JP2000185916A - Metal oxide-based particle, its production and use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide metal oxide-based particles having excellent dispersibility, to provide a method for producing the same, and to provide a use of the same. SOLUTION: The metal oxide-based particles contain the oxide of a metal element (M) as a main component. Therein, the particles contains a carboxylic acid (residual) group in an amount of 0.01-14 mol.% based on the metal element (M), and further satisfies follows (1) and/or (2). (1) The particles exhibit crystallinity based on the oxide of the metal element (M) by X-ray diffraction, and have crystal sizes Dw of 1 to 100 nm measured by Wilson method. (2) The particles have a specific surface area diameter Ds of 1 to 100 nm calculated from the following numerical formula: Ds=6/(ρ×S) [ρ is the true specific gravity of the metal oxide-based particles; S is the specific surface area (m2/g) of the metal oxide-based particles, measured by B. E. T. method].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to metal oxide particles having excellent monodispersibility, a method for producing the same, and uses thereof.

[0002]

2. Description of the Related Art Metal oxide particles are used in vulcanization accelerators for rubber, various paints, printing inks, paints, glass, catalysts, pharmaceuticals, pigments, ferrites, and other raw materials.
Particles having a particle diameter of 0.1 μm or less and having high dispersibility are required. It is known that ultrafine particles of metal oxides can be obtained by gas phase methods such as oxidative pyrolysis of metal halides or oxidation of metal vapor. However, there is a problem that only a powder having a strong secondary cohesion can be obtained. Taking zinc oxide particles whose metal oxide is zinc oxide as an example, zinc oxide particles having a particle diameter of 0.1 μm or less can be obtained by a method of vapor-phase oxidation of zinc vapor. The system particles contain coarse crystals, and
At present, it has a low secondary dispersibility due to strong secondary aggregation, and the physical properties based on the fine particle diameter cannot be sufficiently exhibited.

In order to solve the problem of dispersibility, various attempts have been made, and the inventor of the present invention has attempted to disperse the solution by heating a solution containing a zinc compound, a carboxyl group-containing compound and an alcohol, and a large amount of water. Has been confirmed (JP-A-7-232919). However, at present, it is required to further improve the dispersibility of the metal oxide-based particles.

[0004]

Accordingly, an object of the present invention is to provide metal oxide-based particles having excellent dispersibility, a method for producing the same, and uses thereof.

[0005]

Means for Solving the Problems The present inventors diligently studied to solve the above-mentioned problems, improved the method for producing zinc oxide-based particles developed earlier, and obtained the metal represented by the above general formula (I). The present inventors have found that by reacting a compound under a condition of a small amount of water, metal oxide-based particles having further excellent dispersibility can be obtained, and the present invention has been completed.

That is, according to the metal oxide-based particles of the present invention, in the metal oxide-based particles mainly containing an oxide of the metal element (M), a carboxylic acid (remaining) group is added to the metal element (M). 0.01 to 14 mol%, and the following (1)
And / or (2) is satisfied. (1) X-ray diffraction indicates crystallinity based on an oxide of a metal element (M), and when the size of a crystallite is Dw, which is determined by the Wilson method, 1 nm ≦ Dw ≦ 100 nm. (2) Assuming that the specific surface area diameter calculated by the following formula is Ds, 1 nm ≦ Ds ≦ 100 nm Ds = 6 / (ρ × S) (where, ρ: true specific gravity of metal oxide particles, S: BE
T. Specific surface area (m ²
/ G)) The method for producing metal oxide-based particles according to the present invention comprises heating a solution containing a compound of a metal element (M) and / or a hydrolyzed condensate thereof and an alcohol to form a metal oxide. In the method for producing metal oxide-based particles, wherein the compound is represented by the following general formula (I), and the amount of water contained in the solution is adjusted by adjusting the amount of water contained in the metal oxide-based particles as a main component of the metal oxide-based particles. The method is characterized in that the solution is heated to 100 ° C. or higher in a molar ratio of 4 or less to the element (M).

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. The metal oxide-based particle-containing composition according to the present invention contains the metal oxide-based particles described above and a binder component, and the ratio of the metal oxide-based particles to the total solid content of the two is 0. 1 to 99% by weight of the composition.

The film containing metal oxide particles according to the present invention is obtained by forming a coating film obtained from the composition containing metal oxide particles on a base film.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Metal oxide-based particles] The metal oxide-based particles according to the present invention are particles containing an oxide of a metal element (M) as a main component. The content of the oxide of the metal element (M) is preferably from 80 to
99.99% by weight, more preferably 90-99% by weight
It is.

The metal element (M) is not particularly limited, but includes, 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 element; Sc,
Group IIIa metal element such as Y; Group IVa metal element such as Ti, Zr, Hf; Group Va metal element such as V, Nb, Ta; Cr, M
Group VIa metal elements such as o and W; VIIa such as Mn, Tc and Re
Group metal element: Fe, Co, Ni, Ru, Rh, Pd, O
Group VIII metal elements such as s, Ir, Pt; Cu, Ag, Au
Group Ib metal element such as Zn, Cd, Hg; Group IIIb metal element such as Al, Ga, In, Tl; G
Group IVb metal elements such as e, Sn and Pb; Vb such as Sb and Bi
Group VI metal elements; Group VIb metal elements such as Se and Te; and the like, and these may be used alone or in combination of two or more. However, the metal oxide-based particles show zinc oxide crystallinity in an X-ray diffraction manner, and the metal element (Md) which can take a trivalent and / or tetravalent state in the zinc oxide is 0.1% based on Zn.
Those containing up to 20 atomic% are not included in the present invention.

Among the specific examples of the metal element (M), Z
n, Ti, Ce, Fe, Ni, V, Nb, Be, La,
Mo, W, Re, In, Ga, Sn, Sb, and the like control light, electric, and magnetic functions by metal valence, particle size, crystal structure, impurity implantation, defect implantation, and the like. be able to. Therefore, it is preferable in that it has an optical function such as a light selective transmission function such as an ultraviolet absorbing property and an infrared shielding property, a (light) conductive function, a magnetic function and the like. Further, F
For e, Ni, V, Nb, Be, La, Mo, W, etc., stable particles having high transparency can be obtained. Zn is preferable because optical characteristics such as ultraviolet absorption and electrical properties can be controlled by controlling the crystal structure and the impurity concentration.

The metal oxide-based particles according to the present invention contain a carboxylic acid (residual) group. The carboxylic acid (residue) group in the present invention means a -COO- group, specifically, a carboxyl group (-COOH), a carboxylate group (-
COO ^-), a carboxyl group and by hydrolysis /
Or an ester group that generates a carboxylate group.

The carboxylic acid (remaining) group is adsorbed and / or chemically bonded to be present on the surface of the metal oxide-based particles, whereby secondary aggregation is suppressed, dispersibility is improved, and the carboxylic acid (residue) group is used as a paint. Transparency increases. As the carboxylic acid (residue) group, a saturated fatty acid (residue) group is preferable, and has 1 to 4 carbon atoms.
Are more preferred, and the acetoxy group (C
H ₃ COO-) is most preferred.

The content of the carboxylic acid (residual) group is 0.01 to 14 mol%, preferably 0.1 to 7 mol%, more preferably 1 to 5 mol%, based on the metal element (M). is there. When the content of the carboxylic acid (residual) group is less than 0.01 mol% based on the metal element (M), the dispersibility of the particles is reduced, and the particles are likely 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 deteriorated.

The metal oxide-based particles may contain a carbonate group in a range of 10% by weight or less, preferably 3% by weight or less based on the metal element (M). The metal oxide particles according to the present invention satisfy the following (1) and / or (2). (1) X-ray diffraction indicates crystallinity based on an oxide of a metal element (M), and when the size of a crystallite is Dw, which is determined by the Wilson method, 1 nm ≦ Dw ≦ 100 nm. (2) Assuming that the specific surface area diameter calculated by the following formula is Ds, 1 nm ≦ Ds ≦ 100 nm Ds = 6 / (ρ × S) (where, ρ: true specific gravity of metal oxide particles, S: BE
T. Specific surface area (m ²
/ G)) The above Dw is more preferably 2 nm <Dw <30 nm,
The range is more preferably 5 nm <Dw <20 nm, and most preferably 5 nm <Dw <15 nm. If Dw is too small, the ultraviolet shielding property, the conductivity and the like will be reduced. On the other hand, if it is too large, transparency to visible light decreases.

