JP2007031216A - Metal oxide particle, and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal oxide particle not only exhibiting more excellent ultraviolet absorbability, but also combining advantages, e.g., that an ultraviolet absorption edge is more shifted to a long wavelength side, the absorbing efficiency of ultraviolet rays in a long wavelength region is excellent as well, further, transparency is satisfactory and, e.g., the transparency and hue of a base material are not damaged even if being internally added or applied to the base material. <P>SOLUTION: Regarding the metal oxide particle in which a dissimilar element(s) is comprised in a particle composed of the oxide of a specified metal element(s)(M), the dissimilar element(s) is at least one specific nonmetallic element and an acyl group(s) is comprised, or the dissimilar elements are at least two kinds of specific nonmetallic elements, or the dissimilar element(s) is at least one specific nonmetallic element(s), and a component(s) originated from a metal element(s)(M') other than the metal element(s)(M) is comprised in the particle. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to metal oxide particles that exhibit excellent ultraviolet absorptivity and uses thereof. Specifically, it exhibits better UV absorption and, for example, metal oxide particles that do not impair the transparency and hue of the substrate even when internally added or coated on the substrate, and the longer UV absorption edge. The present invention relates to a metal oxide particle that is shifted to the wavelength side and has excellent absorption efficiency of ultraviolet rays in a long wavelength region, and a composition, a film, and the like using the metal oxide particle.

Conventionally, for the purpose of imparting ultraviolet shielding ability, for example, an ultraviolet-absorbing material is internally added to plastic molded articles such as fibers, plates and films, paints and cosmetics, and solvents and binder resins are added to glass and plastic films. In addition, a coating agent containing an ultraviolet absorbing material is coated.
For example, UV absorbing materials used in various fields such as cosmetics, building materials, window glass for automobiles or displays, flat panel displays, etc., have recently been generally called ultraviolet rays of 380 nm or less (especially around 380 nm). In addition to ultraviolet rays in the long wavelength region, it is required to have excellent absorption performance for ultraviolet rays in a longer wavelength region (short wavelength visible light). This is because, among visible light, visible light in a short wavelength region has high energy, and therefore there is a concern that it may cause deterioration of the plastic and adverse effects on the human body. In addition, the ultraviolet absorbing material has high transparency and good transparency without scattering visible light, has no coloring such as yellow, does not change the hue of the substrate, and durability and There is a demand for excellent heat resistance.

The ultraviolet absorbing material for imparting ultraviolet shielding properties is preferably an inorganic material in terms of durability and heat resistance. Among them, for example, zinc oxide having physical properties that completely shield ultraviolet rays having a wavelength of 370 nm or less is used. Although known to be effective and generally used in the form of particles, these do not satisfy the above-mentioned demands, for example, the ultraviolet absorption performance is insufficient, for example, ultraviolet rays of 380 nm or less are used. In order to completely shield, a large amount of ultrafine particles must be used per unit area, and there is a problem that the film thickness becomes too thick and lacks practicality.
Therefore, as a means for improving the ultraviolet absorbing performance of the ultraviolet absorbing material, a composite of zinc oxide and a dissimilar metal has been proposed. For example, i) zinc oxide containing (doped) Fe or Co (see Patent Document 1 and Non-Patent Document 1), ii) at least one of Ce, Ti, Al, Fe, Cr and Zr; A composite oxide with Zn (see Patent Document 2), iii) A zinc oxide containing at least one of Ce, Ti, Al, Fe, Co, La and Ni (see Patent Document 3) has been proposed ing.

By the way, although not intended for an ultraviolet absorbing material, zinc oxide in which 10 2 ppm of Cu is dissolved is reported as a technique for incorporating a different metal into zinc oxide (see Non-Patent Document 2). ), It is considered that such zinc oxide can be expected to improve the ultraviolet absorption performance.
JP-A-9-188517 JP 62-275182 A JP-A-5-222317 Satoshi Otsuka, “Inorganic pigment containing ZnO as main component”, Ceramics, Ceramic Association, 1983, 18, No. 11, p. 958-964 Noboru Sakagami, 1 other, "Optical Properties of Impurities-doped Hydrothermally Grown Zinc Oxide", Journal of the Ceramic Industry Association, Association of Ceramic Industry, 1969, 77 [9], p. 309-312

  However, in recent years, metal oxides such as i) to iii) have not yet been able to be said to have sufficient ultraviolet absorption ability, while the applications that require higher ultraviolet blocking ability are increasing. . Specifically, although the absorption performance with respect to light having a wavelength longer than 380 nm is slightly improved, the effect of shifting the ultraviolet absorption edge toward the longer wavelength is not yet sufficient, and Fe and Co are contained as in i) above. In this case, the absorption performance at 380 nm, which has the highest shielding requirement, will be reduced. Moreover, since an absorption band exists in the visible light region, Fe is colored yellow and Co is colored blue. As a result, there has been a problem that when the substrate is internally added or coated as an ultraviolet absorbing material, the transparency and hue of the substrate are impaired. Furthermore, in the prior art, it has been substantially difficult to produce fine particles that are doped with these metals and have excellent isolation and dispersibility.

The solid solution of zinc oxide reported in Non-Patent Document 2 was synthesized by a hydrothermal method, and the size of the particles was as large as 10 to 25 mm, and it was colored yellow. Met. Therefore, when such a zinc oxide is used as an ultraviolet absorbing material, the properties of high visible light transmission and good transparency cannot be obtained. This causes problems such as loss of transparency and hue.
Therefore, the problem to be solved by the present invention is not only to exhibit better ultraviolet absorption, but also, for example, the ultraviolet absorption edge is shifted to the longer wavelength side and the absorption efficiency of ultraviolet rays in the long wavelength region is increased. The metal oxide particles having excellent transparency, good transparency, for example, the advantage that the transparency and hue of the substrate are not impaired even when the substrate is internally added or coated, and The object is to provide a composition, a film, a metal oxide-containing article and an ultraviolet absorber using the same.

  In the present invention, the wavelength range of ultraviolet rays to be blocked (blocked) is not limited to 380 nm or less, which is generally referred to conventionally, but also includes a visible light short wavelength region, specifically a wavelength region of 380 to 450 nm. Shall be included. Hereinafter, ultraviolet rays and ultraviolet rays in ultraviolet shielding (blocking) and ultraviolet absorption mean light having a wavelength in the above range (450 nm or less).

  In order to solve the above-mentioned problems, the present inventor has eagerly studied that a different element different from a metal element (M) such as a different metal element (M ′) is contained in the oxide of the metal element (M). . As a result, as the oxide of the metal element (M), a single oxide or composite oxide made of at least one metal element selected from the group consisting of Zn, Ti, Ce, In, Sn, Al, and Si is used. And selecting the oxide to contain at least one selected from the group consisting of N, S, and Group 17 (Group 7B) elements, and optimum conditions such as composition (surface composition, internal composition), etc. It has been found that the particles can be made excellent in ultraviolet absorption performance, visible light transmission performance and hue.

Furthermore, together with each of the metal oxide particles described above, metal oxide particles containing a specific metal element (metal element selected from the group consisting of Cu, Fe, Ag and Bi) as a metal component, and / or Ag, Cu, It has been found that the effect of blocking visible light in the short wavelength region can be further enhanced by combining ultrafine metal particles having at least one selected from the group consisting of Au and a platinum group metal element as a metal element.
The present invention has been completed based on these findings.
That is, the first metal oxide particle of the present invention is a metal oxide particle composed of an oxide of a metal element (M), wherein the metal element (M) is Zn, Ti, Ce, In, Sn, Al and Si. And at least one selected from the group consisting of N, S, and Group 17 (Group 7B) elements is contained in the oxide of the metal element (M). And an acyl group.

The second metal oxide particle of the present invention is a metal oxide particle comprising an oxide of a metal element (M), wherein the metal element (M) comprises Zn, Ti, Ce, In, Sn, Al and Si. It is at least one selected from the group, and the oxide of the metal element (M) contains two or more selected from the group consisting of N, S, and Group 17 (Group 7B) elements. Features.
The third metal oxide particle of the present invention is a metal oxide particle comprising an oxide of a metal element (M), wherein the metal element (M) comprises Zn, Ti, Ce, In, Sn, Al and Si. At least one selected from the group, the oxide of the metal element (M) contains at least one selected from the group consisting of N, S, and a group 17 (group 7B) element, and A component derived from a metal element (M ′) other than the metal element (M) is contained in the particles.

The composition of the present invention comprises metal oxide particles dispersed in a medium, and the metal oxide particles essentially comprise the metal oxide particles of the present invention.
The composition for forming a film of the present invention comprises the metal oxide particles of the present invention and a dispersion solvent and / or a binder as essential components in the composition of the present invention.
The film of the present invention comprises a metal oxide as an essential component, and the metal oxide essentially comprises the metal oxide particles of the present invention and / or metal oxide crystals derived from the particles.
The metal oxide-containing article of the present invention is an article containing metal oxide particles and / or metal oxide crystals derived from the particles, and the metal oxide particles of the present invention, Cu, Fe, Ag and Bi. Metal oxide particles having at least one selected from the group consisting of metal elements as metal elements and / or metal superoxide having at least one selected from the group consisting of Cu, Ag, Au, and platinum group metal elements as metal elements A combination with fine particles is essential.

  The ultraviolet absorber of the present invention comprises the metal oxide particles of the present invention.

  According to the present invention, as well as exhibiting more excellent ultraviolet absorption performance, for example, the ultraviolet absorption edge is shifted to the longer wavelength side and the absorption efficiency of ultraviolet rays in the long wavelength region is excellent, Metal oxide particles having good transparency, for example, having the advantage that the transparency and hue of the substrate are not impaired even when internally added or coated on the substrate, and a composition using the same (For example, a film-forming composition), a film, a metal oxide-containing article, and an ultraviolet absorber can be provided.

Hereinafter, the present invention will be described in detail. However, the scope of the present invention is not limited to these descriptions, and modifications other than the following examples can be made as appropriate without departing from the spirit of the present invention.
[Metal oxide particles]
As described above, each of the metal oxide particles of the present invention is a metal oxide particle made of an oxide of a metal element (M) and made of Zn, Ti, Ce, In, Sn, Al, and Si. The oxide of at least one metal element (M) selected from the group is at least one selected from the group consisting of N, S, and Group 17 (Group 7B) elements (hereinafter referred to as “different non-metallic elements”) In some cases). Specifically, in the first metal oxide particle of the present invention, the oxide of the metal element (M) contains at least one selected from the group consisting of N, S, and a group 17 (group 7B) element. And an acyl group is contained. In the second metal oxide particles of the present invention, the metal element (M) oxide contains two or more selected from the group consisting of N, S, and Group 17 (Group 7B) elements. It is characterized by. The third metal oxide particle of the present invention is characterized in that a component derived from a metal element (M ′) other than the metal element (M) is contained in the particle.

In the present invention, the inclusion of the different non-metallic element means that the metal oxide constituting the metal oxide particles of the present invention may be a metal oxide containing the different non-metallic element. It does not matter whether it is contained in the existing form. Similarly, in the present invention, the phrase “containing a component derived from the metal element (M ′)” means that the metal oxide constituting the metal oxide particle of the present invention is a metal oxide containing the metal element (M ′). It does not matter what form the metal element (M ′) is contained in. Hereinafter, the different non-metallic element and the metal element (M ′) may be collectively referred to as “different (non-metal / metal) element”.
In the metal oxide constituting the metal oxide particle of the present invention, specific examples of the form of the dissimilar (nonmetal / metal) element include, for example, (I) a dissimilar (nonmetal / metal) element is a metal element ( M) in the form of a solid solution in the oxide crystal, (II) a state in which a different (non-metal / metal) element is contained as the metal component of the metal element (M) oxide (preferably a composite) Oxide), (III) Different (nonmetal / metal) elements adsorbed on the crystal surface of the metal element (M) oxide, (IV) Different (nonmetal / metal) Examples include a form in which the element is in the form of particles or a film as a metal or a simple substance and adhered to the surface of the oxide of the metal element (M). Among them, the effect of the solid (non-metallic / metallic) element brought about by the solid solution form uniformly dispersed in an atomic state (including ionic state) in the crystal of the oxide of the metal element (M), that is, It is preferable in that it is excellent in ultraviolet absorptivity, has a small degree of coloring due to addition of a different (non-metal / metal) element, and can maintain good transparency.

  In the metal oxide particles of the present invention, the dissimilar (non-metal / metal) element may be dispersed in the state of (i) uniformly dispersed in the particles, or (ii) partially (Instead of meaning of segregation, it may be contained locally at a high concentration when viewed with respect to one particle). As the case of (i) above, for example, in the form of (I), there is a case where it is uniformly dissolved (from the surface layer to the inside of the crystallite) in the oxide crystal of the metal element (M). Can be mentioned. In the case of (ii) above, a metal oxide solid solution phase in which a different (non-metal / metal) element is solid-dissolved as a surface layer on the surface of the oxide crystal of the metal element (M) (form (I) above ), Or in the case of a metal element (M ′), a composite oxide of a metal element (M ′) and a metal element (M), and in the case of a dissimilar nonmetallic element, a metal oxynitride (dissimilar nonmetallic element is N), when a phase of the metal oxysulfide (the different nonmetallic element is S) or a metal acid halide (the different nonmetallic element is a group 17 element) (form (II)) is mentioned. . These are referred to as “metal oxide” in the present invention.

In general, metal oxides are classified into those showing crystallinity (crystals) and those showing no crystallinity (non-crystals). The crystal body can be defined as a metal oxide composed of crystallites in which a regular atomic arrangement is recognized with periodicity, and has a lattice constant in terms of electron diffraction and / or X-ray diffraction. And / or refers to what can identify a metal oxide from a diffraction pattern, otherwise it can be defined as amorphous. In terms of excellent ultraviolet absorption ability, it is preferably a crystal, and the same applies to the metal oxide constituting the metal oxide particles of the present invention.
The crystal body may be a single crystal body or a polycrystal body, and examples of the shape of the crystallite constituting them include, for example, a spherical shape, an elliptical spherical shape, a cubic shape, a rectangular parallelepiped shape, a polyhedral shape, and a pyramid. , Columnar, tube-like, flake-like, (hexagonal) plate-like flakes, dendrites, skeletons, etc. produced by preferentially extending crystal edges and corners under conditions of high supersaturation Can be mentioned. The orientation of the crystallites is not limited, and even if all the orientations of the crystallites are uniform or random, some of them may be the same orientation and the rest may be random. Not.

The shape of the metal oxide particles of the present invention is not limited. Specifically, when the metal oxide particle of the present invention is a particle made of a single crystal of a metal oxide, it is the same as the above-mentioned crystallite shape, but it is a particle made of a polycrystal or a crystal When the particles are fixed or agglomerated particles, the shape of the particles is not necessarily the same as the shape of the crystallites. , Needle-like, columnar, rod-like, cylindrical, flake-like, (hexagonal) plate-like, etc.
The metal oxide constituting the metal oxide particles of the present invention comprises a single oxide (specifically, an oxide of a metal element (M)) or a composite oxide (two or more metal elements (M)). It is preferably a solid solution metal oxide (solid solution oxide) in which a different (non-metal / metal) element is dissolved (doped) in (oxide). In addition, the metal oxide may be a non-stoichiometric composition or a metal element and oxygen, and is not limited.

