JP2005162914A - Ultraviolet light-shielding film, metal oxide particle for ultraviolet light shielding, and composition for formation of ultraviolet light shielding material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prepare an ultraviolet light-shielding film capable of effectively absorbing and cutting UV in a wavelength area ranging from long wavelength UV, namely 400-450 nm wavelength to short wavelength side and excellent in transparency to visible light, to provide metal oxide particles for ultraviolet light shielding which can be used for the film, and to obtain a composition for formation of an ultraviolet light-shielding material capable of giving the film. <P>SOLUTION: In the ultraviolet light-shielding film, a first film comprises, as an essential component, a mixed crystal (Bi mixed crystal) composed of a metal other than bismuth and metal oxides containing bismuth as metal elements and a second film comprising metal oxide particles as an essential component. The metal oxide particles are composed of a coexisting substance of metal oxides in which a metal oxide comprising a metal element other than bismuth as a metal element and a metal oxide (excluding the Bi-mixed crystal) containing bismuth coexist. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an ultraviolet blocking film, an ultraviolet blocking metal oxide particle, and an ultraviolet blocking material forming composition.

  Conventionally, metal oxides vary depending on what kind of metal element is a metal oxide containing a metal element or whether the metal oxide is a single oxide or a complex oxide. It is known that it can exhibit its excellent functions, and it is used for various purposes by taking advantage of such characteristics. Among them, there have been many proposals and actual implementations in recent years that such metal oxides are formed as a film on the surface of the substrate or used as an essential component of the film and used for various functional applications. . For example, the use as a functional film (ultraviolet blocking film) that cuts ultraviolet rays (UV) is well known, and various functional films that can cut ultraviolet rays more effectively have been developed (for example, patent documents). 1).

Moreover, the cosmetic which is excellent in barrier properties of 400nm UV light below by incorporating _Bi 2 _{O 3} fine particles powder of particle diameter 5 to 200 nm (e.g., see Patent Document 2.) It has been proposed.
Japanese Unexamined Patent Publication No. 1-217084 Japanese Patent No. 3441553

However, there has been no functional film that can effectively absorb and cut long wavelength UV, that is, UV in the wavelength region from 400 to 450 nm to the short wavelength side. In addition, since Bi ₂ O ₃ has a strong coloring (yellow), providing an ultraviolet blocking film containing Bi ₂ O ₃ for applications such as window glass is not good in appearance and is inferior in transparency to visible light, etc. Practicality was poor.
Therefore, the problem to be solved by the present invention is that an ultraviolet blocking film that can effectively absorb and cut the long wavelength UV and has excellent transparency to visible light, and an ultraviolet blocking metal oxide particle that can be used for this film. Another object of the present invention is to provide a composition for forming an ultraviolet blocking material capable of obtaining this film.

The present inventor has intensively studied to solve the above problems. As a result, the present inventors have found that the above-mentioned problems can be solved at once by using a functional film in which a metal oxide containing a bismuth element or an oxide thereof is essential, and the present invention has been completed.
That is, among the ultraviolet blocking films according to the present invention, the first film has a mixed element (Bi mixed crystal) of a metal oxide containing a metal element other than bismuth and bismuth as a metal element as an essential component.
The second film has metal oxide particles as an essential component, and the metal oxide particles include a metal oxide containing a metal element other than bismuth and a metal oxide containing bismuth (excluding Bi mixed crystals). Is a coexisting body of metal oxides which must be coexisted with.

Among the compositions for forming an ultraviolet blocking material according to the present invention, the first composition is derived from a mixture of a metal element other than bismuth as a metal element and a composite metal carboxylate containing bismuth and an alcohol and / or the mixture. This component is an essential component.
The second composition comprises metal oxide particles and a dispersion solvent and / or a binder as essential components, and the metal oxide particles are a mixture of a metal oxide containing a metal element other than bismuth and bismuth as a metal element. A metal that requires the coexistence of a crystal (Bi mixed crystal) and / or a metal oxide containing a metal element other than bismuth as a metal element and a metal oxide containing bismuth (excluding Bi mixed crystal) It is an oxide coexistent.

The third composition comprises a metal oxide particle, a mixture of a metal carboxylate and an alcohol and / or a component derived from the mixture as an essential component, and the metal oxide particle is a metal element other than bismuth. Metal oxides containing bismuth and metal oxides (Bi mixed crystals) and / or metal oxides containing metal elements other than bismuth as metal elements and bismuth (except for Bi mixed crystals) Is a coexisting body of metal oxides which must be coexisted with.
Among the metal oxide particles for blocking ultraviolet rays according to the present invention, the first particles have a mixed crystal (Bi mixed crystal) of a metal oxide containing a metal element other than bismuth and bismuth as a metal element as an essential component.

  The second particle is a metal oxide coexistant that requires that a metal oxide containing a metal element other than bismuth as a metal element and a metal oxide containing bismuth (excluding Bi mixed crystals) coexist. As an essential component.

  According to the present invention, it is possible to effectively absorb and cut long wavelength UV, that is, UV in a wavelength region from 400 to 450 nm to the short wavelength side, and to be used for this film. It is possible to provide a metal oxide particle for ultraviolet blocking and a composition for forming an ultraviolet blocking material capable of obtaining this film.

Hereinafter, the ultraviolet blocking film, the ultraviolet blocking metal oxide particles, and the ultraviolet blocking material forming composition according to the present invention will be described in detail, but the scope of the present invention is not limited to these descriptions, and the following examples are given. Other than the above, the present invention can be modified as appropriate without departing from the spirit of the present invention.
[UV blocking film]
In the ultraviolet blocking film according to the present invention, as described above, the first film contains a metal element other than bismuth and a metal oxide containing bismuth (Bi) as a metal element (containing bismuth as an essential metal element). Crystal (hereinafter sometimes referred to as Bi mixed crystal) as an essential component, the second film has metal oxide particles as essential components, and the metal oxide particles have a metal element other than bismuth as a metal element. It is a coexisting body of a metal oxide that requires the coexistence of a metal oxide to be formed and a metal oxide containing bismuth (excluding Bi mixed crystals). In the second film, the metal oxide composed of the coexisting metal oxide is present in the form of particles in the film.

In the following, various metal oxides that can be constituent materials of the ultraviolet blocking film of the present invention will be described, and then individual items in each of the first film and the second film will be described.
Metal oxides are generally classified into those that exhibit crystallinity (crystals) and those that do not exhibit 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. Other functions (conductivity, semiconductor characteristics, thermal conductivity, (light) magnetic characteristics, dielectric characteristics, light emission characteristics, reflection characteristics, etc., electrical functions, magnetic functions, semiconductors, etc.) From the viewpoint of excellent function and optical function, it can be said that a crystal is preferable.

  In the present specification, the crystal body includes a single metal oxide (single oxide) containing only one kind of metal element as a metal element (metal component) or two or more kinds as a metal element (metal component). It shall be classified into complex metal oxides containing metal elements (complex oxides), solid solution metal oxides (solid solution oxides) in which different metal elements are dissolved in a single oxide or complex oxide, In these, the metal element and oxygen may have a stoichiometric composition or a non-stoichiometric composition, and are not limited. In addition, a crystalline metal oxide other than a single oxide, exemplified by the above complex oxide and solid solution oxide, is referred to as a metal oxide mixed crystal (sometimes simply referred to as a mixed crystal). In contrast, the single oxide may be referred to as a non-mixed crystal. Note that even in the above-described amorphous body, there can be oxides similar to the oxides listed in the classification of the crystal body, but all of them do not exhibit crystallinity.

  The crystalline body may be a single crystalline body or a polycrystalline 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 pyramidal shape. , 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 It is done. The size of the crystallite is not limited. Specifically, the size of the crystallite in the direction of the crystal axis is usually preferably 1 nm to 10 μm. The orientation of the crystallite is not limited, but, for example, the crystal axis direction of the crystallite may be oriented perpendicular to the surface of the substrate that is the target of film formation or oriented at a specific angle. Alternatively, it may be oriented parallel to the surface along the surface of the substrate. Moreover, even if all the crystallites have the same orientation, they may be random, or some of them may have the same orientation and the rest may be random, and there is no limitation.

Bi mixed crystal is defined as a crystal of a metal oxide containing a metal element other than bismuth as a metal component. For example, a crystal of a compound represented by the following general formula (1) or (2) can be exemplified.
_{Bi x M y O z (1} )
^{_{Bi x M 1 y1 M 2 y2}} M 1 y2 O z (2)
(Bi represents bismuth, M, M ¹ , M ² and M ³ represent metal elements other than bismuth. X, y, y1, y2 and y3 each represents an integer of 1 or more.)
In particular, when the Bi mixed crystal has a stoichiometric composition, the following general formula (1) satisfies the following formula (1 ′), and the above general formula (2) satisfies the following formula (2 ′).

_{X · n Bi + y · n} M = 2Z (1 ')
X · n _Bi + y1 · n _M1 + y2 · n _M2 + y3 · n _M3 = 2Z (2 ′)
(However, n _Bi represents the valence of bismuth, and n _M , n _M1 , n _M2 and n _M3 represent the valence of M, M ¹ , M ² and M ³ which are metal elements other than bismuth, respectively.)
The valence (n _Bi ) of bismuth is not limited, but is preferably positive trivalent.
As the Bi mixed crystal, specifically, bismuth (for example, bismuth ion (Bi (III)) is dissolved in a crystalline metal oxide (metal oxide crystal) containing a metal element other than bismuth as a metal element. The solid solution oxide (a) or a crystalline complex oxide (b) containing a metal element other than bismuth and bismuth as a metal element is preferably exemplified, and these solid solution oxide (a) and The composite metal oxide (b) and the like may be mixed, but it is particularly preferable that at least a part thereof contains the solid solution oxide (a).