The above Ds is more preferably 3 nm <Ds
<50 nm, more preferably 8 nm <Ds <40 nm
Range. If Ds is too small, the ultraviolet shielding property, the conductivity and the like are reduced. On the other hand, if it is too large, transparency to visible light decreases. The dispersed particle diameter Dd of the metal oxide-based particles of the present invention is preferably 0.5 μm or less from the viewpoint that transparency is high and the hue of the composition containing the metal oxide-based particles is not substantially affected. . It is more preferably 0.1 μm or less, and further preferably 0.05 μm or less. In particular, it is preferably 0.03 μm or less. It is preferable that the monodispersity is high from the viewpoint of transparency. The monodispersity is defined by the ratio (Dd / Dw) of the size (crystallite diameter) Dw and Dd of the crystallite or the ratio (Dd / Ds) of the diameter Ds and Dd of the specific surface area. It is preferably at most 3, more preferably at most 3, particularly preferably at most 1.5.

The dispersion particle size Dd can be measured by a dynamic light scattering method, a centrifugal sedimentation method or the like. In the present invention, when the dispersion particle size is less than 1 μm, the former value is 1 μm or more. In the case of, the value measured by the latter measuring device is adopted. When the metal oxide-based particles of the present invention have a UV transmission end of TI _UV , preferably TI _UV ≧ 370 n
m, more preferably TI _UV ≧ 372 nm, most preferably TI _UV ≧ 374 nm. TI _UV is an important physical property when the metal element (M) is Zn, Ti, Ce, Fe, or the like. In addition, the TI _UV performs diffuse reflectance measurement on the metal oxide-based particles, and the reflectance at 350 nm at which the reflectance becomes substantially 0% in a wavelength range of 300 to 400 nm is defined as R (350) (%). , The reflectance is [R (35
0) +2] (%). TI _UV is 370n
If it is less than m, the ultraviolet shielding properties will be reduced. In particular, when the metal element (M) is Zn, if the TI _UV is within the above range,
By including these particles in a film, a film having high transparency and excellent ultraviolet shielding properties can be obtained with a small amount of particles.

The shape of the metal oxide particles of the present invention is not particularly limited. Specific examples of the shape include a sphere, an elliptical sphere, a cube, a cuboid, a pyramid, a needle, a column,
Examples of the shape include a flake shape such as a rod shape, a tubular shape, a scale shape, and a (hexagonal) plate shape. The metal oxide-based particles of the present invention include those in which a polymer forms a matrix and the particles are dispersed in the matrix (polymer composite particles). It will be excellent. The content of the metal oxide-based particles in the particles is not particularly limited, but is preferably in the range of 1 to 90% by weight based on the total amount of the composite particles in terms of the oxide of the metal element (M).

Examples of the polymer used for the composite include an acrylic resin polymer, an alkyd resin polymer, an amino resin polymer, a vinyl resin polymer, an epoxy resin polymer, a polyamide resin polymer, a polyimide resin polymer, and a polyurethane resin polymer. In addition to polymers, polyester resin-based polymers, phenolic resin-based polymers, organopolysiloxane-based polymers, acrylic silicone resin-based polymers, polyalkylene glycols, etc., polyolefin-based polymers such as polyethylene and polypropylene, polystyrene-based polymers, and fluororesin-based heat Plastic or thermosetting resin; synthetic rubber or natural rubber such as ethylene-propylene copolymer rubber, polybutadiene rubber, acrylonitrile-butadiene rubber; polysiloxane group-containing polymer, etc. It can be mentioned.

The shape of the composite particles is preferably spherical or elliptical spherical. Regardless of the outer shape of the particles, it is preferable that the surface has rich irregularities. This is because if the surface has irregularities, the affinity for a binder component or the like in a coating film or the like containing the composite particles increases. The average particle size of the composite particles is not particularly limited, but is usually 0.0
The range is from 01 to 10 μm.

The metal oxide-based particles of the present invention have good dispersibility and dispersion stability in a binder component described later, and the metal element (M) is Ti, Ce, Zn, Fe, or the like. When the object exhibits strong ultraviolet absorption, it may be treated with a surface modifier for the purpose of reducing the photocatalytic activity of the metal oxide and imparting weather resistance. As the preferable surface modifier, the above-mentioned polymer can be used, but for the purpose of imparting weather resistance, a compound containing an MX group is exemplified. X is an alkoxy group, an acyloxy group, a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a β-dicarbonyl group (ligand),
is at least one member selected from the group consisting of β-ketoester groups (ligands), and M is a metal element, especially Si, T
At least one selected from the group consisting of i, Zr, and Al is preferable. From the viewpoint of imparting dispersibility (dispersibility in a paint or a solvent, stability of a paint, and the like), a polymer having an organic polymer chain is exemplified. Preferred in terms of both weather resistance and dispersibility are polymers containing an MX group and having an organic polymer chain, such as a polysiloxane group-containing polymer and acrylic silicone.

When the metal oxide-based particles of the present invention are zinc oxide-based particles, they may be surface-treated with a surface treating agent. The surface treatment agent may be any of an organic compound and an inorganic compound, and includes the following electron conductive metal (water)
Oxides and / or non-electroconductive metal (hydr) oxides are preferred. Examples of the electron conductive metal (hydroxide) include Re, In, Sn, Zn, Ni, Fe, Ti, and S.
b) or other metal elements, and (d) oxides further having a dopant (for example, Sb for tin oxide, Sn for indium oxide, and Al for zinc oxide). ) Oxides.

As the non-electroconductive metal (hydr) oxide,
For example, Al, Si, Zr, Mg, Ca, La, Y,
Examples include (hydr) oxides of metal elements having non-electronic conductivity, such as (hydr) oxides of metal elements such as Be, Sr, and Ba. Zinc oxide-based particles having a lower photocatalytic activity than Zn (hydr) oxide, Al, Si, Zr, Mg, Ca,
When treated with a (hydr) oxide of a metal element such as Re, In, and Sn, the weather resistance of a film or the like containing zinc oxide-based particles increases. When the zinc oxide-based particles are treated with an electron conductive metal (hydroxide), electron conductivity is imparted, and the film containing the zinc oxide-based particles has an antistatic property or an electrostatic property. Physical properties such as prevention properties are imparted, and stain resistance and the like are improved.

Regarding the surface treatment amount of the surface treatment agent,
Although not limited, preferably, zinc oxide is a metal acid.
It is 0.1 to 20% by weight in terms of a compound. Metallic acid of the present invention
When the oxide-based particles are zinc oxide-based particles,
Alkaline earth metal M_alIs 0.0001 <M_al/ Zn <
2 atomic% and / or alkaline earth gold
Electronegativity X of non-genus ions_iN less than 10
Of 0.0001 <N / Zn <0.1 atomic%
It is preferable that the affinity described later is increased and highly dispersed.
Paint can be obtained. As the metal N, 4 <X
_iThose satisfying <8.5 are preferred. Note that the ion
Qi negativity X_iIs Allred-Rochow of metal N
Is the electronegativity of X and the valence n of metal N, X _i= (1
+ 2n) It can be calculated by the formula of X.

The metal oxide particles of the present invention may have crystallinity based on the oxide of the metal element (M).
The particles having no crystallinity may be used, but the particles having crystallinity are preferable because they have properties such as conductivity and ultraviolet shielding properties.
When the metal oxide-based particles of the present invention have crystallinity, it is preferable to satisfy the following (a) to (d).

(A) The metal element (M) preferably contains a monovalent or divalent metal element Ma having a different metal species.
0.0001-5% by atomic ratio to metal element (M)
Is more preferably in the range of 0.001 to 2%, and most preferably in the range of 0.01 to 0.2%. The effect of the presence of Ma is to stabilize the oxide crystal surface of the metal element (M) and suppress secondary aggregation and coarse crystal growth. Therefore, fine particles having high monodispersity are obtained. If the amount of Ma is too small, such an effect will not be exhibited, and if the amount of Ma is too large, the weather resistance and the like of the coating containing these particles may decrease. The monovalent or divalent metal element Ma is an alkali metal element and / or an alkaline earth metal element, and includes lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like. Of these, rubidium,
Cesium, beryllium, magnesium, calcium, strontium and barium are preferred, and beryllium, magnesium, calcium, strontium and barium are more preferred.

(B) Halogen elements except F (ie,
Ions and / or atoms of chlorine Cl, bromine Br, iodine I) and sulfate SO ₄ ²⁻ and nitrate NO ₃ ⁻ (hereinafter, referred to as
The total content of the metal element (M) with the total content of the metal element (M) (calculated as the number of S atoms in the case of sulfate, and the number of N atoms in the case of nitrate). Is preferably 0.5% or less. It is more preferably at most 0.1%, further preferably at most 0.01%, particularly preferably at most 0.001%. This includes the case where no impurity H is contained. Only when the impurity H is not contained or does not exceed this range even if the impurity H is contained, particles having excellent functions of the metal oxide can be obtained.

