JP2002020107A - Metal oxide particle containing foreign metal, method for producing the same and use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide metal oxide particles containing a foreign metal and excellent particularly in functions such as heat ray shielding performance and visible light transmittance and to provide a method for producing the particles and their use. SOLUTION: The metal oxide particles have 0.5-20 at.% average foreign metal content and the central parts of the primary particles have >=0.5 at.% foreign metal content. In the method for producing the metal oxide particles, a solution containing a compound of the principal metal and/or a product prepared by hydrolyzing and condensing the compound, a compound of the foreign metal and an alcohol is heated under pressure to deposit the metal oxide particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a metal oxide particle which is imparted with properties such as heat ray shielding properties by adding a dissimilar metal and which has excellent properties, a method for producing the same and its use. About.

[0002]

2. Description of the Related Art Sn-containing indium oxide (ITO), S
b-containing tin oxide (ATO), Al-containing zinc oxide, and the like are known as white conductive particles. These metal oxide particles contain different metals, such as Sn, Sb, and Al, from 0.1 to 0.1%.
When it is contained in an amount of 20%, it may become a heat ray shielding agent excellent in visible light transmittance depending on the method of making it. For example, in the case of indium oxide-based or tin oxide-based metal, these different metal-added metal oxide particles are formed by hydroxide of each compound (chloride, nitrate, etc.) of the main component metal and the different metal with an alkali. Is obtained by firing at a high temperature.

[0003] However, zinc oxide (ZnO) containing dissimilar metals such as Al and In is produced by the above method.
Although it is conductive, it does not have heat ray shielding performance or does not reach a practical level. On the other hand, according to the manufacturing method developed by the present inventors (see Japanese Patent Application Laid-Open No. 8-253317), ZnO-based particles having heat ray shielding performance can be obtained. In this method, a mixture of a zinc source, a monocarboxylic acid, and an alcohol is heated in the presence of a compound of a Group IIIb metal element such as Al or In or a Group IVb metal element.

However, even the ZnO particles containing Al, In, etc. obtained by this method described in Japanese Patent Application Laid-Open No. 8-253317 are inferior in heat ray shielding performance as compared with ITO particles and ATO particles. When used as IT
In order to obtain the same heat ray shielding rate as a heat ray shielding film containing O or ATO, there is a problem that the coating amount has to be increased.

[0005] Since ITO particles and ATO particles are also expensive, it is required to reduce the amount of use by using particles having higher heat ray shielding performance.

[0006]

Accordingly, an object of the present invention is to provide a dissimilar metal-containing metal oxide particle having particularly excellent functions such as heat ray shielding performance and visible light transmittance, and particularly excellent heat ray shielding performance. ZnO, In ₂ O ₃ , Sn
An object of the present invention is to provide a conductive metal oxide particle such as an O ₂ -based particle, a method for producing the same and a use thereof.

[0007]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have analyzed ZnO-based particles containing Al, In, etc. from various aspects and pursued the causes of the above problems. As a result, it was found that the cause was that the added dissimilar metal was biased toward the surface of the primary particles and did not sufficiently exist inside. The inventors have found that the above-mentioned cause is solved by the presence of the added heterogeneous metal in the central portion of the primary particles at a certain value or more. Furthermore, a method suitable for producing such ZnO-based particles containing Al, In and the like has been found. Then, they have found that the above can be applied to metal oxide particles other than ZnO-based particles containing Al, In, etc., and completed the present invention.

Accordingly, the metal oxide particles containing different metals according to the present invention (hereinafter simply referred to as “metal oxide particles”).
Is the content (Md) of the different metal (Md) in the metal oxide-based particles obtained by adding the different metal (Md) to the metal (M).
d / M) is 0.5 to 20 atomic% on average, and 1
It is characterized by being at least 0.5 atomic% in the central part of the next particle.

According to the method of the present invention for producing a metal oxide particle containing a foreign metal, a compound of the metal (M) represented by the following general formula (I) and / or a compound of a hydrolysis condensate and a foreign metal (Md) And a step of heating a solution containing an alcohol to precipitate metal oxide particles, and is characterized by the following (a) and / or (b).

(A) The heating is performed under pressure.

(B) The amount of water in the solution is not more than 100 times by mole relative to the dissimilar metal (Md).

M (O) _{(mxyz) / 2} (OCOR) _x (OH) _y (OR ′) _z (I) (where M is an m-valent metal atom; R is a hydrogen atom, At least one selected from an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group;
R ′ is at least one selected from an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group which may have a substituent; m, x, y and z are x + y + z ≦
m, 0 <x ≦ m, 0 ≦ y <m, and 0 ≦ z <m. And, the metal oxide particle-containing composition according to the present invention,
It comprises the metal oxide particles according to the present invention in an amount of 0.1% by weight or more.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION [Metal Oxide Particles] In the metal oxide particles according to the present invention, the content (Md / M) of the foreign metal (Md) is such that the average of the entire primary particles is 0.5 to 0.5%. 20
Atomic% (preferably 1 to 10 atomic%, more preferably 2 atomic%
-10 at%, particularly preferably 4 at% or more),
And it is 0.5 atomic% or more (preferably 1 atomic% or more, more preferably 2 atomic% or more, particularly preferably 4 atomic% or more) in the central part of the primary particles.

[0014] The content of the different metal (Md) (Md /
The average value (average content) of all the primary particles in M) is α
av and the value of the central part of the primary particles (central content) as αc, the median content (αc / αav) with respect to the average content is
It is preferably 0.2 or more, more preferably 0.5
Above, most preferably 0.8 or more.

The method for measuring the average content αav and the median content αc is as follows. For an aggregate (in the case of αav) or a simple substance (in the case of αc) of primary particles, the FE-TEM (transmission electron microscope) While observing the transmission image, search for the place where there is no metal segregation outside the particle,
Perform elemental analysis with the following desired spatial resolution (spot diameter). Then, from the peak intensity belonging to each metal, the content of the dissimilar metal (Md) is determined. The lower limit of the spot diameter is 1 by narrowing the probe.
The diameter of the spot can be increased, and the spot diameter can be arbitrarily and continuously increased. For confirmation of segregated substances, see FE
-In a projection view obtained by observation with a TEM, it is generally assumed that there is no segregated substance if the level cannot be confirmed with the naked eye.

Regarding the measurement of the average content αav, more specifically, about 10 particles in which no segregation is observed as an aggregate of primary particles as observed by FE-TEM are included. The analysis is performed by elemental analysis at such a spatial resolution (spot diameter).