The solid solution oxide may be a so-called interstitial solid solution oxide, a substitutional solid solution oxide, or a combination thereof, and is not limited.
In the present invention, the metal element (M) is selected from the group consisting of Zn (zinc), Ti (titanium), Ce (cerium), In (indium), Sn (tin), Al (aluminum), and Si (silicon). At least one selected. Among these, it is excellent in ultraviolet absorption performance, and in particular, in the third metal oxide particles, Zn, Ti, Ce, In, Sn is preferred. In particular, Zn, Ti, and Ce are capable of exhibiting excellent ultraviolet absorption performance even in their single oxides, so that they have a high shielding effect against ultraviolet rays of 380 nm or less, which is generally known in the past, and they are of different types. This is preferable in that the effect of the (nonmetal / metal) element, that is, the effect that the ultraviolet absorption edge is shifted to the longer wavelength side can be remarkably exhibited. Furthermore, Zn is more preferable as the metal element (M) from the viewpoint of excellent transparency to visible light, and zinc oxide-based particles are a preferable embodiment of the metal oxide particles of the present invention.

The oxide of the metal element (M) may be a single oxide or a complex oxide. For example, composite oxides such as ZnIn ₂ O ₄ , Zn ₂ In ₂ O ₅ , Zn ₃ In ₂ O ₆ , GaInO ₃ , In ₄ Sn ₃ O ₁₂ , Zn ₂ SnO ₄ , ZnSnO _3, etc. Examples thereof include composite oxides composed of M or more species and composite oxides containing metal elements (M) and metal elements other than the metal elements (M) as metal components. As a representative example, when the metal element (M) is Zn, ZnAl ₂ O ₄ , Zn ₂ B ₆ O ₁₁ , ZnFe ₂ O ₄ , ZnMoO ₄ , ZnSeO ₃ , Zn ₂ SiO ₄ , ZnWO _4, etc. Preferably mentioned. Further, in the present invention, the metal oxide (M) oxide in which part of oxygen in the metal oxide is substituted with a different element such as the different non-metallic element is also included in the oxide described above. It can also take the form of a solid solution or a metal oxynitride, oxysulfide, acid halide or the like in which a different nonmetallic element is dissolved in place of oxygen. In particular, a preferred embodiment is a solid solution in which the heterogeneous nonmetallic element (N, S, group 17 (group 7B) element) substitutes a part of oxygen atoms in the oxide of the metal element (M).

In the metal oxide particles of the present invention, the inclusion of the different non-metallic elements (N, S, and Group 17 (Group 7B) elements) improves the ultraviolet absorption performance, more specifically, the metal element (M). The effect that the absorption performance with respect to light having a wavelength longer than that of the light absorption edge inherent to the oxide can be obtained.
The dissimilar non-metallic elements (N, S, and Group 17 (Group 7B) elements) are preferably nitrogen, fluorine, and sulfur. In particular, nitrogen is more effective for increasing the wavelength of the light absorption edge.
In the metal oxide particles of the present invention, the content of the different non-metallic element (N, S, group 17 (group 7B)) is 0.01 to 20 atomic% with respect to the metal element (M). Is more preferable, and 0.05 to 10 atomic% is more preferable. If it is less than 0.01 atomic%, the effect of improving the ultraviolet absorption performance becomes insufficient. On the other hand, if it exceeds 20 atomic%, the absorption ability of less than 370 nm may be reduced.

  In the first metal oxide particles of the present invention, the oxide of the metal element (M) contains at least one kind of the different non-metal elements and an acyl group. By including an acyl group together with the different non-metallic element, the dispersibility is improved and an effect that a transparent film can be formed can be obtained. For example, when nitrogen is contained, the particles are colored yellow, and yellow coloring becomes conspicuous even when a dispersion film is formed. However, the inclusion of an acyl group improves the degree of coloring. As will be described later, at least one metal element (preferably Si, Ti, Al, Zr) different from the metal element (M ′) contained in the oxide on the surface of the oxide of the metal element (M). The same effect can also be obtained by combining an alkoxide consisting of one kind selected from the group consisting of or a (partial) hydrolyzate thereof, and such an alkoxide or their (partial) hydrolyzate. By combining the decomposition product with the acyl group, a further excellent color reduction effect can be exhibited.

In the second metal oxide particles of the present invention, the metal element (M) oxide contains two or more of the different non-metallic elements. By using two or more different non-metallic elements in combination, the ultraviolet absorption effect is further improved. It is preferable that at least one of the two or more kinds of different metal elements is any one of nitrogen, fluorine, and sulfur.
In the third metal oxide particle of the present invention, a component derived from a metal element (M ′) other than the metal element (M) is contained in the particle.
The metal element (M ′) is not particularly limited and can be arbitrarily selected, but is preferably a metal element different from the metal element (M) and includes Co, Cu, Fe, Bi, In, and Al. , Ga, Ti, Sn, Ce, Ni, B, Mn, Ag, Au, at least one selected from the group consisting of a platinum group metal element, an alkali metal element, and an alkaline earth metal element. In particular, Co, Fe, Bi, Ni, Mn, and Ag are effective for increasing the wavelength of the light absorption edge, and to reduce coloring in the dispersion film that occurs when the dissimilar nonmetallic element is N. Co (II), Fe (II), Ni (II), Cu (I), and Cu (II) are effective for increasing the light absorption coefficient near the band absorption edge of the oxide of the metal element (M). For this purpose, In, Al, Ga, Ti, Sn, Ce, and B are effective. Of the groups that can be selected as a preferred metal element (M ′), In, Al, Ga, Ti, Ce, and Sn are generally referred to as n-type dopants.

Among the groups that can be selected as a preferred metal element (M ′), Co includes, for example, Co (II) and Co (III). Examples of Fe include Fe (II) and Fe (III). In the case where Co and Fe are solid solution components, the bivalent one shows better ultraviolet absorption than the trivalent one. Therefore, it is preferable that divalent monovalent or divalent and trivalent coexist with each other rather than trivalent alone. In particular, in the case of Fe, if it is trivalent, yellow coloring is strong, but if it is divalent, Fe is preferably divalent because it gives a greenish color.
Among the group that can be selected as a preferred metal element (M ′), examples of Cu include Cu (0), Cu (I), and Cu (II). Examples of Bi include Bi (III). Examples of In include In (I) and In (III). Examples of Al include Al (III). An example of Ga is Ga (III). Examples of Ti include Ti (IV) and Ti (III). Examples of Sn include Sn (II) and Sn (IV). Examples of Ce include Ce (IV) and Ce (III). Examples of Ni include Ni (0), Ni (II), Ni (I), and Ni (III). Examples of Mn include Mn (I), Mn (II), Mn (III), Mn (IV), Mn (V), Mn (VI), and Mn (VII). Examples of Ag include Ag (0), Ag (I), and Ag (III). Of these, Cu, Ag, and Ni are effective as Cu (0), Ag (0), and Ni (0), that is, adhere to (deposit) the surface of the metal oxide particles as a metal. it can. Among these, Bi is Bi (III), In is In (III), Ag is Ag (I), Mn is Mn (II) or Mn (III), Ni is Ni (II), UV shielding property, etc. It is preferable at the point which is excellent in.

In the metal oxide particles of the present invention, in addition to the above-described different non-metallic elements and metal elements (M ′), alkali metal elements and / Or the aspect which also contains the component derived from an alkaline-earth metal element is preferable at the point which further improves ultraviolet-ray absorption performance. The content of the alkali metal element and / or alkaline earth metal element is more preferably in the range of 0.001 to 1 atomic% with respect to the metal element (M).
In the metal oxide particles of the present invention, the above-mentioned different non-metal elements, metal elements (M ′), alkali metal elements and Alternatively, in addition to the alkaline earth metal element, other metal elements other than these can be contained.

  In the metal oxide particles of the present invention, any metal element to be included in the oxide of the metal element (M) in addition to the different element (that is, the different non-metal element and the metal element (M ′)). The presence of metal segregates in addition to the particles while observing their transmission images with FE-TEM (field emission transmission electron microscope) for the primary particles of metal oxide particles and their aggregates. It can be confirmed by searching for an unacceptable place, performing elemental analysis with high resolution XMA, and detecting peaks attributed to each element. The confirmation of the segregated material is that there is no segregated material in a transmission image observed with FE-TEM, if it is a level that cannot be confirmed directly from the transmission image or in combination with XMA.

  X-ray fluorescence analysis is used to measure the content of the different element (that is, the metal element contained in the oxide of the metal element (M) in addition to the different non-metallic element and the metal element (M ′)). , Atomic absorption analysis and trace component analysis techniques such as ICP (High Frequency Inductively Coupled Plasma Emission Spectroscopy) can be used. Elemental analysis using the above high resolution XMA is performed with the desired spatial resolution (spot diameter). It is preferable to carry out by a method of measuring the assigned peak intensity and calculating from the result. The spot diameter can be lowered to 1 nmφ by narrowing down the probe, and can be arbitrarily increased. Specifically, in the transmission image by FE-TEM, an aggregate of about 10 metal oxide particles, in which segregation is not normally observed, is selected, and all of these about 10 (fine) particles are included. Elemental analysis is performed with spatial resolution (spot diameter).

Each particle contains a different element (that is, a metal element to be included in the oxide of the metal element (M) in addition to the different non-metallic element or the metal element (M ′)), or Whether or not different elements are uniformly dispersed in the individual particles can be confirmed by performing local elemental analysis with a narrowed beam diameter (for example, 1 nmφ).
As the FE-TEM, for example, a field emission transmission electron microscope (HF-2000 type, acceleration voltage 200 kV) manufactured by Hitachi, Ltd. can be used. As the high-resolution XMA, for example, an X-ray microanalyzer (Sigma type, energy dispersive type, beam diameter: spatial resolution of 10Åφ) manufactured by Kevex can be used.

  The size of the metal oxide particles of the present invention includes everything referred to as ultrafine particles and fine particles, and is not limited. Usually, the average particle size (primary particle size) of primary particles is 1 to 100 nm. It is preferable that A particularly preferred embodiment is that the primary particle diameter is 3 to 50 nm, more preferably 5 to 30 nm, still more preferably 5 to 20 nm, and particularly preferably 10 to 20 nm. When the average particle diameter of the primary particles exceeds 100 nm, the transparency may be lowered. If the average particle diameter of the primary particles is too small, the ultraviolet absorption end tends to shift to the short wavelength side due to the quantum effect, which is not preferable as an ultraviolet absorbing material. On the other hand, if it is too large, the transparency may be lowered. .

  In the present invention, the average particle diameter of primary particles means a crystallite diameter (Dw) or a specific surface area diameter (Ds), and more specifically, when the particles are crystalline, a crystal The child diameter (Dw) means the specific surface area diameter (Ds) when the particles are amorphous. Accordingly, it is preferable that either the crystallite diameter (Dw) or the specific surface area diameter (Ds) falls within the above range. More specifically, the crystallite diameter (Dw) is applied in the case of a crystal in X-ray diffraction, and is the size of a crystallite obtained by Scherrer's equation. The crystallite diameter (Dw) is usually determined by measuring a powder X-ray diffraction pattern of metal oxide particles. Three strong lines (diffractive line having the largest peak (1), second largest diffraction line (2), 3 For the second largest diffraction line (3)), the crystallite diameters D1, D2, and D3 in the direction perpendicular to the diffraction planes assigned to the diffraction lines (1) to (3) from the Scherrer formula from the respective half widths or integral widths. The average value ((D1 + D2 + D3) / 3) can be calculated as the crystallite diameter (Dw). On the other hand, the specific surface area diameter (Ds) can be calculated by the following formula by measuring the true specific gravity and specific surface area of the powder of metal oxide particles.

Ds (nm) = 6000 / (ρ × S)
Where ρ is the true specific gravity of the particle (dimensionless)
S: B. E. T.A. Specific surface area (m ² / g) of particles measured by the method
In the metal oxide particles of the present invention, the oxide of the metal element (M) is a crystal, and the crystallite diameter (Dw) (average value of each value calculated according to Scherrer's equation for the three strong lines of the XRD peak) Is preferably 30 nm or less.
In particular, in the metal oxide particles of the present invention, when the oxide of the metal element (M) is a zinc oxide crystal, the crystallite diameter by X-ray diffraction measurement is excellent in terms of both transparency and ultraviolet absorption. Of these, the crystallite diameter in the direction perpendicular to the lattice plane (002) is preferably 30 nm or less, and the crystallite diameter in the direction perpendicular to the lattice plane (100) and / or the lattice plane (110) is preferably 8 nm or more. More preferably, the crystallite diameter perpendicular to the lattice plane (002) is 20 nm or less, and the crystallite diameter perpendicular to the lattice plane (100) and / or the lattice plane (110) is 10 nm or more. Specifically, the crystallite diameter in the direction perpendicular to the lattice plane (002) (optical axis direction) does not significantly affect the ultraviolet absorption performance, and is preferably smaller in terms of enhancing transparency. On the other hand, if the crystallite diameter in the direction of the lattice plane (002) (perpendicular to the optical axis), for example, the crystallite diameter perpendicular to the lattice plane (100) and / or the lattice plane (110) is too small. The ultraviolet absorption performance will be reduced. In addition, the crystallite diameter in the direction perpendicular to each lattice plane can be obtained by performing powder X-ray diffraction measurement and performing Scherrer analysis.

The metal oxide particles of the present invention have a dispersed particle diameter of 500 nm or less when dispersed in an arbitrary solvent or resin, in order to improve the transparency of the resulting coating film or resin composite. Is preferable. More preferably, it is 200 nm or less, and further preferably 100 nm or less. In particular, it is desirable that the primary particles can be dispersed in a monodispersed state or a state close thereto, and 50 nm or less is most preferable. The dispersed particle diameter can be measured by, for example, a dynamic light scattering particle size distribution measuring apparatus (for example, “LB-500” manufactured by Horiba, Ltd.).
The optical performance of the metal oxide particles of the present invention includes light blocking properties (ultraviolet blocking properties) in the ultraviolet region (ultraviolet light at 380 nm or less and visible light at 450 nm or less) and transparency in visible light (450 nm to 780 nm) ( Visible light transmission) can be used as an index. As the ultraviolet absorbing functional material, it is preferable that the ultraviolet blocking property is high and the visible light transmittance is high. In general, the ultraviolet blocking property and the visible light transmission property are measured in a state where only particles are present, a state obtained as a film obtained from a film-forming composition described later, or a state where particles are dispersed in a dispersion medium such as a solvent. This can be determined by evaluating the transmittance characteristics. Specifically, the ultraviolet blocking property is evaluated by using the transmittance at an arbitrary wavelength (for example, 380 nm, 400 nm, 420 nm, etc.) in the ultraviolet region as a representative value, or evaluating an average transmittance of 450 nm or less or 380 nm or less. Is determined by On the other hand, the visible light transmittance is evaluated with the transmittance at an arbitrary wavelength in the visible light region (for example, 500 nm, 600 nm, 700 nm, etc.) as a representative value, or the average transmittance at 450 nm to 780 nm or 380 nm to 780 nm. Determined by evaluating. These transmittance values can be obtained by measuring the transmittance including parallel-line transmitted light and diffused transmitted light at each wavelength, and can be measured by, for example, a spectrophotometer equipped with an integrating sphere. However, when the sample is highly transparent and diffusely transmitted light is substantially negligible (specifically, when the haze of the sample is less than 5%), only the parallel line transmittance is used as the measurement value. Also good.