(C) Assuming that the lattice distortion of the crystallite obtained by the Wilson method is Aw, it is preferable that 0 ≦ Aw ≦ 1 (%) is satisfied, and that 0 ≦ Aw ≦ 0.5 (%) is satisfied. More preferred. If Aw exceeds 1, the function of the metal oxide may be reduced. (D) when the metal oxide-based particles are zinc oxide-based particles,
Lattice plane (10
It is important that the particles show diffraction peaks at (0), (002), and (101) and satisfy the following crystallite parameters.

Using the Cauchy function approximation (Schacher method) and the Cauchy function approximation, the size Dc of the crystallite in the direction perpendicular to each diffraction plane (hkl)
When (hkl) is obtained, 0 <Dc (002) / Dc
(100) <1.5, preferably 0 <Dc (0
02) / Dc (100) <1.2, more preferably 0 <
Dc (002) / Dc (100) <1.1, more preferably 0.2 <Dc (002) / Dc (100) <1.
0, most preferably 0.4 <Dc (002) / Dc (1
00) <0.8. This is because transparency is high when it is in this range.

The metal oxide particles of the present invention are preferable because they can be easily produced by the production method of the present invention described in detail below, but may be produced by other methods. [Production Method of Metal Oxide Particles] The compound of the metal element (M) used in the production method of the present invention is represented by the above general formula (I)
It has a structure shown by.

As the metal element (M) in the compound of the metal element (M), the above-mentioned metal elements can be mentioned, and the same applies to preferred ones. As R or R ′ in the compound of the metal element (M), a metal oxide-based particle having high dispersibility is easily obtained, and therefore, an alkyl group having 1 to 4 carbon atoms such as a methyl group is preferable, and a methyl group is particularly preferable. preferable.

In the compound of the metal element (M), x preferably satisfies 1 ≦ x ≦ m, and y is 0 ≦
Those satisfying x <m / 2 are preferable, and z is 1 ≦ x
<M / 2 are preferable, and in these cases,
Metal oxide particles having high dispersibility can be easily obtained. The compound of the metal element (M) preferably has a high dissolution rate,
Particles having excellent dispersibility can be obtained. The dissolution rate is 25
At 25 ° C, 2 parts of compound of metal element (M)
Is mixed with 200 parts of ion-exchanged water (pH 5 to 8) and completely dissolved by stirring to define a time t until a transparent solution is obtained. The dissolution rate of the compound of the metal element (M) is preferably within 2 minutes, more preferably within 1 minute, and most preferably within 30 seconds.

The hydrolysis condensate of the compound of the metal element (M) includes a hydrolyzate obtained by hydrolyzing and / or condensing the compound of the metal element (M) having a structure represented by the general formula (I). And / or a condensate, which 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 metal element (M) and oxygen (O) are metalloxane-bonded. The degree of condensation of the condensate is not limited. In order to obtain metal oxide-based particles having uniform crystallite size and morphology, the degree of condensation (average) is preferably 100 or less, more preferably 10 or less. is there.

The alcohol used in the production method of the present invention is not particularly restricted but includes, for example, aliphatic monohydric alcohols (methanol, ethanol, isopropyl alcohol, n-butanol, t-butyl alcohol, stearyl alcohol, etc.), Aliphatic unsaturated monohydric alcohol (allyl alcohol, crotyl alcohol, propargyl alcohol, etc.), alicyclic monohydric alcohol (cyclopentanol, cyclohexanol, etc.), aromatic monohydric alcohol (benzyl alcohol, cinnamyl alcohol, Monohydric alcohols such as methylphenylcarbinol and heterocyclic monohydric alcohols (furfuryl alcohol and the like); alkylene glycols (ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5- Butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, pinacol, diethylene glycol, triethylene glycol, etc., and aliphatic glycols having an aromatic ring (hydrobenzoin, benzpinacol, phthalate) Alcohols), alicyclic glycols (cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, etc.), polyoxyalkylene glycols (polyethylene glycol, polypropylene glycol, etc.) Glycols such as;
Propylene glycol monoethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, triethylene glycol monomethyl ether, Derivatives such as monoethers and monoesters of the above glycols such as ethylene glycol monoacetate; hydroquinone, resorcinol, 2,2
Aromatic diols such as -bis (4-hydroxyphenyl) propane and their monoethers and monoesters; trihydric alcohols such as glycerin and their monoethers, monoesters, diethers and diesters. Or two or more are used.

In the production method of the present invention, a compound of a metal element (M) and / or a hydrolytic condensate thereof (hereinafter, sometimes simply referred to as a metal compound) is blended with an alcohol, and a solution containing these is mixed. Is prepared. The metal compound is
It may be in a completely dissolved state in a solution, or in a suspended or emulsified state. In order to improve the dispersibility of the obtained metal oxide-based particles, it is preferable that the solution is heated before the particles are precipitated to completely dissolve the metal compound. The amount of the alcohol is not particularly limited, but is preferably 1 to 30 times the weight of the metal compound in terms of metal oxide, and is preferably 15 to 15 times.
More preferably, the amount is 25 times.

When compounding the metal compound and the alcohol,
The alcohol is preferably heated at normal pressure or under pressure. The temperature is preferably 100-250 ° C, more preferably 120-200 ° C, most preferably 15-200 ° C.
0-200 ° C. If the alcohol is heated,
The conversion reaction rate from the metal compound to the zinc oxide-based particles is increased, so that secondary aggregation is suppressed, and particles having a uniform crystallite diameter can be obtained with high productivity. Further, if the temperature between the time when the metal compound is mixed with the alcohol and the time when the particles are formed is maintained at preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and most preferably 150 ° C. or higher, the same reason as described above can be obtained. Is preferred. Here, when the metal compound is mixed with the heated alcohol, the temperature of the alcohol decreases due to the sensible heat effect. However, the lowering temperature is preferably suppressed to 20 ° C. or lower, more preferably 10 ° C. or lower. As a method of suppression, it is preferable to previously heat the metal compound or a solution containing the metal compound, and the heating temperature is preferably 50 to 100 ° C.
If it exceeds 0 ° C., the metal compound may be altered.

The solution containing the metal compound and the alcohol is
It may contain a metal compound such as a carboxyl group-containing compound and a component other than alcohol. Examples of the carboxyl group-containing compound include compounds having only one carboxyl group in the molecule, such as a monocarboxylic acid compound. Specific examples of the monocarboxylic acid compound include saturated fatty acids (saturated monocarboxylic acids) such as formic acid, acetic acid, propionic acid, isobutyric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, and stearic acid; Unsaturated fatty acids (unsaturated monocarboxylic acids) such as methacrylic acid, crotonic acid, oleic acid, and linolenic acid; cyclic saturated monocarboxylic acids such as cyclohexanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, phenylacetic acid, and toluic acid Carboxylic acid; anhydrides of the above monocarboxylic acids such as acetic anhydride; trifluoroacetic acid, monochloroacetic acid, o-
Halogen-containing monocarboxylic acids such as chlorobenzoic acid; and compounds such as lactic acid can be mentioned, and one or more kinds are used. Preferred monocarboxylic acid compounds are those having 1 carbon atom.
~ 20 saturated fatty acids. Specifically, acetic acid, propionic acid, butyric acid, and isobutyric acid are preferable in that particles having excellent monodispersity can be easily obtained. This saturated fatty acid is preferably used in the range of 60 to 100 mol%, more preferably in the range of 80 to 100 mol%, based on the total amount of the monocarboxylic acid compound. If the ratio is less than the above range, the crystallinity of the oxide of the metal element (M) in the obtained particles may be low.

The amount of the carboxyl group-containing compound contained in the solution is not particularly limited, and is preferably 1 or less in terms of a molar ratio of the metal compound to the metal element (M).
More preferably 0.5 or less, most preferably 0.01
To 0.3, particles having high dispersibility can be obtained. The carboxyl group-containing compound is prepared by blending a metal compound with a heated alcohol and heating the solution as it is to produce the metal oxide-based particles. It may be added to the metal compound. Further, the solution may be heated and mixed before, after or simultaneously with the generation of the metal oxide-based particles.

[0039] When the metal element of the metal compound (M) is zinc, i.e., the case of M = Zn, an alkaline earth metal M _al of _{Ma 0.0001 <M al / Zn <} 2 atomic%
Or it is contained, and / or a metal N electronegativity X _i of ions other than alkaline earth metals is less than 10, 0.
If it is further contained in a solution containing a metal compound and an alcohol so as to contain 0001 <N / Zn <0.1 atomic%, 8 ≦ Dw ≦ 17 (nm), high dispersibility, and transparency Zinc oxide particles having excellent properties can be obtained. The zinc oxide particles have a high affinity for a resin component described later. The metal N preferably satisfies 4 <X _i <8.5.

The alkaline earth metal _Mal , metal N and / or
Or, as the compound, it is easily dissolved in alcohol,
Moreover, those containing no impurity H are preferable. For example, carboxylate salts (hydrates, such as acetates of alkaline earth metals such as Mg, Ca, Sr, and Ba; acetates of metal N such as Y and La, etc.) Anhydrides) and (basic) carbonates.