More specifically, regarding the measurement of the center content αc, a projection image of one primary particle is observed by a FE-TEM without segregation, and the central part of the projection image is spatially resolved by 1 nmφ. (Spot diameter) is to be performed by elemental analysis. When analyzing the central part of the projected image, it is usually sufficient to perform the part that is considered to be about the center of the projected image based on common sense, but at least the projection so that the spot does not touch the contour line of the projected image This may be performed inside the image. Preferably, the shape of the projected image is reduced in an area reduced to 80% on a length basis, more preferably in an area reduced to 50%, and still more preferably in a region based on the above-mentioned center. What is necessary is just to perform within the area reduced to%. Note that, for example, if the particle shape is a needle shape or the like and the shape of the projected image is a needle shape or the like, even if it is a common sense to determine the approximate center of the projected image, the spot set there is the spot of the projected image. Although it may be possible to come into contact with the contour line, in such a case, a region having a diameter equal to 50% of the length of the maximum length portion, centered on a portion that is considered to be approximately the center of the projected image is used. It should be done within. The final measurement result of the median content αc was an average value of 10 particles.

When the primary particles have a portion having a thickness (particle diameter) exceeding 30 nm (100 nm depending on the particles).
For example, a powder sample is mixed with an epoxy resin, and after curing, a thin section is obtained. From the thin section, the cross section of the primary particle is exposed by an ion milling method. It is preferable that the following ultra-thinned sample is obtained, and the above measurement is performed on the cross section of the primary particles of this ultra-thinned sample. The reason is that the thickness is 3
When the thickness exceeds 0 nm, the electron beam transmission of the FE-TEM becomes incomplete or the resolution of the XAM decreases, and the accuracy of the measurement result is lacking as all the information in the thickness direction is related to the analysis. It is because it is.

In the above measurement, a FE-TEM, for example, a field emission transmission electron microscope (H
F-2000 type, acceleration voltage 200 kV)
For example, an X-ray microanalyzer (Sigma type, energy dispersive type, beam diameter: spatial resolution 10 ° φ) manufactured by Kevex can be mentioned.

The main metal (M) and the dissimilar metal (Md) are not particularly limited. For example, Be, Mg, Ca,
Alkaline earth metal elements such as Sr, Ba, Ra; La, C
e; lanthanoid metal elements such as e; actinoid metal elements such as Ac; Group IIIa metal elements such as Sc and Y; Ti and Z
Group IVa metal elements such as r and Hf; Group Va metal elements such as V, Nb and Ta; Group VIa metal elements such as Cr, Mo and W;
Group VIIa metal elements such as Tc and Re; Fe, Co, Ni, R
Group VIII metal elements such as u, Rh, Pd, Os, Ir, and Pt; Group Ib metal elements such as Cu, Ag, and Au; Zn, Cd;
Group IIb metal element such as Hg; I such as Al, Ga, In, Tl
Group IIb metal elements; Group IVb metal elements such as Ge, Sn, and Pb;
Vb group metal elements such as Sb and Bi; VIb group metal elements such as Se and Te; and the like, and one or more kinds thereof may be present.

As the main metal (M), of the above specific examples, Zn, Ti, Ce, Fe, Ni, V, Nb, Be,
La, Mo, W, Re, In, Ga, Sn, Sb, etc.
Light, electricity, and magnetic functions can be controlled by metal valence, particle size, crystal structure, impurity implantation, defect implantation, and the like. For this reason, an optical function such as having a light selective transmission function such as an ultraviolet absorbing property and an infrared shielding property,
It is preferable in that it has a (photo) conductive function, a magnetic function and the like. Further, with Fe, Ni, V, Nb, Be, La, Mo, W and the like, highly transparent and stable particles can be obtained. Zn is
By controlling the crystal structure and controlling the impurity concentration, it becomes possible to control optical properties such as ultraviolet absorption and electrical properties, which is preferable.

The main metal (M) is, for example, In, S, because of its high heat ray shielding property and high transmittance of visible light.
n and Zn are preferred.

As the dissimilar metal (Md), a tetravalent metal is preferable when the metal oxide particles are indium oxide particles, for example, Sn, Ti, etc., because both the heat ray shielding property and the visible light transmittance are high. Is particularly preferred. When the metal oxide particles are tin oxide particles, a pentavalent metal element is preferable.
b, P, etc. are particularly preferred. When the metal oxide particles are zinc oxide particles, a trivalent metal element is preferable, and In, Al,
Ga and the like are particularly preferred.

The metal oxide particles according to the present invention include amorphous particles, and the oxide crystallinity of the metal (M) is determined by X-ray diffraction or electron diffraction. The ones shown are preferred. Usually, when the primary particle size is 5 nm or more, the primary particle size is 5 nm.
In the following cases, it is possible to confirm whether the compound is crystalline or not and to identify the crystal structure and physical properties by using an electron diffraction method.

The primary particle diameter of the metal oxide particles according to the present invention is preferably 0.1 μm or less from the viewpoint of high transparency. Specifically, the following (1) and / or (2) and / or
Or, it is particularly preferable to satisfy the condition (3).

(1) The size of a crystallite determined by X-ray diffraction (Wilson method) or electron beam diffraction method is expressed by Dw
1 nm ≦ Dw ≦ 100 nm.

(2) When the specific surface area diameter calculated by the following equation is Ds, 1 nm ≦ Ds ≦ 100 nm.

Ds = 6 / (ρ × S) Here, Ds: μm (provided that ρ: true specific gravity of metal oxide particles, S: BE.
T. Specific surface area (m ²
/ G)) (3) When a particle image is measured with a transmission electron microscope and the primary particle diameter obtained from the observation of the crystal lattice image and the size is defined as De, 1 nm ≦ De ≦ 100 nm.

The metal oxide particles of the present invention preferably have a primary particle diameter of 1 to 30 nm from the viewpoint of excellent transparency, and have a primary particle size of 5 to 30 nm when used as a heat ray shielding agent or a conductive material.
It is preferable that nm ≦ Dw ≦ 30 nm.

The metal oxide particles according to the present invention preferably contain a carboxylic acid (residual) group. Here, the carboxylic acid (residue) group means a -COO- group, specifically, a carboxyl group (-COOH), carboxylate group (-COO ^-), a carboxyl group and / or carboxy by hydrolysis It means an ester group that generates a rate group. As the carboxylic acid (remaining) group, a saturated fatty acid (remaining) group is preferable, and a fatty acid having 1 to 4 carbon atoms (remaining).
Group is more preferable, and an acetoxy group (CH ₃ COO—)
Is most preferred.

Since the carboxylic acid (residue) group is present on the surface of the metal oxide particles by adsorption and / or chemical bonding, secondary aggregation is suppressed and dispersibility is improved. When the resulting resin composition is used as a coating material, the transparency of the coating film increases.

The content of the carboxylic acid (residual) group is preferably 0.01 to 14 mol%, more preferably 0.1 to 7 mol%, and most preferably 1 to 5 mol% based on the metal (M). is there. When the content of the carboxylic acid (residual) group is less than 0.01 mol% based on the metal (M), the dispersibility of the particles is reduced, and the particles are liable to undergo secondary aggregation. On the other hand, when the content of the carboxylic acid (residual) group is more than 14 mol% with respect to the metal element (M), the function as a metal oxide, for example, the infrared ray shielding property and the ultraviolet ray shielding property are reduced.

