solution. When forming a membrane, this solution can be used as it is, or can be used after diluting with an appropriate solvent, distilling off the solvent and re-dissolving in another solvent. As a result, when this dispersion is used, gel films, gel fibers, bulk gels, and the like having a low content of organic substances are obtained. When the organic substances are desorbed from these gels by heat treatment, etc., The destruction of the microstructure and the amount of residual pores can be reduced. When the various spectra of the metal alkoxide hydrolysis product obtained as described above were measured, it was found that the metal alkoxide had features not found in the past. The details will be described in Examples.

BRIEF DESCRIPTION OF THE DRAWINGS:

FIG. 1 shows the results of the titanium alkoxide hydrolysis product prepared in Example 1.

1 shows a spectrum diagram of MR.

FIG. 2 shows a ¹³ C NMR spectrum diagram of the hydrolysis product of titanium alkoxide prepared in Example 1.

FIG. 3 shows a spectrum diagram of ¹³ C NMR in which the relaxation time of the titanium alkoxide hydrolysis product prepared in Example 1 was changed.

FIG. 4 shows a ¹⁷ O NMR spectrum diagram of the titanium alkoxide hydrolysis product prepared in Example 2.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to Examples.

Example 1

Titanium tetraisopropoxide (A-1 manufactured by Nippon Soda Co., Ltd .: purity 99.9%, acid In a four-necked flask, 30 g (1.86 mol 1) of toluene was dissolved in 190 g of toluene, and after displacing with nitrogen gas, a methanol bath containing dry ice was added (approximately 11%). (5 ° C). A mixed solution of 30 · 4 g of ion-exchanged water (H ₂₀ / T i = 0.9 mo I / mo I) diluted with 274 g of isopropanol, which was separately prepared, was added dropwise over 90 minutes while stirring. The liquid temperature of the flask during the dropwise addition was kept at −15 to 110 ° C. After completion of the dropwise addition, the temperature was maintained at 110 ° C. for 30 minutes, the temperature was further raised to room temperature, and stirring was continued for 1 hour to obtain a colorless transparent liquid. Next, the mixture was cooled to about 180 ° C in a methanol bath containing dry ice, and 20.3 g of ion-exchanged water diluted with 183 g of isopropanol (H ₂ 0 / Ti = 0.6 mo 1 “mo The mixed solution of 1) was added dropwise over 90 minutes with stirring, and after completion of the addition, the temperature was raised to room temperature in 3 hours, and the solution was refluxed at 90 to 100 ° C for 2 hours to obtain a colorless and transparent oxidation. A sol having a concentration of 5% by weight in terms of titanium was obtained, and the light transmission wavelength of this solution at a light transmittance of 50% was 358 nm, and the sol had a sharp average particle size of 5.6 nm. the particle size distribution of monodisperse was shown. the obtained sol solution a vacuum heating under solvent was distilled off to give a solid. election solid was dissolved in heavy benzene, IHNMR and ¹³ CNMR Figures 1 and 2 show the results.

In ¹³ CNMR, the relaxation time (T was measured while changing T. The results are shown in FIG. 3).

From FIG. 1, it was found that the solid product had an isopropyl group, and the solid product was shifted to a lower magnetic field than the chemical shift of the isopropyl group of the tetraisopropoxytitanium material. In the present invention, having a hydrogen atom shifted to a low magnetic field means that all the hydrogen atoms are shifted to a low magnetic field as compared with the raw material, and Including cases.

From Fig. 2, it was found that a part of the methine carbon of the isopropyl group of tetraisopropoxytitanium as a raw material was shifted to a low magnetic field, and a part of the methyl carbon was shifted to a high magnetic field.

From Fig. 3, it can be seen that the relaxation time of the peak shifted to the high magnetic field side and the peak shifted to the low magnetic field side is shorter than that of the peak that does not shift, and the two carbons with the same bonding state but different environments exist. I understand. Example 2

Using H ₂ 0 ¹⁷ (O ¹⁷ content: 20.3 atomic%) instead of ion-exchanged water, the same procedure was carried out on a 1/10 scale of Example 1 to remove solid matter in which 〇 ¹⁷ was incorporated. Obtained. The resulting solid was dissolved in deuterated benzene, were measured 0 ¹⁷ NMR. Figure 4 shows the results.

From FIG. 4, it was measured and the integral value, ³ oxygen atoms: ^ ² oxygen atoms: / molar atomic ratio of X ⁴ oxygen radicals is 85: 13: 1.

Example 3

The solution obtained in Example 1 was applied to a polyethylene terephthalate (PET) substrate whose surface was treated with ozone using No. 3 barco overnight, dried at 100 ° C. for 10 minutes, and dried. A transparent metal oxide film was formed thereon. When the shape of the film surface was measured using an SPM device (Seiko Instruments, SPA-400 (SII)), the average roughness of the surface was 5 nm or less. The surface of the material film was found to be smooth.