In a preferred embodiment of the metal oxide particles of the present invention, for example, when dispersed in an organic solvent at a particle concentration of 0.1 wt%, the transmittance at 380 nm is preferably 10% or less, more preferably 5% or less, The transmittance at 400 nm is preferably 50% or less, more preferably 20% or less, and the transmittance at 600 nm is preferably 70% or more, more preferably 80% or more. Further, the transmittance at 420 nm is preferably 50% or less.
Moreover, the metal oxide particles of the present invention are used not only for purposes intended to block ultraviolet rays, but preferably have high transparency when formed into a film. Specifically, the haze is preferably 10% or less, more preferably 2% or less, and even more preferably 1% or less.

In addition, as a method for measuring the light absorption characteristics of the particles including the ultraviolet blocking property, a method for measuring the diffuse reflectance of the particle powder can be employed. In that case, a low reflectance means that the absorptance is high, and a high reflectance means that the absorptance is low. Therefore, it is preferable that the reflectance in the ultraviolet region referred to in the present invention is low and the reflectance in the visible light region of 450 nm or more is high.
With regard to the metal oxide particles of the present invention, when the particles and / or crystals of the oxide of the metal element (M) derived from the particles are formed as films that are essential constituents, the optical properties of the films are as follows: It is preferable that the particles satisfy the conditions because they are excellent in performance of transmitting visible light and selectively absorbing only ultraviolet rays. Here, as for the form of the film, the film forming method, and the like, the description relating to the film of the present invention described later can be similarly applied. The optical properties of the film shown below are values measured and evaluated by the methods described in the examples described later, and are the physical properties of only the film part (excluding the base material), Assume that the optical properties of the substrate and the optical properties of the substrate alone are taken into consideration. When the metal oxide particles of the present invention contain Co (II) as a metal element, the transmittance (%) of light having a wavelength of 380 nm, which is an index of ultraviolet absorption performance, among the optical characteristics of the film is further obtained. T ³⁸⁰ is defined as T ³⁸⁰ and the transmittance (%) of light having a wavelength of 500 nm, which is an index of visible light transmission performance, is T ^500, and the minimum value of the transmittance (%) of light having a wavelength of 550 nm to 700 nm is T ¹ . , The absolute value of the difference between T ¹ and T ⁵⁰⁰ (| T ¹ −T ⁵⁰⁰ |) is defined as ΔT.

When the metal oxide particles of the present invention are formed into a film as described above, when the coating amount (use amount) per unit area on the substrate is changed, T ³⁸⁰ or T The values of ⁵⁰⁰ and ΔT also change. Therefore, with respect to the optical properties of the film obtained, when a reference value of T ^380, and to evaluate the value of T ⁵⁰⁰ and [Delta] T, the membrane of the preferred embodiment contains Co (II) metal The case of oxide particles (a) and the case of other metal oxide particles (b) are shown below.
In the case of metal oxide particles containing Co (II) (a);
(i) When the film is formed so that T ³⁸⁰ is 40% or less, ΔT is preferably 10% or less, more preferably ΔT is 10% or less and T ⁵⁰⁰ is 90% or more, More preferably, ΔT is 5% or less and ^T500 is 95% or more.

Preferably, (ii) when the film is formed such that T ³⁸⁰ is 30% or less, ΔT is preferably 10% or less, more preferably ΔT is 10% or less and T ⁵⁰⁰ is 90% or more. More preferably, ΔT is 10% or less and T ⁵⁰⁰ is 95% or more, and particularly preferably ΔT is 5% or less and T ⁵⁰⁰ is 95% or more.
More preferably, (iii) when the film is formed so that T ³⁸⁰ is 20% or less, ΔT is preferably less than 10%, more preferably ΔT is less than 10% and T ⁵⁰⁰ is 80%. More preferably, ΔT is 5% or less and T ⁵⁰⁰ is 85% or more, and particularly preferably ΔT is 5% or less and T ⁵⁰⁰ is 90% or more.

Particularly preferably, (iv) when the film is formed so that T ³⁸⁰ is 10% or less, ΔT is preferably less than 10%, more preferably ΔT is less than 10% and T ⁵⁰⁰ is 80%. More preferably, ΔT is 5% or less and T ⁵⁰⁰ is 85% or more, and particularly preferably ΔT is 5% or less and T ⁵⁰⁰ is 90% or more.
In the case of metal oxide particles other than the above (b);
(i) When the film is formed so that T ³⁸⁰ is 20% or less, T ⁵⁰⁰ is preferably 90% or more, and more preferably T ⁵⁰⁰ is 90% or more.
Preferably, (ii) when the film is formed so that T ³⁸⁰ is 10% or less (more preferably T ³⁸⁰ is 5% or less), T ⁵⁰⁰ is preferably 70% or more, and more preferably T ⁵⁰⁰ is 80% or more.

  In the metal oxide particles of the present invention, the particles composed of the oxide of the metal element (M) contain 0.1 to 14 mol% of acyl groups in a molar ratio to the metal element (M). It is preferable at the point from which the film-forming composition and film | membrane which are excellent in dispersibility and excellent in transparency are obtained. In particular, when the metal element (M) is Zn, Ti, Ce, In, or Sn, the refractive index of the crystal is high, so that visible light is likely to be scattered, and haze when dispersed in a binder such as a resin. However, if the particles contain an acyl group as described above, the film has excellent transparency with low haze. The acyl group preferably has 1 to 3 carbon atoms.

  In the metal oxide particles of the present invention, the oxide of the metal element (M) has an alkoxide comprising at least one metal element different from the metal element (M ′) contained in the oxide on the surface, or It is preferable that those (partial) hydrolysates are bonded to each other for the same reason as the particles containing an acyl group are preferable. That is, such particles are preferable in that a film-forming composition or film having excellent dispersibility and excellent transparency can be obtained. In particular, this aspect is effective when the metal element (M) is Zn, Ti, Ce, In, or Sn. The at least one metal element different from the metal element (M ′) contained in the oxide of the metal element (M) is preferably selected from the group consisting of Si, Ti, Al, and Zr. The surface of the oxide of the metal element (M) is selected from the group consisting of at least one metal element (preferably Si, Ti, Al, Zr) different from the metal element (M ′) contained in the oxide. Surface treatment with at least one of the following metal compounds (1) to (3) to form particles in which alkoxides comprising at least one metal element) or a (partial) hydrolyzate thereof are bonded. do it.

The metal compounds (1) to (3) will be described below.
Metal compound (1): Metal alkoxides comprising at least one metal element different from the metal element (M ′) contained in the oxide of the metal element (M), such as tetramethoxysilane and tetrabutoxysilane.
Metal compound (2): An organic group-containing metal compound represented by the following general formula (a). In addition, the kind of metal element in this metal compound is not limited.
Y ¹ _i M ¹ X ¹ _j (a)
(Where Y ¹ is an organic functional group, M ¹ is a metal atom, and X ¹ is a hydrolyzable group. I and j are integers of 1 to (s-1), and i + j = s (s is M ¹ Valence).)
As an organic group containing metal compound represented by general formula (a), the following are mentioned, for example.

Examples of the organic group-containing compound in which M ¹ is aluminum include diisopropoxy aluminum ethyl acetoacetate, diisopropoxy aluminum alkyl acetoacetate, diisopropoxy aluminum monomethacrylate, aluminum stearate oxide trimer, and isopropoxy aluminum alkyl acetoacetate. Various aluminum-based coupling agents such as mono (dioctyl phosphate) can be used.
Examples of the organic group-containing compound in which M ¹ is silicon include vinyl-based silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, and vinyltriacetoxysilane; N- ( Amino silanes such as 2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-N-phenyl-γ-aminopropyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine Coupling agent; Epoxy silane coupling agent such as γ-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; Chlorine silane cup such as 3-chloropropyltrimethoxysilane Ring agent: Acryloxypropyl Acryloxy silane coupling agents such as methoxysilane and acryloxypropyltriethoxysilane; methacryloxy silane coupling agents such as 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane; 3-mercaptopropyltrimethoxy Mercapto silane coupling agents such as silane; Ketimine silane coupling agents such as N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine; N- [2- (vinyl Benzylamino) ethyl] -3-aminopropyltrimethoxysilane / hydrochloride cationic silane coupling agent; methyltrimethoxysilane, trimethylmethoxysilane, decyltriethoxysilane, hydroxyethyltrimethoxysilane, etc. Kill-based silane coupling agent; (tridecafluoro-1,1,2,2-tetrahydrooctyl) silicon compound having fluorine-containing organic group such as triethoxysilane; isocyanato group-containing organic group such as propyltrimethoxysilane isocyanate A silane coupling agent having the following general formula (b):
_{R'O (C 2 H 4 O)} n C 3 H 6 Si (OR ") 3 (b)
(However, R ′ is a group in which at least one selected from hydrogen or an alkyl group such as a methyl group, a cycloalkyl group, an aryl group, an acyl group, and an aralkyl group may be substituted. Is a group in which at least one selected from an alkyl group such as a methyl group, a cycloalkyl group, an aryl group, an acyl group and an aralkyl group may be substituted, and n is an integer of 1 or more.)
And various silane coupling agents such as γ-ureidopropyltriethoxysilane and hexamethyldisilazane.

Examples of the organic group-containing compound in which M ¹ is zirconium include various zirconiums such as zirconium di-n-butoxide (bis-2,4-pentanedionate), zirconium tri-n-butoxide pentanedionate, and zirconium dimethacrylate dibutoxide. Compounds and the like.
Metal compound (3): (partial) hydrolyzate or condensate of metal alkoxide (metal is optional) or (partial) hydrolyzate or condensate of (2) above, for example, in the following general formula (c) expressed.
_{^{R 1 - (O-M (}} -R 2 m1) (- R 3 m2)) n -R 4 (c)
(However, R ¹ and R ² are any one selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an acyl group, or a group in which the one type may be substituted. R ³ is a hydrolyzable group (same as X ¹ in the general formula (a)) or a hydroxyl group, R ⁴ is R ² or R ³ , M is a metal atom, and m 1 and m 2 are (M valence-2), and n is an integer from 2 to 10000. The types of R ² and R ³ bonded to the metal atom M and the valence (m1 and m2) are metal atoms. All of M may be the same, or at least some of them may be different.)
For example, in the case of the hydrolysis condensate of the metal compound (2), a part or all of the hydrolyzable group X ¹ bonded to the metal atom M ¹ in the general formula (a) is hydrolyzed. Examples of the compound in which X ¹ is an OH group, and a compound in which an M ¹ -O-M ¹ bond is formed by a condensation reaction such as dehydration condensation between M ¹ -OH, and the like are specifically mentioned. , Linear (including branched chains), including linear and cyclic trimers, obtained by hydrolytic condensation and / or partial hydrolytic condensation of organic group-containing compounds listed as metal compounds (2) And cyclic hydrolysis condensates.

Metal compound as the (3), for example, titanium (IV) tetra -n- butoxide tetramer _{(C 4 H} 9 _{O-[Ti (OC 4 H 9) 2} O ] ₄ -C ₄ H _9, manufactured by Wako Pure Chemical Industries, Ltd. ), Silicon (IV) tetramethoxide tetramer, methyltrimethoxysilane tetramer, tetramethoxysilane-methyltrimethoxysilane co-hydrolysis condensate, aluminum (III) tributoxide trimer, and the like.
The method for producing the metal oxide particles of the present invention is not limited, and any method can be used as long as it is a known method that can obtain (doped) particles in which metal oxide particles contain a desired different element. This method can also be adopted. For example, a metal element (M) compound and / or a hydrolysis condensate thereof, a heterogeneous non-metal element compound, and a metal element (M ′) compound and alcohol are used in the case of obtaining third metal oxide particles. A production method (hereinafter referred to as production method (A)) including a step of forming (precipitating) metal oxide particles by using the mixed system as a raw material at a high temperature is preferable. Specifically, in the case of obtaining the metal element (M) compound and / or its hydrolysis condensate, the different non-metal element compound, and the third metal oxide particles, the production method (A) is used as the starting material. This is a method comprising a step of bringing the mixed system into a high temperature state simultaneously with or after mixing the metal element (M ′) compound and the alcohol. Thus, by making it a high temperature state, a metal oxide particle can be produced | generated in a reaction system.

Although it does not limit as a metal element (M) compound which can be used in a manufacturing method (A), The carboxylate of a metal element (M) is preferable. Moreover, the hydrolysis condensate of a metal element (M) compound is a hydrolyzate and / or condensate obtained by hydrolyzing and / or condensing the compound, and includes a monomer compound to a polymer compound ( Hereinafter, “metal element (M) compound” may mean “metal element (M) compound and / or hydrolysis condensate thereof”.
As the carboxylate of the metal element (M), a compound having at least one substituent in the molecule in which a hydrogen atom of the carboxyl group is substituted with an atom of the metal element (M) is preferable. Specifically, a chain carboxylic acid such as a saturated monocarboxylic acid, an unsaturated monocarboxylic acid, a saturated polycarboxylic acid and an unsaturated polycarboxylic acid; a cyclic saturated carboxylic acid; an aromatic monocarboxylic acid and an aromatic polycarboxylic acid Aromatic carboxylic acids such as saturated polyvalent carboxylic acids; these carboxylic acids further have functional groups or atomic groups such as hydroxyl groups, amino groups, nitro groups, alkoxy groups, sulfone groups, cyano groups and halogen atoms in the molecule. Preferred examples include compounds in which a carboxyl group in a carboxylic acid compound such as a compound is the above substituent.

Among these carboxylates of the metal element (M), the following general formula (I):
_{M (O) (m-x} -y-z) / 2 (OCOR 1) x (OH) y (OR 2) z (I)
(However, M is an atom of metal element (M) (at least one selected from the group consisting of Zn, Ti, Ce, In, Sn, Al, and Si); R ¹ is a hydrogen atom or a substituent. At least one selected from a good alkyl group, cycloalkyl group, aryl group and aralkyl group; R ² is at least one selected from an alkyl group, cycloalkyl group, aryl group and aralkyl group which may have a substituent; Species; m, x, y and z are numbers satisfying x + y + z ≦ m, 0 <x ≦ m, 0 ≦ y <m, 0 ≦ z <m (m is the valence of M).)
(For example, compounds in which a part of the carboxylate of the metal element (M) exemplified above is substituted with a hydroxyl group, an alkoxy group, etc.), saturated carboxylate, unsaturated carboxylate, and basic Acetates are more preferred, more preferred are compounds represented by the above general formula (I), and most preferred are formate, acetate and propionate of metal element (M) and basic salts thereof.