The particle shape of the metal oxide particles according to the present invention is not particularly limited. Specific examples of the shape include a flaky shape such as a spherical shape, an elliptical spherical shape, a cubic shape, a rectangular shape, a pyramid shape, a needle shape, a column shape, a rod shape, a tubular shape, a scale shape, a (hexagonal) plate shape, and the like. [Method for Producing Metal Oxide Particles] The method for producing the above-mentioned metal oxide particles is not particularly limited, and for example, the following method can be mentioned as a preferable method.

The method includes the step of heating a solution containing a compound of a metal (M) and / or a hydrolyzed condensate, a compound of a different metal (Md) and an alcohol to precipitate metal oxide particles, and comprises the following (a) And / or (b).

(A) The heating is performed under pressure.

(B) The amount of water in the solution is not more than 100 times the molar ratio with respect to the dissimilar metal (Md).

Regarding the above (a), the pressure during heating is
If the absolute pressure P is 1 kg / cm ^{2 at} normal pressure (atmospheric pressure), P> 1 kg / cm ² is satisfied, and preferably 1.5 k
g / cm ² ≦ P ≦ 100 kg / cm ² . It is particularly preferable that 3 kg / cm ² ≦ P ≦ 20 kg / cm ² is satisfied in that the effect of pressurization is high and that it can be performed with economical equipment, and 5 kg / cm ² ≦ P ≦ 10 kg /
It is most preferable to satisfy cm ² .

As the pressurizing method, for example, a method of heating to a temperature higher than the boiling point of alcohol, a method of pressurizing the gas phase with an inert gas such as nitrogen gas or argon gas, and the like can be adopted.

The heating temperature depends on the boiling point of the alcohol, etc., but is preferably 50 ° C. to 300 ° C., more preferably 100 ° C. to the critical temperature of the alcohol, and most preferably 20 ° C. or higher than the normal pressure boiling point of the alcohol. Temperature.

In the case of the above (b), the amount of water in the solution means a free amount of water. However, when the compound of the metal (M) or the compound of the different metal (Md) has water of crystallization, Water is also included. This water content can be measured by the Karl Fischer method. The amount of water as used herein refers to the amount of water contained in the raw material used (free water in the used alcohol and other solvent components, water of crystallization in the compound of the metal (M) and the compound of the different metal (Md), etc.). (Sum of water) means the molar ratio of the total foreign metal (Md) to the total foreign metal (Md) in the compound, and does not consider water by-produced in the heating reaction.

The amount of water depends on the type of foreign metal (Md) used.
The molar ratio to the total amount is preferably 50 times or less, more preferably 20 times or less. If the water content is too large, it is difficult for the metal (M) oxide to contain the foreign metal (Md) in the crystallites, and it is difficult to obtain highly functional foreign metal-containing metal oxide particles.

The compound of the main metal (M) has a structure represented by the following general formula (I). Specifically, it has been described above in the description of the metal oxide particles.

M (O) _{(mxyz) / 2} (OCOR) _x (OH) _y (OR ′) _z (I) (where M is an m-valent metal atom; R is a hydrogen atom, At least one selected from an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group;
R ′ is at least one selected from an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group which may have a substituent; m, x, y and z are x + y + z ≦
m, 0 <x ≦ m, 0 ≦ y <m, and 0 ≦ z <m. )
In the general formula (I), R or R ′ is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, since a metal oxide-based particle having high dispersibility is easily obtained. preferable. In the above general formula (I), x preferably satisfies 1 ≦ x ≦ m, and y is 0.
≦ x <m / 2 are preferable, and z is 1 ≦
Those satisfying x <m / 2 are preferable. In these cases,
This is because metal oxide particles having high dispersibility can be easily obtained.

It is preferable to use a compound represented by the general formula (I) having a high dissolution rate because particles having excellent dispersibility can be obtained. Here, the dissolution rate can be measured directly by reaction, but at 25 ° C., the formula (I)
2 parts by weight of the compound (hereinafter abbreviated as "parts") are mixed with 200 parts of 25. +-. 3.degree. C. ion-exchanged water (pH 5-8) and stirred until completely dissolved to obtain a transparent solution. It is defined by t. The dissolution rate of the compound represented by formula (I) is preferably within 2 minutes, more preferably within 1 minute, and most preferably within 30 seconds.

The hydrolysis condensate of the compound represented by the general formula (I) is obtained by hydrolyzing and / or condensing a compound of the metal element (M) having a structure represented by the general formula (I). It is a decomposition product and / or a condensate, and is a compound from a monomer to a polymer compound. The condensate is a compound having a bond chain-(MO) _n (where n is 1 or more) in which a main metal (M) element and oxygen (O) are metalloxane-bonded. The degree of condensation of the condensate is not limited,
In order to obtain metal oxide particles having a uniform crystallite size and shape, the degree of condensation (average) is preferably 100 or less,
More preferably, it is 10 or less.

The compound of the different metal (Md) used in the production method according to the present invention is, for example, a chemical structure in which the metal element (M) in the above general formula (I) is replaced with the above-mentioned metal element (Md). And alkoxides of different metals (Md). The former is specifically described above in the section of metal oxide particles.

The alcohol used in the production method according to the present invention is not particularly limited. For example, a monohydric alcohol having high water solubility is preferable. Such alcohols include, for example, the following A) to C)
Such alcohols having a solubility in water of 1% by weight or more can be mentioned, and alcohols having a solubility in water of 10% by weight or more are more preferable.

A) C 1-3 quaternary aliphatic alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, sec-butanol, t-butyl alcohol; B) cyclohexanol; Benzyl alcohol C) glycol derivative a) ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-
Butyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoisopropyl ether, propylene glycol mono n-butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, 3-methyl-
Alkylene glycol ethers such as 3-methoxybutanol b) alkylene glycol acetates such as ethylene glycol acetate and propylene glycol acetate In the production method according to the present invention, the compound (I) of the main metal (M) and / or its hydrolytic condensation The product and the alcohol are mixed to prepare a solution containing them. The solution mentioned here includes an emulsified or suspended one. The same applies to compounds of different metals. The mixing may be a method in which a powder of a metal compound (hydrolyzed condensate) is directly added to alcohol, or a suspension or a diluted solution is prepared in advance by adding it to another solvent. Alternatively, it may be added to alcohol. As a solvent used for preparing a suspension or a diluted solution, alcohol or an acetate thereof is preferable, and alcohol used for heating and holding is more preferable.