Industrial applicability:

As described above, the hydrolysis product obtained by hydrolyzing the metal alkoxide of the present invention is a monodisperse fine particle having a small average particle size, and is a uniform and transparent solution even in an organic solvent. In addition, the film has a high industrial value because it can form a transparent and smooth metal oxide thin film and can be widely used as an optical material.

Claims

The scope of the claims

1. A product obtained by hydrolyzing a metal alkoxide, wherein 70 atomic% or more of oxygen atoms incorporated in the product in water used for the hydrolysis are ³ oxygen atoms. A metal alkoxide hydrolysis product.

2. A product obtained by hydrolyzing a metal alkoxide, and that at least 80 atomic% of oxygen atoms incorporated in the product in water used for the hydrolysis are i ³ oxygen atoms. Characterized metal alkoxide hydrolysis products.

3. The metal alkoxide hydrolysis product according to claim 1, wherein 30% by atom or less of oxygen atoms incorporated into the product in water used for hydrolysis are oxygen atoms.

4. The metal alkoxide hydrolyzate according to claim 2, wherein 20% by atom or less of oxygen atoms incorporated into the product in water used for the hydrolysis is / X ² oxygen atoms. object.

5. The metal alkoxide according to any one of claims 1 to 4, wherein 10% by atom or less of oxygen atoms incorporated into the product in water used for hydrolysis are / ⁴ oxygen atoms. Hydrolysis products.

6. gold according to any one of the preceding claims, characterized in that 5 atomic% or less of oxygen atoms incorporated into the product in water used in the hydrolysis, a 2 ⁴ oxygen atoms Alkoxide hydrolysis products.

7. When the metal alkoxide has formula (I)

M (OR) _η

(Wherein, M represents a metal atom, R represents a C 1- (10 alkyl group, and n represents a valence)). 7. The hydrolysis product of a metal alkoxide according to any one of 6.

8. Equation (I)

M (OR) _η

(Wherein, M represents a metal atom, R represents a C1-C10 alkyl group, and n represents a valence). A product obtained by hydrolyzing a metal alkoxide represented by Then, the product has a functional group represented by the above R, and the hydrogen atom in the functional group The chemical shift value of the nuclear magnetic resonance spectrum using tetramethylsilane as a standard of 0 ppm was shifted to a lower magnetic field than the chemical shift value of the hydrogen atom in R in the metal alkoxide represented by the formula (I). A metal alkoxide hydrolysis product having a hydrogen atom having the chemical shift value.

9. Formula (I)

M (OR) _η

(Wherein, M represents a metal atom, R represents a C1 to (: 10 alkyl group, and n represents a valence). A product having a functional group represented by the above OR in the product, wherein tetramethylsilane in the carbon-13 nuclear magnetic resonance spectrum of the carbon atom at the α-position of the oxygen atom in the functional group is 0. The standard chemical shift value of ppm is the chemical shift value of the metal alkoxide represented by the formula (I), which is shifted to a lower magnetic field than the chemical shift value of the oxygen atom in R at a lower magnetic field. Wherein the chemical shift value of the carbon atom at the 3-position of the oxygen atom in the functional group is higher than the chemical shift value of the oxygen atom in R in the metal alkoxide represented by the formula (I). The carbon atom having the chemical shift value shifted to A metal alkoxide hydrolysis product comprising:

10. Relaxation time (the metal alkoxide hydrolysis product according to claim 9, wherein the metal alkoxide has two kinds of carbon atoms having different Ts.

1 1. The relaxation time (1 \) of the carbon atom, which is the chemical shift value shifted to the low magnetic field, is the chemical shift value of the chemical shift region on the high magnetic field side higher than the chemical shift value shifted to the low magnetic field. The metal alkoxide hydrolysis product according to claim 9 or 10, wherein the hydrolysis time is shorter than a relaxation time of a certain carbon atom.

1 2. The relaxation time of the carbon atom, which is the chemical shift value shifted to a high magnetic field (Τ is the chemical shift value of the chemical shift region on the low magnetic field side lower than the value of the chemical shift 1, shifted to a high magnetic field) The metal alkoxide hydrolysis product according to any one of claims 9 to 11, wherein the metal alkoxide hydrolysis time is shorter than a relaxation time (1 \) of a certain carbon atom.

13. The metal alkoxide hydrolysis product has the property of being stably dispersed without aggregation in an organic solvent in the absence of an acid, a base, and Ζ or a dispersion stabilizer. The metal alkoxide hydrolysis product according to any one of claims 1 to 12, characterized in that:

14. The metal alkoxide hydrolyzate according to any one of claims 1 to 13, wherein the metal alkoxide is metal tetraisopropoxide and has a nuclear magnetic resonance spectrum shown in Figs. Decomposition products.