The carboxylate of the metal element (M) may be a hydrate of carboxylate containing crystal water, but is preferably an anhydride.
The compound represented by the general formula (I) will be described in more detail.
R ¹ and R ² in the general formula (I) are preferably alkyl groups having 1 to 4 carbon atoms such as hydrogen and methyl groups in terms of easy obtaining of highly dispersible metal oxide particles. A group and an ethyl group are particularly preferred. For the same reason, x in the general formula (I) preferably satisfies 1 ≦ x ≦ m, y preferably satisfies 0 ≦ y <m / 2, and z is 1 ≦ z <m. It is preferable to satisfy / 2.

As the compound represented by the general formula (I), a compound having a high dissolution rate is preferable in that metal oxide particles having high dispersibility are easily obtained. The dissolution rate can be directly measured by reaction. At 25 ° C., 2 parts by weight of the compound represented by the general formula (I) is added to 200 parts by weight of ion-exchanged water (pH 5-8) at 25 ± 3 ° C. When the mixture is mixed and stirred, it is defined as the time t until the solution is completely dissolved and a transparent solution is obtained. The dissolution rate of the compound represented by the general formula (I) is preferably 2 minutes or less, more preferably 1 minute or less, and still more preferably 30 seconds or less.
Among the hydrolyzed condensates of the compound represented by the general formula (I), the condensate is a bonded chain-(MO) _n (wherein the metal element (M) and oxygen (O) are bonded to each other). n is preferably 1 or more). The degree of condensation (average) of the condensate is not limited, but is preferably 100 or less, more preferably 10 or less, in that metal oxide particles having a uniform crystallite size and shape can be obtained. .

As for the metal element (M) compound, only one kind of those described above may be used, or two or more kinds may be used in combination.
The compound of the different non-metallic element that can be used in the production method (A) is not limited. For example, when the different non-metallic element is N, nitrogen compounds such as ammonia, aqueous ammonia, urea, and ammonium carbonate are preferable. When the different nonmetallic element is S, metal sulfides such as hydrogen sulfide and sodium sulfide are preferably mentioned. When the different nonmetallic element is a group 17 element, hydrofluoric acid, hydrochloric acid, odor Preferable examples include acids such as hydrofluoric acid and hydroiodic acid, and fluorides, chlorides, bromides and iodides of metals (preferably metal element (M) or metal element (M ′)). As for the compound of the different non-metallic element, only one of these may be used or two or more of them may be used in combination.

The compound of the metal element (M ′) that can be used in the production method (A) is not limited, but includes a compound of the metal element (M ′) to be included in the metal oxide as the metal element (M ′). Use as essential. For example, metal carboxylates and metal alkoxides are preferable. As for the compound of the metal element (M ′), only one of these may be used, or two or more may be used in combination.
The alcohol that can be used in the production method (A) is not limited, but examples thereof include aliphatic monohydric alcohols (methanol, ethanol, isopropyl alcohol, n-butanol, t-butyl alcohol, stearyl alcohol, etc.), aliphatic unsaturation. Monohydric alcohols (allyl alcohol, crotyl alcohol, propargyl alcohol, etc.), alicyclic monohydric alcohols (cyclopentanol, cyclohexanol, etc.), aromatic monohydric alcohols (benzyl alcohol, cinnamyl alcohol, methylphenyl carbinol) Etc.), phenols (ethylphenol, octylphenol, catechol, xylenol, guaiacol, p-cumylphenol, cresol, m-cresol, o-cresol, p-cresol, dodecylphenol, naphtho , Nonylphenol, phenol, benzylphenol, p-methoxyethylphenol, etc.), monohydric alcohols such as heterocyclic monohydric alcohols (furfuryl alcohol, etc.); alkylene glycols (ethylene glycol, propylene glycol, trimethylene glycol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, pinacol, diethylene glycol, triethylene glycol, etc.), alicyclic glycol (cyclopentane) -1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, etc.) and glycols such as polyoxyalkylene glycol (polyethylene glycol, polypropylene glycol, etc.) Propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, triethylene glycol monomethyl ether, Derivatives such as monoethers or monoesters of the above glycols such as ethylene glycol monoacetate; trihydric alcohols such as glycerin and trimethylolethane; tetrahydric alcohols such as erythritol and pentaerythritol; pentahydric alcohols such as lipitol and xylitol; sorbitol Trihydric or higher polyhydric alcohols such as hexahydric alcohols, hydrobenzoin, benzpinacol, Polyhydric aromatic alcohols such as phthalyl alcohol, dihydric phenols such as catechol, resorcin, and hydroquinone, polyhydric phenols such as trihydric phenols such as pyrogallol and phloroglucin, and a part of OH groups in these polyhydric alcohols (1 to (n-1) (where n is the number of OH groups per molecule)) an ester bond or an ether bond; Alcohol may use only 1 type in these, or may use 2 or more types together.

Among these, the alcohol is preferably an alcohol that easily reacts with a metal element (M) compound, a compound of a different non-metallic element or a compound of a metal element (M ′) to form metal oxide particles, and is aliphatic. Alcohols and alcohols with high water solubility are preferred. Specifically, alcohols having a solubility in water of 1% by weight or more are preferred, and alcohols having a solubility in water of 10% by weight or more are more preferred.
The mutual use ratio (mixing ratio) of the metal element (M) compound and the alcohol as a starting material is not limited, but in the alcohol relative to the number of metal-converted atoms of the metal element (M) compound (derived from the alcohol The ratio of the number of hydroxyl groups is preferably 0.8 to 1000, more preferably 0.8 to 100, still more preferably 1 to 50, and particularly preferably 1 to 20.

Moreover, although there is no limitation on the mutual use ratio (mixing ratio) of the metal element (M) compound and the different non-metal element compound or the metal element (M ′) compound, the metal conversion of the metal element (M) compound The ratio of the number of atoms and the number of atoms of the different non-metallic element of the different non-metallic element compound or the number of metal-converted atoms of the metal element (M ′) compound is the content of the different non-metallic element or the metal element (M ′). What is necessary is just to set suitably so that the preferable range of the content rate of may be satisfy | filled.
The starting material mixing system is preferably a fluid liquid such as a paste, emulsion, suspension or solution. If necessary, it may be made liquid by mixing a reaction solvent described later. Usually, in the mixed system, the metal element (M) compound, the heterogeneous non-metal element compound, and the metal element (M ′) compound are dispersed in the form of particles, dissolved, or partially dissolved. The rest is in a state of being dispersed in the form of particles.

In the production method (A), a reaction solvent may be further used. Specifically, the mixing of the starting materials or the mixing system of the starting materials may be performed after further adding a reaction solvent.
Although there is no limitation about the usage-amount of a reaction solvent, the ratio of the usage-amount of the said metal element (M) compound with respect to the total usage-amount of the said starting material and the reaction solvent shall be 0.1-50 weight%. Is preferable, and metal oxide particles can be obtained economically.
As the reaction solvent, a solvent other than water, that is, a non-aqueous solvent is preferable. Non-aqueous solvents include, for example, hydrocarbons, various halogenated hydrocarbons, alcohols (including phenols, polyhydric alcohols and derivatives thereof having a hydroxyl group), ethers and acetals, ketones and aldehydes, carboxylic acid esters And derivatives such as esters such as phosphate esters, amides, polyhydric alcohols in which all hydroxyl groups are substituted with alkyl groups or acyl groups, carboxylic acids and their anhydrides, silicone oils and mineral oils. be able to. As the reaction solvent, a hydrophilic solvent is particularly preferable. Specifically, a solvent that can be in a solution state containing 5% by weight or more of water at room temperature (25 ° C.) is preferable, and a solvent that can be in a uniform solution state containing any amount of water is more preferable. Preferable examples of the alcohol as the reaction solvent are the same as those listed above as the starting alcohol. Among these, the reaction solvent may be used alone or in combination of two or more.

  In the production method (A), since the amount of moisture contained in the mixed system of the starting materials and the like (including the reaction solvent used as necessary) is less, the resulting metal oxide particles have fewer defects. preferable. Specifically, it is preferable that the mixed system contains only a small amount of water with a molar ratio of less than 4 with respect to the metal atoms in the metal element (M) compound used as the starting material. More preferably, it is less than 1, particularly preferably less than 0.5, and most preferably less than 0.1. If the amount of water is too large, it becomes difficult for the metal oxide crystallites to contain different kinds of non-metallic elements and metal elements (M ′), and metal oxide particles that can sufficiently exhibit the effects of the present invention described above are obtained. There is a risk of not being able to. The water content can be measured, for example, by the Karl Fischer method.

In addition, although the said moisture content generally means the free moisture content, when a metal element (M) compound, a dissimilar nonmetallic element compound, and a metal element (M ') compound have crystal water, the crystal water Water content is also included. In addition, the amount of water is the amount of water contained in the starting material (free water in the alcohol and other reaction solvent components used, as well as metal element (M) compounds, dissimilar non-metal element compounds, metal elements (M ′ ) The sum of water such as crystal water in the compound), and water generated as a by-product in the reaction by bringing the mixed system to a high temperature state is not considered.
In the production method (A), when the mixed system of the starting materials is brought into a high temperature state, the temperature of the mixed system is higher than room temperature and the metal oxide particles can be generated or higher. It is to raise the temperature. Specifically, although it varies depending on the type of metal oxide particles to be obtained (type of metal element (M), heterogeneous non-metallic element compound, metal element (M ′), etc.), generally 50 ° C. or higher In order to obtain highly crystalline metal oxide particles, 80 ° C. or higher is preferable, 100 to 300 ° C. is more preferable, 100 to 200 ° C. is further preferable, and 120 to 200 ° C. is particularly preferable. Note that the temperature of the mixing system is the bottom temperature of the reaction vessel.

The high temperature state of the mixed system is preferably maintained at a predetermined temperature for 30 minutes or more, more preferably 2 from the viewpoint that the crystallinity of the metal oxide particles is improved and an excellent physical property such as ultraviolet shielding property is obtained. More than an hour.
When the generated metal oxide particles are intended to remove residual organic groups or promote further crystal growth, the metal oxide particles may be heated at 300 to 800 ° C. as necessary. Good.
As a specific temperature raising means for bringing the above mixed system into a high temperature state, a heater, heating with warm air or hot air is generally used, but is not limited thereto, and means such as ultraviolet irradiation is adopted. You can also

When the above mixed system is brought into a high temperature state, it may be carried out under normal pressure, under pressure or under reduced pressure, and is not limited, but the starting material may be brought into a high temperature state by heating or the like under pressure. More preferred. In addition, when the boiling point of the starting material or the reaction solvent used in combination is lower than the reaction temperature at which the metal oxide particles are generated, it is also preferable to use a pressure resistant reactor. Usually, the reaction temperature and the gas phase pressure during the reaction are carried out below the critical point of the component serving as the solvent, but it can also be carried out under supercritical conditions.
When the starting material is brought into a high temperature state under pressure, the pressure during heating (pressure in the gas phase part) is not limited, but when indicated by an absolute pressure P with the normal pressure (atmospheric pressure) being 1 kg / cm ² Furthermore, it is preferable that P> 1 kg / cm ² is satisfied, and more preferably 1.5 kg / cm ² ≦ P ≦ 100 kg / cm ² . Furthermore, it is particularly preferable that 3 kg / cm ² ≦ P ≦ 20 kg / cm ² is satisfied in that the pressurizing effect is high and it can be performed with economical equipment. The method of pressurization is not limited, but 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, etc. can be adopted. .

  In the production method (A), as described above, the high temperature state of the mixed system may be obtained at the same time as or after mixing the starting materials, that is, the starting for obtaining the mixed system. The mixing of the raw materials and the like and the temperature raising for bringing the mixed system into a high temperature state may be performed separately or simultaneously (including partly simultaneously), and are not limited. Specifically, specific means (for example, heating) for raising the temperature of the mixed system can be performed by any method and timing regardless of the mixing of the starting materials, for example, starting materials before mixing, etc. The temperature of the mixed system may be raised simultaneously with mixing by heating at least one of the above, or the mixing system obtained by mixing may be mixed or mixed. After the completion, heating or the like may be performed to raise the temperature of the mixed system, and there is no limitation. Therefore, as an embodiment relating to the timing of this mixing and heating for raising the temperature, for example, (i) When obtaining a metal element (M) compound, a different non-metal element compound, and third metal oxide particles Is mixed with a metal element (M ′) compound and an alcohol, and the temperature is raised to a high temperature by heating or the like. (Ii) The alcohol is heated to a predetermined temperature, etc. (M) In the case of obtaining a compound, a heterogeneous nonmetallic element compound, and third metal oxide particles, the mixed system is heated to a high temperature state by mixing the metal element (M ′) compound. ) When obtaining the reaction solvent, the metal element (M) compound, the heterogeneous nonmetal element compound, and the third metal oxide particles, the metal element (M ′) compound is mixed and heated to a predetermined temperature. By mixing alcohol with this, the temperature of the mixed system is raised. (Iv) Each component (metal element (M) compound, heterogeneous non-metallic element compound, metal element (M ′) compound and alcohol for obtaining third metal oxide particles), alcohol, and necessary Preferably, the reaction solvent used in accordance with the above is heated separately, and then mixed to raise the temperature of the mixed system to a high temperature.

The heterogeneous nonmetallic compound is supplied as a source gas of a heterogeneous nonmetallic element (for example, ammonia gas, hydrogen sulfide, etc.) at any stage such as in the process of bringing it into a high temperature state, at a high temperature state, or after generation of metal oxide particles. You may make it do.
In the above embodiment (particularly, embodiments (ii) to (iv)), the method for mixing the starting materials is not limited, but the starting materials to be added are added all at once (for example, within 1 minute). Alternatively, it may be added sequentially (for example, taking a time exceeding 1 minute). The sequential addition may be continuous addition (continuous feed), intermittent addition (pulse addition), or a combination thereof, and is not limited. In intermittent addition (pulse addition), each pulse may be continuous addition or batch addition, and is not limited. As for the above mixing method, a smaller temperature change of the mixed system caused by the addition is preferable from the viewpoint of easily obtaining metal oxide particles having a uniform primary particle diameter, and specifically, the temperature of the mixed system. It is preferable to control the addition rate and the like so that the change is kept within 10 ° C.

In the above embodiment (particularly the embodiment of (ii)), the addition rate when the metal element (M) compound is added to the alcohol and mixed (the metal element per minute relative to the number of moles of alcohol added ( M) The ratio of the number of moles of compound added) 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 an average primary particle size of 0.1 μm or less. If it exceeds 2, it is difficult to control the temperature in the high temperature state described above ( Especially when the reaction scale is large), it may be difficult to obtain particles having a uniform particle size.
In the production method (A), the mixed system is preferably stirred at a power required for stirring of 0.0001 kw / m ³ or more at least while the mixed system of the starting materials is at a high temperature. Is 0.001 kw / m ³ or more, more preferably 0.01 to 10 kw / m ³ .

  In the production method (A), for the purpose of improving the dispersibility of the generated metal oxide particles, the process until the mixed system consisting of the starting materials is brought to a high temperature state to generate the metal oxide particles or any after the generation In this stage, it is preferable to add an aliphatic carboxylic acid, an aliphatic amine, or the metal compounds (1) to (3) described above to the mixed system or reaction system. By this addition, it is possible to effectively suppress the secondary aggregation of the metal oxide particles and to obtain particles having excellent dispersibility. Among these, the addition of the metal compound is particularly preferable in that the crystallite diameter of the metal oxide particles can be controlled to a very small particle diameter, for example. The addition amount (total addition amount) of the aliphatic carboxylic acid or aliphatic amine is preferably 0.1 to 10 mol% with respect to the metal element (M) in the metal element (M) compound. The addition amount (total addition amount) of the metal compounds (1) to (3) is an atomic ratio of the metal element in the metal compound to the metal element (M) in the metal element (M) compound. It is preferable that it is -10 atomic%.

