JP3848545B2 - Dissimilar metal-containing metal oxide particles, production method and use thereof - Google Patents

Description

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【発明の効果】
本発明にかかる金属酸化物粒子は、熱線遮蔽性能や可視光透過性などの機能に優れる。
【０１３１】
本発明にかかる金属酸化物粒子の製造方法は、熱線遮蔽性能や可視光透過性などの機能に優れる金属酸化物粒子を容易に得させることができる。
【０１３２】
本発明にかかる金属酸化物粒子含有組成物は、上記本発明の金属酸化物粒子を含有するため、熱線遮蔽性や透明性等が高く、しかも、光選択透過性機能等の光機能、導電機能等の電気機能、光触媒機能等の触媒機能等の各種機能性に優れ、しかも、耐候性が高い塗膜等を得させる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a metal oxide particle excellent in the above-mentioned characteristics in a metal oxide particle provided with characteristics such as heat ray shielding properties by adding a different metal, and a production method and use thereof.
[0002]
[Prior art]
Sn-containing indium oxide (ITO), Sb-containing tin oxide (ATO), Al-containing zinc oxide and the like are known as white conductive particles. When these metal oxide particles contain 0.1 to 20% of dissimilar metals such as Sn, Sb, Al, etc., they may be heat ray shielding agents with excellent visible light transmittance depending on how they are made. . For example, in the case of indium oxide and tin oxide, these different metal-added metal oxide particles are hydroxides by hydrolyzing each compound (chloride, nitrate, etc.) of the metal as the main component and the different metal with an alkali. Is obtained by baking at a high temperature.
[0003]
However, zinc oxide (ZnO) containing dissimilar metals such as Al and In, when made by the above-described method, is conductive, but has no heat ray shielding performance, or even does not reach a practical level. . On the other hand, according to the manufacturing method developed by the present inventors (see JP-A-8-253317), ZnO-based particles having heat ray shielding performance can be obtained. In this method, a mixture comprising 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 compound of a group IVb metal element.
[0004]
However, even when using ZnO particles containing Al, In or the like obtained by this method described in JP-A-8-253317, the heat ray shielding performance is inferior to that of ITO particles or ATO particles, and therefore this is used as a heat ray shielding film. In order to obtain the same heat ray shielding rate as that of a heat ray shielding film containing ITO 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 used by making particles with higher heat ray shielding performance.
[0006]
[Problems to be solved by the invention]
Therefore, the problem to be solved by the present invention is to dissimilar metal-containing metal oxide particles having particularly excellent functions such as heat ray shielding performance and visible light transmission properties, in particular, ZnO-based, In₂O_ThreeSeries, SnO₂It is to provide conductive metal oxide particles such as a system, and a production method and use thereof.
[0007]
[Means for Solving the Problems]
In order to solve the above-described problems, the present inventors have analyzed the ZnO-based particles containing Al, In and the like from various aspects, and have pursued the cause of the above-described problems. As a result, it has been found that the cause is that the added foreign metal is biased toward the surface side of the primary particles and does not sufficiently exist inside. And it discovered that the said cause was eliminated when the added dissimilar metal exists more than a fixed value in the center part of a primary particle. Furthermore, the present inventors have found a suitable method for producing such Al, In-containing ZnO-based particles. And the above thing was discovered that it can apply also to metal oxide particles other than ZnO type particle | grains containing Al, In, etc., and completed this invention.
[0008]
Therefore, the different metal-containing metal oxide particles according to the present invention (hereinafter simply referred to as “metal oxide particles”) are different from the metal oxide particles obtained by adding different metals (Md) to metal (M). The metal (Md) content (Md / M) is an average of 0.5 to 20 atomic% and 0.5 atomic% or more at the center of the primary particles.
[0009]
    The method for producing different metal-containing metal oxide particles according to the present invention,A method for producing different metal-containing metal oxide particles having an average content (Md / M) of different metal (Md) of 0.5 to 20 atomic%,It contains a compound represented by the following general formula (I) of the metal (M) and / or a hydrolysis condensate, a compound of a different metal (Md), and an alcohol.Does not contain carboxylic acidHeating the solution to precipitate metal oxide particles, and comprising the following (a) and(b).
[0010]
(A) The heating is performed under pressure.
[0011]
(B) The water content in the solution is 100 times or less in terms of a molar ratio to the foreign metal (Md).
[0012]
M (O)_{(mxyz) / 2}(OCOR)_x(OH)_y(OR ’)_z    (I)
(Where M is an m-valent metal atom; R is at least one selected from a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an aryl group and an aralkyl group; R ′ is a substituent group) And at least one selected from an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group; m, x, y and z are x + y + z ≦ m, 0 <x ≦ m, 0 ≦ y <m, 0 ≦ z <m is satisfied.)
And the metal oxide particle containing composition concerning this invention contains the said metal oxide particle concerning this invention 0.1weight% or more.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
[Metal oxide particles]
In the metal oxide particles according to the present invention, the content (Md / M) of the dissimilar metal (Md) is 0.5 to 20 atom% (preferably 1 to 10 atom%, more preferably) of the entire primary particles. Is 2 to 10 atom%, particularly preferably 4 atom% or more, and 0.5 atom% or more (preferably 1 atom% or more, more preferably 2 atom% or more, particularly preferably at the center of the primary particle). Is 4 atomic% or more).
[0014]
When the average value (average content rate) of the entire primary particles in the content rate (Md / M) of the different metal (Md) is αav and the value (center content rate) at the center of the primary particles is αc, the average content rate The median content (αc / αav) with respect to is preferably 0.2 or more, more preferably 0.5 or more, and most preferably 0.8 or more.
[0015]
The measurement method of the average content rate αav and the central content rate αc is as follows. For the aggregate of primary particles (in the case of αav) or simple substance (in the case of αc), those transmission images are obtained by FE-TEM (transmission electron microscope). While observing, a place where there is no metal segregation outside of the particles is searched, and elemental analysis is performed with high resolution XMA at the desired spatial resolution (spot diameter) described below. And it is the method of calculating | requiring the content rate of a dissimilar metal (Md) from the peak intensity which belongs to each metal. Note that the lower limit of the spot diameter can be reduced to 1 nmφ by narrowing the probe, and the spot diameter can be arbitrarily increased continuously. Regarding the confirmation of the segregated material, it is assumed that there is no segregated material as long as it is normally a level that cannot be confirmed with the naked eye in the projection drawing observed with the FE-TEM.