In the production method of the present invention, the amount of water contained in the solution containing the metal compound and the alcohol is set to a molar ratio of 4 or less with respect to the metal element (M) which is the main component of the obtained metal oxide-based particles. It is necessary to carry out the reaction in such a manner that the molar ratio is preferably 2 or less, more preferably 1 or less, most preferably 0.5 or less. When the molar ratio exceeds 4, the dispersibility of the obtained metal oxide-based particles decreases, and the transparency decreases.

In the production method of the present invention, a solution obtained by blending a metal compound and an alcohol is treated at a reaction temperature of 100 ° C.
By heating as described above or maintaining the temperature at 100 ° C. or higher, metal oxide-based particles are deposited. When the reaction temperature is lower than 100 ° C., the dispersibility of the obtained metal oxide-based particles decreases, and the transparency decreases. The total content of impurities H in the solution containing the metal compound and the alcohol,
The ratio of the number of atoms to the metal element (M) (calculated as the number of S atoms in the case of sulfate, and the number of N atoms in the case of nitrate) is 0.5% or less, more preferably 0.1% or less. ,
Further, when the content is 0.01% or less, particularly 0.001% or less, metal oxide-based particles having a small amount of impurities H can be easily obtained. The solution may not contain the impurity H at all.

In the production method according to the present invention, when the metal element (M) of the metal compound is zinc, the surface treatment with a surface treatment agent is performed for the purpose of imparting various physical properties to the obtained zinc oxide particles. Is preferred. Examples of the surface treatment method include a method of adding a surface treatment agent when heating a solution containing a zinc compound and an alcohol, or after heating to precipitate particles.

Examples of the surface treating agent include those described above, and preferred are metal alkoxides, metal carboxylate (especially acetate), and derivatives thereof. According to the production method of the present invention, metal oxide-based particles having excellent dispersibility can be easily obtained. [Metal oxide-based particle-containing composition] The metal oxide-based particle-containing composition according to the present invention is a composition containing the above-described metal oxide-based particles and a binder component. Since this composition contains the metal oxide-based particles according to the present invention,
Excellent dispersibility and high transparency.

The composition containing metal oxide particles according to the present invention is used as a coating composition or a composition for molding materials. Hereinafter, the coating composition and the molding material composition will be described in detail in this order. Coating Composition The metal oxide-based particle-containing composition of the present invention can be used as a coating composition. Since this coating composition contains the highly dispersible metal oxide-based particles of the present invention, a coating film having excellent transparency and high functionality can be obtained.

Examples of the binder component used in the coating composition include various synthetic resins of thermoplastic or thermosetting (including thermosetting, ultraviolet curable, electron beam curable, moisture curable, and combinations thereof). Organic binders such as natural resins and inorganic binders can be exemplified. Examples of the synthetic resin include an alkyd resin, an amino resin, a vinyl resin, an acrylic resin, an epoxy resin, a polyamide resin, a polyurethane resin, a thermosetting unsaturated polyester resin, a phenol resin, a chlorinated polyolefin resin, a silicone resin, and an acrylic silicone resin. , A fluororesin, a xylene resin, a petroleum resin, a ketone resin, a rosin-modified maleic resin, a liquid polybutadiene, a coumarone resin and the like, and one or more of these are used. Examples of natural resins include shellac, rosin (pine resin), ester gum, cured rosin, decolorized shellac,
White shellac and the like can be mentioned, and one or more of these can be used.

As the synthetic resin, a natural or synthetic rubber such as ethylene-propylene copolymer rubber, polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene copolymer rubber, or the like 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 component 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 component 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, and a water-soluble melamine. Resins and the like can be mentioned.

The emulsion-type binder component includes, for example, an alkyl (meth) acrylate copolymer dispersion; a vinyl acetate resin emulsion, a vinyl acetate copolymer resin emulsion, an ethylene-vinyl acetate copolymer resin emulsion, and an 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 in the production of an ultraviolet absorbing film described below, for example, film forming conditions such as film forming temperature, and from the viewpoint of the flexibility and weather resistance of the obtained film,
As the binder component used in the coating composition, a polyurethane resin, an acrylic resin, a fluororesin, or the like is preferable.

The proportion of the metal oxide-based particles in the coating composition is 0.1 to 99% by weight, preferably 1 to 99% by weight based on the total solid content of the metal oxide-based particles and the binder component.
0 to 90% by weight. The ratio of the metal oxide particles is 0.
If the content is less than 1% by weight, the effect obtained by adding particles such as ultraviolet shielding property and conductivity is reduced. On the other hand, when the ratio of the metal oxide-based particles exceeds 90% by weight,
Transparency and flexibility are reduced. When the metal oxide-based 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 metal oxide-based particles in the coating composition are used. 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 component.

The coating composition contains metal oxide particles and a binder component as essential components, and in addition to these, according to required performance, a curing agent such as a crosslinking agent; a curing catalyst such as a curing assistant; a plasticizer; Agents / Leveling Agents; Thixotropic Agents; Matting Agents; Surfactants; Flame Retardants; Pigment Wetting Agents / Dispersants; Lubricants; UV Absorbers; Light Stabilizers; Antioxidants; Other (Heat) Stabilizers; A fungicide; an antialgal agent; an anticorrosive / rust inhibitor; a dye; 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 a binder component having an epoxy group such as an amino resin having a methylol group, 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, and a methylol group A curing agent used for a binder component 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 component having a carboxyl group such as a metal chelating agent; , Polyfunctional epoxy compounds, hydroxyl-containing compounds, etc. Curing agent used in the binder component 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-based 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,
High versatility. 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 according to the purpose of use of the coating composition and the type of the binder component. 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 the coating composition, for example, after adding metal oxide-based particles to an organic solvent to form a slurry, a binder component is mixed with the slurry containing the metal oxide-based particles to form a 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 substrate 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; 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, 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 waste disposal, it is increasingly important to use a biodegradable resin as a base material 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-mentioned base material, or a base material in which a primer layer or the like is previously arranged for the purpose of improving the adhesion between the coating film composed of the coating composition and the base material, etc. It may be something. Among these, among the plastic films and sheets, fluorine-based resins having high weather resistance,
Polyester resins, (meth) acrylic resins, and polycarbonate resins are preferred.

The method for applying the coating composition is not particularly limited, and examples include dipping, roll coater, flow coat, screen printing, bar coater, spin coater, brush coating, spraying, and the like. 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 forming a 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 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 The metal oxide-based particle-containing composition of the present invention can be used as a molding material composition. Since the composition for a molding material contains the metal oxide-based particles of the present invention, a molded article having excellent dispersibility and high transparency, weather resistance and flexibility can be obtained.

As the binder component used in the composition for a molding material, 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,
Thermoplastic resins such as polystyrene, (meth) acrylic resin, ABS resin, silicone resin, fluororesin and monomers used as raw materials for these; phenolic resins (phenol
Thermosetting resins such as formalin resins, cresol / formalin resins), epoxy resins, amino resins (urea resins, melamine resins, guanamine resins, etc.) and monomers used as raw materials for these resins. One or two or more are used.

Examples of the binder component used in the composition for a molding material 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 component used in the composition for a molding material, the above-mentioned inorganic binder may be used.

The ratio of the metal oxide particles in the composition for a molding material is 0.1 to 99% by weight, preferably 0.3% by weight, based on the total solid content of the metal oxide particles and the binder component. -10% by weight. When the proportion of the metal oxide-based 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-based particles exceeds 99% by weight, strength, transparency and flexibility are reduced.

The composition for a molding material contains metal oxide-based particles and a binder component as essential components. In addition to these, according to required performance, a curing agent, a curing accelerator, a coloring agent, a release agent, a coupling agent, It may contain additives such as a silicone compound, a reactive diluent, a plasticizer, a stabilizer, a flame retardant aid, a crosslinking agent and the like. A curing agent may be required when using a thermosetting resin as a binder component. For example, when an epoxy resin is used as the binder component, polyamides, aliphatic polyamines, cycloaliphatic polyamines, aromatic polyamines or partially modified amines, acid anhydrides, dicyandiamides, imidazole , Amine imides, hydrazides,
Novolak-based curing agents such as phenol novolak and cresol novolak can be used, and one or more of these can be used. When a phenol resin is used as the binder component, urotropin and formal can be used, and one or more of these are used. These amounts are used in appropriate amounts with respect to the binder component.

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 a binder component, polyglycols are preferable. The stabilizer suppresses decomposition of the binder component, and examples thereof include lead stearate and zinc stearate.

Examples of the method of producing the composition for a molding material include a method of uniformly mixing metal oxide particles and a binder component using a mixing device such as a roll, a kneader, a mixer, or the like. . Examples of the method for molding the composition for a molding material include extrusion molding, injection molding, casting, compression molding, low-pressure transfer molding, and cast molding.