As described above, the metal oxide particles of the present invention not only exhibit superior ultraviolet absorption, but also, for example, the ultraviolet absorption edge is shifted to the longer wavelength side, and ultraviolet rays in the long wavelength region are absorbed. Metal oxide particles that have excellent absorption efficiency and good transparency, for example, even when they are internally added to or coated on a substrate, they do not impair the transparency and hue of the substrate. It is.
The metal oxide particles of the present invention are, for example, cosmetics, various electronic films for the purpose of shielding ultraviolet rays, packaging materials, etc., windows for buildings such as buildings and houses, automobile windows, sunroofs, railway and airplane windows It is useful as a particle to be contained in a transparent plastic sheet such as glass or polycarbonate used in the above, or as a raw material particle for an ultraviolet absorbing paint that can be formed into a film.

  Specifically, when the metal element (M) in the metal oxide particles of the present invention is Zn, Ti, or Ce, these oxide particles or these oxides contain different elements other than those specified in the present invention. Excellent UV absorption performance, colorlessness, and visible light transmission performance that could not be obtained with the treated particles can be satisfied at the same time. For example, LCD (liquid crystal display), PDP (plasma display), white LED, mercury lamp As a UV-absorbing material that blocks ultraviolet rays derived from excitation sources and light sources in display devices such as fluorescent lamps and lighting, and various types of buildings, vehicles (cars, trains, etc.), air transports (airplanes, helicopters, etc.) Various glasses used for window materials, displays, etc. (inorganic glass such as single glass, multi-layer glass, and laminated glass, and polycarbonate As the ultraviolet absorbing material organic glass) such as a resin, and as UV-absorbing material for various films that require ultraviolet shielding property such as agricultural films, various packaging films useful.

When the metal element (M) in the metal oxide particles of the present invention is Zn, Si, or Al, the whiteness is lower than that of titanium oxide, which has been mainly used as a cosmetic UV absorber. Therefore, it is useful as a UV absorber for cosmetics that can give a better transparency. In particular, when the metal element (M) in the metal oxide particles of the present invention is Si or Al, the particles have a particularly low refractive index. It is also useful as a display device material or an electronic material.
When the metal element (M) in the metal oxide particle of the present invention is Ti, Zn, Ce, In, or Sn, it becomes a particle having a high refractive index, and therefore, it is blended with a resin or silicate as a binder component. By controlling the ratio, it becomes possible to obtain a film having an arbitrary refractive index, which is useful as a raw material for an ultraviolet absorbing film having antireflection properties.

Furthermore, the metal oxide particles of the present invention can be applied to applications other than the purpose of blocking ultraviolet rays. For example, the metal element (M) in the metal oxide particles of the present invention is Ti, Zn, Ce, In In the case of Sn, particles having a high refractive index can be suitably used as a high refractive index filler for increasing the refractive index of resins, films, films, etc. When the product particles are ultrafine particles, a transparent film having a high refractive index suitable for an antireflection film and a film can be obtained.
Further, when the metal element (M) in the metal oxide particles of the present invention is Zn, In, Sn, or Ti, it is also useful as an infrared (near infrared to far infrared) absorbing material. In particular, particles in which the metal element (M) is Zn, In, Sn, Ti and contains fluorine as a different non-metallic element are useful as an infrared absorbing material.

In addition, when the metal element (M) in the metal oxide particles of the present invention is Zn or Al, it becomes a particle having excellent thermal conductivity, and thus is useful as a thermally conductive filler. For example, heat dissipation is required. In white LED applications, electronic circuit board applications, and the like, it can be suitably used when obtaining a sheet, film, or film having high thermal conductivity.
Further, when the metal element (M) in the metal oxide particles of the present invention is Zn, Ti, In, or Sn, the particles are excellent in electron conductivity, and thus are useful as semiconductors or conductors. In particular, when the metal oxide particles of the present invention are ultrafine particles, it can be preferably used as a transparent antistatic film such as a film or a transparent conductive film by forming a paint.

Further, the metal oxide particles of the present invention contain one or two or more different kinds of non-metallic elements or metal elements (M ′), and are newly added in the band gap of the metal element (M) oxide. Therefore, it is useful as a photocatalyst material or a phosphor material. For example, in recent years, there has been a demand for a photocatalyst with high sunlight utilization efficiency, a so-called visible light actuated photocatalyst. When the metal element (M) in the metal oxide particles of the present invention is Zn or Ti, the photocatalyst is used. It is also useful as a raw material.
In the third metal oxide particle of the present invention, the metal element (M) is any one of Zn, Ti, In, and Sn, and the metal element (M ′) is Fe, Co, Ni, When containing at least one selected from the group consisting of Mn, or the valence of at least one selected from the group consisting of Fe, Co, Ni, Mn and the metal element (M) as the metal element (M ′) (Ferro) (for example, when M is Zn, a trivalent or tetravalent metal element such as In, Al, B, Ga, Sn, etc.) It is also useful as a particle exhibiting semiconductor characteristics.

  The metal oxide particles of the present invention can be adjusted in various colors depending on the kinds and combinations of different non-metallic elements and metal elements (M ′) to be contained, and are also useful, for example, as a coloring pigment. For example, when the metal element (M ′) is Bi or Ag, it is clear yellow, when the metal element (M ′) is Fe (III), it is yellow, and when the metal element (M ′) is Mn. Is orange to beige, green when the metal element (M ′) is Fe (II) or Ni (II), blue to green when the metal element (M ′) is In or Co, metal When the element (M ′) is Cu, it tends to be gray or the like. By making these other metal elements (M ′) and dissimilar non-metal elements coexist with these particles, the particles can be finely or drastically toned.

〔Composition〕
In the composition of the present invention, metal oxide particles are dispersed in a medium, and the metal oxide particles essentially use the metal oxide particles of the present invention described above.
The metal oxide particles of the present invention can be applied to the various uses described above as various liquid or solid compositions. Examples of liquid compositions include solvent dispersions in which particles are dispersed in a dispersion solvent, coating compositions in which particles are dispersed in a film-forming binder, particles in a plasticizer that is a raw material for laminated glass interlayer films and resin molded products. Dispersions in which particles are dispersed in a liquid resin, polymerizable compositions in which particles are dispersed in a polymerizable compound such as an acrylic monomer, and the like. As a solid composition, the liquid composition is used as a raw material. And a resin molded product in the form of a film, a substrate with a film, a fiber, a film, or a sheet. For example, the liquid composition can be easily obtained by dispersing the metal oxide particles of the present invention obtained in powder form or the reaction liquid when the metal oxide particles are produced in various dispersion media by a conventionally known method. Can get to. Hereinafter, practically particularly useful film-forming compositions (corresponding to the solvent dispersion or the coating composition in the above classification) will be described.

In the composition of the present invention (including the film-forming composition of the present invention described later), the metal oxide particles are dispersed with a dispersed particle size of 1 μm or less depending on the composition and the composition. It is preferable in terms of excellent transparency in the resulting film. More preferably, it is 0.2 μm or less, further preferably 0.1 μm or less, and particularly preferably 0.07 μm or less.
[Film-forming composition]
As described above, the film-forming composition according to the present invention is a composition comprising the metal oxide particles according to the present invention, a dispersion solvent and / or a binder as essential components. In addition, the description mentioned above is applicable similarly about the metal oxide particle of this invention which is an essential structural component of the composition of this invention.

With respect to the dispersion solvent and / or binder, which are essential constituents of the composition of the present invention, the mutual ratio (mixing ratio) of the amounts used (dispersion solvent and binder) is not limited, and is an essential constituent. It can be set as appropriate according to the type (composition) and amount of metal oxide particles used and the form of the film to be formed.
Examples of the dispersion solvent include organic solvents such as water, (various halogenated) hydrocarbons, alcohols, ethers, acetals, ketones, aldehydes, carboxylic acid esters, amides, and carboxylic acids (anhydrides), silicone oils, Examples include mineral oil. These may be used alone or in combination of two or more.

  Examples of the binder include organic binders such as various synthetic resins and natural resins that are thermoplastic or thermosetting (including thermosetting, ultraviolet curable, electron beam curable, moisture curable, and combinations thereof). And inorganic binders. Examples of synthetic resins include polyester resins, fluororesins, alkyd resins, amino resins, vinyl resins, acrylic resins, epoxy resins, polyamide resins, polyurethane resins, thermosetting unsaturated polyester resins, phenol resins, chlorinated polyolefin resins, Examples include butyral resin, silicone resin, acrylic silicone resin, fluororesin, xylene resin, petroleum resin, ketone resin, rosin-modified maleic acid resin, liquid polybutadiene, coumarone resin, and the like. The Examples of natural resins include shellac, rosin (pine resin), ester gum, hardened rosin, decolorized shellac, white shellac, and the like, and one or more of these are used. As the synthetic resin, natural or synthetic rubber 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.

The form of the binder component is not 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).
Examples of water-soluble binder components 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.
Examples of emulsion type binder components include (meth) alkyl acrylate copolymer dispersions; vinyl acetate resin emulsions, vinyl acetate copolymer resin emulsions, ethylene-vinyl acetate copolymer resin emulsions, and acrylate (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.

Examples of the inorganic binder include metal oxide sols such as silica sol, alumina sol, titania sol, zirconia sol and ceria sol; alkali silicic acid; metal alkoxides such as silicon alkoxide, zirconium alkoxide and titanium alkoxide and their (hydrolyzed) condensates; Poly) silazane; phosphates and the like. In addition, metal carboxylates such as metal formate, metal acetate and metal oxalate, and basic salts thereof, organometallic complexes such as β-diketone complexes such as metal acetylacetonate, etc. Mention may also be made of metal compounds that can be metal oxides.
These inorganic binders are converted into metal oxides or metal hydroxides by heat and / or humidity after being applied. Among these inorganic binders, the metal oxides and metal hydroxides are UV-absorbing. In terms of superiority, inorganic binders containing Ti, Ce, Zn as metal elements are preferred, and in terms of superior chemical durability of the resulting film, inorganic binders containing Si, Zr, Ti, Al as metal elements are preferred. In terms of excellent dispersibility of the metal oxide particles, inorganic binders of metal alkoxides are preferable, and metal alkoxides containing Si, Ti, and Al as metal elements and their (hydrolyzed) condensates are particularly preferable.

The composition of the present invention is a metal oxide particle containing at least one selected from the group consisting of Cu, Ag, Fe and Bi as a metal element (the metal oxide particle is added as a second component, Hereinafter, the metal ultrafine particles (also referred to as “added metal oxide particles”) and / or metal ultrafine particles containing at least one selected from the group consisting of Ag, Cu, Au and platinum group metal elements (the metal) The ultrafine particles are added as the second component, and it is preferable that the ultrafine particles also include “added metal ultrafine particles”. As a result, the visible light blocking effect in the short wavelength region can be further enhanced.
Among the additive metal oxide particles, as the metal oxide particles containing Cu as a metal element, for example, cuprous oxide (Cu ₂ O), cupric oxide (CuO), copper ferrite (CuFe ₂ O ₄ ), Single oxides such as copper molybdate (CuMoO ₄ ), copper tungstate (CuWO ₄ ), copper titanate (CuTiO ₃ ), copper selenate (CuSeO ₄ ), copper chromite (CuCr ₂ O ₄ ), etc. Oxides, solid solution oxides in which some of the metal elements of single oxides and complex oxides are partially substituted with dissimilar metal elements, and part of oxygen in single oxides and complex oxides are other elements (for example, , Nitrogen, sulfur, halogen elements, etc.) and particles made of solid solution oxides. In addition, in the said oxide, the compound which shifted | deviated from stoichiometric composition like _{Cu1- (delta)} O is also contained, for example. Among these, copper oxide particles or particles in which an organic group such as an acyl group such as an ethanoyl group or an alkoxy group such as an ethoxy group is bonded to the particle surface of the particles are preferable, such as cuprous oxide particles or an ethanoyl group or the like on the particle surface. Particularly preferred is a particle having an organic group such as an alkoxy group such as an acyl group or an ethoxy group bonded thereto.

Among the added metal oxide particles, examples of the metal oxide particles containing Fe as a metal element include iron oxide (ferrous oxide (FeO), ferric oxide (α-Fe ₂ O ₃ , γ-Fe _2). O ₃ ), triiron tetroxide (Fe ₃ O _4, etc.), iron hydroxide (III) (α-FeO (OH), γ-FeO (OH), etc.), general formula M (II) Fe ₂ O ₄ (However, M in the formula is one or more arbitrary metal elements) Various ferrite compounds (for example, manganese ferrite, zinc ferrite, cobalt ferrite, nickel ferrite, barium ferrite, zinc nickel) Ferrite (such as ferrite), iron titanate (FeTiO ₃ ), iron molybdate (FeMoO ₄ ), iron tungstate (FeWO ₄ ), etc., single (water) oxide, composite oxide, single (water) oxide and composite Oxidation Solid solution oxides in which part of the metal element of the product is partially substituted with a different metal element, part of oxygen in the single (hydroxide) oxide or composite oxide is another element (for example, nitrogen, sulfur, halogen element) Etc.) and particles made of solid solution oxide partially substituted. In addition, in the said (water) oxide, the compound which shifted | deviated from stoichiometric composition like _{Fe1- (delta)} O is also contained, for example. Among these, (water) iron oxide particles or particles in which an organic group such as an acyl group such as an ethanoyl group or an alkoxy group such as an ethoxy group is bonded to the particle surface are preferable, α-Fe ₂ O ₃ particles or the particles Particles having an organic group such as an acyl group such as an ethanoyl group or an alkoxy group such as an ethoxy group bonded to the surface are particularly preferred.

Among the additive metal oxide particles, examples of the metal oxide particles containing Bi as a metal element include bismuth trioxide (III) ((Bi ₂ O ₃ ), bismuth titanate (Bi ₄ Ti ₃ O ₁₂ ), and molybdenum. Single oxides such as bismuth acid (Bi ₂ MoO ₆ ), bismuth tungstate (Bi ₂ WO ₆ ), bismuth stannate (Bi ₂ Sn ₂ O ₇ ), bismuth zirconate (2Bi ₂ O ₃ .3ZrO ₂ ), Complex oxides, solid solution oxides in which some of the metal elements in single oxides or complex oxides are partially replaced with dissimilar metal elements, and some of the oxygen in single oxides or complex oxides in other elements ( For example, particles made of a solid solution oxide partially substituted with nitrogen, sulfur, halogen element, etc. In addition, in the oxide, for example, Bi _{2 -δ} O ₃ , from a stoichiometric composition. In particular, oxide particles or particles in which an organic group such as an acyl group such as an ethanoyl group or an alkoxy group such as an ethoxy group is bonded to the particle surface of the particle are preferable, and bismuth trioxide is preferable. Particularly preferred are particles made of bismuth titanate or particles having an organic group such as an acyl group such as an ethanoyl group or an alkoxy group such as an ethoxy group bonded to the particle surface.