[0016]
Regarding the measurement of the average content rate αav, more specifically, a space in which about 10 particles in which no segregated material is observed as an aggregate of primary particles are observed by FE-TEM and all these particles are included. The analysis is performed by elemental analysis with resolution (spot diameter).
[0017]
Regarding the measurement of the center content αc, more specifically, the projection image of one primary particle is observed without a segregated material by FE-TEM, and the central portion of the projection image is observed with a spatial resolution (spot diameter of 1 nmφ). ) To perform by elemental analysis. When analyzing the central part of the projected image, it is usually necessary to use a part that seems to be the approximate center of the projected image based on common sense, but at least the projection that does not touch the contour of the projected image. The shape of the projected image is preferably within the area reduced to 80% on the basis of the length, and more preferably within the area reduced to 50%, and even more preferably 20 It may be performed within the area reduced to%. For example, if the particle shape is needle-like and the projected image is needle-like, the spot set there is the projected image even if it is a part that is commonly determined to be the center of the projected image. In such a case, an area having a diameter that is 50% of the length of the maximum length centered around a portion that is considered to be approximately the center of the projected image. Can be done within. The final measurement result of the median content αc was an average value for 10 particles.
[0018]
In addition, when the primary particle has a portion exceeding 30 nm in thickness (particle size) (some particles may exceed 100 nm), for example, a powder sample is mixed with an epoxy resin, and a thin slice is obtained after curing. Thus, an ultra-thinned sample having a primary particle cross-section exposed by ion milling from the thin slice, usually having a thickness of 30 nm or less, is obtained, and the above measurement is performed on the cross-section portion of the primary particle of this ultra-thinned sample. Preferably it is done. The reason is that if the thickness exceeds 30 nm, the electron beam transmission of the FE-TEM becomes incomplete or the resolution of the XAM is reduced. Since all the information in the thickness direction is related to the analysis, the measurement is performed. This is because the result is inaccurate.
[0019]
In the above measurement, for example, a field emission transmission electron microscope (HF-2000 type, acceleration voltage 200 kV) manufactured by Hitachi, Ltd. is used as FE-TEM, and an X-ray microanalyzer (Sigma, manufactured by Kevex, Inc.) is used as XMA. Type, energy dispersion type, beam diameter: spatial resolution 10 mm).
[0020]
The main metal (M) and the dissimilar metal (Md) are not particularly limited. For example, alkaline earth metal elements such as Be, Mg, Ca, Sr, Ba and Ra; lanthanoid metal elements such as La and Ce Actinoid metal elements such as Ac; Group IIIa metal elements such as Sc and Y; Group IVa metal elements such as Ti, Zr and Hf; Group Va metal elements such as V, Nb and Ta; Cr, Mo, W, etc. Group VIa metal element; Group VIIa metal element such as Mn, Tc, Re; Group VIII metal element such as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt; Group Ib such as Cu, Ag, Au Metal elements; Group IIb metal elements such as Zn, Cd and Hg; Group IIIb metal elements such as Al, Ga, In and Tl; Group IVb metal elements such as Ge, Sn and Pb; Group Vb metal elements such as Sb and Bi ; Group VIb metal elements such as Se and Te, etc., and these may be one or two You may coexist.
[0021]
As the main metal (M), among 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 valence, particle size, crystal structure, impurity injection, defect injection, and the like. For this reason, it is preferable at the point which has optical functions, such as having light selective transmission functions, such as ultraviolet absorptivity and infrared shielding, a (light) conductive function, a magnetic function. Furthermore, Fe, Ni, V, Nb, Be, La, Mo, W, and the like have high transparency and stable particles can be obtained. Zn is preferable because it can control optical properties such as ultraviolet absorption and electrical properties by controlling the crystal structure and impurity concentration.
[0022]
As the main metal (M), for example, In, Sn, and Zn are preferable because both the heat ray shielding property and the visible light transmittance are high.
[0023]
As the dissimilar metal (Md), for example, when the metal oxide particles are indium oxide particles, a tetravalent metal is preferable, and Sn, Ti, and the like are particularly preferable in terms of both high heat ray shielding and visible light transmittance. . When the metal oxide particles are tin oxide particles, pentavalent metal elements are preferable, and Sb, P, and the like are particularly preferable. When the metal oxide particles are zinc oxide particles, trivalent metal elements are preferable, and In, Al, Ga, and the like are particularly preferable.
[0024]
The metal oxide particles according to the present invention include amorphous particles, but those showing the oxide crystallinity of the metal (M) from the viewpoint of X-ray diffraction or electron diffraction. Is preferred. Usually, when the primary particle diameter is 5 nm or more, it is confirmed by X-ray diffraction method, and when the primary particle diameter is 5 nm or less, it is confirmed whether or not it is crystalline by electron beam diffraction method. The crystal structure and physical properties can be identified.
[0025]
The primary particle diameter of the metal oxide particles according to the present invention is preferably 0.1 μm or less in view of high transparency. Specifically, it is particularly preferable that the following (1) and / or (2) and / or (3) is satisfied.
[0026]
(1) When the crystallite size obtained by X-ray diffraction (Wilson method) or electron diffraction is Dw, 1 nm ≦ Dw ≦ 100 nm.
[0027]
(2) When the specific surface area diameter calculated by the following formula is Ds, 1 nm ≦ Ds ≦ 100 nm.
[0028]
Ds = 6 / (ρ × S) where Ds: μm
(Where ρ: true specific gravity of metal oxide particles, S: specific surface area of metal oxide particles measured by BET method (m²/ G))
(3) When a particle image is measured with a transmission electron microscope and the primary particle diameter determined from the observation of the crystal lattice image and the size is De, 1 nm ≦ De ≦ 100 nm.
[0029]
The metal oxide particles of the present invention preferably have a primary particle diameter of 1 to 30 nm in terms of excellent transparency, and when used as a heat ray shielding agent or a conductive material, 5 nm ≦ Dw ≦ 30 nm is preferable. .