In the production method of the present invention, a mixture containing the compound of the main metal (M), the compound of the dissimilar metal (Md) and the alcohol is heated. A series of operation procedures from mixing to heating are not particularly limited. Without, for example, 1) preparing the above mixture at room temperature or at 50 ° C. or lower,
A method of raising the temperature and heating, and 2) heating at least one of the compound of the main metal (M) and the compound of the dissimilar metal (Md) and the alcohol, preferably under heating,
A preheating method in which the other material is mixed with a heated material is preferably used. As the preheating method, specifically, for example, a) a method in which an alcohol is heated and a compound of a main metal (M) and a compound of a different metal (Md) are added; Compounds and compounds of different metals (Md) (or their suspensions, homogeneous solutions)
Is heated and alcohol is added, c) a compound of alcohol and main metal (M) and a different metal (Md)
(Or their suspensions and homogeneous solutions) are separately heated and mixed. Among the methods 1) and 2), the preheating method 2) is more preferable, and the reaction temperature can be easily selected.
Control of particle size and composition can be easily performed. At this time, in the method of mixing at least one of the pre-heated under the pressurized state, the heat treatment under the pressurized state can be started at the same time as the mixing, so that the particles having a high content of the foreign metal (Md) can be obtained. Is preferable because it is easily obtained.

The method of adding and mixing the metal compound (hydrolyzed condensate) with alcohol or another solvent is not particularly limited, and the total amount can be added all at once, for example, a batch addition method of adding and mixing within one minute, or a one-minute addition method. , Or a pulse addition method (each pulse may be a continuous feed, or a batch addition) in which a small amount is added in two or more portions at a time. In this case, it is preferable that the change in temperature of the alcohol-containing solution caused by the addition is small because particles having a uniform primary particle diameter can be easily obtained. Specifically, it is preferable to control the addition rate and the like so that the temperature change of the solution falls within 10 ° C.

When the metal compound (hydrolysis condensate) is mixed with an alcohol or another solvent, the addition rate is determined by the following equation: [Mole of metal compound (hydrolysis condensate) / alcohol (mol) / addition time ( Min)], preferably 0.0001 to 2, more preferably 0.000
5 to 1.0. If the addition rate is less than 0.0001, it may be difficult to obtain primary particles having a particle size of 0.1 μm or less. On the other hand, if the addition rate exceeds 2, the above-mentioned temperature control becomes difficult particularly when the reaction scale is large, and it is difficult to obtain particles having a uniform particle diameter.

The mixing ratio between the metal compound (hydrolysis condensate) and the alcohol is not particularly limited, but is represented by the molar ratio in terms of charge after the completion of the addition of the total amount of the metal compound (hydrolysis condensate). However, in order for the dissimilar metal Md to be uniformly contained in the primary particles, the valence of the metal (M) is preferably m or more, more preferably 2 m or more. The upper limit of the molar ratio is preferably 50 or less, more preferably 20 or less, from the viewpoint of productivity.

In the production method according to the present invention, the predetermined temperature is maintained for 30 minutes or more in order to enhance the crystallinity of the particles and enhance the performance such as the heat ray shielding performance. The temperature is 180 ° C. or more for 1 hour or more, more preferably 200 ° C. or more for 3 hours or more. Here, the heating temperature is represented by the bottom temperature of the reaction vessel.

In the production method according to the present invention, during heating, the solution is preferably stirred with a required stirring power of 0.0001 kw / m ³ or more, more preferably 0.001 kW / m ^3.
w / m ³ or more, and it is particularly preferable that stirring is performed at 0.01 to 10 kw / m ³ .

In the production method according to the present invention, an aliphatic carboxylic acid or aliphatic amine may be added at any stage after the addition of the metal compound (hydrolysis condensate) in order to enhance the dispersibility of the obtained particles. 0.1 to 10 mol% is added to the main metal (M). When no aliphatic carboxylic acid or aliphatic amine is added, the metal oxide particles may become secondary aggregate particles depending on the type of the main metal (M).

According to the production method of the present invention, it is possible to easily obtain metal oxide-based particles containing an additional metal, having excellent functions such as heat ray shielding performance and visible light transmittance. [Uses of Metal Oxide Particles] The metal oxide particles according to the present invention contain 0.1% by weight of the above-described metal oxide particles of the present invention.
It is a composition containing the above. For example, it is a coating composition, a molding material composition, or a film containing the above-mentioned different metal-containing metal oxide particles in an amount of 0.1% by weight or more based on the binder resin. Since this composition contains the metal oxide particles according to the present invention, it has particularly excellent properties such as heat ray shielding properties.

Hereinafter, the coating composition, the molding material composition, and the metal oxide particle-containing film will be described in detail in this order. Coating composition The coating composition is excellent in various functions such as an optical function such as a light selective transmission function, an electrical function such as a conductive function, and a catalytic function such as a photocatalytic function, and also provides a coating film having high weather resistance. be able to. In particular, those containing metal oxide particles having excellent heat ray shielding properties of the present invention are useful because they are economical, have excellent thermal shielding properties and visible light transmittance.

As the binder resin used in the coating composition, various kinds of synthetic resins such as thermoplastic or thermosetting (including thermosetting, ultraviolet curable, electron beam curable, moisture curable, and combinations thereof) and the like can be used. Organic binders such as natural resins and inorganic binders can be exemplified.

Examples of the synthetic resin include alkyd resin, amino resin, vinyl resin, acrylic resin, epoxy resin, polyamide resin, polyurethane resin, thermosetting unsaturated polyester resin, phenol resin, chlorinated polyolefin resin, silicone resin, Acrylic silicone resin, fluororesin, xylene resin, petroleum resin, ketone resin, rosin-modified maleic resin, liquid polybutadiene,
Coumarone resins and the like can be mentioned, and one or more of these are used. As a natural resin, for example,
Shellac, rosin (pine resin), ester gum, cured rosin, decolorized shellac, white shellac, and the like,
One or more of these are used.

As the synthetic resin, natural or synthetic rubbers such as ethylene-propylene copolymer rubber, polybutadiene rubber, styrene-butadiene rubber, and acrylonitrile-butadiene copolymer rubber may be used. Examples of components used in combination with the synthetic resin include cellulose nitrate, cellulose acetate butyrate, cellulose acetate, ethyl cellulose, hydroxypropylmethyl cellulose, and hydroxyethyl cellulose.

The form of the binder resin used in the coating composition is not particularly limited, and examples thereof include a solvent-soluble type, a water-soluble type, an emulsion type, and a dispersion type (any solvent such as a water / organic solvent). Can be.

Examples of the water-soluble binder resin include a water-soluble alkyd resin, a water-soluble acryl-modified alkyd resin, a water-soluble oil-free alkyd resin (water-soluble polyester resin), a water-soluble acrylic resin, a water-soluble epoxy ester resin, Water-soluble melamine resins and the like can be mentioned.