Among the additive metal oxide particles, examples of the metal oxide particles containing Ag as a metal element include single oxides such as silver oxide (Ag ₂ O), composite oxides, single oxides, and composite oxides. Solid solution oxide in which part of metal element is partially substituted with dissimilar metal element, part of oxygen in single oxide or composite oxide is partly in other elements (for example, nitrogen, sulfur, halogen elements, etc.) The particle | grains which consist of a substituted solid solution oxide are mentioned. In addition, in the said oxide, the compound which shifted | deviated from stoichiometric composition like _{Ag2- (delta)} O is also contained, for example. Among these, oxide particles or particles in which an organic group such as an acyl group such as an ethanoyl group or an alkoxy group such as an ethoxy group is bonded to the particle surface of the particles are preferable. The particles composed of silver oxide (Ag ₂ O) or the particles Particles having an organic group such as an acyl group such as an ethanoyl group or an alkoxy group such as an ethoxy group bonded to the surface are particularly preferred.

Note that the additive metal oxide particles may have two or more kinds selected from the group consisting of Cu, Fe, Ag and Bi as metal elements, or metal elements other than Cu, Fe, Ag and Bi. Further, it may be included.
The size of the additive metal oxide particles is not particularly limited, but the average particle diameter of the primary particles is preferably 1 to 100 nm and more preferably 5 to 30 nm in order to develop excellent transparency. Preferably, it is 5-20 nm.
The additive metal ultrafine particles are metal ultrafine particles having at least one selected from the group consisting of Cu, Ag, Au, and a platinum group metal element as a metal element. In addition, as described above, the case where a part or all of the particles are oxidized and exist as an oxide is also included. The additive metal ultrafine particles are preferably composed of single metal or alloy particles, and those having a primary particle diameter of 1 to 100 nm, preferably 1 to 20 nm are preferable. Those having strong absorption due to plasmon absorption at 450 nm or less are preferred, and examples include those containing Cu and Ag as metal elements.

  The amount of the metal oxide particles, which are essential constituents of the composition of the present invention, and the dispersion solvent and / or binder is not limited, but specifically, the amount of all metal oxide particles used. However, it is preferable that it is 10 to 90 weight% with respect to the total solid content in this composition, More preferably, it is 20 to 80 weight%. When the amount used is less than 10% by weight, for example, when the composition is used for forming an ultraviolet blocking film, it is necessary to form a thick film in order to obtain sufficient UV blocking properties. In the case of using an inorganic binder or a curable resin as a film component, there is a possibility that cracks are likely to occur in the obtained film, and when it exceeds 90% by weight, for example, when the composition is used for film formation In addition, the mechanical strength of the film may be insufficient. However, when the composition of the present invention is a composition containing a dispersion solvent as an essential constituent, and this is applied to a substrate, heated to a high temperature and fired (sintered) to form a film. The ratio of the metal oxide particles in the composition may exceed 90% by weight, particularly 100% by weight, based on the total solid content in the composition.

The composition of the present invention may further contain other components, and for example, may contain a dispersant, an inorganic binder, a curable resin, and the like.
As the dispersant, for example, the metal compounds (1) to (3) are preferable, and the metal compound (3) is particularly preferable. The addition amount (total addition amount) of the metal compounds (1) to (3) is an atomic ratio of the metal element in the metal compound to the metal element (M) in the metal element (M) compound. It is preferable that it is -10 atomic%.
The use of the composition of the present invention is not limited, and can be handled as, for example, a coating liquid for forming an ultraviolet blocking film or an ultraviolet cut paint. Specifically, for example, a film or glass for blocking ultraviolet rays derived from an excitation source or a light source in a display device or illumination such as an LCD (liquid crystal display), a PDP (plasma display), a white LED, a mercury lamp, or a fluorescent lamp As a coating solution used for forming an ultraviolet blocking film on a glass, various types of glass (single) used for various window materials and displays such as buildings, vehicles (cars, trains, etc.), air transports (airplanes, helicopters, etc.), etc. UV, such as agricultural film and various packaging films, as a coating solution used when forming an ultraviolet blocking film on inorganic glass such as plate glass, multilayer glass, laminated glass, and organic glass such as polycarbonate resin) As a coating solution used when forming an ultraviolet blocking film on various films that require shielding, the window material is further used. As a coating liquid used for forming the ultraviolet blocking layer as an intermediate film of a laminated glass to be used etc., it is useful. Further, as described above in the section of [Metal oxide particles], the composition of the present invention has an infrared absorption film, a high refractive index film, a low refractive index film, and the like depending on the type of metal element of the metal oxide particles contained in the composition. As a coating liquid used for forming various functional films such as a refractive index film, an antireflection film, a heat conductive film, an antistatic film, a transparent conductive film, a photocatalyst film, a phosphor film, and a magnetic film, or as an inkjet ink, Useful. In particular, the composition of the present invention containing metal oxide particles containing Zn as the main metal element (the metal element (M)) can exhibit particularly good characteristics in the various uses described above, and is suitable.

〔film〕
As described above, the film according to the present invention is a film obtained by using the metal oxide particles according to the present invention and / or metal oxide crystals derived from the metal oxide particles as an essential component. That is, the film of the present invention includes (1) a film in which the metal oxide particles according to the present invention are dispersed in a binder, (2) a film made of only the particles, and (3) a film obtained by sintering the particles. And (4) a composition comprising the metal oxide particles of the present invention, such as a film formed by combining these film forms (particularly, a film formed by combining the film (2) and the film (3)). All the films obtained by using the product (intermediate composition etc.) or the film forming composition of the present invention as a raw material component are included.

  The film of (1) is obtained by applying or molding the composition containing a binder. The film (2) is obtained by applying the solvent-dispersed composition. The film of (3) is obtained as a film of metal oxide crystals formed by sintering metal oxide particles by firing the film of (1) or (2) at a high temperature. The film of (4) is obtained by, for example, sintering a part of metal oxide particles by baking the film of (2) at a high temperature, and metal oxide derived from the metal oxide particles. It is obtained as a composite film with physical crystals. Usually, in the films of the above (1) and (2), the metal oxide particles of the present invention exist substantially while maintaining the form thereof, but the film of (3) and (4) above. The portion of the film (3) that can take the form of the film is accompanied by a structural change such as a change in the crystallite diameter of the particle, so that the obtained film is a polycrystal different from the crystal form of the original particle. It may be a film or a single crystal film. In addition, the description mentioned above is applicable similarly about the metal oxide particle of this invention which is an essential structural component (or essential raw material component) of the film | membrane of this invention.

  In a preferred embodiment of the film of the present invention, the film is a metal oxide particle having at least one metal element selected from the group consisting of Cu, Fe, Ag and Bi and / or a metal oxide crystal derived from the particle. And / or metal ultrafine particles having at least one selected from the group consisting of Ag, Cu, Au and platinum group metal elements as metal elements (at least selected from the group consisting of Ag, Cu, Au and platinum group metal elements) (Including metal oxide ultrafine particles obtained by oxidizing a metal having one kind of metal element in the film formation process or in the subsequent process) and / or crystals derived from the metal and / or metal derived from the particle A crystal made of an oxide. Thereby, the visible light blocking effect in the short wavelength region can be further enhanced. In addition, at least one selected from the group consisting of metal oxide particles having at least one selected from the group consisting of Cu, Fe, Ag and Bi as metal elements, and from the group consisting of Ag, Cu, Au and platinum group metal elements. The metal ultrafine particles used as the metal element are the same as the additive metal oxide particles and additive metal ultrafine particles described in the above section [Composition for film formation].

  Although the film of the present invention is not limited, it is generally a film that can be formed on the surface of a desired substrate, and the form of the film exists continuously and continuously spreading over a desired area on the surface of the substrate. (Hereinafter sometimes referred to as a continuous film), or a form that exists discontinuously in a desired area on the substrate surface (hereinafter referred to as a discontinuous film). There is no limitation. In the discontinuous film, the constituent components of the film are partially present (spotted) on the surface of the substrate, but the size, area, thickness, shape, and the like are not limited. Specific forms of the discontinuous film include, for example, a form in which the constituent components of the film are present in the form of fine dots on the surface of the substrate, a form in which the so-called sea-island structure is present, and a striped pattern The form which exists in a shape, the form which combined these forms, etc. are mentioned.

  When the continuous film and the discontinuous film are composed only of metal oxide particles (consisting of metal oxide particles), the structure of these films is not limited. It may be a porous structure having a space of a size, or may be an integrated solid structure (that is, a substantially dense structure) that is not such a porous structure when viewed macroscopically. A denser structure is preferable in that a film having excellent UV blocking properties and no reduction in transparency to visible light due to scattering can be obtained. In the discontinuous film, the structure of the film as described above may be included in all or only a part of the individual film portions that are partially present. .

As an embodiment of the film of the present invention, an aspect meaning the film itself formed on the surface of the base material, an aspect meaning a structure composed of the film formed on the base material and the base material, and Both of them are included.
The base material that can be used for the film of the present invention is not limited, for example, ceramics such as oxides, nitrides and carbides, inorganic substances such as glass; polyester resins such as PET, PBT, and PEN, polycarbonate Resin films known as heat resistant resin films such as resin, polyphenylene sulfide resin, polyether sulfone resin, polyetherimide resin, polyimide resin, amorphous polyolefin resin, polyarylate resin, aramid resin, polyetheretherketone resin, liquid crystal polymer In addition to sheets, conventionally known (meth) acrylic resins, PVC resins, PVDC resins, PVA resins, EVOH resins, polyimide resins, polyamideimide resins, PTFE, PVF, PGF, ETFE, and other fluororesins, epoxy resins, polyols Organic materials such as films and sheets made of various resins such as fin resins, various resin polymers, and processed products such as films obtained by vapor-depositing aluminum, alumina, silica, etc. on these various resin polymers; It is done.

Examples of the shape and form of the base material include a film shape, a sheet shape, a plate shape, a fiber shape, and a laminated body shape, but may be selected according to the use / purpose of use, and is not limited. The base material is not limited in terms of function, and may be optically transparent or opaque, for example, and may be selected according to the intended use and purpose of use.
The film of the present invention is used not only for the purpose of blocking ultraviolet rays, but preferably has high transparency. Specifically, the haze is preferably 10% or less, more preferably 2% or less, and even more preferably 1% or less.
The optical performance of the film of the present invention is as follows: light blocking property (ultraviolet blocking property) in the ultraviolet region (ultraviolet light at 380 nm or less and visible light at 450 nm or less) and transparency (visible light transmission) in visible light (450 nm to 780 nm). Sex) can be used as an index. As the ultraviolet absorbing functional material, it is preferable that the ultraviolet blocking property is high and the visible light transmittance is high. As described above, normally, the ultraviolet blocking property and visible light transmittance of a film can be determined by evaluating the spectral transmittance characteristics in the state of the film. The details of how to determine the ultraviolet blocking property and the visible light transmission property are as described above. Of the optical performance of the film of the present invention, the optical characteristics of the film shown below are values measured and evaluated by the methods described in the examples described later, and only the film part (excluding the substrate) ) And is evaluated in consideration of the optical properties of the film-coated substrate and the optical properties of the substrate alone. Among the optical characteristics of the film of the present invention, the transmittance (%) of light with a wavelength of 380 nm, which is an index of ultraviolet absorption performance, is defined as T ^380, and light with a wavelength of 500 nm, which is an index of visible light transmission performance The transmittance (%) of T is ⁵⁰⁰ , the minimum transmittance (%) of light having a wavelength of 550 nm to 700 nm is T ^1, and the absolute value of the difference between T ¹ and T ⁵⁰⁰ (| T ¹ −T ⁵⁰⁰ | ) Is defined as ΔT.

In particular, regarding the optical characteristics of the film of the present invention when the metal oxide particles of the present invention are used as an ultraviolet absorber, T ³⁸⁰ is preferably 40% or less, more preferably 20% or less, and still more preferably. It is 10% or less, particularly preferably 5% or less. Similarly, ΔT is preferably 10% or less, more preferably 5% or less. Similarly, T ⁵⁰⁰ is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more, and particularly preferably 95% or more. Similarly, the haze value (value obtained by subtracting the haze value of the base material), which is an indicator of transparency to visible light, is preferably less than 3%, more preferably less than 1%, and even more preferably 0.5%. Is less than.

Furthermore, the film of the present invention may satisfy the above ranges at the same time for two or more of the various optical properties described above, and can be selected according to demands depending on the intended use. For example, the following films are exemplified (in any film, the haze value is 1% or less).
^{(i) T 380} is less than 40%, [Delta] T is ^{5%, T 500} is less than 95% of the membrane.
(ii) A film having T ³⁸⁰ of 20% or less, ΔT of 10% or less, and T ⁵⁰⁰ of 90% or more.
(iii) A film having T ³⁸⁰ of 10% or less, ΔT of 10% or less, and T ⁵⁰⁰ of 80% or more.
The method for forming the film of the present invention is not limited, but for example, a method of forming using the film forming composition of the present invention is preferred. In addition, the description mentioned above is applicable similarly about the composition of this invention which can be used for this formation method.

Hereinafter, a method for forming a film using the composition of the present invention will be described.
A method for forming a film using the composition of the present invention is not limited, but the composition is applied to the surface of a substrate by a bar coater method, a roll coater method, a knife coater method, a die coater method, and a spin coat method. A coating method such as a coating method such as a spraying method and a method of forming a film by using a conventionally known film forming method such as a spray method, or a film applied by removing a part or all of a substrate after immersing a part or all of the substrate in the composition of the present invention A so-called dipping method can be employed. In addition, in the case where a dispersion solvent is used as an essential component of the composition of the present invention, a film can be formed by baking at a high temperature after coating, for example, at least a part of metal oxide particles are fused. A crystalline film can be obtained.

The film of the present invention is, for example, an ultraviolet blocking film used in various applications as described above in the section of [Metal oxide particles] and [Film forming composition], and also an infrared absorbing film, a high refractive index film, It is useful as various functional films such as a low refractive index film, antireflection film, heat conductive film, antistatic film, transparent conductive film, photocatalyst film, and phosphor film. Further, it is also useful as a film having two or more kinds of functions that serve both as an ultraviolet shielding film and one of the various functional films (for example, an ultraviolet shielding film having a high refractive index, an ultraviolet shielding film having transparent conductivity, etc.). is there.
[Metal oxide-containing articles]
The metal oxide-containing article of the present invention is an article containing metal oxide particles and / or metal oxide crystals derived from the particles, and the metal oxide particles of the present invention, Cu, Ag, Fe and Bi. Metal oxide particles having at least one selected from the group consisting of metal elements as metal elements and / or metal superoxide having at least one selected from the group consisting of Cu, Ag, Au, and platinum group metal elements as metal elements A combination with fine particles is essential. By such a combination, the metal oxide-containing article of the present invention has an excellent effect of blocking not only ultraviolet rays but also visible light in a short wavelength region. In addition, at least one selected from the group consisting of metal oxide particles having at least one selected from the group consisting of Cu, Ag, Fe and Bi as metal elements, and from the group consisting of Ag, Cu, Au and platinum group metal elements The metal ultrafine particles used as the metal element are the same as the additive metal oxide particles and additive metal ultrafine particles described in the above section [Composition for film formation].