The composition for a molding material may be formed into a film, for example, and the resulting film has a high particle dispersibility and excellent transparency. A laminated glass can be obtained by sandwiching a metal oxide-based particle-containing sheet obtained by molding the composition for a molding material with a transparent plate such as a glass plate and curing it appropriately. The thickness of the metal oxide-based particle-containing sheet is preferably 0.1 to 2 mm, more preferably 0.5 to 1 mm. [Film Containing Metal Oxide Particles] The film containing metal oxide particles according to the present invention is obtained by coating a coating film obtained from the composition (paint composition) containing metal oxide particles according to the present invention with a base film. It is a film formed thereon. Since the film containing metal oxide particles contains the metal oxide particles of the present invention, the film has high transparency and flexibility.

Examples of the substrate film used for the metal oxide-based particle-containing film include a film made of a resin used as a substrate, which has been described in detail in the section of the coating composition. The same applies to preferred ones. There is no particular limitation on the thickness of the base film,
Preferably 5 to 500 µm, more preferably 10 to 2
00 μm.

The method for applying the coating composition on the surface of the substrate film, the dry film thickness, etc. are not particularly limited, and the above-mentioned ones are preferable. The metal oxide-based particle-containing film is not particularly limited as long as the coating film obtained from the coating composition is formed on the base film, and may be further processed according to the application, required characteristics, and the like. . Metal oxide-based particle-containing film, the surface of the coating film not in contact with the base film,
And / or 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. There may be.

The ultraviolet transmittance of the film containing metal oxide particles is not particularly limited, but is preferably 50% or less, more preferably 10% or less. The ultraviolet transmittance is a value obtained by an apparatus and a measuring method described in JIS R 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 was measured in a wavelength range of 380 to 780 nm,
These are values obtained by the apparatus, measurement method and calculation method described in IS R 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 metal oxide-based particle-containing film is determined according to JIS B 77
An accelerated weather resistance test was performed using a shine-shape carbon arc lamp type light resistance and weather resistance tester described in 53-93, and based on the haze value and hue after the initial 100 hours, and after a further 240 hours test When the haze value and the hue are compared, the change in haze is preferably less than 2%, and more preferably no change in color (discoloration).

[0075]

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. Evaluation and the like in this example were performed by the following method. 1. Evaluation of metal oxide particles <Method for preparing 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. <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 the acetoxy group with respect to the metal element 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), the crystallite diameter in the direction perpendicular to each obtained diffraction plane (hkl) Dw: the crystallite size and lattice strain obtained by using the Wilson method Other than <amount of impurity H> F The content of the halogen element was determined by fluorescent X-ray analysis of the powder sample.
It was determined by ion chromatography analysis in the same manner as in the analysis of the carboxylic acid (residue) group content. <Ultraviolet shielding property> The diffuse reflectance of the powdered sample was measured, and the reflectance at 350 nm at which the reflectance became substantially 0% in the wavelength range of 300 to 400 nm was R.
(350) (%), the reflectance is [R (350) +
2] The wavelength at which (%) was obtained was defined as the UV transmission end TI _UV . The diffuse reflectance measurement was performed using a self-recording spectrophotometer (UV-3100 manufactured by Shimadzu Corporation) in which an integrating sphere attachment device (ISR-3100 manufactured by Shimadzu Corporation) was attached to the sample chamber. The ultraviolet shielding property was evaluated according to the following evaluation criteria. ◎: TI _UV ≧ 374 nm ○: 370 nm ≦ TI _UV <374 nm ×: TI _UV <370 nm <monodispersity> The dynamic light scattering method of the dispersion obtained by the particle formation reaction was carried out by the following measuring apparatus and measuring method. To determine the number average particle size Ddn, and the ratio (r =
Ddn / Dw) according to the following evaluation criteria. Examples 5-1 to 5-19, 6-1 to 6-
5 and 7-1 to 7-3 and Comparative Examples 3 and 4 were measured by the measurement method (2). The other examples and comparative examples were measured by the measurement method (1).

Measuring apparatus: DLS-700 dimic light diffuser manufactured by Otsuka Electronics Co., Ltd. Measuring method (1): The dispersion is heated under reduced pressure to a concentration of 25% by weight in terms of oxide (zinc oxide) of metal element (M). The cake is concentrated and centrifuged to obtain a cake. A cake containing 0.5 g of oxide (concentration of oxide (zinc oxide) of metal element (M) (zinc oxide) 50 to 70% by weight) is weighed, and polyesterpolyamine is reduced to 0%. The mixture was mixed with 10 g of a toluene solution containing 0.15% by weight and stirred for 1 hour with a magnetic stirrer, and then measured. Upon measurement, toluene was used as a diluting solvent. A: r <1.5 B: 1.5 ≦ r <3 C: 3 ≦ r <5 D: 5 ≦ r Measurement method (2): The dispersion is centrifuged to obtain a cake. Vacuum drying at 50 ° C. for 10 hours gives powder of particles. Acrylic resin (average molecular weight: 8000, acid number: 2,
A sample was prepared by mixing 4 parts of a toluene solution containing 25% by weight of (hydroxyl value: 20,) and 20 parts of a toluene solution containing 0.15% by weight of a polyester polyamine and subjecting the mixture to a dispersion treatment with an ultrasonic homogenizer for 15 minutes. did. The obtained sample was evaluated by the above-mentioned measuring device. In the measurement, toluene was used as a diluting solvent. A: r <1.5 B: 1.5 ≦ r <3 C: 3 ≦ r <5 D: 5 ≦ r <Transparency> Concentrated dispersion 12 prepared by the above-described measurement of dispersibility.
Acrylic resin binder solution (number average molecular weight: 1)
5000, acid value: 2, hydroxyl value: 10, solid content concentration: 4
(0% by weight, solvent: toluene-butanol) was added and mixed, and the mixture was stirred with a stirring power of 0.1 kw / m ^3. Then, it was dried at 100 ° C. for 5 minutes using a hot air drier. The haze of the obtained film was measured, and the transparency was evaluated. The lower the value, the higher the transparency. The haze was measured using a turbidity meter (NDH-1001 DP, manufactured by Nippon Denshoku Industries Co., Ltd.). <Particle Concentration in Dispersion> A part of the dispersion was weighed in a crucible, vacuum-dried at a temperature 40 ° C. lower than the boiling point of the solvent for 24 hours, and then heated in air at 600 ° C. for 1 hour to obtain an ash content. I asked more. <Powder resistance> Measured under a pressure of 800 kg / cm ² . 2. Evaluation of Compound of Metal Element (M) <Solubility> Compound of metal element (M) (zinc compound) in 20 g of ion-exchanged water at 25 ° C. and pH 6.5 ± 0.3.
2 g was added and mixed, and the mixture was stirred with a stirring power of 0.1 kw / m ³ , then dissolved, and the time until the solution became a transparent solution was measured and evaluated according to the following evaluation criteria. The term “transparent” as used herein means that the haze of the solution is 1% or less. However, when the compound of the metal element (M) (zinc compound) is in the form of a transparent solution (dissolved in an arbitrary solvent), the compound is added to the above ion-exchanged water and stirred for 1 minute. In this case, it was determined to be A. Once a precipitate was formed and became cloudy, the time from the cloudy point until the glass became transparent again was measured and evaluated according to the following criteria. A: less than 1 minute B: 1 minute or more <Water content of compound (zinc compound) of metal element (M)> A compound (zinc compound) of metal element (M) is mixed in methanol, and water released is determined by Karl Fissi. It was measured by the Yer method. When water of crystallization exists and is not liberated at room temperature, a compound (zinc compound) of the metal element (M) is suspended in ethylene glycol monomethyl ether acetate to prepare a suspension.
Heat treatment was performed at 1 ° C. for 1 hour, and the released water was measured. <Water content of solution> The sum of the water content of the compound (zinc compound) of the metal element (M) and the water content contained in the other solution raw materials was determined. <Specific surface area> E. FIG. T. It was measured by the method. The pretreatment temperature was 50 ° C. for 2 hours in a mixed gas of nitrogen and helium. 3. Evaluation of Coated Products and Resin Molded Products Obtained in Examples <Spectral Characteristics> The ultraviolet shielding property and the visible light transmittance were measured by the above-mentioned spectrophotometer (with an integrating sphere) for light in the wavelength range of 300 to 800 nm. The transmittance was measured and evaluated. The wavelength λa at which the ultraviolet ray shielding spectral transmittance was 2% was determined and evaluated according to the following evaluation criteria. ：: λa ≧ 370 nm ○: 365 nm ≦ λa <370 nm ×: λa <365 nm Visible light transmittance Visible light transmittance using the transmittance and the weighting factor for light of each wavelength according to the method described in JIS R 3106-1985. Tv was calculated and evaluated according to the following evaluation criteria. ：: Tv ≧ 80% △: 70% ≦ Tv <80% ×: Tv <70% <Transparency> Turbidity meter (NDH-10 manufactured by Nippon Denshoku Industries Co., Ltd.)
01 DP) was measured for haze (actual measurement). <Surface resistance> A gold comb-shaped electrode is deposited on the coating film surface (thickness: 3).
0 nm ± 5 nm), left for 1 hour under the conditions of a temperature of 25 ° C. and a relative humidity of 50%, and shielded from light, and then measured the surface resistance under the same conditions using an electrometer 617 manufactured by Kesley (under an applied voltage of 0. 1V). <Weather Resistance> The film-coated glass was subjected to an accelerated weather resistance test using a sunshine carbon arc lamp type light resistance and weather resistance tester described in JIS B 7753-93. Based on the haze value and the hue after the initial 100 hours, the haze value and the hue after the 240-hour test were further compared and evaluated according to the following evaluation criteria. A: Haze change is less than 2%, and there is no coloring (discoloration). B: Haze change is 2% or more and / or coloring (discoloration) is present. <Stain resistance> The test piece was exposed outdoors for 10 days, and the degree of contamination on the surface (coating side) was relatively evaluated.