In the Bi mixed crystal, the ratio of bismuth to the total amount of metal elements other than bismuth and bismuth contained as metal elements is preferably 0.01 to 90 atom%, more preferably 0.1 to 60 atoms. %. If the above ratio is less than 0.01 atomic%, the UV blocking property based on Bi may be insufficient, and if it exceeds 90 atomic%, coloring is remarkable, for example, forming a film on a window or a film. When this is taken into consideration, there is a possibility that the color tone is unfavorable as a UV blocking film.
The solid solution oxide (a) may be a so-called interstitial solid solution oxide or a substitutional solid solution oxide, and is not limited.

In the solid solution oxide (a), the metal oxide in which bismuth is solid-solved and the metal element other than bismuth is a metal element is, for example, 1A group, 2A group, 3A group, 4A group, 5A group, 6A group , 7A group, 8 group, lanthanoid element, actinide element, 1B group, 2B group, 3B group, 4B group, 5B group (excluding Bi), 1B or more of metal elements contained in 6B group Preferred are single oxides or composite oxides as elements, and these metal oxides may be used alone or in combination of two or more, more preferably Sr, Ce, Y, Ti, Zr, V, Nb, Ta, Cr, Mn, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Zn, Cd, Al, Ga, In, Ge, Sn, Sb and Contains one or more of La, etc. It is a single oxide or composite oxide to elemental. More preferably, ZnO, TiO ₂ , CeO ₂ , ZnMgO, SnO ₂ and In ₂ O ₃ having a band gap in the UV region, and the film obtained using them effectively cuts a wide range of UV. In addition, based on the Bi content, it effectively absorbs and cuts long wavelength UV (that is, UV in the wavelength region from 400 to 450 nm to the short wavelength side) and transmits visible light of 450 nm or more. be able to. Among these, those having a band gap in the UV region are particularly preferably ZnO, TiO ₂ and CeO ₂ in terms of excellent visible light transmittance and high UV absorption ability of 360 nm or less, and most preferably other than the above bismuth. When the metal element is zinc, that is, ZnO. In this specification, the periodic table uses the “periodic table of elements (1993)” published in the revised 5th edition “Chemical Handbook (edited by the Chemical Society of Japan)” (published by Maruzen Co., Ltd.) The group number is written in the sub-group system.

  In the solid solution oxide (a), the content ratio of bismuth to be dissolved is not limited, but specifically, 0.01 to 20 atomic% with respect to a metal element other than bismuth in the solid solution oxide. More preferably, it is 0.1-10 atomic%, More preferably, it is 0.5-10 atomic%, Especially preferably, a minimum is 1 atomic%, Most preferably, a minimum is 3 atomic%. If the bismuth content in the solid solution oxide is less than 0.01 atomic%, the light absorption performance from 400 to 450 nm, which is the solid solution effect of Bi, to short wavelengths may be insufficient, and 20 atomic%. If it exceeds 1, the crystallinity as a solid solution is lowered, and the solid solution effect may be insufficient.

  As the composite oxide (b), bismuth and metal elements other than bismuth, 1A group, 2A group, 3A group, 4A group, 5A group, 6A group, 7A group, 8 group, lanthanoid element, actinoid element, 1B group Preferred examples include 2B, 3B, 4B, 5B (excluding Bi), and complex oxides containing one or more of the metal elements contained in group 6B, and these may be used alone. Two or more kinds may be used in combination. More preferably, together with bismuth, Sr, Ce, Y, Ti, Zr, V, Nb, Ta, Cr, Mn, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Zn , Cd, Al, Ga, In, Ge, Sn, Sb, La, and the like. More preferably, it is a complex oxide having a band gap in the UV region containing one or more of Zn, Ti, Ce, Sn and In together with bismuth, and a film obtained using these is a wide range Can effectively cut UV, and further absorb and cut particularly long wavelength UV (that is, UV in the wavelength region from 400 to 450 nm to the short wavelength side), based on the Bi content, Visible light of 450 nm or more can be transmitted. Among those having a band gap in the UV region, particularly preferable is bismuth and one or more of Zn, Ti, and Ce in terms of excellent visible light transmittance and high UV absorption ability of 360 nm or less. Most preferably, when the metal element other than bismuth is zinc, that is, a composite oxide containing bismuth and Zn.

Examples of metal oxides other than Bi mixed crystals (simply referred to as non-Bi mixed crystals) include non-mixed crystals (single oxides), mixed crystals containing metal elements other than bismuth as metal elements, and An amorphous body is mentioned. Among these, non-mixed crystals include those containing bismuth as a metal element and those containing a metal element other than bismuth as a metal element, and non-crystals include metal elements other than bismuth and / or bismuth. Is a metal element.
In this specification, a non-Bi mixed crystal containing bismuth as a metal element is referred to as a non-Bi mixed crystal (a). Specifically, a non-mixed crystal (single oxide) containing bismuth as a metal element. Product: for example, an oxide of Bi (III), specifically Bi ₂ O ₃ and an oxide having a non-stoichiometric composition thereof, and bismuth alone or a metal element other than bismuth and bismuth And an amorphous material as a metal element. A non-Bi mixed crystal that does not contain bismuth as a metal element is referred to as a non-Bi mixed crystal (b). Specifically, a non-mixed crystal (single crystal) having a metal element other than bismuth as a metal element. Oxide), a mixed crystal containing a metal element other than bismuth as a metal element, and an amorphous body containing a metal element other than bismuth as a metal element.

  The metal elements other than bismuth in the non-Bi mixed crystals (a) and (b) include 1A group, 2A group, 3A group, 4A group, 5A group, 6A group, 7A group, 8 group, lanthanoid element, Actinoid elements, 1B group, 2B group, 3B group, 4B group, 5B group (excluding Bi), 1 type or 2 or more types of metal elements included in 6B group are preferably mentioned, more preferably Sr, Ce, Y, Ti, Zr, V, Nb, Ta, Cr, Mn, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Zn, Cd, Al, Ga, In, Ge, It is 1 type (s) or 2 or more types, such as Sn, Sb, and La. More preferably, the oxide is one or more of Zn, Ti, Ce, Sn and In having a band gap in the UV region, and the film obtained using these oxides has a wide range of UV. In addition to being able to cut effectively, it also absorbs and cuts long wavelength UV (that is, UV in the wavelength region from the wavelength 400 to 450 nm to the short wavelength side), especially based on the content of Bi, and more than 450 nm Visible light can be transmitted. Among these oxides having a band gap in the UV region, one or two of Zn, Ti, and Ce are particularly preferable because they are excellent in visible light transmission and have a high ability to absorb UV of 360 nm or less. Above, most preferably, Zn.

More specifically, among the non-Bi mixed crystals (b), the non-mixed crystal (single oxide) having a metal element other than bismuth as a metal element is not limited, but ZnO, TiO ₂ , CeO _2. , SnO ₂ , SiO ₂ , ZrO ₂ , Al ₂ O ₃ and In ₂ O ₃ are preferable, ZnO, TiO ₂ and CeO ₂ are more preferable, and ZnO is most preferable.
Among the non-Bi mixed crystals (b), the mixed crystal having a metal element other than bismuth as a metal element is specifically a solid solution oxide and / or a complex oxide, of which a solid solution Examples of the oxide include ZnO in which a trivalent or higher valent metal element such as In and Al or fluorine is dissolved, ZnO in which a monovalent metal element such as Na and Li is dissolved, Mg and Be ZnO in which a divalent metal element such as ZnO is dissolved; tetravalent or higher Invalent metal element such as Sn, Ti and Zr or In ₂ O ₃ in which fluorine is dissolved; pentavalent such as Sb and P; Preferable examples include SnO _{2 in} which a valence metal element or fluorine or the like is dissolved, TiO ₂ or CeO ₂ in which Fe, Sb, V, or the like is dissolved. Of these, ZnO-based, TiO ₂ -based, and CeO ₂ -based solid solution oxides are more preferable. As the composite oxide, MgIn ₂ O ₄ , GaInO ₃ , Zn ₂ In ₂ O ₅ , Zn ₃ In ₂ O ₆ , In ₄ Sn ₃ O ₁₂ , Zn ₂ SnO ₄ , ZnSnO ₃ and GaInO ₃ are preferable. Can be mentioned.

The first film is composed of the aforementioned Bi mixed crystal as an essential constituent, and the content ratio of the Bi mixed crystal in the film is preferably 0.1% by weight or more, more preferably 1% by weight. % Or more, more preferably 10% by weight or more, particularly preferably 50% by weight or more, and most preferably 80% by weight or more. If the content is less than 0.1% by weight, the UV blocking property may be insufficient.
The Bi mixed crystal, which is an essential component of the first film, may be composed of only one type or two or more types, and is not limited. When it consists of two or more types, for example, a form that is a coexisting body in which the respective Bi mixed crystals are integrated may be used, or a form that is present in the film without being integrated. Especially, the former form is preferable at the point which can exhibit the synergistic effect of containing 2 or more types of Bi mixed crystals. In addition, when it is composed of two or more types (in particular, in the case of a coexistant described later), the types of constituent elements of Bi mixed crystals (metal elements other than bismuth), the existence ratio of each constituent element, etc. At least a part may be the same or all may be different and is not limited.