[0030]
The metal oxide particles according to the present invention preferably contain a carboxylic acid (residual) group. Here, the carboxylic acid (residual) group means a —COO— group, specifically, a carboxyl group (—COOH), a carboxylate group (—COO).^-), An ester group that generates a carboxyl group and / or a carboxylate group by hydrolysis. The carboxylic acid (residual) group is preferably a saturated fatty acid (residual) group, more preferably a fatty acid (residual) group having 1 to 4 carbon atoms, and an acetoxy group (CH_ThreeCOO-) is most preferred.
[0031]
Since the carboxylic acid (residual) 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. Therefore, the resin composition containing the metal oxide particles When the object is a paint, the transparency of the coating film is increased.
[0032]
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% with respect to the metal (M). When the content of the carboxylic acid (residual) group is less than 0.01 mol% with respect to the metal (M), the dispersibility of the particles is lowered, and the particles are easily agglomerated. 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, infrared shielding property or ultraviolet shielding property is lowered.
[0033]
The particle shape of the metal oxide particles according to the present invention is not particularly limited. Specific examples of the shape include a spherical shape, an elliptical spherical shape, a cubic shape, a rectangular parallelepiped shape, a pyramid shape, a needle shape, a column shape, a rod shape, a cylindrical shape, a flake shape, and a (hexagonal) plate shape.
[Method for producing metal oxide particles]
The method for producing the metal oxide particles is not particularly limited. For example, the following method can be mentioned as a preferable one.
[0034]
Heating the solution containing the compound of metal (M) and / or hydrolysis condensate, the compound of different metal (Md) and alcohol to precipitate metal oxide particles, comprising the following (a) and / or (B).
[0035]
(A) The heating is performed under pressure.
[0036]
(B) The water content in the solution is 100 times or less in terms of a molar ratio to the foreign metal (Md).
[0037]
As for the above (a), the heating pressure is 1 kg / cm at normal pressure (atmospheric pressure).²In the absolute pressure P, P> 1 kg / cm²Preferably 1.5 kg / cm²≦ P ≦ 100kg / cm²Is to satisfy. 3kg / cm in terms of high pressure effect and economical equipment²≦ P ≦ 20kg / cm²It is particularly preferable to satisfy 5 kg / cm²≦ P ≦ 10kg / cm²Most preferably.
[0038]
As a 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 part with an inert gas such as nitrogen gas or argon gas, or the like can be adopted.
[0039]
The heating temperature is preferably 50 ° C to 300 ° C, more preferably 100 ° C to the critical temperature of the alcohol, most preferably 20 ° C higher than the normal pressure boiling point of the alcohol, although it depends on the boiling point of the alcohol. .
[0040]
For (b) above, the water content in the solution means free water content, but also includes water of crystallization when the metal (M) compound or the dissimilar metal (Md) compound has water of crystallization. It is. This water content can be measured by the Karl Fischer method. The amount of water referred to here is water contained in the raw material used (free water in the alcohol and other solvent components used, water of crystallization in the compound of metal (M) or compound of different metal (Md), etc. This means the molar ratio of the total sum of water) to the total dissimilar metal (Md) in the compound of all the dissimilar metals (Md) used, and water generated as a by-product in the heating reaction is not considered.
[0041]
This water content is preferably 50 times mol or less, and more preferably 20 times mol or less in terms of the molar ratio to the total amount of different metal (Md) used. When the amount of water is too large, it becomes difficult for the dissimilar metal (Md) to be contained in the crystallites of the metal (M) oxide, and it becomes difficult to obtain dissimilar metal-containing metal oxide particles having high functionality.
[0042]
The compound of the main metal (M) has a structure represented by the following general formula (I). Specifically, as described above in the description of the metal oxide particles.
[0043]
M (O)_{(mxyz) / 2}(OCOR)_x(OH)_y(OR ’)_z    (I)
(Where M is an m-valent metal atom; R is at least one selected from a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an aryl group and an aralkyl group; R ′ is a substituent group) And at least one selected from an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group; m, x, y and z are x + y + z ≦ m, 0 <x ≦ m, 0 ≦ y <m, 0 ≦ z <m is satisfied.)
In the general formula (I), R or R ′ is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, because a highly dispersible metal oxide particle is easily obtained. preferable. In the general formula (I), x preferably satisfies 1 ≦ x ≦ m, y preferably satisfies 0 ≦ x <m / 2, and z satisfies 1 ≦ x <m / 2. Those are preferred. This is because in these cases, highly dispersible metal oxide particles are easily obtained.
[0044]
As the compound represented by the general formula (I), it is preferable to use a compound having a high dissolution rate because particles having excellent dispersibility can be obtained. Here, the dissolution rate can be directly measured by reaction, but at 25 ° C., 2 parts by weight of the compound of the formula (I) (hereinafter abbreviated as “part”) is ion-exchanged water (pH 5 to 3 ° C.). 8) It is defined as the time t required to completely dissolve and obtain a transparent solution when mixed with 200 parts and stirred. 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.
[0045]
The hydrolyzed condensate of the compound represented by the general formula (I) includes a hydrolyzate obtained by hydrolyzing and / or condensing the compound of the metal element (M) having the structure represented by the general formula (I), and It is a condensate and is a compound from a monomer to a polymer compound. The condensate is a bond chain in which the main metal (M) element and oxygen (O) are metalloxane-bonded (MO)._n(Where n is 1 or more). The degree of condensation of the condensate is not limited, and the degree of condensation (average) is preferably 100 or less, and more preferably 10 or less, in order to obtain metal oxide particles having a uniform crystallite size and shape. is there.
[0046]
Examples of the compound of the dissimilar metal (Md) used in the production method according to the present invention include a compound having a chemical structure in which the metal element (M) in the general formula (I) is replaced with the metal element (Md) described above. And metal alkoxides of different metals (Md). The former is specifically described above in the section of metal oxide particles.