Examples of the emulsion-type binder resin include alkyl (meth) acrylate copolymer dispersion; vinyl acetate resin emulsion, vinyl acetate copolymer resin emulsion, ethylene-vinyl acetate copolymer resin emulsion, and acrylic acid ester (copolymer). ) Polymerized resin emulsion, styrene-acrylate (co)
Examples thereof include a polymerized resin emulsion, an epoxy resin emulsion, a urethane resin emulsion, an acryl-silicone emulsion, and a fluororesin emulsion.

As the inorganic binder, silica gel,
Examples thereof include metal alkoxides such as alkali silicic acid and silicon alkoxide, (hydrolyzed) condensates thereof, and phosphates.

When the coating composition is used for the production of an ultraviolet-absorbing film to be described later or the like, the coating composition is used in view of the film-forming conditions such as the film-forming temperature and the flexibility and weather resistance of the obtained film. As the binder resin to be obtained, polyurethane resin, acrylic resin, fluorine resin and the like are preferable.

The proportion of metal oxide particles in the coating composition is
For example, the content is 0.1 to 99% by weight, preferably 10 to 90% by weight, based on the total solid content of the metal oxide particles and the binder resin. When the proportion of the metal oxide particles is less than 0.1% by weight, the effect obtained by adding particles having ultraviolet shielding properties, conductivity and the like is reduced.
On the other hand, when the ratio of the metal oxide particles exceeds 90% by weight,
Visible light transmission and flexibility are reduced. When the metal oxide particles contained in the coating composition are conductive and the coating film obtained from the coating composition is used as a functional film such as a conductive film or an antistatic film, the proportion of the metal oxide particles in the coating composition Is more preferably 50 to 90% by weight, and most preferably 70 to 85% by weight, based on the total solid content of the metal oxide particles and the binder resin.

In addition to the metal oxide particles and the binder resin, the coating composition comprises a curing agent such as a crosslinking agent, a curing catalyst such as a curing assistant, a plasticizer, an antifoaming agent and a leveling agent, in accordance with required performance.
Thixotropic agents; matting agents; surfactants; flame retardants;
Pigment wetting agents / dispersants; lubricants; UV absorbers; light stabilizers;
Antioxidants; other (heat) stabilizers; preservatives; fungicides;
It may contain additives such as an anti-algal agent; an anticorrosion / rust inhibitor; a dye; and a pigment.

As the curing agent, for example, air (oxygen)
A curing agent used for a drying oil system such as a polyester resin such as a monofunctional or polyfunctional unsaturated monomer, a polyacrylic resin, an epoxy resin; a polyamine containing a primary or secondary amino group, a polyamide or the like; , A curing agent used for an amino resin having a methylol group, a binder resin having an epoxy group such as a polybasic acid having a carboxyl group or a high acid value polyester; a polyisocyanate having an isocyanate group, a polyisocyanate having a urethane group, a methylol group A curing agent used for a binder resin having a hydroxyl group such as an amino resin having a primary and / or secondary amino group or an alkoxymethylene group; a curing agent used for a binder resin having a carboxyl group such as a metal chelating agent; , Polyfunctional epoxy compounds, hydroxyl-containing compounds, etc. Curing agent used in the binder resin having a silicone group can be exemplified, and these are used singly or in combination.

When the coating composition is used for the production of a film containing metal oxide particles described later, weather resistance is improved if the coating composition contains a light stabilizer. When the coating composition contains a polyisocyanate as a curing agent, the versatility is high. As a method for curing the coating composition when producing a film, a heat curing method is economically preferable.

The coating composition may contain a solvent,
It is appropriately selected depending on the purpose of use of the coating composition and the type of the binder resin. Examples of the solvent include organic solvents such as alcohols, aliphatic and aromatic carboxylic esters, ketones, ethers, ether esters, aliphatic and aromatic hydrocarbons, and halogenated hydrocarbons; Mineral oil; vegetable oils, wax oils, silicone oils, etc., and one or more of these are used.

As a method for producing a coating composition, for example, after adding metal oxide particles to an organic solvent to form a slurry, a slurry containing the metal oxide particles is mixed with a binder resin to prepare the coating composition. And the like.

The coating composition can be applied to the surface of a substrate such as an inorganic substance such as glass and ceramics, or an organic substance such as a resin. In particular, a coating film obtained by coating an organic substrate surface has high weather resistance and excellent flexibility. The shape of the inorganic or organic substance is not particularly limited, and examples thereof include a film, a sheet, a plate, and a fiber. Among these, they are useful for films, fibers, and the like described below.

The material of the resin used as the base material is not particularly limited. For example, LDPE, HDP
E, polypropylene such as amorphous polyethylene, OPP (stretched polypropylene) and CPP (crystallized polypropylene), and polyolefins such as polyisobutylene;
EVA (ethylene / vinyl acetate copolymer) system; polystyrene system; soft or hard polyvinyl chloride; EVOH (ethylene / vinyl alcohol copolymer) system; PVA system (vinylon system); PVDC system (polyvinylidene chloride); Polyesters such as terephthalate, polyethylene naphthalate and polybutylene naphthalate; polycarbonates; polyurethanes; polyamides; polyimides; polyacrylonitriles; polysulfones; polyethersulfones; polyphenylene sulfides; Imide type; aramid type; (meth) acrylic type; polyether ether ketone type; tetrafluoroethylene / ethylene copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, polytetra Ruoroechiren, polytrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride,
Examples thereof include tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene / hexafluoropropylene / perfluoroalkyl vinyl ether copolymer, and fluorine-based resins such as polychlorotrifluoroethylene.

When used in applications requiring extremely high visible light transmittance and transparency, such as optical lenses, the PMM
A, MMA-styrene random copolymer, polycarbonate, transparent polypropylene, MMA and a copolymer such as α-methylstyrene or cyclohexyl methacrylate,
MMA modified type of ABS resin, polystyrene, polyarylate, polysulfone, polyethersulfone,
Various resins such as transparent epoxy resin, poly-4-methylpentene-1, fluorinated polyimide, amorphous fluorine resin, transparent phenoxy resin, amorphous nylon resin, and fluorene-based resin can be used as the base material.

From the viewpoint of disposal, the use of a biodegradable resin as a base material becomes more and more important in order to meet the demand for biodegradability. In such a case, for example, poly-3-hydroxybutyrate,
Chitin / chitosan, polyamino acid, cellulose,
It is preferable to use biodegradable plastics such as polycaprolactone, alginic acid, polyvinyl alcohol, aliphatic polyester, saccharide, polyurethane, and polyether as base materials.

As the base material, a base material in which a UV absorbing film is previously arranged on the above-described base material, or a base material in which a primer layer or the like is previously arranged for the purpose of enhancing the adhesion between a coating film composed of a coating composition and the base material, etc. It may be something.