In the metal oxide-containing article of the present invention, the ratio of the metal oxide particles of the present invention to the additive metal oxide particles and / or the additive metal ultrafine particles is not limited, but the metal oxide of the present invention The amount is preferably 0.1 to 50 parts by weight and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the particles. If the added metal oxide particles and / or the added metal ultrafine particles are less than the above range, the effect of the combination becomes insufficient. Problems such as an increase may occur.
[Ultraviolet absorber]
The ultraviolet absorber of the present invention comprises the metal oxide particles of the present invention. In addition, the description mentioned above is applicable similarly about the metal oxide particle of this invention which is an essential structural component of the ultraviolet absorber of this invention.

  The ultraviolet absorber of the present invention is a metal oxide particle having at least one selected from the group consisting of Cu, Ag, Fe and Bi as a metal element, and / or Ag, Cu, Au and a platinum group metal element. It is also preferable to include metal ultrafine particles having at least one selected from the group consisting of metal elements as metal elements. Thereby, the visible light blocking effect in the short wavelength region can be further enhanced. In addition, at least one selected from the group consisting of metal oxide particles having at least one selected from the group consisting of Cu, Ag, Fe and Bi as metal elements, and from the group consisting of Ag, Cu, Au and platinum group metal elements. The metal ultrafine particles used as the metal element are the same as the additive metal oxide particles and additive metal ultrafine particles described in the above section [Composition for film formation].

  When the ultraviolet absorber of the present invention also contains the added metal oxide particles and / or the added metal ultrafine particles, the metal oxide particles of the present invention and the added metal oxide particles and / or the added metal ultrafine particles. Although the ratio is not limited, it is preferably 0.1 to 50 parts by weight and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the metal oxide particles of the present invention. When the added metal oxide particles and / or the added metal ultrafine particles are less than the above range, the effect of the combination becomes insufficient. On the other hand, when the added metal oxide particles and the added metal ultrafine particles are more than the above range, the visible light transmittance is reduced and the degree of coloring is reduced. Problems such as an increase may occur.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, for convenience, “parts by weight” may be simply referred to as “parts” and “wt%” may be referred to as “wt%”.
Measurement methods and evaluation methods in Examples and Comparative Examples are shown below.
In addition, preparation of the powder sample used by evaluation of each Example and a comparative example was performed as follows unless there is particular notice. That is, after centrifuging the reaction solution obtained by the formation reaction of metal oxide particles, washing the precipitate with a reaction solvent (redispersing the precipitate in the reaction solvent and centrifuging) is repeated three times, The obtained precipitate was vacuum-dried at 60 ° C. for 12 hours with a vacuum dryer to obtain a powder sample of metal oxide particles.

<Evaluation of metal oxide particles>
(1) Crystal Identification of Metal Oxide Particles Regarding the above powder sample, the crystal system / crystal of the metal oxide particles by powder X-ray diffraction using a powder X-ray diffractometer (manufactured by Rigaku Corporation, product name: RINT2400). The structure was evaluated. The measurement conditions are shown below.
X-ray: CuKα1 ray (wavelength: 1.54056Å) / 40 kV / 200 mA
Scanning range: 2θ = 20-80 °
Scan speed: 5 ° / min
In the case where the metal oxide particles have Zn as the main metal component, whether or not they have a crystal system / crystal structure equivalent to ZnO depends on whether or not a peak of three strong lines peculiar to hexagonal ZnO is observed. Judged by. Specifically, when diffraction peaks exist at all of the following three diffraction angles (a) to (c), the crystal system / crystal structure equivalent to ZnO was determined.

(a) 2θ = 31.65 to 31.95 °
(b) 2θ = 34.30 to 34.60 °
(c) 2θ = 36.10 to 36.40 °
It is determined that the diffraction peak existing at the position (a) is based on the diffraction line with respect to the (100) plane of the ZnO crystal, and the diffraction peak existing at the position (b) is the (002) plane of the ZnO crystal. The diffraction peak existing at the position (c) is determined to be based on the diffraction line for the (101) plane of the ZnO crystal.
Similarly, when a metal element other than Zn was used as the main metal component, the determination was similarly made based on whether or not a peak of three strong lines peculiar to the oxide crystal of the metal element was observed.

(2) Particle diameter of metal oxide particles (2-1) Primary particle diameter The crystallite diameter (Dw) of metal oxide particles was measured and evaluated as the primary particle diameter.
The crystallite diameter (Dw) is related to the above powder sample by the powder X-ray diffraction using a powder X-ray diffractometer (manufactured by Rigaku Corporation, product name: RINT2400). Was evaluated. Specifically, from the diffraction line width of each diffraction line in the obtained X-ray diffraction pattern, according to Scherrer's formula (analysis), the crystallite diameter Ds (hkl) (where hkl represents the Miller index. Ds (hkl). ) Is the crystallite size in the direction perpendicular to the lattice plane of the Miller index (hkl).) The average value of each Ds of the three strong glands was defined as Dw. In other words, unless otherwise specified, the crystallite diameter (Dw) is usually determined by measuring the powder X-ray diffraction pattern of the metal oxide particles. For the line (2) and the third largest diffraction line (3), based on the Scherrer's formula from the respective half width or integral width, the direction perpendicular to the diffraction plane belonging to the diffraction lines (1) to (3) The crystallite diameters Ds1, Ds2, and Ds3 are calculated, and the average value ((Ds1 + Ds2 + Ds3) / 3) is calculated as the crystallite diameter (Dw).

(2-2) Dispersed particle size Using the obtained reaction solution or a solvent dispersion obtained by solvent substitution from the reaction solution as a sample, a dynamic light scattering particle size distribution measuring apparatus ("LB-500" manufactured by Horiba, Ltd.) was used. The median diameter measured in “)” was defined as the dispersed particle diameter. In the case of dilution, the solvent used in the reaction was used as a dilution solvent. The evaluation criteria are as follows.
A: Dispersion particle size <0.1 μm
B: 0.1 μm ≦ dispersed particle size <0.5 μm
C: 0.5 μm ≦ dispersed particle size (3) Composition of metal oxide particles (3-1) Content of N, S, and Group 17 element It was determined by conducting elemental analysis using the above powder sample.

(3-2) Content of Added Metal Element (M ′) The above powder sample was dissolved in a strong acid aqueous solution and obtained by ICP analysis.
(3-3) Acyl group binding amount 1 g of the above powder sample was added to a 0.1 N aqueous sodium hydroxide solution and stirred for 24 hours, and then the acyl group was identified and the binding amount was determined by ion chromatography.
(3-4) Evaluation of valence of added metal element (M ′) The valence of the added metal element (M ′) in the metal oxide particles was evaluated as follows. That is, with respect to the powder sample, an additive metal element contained in the metal oxide particles (XPS) using a photoelectron spectrometer (manufactured by JEOL Ltd., product name: JPS-90 type) is used. The 2p _3/2 spectrum of M ′) was measured, the binding energy value was determined from the peak position, and the valence of the added metal element (M ′) was determined.

The binding energy value was obtained by correcting with reference to the position of the C1s peak of the surface hydrocarbon in order to reduce the error in the measured value due to the energy shift due to the charging property.
Further, as known data for comparison, 2p _3/2 spectrum peak positions of various metal element compounds in “Handbook of X-ray Photoelectron Spectroscopy” (1991) published by JEOL Ltd. were referred to.
(4) Optical characteristics of metal oxide particles (4-1) Absorption characteristics A sample obtained by diluting the obtained dispersion with 1-butanol as a diluent solvent to a fine particle concentration of 0.1 wt% was used. Spectral transmittance curves in the ultraviolet and visible regions were measured using a self-recording spectrophotometer with an integrating sphere (Shimadzu "UV-3100"). The ultraviolet absorptivity was evaluated by the transmittance (T1) at 400 nm, and the visible light transmittance was evaluated by the transmittance (T2) at 600 nm.

UV absorption; A: T1 <30%
B: 30% ≦ T1 <60%
C: 60% ≦ T1
Visible light transmittance; A: T2 ≧ 80%
B: 80%> T2 ≧ 60%
C: 60%> T2
(4-2) Evaluation of degree of coloring / transparency A fine particle dispersion film was formed and evaluated. That is, 100 parts of the resulting dispersion was mixed with 20 parts of a silicate binder (solid content in terms of SiO ₂ : 51 wt%) and 0.5 part of a catalyst (n-butylamine) to prepare a paint.

The obtained paint was applied to alkali-free glass (Corning International, Barium Borosilicate Glass, glass code number: 7059, thickness: 0.6 mm) with a bar coater so that the wet film thickness was 24 μm. Then, the glass in which the dispersion film in which the metal oxide particles were dispersed was formed on the surface by performing normal drying at 25 ° C.
And about the degree of coloring, the external appearance of the said glass with a dispersion film was observed visually, and the following reference | standard determined.
○: Coloring is not recognized Δ: Slightly colored ×: Remarkably colored is observed The degree of transparency was determined by visually observing the appearance of the glass with the dispersion film and based on the following criteria.

○: High transparency Δ: Transparent but slightly turbid ×: Turbid (5) Hue of powder sample The appearance of the powder sample was visually observed and evaluated.
(6) Fine Particle Concentration The fine particle concentration in the reaction solution or dispersion was calculated by measuring 0.5 g of the reaction solution or dispersion in a crucible and measuring the dry powder weight after vacuum drying at 120 ° C. for 1 hour.

[Example 1-1]
Stirrer, addition port directly connected to the addition tank, thermometer, distillate gas outlet and nitrogen gas inlet, pressure-resistant glass reactor that can be heated from the outside, addition tank connected to the addition port, and the above A reactor equipped with a cooler (directly connected to the trap) connected to the distillate gas outlet was prepared.
In the reactor, a mixture of 156 parts of zinc formate anhydrous powder, 3912 parts of 1-butanol and 0.1 part of urea was charged, and the gas phase part was purged with nitrogen gas. The reaction solution (11) containing fine particles at a concentration of 2 wt% was heated to 150 ° C. and heated and held at 150 ° C. ± 1 ° C. for 10 hours to form a metal oxide particle and then cooled. Obtained. The obtained reaction liquid (11) was heated under reduced pressure to distill off a part of the solvent component in the reaction liquid, thereby obtaining a dispersion (11) containing fine particles in a proportion of 20 wt%.

Table 2 shows the results of evaluating the obtained dispersion and the metal oxide particles in the dispersion based on the various evaluation methods described above.
[Examples 1-2 to 1-5]
In Example 1-1, each reaction liquid (12)-(15) was obtained like Example 1-1 except having changed the kind and usage-amount of the raw material as shown in Table 1. In the same manner, dispersions (12) to (15) containing fine particles at a ratio of 20 wt% were obtained.
Table 2 shows the results of evaluating the obtained dispersion and the metal oxide particles in the dispersion based on the various evaluation methods described above.

[Example 1-6]
After obtaining the reaction liquid (12) in the same manner as in Example 1-2, the obtained reaction liquid (12) is centrifuged, and the precipitate is vacuum-dried at 80 ° C. and then pulverized to obtain fine particle powder. Obtained. After heat-treating the powder in hydrogen sulfide-containing nitrogen gas at 300 ° C., the obtained powder is dispersed in 1-butanol at a fine particle concentration of 20 wt% using a bead mill to obtain a dispersion (16). It was.
Table 2 shows the results of evaluating the obtained dispersion and the metal oxide particles in the dispersion based on the various evaluation methods described above.

[Comparative Example 1-1]
In Example 1-6, a dispersion (c11) was obtained in the same manner except that the hydrogen sulfide-containing nitrogen gas was changed to nitrogen gas and the temperature of the heat treatment was changed from 300 ° C to 400 ° C.
Table 2 shows the results of evaluating the obtained dispersion and the metal oxide particles in the dispersion based on the various evaluation methods described above.
[Comparative Example 1-2]
After obtaining the reaction liquid (13) in the same manner as in Example 1-3, the obtained reaction liquid (13) is centrifuged, and the precipitate is vacuum-dried at 80 ° C. and then pulverized to obtain fine particle powder. Obtained. After the powder was bound with ammonia-containing nitrogen gas, the powder obtained by heat treatment at 350 ° C. in nitrogen was dispersed in 1-butanol at a fine particle concentration of 20 wt% using a bead mill, whereby a dispersion was obtained. (C12) was obtained.

Table 2 shows the results of evaluating the obtained dispersion and the metal oxide particles in the dispersion based on the various evaluation methods described above.
[Example 1-7]
After obtaining the reaction liquid (12) in the same manner as in Example 1-2, the obtained reaction liquid (12) is centrifuged, and the precipitate is vacuum-dried at 80 ° C. and then pulverized to obtain fine particle powder. Obtained.
Dispersion (17) was obtained by dispersing the powder in 1-butanol at a fine particle concentration of 20 wt% using a bead mill.
Table 2 shows the results of evaluating the obtained dispersion and the metal oxide particles in the dispersion based on the various evaluation methods described above.

  The degree of transparency and coloring of the fine particles in the dispersions obtained in Example 1-1 to Example 1-5 and Example 1-7 in the state of the dispersion film was determined by the dispersion obtained in Comparative Example 1-2. Compared with fine particles in the body, yellow coloration was alleviated. In addition, since the dispersion film obtained from the dispersion obtained in Comparative Example 1-1 was cloudy, the degree of coloring was evaluated as “Δ”.

〔実施例２−１〕
実施例１−１において、原料混合物に、酢酸第一鉄（II）無水物粉末１．８部をさらに含有させた以外は、実施例１−１と同様にして、反応液（２１）を得、さらに同様にして、微粒子が２０ｗｔ％の割合で含有された分散体（２１）を得た。
得られた分散体および分散体中の金属酸化物粒子について、前述の各種評価方法に基づき評価した結果を表３に示す。

[Example 2-1]
In Example 1-1, a reaction liquid (21) was obtained in the same manner as in Example 1-1 except that 1.8 parts of ferrous acetate (II) anhydride powder was further added to the raw material mixture. In the same manner, a dispersion (21) containing fine particles at a ratio of 20 wt% was obtained.
Table 3 shows the results of evaluating the obtained dispersion and the metal oxide particles in the dispersion based on the various evaluation methods described above.

[Comparative Example 2-1]
In Example 1-1, the reaction mixture was used in the same manner as in Example 1-1 except that the raw material mixture did not contain urea and further contained 1.8 parts of ferrous acetate (II) anhydride powder. (C21) was obtained, and in the same manner, a dispersion (c21) containing fine particles in a proportion of 20 wt% was obtained.
Table 3 shows the results of evaluating the obtained dispersion and the metal oxide particles in the dispersion based on the various evaluation methods described above.
As shown in Table 3, the fine particles in the dispersion (21) obtained in Example 2-1 are yellowish green, and in the dispersion (11) obtained in Example 1-1. Dispersion film coloring was not conspicuous as compared with the fine particles, and the ultraviolet absorption was superior to the fine particles obtained in Example 1-1 and Comparative Example 2-1.