[0047]
The alcohol used in the production method according to the present invention is not particularly limited. For example, monohydric alcohols with high water solubility are preferable. Examples of such alcohols include alcohols having a solubility in water of 1% by weight or more, such as the following A) to C), and alcohols having a solubility in water of 10% by weight or more are more preferable.
[0048]
A) 1-3 grade aliphatic alcohols having 1 to 4 carbon atoms such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, sec-butanol, t-butyl alcohol, etc.
B) Cyclohexanol, benzyl alcohol
C) Glycol derivatives
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, Alkylene glycol ethers such as propylene glycol mono n-butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, 3-methyl-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 the hydrolysis condensate thereof is mixed with an alcohol to prepare a solution containing them. The solution here includes emulsions and suspensions. The same applies to compounds of different metals. The above mixing may be a method in which the powder of the metal compound (hydrolysis condensate) is added as it is to the alcohol, or once added to another solvent to prepare a suspension or diluted solution in advance. Alternatively, this may be added to the alcohol. As the solvent used for preparing the suspension or diluted solution, alcohol or an acetate thereof is preferable, and alcohol used for heating and holding is more preferable.
[0049]
  In the production method of the present invention, the mixture containing the main metal (M) compound, the dissimilar metal (Md) compound and the alcohol is heated. The series of operation procedures from mixing to heating is not particularly limited. 1) A method in which the above mixture is prepared at normal temperature or 50 ° C. or less, and a temperature is raised and heated. 2) At least one of a main metal (M) compound, a dissimilar metal (Md) compound and an alcohol is preferable. IsUnder pressureA preheating method or the like in which the other is heated and mixed with the heated one can be preferably mentioned. Specifically, as the preheating method, 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, and b) of a main metal (M) A method in which a compound and a compound of a different metal (Md) (or a suspension or a homogeneous solution thereof) are heated and an alcohol is added; c) a compound of an alcohol and a main metal (M) and a different metal (Md) A method in which the compound (or a suspension or a homogeneous solution thereof) is heated separately and the both are mixed is preferred. Among the methods 1) and 2), the preheating method 2) is more preferable, the reaction temperature can be easily selected, and the particle size and composition can be easily controlled. At this time, in the method of mixing with at least one preheated in a pressurized state, the heat treatment under pressure can be started simultaneously with mixing, so particles with a high content of different metal (Md) Is preferable because
[0050]
The method of adding and mixing the metal compound (hydrolysis condensate) to alcohol or other solvent is not particularly limited. (1) The total amount is added all at once, for example, within 1 minute. ▼ Continuous feed added continuously over a period of more than 1 minute, or (3) Pulse addition method of adding a small amount in two or more portions (each pulse may be continuous feed or batch addition), etc. This method can be adopted. In the case of {circle around (2)} or {circle around (3)}, it is preferable that the temperature change of the solution containing the alcohol generated by the addition is smaller because particles having a uniform primary particle size are easily obtained. Specifically, it is preferable to control the addition rate or the like so that the temperature change of the solution is within 10 ° C.
[0051]
When the metal compound (hydrolysis condensate) is mixed with alcohol or another solvent, the addition rate is [metal compound (hydrolysis condensate) mol / alcohol (mol) / addition time (min)]. Is preferably 0.0001 to 2, more preferably 0.0005 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, when the addition rate exceeds 2, it becomes difficult to control the above-mentioned temperature especially when the reaction scale is large, and it becomes difficult to obtain particles having a uniform particle diameter.
[0052]
The mixing ratio of the metal compound (hydrolysis condensate) and alcohol is not particularly limited, but the lower limit is expressed in terms of the molar ratio in terms of charge after completion of the total addition of the metal compound (hydrolysis condensate). In order for the metal Md to be uniformly contained in the primary particles, it is preferably m or more, more preferably 2 m or more, which is the valence of the metal (M). The upper limit of the molar ratio is preferably 50 or less, more preferably 20 or less, from the viewpoint of productivity.
[0053]
In the production method according to the present invention, the predetermined temperature is maintained for 30 minutes or more in order to increase the crystallinity of the particles and enhance the performance such as heat ray shielding performance, but the specific heating condition is preferably 180 ° C. or more. 1 hour or more, more preferably 200 ° C. or more and 3 hours or more. Here, the heating temperature is represented by the bottom temperature of the reaction vessel.
[0054]
In the production method according to the present invention, during heating, the solution is stirred for a required power of 0.0001 kw / m.^ThreeIt is preferable that stirring is performed as described above, and more preferably 0.001 kw / m.^ThreeIn particular, 0.01 to 10 kw / m^ThreeIt is preferable that it is stirred at.
[0055]
In the production method according to the present invention, for the purpose of enhancing the dispersibility of the obtained particles, an aliphatic carboxylic acid or an aliphatic amine is added to the main metal (at any stage after the addition of the metal compound (hydrolysis condensate)). 0.1 to 10 mol% is added to 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).
[0056]
According to the production method of the present invention, it is possible to easily obtain metal oxide-based particles that are excellent in functions such as heat ray shielding performance and visible light transmittance and that contain an additive metal.
[Use of metal oxide particles]
The metal oxide particle according to the present invention is a composition containing 0.1% by weight or more of the metal oxide particle of the present invention described above. For example, it is a coating composition, a molding material composition or a film containing 0.1% by weight or more of the above-mentioned different metal-containing metal oxide particles with respect to 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.
[0057]
Below, this composition explains in detail in order about a paint constituent, a molding material constituent, and a metal oxide particle content film.
Paint composition
The coating composition is excellent in various functions such as a light function such as a light selective permeability function, an electrical function such as a conductive function, and a catalyst function such as a photocatalytic function, and can provide a coating film having high weather resistance. . In particular, those containing metal oxide particles having excellent heat ray shielding properties of the present invention are useful because they are excellent in economic efficiency, thermal shielding properties and visible light transmittance.
[0058]
The binder resin used in the coating composition includes various synthetic resins and natural resins that are thermoplastic or thermosetting (including thermosetting, ultraviolet curable, electron beam curable, moisture curable, and combinations thereof). Organic binders, inorganic binders, and the like.