  The first film may further include a non-Bi mixed crystal as a constituent component in addition to the Bi mixed crystal described above. Specifically, a metal oxide having a metal element other than bismuth as a metal element (that is, non-Bi mixed crystal (b)) and / or a metal oxide containing bismuth (except for a Bi mixed crystal) (that is, non-Bi crystal). A mixed crystal (a)) may further be included. Furthermore, it is possible to exert a functional effect accompanying the metal oxide (non-Bi mixed crystal) to be contained, for example, an effect of increasing the water resistance, acid resistance and alkali resistance of the film, which is preferable. Among these, when the non-Bi mixed crystal (a) is further included, UV in the wavelength region from the wavelength of 400 to 450 nm to the short wavelength side can be more effectively absorbed and cut, which is more preferable. In addition, when the non-Bi mixed crystal is also a mixed crystal (especially in the case of a coexistant described later), the types of constituent elements of each mixed crystal (particularly metal elements other than bismuth) and the presence of each constituent element The proportions and the like may be at least partially the same or different, and are not limited.

When the first film further includes a non-Bi mixed crystal, the content ratio of the non-Bi mixed crystal is preferably 0.1 to 300% by weight with respect to the entire Bi mixed crystal. More preferably, the upper limit is 60% by weight, and still more preferably the upper limit is 30% by weight. If the content ratio is less than 0.1% by weight, the coexistence effect of the Bi mixed crystal and the non-Bi mixed crystal, in particular, the coexistence effect in the case where these coexist may coexist sufficiently. If it exceeds 300% by weight, the visible light transmittance of 450 nm or more of the film is lowered, and there is a possibility that it becomes an opaque film.
In the first film, the film form in the case of further including a non-Bi mixed crystal is not limited as long as the Bi mixed crystal and the non-Bi mixed crystal coexist in the film. And a non-Bi mixed crystal may exist in the film as a coexisting body in which they coexist and be integrated, or the Bi mixed crystal and the non-Bi mixed crystal exist in the film without being integrated. It may be a form. Among these, the former form is preferable in that the effect of containing a non-Bi mixed crystal can be exhibited synergistically.

The existence form of the Bi mixed crystal in the first film is not limited, and may be a form in which a Bi mixed single crystal or polycrystal is formed as a film, or at least the Bi mixed crystal. A part may be in the form of at least a part as an essential constituent and in the form of particles. In the latter case, specifically, it may be in the form of particles containing only the Bi mixed crystal as a constituent component, or in the form of particles as a coexisting body containing a Bi mixed crystal and a non-Bi mixed crystal as constituent components. Well, it is not limited.
The second film is a non-Bi mixed crystal particle as described above, specifically, a metal oxide that requires that the non-Bi mixed crystal (a) and the non-Bi mixed crystal (b) coexist and be integrated. The coexisting particles are essential constituents. That is, the second film is a film in which the coexisting body is an essential constituent, and at least a part thereof is in the form of particles with the at least part being an essential constituent.

  In the second film, the mutual content of the non-Bi mixed crystal (a) and the non-Bi mixed crystal (b) is not limited, but specifically, the content of the non-Bi mixed crystal (a). However, it is preferable that it is 0.2-300 weight% with respect to non-Bi mixed crystal (b), More preferably, it is 1-170 weight%, More preferably, it is 2-60 weight%. When the content ratio of the non-Bi mixed crystal (a) is less than 0.2% by weight, the coexistence effect of the non-Bi mixed crystal (a) may not be sufficiently exhibited. The visible light transmittance of 450 nm or more of the film is lowered, and there is a possibility of becoming an opaque film. This range of the content is preferably satisfied at least in the particles of the coexisting body.

In the second film, the ratio of bismuth to metal elements other than bismuth is preferably 0.1 to 100 atomic%, more preferably 0.5 to 60 atomic%, and still more preferably 1 to 20 atomic%. It is. If the bismuth ratio is less than 0.1 atomic%, the UV blocking property in the wavelength region from 400 to 450 nm to the short wavelength side may be insufficient, and if it exceeds 100 atomic%, it is opaque. There is a risk of forming a thick film. The range of this ratio is preferably satisfied at least in the particles of the coexisting body.
In the second film, the coexisting particles may be particles in which a Bi mixed crystal is also present in addition to the non-Bi mixed crystal (a) and the non-Bi mixed crystal (b).

  As the coexistence form of the coexisting body in the first and second films, the other crystal body or non-crystal body may exist on the surface of one crystal body or non-crystal body. In the case of a body or an amorphous body, the other may be present at the interface between crystallites or inside an amorphous part, and is not limited. For example, in the case of the particulate coexistent, the other crystal or non-crystal is present on at least part of the surface of one crystal or non-crystal and / or the above-mentioned one Is a polycrystalline or non-crystalline material, it is preferable that the other is present in at least a part of the inside of the particle, and there is no limitation, but in particular, when the other contains bismuth as a metal element, It is preferable that it exists on the particle | grain surface at the point with high transparency with respect to visible light of 450 nm or more.

In the first and second films, when at least a part of the Bi mixed crystal or coexistent body is in the form of particles and is present in the film, the particle shape is not limited. Examples include a spherical shape, a cubic shape, a rectangular parallelepiped shape, a polyhedron shape, a pyramid shape, a column shape, a tube shape, a flake shape, and a flake shape such as a (hexagonal) plate shape. Regarding the size of the particles, it is assumed that all the particles referred to as ultrafine particles and fine particles are included, and is not limited. However, it is usually preferable that the average particle size is 1 to 100 nm, more preferably 5 to 30 nm, Preferably it is 5-20 nm.
In the first and second films, the Bi mixed crystal or coexisting substance is present in the film in the form of at least a part of the Bi mixed crystal or coexisting substance as described above. Depending on whether part of the body is in the form of particles or all of it is in the form of particles, for example, when part of the body is in the form of particles, it is the same as the film in the Bi mixed crystal or coexisting film. Examples include a form in which particles composed of constituents are dispersed. On the other hand, when all of the particles are in the form of particles, the particles are aggregated together to form a film, or the particles are dispersed in various binders. And the like, and a form in which the particles are dispersed in a film of another metal oxide having the same or different constituent component. The other metal oxide may be crystalline or non-crystalline, and may be any one of a single metal oxide, a composite metal oxide, and a solid solution oxide. Not.

When the whole is in the form of particles, the ratio of the particles in the formed film is not limited, but is preferably 10 to 90% by weight, and more preferably 20 to 80% by weight. When the above ratio is less than 10% by weight, it is necessary to form a thick film in order to obtain UV blocking properties. In particular, when an inorganic binder or a metal oxide is used as a film component in addition to the particles, it is obtained. If the film exceeds 90% by weight, the mechanical strength of the film may be insufficient.
The first and second films are films that can be formed on the surface of the base material, and the form of the first and second films is a form that continuously spreads in a desired area portion on the surface of the base material (hereinafter referred to as “the following”). It may be referred to as a continuous film.) Or may be present in a discontinuous manner in a desired area on the surface of the substrate (hereinafter sometimes 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. As a specific form of the discontinuous film, 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 base material, a form in which the so-called sea-island structure is present, or 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 a metal oxide component, the structure of the metal oxide (Bi mixed crystal or coexisting body) is not limited, but specifically, a space having a desired size. It may be a porous structure having a solid structure that is not such a porous structure macroscopically (that is, a substantially dense structure). The 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. Further, in any of the above structures, when the film is made of metal oxide particles, even when the film is a structure in which metal oxides as primary particles are aggregated in a macro view, the particles are formed into secondary particles. The structure may be a structure in which metal oxides are aggregated, a structure in which metal oxides that are further formed into particles are aggregated, or a structure in which these forms are mixed, and is not limited. . In the discontinuous film, the structure of the metal oxide as described above may be included in all or only a part of individual film portions that are partially present. .

Embodiments of the first and second films include an aspect that means the film itself formed on the base material, and an aspect that includes the film formed on the base material and the base material. , And any of them.
The base material that can be used for the first and second films is not limited, for example, ceramics such as oxide, nitride, and carbide, inorganic materials such as glass; polyester such as PET, PBT, and PEN. Known as heat-resistant resin film for resin, polycarbonate resin, polyphenylene sulfide resin, polyethersulfone resin, polyetherimide resin, polyimide resin, amorphous polyolefin resin, polyarylate resin, aramid resin, polyetheretherketone resin, liquid crystal polymer, etc. In addition to resin films and sheets, conventionally known (meth) acrylic resin, PVC resin, PVDC resin, PVA resin, EVOH resin, polyimide resin, polyamideimide resin, PTFE, PVF, PGF, ETFE, etc. fluorine resin, epoxy resin Organic materials such as films and sheets made of various resins such as polyolefin resins, various resin polymers, and processed products such as films obtained by vapor-depositing these various resin polymers with aluminum, alumina, silica, etc .; various metals are preferred. 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. Further, the substrate is not particularly limited in terms of function, for example, optically transparent and opaque; electrically, an insulator, a conductor, a p-type or n-type semiconductor or dielectric; magnetic Specifically, a magnetic material, a non-magnetic material, etc. may be selected according to the use / purpose of use.
The ultraviolet blocking film according to the present invention can be used, for example, for window glass for buildings, window glass for vehicles such as automobiles and trains, window glass for air transportation such as airplanes and helicopters, agricultural films, and various packaging films. However, the application is not limited to these, and in addition to providing an ultraviolet blocking function to various functional films, it can be used for various applications for the purpose of providing light resistance and weather resistance.