Among these, plastic films,
Among the sheets, a fluororesin, a polyester resin, a (meth) acrylic resin, and a polycarbonate resin are preferable from the viewpoint of high weather resistance.

The method for applying the coating composition is not particularly limited, and examples thereof include dipping, roll coater, flow coating, screen printing, bar coater, spin coater, brush coating, and spraying. be able to. The dry film thickness obtained by applying the coating composition is not particularly limited, and is preferably 0.5 to
It is 100 μm, more preferably 1 to 30 μm.

After coating and film formation of the coating composition, water resistance,
In terms of chemical resistance such as solvent resistance, acid resistance, alkali resistance, etc., and abrasion resistance, it should be a cured film by a curing method such as thermal curing (including room temperature curing), moisture curing, ultraviolet curing, and electron beam curing. Is preferred.

A laminated glass can be obtained by using a coated transparent plate in which an intermediate film obtained by applying the coating composition to a transparent plate such as a glass plate is formed on the transparent plate. Laminated glass can be manufactured by stacking an adhesive sheet so as to be sandwiched between a coated transparent plate and a separately prepared transparent plate. The interlayer of the coated transparent plate and the adhesive sheet are overlapped.

As the adhesive sheet, a sheet made of a soft resin or a hard resin such as a polyvinyl butyral resin, a polyurethane resin, an ethylene-vinyl acetate copolymer resin, an ethylene- (meth) acrylate copolymer resin, or the like is used. And a soft resin is preferable.
The thickness of the adhesive sheet is preferably 0.1 to 2 mm, more preferably 0.5 to 1 mm. Molding material composition This molding material composition has an optical function such as a light selective transmission function,
It is possible to obtain a molded article excellent in various functions such as an electric function such as a conductive function and a catalytic function such as a photocatalytic function, and having high weather resistance and flexibility.

As the binder resin used in the molding material composition, polyamide (6-nylon, 66-nylon, 12-nylon, etc.), polyimide, polyurethane,
Polyolefin (polyethylene, polypropylene, etc.),
Heat of polyester (PET, PBT, PEN, etc.), polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polystyrene, (meth) acrylic resin, ABS resin, silicone resin, fluororesin, and monomers used as raw materials for these Thermoplastic resins such as phenolic resins (phenol-formalin resins, cresol-formalin resins, etc.), epoxy resins, amino resins (urea resins, melamine resins, guanamine resins, etc.) and monomers used as raw materials for these resins These may be used alone or in combination of two or more.

Examples of the binder resin used in the molding material composition include soft or hard resins such as polyvinyl butyral, polyurethane, ethylene-vinyl acetate copolymer, and ethylene- (meth) acrylate copolymer. And these may be one or two
Used over seeds.

As the binder resin used in the molding material composition, the above-mentioned inorganic binder may be used.

The proportion of the metal oxide particles in the molding material composition is, for example, 0.1 to 99% by weight, preferably 0.3 to 99% by weight, based on the total solid content of the metal oxide particles and the binder resin. 10% by weight. When the proportion of the metal oxide particles is less than 0.1% by weight, the effect obtained by adding particles having ultraviolet shielding properties, conductivity and the like is reduced. On the other hand, when the proportion of the metal oxide particles exceeds 99% by weight, the strength, the visible light transmittance and the flexibility are reduced.

In addition to the metal oxide particles and the binder resin, the molding material composition comprises a curing agent, a curing accelerator, a coloring agent, a release agent, a coupling agent, a silicone compound, a reactive diluent, a plasticizer, in accordance with required performance. And additives such as a stabilizer, a flame retardant auxiliary, a crosslinking agent and the like.

A curing agent may be required when a thermosetting resin is used as a binder resin. For example, when an epoxy resin is used as the binder resin, polyamides, aliphatic polyamines, cycloaliphatic polyamines, aromatic polyamines or partially modified amines, acid anhydrides, dicyandiamides, imidazole , Amine imides, hydrazides, phenol novolak, novolak-based curing agents such as cresol novolak, and the like, and one or more of these are used. When a phenol resin is used as the binder resin, urotropin, formal, and the like can be used, and one or more of these are used. These amounts are used in appropriate amounts with respect to the binder resin.

The plasticizer is used to further improve the processability of the composition and includes, for example, phosphates, phthalates, aliphatic- or dibasic esters,
Examples thereof include dihydric alcohol esters, oxyacid esters, and polyglycols. Particularly, when an epoxy resin is used as the binder resin, polyglycols are preferable. The stabilizer suppresses decomposition of the binder resin, and examples thereof include lead stearate and zinc stearate.

As a method for producing a molding material composition, for example, metal oxide particles and a binder resin are rolled,
Examples thereof include a method of uniformly mixing using a mixing device such as a kneader and a mixer.

Examples of the molding method of the molding material composition include extrusion molding, injection molding, casting, compression molding, low-pressure transfer molding, and cast molding.

The molding material composition may be formed into a film, for example, and the resulting film has high heat ray shielding properties of particles and excellent visible light transmittance.

A laminated glass can be obtained by sandwiching a metal oxide particle-containing sheet obtained by molding the molding material composition between transparent plates such as a glass plate and curing it appropriately. The thickness of the metal oxide particle-containing sheet is preferably 0.1 to 2 mm, more preferably 0.5 to 1 mm. Metal oxide particle-containing film The metal oxide particle-containing film is a film in which a coating film obtained from the metal oxide particle-containing composition (coating composition) according to the present invention is formed on a base film. Since the metal oxide particle-containing film contains the metal oxide particles of the present invention, it is excellent in various functions such as an optical function such as a light selective transmission function, an electric function such as a conductive function, and a catalytic function such as a photocatalytic function. , High weather resistance.

Examples of the base film used for the metal oxide particle-containing film include a film made of a resin used as a base, which has been described in detail in the section of the coating composition. The same applies to preferred ones.

The thickness of the substrate film is not particularly limited, and is preferably 5 to 500 μm, more preferably 10 to 200 μm.

The method of applying the coating composition on the surface of the base film, the dry film thickness, and the like are not particularly limited, and those described above are preferable.

The metal oxide particle-containing film is not particularly limited as long as the coating film obtained from the coating composition is formed on a base film, and is further processed according to the intended use, required characteristics and the like. May be. The metal oxide particle-containing film has a surface of a coating film that is not in contact with the base film, and / or
Alternatively, an adhesive layer or a protective layer (such as a hard coat film for imparting abrasion resistance) may be formed on the surface of the base film which does not come into contact with the coating film, and may be a laminated film laminated with another film. Is also good.

The ultraviolet transmittance when the film containing metal oxide particles is used as an ultraviolet shielding film is not particularly limited, but is preferably 50% or less, more preferably 10% or less. UV transmittance is based on JIS R
This is a value obtained by the apparatus and measuring method described in 3106.