[0059]
Synthetic resins include, for example, alkyd resins, amino resins, vinyl resins, acrylic resins, epoxy resins, polyamide resins, polyurethane resins, thermosetting unsaturated polyester resins, phenol resins, chlorinated polyolefin resins, silicone resins, acrylic silicone resins. Fluorine resin, xylene resin, petroleum resin, ketone resin, rosin-modified maleic acid resin, liquid polybutadiene, coumarone resin, and the like, and one or more of these are used. Examples of the natural resin include shellac, rosin (pine resin), ester gum, hardened rosin, decolorized shellac, white shellac, and the like, and one or more of these are used.
[0060]
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 the component used in combination with the synthetic resin include cellulose nitrate, cellulose acetate butyrate, cellulose acetate, ethyl cellulose, hydroxypropyl methylcellulose, and hydroxyethyl cellulose.
[0061]
The form of the binder resin used in the coating composition is not particularly limited, and examples include a solvent-soluble type, a water-soluble type, an emulsion type, and a dispersion type (any solvent such as water / organic solvent).
[0062]
Examples of water-soluble binder resins include water-soluble alkyd resins, water-soluble acrylic-modified alkyd resins, water-soluble oil-free alkyd resins (water-soluble polyester resins), water-soluble acrylic resins, water-soluble epoxy ester resins, and water-soluble melamines. Examples thereof include resins.
[0063]
Examples of emulsion type binder resins include (meth) acrylic acid alkyl copolymer dispersions; vinyl acetate resin emulsions, vinyl acetate copolymer resin emulsions, ethylene-vinyl acetate copolymer resin emulsions, acrylic ester (co) polymer resins. An emulsion, a styrene-acrylic ester (co) polymer resin emulsion, an epoxy resin emulsion, a urethane resin emulsion, an acrylic-silicone emulsion, a fluororesin emulsion, and the like can be given.
[0064]
Examples of the inorganic binder include metal alkoxides such as silica gel, alkali silicic acid, and silicon alkoxide, their (hydrolyzed) condensates, and phosphates.
[0065]
When the coating composition is used for the production of an ultraviolet-absorbing film, which will be described later, the binder resin used in the coating composition from the viewpoint of film forming conditions such as film forming temperature and the flexibility and weather resistance of the film obtained. As these, polyurethane resin, acrylic resin, fluororesin and the like are preferable.
[0066]
The ratio of the metal oxide particles in the coating composition is, for example, 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 ratio of the metal oxide particles is less than 0.1% by weight, the effect obtained by adding particles such as ultraviolet shielding property and conductivity is lowered. On the other hand, when the ratio of the metal oxide particles exceeds 90% by weight, the visible light transmittance and flexibility are lowered. 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 ratio 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.
[0067]
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 aid, a plasticizer, an antifoaming agent / leveling agent, a thixotropic agent, and a matting agent. Surfactant; Flame retardant; Pigment wetting agent / dispersant; Lubricant; UV absorber; Light stabilizer; Antioxidant; Other (thermal) stabilizer; Preservative; It may contain additives such as rusting agents; dyes; pigments.
[0068]
As the curing agent, for example, a curing agent used in a dry oil system such as air (oxygen); a curing agent used in a polyester resin such as a monofunctional or polyfunctional unsaturated monomer, a polyacrylic resin, or an epoxy resin; first grade Curing agents used for binder resins having epoxy groups such as polyamines having secondary amino groups, polyamides, amino resins having methylol groups, polybasic acids having carboxyl groups, and high acid value polyesters; polymers having isocyanate groups Curing agents used for binder resins having hydroxyl groups such as isocyanates, polyisocyanates having urethane groups, methylol groups, primary and / or secondary amino groups, and amino resins having alkoxymethylene groups; carboxyl groups such as metal chelating agents Curing agent used for binder resin having water; Ability epoxy compounds, mention may be made of a hydroxyl group-containing compound curing agent used in the binder resin having a silicone base such as such, it is used alone or in combination.
[0069]
When the coating composition is used for production of a metal oxide particle-containing film, which will be described later, the weather resistance is improved when the coating composition contains a light stabilizer. When the coating composition contains polyisocyanate as a curing agent, versatility is high. As a method for curing the coating composition in the case of producing a film, a heat curing method is economically preferable.
[0070]
The coating composition may contain a solvent, and is appropriately selected depending on the intended use of the coating composition and the type of binder resin. Examples of the solvent include organic solvents such as alcohols, aliphatic and aromatic carboxylic acid esters, ketones, ethers, ether esters, aliphatic and aromatic hydrocarbons, and halogenated hydrocarbons; water Mineral oil; vegetable oil, wax oil, silicone oil and the like can be mentioned, and these are used alone or in combination.
[0071]
As a method for producing a coating composition, for example, a method of producing a coating composition by adding metal oxide particles to an organic solvent to form a slurry, and then mixing a binder resin with the slurry containing the metal oxide particles. Can be mentioned.
[0072]
A coating composition can be apply | coated to the surface of base materials, such as inorganic substances, such as glass and earthenware, and organic substances, such as resin, for example. In particular, a coating film obtained by coating on the surface of an organic material has high weather resistance and excellent flexibility. The shape of the inorganic material or organic material is not particularly limited, and examples thereof include a film shape, a sheet shape, a plate shape, and a fiber shape. Among these, it is useful for the below-mentioned film, fiber, etc.
[0073]
The material of the resin used as the substrate is not particularly limited. For example, LDPE, HDPE, amorphous polyethylene, polypropylene such as OPP (drawn polypropylene), 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); polyethylene terephthalate Polyesters such as polyethylene naphthalate and polybutylene naphthalate; polycarbonates; polyurethanes; polyamides; polyimides; polyacrylonitriles; polysulphones; Nylen sulfide type; polyarylate type; polyether imide type; aramid type; (meth) acrylic type; polyether ether ketone type; tetrafluoroethylene / ethylene copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, polytetra Fluoroethylene, polytrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene / hexafluoropropylene / perfluoroalkyl vinyl ether copolymer, polychlorotrifluoro Fluorine resins such as ethylene can be used.