Example 1-1 Externally heatable 100 liter stainless steel (SUS316) reactor equipped with a stirrer, addition port, thermometer, distillate gas outlet and nitrogen gas inlet, and addition 1000 parts of benzyl alcohol was charged into a reactor equipped with an addition tank directly connected to a mouth via a ball valve, a cooler directly connected to a distillate gas outlet, and a distillate trap.
The temperature rose. To this reactor, 147 parts of zinc acetate dihydrate powder (manufactured by Kanto Chemical Co., industrial) was added from the addition tank over 30 seconds, and the temperature was raised. After reaching 200 ° C., the temperature was maintained for 1 hour. Thus, 896 parts of a dispersion in which particles were precipitated were obtained. The minimum temperature of the bottom in the process of increasing the temperature to 200 ° C. from the time of zinc acetate dihydrate addition was 145 ° C. immediately after the addition. When the bottom temperature of the heating process reaches 170 ° C,
34 parts of a benzyl alcohol solution containing 20% by weight of lauric acid was added to the bottom from the addition tank over 1 minute.

The resulting dispersion (d1) contained 6.2% by weight of zinc oxide-based particles (P1) having the physical properties shown in Table 4. The solvent of the dispersion (d1) was mainly benzyl alcohol, but benzyl acetate was also used in addition to the solvent.
0% by weight was contained. The water content in the dispersion was less than 0.1% by weight. The specific surface area and the true specific gravity of the zinc oxide-based particles (P1) were measured, and the specific surface area diameter was 40 nm.

Comparative Example 1-1 147 parts of the zinc acetate dihydrate powder used in Example 1-1,
41 parts of acetic acid, 97 parts of ion-exchanged water and 1220 parts of benzyl alcohol were charged into the same reactor as in Example 1-1, and the temperature was raised from room temperature (25 ° C.) at a rate of 1 ° C./min.
It was kept at 200 ° C. for 1 hour. Obtained dispersion (cd1)
Contained the zinc oxide-based particles (CP1) having the physical properties shown in Table 4. The specific surface area and the true specific gravity of the zinc oxide-based particles (CP1) were measured, and the specific surface area diameter was 107 nm.

-Examples 1-2 to 1-10- Using the same reactor as in Example 1-1, the reaction was carried out under the zinc compounds and temperature conditions shown in Tables 1 to 3.
Dispersions (d2) to (d10) containing zinc oxide particles (P2) to (P10) were obtained. Table 4 shows the physical properties of the dispersions (d2) to (d10) obtained above and the zinc oxide-based particles (P2) to (P10) in these dispersions. In each of these dispersions, particles were dispersed in a mixed solvent containing the alcohol used as a main solvent component.

The zinc oxide particles (P3) obtained in Example 1-3 and the zinc oxide particles (P3) obtained in Example 1-4
4) and the zinc oxide-based particles (P
9) was excellent in colorlessness. The specific surface area and the true specific gravity of the zinc oxide-based particles (P4) were measured, and the specific surface area diameter was 20 nm. In addition, zinc oxide particles (P8)
The specific surface area and the true specific gravity were measured.
nm.

The dispersion (d3) prepared in Example 1-3 was centrifuged to remove 50% of zinc oxide particles.
A cake containing the weight% was obtained. This cake was suspended to a particle concentration of 7% by weight, and then centrifuged again to obtain a cake containing zinc oxide-based particles at 65% by weight. A dispersion (DE3) of 40% by weight was obtained.

Further, as shown in Table 5, Examples 1-4
From dispersions (d4) to (d10) obtained in to 1-10, various dispersions (DE4) to (DE10) and dispersions (DO)
8) was prepared.

[0085]

[Table 1]

(Note) Metal added: An alcohol in which an acetate of each metal was dissolved in advance was used. Acetic acid addition amount: The amount of acetic acid added by adding an alcohol in which a predetermined amount of acetic acid is dissolved just before adding and mixing the zinc compound.

Water content: The total amount of the water content in the zinc compound or the slurry in which the zinc compound or the zinc compound is dissolved or suspended, and the water content in the alcohol is represented by a molar ratio to zinc. Mixing ratio: a mixing ratio of an alcohol and a zinc compound, which is an alcohol / zinc oxide (weight ratio) calculated in terms of zinc oxide.

[0088]

[Table 2]

(Note) Additive: Added 1 minute after 1 to 5 minutes of particle precipitation.

[0090]

[Table 3]

(Note) Water content: Water content (including crystallization water) contained as water in the zinc compound.

[0092]

[Table 4]

(Note) Impurity H was 0.001% by weight or less in all cases.

[0094]

[Table 5]

-Example 1-11- 30 minutes after the particles were precipitated in Example 1-1,
Hydrolysis condensate of tetramethoxysilane (average tetramer)
Containing zinc oxide-based particles (P11) in the same manner as in Example 1-1, except that the 20% by weight benzyl alcohol solution was mixed so as to be 0.5% by weight with respect to zinc oxide in terms of silicon oxide. A dispersion (d11) was obtained. Table 6 shows these physical properties.

In the same manner as in Example 1-3, a centrifugal separation operation and a dispersion operation were performed, and the solvent was replaced to obtain a toluene dispersion (DE11) having a particle concentration of 40% by weight. -Example 1-12-30 minutes after the particles are precipitated in Example 1-4,
Examples 1-4 except that a 20% by weight solution of aluminum sec-butoxide in 1-butanol was mixed at 2% by weight with respect to zinc oxide in terms of aluminum oxide.
In the same manner as in the above, a dispersion liquid (d12) containing zinc oxide-based particles (P12) was obtained. Table 6 shows these physical properties.

In the same manner as in Example 1-3, a centrifugal separation operation and a dispersion operation were performed, and the solvent was replaced to obtain a toluene dispersion (DE12) having a particle concentration of 40% by weight. -Example 1-13-30 minutes after the particles were precipitated in Example 1-5,
A 1% butanol solution of 20% by weight of indium mequitociethoxide was added to zinc oxide in terms of indium oxide.
A dispersion liquid (d13) containing zinc oxide-based particles (P13) was obtained in the same manner as in Example 1-5, except that the mixture was adjusted to be in a weight%. Table 6 shows these physical properties.

In the same manner as in Example 1-3, centrifugation and dispersion were performed, and the solvent was replaced to obtain a toluene dispersion (DE13) having a particle concentration of 40% by weight. -Example 1-14- 30 minutes after the particles were precipitated in Example 1-6,
A butyl cellosolve solution of 20% by weight of tetra-t-butoxytin was converted to 10% by weight of zinc oxide in terms of tin oxide.
A dispersion (d1) containing zinc oxide-based particles (P14) was prepared in the same manner as in Example 1-6, except that the dispersion liquid (d1) was mixed.
4) was obtained. Table 6 shows these physical properties. Example 1
In the same manner as in Example 3, a centrifugal separation operation and a dispersion operation were performed, and the solvent was replaced with a toluene dispersion (D) having a particle concentration of 40% by weight.
E14) was obtained.

-Example 1-15- 30 minutes after the particles were precipitated in Example 1-8,
A 20% by weight solution of a suspension of indium acetate dihydrate and zinc acetate anhydride (Zn (4)) (the mixing ratio of which is In / Zn = 3 atomic%) in 2-propanol is
A dispersion liquid (d15) containing zinc oxide-based particles (P15) was obtained in the same manner as in Example 1-8, except that the mixture was mixed so as to be 0.5% by weight with respect to zinc oxide in terms of oxide. .
Table 6 shows these physical properties.