[Ultraviolet-blocking metal oxide particles]
As described above, in the ultraviolet-blocking metal oxide particles according to the present invention, the first particles essentially comprise a mixed crystal (Bi mixed crystal) of a metal oxide containing a metal element other than bismuth and bismuth as a metal element. As a component, the second particle has a metal oxide containing a metal element other than bismuth as a metal element (that is, a non-Bi mixed crystal (b)) and a metal oxide containing bismuth (except for a Bi mixed crystal) (that is, non-mixed). A coexisting body of a metal oxide, which is essential to coexist with Bi mixed crystal (a)), is an essential constituent.
The first particle may be a particle having only a Bi mixed crystal as a constituent component, or may be a particle made of a coexisting body in which a Bi mixed crystal and a non-Bi mixed crystal are constituent components and they coexist. There is no limitation. As the explanation regarding the first particles, the explanation regarding the particles in the case where the Bi mixed crystal, which is an essential constituent of the first film, is in the form of particles having itself as an essential constituent is the same. Applicable.

The second particle may be a particle composed only of a metal oxide coexisting substance in which the non-Bi mixed crystal (a) and the non-Bi mixed crystal (b) coexist, or the coexisting substance. Furthermore, the particles may be composed of a metal oxide coexisting substance in which a Bi mixed crystal coexists, and is not limited. As the explanation about the second particles, all the explanations of the metal oxide particles which are essential constituent components of the second film can be applied in the same manner.
The metal oxide particles for ultraviolet blocking according to the present invention can be preferably used as, for example, a component of the composition for forming an ultraviolet blocking film or an ultraviolet blocking material according to the present invention. It may be used as a component of various known films, as a component of various compositions such as cosmetics, or used by being directly contained in various conventionally known base materials (such as glass) and various materials. Also good. When contained in various base materials and various materials, various base materials and various materials having an ultraviolet blocking ability can be easily obtained.

[Composition for forming ultraviolet blocking material]
In the composition for forming an ultraviolet blocking material according to the present invention, as described above, the first composition is a mixture of a composite metal carboxylate containing a metal element other than bismuth as a metal element and bismuth and an alcohol and / or The component derived from the mixture is an essential component, the second composition is a metal oxide particle and a dispersion solvent and / or a binder, and the metal oxide particle is a metal element other than bismuth. Metal oxides containing bismuth and metal oxides (Bi mixed crystals) and / or metal oxides containing metal elements other than bismuth as metal elements and bismuth (except for Bi mixed crystals) And a third composition comprising a mixture of metal oxide particles, a metal carboxylate and an alcohol, And / or a component derived from the mixture as an essential constituent, wherein the metal oxide particles include a metal element other than bismuth as a metal element and a metal oxide mixed crystal (Bi mixed crystal), and / or It is a coexisting body of metal oxides indispensable that a metal oxide containing a metal element other than bismuth as a metal element and a metal oxide containing bismuth (excluding Bi mixed crystals) coexist.

  The composite metal carboxylate referred to in the first composition contains bismuth and other metal elements as metal elements. Specifically, (i) a compound having in the molecule at least one each a bond in which a hydrogen atom of a carboxyl group is substituted with a bismuth atom and a bond in which a metal element other than bismuth is substituted, (Ii) a compound having at least one bond in which the hydrogen atom of the carboxyl group is substituted with a bismuth atom in the molecule, and a bond in which the hydrogen atom of the carboxyl group is substituted with a metal atom of a metal element other than bismuth in the molecule. Examples include compounds formed by complex integration with at least one compound. For example, chain monocarboxylic acids such as saturated monocarboxylic acids, unsaturated monocarboxylic acids, saturated polycarboxylic acids and unsaturated polycarboxylic acids; cyclic saturated carboxylic acids; aromatic monocarboxylic acids and aromatic unsaturated polyvalent acids Aromatic carboxylic acids such as carboxylic acids; compounds having functional groups or atomic groups such as hydroxyl groups, amino groups, nitro groups, alkoxy groups, sulfone groups, cyano groups and halogen atoms in the molecules of these carboxylic acids; Although a composite metal salt is mentioned preferably, it is not limited to these. Among these, a composite metal salt of a carboxyl group-containing compound described later, a basic composite metal acetate, and the like can be preferably exemplified. Among them, a composite metal salt of a carboxyl group-containing compound described later, which is a composite metal saturated carboxylate or composite metal unsaturated carboxylate, more preferably a composite metal acetate or composite metal propionic acid. When the metal element other than bismuth is Zn, a composite metal acetate is particularly preferable. The composite metal carboxylate may be a hydrate of composite metal carboxylate containing crystal water, but is preferably an anhydride.

  The carboxyl group-containing compound described above is not limited as long as it is a compound having at least one carboxyl group in the molecule. For example, formic acid, acetic acid, propionic acid, isobutyric acid, caproic acid, caprylic acid, lauric acid, Saturated fatty acids (saturated monocarboxylic acids) such as myristic acid, palmitic acid, stearic acid; unsaturated fatty acids (unsaturated monocarboxylic acids) such as acrylic acid, methacrylic acid, crotonic acid, oleic acid, linolenic acid; oxalic acid, malon Saturated polycarboxylic acids such as acids, succinic acid, adipic acid, suberic acid, β, β-dimethylglutaric acid; chain carboxylic acids such as unsaturated polycarboxylic acids such as maleic acid and fumaric acid; cyclohexanecarboxylic acid, etc. Cyclic saturated carboxylic acids of the above; aromatic monocarboxylic acids such as benzoic acid, phenylacetic acid and toluic acid; phthalic acid, Aromatic carboxylic acids such as unsaturated polycarboxylic acids such as sophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid; carboxylic acid anhydrides such as acetic anhydride, maleic anhydride, pyromellitic anhydride; trifluoroacetic acid , O-chlorobenzoic acid, o-nitrobenzoic acid, anthranilic acid, p-aminobenzoic acid, anisic acid (p-methoxybenzoic acid), toluic acid, lactic acid, salicylic acid (o-hydroxybenzoic acid) And compounds having functional groups or atomic groups such as hydroxyl groups, amino groups, nitro groups, alkoxy groups, sulfonic acid groups, cyano groups, and halogen atoms other than carboxyl groups.

Regarding the explanation of the metal elements other than bismuth contained in the composite metal carboxylate, the “metal other than bismuth” in the non-Bi mixed crystal (a) and (b) in the ultraviolet blocking film of the present invention is described. All descriptions of “elements” are equally applicable.
The composite metal carboxylate is obtained by heating a metal carboxylate (b) containing a metal element other than bismuth as a metal element and a metal carboxylate (a) containing bismuth with a carboxylic acid-containing solution (for example, an aqueous solution). It is preferable that it was obtained through the process of performing. Specifically, for example, the composite metal carboxylate is dissolved by heating and stirring the metal carboxylate (a) and (b) in the carboxylic acid-containing solution, and then cooling or poor It is preferably obtained by precipitation using a solvent. After the precipitation, it usually becomes a slurry, but then it is preferable to obtain a composite metal carboxylate in a powder form by removing the solvent component under reduced pressure or the like, and drying by heating or vacuum as necessary. .

The metal carboxylate (a) may be a metal carboxylate containing only bismuth as a metal element, or may be a metal carboxylate containing a metal element other than bismuth and bismuth as a metal element. There is no limitation. About description of the metal carboxylate which uses only the former bismuth as a metal element, explanation of the composite metal carboxylate referred to in the first composition except that it is a single metal carboxylate whose metal element is only bismuth But all are equally applicable. Regarding the explanation regarding the latter metal carboxylate, all the explanations regarding the composite metal carboxylate referred to in the first composition can be similarly applied.
The metal carboxylate (a) is not limited, but preferred examples include bismuth acetate, basic bismuth acetate, bismuth 2-ethylhexanoate, bismuth subsalicylate, bismuth naphthenate, and bismuth oxalate.

The metal carboxylate (b) may be a metal carboxylate containing only one metal element other than bismuth as a metal element, or a metal carboxylate containing two or more metal elements. Well, it is not limited. Except for the metal carboxylate (b), one or more metal elements other than bismuth are used as the metal element, all the descriptions of the composite metal carboxylate referred to in the first composition are equally applicable.
The metal carboxylate (b) is not limited, but preferred examples include zinc formate, zinc acetate, zinc propionate, indium oxalate, basic indium 2-ethylhexanoate and indium acetate anhydride.

The carboxylic acid-containing solution is not limited, and a solution or an aqueous solution of the above-described carboxyl group-containing compound can be preferably used. For example, an acetic acid aqueous solution is preferable.
The heating temperature (reaction temperature) for heating the metal carboxylates (a) and (b) in the carboxylic acid-containing solution varies depending on the type of carboxylic acid and solvent in the carboxylic acid-containing solution, but the metal A temperature that does not cause thermal decomposition of the carboxylates (a) and (b) and the resulting composite metal carboxylate, and can maintain the dissolved state of the metal carboxylates (a) and (b) It is preferable to control to, for example, it is preferable that it is 50-200 degreeC, More preferably, it is 80-150 degreeC. The heating time is not limited, but specifically, it is preferably 0.1 to 5 hours. As described above, the composite metal carboxylate is obtained by precipitating, and thereafter, various procedures and conditions until it is obtained in powder form are not limited, and known methods and conditions can be appropriately employed.