[0074]
PMMA, MMA-styrene random copolymer, polycarbonate, transparent polypropylene, MMA and α-methylstyrene or cyclohexyl methacrylate, etc. when used in applications requiring extremely high visible light transparency and transparency, such as optical lenses MMA modified type of ABS resin, polystyrene, polyarylate, polysulfone, polyethersulfone, transparent epoxy resin, poly-4-methylpentene-1, fluorinated polyimide, amorphous fluororesin, transparent phenoxy resin Various resins such as amorphous nylon resin and fluorene can be used as the base material.
[0075]
Moreover, it becomes increasingly important to use biodegradable resin as a base material in order to meet the demand for biodegradability due to disposal problems. In such a case, for example, poly-3-hydroxybutyric acid ester, chitin / chitosan, polyamino acid, cellulose, polycaprolactone, alginic acid, polyvinyl alcohol, aliphatic polyester, saccharide, polyurethane, poly It is preferable to use an ether-based biodegradable plastic or the like as the base material.
[0076]
The base material may be one in which a UV absorbing film is previously disposed on the above-mentioned base material, or one in which a primer layer is disposed in advance for the purpose of improving the adhesion between the coating film composed of the coating composition and the base material. .
[0077]
Among these, among plastic films and sheets, fluorine resins, polyester resins, (meth) acrylic resins, and polycarbonate resins are preferable in terms of high weather resistance.
[0078]
The method for applying the coating composition is not particularly limited, and examples thereof include a dipping method, a roll coater method, a flow coat method, a screen printing method, a bar coater method, a spin coater method, a brush coating method, and a spray method. . Moreover, there is no limitation in particular about the dry film thickness obtained by apply | coating a coating composition, Preferably it is 0.5-100 micrometers, More preferably, it is 1-30 micrometers.
[0079]
After coating / coating the coating composition, heat curing (including room temperature curing), moisture curing, UV curing in terms of water resistance, solvent resistance, acid resistance, chemical resistance such as alkali resistance, scratch resistance, etc. The cured film is preferably formed by a curing method such as electron beam curing.
[0080]
A laminated glass can be obtained 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 transparent plate prepared separately. Note that the intermediate film of the coated transparent plate and the adhesive sheet are stacked.
[0081]
Examples of the adhesive sheet include sheets made of soft resin or hard resin such as polyvinyl butyral resin, polyurethane resin, ethylene-vinyl acetate copolymer resin, ethylene- (meth) acrylate copolymer resin, etc. 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 is excellent in various functions such as light functions such as a light selective permeability function, electrical functions such as a conductive function, and catalytic functions such as a photocatalytic function, and obtains a molded article having high weather resistance and flexibility. Can be made.
[0082]
Binder resins used in the molding material composition include polyamide (6-nylon, 66-nylon, 12-nylon, etc.), polyimide, polyurethane, polyolefin (polyethylene, polypropylene, etc.), polyester (PET, PBT, PEN, etc.) , Polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polystyrene, (meth) acrylic resin, ABS resin, silicone resin, fluororesin, and thermoplastic resins such as these monomers; phenol resin (phenol formalin Resin, cresol / formalin resin, etc.), epoxy resin, amino resin (urea resin, melamine resin, guanamine resin, etc.) and thermosetting resins such as monomers used as raw materials thereof. Species or two or more are used.
[0083]
Examples of the binder resin used in the molding material composition include soft resins or hard resins such as polyvinyl butyral, polyurethane, ethylene-vinyl acetate copolymer, and ethylene- (meth) acrylate copolymer. These can be used alone or in combination of two or more.
[0084]
As the binder resin used in the molding material composition, the above-described inorganic binder may be used.
[0085]
The ratio of the metal oxide particles in the molding material composition is, for example, 0.1 to 99% by weight, preferably 0.3 to 10% by weight, based on the total solid content of the metal oxide particles and the binder resin. It is. When the ratio of the metal oxide particles is less than 0.1% by weight, the effect obtained by adding particles such as ultraviolet shielding property and conductivity is lowered. On the other hand, when the ratio of the metal oxide particles exceeds 99% by weight, strength, visible light permeability and flexibility are lowered.
[0086]
Molding composition is hardener, cure accelerator, colorant, mold release agent, coupling agent, silicone compound, reactive diluent, plasticizer, stabilization according to required performance in addition to metal oxide particles and binder resin It may contain additives such as an agent, a flame retardant aid and a crosslinking agent.
[0087]
The curing agent may be required when using a thermosetting resin as the binder resin. For example, when an epoxy resin is used as the binder resin, polyamides, aliphatic polyamines, cycloaliphatic polyamines, aromatic polyamines or amines modified with a part thereof, acid anhydrides, dicyandiamides, imidazole , Amine imides, hydrazides, phenol novolacs, cresol novolacs and other novolac-based curing agents, and the like are used alone or in combination. Moreover, when using a phenol resin as binder resin, urotropin, formal, etc. can be mentioned, These are 1 type (s) or 2 or more types used. These amounts are used in an appropriate amount with respect to the binder resin.
[0088]
Plasticizers are intended to further improve the processability of the composition, such as phosphate esters, phthalate esters, aliphatic- or dibasic acid esters, dihydric alcohol esters, oxyacid esters. Polyglycols, and the like, and particularly when an epoxy resin is used as the binder resin, polyglycols are preferred. The stabilizer suppresses the decomposition of the binder resin, and examples thereof include lead stearate and zinc stearate.
[0089]
As a manufacturing method of a molding material composition, the method etc. which mix a metal oxide particle and binder resin uniformly using mixing apparatuses, such as a roll, a kneader, a mixer, etc. can be mentioned, for example.
[0090]
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.
[0091]
The molding material composition may be molded into a film, for example, and the obtained film has high heat ray shielding properties for particles and excellent visible light transmittance.
[0092]
Laminated glass can be obtained by sandwiching a metal oxide particle-containing sheet obtained by molding a molding material composition with a transparent plate 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.
Film containing metal oxide particles
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 substrate film. Since this metal oxide particle-containing film contains the metal oxide particles of the present invention, it is excellent in various functions such as a light function such as a light selective transmission function, an electric function such as a conductive function, and a catalyst function such as a photocatalytic function. High weather resistance.
[0093]
As a base film used for a metal oxide particle containing film, the film etc. which consist of resin used as a base material demonstrated in the term of the coating composition in detail can be mentioned. The same applies to the preferred ones.