In the same manner as in Example 1-3, centrifugation and dispersion were carried out, and the solvent was replaced to obtain a toluene dispersion (DE15) having a particle concentration of 40% by weight. -Example 1-16- 147 parts of zinc acetate dihydrate powder used in Example 1-1,
A mixture consisting of 41 parts of acetic acid and 24 parts of ion-exchanged water was prepared. The same reactor as in Example 1-1 was charged with 1220 parts of benzyl alcohol and heated to 130 ° C. 130 ° C
The mixture was added to benzyl alcohol heated to a temperature of 100 ° C., and the temperature was increased from 100 ° C. at a rate of 2 ° C./min.
The dispersion was maintained at 0 ° C. for 1 hour to obtain a dispersion (d16) containing zinc oxide-based particles (P16). Table 4 shows these physical properties.

[0101]

[Table 6]

(Note) Impurity H was 0.001% by weight or less in all cases. The lattice distortion Aw of each crystallite was less than 0.5%. The surface treatment amount was determined by measuring the content of metal derived from the surface treatment agent by particle analysis, and expressed as an oxide-converted weight (%) of the metal contained in the surface treatment agent with respect to zinc oxide.

Example 2-1 The acrylic resin solution shown in Table 7 was added to the dispersion (DE3), mixed, and dispersed using a sand mill. further,
Isocyanurate-modified hexamethylene diisocyanate as a curing agent was added and mixed, followed by stirring at 25 ° C. for 30 minutes to prepare a coating (1) shown in Table 8, which was then mixed with PE.
It was applied to a T film and dried at 90 ° C. for 2 minutes with a hot air drier to obtain a coated product (1). Table 9 shows the results of the evaluation of the coated product (1). The UV transmittance of the coated product (1) is 50.
%, Weather resistance evaluation is B, surface resistance is> 10 ¹⁰ Ω /
□, stain resistance was low and stained.

-Examples 2-2 to 2-9 and Comparative Example 2-Table 8 comprising the binder resin shown in Table 7, the respective dispersions produced in Example 1, and a curing agent and a curing catalyst as required. The paints (2) to (9) and the paint (c) shown in are prepared.
Coated products (2) to (9) and coated product (c) shown in Table 9
I got Table 9 shows the evaluation results of these coated products. The UV transmittance of the coated products (2) to (9) was 5
It was less than 0%.

[0105]

[Table 7]

(Note) * 1: Tetramethoxysilane-methylmethoxysilane-
Dimethyldimethoxysilane co-hydrolysis condensate

[0107]

[Table 8]

(Note) The curing agent was added in an amount equivalent to the amount of hydroxyl groups in the binder resin.

[0109]

[Table 9]

-Examples 2-10 to 2-14- Coatings (10) to () comprising the binder resins shown in Table 7, the respective dispersions produced in Example 1, and, if necessary, a curing agent and a curing catalyst. 14) was prepared, and coated products (10) to (14) shown in Table 10 were obtained. Each of these coated products is a coated product in which a film in which particles are dispersed and contained is formed on a PET film having a thickness of 100 μm similar to that of the agent 2-1 and the evaluation results are shown in Table 10. . The drying conditions after application of the paint were all 90 ° C. for 2 minutes.

The weather resistance of the coated products (10) to (14) was A. Surface resistance is 2 × 1 for coated product (12)
0 ⁷ Ω / □, 6 × 10 ⁵ Ω / □ for the coated product (13), and 7 × 10 ⁸ Ω / □ for the coated product (14). Coated product (1
With respect to the stain resistance of (0) to (14), the stain was suppressed as compared with the coated product (1).

[0112]

[Table 10]

(Note) The curing agent was added in an amount equivalent to the amount of hydroxyl groups in the binder resin. -Example 2-15-A coating material was prepared by mixing an aqueous dispersion (DE8) and an acrylic resin emulsion. The concentration of the particles in the solid content contained in the paint was 20% by weight. A nylon fiber is immersed in the paint and dried to obtain a particle weight of 3 g / m.
² fibers were obtained. This fiber was excellent in weather resistance.

Example 3-1 The dispersion (d4) obtained in Example 1-4 was concentrated under reduced pressure using an evaporator, further dried, dried at 80 ° C. under vacuum, and dried. I got a body. 3 parts of this particle powder and 1000 parts of polycarbonate resin pellets were melt-kneaded to obtain a composition containing 0.3% by weight of particles dispersed therein. This composition is extruded into a sheet and has a thickness of 3 m.
m was obtained.

The obtained polycarbonate sheet has an ultraviolet shielding property of ◎, a visible light transmittance of ○, and a transparency of haze of 4%.
Met. -Example 4-1 After mixing 32 parts of the dispersion (DE4) obtained in Example 1-4 and 330 parts of dioctyl phthalate, the mixture was heated under reduced pressure using an evaporator to evaporate the solvent component in the dispersion. By distilling off, a dioctyl phthalate dispersion having a particle concentration of 3.7% by weight was obtained.

Example 4-2 40 parts of the dioctyl phthalate dispersion obtained in Example 4-1 were mixed and kneaded with 100 parts of a polyvinyl butyral resin to obtain a resin composition containing 2% by weight of particles. Obtained. This resin composition was molded by an extrusion molding machine and had a thickness of 0.8 mm.
Was obtained.

This sheet was sandwiched between 3 mm-thick glass sheets, kept at 100 ° C. under reduced pressure for 1 hour, then cooled to room temperature, and then placed in an autoclave, where the pressure was 8 kg / cm ² .
The treatment was performed at a temperature of 130 ± 7 ° C. for 30 minutes to obtain a laminated glass. This laminated glass was an ultraviolet-shielding transparent laminated glass, and the ultraviolet-shielding property was ◎, the visible light transmittance was Δ, and the transparency was less than 2%.

-Example 4-3- Ethylene vinyl acetate resin sheet containing 0.8% by weight of dioctyl phthalate as a plasticizer (0.8 mm in thickness)
Were overlapped so as to be sandwiched between the coated product (6) obtained in Example 2-6 and a transparent glass separately prepared. Here, the side of the coated product (6) where the coating film was formed was overlapped with the resin sheet. Next, the same treatment as in Example 4-2 was performed to obtain a laminated glass.

The laminated glass was a transparent laminated glass having an ultraviolet shielding property. The ultraviolet shielding property was ◎, the visible light transmittance was ○, and the transparency was less than 1%. -Example 4-4- 175 parts of the methyl ethyl ketone-based dispersion (DE5) obtained in Example 1-5, 60 parts of an acrylic resin (OHV50 / resin, solid content resin concentration of 50% by weight), a curing agent resin ( A coating composition comprising 5 parts of isocyanurate-modified hexamethylene diisocyanate (containing 23% by weight of NCO group) was prepared. This paint was formed on one side (corona treated) of a PET film (base film) having a thickness of 25 μm by a gravure coating method to a dry film thickness of 4.3 μm, and dried (9).
(5 ° C., 2 minutes) to obtain a PET film provided with a particle dispersion coating.

Next, an acrylic pressure-sensitive adhesive was applied to the dispersion film side of the PET film provided with the particle dispersion coating with a comma coater to a dry film thickness of 16 μm. On this coated surface, a release-treated PET film (release film,
(Thickness: 50 μm) to obtain a laminated film composed of a substrate film, a zinc oxide-based fine particle dispersion layer, an adhesive layer, and a release film layer.

This laminated film was an adhesive laminated film having excellent ultraviolet shielding properties, and had a ultraviolet shielding property of ◎, a visible light transmittance of ○, and a transparency of less than 4%. -Example 4-5 In Example 4-4, a PET in which a hard coat layer (film thickness 2 µm) made of an ultraviolet-curable urethane acrylate resin was previously formed as a base film.
Example 4 using a film on one side of the hard coat layer
In the same manner as in -4, a laminated film in which a zinc oxide-based fine particle dispersion layer, an adhesive layer, and a release film layer were sequentially formed was obtained. This laminated film was excellent in ultraviolet shielding property, transparency, light resistance, weather resistance and scratch resistance.

Example 5-1 In a reactor similar to that of Example 1-1: 1 as an alcohol
After charging 1000 parts of butanol and purging the system with nitrogen, the bottom temperature was raised to 250 ° C., and while stirring the alcohol, 106 parts of calcium acetate hydrate as a metal element compound was added from the addition tank to 1 part. The mixture was added over a period of minutes and heated for 5 hours while maintaining the bottom temperature at 240 ° C. ± 10 ° C. During the heating and holding, a part of the solvent containing water generated by the reaction was distilled off.