  Examples of the alcohol used in the first composition include, but are not limited to, aliphatic monohydric alcohols (methanol, ethanol, isopropyl alcohol, n-butanol, t-butyl alcohol, stearyl alcohol, etc.), aliphatic unsaturated 1 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, naphthol, nonylph And 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.); 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, ethylene glycol Derivatives such as monoethers or monoesters of the above glycols such as 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 alcohol, hydrobenzoin, benzpinacol, phthalylal Polyhydric aromatic alcohols such as chol, 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 Derivatives in which .about. (N-1) (where n is the number of OH groups per molecule) are ester bonds or ether bonds;

As the alcohol, an alcohol that easily generates a metal oxide at a lower temperature state is preferable, and an alcohol having a primary or secondary, particularly a primary hydroxyl group, with respect to an alcoholic hydroxyl group is a metal oxide at a lower temperature state. Since it is obtained, it is the most preferable. For similar reasons, aliphatic alcohols are also preferred.
In the first composition, the amount of the composite metal carboxylate and the alcohol used is not limited, but the number of hydroxyl groups (derived from the alcohol) in the alcohol relative to the number of metal-converted atoms of the composite metal carboxylate is not limited. The ratio is preferably 0.8 to 1000. In addition, regarding the amount used, it is also preferable that the ratio of the total number of hydroxyl groups (derived from alcohol) in the alcohol to the total number of carboxyl groups of the composite metal carboxylate is 0.8 to 100, more Preferably it is 1-50, More preferably, it is 1-20.

  In the first composition, the composite metal carboxylate and the alcohol may be provided separately, or may be in a premixed state. Although not limited, the mixed system of the composite metal carboxylate and the alcohol Is preferably a fluid liquid such as a paste, suspension, or solution, and particularly preferably a solution. Further, if necessary, the above-mentioned liquid may be obtained by mixing a reaction solvent described later. Usually, in the above mixed system, the composite metal carboxylate is present in a state of being dispersed in the form of particles, dissolved, or partly dissolved and the rest being dispersed in the form of particles. However, it is preferably in a state in which at least a part is dissolved, and more preferably in a state in which it is completely dissolved. In the first composition, the composite metal carboxylate and alcohol may be referred to as starting materials.

  The mixed system of the composite metal carboxylate and alcohol as the starting material means a system after the stage where at least a part of the composite metal carboxylate and the alcohol are mixed together. The internal state of this mixed system is not limited to the state in which both the composite metal carboxylate and the alcohol exist without changing the chemical structure of the raw material state. At least one of the alcohols may be in a state of being changed to a specific chemical structure in a dissolved state, or a composite metal carboxylate and an alcohol are present as these pre-reactants. It may be in a state, that is, it may be changed from the starting raw material as it is to another state. Thus, when the starting material is present in a different state after mixing, this is referred to as “a component derived from a mixture of starting materials”.

The first composition may further contain a reaction solvent. That is, when obtaining a metal oxide using a metal carboxylate and an alcohol as starting materials, a reaction solvent may be further used. Specifically, these starting materials may be mixed, or the mixture of these starting materials may be brought into a high temperature state after further adding a reaction solvent.
The amount of the reaction solvent used is not limited, but the ratio of the amount of the composite metal carboxylate used relative to the total amount of the composite metal carboxylate used as the starting material and the alcohol and the reaction solvent is 0.1 to 0.1%. The amount is preferably 50% by weight, and a metal oxide 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, and carboxylic acid esters. And derivatives such as esters, amides, and 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 wt% or more of water at room temperature (25 ° C.) is preferable, and a solvent that can be in a uniform solution state containing an arbitrary amount of water is more preferable. As the alcohol as the reaction solvent, the same alcohols as those mentioned above as the starting material can be preferably mentioned.

The metal oxide particles that are essential components of the second film and the third film are not limited, but the first particles and / or the second particles can be preferably used.
In the second composition, a dispersion solvent and / or a binder are further essential components. The mutual ratio of the amount of the dispersion solvent and the binder used is not limited, and may be appropriately set according to the type and amount of metal oxide particles that are essential components and the form of the film to be formed. it can.
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 silicon alkoxide binders, acrylic resins, polyester resins, fluororesins, etc., thermoplastic or thermosetting (thermosetting, ultraviolet curable, electron beam curable, moisture curable, combined use thereof, etc. And organic binders such as various synthetic resins and natural resins, inorganic binders, and the like. Synthetic resins include, for example, alkyd resins, amino resins, vinyl resins, acrylic resins, epoxy resins, polyamide resins, polyurethane resins, thermosetting unsaturated polyester resins, phenol resins, chlorinated polyolefin resins, silicone resins, acrylic silicone resins. Fluorine resin, xylene resin, petroleum resin, ketone resin, rosin-modified maleic acid resin, liquid polybutadiene, coumarone resin, and the like, and one or more of these are used. Examples of 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 alkoxides such as silica sol, alumina sol, titania sol, alkali silicic acid, and silicon alkoxide, their (hydrolyzed) condensates, and phosphates.
The amount of the metal oxide particles, the dispersion solvent and / or the binder, which are essential components in the second composition, is not limited, but specifically, the amount of the metal oxide particles used is not limited. 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 of use is less than 10% by weight, for example, when the composition is used for forming an ultraviolet blocking film, it is necessary to make it thick to obtain sufficient UV blocking properties. In the case where an inorganic binder or curable resin is used as a film component, cracks may easily occur in the obtained film, and when it exceeds 90% by weight, for example, when the composition is used for film formation. The mechanical strength of the film may be insufficient. However, when forming a film by using a composition containing a dispersion solvent as an essential component as the second composition, applying it to a base material, heating it to a high temperature and firing (sintering) it. 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.

In the third composition, a mixture of a metal carboxylate and an alcohol and / or a component derived from the mixture is an essential constituent.
Regarding the description of the mixture of metal carboxylate and alcohol and / or components derived therefrom, the metal carboxylate is not limited to a complex metal salt, but may be a single metal salt. The description of “mixture of composite metal carboxylate and alcohol and / or component derived therefrom” in the first composition is equally applicable.
The amount of the metal oxide particles, the mixture of the metal carboxylate and the alcohol, and / or the component derived from the mixture, which are essential components in the third composition, is not limited, The amount of the metal oxide particles used is preferably 0.05 to 5 and more preferably 0.1 to 1 by weight ratio with respect to the amount of metal carboxylate used. When the amount of the metal oxide particles used is less than 0.05 in the weight ratio, for example, when the composition is used for forming an ultraviolet blocking film, the obtained film has insufficient UV blocking properties. If it exceeds 5, for example, when the composition is used for forming a film, the mechanical strength of the film may be insufficient.

The composition for forming an ultraviolet blocking material according to the present invention may further contain other components, and may contain, for example, a dispersant.
The composition for forming an ultraviolet blocking material according to the present invention can be preferably used, for example, as a raw material composition used for producing the ultraviolet blocking film or the metal oxide particles for ultraviolet blocking according to the present invention. Not. The composition for forming an ultraviolet blocking material of the present invention can also be handled as a coating liquid for producing an ultraviolet blocking film or an ultraviolet cut coating.
[Method of forming ultraviolet blocking film]
The ultraviolet blocking film according to the present invention can be preferably formed by using, for example, the composition for forming an ultraviolet blocking material of the present invention as a raw material composition, but is not limited thereto. Hereinafter, a method for forming a film using the composition for forming an ultraviolet blocking material of the present invention will be described.

As a method of forming a film using the first composition, a method of bringing a composite metal carboxylate and alcohol as a starting material and / or a component derived from the mixture into a high temperature state, that is, the above-described starting material A method of bringing the mixed system to a high temperature state at the same time as or after mixing the raw materials is used. Thus, a metal oxide is produced | generated by making it a high temperature state.
To bring the mixed system into a high temperature state is to raise the temperature of the mixed system to a temperature higher than normal temperature and capable of forming a metal oxide, or higher. The temperature in the high temperature state (temperature at which the metal oxide can be generated) varies depending on the type of metal oxide to be obtained, but is usually 50 ° C. or higher, and in order to obtain a metal oxide with high crystallinity 80 ° C. or more, preferably 100 to 300 ° C., more preferably 100 to 200 ° C., particularly preferably 120 to 200 ° C., and most preferably 120 to 150 ° C. Specifically, for example, the metal oxide to be obtained is a Bi mixed crystal (or a coexisting substance with a non-Bi mixed crystal) like the first film, or like the second film. The temperature in the high temperature state may be set as appropriate depending on whether the non-Bi mixed crystal is a coexisting substance (or a coexisting substance with the Bi mixed crystal). In addition, with respect to the obtained metal oxide, the obtained metal oxide is heated at 300 to 800 ° C. as necessary for the purpose of removing remaining organic groups or further promoting crystal growth. May be.

  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. Further, 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 is 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 solvent component, but it can also be carried out under supercritical conditions.