[0094]
There is no limitation in particular about the film thickness of a base film, Preferably it is 5-500 micrometers, More preferably, it is 10-200 micrometers.
[0095]
There are no particular limitations on the method of applying the coating composition on the surface of the substrate film, the dry film thickness, and the like, and the above-mentioned ones are preferred.
[0096]
The metal oxide particle-containing film is not particularly limited as long as the coating film obtained from the coating composition is formed on the substrate film, and may be further processed according to the application, required characteristics, and the like. The metal oxide particle-containing film is applied to the surface of the coating film that does not contact the base film and / or the surface of the base film that does not contact the coating film. Film or the like), or a laminate film laminated with another film.
[0097]
The ultraviolet transmittance when the metal oxide particle-containing film is used as an ultraviolet shielding film is not particularly limited, but is preferably 50% or less, and more preferably 10% or less. The ultraviolet transmittance is a value obtained by the apparatus and measurement method described in JIS R 3106.
[0098]
The visible light transmittance of the metal oxide particle-containing film is not particularly limited, but is preferably 70% or more, and more preferably 80% or more. The visible light transmittance is a value obtained by measuring in the wavelength range of 380 to 780 nm and using the apparatus, measurement method, and calculation method described in JIS R 3106.
[0099]
The haze of the metal oxide particle-containing film is not particularly limited, but is preferably 10% or less, more preferably 5% or less, and most preferably 3% or less. The haze is a value obtained by measuring with a turbidimeter.
[0100]
The weather resistance of the metal oxide particle-containing film is determined by performing an accelerated weather resistance test using a shine carbon arc lamp type light resistance and weather resistance tester described in JIS B 7753-93, and haze after an initial 100 hours. When the haze value and hue after 1000 hours test are further compared on the basis of the value and hue, the change in haze is preferably less than 2%, and more preferably not colored (discoloration).
[0101]
【Example】
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
[0102]
Evaluation in this example was performed by the following method.
1. Evaluation of metal oxide particles
<Preparation method of powder sample>
After the fine particles in the obtained dispersion are separated by centrifugation, washing with methanol and further washing with acetone are sufficiently performed, followed by vacuum drying at 30 ° C. for one day, and further vacuum drying at 80 ° C. for one day. The volatile component was completely removed to obtain a fine particle powder, which was used as a powder sample.
<Content of different metal (Md)>
The average content rate αav and the central content rate αc were determined by the method defined above.
[0103]
The content rate αav-1 shown in Table 2 was measured by setting a spot diameter including all of about 1000 particles even in a state where segregated materials were observed in the above-described method for measuring the average content rate αav. It is the content rate of the dissimilar metal (Md). In Table 2, when the value of the content rate αav is lower than the value of the content rate αav-1 in the particles P-1 and the particles Pc-1, a slight segregation is observed for the particles P-1, and the particles Pc − For 1, it means that a large amount of segregated material was observed.
[0104]
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, manufactured by Kevex, Sigma type, energy dispersion type, beam diameter ( The average content (αav) and the central content (αc) of the dissimilar metal (Md) with respect to the main metal (M) were determined using the spatial resolution (10Åφ).
<Carboxylic acid (residual) group content>
1 g of the powder sample was mixed with 0.01N sodium hydroxide aqueous solution and stirred for 3 days, and then the supernatant obtained by centrifugation was measured by ion chromatography analysis. Here, mol% of carboxylic acid (residual) groups such as an acetoxy group relative to the main metal (M) was calculated.
<Crystallinity>
Evaluation was made by powder X-ray diffraction.
<Crystallite diameter Dc (hkl), Dw>
The powder sample was determined by powder X-ray diffraction measurement.
[0105]
Dc (hkl): crystallite diameter in a direction perpendicular to each diffraction surface (hkl) obtained by the Scherrer method (by Cauchy function approximation)
Dw: Crystallite size and lattice strain determined using the Wilson method
1. Evaluation of coating film
<Heat shielding performance>
Particles are dispersed in an acrylic resin binder, and the particles are 10 g / m²The film is formed on a PET film so that the transmittance T is 1.5 μm._1.5Was measured and judged according to the following criteria.
[0106]
○: T_1.5<40%
X: T_1.5≧ 40%
-Example 1 (1)-
With a stirrer, addition port, thermometer, distillate gas outlet, nitrogen gas inlet and pressure control valve, withstand pressure of 100 kg / cm that can be heated from the outside²Reactor made of stainless steel (SUS316), an addition tank directly connected to the addition port via a ball valve, a reactor directly connected to the distillate gas outlet, and a distillate trap (the whole reaction apparatus is 100 kg / cm²(Withstand pressure specification) was prepared. The reactor was charged with 1000 parts of 2-butoxyethanol (hereinafter referred to as EGB), the gas phase part was replaced with nitrogen gas, the temperature was raised from room temperature, nitrogen was introduced, and the gas phase part pressure was 5 kg / cm.²The liquid temperature was maintained at 160 ° C.
[0107]
Next, a raw material suspension (A-1) is prepared by mixing 152 parts of anhydrous zinc acetate (manufactured by Matsugaki Pharmaceutical Co., Ltd.) and 4.85 parts of anhydrous indium acetate with 191 parts of EGB, and charging it into the addition tank. It is. Gas phase pressure 5kg / cm²The raw material suspension (A-1) was added and mixed in 30 seconds from the addition tank to the EGB solvent maintained at a bottom temperature of 160 ° C. The liquid temperature once decreased to 140 ° C. due to the addition, but returned to 160 ° C. after 13 minutes, and thereafter, the vapor phase pressure was 5 kg / cm at 160 ° C. ± 3 ° C.²For 6 hours to obtain a suspension (D-1) of In-containing ZnO particles (P-1).
[0108]
                              -Comparative Example 1-
  In Example 1 (1),It was obtained by replacing anhydrous zinc acetate with zinc acetate dihydrate and changing the raw material formulation so that the water / Md molar ratio was 110.A suspension (Dc-1) of In-containing ZnO particles (Pc-1) was similarly obtained except that the raw material suspension (Ac-1) was added to EGB maintained at 160 ° C. under normal pressure. Obtained.