The visible light transmittance of the film containing metal oxide particles is not particularly limited, but is preferably 70% or more, more preferably 80% or more. The visible light transmittance is measured in a wavelength range of 380 to 780 nm, and is measured according to JIS R
This is a value obtained by the apparatus, measurement method, and calculation method described in 3106.

The haze of the film containing metal oxide particles is not particularly limited, but is preferably 10% or less, more preferably 5% or less, and most preferably 3% or less. Haze is a value obtained by measuring with a turbidimeter.

The weather resistance of the film containing metal oxide particles is as follows:
An accelerated weather resistance test was performed using a shine-shine carbon arc lamp type light resistance and weather resistance tester described in JIS B 7753-93, and the haze value and the hue after the initial 100 hours were further referred to as an additional 1000 hours. When the haze value and hue after the test were compared, the change in haze was 2%.
It is preferable that it is less than, and it is more preferable that there is no coloring (color change).

[0101]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

The evaluation and the like in this embodiment were performed by the following method. 1. Evaluation of metal oxide particles <Preparation method of powder sample> After separating the fine particles in the obtained dispersion by centrifugation, washing with methanol,
After sufficient washing with acetone, 30 ° C
It was vacuum-dried daily, and further vacuum-dried at 80 ° C. for one day to completely remove volatile components to obtain fine particle powder, which was used as a powder sample. <Content of Different Metals (Md)> The average content αav and the median content αc were determined by the method defined above.

The content αav-1 shown in Table 2 is determined by setting the spot diameter in which all of about 1000 particles are included even in a state where segregation is observed in the above-described method for measuring the average content αav. Metals (M
d) content rate. In Table 2, the fact that the value of the content αav is lower than the value of the content αav-1 in the particles P-1 and Pc-1 means that the particles P-1 are slightly segregated and the particles Pc − 1 means that a large amount of segregation was observed.

For the above measurement, FE-TEM (field emission type transmission electron microscope, manufactured by Hitachi, HF-2000 type, acceleration voltage 200 kV) and XMA (X-ray microanalyzer,
Kevex, Sigma type, energy dispersive type, beam diameter (spatial resolution: 10Åφ), and main metal (M)
The average content (αav) and the median content (αc) of different metals (Md) were determined. <Carboxylic acid (remaining) group content>
After mixing with an aqueous solution of N sodium hydroxide and stirring for 3 days, the supernatant obtained by centrifugation was measured by ion chromatography analysis. Here, the mole% of the carboxylic acid (remaining) group such as an acetoxy group relative to the main metal (M) was calculated. <Crystallinity> Evaluated by powder X-ray diffraction. <Crystallite diameter Dc (hkl), Dw> The powder sample was determined by powder X-ray diffraction measurement.

Dc (hkl): Scherrer method (C
Auxiliary function approximation) to obtain a crystallite diameter in a direction perpendicular to each diffraction plane (hkl) Dw: crystallite size and lattice strain obtained by using the Wilson method Evaluation of Coated Film <Heat ray shielding performance> Particles were dispersed in an acrylic resin binder, formed into a film on a PET film so that the particles became 10 g / m ^2, and the transmittance T _1.5 at _1.5 μm light was measured. It was determined based on the following criteria.

：: T _1.5 <40% ×: T _1.5 ≧ 40%-Example 1 (1)-Equipped with a stirrer, an addition port, a thermometer, a distillate gas outlet, a nitrogen gas inlet, and a pressure regulating valve, Pressure 1 that can be heated more
A stainless steel (SUS316) reactor of 00 kg / cm ² , and an addition tank directly connected to the addition port via a ball valve,
A reactor equipped with a cooler directly connected to the distillate gas outlet and a distillate trap (withstand pressure of 100 kg / cm ^{2 for} the entire reactor) was prepared. This reactor was charged with 1000 parts of 2-butoxyethanol (hereinafter, EGB), and the gas phase was replaced with nitrogen gas. Then, the temperature was raised from room temperature, and nitrogen was introduced to bring the gas phase pressure to 5 kg / cm ² . Keep the liquid temperature at 160
C. was maintained.

Then, anhydrous zinc acetate (manufactured by Matsugaki Pharmaceutical Co., Ltd.)
E. 152 parts and 4.85 parts of indium acetate anhydride were powdered with E
The raw material suspension (A-
1) was prepared and charged in an addition tank. Gas phase pressure 5kg / c
m ² , the EGB solvent maintained at a bottom temperature of 160 ° C.
The raw material suspension (A-1) was added and mixed from the addition tank in 30 seconds. The liquid temperature was once decreased to 140 ° C. by the addition, but returned to 160 ° C. after 13 minutes, and thereafter, 160 ° C. ±
By maintaining the gas phase pressure at 5 ° C./cm ² for 6 hours at 3 ° C., a suspension of In-containing ZnO particles (P-1) (D-
1) was obtained.

-Comparative Example 1- The same raw material suspension (A) as in A-1 in Example 1 (1)
c-1) was added to EGB maintained at normal pressure and 160 ° C. in the same manner, except that the In-containing ZnO particles (Pc-
A suspension (Dc-1) of 1) was obtained.

Table 2 shows the analysis results of the particles obtained in Example 1 (1) and Comparative Example 1.

-Examples 1 (2) to 1 (4)-Each raw material suspension shown in Table 1 was prepared and added under the temperature and pressure conditions shown in Table 1, and the temperature and pressure shown in Table 1 were added. Except that the heat treatment was performed under the same conditions as in Example 1 (1),
The reaction was performed to obtain suspensions (D-2 to D-4) of the respective oxide particles (P-2 to P-4). The propylene glycol monomethyl ether used as a solvent is referred to as PGM hereinafter.
Called.

Table 2 shows the analysis results of the particles P-1, P-2, and Pc-1 obtained in Example 1 (1), Example 1 (2), and Comparative Example 1.

-Example 1 (5)-n-butanol 90 was added to the reactor in Example 1 (1).
After charging 0 parts and replacing the gas phase with nitrogen gas, the temperature was raised from room temperature, and the liquid temperature was maintained at 280 ° C. The gas phase pressure was 43 kg / cm ² gauge pressure.

Indium (III) acetate powder 216
Part, titanium (IV) n-butoxide 12.6 parts, n-
A raw material suspension (A-5) was prepared by mixing 270 parts of butanol, and charged in an addition tank.

To the n-butanol solvent maintained at the bottom temperature of 280 ° C., the raw material suspension (A-5) was added from
The mixture was added and mixed at 0 sec. Once added, once at 240 ° C
The temperature dropped to 280 ° C.
By holding at 3 ° C. for 4 hours, Ti-containing In ₂ O
A suspension (D) in which _three particles (P-5) are dispersed at 7.3% by weight.
-5) was obtained. Table 3 shows the analysis result of the obtained particles P-5.