In the case of producing a metal oxide, it is preferable that the amount of water contained in the mixed system is less because defects of the obtained metal oxide are reduced. Specifically, it is preferable that the mixed system contains only a small amount of water having a molar ratio of less than 4 with respect to the metal atoms in the composite metal carboxylate used as the starting material. Is more preferably less than 0.5, particularly preferably less than 0.5, and most preferably less than 0.1.
The high temperature state of the mixed system only needs to be obtained at the same time as or after mixing the composite metal carboxylate and the alcohol as a starting material, that is, mixing the starting materials to obtain the mixed system. The temperature rise for bringing the mixed system into a high temperature state may be separate or simultaneous (including partly simultaneous), and is not limited. More specifically, the specific means (for example, heating) for raising the temperature of the mixing system can be performed by any method and timing regardless of the mixing of the starting materials. For example, the starting materials before mixing The temperature of the mixed system may be raised at the same time as mixing by heating at least one or the like, or the mixing system obtained by mixing is mixed or terminated. Later, heating or the like may be performed to raise the temperature of the mixed system, but there is no limitation. Therefore, the timing of the mixing and the heating for raising the temperature is not limited. Specifically, 1) the mixed metal carboxylate and the alcohol are mixed and heated. 2) The alcohol is heated to a predetermined temperature, etc., and the mixed metal carboxylate is mixed with this to raise the temperature of the mixed system to a high temperature state. 3) Reaction solvent And the composite metal carboxylate are mixed and heated to a predetermined temperature, etc., and mixed with alcohol to raise the temperature of the mixed system to a high temperature state. 4) Each component (composite metal carboxylate) In addition, after the alcohol and the alcohol, and if necessary, the reaction solvent) are separately heated, etc., they are preferably mixed to raise the temperature of the mixed system to a high temperature state.

  In the method of forming a film using the first composition, as described above, a step of bringing the mixed system to a high temperature state is required. More specifically, the mixed system of the starting materials is brought into contact with the substrate. And a step of bringing the contact system into a high temperature state is required, and it is preferable to form and fix a metal oxide as a film on the surface of the substrate by this step. Specifically, the contact system is brought to a high temperature state, the base material formed by applying the mixed system on the surface is brought to a high temperature state, or the base material is immersed in the mixed system and the high temperature state is set. It is more preferable to form and fix a metal oxide as a film on the surface of the base material, the former belonging to the so-called coating method and the latter belonging to the so-called submerged deposition method (immersion method). It is. In addition, while the mixed system is kept in a high temperature state or in a high temperature state, it is applied to the surface of the base material so that a metal oxide is formed and fixed on the surface of the base material as a film. More preferably, this is a method belonging to the so-called coating method. In the above, for the details of the specific procedures of the precipitation method in liquid (immersion method) and the coating method, for example, the description in paragraphs 0078 to 0095 of JP-A-2003-267705 can be preferably applied, but the limitation is not limited. Not.

A method of forming a film using the second composition is not limited, but the composition is applied to the surface of the substrate by a bar coater method, a roll coater method, a knife coater method, a die coater method, a spin coat method, or the like. A method of forming a film by coating using a conventionally known film forming method, or a so-called dipping method in which a part or all of a substrate is immersed in the composition and then taken out to form a film. it can. In addition, when a dispersion solvent is used as an essential component of the composition, it can be formed by baking at a high temperature after coating, for example, crystallinity in which at least a part of metal oxide particles are fused. The film can be obtained.
The method for forming a film using the third composition is not limited. However, the first composition is formed except that the film is formed in the presence of metal oxide particles that are essential constituents of the composition. All the descriptions of the method of forming a film using the composition can be similarly applied.

[Method for producing metal oxide particles for ultraviolet blocking]
The ultraviolet-blocking metal oxide particles according to the present invention can be preferably produced using, for example, the composition for forming an ultraviolet-blocking material of the present invention (specifically, the first composition) as a raw material composition. However, this is not a limitation. Below, the manufacturing method of the metal oxide particle using a 1st composition is demonstrated.
With respect to the description of the specific procedure and conditions in the case of producing the ultraviolet blocking metal oxide particles (first and second particles) of the present invention using the first composition, without using a substrate. Except for obtaining particles by carrying out a metal oxide production reaction, the description for producing the ultraviolet blocking film of the present invention using the first composition can be applied in the same manner. When obtaining the metal oxide particles, all the processes described above, such as when mixing the starting materials, or when the starting material mixture system is brought to a high temperature state or when the temperature is raised to the high temperature state, etc. Is preferably carried out under stirring. By always carrying out stirring, metal oxide particles having a high metal oxide content and excellent metal oxide crystallinity can be easily obtained. In addition, metal oxide particles having a uniform particle diameter, particle shape, and the like can be easily obtained. The metal oxide to be obtained is a particle of Bi mixed crystal (or a coexisting substance with non-Bi mixed crystal) like the first particle, or non-Bi like the second particle. What is necessary is just to set the temperature of the said high temperature state suitably by the particle | grains of the coexistence body of mixed crystals (or also the coexistence body with Bi mixed crystal).

  In particular, as a production method in the case where the first and second particles are composed of the above-mentioned coexisting body, a metal oxide that is a constituent component of the coexisting body is obtained in advance as particles (mother particles). A method in which a metal oxide serving as another constituent component is present in at least a part of the surface of the mother particle by performing a production reaction of the metal oxide serving as another constituent component in the presence is also preferable. Here, as a method for producing the mother particles and a method for producing a metal oxide as another constituent component, a conventionally known metal oxide (particle) method can be used as appropriate. The method of producing and producing using the composition can also be preferably used, and is not limited.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these. Hereinafter, for convenience, “parts by weight” may be simply referred to as “parts”. In addition, “wt%” may be described as “wt%”.
Measurement methods and evaluation methods in Examples and Comparative Examples are shown below.
<Average particle size>
From the transmission electron microscope image, the particle diameter of 30 primary particles was obtained by number average.
<Identification of crystal>
About the powder sample, the X-ray-diffraction pattern was evaluated with the powder X-ray-diffraction apparatus (Rigaku company make, product name: RINT2400), and the identification and crystal structure of the crystal | crystallization were analyzed.

<Single crystal or polycrystal>
In the case of fine particles, observation of lattice fringes in a transmission electron microscope image, comparison of the average particle diameter in the transmission electron microscope image and the crystallite diameter obtained by the Scherrer method using the half width of each peak in the powder X-ray diffraction pattern From the above, it was determined whether the fine particles consist of single crystals or polycrystals.
In the case of a film, the crystallite diameter determined by the Scherrer method using the half width of each peak in the powder X-ray diffraction pattern, the presence or absence of crystal orientation by the thin film X-ray diffraction method, and the results of electron microscopic analysis of the cross-sectional structure of the film In total, it was determined whether the film was made of single crystal or polycrystalline.

<Fine particle composition (Bi content, metal element composition)>
While observing with an FE-TEM (electrolytic emission transmission electron microscope) with an XMA device (X-ray microanalyzer) with a resolution of 1 nmφ, local elemental analysis is performed at each part from the surface to the center of the particle. And the result of fluorescent X-ray analysis (average composition evaluation) of the powder sample. Moreover, when performing local elemental analysis of each particle | grain, the presence or absence of the segregation of the single oxide of Bi was also evaluated.
<Film composition (Bi content ratio, metal element composition)>
When the sample is a membrane, it is collected by scraping a part of it, and a thin slice sample is prepared from the sample embedded in resin using mitochrome, and if necessary, an ultra-thin film is prepared by ion milling. A sample was prepared, and this was judged and evaluated by the same method using the same apparatus as in the case of the fine particles.

<Diffusion reflection spectrum of fine particles>
The diffuse reflection spectrum of the sample was measured using a self-recording spectrophotometer with an integrating sphere (manufactured by Shimadzu Corporation, product name: UV-3100).
<Spectral characteristics of film>
Using a self-recording spectrophotometer with an integrating sphere (manufactured by Shimadzu Corporation, product name: UV-3100), the spectral transmittance curve of the sample was measured.
<Transparency to visible light>
Using a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd., product name: NDH-1001 DP), the total light transmittance, diffuse light transmittance, parallel line transmittance and haze of the sample were measured. Evaluated by criteria. The haze value of only the film portion was evaluated as a value obtained by subtracting the haze value of the base material from the haze value of the base material with a film.

Haze <3%: Transparency “○”
Haze ≧ 3%: Transparency “×”
<Coloring>
It was evaluated whether the degree of coloring was visually higher than the appearance.
“Synthesis of Bi-containing complex metal carboxylates”
[Synthesis Example 1]
(Synthesis of Bi-containing zinc acetate)
A glass reactor equipped with a stirrer, an addition port, and a thermometer, which can be heated from the outside, is charged with 250 parts of an 80 wt% aqueous acetic acid solution, 36.7 parts of zinc acetate, and 2.84 parts of basic bismuth acetate. The mixture was heated with stirring to raise the temperature, and stirred at 100 ° C. for 5 hours to obtain a uniform transparent solution. Then, after heating up to 120 degreeC of internal temperature, the white slurry was obtained by cooling. About the obtained slurry, the solvent component was removed under reduced pressure at a bath temperature of 50 ° C. using an evaporator, and the obtained white powder was dried by heating at 40 ° C. for 10 hours using a vacuum drier. 1) was obtained.

As a result of elemental analysis by fluorescent X-ray analysis and crystal analysis by powder XRD, it was confirmed that the obtained powder (1) was zinc acetate containing Bi at 5 atomic% with respect to Zn.
[Synthesis Example 2]
(Synthesis of Bi / In-containing zinc acetate)
A powder (2) was obtained in the same manner as in Synthesis Example 1 except that the amount of basic bismuth acetate used was 1.7 parts and 1.8 parts of indium acetate anhydride was further used.
As a result of elemental analysis by fluorescent X-ray analysis and crystal analysis by powder XRD, it was confirmed that the obtained powder (2) was zinc acetate containing 3 atomic% of Bi and In with respect to Zn.