[0109]
Table 2 shows the analysis results of the particles obtained in Example 1 (1) and Comparative Example 1.
[0110]
                      -Example 1 (2)−
  Shown in Table 1SuharaA suspension of the sample is prepared and shown in Table 1.WarmThe reaction was conducted in the same manner as in Example 1 (1) except that the addition was performed under the conditions of temperature and pressure and the heat treatment was performed under the conditions of temperature and pressure shown in Table 1.,acidCompound particles (P-2) Suspension (D-2) In addition,At this time,As solventIsPropylene glycol monomethyl ether(Hereinafter referred to as PGM).
[0111]
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.
[0112]
-Example 1 (5)-
After charging 900 parts of n-butanol into the reactor in Example 1 (1) and replacing the gas phase part with nitrogen gas, the temperature was raised from room temperature and the liquid temperature was maintained at 280 ° C. Gas phase pressure is gauge pressure 43kg / cm²Met.
[0113]
A raw material suspension (A-5) was prepared by mixing 216 parts of anhydrous indium acetate (III) powder, 12.6 parts of titanium (IV) n-butoxide and 270 parts of n-butanol, and charged into the addition tank. It is.
[0114]
The raw material suspension (A-5) was added to and mixed with the n-butanol solvent maintained at the bottom temperature of 280 ° C. in 30 seconds from the addition tank. The temperature once decreased to 240 ° C. due to the addition, but after increasing the temperature to 280 ° C. again, by holding at 280 ± 3 ° C. for 4 hours, Ti-containing In₂O_ThreeA suspension (D-5) in which the particles (P-5) were dispersed at 7.3% by weight was obtained. Table 3 shows the analysis results of the obtained particle P-5.
[0115]
-Examples 1 (6) to 1 (16)-
By adding the additive raw material shown in Table 4 or 5 to the bottom solution under the addition conditions (temperature and pressure) shown in the same table, and maintaining the heat treatment holding conditions shown in the same table for a certain time, oxide fine particles ( Suspensions (D-6 to D-16) in which P-6 to P-16) were dispersed were obtained. The ethylene glycol monoethyl ether acetate used as a solvent is hereinafter referred to as EGEA. Table 6 shows the analysis results of the obtained particles P-6 to P-16.
[0116]
-Example 2 (1)-
The suspension (D-1) obtained in Example 1 (1) was centrifuged to obtain a solid content. This solid content was dried to obtain a powder of In-containing ZnO particles (P-1).
[0117]
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 dispersing the mixture with a homogenizer. A coating film (F-1) was obtained by applying and drying this composition on a PET film to a dry film thickness of 10 μm.
[0118]
The light transmittance in 1.5 micrometers of the obtained coating film (F-1) was 30%.
[0119]
-Comparative Example 2-
In Example 2, In-containing ZnO particles (Pc-1) were obtained using the suspension (Dc-1) instead of the suspension (D-1). Using this, a coating composition (Cc-1) and a coating film (Fc-1) were obtained in the same manner as in Example 2 (1). The light transmittance at 1.5 μm of the obtained coated film (Fc-1) was 52%.
[0120]
-Example 2 (2)-
In Example 2 (1), In-containing ZnO particles (P-2) were obtained using the suspension (D-2) instead of the suspension (D-1). Using this, a coating composition (C-2) and a coating film (F-2) having a dry film thickness of 10 μm were obtained in the same manner as in Example 2 (1).
[0121]
The light transmittance in 1.5 micrometers of the obtained coating film (F-2) was 25%.
[0122]
-Example 2 (3)-
In Example 2 (1), using the suspension (D-5) instead of the suspension (D-1), the Ti-containing In₂O_ThreeParticles (P-5) were obtained. Using this, in the same manner as in Example 2 (1), a coating composition (C-5) and a coating film (F-5) having a dry film thickness of 10 μm were obtained.
[0123]
The light transmittance in 1.5 micrometers of the obtained coating film (F-5) was 10% or less.
[0124]
[Table 1]

[0125]
[Table 2]

[0126]
[Table 3]

[0127]
[Table 4]

[0128]
[Table 5]

[0129]
[Table 6]

[0130]
【The invention's effect】
The metal oxide particles according to the present invention are excellent in functions such as heat ray shielding performance and visible light permeability.
[0131]
The method for producing metal oxide particles according to the present invention makes it possible to easily obtain metal oxide particles having excellent functions such as heat ray shielding performance and visible light permeability.
[0132]
Since the metal oxide particle-containing composition according to the present invention contains the metal oxide particles of the present invention, the heat ray shielding property and transparency are high. It is excellent in various functionalities such as electrical functions such as photocatalytic functions such as photocatalytic functions, and has high weather resistance.

Claims (3)

In the metal oxide particles obtained by adding the different metal (Md) to the metal (M), the content (Md / M) of the different metal (Md) is 0.5 to 20 atomic% on average, and there 0.5 atomic% or more primary particles central, characterized in that, different type metal-containing metal oxide particles. A method for producing different metal-containing metal oxide particles having an average content (Md / M) of different metal (Md) of 0.5 to 20 atomic%, wherein the metal (M) has the following general formula (I) And a step of precipitating metal oxide particles by heating a solution containing the compound represented by formula (1) and / or a hydrolysis condensate, a compound of a different metal (Md), and an alcohol but no carboxylic acid , with water content of 100 moles in terms of a molar ratio relative to the dissimilar metals (Md), said heating is carried out under pressure, and wherein the method of dissimilar metal-containing metal oxide particles.
M (O) _{(mxyz) / 2} (OCOR) _x (OH) _y (OR ') _z (I)
(Where M is an m-valent metal atom; R is at least one selected from a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an aryl group and an aralkyl group; R ′ is a substituent group) And at least one selected from an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group, and m, x, y, and z are x + y + z ≦ m, 0 <x ≦ m, 0 ≦ y <m, 0 ≦ z <m is satisfied.)   A metal oxide particle-containing composition comprising 0.1% by weight or more of the dissimilar metal-containing metal oxide particles according to claim 1 with respect to the binder resin.