-Examples 1 (6) to 1 (16)-The added raw materials shown in Table 4 or 5 were added to the bottom solution under the addition conditions (temperature and pressure) shown in the same table, and the heating shown in the same table was carried out. The suspension (D-6 to D-16) in which the oxide fine particles (P-6 to P-16) were dispersed was obtained by holding for a predetermined time under the treatment holding conditions. In addition, ethylene glycol monoethyl ether acetate used as a solvent is hereinafter referred to as EGEA. Obtained particles P-6 to P-1
Table 6 shows the analysis results of Sample No. 6.

-Example 2 (1)-The suspension (D-1) obtained in Example 1 (1) was centrifuged to obtain a solid content. The solid was dried to obtain a powder of In-containing ZnO particles (P-1).

A coating composition (C-1) was obtained by mixing 10 parts of this powder, 20 parts of an acrylic resin solution (solid content concentration: 50%), and 20 parts of toluene and performing a dispersion treatment with a homogenizer. This composition was applied to a PET film to a dry film thickness of 10 μm and dried to obtain a coated film (F-1).

The obtained coated film (F-1) had a thickness of 1.5
The light transmittance at μm was 30%.

Comparative Example 2 In Example 2, the In-containing ZnO particles (Pc-) were replaced with the suspension (Dc-1) in place of the suspension (D-1).
1) was obtained. Using this, in the same manner as in Example 2 (1), the coating composition (Cc-1) and the coating film (Fc-
1) was obtained. 1. of the obtained coated film (Fc-1)
The light transmittance at 5 μm was 52%.

Example 2 (2) In Example 2 (1), the suspension (D-2) was used instead of the suspension (D-1), and the In-containing ZnO particles (P-
2) was obtained. Using this, a coating composition (C-2) and a coated film (F-2) having a dry film thickness of 10 μm were obtained in the same manner as in Example 2 (1).

The obtained coated film (F-2) had a thickness of 1.5
The light transmittance at μm was 25%.

-Example 2 (3)-In Example 2 (1), the suspension (D-5) was used instead of the suspension (D-1), and Ti-containing In ₂ O ₃ particles ( P-5) was obtained. Using this, a coating composition (C-5) and a coated film (F-5) having a dry film thickness of 10 μm were obtained in the same manner as in Example 2 (1).

The obtained coated film (F-5) had a thickness of 1.5
The light transmittance at μm was 10% or less.

[0124]

[Table 1]

[0125]

[Table 2]

[0126]

[Table 3]

[0127]

[Table 4]

[0128]

[Table 5]

[0129]

[Table 6]

[0130]

The metal oxide particles according to the present invention are excellent in functions such as heat ray shielding performance and visible light transmittance.

The method for producing metal oxide particles according to the present invention can easily obtain metal oxide particles excellent in functions such as heat ray shielding performance and visible light transmittance.

Since the composition containing metal oxide particles according to the present invention contains the above-described metal oxide particles of the present invention, the composition has high heat-ray shielding properties, high transparency and the like, and also has an optical function such as a light selective transmission function. In addition, it is possible to obtain a coating film or the like which is excellent in various functions such as an electric function such as a conductive function and a catalytic function such as a photocatalytic function and has high weather resistance.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C01G 15/00 C01G 15/00 B 4J037 19/02 19/02 Z 4J038 25/02 25/02 5G307 31 / 02 31/02 53/04 53/04 C08K 3/22 C08K 3/22 C08L 101/00 C08L 101/00 C09C 1/00 C09C 1/00 3/08 3/08 H01B 5/00 H01B 5/00 Z13 / 00 501 13/00 501Z // C09D 7/12 C09D 7/12 201/00 201/00 F term (reference) 4G042 DA01 DB10 DC03 DE08 DE14 4G047 AA02 AA04 AB02 AB05 AC02 AC03 AD03 4G048 AA02 AB02 AC04 AC05 AC08 AD03 AE05 AE08 4G076 AA02 AB02 AB11 AB12 BA11 BA13 BA23 BA24 CA02 CA23 DA01 DA15 DA30 4J002 AA001 BB031 BB061 BB071 BB121 BC031 BD041 BD101 BD121 BE061 BF021 BG041 BG051 BN151 CC041 CC051 CC161 CC181 CC191 CD001 CF 081 CK021 CL011 CL031 CM041 CP031 DE066 DE076 DE086 DE096 DE106 DE116 DE126 DE136 DE146 DE156 FD020 FD140 GH01 4J037 AA08 AA09 AA11 AA12 AA13 AA14 AA19 AA21 AA24 CB04 CB26 DD03 DD01 001 001 001 001 001 001 001 DG001 DH001 DL001 DL031 HA21 HA386 HA446 HA456 KA04 KA12 KA20 MA08 NA17 NA19 NA20 5G307 AA08

Claims (4)

[Claims] In a metal oxide-based particle obtained by adding a different metal (Md) to a metal (M), the content (Md / M) of the different metal (Md) is 0.5 to 20 atomic% on average. And
And metal oxide particles containing a different metal, wherein the content is 0.5 atomic% or more in the central part of the primary particles. 2. A method for producing metal oxide particles, comprising:
A step of heating a solution containing a compound of the metal (M) represented by the following general formula (I) and / or a hydrolyzed condensate, a compound of a different metal (Md) and an alcohol to precipitate metal oxide particles. A method for producing metal oxide particles containing different kinds of metals, wherein the heating is performed under pressure. M (O) _{(mxyz) / 2} (OCOR) _x (OH) _y (OR ′) _z (I) (where M is an m-valent metal atom; R is a hydrogen atom, alkyl which may have a substituent) At least one selected from a group, a cycloalkyl group, an aryl group and an aralkyl group;
R ′ is at least one selected from an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group which may have a substituent; m, x, y and z are x + y + z ≦
m, 0 <x ≦ m, 0 ≦ y <m, and 0 ≦ z <m. ) 3. A method for producing metal oxide particles, comprising:
A step of heating a solution containing a compound of the metal (M) represented by the following general formula (I) and / or a hydrolyzed condensate, a compound of a different metal (Md) and an alcohol to precipitate metal oxide particles. Wherein the amount of water in the solution is at most 100 times the molar ratio of the different metal (Md) to the different metal (Md). M (O) _{(mxyz) / 2} (OCOR) _x (OH) _y (OR ′) _z (I) (where M is an m-valent metal atom; R is a hydrogen atom, alkyl which may have a substituent) At least one selected from a group, a cycloalkyl group, an aryl group and an aralkyl group;
R ′ is at least one selected from an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group which may have a substituent; m, x, y and z are x + y + z ≦
m, 0 <x ≦ m, 0 ≦ y <m, and 0 ≦ z <m. ) 4. A metal oxide particle-containing composition comprising 0.1% by weight or more of the different metal-containing metal oxide particles according to claim 1 with respect to a binder resin.