The resulting dispersion was 998 parts, and was a butanol solvent dispersion (d5-1) containing 3.4% by weight of calcium oxide particles, 10% by weight of butyl acetate, and 0.21% by weight of water. Water and butyl acetate contained in the distillate were 18.6 parts and 27.5 parts, respectively. Metal oxide-based particles in the dispersion (5-1)
The “metal oxide particles” may be simply referred to as “particles”. ) Are particles in which 12 mol% of acetoxy groups relative to Ca are bonded to calcium oxide, and have the physical properties shown in Table 12. The particle formation yield based on the raw material calcium acetate hydrate was 98%.

-Examples 5-2 to 5-19- In the same manner as in Example 5-1 except that the compound of the metal element was changed, dispersions of various oxide fine particles ( d5-2 to d5-19) were obtained. Tables 11 and 12 show the particle concentration, water concentration, physical properties of the particles, and the like of the obtained dispersion. The oxide yield of each particle was 8
0% or more.

From the silica particle dispersion (d5-14) obtained in Example 5-14, the solvent was removed by centrifugation, and the sediment was dried to obtain a powder of the silica particles (P5-14). Obtained. The particles had an acetoxy group as well as a butoxy group of 0.5 mm / g of particles.
ol / g binding was confirmed.

[0126]

[Table 11]

(Note) Water content: The total amount of the water content in the compound of the metal element or the slurry in which the compound is dissolved or suspended and the water content in the alcohol is represented by the molar ratio to the metal element. .

[0128]

[Table 12]

Comparative Example 3 A commercially available silica powder (having a specific surface area of 20 nm) was subjected to heat treatment in butanol to reduce the number of putoxy groups to 1 mm.
1 / g bound particles were obtained. It was D as a result of evaluating the monodispersity of a commercially available silica powder and a particle powder having a butoxy group bonded thereto.

Example 6-1 1000 parts of ethylene glycol monoethyl ether as an alcohol and tetrabutoxy tin (IV) as a metal element compound (II) in a reactor similar to that of Example 1-1.
2.6 parts and 175 parts of indium acetate as a metal element compound (I) were charged, and the inside of the system was purged with nitrogen. Then, the bottom temperature was raised to 250 ° C., and the bottom temperature was 250 ° C. ± 10 ° C.
Heated at ° C. for 5 hours.

The resulting dispersion (d6-1) was prepared from Sn (I
It was a dispersion containing 8 wt% of indium oxide particles containing 1 mol% of V) with respect to In. Table 13 shows the physical properties of the obtained particles. The particle formation yield was 95%
Met. -Examples 6-1 to 6-3- A reaction was carried out in the same manner as in Example 6-1 except that the amount of tetrabutoxy tin (1 V) was changed. Table 13 shows the physical properties of the obtained particles.

Example 6-4- 1000 parts of propylene glycol monomethyl ether as an alcohol, 7.2 parts of yttrium acetate pentahydrate as a metal compound (II) were placed in a reactor similar to that of Example 1-1. After 135 parts of zirconyl acetate as the metal element compound (I) was charged and the inside of the system was purged with nitrogen, the bottom temperature was raised to 280 ° C, and the bottom temperature was 280 ° C ± 10 ° C.
Heated at ° C for 10 hours.

The obtained dispersion (d6-4) was prepared using Y (III)
) Was 7% by weight of zirconium oxide particles containing 5 mol% based on Zr. Table 13 shows the physical properties of the obtained particles. The particle formation yield was 90%.
Met. -Example 6-5 A reaction was carried out in the same manner as in Example 6-4, except that the amount of yttrium acetate pentahydrate was changed, to convert Y (III) into Zr. A dispersion (d6-5) of zirconium oxide particles containing 15 mol% was obtained. Table 13 shows the physical properties of the obtained particles.

[0134]

[Table 13]

Example 7-1 1000 parts of cyclohexanol as an alcohol, 53 parts of cadmium acetate dihydrate as a metal MA compound, and antimony acetate as a metal MB compound were placed in the same reactor as in Example 1-1. (V) After charging 167 parts and purging the system with nitrogen, the bottom temperature was raised to 280 ° C., and the system was heated at a bottom temperature of 280 ° C. ± 10 ° C. for 10 hours. The obtained dispersion liquid (d7-1) was a dispersion liquid containing 11 wt% of composite oxide particles of antimony and cadmium. Table 14 shows the physical properties of the obtained particles. The particle generation yield was 9
4%.

Examples 7-2 to 7-3-Examples 7-1 are the same as Example 7-1 except that the types and amounts of the metal MA compound and the metal MB compound were changed.
The reaction was carried out in the same manner as described above to obtain dispersions (d7-2 to 7-3) of the respective composite oxide particles shown in Table 14. Table 14 shows the physical properties of the obtained particles.

[0137]

[Table 14]

(Note) Water content: The total amount of the water content in the metal MA compound and the metal MB compound and the water content in the alcohol is represented by the molar ratio to the metal element in the metal MA compound and the metal MB compound. . Examples 6-1 to 6-3 and 7-1 to 7-
From each of the dispersions obtained in 3, the solvent was removed by centrifugation, and the precipitate was dried to obtain powder of each particle. As a result of evaluating the spectral reflectance characteristics of the particle powder, it was found that the particle powder had an absorbing ability in an infrared region including a heat ray.

Each particle was dispersed in an acrylic resin solution by an ultrasonic homogenizer, and a film was formed on a PET film so as to have a particle conversion of 5 g / m ^2. As a result, it was confirmed that a heat ray cut film transparent to visible light was obtained. Was done. The haze of all films was 10% or less (the haze of the PET film as the substrate was 2.0%). Comparative Example 4 From the dispersion obtained in Example 6-1, the solvent was removed by centrifugation, and the precipitate was dried to obtain powder of each particle. As a result of firing this particle powder at 350 ° C. in air, Sn-containing indium oxide particles containing no acetoxy group were obtained. The particles were dispersed in an acrylic resin solution using an ultrasonic homogenizer, and formed on a PET film so as to have a particle conversion of 5 g / m ^2. As a result, a film opaque to visible light was confirmed. The haze of the film was 40%.

-Examples 8-1 to 8-4- In 1000 parts of 2-butoxyethanol, respectively, Table 1
A compound of a metal element including nickel shown in 5 is added, and 2
The temperature was raised to 60 ° C. and held for 1 hour.
A dispersion liquid containing particles containing nickel as a metal having the physical properties shown in No. 5 was obtained.

[0141]

[Table 15]

[0142]

The metal oxide particles according to the present invention have excellent dispersibility. When the metal oxide-based particles are zinc oxide-based particles, they also have excellent ultraviolet shielding properties. The method for producing metal oxide-based particles according to the present invention can easily obtain metal oxide-based particles having excellent dispersibility.

Since the composition containing metal oxide particles according to the present invention contains metal oxide particles having excellent dispersibility, a coating film having excellent transparency and the like can be obtained. The metal oxide-based particle-containing film according to the present invention is excellent in transparency and the like.

Claims (6)

[Claims] 1. A metal oxide-based particle containing an oxide of a metal element (M) as a main component, wherein a carboxylic acid (residual) group is contained in an amount of 0.01 to 14 mol% based on the metal element (M). Metal oxide particles satisfying the following (1) and / or (2). (1) X-ray diffraction indicates crystallinity based on an oxide of a metal element (M), and when the size of a crystallite is Dw, which is determined by the Wilson method, 1 nm ≦ Dw ≦ 100 nm. (2) Assuming that the specific surface area diameter calculated by the following formula is Ds, 1 nm ≦ Ds ≦ 100 nm Ds = 6 / (ρ × S) (where, ρ: true specific gravity of metal oxide particles, S: BE
T. Specific surface area (m ²
/ G)) 2. The metal oxide particles according to claim 1, wherein the ratio of the dispersed particle diameter Dd to the crystallite size Dw and / or the specific surface area diameter Ds is 5 or less. 3. The two lattice planes (100) and (002).
, Using the Scherrer method (Cauchy function approximation)
The metal oxide-based particles according to claim 1 or 2, satisfying 0 <Dc (002) / Dc (100) <1.5 when the size Dc (hkl) of the crystallite in the vertical direction is determined. 4. Production of metal oxide particles by heating a solution containing a compound of a metal element (M) and / or a hydrolytic condensate thereof and an alcohol to precipitate metal oxide particles. In the method, the compound is represented by the following general formula (I), and the amount of water contained in the solution is 4 or less in a molar ratio to a metal element (M) which is a main component of the metal oxide-based particles. Wherein the solution is heated to 100 ° C. or higher. 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. ) 5. The composition according to claim 1, which comprises the metal oxide-based particles according to claim 1 and a binder component, wherein the ratio of the metal oxide-based particles to the total solid content of the two is 0.1%.
A metal oxide-based particle-containing composition in an amount of up to 99% by weight. 6. A metal oxide-based particle-containing film obtained by forming a coating film obtained from the metal oxide-based particle-containing composition according to claim 5 on a base film.