“Synthesis of Bi-containing metal oxide crystal particles (UV-blocking metal oxide particles)”
[Example 1-1]
(Synthesis of ZnO ultrafine particles with Bi dissolved)
A pressure-resistant glass reactor equipped with an agitator, an addition port directly connected to the addition tank, a thermometer, a distillate gas outlet, and a nitrogen gas inlet was prepared.
In this reactor, a mixture consisting of 18 parts of the powder (1) obtained in Synthesis Example 1 and 180 parts of methanol was charged, and the gas phase part was purged with nitrogen gas and stirred from 20 ° C. to 150 ° C. The temperature was raised, held at 150 ° C. ± 1 ° C. for 5 hours, and then cooled to obtain a reaction liquid (1a) containing yellow fine particles.

The reaction solution (1a) is a dispersion in which fine particles (average particle size: 10 nm) made of ZnO crystals in which Bi (III) is solid-dissolved in a proportion of 5 atomic% with respect to Zn are contained and dispersed at 4 wt%. confirmed.
As a result of evaluating the diffuse reflection spectrum of the fine particles in the reaction solution (1a), the absorption maximum at 422 nm based on containing Bi and the band edge absorption based on ZnO crystal (400 nm as the absorption edge on the long wavelength side) Absorption). In addition, the fine particles have a weak absorption on the longer wavelength side (infrared wavelength region) from around 650 nm but exhibit absorption, and the ultraviolet absorption edge wavelength (short wavelength side) has a diffuse reflection spectrum of ZnO not containing Bi. In comparison, it was confirmed that a blue shift (absorption edge is present on the short wavelength side) and the like was confirmed indirectly by the fact that trivalent Bi ions were dissolved.

The obtained reaction liquid (1a) was replaced with a heated solvent to obtain a dispersion (1b) in which the fine particles were contained and dispersed in 2-propanol at 20 wt%.
[Example 1-2]
(Synthesis of CeO ₂ ultrafine particles coated with Bi ₂ O ₃ )
In a reactor similar to Example 1-1, a dispersion in which 10 parts of CeO ₂ ultrafine particles (average particle diameter: 8 nm) were dispersed in 190 parts of n-butanol was charged and stirred.
On the other hand, 44 parts of a solution prepared by dissolving basic bismuth acetate in a mixed solvent of propionic acid and n-butanol so as to be 20 wt% was prepared and charged into an addition tank.

While stirring the above dispersion of CeO ₂ ultrafine particles, the temperature was raised and maintained at 200 ° C.
From the addition layer, a basic bismuth acetate solution was added. Even after completion of the addition, the reaction solution (2a) containing yellow fine particles was obtained by holding at 200 ° C. for 5 hours and then cooling.
The reaction liquid (2a) is composed of fine particles (average particle size: 10 nm) in which the surface of CeO ₂ ultrafine particles is coated with a Bi oxide (Bi ₂ O ₃ ) layer having a thickness of about 1 nm, and the main solvent is n-butanol. It was confirmed that the average metal composition of the fine particles was Bi / Ce = 0.53 / 1 (atomic ratio).
By substituting the obtained reaction liquid (2a) with a heating solvent, a dispersion (2b) in which the fine particles were contained and dispersed in butyl acetate at 20 wt% was obtained.

[Example 1-3]
(Synthesis of TiO ₂ ultrafine particles coated with Bi ₂ O ₃ )
In Example 1-2, a reaction liquid containing yellow fine particles was similarly obtained except that TiO ₂ ultrafine particles (average particle size: 12 nm) were used instead of CeO ₂ ultrafine particles and all n-butanol was ethanol. 3a) was obtained.
The reaction liquid (3a) is a solvent in which fine particles (average particle size: 14 nm) in which the surface of TiO ₂ ultrafine particles is coated with a Bi oxide (Bi ₂ O ₃ ) layer having a thickness of about 1 nm is ethanol as a main solvent. It was confirmed that the average metal composition of the fine particles was Bi / Ti = 0.25 / 1 (atomic ratio).

By substituting the obtained reaction liquid (3a) with a heating solvent, a dispersion (3b) obtained by containing and dispersing the fine particles in water at 20 wt% was obtained.
[Example 1-4]
(Synthesis of InO solid solution ZnO ultrafine particles coated with Bi solid solution ZnO)
A reactor similar to Example 1-1 was charged with a mixture of 18 parts of zinc acetate anhydrous powder, 0.9 parts of indium acetate anhydrous powder and 160 parts of 2-butoxyethanol, and the gas phase part was purged with nitrogen gas. The temperature was raised with stirring. Suspension in which 18 parts of the powder (1) obtained in Synthesis Example 1 was dispersed in 18 parts of 2-butoxyethanol after maintaining at 200 ° C. for 3 hours (production of ZnO ultrafine particles in which In was dissolved at this time). The liquid was added from the addition tank. After the addition, the reaction solution (4a) containing fine particles was obtained by holding at 200 ° C. for 3 hours and then cooling.

The reaction solution (4a) is fine particles composed of ZnO crystals in which Bi (III) is solid-solved at a ratio of 2.5 atomic% to Zn and In (III) is 1.5 atomic% to Zn. , Bi (III) was confirmed to contain and disperse 7.4 wt% of fine particles (average particle size: 18 nm) localized and dissolved in the surface ZnO layer.
As a result of evaluating the diffuse reflection spectrum of the fine particles in the reaction liquid (4a), the absorption maximum at 422 nm based on containing Bi and the band edge absorption based on ZnO crystal (400 nm as the absorption edge on the long wavelength side) In addition, it was confirmed that strong absorption is exhibited in the near infrared region, which is considered to be mainly caused by plasma absorption due to the solid solution of In.

The obtained reaction liquid (4a) was concentrated by heating under reduced pressure using an evaporator to obtain a dispersion (4b) having a fine particle concentration of 20 wt%.
[Example 1-5]
(Synthesis of ZnO ultrafine particles in which Bi · In is dissolved)
A reactor similar to Example 1-1 was charged with a mixture of 18 parts of the powder (2) obtained in Synthesis Example 2 and 160 parts of 2-butoxyethanol, and the gas phase part was purged with nitrogen gas and stirred. While raising the temperature. After maintaining at 200 ° C. for 3 hours, the reaction solution (5a) containing fine particles was obtained by cooling.

In the reaction solution (5a), fine particles (average particle diameter: 8 nm) composed of ZnO crystals in which Bi (III) and In (III) are both solid-dissolved in a proportion of 3 atomic% with respect to Zn are 4.5 wt%. It was confirmed that it was contained and dispersed.
The obtained reaction liquid (5a) was heated and concentrated under reduced pressure using an evaporator to obtain a dispersion (5b) having a fine particle concentration of 20 wt%.
[Comparative Example 1-1]
A reaction liquid (C1a) containing white fine particles was obtained in the same manner as in Example 1-1 except that 18 parts of zinc acetate anhydride was used instead of powder (1).

The fine particles in the reaction solution (C1a) are fine particles having an average particle diameter of 20 nm that do not contain Bi as a metal element. As a result of evaluating the diffuse reflection spectrum, absorption based on transition between bands of ZnO crystals was observed, but 400 nm. It was confirmed that no absorption in the above wavelength range was exhibited.
The obtained reaction liquid (C1a) was replaced with a heating solvent to obtain a dispersion (C1b) in which the fine particles were contained and dispersed in 2-propanol at 20 wt%.
"Formation of Bi-containing metal oxide thin film (ultraviolet blocking film)"
[Example 2-1]
10 parts of the powder (1) obtained in Synthesis Example 1, 180 parts of 2-butoxyethanol and 10 parts of acetic acid are mixed and heated at 100 ° C. to thereby form a composition (1) for forming an ultraviolet blocking material (uniform) Solution).

By applying the composition (1) to a glass plate (acrylic glass) as a substrate with a spin coater, raising the temperature in a heating furnace, and holding it for 30 minutes after reaching 500 ° C., by repeating 10 times. A film having a thickness of 0.5 μm was formed on the surface of the glass plate.
As a result of analyzing the formed film, it was a ZnO film made of ZnO crystal like powder XRD and containing 5 atomic% of Bi (III) with respect to Zn.
As a result of evaluating the spectral characteristics of the glass plate (film-coated glass plate) with a film formed on the surface, it absorbs ultraviolet rays over a wide range. Specifically, absorption of 370 nm or less based on the band gap of ZnO (first 1), and absorption (second absorption) based on containing Bi on the long wavelength side having an absorption edge of 416 nm. The transmittance of light of each wavelength was 600 nm: 88%, 500 nm: 86%, 410 nm: 62%, 370 nm: less than 1%. (Note that the transmittance of only the glass plate as the base material was 600 nm: 92%, 410 nm: 90%, 370 nm: 90%.)
The transparency with respect to visible light of the glass plate with a film was “◯”, and coloring was inconspicuous.

[Example 2-2]
By mixing 100 parts of the dispersion (1b) obtained in Example 1-1, 40 parts of a silicate binder (tetramethoxysilane hydrolysis condensate, silica equivalent concentration: 50 wt%) and 1 part of amine as a catalyst, A composition (2) for forming an ultraviolet blocking material was obtained.
The composition (2) was applied to a glass plate similar to that of Example 2-1 with a bar coater, moisture-cured at room temperature, and then heated from room temperature at a temperature increase rate of 2 ° C./min in a heating furnace, By holding at 300 ° C. for 2 hours, a film having a thickness of 4 μm was formed on the surface of the glass plate.
The formed film was a film in which ZnO ultrafine particles in which Bi was dissolved were dispersed and contained in an amorphous silica film.