[Example 2-2]
In Example 1-3, a reaction liquid (22) was obtained in the same manner as in Example 1-3, except that the raw material mixture further contained 0.25 part of cuprous acetate (I) anhydride powder. In the same manner, a dispersion (22) containing fine particles at a ratio of 20 wt% was obtained.
Table 3 shows the results of evaluating the obtained dispersion and the metal oxide particles in the dispersion based on the various evaluation methods described above.
[Comparative Example 2-2]
In Example 1-3, the reaction mixture was used in the same manner as in Example 1-3 except that the raw material mixture did not contain urea and further contained 0.25 part of cuprous acetate (I) anhydride powder. (C22) was obtained, and similarly, a dispersion (c22) containing fine particles at a ratio of 20 wt% was obtained.

Table 3 shows the results of evaluating the obtained dispersion and the metal oxide particles in the dispersion based on the various evaluation methods described above.
As shown in Table 3, the fine particles in the dispersion (22) obtained in Example 2-2 are light gray, compared with the fine particles in the dispersion (13) obtained in Example 1-3. Thus, the coloring of the dispersed film was inconspicuous, and the ultraviolet absorptivity was superior to the fine particles obtained in Example 1-3 and Comparative Example 2-2.
[Example 2-3]
In Example 1-2, a reaction liquid (23) was obtained in the same manner as in Example 1-2, except that the raw material mixture further contained 1.3 parts of nickel acetate (II) tetrahydrate powder. Further, a dispersion (23) containing fine particles at a ratio of 20 wt% was obtained in the same manner.

Table 3 shows the results of evaluating the obtained dispersion and the metal oxide particles in the dispersion based on the various evaluation methods described above.
[Example 2-4]
In Example 1-2, a reaction liquid (24) was obtained in the same manner as in Example 1-2, except that 1.8 parts of cobalt (II) acetate anhydrous powder was further added to the raw material mixture. Similarly, a dispersion (24) containing fine particles at a ratio of 20 wt% was obtained.
Table 3 shows the results of evaluating the obtained dispersion and the metal oxide particles in the dispersion based on the various evaluation methods described above.

  As shown in Table 3, the fine particles in the dispersions (23) and (24) obtained in Example 2-3 and Example 2-4 were dispersed in the dispersion (12) obtained in Example 1-2. Dispersion film coloring was not conspicuous compared to the fine particles therein, and the ultraviolet absorption was superior to the fine particles obtained in Example 1-2.

〔実施例２−５〕
実施例１−１と同様の反応器に、酢酸亜鉛無水物粉末１８３部、フッ化亜鉛無水物０．０５部、酢酸酸化ビスマス（III）粉末１２部、酢酸第一銅（I）無水物０．０７部、メタノール３８８０部からなる混合物を仕込み、気相部を窒素ガスでパージした後、撹拌しながら、２０℃から１８０℃まで昇温し、１８０℃±１℃で１０時間加熱保持して、金属酸化物粒子の生成反応を行った後、冷却することにより、微粒子を２ｗｔ％の濃度で含む反応液（２５）を得た。得られた反応液（２５）を減圧下で加熱して反応液中の溶媒成分の一部を留去することにより、微粒子が２０ｗｔ％の割合で含有された分散体（２５）を得た。

[Example 2-5]
In a reactor similar to Example 1-1, 183 parts of zinc acetate anhydrous powder, 0.05 part of zinc fluoride anhydride, 12 parts of bismuth acetate (III) acetate powder, cuprous acetate (I) anhydride 0 0.07 parts and a mixture consisting of 3880 parts of methanol were charged, and the gas phase part was purged with nitrogen gas, then the temperature was raised from 20 ° C. to 180 ° C. with stirring, and heated and held at 180 ° C. ± 1 ° C. for 10 hours. After the reaction for generating metal oxide particles, the reaction liquid (25) containing fine particles at a concentration of 2 wt% was obtained by cooling. The obtained reaction liquid (25) was heated under reduced pressure to distill off a part of the solvent component in the reaction liquid, thereby obtaining a dispersion (25) containing fine particles in a proportion of 20 wt%.

Table 5 shows the results of evaluating the obtained dispersion and the metal oxide particles in the dispersion based on the various evaluation methods described above.
[Examples 2-6 to 2-12]
In Example 2-5, each reaction liquid (26)-(212) was obtained like Example 2-5 except having changed the kind and usage-amount of the raw material as shown in Table 4. Further, in the same manner, dispersions (26) to (212) containing fine particles at a ratio of 20 wt% were obtained.
Table 5 shows the results of evaluating the obtained dispersion and the metal oxide particles in the dispersion based on the various evaluation methods described above.

〔実施例３−１〕
実施例１−１と同様の反応器に、テトラ−ｎ−ブトキシチタン３４０部、酢酸３００部、尿素１部、２−ブロパノール３３６０部からなる混合物を仕込み、気相部を窒素ガスでパージした後、撹拌しながら、２０℃から１６０℃まで昇温し、１６０℃±１℃で５時間加熱保持して、金属酸化物粒子の生成反応を行った後、冷却することにより、黄色を呈する微粒子濃度２ｗｔ％の反応液（３１）を得た。さらに、得られた反応液より、実施例１−１と同様にして、微粒子濃度２０ｗｔ％の１−ブタノール分散体（３１）を得た。

[Example 3-1]
A reactor similar to Example 1-1 was charged with a mixture of 340 parts of tetra-n-butoxytitanium, 300 parts of acetic acid, 1 part of urea, and 3360 parts of 2-propanol, and the gas phase part was purged with nitrogen gas. While stirring, the temperature is raised from 20 ° C. to 160 ° C., heated and held at 160 ° C. ± 1 ° C. for 5 hours, and after the formation reaction of the metal oxide particles, the fine particle concentration exhibiting yellow by cooling A 2 wt% reaction solution (31) was obtained. Further, a 1-butanol dispersion (31) having a fine particle concentration of 20 wt% was obtained from the obtained reaction solution in the same manner as in Example 1-1.

The fine particles in the obtained dispersion were those in which ethanoyl groups were bonded to Ti in a molar ratio of 0.2%.
Table 7 shows the results of evaluating the obtained dispersion and the metal oxide particles in the dispersion based on the various evaluation methods described above.
[Examples 3-2 to 3-6]
In Example 3-1, the reaction liquids (32) to (36) were obtained in the same manner as in Example 3-1, except that the types and amounts used of the charged raw materials were changed as shown in Table 6. In the same manner, dispersions (32) to (36) containing fine particles at a ratio of 20 wt% were obtained.

  Table 7 shows the results of evaluating the obtained dispersion and the metal oxide particles in the dispersion based on the various evaluation methods described above.

〔実施例４−１〕
実施例２−１で得られた分散体（２１）１００部に、シリケートバインダー（ＳｉＯ_２
換算の固形分：５１ｗｔ％）２０部および触媒（ｎ−ブチルアミン）０．２部を配合し、塗料を調製した。
得られた塗料を、アルカリガラス上にバーコ−ターで塗布し、常温乾燥したのち、窒素雰囲気下２００℃で１時間加熱することにより、金属酸化物粒子分散膜が表面に形成された分散膜付きガラスを得た。

[Example 4-1]
To 100 parts of the dispersion (21) obtained in Example 2-1, a silicate binder (SiO ₂
20 parts of converted solid content (51 wt%) and 0.2 part of catalyst (n-butylamine) were blended to prepare a paint.
The obtained coating material is coated on an alkali glass with a bar coater, dried at room temperature, and then heated at 200 ° C. for 1 hour in a nitrogen atmosphere, whereby a metal oxide particle dispersed film is formed on the surface. Glass was obtained.

As a result of evaluating the optical performance of the obtained glass with a dispersion film, the ultraviolet blocking glass excellent in colorlessness having a transmittance at 600 nm of 92%, a transmittance at 400 nm of 25%, and a haze of 0.3%. Met.
In addition, the transmittance | permeability in each wavelength was calculated | required by measuring a spectral transmittance curve with the same apparatus as used in the said evaluation method (4), and the haze was evaluated with the turbidimeter. The degree of coloring was evaluated by visually observing the appearance.
[Example 4-2]
To 100 parts of the dispersion (25) obtained in Example 2-5, 50 parts of an acrylic resin binder (solid content: 50 wt%) was blended to prepare a paint.

The obtained paint is applied onto a polyester film with a bar coater, dried at room temperature, and then heated at 100 ° C. for 10 minutes to obtain a film with a dispersion film on which a metal oxide particle dispersion film is formed. It was.
About the obtained film with a dispersion film, the optical performance was evaluated in the same manner as in Example 4-1. As a result, the transmittance at 600 nm was 88%, the transmittance at 400 nm was 25%, and the haze was 0.5%. It was a UV-blocking film excellent in colorlessness.
[Example 4-3]
The dispersion (210) obtained in Example 2-10 was coated on an alkali glass with a bar coater, dried at room temperature, and then heated at 300 ° C. for 30 minutes in a nitrogen atmosphere, whereby a metal oxide film was formed. A glass with a film formed on the surface was obtained.

The obtained glass with a film was provided with a ZnO crystal film containing 3.4 atomic% of nitrogen, 2 atomic% of Ce, and 0.1 atomic% of Cu with respect to Zn. As a result of evaluating the optical performance in the same manner as in Example 1, it was an ultraviolet blocking glass excellent in colorlessness, having a transmittance at 600 nm of 90%, a transmittance at 400 nm of 20%, and a haze of 0.2%.
[Example 4-4]
The dispersion (35) obtained in Example 3-5 was coated on an alkali glass with a bar coater, dried at room temperature, and then heated at 400 ° C. in a nitrogen atmosphere, whereby the metal oxide film was formed on the surface. The formed glass with film was obtained.

The obtained glass with a film was provided with a TiO ₂ crystal film containing 0.8 atomic% iodine and 0.8 atomic% Cu with respect to Ti, and in the same manner as in Example 4-1. As a result of evaluating the optical performance, it was an ultraviolet blocking glass excellent in colorlessness having a transmittance at 600 nm of 90%, a transmittance at 400 nm of 30%, and a haze of 0.3%.

The film of the present invention is suitable for window glass for buildings, window glass for vehicles such as automobiles and trains, window glass for air transport such as airplanes and helicopters, agricultural films, various packaging films, etc. Is not limited to these, and can be suitably used for various purposes in addition to imparting an ultraviolet shielding function to various functional films and for the purpose of imparting an infrared shielding function, a conductive function, and the like.
The film-forming composition of the present invention is suitable, for example, as a coating liquid for forming an ultraviolet blocking film or an ultraviolet-cut paint, and also suitable as a material for forming the film of the present invention.
The metal oxide particles of the present invention are suitable as components for imparting ultraviolet shielding properties in various applications such as films, films, paints, cosmetics, etc. It is suitable as a component of the composition.

Claims (18)

In metal oxide particles comprising an oxide of a metal element (M),
The metal element (M) is at least one selected from the group consisting of Zn, Ti, Ce, In, Sn, Al and Si,
The oxide of the metal element (M) contains at least one selected from the group consisting of N, S, and a group 17 (group 7B) element, and an acyl group.
Metal oxide particles characterized by the above. In metal oxide particles comprising an oxide of a metal element (M),
The metal element (M) is at least one selected from the group consisting of Zn, Ti, Ce, In, Sn, Al and Si,
The oxide of the metal element (M) contains two or more selected from the group consisting of N, S, and a group 17 (group 7B) element.
Metal oxide particles characterized by the above. In metal oxide particles comprising an oxide of a metal element (M),
The metal element (M) is at least one selected from the group consisting of Zn, Ti, Ce, In, Sn, Al and Si,
The oxide of the metal element (M) contains at least one selected from the group consisting of N, S, and a group 17 (group 7B) element,
And the component derived from metal elements (M ') other than the metal element (M) is contained in the particles,
Metal oxide particles characterized by the above.   The metal element (M ′) is a metal element different from the metal element (M) and includes Co, Cu, Fe, Bi, In, Al, Ga, Ti, Sn, Ce, Ni, B, Mn, Ag, The metal oxide particle according to claim 3, which is at least one selected from the group consisting of Au, a platinum group metal element, an alkali metal element, and an alkaline earth metal element.   The metal oxide particles according to any one of claims 1 to 4, wherein the primary particle diameter is 3 to 50 nm.   The oxide of the metal element (M) is a crystal, and the crystallite diameter (average value of each value measured according to the Scherrer method for the three strong lines of the XRD peak) is 30 nm or less. The metal oxide particles according to any one of the above.   The oxide of the metal element (M) is a zinc oxide crystal, a crystallite diameter perpendicular to the lattice plane (002) is 30 nm or less, and a crystal perpendicular to the lattice plane (100) and / or the lattice plane (110). The metal oxide particle according to any one of claims 1 to 6, wherein the child diameter is 10 nm or more.   8. The particle according to claim 1, wherein the particles made of the oxide of the metal element (M) contain 0.1 to 14 mol% of acyl groups in a molar ratio with respect to the metal element (M). Metal oxide particles.   The oxide of the metal element (M) has, on its surface, alkoxides composed of at least one metal element different from the metal element (M ′) contained in the oxide or a (partial) hydrolyzate thereof. The metal oxide particles according to any one of claims 1 to 8, which are bonded.   In addition to the metal element (M ′), a component derived from an alkali metal element and / or an alkaline earth metal element is contained in the range of 0.001 to 5 atomic% with respect to the metal element (M). The metal oxide particles according to any one of claims 1 to 9.   A composition comprising metal oxide particles dispersed in a medium, wherein the metal oxide particles essentially comprise the metal oxide particles according to claim 1.   The composition for forming a film according to claim 11, comprising the metal oxide particles according to any one of claims 1 to 17 and a dispersion solvent and / or a binder as essential components.   The composition according to claim 11, wherein the metal oxide particles are dispersed with a dispersed particle diameter of 1 μm or less.   Metal oxide particles having at least one selected from the group consisting of Cu, Fe, Ag and Bi as metal elements, and / or at least one selected from the group consisting of Ag, Cu, Au and platinum group metal elements The composition according to any one of claims 11 to 13, further comprising metal ultrafine particles as a metal element.   A film comprising a metal oxide as an essential component, wherein the metal oxide essentially comprises the metal oxide particles according to any one of claims 1 to 10 and / or metal oxide crystals derived from the particles. .   Metal oxide particles having at least one selected from the group consisting of Cu, Fe, Ag and Bi as metal elements and / or metal oxide crystals derived from the particles, and / or Ag, Cu, Au and platinum groups Including metal ultrafine particles having at least one selected from the group consisting of metal elements as metal elements and / or crystals composed of metals derived from the particles and / or crystals composed of metal oxides derived from the particles, The membrane according to claim 15.   An article comprising metal oxide particles and / or metal oxide crystals derived from the particles, comprising the metal oxide particles according to any one of claims 1 to 10, and Cu, Fe, Ag and Bi. Metal oxide particles having at least one selected from the group as a metal element, and / or metal ultrafine particles having at least one selected from the group consisting of Cu, Ag, Au, and a platinum group metal element as a metal element; Metal oxide-containing articles that require a combination of   The ultraviolet absorber formed by containing the metal oxide particle in any one of Claim 1-10.