As a result of evaluating the spectral characteristics of the glass plate with the film formed on the surface (glass plate with film), the film absorbs ultraviolet rays over a wide range, like the glass plate with film of Example 2-1. Indicates the above-described first and second absorptions. The transmittance of light of each wavelength was 600 nm: 84%, 500 nm: 77%, 410 nm: 37%, 370 nm: 1.5%.
The transparency with respect to visible light of the glass plate with a film was “◯”, and coloring was inconspicuous.
[Example 2-3]
By mixing 24 parts of the dispersion (1b) obtained in Example 1-1, 16 parts of an acrylic resin binder (including a polyisocyanurate curing agent) and 50 parts of butyl acetate-toluene as a solvent, an ultraviolet blocking material. A forming composition (3) was obtained.

The composition (3) is applied to a PET film as a substrate with a bar coater so that the dry film thickness is 8 μm, and held at 100 ° C. for 5 minutes, whereby a film with a film thickness of 8 μm is formed on the surface of the PET film. Formed.
The formed film was a film in which ZnO ultrafine particles in which Bi was dissolved were dispersed and contained in an acrylic resin film.
As a result of evaluating the spectral characteristics of the PET film (PET film with film) having a film formed on the surface, excellent ultraviolet rays exhibiting the first and second absorptions as with the film-coated glass plate of Example 2-1. It was a film showing cutability.

The transparency with respect to visible light of the film-coated PET film was “◯”, and coloring was inconspicuous.
[Examples 2-4 and 2-5]
By mixing 100 parts of the dispersion (2b) obtained in Example 1-2 and 100 parts of silica sol (solvent: IPA, silica concentration: 20 wt%) as a binder, a composition for forming an ultraviolet blocking material (4) Got.
By mixing 100 parts of the dispersion (3b) obtained in Example 1-3 and 100 parts of silica sol (solvent: water, silica concentration: 20 wt%) as a binder, a composition for forming an ultraviolet blocking material (5) Got.

The composition (4) and the composition (5) were separately applied to the same glass plate as in Example 2-1, using a bar coater, and heated at 300 ° C., so that the surface of the glass plate had a thickness of 2 μm. A film was formed.
The film formed using the composition (4) was a film in which CeO ₂ ultrafine particles coated with Bi ₂ O ₃ were dispersed and contained in an amorphous silica film. The film formed using the composition (5) was a film in which TiO ₂ ultrafine particles coated with Bi ₂ O ₃ were dispersed and contained in an amorphous silica film.
As a result of evaluating the spectral characteristics of the glass plate (film-attached glass plate) having a film formed on the surface, any of the glass plates with a film absorbs ultraviolet rays having a wavelength of 360 nm or less and further contains Bi. Absorption at 420 nm or less was also shown.

[Example 2-6]
In a reactor similar to Example 1-1, 18 parts of zinc acetate anhydrous powder, 130 parts of methanol and 12 parts of ethylene glycol were charged and heated at 105 ° C. to obtain a uniform solution. By mixing 100 parts of this homogeneous solution and 25 parts of the dispersion (5b) obtained in Example 1-5, an ultraviolet blocking material forming composition (6) was obtained.
The composition (6) was applied to the same glass plate as in Example 2-1 with a spin coater, heated in a heating furnace under a nitrogen atmosphere, and after reaching 350 ° C., held for 30 minutes to form a film did. By repeating this coating to film formation process 20 times, a film having a thickness of 2 μm was formed on the surface of the glass plate.

As a result of analyzing the formed film, it was a ZnO film made of ZnO crystals in powder XRD, and containing both Bi (III) and In (III) at 1.5 atomic% with respect to Zn.
As a result of evaluating the spectral characteristics of the glass plate with the film formed on the surface (glass plate with film), the film absorbs ultraviolet rays over a wide range, like the glass plate with film of Example 2-1. Indicates the above-described first and second absorptions, and further shows a shielding property against light in the near-infrared region.
The transparency with respect to visible light of the film-coated PET film was “◯”, and coloring was inconspicuous.

[Comparative Example 2-1]
In Example 2-2, a composition (C1) for forming an ultraviolet blocking material was similarly obtained except that the dispersion (C1b) obtained in Comparative Example 1-1 was used instead of the dispersion (1b). Got.
Using the composition (C1), a 4 μm-thick film was formed on the surface of the glass plate in the same manner as in Example 2-2.
The formed film was a film in which ZnO fine particles were dispersed and contained in an amorphous silica film.
As a result of evaluating the spectral characteristics of the glass plate with the film formed on the surface (glass plate with film), it absorbs ultraviolet rays of 370 nm or less but does not substantially absorb in the wavelength region of 400 to 800 nm. It was.

[Comparative Example 2-2]
In Example 2-2, instead of the dispersion (1b), except that 100 parts of a dispersion in which Bi ₂ O ₃ fine particles with an average particle diameter of 30 nm were dispersed in 20% by weight in n-propanol was used, Similarly, a composition (C2) for forming an ultraviolet blocking material was obtained.
Using the composition (C2), a film having a thickness of 4 μm was formed on the surface of the glass plate in the same manner as in Example 2-2.
The formed film was a film in which Bi ₂ O ₃ fine particles were dispersed and contained in an amorphous silica film.

  As a result of evaluating the spectral characteristics of the glass plate (film-attached glass plate) having a film formed on the surface, it was capable of blocking ultraviolet rays of 400 nm or less. It was a strong yellowish coloring.

  The ultraviolet blocking film according to the present invention is particularly suitable as a functional film that can effectively cut the long wavelength UV from the wavelength of 400 to 450 nm to the short wavelength side and is excellent in transparency to visible light. By using the ultraviolet blocking metal oxide particles or the ultraviolet blocking material forming composition according to the present invention, the ultraviolet blocking film of the present invention can be easily obtained.

Claims (14)

  An ultraviolet blocking film comprising, as an essential constituent, a mixed crystal (Bi mixed crystal) of a metal oxide containing a metal element other than bismuth as a metal element and bismuth.   The ultraviolet blocking film according to claim 1, further comprising a metal oxide containing a metal element other than bismuth and / or a metal oxide containing bismuth (excluding Bi mixed crystals) as a constituent component.   The ultraviolet blocking film according to claim 1, wherein at least a part of the Bi mixed crystal is present in the film in the form of particles having at least a part as an essential constituent.   The metal oxide particle is an essential constituent component, and the metal oxide particle coexists with a metal oxide containing a metal element other than bismuth as a metal element and a metal oxide containing bismuth (excluding Bi mixed crystals). An ultraviolet blocking film that is a coexistent of metal oxides.   The Bi mixed crystal or the coexisting body is obtained by heating a mixture of a metal element other than bismuth as a metal element and a composite metal carboxylate containing bismuth and an alcohol and / or a component derived from the mixture. The ultraviolet blocking film according to any one of claims 1 to 4, wherein:   The composite metal carboxylate is obtained through a step of heating a metal carboxylate containing a metal element other than bismuth as a metal element and a metal carboxylate containing bismuth with a carboxylic acid-containing solution, Item 6. The ultraviolet blocking film according to Item 5.   A composition for forming an ultraviolet light shielding material, comprising as an essential component a mixture of a metal complex other than bismuth as a metal element and a composite metal carboxylate containing bismuth and an alcohol and / or a component derived from the mixture. Metal oxide particles, a dispersion solvent and / or a binder as essential components,
The metal oxide particles include a metal element other than bismuth as a metal element and a mixed crystal of metal oxide containing bismuth (Bi mixed crystal) and / or a metal oxide and bismuth having a metal element other than bismuth as a metal element. A metal oxide coexisting substance that is essential to coexist with a metal oxide (except for Bi mixed crystals) containing
Composition for forming ultraviolet blocking material. Metal oxide particles, a mixture of a metal carboxylate and an alcohol and / or a component derived from the mixture as an essential constituent,
The metal oxide particles include a metal element other than bismuth as a metal element and a mixed crystal of metal oxide containing bismuth (Bi mixed crystal) and / or a metal oxide and bismuth having a metal element other than bismuth as a metal element. A metal oxide coexisting substance that is essential to coexist with a metal oxide (except for Bi mixed crystals) containing
Composition for forming ultraviolet blocking material.   Metal oxide particles for blocking ultraviolet rays, comprising a mixed element (Bi mixed crystal) of a metal oxide containing a metal element other than bismuth as a metal element and bismuth as an essential component.   The particle according to claim 10, further comprising a metal oxide containing a metal element other than bismuth and / or a metal oxide containing bismuth (excluding the Bi mixed crystal) as a constituent component.   An essential component is a coexistent of a metal oxide that requires that a metal oxide containing a metal element other than bismuth as a metal element and a metal oxide containing bismuth (excluding Bi mixed crystals) coexist. , UV-blocking metal oxide particles.   The Bi mixed crystal or the coexisting body is obtained by heating a mixture of a metal element other than bismuth as a metal element and a composite metal carboxylate containing bismuth and an alcohol and / or a component derived from the mixture. The particle according to any one of claims 10 to 12, wherein:   The composite metal carboxylate is obtained through a step of heating a metal carboxylate containing a metal element other than bismuth as a metal element and a metal carboxylate containing bismuth with a carboxylic acid-containing solution, Item 14. The particle according to Item 13.